WorldWideScience

Sample records for carbon-hydrogen bond functionalization

  1. FINAL TECHNICAL REPORT for grant DE-FG02-93ER14353 "Carbon-Hydrogen Bond Functionalization Catalyzed by Transition Metal Systems"

    Energy Technology Data Exchange (ETDEWEB)

    Goldman, Alan S

    2012-05-21

    Alkanes are our most abundant organic resource but are highly resistant to selective chemical transformations. Alkenes (olefins) by contrast are the single most versatile class of molecules for selective transformations, and are intermediates in virtually every petrochemical process as well as a vast range of commodity and fine chemical processes. Over the course of this project we have developed the most efficient catalysts to date for the selective conversion of alkanes to give olefins, and have applied these catalysts to other dehydrogenation reactions. We have also developed some of the first efficient catalysts for carbonylation of alkanes and arenes to give aldehydes. The development of these catalysts has been accompanied by elucidation of the mechanism of their operation and the factors controlling the kinetics and thermodynamics of C-H bond activation and other individual steps of the catalytic cycles. This fundamental understanding will allow the further improvement of these catalysts, as well as the development of the next generation of catalysts for the functionalization of alkanes and other molecules containing C-H bonds.

  2. Merging allylic carbon-hydrogen and selective carbon-carbon bond activation

    Science.gov (United States)

    Masarwa, Ahmad; Didier, Dorian; Zabrodski, Tamar; Schinkel, Marvin; Ackermann, Lutz; Marek, Ilan

    2014-01-01

    Since the nineteenth century, many synthetic organic chemists have focused on developing new strategies to regio-, diastereo- and enantioselectively build carbon-carbon and carbon-heteroatom bonds in a predictable and efficient manner. Ideal syntheses should use the least number of synthetic steps, with few or no functional group transformations and by-products, and maximum atom efficiency. One potentially attractive method for the synthesis of molecular skeletons that are difficult to prepare would be through the selective activation of C-H and C-C bonds, instead of the conventional construction of new C-C bonds. Here we present an approach that exploits the multifold reactivity of easily accessible substrates with a single organometallic species to furnish complex molecular scaffolds through the merging of otherwise difficult transformations: allylic C-H and selective C-C bond activations. The resulting bifunctional nucleophilic species, all of which have an all-carbon quaternary stereogenic centre, can then be selectively derivatized by the addition of two different electrophiles to obtain more complex molecular architecture from these easily available starting materials.

  3. Dynamic response of a carbon nanotube-based rotary nano device with different carbon-hydrogen bonding layout

    Science.gov (United States)

    Yin, Hang; Cai, Kun; Wan, Jing; Gao, Zhaoliang; Chen, Zhen

    2016-03-01

    In a nano rotational transmission system (RTS) which consists of a single walled carbon nanotube (SWCNT) as the motor and a coaxially arranged double walled carbon nanotube (DWCNT) as a bearing, the interaction between the motor and the rotor in bearing, which has great effects on the response of the RTS, is determined by their adjacent edges. Using molecular dynamics (MD) simulation, the interaction is analyzed when the adjacent edges have different carbon-hydrogen (Csbnd H) bonding layouts. In the computational models, the rotor in bearing and the motor with a specific input rotational speed are made from the same armchair SWCNT. Simulation results demonstrate that a perfect rotational transmission could happen when the motor and rotor have the same Csbnd H bonding layout on their adjacent ends. If only half or less of the carbon atoms on the adjacent ends are bonded with hydrogen atoms, the strong attraction between the lower speed (100 GHz) motor and rotor leads to a synchronous rotational transmission. If only the motor or the rotor has Csbnd H bonds on their adjacent ends, no rotational transmission happens due to weak interaction between the bonded hydrogen atoms on one end with the sp1 bonded carbon atoms on the other end.

  4. Ultrafast studies of organometallic photochemistry: The mechanism of carbon-hydrogen bond activation in solution

    Energy Technology Data Exchange (ETDEWEB)

    Bromberg, S.E.

    1998-05-01

    When certain organometallic compounds are photoexcited in room temperature alkane solution, they are able to break or activate the C-H bonds of the solvent. Understanding this potentially practical reaction requires a detailed knowledge of the entire reaction mechanism. Because of the dynamic nature of chemical reactions, time-resolved spectroscopy is commonly employed to follow the important events that take place as reactants are converted to products. For the organometallic reactions examined here, the electronic/structural characteristics of the chemical systems along with the time scales for the key steps in the reaction make ultrafast UV/Vis and IR spectroscopy along with nanosecond Step-Scan FTIR spectroscopy the ideal techniques to use for this study. An initial study of the photophysics of (non-activating) model metal carbonyls centering on the photodissociation of M(CO){sub 6} (M = Cr, W, Mo) was carried out in alkane solutions using ultrafast IR spectroscopy. Next, picosecond UV/vis studies of the C-H bond activation reaction of Cp{sup *}M(CO){sub 2} (M = Rh, Ir), conducted in room temperature alkane solution, are described in an effort to investigate the origin of the low quantum yield for bond cleavage ({approximately}1%). To monitor the chemistry that takes place in the reaction after CO is lost, a system with higher quantum yield is required. The reaction of Tp{sup *}Rh(CO){sub 2} (Tp{sup *} = HB-Pz{sub 3}{sup *}, Pz{sup *} = 3,5-dimethylpyrazolyl) in alkanes has a quantum yield of {approximately}30%, making time resolved spectroscopic measurements possible. From ultrafast IR experiments, two subsequently formed intermediates were observed. The nature of these intermediates are discussed and the first comprehensive reaction mechanism for a photochemical C-H activating organometallic complex is presented.

  5. Automating Partial Period Bond Valuation with Excel's Day Counting Functions

    Science.gov (United States)

    Vicknair, David; Spruell, James

    2009-01-01

    An Excel model for calculating the actual price of bonds under a 30 day/month, 360 day/year day counting assumption by nesting the DAYS360 function within the PV function is developed. When programmed into an Excel spreadsheet, the model can accommodate annual and semiannual payment bonds sold on or between interest dates using six fundamental…

  6. Two different carbon-hydrogen complexes in silicon with closely spaced energy levels

    International Nuclear Information System (INIS)

    An acceptor and a single donor state of carbon-hydrogen defects (CHA and CHB) are observed by Laplace deep level transient spectroscopy at 90 K. CHA appears directly after hydrogenation by wet chemical etching or hydrogen plasma treatment, whereas CHB can be observed only after a successive annealing under reverse bias at about 320 K. The activation enthalpies of these states are 0.16 eV for CHA and 0.14 eV for CHB. Our results reconcile previous controversial experimental results. We attribute CHA to the configuration where substitutional carbon binds a hydrogen atom on a bond centered position between carbon and the neighboring silicon and CHB to another carbon-hydrogen defect

  7. Organic chemistry. Functionalization of C(sp3)-H bonds using a transient directing group.

    Science.gov (United States)

    Zhang, Fang-Lin; Hong, Kai; Li, Tuan-Jie; Park, Hojoon; Yu, Jin-Quan

    2016-01-15

    Proximity-driven metalation has been extensively exploited to achieve reactivity and selectivity in carbon-hydrogen (C-H) bond activation. Despite the substantial improvement in developing more efficient and practical directing groups, their stoichiometric installation and removal limit efficiency and, often, applicability as well. Here we report the development of an amino acid reagent that reversibly reacts with aldehydes and ketones in situ via imine formation to serve as a transient directing group for activation of inert C-H bonds. Arylation of a wide range of aldehydes and ketones at the β or γ positions proceeds in the presence of a palladium catalyst and a catalytic amount of amino acid. The feasibility of achieving enantioselective C-H activation reactions using a chiral amino acid as the transient directing group is also demonstrated.

  8. Universal bond correlation function for two-dimensional polymer rings

    OpenAIRE

    Sakaue, Takahiro; Witz, Guillaume; Dietler, Giovanni; Wada, Hirofumi

    2010-01-01

    The bond orientational correlation function (BCF) of a semiflexible ring polymer on a flat surface is studied theoretically. For a stiff chain, we give an exact analytic form of BCF with perturbation calculations. For a chain sufficiently longer than its persistence length, the conventional exponential decay vanishes and a long-range order along the chain contour appears. We demonstrate that the bond orientational correlation satisfies the scaling properties, and construct an interpolating fo...

  9. Density functional study of the bonding in small silicon clusters

    International Nuclear Information System (INIS)

    We report the ground electronic state, equilibrium geometry, vibrational frequencies, and binding energy for various isomers of Sin(n = 2--8) obtained with the linear combination of atomic orbitals-density functional method. We used both a local density approximation approach and one with gradient corrections. Our local density approximation results concerning the relative stability of electronic states and isomers are in agreement with Hartree--Fock and Moller--Plesset (MP2) calculations [K. Raghavachari and C. M. Rohlfing, J. Chem. Phys. 89, 2219 (1988)]. The binding energies calculated with the gradient corrected functional are in good agreement with experiment (Si2 and Si3) and with the best theoretical estimates. Our analysis of the bonding reveals two limiting modes of bonding and classes of silicon clusters. One class of clusters is characterized by relatively large s atomic populations and a large number of weak bonds, while the other class of clusters is characterized by relatively small s atomic populations and a small number of strong bonds

  10. Metal nanoparticles functionalized with metal-ligand covalent bonds

    Science.gov (United States)

    Kang, Xiongwu

    Metal-organic contact has been recognized to play important roles in regulation of optical and electronic properties of nanoparticles. In this thesis, significant efforts have been devoted into synthesis of ruthenium nanoparticles with various metal-ligand interfacial linkages and investigation of their electronic and optical properties. Ruthenium nanoparticles were prepared by the self-assembly of functional group onto bare Ru colloid surface. As to Ru-alkyne nanoparticles, the formation of a Ru-vinylidene (Ru=C=CH--R) interfacial bonding linkage was confirmed by the specific reactivity of the nanoparticles with imine derivatives and olefin at the metal-ligand interface, as manifested in NMR, photoluminescence, and electrochemical measurements. Interestingly, it was found the electronic coupling coefficient (beta)for strongly depend upon such metal-ligand interfacial bonding. Next, such metal-ligand interfacial bonding was extended to ruthenium-nitrene pi bonds on ruthenium colloids, which were investigated by XPS. The nanoparticles exhibited a 1:1 atomic ratio of nitrogen to sulfur, consistent with that of sulfonyl nitrene fragments. In addition, the nanoparticle-bound nitrene moieties behaved analogously to azo derivatives, as manifested in UV-vis and fluorescence measurements. Further testimony of the formation of Ru=N interfacial linkages was highlighted in the unique reactivity of the nanoparticles with alkenes by imido transfer. Extensive conjugation between metal-ligand interfacial bond results in remarkable intraparticle charge delocalization on Ru-alkynide nanoparticles, which was manipulated by simple chemical reduction or oxidation. Charging of extra electrons into the nanoparticle cores led to an electron-rich metal core and hence red-shift of the triple bond stretching mode, lower binding energy of sp hybridized C 1s and dimmed fluorescence of nanoparticles. Instead, chemical oxidation resulted in the opposite impacts on these properties. By taking

  11. Density Functional Calculations on a Double Hydrogen-bonded Dimer

    Institute of Scientific and Technical Information of China (English)

    建方方; 赵朴素; 汪庆祥

    2005-01-01

    Density functional theory (DFT) calculations on a double hydrogen-bonded dimer of o-hydroxybenzoic acid were carried out at the B3LYP/6-31G* level. The optimized geometry of the dimer closely resembles that of the crystal. The calculated results show that the total energy of the dimer is much lower than the sum energies of the two monomers, and the average strength of the double hydrogen bonds is about 38.37 kJ/mol. In order to probe the origin of the interactions in the dimer, natural bond orbital analyses were performed. The thermodynamic properties of the title compound at different temperatures have also been calculated on the basis of vibrational analyses and AGT, the change of Gibbs free energy for the aggregation from monomer to the dimmer, is 26.47 k J/mol at 298.15 K and 0. 1 Mpa, implying the spontaneous process of forming the dimer. The correlation graphics of Som, Hom and temperatures is depicted.

  12. Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

    Science.gov (United States)

    Sharma, Ankit; Hartwig, John F

    2013-11-27

    We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

  13. Covalent bonding from alchemical linear response density functional theory

    CERN Document Server

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

    2015-01-01

    We assess the predictive accuracy of linear response based estimates of changes in covalent bonding due to linear alchemical interpolations among molecules. We have investigated single bonds to hydrogen, as well as single, double, and triple bonds between main-group elements, occurring in small iso-electronic molecular spaces with atomic elements drawn from rows 2-3 in the $p$-block of the periodic table. Numerical evidence suggests that first order estimates of bonding potentials can achieve chemical accuracy if the alchemical interpolation connects molecules containing late elements in the periodic table (3$^{rd}$ and 4$^{th}$ row) and identical number of atoms and molecular geometries. For these interpolations, changes in bonding potential are near-linear in the coupling parameter, resulting in accurate Hellmann-Feynman predictions. Second order estimates for such interpolations yield worse predictions. The predictions become substantially worse if initial and final molecules differ not only in composition...

  14. Cavity partition and functionalization of a [2+3] organic molecular cage by inserting polar P[double bond, length as m-dash]O bonds.

    Science.gov (United States)

    Feng, Genfeng; Liu, Wei; Peng, Yuxin; Zhao, Bo; Huang, Wei; Dai, Yafei

    2016-07-28

    The cavity of a [2+3] organic molecular cage was partitioned and functionalized by inserting inner-directed P[double bond, length as m-dash]O bonds, which shows CO2 capture and CH4 exclusion due to the size-matching and polarity effects. Computational results demonstrate that the successful segmentation via polar P[double bond, length as m-dash]O bonds facilitates the CO2 molecules to reside selectively inside the cavity. PMID:27356151

  15. Haruspicy 3: The directed bond-animal generating function is not D-finite

    OpenAIRE

    Rechnitzer, Andrew

    2004-01-01

    While directed site-animals have been solved on several lattices, directed bond-animals remain unsolved on any non-trivial lattice. In this paper we demonstrate that the anisotropic generating function of directed bond-animals on the square lattice is fundamentally different from that of directed site-animals in that it is not differentiably finite. We also extend this result to directed bond-animals on hypercubic lattices. This indicates that directed bond-animals are unlikely to be solved b...

  16. The Breathing Orbital Valence Bond Method in Diffusion Monte Carlo: C-H Bond Dissociation ofAcetylene

    Energy Technology Data Exchange (ETDEWEB)

    Domin, D.; Braida, Benoit; Lester Jr., William A.

    2008-05-30

    This study explores the use of breathing orbital valence bond (BOVB) trial wave functions for diffusion Monte Carlo (DMC). The approach is applied to the computation of the carbon-hydrogen (C-H) bond dissociation energy (BDE) of acetylene. DMC with BOVB trial wave functions yields a C-H BDE of 132.4 {+-} 0.9 kcal/mol, which is in excellent accord with the recommended experimental value of 132.8 {+-} 0.7 kcal/mol. These values are to be compared with DMC results obtained with single determinant trial wave functions, using Hartree-Fock orbitals (137.5 {+-} 0.5 kcal/mol) and local spin density (LDA) Kohn-Sham orbitals (135.6 {+-} 0.5 kcal/mol).

  17. Hydrogen bonding in the protic ionic liquid triethylammonium nitrate explored by density functional tight binding simulations

    CERN Document Server

    Zentel, Tobias

    2016-01-01

    The applicability of the density functional based tight binding (DFTB) method to the description of hydrogen bond dynamics and infrared spectroscopy is addressed for the exemplary protic ionic liquid triethylammonium nitrate. Potential energy curves for proton transfer in gas and liquid phase are shown to be comparable to high level coupled cluster theory in the thermally accessible range of bond lengths. Geometric correlations in the hydrogen bond dynamics are analyzed for a cluster of six ion pairs. Comparing DFTB and regular DFT data lends further support for the reliability of the DFTB method. Therefore, DFTB bulk simulations are performed to quantify the extent of geometric correlations in terms of Pauling's bond order model. Further, infrared (IR) absorption spectra are obtained and analyzed putting emphasis on the signatures of hydrogen bonding in the NH-stretching and far IR hydrogen bond range.

  18. Atom and Bond Fukui Functions and Matrices: A Hirshfeld-I Atoms-in-Molecule Approach.

    Science.gov (United States)

    Oña, Ofelia B; De Clercq, Olivier; Alcoba, Diego R; Torre, Alicia; Lain, Luis; Van Neck, Dimitri; Bultinck, Patrick

    2016-09-19

    The Fukui function is often used in its atom-condensed form by isolating it from the molecular Fukui function using a chosen weight function for the atom in the molecule. Recently, Fukui functions and matrices for both atoms and bonds separately were introduced for semiempirical and ab initio levels of theory using Hückel and Mulliken atoms-in-molecule models. In this work, a double partitioning method of the Fukui matrix is proposed within the Hirshfeld-I atoms-in-molecule framework. Diagonalizing the resulting atomic and bond matrices gives eigenvalues and eigenvectors (Fukui orbitals) describing the reactivity of atoms and bonds. The Fukui function is the diagonal element of the Fukui matrix and may be resolved in atom and bond contributions. The extra information contained in the atom and bond resolution of the Fukui matrices and functions is highlighted. The effect of the choice of weight function arising from the Hirshfeld-I approach to obtain atom- and bond-condensed Fukui functions is studied. A comparison of the results with those generated by using the Mulliken atoms-in-molecule approach shows low correlation between the two partitioning schemes.

  19. Performance of a Nonempirical Density Functional on Molecules and Hydrogen-Bonded Complexes

    CERN Document Server

    Mo, Yuxiang; Car, Roberto; Staroverov, Viktor N; Scuseria, Gustavo E; Tao, Jianmin

    2016-01-01

    Recently, Tao and Mo (TM) derived a new meta-generalized gradient approximation based on a model exchange hole. In this work, the performance of this functional is assessed on standard test sets, using the 6-311++G(3df,3pd) basis set. These test sets include 223 G3/99 enthalpies of formation, 58 electron affinities, 8 proton affinities, 96 bond lengths, 82 harmonic vibrational frequencies, and 10 hydrogen-bonded molecular complexes. Our calculations show that the TM functional can achieve remarkable accuracy for most molecular properties, improving upon non-empirical density functionals considered here. In particular, it delivers the best accuracy for proton affinities, harmonic vibrational frequencies, and hydrogen-bonded dissociation energies and bond lengths, compared to other semilocal density-functional approximations considered in this work.

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

    Science.gov (United States)

    Schmiedekamp, Ann; Nanda, Vikas

    2009-07-01

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

  1. SCAN: An Efficient Density Functional Yielding Accurate Structures and Energies of Diversely-Bonded Materials

    Science.gov (United States)

    Sun, Jianwei

    The accuracy and computational efficiency of the widely used Kohn-Sham density functional theory (DFT) are limited by the approximation to its exchange-correlation energy Exc. The earliest local density approximation (LDA) overestimates the strengths of all bonds near equilibrium (even the vdW bonds). By adding the electron density gradient to model Exc, generalized gradient approximations (GGAs) generally soften the bonds to give robust and overall more accurate descriptions, except for the vdW interaction which is largely lost. Further improvement for covalent, ionic, and hydrogen bonds can be obtained by the computationally more expensive hybrid GGAs, which mix GGAs with the nonlocal exact exchange. Meta-GGAs are still semilocal in computation and thus efficient. Compared to GGAs, they add the kinetic energy density that enables them to recognize and accordingly treat different bonds, which no LDA or GGA can. We show here that the recently developed non-empirical strongly constrained and appropriately normed (SCAN) meta-GGA improves significantly over LDA and the standard Perdew-Burke-Ernzerhof GGA for geometries and energies of diversely-bonded materials (including covalent, metallic, ionic, hydrogen, and vdW bonds) at comparable efficiency. Often SCAN matches or improves upon the accuracy of a hybrid functional, at almost-GGA cost. This work has been supported by NSF under DMR-1305135 and CNS-09-58854, and by DOE BES EFRC CCDM under DE-SC0012575.

  2. van der Waals Bonding in Layered Compounds from Advanced Density-Functional First-Principles Calculations

    OpenAIRE

    Björkman, T.; Gulans, A.; Krasheninnikov, A. V.; Nieminen, Risto M.

    2012-01-01

    Although the precise microscopic knowledge of van der Waals interactions is crucial for understanding bonding in weakly bonded layered compounds, very little quantitative information on the strength of interlayer interaction in these materials is available, either from experiments or simulations. Here, using many-body perturbation and advanced density-functional theory techniques, we calculate the interlayer binding and exfoliation energies for a large number of layered compounds and show tha...

  3. The anchoring function: parental authority and the parent-child bond.

    Science.gov (United States)

    Omer, Haim; Steinmetz, Sarit G; Carthy, Tal; von Schlippe, Arist

    2013-06-01

    Descriptions of parental authority and of the formation of a secure parent-child bond have remained unconnected in conceptualizations about parenting and child development. The parental anchoring function is here presented as an integrative metaphor for the two fields. Parents who fulfill an anchoring function offer a secure relational frame for the child, while also manifesting a stabilizing and legitimate kind of authority. The anchoring function enriches the two fields by: (1) adding a dimension of authority to the acknowledged functions of the safe haven and the secure base that are seen as core to a secure parent-child bond, and (2) adding considerations about the parent-child bond to Baumrind's classical description of authoritative parenting.

  4. The anchoring function: parental authority and the parent-child bond.

    Science.gov (United States)

    Omer, Haim; Steinmetz, Sarit G; Carthy, Tal; von Schlippe, Arist

    2013-06-01

    Descriptions of parental authority and of the formation of a secure parent-child bond have remained unconnected in conceptualizations about parenting and child development. The parental anchoring function is here presented as an integrative metaphor for the two fields. Parents who fulfill an anchoring function offer a secure relational frame for the child, while also manifesting a stabilizing and legitimate kind of authority. The anchoring function enriches the two fields by: (1) adding a dimension of authority to the acknowledged functions of the safe haven and the secure base that are seen as core to a secure parent-child bond, and (2) adding considerations about the parent-child bond to Baumrind's classical description of authoritative parenting. PMID:23763680

  5. METAL NANOPARTICLES FUNCTIONALIZED WITH METAL-LIGAND COVALENT BONDS

    OpenAIRE

    Kang, Xiongwu

    2012-01-01

    Metal-organic contact has been recognized to play important roles in regulation of optical and electronic properties of nanoparticles. In this thesis, significant efforts have been devoted into synthesis of ruthenium nanoparticles with various metal-ligand interfacial linkages and investigation of their electronic and optical properties. Ruthenium nanoparticles were prepared by the self-assembly of functional group onto bare Ru colloid surface. As to Ru-alkyne nanoparticles, the formation of ...

  6. Performance of a Nonempirical Density Functional on Molecules and Hydrogen-Bonded Complexes

    OpenAIRE

    Mo, Yuxiang; Tian, Guocai; Car, Roberto; Viktor N. Staroverov; Scuseria, Gustavo E.; Tao, Jianmin

    2016-01-01

    Recently, Tao and Mo (TM) derived a new meta-generalized gradient approximation based on a model exchange hole. In this work, the performance of this functional is assessed on standard test sets, using the 6-311++G(3df,3pd) basis set. These test sets include 223 G3/99 enthalpies of formation, 58 electron affinities, 8 proton affinities, 96 bond lengths, 82 harmonic vibrational frequencies, and 10 hydrogen-bonded molecular complexes. Our calculations show that the TM functional can achieve rem...

  7. Structure-directing factors when introducing hydrogen bond functionality to metal-organic frameworks

    OpenAIRE

    Forgan, Ross S.; Marshall, Ross J.; Struckmann, Mona; Bleine, Aurore; Long, De-Liang; Bernini, Maria Celeste; Fairen-Jimenez, David

    2015-01-01

    The introduction of H-bond donor/acceptor functionality into metal-organic frameworks (MOFs) can have a beneficial effect on their molecular recognition, uptake selectivity and catalytic properties. The changes in ligand geometry induced by incorporation of functional groups may also affect the topology and composition of the resultant MOFs. Herein, we present a comprehensive study of functional group incorporation into MOFs, linked by either Zn2+ paddlewheel units or monomeric Zn2+ corners, ...

  8. Site-selective and stereoselective functionalization of unactivated C–H bonds

    Science.gov (United States)

    Liao, Kuangbiao; Negretti, Solymar; Musaev, Djamaladdin G.; Bacsa, John; Davies, Huw M. L.

    2016-05-01

    The laboratory synthesis of complex organic molecules relies heavily on the introduction and manipulation of functional groups, such as carbon–oxygen or carbon–halogen bonds; carbon–hydrogen bonds are far less reactive and harder to functionalize selectively. The idea of C–H functionalization, in which C–H bonds are modified at will instead of the functional groups, represents a paradigm shift in the standard logic of organic synthesis. For this approach to be generally useful, effective strategies for site-selective C–H functionalization need to be developed. The most practical solutions to the site-selectivity problem rely on either intramolecular reactions or the use of directing groups within the substrate. A challenging, but potentially more flexible approach, would be to use catalyst control to determine which site in a particular substrate would be functionalized. Here we describe the use of dirhodium catalysts to achieve highly site-selective, diastereoselective and enantioselective C–H functionalization of n-alkanes and terminally substituted n-alkyl compounds. The reactions proceed in high yield, and functional groups such as halides, silanes and esters are compatible with this chemistry. These studies demonstrate that high site selectivity is possible in C–H functionalization reactions without the need for a directing or anchoring group present in the molecule.

  9. Efficient photolytic C-H bond functionalization of alkylbenzene with hypervalent iodine(iii) reagent.

    Science.gov (United States)

    Sakamoto, Ryu; Inada, Tsubasa; Selvakumar, Sermadurai; Moteki, Shin A; Maruoka, Keiji

    2016-03-01

    A practical approach to radical C-H bond functionalization by the photolysis of a hypervalent iodine(iii) reagent is presented. The photolysis of [bis(trifluoroacetoxy)iodo]benzene (PIFA) leads to the generation of trifluoroacetoxy radicals, which allows the smooth transformation of various alkylbenzenes to the corresponding benzyl ester compounds under mild reaction conditions. PMID:26686276

  10. Tensile bond strength of polyvinyl siloxane impressions bonded to a custom tray as a function of drying time: Part I.

    Science.gov (United States)

    Cho, G C; Donovan, T E; Chee, W W; White, S N

    1995-05-01

    Time-dependent bond strength studies of two polyvinyl siloxane impression materials to acrylic resin disks with their respective adhesives were studied to determine the optimal time for maximum bond strength. Six groups were tested with varying adhesive dry times of 0, 7, 15, and 60 minutes and 8 and 24 hours before testing. The results indicated that the bond strength of the adhesive increased at least twofold from time zero to 7 minutes adhesive dry time and peaked at 60 minutes for one of the materials and at 8 hours for the other. Bond strengths increased rapidly to the 15-minute test interval and then seemed to plateau. Both materials exhibited decreased adhesive bond strengths at 24 hours.

  11. Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional

    Science.gov (United States)

    Sun, Jianwei; Remsing, Richard C.; Zhang, Yubo; Sun, Zhaoru; Ruzsinszky, Adrienn; Peng, Haowei; Yang, Zenghui; Paul, Arpita; Waghmare, Umesh; Wu, Xifan; Klein, Michael L.; Perdew, John P.

    2016-09-01

    One atom or molecule binds to another through various types of bond, the strengths of which range from several meV to several eV. Although some computational methods can provide accurate descriptions of all bond types, those methods are not efficient enough for many studies (for example, large systems, ab initio molecular dynamics and high-throughput searches for functional materials). Here, we show that the recently developed non-empirical strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation (meta-GGA) within the density functional theory framework predicts accurate geometries and energies of diversely bonded molecules and materials (including covalent, metallic, ionic, hydrogen and van der Waals bonds). This represents a significant improvement at comparable efficiency over its predecessors, the GGAs that currently dominate materials computation. Often, SCAN matches or improves on the accuracy of a computationally expensive hybrid functional, at almost-GGA cost. SCAN is therefore expected to have a broad impact on chemistry and materials science.

  12. Atom probe tomography simulations and density functional theory calculations of bonding energies in Cu3Au

    KAUST Repository

    Boll, Torben

    2012-10-01

    In this article the Cu-Au binding energy in Cu3Au is determined by comparing experimental atom probe tomography (APT) results to simulations. The resulting bonding energy is supported by density functional theory calculations. The APT simulations are based on the Müller-Schottky equation, which is modified to include different atomic neighborhoods and their characteristic bonds. The local environment is considered up to the fifth next nearest neighbors. To compare the experimental with simulated APT data, the AtomVicinity algorithm, which provides statistical information about the positions of the neighboring atoms, is applied. The quality of this information is influenced by the field evaporation behavior of the different species, which is connected to the bonding energies. © Microscopy Society of America 2012.

  13. Silver-catalyzed silicon-hydrogen bond functionalization by carbene insertion.

    Science.gov (United States)

    Iglesias, M José; Nicasio, M Carmen; Caballero, Ana; Pérez, Pedro J

    2013-01-28

    The catalytic functionalization of silicon-hydrogen bonds by means of the insertion of carbene units :CHCO(2)Et from ethyl diazoacetate (EDA) has been achieved using a silver-based catalyst, constituting the first example of this metal to promote this transformation. Competition experiments have revealed that the relative reactivity of substituted silanes depends on the bond dissociation energy of the Si-H bond (tertiary > secondary > primary for ethyl substituted). In the presence of bulky substituents such order reverts to secondary > primary ≈ tertiary (for phenyl substituted). Screening with other diazo compounds has shown that N(2)C(Ph)CO(2)Et displays similar reactivity to that of EDA, whereas other N(2)C(R)CO(2)Et (R = Me, CO(2)Et) gave lower conversions. PMID:23114570

  14. Density Functional Theory Study of Hydrogen Bonds of Bipyridine with 1,3,5-Benzenetricarboxylic Acid

    Institute of Scientific and Technical Information of China (English)

    LI Quan; ZHAO Keqing

    2009-01-01

    The hydrogen-bonded dimer and trimer formed between 1,3,5-benzenetricarboxylic acid and bipyridine have been investigated using a density functional theory(DFT)method and 6-31++G** basis set.The interaction enerstretching modes in the dimer and trimer red-shifted relative to those of the 1,3,5-benzenetricarhoxylic acid monomer.The natural bond orbit analysis shows that the inter-molecular charge transfers are 0.60475e and 1.20225e for the dimer and trimer,respectively.Thermodynamic analysis indicates that the formation of trimer is an exothermic H-O intermolecular hydrogen bonds between bipyridine and 1,3,5-benzenetricarboxylic acid,which is in good agreement with the experimental results.

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

    International Nuclear Information System (INIS)

    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

  16. 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.

  17. Development of Affordable, Low-Carbon Hydrogen Supplies at an Industrial Scale

    Science.gov (United States)

    Roddy, Dermot J.

    2008-01-01

    An existing industrial hydrogen generation and distribution infrastructure is described, and a number of large-scale investment projects are outlined. All of these projects have the potential to generate significant volumes of low-cost, low-carbon hydrogen. The technologies concerned range from gasification of coal with carbon capture and storage…

  18. Hydrogen-bonded Intramolecular Charge Transfer Excited State of Dimethylaminobenzophenone using Time Dependent Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    Yu-ling Chu; Zhong Yang; Zhe-feng Pan; Jing Liu; Yue-yi Han; Yong Ding; Peng Song

    2012-01-01

    Density functional theory and time-dependent density-functional theory have been used to investigate the photophysical properties and relaxation dynamics of dimethylaminobenzophenone (DMABP) and its hydrogen-bonded DMABP-MeOH dimer.It is found that,in nonpolar aprotic solvent,the transitions from S0 to S1 and S2 states of DMABP have both n→π* and π→π* characters,with the locally excited feature mainly located on the C=O group and the partial CT one characterized by electron transfer mainly from the dimethylaminophenyl group to the C=O group.But when the intermolecular hydrogen bond C=O…H-O is formed,the highly polar intramolecular charge transfer character switches over to the first excited state of DMABP-MeOH dimer and the energy difference between the two lowlying electronically excited states increases.To gain insight into the relaxation dynamics of DMABP and DMABP-MeOH dimer in the excited state,the potential energy curves for conformational relaxation are calculated.The formation of twisted intramolecular charge transfer state via diffusive twisting motion of the dimethylamino/dimethylaminophenyl groups is found to be the major relaxation process.In addition,the decay of the S1 state of DMABP-MeOH dimer to the ground state,through nonradiative intermolecular hydrogen bond stretching vibrations,is facilitated by the formation of the hydrogen bond between DMABP and alcohols.

  19. Enhancement of dispersion and bonding of graphene-polymer through wet transfer of functionalized graphene oxide

    Directory of Open Access Journals (Sweden)

    F. Sharif

    2012-12-01

    Full Text Available Dispersion of nanomaterials in polymeric matrices plays an important role in determining the final properties of the composites. Dispersion in nano scale, and especially in single layers, provides best opportunity for bonding. In this study, we propose that by proper functionalization and mixing strategy of graphene its dispersion, and bonding to the polymeric matrix can be improved. We then apply this strategy to graphene-epoxy system by amino functionalization of graphene oxide (GO. The process included two phase extraction, and resulted in better dispersion and higher loading of graphene in epoxy matrix. Rheological evaluation of different graphene-epoxy dispersions showed a rheological percolation threshold of 0.2 vol% which is an indication of highly dispersed nanosheets. Observation of the samples by optical microscopy, scanning electron microscopy (SEM, and atomic force microscopy (AFM, showed dispersion homogeneity of the sheets at micro and nano scales. Study of graphene-epoxy composites showed good bonding between graphene and epoxy. Mechanical properties of the samples were consistent with theoretical predictions for ideal composites indicating molecular level dispersion and good bonding between nanosheets and epoxy matrix.

  20. Electronic Structure of Dangling Bonds in Amorphous Silicon Studied via a Density-Matrix Functional Method

    OpenAIRE

    Hennig, R. G.; Fedders, P. A.; Carlsson, A. E.

    2002-01-01

    A structural model of hydrogenated amorphous silicon containing an isolated dangling bond is used to investigate the effects of electron interactions on the electronic level splittings, localization of charge and spin, and fluctuations in charge and spin. These properties are calculated with a recently developed density-matrix correlation-energy functional applied to a generalized Anderson Hamiltonian, consisting of tight-binding one-electron terms parametrizing hydrogenated amorphous silicon...

  1. Stressful parental bonding exaggerate the functional and emotional disturbances of primary dysmenorrhea

    OpenAIRE

    Kai XU; Chen, Liuxi; Fu, Lingyun; Mao, Hongjing; Liu, Jian; Wang, Wei

    2014-01-01

    Background: Some evidence suggests that women with primary dysmenorrhea (or painful period) often have traumatic experience with parental attachments, but the exact relationship between styles of the parental bonding and the detailed aspects of the disorder is unclear.Methods: From university-student women, we invited 50 primary dysmenorrhea patients and 111 healthy volunteers to undergo tests of the functional and emotional measure of dysmenorrhea (FEMD), the Family Relationship Questionnair...

  2. Density Functional Theory Study of Red-shifted Hydrogen Bonds of 4-Pyridinemethanol with Water

    Institute of Scientific and Technical Information of China (English)

    LI Quan; CAI Jing; CHEN Jun-Rong; ZHAO Ke-Qing

    2008-01-01

    The hydrogen bonds of 1∶1 and 1∶2 complexes formed between 4-pyridinemethanol and water have been investigated using a density functional theory (DFT) method and 6-311++G** basis set, and three and eight stable geometries have been obtained for 1∶1 and 1∶2 complexes, respectively.The interaction energy is -20.536 and -44.256 kJ/mol for the most stable 1∶1 and 1∶2 complexes, respectively, after the basis set superposition error and zero-point corrections.The formation of O-H…N(O) hydrogen bonds makes O-H symmetric stretching modes in the complexes red-shifted relative to those of the monomer.The natural bond orbit analysis indicates that the intermolecular charge transfer between 4-pyridinemethanol and water is 0.02642 e and 0.03813 e for the most stable 1∶1 and 1∶2 complexes, respectively.In addition, TD-B3LYP/6-311++G** calculations show that formation of water-OH…N and water-OH…OH hydrogen bonds makes maximum absorbance wavelength λmax blue-shifted 8-16 nm and red-shifted 4-11 nm compared to that of 4-pyridinemethanol monomer molecule, respectively.

  3. Functionalization and bioimmobilization of silicon surfaces with Si–N bonded monolayer

    Energy Technology Data Exchange (ETDEWEB)

    Masood, Muhammad Nasir, E-mail: chemnasir_76@yahoo.com [Bios Lab on a Chip Group, MESA+ Institute for Nanotechnology, University of Twente, Enschede (Netherlands); Department of Physics and Applied Mathematics, Pakistan Institute of Engineering and Applied Sciences (PIEAS), Nilore, Islamabad (Pakistan); Carlen, Edwin T.; Berg, Albert van den [Bios Lab on a Chip Group, MESA+ Institute for Nanotechnology, University of Twente, Enschede (Netherlands)

    2015-05-15

    Highlights: • Chemistry of Ethylene diamine (EDA) studied by X-ray photoelectron spectroscopy (XPS) on hydrogen terminated Si (1 1 1) surface under UV-irradiation. • Fast, efficient and selective surface modification via symmetric functional molecule. • Do not involve protection and deprotection steps which deteoriate the monolayer integrity, time consuming and expensive. • Si–N bond remain intact on sub-oxidized silicon surface. • Free amine groups availability for bioimmobilization. • Selectivity and sensitivity was demonstrated by SEM, fluorscence and electrochemical (C–V) measurements. - Abstract: A new method for selective surface functionalization of silicon with a silicon–nitrogen bonded (Si–N) monolayer and subsequent bioimmobilization is presented. The Si–N monolayer was studied using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), fluorescence spectroscopy, and capacitance–voltage (C–V) measurements using an electrolyte insulator semiconductor (EIS) sensor. A symmetric ethylene diamine (EDA, C{sub 2}H{sub 4} (NH{sub 2}){sub 2}) molecule was used as a precursor compound for monolayer formation in an inert environment in the liquid phase. XPS results show the attachment of EDA molecules proceeds via dissociative and dative bond formation whereas free amine groups on the surface were used for further immobilization of biomolecules. SEM shows selective functionalization and bioimmobilization on a patterned surface such as a silicon nanowire on silicon oxide substrate. Biosensing experiments with bioimmobilized surfaces were carried out in aqueous buffer and show high sensitivity for biosensing.

  4. Renormalisation group calculation of correlation functions for the 2D random bond Ising and Potts models

    CERN Document Server

    Dotsenko, V S; Pujol, P; Dotsenko, Vladimir; Picco, Marco; Pujol, Pierre

    1995-01-01

    We find the cross-over behavior for the spin-spin correlation function for the 2D Ising and 3-states Potts model with random bonds at the critical point. The procedure employed is the renormalisation approach of the perturbation series around the conformal field theories representing the pure models. We obtain a crossover in the amplitude for the correlation function for the Ising model which doesn't change the critical exponent, and a shift in the critical exponent produced by randomness in the case of the Potts model. A comparison with numerical data is discussed briefly.

  5. Bond centred functions in relativistic and non-relativistic calculations for diatomics

    International Nuclear Information System (INIS)

    In this paper, we discuss the performance of molecular basis sets consisting of atomic centred (AC) functions augmented with bond centred (BC) functions in relativistic and non-relativistic calculations carried out at the Hartree-Fock and several correlated levels of approximation. While usually non-correlated calculations employing BC functions can be performed at a lower computational cost as compared with those making use of energy optimized AC basis sets, the correlated calculations are always more accurate and less expensive with the latter. It is demonstrated that both correlated or non-correlated calculations always benefit from the addition of a few BC functions with a moderate increase of computational effort. The performance of basis sets containing even-tempered BC functions is also studied and their usage is advocated in case of relativistic calculations

  6. 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).

  7. Role of functional groups in surface bonding of planar π-conjugated molecules

    Science.gov (United States)

    Bauer, Oliver; Mercurio, Giuseppe; Willenbockel, Martin; Reckien, Werner; Heinrich Schmitz, Christoph; Fiedler, Benjamin; Soubatch, Serguei; Bredow, Thomas; Tautz, Frank Stefan; Sokolowski, Moritz

    2012-12-01

    The trends in the bonding mechanism of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) to the Ag(111), Ag(100), and Ag(110) surfaces were analyzed on the basis of data obtained from x-ray standing waves and dispersion-corrected density functional theory. Of importance are the attractive local O-Ag bonds on the anhydride groups. They are the shorter, the more open the surface is, and lead even to partly repulsive interactions between the perylene core and the surface. In parallel, there is an increasing charge donation from the Ag surface into the π system of the PTCDA. This synergism explains the out-of-plane distortion of the adsorbed PTCDA and the surface buckling.

  8. C-F sp(2) bond functionalization mediated by niobium complexes.

    Science.gov (United States)

    Nechayev, Michael; Gianetti, Thomas L; Bergman, Robert G; Arnold, John

    2015-12-01

    Insertion chemistry of isocyanide molecules was used to functionalize C-F sp(2) bonds after their oxidative addition across the metal center in a β-diketiminate niobium(iii) imido complex (BDI)Nb(N(t)Bu)(C6H6). The complexes formed, 3a-b ([BDI]Nb(PhC[double bond, length as m-dash]N)(N(t)Bu)(F) (R = 1,6-diisopropylphenyl, tert-butyl), were characterized by NMR spectroscopy and X-ray analysis. Further treatment with phenylsilane induced H/F exchange under mild conditions, which was followed by hydride transfer to the inserted isocyanide. Divergent reactivity was observed when the two analogous aryl and tert-butyl isocyanide insertion products were treated with phenylsilane. PMID:26216334

  9. Spectroscopic examinations of hydrogen bonding in hydroxy-functionalized ADMET chemistry.

    Science.gov (United States)

    Thompson, Donovan L; Wagener, Kenneth B; Schulze, Ulrich; Voit, Brigitte; Jehnichen, Dieter; Malanin, Mikhail

    2015-01-01

    Wide-angle X-ray scattering (WAXS) and temperature-dependent Fourier transform infrared spectroscopy (FTIR) spectroscopy are used to study hydrogen bonding interactions of a hydroxyl-functionalized polyethylene (PE) prepared by acyclic diene metathesis (ADMET) chemistry. The hydroxyl polymer exhibits an orthorhombic unit cell structure with characteristic reflection planes at (110) and (200), comparable to pure crystalline PE. These data unequivocally demonstrate that the OH branch is excluded from the PE lamellae. Furthermore, the polymer melts 100 °C higher than all previous analogous polymers possessing precision placed long aliphatic branches that also are excluded from PE lamellae. Temperature-dependent FTIR spectroscopy from ambient to 150 °C, followed by cooling to 125 °C supports exclusion of the hydroxyl group from the crystalline lattice. It is concluded that these hydroxyl groups form stable physical networks in the amorphous region via hydrogen bonding and are important for the overall morphology of such polymers. PMID:25393938

  10. An application of the van der Waals density functional: Hydrogen bonding and stacking interactions between nucleobases.

    Science.gov (United States)

    Cooper, Valentino R; Thonhauser, T; Langreth, David C

    2008-05-28

    We apply the van der Waals density functional (vdW-DF) to study hydrogen bonding and stacking interactions between nucleobases. The excellent agreement of our results with high level quantum chemical calculations highlights the value of the vdW-DF for first-principles investigations of biologically important molecules. Our results suggest that, in the case of hydrogen-bonded nucleobase pairs, dispersion interactions reduce the cost of propeller twists while having a negligible effect on buckling. Furthermore, the efficient scaling of DFT methods allowed for the easy optimization of separation distance between nucleobase stacks, indicating enhancements in the interaction energy of up to 3 kcalmol over previous fixed distance calculations. We anticipate that these results are significant for extending the vdW-DF method to model larger vdW complexes and biological molecules. PMID:18513005

  11. Transitioning Towards a Low-Carbon Hydrogen Economy in the United States: Role of Transition Management

    OpenAIRE

    Jacqueline C. K. Lam; Peter Hills; Esther C. T. Wong

    2012-01-01

    This paper describes the process of transitioning to a low-carbon hydrogen economy in the United States and the role of transition management (TM) in this process. Focusing on the transition process for hydrogen-based energy and transport systems in the United States, especially California, this study outlines the key characteristics of TM that have been employed in managing the transition. Several characteristics of TM have been noted in the United States’ hydrogen transition, including: (...

  12. SISGR - Hydrogen Caged in Carbon-Exploration of Novel Carbon-Hydrogen Interactions

    Energy Technology Data Exchange (ETDEWEB)

    Lueking, Angela [Pennsylvania State Univ., State College, PA (United States); Badding, John [Pennsylvania State Univ., State College, PA (United States); Crespi, Vinent [Pennsylvania State Univ., State College, PA (United States)

    2015-12-01

    Hydrogen trapped in a carbon cage, captured through repulsive interactions, is a novel concept in hydrogen storage. Trapping hydrogen via repulsive interactions borrows an idea from macroscale hydrogen storage (i.e. compressed gas storage tanks) and reapplies these concepts on the nanoscale in specially designed molecular containers. Under extreme conditions of pressure, hydrogen solubility in carbon materials is expected to increase and carbon is expected to restructure to minimize volume via a mixed sp2/sp3 hydrogenated state. Thermodynamics dictate that pre-formed C-H structures will rearrange with increased pressure, yet the final carbon-hydrogen interactions may be dependent upon the mechanism by which hydrogen is introduced. Gas “trapping” is meant to denote gas present in a solid in a high density, adsorbed-like state, when the external pressure is much less than that necessary to provide a comparable fluid density. Trapping thus denotes a kinetically metastable state rather than thermodynamic equilibrium. This project probed mechanochemical means to polymerize select hydrocarbons in the presence of gases, in an attempt to form localized carbon cages that trap gases via repulsive interactions. Aromatic, polyaromatic, and hydroaromatic molecules expected to undergo cyclo-addition reactions were polymerized at high (~GPa) pressures to form extended hydrogenated amorphous carbon networks. Notably, aromatics with a pre-existing internal free volume (such as Triptycene) appeared to retain an internal porosity upon application of pressure. However, a high photoluminescence background after polymerization precluded in situ identification of trapped gases. No spectroscopic evidence was found after depressurization that would be indicative of pockets of trapped gases in a localized high-pressure environment. Control studies suggested this measurement may be insensitive to gases at low pressure. Similarly, no spectral fingerprint was found for gas-imbued spherical

  13. Bonding in elemental boron: a view from electronic structure calculations using maximally localized Wannier functions

    Science.gov (United States)

    Ogitsu, Tadashi; Gygi, Francois; Reed, John; Schwegler, Eric; Galli, Giulia

    2007-03-01

    Boron exhibits the most complex structure of all elemental solids, with more than 300 atoms per unit cell arranged in interconnecting icosahedra, and some crystallographic positions occupied with a probability of less than one. The precise determination of the ground state geometry of boron---the so-called β-boron structure--has been elusive and its electronic and bonding properties have been difficult to rationalize. Using lattice model Monte Carlo optimization techniques and ab-initio simulations, we have shown that a defective, quasi-ordered β solid is the most stable structure at zero as well as finite T. In the absence of partially occupied sites (POS), the perfect β-boron crystal is unstable; the presence of POS lower its internal energy below that of an ordered α-phase, not mere an entropic effect. We present a picture of the intricate and unique bonding in boron based on maximally localized Wannier (MLWF) functions, which indicates that the presence of POS provides a subtle, yet essential spatial balance between electron deficient and fully saturated bonds. This work was performed under the auspices of the U.S. Dept. of Energy at the University of California/ LLNL under contract no. W-7405-Eng-48.

  14. Density Functional Calculations of C-NO2 Bond Dissociation Energies for Nitroalkanes Molecules

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Bond dissociation energies for the removal of nitrogen dioxide group in some nitroalkane energetic materials have been calculated by using the three hybrid density functional theory (DFT) methods B3LYP, B3PW91 and B3P86 with 6-31g** and 6-311g** basis sets. The computed BDEs have been compared with the available experimental results. It is found that the B3P86 method with 6-31g** and 6-311g** basis sets can obtain satisfactory bond dissociation energies (BDEs), which are in extraordinary agreement with the experimental data. Considering the smaller mean absolute deviation and maximum difference, the reliable B3P86/6-311g** method was recommended to compute the BDEs for the removal of nitrogen dioxide group in the nitroalkane energetic materials. Using the method, the BDEs of 8 other nitroalkane energetic materials have been calculated and the maximum difference from experimental value is 1.76 kcal·mol-1 (for the BDE of tC4H9-NO2), which further proves the reliability of B3P86/6-311g** method. In addition, it is noted that the BDEs of C-NO2 bond change slightly for main chain nitroalkane compounds with the maximum difference of only 3.43 kcal mol-1.

  15. Glycol-Water Interactions and co-existing phases and Temperature Dependent Solubility. An Example Of Carbon-Hydrogen Chemistry In Water

    CERN Document Server

    Michael, Fredrick

    2010-01-01

    Recently there has been great interest in Glycol-Water chemistry and solubility and temperature dependent phase dynamics. The Glycol-Water biochemistry of interactions is present in plant biology and chemistry, is of great interest to chemical engineers and biochemists as it is a paradigm of Carbon-Hydrogen Water organic chemistry. There is an interest moreover in formulating a simpler theory and computation model for the Glycol-Water interaction and phase dynamics, that is not fully quantum mechanical yet has the high accuracy available from a fully quantum mechanical theory of phase transitions of fluids and Fermi systems. Along these lines of research interest we have derived a Lennard-Jones -like theory of interacting molecules-Water in a dissolved adducts of Glycol-Water system interacting by Hydrogen bonds whose validity is supported at the scale of interactions by other independent molecular dynamics investigations that utilize force fields dependent on their experimental fittings to the Lennard-Jones ...

  16. Tuning and probing interfacial bonding channels for a functionalized organic molecule by surface modification

    Science.gov (United States)

    Mercurio, G.; Bauer, O.; Willenbockel, M.; Fiedler, B.; Sueyoshi, T.; Weiss, C.; Temirov, R.; Soubatch, S.; Sokolowski, M.; Tautz, F. S.

    2013-03-01

    The potassium-induced missing row reconstruction of Ag(110) is used to selectively modify the local chemical interaction between the functional anhydride groups of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) and Ag(110). We find a significant upward shift of the anhydride groups, while the adsorption height of the perylene core is essentially preserved. This demonstrates an attractive perylene/substrate interaction for PTCDA/K:Ag(110), elucidating also the bonding situation for the potassium-free system.

  17. Understanding the bonding nature of uranyl ion and functionalized graphene: a theoretical study.

    Science.gov (United States)

    Wu, Qun-Yan; Lan, Jian-Hui; Wang, Cong-Zhi; Xiao, Cheng-Liang; Zhao, Yu-Liang; Wei, Yue-Zhou; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-03-20

    Studying the bonding nature of uranyl ion and graphene oxide (GO) is very important for understanding the mechanism of the removal of uranium from radioactive wastewater with GO-based materials. We have optimized 22 complexes between uranyl ion and GO applying density functional theory (DFT) combined with quasi-relativistic small-core pseudopotentials. The studied oxygen-containing functional groups include hydroxyl, carboxyl, amido, and dimethylformamide. It is observed that the distances between uranium atoms and oxygen atoms of GO (U-OG) are shorter in the anionic GO complexes (uranyl/GO(-/2-)) compared to the neutral GO ones (uranyl/GO). The formation of hydrogen bonds in the uranyl/GO(-/2-) complexes can enhance the binding ability of anionic GO toward uranyl ions. Furthermore, the thermodynamic calculations show that the changes of the Gibbs free energies in solution are relatively more negative for complexation reactions concerning the hydroxyl and carboxyl functionalized anionic GO complexes. Therefore, both the geometries and thermodynamic energies indicate that the binding abilities of uranyl ions toward GO modified by hydroxyl and carboxyl groups are much stronger compared to those by amido and dimethylformamide groups. This study can provide insights for designing new nanomaterials that can efficiently remove radionuclides from radioactive wastewater.

  18. Density functional for van der Waals forces accounts for hydrogen bond in benchmark set of water hexamers

    DEFF Research Database (Denmark)

    Kelkkanen, Kari André; Lundqvist, Bengt; Nørskov, Jens Kehlet

    2009-01-01

    A recent extensive study has investigated how various exchange-correlation (XC) functionals treat hydrogen bonds in water hexamers and has shown traditional generalized gradient approximation and hybrid functionals used in density-functional (DF) theory to give the wrong dissociation-energy trend...

  19. Density Functional Studies of the C-F Bond Activation of CF3 Radical by Bare Co +

    Institute of Scientific and Technical Information of China (English)

    张冬菊; 刘成卜; 胡海泉; 刘永军

    2001-01-01

    The C—F bond activation mechanism of CF3 radical by bare Co + has been studied by density functional theory. Three local minima and two first-order saddle points were located for the potential energy surface (PES) of [Co, C, F3] + . The activation barrier involving C-F bond activation was calculated to be only 14.73 kJ/mol, while the largest barrier of 149.29 kJ/mol on the PES involves Co-C bond rupture.The bonding mechanism between Co + , C and F atoms were discussed based on Mulliken population. The relevant bond dissociation energy and thermochmistry data were calculated with the limited experimental values, and the results are in good agreement with the experimental findings.

  20. Hydrogen bonds in the nucleobase-gold complexes: Photoelectron spectroscopy and density functional calculations

    Science.gov (United States)

    Cao, Guo-Jin; Xu, Hong-Guang; Li, Ren-Zhong; Zheng, Weijun

    2012-01-01

    The nucleobase-gold complexes were studied with anion photoelectron spectroscopy and density functional calculations. The vertical detachment energies of uracil-Au-, thymine-Au-, cytosine-Au-, adenine-Au-, and guanine-Au- were estimated to be 3.37 ± 0.08 eV, 3.40 ± 0.08 eV, 3.23 ± 0.08 eV, 3.28 ± 0.08 eV, and 3.43 ± 0.08 eV, respectively, based on their photoelectron spectra. The combination of photoelectron spectroscopy experiments and density functional calculations reveals the presence of two or more isomers for these nucleobase-gold complexes. The major isomers detected in the experiments probably are formed by Au anion with the canonical tautomers of the nucleobases. The gold anion essentially interacts with the nucleobases through N-H...Au hydrogen bonds.

  1. Hydrogen-bonding interactions between a nitrile-based functional ionic liquid and DMSO

    Science.gov (United States)

    Zheng, Yan-Zhen; Zhou, Yu; Deng, Geng; Yu, Zhi-Wu

    2016-11-01

    Task-specific ionic liquids (TSILs) have been introduced by incorporating additional functional groups in the cation or anion to impart specific properties or reactivates. In this work, the hydrogen-bonding interactions between a nitrile-functional TSIL 1-propylnitrile-3-methylimidazolium tetrafluoroborate ([PCNMIM][BF4]) and dimethyl sulphoxide (DMSO) were investigated in detail by attenuated total reflection infrared spectroscopy (ATR-IR), combined with hydrogen nuclear magnetic resonance (1H NMR) and density functional theory calculations (DFT). It was found that, first, introducing a nitrile group into the alkyl chain does not change the main interaction site in the cation. It is still the C2 hydrogen. So the v(C2-H) is more sensitive to the environmental change and can be used as an indicator of the environments change of IL. Second, the wavenumber shift changes of v(C2-H) have two turning points (xDMSO ≈ 0.6 and 0.9), dividing the dilution process into three stages. Combined with the calculation results, the dilution process is identified as: From larger ion clusters to smaller ion clusters (xDMSO 0.9). Introducing a nitrile group into the alkyl chain does not influence the dilution process of IL dissolving in DMSO. Third, the Ctbnd N in [PCNMIM][BF4] can work as an electron donor in forming hydrogen-bonds with the methyl group of [PCNMIM]+ and DMSO, but its strength is weaker than that formed by the imidazolium ring C-Hs. The dual roles of the cation to work as both electron acceptor and donor expand the wide applications of this nitrile-functional ionic liquid.

  2. Investigation of structure and hydrogen bonding of superhydrous phase B (HT) under pressure using first-principles density functional calculations

    Science.gov (United States)

    Poswal, H. K.; Sharma, Surinder M.; Sikka, S. K.

    2010-03-01

    High-pressure behaviour of superhydrous phase B (high temperature; HT) of Mg10Si3O14(OH)4 (Shy B) is investigated with the help of density functional theory-based first-principles calculations. In addition to the lattice parameters and equation of state, we use these calculations to determine the positional parameters of atoms as a function of pressure. Our results show that the compression induced structural changes involve cooperative distortions in the full geometry of the hydrogen bonds. The bond-bending mechanism proposed by Hofmeister et al. (Vibrational spectra of dense hydrous magnesium silicates at high pressure: Importance of the hydrogen bond angle, Am. Miner. 84 (1999), pp. 454-464) for hydrogen bonds to relieve the heightened repulsion due to short H- - -H contacts is not found to be effective in Shy B. The calculated O-H bond contraction is consistent with the observed blue shift in the stretching frequency of the hydrogen bond. These results establish that one can use first-principles calculations to obtain reliable insights into the pressure-induced bonding changes of complex minerals.

  3. Covalent functionalization of graphene by azobenzene with molecular hydrogen bonds for long-term solar thermal storage

    OpenAIRE

    Feng, Yiyu; Liu, Hongpo; Luo, Wen; Liu, Enzuo; Zhao, Naiqin; Yoshino, Katsumi; Feng, Wei

    2013-01-01

    Reduced graphene oxide-azobenzene (RGO-AZO) hybrids were prepared via covalent functionalization for long-term solar thermal storage. Thermal barrier (ΔEa ) of cis to tran reversion and thermal storage (ΔH) were improved by molecular hydrogen bonds (H-bonds) through ortho- or para-substitution of AZO. Intramolecular H-bonds thermally stabilized cis-ortho-AZO on RGO with a long-term half-life of 5400 h (ΔEa = 1.2 eV), which was much longer than that of RGO-para-AZO (116 h). RGO-para-AZO with o...

  4. Recent advances in C(sp3)–H bond functionalization via metal–carbene insertions

    Science.gov (United States)

    Wang, Bo; Qiu, Di; Zhang, Yan

    2016-01-01

    Summary The recent development of intermolecular C–H insertion in the application of C(sp3)–H bond functionalizations, especially for light alkanes, is reviewed. The challenging problem of regioselectivity in C–H bond insertions has been tackled by the use of sterically bulky metal catalysts, such as metal porphyrins and silver(I) complexes. In some cases, high regioselectivity and enantioselectivity have been achieved in the C–H bond insertion of small alkanes. This review highlights the most recent accomplishments in this field. PMID:27340470

  5. Trends in bond dissociation energies of alcohols and aldehydes computed with multireference averaged coupled-pair functional theory.

    Science.gov (United States)

    Oyeyemi, Victor B; Keith, John A; Carter, Emily A

    2014-05-01

    As part of our ongoing investigation of the combustion chemistry of oxygenated molecules using multireference correlated wave function methods, we report bond dissociation energies (BDEs) in C1-C4 alcohols (from methanol to the four isomers of butanol) and C1-C4 aldehydes (from methanal to butanal). The BDEs are calculated with a multireference averaged coupled-pair functional-based scheme. We compare these multireference BDEs with those derived from experiment and single-reference methods. Trends in BDEs for the alcohols and aldehydes are rationalized by considering geometry relaxations of dissociated radical fragments, resonance stabilization, and hyperconjugation. Lastly, we discuss the conjectured association between bond strengths and rates of hydrogen abstraction by hydroxyl radicals. In general, abstraction reaction rates are higher at sites where the C-H bond energies are lower (and vice versa). However, comparison with available rate data shows this inverse relationship between bond strengths and abstraction rates does not hold at all temperatures.

  6. The Bond Order of C2 from a Strictly N-Representable Natural Orbital Energy Functional Perspective.

    Science.gov (United States)

    Piris, Mario; Lopez, Xabier; Ugalde, Jesus M

    2016-03-14

    The bond order of the ground electronic state of the carbon dimer has been analyzed in the light of natural orbital functional theory calculations carried out with an approximate, albeit strictly N-representable, energy functional. Three distinct solutions have been found from the Euler equations of the minimization of the energy functional with respect to the natural orbitals and their occupation numbers, which expand upon increasing values of the internuclear coordinate. In the close vicinity of the minimum energy region, two of the solutions compete around a discontinuity point. The former, corresponding to the absolute minimum energy, features two valence natural orbitals of each of the following symmetries, σ, σ*, π and π*, and has three bonding interactions and one antibonding interaction, which is very suggestive of a bond order large than two but smaller than three. The latter, features one σ-σ* linked pair of natural orbitals and three degenerate pseudo-bonding like orbitals, paired each with one triply degenerate pseudo-antibonding orbital, which points to a bond order larger than three. When correlation effects, other than Hartree-Fock for example, between the paired natural orbitals are accounted for, this second solution vanishes yielding a smooth continuous dissociation curve. Comparison of the vibrational energies and electron ionization energies, calculated on this curve, with their corresponding experimental marks, lend further support to a bond order for C2 intermediate between acetylene and ethylene.

  7. The Bond Order of C2 from a Strictly N-Representable Natural Orbital Energy Functional Perspective.

    Science.gov (United States)

    Piris, Mario; Lopez, Xabier; Ugalde, Jesus M

    2016-03-14

    The bond order of the ground electronic state of the carbon dimer has been analyzed in the light of natural orbital functional theory calculations carried out with an approximate, albeit strictly N-representable, energy functional. Three distinct solutions have been found from the Euler equations of the minimization of the energy functional with respect to the natural orbitals and their occupation numbers, which expand upon increasing values of the internuclear coordinate. In the close vicinity of the minimum energy region, two of the solutions compete around a discontinuity point. The former, corresponding to the absolute minimum energy, features two valence natural orbitals of each of the following symmetries, σ, σ*, π and π*, and has three bonding interactions and one antibonding interaction, which is very suggestive of a bond order large than two but smaller than three. The latter, features one σ-σ* linked pair of natural orbitals and three degenerate pseudo-bonding like orbitals, paired each with one triply degenerate pseudo-antibonding orbital, which points to a bond order larger than three. When correlation effects, other than Hartree-Fock for example, between the paired natural orbitals are accounted for, this second solution vanishes yielding a smooth continuous dissociation curve. Comparison of the vibrational energies and electron ionization energies, calculated on this curve, with their corresponding experimental marks, lend further support to a bond order for C2 intermediate between acetylene and ethylene. PMID:26822104

  8. CRACK PROPAGATING IN FUNCTIONALLY GRADED COATING WITH ARBITRARILY DISTRIBUTED MATERIAL PROPERTIES BONDED TO HOMOGENEOUS SUBSTRATE

    Institute of Scientific and Technical Information of China (English)

    Zhanqi Cheng; Danying Gao; Zheng Zhong

    2010-01-01

    In this paper,a finite crack with constant length(Yoffe type crack)propagating in a functionally graded coating with spatially varying elastic properties bonded to a homoge-neous substrate of finite thickness under anti-plane loading was studied.A multi-layered model is employed to model arbitrary variations of material properties based on two linearly-distributed material compliance parameters.The mixed boundary problem is reduced to a system of singular integral equations that are solved numerically.Some numerical examples are given to demonstrate the accuracy,efficiency and versatility of the model.The numerical results show that the graded parameters,the thicknesses of the interracial layer and the two homogeneous layers,the crack size and speed have significant effects on the dynamic fracture behavior.

  9. Adaptive Shape Functions and Internal Mesh Adaptation for Modelling Progressive Failure in Adhesively Bonded Joints

    Science.gov (United States)

    Stapleton, Scott; Gries, Thomas; Waas, Anthony M.; Pineda, Evan J.

    2014-01-01

    Enhanced finite elements are elements with an embedded analytical solution that can capture detailed local fields, enabling more efficient, mesh independent finite element analysis. The shape functions are determined based on the analytical model rather than prescribed. This method was applied to adhesively bonded joints to model joint behavior with one element through the thickness. This study demonstrates two methods of maintaining the fidelity of such elements during adhesive non-linearity and cracking without increasing the mesh needed for an accurate solution. The first method uses adaptive shape functions, where the shape functions are recalculated at each load step based on the softening of the adhesive. The second method is internal mesh adaption, where cracking of the adhesive within an element is captured by further discretizing the element internally to represent the partially cracked geometry. By keeping mesh adaptations within an element, a finer mesh can be used during the analysis without affecting the global finite element model mesh. Examples are shown which highlight when each method is most effective in reducing the number of elements needed to capture adhesive nonlinearity and cracking. These methods are validated against analogous finite element models utilizing cohesive zone elements.

  10. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan

    2008-02-04

    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  11. Interface of covalently bonded phospholipids with a phosphorylcholine head: characterization, protein nonadsorption, and further functionalization.

    Science.gov (United States)

    Ferez, Lynda; Thami, Thierry; Akpalo, Edefia; Flaud, Valérie; Tauk, Lara; Janot, Jean-Marc; Déjardin, Philippe

    2011-09-20

    Surface anchored poly(methylhydrosiloxane) (PMHS) thin films on oxidized silicon wafers or glass substrates were functionalized via the SiH hydrosilylation reaction with the internal double bonds of 1,2-dilinoleoyl-sn-glycero-3-phosphorylcholine (18:2 Cis). The surface was characterized by X-ray photoelectron spectroscopy, contact angle measurements, atomic force microscopy, and scanning electron microscopy. These studies showed that the PMHS top layer could be efficiently modified resulting in an interfacial high density of phospholipids. Grafted phospholipids made the initially hydrophobic surface (θ = 106°) very hydrophilic and repellent toward avidin, bovine serum albumin, bovine fibrinogen, lysozyme, and α-chymotrypsin adsorption in phosphate saline buffer pH 7.4. The surface may constitute a new background-stable support with increased biocompatibility. Further possibilities of functionalization on the surface remain available owing to the formation of interfacial SiOH groups by Karstedt-catalyzed side reactions of SiH groups with water. The presence of interfacial SiOH groups was shown by zeta potential measurements. The reactivity and surface density of SiOH groups were checked by fluorescence after reaction of a monoethoxy silane coupling agent bearing Alexa as fluorescent probe.

  12. Communication: Bond length alternation of conjugated oligomers: Another step on the fifth rung of Perdew's ladder of functional

    Science.gov (United States)

    Chabbal, Sylvain; Jacquemin, Denis; Adamo, Carlo; Stoll, Hermann; Leininger, Thierry

    2010-10-01

    In this work, we present the application of the hybrid short-range density functional theory/long-range MP2 energy gradients to the bond length alternation in polymethineimine and polyacetylene conjugated oligomers. Compared to other density functional calculations, our results are quite superior, even to fourth rung functionals, usually better than MP2 and very close to the available CCSD(T) values.

  13. Rapid Construction of a Benzo-Fused Indoxamycin Core Enabled by Site-Selective C-H Functionalizations.

    Science.gov (United States)

    Bedell, T Aaron; Hone, Graham A B; Valette, Damien; Yu, Jin-Quan; Davies, Huw M L; Sorensen, Erik J

    2016-07-11

    Methods for functionalizing carbon-hydrogen bonds are featured in a new synthesis of the tricyclic core architecture that characterizes the indoxamycin family of secondary metabolites. A unique collaboration between three laboratories has engendered a design for synthesis featuring two sequential C-H functionalization reactions, namely a diastereoselective dirhodium carbene insertion followed by an ester-directed oxidative Heck cyclization, to rapidly assemble the congested tricyclic core of the indoxamycins. This project exemplifies how multi-laboratory collaborations can foster conceptually novel approaches to challenging problems in chemical synthesis. PMID:27206223

  14. Efficient Synthesis of Functionalized Benzimidazoles and Perimidines: Ytterbium Chloride Catalyzed CmC Bond Cleavage%Efficient Synthesis of Functionalized Benzimidazoles and Perimidines: Ytterbium Chloride Catalyzed CmC Bond Cleavage

    Institute of Scientific and Technical Information of China (English)

    Cai, Lijian; Ji, Xiaofeng; Yao, Zhigang; Xu, Fan; Shen, Qi

    2011-01-01

    An efficient method is developed for the synthesis of functionalized benzimidazoles and perimidines by the condensation of aryl diamines with β-carbonyl compounds catalyzed by ytterbium chloride. The reactions give good yields under mild conditions. A mechanism involving a lanthanide activated C--C bond cleavage is proposed.

  15. Density functional theory, natural bond orbital and quantum theory of atoms in molecule analyses on the hydrogen bonding interactions in tryptophan-water complexes

    Indian Academy of Sciences (India)

    Xiqian Niu; Zhengguo Huang; Lingling Ma; Tingting Shen; Lingfei Guo

    2013-07-01

    The tryptophan-water (Trp-H2O) complexes formed by hydrogen bonding interactions were investigated at the B97XD/6-311++G(d,p) level. Five Trp-H2O complexes possessing various types of hydrogen bonds (H-bonds) were characterized by geometries, energies, vibrational frequencies. The nature of the H-bonds were characterized by the natural bond orbital (NBO) and the quantum theory of atoms in molecule (QTAIM) analyses as well. The intramolecular H-bond formed between the amino and carboxyl oxygen atom of tryptophan was retained in most of the complexes, and the cooperativity between the intra and intermolecular H-bonds exist in some complexes. The intramolecular H-bond and some intermolecular H-bonds are strong and have partial covalent character. The H-bonds formed between carboxyl and oxygen/nitrogen atoms are stronger than other H-bonds. The H-bonds involving methylene of tryptophan as H-donor are weak H-bonds. For all complexes,ele and ex makes major contributions to the total interaction energy (MP2), while disp is the smallest component of the interaction energy. Both hydrogen bonding interaction and structural deformation play important roles in the relative stabilities of the complexes. Regardless of strong H-bonds, the stabilities of some complexes are weakened by the serious structural deformations.

  16. Correlation hole effect in comblike copolymer systems obtained by hydrogen bonding between homopolymers and end-functionalized oligomers

    NARCIS (Netherlands)

    Huh, J; Ikkala, O; tenBrinke, G

    1997-01-01

    This paper addresses concentration fluctuations in comblike copolymer systems obtained by hydrogen bonding between polymers and end-functionalized oligomers. Monodisperse block copolymer systems in the homogeneous melt exhibit small-angle X-ray scattering peaks at finite nonzero angle due to charact

  17. Graphene Oxide Catalyzed C-H Bond Activation: The Importance Oxygen Functional Groups for Biaryl Construction

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Yongjun; Tang, Pei; Zhou, Hu; Zhang, Wei; Yang, Hanjun; Yan, Ning; Hu, Gang; Mei, Donghai; Wang, Jianguo; Ma, Ding

    2016-02-24

    A heterogeneous, inexpensive and environment-friendly carbon catalytic system was developed for the C-H bond arylation of benzene resulting in the subsequent formation of biaryl compounds. The oxygen-containing groups on these graphene oxide sheets play an essential role in the observed catalytic activity. The catalytic results of model compounds and DFT calculations show that these functional groups promote this reaction by stabilization and activation of K ions at the same time of facilitating the leaving of I. And further mechanisms studies show that it is the charge induced capabilities of oxygen groups connected to specific carbon skeleton together with the giant π-reaction platform provided by the π-domain of graphene that played the vital roles in the observed excellent catalytic activity. D. Mei acknowledges the support from the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory.

  18. Extraction of consensus protein patterns in regions containing non-proline cis peptide bonds and their functional assessment

    Directory of Open Access Journals (Sweden)

    Rigas Georgios

    2011-05-01

    Full Text Available Abstract Background In peptides and proteins, only a small percentile of peptide bonds adopts the cis configuration. Especially in the case of amide peptide bonds, the amount of cis conformations is quite limited thus hampering systematic studies, until recently. However, lately the emerging population of databases with more 3D structures of proteins has produced a considerable number of sequences containing non-proline cis formations (cis-nonPro. Results In our work, we extract regular expression-type patterns that are descriptive of regions surrounding the cis-nonPro formations. For this purpose, three types of pattern discovery are performed: i exact pattern discovery, ii pattern discovery using a chemical equivalency set, and iii pattern discovery using a structural equivalency set. Afterwards, using each pattern as predicate, we search the Eukaryotic Linear Motif (ELM resource to identify potential functional implications of regions with cis-nonPro peptide bonds. The patterns extracted from each type of pattern discovery are further employed, in order to formulate a pattern-based classifier, which is used to discriminate between cis-nonPro and trans-nonPro formations. Conclusions In terms of functional implications, we observe a significant association of cis-nonPro peptide bonds towards ligand/binding functionalities. As for the pattern-based classification scheme, the highest results were obtained using the structural equivalency set, which yielded 70% accuracy, 77% sensitivity and 63% specificity.

  19. Theoretical Study of the N-NO2 Bond Dissociation Energies for Energetic Materials with Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    LI Xiao-Hong; TANG Zheng-Xin; Abraham F.Jalbout; ZHANG Xian-Zhou; CHENG Xin-Lu

    2008-01-01

    The N-NO2 bond dissociation energies (BDEs) for 7 energetic materials were computed by means of accurate density functional theory (B3LYP, B3PW91 and B3P86) with 6-31G** and 6-311G** basis sets. By comparing the computed energies and experimental results, we find that the B3P86/6-311G** method can give good results of BDE, which has the mean absolute deviation of 1.30 kcal/mol. In addition, substituent effects were also taken into account. It is noted that the Hammett constants of substituent groups are related to the BDEs of the N-NO2 bond and the bond dissociation energies of the energetic materials studied decrease when increasing the number of NO2 group.

  20. Bonding to dentin as a function of air-stream temperatures for solvent evaporation

    Directory of Open Access Journals (Sweden)

    Andréia Aquino Marsiglio

    2012-06-01

    Full Text Available This study evaluated the influence of solvent evaporation conditions of acid-etching adhesives. The medium dentin of thirty extracted human third molars was exposed and bonded to different types of etch-and-rinse adhesives: 1 Scotchbond Multi-Purpose (SBMP ; water-based; 2 Adper Single Bond 2 (SB ; ethanol/water-based, and 3 Prime & Bond 2.1 (PB ; acetone-based. Solvents were evaporated at air-drying temperatures of 21ºC or 38ºC. Composite buildups were incrementally constructed. After storage in water for 24 h at 37ºC, the specimens were prepared for bond strength testing. Data were analyzed by two-way ANOVA and Tukey's test (5%. SBMP performed better when the solvents were evaporated at a higher temperature (p < 0.05. Higher temperatures did not affect the performance of SB or PB. Bond strength at room temperature was material-dependent, and air-drying temperatures affected bonding of the water-based, acid-etching adhesive.

  1. Detection of discriminative sequence patterns in the neighborhood of proline cis peptide bonds and their functional annotation

    Directory of Open Access Journals (Sweden)

    Papaloukas Costas

    2009-04-01

    Full Text Available Abstract Background Polypeptides are composed of amino acids covalently bonded via a peptide bond. The majority of peptide bonds in proteins is found to occur in the trans conformation. In spite of their infrequent occurrence, cis peptide bonds play a key role in the protein structure and function, as well as in many significant biological processes. Results We perform a systematic analysis of regions in protein sequences that contain a proline cis peptide bond in order to discover non-random associations between the primary sequence and the nature of proline cis/trans isomerization. For this purpose an efficient pattern discovery algorithm is employed which discovers regular expression-type patterns that are overrepresented (i.e. appear frequently repeated in a set of sequences. Four types of pattern discovery are performed: i exact pattern discovery, ii pattern discovery using a chemical equivalency set, iii pattern discovery using a structural equivalency set and iv pattern discovery using certain amino acids' physicochemical properties. The extracted patterns are carefully validated using a specially implemented scoring function and a significance measure (i.e. log-probability estimate indicative of their specificity. The score threshold for the first three types of pattern discovery is 0.90 while for the last type of pattern discovery 0.80. Regarding the significance measure, all patterns yielded values in the range [-9, -31] which ensure that the derived patterns are highly unlikely to have emerged by chance. Among the highest scoring patterns, most of them are consistent with previous investigations concerning the neighborhood of cis proline peptide bonds, and many new ones are identified. Finally, the extracted patterns are systematically compared against the PROSITE database, in order to gain insight into the functional implications of cis prolyl bonds. Conclusion Cis patterns with matches in the PROSITE database fell mostly into two

  2. Hydrogen bonding strength of diblock copolymers affects the self-assembled structures with octa-functionalized phenol POSS nanoparticles.

    Science.gov (United States)

    Lu, Yi-Syuan; Yu, Chia-Yu; Lin, Yung-Chih; Kuo, Shiao-Wei

    2016-02-28

    In this study, the influence of the functional groups by the diblock copolymers of poly(styrene-b-4-vinylpyridine) (PS-b-P4VP), poly(styrene-b-2-vinylpyridine) (PS-b-P2VP), and poly(styrene-b-methyl methacrylate) (PS-b-PMMA) on their blends with octa-functionalized phenol polyhedral oligomeric silsesquioxane (OP-POSS) nanoparticles (NPs) was investigated. The relative hydrogen bonding strengths in these blends follow the order PS-b-P4VP/OP-POSS > PS-b-P2VP/OP-POSS > PS-b-PMMA/OP-POSS based on the Kwei equation from differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopic analyses. Small-angle X-ray scattering and transmission electron microscopic analyses show that the morphologies of the self-assembly structures are strongly dependent on the hydrogen bonding strength at relatively higher OP-POSS content. The PS-b-P4VP/OP-POSS hybrid complex system with the strongest hydrogen bonds shows the order-order transition from lamellae to cylinders and finally to body-centered cubic spheres upon increasing OP-POSS content. However, PS-b-P2VP/OP-POSS and PS-b-PMMA/OP-POSS hybrid complex systems, having relatively weaker hydrogen bonds, transformed from lamellae to cylinder structures at lower OP-POSS content (50 wt%). PMID:26781581

  3. Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. I. Hamiltonian matrix elements between internally contracted excited valence bond wave functions

    Science.gov (United States)

    Chen, Zhenhua; Chen, Xun; Wu, Wei

    2013-04-01

    In this series, the n-body reduced density matrix (n-RDM) approach for nonorthogonal orbitals and their applications to ab initio valence bond (VB) methods are presented. As the first paper of this series, Hamiltonian matrix elements between internally contracted VB wave functions are explicitly provided by means of nonorthogonal orbital based RDM approach. To this end, a more generalized Wick's theorem, called enhanced Wick's theorem, is presented both in arithmetical and in graphical forms, by which the deduction of expressions for the matrix elements between internally contracted VB wave functions is dramatically simplified, and the matrix elements are finally expressed in terms of tensor contractions of electronic integrals and n-RDMs of the reference VB self-consistent field wave function. A string-based algorithm is developed for the purpose of evaluating n-RDMs in an efficient way. Using the techniques presented in this paper, one is able to develop new methods and efficient algorithms for nonorthogonal orbital based many-electron theory much easier than by use of the first quantized formulism.

  4. On Bond Portfolio Management

    OpenAIRE

    Vladislav Kargin

    2002-01-01

    This paper describes a new method of bond portfolio optimization based on stochastic string models of correlation structure in bond returns. The paper shows how to approximate correlation function of bond returns, compute the optimal portfolio allocation using Wiener-Hopf factorization, and check whether a collection of bonds presents arbitrage opportunities.

  5. Direct space decomposition of ELI-D: interplay of charge density and pair-volume function for different bonding situations.

    Science.gov (United States)

    Wagner, Frank R; Kohout, Miroslav; Grin, Yuri

    2008-10-01

    The topological features, i.e., gradients and curvatures of the same-spin electron pair restricted electron localizability indicator (ELI-D) in position space are analyzed in terms of those of the electron density and the pair-volume function. The analysis of the topology of these constituent functions and their interplay on ELI-D attractor formation for a number of molecules representing chemically different bonding situations allows distinguishing between different chemical bonding scenarios on a quantum mechanical basis without the recourse to orbitals. The occurrence of the Laplacian of the electron density in the expression for the Laplacian of ELI-D allows us to establish a physical link between electron localizability and electron pairing as displayed by ELI-D and the role of Laplacian of the density in this context.

  6. Compact two-electron wave function for bond dissociation and Van der Waals interactions: A natural amplitude assessment

    International Nuclear Information System (INIS)

    Electron correlations in molecules can be divided in short range dynamical correlations, long range Van der Waals type interactions, and near degeneracy static correlations. In this work, we analyze for a one-dimensional model of a two-electron system how these three types of correlations can be incorporated in a simple wave function of restricted functional form consisting of an orbital product multiplied by a single correlation function f (r12) depending on the interelectronic distance r12. Since the three types of correlations mentioned lead to different signatures in terms of the natural orbital (NO) amplitudes in two-electron systems, we make an analysis of the wave function in terms of the NO amplitudes for a model system of a diatomic molecule. In our numerical implementation, we fully optimize the orbitals and the correlation function on a spatial grid without restrictions on their functional form. Due to this particular form of the wave function, we can prove that none of the amplitudes vanishes and moreover that it displays a distinct sign pattern and a series of avoided crossings as a function of the bond distance in agreement with the exact solution. This shows that the wave function ansatz correctly incorporates the long range Van der Waals interactions. We further show that the approximate wave function gives an excellent binding curve and is able to describe static correlations. We show that in order to do this the correlation function f (r12) needs to diverge for large r12 at large internuclear distances while for shorter bond distances it increases as a function of r12 to a maximum value after which it decays exponentially. We further give a physical interpretation of this behavior

  7. Assessment of recently developed density functional approaches for the evaluation of the bond length alternation in polyacetylene

    Science.gov (United States)

    Jacquemin, Denis; Perpète, Eric. A.; Ciofini, Ilaria; Adamo, Carlo

    2005-04-01

    The bond length alternation (BLA) of increasingly long polyacetylene oligomers has been computed using various wavefunction methods of increasing accuracy and several DFT models, including standard GGA and the most-recent meta-GGA and hybrid functionals. Our results show the meta-GGA functionals do not offer any significant improvement with respect to the GGA approaches, both providing too small values for the BLA. More accurate results are obtained with hybrid approaches, where, instead, the percent of HF exchange rules the quantitative result. In particular, hybrids including 25% of HF exchange are the most accurate, whereas TPSSh, O3LYP, τ-HCTHh provide only poor estimates.

  8. Spin-spin critical point correlation functions for the 2D random bond Ising and Potts models

    CERN Document Server

    Dotsenko, V S; Pujol, P; Vladimir Dotsenko; Marco Picco; Pierre Pujol

    1994-01-01

    We compute the combined two and three loop order correction to the spin-spin correlation functions for the 2D Ising and q-states Potts model with random bonds at the critical point. The procedure employed is the renormalisation group approach for the perturbation series around the conformal field theories representing the pure models. We obtain corrections for the correlations functions which produce crossover in the amplitude but don't change the critical exponent in the case of the Ising model and which produce a shift in the critical exponent, due to randomness, in the case of the Potts model. Comparison with numerical data is discussed briefly.

  9. X-ray Absorption Spectroscopy and Density Functional Theory Studies of [(H3buea)FeIII-X]n1 (X= S2-, O2-,OH-): Comparison of Bonding and Hydrogen Bonding in Oxo and Sulfido Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Dey, Abhishek; Hocking, Rosalie K.; /Stanford U., Chem. Dept.; Larsen, Peter; Borovik, Andrew S.; /Kansas U.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; /SLAC,

    2006-09-27

    Iron L-edge, iron K-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [Fe{sup III}H{sub 3}buea(X)]{sup n-} (X = S{sup 2-}, O{sup 2-}, OH{sup -}). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were then used to compare the metal-ligand bonding and to evaluate the effects of H-bonding in Fe{sup III}-O vs Fe{sup III-}S complexes. It was found that the Fe{sup III-}O bond, while less covalent, is stronger than the FeIII-S bond. This dominantly reflects the larger ionic contribution to the Fe{sup III-}O bond. The H-bonding energy (for three H-bonds) was estimated to be -25 kcal/mol for the oxo as compared to -12 kcal/mol for the sulfide ligand. This difference is attributed to the larger charge density on the oxo ligand resulting from the lower covalency of the Fe-O bond. These results were extended to consider an Fe{sup IV-}O complex with the same ligand environment. It was found that hydrogen bonding to Fe{sup IV-}O is less energetically favorable than that to Fe{sup III-}O, which reflects the highly covalent nature of the Fe{sup IV-}O bond.

  10. Spectroscopically determined force field for water dimer: physically enhanced treatment of hydrogen bonding in molecular mechanics energy functions.

    Science.gov (United States)

    Mannfors, Berit; Palmo, Kim; Krimm, Samuel

    2008-12-11

    Our ab initio transformed spectroscopically determined force field (SDFF) methodology emphasizes, in addition to accurate structure and energy performance, comparable prediction of vibrational properties in order to improve reproduction of interaction forces. It is now applied to the determination of a molecular mechanics (MM) force field for the water monomer and dimer as an initial step in developing a more physically based treatment of the hydrogen bonding that not only underlies condensed-phase water but also must be important in molecular-level protein-water interactions. Essential electrical components of the SDFF for monomer water are found to be the following: an off-plane charge distribution, this distribution consisting of four off-atom charge sites in traditional lone pair (LP) but also in inverted lone pair (ILP) positions; allowance for a diffuse size to these off-atom sites; and the incorporation of charge fluxes (i.e., the change in charge with change in internal coordinate). Parametrization of such an LP/ILP model together with the SDFF analytically transformed valence force field results in essentially exact agreement with ab initio (in this case MP2/6-31++G(d,p)) structure, electrical, and vibrational properties. Although we demonstrate that the properties of this monomer electrical model together with its van der Waals and polarization interactions are transferable to the dimer, this is not sufficient in reproducing comparable dimer properties, most notably the huge increase in infrared intensity of a donor OH stretch mode. This deficiency, which can be eliminated by a large dipole-derivative-determined change in the effective charge flux of the donor hydrogen-bonded OH bond, is not accounted for by the charge flux change in this bond due to the induction effects of the acceptor electric field alone, and can only be fully removed by an added bond flux associated with the extent of overlap of the wave functions of the two molecules. We show that

  11. The Microstructure and Chemical Bonds of β-C2S Under the High Energy Ball Grinding Function

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Using the laser granularity survey technology, X- ray powder diffraction, scanning electron mi croscopy (SEM) and infrared spectrum analysis methods, we studied the microscopic structure and chemical bonds changes of β- C2 S monomineral under the high energy ball grinding function .The result indicates that, continuously under the mechanical power, β-C2 S crystal size would decrease, the micro strain and the effective Beff parameter would increase, and the amorphous phases would be presented. Furthermore, the mechanical power would cause Si- O bond broken and reorganized, the specific surface area would increase, the energy of micro-pow der agglomeration vibration would be enhanced and the crystal would be disordered .Finally, β- C2 S was caused to have the mechanochemical change and the activity enhancement.

  12. The synthesis of functionalized bridged polycycles via C–H bond insertion

    Science.gov (United States)

    Shih, Jiun-Le; Chen, Po-An

    2016-01-01

    Summary This review presents examples from the chemical literature of syntheses of bridged-polycyclic products via C–H bond insertion by carbenes and nitrenes. Applications to natural product synthesis, a description of the essential elements in substrate-controlled reactions, and mechanistic details of transformations are presented. Overall, these transformations allow the construction of important ring systems rapidly and efficiently, though additional catalyst development is needed. PMID:27340489

  13. Effects of density functionals and dispersion interactions on geometries, bond energies and harmonic frequencies of Etbnd UX3 (E = N, P, CH; X = H, F, Cl)

    Science.gov (United States)

    Pandey, Krishna Kumar; Patidar, Pankaj; Patidar, Sunil Kumar; Vishwakarma, Ravi

    2014-12-01

    Quantum-chemical calculations have been performed to evaluate the geometries, bonding nature and harmonic frequencies of the compounds [Etbnd UX3] at DFT, DFT-D3, DFT-D3(BJ) and DFT-dDSc levels using different density functionals BP86, BLYP, PBE, revPBE, PW91, TPSS and M06-L. The stretching frequency of Utbnd N bond in [Ntbnd UF3] calculated with DFT/BLYP closely resembles with the experimental value. The performance of different density functionals for accurate Utbnd N vibrational frequencies follows the order BLYP > revPBE > BP86 > PW91 > TPSS > PBE > M06-L. The BLYP functional gives accurate value of the Utbnd E bond distances. The uranium atom in the studied compounds [Etbnd UX3] is positively charged. Upon going from [Etbnd UF3] to [Etbnd UCl3], the partial Hirshfeld charge on uranium atom decreases because of the lower electronegativity of chlorine compared to flourine. The Gopinathan-Jug bond order for Utbnd E bonds ranges from 2.90 to 3.29. The Utbnd E bond dissociation energies vary with different density functionals as M06-L UX3] are larger than the electrostatic interaction ΔEelstat, which means the Utbnd N bonds in these compound have greater degree of covalent character (in the range 63.8-77.2%). The Usbnd E σ-bonding interaction is the dominant bonding interaction in the nitride and methylidyne complexes while it is weaker in [Ptbnd UX3]. The dispersion energy contributions to the total bond dissociation energies are rather small. Compared to the Grimme's D3(BJ) corrections, the Corminboeuf's dispersion corrections are larger with metaGGA functionals (TPSS, M06-L) while smaller with GGA functionals.

  14. Molecular dynamics simulations on pars intercerebralis major peptide-C (PMP-C) reveal the role of glycosylation and disulfide bonds in its enhanced structural stability and function.

    Science.gov (United States)

    Kaushik, Sandeep; Mohanty, Debasisa; Surolia, Avadhesha

    2012-01-01

    Fucosylation of Thr 9 in pars intercerebralis major peptide-C (PMP-C) enhances its structural stability and functional ability as a serine protease inhibitor. In order to understand the role of disulfide bonds and glycosylation on the structure and function of PMP-C, we have carried out multiple explicit solvent molecular dynamics (MD) simulations on fucosylated and non-fucosylated forms of PMP-C, both in the presence and absence of the disulfide bonds. Our simulations revealed that there were no significant structural changes in the native disulfide bonded forms of PMP-C due to fucosylation. On the other hand, the non-fucosylated form of PMP-C without disulfide bonds showed larger deviations from the starting structure than the fucosylated form. However, the structural deviations were restricted to the terminal regions while core β-sheet retained its hydrogen bonded structure even in absence of disulfide bonds as well as fucosylation. Interestingly, fucosylation of disulfide bonded native PMP-C led to a decreased thermal flexibility in the residue stretch 29-32 which is known to interact with the active site of the target proteases. Our analysis revealed that disulfide bonds covalently connect the residue stretch 29-32 to the central β-sheet of PMP-C and using a novel network of side chain interactions and disulfide bonds fucosylation at Thr 9 is altering the flexibility of the stretch 29-32 located at a distal site. Thus, our simulations explain for the first time, how presence of disulfide bonds between conserved cysteines and fucosylation enhance the function of PMP-C as a protease inhibitor.

  15. The bonding of heavy metals on nitric acid-etched coal fly ashes functionalized with 2-mercaptoethanol or thioglycolic acid

    International Nuclear Information System (INIS)

    Coal fly ash is a waste by-product of the coal fire industry, which generates many environmental problems. Alternative uses of this material would provide efficient solutions for this by-product. In this work, nitric acid-etched coal fly ash labelled with 2-mercaptoethanol or thioglycolic acid was assessed for retention of Al(III), As(III), Cu(II), Cd(II), Fe(III), Mn(II), Hg(II), Ni(II), Pb(II) and Zn(II) ions. The bonding characteristics between the organic compounds with the solid support, as well as with the metal ions, were evaluated using various surface analytical techniques. Visualization of the organically-functionalized coal fly ash particle was possible using scanning electron microscopy (SEM), while the elemental composition of the functionalized material, before and after retention of the metal ions, was obtained by energy dispersive (ED)-X ray spectrometry (XRS) and electrothermal atomic absorption spectrometry (ETAAS). Fourier transform infrared (FT-IR) spectrometry and Raman spectrometry were used to obtain information about the functional groups. It was found that some metal(oid) ions (As, Ni, Pb, Zn) were coordinated through the mercaptan group, while other metal(oid)s (Al, Cd, Cu, Fe, Hg, Mn) were apparently bonded to oxygen atoms. A low-cost and effective solid phase retention system for extraction of heavy metals from aqueous solutions was thus developed. - Graphical abstract: Nitric acid-etched coal fly ash labelled with 2-mercaptoethanol or thioglycolic acid was intended for the retention of heavy metals. The bonding characteristics between the organic compounds with the solid support, as well as with the metal ions, were evaluated using surface analytical techniques. - Highlights: • Coal fly ashes were organically-functionalized. • Organically-functionalized coal fly ashes were spectrometrically characterized. • Organically-functionalized coal fly ashes can be used as an effective solid sorbent for metal(oid)s. • This retention

  16. Oxidation of MCrAlY bonding layers of thermal insulation coatings as a function of production parameters and alloy composition

    International Nuclear Information System (INIS)

    The oxidation behaviour of intermediate or bonding layers on a given gas turbine material (IN 100) is reported. The layers were brought onto the base material by plasma arc spraying in free air or controlled atmosphere, and consisted of spray powders of different aluminium content (Co-31 Ni-21Cr8Al0.5Y; Co-33Ni-21Cr-16Al0.5Y; composite powder with a Ni-19 Cr alloy core and 6% Al cladding). These bonding layers received a ceramic cover (ZrO2 + 7% of Y2O3) to serve as a thermal insulation coating. The oxidation behaviour of the bonding layers were analysed as a function of different spray powders, spraying techniques, surface roughness of bonding layer, and thickness of insulation coating or bonding layer. (MM)

  17. Enhanced dispersion stability and mobility of carboxyl-functionalized carbon nanotubes in aqueous solutions through strong hydrogen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Bahk, Yeon Kyoung; He, Xu; Gitsis, Emmanouil; Kuo, Yu-Ying [ETH Zurich, Institute of Environmental Engineering (Switzerland); Kim, Nayoung [EMPA, Building Energy Materials and Components (Switzerland); Wang, Jing, E-mail: jing.wang@ifu.baug.ethz.ch [ETH Zurich, Institute of Environmental Engineering (Switzerland)

    2015-10-15

    Dispersion of carbon nanotubes has been heavily studied due to its importance for their technical applications, toxic effects, and environmental impacts. Common electrolytes, such as sodium chloride and potassium chloride, promote agglomeration of nanoparticles in aqueous solutions. On the contrary, we discovered that acetic electrolytes enhanced the dispersion of multi-walled carbon nanotubes (MWCNTs) with carboxyl functional group through the strong hydrogen bond, which was confirmed by UV–Vis spectrometry, dispersion observations and aerosolization-quantification method. When concentrations of acetate electrolytes such as ammonium acetate (CH{sub 3}CO{sub 2}NH{sub 4}) and sodium acetate (CH{sub 3}CO{sub 2}Na) were lower than 0.03 mol per liter, MWCNT suspensions showed better dispersion and had higher mobility in porous media. The effects by the acetic environment are also applicable to other nanoparticles with the carboxyl functional group, which was demonstrated with polystyrene latex particles as an example.

  18. Design of Au/SPIO composite nanoparticle for facile and biocompatible surface functionalization via Au-S bond

    Energy Technology Data Exchange (ETDEWEB)

    Seino, Satoshi, E-mail: seino@mit.eng.osaka-u.ac.jp; Shibata, Yujin; Yamanaka, Masayuki; Nakagawa, Takashi [Osaka University, Graduate School of Engineering (Japan); Mukai, Yohei; Nakagawa, Shinsaku [Osaka University, Graduate School of Pharmaceutical Sciences and Center for Advanced Medical Engineering and Informatics (Japan); Yamamoto, Takao A. [Osaka University, Graduate School of Engineering (Japan)

    2013-01-15

    Immobilization of Au nanoparticles on super-paramagnetic iron-oxide (SPIO) enables facile and biocompatible surface functionalization via Au-S bond. Au/SPIO composite nanoparticle is easily modified by thiol-modified polyethylene glycol (PEG-SH), and they are successfully applied on MR tumor imaging. However, its large hydrodynamic size ({approx}150 nm) still causes the accumulation to liver in vivo. In this study, we controlled the hydrodynamic size of Au/SPIO by testing different raw SPIOs and stabilizing polymers. As the best candidate, Au/Molday-ION which was synthesized from Molday-ION and polyvinyl alcohol comprised the hydrodynamic size of 56 nm. Moreover, PEGylated Au/Molday-ION showed excellent dispersibility in blood serum, with the hydrodynamic size of 65 nm. This surface functionalization strategy is effective for the constructions of magnetic nanocarriers for in vivo applications.

  19. The Variety of Carbon-Metal Bonds inside Cu-ZSM-5 Zeolites: A Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Takashi Yumura

    2010-04-01

    Full Text Available Large-scale density functional theory calculations (DFT found various types of binding of an unsaturated hydrocarbon (C2H2 and C2H4 to a ZSM-5 zeolite extraframework copper cation. We employed the DFT calculations based on the B3LYP functional to obtain local minima of an unsaturated hydrocarbon adsorbed on one or two copper cations embedded inside ZSM-5, and then compared their stabilization energies. The DFT results show that the stabilization energies are strongly dependent on the copper coordination environment as well as configurations of two copper cations. Consequently, the inner copper-carbon bonds are influenced substantially by a nanometer-scale cavity of ZSM-5.

  20. Enhanced dispersion stability and mobility of carboxyl-functionalized carbon nanotubes in aqueous solutions through strong hydrogen bonds

    International Nuclear Information System (INIS)

    Dispersion of carbon nanotubes has been heavily studied due to its importance for their technical applications, toxic effects, and environmental impacts. Common electrolytes, such as sodium chloride and potassium chloride, promote agglomeration of nanoparticles in aqueous solutions. On the contrary, we discovered that acetic electrolytes enhanced the dispersion of multi-walled carbon nanotubes (MWCNTs) with carboxyl functional group through the strong hydrogen bond, which was confirmed by UV–Vis spectrometry, dispersion observations and aerosolization-quantification method. When concentrations of acetate electrolytes such as ammonium acetate (CH3CO2NH4) and sodium acetate (CH3CO2Na) were lower than 0.03 mol per liter, MWCNT suspensions showed better dispersion and had higher mobility in porous media. The effects by the acetic environment are also applicable to other nanoparticles with the carboxyl functional group, which was demonstrated with polystyrene latex particles as an example

  1. Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt

    Science.gov (United States)

    Johnson, Craig A.; Bookstrom, Arthur A.; Slack, John F.

    2012-01-01

    Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ34S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ (n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H2S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit

  2. Thymine- and Adenine-Functionalized Polystyrene Form Self-Assembled Structures through Multiple Complementary Hydrogen Bonds

    Directory of Open Access Journals (Sweden)

    Yu-Shian Wu

    2014-06-01

    Full Text Available In this study, we investigated the self-assembly of two homopolymers of the same molecular weight, but containing complementary nucleobases. After employing nitroxide-mediated radical polymerization to synthesize poly(vinylbenzyl chloride, we converted the polymer into poly(vinylbenzyl azide through a reaction with NaN3 and then performed click chemistry with propargyl thymine and propargyl adenine to yield the homopolymers, poly(vinylbenzyl triazolylmethyl methylthymine (PVBT and poly(vinylbenzyl triazolylmethyl methyladenine (PVBA, respectively. This PVBT/PVBA blend system exhibited a single glass transition temperature over the entire range of compositions, indicative of a miscible phase arising from the formation of multiple strong complementary hydrogen bonds between the thymine and adenine groups of PVBT and PVBA, respectively; Fourier transform infrared and 1H nuclear magnetic resonance spectroscopy confirmed the presence of these noncovalent interactions. In addition, dynamic rheology, dynamic light scattering and transmission electron microscopy provided evidence for the formation of supramolecular network structures in these binary PVBT/PVBA blend systems.

  3. Compact wave function for bond dissociation and Van der Waals interactions: A natural amplitude assessment

    CERN Document Server

    Giesbertz, K J H

    2014-01-01

    Electron correlations in molecules can be divided in short range dynamical correlations, long range Van der Waals type interactions and near degeneracy static correlations. In this work we analyze how these three types of correlations can be incorporated in a simple wave function of restricted functional form consisting of an orbital product multiplied by a single correlation function $f(r_{12})$ depending on the interelectronic distance $r_{12}$. Since the three types of correlations mentioned lead to different signatures in terms of the natural orbital (NO) amplitudes in two-electron systems we make an analysis of the wave function in terms of the NO amplitudes for a model system of a diatomic molecule. In our numerical implementation we fully optimize the orbitals and the correlation function on a spatial grid without restrictions on their functional form. For the model system we can prove that none of the amplitudes vanishes and moreover that it displays a distinct sign pattern and a series of avoided cro...

  4. Copper-Catalyzed Redox-Triggered Remote C-H Functionalization: Highly Selective Formation of C-CF3 and C-O Bonds

    Institute of Scientific and Technical Information of China (English)

    Taotao Li; Peng Yu; Jin-Shun Lin; Yonggang Zhi; Xin-Yuan Liu

    2016-01-01

    A Cu-catalyzed remote sp3 C-H/unactivated alkenes functionalization reaction for the concomitant construction ofC-CF3 and C-O bonds was described.An 1,5-H radical transfer involving an sp3 C-H bond adjacent to a nitrogen atom and an α-CF3-alkyl radical intermediate derived from unactivated alkenes was observed and demonstrated to proceed via the radical process.

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

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2009-01-01

    metal-ligand bond lengths, and bond enthalpies for many as yet uncharacterized diatomics, of interest to researchers in the field of second- and third-row d-block chemistry. We stress that the success of TPSSh cannot be naively extrapolated to other special situations such as, e.g., metal-metal bonds...

  6. Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)

    OpenAIRE

    Tenn, William J., III; Conley, Brian L.; Hovelmann, Claas H.; Ahlquist, Marten; Nielsen, Robert J.; Ess, Daniel H.; Oxgaard, Jonas; Bischof, Steven M.; Goddard, William A.; Periana, Roy A.

    2009-01-01

    We report that SeO_2 catalyzes the facile oxy-functionalization of (CO)_5Re(I)-Me^(δ−) with IO_4− to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH_3Se(VI) species. Furthermore, (CO)_3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO_2 to generate the primary alcohols. T...

  7. Reaction Development on π- and σ-Conjugated Bonds and Creation of Innovative Functions.

    Science.gov (United States)

    Takita, Ryo

    2016-01-01

    Monocarba-closo-dodecaborate (1; [closo-CB11H12](-), or C1-carborane anion) is a symmetrical, stable anionic cluster, which possesses low nucleophilicity/basicity and exhibits three-dimensional aromaticity. In contrast to the rich applications of C2-carborane molecules (C2B10H12), the chemistry of the C1-carborane anion as a platform for functional molecules has not been thoroughly studied thus far due to the lack of its efficient functionalization. In particular, no efficient general methods are available for the introduction of aryl and sp(2)/sp-carbon groups at the carbon vertex of the C1-carborane anion. The unique electronic structure and potential applications of the C1-carborane anion prompted us to investigate methods to functionalize it. We developed a general, efficient C-C cross-coupling reaction of 1 under palladium catalysis which yields a variety of 1-C-functionalized C1-carborane derivatives. The use of copper(I) or lithium species as a transmetalating partner facilitated the cross-coupling process of the sterically hindered C1-carborane anion. The potential application of 1-C-arylated C1-carborane anion derivatives thus obtained were explored, some of which showed potential as pharmacophores and ionic liquid crystal behavior. Furthermore, conjugation between σ- and π-aromatic moieties in 1-C-arylated monocarba-closo-dodecaborate anion derivatives was identified by means of kinetic experimental studies combined with theoretical calculations. PMID:27252066

  8. The Specific Role of Childhood Abuse, Parental Bonding, and Family Functioning in Female Adolescents With Borderline Personality Disorder.

    Science.gov (United States)

    Infurna, Maria Rita; Brunner, Romuald; Holz, Birger; Parzer, Peter; Giannone, Francesca; Reichl, Corinna; Fischer, Gloria; Resch, Franz; Kaess, Michael

    2016-04-01

    This study examined a broad variety of adverse childhood experiences in a consecutive sample of female adolescent inpatients with borderline personality disorder (BPD; n = 44) compared with a clinical control (CC; n = 47) group with mixed psychiatric diagnoses. BPD was diagnosed using a structured clinical interview; different dimensions of childhood adversity were assessed using the Childhood Experiences of Care and Abuse Questionnaire, the Parental Bonding Instrument, and the Family Assessment Device. A history of childhood adversity was significantly more common in patients with BPD than in the CC group. Using a multivariate model, sexual abuse (OR = 13.8), general family functioning (OR = 8.9), and low maternal care (OR = 7.6) were specific and independent predictors of adolescent BPD. The results increase our knowledge of the specific role of different dimensions of childhood adversity in adolescent BPD. They have important implications for prevention and early intervention as they highlight the need for specific strategies for involving the family. PMID:25905734

  9. A hybrid-exchange density functional study of the bonding and electronic structure in bulk CuFeS2

    Science.gov (United States)

    Martínez-Casado, Ruth; Chen, Vincent H.-Y.; Mallia, Giuseppe; Harrison, Nicholas M.

    2016-05-01

    The geometric, electronic, and magnetic properties of bulk chalcopyrite CuFeS2 have been investigated using hybrid-exchange density functional theory calculations. The results are compared with available theoretical and experimental data. The theoretical description of the bonding and electronic structure in CuFeS2 is analyzed in detail and compared to those computed for chalcocite (CuS2) and greigite (Fe3S4). In particular, the behavior of the 3d electrons of Fe3+ is discussed in terms of the Hubbard-Anderson model in the strongly correlated regime and found to be similarly described in both materials by an on-site Coulomb repulsion (U) of ˜8.9 eV and a transfer integral (t) of ˜0.3 eV.

  10. Ensemble density functional theory method correctly describes bond dissociation, excited state electron transfer, and double excitations

    Energy Technology Data Exchange (ETDEWEB)

    Filatov, Michael, E-mail: mike.filatov@gmail.com [Department of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, Texas 75275-0314 (United States); Huix-Rotllant, Miquel; Burghardt, Irene [Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, D-60438 Frankfurt am Main (Germany)

    2015-05-14

    State-averaged (SA) variants of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, SA-REKS and state-interaction (SI)-SA-REKS, implement ensemble density functional theory for variationally obtaining excitation energies of molecular systems. In this work, the currently existing version of the SA-REKS method, which included only one excited state into the ensemble averaging, is extended by adding more excited states to the averaged energy functional. A general strategy for extension of the REKS-type methods to larger ensembles of ground and excited states is outlined and implemented in extended versions of the SA-REKS and SI-SA-REKS methods. The newly developed methods are tested in the calculation of several excited states of ground-state multi-reference systems, such as dissociating hydrogen molecule, and excited states of donor–acceptor molecular systems. For hydrogen molecule, the new method correctly reproduces the distance dependence of the lowest excited state energies and describes an avoided crossing between the doubly excited and singly excited states. For bithiophene–perylenediimide stacked complex, the SI-SA-REKS method correctly describes crossing between the locally excited state and the charge transfer excited state and yields vertical excitation energies in good agreement with the ab initio wavefunction methods.

  11. Linear optical properties and their bond length dependence of yttrium bromide from ab initio and density functional theory calculations

    Energy Technology Data Exchange (ETDEWEB)

    Alipour, Mojtaba, E-mail: malipour@shirazu.ac.ir [Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454 (Iran, Islamic Republic of); Mohajeri, Afshan, E-mail: amohajeri@shirazu.ac.ir [Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454 (Iran, Islamic Republic of)

    2011-08-25

    Graphical abstract: The electronic properties such as the static dipole polarizability, anisotropy of the polarizability, and dipole moment of yttrium bromide, YBr (X{sup 1}{Sigma}) have been theoretically studied. Highlights: {yields} Conventional ab initio and density functional theory methods were employed to study linear optical properties of YBr molecule. {yields} Properties derivatives and their level of theory dependence were studied. {yields} Electron correlation effects and rovibrational corrections have also been discussed. - Abstract: We have employed conventional ab initio and density functional theory methods to study the electronic properties such as the mean static dipole polarizability, {alpha}-bar, anisotropy of the polarizability, {Delta}{alpha}, and dipole moment, {mu}, of yttrium bromide. The bond length dependence of properties is determined at different levels of theory and appropriate expansions around experimental internuclear distance have been presented. Moreover, the first and second geometrical derivatives for each property are quantified and their level of theory dependence has been analyzed. To study the effect of molecular rotation and vibration on the electronic properties, the rovibrational corrections have also been carried out. It is found that these corrections are less pronounced for considered properties of YBr. In all calculations, the electron correlation effects have been considered and discussed. The obtained results show that the electron correlation is more significant in the calculation of the mean and the anisotropy of dipole polarizability.

  12. 样条函数在构造债券收益率曲线中的应用%APPLICATION OF SPLINE FUNCTION IN CONSTRUCTING BOND YIELD CURVE

    Institute of Scientific and Technical Information of China (English)

    杨柳

    2016-01-01

    针对债券市场上芜杂的行情数据,提出将DBSCAN聚类算法应用于构造债券收益率曲线样条函数。通过运用DBSCAN算法对用于构造债券收益率曲线的行情数据进行聚类分析,能够有效地剔除市场上的异常交易数据。在聚类分析结果的基础上,再次应用DBSCAN算法于构造债券收益率曲线,根据市场上行情数据的密集区域对样条函数进行分段。此外,针对传统的依赖于经验进行债券收益率曲线样条函数分段点选取的缺点,使用DBSCAN算法可有效地提高债券收益率曲线和行情数据的符合程度。实验结果表明,将DBSCAN算法用于构建债券收益率曲线样条函数,可以提高收益率曲线反映利率期限结构波动及准确性的效果。%In light of the miscellaneous quotation data in bond market,we proposed to apply the DBSCAN algorithm to constructing the spline function of bond yield curve.By employing DBSCAN algorithm to the cluster analysis of the quotation data,which is used to construct bond yield curve,it is able to eliminate effectively the abnormal transaction data on the market.On the basis of cluster analysis results,we used the DBSCAN algorithm once again to construct the bond yield curve,and segmented the spline function into sections according to the dense regions of quotation data on the market.Besides,targeted at the defect of traditional way that it selects the segment points of spline function of bond yield curve depending on experience,the use of DBSCAN algorithm can effectively improve the conformance between the bond yield curve and the bond quotation data.From the experimental results it is illustrated that to apply the DBSCAN algorithm to constructing the spline function of bond yield curve can improve the effects of reflecting the fluctuations of interest term structure by bond yield curve and its accuracy.

  13. Theoretical study on β-aminoacroleine; Density functional theory, atoms in molecules theory and natural bond orbitals studies

    Indian Academy of Sciences (India)

    Heidar Raissi; Mehdi Yoosefian; Effat Moshfeghi; Farzaneh Farzad

    2012-05-01

    The characteristics of the intramolecular hydrogen bonding for a series of 19 different derivatives of -aminoacroleine have been systematically analysed at the B3LYP/6-31G∗∗ level of theory. The topological properties of the electron density distributions for N-H$\\cdots$O intramolecular bridges have been analysed by the Bader theory of atoms in molecules. The electron density () and Laplacian (∇2 ρ) properties at critical points of the relevant bonds, estimated by AIM calculations, showed that N-H$\\cdots$O have low and positive character (∇2 ρ > 0), consistent with electrostatic character of the hydrogen bond. The vibrational study of the hydrogen bonded systems showed negative (red) shifts for the (N−H) stretching mode. The -electron delocalization parameter () as a geometrical indicator of a local aromaticity and the geometry-based HOMA have also been calculated. Furthermore, the analysis of hydrogen bond in this molecule and its derivatives by natural bond orbital (NBO) methods support the DFT results. The results of AIM and NBO analysis as well as (N−H) were further used for estimation of the hydrogen bonding interactions and the forces driving their formation. The various correlations were found between geometrical, energetic and topological parameters. The substituent effect was also analysed and it was found that the strongest hydrogen bonds exist for N+(CH3)3 and Cl substituents while the weakest ones for COOCH3.

  14. The analysis of irradiated nuclear fuel and cladding materials, determination of carbon, hydrogen and oxygen/metal ratio

    International Nuclear Information System (INIS)

    Equipment has been developed for the determination of carbon, hydrogen and oxygen/metal ratio on irradiated fuels, of carbon in stainless steel cladding materials and in graphite rich deposits, and of hydrogen in zircaloy. Carbon is determined by combustion to carbon dioxide which is collected and measured manometrically, hydrogen by vacuum extraction followed by diffusion through a palladium thimble, and oxygen/metal ratio by CO/CO2 equilibration. A single set of equipment was devised in order to minimise the time and work involved in changing to a different set of equipment in a separate box, for each type of analysis. For each kind of analysis, alterations to the apparatus are involved but these can be carried out with the basic set in position in a shielded cell, although to do so it is necessary to obtain access via the gloves on the fibre-glass inner glove box. This requires a removal of samples emitting radiation, by transfer to an adjoining cell. A single vacuum system is employed. This is connected through a plug in the lead wall of the shielded cell, and couplings in the glove box wall to the appropriate furnaces. Carbon may be determined, in stainless steel containing 400 to 800 ppm C, with a coefficient of variation of +- 2%. On deposits containing carbon, the coefficient of variation is better than +- 1% for 2 to 30 mg of carbon. Hydrogen, at levels between 30 and 200 ppm in titanium can be determined with a coefficient of variation of better than +- 5%. Titanium has been used in lieu of zircaloy since standardised zircaloy specimens are not available. The precision for oxygen/metal ratio is estimated to be +- 0.001 Atoms oxygen. Sample weights of 200 mg are adequate for most analyses. (author)

  15. Self-Reported Emotional and Behavioral Problems, Family Functioning and Parental Bonding among Psychiatric Outpatient Adolescent Offspring of Croatian Male Veterans with Partial PTSD

    Science.gov (United States)

    Sarajlic Vukovic, Iris; Boricevic Maršanic, Vlatka; Aukst Margetic, Branka; Paradžik, Ljubica; Vidovic, Domagoj; Buljan Flander, Gordana

    2015-01-01

    Background: Posttraumatic stress disorder (PTSD) in male veterans has been linked with impaired family relationships and psychopathology in their children. Less is known about symptoms in children of veterans with partial PTSD. Objective: To compare mental health problems, family functioning and parent-child bonding among adolescent offspring of…

  16. Density functional theory study of interaction, bonding and affinity of group IIb transition metal cations with nucleic acid bases

    Science.gov (United States)

    Bagchi, Sabyasachi; Mandal, Debasish; Ghosh, Deepanwita; Das, Abhijit K.

    2012-05-01

    The structure, bonding, and energetics of the complexes obtained from the interaction between the most stable tautomeric forms of free DNA and RNA bases and Zn2+, Cd2+ and Hg2+ cations have been studied using density functional B3LYP method. The 6-311+G (2df, 2p) basis set along with LANL2DZ pseudopotentials for the cations are used in the calculations. The tautomerization paths of the nucleobases are investigated and transition states between the tautomeric forms of the free bases are located. The relative stability of the complexes and the tautomers of the free nucleobases are discussed referring to MIA and relative energy values. For uracil, thymine and adenine, interaction of the metal cations with the most stable tautomers form the least stable molecular complexes. For cytosine and guanine, the stability of the metalated complexes differs significantly. The enthalpy (ΔH), entropy (TΔS) and free energy (ΔG) of the complexes at 298 K have also been calculated.

  17. Density Functional Method Studies of X-H (X=C, N, O, Si, P, S) Bond Dissociation Energies

    Institute of Scientific and Technical Information of China (English)

    FU Yao; DONG Xiao-Yu; WANG Yi-Min; LIU Lei; GUO Qing-Xiang

    2005-01-01

    The performances of the density functional theory (DFT) methods in calculating X-H bond dissociation energies (BDE, X=C, N, O, Si, P, S) were evaluated. It was found that most DFT methods including B3LYP, B3PW91,G96LYP, PBE1PBE and BH&HLYP significantly underestimated the X-H BDE by as much as 13-24 kJ/mol.The underestimation is not due to the use of finite basis set, because the DFT methods still significantly underestimate the X-H BDE with the complete basis set. Therefore, these DFT methods can not be used to calculate the BDE directly. Nevertheless, the B3P86 method shows very small underestimation for the X-H BDE. Further analysis suggests that there be no advantage for using the restricted open-shell DFT methods. The unrestricted DFT methods actually perform slightly better than the restricted open-shell DFT methods in most cases. Finally, it was found that the underestimation by the DFT methods was largely systematic. The use of the calibrated UDFT/6-311+ + G(d, p) method was recommended to calculate the X-H BDE.

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

    Science.gov (United States)

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

    2015-02-01

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

  19. 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

  20. Coupled valence bond theory

    NARCIS (Netherlands)

    Havenith, R.W.A.

    2005-01-01

    In this Letter, the formulation and implementation of a parallel response property code for non-orthogonal, valence bond wave-functions are described. Test calculations on benzene and cyclobutadiene show that the polarisability and magnetisability tensors obtained using valence bond theory are compa

  1. Structural, bonding, and electronic properties of the hexagonal ferroelectric and paraelectric phases of LuMnO{sub 3} compound: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Sousa, A. M.; Coutinho, W. S.; Lima, A. F.; Lalic, M. V., E-mail: mlalicbr@gmail.com [Physics Department, Federal University of Sergipe, São Cristóvão 49100-000 (Brazil)

    2015-02-21

    We have investigated the structural, bonding, and electronic properties of both ferroelectric (FE) and paraelectric (PE) phases of the hexagonal LuMnO{sub 3} compound using calculations based on density functional theory. The structural properties have been determined by employing the generalized gradient approximation with Perdew-Burke-Ernzerhof and Wu-Cohen parameterization. The bonding and electronic properties have been treated by recently developed modified Becke-Johnson exchange potential, which succeeded to open a band gap for both PE and FE phases, in agreement with experimental predictions. The Bader’s topological analysis of electronic density showed that the character of the Lu–O axial bonds changes when the crystal exhibits the PE → FE structural transition. This fact is in agreement with experimental findings. The covalent character of the Lu–O bond significantly increases due to orbital hybridization between the Lu 5d{sub z}{sup 2} and O 2p{sub z}-states. This bonding mechanism causes the ferroelectricity in the hexagonal LuMnO{sub 3} compound.

  2. Decomposition Pathways of Glycerol via C–H, O–H, and C–C Bond Scission on Pt(111): A Density Functional Theory Study

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Bin [Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials; Greeley, Jeffrey [Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials

    2011-09-01

    Glycerol decomposition on Pt(111) via dehydrogenation or C–C bond scission is examined with periodic density functional theory (DFT) calculations. The thermochemistry of dehydrogenation intermediates is first estimated using an empirical correlation scheme with parameters fit to selected DFT calculations; the resulting estimates for the more stable intermediates are refined with full DFT calculations. Brønsted–Evans–Polanyi (BEP) relationships for dehydrogenation and C–C bond scission reactions are developed and used to estimate the kinetics of elementary dehydrogenation and C–C bond scission steps in the reaction network. The combined thermochemical and kinetic analysis implies that glycerol dehydrogenation products at intermediate levels of dehydrogenation are the most thermochemically stable. Additionally, although C–C bond scission transition state energies are high for glycerol and for intermediates at early stages of dehydrogenation, these energies decrease as the intermediates are successively dehydrogenated, reaching a minimum after the removal of several hydrogen atoms from glycerol. At these levels of dehydrogenation, the C–C scission transition state energies become comparable to those of O–H or C–H scission. These results suggest that C–C bonds are only broken after glycerol has been significantly dehydrogenated and demonstrate that DFT-based analyses, combined with simple correlation schemes, can be effective for elucidating general features of complex biomassic reaction networks.

  3. Decomposition Pathways of Glycerol via C–H, O–H, and C–C Bond Scission on Pt(111): A Density Functional Theory Study

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Bin; Greeley, Jeffrey P.

    2011-10-13

    Glycerol decomposition on Pt(111) via dehydrogenation or C–C bond scission is examined with periodic density functional theory (DFT) calculations. The thermochemistry of dehydrogenation intermediates is first estimated using an empirical correlation scheme with parameters fit to selected DFT calculations; the resulting estimates for the more stable intermediates are refined with full DFT calculations. Brønsted–Evans–Polanyi (BEP) relationships for dehydrogenation and C–C bond scission reactions are developed and used to estimate the kinetics of elementary dehydrogenation and C–C bond scission steps in the reaction network. The combined thermochemical and kinetic analysis implies that glycerol dehydrogenation products at intermediate levels of dehydrogenation are the most thermochemically stable. Additionally, although C–C bond scission transition state energies are high for glycerol and for intermediates at early stages of dehydrogenation, these energies decrease as the intermediates are successively dehydrogenated, reaching a minimum after the removal of several hydrogen atoms from glycerol. At these levels of dehydrogenation, the C–C scission transition state energies become comparable to those of O–H or C–H scission. These results suggest that C–C bonds are only broken after glycerol has been significantly dehydrogenated and demonstrate that DFT-based analyses, combined with simple correlation schemes, can be effective for elucidating general features of complex biomassic reaction networks.

  4. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  5. Molecular and environmental factors governing non-covalent bonding interactions and conformations of phosphorous functionalized γ-cyclodextrin hydrate systems.

    Science.gov (United States)

    Ivanova, Bojidarka; Spiteller, Michael

    2016-06-01

    Recent strategies in molecular drugs-design shift efforts to nanomedicine. Large supra-molecular inclusion systems are implemented as therapeutics. The sophistication of design is based on major advances of cyclodextrins (CDs) as host molecules. They are friendly towards biological environment. CDs have good (bio)compatibility as well. CDs can form host-guest macromolecular systems incorporating small molecules with suitable shapes due to non-covalent interactions. Innovative strategies yield to polymeric nano-particles; micelles; linear polymers and/or CDs-functionalized dendrimeric nanostructures; nanofibers as well as hydrogels. Attractive are phosphorous containing (bio)matrerials, having high selectivity toward biological active molecules. The non-covalent interactions in aquatic CD-systems contribute to stability of host-guest systems under physiological conditions, determining conformational preferences of host-CD macromolecule and guest small molecular template. In this paper we have reported complementation application of mass spectrometric (MS) and quantum chemical analysis of phosphorous chemically substituted γ-cyclodextrin hydrates γ-CDPO/nH2O (n ∊ [0-14]), studying neutral and polynegatively charged molecules as an effort to describe realistic a representative scale of physiological conditions. The binding affinity and molecular conformations are discussed. The 250 neutral and charged systems (γ-CDPOHm/nH2O, n ∊ [10][0,14], m ∊ [0,15], γ-CDPOH-8/nH2O.8Na(+), and γ-CDPOH-16/nH2O.16Na(+)) in four main domains of non-covalent hydrogen bonding interactions are studied. PMID:26944657

  6. Theoretical analysis of the geometrical isotope effect on the hydrogen bonds in photoactive yellow protein with multi-component density functional theory

    International Nuclear Information System (INIS)

    Highlights: • We analyze nuclear quantum effects on hydrogen bonds around the chromophore in the photoactive yellow protein. • Multi-component density functional theory is used to analyze the H/D isotope effect on hydrogen bond distances. • The donor–acceptor distance in the hydrogen bonds are elongated by the deuterium substitution. - Abstract: To theoretically analyze the nuclear quantum effects of protons on two hydrogen bonds around the chromophore (CRO) in the photoactive yellow protein (PYP), we have calculated simple cluster model consisting of CRO, Glu46, and Tyr42 residues in PYP with the multi-component molecular orbital method and multi-component density functional theory, which can take account of quantum fluctuations of light mass particles. The average OO distances between CRO and Glu46 and between CRO and Tyr42 with our methods are shorter than the corresponding equilibrium ones, while the OH distances become longer due to the anharmonicity of the potential. The H/D geometrical isotope effect is also found, that is, the distances between oxygen atoms are elongated by the deuterium substitution, known as Ubbelohde effect

  7. Band alignment and chemical bonding at the GaAs/Al{sub 2}O{sub 3} interface: A hybrid functional study

    Energy Technology Data Exchange (ETDEWEB)

    Colleoni, Davide, E-mail: davide.colleoni@epfl.ch; Miceli, Giacomo; Pasquarello, Alfredo [Chaire de Simulation à l' Echelle Atomique (CSEA), Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland)

    2015-11-23

    The band alignment at the interface between GaAs and amorphous Al{sub 2}O{sub 3} is studied through the use of hybrid functionals. For the oxide component, a disordered model is generated through density-functional molecular dynamics. The achieved structure shows good agreement with the experimental characterization. The potential line-up across the interface is obtained for two atomistic GaAs/Al{sub 2}O{sub 3} interface models, which differ by the GaAs substrate termination. The calculated valence band offset amounts to 3.9 eV for an interface characterized by the occurrence of Ga–O bonds as dominant chemical bonding, favoring the high-energy side in the range of experimental values (2.6–3.8 eV). The effect of As antisite and As–As dimer defects on the band alignment is shown to be negligible.

  8. Multidimensional isotope analysis of carbon, hydrogen and oxygen as tool for identification of the origin of ibuprofen.

    Science.gov (United States)

    Gilevska, Tetyana; Gehre, Matthias; Richnow, Hans Hermann

    2015-11-10

    Multidimensional isotope profiling is a useful tool for the characterization of the provenance of active pharmaceutical ingredients (API). To evaluate this approach, samples of the nonsteroidal anti-inflammatory drug (NSAIDs) ibuprofen were collected from 32 manufactures and 13 countries, and carbon, hydrogen and oxygen isotope ratios were analyzed by elemental analyzer, chromium-filled elemental analyzer and high temperature conversion elemental analyzer (EA, Cr-EA and TC/EA) coupled to an isotope ratio mass spectrometry (IRMS). The range of isotope values of ibuprofen (δ(13)C: -33.2±0.1‰ to -27.4±0.1‰; δ(2)H: -121.4±1.5‰ to -41.2±0.8‰; and δ(18)O: -12.6±0.3‰ to 19.0±0.6‰) allowed characterization and distinction of 5 groups, which reflect synthetic pathways and/or use of different raw materials, as well as possible isotope fractionation during the synthesis reactions. This study highlights that multi isotope fingerprinting has potential for identification of sources, and provides a database of isotope composition of ibuprofen (δ(2)H, δ(13)C, δ(18)O) that might improve the tracing of origin, transport pathways and environmental fate of ibuprofen.

  9. Adsorptive Removal of Pharmaceuticals and Personal Care Products from Water with Functionalized Metal-organic Frameworks: Remarkable Adsorbents with Hydrogen-bonding Abilities

    Science.gov (United States)

    Seo, Pill Won; Bhadra, Biswa Nath; Ahmed, Imteaz; Khan, Nazmul Abedin; Jhung, Sung Hwa

    2016-01-01

    Adsorption of typical pharmaceuticals and personal care products (PPCPs) (such as naproxen, ibuprofen and oxybenzone) from aqueous solutions was studied by using the highly porous metal-organic framework (MOF) MIL-101 with and without functionalization. Adsorption results showed that MIL-101s with H-donor functional groups such as –OH and –NH2 were very effective for naproxen adsorption, despite a decrease in porosity, probably because of H-bonding between O atoms on naproxen and H atoms on the adsorbent. For this reason, MIL-101 with two functional groups capable of H-bonding (MIL-101-(OH)2) exhibited remarkable adsorption capacity based on adsorbent surface area. The favorable contributions of –OH and –(OH)2 on MIL-101 in the increased adsorption of ibuprofen and oxybenzone (especially based on porosity) confirmed again the importance of H-bonding mechanism. The adsorbent with the highest adsorption capacity, MIL-101-OH, was very competitive when compared with carbonaceous materials, mesoporous materials, and pristine MIL-101. Moreover, the MIL-101-OH could be recycled several times by simply washing with ethanol, suggesting potential application in the adsorptive removal of PPCPs from water. PMID:27695005

  10. 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.

  11. Number series of atoms, interatomic bonds and interface bonds defining zinc-blende nanocrystals as function of size, shape and surface orientation: Analytic tools to interpret solid state spectroscopy data

    Directory of Open Access Journals (Sweden)

    Dirk König

    2016-08-01

    Full Text Available Semiconductor nanocrystals (NCs experience stress and charge transfer by embedding materials or ligands and impurity atoms. In return, the environment of NCs experiences a NC stress response which may lead to matrix deformation and propagated strain. Up to now, there is no universal gauge to evaluate the stress impact on NCs and their response as a function of NC size dNC. I deduce geometrical number series as analytical tools to obtain the number of NC atoms NNC(dNC[i], bonds between NC atoms Nbnd(dNC[i] and interface bonds NIF(dNC[i] for seven high symmetry zinc-blende (zb NCs with low-index faceting: {001} cubes, {111} octahedra, {110} dodecahedra, {001}-{111} pyramids, {111} tetrahedra, {111}-{001} quatrodecahedra and {001}-{111} quadrodecahedra. The fundamental insights into NC structures revealed here allow for major advancements in data interpretation and understanding of zb- and diamond-lattice based nanomaterials. The analytical number series can serve as a standard procedure for stress evaluation in solid state spectroscopy due to their deterministic nature, easy use and general applicability over a wide range of spectroscopy methods as well as NC sizes, forms and materials.

  12. Number series of atoms, interatomic bonds and interface bonds defining zinc-blende nanocrystals as function of size, shape and surface orientation: Analytic tools to interpret solid state spectroscopy data

    Science.gov (United States)

    König, Dirk

    2016-08-01

    Semiconductor nanocrystals (NCs) experience stress and charge transfer by embedding materials or ligands and impurity atoms. In return, the environment of NCs experiences a NC stress response which may lead to matrix deformation and propagated strain. Up to now, there is no universal gauge to evaluate the stress impact on NCs and their response as a function of NC size dNC. I deduce geometrical number series as analytical tools to obtain the number of NC atoms NNC(dNC[i]), bonds between NC atoms Nbnd(dNC[i]) and interface bonds NIF(dNC[i]) for seven high symmetry zinc-blende (zb) NCs with low-index faceting: {001} cubes, {111} octahedra, {110} dodecahedra, {001}-{111} pyramids, {111} tetrahedra, {111}-{001} quatrodecahedra and {001}-{111} quadrodecahedra. The fundamental insights into NC structures revealed here allow for major advancements in data interpretation and understanding of zb- and diamond-lattice based nanomaterials. The analytical number series can serve as a standard procedure for stress evaluation in solid state spectroscopy due to their deterministic nature, easy use and general applicability over a wide range of spectroscopy methods as well as NC sizes, forms and materials.

  13. The unique functional role of the C-HS hydrogen bond in the substrate specificity and enzyme catalysis of type 1 methionine aminopeptidase.

    Science.gov (United States)

    Reddi, Ravikumar; Singarapu, Kiran Kumar; Pal, Debnath; Addlagatta, Anthony

    2016-07-19

    It is intriguing how nature attains recognition specificity between molecular interfaces where there is no apparent scope for classical hydrogen bonding or polar interactions. Methionine aminopeptidase (MetAP) is one such enzyme where this fascinating conundrum is at play. In this study, we demonstrate that a unique C-HS hydrogen bond exists between the enzyme methionine aminopeptidase (MetAP) and its N-terminal-methionine polypeptide substrate, which allows specific interaction between apparent apolar interfaces, imposing a strict substrate recognition specificity and efficient catalysis, a feature replicated in Type I MetAPs across all kingdoms of life. We evidence this evolutionarily conserved C-HS hydrogen bond through enzyme assays on wild-type and mutant MetAP proteins from Mycobacterium tuberculosis that show a drastic difference in catalytic efficiency. The X-ray crystallographic structure of the methionine bound protein revealed a conserved water bridge and short contacts involving the Met side-chain, a feature also observed in MetAPs from other organisms. Thermal shift assays showed a remarkable 3.3 °C increase in melting temperature for methionine bound protein compared to its norleucine homolog, where C-HS interaction is absent. The presence of C-HS hydrogen bonding was also corroborated by nuclear magnetic resonance spectroscopy through a change in chemical shift. Computational chemistry studies revealed the unique role of the electrostatic environment in facilitating the C-HS interaction. The significance of this atypical hydrogen bond is underscored by the fact that the function of MetAP is essential for any living cell. PMID:27225936

  14. Excitation energies with linear response density matrix functional theory along the dissociation coordinate of an electron-pair bond in N-electron systems.

    Science.gov (United States)

    van Meer, R; Gritsenko, O V; Baerends, E J

    2014-01-14

    Time dependent density matrix functional theory in its adiabatic linear response formulation delivers exact excitation energies ωα and oscillator strengths fα for two-electron systems if extended to the so-called phase including natural orbital (PINO) theory. The Löwdin-Shull expression for the energy of two-electron systems in terms of the natural orbitals and their phases affords in this case an exact phase-including natural orbital functional (PILS), which is non-primitive (contains other than just J and K integrals). In this paper, the extension of the PILS functional to N-electron systems is investigated. With the example of an elementary primitive NO functional (BBC1) it is shown that current density matrix functional theory ground state functionals, which were designed to produce decent approximations to the total energy, fail to deliver a qualitatively correct structure of the (inverse) response function, due to essential deficiencies in the reconstruction of the two-body reduced density matrix (2RDM). We now deduce essential features of an N-electron functional from a wavefunction Ansatz: The extension of the two-electron Löwdin-Shull wavefunction to the N-electron case informs about the phase information. In this paper, applications of this extended Löwdin-Shull (ELS) functional are considered for the simplest case, ELS(1): one (dissociating) two-electron bond in the field of occupied (including core) orbitals. ELS(1) produces high quality ωα(R) curves along the bond dissociation coordinate R for the molecules LiH, Li2, and BH with the two outer valence electrons correlated. All of these results indicate that response properties are much more sensitive to deficiencies in the reconstruction of the 2RDM than the ground state energy, since derivatives of the functional with respect to both the NOs and the occupation numbers need to be accurate. PMID:24437859

  15. Supersymmetric Valence Bond Solid States

    OpenAIRE

    Arovas, Daniel P.; Hasebe, Kazuki; Qi, Xiao-Liang; Zhang, Shou-Cheng

    2009-01-01

    In this work we investigate the supersymmetric version of the valence bond solid (SVBS) state. In one dimension, the SVBS states continuously interpolate between the valence bond states for integer and half-integer spin chains, and they generally describe superconducting valence bond liquid states. Spin and superconducting correlation functions can be computed exactly for these states, and their correlation lengths are equal at the supersymmetric point. In higher dimensions, the wave function...

  16. 1, 4-Pyrone Effects on O-H Bond Dissociation Energies of Catechols in Flavonoids: A Density Functional Theory Study

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Through B3LYP/6-31G** calculations, the 1, 4-pyrone effects on O-H bond dissociation energies (BDEs) of catechols in rings A or B of flavonoids were investigated. For the catechol in ring A, although 1, 4-pyrone enlarged the conjugation system, its electron-withdrawing property increased the O-H BDE 3 ( 4.184 kJ/mol compared with that of catechol. However, for the catechol in ring B, 1, 4-pyrone was poorly conjugated with the moiety, and therefore, had little effect on the O-H BDE.

  17. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  18. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  19. Optimal Investment in Structured Bonds

    DEFF Research Database (Denmark)

    Jessen, Pernille; Jørgensen, Peter Løchte

    The paper examines the role of structured bonds in the optimal portfolio of a small retail investor. We consider the typical structured bond essentially repacking an exotic option and a zero coupon bond, i.e. an investment with portfolio insurance. The optimal portfolio is found when the investment...... opportunities consist of a risky reference fund, a risk-free asset and a structured bond. Key model elements are the trading strategy and utility function of the investor. Our numerical results indicate structured bonds do have basis for consideration in the optimal portfolio. The product holdings...

  20. 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.

  1. 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.

  2. Hydrogen bonding and coordination bonding in the electronically excited states of the MOF Cu{sub 2} (L){sub 2} (L=5-(4-pyridyl)tetrazole) CH{sub 2}Cl{sub 2}: A time-dependent density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Sui, Xiao; Mi, Weihong; Ji, Min [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Hao, Ce, E-mail: haoce_dlut@126.com [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Qiu, Jieshan [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China)

    2013-10-15

    The solvent-dependent luminescent metal-organic framework (MOF), Cu{sub 2}(L){sub 2}·CH{sub 2}Cl{sub 2} (L=5-(4-pyridyl)tetrazole), in the electronically excited states was studied using time-dependent density functional theory (TDDFT) method. Based on the analysis of the frontier molecular orbitals and electronic configuration, it revealed that the emission is attributed to a ligand-to-metal charge transfer (LMCT). Besides, we investigated the behavior of the hydrogen bonding and coordination bonding in the excited state S{sub 1} of Cu{sub 2}(L){sub 2}·CH{sub 2}Cl{sub 2}. The results indicated that the strength of the hydrogen bonding N5⋯H39-C2 between the dichloromethane molecule and the tetrazole ligand was decreased in the S{sub 1} state, while the coordination bond Cu2-N8 was strengthened in the excited state. Moreover, we further demonstrated that the hydrogen bonding weakening and coordination bonding strengthening should be beneficial to the luminescent process of the MOF. Highlights: ► Solvent-dependent luminescent MOF was studied by TDDFT. ► Emission mechanism was a ligand to metal charge transition (LMCT). ► {sup 1}H NMR and binding energies indicate H-bond weakening in excited states. ► The coordination bonds become stronger in the excited states.

  3. Beta-1 integrin-mediated adhesion may be initiated by multiple incomplete bonds, thus accounting for the functional importance of receptor clustering.

    Science.gov (United States)

    Vitte, Joana; Benoliel, Anne-Marie; Eymeric, Philippe; Bongrand, Pierre; Pierres, Anne

    2004-06-01

    The regulation of cell integrin receptors involves modulation of membrane expression, shift between different affinity states, and topographical redistribution on the cell membrane. Here we attempted to assess quantitatively the functional importance of receptor clustering. We studied beta-1 integrin-mediated attachment of THP-1 cells to fibronectin-coated surfaces under low shear flow. Cells displayed multiple binding events with a half-life of the order of 1 s. The duration of binding events after the first second after arrest was quantitatively accounted for by a model assuming the existence of a short-time intermediate binding state with 3.6 s(-1) dissociation rate and 1.3 s(-1) transition frequency toward a more stable state. Cell binding to surfaces coated with lower fibronectin densities was concluded to be mediated by single molecular interactions, whereas multiple bonds were formed intermediate state. Receptor aggregation was induced by treating cells with neutral antiintegrin antibody and antiimmunoglobulin antibodies. A semiquantitative confocal microscopy study suggested that this treatment increased between 40% and 100% the average number of integrin receptors located in a volume of approximately 0.045 microm(3) surrounding each integrin. This aggregation induced up to 2.7-fold increase of the average number of bonds. Flow cytometric analysis of fluorescent ligand binding showed that THP-1 cells displayed low-affinity beta-1 integrins with a dissociation constant in the micromolar range. It is concluded that the initial step of cell adhesion was mediated by multiple incomplete bonds rather than a single equilibrium-state ligand receptor association. This interpretation accounts for the functional importance of integrin clustering.

  4. A PBE hybrid functional study of blue-shifting and red-shifting hydrogen bonds in p hydrocarbons

    Directory of Open Access Journals (Sweden)

    Boaz Galdino de Oliveira

    2009-07-01

    Full Text Available This study examines a selected group of p hydrocarbon complexes, represented by C2H4•••HCF3, C2H2•••HCF3, C2H4•••HCF3 and C2H2•••HCF3, from a theoretical point of view. From BPBE/6-311++G(d,p calculations, the geometrical results of these complexes revealed an elongation and shortening of the H—C bond lengths of chloroform (HCCl3 and fluoroform (HCF3, respectively. In terms of the infrared spectrum, the analysis of stretch frequencies revealed that the variations in the H—C modes are essentially recognized as red and blue-shifting modes. For the purposes of understanding the two vibrational phenomena of the p hydrocarbon complexes studied here, PBE/6-311++G(d,p calculations were carried out and partitioning of atomic charges derived from the ChelpG algorithm were also used. A theoretical justification of red- and blue-shift effects was drawn up using charge-transfer analysis, which is manifested in the p bonds of acetylene and ethylene to chloroform (H—CCl3 and fluoroform (H—CF3, respectively. Finally, a further debate regarding the distinct polarizability power of chloroform and fluoroform is presented, concluding that, in comparison with fluoroform, chloroform possesses the requisite features for conventional proton donors and a red-shift is therefore observed in the C2H4•••HCCl3 and C2H2•••HCCl3 complexes.

  5. Determination of the carbon, hydrogen and nitrogen contents of alanine and their uncertainties using the certified reference material L-alanine (NMIJ CRM 6011-a).

    Science.gov (United States)

    Itoh, Nobuyasu; Sato, Ayako; Yamazaki, Taichi; Numata, Masahiko; Takatsu, Akiko

    2013-01-01

    The carbon, hydrogen, and nitrogen (CHN) contents of alanine and their uncertainties were estimated using a CHN analyzer and the certified reference material (CRM) L-alanine. The CHN contents and their uncertainties, as measured using the single-point calibration method, were 40.36 ± 0.20% for C, 7.86 ± 0.13% for H, and 15.66 ± 0.09% for N; the results obtained using the bracket calibration method were also comparable. The method described in this study is reasonable, convenient, and meets the general requirement of having uncertainties ≤ 0.4%.

  6. The structure, energetics, and nature of the chemical bonding of phenylthiol adsorbed on the Au(111) surface: implications for density-functional calculations of molecular-electronic conduction.

    Science.gov (United States)

    Bilić, Ante; Reimers, Jeffrey R; Hush, Noel S

    2005-03-01

    The adsorption of phenylthiol on the Au(111) surface is modeled using Perdew and Wang density-functional calculations. Both direct molecular physisorption and dissociative chemisorption via S-H bond cleavage are considered as well as dimerization to form disulfides. For the major observed product, the chemisorbed thiol, an extensive potential-energy surface is produced as a function of both the azimuthal orientation of the adsorbate and the linear translation of the adsorbate through the key fcc, hcp, bridge, and top binding sites. Key structures are characterized, the lowest-energy one being a broad minimum of tilted orientation ranging from the bridge structure halfway towards the fcc one. The vertically oriented threefold binding sites, often assumed to dominate molecular electronics measurements, are identified as transition states at low coverage but become favored in dense monolayers. A similar surface is also produced for chemisorption of phenylthiol on Ag(111); this displays significant qualitative differences, consistent with the qualitatively different observed structures for thiol chemisorption on Ag and Au. Full contours of the minimum potential energy as a function of sulfur translation over the crystal face are described, from which the barrier to diffusion is deduced to be 5.8 kcal mol(-1), indicating that the potential-energy surface has low corrugation. The calculated bond lengths, adsorbate charge and spin density, and the density of electronic states all indicate that, at all sulfur locations, the adsorbate can be regarded as a thiyl species that forms a net single covalent bond to the surface of strength 31 kcal mol(-1). No detectable thiolate character is predicted, however, contrary to experimental results for alkyl thiols that indicate up to 20%-30% thiolate involvement. This effect is attributed to the asymptotic-potential error of all modern density functionals that becomes manifest through a 3-4 eV error in the lineup of the adsorbate and

  7. LAMMPS Framework for Directional Dynamic Bonding

    DEFF Research Database (Denmark)

    2012-01-01

    and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework.......We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled...... to limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead...

  8. Bonding in Zintl phase hydrides: density functional calculations for SrAlSiH, SrAl2H2, SrGa2H2 and BaGa2H2

    Energy Technology Data Exchange (ETDEWEB)

    Subedi, Alaska P [ORNL; Singh, David J [ORNL

    2008-01-01

    We investigate the bonding characteristics of SrAlSiH, SrAl{sub 2}H{sub 2}, SrGa{sub 2}H{sub 2}, and BaGa{sub 2}H{sub 2} using density functional calculations. The mixed bonding characteristic of other families of Zintl phases is found, with the formation of covalent sp{sup 2} bonds in the Al/Ga/Al-Si planes of the various compounds. On the other hand the Sr and Ba atoms occur as divalent cations, while the H is anionic. The results indicate that insulating SrSiAlH may be a switchable ferroelectric.

  9. Anomalous scaling and breakdown of conventional density functional theory methods for the description of Mott phenomena and stretched bonds

    Science.gov (United States)

    Ying, Zu-Jian; Brosco, Valentina; Lopez, Giorgia Maria; Varsano, Daniele; Gori-Giorgi, Paola; Lorenzana, José

    2016-08-01

    Density functional theory provides the most widespread framework for the realistic description of the electronic structure of solids, but the description of strongly correlated systems has remained so far elusive. We consider a particular limit of electrons and ions in which a one-band description becomes exact all the way from the weakly correlated metallic regime to the strongly correlated Mott-Hubbard regime. We provide a necessary condition a density functional should fulfill to describe Mott-Hubbard behavior in this one-band limit and show that it is not satisfied by standard and widely used local, semilocal, and hybrid functionals. We illustrate the condition in the case of few-atom systems and provide an analytic approximation to the exact exchange-correlation potential based on a variational wave function which shows explicitly the correct behavior, combining in a neat way lattice and continuum methods.

  10. Hybrid materials of MCM-41 functionalized by lanthanide (Tb3+, Eu3+) complexes of modified meta-methylbenzoic acid: Covalently bonded assembly and photoluminescence

    International Nuclear Information System (INIS)

    Novel organic-inorganic mesoporous hybrid materials were synthesized by linking lanthanide (Tb3+, Eu3+) complexes to the mesoporous MCM-41 through the modified meta-methylbenzoic acid (MMBA-Si) using co-condensation method in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as template. The luminescence properties of these resulting materials (denoted as Ln-MMBA-MCM-41, Ln=Tb, Eu) were characterized in detail, and the results reveal that luminescent mesoporous materials have high surface area, uniformity in the ordered mesoporous structure. Moreover, the mesoporous material covalently bonded Tb3+ complex (Tb-MMBA-MCM-41) exhibits the stronger characteristic emission of Tb3+ and longer lifetime than Eu-MMBA-MCM-41 due to the triplet state energy of organic legend MMBA-Si matches with the emissive energy level of Tb3+ very well. - Graphical abstract: Novel organic-inorganic mesoporous luminescent materials were synthesized by linking lanthanide (Tb3+, Eu3+) complexes to covalently bond the functionalized ordered mesoporous MCM-41 with modified meta-methylbenzoic acid (MMBA)-Si by co-condensation of tetraethoxysilane (TEOS) in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as template

  11. Ligand-Mediated and Copper-Catalyzed C(sp3)-H Bond Functionalization of Aryl Ketones with Sodium Sulfinates under Mild Conditions

    Science.gov (United States)

    Lan, Xing-Wang; Wang, Nai-Xing; Bai, Cui-Bing; Zhang, Wei; Xing, Yalan; Wen, Jia-Long; Wang, Yan-Jing; Li, Yi-He

    2015-12-01

    A novel and convenient copper (II) bromide and 1,8-diazabicyclo[5.4.1]undec-7-ene (DBU) or 1,10-phenanthroline catalysis protocol for the construction of α-alkyl-β-keto sulfones via C(sp3)-H bond functionalization followed by C(sp3)-S bond formation between aryl ketones and sodium sulfinates at room temperature has been developed. This method is applicable to a wide range of aryl ketones and sodium sulfinates. The electronic effects of aryl ketones and ligands effects of the copper salts are crucial for this transformation. Typically, substituted aryl ketones with electron-withdrawing group do not need any ligand to give a good to excellent yield, while substituted aryl ketones with electron-donating group and electron-rich heteroaromatic ketones offer a good to excellent yield only under the nitrogen-based ligands. The practical value of this transformation highlights the efficient and robust one-pot synthesis of α-alkyl-β-keto sulfones.

  12. Binary and Ternary Heterometallic (La3+, Gd3+, Y3+–Eu3+ Functionalized SBA-15 Mesoporous Hybrids: Chemically Bonded Assembly and Photoluminescence

    Directory of Open Access Journals (Sweden)

    Yan Bing

    2010-01-01

    Full Text Available Abstract A novel kind of organic–inorganic monomer SUASi has been achieved by modifying 5-sulfosalicylic acid (SUA with 3-aminopropyltrimethoxysilane (APS, subsequently binary and ternary Eu3+ mesoporous hybrid materials with 5-sulfosalicylic acid (SUA-functionalized SBA-15 and 1,10-phenanthroline (phen are synthesized by co-condensation of SUASi and TEOS in the presence of Eu3+ complex and Pluronic P123 as a template. Finally, luminescent hybrid mesoporous materials consisting of active rare earth ions (Eu3+—inert rare earth ions (Y3+, La3+, Gd3+ complex covalently bonded to the mesoporous materials network have been obtained via this sol–gel approach. The physical characterization and photoluminescence of all these resulting materials are studied in detail. Especially the luminescent behavior has been studied with the different ratios of Eu3+–(Y3+, La3+, Gd3+, which suggests that the existence of inert rare earth ions can enhance the luminescence intensity of Eu3+. This may be due to the intramolecular energy transfer between Y3+, La3+, Gd3+, and Eu3+ through the covalently bonded mesoporous framework.

  13. Amino-Functionalized Multiwalled Carbon Nanotubes Lead to Successful Ring-Opening Polymerization of Poly(ε-caprolactone): Enhanced Interfacial Bonding and Optimized Mechanical Properties.

    Science.gov (United States)

    Roumeli, Eleftheria; Papageorgiou, Dimitrios G; Tsanaktsis, Vasilios; Terzopoulou, Zoe; Chrissafis, Konstantinos; Avgeropoulos, Apostolos; Bikiaris, Dimitrios N

    2015-06-01

    In this work, the synthesis, structural characteristics, interfacial bonding, and mechanical properties of poly(ε-caprolactone) (PCL) nanocomposites with small amounts (0.5, 1.0, and 2.5 wt %) of amino-functionalized multiwalled carbon nanotubes (f-MWCNTs) prepared by ring-opening polymerization (ROP) are reported. This method allows the creation of a covalent-bonding zone on the surface of nanotubes, which leads to efficient debundling and therefore satisfactory dispersion and effective load transfer in the nanocomposites. The high covalent grafting extent combined with the higher crystallinity provide the basis for a significant enhancement of the mechanical properties, which was detected in the composites with up to 1 wt % f-MWCNTs. Increasing filler concentration encourages intrinsic aggregation forces, which allow only minor grafting efficiency and poorer dispersion and hence inferior mechanical performance. f-MWCNTs also cause a significant improvement on the polymerization reaction of PCL. Indeed, the in situ polymerization kinetics studies reveal a significant decrease in the reaction temperature, by a factor of 30-40 °C, combined with accelerated the reaction kinetics during initiation and propagation and a drastically reduced effective activation energy.

  14. Free-Radical Triggered Ordered Domino Reaction: An Approach to C-C Bond Formation via Selective Functionalization of α-Hydroxyl-(sp(3))C-H in Fluorinated Alcohols.

    Science.gov (United States)

    Xu, Zhengbao; Hang, Zhaojia; Liu, Zhong-Quan

    2016-09-16

    A free-radical mediated highly ordered radical addition/cyclization/(sp(3))C-C(sp(3)) formation domino reaction is developed. Three new C-C bonds are formed one by one in a mixed system. Furthermore, it represents the first example of cascade C-C bond formation via selective functionalization of α-hydroxyl-C(sp(3))-H in fluorinated alcohols.

  15. I2/O2-Enabled N-S Bond Formation to Access Functionalized 1,2,3-Thiadiazoles.

    Science.gov (United States)

    Fan, Wei; Li, Qun; Li, Yanrong; Sun, Hao; Jiang, Bo; Li, Guigen

    2016-03-18

    A new, metal-free intermolecular formal [3 + 2] heterocyclization between triethylammonium thiolates and aryl hydrazines has been established by using the combination of I2 and O2 as efficient oxidation sources, allowing a concise and low-cost access to new densely functionalized 1,2,3-thiadiazoles with good to excellent yields. The reaction showed a broad scope of substrates of both reactants and attractive characteristics consisting of eco-friendly oxidants, flexible structural modification, broad functional group compatibility, and mild reaction conditions. PMID:26927417

  16. Effect of self-interaction error in the evaluation of the bond length alternation in trans-polyacetylene using density-functional theory

    Science.gov (United States)

    Ciofini, I.; Adamo, C.; Chermette, H.

    2005-09-01

    The calculation of the bond-length alternation (BLA) in trans-polyacetylene has been chosen as benchmark to emphasize the effect of the self-interaction error within density-functional theory (DFT). In particular, the BLA of increasingly long acetylene oligomers has been computed using the Møller-Plesset wave-function method truncated at the second order and several DFT models. While local-density approximation (LDA) or generalized gradient corrected (GGA) functionals strongly underestimate the BLA, approaches including self-interaction corrections (SIC) provide significant improvements. Indeed, the simple averaged-density SIC scheme (ADSIC), recently proposed by Legrand et al. [J. Phys. B 35, 1115 (2002)], provides better results for the structure of large oligomers than the more complex approach of Krieger et al. [Phys. Rev. A 45, 101 (1992)]. The ADSIC method is particularly promising since both the exchange-correlation energy and potential are improved with respect to standard LDA/GGA using a physically appealing correction, through a different route than the more popular approach through the Hartree-Fock exchange inclusion within the hybrid functionals.

  17. Diffusion bonding

    Science.gov (United States)

    Anderson, Robert C.

    1976-06-22

    1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

  18. Role of Cell-Cell bond for the viability and the function of vascular smooth muscle cells

    Directory of Open Access Journals (Sweden)

    M. Mura

    2010-01-01

    Full Text Available Vascular smooth muscle cell (VSMC viability and homeostasis is regulated by cell-matrix and cell-cell contact: disruption of these interactions are responsible of a switch from a mature to a high proliferative phenotype. VSMCs migration, rate of growth and apoptosis, and the extent of their extracellular matrix (ECM deposition can be also modulated by proatherogenic peptides. Among them, ATII induces the transactivation of IGF I R, which, together with the binding protein IGFBP3, represents a determinant of cell survival, growth and proliferation. Aim of our in vitro study was to verify the role of elective cell-cell bond in moulating the response to ATII. Thus, we evaluated viability, proliferation, IGFIR, IGFBP3 expression and the long term survival and production of ECM in a provisional tissue. A7r5 cell-line was used in adherent cultures or incubated in agarose-coated culture plates to inhibit cell-matrix interactions. Cells, treated or not with ATII 100 nM, were evaluated for apoptosis rate, cell cycle, IGFIR and IGFBP3 protei expression. Fibrin provisional tissue was developed polymerizing a fibrin solution. cantaining A7r5 cells with thrombin. Histological stainings for ECM components were performed on sections of prvisional tissue. An exclusive cell-cell contact resulted to monolayer cell cultures. ATII did not affect the cell survival in both culture conditions, but promoted a 10% decrease in "S" phase and an increases IGFIR expression only in adherent cells. while suspended cell aggregates were resistant to ATII administration; IGFBP3 was reduced both in ATII treated adherent cells and in floating clustered cells, irrespective of the treatmentn. VSMC conditioning in agarose-coated plates before seeding in fibrin provisional matrix reduced, but not abolished, the cell ability to colonize the clot and to produce ECM. This study demonstrates that the elective cell-cell contact induces a quiescent status in cells lacking of cell

  19. Water as a green solvent for efficient synthesis of isocoumarins through microwave-accelerated and Rh/Cu-catalyzed C-H/O-H bond functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Li, Qiu; Yan, Yunnan; Wang, Xiaowei; Gong, Binwei; Tang, Xiaobo; Shi, JingJing; Xu, H. Eric; Yi, Wei [Shenyang; (Gannan); (Van Andel); (UST - China); (Chinese Aca. Sci.)

    2014-08-14

    Green chemistry that uses water as a solvent has recently received great attention in organic synthesis. Here we report an efficient synthesis of biologically important isocoumarins through direct cleavage of C–H/O–H bonds by microwave-accelerated and Rh/Cu-catalyzed oxidative annulation of various substituted benzoic acids, where water is used as the only solvent in the reactions. The remarkable features of this “green” methodology include high product yields, wide tolerance of various functional groups as substrates, and excellent region-/site-specificities, thus rendering this methodology a highly versatile and eco-friendly alternative to the existing methods for synthesizing isocoumarins and other biologically important derivatives such as isoquinolones.

  20. Density Functional Studies of the Reaction of Ytterbium Monocation with Fluoromethane: C-F Bond Activation and Electron-Transfer Reactivity

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The potential energy surface and reaction mechanism corresponding to the reaction of ytterbium monocation with fluoromethane,which represents a prototype of the activation of C-F bond in fluorohydrocarbons by bare lanthanide cations,have been investigated for the first time by using density functional theory.A direct fluorine abstraction mechanism was revealed,and the related thermochemistry data were determined.The electron-transfer reactivity of the reaction was analyzed using the two-state model,and a strongly avoided crossing behavior on the transition state region was shown.The present results support the reaction mechanism inferred from early experimental data and the related thermochemistry data can provide a guide for further experimental researches.

  1. Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding.

    Science.gov (United States)

    Fliedel, Christophe; Rosa, Vitor; Falceto, Andrés; Rosa, Patrick; Alvarez, Santiago; Braunstein, Pierre

    2015-07-01

    Starting from the short-bite ligands N-thioether-functionalized bis(diphenylphosphino)amine-type (Ph2P)2N(CH2)3SMe (1) and (Ph2P)2N(p-C6H4)SMe (2), the Fe(II) complexes [FeCl2(1)]n (3), [FeCl2(2)]2 (4), [Fe(OAc)(1)2]PF6 (5), and [Fe(OAc)(2)2]PF6 (6) were synthesized and characterized by Fourier transform IR, mass spectrometry, elemental analysis, and also by X-ray diffraction for 3, 4, and 6. Complex 3 is a coordination polymer in which 1 acts as a P,P-pseudochelate and a (P,P),S-bridge, whereas 4 has a chlorido-bridged dinuclear structure in which 2 acts only as a P,P-pseudochelate. Since these complexes were obtained under strictly similar synthetic and crystallization conditions, these unexpected differences were ascribed to the different spacer between the nitrogen atom and the −SMe group. In both compounds, one Fe–P bond was found to be unusually long, and a theoretical analysis was performed to unravel the electronic or steric reasons for this difference. Density functional theory calculations were performed for a set of complexes of general formula [FeCl2(SR2){R21PN(R2)P′R23}] (R = H, Me; R1, R2, and R3 = H, Me, Ph), to understand the reasons for the significant deviation of the iron coordination sphere away from tetrahedral as well as from trigonal bipyramidal and the varying degree of unsymmetry of the two Fe–P bonds involving pseudochelating PN(R)P ligands. Electronic factors nicely explain the observed structures, and steric reasons were further ruled out by the structural analysis in the solid-state of the bis-chelated complex 6, which displays usual and equivalent Fe–P bond lengths. Magnetic susceptibility studies were performed to examine how the structural differences between 3 and 4 would affect the interactions between the iron centers, and it was concluded that 3 behaves as an isolated high-spin Fe(II) mononuclear complex, while significant intra- and intermolecular ferromagnetic interactions were evidenced for 4 at low temperatures

  2. Properties and structure of the functional composite materials - Nd-Fe-Co-B powder bonded with polymer

    OpenAIRE

    B. Ziębowicz; M. Dziekońska; L.A. Dobrzański

    2011-01-01

    Purpose: This paper presents the material and technological solution which makes it possible obtaining functional composite materials based on the nanocrystalline Nd-Fe-Co-B powder with polymer matrix and shows the possibility of application in different branches of the techniques.Design/methodology/approach: For fabrication of composite materials: Nd-Fe-Co-B powder obtained by rapid quenched technique and for matrix - high density pressureless polyethylene (PEHD) and polyamide (PA12) (2.5 %...

  3. A statistical mechanical theory of proton transport kinetics in hydrogen-bonded networks based on population correlation functions with applications to acids and bases.

    Science.gov (United States)

    Tuckerman, Mark E; Chandra, Amalendu; Marx, Dominik

    2010-09-28

    Extraction of relaxation times, lifetimes, and rates associated with the transport of topological charge defects in hydrogen-bonded networks from molecular dynamics simulations is a challenge because proton transfer reactions continually change the identity of the defect core. In this paper, we present a statistical mechanical theory that allows these quantities to be computed in an unbiased manner. The theory employs a set of suitably defined indicator or population functions for locating a defect structure and their associated correlation functions. These functions are then used to develop a chemical master equation framework from which the rates and lifetimes can be determined. Furthermore, we develop an integral equation formalism for connecting various types of population correlation functions and derive an iterative solution to the equation, which is given a graphical interpretation. The chemical master equation framework is applied to the problems of both hydronium and hydroxide transport in bulk water. For each case it is shown that the theory establishes direct links between the defect's dominant solvation structures, the kinetics of charge transfer, and the mechanism of structural diffusion. A detailed analysis is presented for aqueous hydroxide, examining both reorientational time scales and relaxation of the rotational anisotropy, which is correlated with recent experimental results for these quantities. Finally, for OH(-)(aq) it is demonstrated that the "dynamical hypercoordination mechanism" is consistent with available experimental data while other mechanistic proposals are shown to fail. As a means of going beyond the linear rate theory valid from short up to intermediate time scales, a fractional kinetic model is introduced in the Appendix in order to describe the nonexponential long-time behavior of time-correlation functions. Within the mathematical framework of fractional calculus the power law decay ∼t(-σ), where σ is a parameter of the

  4. Effects of Bonding Types and Functional Groups on CO 2 Capture using Novel Multiphase Systems of Liquid-like Nanoparticle Organic Hybrid Materials

    KAUST Repository

    Lin, Kun-Yi Andrew

    2011-08-01

    Novel liquid-like nanoparticle organic hybrid materials (NOHMs) which possess unique features including negligible vapor pressure and a high degree of tunability were synthesized and their physical and chemical properties as well as CO 2 capture capacities were investigated. NOHMs can be classified based on the synthesis methods involving different bonding types, the existence of linkers, and the addition of task-specific functional groups including amines for CO 2 capture. As a canopy of polymeric chains was grafted onto the nanoparticle cores, the thermal stability of the resulting NOHMs was improved. In order to isolate the entropy effect during CO 2 capture, NOHMs were first prepared using polymers that do not contain functional groups with strong chemical affinity toward CO 2. However, it was found that even ether groups on the polymeric canopy contributed to CO 2 capture in NOHMs via Lewis acid-base interactions, although this effect was insignificant compared to the effect of task-specific functional groups such as amine. In all cases, a higher partial pressure of CO 2 was more favorable for CO 2 capture, while a higher temperature caused an adverse effect. Multicyclic CO 2 capture tests confirmed superior recyclability of NOHMs and NOHMs also showed a higher selectivity toward CO 2 over N 2O, O 2 and N 2. © 2011 American Chemical Society.

  5. Effects of bonding types and functional groups on CO2 capture using novel multiphase systems of liquid-like nanoparticle organic hybrid materials.

    Science.gov (United States)

    Lin, Kun-Yi Andrew; Park, Ah-Hyung Alissa

    2011-08-01

    Novel liquid-like nanoparticle organic hybrid materials (NOHMs) which possess unique features including negligible vapor pressure and a high degree of tunability were synthesized and their physical and chemical properties as well as CO(2) capture capacities were investigated. NOHMs can be classified based on the synthesis methods involving different bonding types, the existence of linkers, and the addition of task-specific functional groups including amines for CO(2) capture. As a canopy of polymeric chains was grafted onto the nanoparticle cores, the thermal stability of the resulting NOHMs was improved. In order to isolate the entropy effect during CO(2) capture, NOHMs were first prepared using polymers that do not contain functional groups with strong chemical affinity toward CO(2). However, it was found that even ether groups on the polymeric canopy contributed to CO(2) capture in NOHMs via Lewis acid-base interactions, although this effect was insignificant compared to the effect of task-specific functional groups such as amine. In all cases, a higher partial pressure of CO(2) was more favorable for CO(2) capture, while a higher temperature caused an adverse effect. Multicyclic CO(2) capture tests confirmed superior recyclability of NOHMs and NOHMs also showed a higher selectivity toward CO(2) over N(2)O, O(2) and N(2).

  6. A3-Coupling catalyzed by robust Au nanoparticles covalently bonded to HS-functionalized cellulose nanocrystalline films

    Directory of Open Access Journals (Sweden)

    Jian-Lin Huang

    2013-07-01

    Full Text Available We decorated HS-functionalized cellulose nanocrystallite (CNC films with monodisperse Au nanoparticles (AuNPs to form a novel nanocomposite catalyst AuNPs@HS-CNC. The uniform, fine AuNPs were made by the reduction of HAuCl4 solution with thiol (HS- group-functionalized CNC films. The AuNPs@HS-CNC nanocomposites were examined by X-ray photoelectron spectroscopy (XPS, TEM, ATR-IR and solid-state NMR. Characterizations suggested that the size of the AuNPs was about 2–3 nm and they were evenly distributed onto the surface of CNC films. Furthermore, the unique nanocomposite Au@HS-CNC catalyst displayed high catalytic efficiency in promoting three-component coupling of an aldehyde, an alkyne, and an amine (A3-coupling either in water or without solvent. Most importantly, the catalyst could be used repetitively more than 11 times without significant deactivation. Our strategy also promotes the use of naturally renewable cellulose to prepare reusable nanocomposite catalysts for organic synthesis.

  7. Modified bonded bridge space maintainer.

    Science.gov (United States)

    Liegeois, F; Limme, M

    1999-01-01

    The premature loss of primary teeth can create the need for space maintenance and restoration of function. This article presents a fixed bonded space maintainer, which allows space to be maintained with economy of dental tissues.

  8. Properties and structure of the functional composite materials - Nd-Fe-Co-B powder bonded with polymer

    Directory of Open Access Journals (Sweden)

    B. Ziębowicz

    2011-12-01

    Full Text Available Purpose: This paper presents the material and technological solution which makes it possible obtaining functional composite materials based on the nanocrystalline Nd-Fe-Co-B powder with polymer matrix and shows the possibility of application in different branches of the techniques.Design/methodology/approach: For fabrication of composite materials: Nd-Fe-Co-B powder obtained by rapid quenched technique and for matrix - high density pressureless polyethylene (PEHD and polyamide (PA12 (2.5 % wt. were used. Composite materials were compacted by the one-sided uniaxial pressing. The complex relationships among the manufacturing technology of these materials, their microstructure, as well as their mechanical and physical properties were evaluated. Materialographic examination of the structure of composite materials and fractures after decohesion were made.Findings: The main purpose of obtaining this kind of composite materials is broadening possibilities of nanocrystalline magnetic materials application that influence on the miniaturization, simplification and lowering the costs of devices. Composite materials show regular distribution of magnetic powder in polymer matrix. Examination of mechanical properties show that these materials have satisfactory compression strength.Practical implications: The manufacturing of composite materials Nd-Fe-Co-B powder – polymer greatly expand the applicable possibilities of nanocrystalline powders of magnetically hard materials however further examination to obtain improved properties of magnetic composite materials and investigations of constructions of new machines and devices with these materials elements are still needed.Originality/value: Manufacturing processes of functional composite materials obtaining Nd-Fe-Co-B – polymer matrix and determination of their mechanical properties. Results are the base for further investigations such composite materials.

  9. The properties of mesoporous silica nanoparticles functionalized with different PEG-chain length via the disulfide bond linker and drug release in glutathione medium.

    Science.gov (United States)

    Xie, Zhifei; Gong, Huameng; Liu, Mingxing; Zhu, Hongda; Sun, Honghao

    2016-01-01

    In this paper, a novel drug-loaded material (MSNs-SS-PEG) was obtained by grafting the thiol-linked methoxy polyethylene glycol (MeOPEG-SH) onto the thiol-functionalized mesoporous silica nanoparticles (MSNs-SH) via the disulfide bond linker. In our designed experiment, three different chain lengths of PEG (PEG(1000), PEG(5000), and PEG(1000)-PEG(5000)) were used. The silica materials were characterized by Fourier transform infrared spectroscopy (FT-IR), dynamic light scattering, field emission scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, and X-ray diffraction. The morphology of the MSNs-SS-PEG was spherical with an average diameter of about 150 nm. Due to the covalent modification of hydrophilic MeOPEG, the MSNs-SS-PEG was coated by a thin polymer shell, showing stable and inerratic MCM-41 type mesoporous structure as well as high specific surface areas and large pore volumes. Moreover, the releases of doxorubicin hydrochloride (DOX) from these materials at 10 mM of glutathione were investigated. The PEG functionalization could effectively cap drugs in the mesoporous channels. The release of DOX from the MSNs-SS-PEG(n) revealed redox-responsive characteristic. The obtained results showed that the MSNs-SS-PEG might be promising drug delivery carrier materials, which could play an important role in the development of drug delivery. PMID:26540096

  10. Thread bonds in molecules

    CERN Document Server

    Ivlev, B

    2015-01-01

    Unusual chemical bonds are proposed. Each bond is almost covalent but is characterized by the thread of a small radius $\\sim 0.6\\times 10^{-11}$cm, between two nuclei in a molecule. The main electron density is concentrated outside the thread as in a covalent bond. The thread is formed by the electron wave function which has a tendency to be singular on it. The singularity along the thread is cut off by electron "vibrations" due to the interaction with zero point electromagnetic oscillations. The electron energy has its typical value of (1-10)eV. Due to the small tread radius the uncertainty of the electron momentum inside the thread is large resulting in a large electron kinetic energy $\\sim 1 MeV$. This energy is compensated by formation of a potential well due to the reduction of the energy of electromagnetic zero point oscillations. This is similar to formation of a negative van der Waals potential. Thread bonds are stable and cannot be created or destructed in chemical or optical processes.

  11. Quantum Confinement in Hydrogen Bond

    CERN Document Server

    Santos, Carlos da Silva dos; Ricotta, Regina Maria

    2015-01-01

    In this work, the quantum confinement effect is proposed as the cause of the displacement of the vibrational spectrum of molecular groups that involve hydrogen bonds. In this approach the hydrogen bond imposes a space barrier to hydrogen and constrains its oscillatory motion. We studied the vibrational transitions through the Morse potential, for the NH and OH molecular groups inside macromolecules in situation of confinement (when hydrogen bonding is formed) and non-confinement (when there is no hydrogen bonding). The energies were obtained through the variational method with the trial wave functions obtained from Supersymmetric Quantum Mechanics (SQM) formalism. The results indicate that it is possible to distinguish the emission peaks related to the existence of the hydrogen bonds. These analytical results were satisfactorily compared with experimental results obtained from infrared spectroscopy.

  12. Hexacoordinate bonding and aromaticity in silicon phthalocyanine.

    Science.gov (United States)

    Yang, Yang

    2010-12-23

    Si-E bondings in hexacoordinate silicon phthalocyanine were analyzed using bond order (BO), energy partition, atoms in molecules (AIM), electron localization function (ELF), and localized orbital locator (LOL). Bond models were proposed to explain differences between hexacoordinate and tetracoordinate Si-E bondings. Aromaticity of silicon phthalocyanine was investigated using nucleus-independent chemical shift (NICS), harmonic oscillator model of aromaticity (HOMA), conceptual density functional theory (DFT), ring critical point (RCP) descriptors, and delocalization index (DI). Structure, energy, bonding, and aromaticity of tetracoordinate silicon phthalocyanine were studied and compared with hexacoordinate one. PMID:21105726

  13. Optimal Investment in Structured Bonds

    DEFF Research Database (Denmark)

    Jessen, Pernille; Jørgensen, Peter Løchte

    2012-01-01

    of the article is to provide possible explanations for the puzzle of why small retail investors hold structured bonds. The investment universe consists of a stock index, a risk-free bank account, and a structured bond containing an option written on another index. We apply expected utility maximization...... and consider different utility functions and trading strategies. Our results show that investors should include structured bonds in their optimal portfolio only if they cannot access the index underlying the option directly and only if the products then provide sufficient diversification to compensate...

  14. Probing the Conformational and Functional Consequences of Disulfide Bond Engineering in Growth Hormone by Hydrogen-Deuterium Exchange Mass Spectrometry Coupled to Electron Transfer Dissociation

    DEFF Research Database (Denmark)

    Seger, Signe T; Breinholt, Jens; Faber, Johan H;

    2015-01-01

    spectrometry (HDX-MS) to map the impact of the new disulfide bond on the conformational dynamics of this new hGH variant. Compared to wild type hGH, the variant exhibits reduced loop dynamics, indicating a stabilizing effect of the introduced disulfide bond. Furthermore, the disulfide bond exhibits longer...... ranging effects, stabilizing a short α-helix quite distant from the mutation sites, but also rendering a part of the α-helical hGH core slightly more dynamic. In the regions where the hGH variant exhibits a different deuterium uptake than the wild type protein, electron transfer dissociation (ETD...

  15. Single and double acceptor-levels of a carbon-hydrogen defect in n-type silicon

    Science.gov (United States)

    Stübner, R.; Scheffler, L.; Kolkovsky, Vl.; Weber, J.

    2016-05-01

    In the present study, we discuss the origin of two dominant deep levels (E42 and E262) observed in n-type Si, which is subjected to hydrogenation by wet chemical etching or a dc H-plasma treatment. Their activation enthalpies determined from Laplace deep level transient spectroscopy measurements are EC-0.06 eV (E42) and EC-0.51 eV (E262). The similar annealing behavior and identical depth profiles of E42 and E262 correlate them with two different charge states of the same defect. E262 is attributed to a single acceptor state due to the absence of the Poole-Frenkel effect and the lack of a capture barrier for electrons. The emission rate of E42 shows a characteristic enhancement with the electric field, which is consistent with the assignment to a double acceptor state. In samples with different carbon and hydrogen content, the depth profiles of E262 can be explained by a defect with one H-atom and one C-atom. From a comparison with earlier calculations [Andersen et al., Phys. Rev. B 66, 235205 (2002)], we attribute E42 to the double acceptor and E262 to the single acceptor state of the CH1AB configuration, where one H atom is directly bound to carbon in the anti-bonding position.

  16. Bond length and electric current oscillation of long linear carbon chains: Density functional theory, MpB model, and quantum spin transport studies

    Science.gov (United States)

    Oeiras, R. Y.; da Silva, E. Z.

    2014-04-01

    Carbon linear atomic chains attached to graphene have experimentally been produced. Motivated by these results, we study the nature of the carbon bonds in these nanowires and how it affects their electrical properties. In the present study we investigate chains with different numbers of atoms and we observe that nanowires with odd number of atoms present a distinct behavior than the ones with even numbers. Using graphene nanoribbons as leads, we identify differences in the quantum transport of the chains with the consequence that even and odd numbered chains have low and high electrical conduction, respectively. We also noted a dependence of current with the wire size. We study this unexpected behavior using a combination of first principles calculations and simple models based on chemical bond theory. From our studies, the electrons of carbon nanowires present a quasi-free electron behavior and this explains qualitatively the high electrical conduction and the bond lengths with unexpected values for the case of odd nanowires. Our study also allows the understanding of the electric conduction dependence with the number of atoms and their parity in the chain. In the case of odd number chains a proposed π-bond (MpB) model describes unsaturated carbons that introduce a mobile π-bond that changes dramatically the structure and transport properties of these wires. Our results indicate that the nature of bonds plays the main role in the oscillation of quantum electrical conduction for chains with even and odd number of atoms and also that nanowires bonded to graphene nanoribbons behave as a quasi-free electron system, suggesting that this behavior is general and it could also remain if the chains are bonded to other materials.

  17. Bond length and electric current oscillation of long linear carbon chains: Density functional theory, MpB model, and quantum spin transport studies

    Energy Technology Data Exchange (ETDEWEB)

    Oeiras, R. Y.; Silva, E. Z. da [Institute of Physics “Gleb Wataghin”, University of Campinas-Unicamp, 13083-859 Campinas, SP (Brazil)

    2014-04-07

    Carbon linear atomic chains attached to graphene have experimentally been produced. Motivated by these results, we study the nature of the carbon bonds in these nanowires and how it affects their electrical properties. In the present study we investigate chains with different numbers of atoms and we observe that nanowires with odd number of atoms present a distinct behavior than the ones with even numbers. Using graphene nanoribbons as leads, we identify differences in the quantum transport of the chains with the consequence that even and odd numbered chains have low and high electrical conduction, respectively. We also noted a dependence of current with the wire size. We study this unexpected behavior using a combination of first principles calculations and simple models based on chemical bond theory. From our studies, the electrons of carbon nanowires present a quasi-free electron behavior and this explains qualitatively the high electrical conduction and the bond lengths with unexpected values for the case of odd nanowires. Our study also allows the understanding of the electric conduction dependence with the number of atoms and their parity in the chain. In the case of odd number chains a proposed π-bond (MpB) model describes unsaturated carbons that introduce a mobile π-bond that changes dramatically the structure and transport properties of these wires. Our results indicate that the nature of bonds plays the main role in the oscillation of quantum electrical conduction for chains with even and odd number of atoms and also that nanowires bonded to graphene nanoribbons behave as a quasi-free electron system, suggesting that this behavior is general and it could also remain if the chains are bonded to other materials.

  18. Dynamics of carbon-hydrogen and carbon-methyl exchanges in the collision of 3P atomic carbon with propene

    Science.gov (United States)

    Lee, Shih-Huang; Chen, Wei-Kan; Chin, Chih-Hao; Huang, Wen-Jian

    2013-11-01

    We investigated the dynamics of the reaction of 3P atomic carbon with propene (C3H6) at reactant collision energy 3.8 kcal mol-1 in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet ionization. Products C4H5, C4H4, C3H3, and CH3 were observed and attributed to exit channels C4H5 + H, C4H4 + 2H, and C3H3 + CH3; their translational-energy distributions and angular distributions were derived from the measurements of product time-of-flight spectra. Following the addition of a 3P carbon atom to the C=C bond of propene, cyclic complex c-H2C(C)CHCH3 undergoes two separate stereoisomerization mechanisms to form intermediates E- and Z-H2CCCHCH3. Both the isomers of H2CCCHCH3 in turns decompose to C4H5 + H and C3H3 + CH3. A portion of C4H5 that has enough internal energy further decomposes to C4H4 + H. The three exit channels C4H5 + H, C4H4 + 2H, and C3H3 + CH3 have average translational energy releases 13.5, 3.2, and 15.2 kcal mol-1, respectively, corresponding to fractions 0.26, 0.41, and 0.26 of available energy deposited to the translational degrees of freedom. The H-loss and 2H-loss channels have nearly isotropic angular distributions with a slight preference at the forward direction particularly for the 2H-loss channel. In contrast, the CH3-loss channel has a forward and backward peaked angular distribution with an enhancement at the forward direction. Comparisons with reactions of 3P carbon atoms with ethene, vinyl fluoride, and vinyl chloride are stated.

  19. Cross Shear Roll Bonding

    DEFF Research Database (Denmark)

    Bay, Niels; Bjerregaard, Henrik; Petersen, Søren. B;

    1994-01-01

    The present paper describes an investigation of roll bonding an AlZn alloy to mild steel. Application of cross shear roll bonding, where the two equal sized rolls run with different peripheral speed, is shown to give better bond strength than conventional roll bonding. Improvements of up to 20......-23% in bond strength are found and full bond strength is obtained at a reduction of 50% whereas 65% is required in case of conventional roll bonding. Pseudo cross shear roll bonding, where the cross shear effect is obtained by running two equal sized rolls with different speed, gives the same results....

  20. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G

    2010-01-01

    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  1. Portfolio Management for a Random Field of Bond Returns

    OpenAIRE

    Vladislav Kargin

    2003-01-01

    A new method of bond portfolio optimization is described. The method is based on stochastic string models of bond returns. It is shown how to approximate the bond return correlation function with Padé approximations and how to compute the optimal portfolio allocation using Wiener-Hopf factorization. The technique is illustrated with an example of the Treasury bond portfolio.

  2. Study on the covalence of Cu and chemical bonding in an inorganic fullerene-like molecule, [CuCl]20[Cp*FeP5]12[Cu-(CH3CN)2+Cl-]5, by a density functional approach

    Institute of Scientific and Technical Information of China (English)

    WANG Bingwu; XU Guangxian; CHEN Zhida

    2004-01-01

    The electronic structure and chemical bonding in a recently synthesized inorganic fullerene-like molecule, {[CuCl]20[Cp*FeP5]12 [Cu(CH3CN)+2Cl-]5}, has been studied by a density functional approach. Geometrical optimization of the three basic structural units of the molecule is performed with Amsterdam Density Functional Program. The results are in agreement with the experiment. Localized MO's obtained by Boys-Foster method give a clear picture of the chemical bonding in this molecule. The reason why CuCl can react with Cp*FeP5 in solvent CH3CN to form the fullerene-like molecule is explained in terms of the soft-hard Lewis acid base theory and a new concept of covalence.

  3. Covalently Bonded Polyaniline and para-phenylenediamine Functionalized Graphene Oxide: How the Conductive Two-dimensional Nanostructure Influences the Electrochromic Behaviors of Polyaniline

    International Nuclear Information System (INIS)

    Graphical abstract: - Abstract: Polyaniline (PANI) was attached onto the reduced graphene oxide (rGO) sheets through copolymerization of aniline with a para-phenylenediamine (PPD) functionalized graphene oxide (GO-PPD) using the poly(styrene sulfonate) (PSS) as the macromolecular dopant agent to produce a water-dispersible electrochromic material. The structures and the morphologies analysis confirm that the final electrochromic materials (rGO-PANI) are the mixture of PANI/PSS and the covalently bonded rGO-PANI (rGO-PANI hybrid). The rGO-PANI hybrid can be found to form a parallel arrangement to the substrate in the spin-coated film. This parallel arrangement of the layered two-dimensional nanostructure of rGO-PANI hybrid may narrow the ion transportation pathways of the exchanged ions, which will result in a high charge transfer resistance and slow switching speed. Meanwhile, with the conductive rGO added, the electrical conductivity of the electrochromic layer will be increased, which will benefit to low charge transfer resistance and high optical contrast. So the conductive two-dimensional nanostructure has a double-face influence on the electrochromic performances of PANI, which include a positive influence on the electrical conductivity and a negative influence on the ion diffusion. The overall influences depend on the loading amount of GO-PPD. With 4 wt.% GO-PPD feeding, the optical contrast was enhanced by 36% from 0.38 for PANI/PSS to 0.52 for rGO-PANI-3, while the coloration time was almost same as that of PANI/PSS and the bleaching time was decreased by ∼20% from 9.1s for PANI/PSS to 7.4s for rGO-PANI-3. The electrochemical tests showed that with the increasing of GO-PPD loading, the peak currents of cyclic voltammetry (CV) curves were increased, and the peak locations shifted to the positive potential for oxidation peak and the negative potential for reduction peak, respectively, which confirmed that the double-face influences of rGO-PANI on the

  4. Carbon K-edge X-ray absorption spectroscopy and time-dependent density functional theory examination of metal-carbon bonding in metallocene dichlorides.

    Science.gov (United States)

    Minasian, Stefan G; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Kozimor, Stosh A; Martin, Richard L; Shuh, David K; Tyliszczak, Tolek; Vernon, Louis J

    2013-10-01

    Metal-carbon covalence in (C5H5)2MCl2 (M = Ti, Zr, Hf) has been evaluated using carbon K-edge X-ray absorption spectroscopy (XAS) as well as ground-state and time-dependent hybrid density functional theory (DFT and TDDFT). Differences in orbital mixing were determined experimentally using transmission XAS of thin crystalline material with a scanning transmission X-ray microscope (STXM). Moving down the periodic table (Ti to Hf) has a marked effect on the experimental transition intensities associated with the low-lying antibonding 1a1* and 1b2* orbitals. The peak intensities, which are directly related to the M-(C5H5) orbital mixing coefficients, increase from 0.08(1) and 0.26(3) for (C5H5)2TiCl2 to 0.31(3) and 0.75(8) for (C5H5)2ZrCl2, and finally to 0.54(5) and 0.83(8) for (C5H5)2HfCl2. The experimental trend toward increased peak intensity for transitions associated with 1a1* and 1b2* orbitals agrees with the calculated TDDFT oscillator strengths [0.10 and 0.21, (C5H5)2TiCl2; 0.21 and 0.73, (C5H5)2ZrCl2; 0.35 and 0.69, (C5H5)2HfCl2] and with the amount of C 2p character obtained from the Mulliken populations for the antibonding 1a1* and 1b2* orbitals [8.2 and 23.4%, (C5H5)2TiCl2; 15.3 and 39.7%, (C5H5)2ZrCl2; 20.1 and 50.9%, (C5H5)2HfCl2]. The excellent agreement between experiment, theory, and recent Cl K-edge XAS and DFT measurements shows that C 2p orbital mixing is enhanced for the diffuse Hf (5d) and Zr (4d) atomic orbitals in relation to the more localized Ti (3d) orbitals. These results provide insight into how changes in M-Cl orbital mixing within the metallocene wedge are correlated with periodic trends in covalent bonding between the metal and the cyclopentadienide ancillary ligands.

  5. LAMMPS Framework for Dynamic Bonding and an Application Modeling DNA

    DEFF Research Database (Denmark)

    Svaneborg, Carsten

    2012-01-01

    and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework.......We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled to...... limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead...

  6. Protein folding guides disulfide bond formation

    OpenAIRE

    Qin, Meng; Wang, Wei; Thirumalai, D.

    2015-01-01

    Anfinsen inferred the principles of protein folding by studying a protein containing four disulfide bonds in the native state. However, how protein folding drives disulfide bond formation is poorly understood despite the role such proteins play in variety of extracellular and intracellular functions. We developed a method to mimic the complex chemistry of disulfide bond formation in molecular simulations, which is used to decipher the mechanism of folding of bovine pancreatic trypsin inhibito...

  7. Hydrogen bonded supramolecular structures

    CERN Document Server

    Li, Zhanting

    2015-01-01

    This book covers the advances in the studies of hydrogen-bonding-driven supramolecular systems  made over the past decade. It is divided into four parts, with the first introducing the basics of hydrogen bonding and important hydrogen bonding patterns in solution as well as in the solid state. The second part covers molecular recognition and supramolecular structures driven by hydrogen bonding. The third part introduces the formation of hollow and giant macrocycles directed by hydrogen bonding, while the last part summarizes hydrogen bonded supramolecular polymers. This book is designed to b

  8. Silver- and gold-mediated nucleobase bonding.

    Science.gov (United States)

    Acioli, Paulo H; Srinivas, Sudha

    2014-08-01

    We report the results of a density functional theory investigation of the bonding of nucleobases mediated by silver and gold atoms in the gas phase. Our calculations use the Becke exchange and Perdew-Wang correlation functional (BPW91) combined with the Stuttgart effective core potentials to represent the valence electrons of gold, silver, and platinum, and the all-electron DGTZVP basis set for C, H, N, and O. This combination was chosen based on tests on the metal atoms and tautomers of adenine, cytosine, and guanine. To establish a benchmark to understand the metal-mediated bonding, we calculated the binding energy of each of the base pairs in their canonical forms. Our calculations show rather strong bonds between the Watson-Crick base pairs when compared with typical values for N-H-N and N-H-O hydrogen bonds. The neutral metal atoms tend to bond near the nitrogen atoms. The effect of the metal atoms on the bonding of nucleobases differs depending on whether or not the metal atoms bond to one of the hydrogen-bonding sites. When the silver or gold atoms bond to a non-hydrogen-bonding site, the effect is a slight enhancement of the cytosine-guanine bonding, but there is almost no effect on the adenine-thymine pairing. The metal atoms can block one of the hydrogen-bonding sites, thus preventing the normal cytosine-guanine and adenine-thymine pairings. We also find that both silver and gold can bond to consecutive guanines in a similar fashion to platinum, albeit with a significantly lower binding energy.

  9. Modelling the Fracture Behaviour of Adhesively-Bonded Joints as a Function of Test Rate - A Rate Dependent CZM is Required to Predict the Full Range of Behaviour

    OpenAIRE

    Ivankovic, Alojz; Karac, Aleksandar; Blackman, B.R.K.; et al

    2011-01-01

    Adhesive bonding of lightweight, high-performance materials is regarded as a key enabling technology for the development of vehicles with increased crashworthiness, better fuel economy and reduced exhaust emissions. However, as automotive structures can be exposed to impact events during service, it is necessary to gain a sound understanding of the performance of adhesive joints under different rates of loading. Therefore, characterising the behaviour of adhesive joint...

  10. Water interaction and bond strength to dentin of dye-labelled adhesive as a function of the addition of rhodamine B

    Science.gov (United States)

    WANG, Linda; BIM, Odair; LOPES, Adolfo Coelho de Oliveira; FRANCISCONI-DOS-RIOS, Luciana Fávaro; MAENOSONO, Rafael Massunari; D’ALPINO, Paulo Henrique Perlatti; HONÓRIO, Heitor Marques; ATTA, Maria Teresa

    2016-01-01

    ABSTRACT Objective This study investigated the effect of the fluorescent dye rhodamine B (RB) for interfacial micromorphology analysis of dental composite restorations on water sorption/solubility (WS/WSL) and microtensile bond strength to dentin (µTBS) of a 3-step total etch and a 2-step self-etch adhesive system. Material and Methods The adhesives Adper Scotchbond Multi-Purpose (MP) and Clearfil SE Bond (SE) were mixed with 0.1 mg/mL of RB. For the WS/WSL tests, cured resin disks (5.0 mm in diameter x 0.8 mm thick) were prepared and assigned into four groups (n=10): MP, MP-RB, SE, and SE-RB. For µTBS assessment, extracted human third molars (n=40) had the flat occlusal dentin prepared and assigned into the same experimental groups (n=10). After the bonding and restoration procedures, specimens were sectioned in rectangular beams, stored in water and tested after seven days or after 12 months. The failure mode of fractured specimens was qualitatively evaluated under optical microscope (x40). Data from WS/WSL and µTBS were assessed by one-way and three-way ANOVA, respectively, and Tukey’s test (α=5%). Results RB increased the WSL of MP and SE. On the other hand, WS of both MP and SE was not affected by the addition of RB. No significance in µTBS between MP and MP-RB for seven days or one year was observed, whereas for SE a decrease in the µTBS means occurred in both storage times. Conclusions RB should be incorporated into non-simplified DBSs with caution, as it can interfere with their physical-mechanical properties, leading to a possible misinterpretation of bonded interface. PMID:27556201

  11. 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.

  12. HYDROGEN BONDING IN THE METHANOL DIMER

    Science.gov (United States)

    In this work, two methanol molecules are placed in different arrangements to study hydrogen bonding in carbohydrate materials such as cellulose. Energy was calculated as a function of both hydrogen bond length and angle over wide ranges, using quantum mechanics (QM). The QM wavefunctions are analyze...

  13. Australia's Bond Home Bias

    OpenAIRE

    Mishra, Anil V; Umaru B. Conteh

    2014-01-01

    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  14. Bond percolation in films

    Science.gov (United States)

    Korneta, W.; Pytel, Z.

    1988-04-01

    Bond percolation in films with simple cubic structure is considered. It is assumed that the probability of a bond being present between nearest-neighbor sites depends on the distances to surfaces. Based on the relation between the Potts model and the bond percolation model, and using the mean-field approximation, the phase diagram and profiles of the percolation probability have been obtained.

  15. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    to think in alternative ways such as issuing corporate bonds. A market for corporate bonds exists in countries such as Norway, Germany, France, the United Kingdom and the United States, while Denmark is still behind in this trend. Some large Danish corporations have instead used foreign corporate bonds...

  16. Anion Transport with Chalcogen Bonds.

    Science.gov (United States)

    Benz, Sebastian; Macchione, Mariano; Verolet, Quentin; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2016-07-27

    In this report, we introduce synthetic anion transporters that operate with chalcogen bonds. Electron-deficient dithieno[3,2-b;2',3'-d]thiophenes (DTTs) are identified as ideal to bind anions in the focal point of the σ holes on the cofacial endocyclic sulfur atoms. Anion binding in solution and anion transport across lipid bilayers are found to increase with the depth of the σ holes of the DTT anionophores. These results introduce DTTs and related architectures as a privileged motif to engineer chalcogen bonds into functional systems, complementary in scope to classics such as 2,2'-bipyrroles or 2,2'-bipyridines that operate with hydrogen bonds and lone pairs, respectively. PMID:27433964

  17. Oxide-Free Bonding of III-V-Based Material on Silicon and Nano-Structuration of the Hybrid Waveguide for Advanced Optical Functions

    Directory of Open Access Journals (Sweden)

    Konstantinos Pantzas

    2015-10-01

    Full Text Available Oxide-free bonding of III-V-based materials for integrated optics is demonstrated on both planar Silicon (Si surfaces and nanostructured ones, using Silicon on Isolator (SOI or Si substrates. The hybrid interface is characterized electrically and mechanically. A hybrid InP-on-SOI waveguide, including a bi-periodic nano structuration of the silicon guiding layer is demonstrated to provide wavelength selective transmission. Such an oxide-free interface associated with the nanostructured design of the guiding geometry has great potential for both electrical and optical operation of improved hybrid devices.

  18. Bonding thermoplastic polymers

    Science.gov (United States)

    Wallow, Thomas I.; Hunter, Marion C.; Krafcik, Karen Lee; Morales, Alfredo M.; Simmons, Blake A.; Domeier, Linda A.

    2008-06-24

    We demonstrate a new method for joining patterned thermoplastic parts into layered structures. The method takes advantage of case-II permeant diffusion to generate dimensionally controlled, activated bonding layers at the surfaces being joined. It is capable of producing bonds characterized by cohesive failure while preserving the fidelity of patterned features in the bonding surfaces. This approach is uniquely suited to production of microfluidic multilayer structures, as it allows the bond-forming interface between plastic parts to be precisely manipulated at micrometer length scales. The bond enhancing procedure is easily integrated in standard process flows and requires no specialized equipment.

  19. 基于密度泛函理论研究Watson-Crick碱基对中的氢键特征%Hydrogen bonds in watson-crick base pairs:a density functional theory (DFT) study

    Institute of Scientific and Technical Information of China (English)

    者建武; 金能智; 马尧; 沈玉琳

    2012-01-01

    Density Functional Theory (DFT) calculations performed on adenine,thymine,guanine,cytosine bases and adenine-thymine,guanine-cytosine base pairs are reported.Results at the DFT-B3LYP/6-31G** level and natural bond orbital analysis show that the structurally and electronically complementary DNA bases are in favor of the formation of hydrogen bonds.The effects of the formation of hydrogen bonds on the geometry structures,electronic structures,molecular orbitals and energies are discussed.These results will be helpful to understand the relationship between hydrogen bonds in AT and GC base pairs and their structure and properties.%基于密度泛函理论(DFT)研究腺嘌呤、胸腺嘧啶、鸟嘌呤、胞嘧啶以及腺嘌呤胸腺嘧啶碱基对、鸟嘌呤胞嘧啶碱基对.在DFT-B3 LYP/6-31G**水平上利用自然键轨道理论分析研究结果显示,互补碱基对的结构和电子特征有利于氢键的形成.本文中讨论几何结构、电子结构、分子轨道和能量对于氢键形成的影响.此研究结果将有助于更好的理解AT和GC碱基对中氢键与它们的结构特性之间的关系.

  20. Molecular Orbital and Density Functional Study of the Formation, Charge Transfer, Bonding and the Conformational Isomerism of the Boron Trifluoride (BF3 and Ammonia (NH3 Donor-Acceptor Complex

    Directory of Open Access Journals (Sweden)

    Dulal C. Ghosh

    2004-09-01

    Full Text Available The formation of the F3B–NH3 supermolecule by chemical interaction of its fragment parts, BF3 and NH3, and the dynamics of internal rotation about the ‘B–N’ bond have been studied in terms of parameters provided by the molecular orbital and density functional theories. It is found that the pairs of frontier orbitals of the interacting fragments have matching symmetry and are involved in the charge transfer interaction. The donation process stems from the HOMO of the donor into the LUMO of the acceptor and simultaneously, back donation stems from the HOMO of acceptor into the LUMO of the donor. The density functional computation of chemical activation in the donor and acceptor fragments, associated with the physical process of structural reorganization just prior to the event of chemical reaction, indicates that BF3 becomes more acidic and NH3 becomes more basic, compared to their separate equilibrium states. Theoretically it is observed that the chemical reaction event of the formation of the supermolecule from its fragment parts is in accordance with the chemical potential equalization principle of the density functional theory and the electronegativity equalization principle of Sanderson. The energetics of the chemical reaction, the magnitude of the net charge transfer and the energy of the newly formed bond are quite consistent, both internally and with the principle of maximum hardness, PMH. The dynamics of the internal rotation of one part with respect to the other part of the supermolecule about the ‘B–N’ bond mimics the pattern of the conformational isomerism of the isostructural ethane molecule. It is also observed that the dynamics and evolution of molecular conformations as a function of dihedral angles is also in accordance with the principle of maximum hardness, PMH. Quite consistent with spectroscopic predictions, the height of the molecule

  1. Weak bond screening system

    Science.gov (United States)

    Chuang, S. Y.; Chang, F. H.; Bell, J. R.

    Consideration is given to the development of a weak bond screening system which is based on the utilization of a high power ultrasonic (HPU) technique. The instrumentation of the prototype bond strength screening system is described, and the adhesively bonded specimens used in the system developmental effort are detailed. Test results obtained from these specimens are presented in terms of bond strength and level of high power ultrasound irradiation. The following observations were made: (1) for Al/Al specimens, 2.6 sec of HPU irradiation will screen weak bond conditions due to improper preparation of bonding surfaces; (2) for composite/composite specimens, 2.0 sec of HPU irradiation will disrupt weak bonds due to under-cured conditions; (3) for Al honeycomb core with composite skin structure, 3.5 sec of HPU irradiation will disrupt weak bonds due to bad adhesive or oils contamination of bonding surfaces; and (4) for Nomex honeycomb with Al skin structure, 1.3 sec of HPU irradiation will disrupt weak bonds due to bad adhesive.

  2. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  3. Equilibrium CO bond lengths

    Science.gov (United States)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  4. The Bond Market's q

    OpenAIRE

    Thomas Philippon

    2006-01-01

    I propose an implementation of the q-theory of investment using bond prices instead of equity prices. Credit risk makes corporate bond prices sensitive to future asset values, and q can be inferred from bond prices. The bond market's q performs much better than the usual measure in standard investment equations. With aggregate data, the fit is three times better, cash flows are driven out and the implied adjustment costs are reduced by more than an order of magnitude. The new measure also imp...

  5. Bond strength, bond stress and spallation mechanisms of thermal barrier coatings

    Energy Technology Data Exchange (ETDEWEB)

    Gell, M.; Krishnakumar, V.; McCarron, K.; Barber, B.; Sohn, Y.-H. [Connecticut Univ., Storrs, CT (United States). Dept. of Metall. and Mater. Eng.; Eric, J. [Connecticut Univ., Storrs, CT (United States). Dept. of Mechanical Engineering; Tolpygo, V.K.

    1999-11-01

    Five production thermal barrier coatings were thermally cycled between room temperature and 1121 C (2050 F) to determine relative spallation life. Bond strength measurements were made using a modified ASTM direct pull-test. Bond stress measurements were made in the thermally grown oxide using a laser photoluminescence technique. Bond strength and bond stress measurements were conducted on two electron beam physical vapor deposition coatings as a function of thermal cycling. Each coating showed characteristic values of as-coated strength and stress and changes in strength and stress with thermal cycling. These variations in strength and stress with thermal cycling are related to oxidation and micro-debonding effects. (orig.)

  6. Bond strength, bond stress and spallation mechanisms of thermal barrier coatings

    International Nuclear Information System (INIS)

    Five production thermal barrier coatings were thermally cycled between room temperature and 1121 C (2050 F) to determine relative spallation life. Bond strength measurements were made using a modified ASTM direct pull-test. Bond stress measurements were made in the thermally grown oxide using a laser photoluminescence technique. Bond strength and bond stress measurements were conducted on two electron beam physical vapor deposition coatings as a function of thermal cycling. Each coating showed characteristic values of as-coated strength and stress and changes in strength and stress with thermal cycling. These variations in strength and stress with thermal cycling are related to oxidation and micro-debonding effects. (orig.)

  7. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter

    2009-01-01

    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation energie

  8. Behavior of Halogen Bonds of the Y-X⋅⋅⋅π Type (X, Y=F, Cl, Br, I) in the Benzene π System, Elucidated by Using a Quantum Theory of Atoms in Molecules Dual-Functional Analysis.

    Science.gov (United States)

    Sugibayashi, Yuji; Hayashi, Satoko; Nakanishi, Waro

    2016-08-18

    The nature of halogen bonds of the Y-X-✶-π(C6 H6 ) type (X, Y=F, Cl, Br, and I) have been elucidated by using the quantum theory of atoms in molecules (QTAIM) dual-functional analysis (QTAIM-DFA), which we proposed recently. Asterisks (✶) emphasize the presence of bond-critical points (BCPs) in the interactions in question. Total electron energy densities, Hb (rc ), are plotted versus Hb (rc )-Vb (rc )/2 [=(ħ(2) /8m)∇(2) ρb (rc )] for the interactions in QTAIM-DFA, in which Vb (rc ) are potential energy densities at the BCPs. Data for perturbed structures around fully optimized structures were used for the plots, in addition to those of the fully optimized ones. The plots were analyzed by using the polar (R, θ) coordinate for the data of fully optimized structures with (θp , κp ) for those that contained the perturbed structures; θp corresponds to the tangent line of the plot and κp is the curvature. Whereas (R, θ) corresponds to the static nature, (θp , κp ) represents the dynamic nature of the interactions. All interactions in Y-X-✶-π(C6 H6 ) are classified by pure closed-shell interactions and characterized to have vdW nature, except for Y-I-✶-π(C6 H6 ) (Y=F, Cl, Br) and F-Br-✶-π(C6 H6 ), which have typical hydrogen-bond nature without covalency. I-I-✶-π(C6 H6 ) has a borderline nature between the two. Y-F-✶-π(C6 H6 ) (Y=Br, I) were optimized as bent forms, in which Y-✶-π interactions were detected. The Y-✶-π interactions in the bent forms are predicted to be substantially weaker than those in the linear F-Y-✶-π(C6 H6 ) forms. PMID:27124373

  9. Behavior of Halogen Bonds of the Y-X⋅⋅⋅π Type (X, Y=F, Cl, Br, I) in the Benzene π System, Elucidated by Using a Quantum Theory of Atoms in Molecules Dual-Functional Analysis.

    Science.gov (United States)

    Sugibayashi, Yuji; Hayashi, Satoko; Nakanishi, Waro

    2016-08-18

    The nature of halogen bonds of the Y-X-✶-π(C6 H6 ) type (X, Y=F, Cl, Br, and I) have been elucidated by using the quantum theory of atoms in molecules (QTAIM) dual-functional analysis (QTAIM-DFA), which we proposed recently. Asterisks (✶) emphasize the presence of bond-critical points (BCPs) in the interactions in question. Total electron energy densities, Hb (rc ), are plotted versus Hb (rc )-Vb (rc )/2 [=(ħ(2) /8m)∇(2) ρb (rc )] for the interactions in QTAIM-DFA, in which Vb (rc ) are potential energy densities at the BCPs. Data for perturbed structures around fully optimized structures were used for the plots, in addition to those of the fully optimized ones. The plots were analyzed by using the polar (R, θ) coordinate for the data of fully optimized structures with (θp , κp ) for those that contained the perturbed structures; θp corresponds to the tangent line of the plot and κp is the curvature. Whereas (R, θ) corresponds to the static nature, (θp , κp ) represents the dynamic nature of the interactions. All interactions in Y-X-✶-π(C6 H6 ) are classified by pure closed-shell interactions and characterized to have vdW nature, except for Y-I-✶-π(C6 H6 ) (Y=F, Cl, Br) and F-Br-✶-π(C6 H6 ), which have typical hydrogen-bond nature without covalency. I-I-✶-π(C6 H6 ) has a borderline nature between the two. Y-F-✶-π(C6 H6 ) (Y=Br, I) were optimized as bent forms, in which Y-✶-π interactions were detected. The Y-✶-π interactions in the bent forms are predicted to be substantially weaker than those in the linear F-Y-✶-π(C6 H6 ) forms.

  10. Bonded labour in Pakistan

    OpenAIRE

    Ercelawn, Aly; Nauman, Muhammad

    2001-01-01

    Examines the continuing prevalence of debt bondage in the 1990s despite the introduction of national legislation banning the practice. Makes recommendations to the Government and the international community for actions to be taken to eliminate bonded labour and provide rehabilitation for freed workers. Includes texts of Land Reforms Regulations, 1972, the Sindh Tenancy Act, 1950 and the Bonded Labour System (Abolition) Act, 1992.

  11. Hydrogen bonding in polyanilines

    Energy Technology Data Exchange (ETDEWEB)

    Bahceci, S. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey)); Toppare, L. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey)); Yurtsever, E. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey))

    1994-11-29

    Hydrogen bonding between poly(bisphenol A carbonate) (PC) and polyaniline (PAn) is analyzed using semi-empirical quantum methodology. Fully optimized AM1 molecular orbital calculations are reported for various aniline structures (monomer, dimer and trimer), the monomer of the PC and the hydrogen-bonded model of PAn-PC oligomer. ((orig.))

  12. The dissociative bond.

    Science.gov (United States)

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  13. The samurai bond market

    OpenAIRE

    Frank Packer; Elizabeth Reynolds

    1997-01-01

    Issuance in the samurai bond market has more than tripled over the past several years. Some observers have attributed this growth to a systematic underestimation of credit risk in the market. A detailed review of credit quality, ratings differences, and initial issue pricing in the samurai bond market, however, turns up little evidence to support this concern.

  14. Wood Bond Testing

    Science.gov (United States)

    1989-01-01

    A joint development program between Hartford Steam Boiler Inspection Technologies and The Weyerhaeuser Company resulted in an internal bond analyzer (IBA), a device which combines ultrasonics with acoustic emission testing techniques. It is actually a spinoff from a spinoff, stemming from a NASA Lewis invented acousto-ultrasonic technique that became a system for testing bond strength of composite materials. Hartford's parent company, Acoustic Emission Technology Corporation (AET) refined and commercialized the technology. The IBA builds on the original system and incorporates on-line process control systems. The IBA determines bond strength by measuring changes in pulsar ultrasonic waves injected into a board. Analysis of the wave determines the average internal bond strength for the panel. Results are displayed immediately. Using the system, a mill operator can adjust resin/wood proportion, reduce setup time and waste, produce internal bonds of a consistent quality and automatically mark deficient products.

  15. Water's Hydrogen Bond Strength

    CERN Document Server

    Chaplin, Martin

    2007-01-01

    Water is necessary both for the evolution of life and its continuance. It possesses particular properties that cannot be found in other materials and that are required for life-giving processes. These properties are brought about by the hydrogen bonded environment particularly evident in liquid water. Each liquid water molecule is involved in about four hydrogen bonds with strengths considerably less than covalent bonds but considerably greater than the natural thermal energy. These hydrogen bonds are roughly tetrahedrally arranged such that when strongly formed the local clustering expands, decreasing the density. Such low density structuring naturally occurs at low and supercooled temperatures and gives rise to many physical and chemical properties that evidence the particular uniqueness of liquid water. If aqueous hydrogen bonds were actually somewhat stronger then water would behave similar to a glass, whereas if they were weaker then water would be a gas and only exist as a liquid at sub-zero temperature...

  16. Fatigue de-bond growth in adhesively bonded single lap joints

    Indian Academy of Sciences (India)

    P K Sahoo; B Dattaguru; C M Manjunatha; C R L Murthy

    2012-02-01

    The fatigue de-bond growth studies have been conducted on adhesively bonded lap joint specimens between aluminium and aluminium with Redux-319A adhesive with a pre-defined crack of 3 mm at the bond end. The correlations between fracture parameters and the de-bond growth data are established using both numerical and experimental techniques. In the numerical method, geometrically non-linear finite element analyses were carried out on adhesively bonded joint specimen for various de-bond lengths measured from the lap end along the mid-bond line of the adhesive. The finite element results were post processed to estimate the SERR components $G_I$ and $G_{II}$ using the Modified Virtual Crack Closure Integral (MVCCI) procedure. In experimental work, specimens were fabricated and fatigue de-bond growth tests were conducted at a stress ratio $R = −1$. The results obtained from both numerical analyses and testing have been used to generate de-bond growth curve and establish de-bond growth law in the Paris regime for such joints. The de-bond growth rate is primarily function of mode-I SERR component $G_I$ since the rate of growth in shear mode is relatively small. The value of Paris exponent is found to be 6.55. The high value of de-bond growth exponent in Paris regime is expected, since the adhesive is less ductile than conventional metallic materials. This study is important for estimating the life of adhesively bonded joints under both constant and variable amplitude fatigue loads.

  17. Water-soluble light-emitting nanoparticles prepared by non-covalent bond self-assembly of a hydroxyl group functionalized oligo(p-phenyleneethynylene) with different water-soluble polymers

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Water-soluble light-emitting nanoparticles were prepared from hydroxyl group functionalized oligos(p-phenyleneethynylene) (OHOPEL) and water-soluble polymers(PEG,PAA,and PG) by non-covalent bond self-assembly.Their structure and optoelectronic properties were investigated through dynamic light scattering(DLS) ,UV and PL spectroscopy.The optical properties of OHOPEL-based water-soluble nanoparticles exhibited the same properties as that found in OHOPEL films,indicating the existence of interchain-aggregation of OHOPELs in the nanoparticles.OHOPEL-based nanoparticles prepared from conjugated oligomers show smaller size and lower dispersity than nanoparticles from conjugated polymers,which means that the structures of water-soluble nanoparticles are linked to the conjugated length.Furthermore,the OHOPEL/PG and OHOPEL/PAA systems produced smaller particles and lower polydispersity than the OHOPEL/PEG system,indicating that there may exist influence of the strength of non-covalent bonds on the size and degree of dispersity of the nanoparticles.

  18. Dentin-bonding agents

    Directory of Open Access Journals (Sweden)

    João Carlos Gomes

    2008-01-01

    Full Text Available New dental restorative materials have been developed to meet not only the functional demands, but esthetics as well, and in the last few years an enormous range of new materials has appeared for use in dentistry. Among them, several adhesive systems, and different operative techniques for each group materials. Therefore, is indispensable for the professional to know about the properties, characteristics, and association of these materials with the dental structures, in order to select and use them correctly. Should conventional self-etching adhesive systems be used? This question encouraged this literature review to be conducted, with the aim of comparing the conventional adhesive systems with the self-etching systems and to look for scientific data that would help professionals to choose which adhesive system to use. When compared to conventional systems, it was noted that the self-etching systems show less sensitivity to technique, especially as regards errors the operator could commit. The self-etching systems, particularly the 2-step type, have shown equivalent values of bond strength, marginal microleakage and performance, therefore, will be an option for direct composite resin restorations in posterior teeth.

  19. Transversely Compressed Bonded Joints

    DEFF Research Database (Denmark)

    Hansen, Christian Skodborg; Schmidt, Jacob Wittrup; Stang, Henrik

    2012-01-01

    The load capacity of bonded joints can be increased if transverse pressure is applied at the interface. The transverse pressure is assumed to introduce a Coulomb-friction contribution to the cohesive law for the interface. Response and load capacity for a bonded single-lap joint was derived using...... non-linear fracture mechanics. The results indicated a good correlation between theory and tests. Furthermore, the model is suggested as theoretical base for determining load capacity of bonded anchorages with transverse pressure, in externally reinforced concrete structures....

  20. Influence of mutations at the proximal histidine position on the Fe-O2 bond in hemoglobin from density functional theory

    Science.gov (United States)

    Todde, Guido; Hovmöller, Sven; Laaksonen, Aatto

    2016-03-01

    Four mutated hemoglobin (Hb) variants and wild type hemoglobin as a reference have been investigated using density functional theory methods focusing on oxygen binding. Dispersion-corrected B3LYP functional is used and found to provide reliable oxygen binding energies. It also correctly reproduces the spin distribution of both bound and free heme groups as well as provides correct geometries at their close vicinity. Mutations in hemoglobin are not only an intrigued biological problem and it is also highly important to understand their effects from a clinical point of view. This study clearly shows how even small structural differences close to the heme group can have a significant effect in reducing the oxygen binding of mutated hemoglobins and consequently affecting the health condition of the patient suffering from the mutations. All of the studied mutated Hb variants did exhibit much weaker binding of molecular oxygen compared to the wild type of hemoglobin.

  1. Functionalization of methyl (R)-phenylglycinate through orthopalladation: C-Hal, C-O, C-N, and C-C bond coupling.

    Science.gov (United States)

    Nieto, Sonia; Arnau, Palmira; Serrano, Elena; Navarro, Rafael; Soler, Tatiana; Cativiela, Carlos; Urriolabeitia, Esteban P

    2009-12-21

    The ortho functionalization of methyl R-phenylglycinate has been easily achieved using the known orthopalladated complex [Pd(mu-Cl){R-C(6)H(4)(CH(CO(2)Me)NH(2))-2}](2) (1) as synthetic tool. Different functional groups have been introduced at the ortho position of the aryl ring. The reaction of (R)-1 with X(2) or PhI(OAc)(2) gives XC(6)H(4)(CH(CO(2)Me)NH(2))-2 (X = I, Br, OMe, OEt) through oxidative coupling, while the reaction with CO gives an isoindolone. (R)-1 also reacts with one, two, or three alkyne molecules to give different metal-containing or metal-free heterocycles. The resulting functionalized amino esters or heterocycles retain the chirality of (R)-1, according with the values of the optical rotation and the obtained ee values ranging from 22%-87%. The X-ray structures of six representative compounds have also been determined.

  2. Handbook of wafer bonding

    CERN Document Server

    Ramm, Peter; Taklo, Maaike M V

    2011-01-01

    Written by an author and editor team from microsystems companies and industry-near research organizations, this handbook and reference presents dependable, first-hand information on bonding technologies.In the first part, researchers from companies and institutions around the world discuss the most reliable and reproducible technologies for the production of bonded wafers. The second part is devoted to current and emerging applications, including microresonators, biosensors and precise measuring devices.

  3. Cyclodiphosphazanes as synthetic probes: P-C/P-N bond formation from the reaction with functionalized propargyl alcohols and -hydroxy substrates

    Indian Academy of Sciences (India)

    G Gangadhararao; K C Kumara Swamy

    2015-02-01

    Phosphano-indoles were synthesized in a fairly straightforward route from the reaction of simple cyclodiphosphazanes [XP(-N-t-Bu)2PY] [X=Y=NH--Bu (1a); X=Y=NH-i-Pr (1b)] with o-aminophenyl functionalized propargyl alcohols. The reaction occurs via an allene intermediate formed by PIII-O-C→PV(O)-C rearrangement, followed by cyclization utilizing the central allenic carbon and the –NH2 functionality. In a similar way, cyclodiphosphazanes [XP(-N-t-Bu)2PY] [X=Y=Cl (1c); X=Cl, Y=NH--Bu(1d)] have been treated with N-hydroxy substrates to obtain novel PIII-O-N→PV(O)-N rearranged products.X-ray structures of the four products, 2-(1-phenyl-ethyl)-3-[(t-Bu)NH)P(-N--Bu)2P(O)]-indole [14], cis-{[-C(=O)-C6H4-C(=O)-]-N-P(=O)-N-t-Bu}2[cis-18], trans-{[-C(=O)-C6H4-C(=O)-]-N-P(=O)-N--Bu}2 [trans-18] and cis-[(-BuNH)P(-N-t−Bu)2P(=O)-N{-C(=O)-CH2-CH2-C(=O)-}] [cis-19] are also reported

  4. Valuing Catastrophe Bonds Involving Credit Risks

    Directory of Open Access Journals (Sweden)

    Jian Liu

    2014-01-01

    Full Text Available Catastrophe bonds are the most important products in catastrophe risk securitization market. For the operating mechanism, CAT bonds may have a credit risk, so in this paper we consider the influence of the credit risk on CAT bonds pricing that is different from the other literature. We employ the Jarrow and Turnbull method to model the credit risks and get access to the general pricing formula using the Extreme Value Theory. Furthermore, we present an empirical pricing study of the Property Claim Services data, where the parameters in the loss function distribution are estimated by the MLE method and the default probabilities are deduced by the US financial market data. Then we get the catastrophe bonds value by the Monte Carlo method.

  5. Selective Activation of C=C Bond in Sustainable Phenolic Compounds from Lignin via Photooxidation: Experiment and Density Functional Theory Calculations.

    Science.gov (United States)

    Zielinski Goldberg, Morgan; Burke, Luke A; Samokhvalov, Alexander

    2015-11-01

    Lignocellulosic biomass can be converted to high-value phenolic compounds, such as food additives, antioxidants, fragrances and fine chemicals. We investigated photochemical and heterogeneous photocatalytic oxidation of two isomeric phenolic compounds from lignin, isoeugenol and eugenol, in several nonprotic solvents, for the first time by experiment and the density functional theory (DFT) calculations. Photooxidation was conducted under ambient conditions using air, near-UV light and commercial P25 TiO2 photocatalyst, and the products were determined by TLC, UV-Vis absorption spectroscopy, HPLC-UV and HPLC-MS. Photochemical and photocatalytic oxidation of isoeugenol proceeds via the mild oxidative "dimerization" to produce the lignan dehydrodiisoeugenol (DHDIE), while photooxidation of eugenol does not proceed. The DFT calculations suggest a radical stepwise mechanism for the oxidative "dimerization" of isoeugenol to DHDIE as was calculated for the first time. PMID:26268649

  6. Structural and bonding properties of ScSi-n(n=2~6)clusters:photoelectron spectroscopy and density functional calculations

    Institute of Scientific and Technical Information of China (English)

    Xu Hong-Guang; Wu Miao-Miao; Zhang Zeng-Guang; Sun Qiang; Zheng Wei-Jun

    2011-01-01

    Anion ion photoelectron spectroscopy and density functional theory(DFT)are used to investigate the electronicand structural properties of ScSi-n(n=2~6)clusters and their neutrals. We find that the structures of ScSin are similar to those of Si-n+1. The most stable isomers of ScSin cluster anions and their neutrals are similar for n=2, 3and 5 but different for n=4 and 6, indicating that the charge effect on geometry is size dependent for small scandiumsilicon clusters. The low electron binding energy(EBE)tails observed in the spectra of ScSi-4,6 can be explained by the existence of less stable isomers. A comparison between ScSi-n and VSi-n clusters shows the effects of metal size and electron configuration on cluster geometries.

  7. Density functional theory study of O-H and C-H bond scission of methanol catalyzed by a chemisorbed oxygen layer on Cu(111)

    Science.gov (United States)

    Li, Jonathan; Zhou, Guangwen

    2016-04-01

    Using the density-functional theory within the generalized gradient approximation, we have studied the partial oxidation of methanol on a Cu(111) surface covered with a chemisorbed oxygen layer that resembles a Cu2O layer. Adsorption energies and geometries were computed for methanol, methoxy, hydroxymethyl and formaldehyde on both clean Cu(111) and Cu2O/Cu(111) and electronic structures were computed for the reaction intermediates on Cu2O/Cu(111). We also calculated the energy barrier for partial oxidation of methanol to formaldehyde on Cu2O/Cu(111). These results show that the Cu2O monolayer slightly lowers the stability of each of the surface adsorbates and the oxygen strongly promotes hydrogen dissociation by lowering the energy barrier of methanol decomposition and causing the spontaneous dissociation of methanol into methoxy.

  8. Density functional study of electronic, charge density, and chemical bonding properties of 9-methyl-3-Thiophen-2-YI-Thieno [3,2-e] [1, 2, 4] Thriazolo [4,3-c] pyrimidine-8-Carboxylic acid ethyl ester crystals

    Energy Technology Data Exchange (ETDEWEB)

    Reshak, A.H., E-mail: maalidph@yahoo.co.uk [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, 306 14 Pilsen (Czech Republic); Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Kamarudin, H. [Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Alahmed, Z.A. [Department of Physics and Astronomy, King Saud University, Riyadh 11451 (Saudi Arabia); Auluck, S. [CSIR-National Physical Laboratory, Dr. K S Krishnan Marg, New Delhi 110012 (India); Chyský, Jan [Department of Instrumentation and Control Engineering, Faculty of Mechanical Engineering, CTU in Prague, Technicka 4, 166 07 Prague 6 (Czech Republic)

    2014-06-01

    A comprehensive theoretical density functional investigation of the electronic crystal structure, chemical bonding, and the electron charge densities of 9-Methyl-3-Thiophen-2-YI-Thieno [3, 2-e] [1, 2, 4] Thriazolo [4,3-c] Pyrimidine-8-Carboxylic Acid Ethyl Ester (C{sub 15}H{sub 12}N{sub 4}O{sub 2}S{sub 2}) is performed. The density of states at Fermi level equal to 5.50 (3.45) states/Ry cell, and the calculated bare electronic specific heat coefficient is found to be 0.95 (0.59) mJ/mole-K{sup 2} for the local density approximation (Engel–Vosko generalized gradient approximation). The electronic charge density space distribution contours in (1 0 0) and (1 1 0) planes were calculated. We find that there are two independent molecules (A and B) in the asymmetric unit exhibit intramolecular C–H…O, C–H…N interactions. This intramolecular interaction is different in molecules A and B, where A molecule show C–H…O interaction while B molecule exhibit C–H…N interaction. We should emphasis that there is π–π interaction between the pyrimidine rings of the two neighbors B molecules gives extra strengths and stabilizations to the superamolecular structure. The calculated distance between the two neighbors pyrimidine rings found to be 3.345 Å, in good agreement with the measured one (3.424(1) Å). - Highlights: • Electronic structure, chemical bonding, and electron charge density were studied. • Density of states at Fermi level is 5.50 (3.45) states/Ry cell, for LDA (EVGGA). • Bare electronic specific heat coefficient is 0.95 (0.59) mJ/mole-K{sup 2} for LDA(EVGGA). • There are two independent molecules (A and B) in the asymmetric unit.

  9. Laser assisted and hermetic room temperature bonding based on direct bonding technology

    Science.gov (United States)

    Haneveld, Jeroen; Tijssen, Peter; Oonk, Johannes; Olde Riekerink, Mark; Tigelaar, Hildebrand; van't Oever, Ronny; Blom, Marko

    2014-03-01

    A novel method for laser assisted room temperature bonding of two substrates is presented. The method enables the packaging of delicate (bio)structures and/or finished (MEMS) devices, as there is no need for a high temperature annealing process. This also allows the bonding of two substrates with non-matching thermal expansion coefficients. The basis of the presented technology is the ability to create a direct pre-bond between two substrates. These can be two glass substrates, of which one has a thin film metal coating (e.g. Cr. Ti, Ta, Au…), or a silicon-glass combination. After (aligned) pre-bonding of the two wafers, a laser (e.g. a Nd:YAG laser) is used to form a permanent bond line on the bond interface, using the metal layer as a light absorber (or the silicon, in the case of a glass-silicon combination). The permanent bond line width is in the order of 10-50μm. The use of a laser to form the permanent bond ensures a hermetic sealing of the total package; a distinctive advantage over other, more conventional methods of room temperature bonding (e.g. adhesive bonding). He-leak testing showed leak rates in the order of 10-9 mbar l/s. This meets the failure criteria of the MIL-STD-883H standard of 5x10-8 mbar l/s. An added functionality of the proposed method is the possibility to create electrical circuitry on the bond interface, using the laser to modify the metal interlayer, rendering it electrically non-conductive. Biocompatible packages are also possible, by choosing the appropriate interlayer material. This would allow for the fabrication of implantable packages.

  10. Romanian government bond market

    Directory of Open Access Journals (Sweden)

    Cornelia POP

    2012-12-01

    Full Text Available The present paper aims to present the level of development reached by Romanian government bond market segment, as part of the country financial market. The analysis will be descriptive (the data series available for Romania are short, based on the secondary data offered by the official bodies involved in the process of issuing and trading the Romanian government bonds (Romanian Ministry of Public Finance, Romanian National Bank and Bucharest Stock Exchange, and also on secondary data provided by the Federation of European Stock Exchanges.To enhance the market credibility as a benchmark, a various combination of measures is necessary; among these measures are mentioned: the extension of the yield curve; the issuance calendars in order to improve transparency; increasing the disclosure of information on public debt issuance and statistics; holding regular meetings with dealers, institutional investors and rating agencies; introducing a system of primary dealers; establishing a repurchase (repo market in the government bond market. These measures will be discussed based on the evolution presented inside the paper.The paper conclude with the fact that, until now, the Romanian government bond market did not provide a benchmark for the domestic financial market and that further efforts are needed in order to increase the government bond market transparency and liquidity.

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

    Science.gov (United States)

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-08-01

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

  12. Mean bond-length variation in crystal structures: a bond-valence approach.

    Science.gov (United States)

    Bosi, Ferdinando

    2014-08-01

    The distortion theorem of the bond-valence theory predicts that the mean bond length 〈D〉 increases with increasing deviation of the individual bond lengths from their mean value according to the equation 〈D〉 = (D' + ΔD), where D' is the length found in a polyhedron having equivalent bonds and ΔD is the bond distortion. For a given atom, D' is expected to be similar from one structure to another, whereas 〈D〉 should vary as a function of ΔD. However, in several crystal structures 〈D〉 significantly varies without any relevant contribution from ΔD. In accordance with bond-valence theory, 〈D〉 variation is described here by a new equation: 〈D〉 = (DRU + ΔDtop + ΔDiso + ΔDaniso + ΔDelec), where DRU is a constant related to the type of cation and coordination environment, ΔDtop is the topological distortion related to the way the atoms are linked, ΔDiso is an isotropic effect of compression (or stretching) in the bonds produced by steric strain and represents the same increase (or decrease) in all the bond lengths in the coordination sphere, ΔDaniso is the distortion produced by compression and stretching of bonds in the same coordination sphere, ΔDelec is the distortion produced by electronic effects. If present, ΔDelec can be combined with ΔDaniso because they lead to the same kind of distortions in line with the distortion theorem. Each D-index, in the new equation, corresponds to an algebraic expression containing experimental and theoretical bond valences. On the basis of this study, the ΔD index defined in bond valence theory is a result of both the bond topology and the distortion theorem (ΔD = ΔDtop + ΔDaniso + ΔDelec), and D' is a result of the compression, or stretching, of bonds (D' = DRU + ΔDiso). The deficiencies present in the bond-valence theory in explaining mean bond-length variations can therefore be overcome, and the observed variations of 〈D〉 in crystal structures can be

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

    Science.gov (United States)

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-08-01

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

  14. Insulation bonding test system

    Science.gov (United States)

    Beggs, J. M.; Johnston, G. D.; Coleman, A. D.; Portwood, J. N.; Saunders, J. M.; Redmon, J. W.; Porter, A. C. (Inventor)

    1984-01-01

    A method and a system for testing the bonding of foam insulation attached to metal is described. The system involves the use of an impacter which has a calibrated load cell mounted on a plunger and a hammer head mounted on the end of the plunger. When the impacter strikes the insulation at a point to be tested, the load cell measures the force of the impact and the precise time interval during which the hammer head is in contact with the insulation. This information is transmitted as an electrical signal to a load cell amplifier where the signal is conditioned and then transmitted to a fast Fourier transform (FFT) analyzer. The FFT analyzer produces energy spectral density curves which are displayed on a video screen. The termination frequency of the energy spectral density curve may be compared with a predetermined empirical scale to determine whether a igh quality bond, good bond, or debond is present at the point of impact.

  15. The Illiquidity of Corporate Bonds

    OpenAIRE

    Bao, Jack; Pan, Jun; Wang, Jiang

    2011-01-01

    This paper examines the illiquidity of corporate bonds and its asset-pricing implications. Using transactions data from 2003 to 2009, we show that the illiquidity in corporate bonds is substantial, significantly greater than what can be explained by bid–ask spreads. We establish a strong link between bond illiquidity and bond prices. In aggregate, changes in market-level illiquidity explain a substantial part of the time variation in yield spreads of high-rated (AAA through A) bonds, overshad...

  16. The Trouble With Bonds

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    @@ In early June,global financial markets gyrated downwards in the wake of central banks'tough language on inflation.At one point bond prices reflected expectations of four rate hikes by the US Federal Reserve (Fed) in the next 12 months.As a result,the dollar firmed,oil prices stabilized,and yield curves flattened around the world.If all these inflation-fighting measures are real,the situation bodes well for bonds.But,I think otherwise.

  17. Theoretical study for Bond between Reinforcement steel and Concrete

    Directory of Open Access Journals (Sweden)

    usama mostafa mahran

    2013-04-01

    Full Text Available The behavior and load carrying behavior of reinforced concrete structures is influence by the interaction between the concrete and reinforcement. The stress transfer between reinforcement and concrete in the longitudinal direction of the bars is called bond. An essential feature of reinforced concrete is the bond between steel and concrete. Anchorage of reinforcement depends on the bond between steel and concrete, crack width and crack spacing are mainly governed by it. So, stiffness, deformation and dynamic behavior are influenced by it, and in reverse loading damping and energy dissipation is a function of bond. This is one of the reasons why bond has been, and still is, a topic of fundamental and applied research. Bond stress is the equivalent unit shear stress acting in parallel to the reinforcing bar on the interface between reinforcing steel bar and concrete. Due to the transfer of forces through bond stress, between the reinforcing rebar and concrete, the force in the reinforcing bar changes along its length. Because bond stress is thought of as stress per unit area of bar surface, it is related to the rate of change of steel stress. Consequently, to have bond stress it is necessary to have a changing steel stress. In cases of high stress at the contact interface, near cracks or end anchorages, the bond stresses are related to relative displacements between concrete and steel. These relative displacements, which are caused by different average strains in the concrete and the steel, are usually called bond-slip (t-d.

  18. Photochemical tissue bonding

    Science.gov (United States)

    Redmond, Robert W.; Kochevar, Irene E.

    2012-01-10

    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  19. Bonds Between Atoms.

    Science.gov (United States)

    Holden, Alan

    The field of inquiry into how atoms are bonded together to form molecules and solids crosses the borderlines between physics and chemistry encompassing methods characteristic of both sciences. At one extreme, the inquiry is pursued with care and rigor into the simplest cases; at the other extreme, suggestions derived from the more careful inquiry…

  20. Electronic structure and bonding in crystalline peroxides

    Science.gov (United States)

    Königstein, Markus; Sokol, Alexei A.; Catlow, C. Richard A.

    1999-08-01

    Hartree-Fock and density-functional PW91 theories as realized in the CRYSTAL95 code have been applied to investigate the structural and electronic properties of Ba, Sr, and Ca peroxide materials with the calcium carbide crystal structure, results for which are compared with those for the corresponding oxides. Special attention is paid to the stabilization of the peroxide molecular ion O2-2 in the ionic environment provided by the lattice, and to chemical bonding effects. In order to describe the covalent bonding within the O2-2 ion and the polarization of the O- ion in the crystal electrostatic field, it is essential to include an account of the effects of electron correlation. The PW91 density functional has allowed us to reproduce the crystallographic parameters within a 3% error. The chemical bonding within the peroxide molecular ion has a complex nature with a balance between the weak covalent bond of σz type and the strong electrostatic repulsion of the closed-shell electron groups occupying O 2s and O 2px and 2py states. Compression of the peroxide ion in the ionic crystals gives rise to an excessive overlap of the O 2s closed shells of the two O- ions of a peroxide molecular ion O2-2, which in turn determines the antibonding character of the interaction and chemical bonding in the O2-2 molecular ion.

  1. Recodable surfaces based on switchable hydrogen bonds.

    Science.gov (United States)

    Wedler-Jasinski, Nils; Delbosc, Nicolas; Virolleaud, Marie-Alice; Montarnal, Damien; Welle, Alexander; Barner, Leonie; Walther, Andreas; Bernard, Julien; Barner-Kowollik, Christopher

    2016-07-01

    We introduce recodable surfaces solely based on reversible artificial hydrogen bonding interactions. We show that a symmetrical oligoamide (SOA) attached to poly(methyl methacrylate) (PMMA) can be repeatedly immobilized and cleaved off spatially defined surface domains photochemically functionalized with asymmetric oligoamides (AOAs). The spatially resolved recodability is imaged and quantified via ToF-SIMS. PMID:27339101

  2. Resilient Parenting: Overcoming Poor Parental Bonding

    Science.gov (United States)

    Travis, Wendy J.; Combs-Orme, Terri

    2007-01-01

    This study identified groups of mothers with varying patterns of adaptive functioning and bonds with their own parents. These patterns were related to mothers' parenting of their own children to understand how some mothers avoid repeating the cycle of poor parenting. Data from 210 new mothers were analyzed before hospital discharge about bonding…

  3. Convertible bond valuation focusing on Chinese convertible bond market

    OpenAIRE

    Yang, Ke

    2010-01-01

    This paper mainly discusses the methods of valuation of convertible bonds in Chinese market. Different from common convertible bonds in European market, considering the complicate features of Chinese convertible bond, this paper represents specific pricing approaches for pricing convertible bonds with different provisions along with the increment of complexity of these provisions. More specifically, this paper represents the decomposing method and binomial tree method for pricing both of Non-...

  4. Indirect bonding technique in orthodontics

    Directory of Open Access Journals (Sweden)

    Kübra Yıldırım

    2016-08-01

    Full Text Available ‘Direct Bonding Technique’ which allows the fixed orthodontic appliances to be directly bonded to teeth without using bands decreased the clinic time for bracket bonding and increased esthetics and oral hygiene during orthodontic treatment. However, mistakes in bracket positioning were observed due to decreased direct visual sight and access to posterior teeth. ‘Indirect Bonding Technique’ was developed for eliminating these problems. Initially, decreased bond strength, higher bond failure rate, periodontal tissue irritation, compromised oral hygiene and increased laboratory time were the main disadvantages of this technique when compared to direct bonding. The newly developed materials and modified techniques help to eliminate these negative consequences. Today, the brackets bonded with indirect technique have similar bond strength with brackets bonded directly. Moreover, indirect and direct bonding techniques have similar effects on periodontal tissues. However, indirect bonding technique requires more attention and precision in laboratory and clinical stage, and has higher cost. Orthodontist's preference between these two bonding techniques may differ according to time spent in laboratory and clinic, cost, patient comfort and personal opinion.

  5. Conformational behaviors of trans-2,3- and trans-2,5-dihalo-1,4-diselenanes. A complete basis set, hybrid-density functional theory study and natural bond orbital interpretations.

    Science.gov (United States)

    Nori-Shargh, Davood; Mousavi, Seiedeh Negar; Kayi, Hakan

    2014-05-01

    Complete basis set CBS-4, hybrid-density functional theory (hybrid-DFT: B3LYP/6-311+G**) based methods and natural bond orbital (NBO) interpretations have been used to examine the contributions of the hyperconjugative, electrostatic, and steric effects on the conformational behaviors of trans-2,3-dihalo-1,4-diselenane [halo = F (1), Cl (2), Br (3)] and trans-2,5-dihalo-1,4-diselenane [halo = F (4), Cl (5), Br (6)]. Both levels of theory showed that the axial conformation stability, compared to its corresponding equatorial conformation, decreases from compounds 1 → 3 and 4 → 6. Based on the results obtained from the NBO analysis, there are significant anomeric effects for compounds 1-6. The anomeric effect associated with the electron delocalization is in favor of the axial conformation and increases from compounds 1 → 3 and 4 → 6. On the other hand, dipole moment differences between the axial and equatorial conformations [Δ(μ(eq)-μ(ax)] decrease from compounds 1 → 3. Although Δ(μ(eq)-μ(ax)) parameter decreases from compound 1 to compound 3, the dipole moment values of the axial conformations are smaller than those of their corresponding equatorial conformations. Therefore, the anomeric effect associated with the electron delocalizations (for halogen-C-Se segments) and the electrostatic model associated with the dipole-dipole interactions fail to account for the increase of the equatorial conformations stability on going from compound 1 to compound 3. Since there is no dipole moment for the axial and equatorial conformations of compounds 4-6, consequently, the conformational preferences in compounds 1-6 is in general dictated by the steric hindrance factor associated with the 1,3-syn-axial repulsions. Importantly, the CBS-4 results show that the entropy difference (∆S) between the equatorial axial conformations increases from compounds 1 → 3 and 4 → 6. This fact can be explained by the anomeric effect associated

  6. Continuing bonds in adaptation to bereavement : Toward theoretical integration

    NARCIS (Netherlands)

    Stroebe, Margaret; Schut, Henk; Boerner, Kathrin

    2010-01-01

    There is lack of clarity in the scientific literature concerning the adaptive functions of continuing versus relinquishing bonds to deceased persons. It remains unclear what type of bonds or underlying processes are related to (mal)adaptive bereavement outcomes. Furthermore, empirical research has r

  7. Microphase separation in hydrogen bonding polymer/surfactant melts

    NARCIS (Netherlands)

    Dormidontova, Elena; Brinke, Gerrit ten

    1999-01-01

    Phase behavior of solvent free mixtures of homopolymers and amphiphiles capable of hydrogen bonding is analyzed in weak segregation limit applying a theoretical model describing the main features of the system as a function of composition, temperature and strength of hydrogen bonding. Phase diagrams

  8. Molecular dynamics simulations of the hydration of poly(vinyl methyl ether): Hydrogen bonds and quasi-hydrogen bonds

    Institute of Scientific and Technical Information of China (English)

    WU RongLiang; JI Qing; KONG Bin; YANG XiaoZhen

    2008-01-01

    Atomistic detailed hydration structures of poly(vinyl methyl ether) (PVME) have been investigated by molecular dynamics simulations under 300 K at various concentrations. Both radial distribution func-tions and the distance distributions between donors and acceptors in hydrogen bonds show that the hydrogen bonds between the polymer and water are shorter by 0.005 nm than those between water molecules. The Quasi-hydrogen bonds take only 7.2% of the van der Waals interaction pairs. It was found the hydrogen bonds are not evenly distributed along the polymer chain, and there still exists a significant amount (10%) of ether oxygen atoms that are not hydrogen bonded to water at a concentra-tion as low as 3.3%. This shows that in polymer solutions close contacts occur not only between polymer chains but also between chain segments within the polymer, which leads to inefficient con-tacts between ether oxygen atoms and water molecules. Variation of the quasi-hydrogen bonds with the concentration is similar to that of hydrogen bonds, but the ratio of the repeat units forming quasi-hydrogen bonds to those forming hydrogen bonds approaches 0.2. A transition was found in the demixing enthalpy at around 30% measured by dynamic testing differential scanning calorimetry (DTDSC) for aqueous solutions of a mono-dispersed low molecular weight PVME, which can be related to the transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27%. The transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27% can be used to explain the demixing enthalpy transition at 30% at a molecular scale. In addition, at the concentration of 86%, each ether oxygen atom bonded with water is assigned 1.56 water molecules on average, and 'free' water molecules emerge at the concentration of around 54%.

  9. Molecular dynamics simulations of the hydration of poly(vinyl methyl ether):Hydrogen bonds and quasi-hydrogen bonds

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Atomistic detailed hydration structures of poly(vinyl methyl ether)(PVME) have been investigated by molecular dynamics simulations under 300 K at various concentrations. Both radial distribution functions and the distance distributions between donors and acceptors in hydrogen bonds show that the hydrogen bonds between the polymer and water are shorter by 0.005 nm than those between water molecules. The Quasi-hydrogen bonds take only 7.2% of the van der Waals interaction pairs. It was found the hydrogen bonds are not evenly distributed along the polymer chain,and there still exists a significant amount(10%) of ether oxygen atoms that are not hydrogen bonded to water at a concentration as low as 3.3%. This shows that in polymer solutions close contacts occur not only between polymer chains but also between chain segments within the polymer,which leads to inefficient contacts between ether oxygen atoms and water molecules. Variation of the quasi-hydrogen bonds with the concentration is similar to that of hydrogen bonds,but the ratio of the repeat units forming quasi-hydrogen bonds to those forming hydrogen bonds approaches 0.2. A transition was found in the demixing enthalpy at around 30% measured by dynamic testing differential scanning calorimetry(DTDSC) for aqueous solutions of a mono-dispersed low molecular weight PVME,which can be related to the transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27%. The transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27% can be used to explain the demixing enthalpy transition at 30% at a molecular scale. In addition,at the concentration of 86%,each ether oxygen atom bonded with water is assigned 1.56 water molecules on average,and ’free’ water molecules emerge at the concentration of around 54%.

  10. Bonding in [CuNRR′]4 type clusters

    Institute of Scientific and Technical Information of China (English)

    WANG; Bingwu; XU; Guangxian; CHEN; Zhida

    2004-01-01

    Many polynuclear Cu(I) compounds have been synthesized, but the problem whether there is direct or no direct Cu-Cu bonding in these compounds is not clear. The electronic structure of [CuNRR′]4 type clusters was investigated by using density functional methods. The results of geometrical optimization are in good agreement with experiment, and the localization of MO's shows that there are four Cu-Cu ( bonds to form the square Cu4 ring in addition to the four bridging Cu-N-Cu bonds. A concept of the covalence of molecular fragments is proposed to describe the bonding in these clusters.

  11. China-Russia Bond

    Institute of Scientific and Technical Information of China (English)

    Ji Zhiye; Ma Zongshi

    2007-01-01

    @@ Thanks to China's successful launching of the Year of Russia, 2006 will surely go down as a milestone in the history of the China-Russia bond. Furthermore, a still-warmer climate will continue to prevail in 2007 when Moscow, in its turn, hosts the Year of China, trying to outshine its next-door neighbor in this regard, as Russian President Vladimir Putin promised in the exchange of new year greetings with his Chinese counterpart, President Hu Jintao.

  12. Bayesian field theoretic reconstruction of bond potential and bond mobility in single molecule force spectroscopy

    CERN Document Server

    Chang, Joshua C; Chou, Tom

    2015-01-01

    Quantifying the forces between and within macromolecules is a necessary first step in understanding the mechanics of molecular structure, protein folding, and enzyme function and performance. In such macromolecular settings, dynamic single-molecule force spectroscopy (DFS) has been used to distort bonds. The resulting responses, in the form of rupture forces, work applied, and trajectories of displacements, have been used to reconstruct bond potentials. Such approaches often rely on simple parameterizations of one-dimensional bond potentials, assumptions on equilibrium starting states, and/or large amounts of trajectory data. Parametric approaches typically fail at inferring complex-shaped bond potentials with multiple minima, while piecewise estimation may not guarantee smooth results with the appropriate behavior at large distances. Existing techniques, particularly those based on work theorems, also do not address spatial variations in the diffusivity that may arise from spatially inhomogeneous coupling to...

  13. Direct bonded space maintainers.

    Science.gov (United States)

    Santos, V L; Almeida, M A; Mello, H S; Keith, O

    1993-01-01

    The aim of this study was to evaluate clinically a bonded space maintainer, which would reduce chair-side time and cost. Sixty appliances were fabricated from 0.7 mm stainless steel round wire and bonded using light-cured composite to the two teeth adjacent to the site of extraction of a posterior primary tooth. Twenty males and sixteen females (age range 5-9-years-old) were selected from the Pedodontic clinic of the State University of Rio de Janeiro. The sixty space maintainers were divided into two groups according to the site in which they were placed: a) absent first primary molar and b) absent second primary molar. Impressions and study models were obtained prior to and 6 months after bonding the appliances. During this period only 8.3% of failures were observed, most of them from occlusal or facial trauma. Student t-test did not show statistically significant alterations in the sizes of the maintained spaces during the trial period.

  14. Pricing for Catastrophe Bonds Based on Expected-value Model

    Directory of Open Access Journals (Sweden)

    Junfei Chen

    2013-02-01

    Full Text Available As the catastrophes cannot be avoided and result in huge economic losses, therefore the compensation issue for catastrophe losses become an important research topic. Catastrophe bonds can effectively disperse the catastrophe risks which mainly undertaken by the government and the insurance companies currently and focus on capital more effectively in broad capital market, therefore to be an ideal catastrophe securities product. This study adopts Expectancy Theory to supplement and improve the pricing of catastrophe bonds based on Value Theory. A model of expected utility is established to determine the conditions of the expected revenue R of catastrophe bonds. The pricing model of the value function is used to get the psychological value of R,U (R-R‾, for catastrophe bonds. Finally, the psychological value is improved by the value according to expected utility and this can more accurately evaluate catastrophe bonds at a reasonable price. This research can provide decision-making for the pricing of catastrophe bonds.

  15. 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)

  16. Mittal bonded tongue thrusting appliance

    Directory of Open Access Journals (Sweden)

    Rekha Mittal

    2014-01-01

    Full Text Available These days majority of orthodontist includes bonded molar attachment in their inventory to eliminate the discomfort of molar separation during initial appointment and band spaces left at the end of treatment. This article describes a innovative and economical method of attachment of bonded tongue crib if required during the initial or later stages of treatment along with bonded molar tubes.

  17. Hamiltonian formulation of bond graphs

    NARCIS (Netherlands)

    Golo, Goran; Schaft, van der Arjan; Breedveld, Peter C.; Maschke, Bernhard M.; Johansson, R.; Rantzer, A.

    2003-01-01

    This paper deals with the mathematical formulation of bond graphs. It is proven that the power continuous part of bond graphs, the junction structure, can be associated with a Dirac structure and that the equations describing a bond graph model correspond to a port Hamiltonian system. The conditions

  18. On the nature of blueshifting hydrogen bonds.

    Science.gov (United States)

    Mo, Yirong; Wang, Changwei; Guan, Liangyu; Braïda, Benoît; Hiberty, Philippe C; Wu, Wei

    2014-07-01

    The block-localized wave function (BLW) method can derive the energetic, geometrical, and spectral changes with the deactivation of electron delocalization, and thus provide a unique way to elucidate the origin of improper, blueshifting hydrogen bonds versus proper, redshifting hydrogen bonds. A detailed analysis of the interactions of F(3)CH with NH(3) and OH(2) shows that blueshifting is a long-range phenomenon. Since among the various energy components contributing to hydrogen bonds, only the electrostatic interaction has long-range characteristics, we conclude that the contraction and blueshifting of a hydrogen bond is largely caused by electrostatic interactions. On the other hand, lengthening and redshifting is primarily due to the short-range n(Y)→σ*(X-H) hyperconjugation. The competition between these two opposing factors determines the final frequency change direction, for example, redshifting in F(3)CH⋅⋅⋅NH(3) and blueshifting in F(3)CH⋅⋅⋅OH(2). This mechanism works well in the series F(n)Cl(3)-n CH⋅⋅⋅Y (n=0-3, Y=NH(3), OH(2), SH(2)) and other systems. One exception is the complex of water and benzene. We observe the lengthening and redshifting of the O-H bond of water even with the electron transfer between benzene and water completely quenched. A distance-dependent analysis for this system reveals that the long-range electrostatic interaction is again responsible for the initial lengthening and redshifting.

  19. Amino Acid Patterns around Disulfide Bonds

    Directory of Open Access Journals (Sweden)

    Brett Drury

    2010-11-01

    Full Text Available Disulfide bonds provide an inexhaustible source of information on molecular evolution and biological specificity. In this work, we described the amino acid composition around disulfide bonds in a set of disulfide-rich proteins using appropriate descriptors, based on ANOVA (for all twenty natural amino acids or classes of amino acids clustered according to their chemical similarities and Scheffé (for the disulfide-rich proteins superfamilies statistics. We found that weakly hydrophilic and aromatic amino acids are quite abundant in the regions around disulfide bonds, contrary to aliphatic and hydrophobic amino acids. The density distributions (as a function of the distance to the center of the disulfide bonds for all defined entities presented an overall unimodal behavior: the densities are null at short distances, have maxima at intermediate distances and decrease for long distances. In the end, the amino acid environment around the disulfide bonds was found to be different for different superfamilies, allowing the clustering of proteins in a biologically relevant way, suggesting that this type of chemical information might be used as a tool to assess the relationship between very divergent sets of disulfide-rich proteins.

  20. ASEAN+3 Bond Market Guides

    OpenAIRE

    Asian Development Bank (ADB)

    2012-01-01

    The ASEAN+3 Bond Market Guide contains the comprehensive reports of the ASEAN+3 Bond Market Forum Sub-Forum 1 (SF1) and Sub-Forum 2 (SF2). The SF1 report (Volume 1) analyzes the harmonization and standardization of the existing bond markets in the ASEAN+3. It also contains the individual market guides of 11 economies under the ASEAN+3 Bond Market Forum (ABMF). The SF2 report (Volume 2) provides an overview of the ASEAN+3 bond markets and their infrastructures, as well as issues confronted by ...

  1. Hydrogen bonding in ionic liquids.

    Science.gov (United States)

    Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

    2015-03-01

    Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (ρBCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H σ* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak

  2. Additional disulfide bonds in insulin

    DEFF Research Database (Denmark)

    Vinther, Tine N; Pettersson, Ingrid; Huus, Kasper;

    2015-01-01

    The structure of insulin, a glucose homeostasis-controlling hormone, is highly conserved in all vertebrates and stabilized by three disulfide bonds. Recently, we designed a novel insulin analogue containing a fourth disulfide bond located between positions A10-B4. The N-terminus of insulin's B......-chain is flexible and can adapt multiple conformations. We examined how well disulfide bond predictions algorithms could identify disulfide bonds in this region of insulin. In order to identify stable insulin analogues with additional disulfide bonds, which could be expressed, the Cβ cut-off distance had...... in comparison to analogues with additional disulfide bonds that were more difficult to predict. In contrast, addition of the fourth disulfide bond rendered all analogues resistant to fibrillation under stress conditions and all stable analogues bound to the insulin receptor with picomolar affinities. Thus...

  3. Learning Type Extension Trees for Metal Bonding State Prediction

    DEFF Research Database (Denmark)

    Frasconi, Paolo; Jaeger, Manfred; Passerini, Andrea

    2008-01-01

    and a discriminant function. In predicting the metal bonding state of proteins, TET achieve significant improvements over manually curated motifs, and the expressiveness of combinatorial features significantly contributes to such performance. Preliminary collective classification results seem to indicate...

  4. Molecular orbital analysis of the hydrogen bonded water dimer

    Science.gov (United States)

    Wang, Bo; Jiang, Wanrun; Dai, Xin; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin

    2016-01-01

    As an essential interaction in nature, hydrogen bonding plays a crucial role in many material formations and biological processes, requiring deeper understanding. Here, using density functional theory and post-Hartree-Fock methods, we reveal two hydrogen bonding molecular orbitals crossing the hydrogen-bond’s O and H atoms in the water dimer. Energy decomposition analysis also shows a non-negligible contribution of the induction term. Our finding sheds light on the essential understanding of hydrogen bonding in ice, liquid water, functional materials and biological systems. PMID:26905305

  5. Is There a Quadruple Bond in C2?

    Science.gov (United States)

    de Sousa, David Wilian Oliveira; Nascimento, Marco Antonio Chaer

    2016-05-10

    The chemical structure of the ground state of C2 has been the subject of intense debate after the suggestion that the molecule could exhibit a "fourth" covalent bond. In this paper, we investigate this problem explicitly avoiding all the points of conflict from the previous papers to show that there is no quadruple bond in C2. The generalized product function energy partitioning (GPF-EP) method has been applied to calculate the interference energy (IE) that accounts for the formation of covalent bonds for each bond of the molecule. The IE analysis shows that for the standard σ and π bonds interference exhibits the expected behavior, while for the "fourth" bond interference is a destabilizing factor. To make sure this could not be attributed to a new kind of bond, we performed an equivalent analysis for the (3)Σ(-) excited state of C3 molecule in which similar "bonding" occurs between the two ending carbon atoms. We also show that the difference in force constants of C2 and acetylene can be rationalized in terms of the amount of charge density in the internuclear region by looking at the changes in the overlaps between orbitals along the bond axis. PMID:27045682

  6. Credit default swaps, bond spreads and the bond market

    OpenAIRE

    Zhu, Meicheng

    2014-01-01

    With the rapid development of the credit default swap (CDS) market, the issue of how the introduction of CDSs affects the corporate bond market has been of particular interest to researchers and policy makers. This has been investigated in the literature from two perspectives. One is to examine the relationship between the CDS and the bond markets in price discovery, and the other is concerned with researching the CDS trading effects on bond spreads. Referring to the former approach, most rel...

  7. Solder extrusion pressure bonding process and bonded products produced thereby

    Science.gov (United States)

    Beavis, Leonard C.; Karnowsky, Maurice M.; Yost, Frederick G.

    1992-01-01

    Production of soldered joints which are highly reliable and capable of surviving 10,000 thermal cycles between about -40.degree. C. and 110.degree. C. Process involves interposing a thin layer of a metal solder composition between the metal surfaces of members to be bonded and applying heat and up to about 1000 psi compression pressure to the superposed members, in the presence of a reducing atmosphere, to extrude the major amount of the solder composition, contaminants including fluxing gases and air, from between the members being bonded, to form a very thin, strong intermetallic bonding layer having a thermal expansion tolerant with that of the bonded members.

  8. Avoiding silicon/glass bonding damage with fusion bonding method

    Institute of Scientific and Technical Information of China (English)

    Daohong Yang(杨道虹); Chen Xu(徐晨); Guangdi Shen(沈光地)

    2004-01-01

    A novel fusion bonding method between silicon and glass with Nd:YAG laser is described.This method overcomes the movable mechanical parts damage caused by the electrostatics force in micro-electronic machine-system(MEMS)device during the anodic bonding. The diameter of laser spot is 300 μm,the power of laser is 100 W,the laser velocity for bonding is 0.05 m/s,the average bonding tension is 6.3 MPa.It could distinctly reduce and eliminate the defects and damage,especially in movable sensitive mechanical parts of MEMS device.

  9. Activation of C-H and B-H bonds through agostic bonding: an ELF/QTAIM insight.

    Science.gov (United States)

    Zins, Emilie-Laure; Silvi, Bernard; Alikhani, M Esmaïl

    2015-04-14

    Agostic bonding is of paramount importance in C-H bond activation processes. The reactivity of the σ C-H bond thus activated will depend on the nature of the metallic center, the nature of the ligand involved in the interaction and co-ligands, as well as on geometric parameters. Because of their importance in organometallic chemistry, a qualitative classification of agostic bonding could be very much helpful. Herein we propose descriptors of the agostic character of bonding based on the electron localization function (ELF) and Quantum Theory of Atoms in Molecules (QTAIM) topological analysis. A set of 31 metallic complexes taken, or derived, from the literature was chosen to illustrate our methodology. First, some criteria should prove that an interaction between a metallic center and a σ X-H bond can indeed be described as "agostic" bonding. Then, the contribution of the metallic center in the protonated agostic basin, in the ELF topological description, may be used to evaluate the agostic character of bonding. A σ X-H bond is in agostic interaction with a metal center when the protonated X-H basin is a trisynaptic basin with a metal contribution strictly larger than the numerical uncertainty, i.e. 0.01 e. In addition, it was shown that the weakening of the electron density at the X-Hagostic bond critical point with respect to that of X-Hfree well correlates with the lengthening of the agostic X-H bond distance as well as with the shift of the vibrational frequency associated with the νX-H stretching mode. Furthermore, the use of a normalized parameter that takes into account the total population of the protonated basin, allows the comparison of the agostic character of bonding involved in different complexes. PMID:25760795

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

    NARCIS (Netherlands)

    L.S. Jongbloed

    2016-01-01

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

  11. Mezzanine finance and corporate bonds

    OpenAIRE

    Libena TETREVOVA

    2009-01-01

    The article deals with the problems of mezzanine finance in relation to corporate bonds. Firstly, attention is paid to definition of mezzanine finance. The term mezzanine finance is used as a term for hybrid forms of financing that combine elements of debt and equity financing. Mezzanine finance represents an alternative form of financing corporate activities. Secondly, possible forms of mezzanine finance are characterized. We can say that special types of corporate bonds (convertible bonds a...

  12. Hydrogen Bonds Involving Metal Centers

    OpenAIRE

    Pavlović, G.; Raos, N.

    2006-01-01

    Hydrogen bonds involving metal center as a hydrogen donor or hydrogen acceptor are only a specific type of metal-hydrogen interactions; it is therefore not easy to differentiate hydrogen bond from other metal-hydrogen interactions, especially agostic ones. The first part of the review is therefore devoted to the results of structural chemistry and molecular spectroscopy (NMR, IR), as a tool for differentiating hydrogen bondings from other hydrogen interactions. The classical examples of Pt···...

  13. Bond failure patterns in vivo.

    Science.gov (United States)

    Linklater, Rognvald A; Gordon, Peter H

    2003-05-01

    The aim of this study was to identify the presence and pattern of differences in bond failure between tooth types in vivo when bonding orthodontic brackets with the no-mix orthodontic composite adhesive Right-On. In vivo bond failure for a single operator was recorded for 108 consecutive patients undergoing fixed-appliance orthodontic treatment. The bond failure data were analyzed by survival analysis. Time to first failure or censorship was recorded for each bonded attachment. Overall failure in the sample matched previous clinical studies but conflicted with previous ex vivo bond strength data. Mandibular and posterior teeth had significantly higher rates of failure than did maxillary and anterior teeth. The type of attachment used had a significant effect on bond survival. The results of this study confirm that in vivo bond survival is not uniform for all teeth. Comparisons between the findings of this study and those of a previous ex vivo study by the same authors failed to validate ex vivo bond strength testing as clinically relevant.

  14. Wafer bonding applications and technology

    CERN Document Server

    Gösele, Ulrich

    2004-01-01

    During the past decade direct wafer bonding has developed into a mature materials integration technology. This book presents state-of-the-art reviews of the most important applications of wafer bonding written by experts from industry and academia. The topics include bonding-based fabrication methods of silicon-on-insulator, photonic crystals, VCSELs, SiGe-based FETs, MEMS together with hybrid integration and laser lift-off. The non-specialist will learn about the basics of wafer bonding and its various application areas, while the researcher in the field will find up-to-date information about this fast-moving area, including relevant patent information.

  15. Photoinduced hydrogen-bonding dynamics.

    Science.gov (United States)

    Chu, Tian-Shu; Xu, Jinmei

    2016-09-01

    Hydrogen bonding dynamics has received extensive research attention in recent years due to the significant advances in femtolaser spectroscopy experiments and quantum chemistry calculations. Usually, photoexcitation would cause changes in the hydrogen bonding formed through the interaction between hydrogen donor and acceptor molecules on their ground electronic states, and such transient strengthening or weakening of hydrogen bonding could be crucial for the photophysical transformations and the subsequent photochemical reactions that occurred on a time scale from tens of femtosecond to a few nanoseconds. In this article, we review the combined experimental and theoretical studies focusing on the ultrafast electronic and vibrational hydrogen bonding dynamics. Through these studies, new mechanisms and proposals and common rules have been put forward to advance our understanding of the hydrogen bondings dynamics in a variety of important photoinduced phenomena like photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer processes, chemosensor fluorescence sensing, rearrangements of the hydrogen-bond network including forming and breaking hydrogen bond in water. Graphical Abstract We review the recent advances on exploring the photoinduced hydrogen bonding dynamics in solutions through a joint approach of laser spectroscopy and theoretical calculation. The reviewed studies have put forward a new mechanism, new proposal, and new rule for a variety of photoinduced phenomena such as photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer, chemosensor fluorescence sensing, and rearrangements of the hydrogen-bond network in water. PMID:27491849

  16. Bond Growth under Temperature Gradient.

    Directory of Open Access Journals (Sweden)

    P.K. Satyawali

    1999-12-01

    Full Text Available Grain and bond growth for dry snow are determined by the distribution of temperature andtemperature gradient in the snow matrix. From the standpoint of particle approach and based oncubic packing structure, a bond growth model has been developed for TG metamorphism. The paper.highlights the importance of bond formation and its effect on snow viscosity and finally on the rateof settlement. This is very important for developing a numerical snow pack model if microstructureis considered to be a basic parameter. A few experiments have been carried out to validate bond formation under temperature gradient.

  17. A simplified indirect bonding technique

    Directory of Open Access Journals (Sweden)

    Radha Katiyar

    2014-01-01

    Full Text Available With the advent of lingual orthodontics, indirect bonding technique has become an integral part of practice. It involves placement of brackets initially on the models and then their transfer to teeth with the help of transfer trays. Problems encountered with current indirect bonding techniques used are (1 the possibility of adhesive flash remaining around the base of the brackets which requires removal (2 longer time required for the adhesive to gain enough bond strength for secure tray removal. The new simplified indirect bonding technique presented here overcomes both these problems.

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

    CERN Document Server

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

    2016-01-01

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

  19. Digital Control of Bonding Force for Gold Wire Bonding Machine

    Directory of Open Access Journals (Sweden)

    Xiaochu Wang

    2013-01-01

    Full Text Available In order to digitally control the bonding force of a wire bonder precisely, this paper uses a DC solenoid as a force source, and by controlling the solenoid’s current, which causes the electromagnetic force, we can control the bonding force that capillary applies. The bonding force control system in this paper is composed of PC (Personal Computer and hypogyny MCU (Micro Controller Unit, which communicate using a RS485 interface. The digital value of a given bonding force is given by the PC to the MCU. By comparing the sampling current of the solenoid, and through PID regulation, D/A converter of the digital potentiometer and the solenoid driver circuit, the half-closed loop control system of bonding force is accomplished. Tuning of the PID parameters is accomplished with fuzzy adaptive control theory and simulated by Matlab simulink. The control system is tested by comparing the desired bonding force and the force actually applied and examming the relationship between bonding quality and bonding force.

  20. Dividends Sharing Convertible Bonds Pricing and Numerical Evaluation

    Directory of Open Access Journals (Sweden)

    Xu Guo

    2013-01-01

    Full Text Available The convertible bond is becoming one of the most important financial instruments for the company to raise capital fund since it was first issued by American New York Erie Company in 1843. In this paper, it is the first time to study the pricing problem for convertible bond whose underlying stocks pay dividends via the reflected backward stochastic differential equations. Associating the solutions of reflected BSDEs with the obstacle problems for nonlinear parabolic PDEs, we establish the pricing formulas for convertible bonds with continuous and discrete dividends by means of the viscosity solutions for some PDEs. Besides, we also derive the price of convertible bonds with higher borrowing rate which is realistic in the financial market. Then the numerical evaluations are provided by the radial basis functions method. Moreover, we discuss the influence of dividends paying as well as higher borrowing rate on the convertible bond price at last.

  1. Bonding in Molecular Crystals from the Local Electronic Pressure Viewpoint

    CERN Document Server

    Tsirelson, Vladimir G; Tokatly, Ilya V

    2015-01-01

    The spatial distribution of the internal pressure of an electron fluid, which spontaneously arises at the formation of a molecule or a crystal, is linked to the main features of chemical bonding in molecular crystals. The local pressure is approximately expressed in terms of the experimental electron density and its derivatives using the density functional formalism and is applied to identify the bonding features in benzene, formamide and chromium hexacarbonyl. We established how the spatial regions of compression and stretching of the electron fluid in these solids reflect the typical features of chemical bonds of different types. Thus, the internal electronic pressure can serve as a bonding descriptor, which has a clear physical meaning and reveals the specific features of variety of the chemical bonds expressing them in terms of the electron density.

  2. 29 CFR 2580.412-19 - Term of the bond, discovery period, other bond clauses.

    Science.gov (United States)

    2010-07-01

    ... SECURITY ACT OF 1974 TEMPORARY BONDING RULES General Bond Rules § 2580.412-19 Term of the bond, discovery... 29 Labor 9 2010-07-01 2010-07-01 false Term of the bond, discovery period, other bond clauses... new bond must be obtained each year. There is nothing in the Act that prohibits a bond for a...

  3. Insights into and relative effect of chitosan-krill oil, chitosan-H-aspirin, chitosan-H-krill oil-nystatin and chitosan-H-krill oil-aspirin-nystatin on dentin bond strength and functional drug delivery capacity: In-vitro studies

    Directory of Open Access Journals (Sweden)

    Victoria Tamara Perchyonok

    2014-01-01

    Full Text Available Background: Restorative materials in the new era aim to be "bio-active" and long-lasting. The purpose of this study was to design and to evaluate a novel chitosan hydrogels containing krill oil (antioxidant containing material, nystatin (antifungal, aspirin (pain relieve medication and free radical scavengers and combinations thereof (chitosan-H-krill oil, chitosan-H-krill oil-nystatin and chitosan-H-aspirin, chitosan-H-aspirin-nystatin, chitosan-H-krill oil-aspirin and chitosan-H-krill oil-aspirin-nystatin as functional additive prototypes for further development of "dual function restorative materials," and secondly to determine their effect on the dentin bond strength of a composite. Materials and Methods: The above-mentioned hydrogels were prepared by dispersion the corresponding component in glycerol and acetic acid with the addition of chitosan gelling agent. The surface morphology (scanning electron microscope (SEM, release behaviors (physiological pH and also in acidic conditions, stability of the therapeutic agent-antioxidant-chitosan and the effect of the hydrogels on the shear bond strength of dentin were also evaluated. Results: The release of nystatin and aspirin confer the added benefit of synergistic action of a functional therapeutic delivery when comparing the newly designed chitosan-based hydrogel restorative materials to the commercially available products alone. Neither the release of nystatin and aspirin nor the antioxidant stability was affected by storage over a 6 month period. The hydrogel formulations have a uniform distribution of drug content, homogenous texture and yellow color (SEM study. All chitosan dentin treated hydrogels gave significantly (P<0.05; non-parametric ANOVA test higher shear bond values (P<0.05 than dentin treated or not treated with phosphoric acid. Conclusion: The added benefits of the chitosan treated hydrogels involved positive influence on the nystatin and aspirin release as well as increased

  4. Computational Chemistry of Adhesive Bonds

    Science.gov (United States)

    Phillips, Donald H.

    1999-01-01

    This investigation is intended to determine the electrical mechanical, and chemical properties of adhesive bonds at the molecular level. The initial determinations will be followed by investigations of the effects of environmental effects on the chemistry and properties of the bond layer.

  5. 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.

  6. Oxytocin and mutual communication in mother-infant bonding

    Directory of Open Access Journals (Sweden)

    Miho eNagasawa

    2012-02-01

    Full Text Available Mother-infant bonding is universal to all mammalian species. In this review, we describe the manner in which reciprocal communication between the mother and infant leads to mother-infant bonding in rodents. In rats and mice, mother-infant bond formation is reinforced by various social stimuli, such as tactile stimuli and ultrasonic vocalizations from the pups to the mother, and feeding and tactile stimulation from the mother to the pups. Some evidence suggests that mother and infant can develop a cross-modal sensory recognition of their counterpart during this bonding process. Neurochemically, oxytocin in the neural system plays a pivotal role in each side of the mother-infant bonding process, although the mechanisms underlying bond formation in the brains of infants has not yet been clarified. Impairment of mother-infant bonding, that is, deprivation of social stimuli from the mother, strongly influences offspring sociality, including maternal behavior toward their own offspring in their adulthood, implying a non-genomic transmission of maternal environment, even in rodents. The comparative understanding of cognitive functions between mother and infants, and the biological mechanisms involved in mother-infant bonding may help us understand psychiatric disorders associated with mother-infant relationships.

  7. Using Diffusion Bonding in Making Piezoelectric Actuators

    Science.gov (United States)

    Sager, Frank E.

    2003-01-01

    and pressure for a specified curing time. The pressure, temperature, and time depend on the piezoelectric material selected. At the end of the diffusion-bonding process, the resulting laminated piezoelectric actuator is tested to verify the adequacy of the mechanical output as a function of an applied DC voltage.

  8. Stability of Cu-Nb layered nanocomposite from chemical bonding

    Science.gov (United States)

    Saikia, Ujjal; Sahariah, Munima B.; Pandey, Ravindra

    2016-07-01

    The potential use of layered metallic nanocomposites in radiation-resistant materials has been recognized with ultra-high mechanical strengths. Here we present results on layered Cu-Nb composite examining its stability in terms of chemical bond via charge density and transfer analysis, QTAIM, electron localization function and density of states using DFT. An intermediate character of bonding with a significant amount of charge transfer at the interface has been predicted. Shortening of intraplanar bond length is a good manifestation of their observed structural stability which may be due to electron promotion of 3 d → (4 s, 4 p) orbitals associated with the constituent atoms of the composite.

  9. Minimal model for dynamic bonding in colloidal transient networks

    Science.gov (United States)

    Krinninger, Philip; Fortini, Andrea; Schmidt, Matthias

    2016-04-01

    We investigate a model for colloidal network formation using Brownian dynamics computer simulations. Hysteretic springs establish transient bonds between particles with repulsive cores. If a bonded pair of particles is separated by a cutoff distance, the spring vanishes and reappears only if the two particles contact each other. We present results for the bond lifetime distribution and investigate the properties of the van Hove dynamical two-body correlation function. The model displays crossover from fluidlike dynamics, via transient network formation, to arrested quasistatic network behavior.

  10. Chemical bonding and electronic structure of fullerene-based compounds

    International Nuclear Information System (INIS)

    This talk will focus on the nature of bonding of fullerenes with other materials as demonstrated by synchrotron radiation and x-ray photoemission. Adsorption of C60 on metallic and semiconducting substrates occurs via charge transfer from the substrate to a LUMO-derived resonance, resulting in Fermi level alignment and dipole formation. Bonding of metal atoms to C60 depends on the metal work function and bulk cohesive energy. Evaporation of high cohesive energy materials onto a fullerene substrate results in metal cluster nucleation and limited C60 disruption for transition metals. Low cohesive energy metals form compounds with a degree of ionic character related to the metal work function. Photoemission results show the formation of ionic K-fulleride compounds while greater hybridization is observed for Ca-rich fullerides. Finally the electronic structure of fluorinated and hydrogenated fullerenes demonstrate changes in states derived from C60 π bonds due to reaction of dangling bonds

  11. Atomic bonding between metal and graphene

    KAUST Repository

    Wang, Hongtao

    2013-03-07

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

  12. Water lubricates hydrogen-bonded molecular machines

    Science.gov (United States)

    Panman, Matthijs R.; Bakker, Bert H.; den Uyl, David; Kay, Euan R.; Leigh, David A.; Buma, Wybren Jan; Brouwer, Albert M.; Geenevasen, Jan A. J.; Woutersen, Sander

    2013-11-01

    The mechanical behaviour of molecular machines differs greatly from that of their macroscopic counterparts. This applies particularly when considering concepts such as friction and lubrication, which are key to optimizing the operation of macroscopic machinery. Here, using time-resolved vibrational spectroscopy and NMR-lineshape analysis, we show that for molecular machinery consisting of hydrogen-bonded components the relative motion of the components is accelerated strongly by adding small amounts of water. The translation of a macrocycle along a thread and the rotation of a molecular wheel around an axle both accelerate significantly on the addition of water, whereas other protic liquids have much weaker or opposite effects. We tentatively assign the superior accelerating effect of water to its ability to form a three-dimensional hydrogen-bond network between the moving parts of the molecular machine. These results may indicate a more general phenomenon that helps explain the function of water as the ‘lubricant of life’.

  13. Statistical Parameters for Hydrogen Bonding Networks: One Component Case

    Institute of Scientific and Technical Information of China (English)

    王海军; 洪晓钟; 赵敏; 巴信武

    2001-01-01

    Based on the analysis of network structures formed by hydrogen bonds as the sol-gel phase transition takesplace in a single component hydrogen bonding system, the theory of reversible gelation is applied to calculatesome statistical parameters that determine many physical and chemical properties of the networks. Then, thentunerical simulation of the number of active chains and dangling chains, the number of effective cross-linkages,the number of active and dangling mers and the modulus as a function of conversion are undertaken.

  14. A New Model of Interfacial Physical Contact in Diffusion Bonding

    Institute of Scientific and Technical Information of China (English)

    Peng HE; Jicai FENG; Yiyu QIAN

    2004-01-01

    Through eliminating voids not affecting the primary bonding process, and incorporating interlayer and flexible base material, the interface geometry character and brief mathematics process were put forth. Through analyzing contact process of diffusion bonding, contact area model was settled. It can interpret the phenomenon of different interface areas taking on different strengths. In the course of physical contact, shear stresses serve an important function for the plastic deformation and the cohesion of interface voids.

  15. Why are Hydrogen Bonds Directional?

    Indian Academy of Sciences (India)

    ABHISHEK SHAHI; ELANGANNAN ARUNAN

    2016-10-01

    The recent IUPAC recommendation on the definition of hydrogen bonding points out that directionality is a defining characteristic of a hydrogen bond and the angle ∠X-H-Y is generally linear or 180◦. It also suggests that the X-H· · ·Y angle be greater than 110◦ for an interaction to be characterized as a hydrogenbond but does not provide any rationale for the same. This article reports a rationale for limiting the angle, based on the electron density topology using the quantum theory of atoms in molecules. Electron density topology for common hydrogen bond donors HF, HCl, HBr, HNC, HCN and HCCH are reported in this work. These calculations lead to an interesting observation that the atomic basins of H atom in all these donor molecules are limited justifying the restriction of hydrogen bond angle. Moreover, similar analysis on some hydrogen bonded complexes confirms that beyond this angle the acceptor atom Y starts interacting with the atomic basin on X. However, conclusions based on bond lengths and angles have to be treated with care and as the IUPAC recommendation points out that independent ‘evidence for bond formation’ in every case is important.

  16. Physical Nature of Hydrogen Bond

    CERN Document Server

    Zhyganiuk, I V

    2015-01-01

    The physical nature and the correct definition of hydrogen bond (H-bond) are considered.\\,\\,The influence of H-bonds on the thermodynamic, kinetic, and spectroscopic properties of water is analyzed.\\,\\,The conventional model of H-bonds as sharply directed and saturated bridges between water molecules is incompatible with the behavior of the specific volume, evaporation heat, and self-diffusion and kinematic shear viscosity coefficients of water. On the other hand, it is shown that the variation of the dipole moment of a water molecule and the frequency shift of valence vibrations of a hydroxyl group can be totally explained in the framework of the electrostatic model of H-bond.\\,\\,At the same time, the temperature dependences of the heat capacity of water in the liquid and vapor states clearly testify to the existence of weak H-bonds.\\,\\,The analysis of a water dimer shows that the contribution of weak H-bonds to its ground state energy is approximately 4--5 times lower in comparison with the energy of electr...

  17. Roll bonding of strained aluminium

    DEFF Research Database (Denmark)

    Staun, Jakob M.

    2003-01-01

    This report investigates roll bonding of pre-strained (å ~ 4) aluminium sheets to produce high strain material from high purity aluminium (99.996%) and commercial pure aluminium (99.6%). The degree of bonding is investigated by optical microscopy and ultrasonic scanning. Under the right circumsta......This report investigates roll bonding of pre-strained (å ~ 4) aluminium sheets to produce high strain material from high purity aluminium (99.996%) and commercial pure aluminium (99.6%). The degree of bonding is investigated by optical microscopy and ultrasonic scanning. Under the right...... circumstances both materials show good bonding, but the high purity material is excluded because of recrystallisation and the resulting loss of mechanical properties. The effect of cross stacking and roll bonding pre-strained sheets of the commercial purity material is investigated and some dependence...... of the cross rolled volume fraction is found. To further asses this effect, and the anisotropy, it is necessary to acquire knowledge about both texture and microstructure, e.g. by TEM. Roll bonding of pre-strained aluminium is found to be a possible alternative to ARB in the quest for ultra-fine grained...

  18. VB studies on bonding features of HNC(←→)HCN

    Institute of Scientific and Technical Information of China (English)

    廖新丽; 吴玮; 莫亦荣; 张乾二

    2003-01-01

    Within the bonded tableau unitary group approach (BTUGA), a scheme, combined with Pauling's resonance theory to select the predominant valence bond structures for VB calculations, is proposed. This scheme ensures a reliable and illustrative bonding picture in the description of chemical reactions, as exemplified by the isomerization reaction HNCHCN. The computation results account for important bonding features about this isomerization at the ab initio level and explore the mechanism of phenomena such as (i) HCN is more stable than HNC; (ii) the C-N bond first lengthens and then shortens in the vicinity of the transition state; (iii) only H-atom migration is observed in the isomerization process, without the breaking of the CN bond. Our results demonstrate that only a few bonded tableau functions are sufficient enough to provide a visual and reliable bonding picture.

  19. First-principle study on bonding mechanism of ZnO by LDA+U method

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, G.C. [Key Laboratory of Low Dimensional Materials and Application Technology (Xiangtan University), Ministry of Education, Institute of Modern Physics, Xiangtan University, Xiangtan 411105 (China); Sun, L.Z. [Key Laboratory of Low Dimensional Materials and Application Technology (Xiangtan University), Ministry of Education, Institute of Modern Physics, Xiangtan University, Xiangtan 411105 (China) and National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Science, 200083 Shanghai (China)]. E-mail: lzsun@xtu.edu.cn; Zhong, X.L. [Key Laboratory of Low Dimensional Materials and Application Technology (Xiangtan University), Ministry of Education, Institute of Modern Physics, Xiangtan University, Xiangtan 411105 (China); Chen Xiaoshuang [National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Science, 200083 Shanghai (China)]. E-mail: xschen@mail.sitp.ac.cn; Wei Lu [National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Science, 200083 Shanghai (China); Wang, J.B. [Key Laboratory of Low Dimensional Materials and Application Technology (Xiangtan University), Ministry of Education, Institute of Modern Physics, Xiangtan University, Xiangtan 411105 (China)]. E-mail: jbwang@xtu.edu.cn

    2007-08-13

    The electronic structure and the bonding mechanism of ZnO have been studied by using the Full-Potential Linear Augmented Plane Wave (FP-LAPW) method within the density-functional theory (DFT) based on LDA+U exchange correlation potential. The valence and the bonding charge density are calculated and compared with those derived from LDA and GGA to describe the bonding mechanism. The charge transfer along with the bonding process is analyzed by using the theory of Atoms in Molecules (AIM). The bonding, the topological characteristics and the p-d coupling effects on the bonding mechanism of ZnO are shown quantitatively with the critical points (CPs) along the bonding trajectory and the charge in the atomic basins. Meanwhile, the bonding characteristics for wurtzite, zinc blende and rocksalt phase of ZnO are discussed systematically in the present paper.

  20. Tensile Bond Strength of Latex-Modified Bonded Concrete Overlays

    Science.gov (United States)

    Dubois, Cameron; Ramseyer, Chris

    2010-10-01

    The tensile bond strength of bonded concrete overlays was tested using the in-situ pull-off method described in ASTM C 1583 with the goal of determining whether adding latex to the mix design increases bond strength. One slab of ductile concrete (f'c > 12,000 psi) was cast with one half tined, i.e. roughened, and one half steel-troweled, i.e. smooth. The slab surface was sectioned off and overlay mixtures containing different latex contents cast in each section. Partial cores were drilled perpendicular to the surface through the overlay into the substrate. A tensile loading device applied a direct tensile load to each specimen and the load was increased until failure occurred. The tensile bond strength was then calculated for comparison between the specimens.

  1. Direct Bonded Pontic (Laporan Kasus

    Directory of Open Access Journals (Sweden)

    Suhandi Sidjaja

    2015-10-01

    Full Text Available Advanced science and technology in dentistry enable dental practitioners to modified she bonding techniques in tooth replacement. A pontic made of composite resin bonded to etched enamel of the adjacent teeth can be used in the replacement of one missing anterior tooth with a virgin or sowed adpicent tooth. The advantages of this technique include a one visit treatment, cow cost, good esthetics, less side effects and easy repair or rebounding. Clinical evaluation showed a high success rate therefore with a proper diagnosis and a perfect skill of the direct bonded technique this treatment can be used as an alternative restoration.

  2. Integration of European Bond Markets

    DEFF Research Database (Denmark)

    Christiansen, Charlotte

    2014-01-01

    I investigate the time variation in the integration of EU government bond markets. The integration is measured by the explanatory power of European factor portfolios for the individual bond markets for each year. The integration of the government bond markets is stronger for EMU than non-EMU memb......-EMU members and stronger for old than new EU members. For EMU countries, the integration is weaker the lower the credit rating is. During the recent crisis periods, the integration is weaker, particularly for EMU countries....

  3. The chemisorptive bond basic concepts

    CERN Document Server

    Clark, Alfred

    1974-01-01

    The Chemisorptive Bond: Basic Concepts describes the basic concepts of the chemisorptive bond on solid surfaces from the simple analogies with ordinary chemical bonds to the quantum-mechanical approaches.This book is composed of 10 chapters and begins with discussions of simple formulas for correlating measurable quantities in chemisorptions and catalysis. The succeeding chapters deal with theories based on quantum-mechanical principles that describe the mutual interactions of atoms of the solid and foreign atoms on the surface. The remaining chapters consider the possible arrangements

  4. Adhesives for orthodontic bracket bonding

    Directory of Open Access Journals (Sweden)

    Déborah Daniella Diniz Fonseca

    2010-04-01

    Full Text Available The advent of acid etching, introduced by Buonocore in 1955, brought the possibility of bonding between the bracket base and enamel, contributing to more esthetic and conservative orthodontics. This direct bracket bonding technique has brought benefits such as reduced cost and time in performing the treatment, as well as making it easier to perform oral hygiene. The aim of this study was to conduct a survey of published studies on orthodontic bracket bonding to dental enamel. It was verified that resin composites and glass ionomer are the most studied and researched materials for this purpose. Resin-modified glass ionomer, with its biocompatibility, capacity of releasing fluoride and no need for acid etching on the tooth structure, has become increasingly popular among dentists. However, due to the esthetic and mechanical properties of light polymerizable resin composite, it continues to be one of the adhesives of choice in the bracket bonding technique and its use is widely disseminated.

  5. Hydrogen bonding in tight environments

    DEFF Research Database (Denmark)

    Pirrotta, Alessandro; Solomon, Gemma C.; Franco, Ignacio

    2016-01-01

    The single-molecule force spectroscopy of a prototypical class of hydrogen-bonded complexes is computationally investigated. The complexes consist of derivatives of a barbituric acid and a Hamilton receptor that can form up to six simultaneous hydrogen bonds. The force-extension (F-L) isotherms...... of the host-guest complexes are simulated using classical molecular dynamics and the MM3 force field, for which a refined set of hydrogen bond parameters was developed from MP2 ab initio computations. The F-L curves exhibit peaks that signal conformational changes during elongation, the most prominent...... of which is in the 60-180 pN range and corresponds to the force required to break the hydrogen bonds. These peaks in the F-L curves are shown to be sensitive to relatively small changes in the chemical structure of the host molecule. Thermodynamic insights into the supramolecular assembly were obtained...

  6. Hydrogen Bonds in Polymer Folding

    OpenAIRE

    Borg, J; Jensen, M. H.; K. Sneppen; Tiana, G.

    2000-01-01

    The thermodynamics of a homopolymeric chain with both Van der Waals and highly-directional hydrogen bond interaction is studied. The effect of hydrogen bonds is to reduce dramatically the entropy of low-lying states and to give raise to long-range order and to conformations displaying secondary structures. For compact polymers a transition is found between helix-rich states and low-entropy sheet-dominated states. The consequences of this transition for protein folding and, in particular, for ...

  7. Weld bonding of stainless steel

    DEFF Research Database (Denmark)

    Santos, I. O.; Zhang, Wenqi; Goncalves, V.M.;

    2004-01-01

    This paper presents a comprehensive theoretical and experimental investigation of the weld bonding process with the purpose of evaluating its relative performance in case of joining stainless steel parts, against alternative solutions based on structural adhesives or conventional spot-welding. Th......This paper presents a comprehensive theoretical and experimental investigation of the weld bonding process with the purpose of evaluating its relative performance in case of joining stainless steel parts, against alternative solutions based on structural adhesives or conventional spot...

  8. Seeking hydrogen bonds- with and without neutron diffraction

    International Nuclear Information System (INIS)

    The hydrogen-bond interaction can be studied using a variety of spectroscopic and crystallographic techniques, as well as theoretical studies based on quantum chemical principles, semi-empirical procedures, and statistical interpretations. A degree of specificity, along with flexibility, provides H-bonded systems with a variety of unusual and interesting physical, chemical and biological properties. Neutron diffraction is the method of choice for obtaining high-precision data on hydrogen-atom positions and hydrogen-bond stereo-chemistry in crystals. Neutron inelastic scattering can provide information on the dynamics of H-bonded systems. High-precision neutron diffraction studies on a variety of crystal hydrates, amino acids and small peptides, development of semi-empirical potential functions for bent-hydrogen bonds, and statistical analysis of H-bond populations associated with various donor and acceptor groups are some of the investigations on hydrogen bonding, carried out at Trombay during the past three decades. (author). 39 refs., 7 figs., 3 tabs

  9. Thioamides: versatile bonds to induce directional and cooperative hydrogen bonding in supramolecular polymers.

    Science.gov (United States)

    Mes, Tristan; Cantekin, Seda; Balkenende, Dirk W R; Frissen, Martijn M M; Gillissen, Martijn A J; De Waal, Bas F M; Voets, Ilja K; Meijer, E W; Palmans, Anja R A

    2013-06-24

    The amide bond is a versatile functional group and its directional hydrogen-bonding capabilities are widely applied in, for example, supramolecular chemistry. The potential of the thioamide bond, in contrast, is virtually unexplored as a structuring moiety in hydrogen-bonding-based self-assembling systems. We report herein the synthesis and characterisation of a new self-assembling motif comprising thioamides to induce directional hydrogen bonding. N,N',N''-Trialkylbenzene-1,3,5-tris(carbothioamide)s (thioBTAs) with either achiral or chiral side-chains have been readily obtained by treating their amide-based precursors with P2S5. The thioBTAs showed thermotropic liquid crystalline behaviour and a columnar mesophase was assigned. IR spectroscopy revealed that strong, three-fold, intermolecular hydrogen-bonding interactions stabilise the columnar structures. In apolar alkane solutions, thioBTAs self-assemble into one-dimensional, helical supramolecular polymers stabilised by three-fold hydrogen bonding. Concentration- and temperature-dependent self-assembly studies performed by using a combination of UV and CD spectroscopy demonstrated a cooperative supramolecular polymerisation mechanism and a strong amplification of supramolecular chirality. The high dipole moment of the thioamide bond in combination with the anisotropic shape of the resulting cylindrical aggregate gives rise to sufficiently strong depolarised light scattering to enable depolarised dynamic light scattering (DDLS) experiments in dilute alkane solution. The rotational and translational diffusion coefficients, D(trans) and D(rot), were obtained from the DDLS measurements, and the average length, L, and diameter, d, of the thioBTA aggregates were derived (L = 490 nm and d = 3.6 nm). These measured values are in good agreement with the value L(w) = 755 nm obtained from fitting the temperature-dependent CD data by using a recently developed equilibrium model. This experimental verification

  10. Atomically Bonded Transparent Superhydrophobic Coatings

    Energy Technology Data Exchange (ETDEWEB)

    Aytug, Tolga [ORNL

    2015-08-01

    Maintaining clarity and avoiding the accumulation of water and dirt on optically transparent surfaces such as US military vehicle windshields, viewports, periscope optical head windows, and electronic equipment cover glasses are critical to providing a high level of visibility, improved survivability, and much-needed safety for warfighters in the field. Through a combination of physical vapor deposition techniques and the exploitation of metastable phase separation in low-alkali borosilicate, a novel technology was developed for the fabrication of optically transparent, porous nanostructured silica thin film coatings that are strongly bonded to glass platforms. The nanotextured films, initially structurally superhydrophilic, exhibit superior superhydrophobicity, hence antisoiling ability, following a simple but robust modification in surface chemistry. The surfaces yield water droplet contact angles as high as 172°. Moreover, the nanostructured nature of these coatings provides increased light scattering in the UV regime and reduced reflectivity (i.e., enhanced transmission) over a broad range of the visible spectrum. In addition to these functionalities, the coatings exhibit superior mechanical resistance to abrasion and are thermally stable to temperatures approaching 500°C. The overall process technology relies on industry standard equipment and inherently scalable manufacturing processes and demands only nontoxic, naturally abundant, and inexpensive base materials. Such coatings, applied to the optical components of current and future combat equipment and military vehicles will provide a significant strategic advantage for warfighters. The inherent self-cleaning properties of such superhydrophobic coatings will also mitigate biofouling of optical windows exposed to high-humidity conditions and can help decrease repair/replacement costs, reduce maintenance, and increase readiness by limiting equipment downtime.

  11. On the bonding in Fe2(CO)9

    Science.gov (United States)

    Bauschlicher, C. W., Jr.

    1986-01-01

    The present paper is concerned with an analysis of the bonding in Fe2(CO)9, taking into account the results of self-consistent-field (SCF) calculations. The basis sets used are the same as those employed in the study of Fe(CO)5 conducted by Bauschlicher and Bagus (1985). The Fe basis set starts with the 14s9p5d primitive set optimized by Wachters (1970), which is contracted to 8s4p5d. An SCF wave function, consisting of only the core electrons, was determined, and then electrons were slowly added to the virtual orbitals with the lowest eigenvalues. The conducted calculations show no direct Fe-Fe bonding, but rather bonding resulting from the bridging CO's. The bonding is found to involve both the 5 sigma and 2 pi(asterisk) orbitals of the bridging CO's.

  12. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

  13. Influence of chain topology and bond potential on the glass transition of polymer chains simulated with the bond fluctuation model

    Energy Technology Data Exchange (ETDEWEB)

    Freire, J J [Departamento de Ciencias y Tecnicas FisicoquImicas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), Senda del Rey 9, 28040 Madrid (Spain)], E-mail: jfreire@invi.uned.es

    2008-07-16

    The bond fluctuation model with a bond potential has been applied to investigation of the glass transition of linear chains and chains with a regular disposition of small branches. Cooling and subsequent heating curves are obtained for the chain energies and also for the mean acceptance probability of a bead jump. In order to mimic different trends to vitrification, a factor B gauging the strength of the bond potential with respect to the long-range potential (i.e. the intramolecular or intermolecular potential between indirectly bonded beads) has been introduced. (A higher value of B leads to a preference for the highest bond lengths and a higher total energy, implying a greater tendency to vitrify.) Different cases have been considered for linear chains: no long-range potential, no bond potential and several choices for B. Furthermore, two distinct values of B have been considered for alternate bonds in linear chains. In the case of the branched chains, mixed models with different values of B for bonds in the main chain and in the branches have also been investigated. The possible presence of ordering or crystallization has been characterized by calculating the collective light scattering function of the different samples after annealing at a convenient temperature below the onset of the abrupt change in the curves associated with a thermodynamic transition. It is concluded that ordering is inherited more efficiently in the systems with branched chains and also for higher values of B. The branched molecules with the highest B values in the main chain bonds exhibit two distinct transitions in the heating curves, which may be associated with two glass transitions. This behavior has been detected experimentally for chains with relatively long flexible branches.

  14. Reduced form models of bond portfolios

    OpenAIRE

    Matti Koivu; Teemu Pennanen

    2010-01-01

    We derive simple return models for several classes of bond portfolios. With only one or two risk factors our models are able to explain most of the return variations in portfolios of fixed rate government bonds, inflation linked government bonds and investment grade corporate bonds. The underlying risk factors have natural interpretations which make the models well suited for risk management and portfolio design.

  15. Evaluating Callable and Putable Bonds: An Eigenfunction Expansion Approach

    OpenAIRE

    Dongjae Lim; Lingfei Li; Vadim Linetsky

    2012-01-01

    We propose an efficient method to evaluate callable and putable bonds under a wide class of interest rate models, including the popular short rate diffusion models, as well as their time changed versions with jumps. The method is based on the eigenfunction expansion of the pricing operator. Given the set of call and put dates, the callable and putable bond pricing function is the value function of a stochastic game with stopping times. Under some technical conditions, it is shown to have an e...

  16. CrCl3对石油稠油O-H�X(X=N、O、S)氢键削弱的密度泛函理论研究%Study on O-H X(X=N、O、S) Hydrogen Bond Heavy Oil Weaken by CrCl3 Using Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    刘红飞

    2015-01-01

    There was a large number of O-H�X(X=N、O、S) hydrogen in thick oil which resulted the poor flowability, high vis-cosity and large intermolecular force. Using a transition metal compound as a catalyst to weaken the hydrogen bond was the primary method of reducing the intermolecular forces. CrCl3 attacking the O-H�X(X=N、O、S) hydrogen to weaken hydrogen was cal-culated with GAUSSIAN 03 package. The density functional method in its hybrid B3LYP functional was used in the calculations. The results showed that the hydrogen bond length was increased, the charge of N, O and S atom transfer, the system front energy gap drop. The hydrogen bonds were effectively weaken by CrCl3.%稠油分子间大量O-H�X(X=N、O、S)氢键,造成其分子间作用力、黏度较大,使用过渡金属化合物作为催化剂削弱氢键是降低分子间作用力的主要方法。采用密度泛函理论B3LYP方法,使用Gaussian 03程序,CrCl3作为催化剂,对稠油间CrCl3-O-H�X(X=N、O、S)氢键的攻击削弱情况进行了计算。结果表明,CrCl3不仅增加了氢键的键长,N、O、S的电荷发生了转移,同时还使得系统的前线能隙下降,有效地削弱了氢键。

  17. Insulin analog with additional disulfide bond has increased stability and preserved activity

    DEFF Research Database (Denmark)

    Vinther, Tine N.; Norrman, Mathias; Ribel, Ulla;

    2013-01-01

    Insulin is a key hormone controlling glucose homeostasis. All known vertebrate insulin analogs have a classical structure with three 100% conserved disulfide bonds that are essential for structural stability and thus the function of insulin. It might be hypothesized that an additional disulfide...... bond may enhance insulin structural stability which would be highly desirable in a pharmaceutical use. To address this hypothesis, we designed insulin with an additional interchain disulfide bond in positions A10/B4 based on Cα-Cα distances, solvent exposure, and side-chain orientation in human insulin...... of an insulin analog featuring a fourth disulfide bond with increased structural stability and retained function....

  18. Halogen Bonding in Organic Synthesis and Organocatalysis.

    Science.gov (United States)

    Bulfield, David; Huber, Stefan M

    2016-10-01

    Halogen bonding is a noncovalent interaction similar to hydrogen bonding, which is based on electrophilic halogen substituents. Hydrogen-bonding-based organocatalysis is a well-established strategy which has found numerous applications in recent years. In light of this, halogen bonding has recently been introduced as a key interaction for the design of activators or organocatalysts that is complementary to hydrogen bonding. This Concept features a discussion on the history and electronic origin of halogen bonding, summarizes all relevant examples of its application in organocatalysis, and provides an overview on the use of cationic or polyfluorinated halogen-bond donors in halide abstraction reactions or in the activation of neutral organic substrates.

  19. A DFT Study on Intramolecular Hydrogen Bond in Substituted Catechols and Their Radicals

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Density functional theory (DFT) at B3LYP/6-31G(d,p) level was employed to calculate intramolecular hydrogen bond enthalpies (HIHB), O-H charge differences, O-H bond lengths and bond orders for various substituted catechols and their radicals generated after H-abstraction. It was found that although the charge difference between hydrogen-bonded H and O played a role in determining HIHB, HIHB was mainly governed by the hydrogen bond length. As the oxygen-centered radical has great tendency to form a chemical bond with the H atom, hydrogen bond lengths in catecholic radicals are systematically shorter than those in catechols. Hence, the HIHB for the former are higher than those for the latter.

  20. Evaluating the potential for halogen bonding in ketosteroid isomerase’s oxyanion hole using unnatural amino acid mutagenesis

    Science.gov (United States)

    Kraut, Daniel A; Churchil, Michael J; Dawson, Phillip E

    2009-01-01

    There has recently been an increasing interest in controlling macromolecular conformations and interactions through halogen bonding. Halogen bonds are favorable electrostatic interactions between polarized, electropositive chlorine, bromine or iodine atoms and electronegative atoms such as oxygen or nitrogen. These interactions have been likened to hydrogen bonds both in terms of their favored acceptor molecules, their geometries, and their energetics. We asked whether a halogen bond could replace a hydrogen bond in the oxyanion hole of ketosteroid isomerase, using semi-synthetic enzyme containing para-halogenated phenylalanine derivatives to replace the tyrosine hydrogen bond donor. Formation of a halogen bond to the oxyanion in the transition state would be expected to rescue the effects of mutation to phenylalanine, but all of the halogenated enzymes were comparable in activity to the phenylalanine mutant. We conclude that, at least in this active site, a halogen bond cannot functionally replace a hydrogen bond. PMID:19260691

  1. Effect of hydrogen bonding on infrared absorption intensity

    CERN Document Server

    Athokpam, Bijyalaxmi; McKenzie, Ross H

    2016-01-01

    We consider how the infrared intensity of an O-H stretch in a hydrogen bonded complex varies as the strength of the H-bond varies from weak to strong. We obtain trends for the fundamental and overtone transitions as a function of donor-acceptor distance R, which is a common measure of H-bond strength. Our calculations use a simple two-diabatic state model that permits symmetric and asymmetric bonds, i.e. where the proton affinity of the donor and acceptor are equal and unequal, respectively. The dipole moment function uses a Mecke form for the free OH dipole moment, associated with the diabatic states. The transition dipole moment is calculated using one-dimensional vibrational eigenstates associated with the H-atom transfer coordinate on the ground state adiabatic surface of our model. Over 20-fold intensity enhancements for the fundamental are found for strong H-bonds, where there are significant non-Condon effects. The isotope effect on the intensity yields a non-monotonic H/D intensity ratio as a function...

  2. Two Comments on Bond Angles

    Science.gov (United States)

    Glaister, P.

    1997-09-01

    Tetrahedral Bond Angle from Elementary Trigonometry The alternative approach of using the scalar (or dot) product of vectors enables the determination of the bond angle in a tetrahedral molecule in a simple way. There is, of course, an even more straightforward derivation suitable for students who are unfamiliar with vectors, or products thereof, but who do know some elementary trigonometry. The starting point is the figure showing triangle OAB. The point O is the center of a cube, and A and B are at opposite corners of a face of that cube in which fits a regular tetrahedron. The required bond angle alpha = AÔB; and using Pythagoras' theorem, AB = 2(square root 2) is the diagonal of a face of the cube. Hence from right-angled triangle OEB, tan(alpha/2) = (square root 2) and therefore alpha = 2tan-1(square root 2) is approx. 109° 28' (see Fig. 1).

  3. Bond percolation on multiplex networks

    CERN Document Server

    Hackett, A; Gómez, S; Arenas, A; Gleeson, J P

    2015-01-01

    We present an analytical approach for bond percolation on multiplex networks and use it to determine the expected size of the giant connected component and the value of the critical bond occupation probability in these networks. We advocate the relevance of these tools to the modeling of multilayer robustness and contribute to the debate on whether any benefit is to be yielded from studying a full multiplex structure as opposed to its monoplex projection, especially in the seemingly irrelevant case of a bond occupation probability that does not depend on the layer. Although we find that in many cases the predictions of our theory for multiplex networks coincide with previously derived results for monoplex networks, we also uncover the remarkable result that for a certain class of multiplex networks, well described by our theory, new critical phenomena occur as multiple percolation phase transitions are present. We provide an instance of this phenomenon in a multipex network constructed from London rail and Eu...

  4. Bond breaking in a Morse chain under tension: Fragmentation patterns, higher index saddles, and bond healing

    Science.gov (United States)

    Mauguière, F. A. L.; Collins, P.; Ezra, G. S.; Wiggins, S.

    2013-04-01

    We investigate the fragmentation dynamics of an atomic chain under tensile stress. We have classified the location, stability type (indices), and energy of all equilibria for the general n-particle chain, and have highlighted the importance of saddle points with index >1. We show that for an n = 2-particle chain under tensile stress the index 2 saddle plays a central role in organizing the dynamics. We apply normal form theory to analyze phase space structure and dynamics in a neighborhood of the index 2 saddle. We define a phase dividing surface (DS) that enables us to classify trajectories passing through a neighborhood of the saddle point using the values of the integrals associated with the normal form. We also generalize our definition of the dividing surface and define an extended dividing surface (EDS), which is used to sample and classify all trajectories that pass through a phase space neighborhood of the index 2 saddle at total energies less than that of the saddle. Classical trajectory simulations are used to study fragmentation patterns for the n = 2 chain under tension. That is, we investigate the relative probability for breaking one bond versus concerted fission of several (two, in this case) bonds. Initial conditions for trajectories are obtained by sampling the EDS at constant energy. We sample trajectories at fixed energies both above and below the energy of the saddle. The fate of trajectories (single versus multiple bond breakage) is explored as a function of the location of the initial condition on the EDS, and a connection made to the work of Chesnavich on collision-induced dissociation. A significant finding is that we can readily identify trajectories that exhibit bond healing. Such trajectories pass outside the nominal (index 1) transition state for single bond dissociation, but return to the potential well region, possibly several times, before ultimately dissociating.

  5. Choosing a density functional for static molecular polarizabilities

    CERN Document Server

    Wu, Taozhe; Thakkar, Ajit J

    2015-01-01

    Coupled-cluster calculations of static electronic dipole polarizabilities for 145 organic molecules are performed to create a reference data set. The molecules are composed from carbon, hydrogen, nitrogen, oxygen, fluorine, sulfur, chlorine, and bromine atoms. They range in size from triatomics to 14 atoms. The Hartree-Fock and 2nd-order M{\\o}ller-Plesset methods and 34 density functionals, including local functionals, global hybrid functionals, and range-separated functionals of the long-range-corrected and screened-exchange varieties, are tested against this data set. On the basis of the test results, detailed recommendations are made for selecting density functionals for polarizability computations on relatively small organic molecules.

  6. Probing the Hydrogen Bond Strength at Single Bond Limit

    Science.gov (United States)

    Guo, Jing; Lü, Jing-Tao; Chen, Ji; Peng, Jinbo; Meng, Xiangzhi; Wang, Zhichang; Li, Xin-Zheng; Wang, Enge; Jiang, Ying

    2015-03-01

    Many extraordinary physical, chemical and biological properties of water are determined by hydrogen-bonding interaction between the water molecules. So far, the routine way to determine the hydrogen-bonding strength of water is probing the frequency shift of O-H stretching mode using various spectroscopic techniques, which all suffer from the difficulty of spectral assignment and the broadening of vibrational signals due to the lack of spatial resolution. In this talk, we show the ability to probe the hydrogen-bonding strength of interfacial water at single bond limit using resonantly enhanced inelastic electron tunneling spectroscopy (IETS) with a scanning tunneling microscope (STM). The conventional IET signals of water molecules are extremely weak and far beyond the experimental detection limit due to the negligible molecular density of states (DOS) around the Fermi level. This difficulty can be surmounted by turning on the tip-water coupling, which shifts and broadens the frontier molecular orbitals of water to the proximity of Fermi level, resulting in a resonantly enhanced IET process. International Center for Quantum Materials, School of Physics, Peking University.

  7. To Bond or Not to Bond? That Is the Question

    Science.gov (United States)

    Balzer, Wayne E.

    2015-01-01

    This case, inspired by a real school district scenario, was developed for use in a graduate-level course in school finance. James Spencer had just been selected as the new superintendent of a low-income, 400-student, rural school district in need of many capital improvements. The previous superintendent had refused to hold a bond election because…

  8. Molecularly Tuning the Radicaloid N-H···O═C Hydrogen Bond.

    Science.gov (United States)

    Lu, Norman; Chung, Wei-Cheng; Ley, Rebecca M; Lin, Kwan-Yu; Francisco, Joseph S; Negishi, Ei-Ichi

    2016-03-01

    Substituent effects on the open shell N-H···O═C hydrogen-bond has never been reported. This study examines how 12 functional groups composed of electron donating groups (EDG), halogen atoms and electron withdrawing groups (EWG) affect the N-H···O═C hydrogen-bond properties in a six-membered cyclic model system of O═C(Y)-CH═C(X)N-H. It is found that group effects on this open shell H-bonding system are significant and have predictive trends when X = H and Y is varied. When Y is an EDG, the N-H···O═C hydrogen-bond is strengthened; and when Y is an EWG, the bond is weakened; whereas the variation in electronic properties of X group do not exhibit a significant impact upon the hydrogen bond strength. The structural impact of the stronger N-H···O═C hydrogen-bond are (1) shorter H and O distance, r(H···O) and (2) a longer N-H bond length, r(NH). The stronger N-H···O═C hydrogen-bond also acts to pull the H and O in toward one another which has an effect on the bond angles. Our findings show that there is a linear relationship between hydrogen-bond angle and N-H···O═C hydrogen-bond energy in this unusual H-bonding system. In addition, there is a linear correlation of the r(H···O) and the hydrogen bond energy. A short r(H···O) distance corresponds to a large hydrogen bond energy when Y is varied. The observed trends and findings have been validated using three different methods (UB3LYP, M06-2X, and UMP2) with two different basis sets. PMID:26855203

  9. Molecularly Tuning the Radicaloid N-H···O═C Hydrogen Bond.

    Science.gov (United States)

    Lu, Norman; Chung, Wei-Cheng; Ley, Rebecca M; Lin, Kwan-Yu; Francisco, Joseph S; Negishi, Ei-Ichi

    2016-03-01

    Substituent effects on the open shell N-H···O═C hydrogen-bond has never been reported. This study examines how 12 functional groups composed of electron donating groups (EDG), halogen atoms and electron withdrawing groups (EWG) affect the N-H···O═C hydrogen-bond properties in a six-membered cyclic model system of O═C(Y)-CH═C(X)N-H. It is found that group effects on this open shell H-bonding system are significant and have predictive trends when X = H and Y is varied. When Y is an EDG, the N-H···O═C hydrogen-bond is strengthened; and when Y is an EWG, the bond is weakened; whereas the variation in electronic properties of X group do not exhibit a significant impact upon the hydrogen bond strength. The structural impact of the stronger N-H···O═C hydrogen-bond are (1) shorter H and O distance, r(H···O) and (2) a longer N-H bond length, r(NH). The stronger N-H···O═C hydrogen-bond also acts to pull the H and O in toward one another which has an effect on the bond angles. Our findings show that there is a linear relationship between hydrogen-bond angle and N-H···O═C hydrogen-bond energy in this unusual H-bonding system. In addition, there is a linear correlation of the r(H···O) and the hydrogen bond energy. A short r(H···O) distance corresponds to a large hydrogen bond energy when Y is varied. The observed trends and findings have been validated using three different methods (UB3LYP, M06-2X, and UMP2) with two different basis sets.

  10. Reliability of flip-chip bonded RFID die using anisotropic conductive paste hybrid material

    Institute of Scientific and Technical Information of China (English)

    Jun-Sik LEE; Jun-Ki KIM; Mok-Soon KIM; Namhyun KANG; Jong-Hyun LEE

    2011-01-01

    A reliability of flip-chip bonded die as a function of anisotropic conductive paste (ACP) hybrid materials. bonding conditions, and antenna pattern materials was investigated during the assembly of radio frequency identification(RFID) inlay. The optimization condition for flip-chip bonding was determined from the behavior of bonding strength. Under the optimized condition,the shear strength for the antenna printed with paste-type Ag ink was larger than that for Cu antenna. Furthermore, an identification distance was varied from the antenna materials. Comparing with the Ag antenna pattern, the as-bonded die on Cu antenna showed a larger distance of identification, However, the long-term reliability of inlay using the Cu antenna was decreased significantly as a function of aging time at room temperature because of the bended shape of Cu antenna formed during the flip-chip bonding process.

  11. An Analytical Modified Model of Clad Sheet Bonding by Cold Rolling Using Upper Bond Theorem

    Science.gov (United States)

    Pishbin, H.; Parsa, M. H.; Dastvareh, A.

    2010-10-01

    In this paper, clad sheet bonding by cold rolling was investigated using the upper bond theorem. Plastic deformation behavior of the strip at the roll gap was investigated, unlike previous methods; distinctive angular velocities are used for different zones in roll gap in present model and absolute minimum of rolling power function is achieved. Rolling power, rolling force, and thickness ratio of the rolled product affected by various rolling condition such as flow stress of sheets, initial thickness ratio, roller radius, total thickness reduction, coefficient of friction between rollers and metals and between components layer, roll speed, etc., are discussed. It was found that the theoretical prediction of the thickness ratio of the rolled product, rolling force, and rolling power are in good agreement with the experimental measurement.

  12. 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.

  13. Continuous feelings of love? The parental bond from pregnancy to toddlerhood.

    Science.gov (United States)

    de Cock, Evi S A; Henrichs, Jens; Vreeswijk, Charlotte M J M; Maas, A Janneke B M; Rijk, Catharina H A M; van Bakel, Hedwig J A

    2016-02-01

    Both prenatal and postnatal parental bonding (i.e., the affective tie from parent to child) have important effects on parental and child functioning. However, research on the continuity and correlates of parental bonding is lacking. Therefore, the goal of the present study was to examine the stability of bonding levels and to explore distinct bonding patterns with a latent class analysis. Moreover, the correlates of these bonding patterns in the parental-, child-, and contextual domain were studied. Levels of maternal (N = 370) and paternal (N = 292) bonding and potential correlates were assessed at 26 weeks of pregnancy, 6 months, and 24 months postpartum. Results showed moderate stability of bonding from pregnancy to toddlerhood. For both mothers and fathers, 4 distinct bonding patterns were found. Parents with low bonding patterns were characterized by increased anxiety and parenting stress, less partner support, less adaptive personality profiles, and children with difficult temperament. These findings indicate the importance of monitoring young children's parents with poor levels of bonding as their bonding patterns remain stable from pregnancy until toddlerhood and because those parents experience problems in multiple domains.

  14. Continuous feelings of love? The parental bond from pregnancy to toddlerhood.

    Science.gov (United States)

    de Cock, Evi S A; Henrichs, Jens; Vreeswijk, Charlotte M J M; Maas, A Janneke B M; Rijk, Catharina H A M; van Bakel, Hedwig J A

    2016-02-01

    Both prenatal and postnatal parental bonding (i.e., the affective tie from parent to child) have important effects on parental and child functioning. However, research on the continuity and correlates of parental bonding is lacking. Therefore, the goal of the present study was to examine the stability of bonding levels and to explore distinct bonding patterns with a latent class analysis. Moreover, the correlates of these bonding patterns in the parental-, child-, and contextual domain were studied. Levels of maternal (N = 370) and paternal (N = 292) bonding and potential correlates were assessed at 26 weeks of pregnancy, 6 months, and 24 months postpartum. Results showed moderate stability of bonding from pregnancy to toddlerhood. For both mothers and fathers, 4 distinct bonding patterns were found. Parents with low bonding patterns were characterized by increased anxiety and parenting stress, less partner support, less adaptive personality profiles, and children with difficult temperament. These findings indicate the importance of monitoring young children's parents with poor levels of bonding as their bonding patterns remain stable from pregnancy until toddlerhood and because those parents experience problems in multiple domains. PMID:26280095

  15. Covered bonds vs. assets securitization

    OpenAIRE

    Silviu Eduard DINCĂ

    2014-01-01

    During the past few years, in the recent post-crisis global banking and capital markets context, financial institutions around the globe are exploring new options to better secure their financing and refinancing demands. We will exhibit herewith a comparison between covered bonds and asset securitizations as financial markets-based funding techniques, highlighting certain key structuring and implementation specifics on each of them.

  16. On double bonds in fullerenes

    OpenAIRE

    Stepenshchikov D. G.; Voytekhovsky Yu. L.

    2016-01-01

    Various distributions of double carbon bonds in the fullerenes have been considered in the paper from the point that they are absent in the pentagonal rings. The appropriate classification of the fullerenes has been built. The results may be used when modeling the fullerenes of a given topology and calculating their physical-chemical properties

  17. Essays on European bond markets

    NARCIS (Netherlands)

    Y.C. Cheung

    2005-01-01

    This dissertation focused on a number of issues that are of importance in the current European bond market. In the past years, the fiscal policy of the Eurozone members, advances in the technology of trading platforms and the introduction of a single currency have reshaped the fixed income markets i

  18. Aromatic C-H Bond Functionalization Induced by Electrochemically in Situ Generated Tris(p-bromophenyl)aminium Radical Cation: Cationic Chain Reactions of Electron-Rich Aromatics with Enamides.

    Science.gov (United States)

    Li, Long-Ji; Jiang, Yang-Ye; Lam, Chiu Marco; Zeng, Cheng-Chu; Hu, Li-Ming; Little, R Daniel

    2015-11-01

    An effective Friedel-Crafts alkylation reaction of electron-rich aromatics with N-vinylamides, induced by electrochemically in situ-generated TBPA radical cation, has been developed; the resulting adducts are produced in good to excellent yields. In the "ex-cell" type electrolysis, TBPA is transformed to its oxidized form in situ and subsequently employed as an electron transfer reagent to initiate a cationic chain reaction. An easily recoverable and reusable polymeric ionic liquid-carbon black (PIL-CB) composite was also utilized as a supporting electrolyte for the electrochemical generation of TBPA cation radical, without sacrificing efficiency or stability after four electrolyses. Cyclic voltammetry analysis and the results of control experiments demonstrate that the reaction of electron-rich aromatics and N-vinylamides occurs via a cationic chain reaction, which takes place though an oxidative activation of a C-H bond of electron-rich aromatics instead of oxidation of the N-vinylamide as previously assumed.

  19. Fusion bonding of silicon nitride surfaces

    DEFF Research Database (Denmark)

    Reck, Kasper; Østergaard, Christian; Thomsen, Erik Vilain;

    2011-01-01

    While silicon nitride surfaces are widely used in many micro electrical mechanical system devices, e.g. for chemical passivation, electrical isolation or environmental protection, studies on fusion bonding of two silicon nitride surfaces (Si3N4–Si3N4 bonding) are very few and highly application...... results on bonding of thin and thick Si3N4 layers. The new results include high temperature bonding without any pretreatment, along with improved bonding ability achieved by thermal oxidation and chemical pretreatment. The bonded wafers include both unprocessed and processed wafers with a total silicon...... nitride thickness of up to 440 nm. Measurements of bonding strength, void characterization, oxidation rate and surface roughness are also presented. Bonding strengths for stoichiometric low pressure chemical vapor deposition Si3N4–Si3N4 direct fusion bonding in excess of 2 J cm−2 are found...

  20. Effect of moisture, saliva, and blood contamination on the shear bond strength of brackets bonded with a conventional bonding system and self-etched bonding system

    Science.gov (United States)

    Prasad, Mandava; Mohamed, Shamil; Nayak, Krishna; Shetty, Sharath Kumar; Talapaneni, Ashok Kumar

    2014-01-01

    Background: The success of bonding brackets to enamel with resin bonding systems is negatively affected by contamination with oral fluids such as blood and saliva. The new self-etch primer systems combine conditioning and priming agents into a single application, making the procedure more cost effective. Objective: The purpose of the study was to investigate the effect of moisture, saliva and blood contamination on shear bond strength of orthodontic brackets bonded with conventional bonding system and self-etch bonding system. Materials and Methods: Each system was examined under four enamel surface conditions (dry, water, saliva, and blood), and 80 human teeth were divided into two groups with four subgroups each of 10 according to enamel surface condition. Group 1 used conventional bonding system and Group 2 used self-etched bonding system. Subgroups 1a and 2a under dry enamel surface conditions; Subgroups 1b and 2b under moist enamel surface condition; Subgroups 3a and 3b under saliva enamel surface condition and Subgroup 4a and 4b under blood enamel surface condition. Brackets were bonded, and all the samples were then submitted to a shear bond test with a universal testing machine with a cross head speed of 1mm/sec. Results: The results showed that the contamination reduced the shear bond strength of all groups. In self-etch bonding system water and saliva had significantly higher bond strength when compared to other groups. Conclusion: It was concluded that the blood contamination showed lowest bond strength from both bonding systems. Self-etch bonding system resulted in higher bond strength than conventional bonding system under all conditions except the dry enamel surface. PMID:24678210

  1. VB studies on bonding features of HNCHCN

    Institute of Scientific and Technical Information of China (English)

    LIAO; Xinli(

    2003-01-01

    [1]Skurski, P., Gutowski, M., Simons, J., Ab initio electronic structure of HCN- and HNC-dipole-bound anions and a description of electron loss upon tautomerization, J. Chem. Phys., 2001, 114(17): 7443-7449.[2]Jursic, B. S., Complete basis set ab initio study of potential energy surfaces of the dissociation recombination reaction HCNH++e(-), J. Mol. Struct., 1999, 487(3): 211-220.[3]Abashkin, Y., Russo, N., Toscano, M., Transition states and energy barriers from density functional studies: representative isomerization reactions, Int. J. Quantum Chem., 1994, 52: 695-704.[4]Bentley, J. A., Bowman, J. M., Gazdy, B. et al., A global ab initio potential for HCN/HNC exact vibrational energies and comparision to experiment, Chem. Phys. Lett., 1992, 198(6): 563-569.[5]Bentley, J. A., Huang, C. M., Wyatt, R. E., Highly vibrationally excited HCN/HNC: eigenvalues, wave functions, and stimulated emission pumping spectra, J. Chem. Phys., 1992, 98(7): 5207-5221.[6]Peric, M., Mladrenovic, M., Peyerimhoff, S. D. et al., Ab initio study of the isomerization HNC-HCN, 1. Ab initio calculation of the HNV reversible HCN potential surface and the corresponding energy-levels, Chem. Phys., 1983, 82: 317-336.[7]Zhang, Q. E., Li, X. Z., Bonded tableau method for many-electron systems, J. Mol. Struct. (Theochem.), 1989, 198: 413-425.[8]Li, X. Z., Zhang, Q. E., Bonded tableau unitary group approach to the many-electron correlation problem, Int. J. Quantum Chem., 1989, 36: 599-632.[9]Li, J. B., Wu, W., New algorithm for nonorthogonal ab initio valence-bond calculations, Theor. Chim. Acta, 1994, 89: 105-121.[10]Wu, W., Mo, Y. R., Zhang, Q. E., On the resonance theory, J. Mol. Struct., 1993, 283: 227-236.[11]Mo, Y. R., Wu, W., Zhang, Q. E., Valence bond description for the ground state and several low-lying excited states of LiH, J. Mol. Struct., 1993, 283: 237-249.[12]Pauling, L., The Nature of Chemical Bond, 3rd ed., Ithaca, New York: Cornell

  2. Method for fusion bonding thermoplastic composites

    Energy Technology Data Exchange (ETDEWEB)

    Benatar, A.; Gutowski, T.G.

    1986-10-01

    Bonding of thermoplastic composites is a critical step in the manufacture of aerospace structures. The objective of this project is to investigate different methods for fusion bonding thermoplastic composites quickly, with a good bond strength, and without warping and deconsolidation. This is best accomplished by heating and melting the thermoplastic on the bond surface only, and then pressing the parts together for a fusion bond. For this purpose, a variety of surface heating techniques were examined for bonding of PEEK and J Polymer composites. These included: resistance heating, infrared heating, induction heating, dielectric/microwave heating, and ultrasonic welding. 20 references, 10 figures, 1 table.

  3. Strength of Bond Covenants and Bond Assessment Framework

    Directory of Open Access Journals (Sweden)

    Noel Yahanpath

    2012-06-01

    Full Text Available We examine bond covenants of 29 New Zealand bond issues between 2001 and 2007.Results from the study indicate that protection provided for bondholders is weak and limited.On average, only 2-3 types of covenants are embedded with the issues and only 27% of thesecovenants provide full protection to the bondholders. However, bondholders are not compensated for taking the additional risk. We propose an alternative assessment framework that directly assesses the level of protection offered to bondholders. We calculate thecovenant quality score for the issues and classify them into four levels of protection: very high protection, moderate, low and very low. Recent legislative changes will go some way towards improving investor protection and confidence, but the effect is yet to be seen. This proposed scoring framework can be used by potential investors to complement the traditional credit ratings when making their investment decisions.

  4. Fusion bonding of Si wafers investigated by x ray diffraction

    DEFF Research Database (Denmark)

    Weichel, Steen; Grey, Francois; Rasmussen, Kurt;

    2000-01-01

    The interface structure of bonded Si(001) wafers with twist angle 6.5 degrees is studied as a function of annealing temperature. An ordered structure is observed in x-ray diffraction by monitoring a satellite reflection due to the periodic modulation near the interface, which results from...

  5. A direct bonded fixed partial dental prosthesis: a clinical report.

    Science.gov (United States)

    Tanoue, Naomi; Tanaka, Takuo

    2015-01-01

    A direct bonded fixed partial dental prosthesis, with a composite resin denture tooth as a pontic, a tri-n-butylborane initiated adhesive resin, and screw posts for reinforcement, was still functioning after an observation period of 20 years. The prosthesis was found to be reliable for long-term clinical use when chemically and mechanically reinforced. PMID:25277033

  6. A direct bonded fixed partial dental prosthesis: A clinical report

    OpenAIRE

    Tanoue, Naomi; Tanaka, Takuo

    2015-01-01

    A direct bonded fixed partial dental prosthesis, with a composite resin denture tooth as a pontic, a tri-n-butylborane initiated adhesive resin, and screw posts for reinforcement, was still functioning after an observation period of 20 years. The prosthesis was found to be reliable for long-term clinical use when chemically and mechanically reinforced.

  7. Learning probabilistic models of hydrogen bond stability from molecular dynamics simulation trajectories

    KAUST Repository

    Chikalov, Igor

    2011-02-15

    Background: Hydrogen bonds (H-bonds) play a key role in both the formation and stabilization of protein structures. They form and break while a protein deforms, for instance during the transition from a non-functional to a functional state. The intrinsic strength of an individual H-bond has been studied from an energetic viewpoint, but energy alone may not be a very good predictor.Methods: This paper describes inductive learning methods to train protein-independent probabilistic models of H-bond stability from molecular dynamics (MD) simulation trajectories of various proteins. The training data contains 32 input attributes (predictors) that describe an H-bond and its local environment in a conformation c and the output attribute is the probability that the H-bond will be present in an arbitrary conformation of this protein achievable from c within a time duration ?. We model dependence of the output variable on the predictors by a regression tree.Results: Several models are built using 6 MD simulation trajectories containing over 4000 distinct H-bonds (millions of occurrences). Experimental results demonstrate that such models can predict H-bond stability quite well. They perform roughly 20% better than models based on H-bond energy alone. In addition, they can accurately identify a large fraction of the least stable H-bonds in a conformation. In most tests, about 80% of the 10% H-bonds predicted as the least stable are actually among the 10% truly least stable. The important attributes identified during the tree construction are consistent with previous findings.Conclusions: We use inductive learning methods to build protein-independent probabilistic models to study H-bond stability, and demonstrate that the models perform better than H-bond energy alone. 2011 Chikalov et al; licensee BioMed Central Ltd.

  8. Learning Probabilistic Models of Hydrogen Bond Stability from Molecular Dynamics Simulation Trajectories

    KAUST Repository

    Chikalov, Igor

    2011-04-02

    Hydrogen bonds (H-bonds) play a key role in both the formation and stabilization of protein structures. H-bonds involving atoms from residues that are close to each other in the main-chain sequence stabilize secondary structure elements. H-bonds between atoms from distant residues stabilize a protein’s tertiary structure. However, H-bonds greatly vary in stability. They form and break while a protein deforms. For instance, the transition of a protein from a nonfunctional to a functional state may require some H-bonds to break and others to form. The intrinsic strength of an individual H-bond has been studied from an energetic viewpoint, but energy alone may not be a very good predictor. Other local interactions may reinforce (or weaken) an H-bond. This paper describes inductive learning methods to train a protein-independent probabilistic model of H-bond stability from molecular dynamics (MD) simulation trajectories. The training data describes H-bond occurrences at successive times along these trajectories by the values of attributes called predictors. A trained model is constructed in the form of a regression tree in which each non-leaf node is a Boolean test (split) on a predictor. Each occurrence of an H-bond maps to a path in this tree from the root to a leaf node. Its predicted stability is associated with the leaf node. Experimental results demonstrate that such models can predict H-bond stability quite well. In particular, their performance is roughly 20% better than that of models based on H-bond energy alone. In addition, they can accurately identify a large fraction of the least stable H-bonds in a given conformation. The paper discusses several extensions that may yield further improvements.

  9. Stable alkanes containing very long carbon-carbon bonds.

    Science.gov (United States)

    Fokin, Andrey A; Chernish, Lesya V; Gunchenko, Pavel A; Tikhonchuk, Evgeniya Yu; Hausmann, Heike; Serafin, Michael; Dahl, Jeremy E P; Carlson, Robert M K; Schreiner, Peter R

    2012-08-22

    The metal-induced coupling of tertiary diamondoid bromides gave highly sterically congested hydrocarbon (hetero)dimers with exceptionally long central C-C bonds of up to 1.71 Å in 2-(1-diamantyl)[121]tetramantane. Yet, these dimers are thermally very stable even at temperatures above 200 °C, which is not in line with common C-C bond length versus bond strengths correlations. We suggest that the extraordinary stabilization arises from numerous intramolecular van der Waals attractions between the neighboring H-terminated diamond-like surfaces. The C-C bond rotational dynamics of 1-(1-adamantyl)diamantane, 1-(1-diamantyl)diamantane, 2-(1-adamantyl)triamantane, 2-(1-diamantyl)triamantane, and 2-(1-diamantyl)[121]tetramantane were studied through variable-temperature (1)H- and (13)C NMR spectroscopies. The shapes of the inward (endo) CH surfaces determine the dynamic behavior, changing the central C-C bond rotation barriers from 7 to 33 kcal mol(-1). We probe the ability of popular density functional theory (DFT) approaches (including BLYP, B3LYP, B98, B3LYP-Dn, B97D, B3PW91, BHandHLYP, B3P86, PBE1PBE, wB97XD, and M06-2X) with 6-31G(d,p) and cc-pVDZ basis sets to describe such an unusual bonding situation. Only functionals accounting for dispersion are able to reproduce the experimental geometries, while most DFT functionals are able to reproduce the experimental rotational barriers due to error cancellations. Computations on larger diamondoids reveal that the interplay between the shapes and the sizes of the CH surfaces may even allow the preparation of open-shell alkyl radical dimers (and possibly polymers) that are strongly held together exclusively by dispersion forces. PMID:22835264

  10. Shear bond strength of two resin cements to human root dentin using three dentin bonding agents.

    Science.gov (United States)

    Gogos, C; Stavrianos, C; Kolokouris, I; Economides, N; Papadoyannis, I

    2007-01-01

    This study compared the bond strength of two resin cements to human root dentin when used with three bonding agents. The materials used were Rely X ARC and Perma Cem, two one-bottle bonding agents (Single Bond, Bond-1) and one self-etching bonding agent (Clearfil SE Bond). The dentin was obtained from single rooted human teeth, and the specimens were treated with either 15% EDTA or 37% phosphoric acid to remove the smear layer, except in groups where the self-etching bonding agent was used. The resin cements were placed on dentin surfaces with the use of bonding agents. Shear bond strength (SBS) was tested using a single plane shear test assembly. The dentin specimens were divided into 10 groups. Eight groups were pre-treated with EDTA or phosphoric acid to remove the smear layer, followed by a bonding agent (Bond-1 or Single Bond) and resin cement (Rely X or Perma Cem). In the two remaining groups, the smear layer was left intact, and the two resins cements were used in combination with the self-etching bonding agent (Clearfil SE Bond). No statistically significant differences were observed among the eight groups treated with one-bottle bonding agents. The mean bond strengths of the two groups treated with the self-etching bonding agent did not differ significantly from each other but were both significantly greater than the bond strengths of all the other groups. The results of this study also showed that EDTA can be used as an alternative to phosphoric acid in bonding procedures for resin cements. However, the bond strengths of resin cements, in combination with a self-etching bonding agent, were significantly greater than those of the same cements when used with one-bottle bonding agents.

  11. Ravens intervene in others' bonding attempts.

    Science.gov (United States)

    Massen, Jorg J M; Szipl, Georgine; Spreafico, Michela; Bugnyar, Thomas

    2014-11-17

    The competition for power in a complex social world is hypothesized to be a driving force in the evolution of intelligence. More specifically, power may be obtained not only by brute force but also by social strategies resembling human politics. Most empirical evidence comes from primate studies that report unprovoked aggression by dominants to maintain power by spreading fear and third-party interventions in conflicts. Coalitionary support has also been described in other animals and is often linked to social bonding. As coalitions can lead to a gain in power and fitness benefits, individuals may try to prevent coalitionary support or indirectly prevent others from forming social bonds that might lead to coalitions. Although there is some empirical evidence that coalitionary support can be manipulated, little is known about the indirect strategy. We show here that wild ravens (Corvus corax) regularly intervene in affiliative interactions of others even though such interventions are potentially risky and without immediate benefits. Moreover, the identities of both interveners and intervened pairs are not randomly distributed. Ravens with existing ties initiate most interventions, and ravens that are creating new ties are most likely to be the targets of interventions. These patterns are consistent with the idea that interventions function to prevent others from forming alliances and consequently becoming future competitors. We thus show previously undescribed social maneuvers in the struggle for power. These maneuvers are likely to be of importance in other social species as well.

  12. Reviving the Case for GDP-Indexed Bonds

    OpenAIRE

    Eduardo Borensztein; Paolo Mauro

    2002-01-01

    This paper seeks to revive the case for countries to self-insure against economic growth slowdowns by issuing GDP-indexed bonds. We simulate the effects of GDP-indexed bonds under different assumptions about fiscal policy reaction functions and their output effects and find that they could substantially reduce the likelihood that debt/GDP paths become explosive. The insurance premium would likely be small, because cross-country comovement of GDP growth rates is low and cross-country GDP growt...

  13. Elastic effects behind cooperative bonding inβ-sheets

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Nørskov, Jens Kehlet; Jacobsen, Karsten Wedel

    2004-01-01

    We present extensive density functional theory calculations of the bonding between strands in â-sheets. We identify a significant cooperative effect whereby the interaction increases in strength with the number of strands. We show that the effect is related to a coupling between interstrand bonding...... and intrastrand elastic properties. It is found that a direct consequence of this coupling is that the pitch of â-sheets should contract with increasing number of strands, and we show that the effect can be observed directly in experimental data from the Protein Data Bank....

  14. The importance of bonding - A historic overview and future possibilities

    DEFF Research Database (Denmark)

    Täljsten, Björn

    2006-01-01

    An adhesive is a substance that has the capability to hold materials together. The manner by which adhesives are able to serve this function is due to a surface attachment that is resistant to separation. A bond occurs when the adhesive molecules adsorb onto a solid surface and chemically react...... transfer than welded structures. In this paper, an overview of the use of adhesive in the service of man is presented. The overview is brief, but nonetheless gives an idea of the possibilities of adhering materials by bonding. The paper briefly discusses the use of adhesives in the aerospace, automotive...

  15. Recent progress in hydrogen-rich materials from the perspective of bonding flexibility of hydrogen

    International Nuclear Information System (INIS)

    The bonding flexibility of hydrogen is a source of various interesting functionalities in hydrides. Here, we illustrate the benefits of this flexibility through several selected examples of recent progress in the development of hydrogen storage materials. From the viewpoint of electronegativity, we discuss the diverse cohesion and materials science underlying the bonding flexibility of hydrogen in hydrides

  16. Exploring the uranyl organometallic chemistry: from single to double uranium carbon bonds

    International Nuclear Information System (INIS)

    Uranyl organometallic complexes featuring uranium(VI) carbon single and double bonds have been obtained from uranyl UO2X2 precursors by avoiding reduction of the metal center. X-ray diffraction and density functional theory analyses of these complexes showed that the UC and UdC bonds are polarized toward the nucleophilic carbon. (authors)

  17. Statistical theory for hydrogen bonding fluid system of AaDd type (Ⅲ): Equation of state and fluctuations

    Institute of Scientific and Technical Information of China (English)

    WANG HaiJun; GU Fang; HONG XiaoZhong; BA XinWu

    2007-01-01

    The equation of the state of the hydrogen bonding fluid system of AaDd type is studied by the principle of statistical mechanics. The influences of hydrogen bonds on the equation of state of the system are obtained based on the change in volume due to hydrogen bonds. Moreover, the number density fluctuations of both molecules and hydrogen bonds as well as their spatial correlation property are investigated. Furthermore, an equation describing relation between the number density correlation function of "molecules-hydrogen bonds" and that of molecules and hydrogen bonds is derived. As application,taking the van der Waals hydrogen bonding fluid as an example, we considered the effect of hydrogen bonds on its relevant statistical properties.

  18. 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.

  19. Essays on European bond markets

    OpenAIRE

    Cheung, Y.C.

    2005-01-01

    This dissertation focused on a number of issues that are of importance in the current European bond market. In the past years, the fiscal policy of the Eurozone members, advances in the technology of trading platforms and the introduction of a single currency have reshaped the fixed income markets in Europe. These developments have resulted in a far going integration of Eurozone capital markets. Moreover, the massive amounts of debt issued by Japan and the United States combined with the dete...

  20. Functionalization of N2 to NH3 via direct N ≡ N bond cleavage using M(III)(NMe2)3 (M=W/Mo): A theoretical study

    Indian Academy of Sciences (India)

    Sambath Baskaran; Perumal Balu; Chinnappan Sivasankar

    2015-01-01

    Atmospheric N2 can be cleaved directly to yield metal-nitride (before proceeding to the functionalization of N of coordinated N2) and subsequently functionalized to ammonia using M(III)(NMe2)3 (M = W/Mo) as a catalyst, and suitable proton and electron sources. The calculated energies of thermodynamic and kinetic states of the various intermediates and transition states in the reaction coordinate to yield ammonia confirmed the viability of the proposed reaction pathway. Rationale of different pathways have been examined and discussed in detail. Changes in the structural features of the catalyst and some important intermediates and transition states have also been examined.

  1. Bond graph modeling of centrifugal compression systems

    OpenAIRE

    Uddin, Nur; Gravdahl, Jan Tommy

    2015-01-01

    A novel approach to model unsteady fluid dynamics in a compressor network by using a bond graph is presented. The model is intended in particular for compressor control system development. First, we develop a bond graph model of a single compression system. Bond graph modeling offers a different perspective to previous work by modeling the compression system based on energy flow instead of fluid dynamics. Analyzing the bond graph model explains the energy flow during compressor surge. Two pri...

  2. Diversification, original sin, and international bond portfolios

    OpenAIRE

    John D. Burger; Warnock, Francis E.

    2003-01-01

    This paper has two main goals: to analyze country allocations in international bond portfolios and to describe the development of bond markets around the world. In the primary analysis, we find that country weights in U.S. investors' foreign bond portfolios are determined by the openness of capital accounts and potential diversification benefits. Positions in local-currency-denominated bonds are particularly sensitive to past and prospective volatility of returns. Analysis of reallocations in...

  3. Three Essays on Corporate Bond Market Liquidity

    OpenAIRE

    Dick-Nielsen, Jens

    2010-01-01

    The three essays study the US corporate bond market with special attention to bond liquidity. All essays are empirical studies which rely heavily on the availability of transactions data. Earlier studies had to use quoted bond prices for empirical studies, but with the introduction of the TRACE system and with the following dissemination of transaction prices the data quality on corporate bonds has improved immensely. In the years after 2000 a range of studies assessed the p...

  4. European corporate bond liquidity and yield spreads

    OpenAIRE

    Pukka, Juhamatti

    2010-01-01

    PURPOSE OF THE STUDY The purpose of this study is to provide new empirical evidence on European corporate bond liquidity determinants and the liquidity effect on yield spreads. European corporate bond market is mostly ignored in corporate bond liquidity literature and this thesis’ purpose is to contribute to literature by being among the first papers to estimate liquidity determinants with comprehensive European corporate bond data, covering both investment grade and speculative grade rati...

  5. Thermally activated solvent bonding of polymers

    OpenAIRE

    Ng, S H; Tjeung, R. T.; Z. F. Wang; Lu, A. C. W.; Rodriguez, I.; de Rooij, Nicolaas F.

    2010-01-01

    We present a thermally activated solvent bonding technique for the formation of embedded microstructures in polymer. It is based on the temperature dependent solubility of polymer in a liquid that is not a solvent at room temperature. With thermal activation, the liquid is transformed into a solvent of the polymer, creating a bonding capability through segmental or chain interdiffusion at the bonding interface. The technique has advantages over the more commonly used thermal bonding due to it...

  6. The two faces of hydrogen-bond strength on triple AAA-DDD arrays.

    Science.gov (United States)

    Lopez, Alfredo Henrique Duarte; Caramori, Giovanni Finoto; Coimbra, Daniel Fernando; Parreira, Renato Luis Tame; da Silva, Éder Henrique

    2013-12-01

    Systems that are connected through multiple hydrogen bonds are the cornerstone of molecular recognition processes in biology, and they are increasingly being employed in supramolecular chemistry, specifically in molecular self-assembly processes. For this reason, the effects of different substituents (NO2, CN, F, Cl, Br, OCH3 and NH2) on the electronic structure, and consequently on the magnitude of hydrogen bonds in triple AAA-DDD arrays (A=acceptor, D=donor) were evaluated in the light of topological [electron localization function (ELF) and quantum theory of atoms in molecules (QTAIM)], energetic [Su-Li energy-decomposition analysis (EDA) and natural bond orbital analysis (NBO)], and geometrical analysis. The results based on local H-bond descriptors (geometries, QTAIM, ELF, and NBO) indicate that substitutions with electron-withdrawing groups on the AAA module tend to strengthen, whereas electron-donating substituents tend to weaken the covalent character of the AAA-DDD intermolecular H-bonds, and also indicate that the magnitude of the effect is dependent on the position of substitution. In contrast, Su-Li EDA results show an opposite behavior when compared to local H-bond descriptors, indicating that electron-donating substituents tend to increase the magnitude of H-bonds in AAA-DDD arrays, and thus suggesting that the use of local H-bond descriptors describes the nature of H bonds only partially, not providing enough insight about the strength of such H bonds.

  7. Bond strength and stress measurements in thermal barrier coatings

    Energy Technology Data Exchange (ETDEWEB)

    Gell, M.; Jordan, E. [Univ. of Connecticut, Storrs, CT (United States)

    1995-10-01

    Thermal barrier coatings have been used extensively in aircraft gas turbines for more than 15 years to insulate combustors and turbine vanes from the hot gas stream. Plasma sprayed thermal barrier coatings (TBCs) provide metal temperature reductions as much as 300{degrees}F, with improvements in durability of two times or more being achieved. The introduction of TBCs deposited by electron beam physical vapor deposition (EB-PVD) processes in the last five years has provided a major improvement in durability and also enabled TBCs to be applied to turbine blades for improved engine performance. To meet the aggressive Advanced Turbine Systems goals for efficiency, durability and the environment, it will be necessary to employ thermal barrier coatings on turbine airfoils and other hot section components. For The successful application of TBCs to ATS engines with 2600{degrees}F turbine inlet temperatures and required component lives 10 times greater than those for aircraft gas turbine engines, it is necessary to develop quantitative assessment techniques for TBC coating integrity with time and cycles in ATS engines. Thermal barrier coatings in production today consist of a metallic bond coat, such as an MCrAlY overlay coating or a platinum aluminide (Pt-Al) diffusion coating. During heat treatment, both these coatings form a thin, tightly adherent alumina (Al{sub 2}O{sub 3}) film. Failure of TBC coatings in engine service occurs by spallation of the ceramic coating at or near the bond coat to alumina or the alumina to zirconia bonds. Thus, it is the initial strength of these bonds and the stresses at the bond plane, and their changes with engine exposure, that determines coating durability. The purpose of this program is to provide, for the first time, a quantitative assessment of TBC bond strength and bond plane stresses as a function of engine time and cycles.

  8. Nanoparticle/Polymer Nanocomposite Bond Coat or Coating

    Science.gov (United States)

    Miller, Sandi G.

    2011-01-01

    This innovation addresses the problem of coatings (meant to reduce gas permeation) applied to polymer matrix composites spalling off in service due to incompatibility with the polymer matrix. A bond coat/coating has been created that uses chemically functionalized nanoparticles (either clay or graphene) to create a barrier film that bonds well to the matrix resin, and provides an outstanding barrier to gas permeation. There is interest in applying clay nanoparticles as a coating/bond coat to a polymer matrix composite. Often, nanoclays are chemically functionalized with an organic compound intended to facilitate dispersion of the clay in a matrix. That organic modifier generally degrades at the processing temperature of many high-temperature polymers, rendering the clay useless as a nano-additive to high-temperature polymers. However, this innovation includes the use of organic compounds compatible with hightemperature polymer matrix, and is suitable for nanoclay functionalization, the preparation of that clay into a coating/bondcoat for high-temperature polymers, the use of the clay as a coating for composites that do not have a hightemperature requirement, and a comparable approach to the preparation of graphene coatings/bond coats for polymer matrix composites.

  9. Hydrogen Bond Formation between the Carotenoid Canthaxanthin and the Silanol Group on MCM-41 Surface.

    Science.gov (United States)

    Gao, Yunlong; Xu, Dayong; Kispert, Lowell D

    2015-08-20

    The formation of one or two hydrogen bonds (H-bonds) between canthaxanthin (CAN), a dye, and the silanol group(s) on the MCM-41 surface has been studied by density functional theory (DFT) calculations and calorimetric experiments. It was found that the formation of the H-bond(s) stabilized the CAN molecule more than its radical cation (CAN(•+)). The charge distribution, bond lengths, and the HOMO and LUMO energies of CAN are also affected. The formation of the H-bond(s) explains the lower photoinduced electron transfer efficiency of CAN imbedded in Cu-MCM-41 versus that for β-carotene (CAR) imbedded in Cu-MCM-41 where complex formation with Cu(2+) dominates. These calculations show that to achieve high electron transfer efficiency for a dye-sensitized solar cell, H-bonding between the dye and the host should be avoided. PMID:26230844

  10. Implicit Hamiltonian formulation of bond graphs

    NARCIS (Netherlands)

    Golo, G.; Schaft, A.J. van der; Breedveld, P.C.; Maschke, B.M.

    2003-01-01

    This paper deals with mathematical formulation of bond graphs. It is proven that the power continuous part of bond graphs, the junction structure, can be associated with a Dirac structure and that equations describing a bond graph model correspond to an implicit port-controlled Hamiltonian system wi

  11. Low temperature anodic bonding to silicon nitride

    DEFF Research Database (Denmark)

    Weichel, Steen; Reus, Roger De; Bouaidat, Salim;

    2000-01-01

    Low-temperature anodic bonding to stoichiometric silicon nitride surfaces has been performed in the temperature range from 3508C to 4008C. It is shown that the bonding is improved considerably if the nitride surfaces are either oxidized or exposed to an oxygen plasma prior to the bonding. Both bulk...

  12. 25 CFR 214.4 - Bonds.

    Science.gov (United States)

    2010-04-01

    ... 25 Indians 1 2010-04-01 2010-04-01 false Bonds. 214.4 Section 214.4 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR ENERGY AND MINERALS LEASING OF OSAGE RESERVATION LANDS, OKLAHOMA, FOR... reserved to change the amount of the bond in any particular case, or to require a new bond in...

  13. Sensor/ROIC Integration using Oxide Bonding

    OpenAIRE

    Ye, Zhenyu; Group, for the Fermilab Pixel R&D

    2009-01-01

    We explore the Ziptronix Direct Bond Interconnect technology for the integration of sensors and readout integrated circuits (ROICs) for high energy physics. The technology utilizes an oxide bond to form a robust mechanical connection between layers which serves to assist with the formation of metallic interlayer connections. We report on testing results of sample sensors bonded to ROICs and thinned to 100 microns.

  14. Hydroxide catalysis bonding of silicon carbide

    NARCIS (Netherlands)

    Veggel, A.A. van; Ende, D.A. van den; Bogenstahl, J.; Rowan, S.; Cunningham, W.; Gubbels, G.H.M.; Nijmeijer, H.

    2008-01-01

    For bonding silicon carbide optics, which require extreme stability, hydroxide catalysis bonding is considered [Rowan, S., Hough, J. and Elliffe, E., Silicon carbide bonding. UK Patent 040 7953.9, 2004. Please contact Mr. D. Whiteford for further information: D.Whiteford@admin.gla.ac.uk]. This techn

  15. Dynamical Crossover in Hot Dense Water: The Hydrogen Bond Role.

    Science.gov (United States)

    Ranieri, Umbertoluca; Giura, Paola; Gorelli, Federico A; Santoro, Mario; Klotz, Stefan; Gillet, Philippe; Paolasini, Luigi; Koza, Michael Marek; Bove, Livia E

    2016-09-01

    We investigate the terahertz dynamics of liquid H2O as a function of pressure along the 450 K isotherm, by coupled quasielastic neutron scattering and inelastic X-ray scattering experiments. The pressure dependence of the single-molecule dynamics is anomalous in terms of both microscopic translation and rotation. In particular, the Stokes-Einstein-Debye equations are shown to be violated in hot water compressed to the GPa regime. The dynamics of the hydrogen bond network is only weakly affected by the pressure variation. The time scale of the structural relaxation driving the collective dynamics increases by a mere factor of 2 along the investigated isotherm, and the structural relaxation strength turns out to be almost pressure independent. Our results point at the persistence of the hydrogen bond network in hot dense water up to ice VII crystallization, thus questioning the long-standing perception that hydrogen bonds are broken in liquid water under the effect of compression. PMID:27479235

  16. 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.

  17. Disulfide bond formation in prokaryotes: history, diversity and design.

    Science.gov (United States)

    Hatahet, Feras; Boyd, Dana; Beckwith, Jon

    2014-08-01

    The formation of structural disulfide bonds is essential for the function and stability of a great number of proteins, particularly those that are secreted. There exists a variety of dedicated cellular catalysts and pathways from archaea to humans that ensure the formation of native disulfide bonds. In this review we describe the initial discoveries of these pathways and report progress in recent years in our understanding of the diversity of these pathways in prokaryotes, including those newly discovered in some archaea. We will also discuss the various successful efforts to achieve laboratory-based evolution and design of synthetic disulfide bond formation machineries in the bacterium Escherichia coli. These latter studies have also led to new more general insights into the redox environment of the cytoplasm and bacterial cell envelope. This article is part of a Special Issue entitled: Thiol-Based Redox Processes.

  18. Diffusion bonding resistant valve development for sodium service

    International Nuclear Information System (INIS)

    Unanticipated functional failures occurred in valves undergoing containment integrity testing for liquid sodium service. The failures resulted from diffusion bonding of the Stellite 6B valve plug to the Type 316 stainless steel (SS) seat. As a result of these failures, a valve development program was undertaken. A modified valve incorporating a Tribaloy 800 plug showed significant improvement in resistance to diffusion bonding but still failed after long term exposure in a closed position. A second modified valve using Tribaloy 800 in both the valve plug and seat successfully resisted diffusion bonding failure. This paper reports the details of the testing and posttest valve examinations. The results of scanning electron microscopy, dispersive x-ray spectrometry, and metallography provide the characteristics of the valve failures. Limitations of the various valve designs are also discussed

  19. Effect of coordination on bond properties: A first principles study

    Indian Academy of Sciences (India)

    Jaita Paul; Shobhana Narasimhan

    2008-06-01

    We have used density functional theory to obtain the binding curves for a variety of hypothetical periodic structures of Al, Si, Pb, Sn and Au. Upon examining the resulting database of results for equilibrium bond lengths and radial force constants (within a nearest-neighbour model), we find that both decrease smoothly as coordination is reduced. The effect of dimensionality appears to be small. We find that the force constants at equilibrium vary as the inverse eighth power of the equilibrium bond length. We also find evidence that the force constants are sensitive only to the bond length, and not to the coordination number. We believe these results will be useful in formulating interatomic potentials, e.g., for nanosystems.

  20. A facile route for irreversible bonding of plastic-PDMS hybrid microdevices at room temperature.

    Science.gov (United States)

    Tang, Linzhi; Lee, Nae Yoon

    2010-05-21

    Plastic materials do not generally form irreversible bonds with poly(dimethylsiloxane) (PDMS) regardless of oxygen plasma treatment and a subsequent thermal process. In this paper, we perform plastic-PDMS bonding at room temperature, mediated by the formation of a chemically robust amine-epoxy bond at the interfaces. Various plastic materials, such as poly(methylmethacrylate) (PMMA), polycarbonate (PC), polyimide (PI), and poly(ethylene terephthalate) (PET) were adopted as choices for plastic materials. Irrespective of the plastic materials used, the surfaces were successfully modified with amine and epoxy functionalities, confirmed by the surface characterizations such as water contact angle measurements and X-ray photoelectron spectroscopy (XPS), and chemically robust and irreversible bonding was successfully achieved within 1 h at room temperature. The bonding strengths of PDMS with PMMA and PC sheets were measured to be 180 and 178 kPa, respectively, and their assemblies containing microchannel structures endured up to 74 and 84 psi (510 and 579 kPa) of introduced compressed air, respectively, without destroying the microdevices, representing a robust and highly stable interfacial bonding. In addition to microchannel-molded PDMS bonded with flat plastic substrates, microchannel-embossed plastics were also bonded with a flat PDMS sheet, and both types of bonded assemblies displayed sufficiently robust bonding, tolerating an intense influx of liquid whose per-minute injection volume was nearly 1000 to 2000 times higher than the total internal volume of the microchannel used. In addition to observing the bonding performance, we also investigated the potential of surface amine and epoxy functionalities as durable chemical adhesives by observing their storage-time-dependent bonding performances. PMID:20445880

  1. Hydrogen bonds in concreto and in computro

    Science.gov (United States)

    Stouten, Pieter F. W.; Kroon, Jan

    1988-07-01

    Molecular dynamics simulations of liquid water and liquid methanol have been carried out. For both liquids an effective pair potential was used. The models were fitted to the heat of vaporization, pressure and various radial distribution functions resulting from diffraction experiments on liquids. In both simulations 216 molecules were put in a cubic periodical ☐. The system was loosely coupled to a temperature bath and to a pressure bath. Following an initial equilibration period relevant data were sampled during 15 ps. The distributions of oxygen—oxygen distances in hydrogen bonds obtained from the two simulations are essentially the same. The distribution obtained from crystal data is somewhat different: the maximum has about the same position, but the curve is much narrower, which can be expected merely from the fact that diffraction experiments only supply average atomic positions and hence average interatomic distances. When thermal motion is taken into account a closer likeness is observed.

  2. Main Chain Noncentrosymmetric Hydrogen Bonded Macromolecules Incorporating Aniline, Alkanol, and Alkanoic Acid Hydrogen Bond Donors

    OpenAIRE

    Jeremy R. Wolf

    2014-01-01

    The syntheses and characterization of three noncentrosymmetric main chain hydrogen bonded macromolecules which incorporate aniline, alkanoic acid, and alkanol hydrogen bond donor units are reported. These macromolecules participate in weak intermolecular hydrogen bonding as demonstrated using attenuated total reflectance (ATR) FTIR. The phase transitions of these macromolecules depend on the identity of the hydrogen bond donor.

  3. 19 CFR 125.32 - Merchandise delivered to a bonded store or bonded warehouse.

    Science.gov (United States)

    2010-04-01

    ... warehouse. 125.32 Section 125.32 Customs Duties U.S. CUSTOMS AND BORDER PROTECTION, DEPARTMENT OF HOMELAND... Merchandise delivered to a bonded store or bonded warehouse. When merchandise is carried, carted or lightered to and received in a bonded store or bonded warehouse, the proprietor or his representative...

  4. Fracturing Behavior of Direct Bonded Ti with Mg Alloys by Solid State Bonding

    OpenAIRE

    Pripanapong, Patchara; Takahashi, Makoto; Umeda, Junko; Kondoh, Katsuyoshi

    2014-01-01

    Ti and Mg alloys (AZ61, AZ80 and AZ91) were directly bonded together by state bonding method in vacuum. These two materials appeared to be bonded well together although there was no intermetallic compound between Ti and Mg. Al element existing in Mg alloys seems to be an important factor involved in the bonding mechanism. The high bonding efficiency as 86% obtained from Ti bonded with AZ91 at 400 ℃ for 1 hr by applying 40 MPa was guaranteed in the successful bonding.

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

    DEFF Research Database (Denmark)

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

    2010-01-01

    of the mixed phase at metal surfaces. The surface bonding can be considered to be similar to accepting a hydrogen bond, and we can thereby apply general cooperativity rules developed for hydrogen-bonded systems. This provides a simple understanding of why water molecules become more strongly bonded...... to the surface upon hydrogen bonding to OH and why the OH surface bonding is instead weakened through hydrogen bonding to water. We extend the application of this simple model to other observed cooperativity effects for pure water adsorption systems and H3O+ on metal surfaces....

  6. Effect of diamond bur cutting efficacy on dentin bond strengths of different bonding systems

    Directory of Open Access Journals (Sweden)

    Shirani F.

    2009-03-01

    Full Text Available "nBackground and Aim: As composite-dentin bond strength is affected by cavity preparation and the bond strength of composite resin to new and used bur prepared dentin has not yet been evaluated, this study evaluated the effects of cutting dentin with different cutting efficacy (new and used of burs on composite-dentin shear bond strength using self-etching primer bonding system and total etching bonding system. "nMaterials and Methods: Sixty caries free human 3rd molar were sectioned in occlosal surface to expose dentin, then polished with silicon carbide paper and randomly divided into four groups. Each group was prepared in a depth of 0.5mm of dentin, using new diamond bur, or used diamond bur. To change into a used bur, each new rough diamond bur had to work on bovine enamel for 30 minutes, under a load of 150g. Then, each group was bonded, using a total etch adhesive (single Bond or a self etch adhesive (clearfil SE Bond So there were 4 groups : 1-SE Bond, New bur; 2-SE Bond , used bur; 3-Single Bond , New bur ; 4-Single Bond, used bur. Similar composite capsules(Filtek Z250 were bonded to dentin surface and cured. specimens were stored in physiologic saline for 48h at 370 c , then put under shearing load to define composite - dentin shear bond strength. Results were interpreted via statistical analysis (T-test & two - way variance. "nResults: Shear bond strength of each group was as follows: 1-(27.3Mpa, 2-(33.5Mpa, 3-(16.9Mpa 4-(19.3Mpa. Statistical analysis proved that shear bond strength of used diamond bur prepared groups (2,4 was more than new diamond bur prepared ones (1,3. This statistical difference, specially, was seen between SE Bond groups (1,2 but not between single Bond groups (3,4. Also, shear bond strength of (SE Bond bonded groups (1,2 were more significantly than (single Bond bonded ones (3,4. "nConclusion: This study show that Bur cutting efficiency influences composite - dentin shear bond strength especially when the

  7. Valuing Convertible Bonds Based on LSRQM Method

    Directory of Open Access Journals (Sweden)

    Jian Liu

    2014-01-01

    Full Text Available Convertible bonds are one of the essential financial products for corporate finance, while the pricing theory is the key problem to the theoretical research of convertible bonds. This paper demonstrates how to price convertible bonds with call and put provisions using Least-Squares Randomized Quasi-Monte Carlo (LSRQM method. We consider the financial market with stochastic interest rates and credit risk and present a detailed description on calculating steps of convertible bonds value. The empirical results show that the model fits well the market prices of convertible bonds in China’s market and the LSRQM method is effective.

  8. Copper Wire Bonding Concerns and Best Practices

    Science.gov (United States)

    Chauhan, Preeti; Zhong, Z. W.; Pecht, Michael

    2013-08-01

    Copper wire bonding of microelectronic parts has developed as a means to cut the costs of using the more mature technology of gold wire bonding. However, with this new technology, changes in the bonding processes as well as bonding metallurgy can affect product reliability. This paper discusses the challenges associated with copper wire bonding and the solutions that the industry has been implementing. The paper also provides information to enable customers to conduct qualification and reliability tests on microelectronic packages to facilitate adoption in their target applications.

  9. Minimization of Basis Risk in Parametric Earthquake Cat Bonds

    Science.gov (United States)

    Franco, G.

    2009-12-01

    A catastrophe -cat- bond is an instrument used by insurance and reinsurance companies, by governments or by groups of nations to cede catastrophic risk to the financial markets, which are capable of supplying cover for highly destructive events, surpassing the typical capacity of traditional reinsurance contracts. Parametric cat bonds, a specific type of cat bonds, use trigger mechanisms or indices that depend on physical event parameters published by respected third parties in order to determine whether a part or the entire bond principal is to be paid for a certain event. First generation cat bonds, or cat-in-a-box bonds, display a trigger mechanism that consists of a set of geographic zones in which certain conditions need to be met by an earthquake’s magnitude and depth in order to trigger payment of the bond principal. Second generation cat bonds use an index formulation that typically consists of a sum of products of a set of weights by a polynomial function of the ground motion variables reported by a geographically distributed seismic network. These instruments are especially appealing to developing countries with incipient insurance industries wishing to cede catastrophic losses to the financial markets because the payment trigger mechanism is transparent and does not involve the parties ceding or accepting the risk, significantly reducing moral hazard. In order to be successful in the market, however, parametric cat bonds have typically been required to specify relatively simple trigger conditions. The consequence of such simplifications is the increase of basis risk. This risk represents the possibility that the trigger mechanism fails to accurately capture the actual losses of a catastrophic event, namely that it does not trigger for a highly destructive event or vice versa, that a payment of the bond principal is caused by an event that produced insignificant losses. The first case disfavors the sponsor who was seeking cover for its losses while the

  10. LETTER TO THE EDITOR: Electronic structure and bonding properties in layered ternary carbide Ti3SiC2

    Science.gov (United States)

    Zhou, Yanchun; Sun, Zhimei

    2000-07-01

    Ab initio calculations based on the density-functional pseudopotential approach have been used to study the electronic structure and chemical bonding in layered machinable Ti3SiC2 ceramic. The calculations reveal that all three types of bonding - metallic, covalent and ionic - contribute to the bonding in Ti3SiC2. The high electric conductivity is attributed to the metallic bonding parallel to the basal plane and the high modulus and high melting point are attributed to the strong Ti-C-Ti-C-Ti covalent bond chains in the structure.

  11. Flip-chip bonding of vertical-cavity surface-emitting lasers using laser-induced forward transfer

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, K. S., E-mail: Kaur.Kamalpreet@elis.ugent.be; Missinne, J.; Van Steenberge, G. [Centre for Microsystems Technology, imec/Ghent University, Technologiepark 914A, B-9052 Gent (Belgium)

    2014-02-10

    This letter reports the use of the Laser-Induced Forward Transfer (LIFT) technique for the fabrication of indium micro-bumps for the flip-chip (FC) bonding of single vertical-cavity surface-emitting laser chips. The FC bonded chips were electrically and optically characterized, and the successful functioning of the devices post-bonding is demonstrated. The die shear and life-time tests carried out on the bonded chips confirmed the mechanical reliability of the LIFT-assisted FC bonded assemblies.

  12. Electronic, optical and bonding properties of MgCO 3

    Science.gov (United States)

    Hossain, Faruque M.; Dlugogorski, B. Z.; Kennedy, E. M.; Belova, I. V.; Murch, Graeme E.

    2010-05-01

    The electronic, optical and bonding properties of MgCO 3 (magnesite, rhombohedral calcite-type structure) are calculated using a first-principles density-functional theory (DFT) method considering the exchange-correlation function within the local density approximation (LDA) and the generalized gradient approximation (GGA). The indirect band gap of magnesite is estimated to be 5.0 eV, which is underestimated by ˜1.0 eV. The fundamental absorption edge, which indicates the exact optical transitions from occupied valence bands to the unoccupied conduction band, is estimated by calculating the photon energy dependent imaginary part of the dielectric function using scissors approximations (rigid shift of unoccupied bands). The optical properties show consistent results with the experimental calcite-type structure and also show a considerable optical anisotropy of the magnesite structure. The density of states and Mulliken population analyses reveal the bonding nature between the atoms.

  13. Quantitative bond energetics in atomic-scale junctions with significant van der Waals character

    Science.gov (United States)

    Venkataraman, Latha; Aradhya, Sriharsha; Hybertsen, Mark

    2015-03-01

    A direct measurement of the potential energy surface that characterizes individual chemical bonds in complex materials has fundamental significance for many disciplines. Here, we demonstrate that the energy profile for metallic single-atom contacts and single-molecule junctions can be mapped by fitting ambient atomic force microscope measurements carried out in the near-equilibrium regime to a physical, but simple, functional form. In particular we are able to extract bond energies for metal-molecule link bonds in cases where the interaction has significant contribution from nonspecific interactions attributed to van der Waals (vdW) interactions at short length scale in addition to specific donor-acceptor bonds. Our approach significantly expands the quantitative information extracted from these measurements, allowing direct comparisons to density functional theory (DFT) calculations instead of relying on trends in bond rupture forces alone. Currently at Cornell University.

  14. Surface-Controlled Mono/Diselective ortho C-H Bond Activation.

    Science.gov (United States)

    Li, Qing; Yang, Biao; Lin, Haiping; Aghdassi, Nabi; Miao, Kangjian; Zhang, Junjie; Zhang, Haiming; Li, Youyong; Duhm, Steffen; Fan, Jian; Chi, Lifeng

    2016-03-01

    One of the most charming and challenging topics in organic chemistry is the selective C-H bond activation. The difficulty arises not only from the relatively large bond-dissociation enthalpy, but also from the poor reaction selectivity. In this work, Au(111) and Ag(111) surfaces were used to address ortho C-H functionalization and ortho-ortho couplings of phenol derivatives. More importantly, the competition between dehydrogenation and deoxygenation drove the diversity of reaction pathways of phenols on surfaces, that is, diselective ortho C-H bond activation on Au(111) surfaces and monoselective ortho C-H bond activation on Ag(111) surfaces. The mechanism of this unprecedented phenomenon was extensively explored by scanning tunneling microscopy, density function theory, and X-ray photoelectron spectroscopy. Our findings provide new pathways for surface-assisted organic synthesis via the mono/diselective C-H bond activation. PMID:26853936

  15. Bonding PMMA microfluidics using commercial microwave ovens

    International Nuclear Information System (INIS)

    In this paper, a novel low-cost, rapid substrate-bonding technique is successfully applied to polymethyl methacrylate (PMMA) microfluidics bonding for the first time. This technique uses a thin intermediate metallic microwave susceptor layer at the interface of the bonding site (microchannels) which produces localized heating required for bonding during microwave irradiation. The metallic susceptor pattern is designed using a multiphysics simulation model developed in ANSYS Multiphysics software (high-frequency structural simulation (HFSS) coupled with ANSYS-Thermal). In our experiments, the required microwave energy for bonding is delivered using a relatively inexpensive, widely accessible commercial microwave oven. Using this technique, simple PMMA microfluidics prototypes are successfully bonded and sealed in less than 35 seconds with a minimum measured bond strength of 1.375 MPa. (paper)

  16. Liquidity in Government versus Covered Bond Markets

    DEFF Research Database (Denmark)

    Dick-Nielsen, Jens; Gyntelberg, Jacob; Sangill, Thomas

    2011. Overall, our findings suggest that Danish benchmark covered bonds by and large are as liquid as Danish government bonds - including in periods of market stress. Before the financial crisis of 2008, government bonds were slightly more liquid than covered bonds. During the crisis, trading continued......We present findings on the secondary market liquidity of government and covered bonds in Denmark before, during and after the 2008 financial crisis. The analysis focuses on wholesale trading in the two markets and is based on a complete transaction level dataset covering November 2007 until end...... in both markets but the government bond market experienced a brief but pronounced decline in market liquidity while liquidity in the covered bond market was more robust - partly reflective of a number of events as well as policy measures introduced in the autumn of 2008. After the crisis, liquidity...

  17. Bonding in ZnSb

    DEFF Research Database (Denmark)

    Bjerg, Lasse; Madsen, Georg K. H.; Iversen, Bo Brummerstedt

    Thermoelectric materials are capable of converting waste heat into usable electric energy. The conversion efficiency depends critically on the electronic band structure. Theoretical calculations predict the semiconducting ZnSb to have a promising efficiency if it is n-doped. The details...... of the lowest conduction band have therefore been investigated. Electrons placed in the lowest conduction band are predicted to increase the bonding between second nearest neighbour atoms. This causes a lowering of the energy at special points in the first Brillouin zone. Thereby, the dispersion of the lowest...

  18. Bonds and bands in semiconductors

    CERN Document Server

    Phillips, Jim

    2009-01-01

    This classic work on the basic chemistry and solid state physics of semiconducting materials is now updated and improved with new chapters on crystalline and amorphous semiconductors. Written by two of the world's pioneering materials scientists in the development of semiconductors, this work offers in a single-volume an authoritative treatment for the learning and understanding of what makes perhaps the world's most important engineered materials actually work. Readers will find: --' The essential principles of chemical bonding, electron energy bands and their relationship to conductive and s

  19. Actor bonds after relationship dissolution

    DEFF Research Database (Denmark)

    Skaates, Maria Anne

    2000-01-01

    Most of the presented papers at the 1st NoRD Workshop can be classified as belonging to the business marketing approach to relationship dissolution. Two papers were conceptual, and the remaining six were empirical studies. The first conceptual study by Skaates (2000) focuses on the nature of the ...... actor bonds that remain after a business relationship has ended. The study suggests that an interdisciplinary approach would provide a richer understanding of the phenomenon; this could be achieved by using e.g. Bourdieu's sociological concepts in dissolution research....

  20. Bump bonding of pixel systems

    CERN Document Server

    Lozano, M; Collado, A; Santander, J; Ullán, M

    2001-01-01

    A pixel detector consists of an array of radiation sensing elements which is connected to an electronic read-out unit. Many different ways of making this connection between these two different devices are currently being used or considered to be used in the next future. Bonding techniques such as flip chip technology can present real advantages because they allow very fine pitch and a high number of I/Os. This paper presents a review of the different flip chip technologies available and their suitability for manufacturing pixel detectors. The particular problems concerning testing of pixel detectors and thermal issues related to them are pointed out.

  1. Bump bonding of pixel systems

    Energy Technology Data Exchange (ETDEWEB)

    Lozano, M. E-mail: manuel.lozano@cnm.es; Cabruja, E.; Collado, A.; Santander, J.; Ullan, M

    2001-11-01

    A pixel detector consists of an array of radiation sensing elements which is connected to an electronic read-out unit. Many different ways of making this connection between these two different devices are currently being used or considered to be used in the next future. Bonding techniques such as flip chip technology can present real advantages because they allow very fine pitch and a high number of I/Os. This paper presents a review of the different flip chip technologies available and their suitability for manufacturing pixel detectors. The particular problems concerning testing of pixel detectors and thermal issues related to them are pointed out.

  2. Bonds futures: Delta? No gamma!

    OpenAIRE

    Henrard, Marc

    2006-01-01

    Bond futures are liquid but complex instruments. Here they are analysed in a one-factor Gaussian HJM model. The in-the-model delta and out-of-the-model delta and gamma are studied. An explicit formula is provided for in-the-model delta. The out-of-the-model delta and gamma are equivalent to partial derivatives with respect to discount factors. In particular cases the derivative can not be obtained by standard techniques. The same situations lead to cases where the gammas (second order partial...

  3. Consistent descriptions of metal–ligand bonds and spin-crossover in inorganic chemistry

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2013-01-01

    Density functional theory (DFT) is today the unchallenged tool for routinely obtaining molecular information on chemical stability, reactivity, and electronic structure across the Periodic Table. The chemical bond is the fundamental unit of molecular structure and reactivity, and thus, large...

  4. 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

  5. Process Simulation of Resistance Weld Bonding and Automotive Light-weight Materials

    DEFF Research Database (Denmark)

    Zhang, Wenqi; Chergui, Azeddine; Nielsen, Chris Valentin

    This paper presents the latest developments in numerical simulation of resistance welding especially with the new functions for simulation of microstructures, weld bonding and spot welding of new light-weight materials. The fundamental functions in SORPAS® are built on coupled modeling...... and predicting welding process window, for weld planning with optimal welding parameter settings, and for modeling microstructures and hardness distribution after welding. Latest developments have been made on simulation of resistance welding with nonconductive materials for applications in weld bonding...

  6. Confinement effects on the steel-concrete bond strength and pull-out failure

    International Nuclear Information System (INIS)

    In this contribution, an experimental campaign based on unconfined and actively confined pull-out tests is presented to investigate the bond stress-slip behavior. This campaign aims at underlining passive (concrete cover) and active (external pressure) confinement effects on the maximal bond stress. Experimental results are associated to a numerical approach in order to predict the evolution of the bond strength. Equations are finally proposed that distinguish splitting failure (function of the concrete tensile properties) and pull-out failure (function of the compressive concrete properties). (authors)

  7. Contribution of Hydrogen Bonds to Protein Stability

    Science.gov (United States)

    Pace, Nick

    2014-03-01

    I will discuss the contribution of the burial of polar groups and their hydrogen bonds to the conformational stability of proteins. We measured the change in stability, Δ(Δ G), for a series of hydrogen bonding mutants in four proteins: villin head piece subdomain (VHP) containing 36 residues, a surface protein from Borrelia burgdorferi (VlsE) containing 341 residues, and two proteins previously studied in our laboratory, ribonucleases Sa (RNase Sa) and T1 (RNase T1). Crystal structures were determined for three of the hydrogen bonding mutants of RNase Sa: S24A (1.1Å), Y51F(1.5Å), and T95A(1.3Å). The structures are very similar to wild type RNase Sa and the hydrogen bonding partners always form intermolecular hydrogen bonds to water in the mutants. We compare our results with previous studies of similar mutants in other proteins and reach the following conclusions: 1) Hydrogen bonds contribute favorably to protein stability. 2) The contribution of hydrogen bonds to protein stability is strongly context dependent. 3) Hydrogen bonds by side chains and peptide groups make similar contributions to protein stability. 4) Polar group burial can make a favorable contribution to protein stability even if the polar groups are not hydrogen bonded. 5) The contribution of hydrogen bonds to protein stability is similar for VHP, a small protein, and VlsE, a large protein.

  8. MICROSTRUCTURE CHARACTERISTICS AT THE BOND INTERFACE

    Institute of Scientific and Technical Information of China (English)

    Li Junhui; Han Lei; Zhong Jue

    2005-01-01

    Lift-off and section characteristics at the interface of thermosonic bond are observed by using scanning electron microscope (KYKY2800) with EDS-test. Results show that the peeling underdeveloped bonds simulate a torus (or doughnut) with an unbonded central region and ridged peripheral region is bonded hardly. Inside roundness at flip chip bonding center are discovered. Bond strength is located between the severely ridged periphery and the non-adhering central area of the bond. For constant force and time, the ridged area of the bond pattern increases when more power is applied. For constant force and power, the ridged location of the bonded region moves closer to the bond center with time. Results of EDS-tests at Au-Al and Au-Ag interfaces show that Kirkendall diffusibility at Au-Ag interface occur and the diffusing speed of Au-atomic is faster than that of Ag,and that intermetallic compounds at Au-A1 interface is generated possibly. And these would be helpful for further research about thermosonic bonding.

  9. 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.

  10. Study of 6- cyclic -perimeter hydrocarbon ruthenium complexes bearing functionalized pyridyl diketones: Isolation of complexes with 2-N∩O and 4-N∩O bonding modes of ligands

    Indian Academy of Sciences (India)

    Saphidabha L Nongbri; Babulal Das; Mohan Rao Kollipara

    2012-11-01

    Chelating mono- and di-pyridyl functionalized -diketones, viz. 1-phenyl-3-(2-pyridyl) propane-1,3-dione (pppdH) and 1,3-di(2-pyridyl)propane-1,3-dione (dppdH) ligands yielded new water soluble 6-arene ruthenium(II) complexes of the formulation [(6-arene)Ru(2-N-O-pppdH)Cl]+ (arene = C6H6 1, pPrC6H4Me 2, C6Me6 3) and [(6-arene)2Ru2(4-N-O-dppd)Cl2]+ (arene = C6H6 4, -PrC6H4Me 5, C6Me6 6), as their (complexes 1-4, 6) PF6 salt or (complex 5) BF4 salt. The complexes were obtained by treatment of respective precursors, [(6-arene)Ru(-Cl)Cl]2 (arene = C6H6, -PrC6H4Me, C6Me6) in 1:2 and 1:1 molar ratio with pppdH and dppdH in the presence of NH4PF6/NH4BF4. All the complexes have been characterized on the basis of FT-IR and NMR spectroscopic data as well as by elemental analysis. Molecular structures of representative complexes 2, 5 and 6 have been confirmed by single crystal X-ray diffraction studies. The `O-C-C-C-O' fragment of the coordinated ligand (pppdH) is neutral in complexes 1-3 and that of the dppdH ligand existed as a neutral as well as concomitantly uninegative fashion in complexes 4-6 due to the delocalization of -electrons.

  11. The Nature of the Hydrogen Bond Outline of a Comprehensive Hydrogen Bond Theory

    CERN Document Server

    Gilli, Gastone

    2009-01-01

    Hydrogen bond (H-bond) effects are known: it makes sea water liquid, joins cellulose microfibrils in trees, shapes DNA into genes and polypeptide chains into wool, hair, muscles or enzymes. Its true nature is less known and we may still wonder why O-H...O bond energies range from less than 1 to more than 30 kcal/mol without apparent reason. This H-bond puzzle is re-examined here from its very beginning and presented as an inclusive compilation of experimental H-bond energies andgeometries.New concepts emerge from this analysis: new classes of systematically strong H-bonds (CAHBs and RAHBs: cha

  12. Imaging Hydrogen Bond in Real Space

    CERN Document Server

    Chen, Xiu; Liu, Lacheng; Liu, Xiaoqing; Cai, Yingxing; Liu, Nianhua; Wang, Li

    2013-01-01

    Hydrogen bond is often assumed to be a purely electrostatic interaction between a electron-deficient hydrogen atom and a region of high electron density. Here, for the first time, we directly image hydrogen bond in real space by room-temperature scanning tunneling microscopy (STM) with the assistance of resonant tunneling effect in double barrier mode. STM observations demonstrate that the C=O:HO hydrogen bonds lifted several angstrom meters above metal surfaces appear shuttle-like features with a significant contrast along the direction connected the oxygen and hydrogen atoms of a single hydrogen bond. The off-center location of the summit and the variance of the appearance height for the hydrogen bond with scanning bias reveal that there are certain hybridizations between the electron orbitals of the involved oxygen and hydrogen atoms in the C=O:HO hydrogen bond.

  13. Influence of hydrogen bonds and temperature on dielectric properties.

    Science.gov (United States)

    Ortiz de Urbina, Jordi; Sesé, Gemma

    2016-07-01

    Dielectric properties are evaluated by means of molecular dynamics simulations on two model systems made up of dipolar molecules. One of them mimics methanol, whereas the other differs from the former only in the ability to form hydrogen bonds. Static dielectric properties such as the permittivity and the Kirkwood factor are evaluated, and results are analyzed by considering the distribution of relative orientations between molecular dipoles. Dipole moment-time correlation functions are also evaluated. The relevance of contributions associated with autocorrelations of molecular dipoles and with cross-correlations between dipoles belonging to different molecules has been investigated. For methanol, the Debye approximation for the overall dipole moment correlation function is not valid at room temperature. The model applies when hydrogen bonds are suppressed, but it fails upon cooling the nonassociated liquid. Important differences between relaxation times associated with dipole auto- versus cross-correlations as well as their relative relevance are at the root of the Debye model breakdown. PMID:27575177

  14. Influence of hydrogen bonds and temperature on dielectric properties

    Science.gov (United States)

    Ortiz de Urbina, Jordi; Sesé, Gemma

    2016-07-01

    Dielectric properties are evaluated by means of molecular dynamics simulations on two model systems made up of dipolar molecules. One of them mimics methanol, whereas the other differs from the former only in the ability to form hydrogen bonds. Static dielectric properties such as the permittivity and the Kirkwood factor are evaluated, and results are analyzed by considering the distribution of relative orientations between molecular dipoles. Dipole moment-time correlation functions are also evaluated. The relevance of contributions associated with autocorrelations of molecular dipoles and with cross-correlations between dipoles belonging to different molecules has been investigated. For methanol, the Debye approximation for the overall dipole moment correlation function is not valid at room temperature. The model applies when hydrogen bonds are suppressed, but it fails upon cooling the nonassociated liquid. Important differences between relaxation times associated with dipole auto- versus cross-correlations as well as their relative relevance are at the root of the Debye model breakdown.

  15. Valuing Catastrophe Bonds Involving Credit Risks

    OpenAIRE

    Jian Liu; Jihong Xiao; Lizhao Yan; Fenghua Wen

    2014-01-01

    Catastrophe bonds are the most important products in catastrophe risk securitization market. For the operating mechanism, CAT bonds may have a credit risk, so in this paper we consider the influence of the credit risk on CAT bonds pricing that is different from the other literature. We employ the Jarrow and Turnbull method to model the credit risks and get access to the general pricing formula using the Extreme Value Theory. Furthermore, we present an empirical pricing study of the Property C...

  16. The Development of James Bond Through Time

    OpenAIRE

    Thorsen, Pernille Groth; Dreyer, Maria; Stepputat, Frida; Minssieux, Nelly

    2012-01-01

    Our main focus in the project is finding out how James Bond has changed through time and culture, while also investigating what an audience finds appealing in a character on screen. We have analyzed the character of James Bond using the method of characterization along with Anthony Giddens’ theory of globalization in order to prove the change in character we believe there is. We will discuss if and why an audience finds the character of James Bond appealing by using Identification and the ...

  17. Sunspots and Inflation-indexed Bonds

    OpenAIRE

    Minwook KANG

    2014-01-01

    An economy with incomplete ?nancial markets, as described by Cass (1989), typically has in?ation volatility driven by sunspots. The purpose of this paper is to investigate how the introduction of in?ation- indexed bonds to the ?Cass?economy in?uences a monetary market, an indexed bond market, and welfare. The introduction of indexed bonds is considered a sunspot-stabilizing policy. However, this introduction unrealistically causes the complete shutdown of monetary markets. This problem can be...

  18. Liquidity Issues in Indian Sovereign Bond Market

    OpenAIRE

    Nath, Golaka

    2013-01-01

    Liquidity is one of the most important factors after credit risk that affects the bond yields. The paper uses various measures of liquidity to understand their determinants in Indian sovereign bond market. The Liquidity measured by parameters like Turnover Ratio and Amihud Illiquidity Indicator show that these parameters not only have instantaneous relationship with bond yield but contemporaneous relationship with themselves. Impact Cost is not found to have any explanatory power. Financial c...

  19. Sensor/ROIC Integration using Oxide Bonding

    International Nuclear Information System (INIS)

    We explore the Ziptronix Direct Bond Interconnect (DBI) technology (2) for the integration of sensors and readout integrated circuits (ROICs) for high energy physics. The technology utilizes an oxide bond to form a robust mechanical connection between layers which serves to assist with the formation of metallic interlayer connections. We report on testing results of sample sensors bonded to ROICs and thinned to 100 (micro)m

  20. Sensor/ROIC Integration using Oxide Bonding

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Zhenyu; /Fermilab

    2009-02-01

    We explore the Ziptronix Direct Bond Interconnect (DBI) technology [2] for the integration of sensors and readout integrated circuits (ROICs) for high energy physics. The technology utilizes an oxide bond to form a robust mechanical connection between layers which serves to assist with the formation of metallic interlayer connections. We report on testing results of sample sensors bonded to ROICs and thinned to 100 {micro}m.

  1. Aspects of solvents in dentine bonding

    OpenAIRE

    Ekambaram, Manikandan

    2015-01-01

    Degradation starts at the resin-dentine bonded interfaces within a few months’ of bonding. There are two major causes of degradation of the bonded interfaces over time. The simplified dental adhesives that are routinely used in the contemporary clinical dental practice are extremely hydrophilic and are prone to water sorption, leading to hydrolytic degradation. Dentine matrix-bound metalloproteinases (MMPs) and cysteine cathepsins (CCs) are proteolytic enzymes that have been shown to degrade ...

  2. Bond percolation on isoradial graphs

    CERN Document Server

    Grimmett, Geoffrey

    2012-01-01

    In an investigation of percolation on isoradial graphs, we prove the criticality of canonical bond percolation on isoradial embeddings of planar graphs, thus extending celebrated earlier results for homogeneous and inhomogeneous square, triangular, and other lattices. This is achieved via the star-triangle transformation, by transporting the box-crossing property across the family of isoradial graphs. As a consequence, we obtain the universality of these models at the critical point, in the sense that the one-arm and 2j-alternating-arm critical exponents (and therefore also the connectivity and volume exponents) are constant across the family of such percolation processes. The isoradial graphs in question are those that satisfy certain weak conditions on their embedding and on their track system. This class of graphs includes, for example, isoradial embeddings of periodic graphs, and graphs derived from rhombic Penrose tilings.

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

    Science.gov (United States)

    Berry, John F

    2016-01-19

    extensive studies using X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, density functional theory, and wave function-based computational methods, as well as chemical oxidation and reduction. The compounds contain E-E 2c/3e σ half-bonds and unprecedented E2(3-) "subchalcogenide" ligands, ushering in a new oxidation state paradigm for transition metal-chalcogen chemistry. PMID:26741459

  4. 用GGA密度泛函及其长程、色散校正方法计算各类氢键的结合能%Calculation of the Binding Energies of Different Types of Hydrogen Bonds Using GGA Density Functional and Its Long-Range, Empirical Dispersion Correction Methods

    Institute of Scientific and Technical Information of China (English)

    孙涛; 王一波

    2011-01-01

    We investigated eleven exchange-correlation energy density functionals including generalized gradient approximation (GGA) (PBE, PW91), meta-GGA (M06-L), hyper-GGA (M06-2X, B3LYP, X3LYP), LC-DFT methods (CAM-B3LYP, LC-wPBE, ioB97X), and density functional theory with dispersion corrections (DFT-D) methods (u)B97X-D, B97-D) for their performance in describing systems with conventional and non-conventional hydrogen bonds. After comparing the results using the benchmark CCSD(T)/aug-cc-pVQZ approach we found that the M06-2X and ca)B97X-D functionals provided the most accurate and reliable results for the fifteen systems studied in this work with strong, moderate, and weak hydrogen bonds. It is important to employ an appropriate basis set to predict the binding energy of hydrogen bonds for all DFT methods and we found that the basis set of 6-311++G(2of, 2p) or aug-cc-pVDZ is adequate. The effect of the basis set superposition error (BSSE) is relatively small for the DFT methods tested. All the methods except for coB97X and WB97X-D were found to produce equally accurate or even more accurate results without BSSE correction.%应用广义梯度近似(GGA) (PW91和PBE)、含动能密度的广义梯度近似(meta-GGA) (M06-L)、杂化泛函(hyper-GGA)(M06-2X、X3LYP和B3LYP)及其长程校正泛函LC-DFT(CAM-B3LYP、LC-ωPBE和ωB97X)和色散校正密度泛函(DFT-D)(ωB97X-D和B97-D),用多种基函数对15种不同强度的传统氢键和非传统氢键体系的结合能进行了系统的计算与分析.并与高精度的CCSD(T)/aug-cc-pVQZ结果比较发现:在上述各类泛函中,对于氢键结合能的计算M06-2X和ωB97X-D泛函较为精确与可靠,且没有必要使用过大的基函数,6-311++G(2d,2p)或aug-cc-pVDZ水平的基组就已足够,各类泛函所计算结合能的基组重叠误差(BSSE)均较小,除ωB97X和ωB97X-D外,其它9种泛函不经BSSE校正也能得到同样甚至更准确的结果.

  5. DICOR surface treatments for enhanced bonding.

    Science.gov (United States)

    Bailey, L F; Bennett, R J

    1988-06-01

    Treatments for preparing castable ceramic surfaces for enhanced bonding to specially formulated resin-based cements were examined. An ammonium bifluoride etch combined with gamma-methacryloxypropyl-trimethoxysilane produced shear bond strengths higher than when an ammonium bifluoride treatment was used alone. The method of curing the silane was highly significant in the contribution to the cement/substrate bond strength, with the heat-cure producing the highest values. Long-term water storage tests indicated that the cement bond with etch plus silane-treated castable ceramic surfaces (whether heat or chemically cured silane was used) demonstrated no significant decrease in strength after a one-year period.

  6. The corporate bond credit spread puzzle

    OpenAIRE

    Jens H. E. Christensen

    2008-01-01

    It is common to view interest on a corporate bond as reflecting the risk-free, longer-term interest rate, such as that on a 10-year Treasury bond, plus a spread related to the credit risk of the corporation issuing the bond. However, empirical analysis of the determinants of corporate bond rates has turned out to be more demanding than it appears on the surface. This has led researchers to talk about a credit spread puzzle. In this Economic Letter we will first detail the evidence for the exi...

  7. Electric current characteristic of anodic bonding

    International Nuclear Information System (INIS)

    In this paper, a novel current–time model of anodic bonding is proposed and verified experimentally in order to investigate underlying mechanisms of anodic bonding and to achieve real-time monitoring of bonding procedure. The proposed model provides a thorough explanation for the electric current characteristic of anodic bonding. More significantly, it explains two issues which other models cannot explain. One is the sharp rise in current when a voltage is initially applied during anodic bonding. The other is the unexpected large width of depletion layers. In addition, enlargement of the intimately contacted area during anodic bonding can be obtained from the proposed model, which can be utilized to monitor the bonding process. To verify the proposed model, Borofloat33 glass and silicon wafers were adopted in bonding experiments in SUSS SB6 with five different bonding conditions (350 °C 1200 V; 370 °C 1200 V; 380 °C 1200 V; 380 °C 1000 V; and 380 °C 1400 V). The results indicate that the observed current data highly coincide with the proposed current-time model. For widths of depletion layers, depth profiling using secondary ion mass spectrometry demonstrates that the calculated values by the model are basically consistent with the experimental values as well. (paper)

  8. Non-silicon substrate bonding mediated by poly(dimethylsiloxane) interfacial coating

    Science.gov (United States)

    Zhang, Hainan; Lee, Nae Yoon

    2015-02-01

    In this paper, we introduce a simple and robust strategy for bonding poly(dimethylsiloxane) (PDMS) with various thermoplastic substrates to fabricate a thermoplastic-based closed microfluidic device and examine the feasibility of using the proposed method for realizing plastic-plastic bonding. The proposed bonding strategy was realized by first coating amine functionality on an oxidized thermoplastic surface. Next, the amine-functionalized surface was reacted with a monolayer of low-molecular-weight PDMS, terminated with epoxy functionality, by forming a robust amine-epoxy bond. Both the PDMS-coated thermoplastic and PDMS were then oxidized and permanently assembled at 25 °C under a pressure of 0.1 MPa for 15 min, resulting in PDMS-like surfaces on all four inner walls of the microchannel. Surface characterizations were conducted, including water contact angle measurement, X-ray photoelectron spectroscopy (XPS), and fluorescence measurement, to confirm the successful coating of the thin PDMS layer on the plastic surface, and the bond strength was analyzed by conducting a peel test, burst test, and leakage test. Using the proposed method, we could successfully bond various thermoplastics such as poly(methylmethacrylate) (PMMA), polycarbonate (PC), polystyrene (PS), and poly(ethylene terephthalate) (PET) with PDMS without the collapse or deformation of the microchannel, and the proposed method was successfully extended to the bonding of two thermoplastics, PMMA, and PC.

  9. Social bonds affect anti-predator behaviour in a tolerant species of macaque, Macaca nigra.

    Science.gov (United States)

    Micheletta, Jérôme; Waller, Bridget M; Panggur, Maria R; Neumann, Christof; Duboscq, Julie; Agil, Muhammad; Engelhardt, Antje

    2012-10-01

    Enduring positive social bonds between individuals are crucial for humans' health and well being. Similar bonds can be found in a wide range of taxa, revealing the evolutionary origins of humans' social bonds. Evidence suggests that these strong social bonds can function to buffer the negative effects of living in groups, but it is not known whether they also function to minimize predation risk. Here, we show that crested macaques (Macaca nigra) react more strongly to playbacks of recruitment alarm calls (i.e. calls signalling the presence of a predator and eliciting cooperative mobbing behaviour) if they were produced by an individual with whom they share a strong social bond. Dominance relationships between caller and listener had no effect on the reaction of the listener. Thus, strong social bonds may improve the coordination and efficiency of cooperative defence against predators, and therefore increase chances of survival. This result broadens our understanding of the evolution and function of social bonds by highlighting their importance in the anti-predator context. PMID:22859593

  10. The Influence of Interatomic Bonding Potentials on Detonation Properties

    OpenAIRE

    Heim, Andrew J.; Grønbech-Jensen, Niels; Germann, Timothy C.; Kober, Edward M.; Holian, Brad Lee; Lomdahl, Peter S.

    2006-01-01

    The dependence of macroscopic detonation properties of a two-dimensional diatomic (AB) molecular system on the fundamental properties of the molecule were investigated. This includes examining the detonation velocity, reaction zone thickness, and critical width as a function of the exothermicity of the gas-phase reaction and the gas-phase dissociation energy for. Following previous work, molecular dynamics (MD) simulations with a reactive empirical bond-order potential were used to characteri...

  11. Fabrication and bonding of thiol-ene-based microfluidic devices

    DEFF Research Database (Denmark)

    Sikanen, Tiina M; Lafleur, Josiane P.; Moilanen, Maria-Elisa;

    2013-01-01

    In this work, the bonding strength of microchips fabricated by thiol-ene free-radical polymerization was characterized in detail by varying the monomeric thiol/allyl composition from the stoichiometric ratio (1:1) up to 100% excess of thiol (2:1) or allyl (1:2) functional groups. Four different...... properties for each application. Here, a capillary electrophoresis separation is performed to demonstrate the attractive properties of stoichiometric thiol-ene microchips....

  12. Indifference of Defaultable Bonds with Stochastic Intensity models

    OpenAIRE

    Regis Houssou; Olivier Besson

    2010-01-01

    The utility-based pricing of defaultable bonds in the case of stochastic intensity models of default risk is discussed. The Hamilton-Jacobi- Bellman (HJB) equations for the value functions is derived. A finite difference method is used to solve this problem. The yield-spreads for both buyer and seller are extracted. The behaviour of the spread curve given the default intensity is analyzed. Finally the impacts of the risk aversion and the correlation coefficient are discussed.

  13. Chemical Bonding and Charge Distribution at Metallic Nanocontacts

    OpenAIRE

    Schwingenschloegl, Udo; Schuster, Cosima

    2006-01-01

    We present results of electronic structure calculations for aluminium contacts of atomic size, based on density functional theory and the local density approximation. Addressing the atomic orbitals at the neck of the nanocontact, we find that the local band structure deviates strongly from bulk fcc aluminium. In particular, hybridization between Al 3s and 3p states is fully suppressed due to directed bonds at the contact. Moreover, a charge transfer of 0.6 electrons off the contact aluminium ...

  14. Hydrogen bonds in concreto and in computro: the sequel

    Science.gov (United States)

    Stouten, Pieter F. W.; Van Eijck, Bouke P.; Kroon, Jan

    1991-02-01

    In the framework of our comparative research concerning hydrogen bonding in the crystalline and liquid phases we have carried out molecular dynamics (MD) simulations of liquid methanol. Six different rigid three site models are compared. Five of them had been reported in the literature and one (OM2) we developed by a fit to the experimental molar volume, heat of vaporization and neutron weighted radial distribution function. In general the agreement with experiment is satisfactory for the different models. None of the models has an explicit hydrogen bond potential, but five of the six models show a degree of hydrogen bonding comparable to experiments on liquid methanol. The analysis of the simulation hydrogen bonds indicates that there is a distinct preference of the O⋯O axis to lie in the acceptor lone pairs plane, but hardly any for the lone pair directions. Ab initio calculations and crystal structure statistics of OH⋯O hydrogen bonds agree with this observation. The O⋯O hydrogen bond length distributions are similar for most models. The crystal structures show a sharper O⋯O distribution. Explicit introduction of harmonic motion with a quite realistic root mean square amplitude of 0.08 Å to the thermally averaged crystal distribution results in a distribution comparable to OM2 although the maximum of the former is found at shorter distance. On the basis of the analysis of the static properties of all models we conclude that our OM2, Jorgenson's OPLS and Haughney, Ferrario and McDonald's HFM1 models are good candidates for simulations of liquid methanol under isothermal, isochoric conditions. Partly flexible and completely rigid OM2 are simulated at constant pressure and with fixed volume. The flexible simulations give essentially the same (correct) results under both conditions, which is not surprising because the flexible form was fitted under both conditions. Rigid OM2 has a similar potential energy but larger pressure in the

  15. Estimating Structural Models of Corporate Bond Prices in Indonesian Corporations

    Directory of Open Access Journals (Sweden)

    Lenny Suardi

    2014-08-01

    Full Text Available This  paper  applies  the  maximum  likelihood  (ML  approaches  to  implementing  the structural  model  of  corporate  bond,  as  suggested  by  Li  and  Wong  (2008,  in  Indonesian corporations.  Two  structural  models,  extended  Merton  and  Longstaff  &  Schwartz  (LS models,  are  used  in  determining  these  prices,  yields,  yield  spreads  and  probabilities  of default. ML estimation is used to determine the volatility of irm value. Since irm value is unobserved variable, Duan (1994 suggested that the irst step of ML estimation is to derive the likelihood function for equity as the option on the irm value. The second step is to ind parameters such as the drift and volatility of irm value, that maximizing this function. The irm value itself is extracted by equating the pricing formula to the observed equity prices. Equity,  total  liabilities,  bond  prices  data  and  the  irm's  parameters  (irm  value,  volatility of irm value, and default barrier are substituted to extended Merton and LS bond pricing formula in order to valuate the corporate bond.These models are implemented to a sample of 24 bond prices in Indonesian corporation during  period  of  2001-2005,  based  on  criteria  of  Eom,  Helwege  and  Huang  (2004.  The equity  and  bond  prices  data  were  obtained  from  Indonesia  Stock  Exchange  for  irms  that issued equity and provided regular inancial statement within this period. The result shows that both models, in average, underestimate the bond prices and overestimate the yields and yield spread. ";} // -->activate javascript

  16. Phase behaviors of supramolecular graft copolymers with reversible bonding

    Science.gov (United States)

    Zhang, Xu; Wang, Liquan; Jiang, Tao; Lin, Jiaping

    2013-11-01

    Phase behaviors of supramolecular graft copolymers with reversible bonding interactions were examined by the random-phase approximation and real-space implemented self-consistent field theory. The studied supramolecular graft copolymers consist of two different types of mutually incompatible yet reactive homopolymers, where one homopolymer (backbone) possesses multifunctional groups that allow second homopolymers (grafts) to be placed on. The calculations carried out show that the bonding strength exerts a pronounced effect on the phase behaviors of supramolecular graft copolymers. The length ratio of backbone to graft and the positions of functional groups along the backbone are also of importance to determine the phase behaviors. Phase diagrams were constructed at high bonding strength to illustrate this architectural dependence. It was found that the excess unbounded homopolymers swell the phase domains and shift the phase boundaries. The results were finally compared with the available experimental observations, and a well agreement is shown. The present work could, in principle, provide a general understanding of the phase behaviors of supramolecular graft copolymers with reversible bonding.

  17. Bond graphs : an integrating tool for design of mechatronic systems

    International Nuclear Information System (INIS)

    Bond graph is a powerful tool well known for dynamic modelling of multi physical systems: This is the only modelling technique to generate automatically state space or non-linear models using dedicated software tools (CAMP-G, 20-Sim, Symbols, Dymola...). Recently several fundamental theories have been developed for using a bond graph model not only for modeling but also as a real integrated tool from conceptual ideas to optimal practical realization of mechatronic system. This keynote presents a synthesis of those new theories which exploit some particular properties (such as causal, structural and behavioral) of this graphical methodology. Based on a pedagogical example, it will be shown how from a physical system (not a transfer function or state equation) and using only one representation (Bond graph), the following results can be performed: modeling (formal state equations generation), Control analysis (observability, controllability, Structural I/O decouplability, dynamic decoupling,...) diagnosis analysis (automatic generation of robust fault indicators, sensor placement, structural diagnosability) and finally sizing of actuators. The presentation will be illustrated by real industrial applications. Limits and perspectives of bond graph theory conclude the keynote.

  18. Piezoelectric hydrogen bonding: computational screening for a design rationale.

    Science.gov (United States)

    Werling, Keith A; Griffin, Maryanne; Hutchison, Geoffrey R; Lambrecht, Daniel S

    2014-09-01

    Organic piezoelectric materials are promising targets in applications such as energy harvesting or mechanical sensors and actuators. In a recent paper (Werling, K. A.; et al. J. Phys. Chem. Lett. 2013, 4, 1365-1370), we have shown that hydrogen bonding gives rise to a significant piezoelectric response. In this article, we aim to find organic hydrogen bonded systems with increased piezo-response by investigating different hydrogen bonding motifs and by tailoring the hydrogen bond strength via functionalization. The largest piezo-coefficient of 23 pm/V is found for the nitrobenzene-aniline dimer. We develop a simple, yet surprisingly accurate rationale to predict piezo-coefficients based on the zero-field compliance matrix and dipole derivatives. This rationale increases the speed of first-principles piezo-coefficient calculations by an order of magnitude. At the same time, it suggests how to understand and further increase the piezo-response. Our rationale also explains the remarkably large piezo-response of 150 pm/V and more for another class of systems, the "molecular springs" (Marvin, C.; et al. J. Phys. Chem. C 2013, 117, 16783-16790.).

  19. Piezoelectric hydrogen bonding: computational screening for a design rationale.

    Science.gov (United States)

    Werling, Keith A; Griffin, Maryanne; Hutchison, Geoffrey R; Lambrecht, Daniel S

    2014-09-01

    Organic piezoelectric materials are promising targets in applications such as energy harvesting or mechanical sensors and actuators. In a recent paper (Werling, K. A.; et al. J. Phys. Chem. Lett. 2013, 4, 1365-1370), we have shown that hydrogen bonding gives rise to a significant piezoelectric response. In this article, we aim to find organic hydrogen bonded systems with increased piezo-response by investigating different hydrogen bonding motifs and by tailoring the hydrogen bond strength via functionalization. The largest piezo-coefficient of 23 pm/V is found for the nitrobenzene-aniline dimer. We develop a simple, yet surprisingly accurate rationale to predict piezo-coefficients based on the zero-field compliance matrix and dipole derivatives. This rationale increases the speed of first-principles piezo-coefficient calculations by an order of magnitude. At the same time, it suggests how to understand and further increase the piezo-response. Our rationale also explains the remarkably large piezo-response of 150 pm/V and more for another class of systems, the "molecular springs" (Marvin, C.; et al. J. Phys. Chem. C 2013, 117, 16783-16790.). PMID:24576213

  20. Theoretical Study on Measure of Hydrogen Bonding Strength: R-C≡N…pyrrole Complexes

    Institute of Scientific and Technical Information of China (English)

    史福强; 安静仪; 俞稼镛

    2005-01-01

    The R-C≡N…pyrrole (R=H, CH3, CH2F, CHF2, CF3, NH2, BH2, OH, F, CH2Cl, CHCl2, CCl3, Li, Na) complexes were considered as the simple sample for measure of hydrogen bonding strength. Density functional theory B3LYP/6-311 + + G** level was applied to the optimization of geometries of complexes and monomers. Measure of hydrogen bonding strength based on geometrical and topological parameters, which were derived from the AIM theory, was analyzed. Additionally, natural bond orbital (NBO) analysis and frequency calculations were performed.From the computation results it was found that the electronic density at N-H bond critical points was also strictly correlated with the hydrogen bonding strength.

  1. Optical characterization of gaps in directly bonded Si compound optics using infrared spectroscopy

    CERN Document Server

    Gully-Santiago, Michael; White, Victor

    2015-01-01

    Silicon direct bonding offers flexibility in the design and development of Si optics by allowing manufacturers to combine subcomponents with a potentially lossless and mechanically stable interface. The bonding process presents challenges in meeting the requirements for optical performance because air gaps at the Si interface cause large Fresnel reflections. Even small (35 nm) gaps reduce transmission through a direct bonded Si compound optic by 4% at $\\lambda = 1.25 \\; \\mu$m at normal incidence. We describe a bond inspection method that makes use of precision slit spectroscopy to detect and measure gaps as small as 14 nm. Our method compares low finesse Fabry-P\\'{e}rot models to high precision measurements of transmission as a function of wavelength. We demonstrate the validity of the approach by measuring bond gaps of known depths produced by microlithography.

  2. Uniaxial Bond Stress-Slip Relationship of Reinforcing Bars in Concrete

    Directory of Open Access Journals (Sweden)

    Sungnam Hong

    2012-01-01

    Full Text Available This paper documents a study carried out on the estimation of the bond stress-slip relationship for reinforced concrete members under axial tension loading. An analytical model is proposed that utilizes the conventional bond stress-slip theories as well as the characteristics of deformed bar and concrete cross-sectional area. An equation for the estimation of the bond stress is formulated as the function of nondimensional factors (e.g., bond stress, slip, etc.. The validity, accuracy, and efficiency of the proposed model are established by comparing the analytical results with the experimental data and the JSCE design codes, as well as the analytical models given by Ikki et al. and Shima. The analytical results presented in this paper indicate that the proposed model can effectively estimate the bond stress-slip relationship of reinforced concrete members under axial tension loading.

  3. Selective Nitrate Recognition by a Halogen-Bonding Four-Station [3]Rotaxane Molecular Shuttle.

    Science.gov (United States)

    Barendt, Timothy A; Docker, Andrew; Marques, Igor; Félix, Vítor; Beer, Paul D

    2016-09-01

    The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. PMID:27436297

  4. 76 FR 14746 - Surety Companies Acceptable on Federal Bonds Change in State of Incorporation; Western Bonding...

    Science.gov (United States)

    2011-03-17

    ... Fiscal Service Surety Companies Acceptable on Federal Bonds Change in State of Incorporation; Western Bonding Company; Western Insurance Company AGENCY: Financial Management Service, Fiscal Service... Circular 570, 2010 Revision, published July 1, 2010, at 75 FR 38192. FOR FURTHER INFORMATION...

  5. Are Bonding Agents being Effective on the Shear Bond Strength of Orthodontic Brackets Bonded to the Composite?

    Directory of Open Access Journals (Sweden)

    Fahimeh Farzanegan

    2014-06-01

    Full Text Available Introduction: One of the clinical problems in orthodontics is the bonding of brackets tocomposite restorations. The aim of this study was to evaluate the shear bondstrength of brackets bonded to composite restorations using Excite. Methods:Forty brackets were bonded to composite surfaces, which were embedded inacrylic resin. One of the following four protocols was employed for surfacepreparation of the composite: group 1 37% phosphoric acid for 60 seconds, group2 roughening with a diamond bur plus 37% phosphoric acid for 60 seconds, group3 37% phosphoric acid for 60 seconds and the applying Excite®, group4 roughening with diamond bur plus 37% phosphoric acid for 60 seconds andapplying Excite®. Maxillary central brackets were bonded onto thecomposite prepared samples with Transbond XT. Shear Bond Strength (SBS wasmeasured by a universal testing machine. The ANOVA and Tukey test was utilizedfor data analysis. Results: There was a significant difference betweenthe four groups (P

  6. Shear bond strength of different retainer wires and bonding adhesives in consideration of the pretreatment process

    OpenAIRE

    Reicheneder, C. (Claudia); Hofrichter, B. (Bernd); Faltermeier, A. (Andreas); P. Proff; Lippold, C. (Carsten); Kirschneck, C.J. (Christian)

    2015-01-01

    Introduction: We aimed to compare the shear bond strength (SBS) of three different retainer wires and three different bonding adhesives in consideration of the pretreatment process of enamel surface sandblasting. Methods: 400 extracted bovine incisors were divided into 10 groups of 20 paired specimens each. 10 specimens of each group were pretreated by enamel sandblasting. The retainer wires Bond-A-Braid™, GAC-Wildcat®-Twistflex and everStick®ORTHO were bonded to the teeth with the adhesives ...

  7. Rh(III)-Catalyzed C-H Bond Addition/Amine-Mediated Cyclization of Bis-Michael Acceptors.

    Science.gov (United States)

    Potter, Tyler J; Ellman, Jonathan A

    2016-08-01

    A Rh(III)-catalyzed C-H bond addition/primary amine-promoted cyclization of bis-Michael acceptors is reported. The C-H bond addition step occurs with high chemoselectivity, and the subsequent intramolecular Michael addition, mediated by a primary amine catalyst, sets three contiguous stereocenters with high diastereoselectivity. A broad range of directing groups and both aromatic and alkenyl C-H bonds were shown to be effective in this transformation, affording functionalized piperidines, tetrahydropyrans, and cyclohexanes.

  8. Effect of delayed insertion of composite resin on the bond strength of etch-and-rinse adhesive systems

    OpenAIRE

    Edson Alves de CAMPOS; SAAD, José Roberto Cury; Sizenando Toledo PORTO NETO; Campos, Lucas Arrais; de Andrade, Marcelo Ferrarezi

    2009-01-01

    Introduction: Etch-and-rinse adhesive systems are characterized bythe dental acid etching previously to the monomer application. Thesematerials can be classified as 3-step (when primer and bond are applied separately) or 2-step (when the primer and bond functions are carried out by a single component). Objective: To determine the influence of immediate or delayed insertion of restorative material on the values of bond strength of 2-step and 3-step etch-and-rinse adhesive systems using the mic...

  9. In Vivo and In Vitro Effects of Chlorhexidine Pretreatment on Immediate and Aged Dentin Bond Strengths.

    Science.gov (United States)

    Gunaydin, Z; Yazici, A R; Cehreli, Z C

    2016-01-01

    This study evaluated the effect of 2% chlorhexidine (CHX) pretreatment of dentin on the immediate and aged microtensile bond strength (μTBS) of different adhesives to dentin in vivo and in vitro. Class I cavities were prepared in 80 caries-free human third molars of 40 patients in a split-mouth fashion. In each tooth pair, one tooth received 2% CHX pretreatment after which both teeth were randomly assigned to one of the following groups with respect to the type of adhesive system applied: Adper Single Bond 2 (etch-and-rinse), Clearfil SE Bond (two-step self-etch), Clearfil S(3) Bond (one-step self-etch), and Adper Prompt-L-Pop (all-in-one self-etch). The teeth were restored with resin composite and extracted for μTBS testing either immediately or after six months in function. In vitro specimen pairs were prepared as with the clinical protocol in intact, freshly extracted human molars, and thereafter, subjected to testing immediately or after 5000× thermocycling. Data were analyzed with four-way analysis of variance (ANOVA). Bonferroni test was utilized for pair-wise comparisons. The immediate bond strength values were significantly higher than "aged" ones for all tested adhesives (p=0.00). The in vitro immediate bond strength values were statistically higher than in vivo bond strength values (p0.05). In the absence of CHX pretreatment, all adhesives showed significantly higher immediate bond strength values than CHX-treated groups, while all "aged", non-pretreated adhesives exhibited significantly lower bond strength values (both pchlorhexidine pretreatment resulted in significantly higher aged bond strengths, regardless of the adhesive system and testing condition. Aging-associated decline in dentin bond strength of etch-and rinse and self-etch adhesives can be counteracted by chlorhexidine application. PMID:26919083

  10. 77 FR 553 - Surety Companies Acceptable on Federal Bonds: Termination; Western Bonding Company

    Science.gov (United States)

    2012-01-05

    ... Supplement No. 4 to the Treasury Department Circular 570; 2011 Revision, published July 1, 2011, at 76 FR... Fiscal Service Surety Companies Acceptable on Federal Bonds: Termination; Western Bonding Company AGENCY... Company (NAIC 13191) under 31 U.S.C. 9305 to qualify as an acceptable surety on Federal bonds...

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

    Science.gov (United States)

    Pauling, Linus; Herman, Zelek S.

    1984-01-01

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

  12. The Effects of Silicone Contamination on Bond Performance of Various Bond Systems

    Science.gov (United States)

    Anderson, G. L.; Stanley, S. D.; Young, G. L.; Brown, R. A.; Evans, K. B.; Wurth, L. A.

    2012-01-01

    The sensitivity to silicone contamination of a wide variety of adhesive bond systems is discussed. Generalizations regarding factors that make some bond systems more sensitive to contamination than others are inferred and discussed. The effect of silane adhesion promoting primer on the contamination sensitivity of two epoxy/steel bond systems is also discussed.

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

    Directory of Open Access Journals (Sweden)

    Jlali H

    1999-12-01

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

  14. Measuring of bond. A comparative experimental research

    NARCIS (Netherlands)

    Pluijm, R. van der

    1996-01-01

    In the framework of European test methods for masonry a simple test method for bond has to be established. The described research, carried out at Eindhoven University of Technology, tried to contribute to the development of such a test method. In this perspective, the research was focused on bond wr

  15. Hydrogen bonds in PC61BM solids

    Directory of Open Access Journals (Sweden)

    Chun-Qi Sheng

    2015-09-01

    Full Text Available We have studied the hydrogen bonds in PC61BM solids. Inter-molecular interaction is analyzed theoretically for the well-defined monoclinic (P21/n structure. The results indicate that PC61BM combines into C–H⋯Od bonded molecular chains, where Od denotes the doubly-bonded O atom of PC61BM. The molecular chains are linked together by C–H⋯Os bonds, where Os denotes the singly-bonded O atom of PC61BM. To reveal the consequences of hydrogen bond formation on the structural properties of PC61BM solids (not limited to the monoclinic structure, we design and perform some experiments for annealed samples with the monoclinic (P21/n PC61BM as starting material. The experiments include differential scanning calorimetry, X-ray diffraction and infrared absorption measurements. Structural phase transitions are observed below the melting point. The C–H⋯Od bonds seem persisting in the altered structures. The inter-molecular hydrogen bonds can help to understand the phase separation in polymer/PC61BM blends and may be responsible for the existence of liquid PC61BM.

  16. Bond strength of thermally recycled metal brackets.

    Science.gov (United States)

    Wheeler, J J; Ackerman, R J

    1983-03-01

    Bracket recycling has emerged concurrently with the practice of direct bonding. This study was undertaken to determine the effect of recycling on the retention of mesh-backed stainless steel brackets. Mesh strand diameter was measured on forty new brackets. These brackets were bonded to recently extracted human premolar teeth, and the tensile force required to fracture each bond was recorded. The brackets were then reconditioned by a thermal process. The mesh strand size was remeasured and the tensile test was repeated. It was found that (1) mesh strand diameter decreased 7 percent during the reconditioning process (93.89 microns +/- 3.17 S.D. compared to 87.07 microns +/- 4.76 S.D., z = 17.62, P less than 1 X 10(-5) ), (2) new bracket bonds were 6 percent stronger than recycled bracket bonds (43.88 pounds +/- 7.98 S.D. bond strength), and (3) reduction in mesh strand diameter during the reconditioning process did not correlate with changes in bond strength between initial and recycled bonding (Pearson r = 0.038). PMID:6338725

  17. The Valence Bond Interpretation of Molecular Geometry.

    Science.gov (United States)

    Smith, Derek W.

    1980-01-01

    Presents ways in which the valence bond (VB) theory describes the bonding and geometry of molecules, following directly from earlier principles laid down by Pauling and others. Two other theories (molecular orbital approach and valence shell electron pair repulsion) are discussed and compared to VB. (CS)

  18. Keeping U.S. Bonds in Hand

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    U.S. bonds still comprise a major share of Chinese foreign reserves People are becoming increasingly uneasy about reports saying China is reducing its holdings of U.S.bonds. Currently, China is the sec-ond largest holder of U.S.

  19. Traumatic Bonding: Clinical Implications in Incest.

    Science.gov (United States)

    deYoung, Mary; Lowry, Judith A.

    1992-01-01

    "Traumatic bonding" is defined as "the evolution of emotional dependency between...a child and an adult [in] a relationship characterized by periodic sexual abuse." Maintains that the concept holds promise for explaining confusing dynamics of incest. Demonstrates ways in which traumatic bonding can be applied to cases of incest and discusses…

  20. 25 CFR 226.6 - Bonds.

    Science.gov (United States)

    2010-04-01

    ... 25 Indians 1 2010-04-01 2010-04-01 false Bonds. 226.6 Section 226.6 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR ENERGY AND MINERALS LEASING OF OSAGE RESERVATION LANDS FOR OIL AND GAS... the lease. (d) The right is specifically reserved to increase the amount of bonds prescribed...

  1. 25 CFR 225.30 - Bonds.

    Science.gov (United States)

    2010-04-01

    ... AFFAIRS, DEPARTMENT OF THE INTERIOR ENERGY AND MINERALS OIL AND GAS, GEOTHERMAL, AND SOLID MINERALS... Circular No. 570). (b) An operator may file a $75,000 bond for all geothermal, mining, or oil and gas... operator may file a $150,000 bond for full nationwide coverage to cover all geothermal or oil and...

  2. Nondestructive testing of thermocompression bonds. Final report

    International Nuclear Information System (INIS)

    A Scanning Laser Acoustic Microscope (SLAM) was used to characterize hybrid microcircuit beam lead bonds formed on thin film networks by a thermocompression process. Results from subsequent pull testing show that the SLAM offered no significant advantage over visual inspection for detecting bad bonds. Infrared microscopy and resistance measurements were also reviewed and rejected as being ineffective inspection methods

  3. Cold pressure welding - the mechanisms governing bonding

    DEFF Research Database (Denmark)

    Bay, Niels

    1979-01-01

    Investigations of the bonding surface in scanning electron microscope after fracture confirm the mechanisms of bond formation in cold pressure welding to be: fracture of work-hardened surface layer, surface expansion increasing the area of virgin surface, extrusion of virgin material through cracks...

  4. 78 FR 36029 - CDFI Bond Guarantee Program

    Science.gov (United States)

    2013-06-14

    ... on February 5, 2013 (78 FR 8296; 12 CFR part 1808) (the Regulations) and provides the regulatory... facilitating Bond principal and interest payments to the Federal Financing Bank, as Bond Purchaser. 3... intervening in payment reconciliation efforts, assisting in appraisal and liquidation of...

  5. 36 CFR 9.48 - Performance bond.

    Science.gov (United States)

    2010-07-01

    ... MINERALS MANAGEMENT Non-Federal Oil and Gas Rights § 9.48 Performance bond. (a) Prior to approval of a plan... Secretary or his designee, cash or negotiable bonds of the U.S. Government. The cash deposit or the market... spill, the escape of gas, wastes, contaminating substances, or fire caused by operations. This...

  6. Wire-bond inspection in IC assembly

    Science.gov (United States)

    Rajeswari, Mandava; Rodd, Mike G.

    1996-02-01

    Wire-bonding in IC assembly process involves making a physical connection between the IC 'die' and the 'lead' by bonding wires between the two. Inspection of wire-bond quality is a' highly labor-intensive process and currently efforts are being made to automate it. This paper presents the results of a research conducted into developing a comprehensive automated wire- bond visual inspection system that is capable of performing final accept/reject inspection, providing on-line process feedback, and assisting in process validation. The proposed inspection system consists of the inspection of the bond on a bond pad, the bond on a lead and the inter-connecting wire between a bond pad and its corresponding lead. The algorithms are based on simple and easily extractable features that ensure achieving the desired accuracy and speed. A novel but simple illumination system is proposed to obtain the images of the inter- connecting wires. The proposed system is validated using several state-of-the-art IC samples. This work is sponsored by the Ministry of Science Technology and Environment, Malaysia and Intel Technology Pvt. Ltd., Malaysia.

  7. 78 FR 687 - Bond Premium Carryforward

    Science.gov (United States)

    2013-01-04

    ... Internal Revenue Service 26 CFR Part 1 RIN 1545-BL28 Bond Premium Carryforward AGENCY: Internal Revenue... temporary regulations that provide guidance on the tax treatment of a debt instrument with a bond premium carryforward in the holder's final accrual period, including a Treasury bill acquired at a premium. The text...

  8. ROLE OF DIASPORA BONDS IN DEVELOPING COUNTRIES

    Directory of Open Access Journals (Sweden)

    Y. Bunyk

    2015-08-01

    Full Text Available The article deals with the problem of the bond issue for the Diaspora as a source of financing of the national economy and a factor of development. We reveal the following factors driving demand in the diaspora bond market: targeting at a project, channels, audience and marketing. The paper shows international experience to attract migrants’ savings and use them to issue bonds. Investors consider diaspora bonds because: firstly, people who have disposable income, who can commit that income or that excess income to a long term investment should look at diaspora bonds: secondly, people who really want to participate in transforming the home country should look at diaspora bond specifically diaspora bonds related to projects: and last but not least, if there are incentives around diaspora bonds for example whether there’s tax incentive and other kinds of incentive, that also should be taken into account. Also we disclosed the possibility of using this type of securities in Ukraine and its expedience.

  9. Hypovalency--a kinetic-energy density description of a 4c-2e bond.

    Science.gov (United States)

    Jacobsen, Heiko

    2009-06-01

    A bond descriptor based on the kinetic energy density, the localized-orbital locator (LOL), is used to characterize the nature of the chemical bond in electron deficient multi-center bonds. The boranes B(2)H(6), B(4)H(4), B(4)H(10), [B(6)H(6)](2-), and [B(6)H(7)](-) serve as prototypical examples of hypovalent 3c-2e and 4c-2e bonding. The kinetic energy density is derived from a set of Kohn-Sham orbitals obtained from pure density functional calculations (PBE/TZVP), and the topology of LOL is analyzed in terms of (3,-3) attractors (Gamma). The B-B-B and B-H-B 3c-2e, and the B-B-H-B 4c-2e bonding situations are defined by their own characteristic LOL profiles. The presence of one attractor in relation to the three or four atoms that are engaged in electron deficient bonding provides sufficient indication of the type of 3c-2e or 4c-2e bond present. For the 4c-2e bond in [B(6)H(7)](-) the LOL analysis is compared to results from an experimental QTAIM study. PMID:19452076

  10. Green and social bonds - A promising tool

    International Nuclear Information System (INIS)

    Issues of green bonds, socially responsible bonds and climate bonds are on the rise. Novethic estimates that some Euro 5 billion in such bonds has been issued since the start of 2013 by development banks, the main issuers of this type of debt. The figure is equal to over half of their total issues since 2007. Including local authorities, corporations and banks, a total Euro 8 billion of these bonds has been issued thus far in 2013. Given the size of the bond market, which the OECD estimated at Euro 95,000 billion in 2011, green and social bonds are still something of a niche but have strong growth potential. A number of large issues, from Euro 500 million to Euro 1 billion, were announced at the end of the year. Unlike conventional bonds, green and social bonds are not intended to finance all the activities of the issuer or refinance its debt. They serve instead to finance specific projects, such as producing renewable energy or adapting to climate change, the risk of which is shouldered by the issuer. This makes them an innovative instrument, used to earmark investments in projects with a direct environmental or social benefit rather than simply on the basis of the issuer's sustainable development policy. With financing being sought for the ecological transition, green and social bonds are promising instruments, sketching out at global level the shape of tools adapted to the financing of a green economy. On the strength of these advantages, the interest of responsible investors - the main target of green and social bond issuers - is growing fast. Judging by issuer press releases and the most commonly used currencies, the main subscribers today are US investors, among them CalSTRS and fund managers like Calvert Investment Management and Trillium Asset Management. European asset owners are also starting to focus on green and social bonds. A Novethic survey shows that 13% of them have already subscribed to such an issue or plan to do so. The present study

  11. Halogen bonding origin properties and applications

    International Nuclear Information System (INIS)

    σ-hole bonding represents an unusual and novel type of noncovalent interactions in which atom with σ- hole interacts with Lewis base such as an electronegative atom (oxygen, nitrogen, …) or aromatic systems. This bonding is of electrostatic nature since the σ-hole bears a positive charge. Dispersion energy forms equally important energy term what is due to the fact that two heavy atoms (e.g. halogen and oxygen) having high polarizability lie close together (the respective distance is typically shorter than the sum of van der Waals radii). Among different types of σ-hole bondings the halogen bonding is by far the most known but chalcogen and pnictogen bondings are important as well

  12. 1 mil gold bond wire study.

    Energy Technology Data Exchange (ETDEWEB)

    Huff, Johnathon; McLean, Michael B.; Jenkins, Mark W.; Rutherford, Brian Milne

    2013-05-01

    In microcircuit fabrication, the diameter and length of a bond wire have been shown to both affect the current versus fusing time ratio of a bond wire as well as the gap length of the fused wire. This study investigated the impact of current level on the time-to-open and gap length of 1 mil by 60 mil gold bond wires. During the experiments, constant current was provided for a control set of bond wires for 250ms, 410ms and until the wire fused; non-destructively pull-tested wires for 250ms; and notched wires. The key findings were that as the current increases, the gap length increases and 73% of the bond wires will fuse at 1.8A, and 100% of the wires fuse at 1.9A within 60ms. Due to the limited scope of experiments and limited data analyzed, further investigation is encouraged to confirm these observations.

  13. Halogen bonding origin properties and applications

    Energy Technology Data Exchange (ETDEWEB)

    Hobza, Pavel [Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10 Prague (Czech Republic); Regional Center of Advanced Technologies and Materials, Department of Physical Chemistry, Palacky University, 77146 Olomouc (Czech Republic)

    2015-12-31

    σ-hole bonding represents an unusual and novel type of noncovalent interactions in which atom with σ- hole interacts with Lewis base such as an electronegative atom (oxygen, nitrogen, …) or aromatic systems. This bonding is of electrostatic nature since the σ-hole bears a positive charge. Dispersion energy forms equally important energy term what is due to the fact that two heavy atoms (e.g. halogen and oxygen) having high polarizability lie close together (the respective distance is typically shorter than the sum of van der Waals radii). Among different types of σ-hole bondings the halogen bonding is by far the most known but chalcogen and pnictogen bondings are important as well.

  14. Atomic diffusion properties in wire bonding

    Institute of Scientific and Technical Information of China (English)

    LI Jun-hui; WANG Fu-liang; HAN Lei; DUAN Ji-an; ZHONG Jue

    2006-01-01

    The lift-off characteristics at the interface of thermosonic bond were observed by using scanning electron microscope (JSM-6360LV). The vertical section of bonding point was produced by punching, grinding and ion-sputter thinning, and was tested by using transmission electron microscope (F30). The results show that the atomic diffusion at the bonded interface appears. The thickness of Au/Al interface characterized by atomic diffusion is about 500 nm under ultrasonic and thermal energy. The fracture morphology of lift-off interface is dimples. The tensile fracture appears by pull-test not in bonded interface but in basis material, and the bonded strength at interface is enhanced by diffused atom from the other side.

  15. Bond resistances in molecular junctions

    Science.gov (United States)

    Painelli, Anna

    2006-03-01

    The description of molecular contacts is one of the hardest problems in modeling molecular junctions. In common approaches macroscopic leads ensure a finite potential drop and hence a driving force for the current. Recently, a different strategy is emerging where a steady-state DC current is forced in the molecule, by making resort to Lagrange multipliers, or by drawing a magnetic flux through the molecule. The strategy is promising, but two main problems remain to be solved: (1) the calculation of the potential drop needed to sustain the current, and (2) the definition of the potential profile along the molecule. Here the Joule law is used to evaluate the potential drop from the electrical power spent on the molecule, and continuity constraints for steady-state DC current are implemented to get information on the potential profile. Borrowing powerful concepts from the field of molecular spectroscopy, emphasis is put on the molecule, while clamping information about contacts in the molecular relaxation matrix. The molecule is described in a real-space approach, leading to a suggestive analogy between the molecule and an electrical circuit where resistances are associated with chemical bonds.

  16. NDT evaluation of long-term bond durability of CFRP-structural systems applied to RC highway bridges

    Science.gov (United States)

    Crawford, Kenneth C.

    2016-06-01

    The long-term durability of CFRP structural systems applied to reinforced-concrete (RC) highway bridges is a function of the system bond behavior over time. The sustained structural load performance of strengthened bridges depends on the carbon fiber-reinforced polymer (CFRP) laminates remaining 100 % bonded to concrete bridge members. Periodic testing of the CFRP-concrete bond condition is necessary to sustain load performance. The objective of this paper is to present a non-destructive testing (NDT) method designed to evaluate the bond condition and long-term durability of CFRP laminate (plate) systems applied to RC highway bridges. Using the impact-echo principle, a mobile mechanical device using light impact hammers moving along the length of a bonded CFRP plate produces unique acoustic frequencies which are a function of existing CFRP plate-concrete bond conditions. The purpose of this method is to test and locate CFRP plates de-bonded from bridge structural members to identify associated deterioration in bridge load performance. Laboratory tests of this NDT device on a CFRP plate bonded to concrete with staged voids (de-laminations) produced different frequencies for bonded and de-bonded areas of the plate. The spectra (bands) of frequencies obtained in these tests show a correlation to the CFRP-concrete bond condition and identify bonded and de-bonded areas of the plate. The results of these tests indicate that this NDT impact machine, with design improvements, can potentially provide bridge engineers a means to rapidly evaluate long lengths of CFRP laminates applied to multiple highway bridges within a national transportation infrastructure.

  17. Regulation of actin catch-slip bonds with a RhoA-formin module

    Science.gov (United States)

    Lee, Cho-Yin; Lou, Jizhong; Wen, Kuo-Kuang; McKane, Melissa; Eskin, Suzanne G.; Rubenstein, Peter A.; Chien, Shu; Ono, Shoichiro; Zhu, Cheng; McIntire, Larry V.

    2016-10-01

    The dynamic turnover of the actin cytoskeleton is regulated cooperatively by force and biochemical signaling. We previously demonstrated that actin depolymerization under force is governed by catch-slip bonds mediated by force-induced K113:E195 salt-bridges. Yet, the biochemical regulation as well as the functional significance of actin catch bonds has not been elucidated. Using AFM force-clamp experiments, we show that formin controlled by RhoA switches the actin catch-slip bonds to slip-only bonds. SMD simulations reveal that the force does not induce the K113:E195 interaction when formin binds to actin K118 and E117 residues located at the helical segment extending to K113. Actin catch-slip bonds are suppressed by single residue replacements K113E and E195K that interrupt the force-induced K113:E195 interaction; and this suppression is rescued by a K113E/E195K double mutant (E/K) restoring the interaction in the opposite orientation. These results support the biological significance of actin catch bonds, as they corroborate reported observations that RhoA and formin switch force-induced actin cytoskeleton alignment and that either K113E or E195K induces yeast cell growth defects rescued by E/K. Our study demonstrates how the mechano-regulation of actin dynamics is modulated by biochemical signaling molecules, and suggests that actin catch bonds may be important in cell functions.

  18. Investigation on the mechanism of aminosilane-mediated bonding of thermoplastics and poly(dimethylsiloxane).

    Science.gov (United States)

    Sunkara, Vijaya; Cho, Yoon-Kyoung

    2012-12-01

    A possible mechanism for the aminosilane-mediated room-temperature (RT) bonding of thermoplastics and poly(dimethylsiloxane) (PDMS) is presented. The plasma-activated thermoplastic or PDMS substrates were modified with alkoxy silanes having different organo functional groups, and their bonding characteristics were studied. Manual peeling tests revealed that strong bonding was realized only when the silane had a free amino group and at least two alkoxy groups on the silicon. Silanization was carried out in both aqueous and anhydrous conditions; bonding occurred readily at RT in the former case, but a longer incubation time or a higher temperature was needed for the latter. The presence of the silane on the surface was confirmed by contact-angle measurements and UV spectrophotometric, attenuated total reflectance infrared spectroscopic (ATR-IR) and X-ray photoelectron spectroscopic (XPS) analyses. In the case where the aminosilane was deposited from aqueous solution, the amino functionality of the silane-catalyzed siloxane bond formation between the silanol on the modified thermoplastic surface and the silanol of the plasma-activated PDMS. In the case of anhydrous phase deposition, the aminosilane first catalyzed the hydrolysis of the ethoxy groups on the silicon, and then, catalyzed the condensation between the silanol groups of both materials. Shelf life tests of the modified thermoplastics showed that the aminosilane was stable over 2 weeks, and that bonding occurred at RT when the substrates were soaked in water before bonding.

  19. Isotopic fractionation in proteins as a measure of hydrogen bond length

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, Ross H., E-mail: r.mckenzie@uq.edu.au [School of Mathematics and Physics, University of Queensland, Brisbane 4072 (Australia); Athokpam, Bijyalaxmi; Ramesh, Sai G. [Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012 (India)

    2015-07-28

    If a deuterated molecule containing strong intramolecular hydrogen bonds is placed in a hydrogenated solvent, it may preferentially exchange deuterium for hydrogen. This preference is due to the difference between the vibrational zero-point energy for hydrogen and deuterium. It is found that the associated fractionation factor Φ is correlated with the strength of the intramolecular hydrogen bonds. This correlation has been used to determine the length of the H-bonds (donor-acceptor separation) in a diverse range of enzymes and has been argued to support the existence of short low-barrier H-bonds. Starting with a potential energy surface based on a simple diabatic state model for H-bonds, we calculate Φ as a function of the proton donor-acceptor distance R. For numerical results, we use a parameterization of the model for symmetric O–H⋯O bonds [R. H. McKenzie, Chem. Phys. Lett. 535, 196 (2012)]. We consider the relative contributions of the O–H stretch vibration, O–H bend vibrations (both in plane and out of plane), tunneling splitting effects at finite temperature, and the secondary geometric isotope effect. We compare our total Φ as a function of R with NMR experimental results for enzymes, and in particular with an earlier model parametrization Φ(R), used previously to determine bond lengths.

  20. Electron correlation and bond-length alternation in polyene chains

    Energy Technology Data Exchange (ETDEWEB)

    Kuprievich, V.A.

    1986-11-01

    The PPP model is used to consider polyene chains in the ground state with allowance for the interaction of the electrons with core deformations. The stationary wave functions describing the electron correlations are derived as antisymmetrized products of two-electron functions optimized with respect to all variational parameters. The bond-length alternation can be related to the characteristics of the electron-electron potential; one can allow approximately for the effects of interaction between electrons at adjacent centers on the alternation by renormalizing the parameters in the Hubbard model.

  1. Shear bond strength of composite resin to amalgam: an experiment in vitro using different bonding systems.

    Science.gov (United States)

    Hadavi, F; Hey, J H; Ambrose, E R

    1991-01-01

    The shear bond strength between amalgam and composite resin with and without the use of adhesive systems was evaluated. It was found that the application of Cover-Up II or Prisma Universal Bond prior to placement of composite resin enhanced the shear bond strength between amalgam and composite resin more than five times; and a shear strength of 4.34 and 4.30 MPa was measured respectively. Acid-etching of the roughened amalgam surface prior to application of Prisma Universal Bond decreased the bond strength by nearly 45%. PMID:1784535

  2. Redox-controlled hydrogen bonding: turning a superbase into a strong hydrogen-bond donor.

    Science.gov (United States)

    Wild, Ute; Neuhäuser, Christiane; Wiesner, Sven; Kaifer, Elisabeth; Wadepohl, Hubert; Himmel, Hans-Jörg

    2014-05-12

    Herein the synthesis, structures and properties of hydrogen-bonded aggregates involving redox-active guanidine superbases are reported. Reversible hydrogen bonding is switched on by oxidation of the hydrogen-donor unit, and leads to formation of aggregates in which the hydrogen-bond donor unit is sandwiched by two hydrogen-bond acceptor units. Further oxidation (of the acceptor units) leads again to deaggregation. Aggregate formation is associated with a distinct color change, and the electronic situation could be described as a frozen stage on the way to hydrogen transfer. A further increase in the basicity of the hydrogen-bond acceptor leads to deprotonation reactions.

  3. PMMA to Polystyrene bonding for polymer based microfluidic systems

    KAUST Repository

    Fan, Yiqiang

    2013-03-29

    A thermal bonding technique for Poly (methylmethacrylate) (PMMA) to Polystyrene (PS) is presented in this paper. The PMMA to PS bonding was achieved using a thermocompression method, and the bonding strength was carefully characterized. The bonding temperature ranged from 110 to 125 C with a varying compression force, from 700 to 1,000 N (0.36-0.51 MPa). After the bonding process, two kinds of adhesion quantification methods were used to measure the bonding strength: the double cantilever beam method and the tensile stress method. The results show that the bonding strength increases with a rising bonding temperature and bonding force. The results also indicate that the bonding strength is independent of bonding time. A deep-UV surface treatment method was also provided in this paper to lower the bonding temperature and compression force. Finally, a PMMA to PS bonded microfluidic device was fabricated successfully. © 2013 Springer-Verlag Berlin Heidelberg.

  4. Delocalized π state between molecules through a surface confined pseudodihydrogen bond.

    Science.gov (United States)

    Chen, Lan; Li, Hui; Wee, Andrew Thye Shen

    2010-11-26

    When 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) and coronene molecules coadsorb on the Ag(111) surface, one-dimensional PTCDA molecular oligomers with efficient electronic connection via noncovalent bonds are observed by low temperature scanning tunneling microscopy. Density functional theory calculations indicate the neighboring PTCDA molecules form oligomers due to strong PTCDA-metal interactions, which result in overlapping of π orbitals and pseudodihydrogen surface bonds between molecules. Our results provide a potential approach for electron transport from molecule to molecule directly through noncovalent bond. PMID:21231400

  5. Selectivity of peptide bond dissociation on excitation of a core electron: Effects of a phenyl group

    Science.gov (United States)

    Tsai, Cheng-Cheng; Chen, Jien-Lian; Hu, Wei-Ping; Lin, Yi-Shiue; Lin, Huei-Ru; Lee, Tsai-Yun; Lee, Yuan T.; Ni, Chi-Kung; Liu, Chen-Lin

    2016-09-01

    The selective dissociation of a peptide bond upon excitation of a core electron in acetanilide and N-benzylacetamide was investigated. The total-ion-yield near-edge X-ray absorption fine structure spectra were recorded and compared with the predictions from time-dependent density functional theory. The branching ratios for the dissociation of a peptide bond are observed as 16-34% which is quite significant. This study explores the core-excitation, the X-ray photodissociation pathways, and the theoretical explanation of the NEXAFS spectra of organic molecules containing both a peptide bond and a phenyl group.

  6. Effect of Hydrogen Bonding on Linear and Nonlinear Rheology of Entangled Polymer Melts

    DEFF Research Database (Denmark)

    Shabbir, Aamir; Goldansaz, Hadi; Hassager, Ole;

    2015-01-01

    . The number of AA side groups (hydrogen-bonding groups) after hydrolysis is determined from NMR measurements. We show that using the theoretical dependency of modulus and reptation time on the packing length, we can account for the changes in linear viscoelasticity due to transformation of nBA side groups...... bonds causes G′ and G″ as a function of frequency to shift to a power law scaling of 0.5. Furthermore, the magnitude of G′ and G″ scales linearly with the number of hydrogen-bonding groups. The nonlinear extensional rheology shows extreme strain hardening. The magnitude of extensional stress has...

  7. Lateral buckling and mechanical stretchability of fractal interconnects partially bonded onto an elastomeric substrate

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Haoran [Department of Civil Engineering and Architecture, Zhejiang University, Hangzhou 310058 (China); Departments of Civil and Environmental Engineering and Mechanical Engineering, Center for Engineering and Health, Skin Disease Research Center, Northwestern University, Evanston, Illinois 60208 (United States); Xu, Sheng; Rogers, John A., E-mail: y-huang@northwestern.edu, E-mail: jrogers@illinois.edu [Department of Materials Science and Engineering, Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Xu, Renxiao; Huang, Yonggang, E-mail: y-huang@northwestern.edu, E-mail: jrogers@illinois.edu [Departments of Civil and Environmental Engineering and Mechanical Engineering, Center for Engineering and Health, Skin Disease Research Center, Northwestern University, Evanston, Illinois 60208 (United States); Jiang, Jianqun [Department of Civil Engineering and Architecture, Zhejiang University, Hangzhou 310058 (China); Zhang, Yihui [Departments of Civil and Environmental Engineering and Mechanical Engineering, Center for Engineering and Health, Skin Disease Research Center, Northwestern University, Evanston, Illinois 60208 (United States); Center for Mechanics and Materials, Tsinghua University, Beijing 100084 (China)

    2015-03-02

    Fractal-inspired designs for interconnects that join rigid, functional devices can ensure mechanical integrity in stretchable electronic systems under extreme deformations. The bonding configuration of such interconnects with the elastomer substrate is crucial to the resulting deformation modes, and therefore the stretchability of the entire system. In this study, both theoretical and experimental analyses are performed for postbuckling of fractal serpentine interconnects partially bonded to the substrate. The deformation behaviors and the elastic stretchability of such systems are systematically explored, and compared to counterparts that are not bonded at all to the substrate.

  8. Modeling of Covalent Bonding in Solids by Inversion of Cohesive Energy Curves

    CERN Document Server

    Bazant, M Z; Bazant, Martin Z.; Kaxiras, Efthimios

    1996-01-01

    We provide a systematic test of empirical theories of covalent bonding in solids using an exact procedure to invert ab initio cohesive energy curves. By considering multiple structures of the same material, it is possible for the first time to test competing angular functions, expose inconsistencies in the basic assumption of a cluster expansion, and extract general features of covalent bonding. We test our methods on silicon, and provide the direct evidence that the Tersoff-type bond order formalism correctly describes coordination dependence. For bond-bending forces, we obtain skewed angular functions that favor small angles, unlike existing models. As a proof-of-principle demonstration, we derive a Si interatomic potential which exhibits comparable accuracy to existing models.

  9. Diagnosis of Switching Systems using Hybrid Bond Graph

    Directory of Open Access Journals (Sweden)

    Taher Mekki

    2013-01-01

    Full Text Available Hybrid Bond Graph (HBG is a Bond Graph-based modelling approach which provides an effective tool not only for dynamic modeling but also for fault detection and isolation (FDI of switching systems. Bond graph (BG has been proven useful for FDI for continuous systems. In addition, BG provides the causal relations between systems variables which allow FDI algorithms to be developed systematically from the graph. There are many methods that exploit structural relations and functional redundancy in the system model to find efficient solutions for the residual generation and residual evaluation steps in FDI of switching systems. This paper describes two different techniques, quantitative and qualitative, based on common modelling approach that employs HBG. In quantitative approach, global analytical redundancy relationships (GARRs are derived from the HBG model with a specified causality assignment procedure. GARRs describe the system behaviour at all of its operating modes. In qualitative approach, functional redundancy can be captured by a Temporal Causal Graph (TCG, a directed graph that may include temporal information.

  10. Dirac cones in the spectrum of bond-decorated graphenes

    Energy Technology Data Exchange (ETDEWEB)

    Van den Heuvel, Willem, E-mail: wvan@unimelb.edu.au; Soncini, Alessandro, E-mail: asoncini@unimelb.edu.au [School of Chemistry, The University of Melbourne, VIC 3010 (Australia)

    2014-06-21

    We present a two-band model based on periodic Hückel theory, which is capable of predicting the existence and position of Dirac cones in the first Brillouin zone of an infinite class of two-dimensional periodic carbon networks, obtained by systematic perturbation of the graphene connectivity by bond decoration, that is by inclusion of arbitrary π-electron Hückel networks into each of the three carbon–carbon π-bonds within the graphene unit cell. The bond decoration process can fundamentally modify the graphene unit cell and honeycomb connectivity, representing a simple and general way to describe many cases of graphene chemical functionalization of experimental interest, such as graphyne, janusgraphenes, and chlorographenes. Exact mathematical conditions for the presence of Dirac cones in the spectrum of the resulting two-dimensional π-networks are formulated in terms of the spectral properties of the decorating graphs. Our method predicts the existence of Dirac cones in experimentally characterized janusgraphenes and chlorographenes, recently speculated on the basis of density functional theory calculations. For these cases, our approach provides a proof of the existence of Dirac cones, and can be carried out at the cost of a back of the envelope calculation, bypassing any diagonalization step, even within Hückel theory.

  11. Tensile bond strength of hydroxyethyl methacrylate (HEMA bonding agent to bovine dentine surface at various humidity

    Directory of Open Access Journals (Sweden)

    Adioro Soetojo

    2006-06-01

    Full Text Available One factor that make bonding agent adhere to dentine surface maximally is the humidity condition around the dentine surface. The best bond strength between bonding agent with dentine surface is depending on the moist surface. It mean that the dentine surface should neither too dry or wet. The objective of this research is to know the tensile bond strength of hydroxyethyl methacrylate (HEMA bonding agent to bovine dentine surface at various humidity. The bovine dentine was grounded to give flat surface, which was then etched with 37% phosphoric acid for 15 seconds. Dentine was washed with 20 ml water and dried with blot dry technique. The dentine, except the control group, was placed in a desiccator for one hour at difference humidity. Dentin was removed from desiccator, then covered with bonding agent and put into tensile tool plunger. Self-cured acrylic resin was applied on this bonding agent layer, which was placed on opposite-plunger. After 24 hours, tensile bond strength was measured with Autograph instrument. Data was statistically analyzed with One-Way ANOVA at 95% confidence level, continued with LSD test. Results of this study showed that 60%–90% humidity gave produce the lower of tensile bond strength of bonding agent to dentine surface (p ≤ 0.05. In conclusion, the treatment in 60% humidity gave the greatest tensile bond strength.

  12. The Effect of Post-Bond Heat Treatment on Tensile Property of Diffusion Bonded Austenitic Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Sunghoon; Kim, Sung Kwan; Jang, Changheui [KAIST, Daejeon (Korea, Republic of); Sah, Injin [KAERI, Daejeon (Korea, Republic of)

    2015-12-15

    Diffusion bonding is the key manufacturing process for the micro-channel type heat exchangers. In this study, austenitic alloys such as Alloy 800HT, Alloy 690, and Alloy 600, were diffusion bonded at various temperatures and the tensile properties were measured up to 650 ℃. Tensile ductility of diffusion bonded Alloy 800HT was significantly lower than that of base metal at all test temperatures. While, for Alloy 690 and Alloy 600, tensile ductility of diffusion bonded specimens was comparable to that of base metals up to 500 ℃, above which the ductility became lower. The poor ductility of diffusion bonded specimen could have caused by the incomplete grain boundary migration and precipitates along the bond-line. Application of post-bond heat treatment (PBHT) improved the ductility close to that of base metals up to 550 ℃. Changes in tensile properties were discussed in view of the microstructure in the diffusionbonded area.

  13. 48 CFR 28.105-2 - Patent infringement bonds.

    Science.gov (United States)

    2010-10-01

    ... 48 Federal Acquisition Regulations System 1 2010-10-01 2010-10-01 false Patent infringement bonds... GENERAL CONTRACTING REQUIREMENTS BONDS AND INSURANCE Bonds and Other Financial Protections 28.105-2 Patent infringement bonds. (a) Contracts providing for patent indemnity may require these bonds only if— (1)...

  14. HYDROGEN BONDING IN POLYMERIC ADSORBENTS BASED ADSORPTION AND SEPARATION

    Institute of Scientific and Technical Information of China (English)

    XUMancai; SHIZuoqing; 等

    2000-01-01

    After a concise introduction of hydrogen bonding effects in solute-solute and solute-solvent bonding,the design of polymeric adsorbents based on hydrogen bonding ,selectivity in adsorption through hydrogen bonding,and characterization of hydrogen bonding in adsorption and separation were reviewed with 28 references.

  15. Bond strength of two component injection moulded MID

    DEFF Research Database (Denmark)

    Islam, Mohammad Aminul; Hansen, Hans Nørgaard; Tang, Peter Torben;

    2006-01-01

    Most products of the future will require industrially adapted, cost effective production processes and on this issue two-component (2K) injection moulding is a potential candidate for MID manufacturing. MID based on 2k injection moulded plastic part with selectively metallised circuit tracks allows...... the integration of electrical and mechanical functionalities in a real 3D structure. If 2k injection moulding is applied with two polymers, of which one is plateable and the other is not, it will be possible to make 3D electrical structures directly on the component. To be applicable in the real engineering field...... the two different plastic materials in the MID structure require good bonding between them. This paper finds suitable combinations of materials for MIDs from both bond strength and metallisation view-point. Plastic parts were made by two-shot injection moulding and the effects of some important process...

  16. The first bump-bonded pixel detectors on CVD diamond

    Energy Technology Data Exchange (ETDEWEB)

    Adam, W.; Bauer, C.; Berdermann, E.; Bergonzo, P.; Bogani, F.; Borchi, E.; Brambilla, A.; Bruzzi, M.; Colledani, C.; Conway, J.; Dabrowski, W.; Delpierre, P.; Deneuville, A.; Dulinski, W.; Eijk, B. van; Fallou, A.; Fizzotti, F.; Foulon, F.; Friedl, M.; Gan, K.K.; Gheeraert, E.; Grigoriev, E.; Hallewell, G.; Hall-Wilton, R.; Han, S.; Hartjes, F.; Hrubec, J.; Husson, D.; Kagan, H.; Kania, D.; Kaplon, J.; Karl, C.; Kass, R.; Krammer, M.; Logiudice, A.; Lu, R.; Manfredi, P.F.; Manfredotti, C.; Marshall, R.D.; Meier, D.; Mishina, M.; Oh, A.; Palmieri, V.G.; Pan, L.S.; Peitz, A.; Pernicka, M.; Pirollo, S.; Polesello, P.; Pretzl, K.; Re, V.; Riester, J.L.; Roe, S.; Roff, D.; Rudge, A.; Schnetzer, S.; Sciortino, S.; Speziali, V.; Stelzer, H.; Steuerer, J.; Stone, R.; Tapper, R.J.; Tesarek, R.; Trawick, M.; Trischuk, W. E-mail: william@physics.utoronto.ca; Turchetta, R.; Vittone, E.; Wagner, A.; Walsh, A.M.; Wedenig, R.; Weilhammer, P.; Zeuner, W.; Ziock, H.; Zoeller, M.; Charles, E.; Ciocio, A.; Dao, K.; Einsweiler, K.; Fasching, D.; Gilchriese, M.; Joshi, A.; Kleinfelder, S.; Milgrome, O.; Palaio, N.; Richardson, J.; Sinervo, P.; Zizka, G

    1999-11-01

    Diamond is a nearly ideal material for detecting ionising radiation. Its outstanding radiation hardness, fast charge collection and low leakage current allow it to be used in high radiation environments. These characteristics make diamond sensors particularly appealing for use in the next generation of pixel detectors. Over the last year, the RD42 collaboration has worked with several groups that have developed pixel readout electronics in order to optimise diamond sensors for bump-bonding. This effort resulted in an operational diamond pixel sensor that was tested in a pion beam. We demonstrate that greater than 98% of the channels were successfully bump-bonded and functioning. The device shows good overall hit efficiency as well as clear spatial hit correlation to tracks measured in a silicon reference telescope. A position resolution of 14.8 {mu}m was observed, consistent with expectations given the detector pitch.

  17. Regioselectivity in the Reductive Bond Cleavage of Diarylalkylsulfonium Salts

    DEFF Research Database (Denmark)

    Kampmeier, Jack; Mansurul Hoque, AKM; D. Saeva, Franklin;

    2009-01-01

    This investigation was stimulated by reports that one-electron reductions of monoaryldialkylsulfonium salts never give aryl bond cleavage whereas reductions of diarylmonoalkylsulfonium salts preferentially give aryl bond cleavage. We studied the product ratios from the reductive cleavage of di-4......- tolylethylsulfonium and di-4-tolyl-2-phenylethylsulfonium salts by a variety of one-electron reducing agents ranging in potential from -0.77 to +2.5 eV (vs SCE) and including thermal reductants, indirect electrolyses mediated by a series of cyanoaromatics, and excited singlet states. We report that the cleavage...... products vary from regiospecific alkyl cleavage to predominant aryl cleavage as a function of the potential of the reducing agent. We conclude that differences between the reductive cleavages of mono- and diarylsulfonium salts are direct consequences of the structures of the sulfuranyl radical...

  18. The first bump-bonded pixel detectors on CVD diamond

    CERN Document Server

    Adam, W; Berdermann, E; Bergonzo, P; Bogani, F; Borchi, E; Brambilla, A; Bruzzi, Mara; Colledani, C; Conway, J; Dabrowski, W; Delpierre, P A; Deneuville, A; Dulinski, W; van Eijk, B; Fallou, A; Fizzotti, F; Foulon, F; Fried, M; Gan, K K; Gheeraert, E; Grigoriev, E; Hallewell, G D; Hall-Wilton, R; Han, S; Hartjes, F G; Hrubec, Josef; Husson, D; Kagan, H; Kania, D R; Kaplon, J; Karl, C; Kass, R; Krammer, Manfred; Lo Giudice, A; Lü, R; Manfredi, P F; Manfredotti, C; Marshall, R D; Meier, D; Mishina, M; Oh, A; Palmieri, V G; Pan, L S; Peitz, A; Pernicka, Manfred; Pirollo, S; Polesello, P; Pretzl, Klaus P; Re, V; Riester, J L; Roe, S; Roff, D G; Rudge, A; Schnetzer, S R; Sciortino, S; Speziali, V; Stelzer, H; Steuerer, J; Stone, R; Tapper, R J; Tesarek, R J; Trawick, M L; Trischuk, W; Turchetta, R; Vittone, E; Wagner, A; Walsh, A M; Wedenig, R; Weilhammer, Peter; Zeuner, W; Ziock, H J; Zöller, M; Charles, E; Ciocio, A; Dao, K; Einsweiler, Kevin F; Fasching, D; Gilchriese, M G D; Joshi, A; Kleinfelder, S A; Milgrome, O; Palaio, N; Richardson, J; Sinervo, P K; Zizka, G

    1999-01-01

    Diamond is a nearly ideal material for detecting ionising radiation. Its outstanding radiation hardness, fast charge collection and low leakage current allow it to be used in high radiation environments. These characteristics make diamond sensors particularly appealing for use in the next generation of pixel detectors. Over the last year, the RD42 collaboration has worked with several groups that have developed pixel readout electronics in order to optimise diamond sensors for bump-bonding. This effort resulted in an operational diamond pixel sensor that was tested in a pion beam. We demonstrate that greater than 98565544f the channels were successfully bump-bonded and functioning. The device shows good overall hit efficiency as well as clear spatial hit correlation to tracks measured in a silicon reference telescope. A position resolution of 14.8 mu m was observed, consistent with expectations given the detector pitch. (13 refs).

  19. The first bump-bonded pixel detectors on CVD diamond

    International Nuclear Information System (INIS)

    Diamond is a nearly ideal material for detecting ionising radiation. Its outstanding radiation hardness, fast charge collection and low leakage current allow it to be used in high radiation environments. These characteristics make diamond sensors particularly appealing for use in the next generation of pixel detectors. Over the last year, the RD42 collaboration has worked with several groups that have developed pixel readout electronics in order to optimise diamond sensors for bump-bonding. This effort resulted in an operational diamond pixel sensor that was tested in a pion beam. We demonstrate that greater than 98% of the channels were successfully bump-bonded and functioning. The device shows good overall hit efficiency as well as clear spatial hit correlation to tracks measured in a silicon reference telescope. A position resolution of 14.8 μm was observed, consistent with expectations given the detector pitch

  20. Infrared intensities and charge mobility in hydrogen bonded complexes

    Science.gov (United States)

    Galimberti, Daria; Milani, Alberto; Castiglioni, Chiara

    2013-08-01

    The analytical model for the study of charge mobility in the molecules presented by Galimberti et al. [J. Chem. Phys. 138, 164115 (2013)] is applied to hydrogen bonded planar dimers. Atomic charges and charge fluxes are obtained from density functional theory computed atomic polar tensors and related first derivatives, thus providing an interpretation of the IR intensity enhancement of the X-H stretching band observed upon aggregation. Our results show that both principal and non-principal charge fluxes have an important role for the rationalization of the spectral behavior; moreover, they demonstrate that the modulation of the charge distribution during vibrational motions of the -XH⋯Y- fragment is not localized exclusively on the atoms directly involved in hydrogen bonding. With these premises we made some correlations between IR intensities, interaction energies, and charge fluxes. The model was tested on small dimers and subsequently to the bigger one cytosine-guanine. Thus, the model can be applied to complex systems.