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Sample records for strong covalent bonds

  1. Average and extreme multi-atom Van der Waals interactions: Strong coupling of multi-atom Van der Waals interactions with covalent bonding

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    Finkelstein Alexei V

    2007-07-01

    Full Text Available Abstract Background The prediction of ligand binding or protein structure requires very accurate force field potentials – even small errors in force field potentials can make a 'wrong' structure (from the billions possible more stable than the single, 'correct' one. However, despite huge efforts to optimize them, currently-used all-atom force fields are still not able, in a vast majority of cases, even to keep a protein molecule in its native conformation in the course of molecular dynamics simulations or to bring an approximate, homology-based model of protein structure closer to its native conformation. Results A strict analysis shows that a specific coupling of multi-atom Van der Waals interactions with covalent bonding can, in extreme cases, increase (or decrease the interaction energy by about 20–40% at certain angles between the direction of interaction and the covalent bond. It is also shown that on average multi-body effects decrease the total Van der Waals energy in proportion to the square root of the electronic component of dielectric permittivity corresponding to dipole-dipole interactions at small distances, where Van der Waals interactions take place. Conclusion The study shows that currently-ignored multi-atom Van der Waals interactions can, in certain instances, lead to significant energy effects, comparable to those caused by the replacement of atoms (for instance, C by N in conventional pairwise Van der Waals interactions.

  2. Collapsed tetragonal phase as a strongly covalent and fully nonmagnetic state: Persistent magnetism with interlayer As-As bond formation in Rh-doped Ca0 .8Sr0 .2Fe2As2

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    Zhao, K.; Glasbrenner, J. K.; Gretarsson, H.; Schmitz, D.; Bednarcik, J.; Etter, M.; Sun, J. P.; Manna, R. S.; Al-Zein, A.; Lafuerza, S.; Scherer, W.; Cheng, J. G.; Gegenwart, P.

    2018-02-01

    A well-known feature of the CaFe2As2 -based superconductors is the pressure-induced collapsed tetragonal phase that is commonly ascribed to the formation of an interlayer As-As bond. Using detailed x-ray scattering and spectroscopy, we find that Rh-doped Ca0.8Sr0.2Fe2As2 does not undergo a first-order phase transition and that local Fe moments persist despite the formation of interlayer As-As bonds. Our density functional theory calculations reveal that the Fe-As bond geometry is critical for stabilizing magnetism and the pressure-induced drop in the c lattice parameter observed in pure CaFe2As2 is mostly due to a constriction within the FeAs planes. The collapsed tetragonal phase emerges when covalent bonding of strongly hybridized Fe 3 d and As 4 p states completely wins out over their exchange splitting. Thus the collapsed tetragonal phase is properly understood as a strong covalent phase that is fully nonmagnetic with the As-As bond forming as a by-product.

  3. Covalent bonds against magnetism in transition metal compounds.

    Science.gov (United States)

    Streltsov, Sergey V; Khomskii, Daniel I

    2016-09-20

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

  4. Design of a covalently bonded glycosphingolipid microarray

    DEFF Research Database (Denmark)

    Arigi, Emma; Blixt, Klas Ola; Buschard, Karsten

    2012-01-01

    Glycosphingolipids (GSLs) are well known ubiquitous constituents of all eukaryotic cell membranes, yet their normal biological functions are not fully understood. As with other glycoconjugates and saccharides, solid phase display on microarrays potentially provides an effective platform for in vi......Glycosphingolipids (GSLs) are well known ubiquitous constituents of all eukaryotic cell membranes, yet their normal biological functions are not fully understood. As with other glycoconjugates and saccharides, solid phase display on microarrays potentially provides an effective platform......, the major classes of plant and fungal GSLs. In this work, a prototype "universal" GSL-based covalent microarray has been designed, and preliminary evaluation of its potential utility in assaying protein-GSL binding interactions investigated. An essential step in development involved the enzymatic release......-mercaptoethylamine, was also tested. Underivatized or linker-derivatized lyso-GSL were then immobilized on N-hydroxysuccinimide- or epoxide-activated glass microarray slides and probed with carbohydrate binding proteins of known or partially known specificities (i.e., cholera toxin B-chain; peanut agglutinin...

  5. Factors Contributing to Students' Misconceptions in Learning Covalent Bonds

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    Erman, Erman

    2017-01-01

    This study aims to identify students' misconceptions regarding covalent bonds. Seventy-seven graduate students in the middle of Indonesia participated in the study. Data were collected in three stages. First, misconceptions were identified by using the Semi Open Diagnostic Test. Ten students who experienced the worst misconceptions were…

  6. Covalency in the f-element-chalcogen bond

    Energy Technology Data Exchange (ETDEWEB)

    Ingram, Kieran I.M. [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom); Kaltsoyannis, Nikolas [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)], E-mail: n.kaltsoyannis@ucl.ac.uk; Gaunt, Andrew J.; Neu, Mary P. [Inorganic, Isotope and Actinide Chemistry (C-IIAC), Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2007-10-11

    The geometric and electronic structures of the title complexes have been studied using gradient corrected density functional theory. Excellent agreement is observed between computed r(M-E) and experimental values in analogous {sup i}Pr complexes. Natural charge analysis indicates that the M-E bond becomes less ionic in the order O>S>S> Te, and that this decrease is largest for U and smallest for La. Natural and Mulliken overlap populations suggest increasing M-E covalency as group 16 is descended, and also in the order Lacovalency down group 16 arises from increased metal d (and s) participation in the bonding, while that from La to Pu and U stems from larger 5f orbital involvement compared with 4f.

  7. Covalent bond symmetry breaking and protein secondary structure

    OpenAIRE

    Lundgren, Martin; Niemi, Antti J.

    2011-01-01

    Both symmetry and organized breaking of symmetry have a pivotal r\\^ole in our understanding of structure and pattern formation in physical systems, including the origin of mass in the Universe and the chiral structure of biological macromolecules. Here we report on a new symmetry breaking phenomenon that takes place in all biologically active proteins, thus this symmetry breaking relates to the inception of life. The unbroken symmetry determines the covalent bond geometry of a sp3 hybridized ...

  8. Competition between Dehydrogenative Organometallic Bonding and Covalent Coupling of an Unfunctionalized Porphyrin on Cu(111).

    Science.gov (United States)

    Xiang, Feifei; Gemeinhardt, Anja; Schneider, M Alexander

    2018-02-27

    We studied the formation of linked porphyrin oligomers from 5,15-diphenylporphyrin (2H-DPP) by thermal, substrate-assisted organometallic and dehydrogenation coupling on Cu(111) by scanning tunneling microscopy. In the range of 300-620 K, we find three distinct stages, at 300 K, the intact 2H-DPP molecules self-assemble into linear structures held together by van der Waals forces. Increasing the substrate temperature, self-metalation and intramolecular ring-closing reactions result in planar and isolated DPP species on the surface. By C-H cleavage, porphyrin oligomers bonded by organometallic and covalent bonds between the modified DPP are formed. The amount of covalently bonded DPP oligomers increases strongly with annealing time and temperature, and they become the dominant species at 570 K. In contrast, the number of organometallically bonded DPP oligomers increases moderately even up to 620 K, indicating that in this case the organometallic bond is no precursor of the covalent bond.

  9. Hydrogels Based on Dynamic Covalent and Non Covalent Bonds: A Chemistry Perspective

    Directory of Open Access Journals (Sweden)

    Francesco Picchioni

    2018-03-01

    Full Text Available Hydrogels based on reversible covalent bonds represent an attractive topic for research at both academic and industrial level. While the concept of reversible covalent bonds dates back a few decades, novel developments continue to appear in the general research area of gels and especially hydrogels. The reversible character of the bonds, when translated at the general level of the polymeric network, allows reversible interaction with substrates as well as responsiveness to variety of external stimuli (e.g., self-healing. These represent crucial characteristics in applications such as drug delivery and, more generally, in the biomedical world. Furthermore, the several possible choices that can be made in terms of reversible interactions generate an almost endless number of possibilities in terms of final product structure and properties. In the present work, we aim at reviewing the latest developments in this field (i.e., the last five years by focusing on the chemistry of the systems at hand. As such, this should allow molecular designers to develop a toolbox for the synthesis of new systems with tailored properties for a given application.

  10. From covalent bonding to coalescence of metallic nanorods

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    Lee Soohwan

    2011-01-01

    Full Text Available Abstract Growth of metallic nanorods by physical vapor deposition is a common practice, and the origin of their dimensions is a characteristic length scale that depends on the three-dimensional Ehrlich-Schwoebel (3D ES barrier. For most metals, the 3D ES barrier is large so the characteristic length scale is on the order of 200 nm. Using density functional theory-based ab initio calculations, this paper reports that the 3D ES barrier of Al is small, making it infeasible to grow Al nanorods. By analyzing electron density distributions, this paper shows that the small barrier is the result of covalent bonding in Al. Beyond the infeasibility of growing Al nanorods by physical vapor deposition, the results of this paper suggest a new mechanism of controlling the 3D ES barrier and thereby nanorod growth. The modification of local degree of covalent bonding, for example, via the introduction of surfactants, can increase the 3D ES barrier and promote nanorod growth, or decrease the 3D ES barrier and promote thin film growth.

  11. Application of the Covalent Bond Classification Method for the Teaching of Inorganic Chemistry

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    Green, Malcolm L. H.; Parkin, Gerard

    2014-01-01

    The Covalent Bond Classification (CBC) method provides a means to classify covalent molecules according to the number and types of bonds that surround an atom of interest. This approach is based on an elementary molecular orbital analysis of the bonding involving the central atom (M), with the various interactions being classified according to the…

  12. Covalent binding of sulfamethazine to natural and synthetic humic acids: assessing laccase catalysis and covalent bond stability.

    Science.gov (United States)

    Gulkowska, Anna; Sander, Michael; Hollender, Juliane; Krauss, Martin

    2013-07-02

    Sulfonamide antibiotics form stable covalent bonds with quinone moieties in organic matter via nucleophilic addition reactions. In this work, we combined analytical electrochemistry with trace analytics to assess the catalytic role of the oxidoreductase laccase in the binding of sulfamethazine (SMZ) to Leonardite humic acid (LHA) and to four synthetic humic acids (SHAs) polymerized from low molecular weight precursors and to determine the stability of the formed bonds. In the absence of laccase, a significant portion of the added SMZ formed covalent bonds with LHA, but only a very small fraction (<0.4%) of the total quinone moieties in LHA reacted. Increasing absolute, but decreasing relative concentrations of SMZ-LHA covalent bonds with increasing initial SMZ concentration suggested that the quinone moieties in LHA covered a wide distribution in reactivity for the nucleophilic addition of SMZ. Laccase catalyzed the formation of covalent bonds by oxidizing unreactive hydroquinone moieties in LHA to reactive, electrophilic quinone moieties, of which a large fraction (5%) reacted with SMZ. Compared to LHA, the SHA showed enhanced covalent bond formation in the absence of laccase, suggesting a higher reactivity of their quinone moieties toward nucleophilic addition. This work supports that binding to soil organic matter (SOM) is an important process governing the fate, bioactivity, and extractability of sulfonamides in soils.

  13. Effective scheme for partitioning covalent bonds in density-functional embedding theory: From molecules to extended covalent systems.

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    Huang, Chen; Muñoz-García, Ana Belén; Pavone, Michele

    2016-12-28

    Density-functional embedding theory provides a general way to perform multi-physics quantum mechanics simulations of large-scale materials by dividing the total system's electron density into a cluster's density and its environment's density. It is then possible to compute the accurate local electronic structures and energetics of the embedded cluster with high-level methods, meanwhile retaining a low-level description of the environment. The prerequisite step in the density-functional embedding theory is the cluster definition. In covalent systems, cutting across the covalent bonds that connect the cluster and its environment leads to dangling bonds (unpaired electrons). These represent a major obstacle for the application of density-functional embedding theory to study extended covalent systems. In this work, we developed a simple scheme to define the cluster in covalent systems. Instead of cutting covalent bonds, we directly split the boundary atoms for maintaining the valency of the cluster. With this new covalent embedding scheme, we compute the dehydrogenation energies of several different molecules, as well as the binding energy of a cobalt atom on graphene. Well localized cluster densities are observed, which can facilitate the use of localized basis sets in high-level calculations. The results are found to converge faster with the embedding method than the other multi-physics approach ONIOM. This work paves the way to perform the density-functional embedding simulations of heterogeneous systems in which different types of chemical bonds are present.

  14. Diazonium-derived aryl films on gold nanoparticles: evidence for a carbon-gold covalent bond.

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    Laurentius, Lars; Stoyanov, Stanislav R; Gusarov, Sergey; Kovalenko, Andriy; Du, Rongbing; Lopinski, Gregory P; McDermott, Mark T

    2011-05-24

    Tailoring the surface chemistry of metallic nanoparticles is generally a key step for their use in a wide range of applications. There are few examples of organic films covalently bound to metal nanoparticles. We demonstrate here that aryl films are formed on gold nanoparticles from the spontaneous reduction of diazonium salts. The structure and the bonding of the film is probed with surface-enhanced Raman scattering (SERS). Extinction spectroscopy and SERS show that a nitrobenzene film forms on gold nanoparticles from the corresponding diazonium salt. Comparison of the SERS spectrum with spectra computed from density functional theory models reveals a band characteristic of a Au-C stretch. The observation of this stretch is direct evidence of a covalent bond. A similar band is observed in high-resolution electron energy loss spectra of nitrobenzene layers on planar gold. The bonding of these types of films through a covalent interaction on gold is consistent with their enhanced stability observed in other studies. These findings provide motivation for the use of diazonium-derived films on gold and other metals in applications where high stability and/or strong adsorbate-substrate coupling are required.

  15. Extending density functional embedding theory for covalently bonded systems.

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    Yu, Kuang; Carter, Emily A

    2017-12-19

    Quantum embedding theory aims to provide an efficient solution to obtain accurate electronic energies for systems too large for full-scale, high-level quantum calculations. It adopts a hierarchical approach that divides the total system into a small embedded region and a larger environment, using different levels of theory to describe each part. Previously, we developed a density-based quantum embedding theory called density functional embedding theory (DFET), which achieved considerable success in metals and semiconductors. In this work, we extend DFET into a density-matrix-based nonlocal form, enabling DFET to study the stronger quantum couplings between covalently bonded subsystems. We name this theory density-matrix functional embedding theory (DMFET), and we demonstrate its performance in several test examples that resemble various real applications in both chemistry and biochemistry. DMFET gives excellent results in all cases tested thus far, including predicting isomerization energies, proton transfer energies, and highest occupied molecular orbital-lowest unoccupied molecular orbital gaps for local chromophores. Here, we show that DMFET systematically improves the quality of the results compared with the widely used state-of-the-art methods, such as the simple capped cluster model or the widely used ONIOM method.

  16. On the covalent character of rare gas bonding interactions: a new kind of weak interaction.

    Science.gov (United States)

    Zou, Wenli; Nori-Shargh, Davood; Boggs, James E

    2013-01-10

    At the averaged quadratic coupled-cluster (AQCC) level, a number of selected rare gas (Rg) containing systems have been studied using the quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO), and several other analysis methods. According to the criteria for a covalent bond, most of the Rg-M (Rg = He, Ne, Ar, Kr, Xe; M = Be, Cu, Ag, Au, Pt) bonds in this study are assigned to weak interactions instead of van der Walls or covalent ones. Our results indicate that the rare gas bond is a new kind of weak interaction, like the hydrogen bond for example.

  17. Emergent property of high hardness for C-rich ruthenium carbides: partial covalent Ru-Ru bonds.

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    Xu, Chunhong; Yu, Hongyu; Kuo, Bao; Ma, Shuailing; Xiao, Xuehui; Li, Da; Duan, Defang; Jin, Xilian; Liu, Bingbing; Cui, Tian

    2018-02-28

    Hard materials are being investigated all the time by combining transition metals with light elements. Combining a structure search with first-principles functional calculations, we first discovered three stable stoichiometric C-rich ruthenium carbides in view of three synthesis routes, namely, the ambient phases of Ru 2 C 3 and RuC, and two high pressure phases of RuC 4 . There is a phase transition of RuC 4 from the P3[combining macron]m1 structure to the R3[combining macron]m structure above 98 GPa. The calculations of elastic constants and phonon dispersions show their mechanical and dynamical stability. The large elastic modulus, high Debye temperature and the estimated hardness values suggest that these hard ruthenium carbides have good mechanical properties. The analyses of electronic structure and chemical bonding indicate that chemical bonding, not carbon content, is the key factor for the hardness in these metallic C-rich ruthenium carbides. The partial covalent Ru-C bonds and strong covalent C-C bonds are responsible for the high hardness. Moreover, the emergence of partial covalent Ru-Ru bonds can enhance the hardness of RuC, while the ionic Ru-Ru bonds can weaken the hardness of Ru 2 C 3 .

  18. Moving beyond Definitions: What Student-Generated Models Reveal about Their Understanding of Covalent Bonding and Ionic Bonding

    Science.gov (United States)

    Luxford, Cynthia J.; Bretz, Stacey Lowery

    2013-01-01

    Chemistry students encounter a variety of terms, definitions, and classification schemes that many instructors expect students to memorize and be able to use. This research investigated students' descriptions of ionic and covalent bonding beyond definitions in order to explore students' knowledge about chemical bonding. Using Johnstone's Multiple…

  19. Competing covalent and ionic bonding in Ge-Sb-Te phase change materials.

    Science.gov (United States)

    Mukhopadhyay, Saikat; Sun, Jifeng; Subedi, Alaska; Siegrist, Theo; Singh, David J

    2016-05-19

    Ge2Sb2Te5 and related phase change materials are highly unusual in that they can be readily transformed between amorphous and crystalline states using very fast melt, quench, anneal cycles, although the resulting states are extremely long lived at ambient temperature. These states have remarkably different physical properties including very different optical constants in the visible in strong contrast to common glass formers such as silicates or phosphates. This behavior has been described in terms of resonant bonding, but puzzles remain, particularly regarding different physical properties of crystalline and amorphous phases. Here we show that there is a strong competition between ionic and covalent bonding in cubic phase providing a link between the chemical basis of phase change memory property and origins of giant responses of piezoelectric materials (PbTiO3, BiFeO3). This has important consequences for dynamical behavior in particular leading to a simultaneous hardening of acoustic modes and softening of high frequency optic modes in crystalline phase relative to amorphous. This different bonding in amorphous and crystalline phases provides a direct explanation for different physical properties and understanding of the combination of long time stability and rapid switching and may be useful in finding new phase change compositions with superior properties.

  20. Covalently Bonded Chitosan on Graphene Oxide via Redox Reaction

    Directory of Open Access Journals (Sweden)

    Víctor M. Castaño

    2013-03-01

    Full Text Available Carbon nanostructures have played an important role in creating a new field of materials based on carbon. Chemical modification of carbon nanostructures through grafting has been a successful step to improve dispersion and compatibility in solvents, with biomolecules and polymers to form nanocomposites. In this sense carbohydrates such as chitosan are extremely valuable because their functional groups play an important role in diversifying the applications of carbon nanomaterials. This paper reports the covalent attachment of chitosan onto graphene oxide, taking advantage of this carbohydrate at the nanometric level. Grafting is an innovative route to modify properties of graphene, a two-dimensional nanometric arrangement, which is one of the most novel and promising nanostructures. Chitosan grafting was achieved by redox reaction using different temperature conditions that impact on the morphology and features of graphene oxide sheets. Transmission Electron Microscopy, Fourier Transform Infrared, Raman and Energy Dispersive spectroscopies were used to study the surface of chitosan-grafted-graphene oxide. Results show a successful modification indicated by the functional groups found in the grafted material. Dispersions of chitosan-grafted-graphene oxide samples in water and hexane revealed different behavior due to the chemical groups attached to the graphene oxide sheet.

  1. A simple approach for immobilization of gold nanoparticles on graphene oxide sheets by covalent bonding

    NARCIS (Netherlands)

    Pham, Tuan Anh; Choi, Byung Choon; Lim, Kwon Taek; Jeong, Yeon Tae

    2011-01-01

    Amino - functionalized gold nanoparticles with a diameter of around 5 nm were immobilized onto the surface of graphene oxide sheets (GOS) by covalent bonding through a simple amidation reaction. Pristine graphite was firstly oxidized and exfoliated to obtain GOS, which further were acylated with

  2. Formation of Me–O–Si covalent bonds at the interface between polysilazane and stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Amouzou, Dodji, E-mail: adodji@gmail.com [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, 5000 Namur (Belgium); Fourdrinier, Lionel; Maseri, Fabrizio [CRM-Group, Boulevard de Colonster, B 57, 4000 Liège (Belgium); Sporken, Robert [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, 5000 Namur (Belgium)

    2014-11-30

    Highlights: • Natural metal-oxides, hydroxides are detected on the top surface of steel substrates we tested. • Polysilazane reacts with hydroxide functional groups on steel substrates to form Cr–O–Si and Fe–O–Si covalent bonds. • Covalent bonding between steel and polysilazane at the interface was probed using spectroscopic techniques. - Abstract: In earlier works, we demonstrated the potential of polysilazane (PSZ) coatings for a use as insulating layers in Cu(In,Ga)Se{sub 2} (CIGS) solar cells prepared on steels substrates and showed a good adhesion between PSZ coatings and both AISI316 and AISI430 steels. In the present paper, spectroscopic techniques are used to elucidate the reason of such adhesion. X-ray Photoelectron Spectroscopy (XPS) was used to investigate surfaces for the two steel substrates and showed the presence of metal oxides and metal hydroxides at the top surface. XPS has been also used to probe interfaces between substrates and PSZ, and metallosiloxane (Me–O–Si) covalent bonds have been detected. These results were confirmed by Infra-Red Reflection Absorption Spectroscopy (IRRAS) analyses since vibrations related to Cr–O–Si and Fe–O–Si compounds were detected. Thus, the good adhesion between steel substrates and PSZ coatings was explained by covalent bonding through chemical reactions between PSZ precursors and hydroxide functional groups present on top surface of the two types of steel. Based on these results, an adhesion mechanism between steel substrates and PSZ coatings is proposed.

  3. Ultrafast cooling by covalently bonded graphene-carbon nanotube hybrid immersed in water

    DEFF Research Database (Denmark)

    Chen, Jie; Walther, Jens Honore; Koumoutsakos, Petros

    2016-01-01

    , we demonstrate, through transient heat-dissipation simulations, that a covalently bonded graphene-carbon nanotube (G-CNT) hybrid immersed in water is a promising solution for the ultrafast cooling of such high-temperature and high heat-flux surfaces. The G-CNT hybrid offers a unique platform...

  4. Covalently Bonded Graphene-Carbon Nanotube Hybrid for High-Performance Thermal Interfaces

    DEFF Research Database (Denmark)

    Chen, Jie; Walther, Jens H.; Koumoutsakos, Petros

    2015-01-01

    their applications as effective thermal interface materials (TIMs). Here, a covalently bonded graphene–CNT (G-CNT) hybrid is presented that multiplies the axial heat transfer capability of individual CNTs through their parallel arrangement, while at the same time it provides a large contact area for efficient heat...

  5. Is there any fundamental difference between ionic, covalent, and others types of bond? A canonical perspective on the question.

    Science.gov (United States)

    Walton, Jay R; Rivera-Rivera, Luis A; Lucchese, Robert R; Bevan, John W

    2017-06-21

    The concept of chemical bonding is normally presented and simplified through two models: the covalent bond and the ionic bond. Expansion of the ideal covalent and ionic models leads chemists to the concepts of electronegativity and polarizability, and thus to the classification of polar and non-polar bonds. In addition, the intermolecular interactions are normally viewed as physical phenomena without direct correlation to the chemical bond in any simplistic model. Contrary to these traditional concepts of chemical bonding, recently developed canonical approaches demonstrate a unified perspective on the nature of binding in pairwise interatomic interactions. This new canonical model, which is a force-based approach with a basis in fundamental molecular quantum mechanics, confirms much earlier assertions that in fact there are no fundamental distinctions among covalent bonds, ionic bonds, and intermolecular interactions including the hydrogen bond, the halogen bond, and van der Waals interactions.

  6. Fast and accurate covalent bond predictions using perturbation theory in chemical space

    Science.gov (United States)

    Chang, Kuang-Yu; von Lilienfeld, Anatole

    I will discuss the predictive accuracy of perturbation theory based estimates of changes in covalent bonding due to linear alchemical interpolations among systems of different chemical composition. We have investigated single, double, and triple bonds occurring in small sets of iso-valence-electronic molecular species with elements drawn from second to fourth rows in the p-block of the periodic table. Numerical evidence suggests that first order estimates of covalent bonding potentials can achieve chemical accuracy (within 1 kcal/mol) if the alchemical interpolation is vertical (fixed geometry) among chemical elements from third and fourth row of the periodic table. When applied to nonbonded systems of molecular dimers or solids such as III-V semiconductors, alanates, alkali halides, and transition metals, similar observations hold, enabling rapid predictions of van der Waals energies, defect energies, band-structures, crystal structures, and lattice constants.

  7. Reversible CO2 Capture by Conjugated Ionic Liquids through Dynamic Covalent Carbon-Oxygen Bonds.

    Science.gov (United States)

    Pan, Mingguang; Cao, Ningning; Lin, Wenjun; Luo, Xiaoyan; Chen, Kaihong; Che, Siying; Li, Haoran; Wang, Congmin

    2016-09-08

    The strong chemisorption of CO2 is always accompanied by a high absorption enthalpy, and traditional methods to reduce the absorption enthalpy lead to decreased CO2 capacities. Through the introduction of a large π-conjugated structure into the anion, a dual-tuning approach for the improvement of CO2 capture by anion-functionalized ionic liquids (ILs) resulted in a high capacity of up to 0.96 molCO2  mol-1IL and excellent reversibility. The increased capacity and improved desorption were supported by quantum chemical calculations, spectroscopic investigations, and thermogravimetric analysis. The increased capacity may be a result of the strengthened dynamic covalent bonds in these π-electron-conjugated structures through anion aggregation upon the uptake of CO2 , and the improved desorption originates from the charge dispersion of interaction sites through the large π-electron delocalization. These results provide important insights into effective strategies for CO2 capture. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Durable Anti-Superbug Polymers: Covalent Bonding of Ionic Liquid onto the Polymer Chains.

    Science.gov (United States)

    Guan, Jipeng; Wang, Yanyuan; Wu, Shilu; Li, Yongjin; Li, Jingye

    2017-12-11

    Here, we fabricated the ionic liquid (IL) grafted poly(vinylidene fluoride) (PVDF) (PVDF-g-IL) via electron-beam irradiation to fight common bacteria and multidrug-resistant "superbugs". Two types of ILs, 1-vinyl-3-butylimmidazolium chloride (IL (Cl)) and 1-vinyl-3-ethylimidazolium tetrafluoroborate (IL (BF 4 )), were used. It was found that the PVDF-g-IL exhibited superior antibacterial performance, with almost the same mechanical and thermal performance as unmodified PVDF. Nonwovens and films made from PVDF-g-IL materials exhibited broad-spectrum antimicrobial activity against common bacteria and "superbugs" with the strong electrostatic interactions between ILs and microbial cell membranes. With extremely low IL loading (0.05 wt %), the cell reduction of PVDF-g-IL (Cl) nonwovens improved from 0.2 to 4.4 against S. aureus. Moreover, the antibacterial activity of PVDF-g-IL nonwovens was permanent for the covalent bonds between ILs and polymer chains. The work provides a simple strategy to immobilize ionic antibacterial agents onto polymer substrates, which may have great potential applications in healthcare and household applications.

  9. Probing covalency in halogen bonds through donor K-edge X-ray absorption spectroscopy: polyhalides as coordination complexes.

    Science.gov (United States)

    Mustoe, Chantal L; Gunabalasingam, Mathusan; Yu, Darren; Patrick, Brian O; Kennepohl, Pierre

    2017-10-13

    The properties of halogen bonds (XBs) in solid-state I 2 X - and I 4 X - materials (where X = Cl, Br) are explored using donor K-edge X-ray absorption spectroscopy (XAS) to experimentally determine the degree of charge transfer in such XB interactions. The degree of covalency in these bonds is substantial, even in cases where significantly weaker secondary interactions are observed. These data, in concert with previous work in this area, suggests that certain halogen bonds have covalent contributions to bonding that are similar to, and even exceed, those observed in transition metal coordinate bonds. For this reason, we suggest that XB interactions of this type be denoted in a similar way to coordination bonds (X → Y) as opposed to using a representation that is the same as for significantly less covalent hydrogen bonds (XY).

  10. Correlations of acute toxicity of metal ions and the covalent/ionic character of their bonds

    Energy Technology Data Exchange (ETDEWEB)

    Turner, J.E.; Williams, M.W.; Jacobson, K.B.; Hingerty, B.E.

    1984-01-01

    We have investigated correlations between physicochemical properties of 24 metal ions and their acute toxicity in mice and Drosophila. A high correlation for a softness parameter suggests that the relative covalent/ionic character of the bonds formed by the metal ions may be important in determining their toxicity. This hypothesis is reinforced by model calculations of metal binding to dinucleotides in water. Since the nature of bonds depends on ligand electronegativity, we searched for correlations involving this parameter. Although electronegativity is useful for interpreting some aspects of metal-ion behavior related to toxicity, it does not yield improved correlations. 8 refs., 3 figs., 1 tab.

  11. Intermolecular covalent pi-pi bonding interaction indicated by bond distances, energy bands, and magnetism in biphenalenyl biradicaloid molecular crystal.

    Science.gov (United States)

    Huang, Jingsong; Kertesz, Miklos

    2007-02-14

    Density-functional theory (DFT) calculations were performed for energy band structure and geometry optimizations on the stepped pi-chain, the isolated molecule and (di)cations of the chain, and various related molecules of a neutral biphenalenyl biradicaloid (BPBR) organic semiconductor 2. The dependence of the geometries on crystal packing provides indirect evidence for the intermolecular covalent pi-pi bonding interaction through space between neighboring pi-stacked phenalenyl units along the chain. The two phenalenyl electrons on each molecule, occupying the singly occupied molecular orbitals (SOMOs), are participating in the intermolecular covalent pi-pi bonding making them partially localized on the phenalenyl units and less available for intramolecular delocalization. The band structure shows a relatively large bandwidth and small band gap indicative of good pi-pi overlap and delocalization between neighboring pi-stacked phenalenyl units. A new interpretation is presented for the magnetism of the stepped pi-chain of 2 using an alternating Heisenberg chain model, which is consistent with DFT total energy calculations for 2 and prevails against the previous interpretation using a Bleaney-Bowers dimer model. The obtained transfer integrals and the magnetic exchange parameters fit well into the framework of a Hubbard model. All presented analyses on molecular geometries, energy bands, and magnetism provide a coherent picture for 2 pointing toward an alternating chain with significant intermolecular through-space covalent pi-pi bonding interactions in the molecular crystal. Surprisingly, both the intermolecular transfer integrals and exchange parameters are larger than the intramolecular through-bond values indicating the effectiveness of the intermolecular overlap of the phenalenyl SOMO electrons.

  12. Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures.

    Science.gov (United States)

    Fan, Qitang; Wang, Tao; Liu, Liming; Zhao, Jin; Zhu, Junfa; Gottfried, J Michael

    2015-03-14

    The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br⋯Br intermolecular bonds. Upon annealing the organic monolayer to ∼140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C-Br bonds and formation of C-Cu-C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands.

  13. Structure, stability and electrochromic properties of polyaniline film covalently bonded to indium tin oxide substrate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Wenzhi, E-mail: zhangwz@xatu.edu.cn [Key Laboratory for Photoelectric Functional Materials and Devices of Shaanxi Province, School of Materials and Chemical Engineering, Xi’an Technological University, Xi’an 710021 (China); Ju, Wenxing; Wu, Xinming; Wang, Yan; Wang, Qiguan; Zhou, Hongwei; Wang, Sumin [Key Laboratory for Photoelectric Functional Materials and Devices of Shaanxi Province, School of Materials and Chemical Engineering, Xi’an Technological University, Xi’an 710021 (China); Hu, Chenglong [Key Laboratory of Optoelectronic Chemical Materials and Devices of Ministry of Education, School of Chemistry and Environmental Engineering, Jianghan University, Wuhan 430056 (China)

    2016-03-30

    Graphical abstract: A chemical bonding approach was proposed to prepare the PANI film covalently bonded to ITO substrate and the film exhibited high electrochemical activities and stability compared with that obtained by conventional film-forming approach. - Highlights: • The PANI film covalently bonded to ITO substrate was prepared using ABPA as modifier. • The oxidative potentials of the obtained PANI film were decreased. • The obtained PANI film exhibits high electrochemical activities and stability. - Abstract: Indium tin oxide (ITO) substrate was modified with 4-aminobenzylphosphonic acid (ABPA), and then the polyaniline (PANI) film covalently bonded to ITO substrate was prepared by the chemical oxidation polymerization. X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR-IR) spectroscopy, and atomic force microscopy (AFM) measurements demonstrated that chemical binding was formed between PANI and ABPA-modified ITO surface, and the maximum thickness of PANI layer is about 30 nm. The adhesive strength of PANI film on ITO substrate was tested by sonication. It was found that the film formed on the modified ITO exhibited a much better stability than that on bare one. Cyclic voltammetry (CV) and UV–vis spectroscopy measurements indicated that the oxidative potentials of PANI film on ABPA-modified ITO substrate were decreased and the film exhibited high electrochemical activities. Moreover, the optical contrast increased from 0.58 for PANI film (without ultrasound) to 1.06 for PANI film (after ultrasound for 60 min), which had an over 83% enhancement. The coloration time was 20.8 s, while the bleaching time was 19.5 s. The increase of electrochromic switching time was due to the lower ion diffusion coefficient of the large cation of (C{sub 4}H{sub 9}){sub 4}N{sup +} under the positive and negative potentials as comparison with the small Li{sup +} ion.

  14. Layer-by-Layer Self-Assembled Graphene Multilayer Films via Covalent Bonds for Supercapacitor Electrodes

    Directory of Open Access Journals (Sweden)

    Xianbin Liu

    2015-05-01

    Full Text Available To maximize the utilization of its single-atom thin nature, a facile scheme to fabricate graphene multilayer films via a layer-by-layer self-assembled process was presented. The structure of multilayer films was constructed by covalently bonding graphene oxide (GO using p-phenylenediamine (PPD as a covalent cross-linking agent. The assembly process was confirmed to be repeatable and the structure was stable. With the π-π conjugated structure and a large number of spaces in the framework, the graphene multi‐ layer films exhibited excellent electrochemical perform‐ ance. The uniform ultrathin electrode exhibited a capacitance of 41.71 μF/cm2 at a discharge current of 0.1 μA/cm2, and displayed excellent stability of 88.9 % after 1000 charge-discharge cycles.

  15. Covalent bonding of chloroanilines to humic constituents: Pathways, kinetics, and stability

    International Nuclear Information System (INIS)

    Kong, Deyang; Xia, Qing; Liu, Guoqiang; Huang, Qingguo; Lu, Junhe

    2013-01-01

    Covalent coupling to natural humic constituents comprises an important transformation pathway for anilinic pollutants in the environment. We systematically investigated the reactions of chlorine substituted anilines with catechol and syringic acid in horseradish peroxidase (HRP) catalyzed systems. It was demonstrated that although nucleophilic addition was the mechanism of covalent bonding to both catechol and syringic acid, chloroanilines coupled to the 2 humic constituents via slightly different pathways. 1,4-addition and 1,2-addition are involved to catechol and syringic acid, respectively. 1,4-addition showed empirical 2nd order kinetics and this pathway seemed to be more permanent than 1,2-addition. Stability experiments demonstrated that cross-coupling products with syringic acid could be easily released in acidic conditions. However, cross-coupling with catechol was relatively stable at similar conditions. Thus, the environmental behavior and bioavailability of the coupling products should be carefully assessed. -- Highlights: •Chloroanilines covalently coupled to humic constituents in HRP catalyzed processes, which facilitated their transformation. •MS technique was employed to analyze the coupling products and therefore elucidate the reaction pathways. •Chloroanilines couple to catechol and syringic acid via 1,4- and 1,2-nucleophilic addition pathways, respectively. •Cross-coupling products formed via 1,4-nucleophilic addition pathway were more stable than those via 1,2-addition pathway. -- Bound residues of chloroanilines formed via 1,2- and 1,4-nucleophilic addition pathways showed different stability

  16. Characteristics of enzyme hydrolyzing natural covalent bond between RNA and protein VPg of encephalomyocarditis virus

    International Nuclear Information System (INIS)

    Drygin, Yu.F.; Siyanova, E.Yu.

    1986-01-01

    The isolation and a preliminary characterization of the enzyme specifically hydrolyzing the phosphodiester bond between protein VPg and the RNA of encephalomyocarditis virus was the goal of the present investigation. The enzyme was isolated from a salt extract of Krebs II mouse ascites carcinoma cells by ion-exchange and affinity chromatography. It was found that the enzyme actually specifically cleaves the covalent bond between the RNA and protein, however, the isolation procedure does not free the enzyme from impurities which partially inhibit it. The enzyme cleaves the RNA-protein VPg complex of polio virus at a high rate, it is completely inactivated at 55 0 C, and is partially inhibited by EDTA

  17. Development of the Bonding Representations Inventory to Identify Student Misconceptions about Covalent and Ionic Bonding Representations

    Science.gov (United States)

    Luxford, Cynthia J.; Bretz, Stacey Lowery

    2014-01-01

    Teachers use multiple representations to communicate the concepts of bonding, including Lewis structures, formulas, space-filling models, and 3D manipulatives. As students learn to interpret these multiple representations, they may develop misconceptions that can create problems in further learning of chemistry. Interviews were conducted with 28…

  18. Strong and weak hydrogen bonds in drug–DNA complexes

    Indian Academy of Sciences (India)

    The dataset was extracted from the protein data bank (PDB). The analysis was performed with an in-house software, hydrogen bond analysis tool (HBAT). In addition to strong hydrogen bonds such as O−H···O and N−H···O, the ubiquitous presence of weak hydrogen bonds such as C−H···O is implicated in molecular ...

  19. H-shaped supra-amphiphiles based on a dynamic covalent bond.

    Science.gov (United States)

    Wang, Guangtong; Wang, Chao; Wang, Zhiqiang; Zhang, Xi

    2012-10-16

    The imine bond, a kind of dynamic covalent bond, is used to bind two bolaform amphiphiles together with spacers, yielding H-shaped supra-amphiphiles. Micellar aggregates formed by the self-assembly of the H-shaped supra-amphiphiles are observed. When pH is tuned down from basic to slightly acidic, the benzoic imine bond can be hydrolyzed, leading to the dissociation of H-shaped supra-amphiphiles. Moreover, H-shaped supra-amphiphiles have a lower critical micelle concentration than their building blocks, which is very helpful in enhancing the stability of the benzoic imine bond being hydrolyzed by acid. The surface tension isotherms of the H-shaped supra-amphiphiles with different spacers indicate their twisty conformation at a gas-water interface. The study of H-shaped supra-amphiphiles can enrich the family of amphiphiles, and moreover, the pH-responsiveness may make them apply to controlled or targetable drug delivery in a biological environment.

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

    Directory of Open Access Journals (Sweden)

    Fabio Lupo

    2014-11-01

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

  1. [Preparation of chiral monolithic column with covalently bonded cellulose and their application to rapid enantioseparation].

    Science.gov (United States)

    Wang, Jiabin; Wang, Xiao; Li, Jianhua; Lü, Haixia; Lin, Xucong; Xie, Zenghong; Zhang, Qiqing

    2011-12-01

    A chiral monolithic capillary column for rapid enantioseparation was prepared by covalently bonding of cellulose tris(4-methylbenzoate) (CTMB) on N-acryloxysuccinimide-based monolith. The preparation and derivatization conditions of the monolithic column were optimized. The successful grafting of CTMB was confirmed on the characterizations of the infrared spectrum and the cathodic electroosmotic flow (EOF). The effects of acetic acid concentration and methanol content on the enantioseparation were studied. The solvent resistance, reproducibility and stability of the monolithic column have also been investigated. The rapid enantioseparation of the five solutes (phenylalanine, tyrosine, tryptophan, propranolol and phenylethanol) with resolution (R(s)) values up to 1.31 was achieved within 1.2 min on the prepared chiral capillary monolithic column by capillary electrochromatography.

  2. Assessment of covalent bond formation between coupling agents and wood by FTIR spectroscopy and pull strength tests

    DEFF Research Database (Denmark)

    Rasmussen, Jonas Stensgaard; Barsberg, Søren Talbro; Venås, Thomas Mark

    2014-01-01

    In the focus was the question whether metal alkoxide coupling agents – titanium, silane, and zirconium – form covalent bonds to wood and how they improve coating adhesion. In a previous work, a downshift of the lignin infrared (IR) band ∼1600 cm-1 was shown to be consistent with the formation of ...... importance for improved wood coating adhesion....

  3. Are Orbital-Resolved Shared-Electron Distribution Indices and Cioslowski Covalent Bond Orders Useful for Molecules?

    Czech Academy of Sciences Publication Activity Database

    Cooper, D.L.; Ponec, Robert; Kohout, M.

    2015-01-01

    Roč. 113, 13-14 (2015), s. 1682-1689 ISSN 0026-8976 Institutional support: RVO:67985858 Keywords : domain averaged fermi holes * shared electron-distribution indices * Cioslowski covalent bond orders Subject RIV: CC - Organic Chemistry Impact factor: 1.837, year: 2015

  4. Molecular single-bond covalent radii for elements 1-118.

    Science.gov (United States)

    Pyykkö, Pekka; Atsumi, Michiko

    2009-01-01

    A self-consistent system of additive covalent radii, R(AB)=r(A) + r(B), is set up for the entire periodic table, Groups 1-18, Z=1-118. The primary bond lengths, R, are taken from experimental or theoretical data corresponding to chosen group valencies. All r(E) values are obtained from the same fit. Both E-E, E-H, and E-CH(3) data are incorporated for most elements, E. Many E-E' data inside the same group are included. For the late main groups, the system is close to that of Pauling. For other elements it is close to the methyl-based one of Suresh and Koga [J. Phys. Chem. A 2001, 105, 5940] and its predecessors. For the diatomic alkalis MM' and halides XX', separate fits give a very high accuracy. These primary data are then absorbed with the rest. The most notable exclusion are the transition-metal halides and chalcogenides which are regarded as partial multiple bonds. Other anomalies include H(2) and F(2). The standard deviation for the 410 included data points is 2.8 pm.

  5. Efficient Vibrational Energy Transfer through Covalent Bond in Indigo Carmine Revealed by Nonlinear IR Spectroscopy.

    Science.gov (United States)

    He, Xuemei; Yu, Pengyun; Zhao, Juan; Wang, Jianping

    2017-10-12

    Ultrafast vibrational relaxation and structural dynamics of indigo carmine in dimethyl sulfoxide were examined using femtosecond pump-probe infrared and two-dimensional infrared (2D IR) spectroscopies. Using the intramolecularly hydrogen-bonded C═O and delocalized C═C stretching modes as infrared probes, local structural and dynamical variations of this blue dye molecule were observed. Energy relaxation of the vibrationally excited C═O stretching mode was found to occur through covalent bond to the delocalized aromatic vibrational modes on the time scale of a few picoseconds or less. Vibrational quantum beating was observed in magic-angle pump-probe, anisotropy, and 2D IR cross-peak dynamics, showing an oscillation period of ca. 1010 fs, which corresponds to the energy difference between the C═O and C═C transition frequency (33 cm -1 ). This confirms a resonant vibrational energy transfer happened between the two vibrators. However, a more efficient energy-accepting mode of the excited C═O stretching was believed to be a nearby combination and/or overtone mode that is more tightly connected to the C═O species. On the structural aspect, dynamical-time-dependent 2D IR spectra reveal an insignificant inhomogeneous contribution to time-correlation relaxation for both the C═O and C═C stretching modes, which is in agreement with the generally believed structural rigidity of such conjugated molecules.

  6. Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds.

    Science.gov (United States)

    Fux, Samuel; Jacob, Christoph R; Neugebauer, Johannes; Visscher, Lucas; Reiher, Markus

    2010-04-28

    The frozen-density embedding (FDE) scheme [Wesolowski and Warshel, J. Phys. Chem. 97, 8050 (1993)] relies on the use of approximations for the kinetic-energy component v(T)[rho(1),rho(2)] of the embedding potential. While with approximations derived from generalized-gradient approximation kinetic-energy density functional weak interactions between subsystems such as hydrogen bonds can be described rather accurately, these approximations break down for bonds with a covalent character. Thus, to be able to directly apply the FDE scheme to subsystems connected by covalent bonds, improved approximations to v(T) are needed. As a first step toward this goal, we have implemented a method for the numerical calculation of accurate references for v(T). We present accurate embedding potentials for a selected set of model systems, in which the subsystems are connected by hydrogen bonds of various strength (water dimer and F-H-F(-)), a coordination bond (ammonia borane), and a prototypical covalent bond (ethane). These accurate potentials are analyzed and compared to those obtained from popular kinetic-energy density functionals.

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

    International Nuclear Information System (INIS)

    Clearfield, Abraham

    2003-01-01

    OAK-B135 The immobilization of crown ethers tends to limit the leveling effect of solvents making the macrocycles more selective. In addition immobilization has the added advantage of relative ease of recovery of the otherwise soluble crown. We have affixed CH2PO3H2 groups to azacrown ethers. The resultant phosphorylated macrocycles may spontaneously aggregate into crystalline supramolecular linear arrays or contacted with cations produce layered or linear polymers. In the linear polymers the metal and phosphonic acids covalently bond into a central stem with the macrocyclic rings protruding from the stem as leaves on a twig. Two types of layered compounds were obtained with group 4 metals. Monoaza-crown ethers form a bilayer where the M4+ plus phosphonic acid groups build the layer and the rings fill the interlayer space. 1, 10-diazadiphosphonic acids cross-link the metal phosphonate layers forming a three-dimensional array of crown ethers. In order to improve diffusion into these 3-D arrays they are spaced by inclusion of phosphate or phosphate groups. Two series of azamacrocylic crown ethers were prepared containing rings with 20 to 32 atoms. These larger rings can complex two cations per ring. Methylene phosphonic acid groups have been bonded to the aza ring atoms to increase the complexing ability of these ligands. Our approach is to carry out acid-base titrations in the absence and presence of cations to determine the pKa values of the protons, both those bonded to aza groups and those associated with the phosphonic acid groups. From the differences in the titration curves obtained with and without the cations present we obtain the stoichiometry of complex formation and the complex stability constants. Some of the applications we are targeting include phase transfer catalysis, separation of cations and the separation of radioisotopes for diagnostic and cancer therapeutic purposes

  8. NMR and IR investigations of strong intramolecular hydrogen bonds

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Spanget-Larsen, Jens

    2017-01-01

    For the purpose of this review, strong hydrogen bonds have been defined on the basis of experimental data, such as OH stretching wavenumbers, vOH, and OH chemical shifts, dOH (in the latter case after correction for ring current effects). Limits for O–H···Y systems are taken as 2800 > vOH > 1800 ...

  9. How strong is it? The interpretation of force and compliance constants as bond strength descriptors.

    Science.gov (United States)

    Brandhorst, Kai; Grunenberg, Jörg

    2008-08-01

    Knowledge about individual covalent or non-covalent bond strengths is the Holy Grail of many modern molecular sciences. Recent developments of new descriptors for such interaction strengths based on potential constants are summarised in this tutorial review. Several publications for and against the use of compliance matrices (inverse force constants matrix) have appeared in the literature in the last few years. However the mathematical basis for understanding, and therefore interpreting, compliance constants is still not well developed. We therefore summarise the theoretical foundations and point to the advantages and disadvantages of the use of force constants versus compliance constants for the description of both non-covalent and covalent interactions.

  10. Evidence of covalent bond formation at the silane-metal interface during plasma polymerization of bis-1,2-(triethoxysilyl)ethane (BTSE) on aluminium

    Science.gov (United States)

    Batan, A.; Mine, N.; Douhard, B.; Brusciotti, F.; De Graeve, I.; Vereecken, J.; Wenkin, M.; Piens, M.; Terryn, H.; Pireaux, J. J.; Reniers, F.

    2010-06-01

    Silane and silane-like films were deposited from bis-1,2-(triethoxysilyl)ethane by vacuum and atmospheric plasma onto aluminium. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used for probing the aluminium/plasma polymer film interface. An AlOSi + fragment was identified at nominal mass m/ z = 70.9539 amu, indicating a strong chemical interaction (formation of a covalent bond) at the substrate/film interface. Until now, this strong silane-aluminium interaction has never been observed in plasma polymer BTSE films. Ageing tests in an ultrasonic water bath combined with X-ray photoelectron spectroscopy measurements allowed to indirectly confirm good adhesion, and therefore the formation of a chemical bond at the interface.

  11. Covalently bonded disordered thin-film materials. Materials Research Society symposium proceedings Volume 498

    International Nuclear Information System (INIS)

    Siegal, M.P.; Milne, W.I.; Jaskie, J.E.

    1998-01-01

    The current and potential impact of covalently bonded disordered thin films is enormous. These materials are amorphous-to-nanocrystalline structures made from light atomic weight elements from the first row of the periodic table. Examples include amorphous tetrahedral diamond-like carbon, boron nitride, carbon nitride, boron carbide, and boron-carbon-nitride. These materials are under development for use as novel low-power, high-visibility elements in flat-panel display technologies, cold-cathode sources for microsensors and vacuum microelectronics, encapsulants for both environmental protection and microelectronics, optical coatings for laser windows, and ultra-hard tribological coatings. researchers from 17 countries and a broad range of academic institutions, national laboratories and industrial organizations come together in this volume to report on the status of key areas and recent discoveries. More specifically, the volume is organized into five sections. The first four highlight ongoing work primarily in the area of amorphous/nanocrystalline (disordered) carbon thin films; theoretical and experimental structural characterization; electrical and optical characterizations; growth methods; and cold-cathode electron emission results. The fifth section describes the growth, characterization and application of boron- and carbon-nitride thin films

  12. Female chacma baboons form strong, equitable, and enduring social bonds.

    Science.gov (United States)

    Silk, Joan B; Beehner, Jacinta C; Bergman, Thore J; Crockford, Catherine; Engh, Anne L; Moscovice, Liza R; Wittig, Roman M; Seyfarth, Robert M; Cheney, Dorothy L

    2010-11-01

    Analyses of the pattern of associations, social interactions, coalitions, and aggression among chacma baboons (Papio hamadryas ursinus) in the Okavango Delta of Botswana over a 16-year period indicate that adult females form close, equitable, supportive, and enduring social relationships. They show strong and stable preferences for close kin, particularly their own mothers and daughters. Females also form strong attachments to unrelated females who are close to their own age and who are likely to be paternal half-sisters. Although absolute rates of aggression among kin are as high as rates of aggression among nonkin, females are more tolerant of close relatives than they are of others with whom they have comparable amounts of contact. These findings complement previous work which indicates that the strength of social bonds enhances the fitness of females in this population and support findings about the structure and function of social bonds in other primate groups.

  13. Hirshfeld atom refinement for modelling strong hydrogen bonds.

    Science.gov (United States)

    Woińska, Magdalena; Jayatilaka, Dylan; Spackman, Mark A; Edwards, Alison J; Dominiak, Paulina M; Woźniak, Krzysztof; Nishibori, Eiji; Sugimoto, Kunihisa; Grabowsky, Simon

    2014-09-01

    High-resolution low-temperature synchrotron X-ray diffraction data of the salt L-phenylalaninium hydrogen maleate are used to test the new automated iterative Hirshfeld atom refinement (HAR) procedure for the modelling of strong hydrogen bonds. The HAR models used present the first examples of Z' > 1 treatments in the framework of wavefunction-based refinement methods. L-Phenylalaninium hydrogen maleate exhibits several hydrogen bonds in its crystal structure, of which the shortest and the most challenging to model is the O-H...O intramolecular hydrogen bond present in the hydrogen maleate anion (O...O distance is about 2.41 Å). In particular, the reconstruction of the electron density in the hydrogen maleate moiety and the determination of hydrogen-atom properties [positions, bond distances and anisotropic displacement parameters (ADPs)] are the focus of the study. For comparison to the HAR results, different spherical (independent atom model, IAM) and aspherical (free multipole model, MM; transferable aspherical atom model, TAAM) X-ray refinement techniques as well as results from a low-temperature neutron-diffraction experiment are employed. Hydrogen-atom ADPs are furthermore compared to those derived from a TLS/rigid-body (SHADE) treatment of the X-ray structures. The reference neutron-diffraction experiment reveals a truly symmetric hydrogen bond in the hydrogen maleate anion. Only with HAR is it possible to freely refine hydrogen-atom positions and ADPs from the X-ray data, which leads to the best electron-density model and the closest agreement with the structural parameters derived from the neutron-diffraction experiment, e.g. the symmetric hydrogen position can be reproduced. The multipole-based refinement techniques (MM and TAAM) yield slightly asymmetric positions, whereas the IAM yields a significantly asymmetric position.

  14. Covalently Bonded Three-Dimensional Carbon Nanotube Solids via Boron Induced Nanojunctions

    Science.gov (United States)

    2012-04-13

    Novel Carbon Morphologies : From Covalent Y-Junctions to Sea - Urchin -Like Structures. Adv. Func. Mater. 19, 1193–1199 (2009). 15. Sumpter, B. G. et al...between carbon nanotubes (CNTs) and the modification of their straight tubular morphology are two strategies needed to successfully synthesize...nitrogen or sulfur can also induce dramatic tubule morphology changes in CNTs, including covalent multi-junctions12–15, however never were these

  15. Chlorophyll a Covalently Bonded to Organo-Modified Translucent Silica Xerogels: Optimizing Fluorescence and Maximum Loading

    Directory of Open Access Journals (Sweden)

    M. A. García-Sánchez

    2016-07-01

    Full Text Available Chlorophyll is a pyrrolic pigment with important optical properties, which is the reason it has been studied for many years. Recently, interest has been rising with respect to this molecule because of its outstanding physicochemical properties, particularly applicable to the design and development of luminescent materials, hybrid sensor systems, and photodynamic therapy devices for the treatment of cancer cells and bacteria. More recently, our research group has been finding evidence for the possibility of preserving these important properties of substrates containing chlorophyll covalently incorporated within solid pore matrices, such as SiO2, TiO2 or ZrO2 synthesized through the sol-gel process. In this work, we study the optical properties of silica xerogels organo-modified on their surface with allyl and phenyl groups and containing different concentrations of chlorophyll bonded to the pore walls, in order to optimize the fluorescence that these macrocyclic species displays in solution. The intention of this investigation was to determine the maximum chlorophyll a concentration at which this molecule can be trapped inside the pores of a given xerogel and to ascertain if this pigment remains trapped as a monomer, a dimer, or aggregate. Allyl and phenyl groups were deposited on the surface of xerogels in view of their important effects on the stability of the molecule, as well as over the fluorescence emission of chlorophyll; however, these organic groups allow the trapping of either chlorophyll a monomers or dimers. The determination of the above parameters allows finding the most adequate systems for subsequent in vitro or in vivo studies. The characterization of the obtained xerogels was performed through spectroscopic absorption, emission and excitation spectra. These hybrid systems can be employed as mimics of natural systems; the entrapment of chlorophyll inside pore matrices indicates that it is possible to exploit some of the most

  16. DFT+DMFT study on soft moment magnetism and covalent bonding in SrRu2O6

    Science.gov (United States)

    Hariki, Atsushi; Hausoel, Andreas; Sangiovanni, Giorgio; Kuneš, Jan

    2017-10-01

    The dynamical mean-field theory is used to study the three-orbital model of the d3 compound SrRu2O3 both with and without explicitly including the O-p states. Depending on the size of the Hund's coupling J , at low to intermediate temperatures we find solutions corresponding to Mott or correlated covalent insulators. The latter can explain the experimentally observed absence of Curie susceptibility in the paramagnetic phase. At high temperatures, a single phase with smoothly varying properties is observed. SrRu2O3 provides an ideal system to study the competition between the local moment physics and covalent bonding, since both effects are maximized, while SO interaction is found to play a minor role.

  17. Donor-Acceptor Interaction Determines the Mechanism of Photoinduced Electron Injection from Graphene Quantum Dots into TiO2: π-Stacking Supersedes Covalent Bonding.

    Science.gov (United States)

    Long, Run; Casanova, David; Fang, Wei-Hai; Prezhdo, Oleg V

    2017-02-22

    Interfacial electron transfer (ET) constitutes the key step in conversion of solar energy into electricity and fuels. Required for fast and efficient charge separation, strong donor-acceptor interaction is typically achieved through covalent chemical bonding and leads to fast, adiabatic ET. Focusing on interfaces of pyrene, coronene, and a graphene quantum dot (GQD) with TiO 2 , we demonstrate the opposite situation: covalent bonding leads to weak coupling and nonadiabatic (NA) ET, while through-space π-electron interaction produces adiabatic ET. Using real-time time-dependent density functional theory combined with NA molecular dynamics, we simulate photoinduced ET into TiO 2 from flat and vertically placed molecules and GQD containing commonly used carboxylic acid linkers. Both arrangements can be achieved experimentally with GQDs and other two-dimensional materials, such as MoS 2 . The weak through-bond donor-acceptor coupling is attributed to the π-electron withdrawing properties of the carboxylic acid group. The calculated ET time scales are in excellent agreement with pump-probe optical experiments. The simulations show that the ET proceeds faster than energy relaxation. The electron couples to a broad spectrum of vibrational modes, ranging from 100 cm -1 large-scale motions to 1600 cm -1 C-C stretches. Compared to graphene/TiO 2 heterojunctions, the molecule/TiO 2 and GQD/TiO 2 systems exhibit energy gaps, allowing for longer-lived excited states and hot electron injection, facilitating charge separation and higher voltage. The reported state-of-the-art simulations generate a detailed time-domain, atomistic description of the interfacial charge and energy transfer and relaxation processes, and demonstrate that the fundamental principles leading to efficient charge separation in nanoscale materials depend strongly and often unexpectedly on the type of donor-acceptor interaction. Understanding these principles is critical to the development of highly

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

    Science.gov (United States)

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

    2013-11-19

    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 one intermolecular H-bond showed a high density of thermal storage up to 269.8 kJ kg(-1) compared with RGO-ortho-AZO (149.6 kJ kg(-1)) with multiple intra- and intermolecular H-bonds of AZO according to relaxed stable structures. Thermal storage in experiment was the same order magnitude to theoretical data based on ΔH calculated by density functional theory and packing density. Photoactive RGO-AZO hybrid can be developed for high-performance solar thermal storage by optimizing molecular H-bonds.

  19. A strategy to synthesize graphene-incorporated lignin polymer composite materials with uniform graphene dispersion and covalently bonded interface engineering

    Science.gov (United States)

    Wang, Mei; Duong, Le Dai; Ma, Yifei; Sun, Yan; Hong, Sung Yong; Kim, Ye Chan; Suhr, Jonghwan; Nam, Jae-Do

    2017-08-01

    Graphene-incorporated polymer composites have been demonstrated to have excellent mechanical and electrical properties. In the field of graphene-incorporated composite material synthesis, there are two main obstacles: Non-uniform dispersion of graphene filler in the matrix and weak interface bonding between the graphene filler and polymer matrix. To overcome these problems, we develop an in-situ polymerization strategy to synthesize uniformly dispersed and covalently bonded graphene/lignin composites. Graphene oxide (GO) was chemically modified by 4,4'-methylene diphenyl diisocyanate (MDI) to introduce isocyanate groups and form the urethane bonds with lignin macromonomers. Subsequential polycondensation reactions of lignin groups with caprolactone and sebacoyl chloride bring about a covalent network of modified GO and lignin-based polymers. The flexible and robust lignin polycaprolactone polycondensate/modified GO (Lig-GOm) composite membranes are achieved after vacuum filtration, which have tunable hydrophilicity and electrical resistance according to the contents of GOm. This research transforms lignin from an abundant biomass into film-state composite materials, paving a new way for the utilization of biomass wastes.

  20. NMR and IR Investigations of Strong Intramolecular Hydrogen Bonds

    Directory of Open Access Journals (Sweden)

    Poul Erik Hansen

    2017-03-01

    Full Text Available For the purpose of this review, strong hydrogen bonds have been defined on the basis of experimental data, such as OH stretching wavenumbers, νOH, and OH chemical shifts, δOH (in the latter case, after correction for ring current effects. Limits for O–H···Y systems are taken as 2800 > νOH > 1800 cm−1, and 19 ppm > δOH > 15 ppm. Recent results as well as an account of theoretical advances are presented for a series of important classes of compounds such as β-diketone enols, β-thioxoketone enols, Mannich bases, proton sponges, quinoline N-oxides and diacid anions. The O···O distance has long been used as a parameter for hydrogen bond strength in O–H···O systems. On a broad scale, a correlation between OH stretching wavenumbers and O···O distances is observed, as demonstrated experimentally as well as theoretically, but for substituted β-diketone enols this correlation is relatively weak.

  1. Charge-Shift Corrected Electronegativities and the Effect of Bond Polarity and Substituents on Covalent-Ionic Resonance Energy.

    Science.gov (United States)

    James, Andrew M; Laconsay, Croix J; Galbraith, John Morrison

    2017-07-13

    Bond dissociation energies and resonance energies for H n A-BH m molecules (A, B = H, C, N, O, F, Cl, Li, and Na) have been determined in order to re-evaluate the concept of electronegativity in the context of modern valence bond theory. Following Pauling's original scheme and using the rigorous definition of the covalent-ionic resonance energy provided by the breathing orbital valence bond method, we have derived a charge-shift corrected electronegativity scale for H, C, N, O, F, Cl, Li, and Na. Atomic charge shift character is defined using a similar approach resulting in values of 0.42, 1.06, 1.43, 1.62, 1.64, 1.44, 0.46, and 0.34 for H, C, N, O, F, Cl, Li, and Na, respectively. The charge-shift corrected electronegativity values presented herein follow the same general trends as Pauling's original values with the exception of Li having a smaller value than Na (1.57 and 1.91 for Li and Na respectively). The resonance energy is then broken down into components derived from the atomic charge shift character and polarization effects. It is then shown that most of the resonance energy in the charge-shift bonds H-F, H 3 C-F, and Li-CH 3 and borderline charge-shift H-OH is associated with polarity rather than the intrinsic atomic charge-shift character of the bonding species. This suggests a rebranding of these bonds as "polar charge-shift" rather than simply "charge-shift". Lastly, using a similar breakdown method, it is shown that the small effect the substituents -CH 3 , -NH 2 , -OH, and -F have on the resonance energy (<10%) is mostly due to changes in the charge-shift character of the bonding atom.

  2. Short, strong hydrogen bonds on enzymes: NMR and mechanistic studies

    Science.gov (United States)

    Mildvan, A. S.; Massiah, M. A.; Harris, T. K.; Marks, G. T.; Harrison, D. H. T.; Viragh, C.; Reddy, P. M.; Kovach, I. M.

    2002-09-01

    The lengths of short, strong hydrogen bonds (SSHBs) on enzymes have been determined with high precision (±0.05 Å) from the chemical shifts ( δ), and independently from the D/ H fractionation factors ( φ) of the highly deshielded protons involved. These H-bond lengths agree well with each other and with those found by protein X-ray crystallography, within the larger errors of the latter method (±0.2 to±0.8 Å) [Proteins 35 (1999) 275]. A model dihydroxynaphthalene compound shows a SSHB of 2.54±0.04 Å based on δ=17.7 ppm and φ=0.56±0.04, in agreement with the high resolution X-ray distance of 2.55±0.06 Å. On ketosteroid isomerase, a SSHB is found (2.50±0.02 Å), based on δ=18.2 ppm and φ=0.34, from Tyr-14 to the 3-O - of estradiol, an analog of the enolate intermediate. Its strength is ˜7 kcal/mol. On triosephosphate isomerase, SSHBs are found from Glu-165 to the 1-NOH of phosphoglycolohydroxamic acid (PGH), an analog of the enolic intermediate (2.55±0.05 Å), and from His-95 to the enolic-O - of PGH (2.62±0.02 Å). In the methylglyoxal synthase-PGH complex, a SSHB (2.51±0.02 Å) forms between Asp-71 and the NOH of PGH with a strength of ≥4.7 kcal/mol. When serine proteases bind mechanism-based inhibitors which form tetrahedral Ser-adducts analogous to the tetrahedral intermediates in catalysis, the Asp⋯His H-bond of the catalytic triad becomes a SSHB [Proc. Natl Acad. Sci. USA 95 (1998) 14664], 2.49-2.63 Å in length. Similarly, on the serine-esterase, butyrylcholinesterase complexed with the mechanism-based inhibitor m-( N, N, N-trimethylammonio)-2,2,2-trifluoroacetophenone, a SSHB forms between Glu-327 and His-438 of the catalytic triad, 2.61±0.04 Å in length, based on δ=18.1 ppm and φ=0.65±0.10. Very similar results are obtained with (human) acetylcholinesterase. The strength of this SSHB is at least 4.9 kcal/mol.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-11-07

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

  4. What Is a Hydrogen Bond? Resonance Covalency in the Supramolecular Domain

    Science.gov (United States)

    Weinhold, Frank; Klein, Roger A.

    2014-01-01

    We address the broader conceptual and pedagogical implications of recent recommendations of the International Union of Pure and Applied Chemistry (IUPAC) concerning the re-definition of hydrogen bonding, drawing upon the recommended IUPAC statistical methodology of mutually correlated experimental and theoretical descriptors to operationally…

  5. Covalent bonds are created by the drive of electron waves to lower their kinetic energy through expansion

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Michael W.; Ruedenberg, Klaus, E-mail: ruedenberg@iastate.edu [Department of Chemistry and Ames Laboratory USDOE, Iowa State University, Ames, Iowa 50011 (United States); Ivanic, Joseph [Advanced Biomedical Computing Center, Information Systems Program, Leidos Biomedical Research, Inc., Frederick National Laboratory for Cancer Research, Frederick, Maryland 21702 (United States)

    2014-05-28

    An analysis based on the variation principle shows that in the molecules H{sub 2}{sup +}, H{sub 2}, B{sub 2}, C{sub 2}, N{sub 2}, O{sub 2}, F{sub 2}, covalent bonding is driven by the attenuation of the kinetic energy that results from the delocalization of the electronic wave function. For molecular geometries around the equilibrium distance, two features of the wave function contribute to this delocalization: (i) Superposition of atomic orbitals extends the electronic wave function from one atom to two or more atoms; (ii) intra-atomic contraction of the atomic orbitals further increases the inter-atomic delocalization. The inter-atomic kinetic energy lowering that (perhaps counter-intuitively) is a consequence of the intra-atomic contractions drives these contractions (which per se would increase the energy). Since the contractions necessarily encompass both, the intra-atomic kinetic and potential energy changes (which add to a positive total), the fact that the intra-atomic potential energy change renders the total potential binding energy negative does not alter the fact that it is the kinetic delocalization energy that drives the bond formation.

  6. Covalent bonds are created by the drive of electron waves to lower their kinetic energy through expansion

    Science.gov (United States)

    Schmidt, Michael W.; Ivanic, Joseph; Ruedenberg, Klaus

    2014-05-01

    An analysis based on the variation principle shows that in the molecules H2+, H2, B2, C2, N2, O2, F2, covalent bonding is driven by the attenuation of the kinetic energy that results from the delocalization of the electronic wave function. For molecular geometries around the equilibrium distance, two features of the wave function contribute to this delocalization: (i) Superposition of atomic orbitals extends the electronic wave function from one atom to two or more atoms; (ii) intra-atomic contraction of the atomic orbitals further increases the inter-atomic delocalization. The inter-atomic kinetic energy lowering that (perhaps counter-intuitively) is a consequence of the intra-atomic contractions drives these contractions (which per se would increase the energy). Since the contractions necessarily encompass both, the intra-atomic kinetic and potential energy changes (which add to a positive total), the fact that the intra-atomic potential energy change renders the total potential binding energy negative does not alter the fact that it is the kinetic delocalization energy that drives the bond formation.

  7. Covalent bonds are created by the drive of electron waves to lower their kinetic energy through expansion

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Michael W; Ivanic, Joseph; Ruedenberg, Klaus

    2014-05-28

    An analysis based on the variation principle shows that in the molecules H2 +, H2, B2, C2, N2, O2, F2, covalent bonding is driven by the attenuation of the kinetic energy that results from the delocalization of the electronic wave function. For molecular geometries around the equilibrium distance, two features of the wave function contribute to this delocalization: (i) Superposition of atomic orbitals extends the electronic wave function from one atom to two or more atoms; (ii) intra-atomic contraction of the atomic orbitals further increases the inter-atomic delocalization. The inter-atomic kinetic energy lowering that (perhaps counter-intuitively) is a consequence of the intra-atomic contractions drives these contractions (which per se would increase the energy). Since the contractions necessarily encompass both, the intra-atomic kinetic and potential energy changes (which add to a positive total), the fact that the intra-atomic potential energy change renders the total potential binding energy negative does not alter the fact that it is the kinetic delocalization energy that drives the bond formation.

  8. Is the decrease of the total electron energy density a covalence indicator in hydrogen and halogen bonds?

    Science.gov (United States)

    Angelina, Emilio L; Duarte, Darío J R; Peruchena, Nélida M

    2013-05-01

    In this work, halogen bonding (XB) and hydrogen bonding (HB) complexes were studied with the aim of analyzing the variation of the total electronic energy density H(r b ) with the interaction strengthening. The calculations were performed at the MP2/6-311++G(2d,2p) level of approximation. To explain the nature of such interactions, the atoms in molecules theory (AIM) in conjunction with reduced variational space self-consistent field (RVS) energy decomposition analysis were carried out. Based on the local virial theorem, an equation to decompose the total electronic energy density H(r b ) in two energy densities, (-G(r b )) and 1/4∇(2)ρ(r b ), was derived. These energy densities were linked with the RVS interaction energy components. Through the connection between both decomposition schemes, it was possible to conclude that the decrease in H(r b ) with the interaction strengthening observed in the HB as well as the XB complexes, is mainly due to the increase in the attractive electrostatic part of the interaction energy and in lesser extent to the increase in its covalent character, as is commonly considered.

  9. σ-Hole Interactions of Covalently-Bonded Nitrogen, Phosphorus and Arsenic: A Survey of Crystal Structures

    Directory of Open Access Journals (Sweden)

    Peter Politzer

    2014-02-01

    Full Text Available Covalently-bonded atoms of Groups IV–VII tend to have anisotropic charge distributions, the electronic densities being less on the extensions of the bonds (σ-holes than in the intervening regions. These σ-holes often give rise to positive electrostatic potentials through which the atom can interact attractively and highly directionally with negative sites (e.g., lone pairs, π electrons and anions, forming noncovalent complexes. For Group VII this is called “halogen bonding” and has been widely studied both computationally and experimentally. For Groups IV–VI, it is only since 2007 that positive σ-holes have been recognized as explaining many noncovalent interactions that have in some instances long been known experimentally. There is considerable experimental evidence for such interactions involving groups IV and VI, particularly in the form of surveys of crystal structures. However we have found less extensive evidence for Group V. Accordingly we have now conducted a survey of the Cambridge Structural Database for crystalline close contacts of trivalent nitrogen, phosphorus and arsenic with six different types of electronegative atoms in neighboring molecules. We have found numerous close contacts that fit the criteria for σ-hole interactions. Some of these are discussed in detail; in two instances, computed molecular electrostatic potentials are presented.

  10. A study on poly (N-vinyl-2-pyrrolidone covalently bonded NiTi surface for inhibiting protein adsorption

    Directory of Open Access Journals (Sweden)

    Hongyan Yu

    2016-12-01

    Full Text Available Near equiatomic NiTi alloys have been extensively applied as biomaterials owing to its unique shape memory effect, superelasticity and biocompatibility. It has been demonstrated that surfaces capable of preventing plasma protein adsorption could reduce the reactivity of biomaterials with human blood. This motivated a lot of researches on the surface modification of NiTi alloy. In the present work, following heat and alkaline treatment and silanization by trichlorovinylsilane (TCVS, coating of poly (N-vinyl-2-pyrrolidone (PVP was produced on the NiTi alloy by gamma ray induced chemical bonding. The structures and properties of modified NiTi were characterized and in vitro biocompatibility of plasma protein adsorption was investigated. The results indicated that heat treatment at 823 K for 1 h could result in the formation of a protective TiO2 layer with “Ni-free” zone on NiTi surface. It was found that PVP was covalently bonded on NiTi surface to create a hydrophilic layer for inhibiting protein adsorption on the surface. The present work offers a green approach to introduce a bioorganic surface on metal and other polymeric or inorganic substrates by gamma irradiation.

  11. Strong and weak hydrogen bonds in drug–DNA complexes: A ...

    Indian Academy of Sciences (India)

    PRAKASH KUMAR

    The metrics for strong hydrogen bonds are consistent with established trends. The geometries are variable for weak hydrogen bonds. .... 'moderate'. Jeffrey's terminology is in keeping with the biological literature where bonds such ... to minimization keeping the heavy atoms rigid. This was carried out in MOE with the MMFFx ...

  12. Acylhydrazone bond dynamic covalent polymer gel monolithic column online coupling to high-performance liquid chromatography for analysis of sulfonamides and fluorescent whitening agents in food.

    Science.gov (United States)

    Zhang, Chengjiang; Luo, Xialin; Wei, Tianfu; Hu, Yufei; Li, Gongke; Zhang, Zhuomin

    2017-10-13

    A new dynamic covalent polymer (DCP) gel was well designed and constructed based on imine chemistry. Polycondensation of 4,4'-biphenyldicarboxaldehyde and 1,3,5-benzenetricarbohydrazide via Schiff-base reaction resulted in an acylhydrazone bond gel (AB-gel) DCP. AB-gel DCP had three-dimensional network of interconnected nanoparticles with hierarchically porous structure. AB-gel DCP was successfully fabricated as a monolithic column by an in-situ chemical bonding method for online enrichment and separation purpose with excellent permeability. AB-gel DCP based monolithic column showed remarkable adsorption affinity towards target analytes including sulfonamides (SAs) and fluorescent whitening agents (FWAs) due to its strong π-π affinity, hydrophobic effect and hydrogen bonding interaction. Then, AB-gel DCP based monolithic column was applied for online separation and analysis of trace SAs and FWAs in food samples coupled with high-performance liquid chromatography (HPLC). Sulfathiazole (ST) and sulfadimidine (SM2) in one positive weever sample were actually found and determined with concentrations of 273.8 and 286.3μg/kg, respectively. 2,5-Bis(5-tert-butyl-2-benzoxazolyl) thiophene (FWA184) was actually quantified in one tea infusion sample with the concentration of 268.5ng/L. The spiked experiments suggested the good recoveries in range of 74.5-110% for SAs in weever and shrimp samples with relative standard deviations (RSDs) less than 9.7% and in range of 74.0-113% for FWAs in milk and tea infusion samples with RSDs less than 9.0%. AB-gel DCP monolithic column was proved to be a promising sample preparation medium for online separation and analysis of trace analytes in food samples with complex matrices. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-01

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

  14. Political Culture and Covalent Bonding. A Conceptual Model of Political Culture Change

    Directory of Open Access Journals (Sweden)

    Camelia Florela Voinea

    2015-01-01

    Full Text Available Our class of models aims at explaining the dynamics of political attitude change by means of the dynamic changes in values, beliefs, norms and knowledge with which it is associated. The model constructs a political culture perspective over the relationship between macro and micro levels of a society and polity. The model defines the bonding mechanism as a basic mechanism of the political culture change by taking inspiration from the valence bonding theory in Chemistry, which has inspired the elaboration of the mechanisms and processes underlying the political culture emergence and the political culture control over the relationship between macro-level political entities and the micro-level individual agents. The model introduces operational definitions of the individual agent in political culture terms. The simulation model is used for the study of emergent political culture change phenomena based on individual interactions (emergent or upward causation as well as the ways in which the macro entities and emergent phenomena influence in turn the behaviors of individual agents (downward causation. The model is used in the ongoing research concerning the quality of democracy and political participation of the citizens in the Eastern European societies after the Fall of Berlin Wall. It is particularly aimed at explaining the long-term effect of the communist legacy and of the communist polity concept and organization onto the political mentalities and behaviors of the citizens with respect to democratic institutions and political power. The model has major implications in political socialization, political involvement, political behavior, corruption and polity modeling.

  15. Strong and weak hydrogen bonds in drug–DNA complexes: A ...

    Indian Academy of Sciences (India)

    PRAKASH KUMAR

    The analysis was performed with an in-house software, hydrogen bond analysis tool (HBAT). In addition to strong hydrogen bonds such as O−H···O and N−H···O, the ubiquitous presence of weak hydrogen bonds such as C−H···O is implicated in molecular recognition. On an average, there are 1.4 weak hydrogen bonds.

  16. Covalent bond formation between amino acids and lignin: cross-coupling between proteins and lignin.

    Science.gov (United States)

    Cong, Fang; Diehl, Brett G; Hill, Joseph Lee; Brown, Nicole R; Tien, Ming

    2013-12-01

    The present study characterized the products formed from the reaction of amino acids and in turn, proteins, with lignin resulting in cross-coupling. When added to reaction mixtures containing coniferyl alcohol, horseradish peroxidase and H2O2, three amino acids (Cys, Tyr, and Thr) are able to form adducts. The low molecular weight products were analyzed by HPLC and from each reaction mixture, one product was isolated and analyzed by LC/MS. LC/MS results are consistent with bond formation between the polar side-chain of these amino acids with Cα. These results are consistent with the cross-coupling of Cys, Tyr and Thr through a quinone methide intermediate. In addition to the free amino acids, it was found that the cross-coupling of proteins with protolignin through Cys or Tyr residues. The findings provide a mechanism by which proteins and lignin can cross-couple in the plant cell wall. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Ambient Mechanochemical Solid-State Reactions of Carbon Nanotubes and Their Reactions via Covalent Coordinate Bond in Solution

    Science.gov (United States)

    Kabbani, Mohamad A.

    In its first part, this thesis deals with ambient mechanochemical solid-state reactions of differently functionalized multiple walled carbon nanotubes (MWCNTs) while in its second part it investigates the cross-linking reactions of CNTs in solution via covalent coordinate bonds with transitions metals and carboxylate groups decorating their surfaces. In the first part a series of mechanochemical reactions involving different reactive functionalities on the CNTs such as COOH/OH, COOH/NH2 and COCl/OH were performed. The solid-state unzipping of CNTs leading to graphene formation was confirmed using spectroscopic, thermal and electron microscopy techniques. The non-grapheme products were established using in-situ quadruple mass spectroscopy. The experimental results were confirmed by theoretical simulation calculations using the 'hot spots' protocol. The kinetics of the reaction between MWCNT-COOH and MWCNT-OH was monitored using variable temperature Raman spectroscopy. The low activation energy was discussed in terms of hydrogen bond mediated proton transfer mechanism. The second part involves the reaction of MWCNTII COOH with Zn (II) and Cu (II) to form CNT metal-organic frame (MOFs) products that were tested for their effective use as counter-electrodes in dyes sensitized solar cells (DSSC). The thesis concludes by the study of the room temperature reaction between the functionalized graphenes, GOH and G'-COOH followed by the application of compressive loads. The 3D solid graphene pellet product ( 0.6gm/cc) is conductive and reflective with a 35MPa ultimate strength as compared to 10MPa strength of graphite electrode ( 2.2gm/cc).

  18. Topologically invariant double Dirac states in bismuth-based perovskites: Consequence of ambivalent charge states and covalent bonding

    Science.gov (United States)

    Khamari, Bramhachari; Kashikar, Ravi; Nanda, B. R. K.

    2018-01-01

    Density functional calculations and model tight-binding Hamiltonian studies are carried out to examine the bulk and surface electronic structure of the largely unexplored perovskite family of A BiO3 , where A is a group I-II element. From the study, we reveal the existence of two TI states, one in valence band (V-TI) and the other in conduction band (C-TI), as the universal feature of A BiO3 . The V-TI and C-TI are, respectively, born out of bonding and antibonding states caused by Bi-{s ,p } -O-{p } coordinated covalent interactions. Further, we outline a classification scheme in this family where one class follows spin orbit coupling and the other follows the second neighbor Bi-Bi hybridization to induce s-p band inversion for the realization of C-TI states. Below a certain critical thickness of the film, which varies with A , TI states of top and bottom surfaces couple to destroy the Dirac type linear dispersion and consequently to open narrow surface energy gaps.

  19. UV-light exposure of insulin: pharmaceutical implications upon covalent insulin dityrosine dimerization and disulphide bond photolysis.

    Directory of Open Access Journals (Sweden)

    Manuel Correia

    Full Text Available In this work we report the effects of continuous UV-light (276 nm, ~2.20 W.m(-2 excitation of human insulin on its absorption and fluorescence properties, structure and functionality. Continuous UV-excitation of the peptide hormone in solution leads to the progressive formation of tyrosine photo-product dityrosine, formed upon tyrosine radical cross-linkage. Absorbance, fluorescence emission and excitation data confirm dityrosine formation, leading to covalent insulin dimerization. Furthermore, UV-excitation of insulin induces disulphide bridge breakage. Near- and far-UV-CD spectroscopy shows that UV-excitation of insulin induces secondary and tertiary structure losses. In native insulin, the A and B chains are held together by two disulphide bridges. Disruption of either of these bonds is likely to affect insulin's structure. The UV-light induced structural changes impair its antibody binding capability and in vitro hormonal function. After 1.5 and 3.5 h of 276 nm excitation there is a 33.7% and 62.1% decrease in concentration of insulin recognized by guinea pig anti-insulin antibodies, respectively. Glucose uptake by human skeletal muscle cells decreases 61.7% when the cells are incubated with pre UV-illuminated insulin during 1.5 h. The observations presented in this work highlight the importance of protecting insulin and other drugs from UV-light exposure, which is of outmost relevance to the pharmaceutical industry. Several drug formulations containing insulin in hexameric, dimeric and monomeric forms can be exposed to natural and artificial UV-light during their production, packaging, storage or administration phases. We can estimate that direct long-term exposure of insulin to sunlight and common light sources for indoors lighting and UV-sterilization in industries can be sufficient to induce irreversible changes to human insulin structure. Routine fluorescence and absorption measurements in laboratory experiments may also induce changes

  20. Phonon driven proton transfer in crystals with short strong hydrogen bonds

    NARCIS (Netherlands)

    Fontaine-Vive, F.; Johnson, M.R.; Kearley, G.J.; Cowan, J.A.; Howard, J.A.K.; Parker, S.F.

    2006-01-01

    Recent work on understanding why protons migrate with increasing temperature in short, strong hydrogen bonds is extended here to three more organic, crystalline systems. Inelastic neutron scattering and density functional theory based simulations are used to investigate structure, vibrations, and

  1. Observation of covalent and electrostatic bonds in nitrogen-containing polycyclic ions formed by gas phase reactions of the benzene radical cation with pyrimidine.

    Science.gov (United States)

    Attah, Isaac Kwame; Soliman, Abdel-Rahman; Platt, Sean P; Meot-Ner Mautner, Michael; Aziz, Saaudallah G; Samy El-Shall, M

    2017-03-01

    Polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocyclics (PANHs) are present in ionizing environments, including interstellar clouds and solar nebulae, where their ions can interact with neutral PAH and PANH molecules leading to the formation of a variety of complex organics including large N-containing ions. Herein, we report on the formation of a covalently-bonded (benzene·pyrimidine) radical cation dimer by the gas phase reaction of pyrimidine with the benzene radical cation at room temperature using the mass-selected ion mobility technique. No ligand exchange reactions with benzene and pyrimidine are observed indicating that the binding energy of the (benzene·pyrimidine)˙ + adduct is significantly higher than both the benzene dimer cation and the proton-bound pyrimidine dimer. The (benzene·pyrimidine)˙ + adduct shows thermal stability up to 541 K. Thermal dissociation of the (C 6 D 6 ·C 4 H 4 N 2 )˙ + adduct at temperatures higher than 500 K produces C 4 H 4 N 2 D + (m/z 82) suggesting the transfer of a D atom from the C 6 D 6 moiety to the C 4 H 4 N 2 moiety before the dissociation of the adduct. Mass-selected ion mobility of the (benzene·pyrimidine)˙ + dimer reveals the presence of two families of isomers formed by electron impact ionization of the neutral (benzene·pyrimidine) dimer. The slower mobility peak corresponds to a non-covalent family of isomers with larger collision cross sections (76.0 ± 1.8 Å 2 ) and the faster peak is consistent with a family of covalent isomers with more compact structures and smaller collision cross sections (67.7 ± 2.2 Å 2 ). The mobility measurements at 509 K show only one peak corresponding to the family of stable covalently bonded isomers characterized by smaller collision cross sections (66.9 ± 1.9 Å 2 at 509 K). DFT calculations at the M06-2X/6-311++G** level show that the most stable (benzene·pyrimidine)˙ + isomer forms a covalent C-N bond with a binding energy of 49

  2. Computational study of the covalent bonding of microcystins to cysteine residues--a reaction involved in the inhibition of the PPP family of protein phosphatases.

    Science.gov (United States)

    Pereira, Susana R; Vasconcelos, Vítor M; Antunes, Agostinho

    2013-01-01

    Microcystins (MCs) are cyclic peptides, produced by cyanobacteria, that are hepatotoxic to mammals. The toxicity mechanism involves the potent inhibition of protein phosphatases, as the toxins bind the catalytic subunits of five enzymes of the phosphoprotein phosphatase (PPP) family of serine/threonine-specific phosphatases: Ppp1 (aka PP1), Ppp2 (aka PP2A), Ppp4, Ppp5 and Ppp6. The interaction with the proteins includes the formation of a covalent bond with a cysteine residue. Although this reaction seems to be accessory for the inhibition of PPP enzymes, it has been suggested to play an important part in the biological role of MCs and furthermore is involved in their nonenzymatic conjugation to glutathione. In this study, the molecular interaction of microcystins with their targeted PPP catalytic subunits is reviewed, including the relevance of the covalent bond for overall inhibition. The chemical reaction that leads to the formation of the covalent bond was evaluated in silico, both thermodynamically and kinetically, using quantum mechanical-based methods. As a result, it was confirmed to be a Michael-type addition, with simultaneous abstraction of the thiol hydrogen by a water molecule, transfer of hydrogen from the water to the α,β-unsaturated carbonyl group of the microcystin and addition of the sulfur to the β-carbon of the microcystin moiety. The calculated kinetics are in agreement with previous experimental results that had indicated the reaction to occur in a second step after a fast noncovalent interaction that inhibited the enzymes per se. © 2011 The Authors Journal compilation © 2011 FEBS.

  3. NMR studies of strong hydrogen bonds in enzymes and in a model compound

    Science.gov (United States)

    Harris, T. K.; Zhao, Q.; Mildvan, A. S.

    2000-09-01

    Hydrogen bond lengths on enzymes have been derived with high precision (≤±0.05 Å) from both the proton chemical shifts (δ) and the fractionation factors (φ) of the proton involved and were compared with those obtained from protein X-ray crystallography. Hydrogen bond lengths derived from proton chemical shifts were obtained from a correlation of 59 O-H⋯O hydrogen bond lengths, measured by small molecule high resolution X-ray crystallography, with chemical shifts determined by solid-state NMR in the same crystals [A. McDermott, C.F. Ridenour, Encyclopedia of NMR, Wiley, Sussex, England, 1996, 3820pp]. Hydrogen bond lengths were independently obtained from fractionation factors which yield distances between the two proton wells in quartic double minimum potential functions [M.M. Kreevoy, T.M. Liang, J. Am. Chem. Soc. 102 (1980) 3315]. The high precision hydrogen bond lengths derived from their corresponding NMR-measured proton chemical shifts and fractionation factors agree well with each other and with those reported in protein X-ray structures within the larger errors (±0.2-0.8 Å) in lengths obtained by protein X-ray crystallography. The increased precision in measurements of hydrogen bond lengths by NMR has provided insight into the contributions of short, strong hydrogen bonds to catalysis for several enzymes including ketosteroid isomerase, triosephosphate isomerase, and serine proteases. The O-H⋯O hydrogen bond length derived from the proton chemical shift in a model dihydroxy-naphthalene compound in aqueous solution agreed well with lengths of such hydrogen bonds determined by high resolution, small molecule X-ray diffraction.

  4. Strong and weak hydrogen bonds in drug–DNA complexes: A ...

    Indian Academy of Sciences (India)

    ... in the list of 70 complexes mentioned above, and 19 inhibitors for which the drug–DNA complex crystal structures are unknown. The virtual geometries so generated correlate well with published activities for these 26 inhibitors, justifying our assumption that strong and weak hydrogen bonds are optimized in the active site.

  5. Density functional theory, natural bond orbital and quantum theory of ...

    Indian Academy of Sciences (India)

    The sign of Hb depends on which contribution, potential or kinetic, will locally prevail on the BCP. The Lapla- cian is negative if the modulus of the potential energy outweighs two times the kinetic energy, which implies the covalent character of interaction, and it may con- cern covalent bonds as well as very strong H-bonds.

  6. Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes

    KAUST Repository

    Minenkov, Yury

    2015-08-27

    The performance of the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method has been tested to reproduce the experimental gas phase ligand dissociation enthalpy in a series of Cu+, Ag+ and Au+ complexes. For 33 Cu+ - non-covalent ligand dissociation enthalpies all-electron calculations with the same method result in MUE below 2.2 kcal/mol, although a MSE of 1.4 kcal/mol indicates systematic underestimation of the experimental values. Inclusion of scalar relativistic effects for Cu either via effective core potential (ECP) or Douglass-Kroll-Hess Hamiltonian, reduces the MUE below 1.7 kcal/mol and the MSE to -1.0 kcal/mol. For 24 Ag+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) method results in a mean unsigned error (MUE) below 2.1 kcal/mol and vanishing mean signed error (MSE). For 15 Au+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) methods provides larger MUE and MSE, equal to 3.2 and 1.7 kcal/mol, which might be related to poor precision of the experimental measurements. Overall, for the combined dataset of 72 coinage metal ion complexes DLPNO-CCSD(T) results in a MUE below 2.2 kcal/mol and an almost vanishing MSE. As for a comparison with computationally cheaper density functional theory (DFT) methods, the routinely used M06 functional results in MUE and MSE equal to 3.6 and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms.

  7. Chemistry of Covalent Organic Frameworks.

    Science.gov (United States)

    Waller, Peter J; Gándara, Felipe; Yaghi, Omar M

    2015-12-15

    Linking organic molecules by covalent bonds into extended solids typically generates amorphous, disordered materials. The ability to develop strategies for obtaining crystals of such solids is of interest because it opens the way for precise control of the geometry and functionality of the extended structure, and the stereochemical orientation of its constituents. Covalent organic frameworks (COFs) are a new class of porous covalent organic structures whose backbone is composed entirely of light elements (B, C, N, O, Si) that represent a successful demonstration of how crystalline materials of covalent solids can be achieved. COFs are made by combination of organic building units covalently linked into extended structures to make crystalline materials. The attainment of crystals is done by several techniques in which a balance is struck between the thermodynamic reversibility of the linking reactions and their kinetics. This success has led to the expansion of COF materials to include organic units linked by these strong covalent bonds: B-O, C-N, B-N, and B-O-Si. Since the organic constituents of COFs, when linked, do not undergo significant change in their overall geometry, it has been possible to predict the structures of the resulting COFs, and this advantage has facilitated their characterization using powder X-ray diffraction (PXRD) techniques. It has also allowed for the synthesis of COF structures by design and for their formation with the desired composition, pore size, and aperture. In practice, the modeled PXRD pattern for a given expected COF is compared with the experimental one, and depending on the quality of the match, this is used as a starting point for solving and then refining the crystal structure of the target COF. These characteristics make COFs an attractive class of new porous materials. Accordingly, they have been used as gas storage materials for energy applications, solid supports for catalysis, and optoelectronic devices. A large and

  8. Atomic Covalent Functionalization of Graphene

    Science.gov (United States)

    Johns, James E.; Hersam, Mark C.

    2012-01-01

    Conspectus Although graphene’s physical structure is a single atom thick, two-dimensional, hexagonal crystal of sp2 bonded carbon, this simple description belies the myriad interesting and complex physical properties attributed to this fascinating material. Because of its unusual electronic structure and superlative properties, graphene serves as a leading candidate for many next generation technologies including high frequency electronics, broadband photodetectors, biological and gas sensors, and transparent conductive coatings. Despite this promise, researchers could apply graphene more routinely in real-world technologies if they could chemically adjust graphene’s electronic properties. For example, the covalent modification of graphene to create a band gap comparable to silicon (~1 eV) would enable its use in digital electronics, and larger band gaps would provide new opportunities for graphene-based photonics. Towards this end, researchers have focused considerable effort on the chemical functionalization of graphene. Due to its high thermodynamic stability and chemical inertness, new methods and techniques are required to create covalent bonds without promoting undesirable side reactions or irreversible damage to the underlying carbon lattice. In this Account, we review and discuss recent theoretical and experimental work studying covalent modifications to graphene using gas phase atomic radicals. Atomic radicals have sufficient energy to overcome the kinetic and thermodynamic barriers associated with covalent reactions on the basal plane of graphene but lack the energy required to break the C-C sigma bonds that would destroy the carbon lattice. Furthermore, because they are atomic species, radicals substantially reduce the likelihood of unwanted side reactions that confound other covalent chemistries. Overall, these methods based on atomic radicals show promise for the homogeneous functionalization of graphene and the production of new classes of two

  9. Strongly Phosphorescent Transition Metal π-Complexes of Boron-Boron Triple Bonds.

    Science.gov (United States)

    Braunschweig, Holger; Dellermann, Theresa; Dewhurst, Rian D; Hupp, Benjamin; Kramer, Thomas; Mattock, James D; Mies, Jan; Phukan, Ashwini K; Steffen, Andreas; Vargas, Alfredo

    2017-04-05

    Herein are reported the first π-complexes of compounds with boron-boron triple bonds with transition metals, in this case Cu I . Three different compounds were isolated that differ in the number of copper atoms bound to the BB unit. Metalation of the B-B triple bonds causes lengthening of the B-B and B-C NHC bonds, as well as large upfield shifts of the 11 B NMR signals, suggesting greater orbital interactions between the boron and transition metal atoms than those observed with recently published diboryne/alkali metal cation complexes. In contrast to previously reported fluorescent copper(I) π-complexes of boron-boron double bonds, the Cu n -π-diboryne compounds (n = 2, 3) show intense phosphorescence in the red to near-IR region from their triplet excited states, according to their microsecond lifetimes, with quantum yields of up to 58%. While the Cu diborene bond is dominated by electrostatic interactions, giving rise to S 1 and T 1 states of pure IL(π-π*) nature, DFT studies show that the Cu I π-complexes of diborynes reported herein exhibit enhanced metal d orbital contributions to HOMO and HOMO-1, which results in S 1 and T 1 having significant MLCT character, enabling strong spin-orbit coupling for highly efficient intersystem-crossing S 1 → T n and phosphorescence T 1 → S 0 .

  10. Can natural fibers be a silver bullet? Antibacterial cellulose fibers through the covalent bonding of silver nanoparticles to electrospun fibers

    Science.gov (United States)

    Zheng, Yingying; Cai, Chao; Zhang, Fuming; Monty, Jonathan; Linhardt, Robert J.; Simmons, Trevor J.

    2016-02-01

    Natural cotton was dissolved in a room-temperature ionic liquid 1-ethyl-3-methyl acetate and wet-jet electrospun to obtain nanoscale cotton fibers with a substantially reduced diameter—and therefore an increased surface area—relative to natural cotton fibers. The resulting nano-cotton fibers were esterified with trityl-3-mercaptopropionic acid, which after selective de-tritylation afforded nano-cotton fibers containing reactive thiol functionality. Silver nanoparticles that were covalently attached to these sulfhydryl groups were assembled next. The microstructure of the resulting nanocomposite was characterized, and the antibacterial activity of the resulting nano-cotton Ag-nanoparticle composite was also studied. This nanocomposite showed significant activity against both Gram-negative and Gram-positive bacteria.

  11. A facile mechanochemical route to a covalently bonded graphitic carbon nitride (g-C3N4) and fullerene hybrid toward enhanced visible light photocatalytic hydrogen production.

    Science.gov (United States)

    Chen, Xiang; Chen, Huanlin; Guan, Jian; Zhen, Jieming; Sun, Zijun; Du, Pingwu; Lu, Yalin; Yang, Shangfeng

    2017-05-04

    Graphitic carbon nitride (g-C 3 N 4 ) as an emerging two-dimensional (2D) nanomaterial has been commonly used as a metal-free photocatalyst with potential applications in visible light photocatalytic water-splitting. However, the photocatalytic activity of g-C 3 N 4 is quite low due to its relatively large band gap and the existence of contact resistance between the nanosheets. Herein we report for the first time the facile synthesis of a covalently bonded g-C 3 N 4 /C 60 hybrid via a solid-state mechanochemical route and its application in photocatalytic hydrogen production under visible light. The g-C 3 N 4 /C 60 hybrid was synthesized by ball-milling g-C 3 N 4 and C 60 in the presence of lithium hydroxide (LiOH) as a catalyst. The hybrid nature and conformation of the g-C 3 N 4 /C 60 hybrid were confirmed by a series of spectroscopic and morphological studies, featuring the covalent bonding of C 60 onto the edges of g-C 3 N 4 nanosheets via a four-membered ring of azetidine, which has never been reported in fullerene chemistry. The g-C 3 N 4 /C 60 hybrid was further applied to metal-free visible light photocatalytic hydrogen production, affording a H 2 production rate of 266 μmol h -1 g -1 without using any noble metal cocatalyst such as Pt, which is about 4.0 times higher than that obtained for the pristine g-C 3 N 4 photocatalyst.

  12. Siroheme- and [Fe4-S4]-dependent NirA from Mycobacterium tuberculosis is a sulfite reductase with a covalent Cys-Tyr bond in the active site.

    Science.gov (United States)

    Schnell, Robert; Sandalova, Tatyana; Hellman, Ulf; Lindqvist, Ylva; Schneider, Gunter

    2005-07-22

    The nirA gene of Mycobacterium tuberculosis is up-regulated in the persistent state of the bacteria, suggesting that it is a potential target for the development of antituberculosis agents particularly active against the pathogen in its dormant phase. This gene encodes a ferredoxin-dependent sulfite reductase, and the structure of the enzyme has been determined using x-ray crystallography. The enzyme is a monomer comprising 555 amino acids and contains a [Fe4-S4] cluster and a siroheme cofactor. The molecule is built up of three domains with an alpha/beta fold. The first domain consists of two ferredoxin-like subdomains, related by a pseudo-2-fold symmetry axis passing through the whole molecule. The other two domains, which provide much of the binding interactions with the cofactors, have a common fold that is unique to the sulfite/nitrite reductase family. The domains form a trilobal structure, with the cofactors and the active site located at the interface of all three domains in the center of the molecule. NirA contains an unusual covalent bond between the side chains of Tyr69 and Cys161 in the active site, in close proximity to the siroheme cofactor. Removal of this covalent bond by site-directed mutagenesis impairs catalytic activity, suggesting that it is important for the enzymatic reaction. These residues are part of a sequence fingerprint, able to distinguish between ferredoxin-dependent sulfite and nitrite reductases. Comparison of NirA with the structure of the truncated NADPH-dependent sulfite reductase from Escherichia coli suggests a binding site for the external electron donor ferredoxin close to the [Fe4-S4] cluster.

  13. A dense and strong bonding collagen film for carbon/carbon composites

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Sheng; Li, Hejun, E-mail: lihejun@nwpu.edu.cn; Li, Kezhi; Lu, Jinhua; Zhang, Leilei

    2015-08-30

    Graphical abstract: - Highlights: • Significantly enhancement of biocompatibility on C/C composites by preparing a collagen film. • The dense and continuous collagen film had a strong bonding strength with C/C composites after dehydrathermal treatment (DHT) crosslink. • Numerous oxygen-containing functional groups formed on the surface of C/C composites without matrix damage. - Abstract: A strong bonding collagen film was successfully prepared on carbon/carbon (C/C) composites. The surface conditions of the modified C/C composites were detected by contact angle measurements, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectra. The roughness, optical morphology, bonding strength and biocompatibility of collagen films at different pH values were detected by confocal laser scanning microscope (CLSM), universal test machine and cytology tests in vitro. After a 4-h modification in 30% H{sub 2}O{sub 2} solution at 100 °C, the contact angle on the surface of C/C composites was decreased from 92.3° to 65.3°. Large quantities of hydroxyl, carboxyl and carbonyl functional groups were formed on the surface of the modified C/C composites. Then a dense and continuous collagen film was prepared on the modified C/C substrate. Bonding strength between collagen film and C/C substrate was reached to 8 MPa level when the pH value of this collagen film was 2.5 after the preparing process. With 2-day dehydrathermal treatment (DHT) crosslinking at 105 °C, the bonding strength was increased to 12 MPa level. At last, the results of in vitro cytological test showed that this collagen film made a great improvement on the biocompatibility on C/C composites.

  14. Intermolecular and very strong intramolecular C-SeO/N chalcogen bonds in nitrophenyl selenocyanate crystals.

    Science.gov (United States)

    Wang, Hui; Liu, Ju; Wang, Weizhou

    2018-02-14

    Single-crystal X-ray diffraction reveals that polymorphic ortho-nitrophenyl selenocyanate (o-NSC, crystals 1a and 1b) and monomorphic para-nitrophenyl selenocyanate (p-NSC, crystal 2) crystals are all stabilized mainly by intermolecular and very strong intramolecular C-SeO/N chalcogen bonds, as well as by other different interactions. Thermogravimetric (TG) and differential scanning calorimetry thermogram (DSC) analyses show that the starting decomposition temperatures and melting points of the three crystals are different, following the order 1b > 1a > 2, which is consistent with the structural characteristics of the crystals. In addition, atoms in molecules (AIM) and natural bond orbital (NBO) analyses indicate that the total strengths of the C-SeO and C-SeN chalcogen bonds decrease in the order 1b > 1a > 2. This study could be significant for engineering functional crystals based on robust C-SeO and C-SeN chalcogen bonds, and for designing drugs containing selenium as well as understanding their interaction in biosystems.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-01

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

  16. Dependence of the length of the hydrogen bond on the covalent and cationic radii of hydrogen, and additivity of bonding distances

    Czech Academy of Sciences Publication Activity Database

    Heyrovská, Raji

    2006-01-01

    Roč. 432, č. 1-3 (2006), s. 348-351 ISSN 0009-2614 R&D Projects: GA MŠk(CZ) LC06035 Institutional research plan: CEZ:AV0Z50040507 Keywords : length of the hydrogen bond * ionic radius * Golden ratio Subject RIV: BO - Biophysics Impact factor: 2.462, year: 2006

  17. Chloramphenicol Biosynthesis: The Structure of CmlS, a Flavin-Dependent Halogenase Shwing a Covalent Flavin-Aspartate Bond

    Energy Technology Data Exchange (ETDEWEB)

    Podzelinska, K.; Latimer, R; Bhattacharya, A; Vining, L; Zechel, D; Jia, Z

    2010-01-01

    Chloramphenicol is a halogenated natural product bearing an unusual dichloroacetyl moiety that is critical for its antibiotic activity. The operon for chloramphenicol biosynthesis in Streptomyces venezuelae encodes the chloramphenicol halogenase CmlS, which belongs to the large and diverse family of flavin-dependent halogenases (FDH's). CmlS was previously shown to be essential for the formation of the dichloroacetyl group. Here we report the X-ray crystal structure of CmlS determined at 2.2 {angstrom} resolution, revealing a flavin monooxygenase domain shared by all FDHs, but also a unique 'winged-helix' C-terminal domain that creates a T-shaped tunnel leading to the halogenation active site. Intriguingly, the C-terminal tail of this domain blocks access to the halogenation active site, suggesting a structurally dynamic role during catalysis. The halogenation active site is notably nonpolar and shares nearly identical residues with Chondromyces crocatus tyrosyl halogenase (CndH), including the conserved Lys (K71) that forms the reactive chloramine intermediate. The exception is Y350, which could be used to stabilize enolate formation during substrate halogenation. The strictly conserved residue E44, located near the isoalloxazine ring of the bound flavin adenine dinucleotide (FAD) cofactor, is optimally positioned to function as a remote general acid, through a water-mediated proton relay, which could accelerate the reaction of the chloramine intermediate during substrate halogenation, or the oxidation of chloride by the FAD(C4{alpha})-OOH intermediate. Strikingly, the 8{alpha} carbon of the FAD cofactor is observed to be covalently attached to D277 of CmlS, a residue that is highly conserved in the FDH family. In addition to representing a new type of flavin modification, this has intriguing implications for the mechanism of FDHs. Based on the crystal structure and in analogy to known halogenases, we propose a reaction mechanism for CmlS.

  18. Channel-coupling theory of covalent bonding in H2: A further application of arrangement-channel quantum mechanics

    International Nuclear Information System (INIS)

    Levin, F.S.; Krueger, H.

    1977-01-01

    The dissociation energy D/sub e/ and the equilibrium proton-proton separation R/sub eq/ of H 2 are calculated using the methods of arrangement-channel quantum mechanics. This theory is the channel component version of the channel-coupling array approach to many-body scattering, applied to bound-state problems. In the approximation used herein, the wave function is identical to that of the classic Heitler-London-Sugiura valence-bond calculation, which gave D/sub e/ = 3.14 eV and R/sub eq/ = 1.65a 0 , values accurate to 34% and 17.8%, respectively. The present method yields D/sub e/ = 4.437 eV and R/sub eq/ approx. = 1.42a 0 , accurate to 6.5% and 1%, respectively. Some implications of these results are discussed

  19. Nonuniform Internal Structure of Fibrin Fibers: Protein Density and Bond Density Strongly Decrease with Increasing Diameter

    Directory of Open Access Journals (Sweden)

    Wei Li

    2017-01-01

    Full Text Available The major structural component of a blood clot is a meshwork of fibrin fibers. It has long been thought that the internal structure of fibrin fibers is homogeneous; that is, the protein density and the bond density between protofibrils are uniform and do not depend on fiber diameter. We performed experiments to investigate the internal structure of fibrin fibers. We formed fibrin fibers with fluorescently labeled fibrinogen and determined the light intensity of a fiber, I, as a function of fiber diameter, D. The intensity and, thus, the total number of fibrin molecules in a cross-section scaled as D1.4. This means that the protein density (fibrin per cross-sectional area, ρp, is not homogeneous but instead strongly decreases with fiber diameter as D-0.6. Thinner fibers are denser than thicker fibers. We also determined Young’s modulus, Y, as a function of fiber diameter. Y decreased strongly with increasing D; Y scaled as D-1.5. This implies that the bond density, ρb, also scales as D-1.5. Thinner fibers are stiffer than thicker fibers. Our data suggest that fibrin fibers have a dense, well-connected core and a sparse, loosely connected periphery. In contrast, electrospun fibrinogen fibers, used as a control, have a homogeneous cross-section.

  20. Bond Lengths and Bond Strengths in Weak and Strong Chemisorption: N2, CO, and CO/H on Nickel Surfaces

    OpenAIRE

    Sayago, David I.; Hoeft, Jon T.; Polcik, Martin; Kittel, Martin; Toomes, Rachel L.; Robinson, J.; Woodruff, David Phillip; Pascal, Mathieu; Lamont, Christine L.A.; Nisbet, Gareth

    2003-01-01

    New chemical-state-specific scanned-energy mode photoelectron diffraction experiments and density functional theory calculations, applied to CO, CO/H, and N2 adsorption on Ni(100), show that chemisorption bond length changes associated with large changes in bond strength are small, but those associated with changes in bond order are much larger, and are similar to those found in molecular systems. Specifically, halving the bond strength of atop CO to Ni increases the Ni-C distance by 0.06 Å...

  1. Analysis of the radical hydrogen transfer pathway for cleaving strong bonds in coal

    Energy Technology Data Exchange (ETDEWEB)

    Autrey, S.T.; Camaioni, D.M.; Ferris, K.F.; Franz, J.A.

    1993-09-01

    Hydrogen transfer processes involving radical intermediates are of key importance in the liquefaction of coal. While the primary function of donor solvents is to transfer H{lg_bullet} to coal-derived radicals that form when weak bonds are cleaved thermolytically, growing evidence suggests that the donor solvent can play a role in promoting cleavage of strong {alpha}-bonds. McMillen and Malhotra have explained the results in terms of a single-step mechanism referred to as radical H-transfer (RHT). Mechanistic kinetic models have been used to suggest the importance of RHT pathways in anthracene- and pyrene-based solvent systems. However, we question the reliability of these approaches because little experimental data exists to support the 16.5 kcal/mol intrinsic barriers they assume for RHT reactions. Unambiguous evidence for RHT is very difficult to obtain experimentally because at the temperatures required to activate the RHT reaction, a suite of multistep reactions can occur, which yield the same products, i.e. H-elimination from hydroaryl radicals followed by ipso addition. For this reason, we have sought to gain insight to barrier heights for RHT from theory. This paper reports our use of Marcus theory in combination with ab initio and semiempirical molecular orbital methods to show how the intrinsic barriers for RHT reactions depend on structural and thermodynamic properties of the reacting partners. In addition, reactions thought to be mediated by RHT are reexamined using mechanistic kinetic modeling (MKM) to determine the extent to which these reactions can be explained by conventional pathways.

  2. Associations Between Participant Ratings of PREP for Strong Bonds and Marital Outcomes 1 Year Postintervention.

    Science.gov (United States)

    Allen, Elizabeth S; Post, Kristina M; Markman, Howard J; Rhoades, Galena K; Stanley, Scott M

    2017-07-01

    After completing a relationship education program, collecting participant evaluations of the program is common practice. These are generally used as an index of "consumer satisfaction" with the program, with implications for feasibility and quality. Rarely have these ratings been used as predictors of changes in marital quality, although such feedback may be the only data providers collect or have immediate access to when considering the success of their efforts. To better understand the utility of such ratings to predict outcomes, we evaluated links between participant ratings and changes in self-reported marital satisfaction and communication scores one year later for a sample of 191 Army couples who had participated in a relationship education program delivered by Army chaplains (PREP for Strong Bonds). Overall ratings of general satisfaction with the program and the leader did not predict changes in marital outcomes one year later, whereas higher ratings of how much was learned, program helpfulness, increased similarity in outlook regarding Army life, and helpfulness of communication skills training predicted greater change in communication skills one year later. Higher ratings of items reflecting intent to invest more time in the relationship, and increased confidence in constructive communication and working as a team with the spouse predicted greater increases in both marital satisfaction and communication skills one year later. The constructs of intention and confidence (akin to perceived behavioral control) suggest that the Theory of Planned Behavior may be particularly useful when considering which Army couples will show ongoing benefit after relationship education.

  3. Electron population uncertainty and atomic covalency

    International Nuclear Information System (INIS)

    Chesnut, D.B.

    2006-01-01

    The atoms-in-molecules (AIM) index of atomic covalency is directly related to the AIM atomic population uncertainty. The covalent bond order, delocalization index, and, therefore, the atomic covalency are maximal when electron pairs are equally shared by the atoms involved. When polarization effects are present, these measures of covalent bond character decrease. We present atomic covalences for the single- and double-heavy atom hydrides of elements of the first and second low rows of the periodic table to illustrate these effects. Some usual behavior is seen in hydrogen-bridged species due in some cases to stronger than expected multicenter bonds and in other cases to many atoms contributing to the covalency index

  4. Covalent Organic

    DEFF Research Database (Denmark)

    Vutti, Surendra

    chemistry of silicon, InAs and GaAs materials, covalentsurface functionalization using organosilanes, liquid-phase, and vapor-phasefunctionalizations, diazo-transfer reaction, CuAAC click chemistry, different types ofbiorthogonal chemistries, SPAAC chemistry, and cellular interactions of chemically...... immobilization of D-amino acid adhesion peptideson azide functionalized silicon, GaAs and InAs materials by using CuAAC-click chemistry.The covalent immobilization of penetration peptide (TAT) on gold nanotips of InAs NWs isalso demonstrated.In chapter four, the covalent immobilization of GFP on silicon wafers......, GaAs wafers andGaAs NWs is demonstrated. Series of Fmoc-Pra-OH, NHS-PEG5-NHS and BCN-NHSfunctionalized silicon surfaces has been prepared, whereby GFP-N3 and GFP-bicyclononyneare immobilized by using CuAAC and SPAAC chemistry. The specific and covalentimmobilization of GFP-N3 on bicyclononyne...

  5. Nine supramolecular assemblies from 5,7-dimethyl-1,8-naphthyridine-2-amine and carboxylic acids by strong classical H-bonds and other noncovalent associations

    Science.gov (United States)

    Ding, Aihua; Jin, Shouwen; Jin, Shide; Guo, Ming; Liu, Hui; Guo, Jianzhong; Wang, Daqi

    2017-12-01

    This article demonstrates 5,7-dimethyl-1,8-naphthyridine-2-amine based organic salt formation in nine crystalline solids 1-9, in which the carboxylates have been integrated. Addition of equivalents of the COOH to the solution of 5,7-dimethyl-1,8-naphthyridine-2-amine generates the singly protonated cationic species which direct the carboxylates. The nine compounds crystallize as their organic salts with the COOH proton transferred to the aromatic N of the 5,7-dimethyl-1,8-naphthyridine-2-amine. All salts have been characterized by IR, mp, EA and XRD technique. The major driving force in 1-9 is the classical H-bonds from 5,7-dimethyl-1,8-naphthyridine-2-amine and the acids, here the Nsbnd H⋯O H-bonds were found in all salts. Other extensive non-covalent interactions also exhibit great functions in space association of the molecular counterparts in relevant crystals. Except 4, all salts had the CHsbnd O, or CH3sbnd O interactions or both. Except 9, the common R22 (8) graph set has been observed in all salts due to the H-bonds and the non-covalent associations. For the synergistic interactions of the classical H-bonds and the various non-covalent associations, the salts displayed 1D-3D structures.

  6. Effect of inter-fibre bonding on the fracture of fibrous networks with strong interactions

    DEFF Research Database (Denmark)

    Goutianos, Stergios; Mao, Rui; Peijs, Ton

    2017-01-01

    Abstract The mechanical response of cellulose nanopaper composites is investigated using a three-dimensional (3D) finite element fibrous network model with focus on the effect of inter-fibre bonds. It is found that the Young’s modulus and strength, for fixed fibre properties, are mainly controlle...

  7. Olefin metathesis for effective polymer healing via dynamic exchange of strong carbon-carbon bonds

    Science.gov (United States)

    Guan, Zhibin; Lu, Yixuan

    2015-09-15

    A method of preparing a malleable and/or self-healing polymeric or composite material is provided. The method includes providing a polymeric or composite material comprising at least one alkene-containing polymer, combining the polymer with at least one homogeneous or heterogeneous transition metal olefin metathesis catalyst to form a polymeric or composite material, and performing an olefin metathesis reaction on the polymer so as to form reversible carbon-carbon double bonds in the polymer. Also provided is a method of healing a fractured surface of a polymeric material. The method includes bringing a fractured surface of a first polymeric material into contact with a second polymeric material, and performing an olefin metathesis reaction in the presence of a transition metal olefin metathesis catalyst such that the first polymeric material forms reversible carbon-carbon double bonds with the second polymeric material. Compositions comprising malleable and/or self-healing polymeric or composite material are also provided.

  8. DFT+DMFT study on soft moment magnetism and covalent bonding in SrRu.sub.2./sub.O.sub.6./sub.

    Czech Academy of Sciences Publication Activity Database

    Hariki, A.; Hausoel, A.; Sangiovanni, G.; Kuneš, Jan

    2017-01-01

    Roč. 96, č. 15 (2017), s. 1-8, č. článku 155135. ISSN 2469-9950 EU Projects: European Commission(XE) 646807 - EXMAG Institutional support: RVO:68378271 Keywords : covalent insulator * dynamical mean-field theory Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.836, year: 2016

  9. Host-Guest Complexes of Cyclodextrins and Nanodiamonds as a Strong Non-Covalent Binding Motif for Self-Assembled Nanomaterials.

    Science.gov (United States)

    Schibilla, Frauke; Voskuhl, Jens; Fokina, Natalie A; Dahl, Jeremy E P; Schreiner, Peter R; Ravoo, Bart Jan

    2017-11-13

    We report the inclusion of carboxy- and amine-substituted molecular nanodiamonds (NDs) adamantane, diamantane, and triamantane by β-cyclodextrin and γ-cyclodextrin (β-CD and γ-CD), which have particularly well-suited hydrophobicity and symmetry for an optimal fit of the host and guest molecules. We studied the host-guest interactions in detail and generally observed 1:1 association of the NDs with the larger γ-CD cavity, but observed 1:2 association for the largest ND in the series (triamantane) with β-CD. We found higher binding affinities for carboxy-substituted NDs than for amine-substituted NDs. Additionally, cyclodextrin vesicles (CDVs) were decorated with d-mannose by using adamantane, diamantane, and triamantane as non-covalent anchors, and the resulting vesicles were compared with the lectin concanavalin A in agglutination experiments. Agglutination was directly correlated to the host-guest association: adamantane showed lower agglutination than di- or triamantane with β-CDV and almost no agglutination with γ-CDV, whereas high agglutination was observed for di- and triamantane with γ-CDV. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Microscopic models for proton transfer in water and strongly hydrogen-bonded complexes with a single-well proton potential

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2004-01-01

    A new mechanism and formalism for proton transfer in donor-acceptor complexes with long hydrogen bonds introduced recently [1], is applied to a proton transfer in liquid water. "Structural diffusion" of hydroxonium ions is regarded as totally adiabatic process, with synchronous hindered translation...... of two closest water molecules to and from the reaction complex as crucial steps. The water molecules induce a "gated" shift of the proton from the donor to the acceptor in the double-well potential with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor...... and acceptor. The short-range and long-range proton transfer as "structural diffusion" of Zundel complexes is also considered. The theoretical formalism is illustrated with the use of Morse, exponential, and harmonic molecular potentials. This approach is extended to proton transfer in strongly hydrogen...

  11. Solid-State17O NMR Reveals Hydrogen-Bonding Energetics: Not All Low-Barrier Hydrogen Bonds Are Strong.

    Science.gov (United States)

    Lu, Jiasheng; Hung, Ivan; Brinkmann, Andreas; Gan, Zhehong; Kong, Xianqi; Wu, Gang

    2017-05-22

    While NMR and IR spectroscopic signatures and structural characteristics of low-barrier hydrogen bond (LBHB) formation are well documented in the literature, direct measurement of the LBHB energy is difficult. Here, we show that solid-state 17 O NMR spectroscopy can provide unique information about the energy required to break a LBHB. Our solid-state 17 O NMR data show that the HB enthalpy of the O⋅⋅⋅H⋅⋅⋅N LBHB formed in crystalline nicotinic acid is only 7.7±0.5 kcal mol -1 , suggesting that not all LBHBs are particularly strong. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. The semiempirical quantum chemical PM6 method augmented by dispersion and H-bonding correction terms describes reliably various types of non-covalent complexes

    Czech Academy of Sciences Publication Activity Database

    Řezáč, Jan; Fanfrlík, Jindřich; Salahub, D.; Hobza, Pavel

    2009-01-01

    Roč. 5, č. 7 (2009), s. 1749-1760 ISSN 1549-9618 R&D Projects: GA MŠk LC512 Institutional research plan: CEZ:AV0Z40550506 Keywords : hydrogen bonding * dispersion Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.804, year: 2009

  13. Structural Analysis of a Viral Ovarian Tumor Domain Protease from the Crimean-Congo Hemorrhagic Fever Virus in Complex with Covalently Bonded Ubiquitin

    Energy Technology Data Exchange (ETDEWEB)

    Capodagli, Glenn C.; McKercher, Marissa A.; Baker, Erica A.; Masters, Emily M.; Brunzelle, Joseph S.; Pegan, Scott D. (Denver); (NWU)

    2014-10-02

    Crimean-Congo hemorrhagic fever (CCHF) virus is a tick-borne, negative-sense, single-stranded RNA [ssRNA(-)] nairovirus that produces fever, prostration, and severe hemorrhages in humans. With fatality rates for CCHF ranging up to 70% based on several factors, CCHF is considered a dangerous emerging disease. Originally identified in the former Soviet Union and the Congo, CCHF has rapidly spread across large sections of Europe, Asia, and Africa. Recent reports have identified a viral homologue of the ovarian tumor protease superfamily (vOTU) within its L protein. This protease has subsequently been implicated in downregulation of the type I interferon immune response through cleavage of posttranslational modifying proteins ubiquitin (Ub) and the Ub-like interferon-simulated gene 15 (ISG15). Additionally, homologues of vOTU have been suggested to perform similar roles in the positive-sense, single-stranded RNA [ssRNA(+)] arteriviruses. By utilizing X-ray crystallographic techniques, the structure of vOTU covalently bound to ubiquitin propylamine, a suicide substrate of the enzyme, was elucidated to 1.7 {angstrom}, revealing unique structural elements that define this new subclass of the OTU superfamily. In addition, kinetic studies were carried out with aminomethylcoumarin (AMC) conjugates of monomeric Ub, ISG15, and NEDD8 (neural precursor cell expressed, developmentally downregulated 8) substrates in order to provide quantitative insights into vOTU's preference for Ub and Ub-like substrates.

  14. A Relativity Enhanced, Medium-Strong Au(I)···H-N Hydrogen Bond in a Protonated Phenylpyridine-Gold(I) Thiolate.

    Science.gov (United States)

    Berger, Raphael J F; Schoiber, Jürgen; Monkowius, Uwe

    2017-01-17

    Gold is an electron-rich metal with a high electronegativity comparable to that of sulfur. Hence, hydrogen bonds of the Au(I)···H-E (E = electronegative element) type should be possible, but their existence is still under debate. Experimental results are scarce and often contradictory. As guidance for possible preparative work, we have theoretically investigated (ppyH)Au(SPh) (ppy = 2-phenylpyridine) bearing two monoanionic ligands which are not strongly electronegative at the same time to further increase the charge density on the gold(I) atom. The protonated pyridine nitrogen atom in ppy is geometrically ideally suited to place a proton in close proximity to the gold atom in a favorable geometry for a classical hydrogen bond arrangement. Indeed, the results of the calculations indicate that the hydrogen bonded conformation of (ppyH)Au(SPh) represents a minimum geometry with bond metrics in the expected range for medium-strong hydrogen bonds [r(N-H) = 1.043 Å, r(H···Au) = 2.060 Å, a(N-H···Au) = 141.4°]. The energy difference between the conformer containing the H···Au bond and another conformer without a hydrogen bond amounts to 7.8 kcal mol -1 , which might serve as an estimate of the hydrogen bond strength. Spectroscopic properties were calculated, yielding further characteristics of such hydrogen bonded gold species.

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

    International Nuclear Information System (INIS)

    Bahk, Yeon Kyoung; He, Xu; Gitsis, Emmanouil; Kuo, Yu-Ying; Kim, Nayoung; Wang, Jing

    2015-01-01

    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 3 CO 2 NH 4 ) and sodium acetate (CH 3 CO 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

  16. NMR studies of solid pentachlorophenol-4-methylpyridine complexes exhibiting strong OHN hydrogen bonds: geometric H/D isotope effects and hydrogen bond coupling cause isotopic polymorphism.

    Science.gov (United States)

    Ip, Brenda C K; Shenderovich, Ilya G; Tolstoy, Peter M; Frydel, Jaroslaw; Denisov, Gleb S; Buntkowsky, Gerd; Limbach, Hans-Heinrich

    2012-11-26

    We have studied the hydrogen bond interactions of (15)N labeled 4-methylpyridine (4-MP) with pentachlorophenol (PCP) in the solid state and in polar solution using various NMR techniques. Previous spectroscopic, X-ray, and neutron crystallographic studies showed that the triclinic 1:1 complex (4-MPPCP) exhibits the strongest known intermolecular OHN hydrogen bond in the solid state. By contrast, deuteration of the hydrogen bond gives rise to the formation of a monoclinic structure exhibiting a weaker hydrogen bond. By performing NMR experiments at different deuterium fractions and taking advantage of dipolar (1)H-(15)N recoupling under combined fast MAS and (1)H decoupling, we provide an explanation of the origin of the isotopic polymorphism of 4-MPPCP and improve previous chemical shift correlations for OHN hydrogen bonds. Because of anharmonic ground state vibrations, an ODN hydrogen bond in the triclinic form exhibits a shorter oxygen-hydron and a longer oxygen-nitrogen distance as compared to surrounding OHN hydrogen bonds, which also implies a reduction of the local dipole moment. The dipole-dipole interaction between adjacent coupled OHN hydrogen bonds which determines the structure of triclinic 4-MPPCP is then reduced by deuteration, and other interactions become dominant, leading to the monoclinic form. Finally, the observation of stronger OHN hydrogen bonds by (1)H NMR in polar solution as compared to the solid state is discussed.

  17. Strong van der Waals attractive forces in nanotechnology

    Science.gov (United States)

    Reimers, Jeffrey

    The Dobson classification scheme for failure of London-like expressions for describing dispersion is reviewed. New ways to measure using STM data and calculate by first principles free energies of organic self-assembly processes from solution will be discussed, considering tetraalkylporphyrins on graphite. How strong van der Waals forces can compete against covalent bonding to produce new molecular isomers and reaction pathways will also be demonstrated, focusing on golds-sulfur bonds for sensors and stabilizing nanoparticles.

  18. Topology of electron charge density for chemical bonds from valence bond theory: a probe of bonding types.

    Science.gov (United States)

    Zhang, Lixian; Ying, Fuming; Wu, Wei; Hiberty, Philippe C; Shaik, Sason

    2009-01-01

    To characterize the nature of bonding we derive the topological properties of the electron charge density of a variety of bonds based on ab initio valence bond methods. The electron density and its associated Laplacian are partitioned into covalent, ionic, and resonance components in the valence bond spirit. The analysis provides a density-based signature of bonding types and reveals, along with the classical covalent and ionic bonds, the existence of two-electron bonds in which most of the bonding arises from the covalent-ionic resonance energy, so-called charge-shift bonds. As expected, the covalent component of the Laplacian at the bond critical point is found to be largely negative for classical covalent bonds. In contrast, for charge-shift bonds, the covalent part of the Laplacian is small or positive, in agreement with the weakly attractive or repulsive character of the covalent interaction in these bonds. On the other hand, the resonance component of the Laplacian is always negative or nearly zero, and it increases in absolute value with the charge-shift character of the bond, in agreement with the decrease of kinetic energy associated with covalent-ionic mixing. A new interpretation of the topology of the total density at the bond critical point is proposed to characterize covalent, ionic, and charge-shift bonding from the density point of view.

  19. Reactions between aromatic hydrocarbons and heterocycles: covalent and proton-bound dimer cations of benzene/pyridine.

    Science.gov (United States)

    El-Shall, M Samy; Ibrahim, Yehia M; Alsharaeh, Edreese H; Meot-Ner Mautner, Michael; Watson, Simon P

    2009-07-29

    Despite the fact that benzene (Bz) and pyridine (Py) are probably the most common and extensively studied organic molecules, the observation of a covalent adduct in the ionized benzene/pyridine system has never been reported. This Article reports the first experimental and theoretical evidence of a covalent (Bz x Py)(*+) adduct that results from the reaction of Bz(*+) with pyridine or Py(*+) with benzene. These reactions are studied using mass-selected ion mobility, chemical reactivity, collisional dissociation, and ab initio calculations. The (Bz x Py)(*+) adduct does not exchange ligands with Bz to form Bz(2)(*+) or with Py to form (Py)(2)H(+) despite the strong bonds in these homodimers. The thermochemistry then suggests that the (Bz x Py)(*+) heterodimer is bonded covalently with a bonding energy of >33 kcal/mol. Correspondingly, ab initio calculations identify covalently bonded propeller-shaped isomers of (Bz x Py)(*+) with bonding energies of 31-38 kcal/mol, containing a C-N bond. The mobility of the (Bz x Py)(*+) adduct in helium is consistent with these covalent dimers. As to noncovalent adducts, the computations identify novel distonic hydrogen-bonded complexes (C(5)H(5)NH(+) x C(6)H(5)(*)) where the charge resides on one component (PyH(+)), while the radical site resides on the other component (C(6)H(5)(*)). Collisional dissociation suggests that the covalent and distonic dimers may interconvert at high energies. The most stable distonic (C(5)H(5)NH(+) x C(6)H(5)(*)) complex contains a hydrogen bond to the phenyl radical carbon site with a calculated dissociation energy of 16.6 kcal/mol. This bond is somewhat stronger than the NH(+) x pi hydrogen bonds of PyH(+) to the pi system of the phenyl radical and of the benzene molecule. For this NH(+) x pi bond in the PyH(+) x Bz dimer, the measured binding energy is 13.4 kcal/mol, and ab initio calculations identify two T-shaped isomers with the NH(+) pointing to the center of the benzene ring or to the

  20. Size-dependent Young’s modulus in ZnO nanowires with strong surface atomic bonds

    Science.gov (United States)

    Fan, Shiwen; Bi, Sheng; Li, Qikun; Guo, Qinglei; Liu, Junshan; Ouyang, Zhongliang; Jiang, Chengming; Song, Jinhui

    2018-03-01

    The mechanical properties of size-dependent nanowires are important in nano-electro-mechanical systems (NEMSs), and have attracted much research interest. Characterization of the size effect of nanowires in atmosphere directly to broaden their practical application instead of just in high vacuum situations, as reported previously, is desperately needed. In this study, we systematically studied the Young’s modulus of vertical ZnO nanowires in atmosphere. The diameters ranged from 48 nm to 239 nm with a resonance method using non-contact atomic force microscopy. The values of Young’s modulus in atmosphere present extremely strong increasing tendency with decreasing diameter of nanowire due to stronger surface atomic bonds compared with that in vacuum. A core-shell model for nanowires is proposed to explore the Young’s modulus enhancement in atmosphere, which is correlated with atoms of oxygen occurring near the nanowire surface. The modified model is more accurate for analyzing the mechanical behavior of nanowires in atmosphere compared with the model in vacuum. Furthermore, it is possible to use this characterization method to measure the size-related elastic properties of similar wire-sharp nanomaterials in atmosphere and estimate the corresponding mechanical behavior. The study of the size-dependent Young’s modulus in ZnO nanowires in atmosphere will improve the understanding of the mechanical properties of nanomaterials as well as providing guidance for applications in NEMSs, nanogenerators, biosensors and other related areas.

  1. Experimental and numerical study of a modified ASTM C633 adhesion test for strongly-bonded coatings

    Energy Technology Data Exchange (ETDEWEB)

    Bernardie, Raphaëlle; Berkouch, Reda; Valette, Stéphane; Absi, Joseph; Lefort, Pierre [University of Limoges, Limoges Cedex (France)

    2017-07-15

    When coatings are strongly bonded to their substrates it is often difficult to measure the adhesion values. The proposed method, which is suggested naming “silver print test”, consists in covering the central part of the samples with a thin layer of silver paint, before coating. The process used for testing this new method was the Air plasma spraying (APS), and the materials used were alumina coatings on C35 steel substrates, previously pre-oxidized in CO{sub 2}. The silver painted area was composed of small grains that did not oxidize but that significantly sintered during the APS process. The silver layer reduced the surface where the coating was linked to the substrate, which allowed its debonding, using the classical adhesion test ASTM C633-13, while the direct use of this test (without silver painting) led to ruptures inside the glue used in this test. The numerical modelling, based on the finite element method with the ABAQUS software, provided results in good agreement with the experimental measurements. This concordance validated the used method and allowed accessing to the values of adherence when the experimental test ASTM C633-13 failed, because of ruptures in the glue. After standardization, the “silver print test” might be used for other kinds of deposition methods, such as PVD, CVD, PECVD.

  2. Protection of iron against corrosion by coverage with ultrathin two-dimensional polymer films of a hydroxymethylbenzene self-assembled monolayer anchored by the formation of a covalent bond

    International Nuclear Information System (INIS)

    Shimura, Tadashi; Aramaki, Kunitsugu

    2008-01-01

    Ultrathin films of two-dimensional polymers were prepared on an iron electrode by modification of a p-hydroxymethylbenzene p-HOCH 2 C 6 H 4 (HOMB) self-assembled monolayer (SAM) with 1,2-bis(triethoxysilyl)ethane (C 2 H 5 O) 3 Si(CH 2 ) 2 Si(OC 2 H 5 ) 3 (BTESE) and alkyltriethoxysilanes C n H 2n+1 Si(OC 2 H 5 ) 3 (C n TES, n = 8 and 18). The electrode was derivatized by cathodic reduction of p-hydroxymethylbenzenediazonium tetrafluoroborate HOCH 2 C 6 H 4 N 2 BF 4 in an electrolytic acetonitrile solution below 10deg. C for 1 h to form the SAM via a covalent bond between carbon and iron atoms. The protective ability of the polymer film against iron corrosion was determined by polarization measurement of the coated electrode in an oxygenated 0.5 M NaCl solution. The protective efficiencies of the polymer films prepared by modification with BTESE plus C 8 TES and C 18 TES were 63.9% and 68.5% after immersion in 0.5 M NaCl for 1.5 h, respectively. These values were higher than those of the one-dimensional polymer films prepared with the respective C n TES. The film of the HOMB SAM modified with BTESE plus C 8 TES was characterized by contact angle measurement using a drop of water and X-ray photoelectron and FTIR reflection spectroscopies. The films of the HOMB SAM modified with BTESE plus C 8 TES and C 18 TES were persistent during immersion of the coated electrodes in 0.5 M NaCl for many hours by far as compared with the alkanethiol SAM anchored on iron by the formation of a coordinate bond

  3. Covalent Bonding of Metal-Organic Framework-5/Graphene Oxide Hybrid Composite to Stainless Steel Fiber for Solid-Phase Microextraction of Triazole Fungicides from Fruit and Vegetable Samples.

    Science.gov (United States)

    Zhang, Shuaihua; Yang, Qian; Wang, Wenchang; Wang, Chun; Wang, Zhi

    2016-04-06

    A hybrid material of the zinc-based metal-organic framework-5 and graphene oxide (metal-organic framework-5/graphene oxide) was prepared as a novel fiber coating material for solid-phase microextraction (SPME). The SPME fibers were fabricated by covalent bonding via chemical cross-linking between the coating material metal-organic framework-5/graphene oxide and stainless steel wire. The prepared fiber was used for the extraction of five triazole fungicides from fruit and vegetable samples. Gas chromatography coupled with microelectron capture detector (GC-μECD) was used for quantification. The developed method gave a low limit of detection (0.05-1.58 ng g(-1)) and good linearity (0.17-100 ng g(-1)) for the determination of the triazole fungicides in fruit and vegetable samples. The relative standard deviations (RSDs) for five replicate extractions of the triazole fungicides ranged from 3.7 to 8.9%. The method recoveries for spiked fungicides (5, 20, and 50 ng g(-1)) in grape, apple, cucumber, celery cabbage, pear, cabbage, and tomato samples were in the range of 85.6-105.8% with the RSDs ranging from 3.6 to 11.4%, respectively, depending on both the analytes and samples. The metal-organic framework-5/graphene oxide coated fiber was stable enough for 120 extraction cycles without a significant loss of extraction efficiency. The method was suitable for the determination of triazole fungicides in fruit and vegetable samples.

  4. Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions

    International Nuclear Information System (INIS)

    Gruner, B.; Plesek, J.; Baca, J.; Cisarova, I.; Dozol, J.F.; Rouquette, H.; Vinas, C.; Selucky, P.; Rais, J.

    2002-01-01

    A new series of boron substituted cobalt bis(dicarbollide)(1-) ion (1) derivatives of the general formula [(8-CMPO-(CH 2 -CH 2 O) 2 -1,2-C 2 B 9 H 10 )(1',2'-C 2 B 9 H 11 )-3,3'-Co] - (CMPO = Ph 2 P(O)-CH 2 C(O)NR, R = C 4 H 9 (3b), -C 12 H 25 (4b), -CH 2 -C 6 H 5 (5b)) was prepared by ring cleavage of the 8-dioxane-cobalt bis(dicarbollide) (2) bi-polar compound by the respective primary amines and by subsequent reaction of the resulting amino derivatives (3a-5a) with the nitrophenyl ester of diphenyl-phosphoryl-acetic acid. The compounds were synthesized with the aim to develop a new class of more efficient extraction agents for liquid/liquid extraction of polyvalent cations, i.e. lanthanides and actinides, from high-level activity nuclear waste. All compounds were characterized by a combination of 11 B NMR, 1 H high field NMR, Mass Spectrometry with Electro-spray and MALDI TOF ionisation, HPLC and other techniques. The molecular structure of the supramolecular Ln 3+ complex of the anion 5b was determined by single crystal X-ray diffraction analysis. Crystallographic results proved that the Ln(m) atom is bonded to three functionalized cobalt bis(dicarbollide) anions in a charge compensated complex. The cation is tightly coordinated by six oxygen atoms of the CMPO terminal groups (two of each ligand) and by three water molecules completing the metal coordination number to 9. Atoms occupying the primary coordination sphere form a tri-capped trigonal prismatic arrangement. Very high liquid-liquid extraction efficiency of all anionic species was observed. Moreover, less polar toluene can be applied as an auxiliary solvent replacing the less environmentally friendly nitro- and chlorinated solvents used in the current dicarbollide liquid-liquid extraction process. The extraction coefficients are sufficiently high for possible technological applications. (authors)

  5. Isotope dependent, temperature regulated, energy repartitioning in a low-barrier, short-strong hydrogen bonded cluster

    NARCIS (Netherlands)

    Li, X. H.; Oomens, J.; Eyler, J. R.; Moore, D. T.; Iyengar, S. S.

    2010-01-01

    We investigate and analyze the vibrational properties, including hydrogen/deuterium isotope effects, in a fundamental organic hydrogen bonded system using multiple experimental (infrared multiple photon dissociation and argon-tagged action spectroscopy) and computational techniques. We note a

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1979-10-10

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

  7. Covalency in Americium(III) Hexachloride.

    Science.gov (United States)

    Cross, Justin N; Su, Jing; Batista, Enrique R; Cary, Samantha K; Evans, William J; Kozimor, Stosh A; Mocko, Veronika; Scott, Brian L; Stein, Benjamin W; Windorff, Cory J; Yang, Ping

    2017-06-28

    Developing a better understanding of covalency (or orbital mixing) is of fundamental importance. Covalency occupies a central role in directing chemical and physical properties for almost any given compound or material. Hence, the concept of covalency has potential to generate broad and substantial scientific advances, ranging from biological applications to condensed matter physics. Given the importance of orbital mixing combined with the difficultly in measuring covalency, estimating or inferring covalency often leads to fiery debate. Consider the 60-year controversy sparked by Seaborg and co-workers ( Diamond, R. M.; Street, K., Jr.; Seaborg, G. T. J. Am. Chem. Soc. 1954 , 76 , 1461 ) when it was proposed that covalency from 5f-orbitals contributed to the unique behavior of americium in chloride matrixes. Herein, we describe the use of ligand K-edge X-ray absorption spectroscopy (XAS) and electronic structure calculations to quantify the extent of covalent bonding in-arguably-one of the most difficult systems to study, the Am-Cl interaction within AmCl 6 3- . We observed both 5f- and 6d-orbital mixing with the Cl-3p orbitals; however, contributions from the 6d-orbitals were more substantial. Comparisons with the isoelectronic EuCl 6 3- indicated that the amount of Cl 3p-mixing with Eu III 5d-orbitals was similar to that observed with the Am III 6d-orbitals. Meanwhile, the results confirmed Seaborg's 1954 hypothesis that Am III 5f-orbital covalency was more substantial than 4f-orbital mixing for Eu III .

  8. Respiratory chain strongly oxidizes the CXXC motif of DsbB in the Escherichia coli disulfide bond formation pathway.

    OpenAIRE

    Kobayashi, T; Ito, K

    1999-01-01

    Escherichia coli DsbB has four essential cysteine residues, among which Cys41 and Cys44 form a CXXC redox active site motif and the Cys104-Cys130 disulfide bond oxidizes the active site cysteines of DsbA, the disulfide bond formation factor in the periplasm. Functional respiratory chain is required for the cell to keep DsbA oxidized. In this study, we characterized the roles of essential cysteines of DsbB in the coupling with the respiratory chain. Cys104 was found to form the inactive comple...

  9. New Raman method for aqueous solutions: xi-function dispersion evidence for strong F(-)-water H-bonds in aqueous CsF and KF solutions.

    Science.gov (United States)

    Walrafen, George E

    2005-08-15

    The Raman xi-function dispersion method recently elucidated for the strong H-bond breaker, ClO4-, in water [G. E. Walrafen, J. Chem. Phys. 122, 094510 (2005)] is extended to the strongly H-bond forming ion, F-. Measuring the xi function is analogous to measuring DeltaG from the thermodynamic activity of the water, aH2O, as the stoichiometric mol fraction of the water in the solution decreases due to addition of an electrolyte or nonelectrolyte. xi is the derivative of the OH-stretching part of the Gibbs free energy with respect to the water mol fraction; xiomega identical with-RT[ partial differential ln(Iomega/IREF) partial differentialX2](T,P). I is the Raman intensity at omega (omega=Raman shift in cm-1); IREF, that at an arbitrary reference omega; and, X2 is the water mol fraction (X1=CsF or KF mol fraction). ln(Iomega/IREF) was found to be linear in X2 for the complete range of OH-stretching omega's, with correlation coefficients as large as 0.999 96. Linearity of ln(Iomega/IREF) versus X2 is an experimental fact for all omega's throughout the spontaneous Raman OH-stretching contour; this fact cannot be negated by relative contributions of ultrafast/fast, homogeneous/inhomogeneous processes which may underlie this linearity. Linearity in ln(Iomega/IREF) versus 1T, or in ln(Iomega/IREF) versus P, was also observed for the Raman H-bond energy DeltaE and pair volume DeltaV dispersions, respectively. A low-frequency maximum (MAX) and a high-frequency minimum (MIN) were observed in the xi function dispersion curve. Deltaxi=xiMIN-xiMAX values of -7000+/-800-cal/mol H2O for CsF, and the experimentally equal Deltaxi=-6400+/-1000-cal/mol H2O for KF, were obtained. These Deltaxi's are opposite in sign but have nearly the same absolute magnitude as the Deltaxi value for NaClO4 in water; Deltaxi=+8050+/-100-cal/mol H2O. A positive Deltaxi corresponds to a water-water H-bond breaker; a negative Deltaxi to a H-bond former; specifically, a F--water H-bond former, in the

  10. Effects of strong inter-hydrogen bond dynamical couplings in the polarized IR spectra of adipic acid crystals

    Energy Technology Data Exchange (ETDEWEB)

    Flakus, Henryk T., E-mail: flakus@ich.us.edu.pl [Institute of Chemistry, University of Silesia, 9 Szkolna Street, Pl-40-006 Katowice (Poland); Tyl, Aleksandra; Jablonska, Magdalena [Institute of Chemistry, University of Silesia, 9 Szkolna Street, Pl-40-006 Katowice (Poland)

    2009-10-16

    This paper presents the results of the re-investigation of polarized IR spectra of adipic acid and of its d{sub 2}, d{sub 8} and d{sub 10} deuterium derivative crystals. The spectra were measured at 77 K by a transmission method using polarized light for two different crystalline faces. Theoretical analysis concerned linear dichroic effects and H/D isotopic effects observed in the spectra of the hydrogen and deuterium bonds in adipic acid crystals at the frequency ranges of the {nu}{sub O-H} and the {nu}{sub O-D} bands. The two-branch fine structure pattern of the {nu}{sub O-H} and {nu}{sub O-D} bands and the basic linear dichroic effects characterizing them were ascribed to the vibronic mechanism of vibrational dipole selection rule breaking for IR transitions in centrosymmetric hydrogen bond dimers. It was proved that for isotopically diluted crystalline samples of adipic acid, a non-random distribution of protons and deuterons occurs in the dimers (H/D isotopic 'self-organization' effect). This effect results from the dynamical co-operative interactions involving the dimeric hydrogen bonds.

  11. Effects of strong inter-hydrogen bond dynamical couplings in the polarized IR spectra of adipic acid crystals

    Science.gov (United States)

    Flakus, Henryk T.; Tyl, Aleksandra; Jablońska, Magdalena

    2009-10-01

    This paper presents the results of the re-investigation of polarized IR spectra of adipic acid and of its d2, d8 and d10 deuterium derivative crystals. The spectra were measured at 77 K by a transmission method using polarized light for two different crystalline faces. Theoretical analysis concerned linear dichroic effects and H/D isotopic effects observed in the spectra of the hydrogen and deuterium bonds in adipic acid crystals at the frequency ranges of the νO-H and the νO-D bands. The two-branch fine structure pattern of the νO-H and νO-D bands and the basic linear dichroic effects characterizing them were ascribed to the vibronic mechanism of vibrational dipole selection rule breaking for IR transitions in centrosymmetric hydrogen bond dimers. It was proved that for isotopically diluted crystalline samples of adipic acid, a non-random distribution of protons and deuterons occurs in the dimers (H/D isotopic " self-organization" effect). This effect results from the dynamical co-operative interactions involving the dimeric hydrogen bonds.

  12. Manufacturing of REBCO coils strongly bonded to cooling members with epoxy resin aimed at its application to Maglev

    International Nuclear Information System (INIS)

    Mizuno, Katsutoshi; Ogata, Masafumi; Hasegawa, Hitoshi

    2014-01-01

    Highlights: • Paraffin has a risk of losing thermal coupling during cooling down. • We propose an epoxy impregnated REBCO coil co-wound with PTFE tape. • The coil is tightly bonded to cooling members by epoxy resin without the degradation. • We made a REBCO racetrack coil with the same outer dimension as the Maglev magnet. - Abstract: The REBCO coated conductor has been attracted attention because of its high current density in the presence of high magnetic field. If the coated conductor is applied to Maglev, the operational temperature of the on-board magnets will be over 40 K and energy consumption of cryocoolers will be reduced. That high operational temperature also means the absence of liquid helium. Therefore, reliable thermal coupling is desirable for cooling the coils. We propose an epoxy impregnated REBCO coil co-wound with PTFE tape. While the PTFE tape prevents the performance degradation of the coil, the epoxy resin bonds the coil to cooling members. We carried out three experiments to confirm that the coil structure which we propose has robust thermal coupling without the degradation. First, thermal resistances of paraffin and epoxy were measured varying the temperature from room temperature to 10 K. The measurement result indicates that paraffin has a risk of losing thermal coupling during cooling down. In another experiment, PTFE (polytetrafluoroethylene) tape insulator prevented performance degradation of a small epoxy impregnated REBCO coil, while another REBCO coil with polyimide tape showed clear performance degradation. Finally, we produced a racetrack REBCO coil with the same outer dimension as a Maglev on-board magnet coil. Although the racetrack coil was installed in a GFRP coil case and tightly bonded to the case by epoxy impregnation, any performance degradation was not observed

  13. Unusually strong H-bonding to the heme ligand and fast geminate recombination dynamics of the carbon monoxide complex of Bacillus subtilis truncated hemoglobin.

    Science.gov (United States)

    Feis, Alessandro; Lapini, Andrea; Catacchio, Bruno; Brogioni, Silvia; Foggi, Paolo; Chiancone, Emilia; Boffi, Alberto; Smulevich, Giulietta

    2008-01-22

    The active site of the oxygen-avid truncated hemoglobin from Bacillus subtilis has been characterized by infrared absorption and resonance Raman spectroscopies, and the dynamics of CO rebinding after photolysis has been investigated by picosecond transient absorption spectroscopy. Resonance Raman experiments on the CO bound adduct revealed the presence of two Fe-CO stretching bands at 545 and 520 cm-1, respectively. Accordingly, two C-O stretching bands at 1924 and 1888 cm-1 were observed in infrared absorption and resonance Raman measurements. The very low C-O stretching frequency at 1888 cm-1 (corresponding to the extremely high RR stretching frequency at 545 cm-1) indicates unusually strong hydrogen bonding between CO and distal residues. On the basis of a comparison with other truncated hemoglobin it is envisaged that the two CO conformers are determined by specific interactions with the TrpG8 and TyrB10 residues. Mutation of TrpG8 to Leu deeply alters the hydrogen-bonding network giving rise mainly to a CO conformer characterized by a Fe-CO stretching band at 489 cm-1 and a CO stretching band at 1958 cm-1. Picosecond laser photolysis experiments carried out on the CO bound adduct revealed dynamical processes that take place within a few nanoseconds after photolysis. Picosecond dynamics is largely dominated by CO geminate rebinding and is consistent with strong H-bonding contributions of TyrB10 and TrpG8 to ligand stabilization.

  14. Strong Coupling between Nanofluidic Transport and Interfacial Chemistry: How Defect Reactivity Controls Liquid-Solid Friction through Hydrogen Bonding.

    Science.gov (United States)

    Joly, Laurent; Tocci, Gabriele; Merabia, Samy; Michaelides, Angelos

    2016-04-07

    Defects are inevitably present in nanofluidic systems, yet the role they play in nanofluidic transport remains poorly understood. Here, we report ab initio molecular dynamics (AIMD) simulations of the friction of liquid water on defective graphene and boron nitride sheets. We show that water dissociates at certain defects and that these "reactive" defects lead to much larger friction than the "nonreactive" defects at which water molecules remain intact. Furthermore, we find that friction is extremely sensitive to the chemical structure of reactive defects and to the number of hydrogen bonds they can partake in with the liquid. Finally, we discuss how the insight obtained from AIMD can be used to quantify the influence of defects on friction in nanofluidic devices for water treatment and sustainable energy harvesting. Overall, we provide new insight into the role of interfacial chemistry on nanofluidic transport in real, defective systems.

  15. Electronic structure and interatomic bonding in Al10V

    International Nuclear Information System (INIS)

    Jahnatek, M; Krajci, M; Hafner, J

    2003-01-01

    On the basis of ab initio calculations we analysed the electron density distribution in the elementary cell of the compound Al 10 V. We found covalent bonding between certain atoms. The Al-V bonds of enhanced covalency are linked into -Al-V-Al-V- chains that extend over the whole crystal. The chains intersect at each V site and together form a Kagome network of corner-sharing tetrahedra. The large voids of this network are filled by Z 16 Friauf polyhedra consisting of Al atoms only. The skeleton of the Friauf polyhedron has the form of a truncated tetrahedron and consists of 12 strongly bonded Al atoms. These Al-Al bonds also have covalent character. The bonding is dominated by sp 2 hybridization. The centre of the Friauf polyhedron may be empty or occupied by an Al atom. The thermodynamic stability of the phase is investigated. The Al 21 V 2 phase with occupied voids is at low temperatures less stable than Al 10 V. The Al 10 V structure can be considered as a special case of the Al 18 Cr 2 Mg 3 structural class. We have found the same picture of bonding as we report here for Al 10 V for several other aluminium-rich alloys belonging to the Al 18 Cr 2 Mg 3 structural class also

  16. Vibrational tug-of-war: The pKA dependence of the broad vibrational features of strongly hydrogen-bonded carboxylic acids

    Science.gov (United States)

    Van Hoozen, Brian L.; Petersen, Poul B.

    2018-04-01

    Medium and strong hydrogen bonds give rise to broad vibrational features frequently spanning several hundred wavenumbers and oftentimes exhibiting unusual substructures. These broad vibrational features can be modeled from first principles, in a reduced dimensional calculation, that adiabatically separates low-frequency modes, which modulate the hydrogen bond length, from high-frequency OH stretch and bend modes that contribute to the vibrational structure. Previously this method was used to investigate the origin of an unusual vibrational feature frequently found in the spectra of dimers between carboxylic acids and nitrogen-containing aromatic bases that spans over 900 cm-1 and contains two broad peaks. It was found that the width of this feature largely originates from low-frequency modes modulating the hydrogen bond length and that the structure results from Fermi resonance interactions. In this report, we examine how these features change with the relative acid and base strength of the components as reflected by their aqueous pKA values. Dimers with large pKA differences are found to have features that can extend to frequencies below 1000 cm-1. The relationships between mean OH/NH frequency, aqueous pKA, and O-N distance are examined in order to obtain a more rigorous understanding of the origin and shape of the vibrational features. The mean OH/NH frequencies are found to correlate well with O-N distances. The lowest OH stretch frequencies are found in dimer geometries with O-N distances between 2.5 and 2.6 Å. At larger O-N distances, the hydrogen bonding interaction is not as strong, resulting in higher OH stretch frequencies. When the O-N distance is smaller than 2.5 Å, the limited space between the O and N determines the OH stretch frequency, which gives rise to frequencies that decrease with O-N distances. These two effects place a lower limit on the OH stretch frequency which is calculated to be near 700 cm-1. Understanding how the vibrational features

  17. Covalent capture: merging covalent and noncovalent synthesis.

    Science.gov (United States)

    Prins, Leonard J; Scrimin, Paolo

    2009-01-01

    This Review is concerned with the search of molecules to find a suitable partner with whom to form a bond. Whether an initial encounter results in a fixed bond depends on many critical issues, such as reciprocal compatibility in terms of size and shape, complementary reactivity, proper alignment of reactive groups, and medium effects. The chemist acts as the master of ceremony and finds a high reward in the case of a successful marriage. Giotto's painting "The wedding of Mary and Joseph" illustrates the principles of supramolecular chemistry involved.

  18. Covalent stabilization of a small molecule-RNA complex.

    Science.gov (United States)

    Peacock, Hayden; Bachu, Radhika; Beal, Peter A

    2011-09-01

    We demonstrate covalent bond formation between an RNA aptamer containing a cysteamine-tethered nucleobase and helix-threading peptides (HTPs) containing α-bromoacetamide N-termini. The reaction is high yielding and inhibited by a DNA strand Watson-Crick complementary to the aptamer sequence indicating covalent reaction is dependent on the high affinity HTP-binding site present in the folded aptamer. These results are important for future structural studies of HTP-RNA complexes and methods for the discovery of new high affinity analogs via covalent tethering strategies. Copyright © 2011 Elsevier Ltd. All rights reserved.

  19. Covalent and non-covalent functionalization and solubilization of ...

    Indian Academy of Sciences (India)

    Wintec

    Abstract. Double-walled carbon nanotubes (DWNTs) have been functionalized by both covalent and non-covalent means. Covalent functionalization has been carried out by attaching an aliphatic amide function to DWNTs which enable solubilization in non-polar solvents. Solubilization in non-polar sol- vents has also been ...

  20. Disorder phenomena in covalent semiconductors

    International Nuclear Information System (INIS)

    Popescu, M.A.

    1975-01-01

    The structure of the amorphous semiconductors has been investigated by means of X-ray diffraction and by computer simulation of random network models. Amorphous germanium contains mainly five and six-membered rings of atoms. In glassy state, the ternary compounds A 2 B 4 C 2 5 , such as CdGeAs 2 contain only even rings of atoms (six-membered and eight-membered rings). In the memory glasses of the type A 2 B 4 C 2 5 , such as GeAs 2 Te 7 , the valency state of every element is that from the crystal and important van der Waals forces are effective in the network. No Ge-Ge, Ge-As and As-As bonds are formed. The high pressure forms of the germanium have been simulated by computer. The force constants of the covalent bonds in Ge III and Ge IV differ from those in Ge I. The bond bending force constant decreases rapidly when the density of the crystal increases, a fact which has been imparted to a reduction of the sp 3 hybridization. The compressibility curve of the Ge I has been explained. The effect of the radial and uniaxial deformation on the non-crystalline networks has been studied. The compressibility of the amorphous germanium is by 1.5 per cent greater than that of crystalline germanium. The Poisson coefficient for a-Ge network is 0.233. The structure of the As 2 S 3 glass doped with different amounts of germanium (up to 40 at. per cent) and silver (up to 12 at. per cent) has been investigated. The As 2 S 3 Gesub(x) compositions are constituted from a disordered packing of structural units whose chemical composition and relative proportion in the glass essentially depends on the germanium content. (author)

  1. Fluorine-enhanced low-temperature wafer bonding of native-oxide covered Si wafers

    Science.gov (United States)

    Tong, Q.-Y.; Gan, Q.; Fountain, G.; Enquist, P.; Scholz, R.; Gösele, U.

    2004-10-01

    The bonding energy of bonded native-oxide-covered silicon wafers treated in the HNO3/H2O/HF or the HNO3/HF solution prior to room-temperature contact is significantly higher than bonded standard RCA1 cleaned wafer pairs after low-temperature annealing. The bonding energy reaches over 2000mJ/m2 after annealing at 100 °C. The very slight etching and fluorine in the chemically grown oxide are believed to be the main contributors to the enhanced bonding energy. Transmission-electron-microscopic images have shown that the chemically formed native oxide at bonding interface is embedded with many flake-like cavities. The cavities can absorb the by-products of the interfacial reactions that result in covalent bond formation at low temperatures allowing the strong bond to be retained.

  2. Electronic bond structure of the H2+ ion in a strong magnetic field: A study of the parallel configuration

    International Nuclear Information System (INIS)

    Kappes, U.; Schmelcher, P.

    1995-01-01

    A large number of magnetically dressed states of the hydrogen molecular ion for parallel internuclear and magnetic field axes are investigated. The numerical calculations of the molecular states and potential-energy curves in the fixed-nuclei approximation are based on a recently established and optimized atomic orbital basis set. We study electronic states within the range 0≤|m|≤10 of magnetic quantum numbers and for several field strengths. In particular, we also investigate many excited states within a subspace for fixed magnetic quantum number and parity. In order to understand the influence of the magnetic field on theof excited molecular states, we perform a detailed comparison of the electronic probability distributions and potential-energy curves in the field-free space with those in the presence of a magnetic field. As a major result we observe the existence of two different classes of strongly bound, i.e., stable, magnetically dressed states whose corresponding counterparts in the field-free space exhibit purely repulsive potential-energy curves, i.e., are unstable. Corrections which are going beyond the fixed-nuclei approach, i.e., the coupling of the center of mass to the electronic motion, as well as the mass corrections are investigated in order to ensure the physical validity of our results

  3. Proton dynamics in the strong chelate hydrogen bond of crystalline picolinic acid N-oxide. A new computational approach and infrared, raman and INS study.

    Science.gov (United States)

    Stare, Jernej; Panek, Jarosław; Eckert, Juergen; Grdadolnik, Joze; Mavri, Janez; Hadzi, Dusan

    2008-02-21

    Infrared, Raman and INS spectra of picolinic acid N-oxide (PANO) were recorded and examined for the location of the hydronic modes, particularly O-H stretching and COH bending. PANO is representative of strong chelate hydrogen bonds (H-bonds) with its short O...O distance (2.425 A). H-bonding is possibly well-characterized by diffraction, NMR and NQR data and calculated potential energy functions. The analysis of the spectra is assisted by DFT frequency calculations both in the gas phase and in the solid state. The Car-Parrinello quantum mechanical solid-state method is also used for the proton dynamics simulation; it shows the hydron to be located about 99% of time in the energy minimum near the carboxylic oxygen; jumps to the N-O acceptor are rare. The infrared spectrum excels by an extended absorption (Zundel's continuum) interrupted by numerous Evans transmissions. The model proton potential functions on which the theories of continuum formation are based do not correspond to the experimental and computed characteristics of the hydrogen bond in PANO, therefore a novel approach has been developed; it is based on crystal dynamics driven hydronium potential fluctuation. The envelope of one hundred 0 --> 1 OH stretching transitions generated by molecular dynamics simulation exhibits a maximum at 1400 cm-1 and a minor hump at approximately 1600 cm-1. These positions square well with ones predicted for the COH bending and OH stretching frequencies derived from various one- and two-dimensional model potentials. The coincidences with experimental features have to be considered with caution because the CPMD transition envelope is based solely on the OH stretching coordinate while the observed infrared bands correspond to heavily mixed modes as was previously shown by the normal coordinate analysis of the IR spectrum of argon matrix isolated PANO, the present CPMD frequency calculation and the empirical analysis of spectra. The experimental infrared spectra show some

  4. Intercalation chemistry and chemical bonding

    Science.gov (United States)

    Hagenmuller, Paul

    In contrast to amphoteric graphite, the layer-type oxides or chalcogenides generally play the role of acceptors in chemical or electrochemical intercalation reactions. Due to the more ionic character of the MO bonds, the structural evolution of the oxides may usually be explained on hand of electrostatic considerations, or in terms of cation oxido-reduction. For the more covalent chalcogenides, the occupancy of higher energy levels in the band structure by the transferred electrons constitute mostly a prevailing factor, giving rise to structural changes but also to modifications of the physical properties. The ionic character of the MO bonds accounts for the strong tendency of the oxides to undergo 2D→3D transformations as a result of intercalation processes. Such features are determining for the choice of the electrode materials for lithium-ion batteries as far as users require high electrode capacity, stability, and cyclability.

  5. Intramolecular interactions in dimedone and phenalen-1,3-dione adducts of 2(4)-pyridinecarboxaldehyde: Enol-enol and ring-chain tautomerism, strong hydrogen bonding, zwitterions

    Science.gov (United States)

    Sigalov, Mark; Shainyan, Bagrat; Krief, Pnina; Ushakov, Igor; Chipanina, Nina; Oznobikhina, Larisa

    2011-12-01

    The 2:1 adducts of dimedone and phenalen-1,3-dione with 2- and 4-pyridine carboxaldehyde, in spite of similar chemical behavior of their diketone precursors, have quite different tautomeric structure both in solid state and in solution. 2,2'-(Pyridin-2-ylmethanediyl)-bis(5,5-dimethyl-cyclohexane-1,3-dione) 5 exists as an equilibrium mixture of its dienol tautomer 5а' with two intramolecular H-bonds ОН⋯О dbnd С and OH ⋯N and the epimeric products of its reversible cyclization, that is, 4a-hydroxy-9-(pyridin-2-yl)-2,3,4,4a,6,7,9,9a-octahydro-5-H-xanthene-1,8-diones 5b (major) and 5c (minor), the latter appears only in polar media like DMSO. 2,2'-(Pyridin-4-ylmethanediyl)bis(5,5-dimethylcyclohexane-1,3-dione) 4, like other 2:1 dimedone-aldehyde adducts, both in solution and in solid state exists as dienol with two intramolecular H-bonds ОН ⋯О dbnd С. 4-[Bis(1H-phenalen-1,3(2H)-dione)methyl]pyridine 6 in nonpolar media like chloroform exists as dienol, but crystallizes from this solvent as zwitter-ion 6b with one very strong ionic hydrogen bond O sbnd H ⋯O sbnd and protonated pyridine nitrogen. The same zwitterion is formed in polar media (DMSO). For 2-[bis(1H-phenalen-1,3(2H)-dione)-methyl]-pyridine 7, fast exchange between its dienol tautomer 7a and zwitter-ion 7b occurs even in CD2Cl2, whereas in DMSO the equilibrium shifts towards zwitter-ion 7b.

  6. Coupled cluster valence bond theory for open-shell systems with application to very long range strong correlation in a polycarbene dimer.

    Science.gov (United States)

    Small, David W; Head-Gordon, Martin

    2017-07-14

    The Coupled Cluster Valence Bond (CCVB) method, previously presented for closed-shell (CS) systems, is extended to open-shell (OS) systems. The theoretical development is based on embedding the basic OS CCVB wavefunction in a fictitious singlet super-system. This approach reveals that the OS CCVB amplitude equations are quite similar to those of CS CCVB, and thus that OS CCVB requires the same level of computational effort as CS CCVB, which is an inexpensive method. We present qualitatively correct CCVB potential energy curves for all low-lying spin states of P 2 and Mn 2 + . CCVB is successfully applied to the low-lying spin states of some model linear polycarbenes, systems that appear to be a hindrance to standard density functionals. We examine an octa-carbene dimer in a side-by-side orientation, which, in the monomer dissociation limit, exhibits maximal strong correlation over the length of the polycarbene.

  7. Effect of photocurrent enhancement in porphyrin–graphene covalent hybrids

    International Nuclear Information System (INIS)

    Tang, Jianguo; Niu, Lin; Liu, Jixian; Wang, Yao; Huang, Zhen; Xie, Shiqiang; Huang, Linjun; Xu, Qingsong; Wang, Yuan; Belfiore, Laurence A.

    2014-01-01

    Graphene oxide (GO) sheets were covalently functionalized with 5-p-aminophenyl-10,15,20-triphenylporphyrin (NH 2 TPP) by an amidation reaction between the amino group in NH 2 TPP and carboxyl groups in GO. The Fourier transform infrared spectroscopy, nuclear magnetic resonance, scanning and transmission electron microscopies reveal that NH 2 TPP covalent bonds form on the double surface of graphene oxide sheets, generating a unique nano-framework, i.e., NH 2 TPP-graphene-NH 2 TPP. Its UV–visible spectroscopy reveals that the absorption spectrum is not a linear superposition of the spectra of NH 2 TPP and graphene oxide, because a 59 nm red shift of the strong graphene oxide absorption is observed from 238 to 297 nm, with significant spectral broadening between 300 and 700 nm. Fluorescence emission spectroscopy indicates efficient quenching of NH 2 TPP photoluminescence in this hybrid material, suggesting that photo-induced electron transfer occurs at the interface between NH 2 TPP and GO. A reversible on/off photo-current density of 47 mA/cm 2 is observed when NH 2 TPP-graphene-NH 2 TPP hybrid sandwiches are subjected to pulsed white-light illumination. Covalently-bound porphyrins decrease the optical HOMO/LUMO band gap of graphene oxide by ≈ 1 eV, according to UV–visible spectroscopy. Cyclic voltammetry predicts a small HOMO/LUMO band gap of 0.84 eV for NH 2 TPP-graphene-NH 2 TPP hybrid sandwiches, which is consistent with efficient electron transfer and fluorescence quenching. - Highlights: • Porphyrins are covalently bound to sheets of graphene oxide via an amidation reaction. • The formed hetero-junction interface decreases the optical band gap of graphene oxide. • Cyclic voltammetry predicts a graphene oxide band gap of 0.84 eV, which is easily photo-excited. • Its on/off photo-current density of 46 μA/cm 2 is 5-fold larger than that for physically stacked hybrid

  8. Effect of photocurrent enhancement in porphyrin–graphene covalent hybrids

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Jianguo, E-mail: jianguotangde@hotmail.com [Institute of Hybrid Materials―the Growing Base for State Key Laboratory, Qingdao University, Qingdao 266071 (China); Niu, Lin; Liu, Jixian; Wang, Yao; Huang, Zhen; Xie, Shiqiang; Huang, Linjun; Xu, Qingsong; Wang, Yuan [Institute of Hybrid Materials―the Growing Base for State Key Laboratory, Qingdao University, Qingdao 266071 (China); Belfiore, Laurence A. [Department of Chemical and Biological Engineering, Colorado State University, Fort Collins, CO 80523 (United States)

    2014-01-01

    Graphene oxide (GO) sheets were covalently functionalized with 5-p-aminophenyl-10,15,20-triphenylporphyrin (NH{sub 2}TPP) by an amidation reaction between the amino group in NH{sub 2}TPP and carboxyl groups in GO. The Fourier transform infrared spectroscopy, nuclear magnetic resonance, scanning and transmission electron microscopies reveal that NH{sub 2}TPP covalent bonds form on the double surface of graphene oxide sheets, generating a unique nano-framework, i.e., NH{sub 2}TPP-graphene-NH{sub 2}TPP. Its UV–visible spectroscopy reveals that the absorption spectrum is not a linear superposition of the spectra of NH{sub 2}TPP and graphene oxide, because a 59 nm red shift of the strong graphene oxide absorption is observed from 238 to 297 nm, with significant spectral broadening between 300 and 700 nm. Fluorescence emission spectroscopy indicates efficient quenching of NH{sub 2}TPP photoluminescence in this hybrid material, suggesting that photo-induced electron transfer occurs at the interface between NH{sub 2}TPP and GO. A reversible on/off photo-current density of 47 mA/cm{sup 2} is observed when NH{sub 2}TPP-graphene-NH{sub 2}TPP hybrid sandwiches are subjected to pulsed white-light illumination. Covalently-bound porphyrins decrease the optical HOMO/LUMO band gap of graphene oxide by ≈ 1 eV, according to UV–visible spectroscopy. Cyclic voltammetry predicts a small HOMO/LUMO band gap of 0.84 eV for NH{sub 2}TPP-graphene-NH{sub 2}TPP hybrid sandwiches, which is consistent with efficient electron transfer and fluorescence quenching. - Highlights: • Porphyrins are covalently bound to sheets of graphene oxide via an amidation reaction. • The formed hetero-junction interface decreases the optical band gap of graphene oxide. • Cyclic voltammetry predicts a graphene oxide band gap of 0.84 eV, which is easily photo-excited. • Its on/off photo-current density of 46 μA/cm{sup 2} is 5-fold larger than that for physically stacked hybrid.

  9. Electrical properties of covalently functionalized graphene

    Directory of Open Access Journals (Sweden)

    Paul Plachinda

    2017-02-01

    Full Text Available We have employed first-principle calculations to study transformation of graphene’s electronic structure under functionalization by covalent bonds with di erent atomic and molecular groups - epoxies, amines, PFPA. It is shown that this functionalization leads to an opening in the graphene’s band gap on order of tens meV, but also leads to reduction of electrical conductivity. We also discuss the influence of charge exchange between the functionalizing molecule and graphene’s conjugated electrons on electron transport properties.

  10. Probing the nature of hydrogen bonds in DNA base pairs.

    Science.gov (United States)

    Mo, Yirong

    2006-07-01

    Energy decomposition analyses based on the block-localized wave-function (BLW-ED) method are conducted to explore the nature of the hydrogen bonds in DNA base pairs in terms of deformation, Heitler-London, polarization, electron-transfer and dispersion-energy terms, where the Heitler-London energy term is composed of electrostatic and Pauli-exchange interactions. A modest electron-transfer effect is found in the Watson-Crick adenine-thymine (AT), guanine-cytosine (GC) and Hoogsteen adenine-thymine (H-AT) pairs, confirming the weak covalence in the hydrogen bonds. The electrostatic attraction and polarization effects account for most of the binding energies, particularly in the GC pair. Both theoretical and experimental data show that the GC pair has a binding energy (-25.4 kcal mol(-1) at the MP2/6-31G** level) twice that of the AT (-12.4 kcal mol(-1)) and H-AT (-12.8 kcal mol(-1)) pairs, compared with three conventional N-H...O(N) hydrogen bonds in the GC pair and two in the AT or H-AT pair. Although the remarkably strong binding between the guanine and cytosine bases benefits from the opposite orientations of the dipole moments in these two bases assisted by the pi-electron delocalization from the amine groups to the carbonyl groups, model calculations demonstrate that pi-resonance has very limited influence on the covalence of the hydrogen bonds. Thus, the often adopted terminology "resonance-assisted hydrogen bonding (RHAB)" may be replaced with "resonance-assisted binding" which highlights the electrostatic rather than electron-transfer nature of the enhanced stabilization, as hydrogen bonds are usually regarded as weak covalent bonds.

  11. Inter- and intramolecular non-covalent interactions in 1-methylimidazole-2-carbaldehyde complexes of copper, silver, and gold

    Science.gov (United States)

    Koskinen, Laura; Jääskeläinen, Sirpa; Hirva, Pipsa; Haukka, Matti

    2014-09-01

    Three new imidazole compounds, [CuBr2(mimc)2] (1), [Ag(mimc)2][CF3SO3] (2), and [AuCl3(mimc)] (3) (mimc = 1-methylimidazole-2-carbaldehyde), have been synthesized, structurally characterized, and further analyzed using the QTAIM analysis. The compounds exhibit self-assembled 3D networks arising from intermolecular non-covalent interactions such as metallophilic interactions, metal-π contacts, halogens-halogen interactions, and hydrogen bonds. These weak interactions have a strong impact on the coordination sphere of the metal atoms and on the packing of compounds 1, 2, and 3.

  12. A two-dimensional molybdenum (V) phosphate with covalently bonded transition metal coordination complexes: hydrothermal synthesis and structure characterization of Na 2[{Mn(phen) 2(H 2O)}{Mn(phen) 2} 3{Mn Mo 12vO 24 (HPO 4) 6(PO 4) 2(OH) 6}]·4H 2O (phen=1, 10-phenanthroline)

    Science.gov (United States)

    Yuan, Mei; Wang, Enbo; Lu, Ying; Li, Yangguang; Hu, Changwen; Hu, Ninghai; Jia, Hengqing

    2003-01-01

    An organic-inorganic hybrid molybdenum phosphate, Na 2[{Mn(phen) 2(H 2O)} {Mn(phen) 2} 3{MnMo 12vO 24 (HPO 4) 6(PO 4) 2(OH) 6}]·4H 2O (phen=1,10-phenanthroline), involving molybdenum present in V oxidation state and covalently bonded transition metal coordination complexes, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Deep brown-red crystals are formed in the triclinic system, space group P 1¯, a=16.581(1) Å, b=18.354(1) Å, c=24.485(2) Å, α=80.589(1)°, β=71.279(1)°, γ=67.084(1)°, V=6493.8(8) Å 3, Z=2, λ(Mo Kα)=0.71073 Å ( R( F)=0.0686 for 29,053 reflections). Data were collected on a Bruker Smart Apex CCD diffractometer at 293 K in the range of 1.76< θ<28.06° using ω-2 θ scans technique. The structure of the title compound may be considered to be based on {Mo 6O 12(HPO 4) 3(PO 4)(OH) 3} units bonded together with {Mn(phen) 2} subunits into a two-dimensional network. Two types of tunnels are observed in the solid of the title compound.

  13. Why are Hydrogen Bonds Directional?

    Indian Academy of Sciences (India)

    Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore,. Karnataka 560 012, India e-mail: ... Lewis succeeded in explaining the 'chemical bonds' that held the neutral molecules together. The covalent bonding has dominated chemistry so much over the last century and most chemists appear ...

  14. Hybrid materials based on novel 2D lanthanide coordination polymers covalently bonded to amine-modified SBA-15 and MCM-41: assembly, characterization, structural features, thermal and luminescence properties.

    Science.gov (United States)

    Wang, Jun; Dou, Wei; Kirillov, Alexander M; Liu, Weisheng; Xu, Cailing; Fang, Ran; Yang, Lizi

    2016-11-22

    Three novel 2D coordination polymers [Tb 2 (μ 4 -L) 2 (μ-HL)(μ-HCOO)(DEF)] n (Tb-L), [Eu(μ 4 -L)(L)(H 2 O) 2 ] n (Eu-L), and [Nd(μ 4 -L)(L)(H 2 O) 2 ] n (Nd-L) were assembled from the corresponding lanthanide(iii) nitrates and 5 methoxy-(4-benzaldehyde)-1,3-benzenedicarboxylic acid (H 2 L) as a main multifunctional building block bearing carboxylate and aldehyde functional groups, using H 2 O/DEF {DEF = N,N-diethylformamide} as a reaction medium. The obtained coordination polymers were isolated as stable microcrystalline solids and fully characterized by elemental analysis, FT-IR spectroscopy, TGA, BET, PXRD, and single-crystal X-ray diffraction methods. Their structures feature intricate 2D metal-organic networks, which were topologically classified as underlying layers with the 4,6L26 (for Tb-L) or sql (for Eu-L and Nd-L) topologies. Besides, a novel series of mesoporous hybrid materials wherein the Tb-L, Eu-L, or Nd-L coordination polymers are covalently grafted into the amine-functionalized SBA-15-NH 2 or MCM-41-NH 2 matrices (via the formation of Schiff-base groups) was also synthesized and fully characterized. These hybrid materials show high thermal and photoluminescence stability, as well as remarkable chemical resistance to boiling water, and acidic or alkaline medium. Luminescent properties of the parent coordination polymers and derived hybrid materials are investigated in detail, showing that the latter combine the luminescent characteristics (intense green or red emissions and excellent stability) of lanthanide coordination polymers and structural features of ordered mesoporous silica molecular sieves. Moreover, light emitting devices were assembled, by coating the hybrid materials onto the surface of UV-LED bulbs, and showed excellent light emitting properties.

  15. Non-bonding interactions and non-covalent delocalization effects play a critical role in the relative stability of group 12 complexes arising from interaction of diethanoldithiocarbamate with the cations of transition metals Zn(II), Cd(II), and Hg(II): a theoretical study.

    Science.gov (United States)

    Bahrami, Homayoon; Farhadi, Saeed; Siadatnasab, Firouzeh

    2016-07-01

    The chelating properties of diethanoldithiocarbamate (DEDC) and π-electron flow from the nitrogen atom to the sulfur atom via a plane-delocalized π-orbital system (quasi ring) was studied using a density functional theory method. The molecular structure of DEDC and its complexes with Zn(II), Cd(II), and Hg(II) were also considered. First, the geometries of this ligand and DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) were optimized, and the formation energies of these complexes were then calculated based on the electronic energy, or sum of electronic energies, with the zero point energy of each species. Formation energies indicated the DEDC-Zn(II) complex as the most stable complex, and DEDC-Cd(II) as the least stable. Structural data showed that the N1-C2 π-bond was localized in the complexes rather than the ligand, and a delocalized π-bond over S7-C2-S8 was also present. The stability of DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) complexes increased in the presence of the non-specific effects of the solvent (PCM model), and their relative stability did not change. There was π-electron flow or resonance along N1-C2-S7 and along S7-C2-S8 in the ligand. The π-electron flow or resonance along N1-C2-S7 was abolished when the metal interacted with sulfur atoms. Energy belonging to van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand was calculated for each complex. The results of nucleus-independent chemical shift (NICS) indicated a decreasing trend as Zn(II) Hg(II) for the aromaticity of the quasi-rings. Finally, by ignoring van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand, the relative stability of the complexes was changed as follows:[Formula: see text] Graphical Abstract Huge electronic cloud localized on Hg(II) in the Hg(II)-DEDC complex.

  16. Non Covalent Interactions and Internal Dynamics in Adducts of Freons

    Science.gov (United States)

    Caminati, Walther; Gou, Qian; Evangelisti, Luca; Feng, Gang; Spada, Lorenzo; Vallejo-López, Montserrat; Lesarri, Alberto; Cocinero, Emilio J.

    2014-06-01

    The complexation of chlorofluorocarbons (CFCs) with atmospheric water and pollutants of the atmosphere affects their reactivity and it seems to accelerate, for example, the decomposition rate of freons in the atmosphere [1]. For this reason we characterized shapes, stabilities, nature of the non-covalent interactions, structures and internal dynamics of a number of complexes of CFCs with water and of their dimers or oligomers by rotational spectroscopy. It has been found that hydrogenated CFCs form adducts with other molecules through weak hydrogen bonds (WHBs). Their C-H groups can act as proton donors, enhanced by the electron withdrawing of the halogen atoms, interacting with the electron rich regions of the partner molecules [2]. Also in adducts or oligomers of hydrogenated CFCs the monomer units are held together by nets of WHBs [3]. When CFCs are perhalogenated, the positive electrostatic region ("σ-hole") can interact electrostatically with negative sites of another, or of the same molecular entity, giving rise, according to IUPAC, to the so called halogen bond (HaB). However, it has been observed that when the perhalogenated CFCs has a Π electron system, a lone pair•••Π interaction (Bürgi-Dunitz) is favoured [4]. We describe here the HaBs that CF4 and CF3Cl form with a variety of partner molecules such as water, ammonia, dimethyl ether, etc. Important spectroscopic features outline strong dynamics effects taking place in this kind of complex. References [1] V. Vaida, H. G. Kjaergaard, K. J. Feierabend, Int. Rev. Phys. Chem. 22 (2003) 203. [2] See, for example: W. Caminati, S. Melandri, A. Maris, P. Ottaviani, Angew. Chem. Int. Ed. 45 (2006) 2438. [3] G. Feng, L. Evangelisti, I. Cacelli, L. Carbonaro, G. Prampolini, W. Caminati, Chem. Commun. 50 (2014) 171. [4] Q. Gou, G. Feng, L. Evangelisti, W. Caminati, Angew. Chem. Int. Ed. 52 (2013) 52 11888.

  17. Generation of Multicomponent Molecular Cages using Simultaneous Dynamic Covalent Reactions.

    Science.gov (United States)

    Drożdż, Wojciech; Bouillon, Camille; Kotras, Clément; Richeter, Sébastien; Barboiu, Mihail; Clément, Sébastien; Stefankiewicz, Artur R; Ulrich, Sébastien

    2017-12-19

    Cage compounds are very attractive structures for a wide range of applications and there is ongoing interest in finding effective ways to access such kinds of complex structures, particularly those possessing dynamic adaptive features. Here we report the accessible synthesis of new type of organic cage architectures, possessing two different dynamic bonds within one structure: hydrazones and disulfides. Implementation of three distinct functional groups (thiols, aldehydes and hydrazides) in the structure of two simple building blocks resulted in their spontaneous and selective self-assembly into aromatic cage-type architectures. These organic cages contain up to ten components linked together by twelve reversible covalent bonds. The advantage provided by the presented approach is that these cage structures can adaptively self-sort from a complex virtual mixture of polymers or macrocycles and that dynamic covalent chemistry enables their deliberate disassembly through controlled component exchange. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Highly selective covalent organic functionalization of epitaxial graphene

    Science.gov (United States)

    Bueno, Rebeca A.; Martínez, José I.; Luccas, Roberto F.; Del Árbol, Nerea Ruiz; Munuera, Carmen; Palacio, Irene; Palomares, Francisco J.; Lauwaet, Koen; Thakur, Sangeeta; Baranowski, Jacek M.; Strupinski, Wlodek; López, María F.; Mompean, Federico; García-Hernández, Mar; Martín-Gago, José A.

    2017-05-01

    Graphene functionalization with organics is expected to be an important step for the development of graphene-based materials with tailored electronic properties. However, its high chemical inertness makes difficult a controlled and selective covalent functionalization, and most of the works performed up to the date report electrostatic molecular adsorption or unruly functionalization. We show hereafter a mechanism for promoting highly specific covalent bonding of any amino-terminated molecule and a description of the operating processes. We show, by different experimental techniques and theoretical methods, that the excess of charge at carbon dangling-bonds formed on single-atomic vacancies at the graphene surface induces enhanced reactivity towards a selective oxidation of the amino group and subsequent integration of the nitrogen within the graphene network. Remarkably, functionalized surfaces retain the electronic properties of pristine graphene. This study opens the door for development of graphene-based interfaces, as nano-bio-hybrid composites, fabrication of dielectrics, plasmonics or spintronics.

  19. The role of London dispersion interactions in strong and moderate intermolecular hydrogen bonds in the crystal and in the gas phase

    Science.gov (United States)

    Katsyuba, Sergey A.; Vener, Mikhail V.; Zvereva, Elena E.; Brandenburg, J. Gerit

    2017-03-01

    Two variants of density functional theory computations have been applied to characterization of hydrogen bonds of the 1-(2-hydroxylethyl)-3-methylimidazolium acetate ([C2OHmim][OAc]), i.e. with and without inclusion of dispersion interactions. A comparison of the results demonstrates that London dispersion interactions have very little impact on the energetical, geometrical, infrared spectroscopic and electron density parameters of charge-assisted intermolecular hydrogen bonds functioning both in the crystal of the [C2OHmim][OAc] and in the isolated [C2OHmim]+ [OAc]- ion pairs.

  20. Covalent and non-covalent functionalization and solubilization of ...

    Indian Academy of Sciences (India)

    Non-covalent functionalization of DWNTs has been carried out by using polyethylene glycol (PEG) and polyoxyethylene(40)nonylphenyl ether (IGPAL), both of which enable solubilization in aqueous media. These functionalized DWNTs have been characterized by transmission electron microscopy, IR and Raman ...

  1. Rationally Designed, Multifunctional Self-Assembled Nanoparticles for Covalently Networked, Flexible and Self-Healable Superhydrophobic Composite Films.

    Science.gov (United States)

    Lee, Yujin; You, Eun-Ah; Ha, Young-Geun

    2018-03-21

    For constructing bioinspired functional films with various superhydrophobic functions, including self-cleaning, anticorrosion, antibioadhesion, and oil-water separation, hydrophobic nanomaterials have been widely used as crucial structural components. In general, hydrophobic nanomaterials, however, cannot form strong chemical bond networks in organic-inorganic hybrid composite films because of the absence of chemically compatible binding components. Herein, we report the rationally designed, multifunctional self-assembled nanoparticles with tunable functionalities of covalent cross-linking and hydrophobicity for constructing three-dimensionally interconnected superhydrophobic composite films via a facile solution-based fabrication at room temperature. The multifunctional self-assembled nanoparticles allow the systematic control of functionalities of composite films, as well as the stable formation of covalently linked superhydrophobic composite films with excellent flexibility (bending radii of 6.5 and 3.0 mm, 1000 cycles) and self-healing ability (water contact angle > 150°, ≥10 cycles). The presented strategy can be a versatile and effective route to generating other advanced functional films with covalently interconnected composite networks.

  2. 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)

  3. Constructing Models in Teaching of Chemical Bonds: Ionic Bond, Covalent Bond, Double and Triple Bonds, Hydrogen Bond and Molecular Geometry

    Science.gov (United States)

    Uce, Musa

    2015-01-01

    Studies in chemistry education show that chemistry topics are considered as abstract, complicated and hard to understand by students. For this reason, it is important to develop new materials and use them in classes for better understanding of abstract concepts. Moving from this point, a student-centered research guided by a teacher was conducted…

  4. A computational study on structure, stability and bonding in Noble ...

    Indian Academy of Sciences (India)

    ... of Kr-Rn bound analogues at 298 K. Natural population analysis along with the computation of Wiberg bond indices, and electron density analyses provide insights into the nature of the Ng-M bonds. The Ng-M bonds can be represented as partial covalent bonds as supported by the different electron density descriptors.

  5. Covalent DNA-protein crosslinking occurs after hyperthermia and radiation

    International Nuclear Information System (INIS)

    Cress, A.E.; Bowden, G.T.

    1983-01-01

    Covalent DNA-protein crosslinks occur in exponentially growing mouse leukemia cells (L1210) after exposure to ionizing radiation. The amount of DNA-protein crosslinks as measured by a filter binding assay is dose dependent upon X irradiation. Although hyperthermia and radiation in combination are synergistic with respect to cell lethality, the combination does not result in an increase of DNA-protein crosslinks when assayed immediately following treatments. Hyperthermia (43 degrees C/15 min) given prior to radiation does not alter the radiation dose dependency of the amount of initial crosslinking. In addition, the amount of DNA-protein crosslinking produced by heat plus radiation is independent of the length of heating the cells at 43 degrees C. The DNA-protein crosslinks produced by 50-Gy X ray alone are removed after 2 hr at 37 degrees C. However, if hyperthermia (43 degrees C/15 min) is given prior to 100-Gy X ray, the removal of DNA-protein crosslinks is delayed until 4.0 hr after radiation. Phospho-serine and phospho-threonine bonds are not produced with either radiation or the combination of hyperthermia plus radiation as judged by the resistance of the bonds to guanidine hydrochloride. However, hyperthermia plus radiation causes an increase in phosphate to nitrogen type bonding. These results show that radiation alone causes covalent DNA-protein crosslinks. Hyperthermia in combination with radiation does not increase the total amount of the crosslinks but delays the removal of the crosslinks and alters the distribution of the types of chemical bonding. These data suggest that the synergistic action on hyperthermia with radiation is more related to the rate of removal and the type of chemical bonding involved in the covalent DNA-protein crosslinks rather than the amount of DNA-protein crosslinks

  6. Novel covalently linked insulin dimer engineered to investigate the function of insulin dimerization

    DEFF Research Database (Denmark)

    Vinther, Tine N.; Norrman, Mathias; Strauss, Holger M.

    2012-01-01

    An ingenious system evolved to facilitate insulin binding to the insulin receptor as a monomer and at the same time ensure sufficient stability of insulin during storage. Insulin dimer is the cornerstone of this system. Insulin dimer is relatively weak, which ensures dissociation into monomers...... and insulin stability and function, we engineered a covalently linked insulin dimer in which two monomers were linked by a disulfide bond. The structure of this covalent dimer was identical to the self-association dimer of human insulin. Importantly, this covalent dimer was capable of further oligomerization...

  7. All-in-One: Achieving Robust, Strongly Luminescent and Highly Dispersible Hybrid Materials by Combining Ionic and Coordinate Bonds in Molecular Crystals.

    Science.gov (United States)

    Liu, Wei; Zhu, Kun; Teat, Simon J; Dey, Gangotri; Shen, Zeqing; Wang, Lu; O'Carroll, Deirdre M; Li, Jing

    2017-07-12

    Extensive research has been pursued to develop low-cost and high-performance functional inorganic-organic hybrid materials for clean/renewable energy related applications. While great progress has been made in the recent years, some key challenges remain to be tackled. One major issue is the generally poor stability of these materials, which originates from relatively fragile/weak bonds between inorganic and organic constituents. Herein, we report a unique "all-in-one" (AIO) approach in constructing robust structures with desired properties. Such approach allows formation of both ionic and coordinate bonds within a molecular cluster, which greatly enhances structural stability while maintaining the molecular identity of the cluster and its high luminescence. The novel AIO structures are composed of various anionic (Cu m I m+n ) n- clusters and cationic N-ligands. They exhibit high luminescence efficiency, significantly improved chemical, thermal and moisture stability, and excellent solution processability. Both temperature dependent photoluminescence experiments and DFT calculations are performed to investigate the luminescence origin and emission mechanism of these materials, and their suitability as energy-saving LED lighting phosphors is assessed. This study offers a new material designing strategy that may be generalized to many other material classes.

  8. Covalent magnetism and magnetic impurities.

    Science.gov (United States)

    Gruber, C; Bedolla, P O; Mohn, P

    2013-05-08

    We use the model of covalent magnetism and its application to magnetic insulators applied to the case of insulating carbon doped BaTiO3. Since the usual Stoner mechanism is not applicable we study the possibility of the formation of magnetic order based on a mechanism favoring singly occupied orbitals. On the basis of our model parameters we formulate a criterion similar to the Stoner criterion but also valid for insulators. We describe the model of covalent magnetism using a molecular orbital picture and determine the occupation numbers for spin-up and spin-down states. Our model allows a simulation of the results of our ab initio calculations for E(ℳ) which are found to be in very good agreement.

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

    CERN Document Server

    Brown, I David

    2016-01-01

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

  10. Preparation and properties of electro-conductive fabrics based on polypyrrole: covalent vs. non-covalent attachment

    Science.gov (United States)

    David, N. C.; Anavi, D.; Milanovich, M.; Popowski, Y.; Frid, L.; Amir, E.

    2017-10-01

    Electro-conductive fabrics were prepared via in situ oxidative polymerization of pyrrole (Py) in the presence of unmodified and chemically modified cotton fabrics. Chemical modification of cotton fabric was achieved by covalent attachment of a bifunctional linker molecule to the surface of the fabric, followed by incorporation of a monomer unit onto the linker. The fabrics were characterized using Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron spectroscopy, and thermal analysis. Furthermore, the effect of Py concentration on the degree of polypyrrole (PPy) grafting, surface morphology, electrical resistivity, and laundering durability were studied for both types of cotton fabrics. Reductions of several orders of magnitude in surface and volume electrical resistivities were observed for both non-covalently and covalently linked cotton-PPy systems, whereas the effect of covalent pre-treatment of the fabric was stronger at low Py concentration. On the other hand, at higher monomer concentration, the electrical properties and laundering durability of the fabrics we comparable for both unmodified and chemically pre-treated cotton fabrics, indicating that only a small fraction of PPy chains were chemically grafted onto the fabric surface with the majority of the polymer being connected to the fabric through hydrogen bonds.

  11. The importance of play in promoting healthy child development and maintaining strong parent-child bond: focus on children in poverty.

    Science.gov (United States)

    Milteer, Regina M; Ginsburg, Kenneth R

    2012-01-01

    Play is essential to the social, emotional, cognitive, and physical well-being of children beginning in early childhood. It is a natural tool for children to develop resiliency as they learn to cooperate, overcome challenges, and negotiate with others. Play also allows children to be creative. It provides time for parents to be fully engaged with their children, to bond with their children, and to see the world from the perspective of their child. However, children who live in poverty often face socioeconomic obstacles that impede their rights to have playtime, thus affecting their healthy social-emotional development. For children who are underresourced to reach their highest potential, it is essential that parents, educators, and pediatricians recognize the importance of lifelong benefits that children gain from play.

  12. Covalent-Bond Formation via On-Surface Chemistry.

    Science.gov (United States)

    Held, Philipp Alexander; Fuchs, Harald; Studer, Armido

    2017-05-02

    In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Shock-Induced Amorphization in Covalently Bonded Solids

    OpenAIRE

    Zhao, Shiteng

    2017-01-01

    Pulsed lasers with a power of the order of terawatts, once deposited on a target surface, will launch a stress pulse that propagates into material. Owing to the ultrashort duration of the laser pulses, unprecedented experimental conditions which combine high pressures (and/or shear stresses), strain rates and temperatures can be generated in materials, yielding a yet unexplored regime of study: materials science at extremes. High-power, short-duration, laser-driven, shock compression and reco...

  14. A novel fluorescence sensor based on covalent immobilization of 3-amino-9-ethylcarbazole by using silver nanoparticles as bridges and carriers.

    Science.gov (United States)

    Tan, Shu-Zhen; Hu, Yan-Jun; Gong, Fu-Chun; Cao, Zhong; Xia, Jiao-Yun; Zhang, Ling

    2009-03-23

    A novel technique of covalent immobilization of indicator dyes in the preparation of fluorescence sensors is developed. Silver nanoparticles are used as bridges and carriers for anchoring indicator dyes. 3-amino-9-ethylcarbazole (AEC) was employed as an example of indicator dyes with terminal amino groups and covalently immobilized onto the outmost surface of a quartz glass slide. First, the glass slide was functionalized by (3-mercaptopropyl) trimethoxysilane (MPS) to form a thiol-terminated self-assembled monolayer, where silver nanoparticles were strongly bound to the surface through covalent bonding. Then, 16-mercaptohexadecanoic acid (MHDA) was self-assembled to bring carboxylic groups onto the surface of silver nanoparticles. A further activation by using 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) converted the carboxylic groups into succinimide esters. Finally, the active succinimide esters on the surface of silver nanoparticles were reacted with AEC. Thus, AEC was covalently bound to the glass slide and an AEC-immobilized sensor was obtained. The sensor exhibited very satisfactory reproducibility and reversibility, rapid response and no dye-leaching. Rutin can quench the fluorescence intensity of the sensor and be measured by using the sensor. The linear response of the sensor to rutin covers the range from 2.0 x 10(-6) to 1.5 x 10(-4) molL(-1) with a detection limit of 8.0 x 10(-7) molL(-1). The proposed technique may be feasible to the covalent immobilization of other dyes with primary amino groups.

  15. Photoactive Zn(II)Porphyrin–multi-walled carbon nanotubes nanohybrids through covalent β-linkages

    Energy Technology Data Exchange (ETDEWEB)

    Lipińska, Monika E., E-mail: m.e.lipinska@gmail.com [REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto (Portugal); Rebelo, Susana L.H., E-mail: susana.rebelo@fc.up.pt [REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto (Portugal); Pereira, M. Fernando R., E-mail: fpereira@fe.up.pt [Laboratório de Catálise e Materiais (LCM), Laboratório Associado LSRE/LCM, Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto (Portugal); Figueiredo, José L., E-mail: jlfig@fe.up.pt [Laboratório de Catálise e Materiais (LCM), Laboratório Associado LSRE/LCM, Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto (Portugal); Freire, Cristina, E-mail: acfreire@fc.up.pt [REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto (Portugal)

    2013-12-16

    Donor–acceptor nanohybrids by a covalent linkage between the β-position of a Zn(II)Porphyrin and multi-walled carbon nanotubes are reported for the first time, in a closer analogy to the natural light harvesting systems, which are based on β-substituted porphyrinoid structures, the chlorophylls. An unique and direct connection was established through the immobilization of the Zn(II)(β-NH{sub 2}-tetraphenylporphyrin), using diazonium chemistry, in order to afford i) a short and conjugated linkage between the two aromatic systems and ii) an amide bond resulting from a three-step functionalization synthesis. Electronic and steady-state fluorescence spectroscopies confirmed high photoinduced electron communication through the β-linkage when compared to analogous meso-phenyl linkers, stating its positive effect. The procedure involving the amide linkage allowed higher chromophore loadings; however, the direct conjugated bond showed improved photoinduced activity and a different emission pattern that can be associated with intense communication within the expanded π-system MWCNT–metalloporphyrin. - Graphical abstract: Preparation and photo-induced activity of two donor–acceptor nanohybrids is reported based on different linkages through β-position of porphyrin core to MWCNT, direct conjugation and amide bond. - Highlights: • β-linked Zn(II)Porphyrin–MWCNT nanohybrids were prepared through direct or amide bond. • Efficient and mild functionalizations were achieved using diazonium chemistry. • Good nanohybrid dispersibility was obtained in low boiling point solvent. • Nanohybrids showed strong photoinduced electronic transfer. • The emission quenching was higher for the π-expanded system.

  16. Understanding M-ligand bonding and mer-/fac-isomerism in tris(8-hydroxyquinolinate) metallic complexes.

    Science.gov (United States)

    Lima, Carlos F R A C; Taveira, Ricardo J S; Costa, José C S; Fernandes, Ana M; Melo, André; Silva, Artur M S; Santos, Luís M N B F

    2016-06-28

    Tris(8-hydroxyquinolinate) metallic complexes, Mq3, are one of the most important classes of organic semiconductor materials. Herein, the nature of the chemical bond in Mq3 complexes and its implications on their molecular properties were investigated by a combined experimental and computational approach. Various Mq3 complexes, resulting from the alteration of the metal and substitution of the 8-hydroxyquinoline ligand in different positions, were prepared. The mer-/fac-isomerism in Mq3 was explored by FTIR and NMR spectroscopy, evidencing that, irrespective of the substituent, mer- and fac-are the most stable molecular configurations of Al(iii) and In(iii) complexes, respectively. The relative M-ligand bond dissociation energies were evaluated experimentally by electrospray ionization tandem mass spectrometry (ESI-MS-MS), showing a non-monotonous variation along the group (Al > In > Ga). The results reveal a strong covalent character in M-ligand bonding, which allows for through-ligand electron delocalization, and explain the preferred molecular structures of Mq3 complexes as resulting from the interplay between bonding and steric factors. The mer-isomer reduces intraligand repulsions, being preferred for smaller metals, while the fac-isomer is favoured for larger metals where stronger covalent M-ligand bonds can be formed due to more extensive through-ligand conjugation mediated by metal "d" orbitals.

  17. How covalence breaks adsorption-energy scaling relations and solvation restores them

    DEFF Research Database (Denmark)

    Vallejo, Federico Calle; Krabbe, Alexander; García Lastra, Juan Maria

    2017-01-01

    of those adsorbates on the metal centers Cr, Mn, Fe, Co, Ni and Cu, using H, F, OH, NH2, CH3, and BH2 as ring ligands. We show that covalence systematically breaks scaling relations under vacuum by strengthening certain M-OOH bonds. However, covalence modifies adsorbate solvation in solution depending...... on the degree of covalence of the metal-adsorbate bonds. The two effects have similar magnitudes and opposite signs, such that scaling relations are restored in solution. Thus, solvation is a crucial ingredient that must be taken into account in studies aimed at breaking scaling relations in solution. Our...... findings suggest that the choice of metal and ligand determines the catalytic activity within the limits imposed by scaling relations, whereas the choice of an appropriate solvent can drive such activity beyond those limits....

  18. Non-covalent O⋅⋅⋅O interactions among isopolyanions using a cis ...

    Indian Academy of Sciences (India)

    WINTEC

    2008-05-09

    May 9, 2008 ... N–H⋅⋅⋅O and C–H⋅⋅⋅O hydrogen bonds, in which the protonated organic cation plays a significant role. The crystal structure also reveals an unusual cluster–cluster (non-covalent O⋅⋅⋅O) interaction using cis-. (MoO2} moieties of the isopolyanion. N–H⋅⋅⋅O hydrogen bonds, originated from ...

  19. Benchmarking Density Functionals for Chemical Bonds of Gold

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2017-01-01

    data set probes all types of bonding to gold from very electronegative halides that force Au+ electronic structure, via covalently bonded systems, hard and soft Lewis acids and bases that either work against or complement the softness of gold, the Au2 molecule probing gold's bond with itself, and weak...

  20. Molecular structure and intramolecular hydrogen bonding in 2 ...

    Indian Academy of Sciences (India)

    (RCP) in the RAHB ring are valuable parameters for describing the bond. Positive values of Laplacian at .... RCP, and (d) Laplacian of total electronic density at RCP. shared interactions such as covalent bonds. In the lat- ..... ing vibrations with hydrogen bond strength have been known for a long time.53,54. The calculated.

  1. Capillary electrophoresis of covalently functionalized single-chirality carbon nanotubes.

    Science.gov (United States)

    He, Pingli; Meany, Brendan; Wang, Chunyan; Piao, Yanmei; Kwon, Hyejin; Deng, Shunliu; Wang, YuHuang

    2017-07-01

    We demonstrate the separation of chirality-enriched single-walled carbon nanotubes (SWCNTs) by degree of surface functionalization using high-performance CE. Controlled amounts of negatively charged and positively charged functional groups were attached to the sidewall of chirality-enriched SWCNTs through covalent functionalization using 4-carboxybenzenediazonium tetrafluoroborate or 4-diazo-N,N-diethylaniline tetrafluoroborate, respectively. Surfactant- and pH-dependent studies confirmed that under conditions that minimized ionic screening effects, separation of these functionalized SWCNTs was strongly dependent on the surface charge density introduced through covalent surface chemistry. For both heterogeneous mixtures and single-chirality-enriched samples, covalently functionalized SWCNTs showed substantially increased peak width in electropherogram spectra compared to nonfunctionalized SWCNTs, which can be attributed to a distribution of surface charges along the functionalized nanotubes. Successful separation of functionalized single-chirality SWCNTs by functional density was confirmed with UV-Vis-NIR absorption and Raman scattering spectroscopies of fraction collected samples. These results suggest a high degree of structural heterogeneity in covalently functionalized SWCNTs, even for chirality-enriched samples, and show the feasibility of applying CE for high-performance separation of nanomaterials based on differences in surface functional density. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. (15)N and (1)H Solid-State NMR Investigation of a Canonical Low-Barrier Hydrogen-Bond Compound: 1,8-Bis(dimethylamino)naphthalene.

    Science.gov (United States)

    White, Paul B; Hong, Mei

    2015-09-03

    Strong or low-barrier hydrogen bonds have often been proposed in proteins to explain enzyme catalysis and proton-transfer reactions. So far (1)H chemical shifts and scalar couplings have been used as the main NMR spectroscopic signatures for strong H-bonds. In this work, we report simultaneous measurements of (15)N and (1)H chemical shifts and N-H bond lengths by solid-state NMR in (15)N-labeled 1,8-bis(dimethylamino)naphthalene (DMAN), which contains a well-known strong NHN H-bond. We complexed DMAN with three different counteranions to examine the effects of the chemical environment on the H-bond lengths and chemical shifts. All three DMAN compounds exhibit significantly elongated N-H distances compared to the covalent bond length, and the (1)H(N) chemical shifts are larger than ∼17 ppm, consistent with strong NHN H-bonds in the DMAN cation. However, the (15)N and (1)H chemical shifts and the precise N-H distances differ among the three compounds, and the (15)N chemical shifts show opposite dependences on the proton localization from the general trend in organic compounds, indicating the significant effects of the counteranions on the electronic structure of the H-bond. These data provide useful NMR benchmarks for strong H-bonds and caution against the sole reliance on chemical shifts for identifying strong H-bonds in proteins since neighboring side chains can exert influences on chemical shifts similar to those of the bulky organic anions in DMAN. Instead, N-H bond lengths should be measured, in conjunction with chemical shifts, as a more fundamental parameter of H-bond strength.

  3. Hydrogen scrambling in non-covalent complexes of peptides.

    Science.gov (United States)

    Modzel, Maciej; Stefanowicz, Piotr; Szewczuk, Zbigniew

    2012-12-15

    Mass spectrometry analysis combined with hydrogen-deuterium exchange (HDX-MS) is arising as a tool for quick analysis of native protein conformation. However, during collision-induced dissociation (CID) the spatial distribution of deuterium is not always conserved. It is therefore important to find out how hydrogen scrambling occurs--this study concentrates on the possibility of scrambling between amino acid residues spatially close together, but not connected by covalent bonds. Peptides used in this study were synthesized by Fmoc strategy. Deuteration occurred in ammonia formate solution in D(2)O. Non-covalent complexes consisting of a deuterated and a non-deuterated peptide were analyzed by electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FT-ICR-MS) with quadrupole mass filter. Low-energy CID was used for complex dissociation. The complexes were isolated on a quadrupole and subjected to CID to cause dissociation. The deuterium distribution before and after the dissociation of a non-covalent complex to its components was measured. The study revealed that no significant scrambling occurred between the constituents of the complexes--the degree of scrambling did not exceed 10%. The results obtained for the complexes should be similar to those for protein parts spatially close together--hydrogen scrambling between them should be negligible. The knowledge that almost all the scrambling occurs along peptide chains gives a better insight into the mechanism of HDX inside a protein. Copyright © 2012 John Wiley & Sons, Ltd.

  4. Theoretical Analysis of Thermal Transport in Graphene Supported on Hexagonal Boron Nitride: The Importance of Strong Adhesion Due to π -Bond Polarization

    Science.gov (United States)

    Pak, Alexander J.; Hwang, Gyeong S.

    2016-09-01

    One important attribute of graphene that makes it attractive for high-performance electronics is its inherently large thermal conductivity (κ ) for the purposes of thermal management. Using a combined density-functional theory and classical molecular-dynamics approach, we predict that the κ of graphene supported on hexagonal boron nitride (h -BN) can be as large as 90% of the κ of suspended graphene, in contrast to the significant suppression of κ (more than 70% reduction) on amorphous silica. Interestingly, we find that this enhanced thermal transport is largely attributed to increased lifetimes of the in-plane acoustic phonon modes, which is a notable contrast from the dominant contribution of out-of-plane acoustic modes in suspended graphene. This behavior is possible due to the charge polarization throughout graphene that induces strong interlayer adhesion between graphene and h -BN. These findings highlight the potential benefit of layered dielectric substrates such as h -BN for graphene-based thermal management, in addition to their electronic advantages. Furthermore, our study brings attention to the importance of understanding the interlayer interactions of graphene with layered dielectric materials which may offer an alternative technological platform for substrates in electronics.

  5. Covalent DNA-protein crosslinking occurs after hyperthermia and radiation

    International Nuclear Information System (INIS)

    Cress, A.E.; Bowden, G.T.

    1983-01-01

    Covalent DNA-protein crosslinks occur in exponentially growing mouse leukemia cells (L1210) after exposure to ionizing radiation. The amount of DNA-protein crosslinks as measured by a filter binding assay is dose dependent upon x irradiation. Although hyperthermia and radiation in combination are synergistic with respect to cell lethality, the combination does not result in an increase of DNA-protein crosslinks when assayed immediately following treatments. Hyperthermia (43 0 C/15 min) given prior to radiation dose not alter the radiation dose dependency of the amount of initial crosslinking. In addition, the amount of DNA-protein crosslinking produced by heat plus radiation is independent of the length of heating the cells at 43 0 C. The DNA-protein crosslinks produced y 50-Gy x ray alone are removed after 2 hr at 37 0 C. However, if hyperthermia (43 0 C/15 min) is given prior to 100-Gy x ray, the removal of DNA-protein crosslinks is delayed until 4.0 hr after radiation. Phospho-serine and phospho-threonine bonds are not produced with either radiation or the combination of hyperthermia plus radiation as judged by the resistance of the bonds to guanidine hydrochloride. However, hyperthermia plus radiation causes an increase in phosphate to nitrogen type bonding. These results show that radiation alone causes covalent DNA-protein crosslinks. Hyperthermia in combination with radiation does not increase the total amount of the crosslinks but delays the removal of the crosslinks and alters the distribution of the types of chemical bonding

  6. The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule

    Directory of Open Access Journals (Sweden)

    Jing Zhou

    2016-03-01

    Full Text Available To shed some light on the metal 3d ground state configuration of cobalt phthalocyanines system, so far in debate, we present an investigation by X-ray absorption spectroscopy (XAS at Co L2,3 edge and theoretical calculation. The density functional theory calculations reveal highly anisotropic covalent bond between central cobalt ion and nitrogen ligands, with the dominant σ donor accompanied by weak π-back acceptor interaction. Our combined experimental and theoretical study on the Co-L2,3 XAS spectra demonstrate a robust ground state of 2A1g symmetry that is built from 73% 3d7 character and 27% 3 d 8 L ¯ ( L ¯ denotes a ligand hole components, as the first excited-state with 2Eg symmetry lies about 158 meV higher in energy. The effect of anisotropic and isotropic covalency on the ground state was also calculated and the results indicate that the ground state with 2A1g symmetry is robust in a large range of anisotropic covalent strength while a transition of ground state from 2A1g to 2Eg configuration when isotropic covalent strength increases to a certain extent. Here, we address a significant anisotropic covalent effect of short Co(II-N bond on the ground state and suggest that it should be taken into account in determining the ground state of analogous cobalt complexes.

  7. The significant role of covalency in determining the ground state of cobalt phthalocyanines molecule

    Science.gov (United States)

    Zhou, Jing; Zhang, Linjuan; Hu, Zhiwei; Kuo, Changyang; Liu, Hengjie; Lin, Xiao; Wang, Yu; Pi, Tun-Wen; Wang, Jianqiang; Zhang, Shuo

    2016-03-01

    To shed some light on the metal 3d ground state configuration of cobalt phthalocyanines system, so far in debate, we present an investigation by X-ray absorption spectroscopy (XAS) at Co L2,3 edge and theoretical calculation. The density functional theory calculations reveal highly anisotropic covalent bond between central cobalt ion and nitrogen ligands, with the dominant σ donor accompanied by weak π-back acceptor interaction. Our combined experimental and theoretical study on the Co-L2,3 XAS spectra demonstrate a robust ground state of 2A1g symmetry that is built from 73% 3d7 character and 27% 3 d 8 L ¯ ( L ¯ denotes a ligand hole) components, as the first excited-state with 2Eg symmetry lies about 158 meV higher in energy. The effect of anisotropic and isotropic covalency on the ground state was also calculated and the results indicate that the ground state with 2A1g symmetry is robust in a large range of anisotropic covalent strength while a transition of ground state from 2A1g to 2Eg configuration when isotropic covalent strength increases to a certain extent. Here, we address a significant anisotropic covalent effect of short Co(II)-N bond on the ground state and suggest that it should be taken into account in determining the ground state of analogous cobalt complexes.

  8. Fabrication of cross-linked hydrazone covalent organic frameworks by click chemistry and application to solid phase microextraction.

    Science.gov (United States)

    Wu, Mingxue; Chen, Gang; Ma, Jiutong; Liu, Ping; Jia, Qiong

    2016-12-01

    Covalent organic frameworks (COFs) are an emerging class of porous organic frameworks with diverse promising applications. Herein, we presented the first example of cross-linked hydrazone COFs (cross-linked COFs) coating via thiol-ene click chemistry for solid phase microextraction (SPME). Strong covalent bonds and interlayer of the prepared networks ensured the adsorption capacity and durability of the novel SPME fiber. π-π conjugated structure existed because of abundant phenyl rings and -C=N groups in the cross-lined COFs. A series of characterizations indicated that the cross-linked COFs possessed large surface areas, high porosities and stabilities as well as hydrophobicities. The fiber was applied to SPME of pesticide residues coupled with gas chromatography with an electron capture detector (GC-ECD). Under the optimum experimental conditions, enhancement factors in the range of 2190-10,998 were obtained, illustrating that the cross-linked COFs possessed remarkable preconcentration ability. The low detection limits of 0.0003-0.0023ngkg -1 were achieved with relative standard deviations (RSDs) in the range of 3.4-7.6% (intra-batch) and 5.7-11.6% (inter-batch), respectively. Recovery values in the range of 78.2-107.0% were obtained when the SPME-GC method was applied to the analysis of pesticides in cucumber samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Origin of trans-bent geometries in maximally bonded transition metal and main group molecules.

    Science.gov (United States)

    Landis, Clark R; Weinhold, Frank

    2006-06-07

    Recent crystallographic data unambiguously demonstrate that neither Ar'GeGeAr' nor Ar'CrCrAr' molecules adopt the expected linear (VSEPR-like) geometries. Does the adoption of trans-bent geometries indicate that Ar'MMAr' molecules are not "maximally bonded" (i.e., bond order of three for M = Ge and five for M = Cr)? We employ theoretical hybrid density functional (B3LYP/6-311++G) computations and natural bond orbital-based analysis to quantify molecular bond orders and to elucidate the electronic origin of such unintuitive structures. Resonance structures based on quintuple M-M bonding dominate for the transition metal compounds, especially for molybdenum and tungsten. For the main group, M-M bonding consists of three shared electron pairs, except for M = Pb. For both d- and p-block compounds, the M-M bond orders are reflected in torsional barriers, bond-antibond splittings, and heats of hydrogenation in a qualitatively intuitive way. Trans-bent structures arise primarily from hybridization tendencies that yield the strongest sigma-bonds. For transition metals, the strong tendency toward sd-hybridization in making covalent bonds naturally results in bent ligand arrangements about the metal. In the p-block, hybridization tendencies favor high p-character, with increasing avidity as one moves down the Group 14 column, and nonlinear structures result. In both the p-block and the d-block, bonding schemes have easily identifiable Lewis-like character but adopt somewhat unconventional orbital interactions. For more common metal-metal multiply bonded compounds such as [Re2Cl8]2-, the core Lewis-like fragment [Re2Cl4]2+ is modified by four hypervalent three-center/four-electron additions.

  10. Reversible Covalent Reaction of Levosimendan with Cardiac Troponin C in Vitro and in Situ.

    Science.gov (United States)

    Klein, Brittney A; Reiz, Béla; Robertson, Ian M; Irving, Malcolm; Li, Liang; Sun, Yin-Biao; Sykes, Brian D

    2018-04-17

    The development of calcium sensitizers for the treatment of systolic heart failure presents difficulties, including judging the optimal efficacy and the specificity to target cardiac muscle. The thin filament is an attractive target because cardiac troponin C (cTnC) is the site of calcium binding and the trigger for subsequent contraction. One widely studied calcium sensitizer is levosimendan. We have recently shown that when a covalent cTnC-levosimendan analogue is exchanged into cardiac muscle cells, they become constitutively active, demonstrating the potency of a covalent complex. We have also demonstrated that levosimendan reacts in vitro to form a reversible covalent thioimidate bond specifically with cysteine 84, unique to cTnC. In this study, we use mass spectrometry to show that the in vitro mechanism of action of levosimendan is consistent with an allosteric, reversible covalent inhibitor; to determine whether the presence of the cTnI switch peptide or changes in either Ca 2+ concentration or pH modify the reaction kinetics; and to determine whether the reaction can occur with cTnC in situ in cardiac myofibrils. Using the derived kinetic rate constants, we predict the degree of covalently modified cTnC in vivo under the conditions studied. We observe that covalent bond formation would be highest under the acidotic conditions resulting from ischemia and discuss whether the predicted level could be sufficient to have therapeutic value. Irrespective of the in vivo mechanism of action for levosimendan, our results provide a rationale and basis for the development of reversible covalent drugs to target the failing heart.

  11. Covalently Bound Nitroxyl Radicals in an Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Hughes, Barbara K.; Braunecker, Wade A.; Bobela, David C.; Nanayakkara, Sanjini U.; Reid, Obadiah G.; Johnson, Justin C.

    2016-09-15

    A series of covalent organic framework (COF) structures is synthesized that possesses a tunable density of covalently bound nitroxyl radicals within the COF pores. The highest density of organic radicals produces an electron paramagnetic resonance (EPR) signal that suggests the majority of radicals strongly interact with other radicals, whereas for smaller loadings the EPR signals indicate the radicals are primarily isolated but with restricted motion. The dielectric loss as determined from microwave absorption of the framework structures compared with an amorphous control suggests that free motion of the radicals is inhibited when more than 25% of available sites are occupied. The ability to tune the mode of radical interactions and the subsequent effect on redox, electrical, and optical characteristics in a porous framework may lead to a class of structures with properties ideal for photoelectrochemistry or energy storage.

  12. Dialing in the Ratio of Covalent and Coordination Cross-links in Self-healing Hydrogels

    DEFF Research Database (Denmark)

    Andersen, Amanda; Krogsgaard, Marie; Birkedal, Henrik

    Mussel-inspired hydrogels have drawn considerable attention. They can be based on either covalent crosslinking through catechol oxidation chemistry or on coordination chemistry through reversible catecholato–metal bonds, which incorporates self-healing properties.1-6 For practical applications......-healing abilities even at high pH but that can be stiffened at will by dialing in the required degree of covalent crosslinking. This dial-in method thus harnesses two aspects of catechol-type chemistries to yield double network hydrogels in a straightforward and highly controllable manner....

  13. Making Weak Bonds (cooling) and Breaking Strong Bonds (heating ...

    Indian Academy of Sciences (India)

    ... THE MOLECULES · Slide 34 · High Temperature Chemical Kinetics Laboratory today · Slide 36 · Ignition delay studies · CH emission and pressure rise to measure ignition delay! JP10 · Log vs 1/T plot · Arrhenius parameters for JP10 and JP10-TEA mixture · triethylamine · CONCLUSIONS · Thank you all for listening.

  14. Flavins as Covalent Catalysts: New Mechanisms Emerge.

    Science.gov (United States)

    Piano, Valentina; Palfey, Bruce A; Mattevi, Andrea

    2017-06-01

    With approximately 1% of proteins being flavoproteins, flavins are at the heart of a plethora of redox reactions in all areas of biology. Thanks to a series of fascinating recent discoveries, in addition to redox chemistry, covalent catalysis is now being recognized more frequently as a common strategy in flavoenzymes, with unprecedented mechanisms becoming apparent. Thus, noncanonical covalent reactions by flavins are emerging as a new pervasive concept in basic enzymology and biochemistry. These diverse enzymes are engaged in most biological processes, positioning the knowledge being gained from these new mechanisms to be translated into drugs that function through covalent mechanisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Dissimilar Impact Welding of 6111-T4, 5052-H32 Aluminum Alloys to 22MnB5, DP980 Steels and the Structure-Property Relationship of a Strongly Bonded Interface

    Science.gov (United States)

    Liu, Bert; Vivek, Anupam; Presley, Michael; Daehn, Glenn S.

    2018-03-01

    The ability to weld high-strength aluminum to high-strength steel is highly desired for vehicle lightweighting but difficult to attain by conventional means. In this work, vaporizing foil actuator welding was used to successfully weld four Al/Fe combinations consisting of high-strength alloys: AA5052-H32, AA6111-T4, DP980, and 22MnB5. Flyer velocities up to 727 m/s were reached using 10 kJ input energy. In lap-shear testing, samples primarily failed in base aluminum near the aluminum's native strength, showing that the welds were stronger than a base metal and that the base metal was not significantly weakened by the welding process. A particularly strong weld area was studied by transmission electron microscopy to shed light on the microstructural features of strong impact welds. It was found to be characterized by a continuously bonded, fully crystalline interface, extremely fine (nanoscale) grains, mesoscopic as well as microscopic wavy features, and lack of large continuous intermetallic compounds.

  16. SU-8-Induced Strong Bonding of Polymer Ligands to Flexible Substrates via in Situ Cross-Linked Reaction for Improved Surface Metallization and Fast Fabrication of High-Quality Flexible Circuits.

    Science.gov (United States)

    Hu, Mingjun; Guo, Qiuquan; Zhang, Tengyuan; Zhou, Shaolin; Yang, Jun

    2016-02-01

    On account of in situ cross-linked reaction of epoxy SU-8 with poly(4-vinylpyridine) (P4VP) and its strong reactive bonding ability with different pretreated substrates, we developed a simple universal one-step solution-based coating method for fast surface modification of various objects. Through this method, a layer of P4VP molecules with controllable thickness can be tethered tightly onto substrates with the assistance of SU-8. P4VP molecules possess a lot of pyridine ligands to immobilize transitional metal ions that can behave as the catalyst of electroless copper plating for surface metallization while functioning as the adhesion-promoting layer between the substrate and deposited metal. Attributed to interpenetrated entanglement of P4VP molecules and as-deposited metal, ultrathick (>7 μm) strongly adhesive high-quality copper layer can be formed on flexible substrates without any delamination. Then through laser printer to print toner mask, a variety of designed circuits can be easily fabricated on modified flexible PET substrate.

  17. Dissimilar Impact Welding of 6111-T4, 5052-H32 Aluminum Alloys to 22MnB5, DP980 Steels and the Structure-Property Relationship of a Strongly Bonded Interface

    Science.gov (United States)

    Liu, Bert; Vivek, Anupam; Presley, Michael; Daehn, Glenn S.

    2018-01-01

    The ability to weld high-strength aluminum to high-strength steel is highly desired for vehicle lightweighting but difficult to attain by conventional means. In this work, vaporizing foil actuator welding was used to successfully weld four Al/Fe combinations consisting of high-strength alloys: AA5052-H32, AA6111-T4, DP980, and 22MnB5. Flyer velocities up to 727 m/s were reached using 10 kJ input energy. In lap-shear testing, samples primarily failed in base aluminum near the aluminum's native strength, showing that the welds were stronger than a base metal and that the base metal was not significantly weakened by the welding process. A particularly strong weld area was studied by transmission electron microscopy to shed light on the microstructural features of strong impact welds. It was found to be characterized by a continuously bonded, fully crystalline interface, extremely fine (nanoscale) grains, mesoscopic as well as microscopic wavy features, and lack of large continuous intermetallic compounds.

  18. Definition of a multicentral bond index

    International Nuclear Information System (INIS)

    Giambiagi, M.; Giambiagi, M.S. de; Mundim, K.C.

    1989-01-01

    The tensor character of the first-order density matrix leads to the definition of an MO multicentral bond index for closed-shell systems. It is here applied to three-center bonds. Satisfactory results are obtained for compounds involving 'secondary' bonds, strong and normal hydrogen bonds; the index for the peptide bond is found to be similar to that of strong hydrogen bonds. (author) [pt

  19. Breaking the dogma: PCB-derived semiquinone free radicals do not form covalent adducts with DNA, GSH, and amino acids.

    Science.gov (United States)

    Wangpradit, Orarat; Rahaman, Asif; Mariappan, S V Santhana; Buettner, Garry R; Robertson, Larry W; Luthe, Gregor

    2016-02-01

    Covalent bond formations of free radical metabolites with biomolecules like DNA and proteins are thought to constitute a major mechanism of toxicity and carcinogenesis. Glutathione (GSH) is generally accepted as a radical scavenger protecting the cell. In the present study, we investigated a semiquinone radical (SQ(●-)) metabolite of the semivolatile 4-chlorobiphenyl, using electron paramagnetic resonance spectroscopy, and oxygen consumption. Proton nuclear magnetic resonance ((1)H NMR) and liquid chromatography-mass spectrometry (LC-MS) were also employed to elucidate the radical interaction with DNA, amino acids, and GSH. We found that DNA and oligonucleotides stabilized SQ(●-) by electron delocalization in the π-stacking system, resulting in persistent radical intercalated, rather than forming a covalent bond with SQ(●-). This finding was strongly supported by the semiempirical calculation of the semioccupied molecular orbital and the linear combination of the atomic orbitals, indicating 9.8 kcal mol(-1) energy gain. The insertion of SQ(●-) into the DNA strand may result in DNA strand breaks and interruption of DNA replication process or even activate radical mediated secondary reactions. The presence of amino acids resulted in a decrease of the electron paramagnetic resonance (EPR) signal of SQ(●-) and correlated with their isoelectric points. The pH shifts the equilibrium of the dianions of hydroquinone and influenced indirectly the formation of SQ(●-). Similar findings were observed with GSH and Cys. GSH and Cys functioned as indirect radical scavengers; their activities depend on their chemical equilibria with the corresponding quinones, and their further reaction via Michael addition. The generally accepted role of GSH as radical scavenger in biological systems should be reconsidered based upon these findings, questioning the generally accepted view of radical interaction of semiquinones with biologically active compounds, like DNA, amino acids

  20. Relation between frequency and H bond length in heavy water: Towards the understanding of the unusual properties of H bond dynamics in nanoporous media

    Energy Technology Data Exchange (ETDEWEB)

    Pommeret, Stanislas [CEA/Saclay, DSM/DRECAM/SCM URA 331 CNRS, Laboratoire de Radiolyse, F-91191 Gif-sur-Yvette (France); Leicknam, Jean-Claude; Bratos, Savo [Laboratoire de Physique Theorique de la Matiere Condensee, Universite Pierre et Marie Curie-Paris 6, UMR 7600 (CNRS), Paris (France); Musat, Raluca; Renault, Jean Philippe, E-mail: stanislas.pommeret@cea.f

    2009-06-01

    The published work on H bond dynamics mainly refers to diluted solutions HDO/D{sub 2}O rather than to normal water. The reasons for this choice are both theoretical and experimental. Mechanical isolation of the OH vibrator eliminating the resonant energy transfer makes it a better probe of the local H bond network, while the dilution in heavy water reduces the infrared absorption, which permits the use of thicker experimental cells. The isotopic substitution does not alter crucially the nature of the problem. The length r of an OH . . . O group is statistically distributed over a large interval comprised between 2.7 and 3.2 A with a mean value r{sub 0} = 2.86 A. Liquid water may thus be viewed as a mixture of hydrogen bonds of different length. Two important characteristics of hydrogen bonding must be mentioned. (i) The OH stretching vibrations are strongly affected by this interaction. The shorter the length r of the hydrogen bond, the strongest the H bond link and the lower is its frequency omega: the covalent OH bond energy is lent to the OH. . .O bond and reinforces the latter. A number of useful relationships between omega and r were published to express this correlation. The one adopted in our previous work is the relationship due to Mikenda. (ii) Not only the OH vibrations, but also the HDO rotations are influenced noticeably by hydrogen bonding. This is due to steric forces that hinder the HDO rotations. As they are stronger in short than in long hydrogen bonds, rotations are slower in the first case than in the second. This effect was only recently discovered, but its existence is hardly to be contested. In the present contribution, we want to revisit the relationship between the frequency of the OH vibrator and the distance OH. . .O.

  1. Relation between frequency and H bond length in heavy water: Towards the understanding of the unusual properties of H bond dynamics in nanoporous media

    International Nuclear Information System (INIS)

    Pommeret, Stanislas; Leicknam, Jean-Claude; Bratos, Savo; Musat, Raluca; Renault, Jean Philippe

    2009-01-01

    The published work on H bond dynamics mainly refers to diluted solutions HDO/D 2 O rather than to normal water. The reasons for this choice are both theoretical and experimental. Mechanical isolation of the OH vibrator eliminating the resonant energy transfer makes it a better probe of the local H bond network, while the dilution in heavy water reduces the infrared absorption, which permits the use of thicker experimental cells. The isotopic substitution does not alter crucially the nature of the problem. The length r of an OH . . . O group is statistically distributed over a large interval comprised between 2.7 and 3.2 A with a mean value r 0 = 2.86 A. Liquid water may thus be viewed as a mixture of hydrogen bonds of different length. Two important characteristics of hydrogen bonding must be mentioned. (i) The OH stretching vibrations are strongly affected by this interaction. The shorter the length r of the hydrogen bond, the strongest the H bond link and the lower is its frequency ω: the covalent OH bond energy is lent to the OH. . .O bond and reinforces the latter. A number of useful relationships between ω and r were published to express this correlation. The one adopted in our previous work is the relationship due to Mikenda. (ii) Not only the OH vibrations, but also the HDO rotations are influenced noticeably by hydrogen bonding. This is due to steric forces that hinder the HDO rotations. As they are stronger in short than in long hydrogen bonds, rotations are slower in the first case than in the second. This effect was only recently discovered, but its existence is hardly to be contested. In the present contribution, we want to revisit the relationship between the frequency of the OH vibrator and the distance OH. . .O.

  2. Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y-(HF) n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator.

    Science.gov (United States)

    Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

    2017-01-01

    Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF) n . The HF molecules were ionized in the form of complex ions associated with the negative core ions Y - produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y - (HF) n (Y=F, O 2 ), where larger clusters with n ≥4 were not detected. The mechanisms for the formation of the HF, F - (HF) n , and O 2 - (HF) n species were discussed from the standpoints of the HF generator and APCDI MS. By performing energy-resolved collision-induced dissociation (CID) experiments on the cluster ions F - (HF) n ( n =1-3), the energies for the loss of HF from F - (HF) 3 , F - (HF) 2 , and F - (HF) were evaluated to be 1 eV or lower, 1 eV or higher, and 2 eV, respectively, on the basis of their center-of-mass energy ( E CM ). These E CM values were consistent with the values of 0.995, 1.308, and 2.048 eV, respectively, obtained by ab initio calculations. The stability of [O 2 (HF) n ] - ( n =1-4) was discussed on the basis of the bond lengths of O 2 H-F - (HF) n and O 2 - H-F(HF) n obtained by ab initio calculations. The calculations indicated that [O 2 (HF) 4 ] - separated into O 2 H and F - (HF) 3 .

  3. Covalent Surface Modifications of Carbon Nanotubes.

    Energy Technology Data Exchange (ETDEWEB)

    Pavia Sanders, Adriana [Sandia National Lab. (SNL-CA), Livermore, CA (United States); O' Bryan, Greg [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2017-07-01

    A report meant to document the chemistries investigated by the author for covalent surface modification of CNTs. Oxidation, cycloaddition, and radical reactions were explored to determine their success at covalently altering the CNT surface. Characterization through infrared spectroscopy, Raman spectroscopy, and thermo gravimetric analysis was performed in order to determine the success of the chemistries employed. This report is not exhaustive and was performed for CNT surface modification exploration as it pertains to the "Next Gen" project.

  4. Halogen Bonds in Novel Polyhalogen Monoanions.

    Science.gov (United States)

    Wang, Changwei; Danovich, David; Shaik, Sason; Mo, Yirong

    2017-06-27

    Polyhalogen monoanions [X 2n+1 ] - (X=Cl and Br; n=1, 2, 3, 4, and 5) have been systematically studied using the block-localized wave function (BLW) method, which offers a valence bond (VB) analysis. For each species, the most stable isomer can be described as a central halide anion X - non-classically bonded to a number of dihalogen molecules X 2 via "halogen bonds". VB analyses confirm the dominant role of the charge-transfer interaction between the lone pair on X - and the σ-anti-bonding orbital of X 2 molecule (n→σ*) in X 3 - and higher analogues. Thus, our study demonstrates that these halogen bonds are essentially dative covalent interactions. Importantly, the charge-transfer interaction between [X 2n-1 ] - and X 2 decreases with the increasing n, in accord with the weakening of the Lewis basicity as characterized by the corresponding HOMO energy. The reduction of the charge transfer interaction underscores the reduction of covalence in halogen bonds in [X 2n+1 ] - . This tendency highlights the anti-cooperative effect in polyhalogen monoanions. All in all, the halogen bond between X - and nX 2 molecules exhibits the same trends as in X - with a single X 2 molecule. In other words, halogen bonding in the larger clusters derives from the same bonding mechanism as the [X 3 ] - anion. As such, the X - ⋅⋅⋅X 2 halogen bond at different bond lengths forms a gauge of covalence for the entire [X 2n+1 ] - family. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Preparation and characterization of PEGylated multiwall carbon nanotubes as covalently conjugated and non-covalent drug carrier: A comparative study.

    Science.gov (United States)

    Habibizadeh, Mina; Rostamizadeh, Kobra; Dalali, Naser; Ramazani, Ali

    2017-05-01

    In this study, PEGylated multiwall carbon nanotubes (MWNTs)-based drug delivery system was developed. Ibuprofen as a model drug was loaded by physical and chemical method. The surface functionalization of nanotubes was carried out by enrichment of acylated groups. In order to synthesis PEGylated MWNTs, hydrophilic diamino-polyethylene glycol was covalently linked to the MWNTs surface via amidation reaction. Finally, ibuprofen was chemically and physically loaded on the PEGylated MWNTs. The resultants were characterized by FTIR, AFM, and DLS techniques. Cytotoxicity of PEGylated MWNTs were examined by MTT assay and the results revealed that PEG functionalized nanotubes did not show significant detrimental effects on the viability of L929 Cells. The percent of drug loading for chemically and physically drug payload carrier were determined to be 52.5% and 38%, respectively. The release of ibuprofen from covalently conjugated and non-covalent drug loaded PEGylated MWNTs at pH=7.4, and 5.3 were investigated, as well. From the results, it was found that chemically loaded MWNTs showed much sustained release behavior compared to the physically loaded one, especially at pH=5.3. The kinetic of drug release was also investigated. The results strongly suggest that the chemically conjugated PEGylated MWNTs could be used as controlled release system for various drugs. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Solvent-free covalent functionalization of nanodiamond with amines

    International Nuclear Information System (INIS)

    Basiuk, Elena V.; Santamaría-Bonfil, Adriana; Meza-Laguna, Victor; Gromovoy, Taras Yu.; Alvares-Zauco, Edgar; Contreras-Torres, Flavio F.; Rizo, Juan; Zavala, Guadalupe; Basiuk, Vladimir A.

    2013-01-01

    Covalent functionalization of pristine nanodiamond (ND) with 1,12-diaminododecane (DAD), 1,5-diaminonaphthalene (DAN), poly(ethylene glycol) diamine (PEGDA), and polyethylenimine (PEI) was carried out by employing solvent-free methodology, which is based on thermal instead of chemical activation of carboxylic groups at ND surface. A simple solubility/dispersibility test in water and isopropanol showed an increased lipophilicity of the functionalized samples. The conversion of intrinsic carboxylic groups into the corresponding amide derivatives was characterized by means of Fourier-transform infrared spectroscopy. Thermogravimetric analysis found the highest organic content of about 18% for ND-PEI, followed by ND-DAD, for which the contribution of covalently bonded diamine was estimated to be of ca. 10%. In temperature programmed desorption measurements with mass spectrometric detection, the presence of organic functionalizing groups changed both mass spectra and thermodesorption curves of ND. The changes in morphology of primary and secondary ND aggregates were characterized by scanning and transmission electron microscopy, as well as by atomic force microscopy. The current–voltage measurements under atmospheric pressure found an increased conductivity for ND-DAN, as compared to that of pristine ND, whereas for ND-DAD, ND-PEGDA and ND-PEI a dramatic decrease in conductivity due to functionalization was observed.

  7. Solvent-free covalent functionalization of nanodiamond with amines

    Energy Technology Data Exchange (ETDEWEB)

    Basiuk, Elena V., E-mail: elenagd@unam.mx [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Santamaría-Bonfil, Adriana; Meza-Laguna, Victor [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Gromovoy, Taras Yu. [Institute of Surface Chemistry, National Academy of Sciences of the Ukraine, Gen. Naumova 17, 03164 Kiev (Ukraine); Alvares-Zauco, Edgar [Facultad de Ciencias, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Contreras-Torres, Flavio F.; Rizo, Juan [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Zavala, Guadalupe [Instituto de Biotecnología, Universidad Nacional Autónoma de México, Av. Universidad 2001, Col. Chamilpa, 62210, Cuernavaca, Morelos (Mexico); Basiuk, Vladimir A. [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México, D.F. (Mexico)

    2013-06-15

    Covalent functionalization of pristine nanodiamond (ND) with 1,12-diaminododecane (DAD), 1,5-diaminonaphthalene (DAN), poly(ethylene glycol) diamine (PEGDA), and polyethylenimine (PEI) was carried out by employing solvent-free methodology, which is based on thermal instead of chemical activation of carboxylic groups at ND surface. A simple solubility/dispersibility test in water and isopropanol showed an increased lipophilicity of the functionalized samples. The conversion of intrinsic carboxylic groups into the corresponding amide derivatives was characterized by means of Fourier-transform infrared spectroscopy. Thermogravimetric analysis found the highest organic content of about 18% for ND-PEI, followed by ND-DAD, for which the contribution of covalently bonded diamine was estimated to be of ca. 10%. In temperature programmed desorption measurements with mass spectrometric detection, the presence of organic functionalizing groups changed both mass spectra and thermodesorption curves of ND. The changes in morphology of primary and secondary ND aggregates were characterized by scanning and transmission electron microscopy, as well as by atomic force microscopy. The current–voltage measurements under atmospheric pressure found an increased conductivity for ND-DAN, as compared to that of pristine ND, whereas for ND-DAD, ND-PEGDA and ND-PEI a dramatic decrease in conductivity due to functionalization was observed.

  8. Immobilization of β-glucosidase onto mesoporous silica support: Physical adsorption and covalent binding of enzyme

    Directory of Open Access Journals (Sweden)

    Ivetić Darjana Ž.

    2014-01-01

    Full Text Available This paper investigates β-glucosidase immobilization onto mesoporous silica support by physical adsorption and covalent binding. The immobilization was carried out onto micro-size silica aggregates with the average pore size of 29 nm. During physical adsorption the highest yield of immobilized β-glucosidase was obtained at initial protein concentration of 0.9 mg ml-1. Addition of NaCl increased 1.7-fold, while Triton X-100 addition decreased 6-fold yield of adsorption in comparison to the one obtained without any addition. Covalently bonded β-glucosidase, via glutaraldehyde previously bonded to silanized silica, had higher yield of immobilized enzyme as well as higher activity and substrate affinity in comparison to the one physically adsorbed. Covalent binding did not considerably changed pH and temperature stability of obtained biocatalyst in range of values that are commonly used in reactions in comparison to unbounded enzyme. Furthermore, covalent binding provided biocatalyst which retained over 70% of its activity after 10 cycles of reuse. [Projekat Ministarstva nauke Republike Srbije, br. III 45021

  9. Alpha-cyclodextrins reversibly capped with disulfide bonds

    Czech Academy of Sciences Publication Activity Database

    Kumprecht, Lukáš; Buděšínský, Miloš; Bouř, Petr; Kraus, Tomáš

    2010-01-01

    Roč. 34, č. 10 (2010), s. 2254-2260 ISSN 1144-0546 R&D Projects: GA AV ČR IAA400550810 Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclodextrin s * disulfide bond * dynamic covalent bond Subject RIV: CC - Organic Chemistry Impact factor: 2.631, year: 2010

  10. A perfluorinated covalent triazine-based framework for highly selective and water-tolerant CO2 capture

    KAUST Repository

    Zhao, Yunfeng

    2013-01-01

    We designed and synthesized a perfluorinated covalent triazine-based framework (FCTF-1) for selective CO2 capture. The incorporation of fluorine (F) groups played multiple roles in improving the framework\\'s CO 2 adsorption and separation capabilities. Thermodynamically, the strongly polar C-F bonds promoted CO2 adsorption via electrostatic interactions, especially at low pressures. FCTF-1\\'s CO2 uptake was 1.76 mmol g-1 at 273 K and 0.1 bar through equilibrium adsorption, exceeding the CO2 adsorption capacity of any reported porous organic polymers to date. In addition, incorporating F groups produced a significant amount of ultra-micropores (<0.5 nm), which offered not only high gas adsorption potential but also kinetic selectivity for CO2-N 2 separation. In mixed-gas breakthrough experiments, FCTF-1 exhibited an exceptional CO2-N2 selectivity of 77 under kinetic flow conditions, much higher than the selectivity (31) predicted from single-gas equilibrium adsorption data. Moreover, FCTF-1 proved to be tolerant to water and its CO2 capture performance remained excellent when there was moisture in the gas mixture, due to the hydrophobic nature of the C-F bonds. In addition, the moderate adsorbate-adsorbent interaction allowed it to be fully regenerated by pressure swing adsorption processes. These attributes make FCTF-1 a promising sorbent for CO2 capture from flue gas. © 2013 The Royal Society of Chemistry.

  11. Effect of cooperative hydrogen bonding in azo-hydrazone tautomerism of azo dyes.

    Science.gov (United States)

    Ozen, Alimet Sema; Doruker, Pemra; Aviyente, Viktorya

    2007-12-27

    Azo-hydrazone tautomerism in azo dyes has been modeled by using density functional theory (DFT) at the B3LYP/6-31+G(d,p) level of theory. The most stable tautomer was determined both for model compounds and for azo dyes Acid Orange 7 and Solvent Yellow 14. The effects of the sulfonate group substitution and the replacement of the phenyl group with naphthyl on the tautomer stability and on the behavior in solvent have been discussed. Intramolecular hydrogen bond energies have been estimated for the azo and hydrazone tautomers to derive a relationship between the tautomer stability and the hydrogen bond strength. The transition structures for proton transfer displayed resonance assisted strong hydrogen bonding properties within the framework of the electrostatic-covalent hydrogen bond model (ECHBM). Evolution of the intramolecular hydrogen bond with changing structural and environmental factors during the tautomeric conversion process has been studied extensively by means of the atoms-in-molecules (AIM) analysis of the electron density. The bulk solvent effect was examined using the self-consistent reaction field model. Special solute-solvent interactions were further investigated by means of quantum mechanical calculations after defining the first-solvation shell by molecular dynamics simulations. The effect of cooperative hydrogen bonding with solvent molecules on the tautomer stability has been discussed.

  12. Description of Non-Covalent Interactions in SCC-DFTB Methods

    Czech Academy of Sciences Publication Activity Database

    Miriyala, Vijay Madhav; Řezáč, Jan

    2017-01-01

    Roč. 38, č. 10 (2017), s. 688-697 ISSN 0192-8651 R&D Projects: GA ČR(CZ) GJ16-11321Y Institutional support: RVO:61388963 Keywords : density functional tight binding * DFTB3 * non-covalent interactions * dispersion correction * hydrogen bonding correction Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.229, year: 2016

  13. Fundamentals of fiber bonding in thermally point-bonded nonwovens

    Science.gov (United States)

    Chidambaram, Aparna

    Thermal point bonding (TPB) uses heat and pressure to bond a web of fibers at discrete points imparting strength to the manufactured fabric. This process significantly reduces the strength and elongation of the bridging fibers between bond points while strengthening the web. Single fiber experiments were performed with four structurally different polypropylene fibers to analyze the inter-relationships between fiber structure, fiber properties and bonding process. Two fiber types had a low birefringence sheath or surface layer while the remaining had uniform birefringence profiles through their thickness. Bonds were formed between isolated pairs of fibers by subjecting the fibers to a calendering process and simulating TPB process conditions. The dependence of bond strength on bonding temperature and on the type of fiber used was evaluated. Fiber strengths before and after bonding were measured and compared to understand the effect of bonding on fiber strength. Additionally, bonded fiber strength was compared to the strength of single fibers which had experienced the same process conditions as the bonded pairs. This comparison estimated the effect of mechanical damage from pressing fibers together with steel rolls while creating bonds in TPB. Interfiber bond strength increased with bonding temperature for all fiber types. Fiber strength decreased with increasing bonding temperature for all fiber types except for one type of low birefringent sheath fibers. Fiber strength degradation was unavoidable at temperatures required for successful bonding. Mechanical damage from compression of fibers between rolls was an insignificant factor in this strength loss. Thermal damage during bonding was the sole significant contributor to fiber strength degradation. Fibers with low birefringence skins formed strong bonds with minimal fiber strength loss and were superior to fibers without such surface layers in TPB performance. A simple model to predict the behavior of a two-bond

  14. Non covalent assembly of coordination superstructures

    CERN Document Server

    Khlobystov, A N

    2002-01-01

    The main topic of this work is the design of discrete and polymeric multi-component coordination structures using non-covalent interactions between organic and inorganic molecular components. All of the structures described herein are based on transition metal cations and N-donor heterocyclic bis-exodentate ligands with different geometries and various spacer functionalities. The predominant method used for the structural characterisation of the complexes was single crystal X-ray crystallography. X-ray powder diffraction, IR and NMR spectroscopies and TEM and AFM imaging were used to characterise the bulk products from the reactions. Chapter 1 is a comparative review of non-covalent interactions relevant to coordination superstructures and covers the latest developments in the area of crystal engineering and supramolecular chemistry. The nature, geometry and relative energy of the non-covalent interactions are considered in detail in order to reveal their influence on the structure and properties of complexes...

  15. Non-covalent conjugates of single-walled carbon nanotubes and folic acid for interaction with cells overexpressing folate receptors

    DEFF Research Database (Denmark)

    Castillo, John J.; Rindzevicius, Tomas; Novoa, Leidy V.

    2013-01-01

    We here present amethod to form a noncovalent conjugate of single-walled carbon nanotubes and folic acid aimed to interact with cells over-expressing folate receptors. The bonding was obtained without covalent chemical functionalization using a simple, rapid “one pot” synthesis method. The zeta p...

  16. C2H5OH···HX (X=OH, SH, F) interactions: Is there a carbon bond?

    Indian Academy of Sciences (India)

    gen bonding interactions, it is now well established that covalently-bonded atoms of ... is a carbon bond donor and Y is a carbon bond acceptor. During the past years, several .... plexes in atomic units and penetration parameters of acceptor and hydrogen ( rY, rX) in Å. Y is acceptor atom and X is donor atom. Complex at.

  17. Self-assembly of bridged silsesquioxanes: modulating structural evolution via cooperative covalent and noncovalent interactions.

    Science.gov (United States)

    Creff, Gaelle; Pichon, Benoît P; Blanc, Christophe; Maurin, David; Sauvajol, Jean-Louis; Carcel, Carole; Moreau, Joël J E; Roy, Pascale; Bartlett, John R; Man, Michel Wong Chi; Bantignies, Jean-Louis

    2013-05-07

    The self-assembly of a bis-urea phenylene-bridged silsesquioxane precursor during sol-gel synthesis has been investigated by in situ infrared spectroscopy, optical microscopy, and light scattering. In particular, the evolution of the system as a function of processing time was correlated with covalent interactions associated with increasing polycondensation and noncovalent interactions such as hydrogen bonding. A comprehensive mechanism based on the hydrolysis of the phenylene-bridged organosilane precursor prior to the crystallization of the corresponding bridged silsesquioxane via H-bonding and subsequent irreversible polycondensation is proposed.

  18. Phase stability, physical properties of rhenium diboride under high pressure and the effect of metallic bonding on its hardness

    International Nuclear Information System (INIS)

    Zhong, Ming-Min; Kuang, Xiao-Yu; Wang, Zhen-Hua; Shao, Peng; Ding, Li-Ping; Huang, Xiao-Fen

    2013-01-01

    Highlights: •The transition pressure P t between the ReB 2 –ReB 2 and MoB 2 –ReB 2 phases is firstly determinate. •The single-bonded B–B feather remains in ReB 2 compounds. •A semiempirical method to evaluate the hardness of crystals with partial metallic bond is presented. •The large hardness (39.1 GPa) of ReB 2 –ReB 2 indicate that it is a superhard material. •The zigzag interconnected B–Re and B–B covalent bonds underlie the ultraincompressibilities. -- Abstract: Using first-principles calculations, the elastic constants, thermodynamic property and structural phase transition of rhenium diboride under pressure are investigated by means of the pseudopotential plane-waves method, as well as the effect of metallic bond on its hardness. Eight candidate structures of known transition-metal compounds are chosen to probe for rhenium diboride ReB 2 . The calculated lattice parameters are consistent with the experimental and theoretical values. Based on the third order Birch–Murnaghan equation of states, the transition pressure P t between the ReB 2 –ReB 2 and MoB 2 –ReB 2 phases is firstly determinate. Elastic constants, shear modulus, Young’s modulus, Poisson’s ratio and Debye temperature are derived. The single-bonded B–B feather remains in ReB 2 compounds. Furthermore, according to Mulliken overlap population analysis, a semiempirical method to evaluate the hardness of multicomponent crystals with partial metallic bond is presented. Both strong covalency and a zigzag topology of interconnected bonds underlie the ultraincompressibilities. In addition, the superior performance and large hardness (39.1 GPa) of ReB 2 –ReB 2 indicate that it is a superhard material

  19. Ionic bonding of lanthanides, as influenced by d- and f-atomic orbitals, by core-shells and by relativity.

    Science.gov (United States)

    Ji, Wen-Xin; Xu, Wei; Schwarz, W H Eugen; Wang, Shu-Guang

    2015-03-15

    Lanthanide trihalide molecules LnX3 (X = F, Cl, Br, I) were quantum chemically investigated, in particular detail for Ln = Lu (lutetium). We applied density functional theory (DFT) at the nonrelativistic and scalar and SO-coupled relativistic levels, and also the ab initio coupled cluster approach. The chemically active electron shells of the lanthanide atoms comprise the 5d and 6s (and 6p) valence atomic orbitals (AO) and also the filled inner 4f semivalence and outer 5p semicore shells. Four different frozen-core approximations for Lu were compared: the (1s(2) -4d(10) ) [Pd] medium core, the [Pd+5s(2) 5p(6) = Xe] and [Pd+4f(14) ] large cores, and the [Pd+4f(14) +5s(2) 5p(6) ] very large core. The errors of LuX bonding are more serious on freezing the 5p(6) shell than the 4f(14) shell, more serious upon core-freezing than on the effective-core-potential approximation. The LnX distances correlate linearly with the AO radii of the ionic outer shells, Ln(3+) -5p(6) and X(-) -np(6) , characteristic for dominantly ionic Ln(3+) -X(-) binding. The heavier halogen atoms also bind covalently with the Ln-5d shell. Scalar relativistic effects contract and destabilize the LuX bonds, spin orbit coupling hardly affects the geometries but the bond energies, owing to SO effects in the free atoms. The relativistic changes of bond energy BE, bond length Re , bond force k, and bond stretching frequency vs do not follow the simple rules of Badger and Gordy (Re ∼BE∼k∼vs ). The so-called degeneracy-driven covalence, meaning strong mixing of accidentally near-degenerate, nearly nonoverlapping AOs without BE contribution is critically discussed. © 2015 Wiley Periodicals, Inc.

  20. Effects of ultraviolet irradiation on bonding strength between Co-Cr alloy and citric acid-crosslinked gelatin matrix.

    Science.gov (United States)

    Inoue, Motoki; Sasaki, Makoto; Katada, Yasuyuki; Taguchi, Tetsushi

    2014-02-01

    Novel techniques for creating a strong bond between polymeric matrices and biometals are required. We immobilized polymeric matrices on the surface of biometal for drug-eluting stents through covalent bond. We performed to improve the bonding strength between a cobalt-chromium alloy and a citric acid-crosslinked gelatin matrix by ultraviolet irradiation on the surface of cobalt-chromium alloy. The ultraviolet irradiation effectively generated hydroxyl groups on the surface of the alloy. The bonding strength between the gelatin matrix and the alloy before ultraviolet irradiation was 0.38 ± 0.02 MPa, whereas it increased to 0.48 ± 0.02 MPa after ultraviolet irradiation. Surface analysis showed that the citric acid derivatives occurred on the surface of the cobalt-chromium alloy through ester bond. Therefore, ester bond formation between the citric acid derivatives active esters and the hydroxyl groups on the cobalt-chromium alloy contributed to the enhanced bonding strength. Ultraviolet irradiation and subsequent immobilization of a gelatin matrix using citric acid derivatives is thus an effective way to functionalize biometal surfaces.

  1. Protein-ligand interfaces are polarized: discovery of a strong trend for intermolecular hydrogen bonds to favor donors on the protein side with implications for predicting and designing ligand complexes

    Science.gov (United States)

    Raschka, Sebastian; Wolf, Alex J.; Bemister-Buffington, Joseph; Kuhn, Leslie A.

    2018-02-01

    Understanding how proteins encode ligand specificity is fascinating and similar in importance to deciphering the genetic code. For protein-ligand recognition, the combination of an almost infinite variety of interfacial shapes and patterns of chemical groups makes the problem especially challenging. Here we analyze data across non-homologous proteins in complex with small biological ligands to address observations made in our inhibitor discovery projects: that proteins favor donating H-bonds to ligands and avoid using groups with both H-bond donor and acceptor capacity. The resulting clear and significant chemical group matching preferences elucidate the code for protein-native ligand binding, similar to the dominant patterns found in nucleic acid base-pairing. On average, 90% of the keto and carboxylate oxygens occurring in the biological ligands formed direct H-bonds to the protein. A two-fold preference was found for protein atoms to act as H-bond donors and ligand atoms to act as acceptors, and 76% of all intermolecular H-bonds involved an amine donor. Together, the tight chemical and geometric constraints associated with satisfying donor groups generate a hydrogen-bonding lock that can be matched only by ligands bearing the right acceptor-rich key. Measuring an index of H-bond preference based on the observed chemical trends proved sufficient to predict other protein-ligand complexes and can be used to guide molecular design. The resulting Hbind and Protein Recognition Index software packages are being made available for rigorously defining intermolecular H-bonds and measuring the extent to which H-bonding patterns in a given complex match the preference key.

  2. Hydrolytic Stability of Boronate Ester-Linked Covalent Organic Frameworks

    KAUST Repository

    Li, Huifang

    2018-01-30

    The stability of covalent organic frameworks (COFs) is essential to their applications. However, the common boronate ester-linked COFs are susceptible to attack by nucleophiles (such as water molecules) at the electron-deficient boron sites. To provide an understanding of the hydrolytic stability of the representative boronate ester-linked COF-5 and of the associated hydrolysis mechanisms, density functional theory (DFT) calculations were performed to characterize the hydrolysis reactions of the molecule formed by the condensation of 1,4-phenylenebis(boronic acid) (PBBA) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) monomers; two cases were considered, one dealing with the freestanding molecule and the other with the molecule interacting with COF layers. It was found that the boronate ester (B–O) bond dissociation, which requires one H2O molecule, has a relatively high energy barrier of 22.3 kcal mol−1. However, the presence of an additional H2O molecule significantly accelerates hydrolysis by reducing the energy barrier by a factor of 3. Importantly, the hydrolysis of boronate ester bonds situated in a COF environment follows reaction pathways that are different and have increased energy barriers. These results point to an enhanced hydrolytic stability of COF-5 crystals.

  3. Recent Advances in Adhesive Bonding - The Role of Biomolecules, Nanocompounds, and Bonding Strategies in Enhancing Resin Bonding to Dental Substrates.

    Science.gov (United States)

    Münchow, Eliseu A; Bottino, Marco C

    2017-09-01

    To present an overview on the main agents (i.e., biomolecules and nanocompounds) and/or strategies currently available to amplify or stabilize resin-dentin bonding. According to studies retrieved for full text reading (2014-2017), there are currently six major strategies available to overcome resin-dentin bond degradation: (i) use of collagen crosslinking agents, which may form stable covalent bonds with collagen fibrils, thus strengthening the hybrid layer; (ii) use of antioxidants, which may allow further polymerization reactions over time; (iii) use of protease inhibitors, which may inhibit or inactivate metalloproteinases; (iv) modification of the bonding procedure, which may be performed by using the ethanol wet-bonding technique or by applying an additional adhesive (hydrophobic) coating, thereby strengthening the hybrid layer; (v) laser treatment of the substrate prior to bonding, which may cause specific topographic changes in the surface of dental substrates, increasing bonding efficacy; and (vi) reinforcement of the resin matrix with inorganic fillers and/or remineralizing agents, which may positively enhance physico-mechanical properties of the hybrid layer. With the present review, we contributed to the better understanding of adhesion concepts and mechanisms of resin-dentin bond degradation, showing the current prospects available to solve that problematic. Also, adhesively-bonded restorations may be benefited by the use of some biomolecules, nanocompounds or alternative bonding strategies in order to minimize bond strength degradation.

  4. The chemical bond as an emergent phenomenon.

    Science.gov (United States)

    Golden, Jon C; Ho, Vinh; Lubchenko, Vassiliy

    2017-05-07

    We first argue that the covalent bond and the various closed-shell interactions can be thought of as symmetry broken versions of one and the same interaction, viz., the multi-center bond. We use specially chosen molecular units to show that the symmetry breaking is controlled by density and electronegativity variation. We show that the bond order changes with bond deformation but in a step-like fashion, regions of near constancy separated by electronic localization transitions. These will often cause displacive transitions as well so that the bond strength, order, and length are established self-consistently. We further argue on the inherent relation of the covalent, closed-shell, and multi-center interactions with ionic and metallic bonding. All of these interactions can be viewed as distinct sectors on a phase diagram with density and electronegativity variation as control variables; the ionic and covalent/secondary sectors are associated with on-site and bond-order charge density wave, respectively, the metallic sector with an electronic fluid. While displaying a contiguity at low densities, the metallic and ionic interactions represent distinct phases separated by discontinuous transitions at sufficiently high densities. Multi-center interactions emerge as a hybrid of the metallic and ionic bond that results from spatial coexistence of delocalized and localized electrons. In the present description, the issue of the stability of a compound is that of the mutual miscibility of electronic fluids with distinct degrees of electron localization, supra-atomic ordering in complex inorganic compounds coming about naturally. The notions of electronic localization advanced hereby suggest a high throughput, automated procedure for screening candidate compounds and structures with regard to stability, without the need for computationally costly geometric optimization.

  5. Mechanisms for Covalent Immobilization of Horseradish Peroxidase on Ion-Beam-Treated Polyethylene

    Directory of Open Access Journals (Sweden)

    Alexey V. Kondyurin

    2012-01-01

    Full Text Available The surface of polyethylene was modified by plasma immersion ion implantation. Structure changes including carbonization and oxidation were observed. High surface energy of the modified polyethylene was attributed to the presence of free radicals on the surface. The surface energy decay with storage time after treatment was explained by a decay of the free radical concentration while the concentration of oxygen-containing groups increased with storage time. Horseradish peroxidase was covalently attached onto the modified surface by the reaction with free radicals. Appropriate blocking agents can block this reaction. All aminoacid residues can take part in the covalent attachment process, providing a universal mechanism of attachment for all proteins. The native conformation of attached protein is retained due to hydrophilic interactions in the interface region. The enzymatic activity of covalently attached protein remained high. The long-term activity of the modified layer to attach protein is explained by stabilisation of unpaired electrons in sp2 carbon structures. A high concentration of free radicals can give multiple covalent bonds to the protein molecule and destroy the native conformation and with it the catalytic activity. The universal mechanism of protein attachment to free radicals could be extended to various methods of radiation damage of polymers.

  6. Identification of covalent active site inhibitors of dengue virus protease

    Directory of Open Access Journals (Sweden)

    Koh-Stenta X

    2015-12-01

    Full Text Available Xiaoying Koh-Stenta,1 Joma Joy,1 Si Fang Wang,1 Perlyn Zekui Kwek,1 John Liang Kuan Wee,1 Kah Fei Wan,2 Shovanlal Gayen,1 Angela Shuyi Chen,1 CongBao Kang,1 May Ann Lee,1 Anders Poulsen,1 Subhash G Vasudevan,3 Jeffrey Hill,1 Kassoum Nacro11Experimental Therapeutics Centre, Agency for Science, Technology and Research (A*STAR, Singapore; 2Novartis Institute for Tropical Diseases, Singapore; 3Program in Emerging Infectious Diseases, Duke-NUS Graduate Medical School, SingaporeAbstract: Dengue virus (DENV protease is an attractive target for drug development; however, no compounds have reached clinical development to date. In this study, we utilized a potent West Nile virus protease inhibitor of the pyrazole ester derivative class as a chemical starting point for DENV protease drug development. Compound potency and selectivity for DENV protease were improved through structure-guided small molecule optimization, and protease-inhibitor binding interactions were validated biophysically using nuclear magnetic resonance. Our work strongly suggests that this class of compounds inhibits flavivirus protease through targeted covalent modification of active site serine, contrary to an allosteric binding mechanism as previously described.Keywords: flavivirus protease, small molecule optimization, covalent inhibitor, active site binding, pyrazole ester derivatives

  7. Dynamic signaling cascades: reversible covalent reaction-coupled molecular switches.

    Science.gov (United States)

    Ren, Yulong; You, Lei

    2015-11-11

    The research of systems chemistry exploring complex mixtures of interacting synthetic molecules has been burgeoning recently. Herein we demonstrate for the first time the coupling of molecular switches with a dynamic covalent reaction (DCR) and the modulation of created chemical cascades with a variety of inputs, thus closely mimicking a biological signaling system. A novel Michael type DCR of 10-methylacridinium perchlorate and monothiols exhibiting excellent regioselectivity and tunable affinity was discovered. A delicate balance between the unique reactivity of the reactant and the stability of the adduct leads to the generation of a strong acid in a thermodynamically controlled system. The dynamic cascade was next created via coupling of the DCR and a protonation-induced configurational switch (E/Z isomerization) through a proton relay. Detailed examination of the interdependence of the equilibrium enabled us to rationally optimize the cascade and also shed light on the possible intermediate of the switching process. Furthermore, relative independence of the coupled reactions was verified by the identification of stimuli that are able to facilitate one reaction but suppress the other. To further enhance systematic complexity, a second DCR of electrophilic aldehydes and thiols was employed for the reversible inhibition of the binary system, thus achieving the interplay of multiple equilibria. Finally, a fluorescence switch was turned on through coupling with the DCR, showcasing the versatility of our strategy. The results described herein should pave the way for the exploitation of multifunctional dynamic covalent cascades.

  8. The covalent effect on the energy levels of d2 ions in tetragonal crystal

    International Nuclear Information System (INIS)

    Li, Dong-yang; Du, Mao-lu

    2014-01-01

    In contrast to the traditional method which is unsuitable for the prediction of optical for the transition metal ion in covalence and low-symmetry crystal, this paper reports a new method to investigate the optical properties of d 2 ions in covalent and tetragonal crystals and provides a new energy matrix. By using the energy matrix, the variation of energy levels and of the energy-level splitting as the parameter ε are studied; the energy-levels calculated by energy matrix taking no account of crystal-field parameter B 00 0 and by energy matrix taking account of B 00 0 are compared. It was found that the effect of the difference of covalence factors N t and N e on the energy levels and the energy-level splitting is very important and cannot be neglected when the optical properties of d 2 ions in strong covalent crystals are investigated; B 00 0 has an important contribution to the energy levels and should not be neglected; the different covalence of t 2 and e orbitals should be considered not only in the electrostatic repulsions part of the energy matrix but also in the crystal-field potential part of the energy matrix. The complete matrix is applied to calculate the energy-levels of GaP:V 3+ semiconductor. The calculated results are in agreement with the experiment data

  9. Unique Bond Breaking in Crystalline Phase Change Materials and the Quest for Metavalent Bonding.

    Science.gov (United States)

    Zhu, Min; Cojocaru-Mirédin, Oana; Mio, Antonio M; Keutgen, Jens; Küpers, Michael; Yu, Yuan; Cho, Ju-Young; Dronskowski, Richard; Wuttig, Matthias

    2018-03-23

    Laser-assisted field evaporation is studied in a large number of compounds, including amorphous and crystalline phase change materials employing atom probe tomography. This study reveals significant differences in field evaporation between amorphous and crystalline phase change materials. High probabilities for multiple events with more than a single ion detected per laser pulse are only found for crystalline phase change materials. The specifics of this unusual field evaporation are unlike any other mechanism shown previously to lead to high probabilities of multiple events. On the contrary, amorphous phase change materials as well as other covalently bonded compounds and metals possess much lower probabilities for multiple events. Hence, laser-assisted field evaporation in amorphous and crystalline phase change materials reveals striking differences in bond rupture. This is indicative for pronounced differences in bonding. These findings imply that the bonding mechanism in crystalline phase change materials differs substantially from conventional bonding mechanisms such as metallic, ionic, and covalent bonding. Instead, the data reported here confirm a recently developed conjecture, namely that metavalent bonding is a novel bonding mechanism besides those mentioned previously. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Construction of a Hierarchical Architecture of Covalent Organic Frameworks via a Postsynthetic Approach.

    Science.gov (United States)

    Zhang, Gen; Tsujimoto, Masahiko; Packwood, Daniel; Duong, Nghia Tuan; Nishiyama, Yusuke; Kadota, Kentaro; Kitagawa, Susumu; Horike, Satoshi

    2018-02-21

    Covalent organic frameworks (COFs) represent an emerging class of crystalline porous materials that are constructed by the assembly of organic building blocks linked via covalent bonds. Several strategies have been developed for the construction of new COF structures; however, a facile approach to fabricate hierarchical COF architectures with controlled domain structures remains a significant challenge, and has not yet been achieved. In this study, a dynamic covalent chemistry (DCC)-based postsynthetic approach was employed at the solid-liquid interface to construct such structures. Two-dimensional imine-bonded COFs having different aromatic groups were prepared, and a homogeneously mixed-linker structure and a heterogeneously core-shell hollow structure were fabricated by controlling the reactivity of the postsynthetic reactions. Solid-state nuclear magnetic resonance (NMR) spectroscopy and transmission electron microscopy (TEM) confirmed the structures. COFs prepared by a postsynthetic approach exhibit several functional advantages compared with their parent phases. Their Brunauer-Emmett-Teller (BET) surface areas are 2-fold greater than those of their parent phases because of the higher crystallinity. In addition, the hydrophilicity of the material and the stepwise adsorption isotherms of H 2 O vapor in the hierarchical frameworks were precisely controlled, which was feasible because of the distribution of various domains of the two COFs by controlling the postsynthetic reaction. The approach opens new routes for constructing COF architectures with functionalities that are not possible in a single phase.

  11. Covalent labeling of the hepatic glucagon receptor

    International Nuclear Information System (INIS)

    Herberg, J.T.; Iyengar, R.

    1985-01-01

    The procedure for covalently labeling the hepatic glucagon receptor utilizes the light-sensitive heterobifunctional cross-linker hydroxysuccinimidyl-p-azidobenzoate (HSAB) to link the bound [ 125 I-Tyr 10 ]monoiodoglucagon ([ 125 I]MIG) to the receptor protein. The method involves first the binding of the labeled hormone to its receptor and the removal of the excess unbound label. This is followed by incubation with the cross-linker, in the dark and then under ultraviolet illumination to covalently couple the bound [ 125 I]MIG. HSAB contains an amino reactive group as well as an aryl azide which, upon light activation, is converted to an aryl nitrene that reacts in a chemically unspecific manner

  12. 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.

  13. Theoretical description of metal-ligand bonding within f-element complexes: A successful and necessary interplay between theory and experiment

    International Nuclear Information System (INIS)

    Maldivi, P.; Petit, L.; Vetere, V.; Petit, L.; Adamo, C.

    2007-01-01

    The quantum chemical study presented here shows various aspects of the bonding of lanthanide (La 3+ , Gd 3+ ) and actinide (U 3+ , Am 3+ , Cm 3+ ) ions with N-heterocyclic ligands (poly-azines, BTP: bis(1,2,4-triazinyl)-2,6-pyridine). Several families of complexes, differing by their coordination sphere, have been examined. Clearly, the lanthanide complexes always show a purely ionic bonding. The behaviour of U(III) is also well defined with a more or less strong back bonding interaction whatever the complex is. In contrast, the heavy actinides (Am 3+ and Cm 3+ ) are changeable, with a weak covalent character, going from donation to back donation, depending on the coordination sphere of the complex. (authors)

  14. Shape-Controlled Synthesis and Self-Sorting of Covalent Organic Cage Compounds.

    Science.gov (United States)

    Klotzbach, Stefanie; Beuerle, Florian

    2015-08-24

    The directional bonding approach is a powerful tool to rationally control both shape and stoichiometry of three-dimensional objects built from rigid building blocks under dynamic covalent conditions. Co-condensation of catechol-functionalized tribenzotriquinacene derivatives which have 90° angles between the reactive sites and diboronic acids with bite angles of 60°, 120°, and 180°, led to the efficient formation of, respectively, bipyramidal, tetrahedral, or cubic covalent organic cage compounds in a predictable manner. Investigations on the self-sorting of ternary mixtures containing two competitive boronic acids revealed either narcissistic or social self-sorting depending on the stability of the segregated cages relative to feasible three-component assemblies. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Essential motions in a fungal lipase with bound substrate, covalently attached inhibitor and product

    DEFF Research Database (Denmark)

    Peters, Günther H.J.; Bywater, R.P.

    2002-01-01

    As an aid to understanding the influence of dynamic fluctuations during esterolytic catalysis, we follow protein flexibility at three different steps along the catalytic pathway from substrate binding to product clearance via a covalently attached inhibitor, which represents a transition-state mi......As an aid to understanding the influence of dynamic fluctuations during esterolytic catalysis, we follow protein flexibility at three different steps along the catalytic pathway from substrate binding to product clearance via a covalently attached inhibitor, which represents a transition...... flexibility suggesting that these processes occur along rough energy surfaces with only a few minima. Detailed energetic analyses along the trajectories indicated that in all cases binding is dominated by van der Waals interactions. The carboxylate form of the product is stabilized by a tight hydrogen bond...

  16. 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.

  17. Elucidating How Wood Adhesives Bond to Wood Cell Walls using High-Resolution Solution-State NMR Spectroscopy

    Science.gov (United States)

    Daniel J. Yelle

    2013-01-01

    Some extensively used wood adhesives, such as pMDI (polymeric methylene diphenyl diisocyanate) and PF (phenol formaldehyde) have shown excellent adhesion properties with wood. However, distinguishing whether the strength is due to physical bonds (i.e., van der Waals, London, or hydrogen bond forces) or covalent bonds between the adherend and the adhesive is not fully...

  18. Covalent modification of platelet proteins by palmitate

    International Nuclear Information System (INIS)

    Muszbek, L.; Laposata, M.

    1989-01-01

    Covalent attachment of fatty acid to proteins plays an important role in association of certain proteins with hydrophobic membrane structures. In platelets, the structure of many membrane glycoproteins (GPs) has been examined in detail, but the question of fatty acid acylation of platelet proteins has not been addressed. In this study, we wished to determine (a) whether platelet proteins could be fatty acid acylated; and, if so, (b) whether these modified proteins were present in isolated platelet membranes and cytoskeletal fractions; and (c) if the pattern of fatty acid acylated proteins changed on stimulation of the platelets with the agonist thrombin. We observed that in platelets allowed to incorporate 3H-palmitate, a small percentage (1.37%) of radioactivity incorporated into the cells became covalently bound to protein. Selective cleavage of thioester, thioester plus O-ester, and amide-linked 3H-fatty acids from proteins, and their subsequent analysis by high-performance liquid chromatography (HPLC) indicated that the greatest part of 3H-fatty acid covalently bound to protein was thioester-linked 3H-palmitate. By sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and fluorography, at least ten major radiolabeled proteins were detected. Activation of platelets by thrombin greatly increased the quantity of 3H-palmitoylated proteins associated with the cytoskeleton. Nearly all radiolabeled proteins were recovered in the membrane fraction, indicating that these proteins are either integral or peripheral membrane proteins or proteins tightly associated to membrane constituents. Components of the GPIIb-IIIa complex were not palmitoylated. Thus, platelet proteins are significantly modified posttranslationally by 3H-palmitate, and incorporation of palmitoylated proteins into the cytoskeleton is a prominent component of the platelet response to thrombin stimulation

  19. Electron beam controlled covalent attachment of small organic molecules to graphene.

    Science.gov (United States)

    Markevich, Alexander; Kurasch, Simon; Lehtinen, Ossi; Reimer, Oliver; Feng, Xinliang; Müllen, Klaus; Turchanin, Andrey; Khlobystov, Andrei N; Kaiser, Ute; Besley, Elena

    2016-02-07

    The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C=C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The "standing up" molecules, covalently anchored to graphene, exhibit two types of oscillatory motion--bending and twisting--caused by the presence of acoustic phonons in graphene and dispersion attraction to the substrate. The theoretically derived mechanisms are confirmed by near atomic resolution imaging of individual perchlorocoronene (C24Cl12) molecules on graphene. Our results facilitate the understanding of controlled functionalization of graphene employing electron irradiation as well as mechanisms of attachment of impurities via the processing of graphene nanoelectronic devices by electron beam lithography.

  20. Clustering of carboxylated magnetite nanoparticles through polyethylenimine: Covalent versus electrostatic approach

    Science.gov (United States)

    Tóth, Ildikó Y.; Nesztor, Dániel; Novák, Levente; Illés, Erzsébet; Szekeres, Márta; Szabó, Tamás; Tombácz, Etelka

    2017-04-01

    Carboxylated magnetite nanoparticles (MNPs) are frequently used to develop materials with enhanced properties for MRI and hyperthermia. The controlled clustering of MNPs via covalent or electrostatic approaches provides opportunity to prepare high quality materials. MNPs were prepared by co-precipitation and coated by poly(acrylic acid-co-maleic acid) (PAM@MNP). The clusters were synthesized from purified PAM@MNPs and polyethylenimine (PEI) solution via electrostatic interaction and covalent bond formation (ES-cluster and CB-cluster, respectively). The electrostatic adhesion (-NH3+ and -COO-) and the formed amide bond were confirmed by ATR-FTIR. The averaged area of CB-clusters was about twice as large as that of ES-cluster, based on TEM. The SAXS results showed that the surface of MNPs was smooth and the nanoparticles were close packed in both clusters. The pH-dependent aggregation state and zeta potential of clusters were characterized by DLS and electrophoresis measurements, the clusters were colloidally stable at pH>5. In hyperthermia experiments, the values of SAR were about two times larger for the chemically bonded cluster. The MRI studies showed exceptionally high transversion relaxivities, the r2 values are 457 mM-1 s-1 and 691 mM-1 s-1 for ES-cluster and CB-cluster, respectively. Based on these results, the chemically clustered product shows greater potential for feasible biomedical applications.

  1. Use of Synergistic Interactions to Fabricate Strong, Tough, and Conductive Artificial Nacre Based on Graphene Oxide and Chitosan.

    Science.gov (United States)

    Wan, Sijie; Peng, Jingsong; Li, Yuchen; Hu, Han; Jiang, Lei; Cheng, Qunfeng

    2015-10-27

    Graphene is the strongest and stiffest material, leading to the development of promising applications in many fields. However, the assembly of graphene nanosheets into macrosized nanocomposites for practical applications remains a challenge. Nacre in its natural form sets the "gold standard" for toughness and strength, which serves as a guide to the assembly of graphene nanosheets into high-performance nanocomposites. Here we show the strong, tough, conductive artificial nacre based on graphene oxide through synergistic interactions of hydrogen and covalent bonding. Tensile strength and toughness was 4 and 10 times higher, respectively, than that of natural nacre. The exceptional integrated strong and tough artificial nacre has promising applications in aerospace, artificial muscle, and tissue engineering, especially for flexible supercapacitor electrodes due to its high electrical conductivity. The use of synergistic interactions is a strategy for the development of high-performance nanocomposites.

  2. A hydrazone covalent organic polymer based micro-solid phase extraction for online analysis of trace Sudan dyes in food samples.

    Science.gov (United States)

    Zhang, Chengjiang; Li, Gongke; Zhang, Zhuomin

    2015-11-06

    Covalent organic polymers (COPs) connected by covalent bonds are a new class of porous network materials with large surface area and potential superiority in sample pretreatment. In this study, a new hydrazone linked covalent organic polymer (HL-COP) adsorbent was well-designed and synthesized based on a simple Schiff-base reaction. The condensation of 1,4-phthalaldehyde and 1,3,5-benzenetricarbohydrazide as organic building blocks led to the synthesis of HL-COP with uniform particle size and good adsorption performance. This HL-COP adsorbent with high hydrophobic property and rich stacking π electrons contained abundant phenyl rings and imine (CN) groups throughout the entire molecular framework. The adsorption mechanism was explored and discussed based on π-π affinity, hydrophobic effect, hydrogen bonding and electron-donor-acceptor (EDA) interaction, which contributed to its strong recognition affinity to target compounds. Enrichment factors were 305-757 for six Sudan dyes by HL-COP micro-solid phase extraction (μ-SPE), indicating its remarkable preconcentration ability. Furthermore, the adsorption amounts by HL-COP μ-SPE were 1.0-11.0 folds as those by three commonly used commercial adsorbents. Then, HL-COP was applied as adsorbent of online μ-SPE coupled with high performance liquid chromatography (HPLC) for enrichment and analysis of trace Sudan dyes in food samples with detection limit of 0.03-0.15μg/L. The method was successfully applied for online analysis of chilli powder and sausage samples. Sudan II and Sudan III in one positive chilli powder sample were actually found and determined with concentrations of 8.3 and 6.8μg/kg, respectively. The recoveries of chilli powder and sausage samples were in range of 75.8-108.2% and 73.8-112.6% with relative standard deviations of 1.2-8.5% and 1.9-9.4% (n=5), respectively. The proposed method was accurate, reliable and convenient for the online simultaneous analysis of trace Sudan dyes in food samples

  3. Non-covalent synthesis of organic nanostructures

    NARCIS (Netherlands)

    Prins, L.J.; Timmerman, P.; Reinhoudt, David

    1998-01-01

    This review describes the synthesis, characterization and functionalization of hydrogen bonded, box-like assemblies. These assemblies are formed upon mixing bismelamine calix[4]arenes with a complementary barbiturate in apolar solvents. Various techniques for the characterization have been used,

  4. The nature of chemical bonds from PNOF5 calculations.

    Science.gov (United States)

    Matxain, Jon M; Piris, Mario; Uranga, Jon; Lopez, Xabier; Merino, Gabriel; Ugalde, Jesus M

    2012-06-18

    Natural orbital functional theory (NOFT) is used for the first time in the analysis of different types of chemical bonds. Concretely, the Piris natural orbital functional PNOF5 is used. It provides a localization scheme that yields an orbital picture which agrees very well with the empirical valence shell electron pair repulsion theory (VSEPR) and Bent's rule, as well as with other theoretical pictures provided by valence bond (VB) or linear combination of atomic orbitals-molecular orbital (LCAO-MO) methods. In this context, PNOF5 provides a novel tool for chemical bond analysis. In this work, PNOF5 is applied to selected molecules that have ionic, polar covalent, covalent, multiple (σ and π), 3c-2e, and 3c-4e bonds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Design Principles for Covalent Organic Frameworks as Efficient Electrocatalysts in Clean Energy Conversion and Green Oxidizer Production.

    Science.gov (United States)

    Lin, Chun-Yu; Zhang, Lipeng; Zhao, Zhenghang; Xia, Zhenhai

    2017-05-01

    Covalent organic frameworks (COFs), an emerging class of framework materials linked by covalent bonds, hold potential for various applications such as efficient electrocatalysts, photovoltaics, and sensors. To rationally design COF-based electrocatalysts for oxygen reduction and evolution reactions in fuel cells and metal-air batteries, activity descriptors, derived from orbital energy and bonding structures, are identified with the first-principle calculations for the COFs, which correlate COF structures with their catalytic activities. The calculations also predict that alkaline-earth metal-porphyrin COFs could catalyze the direct production of H 2 O 2 , a green oxidizer and an energy carrier. These predictions are supported by experimental data, and the design principles derived from the descriptors provide an approach for rational design of new electrocatalysts for both clean energy conversion and green oxidizer production. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Electrospinning covalently cross-linking biocompatible hydrogelators

    Science.gov (United States)

    Schultz, Kelly M.; Campo-Deaño, Laura; Baldwin, Aaron D.; Kiick, Kristi L.; Clasen, Christian; Furst, Eric M.

    2012-01-01

    Many hydrogel materials of interest are homogeneous on the micrometer scale. Electrospinning, the formation of sub-micrometer to micrometer diameter fibers by a jet of fluid formed under an electric field, is one process being explored to create rich microstructures. However, electrospinning a hydrogel system as it reacts requires an understanding of the gelation kinetics and corresponding rheology near the liquid-solid transition. In this study, we correlate the structure of electrospun fibers of a covalently cross-linked hydrogelator with the corresponding gelation transition and kinetics. Polyethylene oxide (PEO) is used as a carrier polymer in a chemically cross-linking poly(ethylene glycol)-high molecular weight heparin (PEG-HMWH) hydrogel. Using measurements of gelation kinetics from multiple particle tracking microrheology (MPT), we correlate the material rheology with the the formation of stable fibers. An equilibrated, cross-linked hydrogel is then spun and the PEO is dissolved. In both cases, microstructural features of the electrospun fibers are retained, confirming the covalent nature of the network. The ability to spin fibers of a cross-linking hydrogel system ultimately enables the engineering of materials and microstructural length scales suitable for biological applications. PMID:23459473

  7. Clustering of carboxylated magnetite nanoparticles through polyethylenimine: Covalent versus electrostatic approach

    Energy Technology Data Exchange (ETDEWEB)

    Tóth, Ildikó Y., E-mail: Ildiko.Toth@chem.u-szeged.hu [Department of Physical Chemistry and Materials Science, University of Szeged, Aradi vt. square 1, Szeged (Hungary); Nesztor, Dániel [Department of Physical Chemistry and Materials Science, University of Szeged, Aradi vt. square 1, Szeged (Hungary); Novák, Levente [Department of Colloid and Environmental Chemistry, University of Debrecen, Egyetem square 1, Debrecen (Hungary); Illés, Erzsébet; Szekeres, Márta; Szabó, Tamás [Department of Physical Chemistry and Materials Science, University of Szeged, Aradi vt. square 1, Szeged (Hungary); Tombácz, Etelka, E-mail: tombacz@chem.u-szeged.hu [Department of Physical Chemistry and Materials Science, University of Szeged, Aradi vt. square 1, Szeged (Hungary)

    2017-04-01

    Carboxylated magnetite nanoparticles (MNPs) are frequently used to develop materials with enhanced properties for MRI and hyperthermia. The controlled clustering of MNPs via covalent or electrostatic approaches provides opportunity to prepare high quality materials. MNPs were prepared by co-precipitation and coated by poly(acrylic acid-co-maleic acid) (PAM@MNP). The clusters were synthesized from purified PAM@MNPs and polyethylenimine (PEI) solution via electrostatic interaction and covalent bond formation (ES-cluster and CB-cluster, respectively). The electrostatic adhesion (–NH{sub 3}{sup +} and –COO{sup –}) and the formed amide bond were confirmed by ATR-FTIR. The averaged area of CB-clusters was about twice as large as that of ES-cluster, based on TEM. The SAXS results showed that the surface of MNPs was smooth and the nanoparticles were close packed in both clusters. The pH-dependent aggregation state and zeta potential of clusters were characterized by DLS and electrophoresis measurements, the clusters were colloidally stable at pH>5. In hyperthermia experiments, the values of SAR were about two times larger for the chemically bonded cluster. The MRI studies showed exceptionally high transversion relaxivities, the r{sub 2} values are 457 mM{sup −1} s{sup −1} and 691 mM{sup −1} s{sup −1} for ES-cluster and CB-cluster, respectively. Based on these results, the chemically clustered product shows greater potential for feasible biomedical applications. - Highlights: • Chemically bonded clusters (CB-cluster) were prepared from PEI and PAM-coated MNPs. • The electrostatically clustered units (ES-cluster) are smaller and more compact. • The electrostatic adhesion and the amide bond formation were confirmed by ATR-FTIR. • CB-cluster dispersions are colloidally stable under physiological conditions. • CB-cluster shows great potential for application in MRI and hyperthermia.

  8. Dispersive and Covalent Interactions between Graphene and Metal Surfaces from the Random Phase Approximation

    DEFF Research Database (Denmark)

    Olsen, Thomas; Yan, Jun; Mortensen, Jens Jørgen

    2011-01-01

    We calculate the potential energy surfaces for graphene adsorbed on Cu(111), Ni(111), and Co(0001) using density functional theory and the random phase approximation (RPA). For these adsorption systems covalent and dispersive interactions are equally important and while commonly used approximations...... for exchange-correlation functionals give inadequate descriptions of either van der Waals or chemical bonds, RPA accounts accurately for both. It is found that the adsorption is a delicate competition between a weak chemisorption minimum close to the surface and a physisorption minimum further from the surface....

  9. New technology for regiospecific covalent coupling of polysaccharide antigens in ELISA for serological detection

    DEFF Research Database (Denmark)

    Jauho, E.S.; Boas, Ulrik; Wiuff, Camilla

    2000-01-01

    into the lipid A part and the polysaccharide part. The polysaccharide was conjugated regiospecifically to a photochemically active compound, anthraquinone, resulting in a polysaccharide-anthraquinone conjugate. Anthraquinones forms active radicals when exposed to soft UV irradiation (350 nm) permitting...... the formation of stable covalent bonds to polymers e.g, microtiter plates. By this technique the polysaccharides are bound through the anthraquinone part of the polysaccharide-anthraquinone conjugates to the microtiter plates. This minimizes denaturation of O-antigen epitopes during binding to the microtiter...

  10. Atomic structures and covalent-to-metallic transition of lead clusters Pbn (n=2-22)

    International Nuclear Information System (INIS)

    Wang Baolin; Zhao Jijun; Chen Xiaoshuang; Shi Daning; Wang Guanghou

    2005-01-01

    The lowest-energy structures and electronic properties of the lead clusters are studied by density-functional-theory calculations with Becke-Lee-Yang-Parr gradient correction. The lowest-energy structures of Pb n (n=2-22) clusters are determined from a number of structural isomers, which are generated from empirical genetic algorithm simulations. The competition between atom-centered compact structures and layered stacking structures leads to the alternative appearance of the two types of structures as global minimum. The size evolution of geometric and electronic properties from covalent bonding towards bulk metallic behavior in Pb clusters is discussed

  11. High strength films from oriented, hydrogen-bonded "graphamid" 2D polymer molecular ensembles.

    Science.gov (United States)

    Sandoz-Rosado, Emil; Beaudet, Todd D; Andzelm, Jan W; Wetzel, Eric D

    2018-02-27

    The linear polymer poly(p-phenylene terephthalamide), better known by its tradename Kevlar, is an icon of modern materials science due to its remarkable strength, stiffness, and environmental resistance. Here, we propose a new two-dimensional (2D) polymer, "graphamid", that closely resembles Kevlar in chemical structure, but is mechanically advantaged by virtue of its 2D structure. Using atomistic calculations, we show that graphamid comprises covalently-bonded sheets bridged by a high population of strong intermolecular hydrogen bonds. Molecular and micromechanical calculations predict that these strong intermolecular interactions allow stiff, high strength (6-8 GPa), and tough films from ensembles of finite graphamid molecules. In contrast, traditional 2D materials like graphene have weak intermolecular interactions, leading to ensembles of low strength (0.1-0.5 GPa) and brittle fracture behavior. These results suggest that hydrogen-bonded 2D polymers like graphamid would be transformative in enabling scalable, lightweight, high performance polymer films of unprecedented mechanical performance.

  12. Covalently functionalized carbon nanostructures and methods for their separation

    Science.gov (United States)

    Wang, YuHuang; Brozena, Alexandra H; Deng, Shunliu; Zhang, Yin

    2015-03-17

    The present invention is directed to carbon nanostructures, e.g., carbon nanotubes, methods of covalently functionalizing carbon nanostructures, and methods of separating and isolating covalently functionalized carbon. In some embodiments, carbon nanotubes are reacted with alkylating agents to provide water soluble covalently functionalized carbon nanotubes. In other embodiments, carbon nanotubes are reacted with a thermally-responsive agent and exposed to light in order to separate carbon nanotubes of a specific chirality from a mixture of carbon nanotubes.

  13. Probing molecular adsorbates with core-level spectroscopies: Electronic structure and bonding models

    Science.gov (United States)

    Fohlisch, Alexander

    Resonantly excited X-ray emission spectroscopy has been applied to study the valence electronic structure of molecular adsorbates in an atom specific and orbital symmetry selective manner. In combination with ab initio cluster calculations, electronic structure and bonding models have been derived. Existing models of surface chemical bonding have been reviewed and partially revised. Most notably, the bonding mechanism of carbon monoxide (CO) on transition and noble metals has been revised and is found to be the result of a strong covalent interaction between the CO orbitals and the metal bands within each orbital symmetry. A characteristic allylic configuration is found in the π system and strong polarization within the σ system. The equilibrium properties of adsorbed CO are the direct result of a balance between the repulsive σ-interaction and the attractive π-interaction both in terms of the total energy and the local bond properties. The bonding of ammonia (NH3) on the Cu(110) surface is found to be dominated by a large covalent interaction, which contrasts the previous model of a strong electrostatic interaction. Furthermore, adsorbate-adsorbate interaction leads to a tilted adsorption geometry. Ethylene (C2H4) on Cu(110) is adsorbed in the di-σ configuration, according to the generally accepted Dewar Chatt Duncanson model for hydrocarbon adsorption. The application and interpretation of resonantly excited X-ray emission on these systems also required a thorough discussion of the spectroscopic process. Another topic was the vibrational fine structure in the X-ray photoemission core-level main lines of adsorbed molecules. The observation of the vibrational fine structure in molecular adsorbates is remarkable, as it was previously thought impossible to observe due to solid state broadening contributions. A detailed analysis of the vibrational fine structure and the line profile makes it possible to study the electronic and geometric properties of the core

  14. Chemical bonding and charge density distribution analysis of ...

    Indian Academy of Sciences (India)

    The mid bond electron density values revealed the enhancement of covalent nature between titanium and oxygen ions and predominant ionic nature between barium and oxygen ions. Average grain sizes were estimated for the undoped and doped samples. SEM investigations showed the existence of smaller grains with ...

  15. Structure, bonding and energetics of N-heterocyclic carbene (NHC ...

    Indian Academy of Sciences (India)

    Mayer bond order and AIM indices. It is also rela- tively less sensitive to basis functions.68 The FBO is also consistent with WBI. The donor-acceptor NBO second order interaction ( Eij)61 energies have also been estimated. It is noticed that there is non-covalent interaction between N-H group of NHC and X, form- ing some ...

  16. Environmentally dependent bond-order potentials: New ...

    Indian Academy of Sciences (India)

    Environmentally dependent bond-order potentials: New developments and applications ... for modelling amorphous structure we found that the and bond integrals are not only transferable between graphite and diamond structures but they are also strongly anisotropic due to inter-plan bonding between graphite sheets.

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

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, T.

    2006-05-22

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

  18. Environmentally dependent bond-order potentials: New ...

    Indian Academy of Sciences (India)

    Firstly, we have found that a simple pair potential is unsuitable for describing the environmental screening effects due to the and orbital overlap repulsion in transition metal alloys and therefore the inability to reproduce the negative Cauchy pressures exhibiting in strong covalent systems. By adding the environmental ...

  19. Hydrogen Bonds and Life in the Universe.

    Science.gov (United States)

    Vladilo, Giovanni; Hassanali, Ali

    2018-01-03

    The scientific community is allocating more and more resources to space missions and astronomical observations dedicated to the search for life beyond Earth. This experimental endeavor needs to be backed by a theoretical framework aimed at defining universal criteria for the existence of life. With this aim in mind, we have explored which chemical and physical properties should be expected for life possibly different from the terrestrial one, but similarly sustained by genetic and catalytic molecules. We show that functional molecules performing genetic and catalytic tasks must feature a hierarchy of chemical interactions operating in distinct energy bands. Of all known chemical bonds and forces, only hydrogen bonds are able to mediate the directional interactions of lower energy that are needed for the operation of genetic and catalytic tasks. For this reason and because of the unique quantum properties of hydrogen bonding, the functional molecules involved in life processes are predicted to have extensive hydrogen-bonding capabilities. A molecular medium generating a hydrogen-bond network is probably essential to support the activity of the functional molecules. These hydrogen-bond requirements constrain the viability of hypothetical biochemistries alternative to the terrestrial one, provide thermal limits to life molecular processes, and offer a conceptual framework to define a transition from a "covalent-bond stage" to a "hydrogen-bond stage" in prebiotic chemistry.

  20. Hydrogen Bonds and Life in the Universe

    Science.gov (United States)

    2018-01-01

    The scientific community is allocating more and more resources to space missions and astronomical observations dedicated to the search for life beyond Earth. This experimental endeavor needs to be backed by a theoretical framework aimed at defining universal criteria for the existence of life. With this aim in mind, we have explored which chemical and physical properties should be expected for life possibly different from the terrestrial one, but similarly sustained by genetic and catalytic molecules. We show that functional molecules performing genetic and catalytic tasks must feature a hierarchy of chemical interactions operating in distinct energy bands. Of all known chemical bonds and forces, only hydrogen bonds are able to mediate the directional interactions of lower energy that are needed for the operation of genetic and catalytic tasks. For this reason and because of the unique quantum properties of hydrogen bonding, the functional molecules involved in life processes are predicted to have extensive hydrogen-bonding capabilities. A molecular medium generating a hydrogen-bond network is probably essential to support the activity of the functional molecules. These hydrogen-bond requirements constrain the viability of hypothetical biochemistries alternative to the terrestrial one, provide thermal limits to life molecular processes, and offer a conceptual framework to define a transition from a “covalent-bond stage” to a “hydrogen-bond stage” in prebiotic chemistry. PMID:29301382

  1. Rehealable, fully recyclable, and malleable electronic skin enabled by dynamic covalent thermoset nanocomposite.

    Science.gov (United States)

    Zou, Zhanan; Zhu, Chengpu; Li, Yan; Lei, Xingfeng; Zhang, Wei; Xiao, Jianliang

    2018-02-01

    Electronic skin (e-skin) mimicking functionalities and mechanical properties of natural skin can find broad applications. We report the first dynamic covalent thermoset-based e-skin, which is connected through robust covalent bonds, rendering the resulting devices good chemical and thermal stability at service condition. By doping the dynamic covalent thermoset with conductive silver nanoparticles, we demonstrate a robust yet rehealable, fully recyclable, and malleable e-skin. Tactile, temperature, flow, and humidity sensing capabilities are realized. The e-skin can be rehealed when it is damaged and can be fully recycled at room temperature, which has rarely, if at all, been demonstrated for e-skin. After rehealing or recycling, the e-skin regains mechanical and electrical properties comparable to the original e-skin. In addition, malleability enables the e-skin to permanently conform to complex, curved surfaces without introducing excessive interfacial stresses. These properties of the e-skin yield an economical and eco-friendly technology that can find broad applications in robotics, prosthetics, health care, and human-computer interface.

  2. Overall conformation of covalently stabilized domain-swapped dimer of human cystatin C in solution

    Science.gov (United States)

    Murawska, Magdalena; Szymańska, Aneta; Grubb, Anders; Kozak, Maciej

    2017-11-01

    Human cystatin C (HCC), a small protein, plays a crucial role in inhibition of cysteine proteases. The most common structural form of human cystatin C in crystals is a dimer, which has been evidenced both for the native protein and its mutants. In these structures, HCC dimers were formed through the mechanism of domain swapping. The structure of the monomeric form of human cystatin C was determined for V57N mutant and the mutant with the engineered disulfide bond (L47C)-(G69C) (known as stab1-HCC). On the basis of stab1-HCC, a number of covalently stabilized oligomers, including also dimers have been obtained. The aim of this study was to analyze the structure of the covalently stabilized dimer HCC in solution by the small angle X-ray scattering (SAXS) technique and synchrotron radiation. Experimental data confirmed that in solution this protein forms a dimer, which is characterized by the radius of gyration RG = 3.1 nm and maximum intramolecular distance Dmax = 10.3 nm. Using the ab initio method and program DAMMIN, we propose a low resolution structure of stabilized covalently cystatin C in solution. Stab-HCC dimer adopts in solution an elongated conformation, which is well reconstructed by the ab initio model.

  3. Watson-Crick hydrogen bonds : Nature and role in DNA replication

    NARCIS (Netherlands)

    Guerra, Célia Fonseca; Bickelhaupt, F. Matthias

    2006-01-01

    The hydrogen bonds in DNA Watson–Crick base pairs have long been considered predominantly electrostatic phenomena. In this chapter, we show with state-of-the-art calculations that this is not true and that electrostatic interactions and covalent contributions in these hydrogen bonds are in fact of

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

    DEFF Research Database (Denmark)

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

    2010-01-01

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

  5. Revisiting nitrogen species in covalent triazine frameworks

    KAUST Repository

    Osadchii, Dmitrii Yu.

    2017-11-28

    Covalent triazine frameworks (CTFs) are porous organic materials promising for applications in catalysis and separation due to their high stability, adjustable porosity and intrinsic nitrogen functionalities. CTFs are prepared by ionothermal trimerization of aromatic nitriles, however, multiple side reactions also occur under synthesis conditions, and their influence on the material properties is still poorly described. Here we report the systematic characterization of nitrogen in CTFs using X-ray photoelectron spectroscopy (XPS). With the use of model compounds, we could distinguish several types of nitrogen species. By combining these data with textural properties, we unravel the influence that the reaction temperature, the catalyst and the monomer structure and composition have on the properties of the resulting CTF materials.

  6. Polymers incorporating covalently attached organoimido polyoxometalates

    Science.gov (United States)

    Maatta, Eric A.; Moore, Aaron R.

    2004-03-16

    New polyoxometalate compounds and polymers comprising recurring monomers of those compounds are provided. The compounds are formed by replacing at least one oxide of the starting polyoxometalate with an organoimido (NR) group bonded to the polyoxometalate via a triple bond to the nitrogen atom. The R of the (NR) group comprises a reactive functional group which renders the compound readily polymerizable, alone or with other monomers (e.g., divinylbenzene), to form the inventive polymers. Additionally, a countercation (e.g., bis(tetra-n-butylammonium)) can be mixed with the polyoxometalate compounds in order to neutralize the negative charge thereof as well as to make those compounds more soluble in organic solvents.

  7. DNA Linked To Single Wall Carbon Nanotubes: Covalent Versus Non-Covalent Approach

    Science.gov (United States)

    Chung, C.-L.; Nguyen, K.; Lyonnais, S.; Streiff, S.; Campidelli, S.; Goux-Capes, L.; Bourgoin, J.-P.; Filoramo, A.

    2008-10-01

    Nanometer-scale structures represent a novel and intriguing field, where scientists and engineers manipulate materials at the atomic and molecular scale levels to produce innovative materials. Carbon nanotubes constitute a relatively new class of materials exhibiting exceptional mechanical and electronic properties and were found to be promising candidates for molecular electronics, sensing or biomedical applications. Considering the bottom-up strategy in nanotechnology, the combination of the recognition properties of DNA with the electronic properties of single walled carbon nanotubes (SWNTs) seems to be a promising approach for the future of electronics. With the aim to assemble DNA with SWNTs, two complementary strategies have been envisioned: the covalent linkage of DNA on carboxylic groups of SWNTs under classical coupling condition and the non-covalent approach based on biotin-streptavidin molecular recognition properties. Here, we present and compare the results that we obtained with these two different methods; we want to objectively show the advantages and disadvantages of each approach.

  8. Constant time INEPT CT-HSQC (CTi-CT-HSQC) – A new NMR method to measure accurate one-bond J and RDCs with strong 1H–1H couplings in natural abundance

    NARCIS (Netherlands)

    Yu, B.; van Ingen, H.|info:eu-repo/dai/nl/297054651; Freedberg, D.I.

    2013-01-01

    Strong (1)H-(1)H coupling can significantly reduce the accuracy of (1)J(CH) measured from frequency differences in coupled HSQC spectra. Although accurate (1)J(CH) values can be extracted from spectral simulation, it would be more convenient if the same accurate (1)J(CH) values can be obtained

  9. Molecular electrostatic potential analysis of non-covalent complexes

    Indian Academy of Sciences (India)

    and acceptor atoms due to complex formation) and interaction energy, Eint for a large variety of the non- covalent dimers in the categories HB, DHB, and XB. The MESP based eDA concept proposed by Mohan and. Suresh has unified the HB, DHB, and XB non-covalent complexes in a single category, the eDA complex.61.

  10. Formation and properties of electroactive fullerene based films with a covalently attached ferrocenyl redox probe

    International Nuclear Information System (INIS)

    Wysocka-Zolopa, Monika; Winkler, Krzysztof; Caballero, Ruben; Langa, Fernando

    2011-01-01

    Highlights: → Formation of redox active films of ferrocene derivatives of C 60 and palladium. → Fullerene moieties are covalently bonded to palladium atoms to form a polymeric network. → Electrochemical activity at both positive and negative potentials. → Charge transfer processes accompanied by transport of supporting electrolyte to and from the polymer layers. - Abstract: Redox active films have been produced via electrochemical reduction in a solution containing palladium(II) acetate and ferrocene derivatives of C 60 (Fc-C 60 and bis-Fc-C 60 ). In these films, fullerene moieties are covalently bonded to palladium atoms to form a polymeric network. Fc-C 60 /Pd and bis-Fc-C 60 /Pd films form uniform and relatively smooth layers on the electrode surface. These films are electrochemically active in both the positive and negative potential regions. At negative potentials, reduction of fullerene moiety takes place resulting in voltammetric behavior resembles typical of conducting polymers. In the positive potential range, oxidation of ferrocene is responsible for the formation of a sharp and symmetrical peak on the voltammograms. In this potential range, studied films behave as typical redox polymers. The charge associated with the oxidation process depends on the number of ferrocene units attached to the C 60 moiety. Oxidation and reduction of these redox active films are accompanied by transport of supporting electrolyte to and from the polymer layer. Films also show a higher permeability to anions than to cations.

  11. Grism manufacturing by low temperature mineral bonding

    Science.gov (United States)

    Kalkowski, G.; Grabowski, K.; Harnisch, G.; Flügel-Paul, T.; Zeitner, U.; Risse, S.

    2017-09-01

    By uniting a grating with a prism to a GRISM compound, the optical characteristics of diffractive and refractive elements can be favorably combined to achieve outstanding spectral resolution features. Ruling the grating structure into the prism surface is common for wavelengths around 1 μm and beyond, while adhesive bonding of two separate parts is generally used for shorter wavelengths and finer structures. We report on a manufacturing approach for joining the corresponding glass elements by the technology of hydrophilic direct bonding. This allows to manufacture the individual parts separately and subsequently combine them quasimonolithically by generating stiff and durable bonds of vanishing thickness, high strength and excellent transmission. With this approach for GRISM bonding, standard direct-write- or mask-lithography equipment may be used for the fabrication of the grating structure and the drawbacks of adhesive bonding (thermal mismatch, creep, aging) are avoided. The technology of hydrophilic bonding originates from "classical" optical contacting [1], but has been much improved and perfected during the last decades in the context of 3-dimensinal stacking Si-wafers for microelectronic applications [2]. It provides joins through covalent bonds of the Si-O-Si type at the nanometer scale, i.e. the elementary bond type in many minerals and glasses. The mineral nature of the bond is perfectly adapted to most optical materials and the extremely thin bonding layers generated with this technology are well suited for transmission optics. Creeping under mechanical load, as commonly observed with adhesive bonding, is not an issue. With respect to diffusion bonding, which operates at rather high temperatures close to the glass transition or crystal melting point, hydrophilic bonding is a low temperature process that needs only moderate heating. This facilitates provision of handling and alignment means for the individual parts during the set-up stages and greatly

  12. Oxygen Evolution at Manganite Perovskite Ruddlesden-Popper Type Particles: Trends of Activity on Structure, Valence and Covalence

    Directory of Open Access Journals (Sweden)

    Majid Ebrahimizadeh Abrishami

    2016-11-01

    Full Text Available An improved understanding of the correlation between the electronic properties of Mn-O bonds, activity and stability of electro-catalysts for the oxygen evolution reaction (OER is of great importance for an improved catalyst design. Here, an in-depth study of the relation between lattice structure, electronic properties and catalyst performance of the perovskite Ca1−xPrxMnO3 and the first-order RP-system Ca2−xPrxMnO4 at doping levels of x = 0, 0.25 and 0.5 is presented. Lattice structure is determined by X-ray powder diffraction and Rietveld refinement. X-ray absorption spectroscopy of Mn-L and O-K edges gives access to Mn valence and covalency of the Mn-O bond. Oxygen evolution activity and stability is measured by rotating ring disc electrode studies. We demonstrate that the highest activity and stability coincidences for systems with a Mn-valence state of +3.7, though also requiring that the covalency of the Mn-O bond has a relative minimum. This observation points to an oxygen evolution mechanism with high redox activity of Mn. Covalency should be large enough for facile electron transfer from adsorbed oxygen species to the MnO6 network; however, it should not be hampered by oxidation of the lattice oxygen, which might cause a crossover to material degradation. Since valence and covalency changes are not entirely independent, the introduction of the energy position of the eg↑ pre-edge peak in the O-K spectra as a new descriptor for oxygen evolution is suggested, leading to a volcano-like representation of the OER activity.

  13. How resonance assists hydrogen bonding interactions: an energy decomposition analysis.

    Science.gov (United States)

    Beck, John Frederick; Mo, Yirong

    2007-01-15

    Block-localized wave function (BLW) method, which is a variant of the ab initio valence bond (VB) theory, was employed to explore the nature of resonance-assisted hydrogen bonds (RAHBs) and to investigate the mechanism of synergistic interplay between pi delocalization and hydrogen-bonding interactions. We examined the dimers of formic acid, formamide, 4-pyrimidinone, 2-pyridinone, 2-hydroxpyridine, and 2-hydroxycyclopenta-2,4-dien-1-one. In addition, we studied the interactions in beta-diketone enols with a simplified model, namely the hydrogen bonds of 3-hydroxypropenal with both ethenol and formaldehyde. The intermolecular interaction energies, either with or without the involvement of pi resonance, were decomposed into the Hitler-London energy (DeltaEHL), polarization energy (DeltaEpol), charge transfer energy (DeltaECT), and electron correlation energy (DeltaEcor) terms. This allows for the examination of the character of hydrogen bonds and the impact of pi conjugation on hydrogen bonding interactions. Although it has been proposed that resonance-assisted hydrogen bonds are accompanied with an increasing of covalency character, our analyses showed that the enhanced interactions mostly originate from the classical dipole-dipole (i.e., electrostatic) attraction, as resonance redistributes the electron density and increases the dipole moments in monomers. The covalency of hydrogen bonds, however, changes very little. This disputes the belief that RAHB is primarily covalent in nature. Accordingly, we recommend the term "resonance-assisted binding (RAB)" instead of "resonance-assisted hydrogen bonding (RHAB)" to highlight the electrostatic, which is a long-range effect, rather than the electron transfer nature of the enhanced stabilization in RAHBs. Copyright (c) 2006 Wiley Periodicals, Inc.

  14. Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran

    Czech Academy of Sciences Publication Activity Database

    Schrauben, J. N.; Akdag, A.; Wen, Jin; Havlas, Zdeněk; Ryerson, J. L.; Smith, M. B.; Michl, Josef; Johnson, J. C.

    2016-01-01

    Roč. 120, č. 20 (2016), s. 3473-3483 ISSN 1089-5639 R&D Projects: GA ČR GA15-19143S Institutional support: RVO:61388963 Keywords : intramolecular singlet fission * density functional theory * exciton fission Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.847, year: 2016

  15. Bonding characteristics, thermal expansibility, and compressibility of RXO(4) (R = rare earths, X = P, As) within monazite and zircon structures.

    Science.gov (United States)

    Li, Huaiyong; Zhang, Siyuan; Zhou, Shihong; Cao, Xueqiang

    2009-05-18

    Systematically theoretical research was performed on the monazite- and zircon-structure RXO(4) (R = Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; X = P, As) series by using the chemical bond theory of dielectric description. The chemical bond properties of R-O and X-O bonds were presented. In the zircon phase, the covalency fractions of X-O bonds increased in the order of V-O zircon phases.

  16. New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

    Directory of Open Access Journals (Sweden)

    Pavel Nagorny

    2016-12-01

    Full Text Available Hydrogen bond donor catalysis represents a rapidly growing subfield of organocatalysis. While traditional hydrogen bond donors containing N–H and O–H moieties have been effectively used for electrophile activation, activation based on other types of non-covalent interactions is less common. This mini review highlights recent progress in developing and exploring new organic catalysts for electrophile activation through the formation of C–H hydrogen bonds and C–X halogen bonds.

  17. 6-Ethynylthieno[3,2-d]- and 6-ethynylthieno[2,3-d]pyrimidin-4-anilines as tunable covalent modifiers of ErbB kinases.

    Science.gov (United States)

    Wood, Edgar R; Shewchuk, Lisa M; Ellis, Byron; Brignola, Perry; Brashear, Ronald L; Caferro, Thomas R; Dickerson, Scott H; Dickson, Hamilton D; Donaldson, Kelly H; Gaul, Michael; Griffin, Robert J; Hassell, Anne M; Keith, Barry; Mullin, Robert; Petrov, Kimberly G; Reno, Michael J; Rusnak, David W; Tadepalli, Sarva M; Ulrich, John C; Wagner, Craig D; Vanderwall, Dana E; Waterson, Alex G; Williams, Jon D; White, Wendy L; Uehling, David E

    2008-02-26

    Analysis of the x-ray crystal structure of mono-substituted acetylenic thienopyrimidine 6 complexed with the ErbB family enzyme ErbB-4 revealed a covalent bond between the terminal carbon of the acetylene moiety and the sulfhydryl group of Cys-803 at the solvent interface. The identification of this covalent adduct suggested that acetylenic thienopyrimidine 6 and related analogs might also be capable of forming an analogous covalent adduct with EGFR, which has a conserved cysteine (797) near the ATP binding pocket. To test this hypothesis, we treated a truncated, catalytically competent form of EGFR (678-1020) with a structurally related propargylic amine (8). An investigation of the resulting complex by mass spectrometry revealed the formation of a covalent complex of thienopyrimidine 8 with Cys-797 of EGFR. This finding enabled us to readily assess the irreversibility of various inhibitors and also facilitated a structure-activity relationship understanding of the covalent modifying potential and biological activity of a series of acetylenic thienopyrimidine compounds with potent antitumor activity. Several ErbB family enzyme and cell potent 6-ethynyl thienopyrimidine kinase inhibitors were found to form covalent adducts with EGFR.

  18. Diffusion bonding

    International Nuclear Information System (INIS)

    Anderson, R.C.

    1976-01-01

    A method is described for joining beryllium to beryllium by diffusion bonding. At least one surface portion of at least two beryllium pieces is coated with nickel. A coated surface portion is positioned in a contiguous relationship with another surface portion and subjected to an environment having an atmosphere at a pressure lower than ambient pressure. A force is applied on the beryllium pieces for causing the contiguous surface portions to abut against each other. The contiguous surface portions are heated to a maximum temperature less than the melting temperature of the beryllium, and the applied force is decreased while increasing the temperature after attaining a temperature substantially above room temperature. A portion of the applied force is maintained at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions

  19. Effect of copper-sulphur bond on the DNA photo-cleavage activity of ...

    Indian Academy of Sciences (India)

    The Cu-N bond lengths are in the range of 1.968(3) to 2.158(4) Å. The Cu-S bond lengths of 2.599(2) and 2.705(2) Å are significantly long indicating weak covalent interaction between copper and sulphur atoms. The thiomethyl groups are cis to each other giving S-Cu-S angle of 75.82(5)°. The Cu-N(pyridyl) bond distances ...

  20. Detection of HBV Covalently Closed Circular DNA

    Directory of Open Access Journals (Sweden)

    Xiaoling Li

    2017-06-01

    Full Text Available Chronic hepatitis B virus (HBV infection affects approximately 240 million people worldwide and remains a serious public health concern because its complete cure is impossible with current treatments. Covalently closed circular DNA (cccDNA in the nucleus of infected cells cannot be eliminated by present therapeutics and may result in persistence and relapse. Drug development targeting cccDNA formation and maintenance is hindered by the lack of efficient cccDNA models and reliable cccDNA detection methods. Southern blotting is regarded as the gold standard for quantitative cccDNA detection, but it is complicated and not suitable for high-throughput drug screening, so more sensitive and simple methods, including polymerase chain reaction (PCR-based methods, Invader assays, in situ hybridization and surrogates, have been developed for cccDNA detection. However, most methods are not reliable enough, and there are no unified standards for these approaches. This review will summarize available methods for cccDNA detection. It is hoped that more robust methods for cccDNA monitoring will be developed and that standard operation procedures for routine cccDNA detection in scientific research and clinical monitoring will be established.

  1. Covalently crosslinked diels-alder polymer networks.

    Energy Technology Data Exchange (ETDEWEB)

    Bowman, Christopher (University of Colorado, Boulder, CO); Adzima, Brian J. (University of Colorado, Boulder, CO); Anderson, Benjamin John

    2011-09-01

    This project examines the utility of cycloaddition reactions for the synthesis of polymer networks. Cycloaddition reactions are desirable because they produce no unwanted side reactions or small molecules, allowing for the formation of high molecular weight species and glassy crosslinked networks. Both the Diels-Alder reaction and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) were studied. Accomplishments include externally triggered healing of a thermoreversible covalent network via self-limited hysteresis heating, the creation of Diels-Alder based photoresists, and the successful photochemical catalysis of CuAAC as an alternative to the use of ascorbic acid for the generation of Cu(I) in click reactions. An analysis of the results reveals that these new methods offer the promise of efficiently creating robust, high molecular weight species and delicate three dimensional structures that incorporate chemical functionality in the patterned material. This work was performed under a Strategic Partnerships LDRD during FY10 and FY11 as part of a Sandia National Laboratories/University of Colorado-Boulder Excellence in Science and Engineering Fellowship awarded to Brian J. Adzima, a graduate student at UC-Boulder. Benjamin J. Anderson (Org. 1833) was the Sandia National Laboratories point-of-contact for this fellowship.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-01

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

  3. Mussel byssus-inspired engineering of synergistic nanointerfacial interactions as sacrificial bonds into carbon nanotube-reinforced soy protein/nanofibrillated cellulose nanocomposites: Versatile mechanical enhancement

    Science.gov (United States)

    Wang, Zhong; Zhao, Shujun; Kang, Haijiao; Zhang, Wei; Zhang, Shifeng; Li, Jianzhang

    2018-03-01

    Achieving flexible and stretchable biobased nanocomposites combining high strength and toughness is still a very challenging endeavor. Herein, we described a novel and versatile biomimetic design for tough and high-performance TEMPO-oxidized nanofibrillated cellulose (TONFC)/soy protein isolate (SPI) nanocomposites, which are triggered by catechol-mimetic carbon nanotubes (PCT) and iron ions (Fe(III)) to yield a strong yet sacrificial metal-ligand motifs into a chemically cross-linked architecture network. Taking advantage of self-polymerization of catechol-inspired natural tannic acid, PCT nanohybrid was prepared through adhering reactive poly-(tannic acid) (PTA) layer onto surfaces of carbon nanotubes via a simple dip-coating process. The high-functionality PCT induced the formation of the metal-ligand bonds through the ionic coordinates between the catechol groups in PCT and -COOH groups of TONFC skeleton with Fe(III) mediation that mimicked mussel byssus. Upon stretching, this tailored TONFC-Fe(III)-catechol coordination bonds served as sacrificial bonds that preferentially detach prior to the covalent network, which gave rise to efficient energy dissipation that the nanocomposites integrity was survived. As a result of these kind of synergistic interfacial interactions (sacrificial and covalent bonding), the optimal nanocomposite films processed high tensile strength (ca. 11.5 MPa), large elongation (ca. 79.3%), remarkable toughness (ca. 6.9 MJ m-3), and favorable water resistance as well as electrical conductivity. The proposed bioinspired strategy for designing plant protein-based materials enables control over their mechanical performance through the synergistic engineering of sacrificial bonds into the composite interface.

  4. Facile route to covalently-jointed graphene/polyaniline composite and it’s enhanced electrochemical performances for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Hanxun [School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China); Han, Xuebin; Qiu, Feilong [School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China); School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200093 (China); Yang, Junhe, E-mail: hxqiu@usst.edu.cn [School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China)

    2016-07-15

    Highlights: • A novel synthetic approach to graphene/polyaniline composite is developed. • Covalently bonds are introduced between graphene and polyaniline. • The composite exhibits great electrochemical property with capacitance of 489 F g{sup −1}. - Abstract: A polyaniline/graphene composite with covalently-bond is synthesized by a novel approach. In this way, graphene oxide is functionalized firstly by introducing amine groups onto the surface with the reduction of graphene oxide in the process and then served as the anchor sites for the growth of polyaniline (PANI) via in-situ polymerization. The composite material is characterized by electron microscopy, the resonant Raman spectra, X-ray diffraction, transform infrared spectroscopy and X-ray photoelectron spectroscopy. The electrochemical properties of the composite are measured by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charging/discharging. With the functionalization process, the graphene/polyaniline composite electrode exhibits remarkably enhanced electrochemical performance with specific capacitance of 489 F g{sup −1} at 0.5 A g{sup −1}, which is superior to those of its individual components. The outstanding electrochemical performance of the hybrid can be attributed to its covalently synergistic effect between graphene and polyaniline, suggesting promising potentials for supercapacitors.

  5. Microsolvation and the Effects of Non-Covalent Interactions on Intramolecular Dynamics

    Science.gov (United States)

    Foguel, Lidor; Vealey, Zachary; Vaccaro, Patrick

    2017-06-01

    Physicochemical processes brought about by non-covalent interactions between neighboring molecules are undeniably of crucial importance in the world around us, being responsible for effects ranging from the subtle (yet precise) control of biomolecular recognition events to the very existence of condensed phases. Of particular interest is the differential ability of distinct non-covalent forces, such as those mediated by dispersion-dominated aryl (π-π) coupling and electrostatically-driven hydrogen bonding, to affect unimolecular transformations by altering potential surface topographies and the nature of reaction coordinates. A concerted experimental and computational investigation of "microsolvation" (solvation at the molecular level) has been undertaken to elucidate the site-specific coupling between solute and solvent degrees of freedom, as well as attendant consequences for the efficiency and pathway of intrinsic proton-transfer dynamics. Targeted species have been synthesized in situ under "cold" supersonic free-jet expansion conditions (T_{rot} ≈ 1-2K) by complexing an active (proton-transfer) substrate with various ligands (e.g., water isotopologs and benzene derivatives) for which competing interaction mechanisms can lead to unique binding motifs. A series of fluorescence-based spectroscopic measurements have been performed on binary adducts formed with the prototypical 6-hydroxy-2-formylfulvene (HFF) system, where a quasi-linear intramolecular O-H...O bond and a zero-point energy that straddles the proton-transfer barrier crest synergistically yield the largest tunneling-induced splitting ever reported for the ground electronic state of an isolated neutral molecule. Such characteristics afford a localized metric for unraveling incipient changes in unimolecular reactivity, with comparison of experimentally observed and quantum-chemical predicted rovibronic landscapes serving to discriminate complexes built upon electrostatic (hydrogen-bonding) and

  6. 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

  7. Layered vanadyl (IV) nitroprusside: Magnetic interaction through a network of hydrogen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Gil, D.M. [Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN San Miguel de Tucumán (Argentina); Osiry, H. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México (Mexico); Pomiro, F.; Varetti, E.L. [CEQUINOR (CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 and 115, 1900, La Plata (Argentina); Carbonio, R.E. [INFIQC – CONICET, Departamento de Físico Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Haya de la Torre esq, Medina Allende, Ciudad Universitaria, X5000HUA Córdoba (Argentina); Alejandro, R.R. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México (Mexico); Ben Altabef, A. [INQUINOA-UNT-CONICET, Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN San Miguel de Tucumán (Argentina); and others

    2016-07-15

    The hydrogen bond and π-π stacking are two non-covalent interactions able to support cooperative magnetic ordering between paramagnetic centers. This contribution reports the crystal structure and related magnetic properties for VO[Fe(CN){sub 5}NO]·2H{sub 2}O, which has a layered structure. This solid crystallizes with an orthorhombic unit cell, in the Pna2{sub 1} space group, with cell parameters a=14.1804(2), b=10.4935(1), c=7.1722(8) Å and four molecules per unit cell (Z=4). Its crystal structure was solved and refined from powder X-ray diffraction data. Neighboring layers remain linked through a network of hydrogen bonds involving a water molecule coordinated to the axial position for the V atom and the unbridged axial NO and CN ligands. An uncoordinated water molecule is found forming a triple bridge between these last two ligands and the coordinated water molecule. The magnetic measurements, recorded down to 2 K, shows a ferromagnetic interaction between V atoms located at neighboring layers, with a Curie-Weiss constant of 3.14 K. Such ferromagnetic behavior was interpreted as resulting from a superexchange interaction through the network of strong OH····O{sub H2O}, OH····N{sub CN}, and OH····O{sub NO} hydrogen bonds that connects neighboring layers. The interaction within the layer must be of antiferromagnetic nature and it was detected close to 2 K. - Graphical abstract: Coordination environment for the metals in vanadyl (II) nitroprusside dihydrate. Display Omitted - Highlights: • Crystal structure of vanadyl nitroprusside dehydrate. • Network of hydrogen bonds. • Magnetic interactions through a network of hydrogen bonds. • Layered transition metal nitroprussides.

  8. On-surface covalent linking of organic building blocks on a bulk insulator.

    Science.gov (United States)

    Kittelmann, Markus; Rahe, Philipp; Nimmrich, Markus; Hauke, Christopher M; Gourdon, André; Kühnle, Angelika

    2011-10-25

    On-surface synthesis in ultrahigh vacuum provides a promising strategy for creating thermally and chemically stable molecular structures at surfaces. The two-dimensional confinement of the educts, the possibility of working at higher (or lower) temperatures in the absence of solvent, and the templating effect of the surface bear the potential of preparing compounds that cannot be obtained in solution. Moreover, covalently linked conjugated molecules allow for efficient electron transport and are, thus, particularly interesting for future molecular electronics applications. When having these applications in mind, electrically insulating substrates are mandatory to provide sufficient decoupling of the molecular structure from the substrate surface. So far, however, on-surface synthesis has been achieved only on metallic substrates. Here we demonstrate the covalent linking of organic molecules on a bulk insulator, namely, calcite. We deliberately employ the strong electrostatic interaction between the carboxylate groups of halide-substituted benzoic acids and the surface calcium cations to prevent molecular desorption and to reach homolytic cleavage temperatures. This allows for the formation of aryl radicals and intermolecular coupling. By varying the number and position of the halide substitution, we rationally design the resulting structures, revealing straight lines, zigzag structures, and dimers, thus providing clear evidence for the covalent linking. Our results constitute an important step toward exploiting on-surface synthesis for molecular electronics and optics applications, which require electrically insulating rather than metallic supporting substrates.

  9. Symmetry and dynamics of FHF-anion in vacuum, in CD2Cl2and in CCl4. Ab initio MD study of fluctuating solvent-solute hydrogen and halogen bonds.

    Science.gov (United States)

    Pylaeva, S A; Elgabarty, H; Sebastiani, D; Tolstoy, P M

    2017-10-04

    FHF - anion is a classic example of a central-symmetric strongly hydrogen bonded system that has been intensively investigated both experimentally and theoretically. In this paper we focus on solvent effects on symmetry, structure and dynamics of the anion. The FHF - anion is studied in vacuum, dissolved in CH 2 Cl 2 and dissolved in CCl 4 by ab initio molecular dynamics simulations. We show that CH 2 Cl 2 molecules form CHF hydrogen bonds with lone pairs of fluorine atoms, while CCl 4 molecules form halogen bonds. These specific non-covalent solvent-solute interactions are cooperatively coupled to the FHF - hydrogen bonds. The fluctuation of solvent molecules' positions is the driving force changing the FHF - hydrogen bond geometry. Most of the time, the anion is solvated asymmetrically, which leads to the asymmetric bridging particle position, though the time-averaged D ∞h symmetry is retained. Interestingly, this transient asymmetrization of FHF - is more pronounced in CCl 4 , than in CH 2 Cl 2 . We show that the 1 H and 19 F NMR chemicals shifts react sensitively to the changes of anion's geometry and the limiting chemical shifts of free solvated FH and F - are strongly solvent-dependent.

  10. Nucleation and Growth of Covalent Organic Frameworks from Solution: The Example of COF-5

    KAUST Repository

    Li, Haoyuan

    2017-10-24

    The preparation of two-dimensional covalent organic frameworks (2D COFs) with large crystalline domains and controlled morphology is necessary for realizing the full potential of their atomically precise structures and uniform, tailorable porosity. Currently 2D COF syntheses are developed empirically, and most materials are isolated as insoluble and unprocessable powders with typical crystalline domain sizes smaller than 50 nm. Little is known about their nucleation and growth processes, which involve a combination of covalent bond formation, degenerate exchange, and non-covalent stacking processes. A deeper understanding of the chemical processes that lead to COF polymerization and crystallization is key to achieving improved materials quality and control. Here, we report a kinetic Monte Carlo (KMC) model that describes the formation of a prototypical boronate-ester linked 2D COF known as COF-5 from its 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylene bis(boronic acid) monomers in solution. The key rate parameters for the KMC model were derived from experimental measurements when possible and complemented with reaction pathway analyses, molecular dynamics simulations, and binding free-energy calculations. The essential features of experimentally measured COF-5 growth kinetics are reproduced well by the KMC simulations. In particular, the simulations successfully captured a nucleation process followed by a subsequent growth process. The nucleating species are found to be multi-layer structures that form through multiple pathways. During the growth of COF-5, extensions in the lateral (in-plane) and vertical (stacking) directions are both seen to be linear with respect to time and are dominated by monomer addition and oligomer association, respectively. Finally, we show that the experimental observations of increased average crystallite size with the addition of water are modeled accurately by the simulations. These results will inform the rational development

  11. Covalent Linkage of HIV-1 Trimers to Synthetic Liposomes Elicits Improved B Cell and Antibody Responses.

    Science.gov (United States)

    Bale, Shridhar; Goebrecht, Geraldine; Stano, Armando; Wilson, Richard; Ota, Takayuki; Tran, Karen; Ingale, Jidnyasa; Zwick, Michael B; Wyatt, Richard T

    2017-08-15

    modified lipid head groups have a unique feature of capturing and displaying antigens on their surfaces, mimicking the native pathogens. Our first-generation nickel-based liposomes captured HIV-1 Env glycoprotein trimers via a noncovalent linkage with improved efficacy over soluble glycoprotein in activating germinal center B cells and eliciting tier-2 autologous neutralizing antibodies. In this study, we report the development of second-generation cobalt- and maleimide-based liposomes that have improved in vitro stability over nickel-based liposomes. In particular, the maleimide liposomes captured HIV-1 Env trimers via a more stable covalent bond, resulting in enhanced germinal center B cell responses that generated higher antibody titers than the soluble trimers and liposome-bearing trimers via noncovalent linkages. We further demonstrate that covalent coupling prevents release of the trimers prior to recognition by B cells and masks a nonneutralizing determinant located at the bottom of the trimer. Copyright © 2017 American Society for Microbiology.

  12. Electronic Coupling between Two Covalently Bonded Dimolybdenum Units Bridged by a Naphthalene Group.

    Science.gov (United States)

    Zhu, Guang Yuan; Meng, Miao; Tan, Ying Ning; Xiao, Xuan; Liu, Chun Y

    2016-06-20

    Using 2,6-naphthalenedicarboxylate and its thiolated derivatives as bridging ligands, three Mo2 dimers of the type [Mo2(DAniF)3](E2CC10H6CE2)[Mo2(DAniF)3] (DAniF = N,N'-di-p-anisylformamidinate; E = O, S) have been synthesized and characterized by X-ray diffraction. These compounds can be generally formulated as [Mo2]-naph-[Mo2], where the complex unit [Mo2] ([Mo2(DAniF)3(μ-E2C)]) functions as an electron donor (acceptor) and the naphthalene (naph) group is the bridge. The mixed-valence (MV) complexes, generated by one-electron oxidation of the neutral precursors, display weak, very broad intervalence charge-transfer absorption bands in the near-to-mid-IR regions. The electronic coupling matrix elements for the MV complexes, Hab = 390-570 cm(-1), are calculated from the Mulliken-Hush equation, which fall between those for the phenyl (ph) and biphenyl (biph) analogues reported previously. The three series consisting of three complexes with the same [Mo2] units exhibit exponential decay of Hab as the bridge changes from ph to biph via naph, with decay factors of 0.21-0.17 Å(-1). Therefore, it is evidenced that while the extent of the bridge conjugacy varies, the electronic coupling between the two [Mo2] units is dominated by the Mo2···Mo2 separation. The absorption band energies for metal-to-ligand charge transfer are in the middle of those for the ph and biph analogues, which is consistent with variation of the HOMO-LUMO energy gaps for the complex series. These results indicate that the interplay of the bridge length and conjugacy is to affect the enegy for charge transfer crossing the intervening moiety, in accordance with a superechange mechanism.

  13. Covalent-bond stabilization of the Si(111)-(3 1 -1 1)-Pb structure

    DEFF Research Database (Denmark)

    Kumpf, C.; Nielsen, M.; Feidenhans'l, R.

    2001-01-01

    At room temperature a monolayer coverage of Pb on Si(1 1 1) forms a hexagonal incommensurate structure which changes into a commensurate Si(1 1 1)-((3 2)(-1 1)) -Pb structure at temperatures below 230 K. A similar ((-1 1) (3 2))- reconstruction, but stable at room temperature, is formed...

  14. Effect of covalent bonding on magnetism and the missing neutron intensity in copper oxide compounds

    NARCIS (Netherlands)

    Walters, A.C.; Perring, T.G.; Caux, J.S.; Savici, A.T.; Gu, G.D.; Lee, C.C.; Ku, W.; Zaliznyak, I.A.

    2009-01-01

    Theories involving highly energetic spin fluctuations are among the leading contenders for explaining high-temperature superconductivity in the cuprates(1). These theories could be tested by inelastic neutron scattering ( INS), as a change in the magnetic scattering intensity that marks the entry

  15. Covalent bonding of PMMA, PBMA, and poly(HEMA) to hydroxyapatite particles

    NARCIS (Netherlands)

    Liu, Q.; de Wijn, J.R.; van Blitterswijk, Clemens

    1998-01-01

    In our earlier study, we showed that the surface hydroxyl groups of hydroxyapatite have the ability to react with organic isocyanate groups. In this study, the feasibility of grafting poly(methyl methacrylate) (PMMA), poly(n-butyl methacrylate) (PBMA), and Poly(hydroxyethyl methacrylate)

  16. Towards a Stronger Covalent Bond: Pedagogical Change for Inclusivity and Equity

    Science.gov (United States)

    Koretsky, Milo; Montfort, Devlin; Nolen, Susan Bobbitt; Bothwell, Michelle; Davis, Susannah; Sweeney, James

    2018-01-01

    We describe progress on a comprehensive, programmatic change initiative whose goal is to create an inclusive culture that fosters diversity and a shift towards more meaningful, consequential work. While this initiative has several elements that target different aspects of unit practices and culture, we focus here on pedagogical change. Our…

  17. Relevant insight of surface characterization techniques to study covalent grafting of a biopolymer to titanium implant and its acidic resistance

    Science.gov (United States)

    D'Almeida, Mélanie; Amalric, Julien; Brunon, Céline; Grosgogeat, Brigitte; Toury, Bérangère

    2015-02-01

    Peri-implant bacterial infections are the main cause of complications in dentistry. Our group has previously proposed the attachment of chitosan on titanium implants via a covalent bond to improve its antibacterial properties while maintaining its biocompatibility. A better knowledge of the coating preparation process allows a better understanding of the bioactive coating in biological conditions. In this work, several relevant characterization techniques were used to assess an implant device during its production phase and its resistance in natural media at different pH. The titanium surface was functionalized with 3-aminopropyltriethoxysilane (APTES) followed by grafting of an organic coupling agent; succinic anhydride, able to form two covalent links, with the substrate through a Ti-O-Si bond and the biopolymer through a peptide bond. Each step of the coating synthesis as well as the presence confirmation of the biopolymer on titanium after saliva immersion was followed by FTIR-ATR, SEM, EDS, 3D profilometry, XPS and ToF-SIMS analyses. Results allowed to highlight the efficiency of each step of the process, and to propose a mechanism occurring during the chitosan coating degradation in saliva media at pH 5 and at pH 3.

  18. The Nature of the Idealized Triple Bonds Between Principal Elements and the σ Origins of Trans-Bent Geometries-A Valence Bond Study.

    Science.gov (United States)

    Ploshnik, Elina; Danovich, David; Hiberty, Philippe C; Shaik, Sason

    2011-04-12

    We describe herein a valence bond (VB) study of 27 triply bonded molecules of the general type X≡Y, where X and Y are main element atoms/fragments from groups 13-15 in the periodic table. The following conclusions were derived from the computational data: (a) Single π-bond and double π-bond energies for the entire set correlate with the "molecular electronegativity", which is the sum of the X and Y electronegativites for X≡Y. The correlation with the molecular electronegativity establishes a simple rule of periodicity: π-bonding strength generally increases from left to right in a period and decreases down a column in the periodic table. (b) The σ frame invariably prefers trans bending, while π-bonding gets destabilized and opposes the trans distortion. In HC≡CH, the π-bonding destabilization overrides the propensity of the σ frame to distort, while in the higher row molecules, the σ frame wins out and establishes trans-bent molecules with 2(1)/2 bonds, in accord with recent experimental evidence based on solid state (29)Si NMR of the Sekiguchi compound. Thus, in the trans-bent molecules "less bonds pay more". (c) All of the π bonds show significant bonding contributions from the resonance energy due to covalent-ionic mixing. This quantity is shown to correlate linearly with the corresponding "molecular electronegativity" and to reflect the mechanism required to satisfy the equilibrium condition for the bond. The π bonds for molecules possessing high molecular electronegativity are charge-shift bonds, wherein bonding is dominated by the resonance energy of the covalent and ionic forms, rather than by either form by itself.

  19. Interfacial design of carbon nanotube polymer composites: a hybrid system of noncovalent and covalent functionalizations

    Science.gov (United States)

    Liu, J. Q.; Xiao, T.; Liao, K.; Wu, P.

    2007-04-01

    Homogeneous dispersion of carbon nanotubes (CNTs) throughout the polymer matrix and their adequate interfacial bonding are critical for load transfer in CNT-polymer composites. However, both cannot be realized simultaneously by either covalent or noncovalent functionalization. A hybrid system integrating both covalent and noncovalent functionalizations is presented for interfacial design of CNT-polymer composites. To investigate the feasibility of this system, examples of the epoxidized single-walled carbon nanotube (SWNT) subsequently wrapped by poly(m-phenylenevinylene- co-2,5-dioctyloxy-p-phenylenevinylene) (PmPV) are studied by means of molecular dynamics simulations. It is shown by our results that PmPV molecules are miscible with epoxy resin and tend to wrap around the epoxidized SWNT, which could be used to weaken the interaction between SWNTs and consequently improve the dispersion of SWNTs into the matrix. The interfacial shear strength of CNT-polymer composites can be improved significantly by properly designed functionalizations, especially the hybrid system.

  20. Chemoselective small molecules that covalently modify one lysine in a non-enzyme protein in plasma

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Sungwook; Connelly, Stephen; Reixach, Natàlia; Wilson, Ian A.; Kelly, Jeffery W. (Scripps)

    2010-02-19

    A small molecule that could bind selectively to and then react chemoselectively with a non-enzyme protein in a complex biological fluid, such as blood, could have numerous practical applications. Herein, we report a family of designed stilbenes that selectively and covalently modify the prominent plasma protein transthyretin in preference to more than 4,000 other human plasma proteins. They react chemoselectively with only one of eight lysine {epsilon}-amino groups within transthyretin. The crystal structure confirms the expected binding orientation of the stilbene substructure and the anticipated conjugating amide bond. These covalent transthyretin kinetic stabilizers exhibit superior amyloid inhibition potency compared to their noncovalent counterparts, and they prevent cytotoxicity associated with amyloidogenesis. Though there are a few prodrugs that, upon metabolic activation, react with a cysteine residue inactivating a specific non-enzyme, we are unaware of designed small molecules that react with one lysine {epsilon}-amine within a specific non-enzyme protein in a complex biological fluid.

  1. A new family of covalent inhibitors block nucleotide binding to the active site of pyruvate kinase.

    Science.gov (United States)

    Morgan, Hugh P; Walsh, Martin J; Blackburn, Elizabeth A; Wear, Martin A; Boxer, Matthew B; Shen, Min; Veith, Henrike; McNae, Iain W; Nowicki, Matthew W; Michels, Paul A M; Auld, Douglas S; Fothergill-Gilmore, Linda A; Walkinshaw, Malcolm D

    2012-11-15

    PYK (pyruvate kinase) plays a central role in the metabolism of many organisms and cell types, but the elucidation of the details of its function in a systems biology context has been hampered by the lack of specific high-affinity small-molecule inhibitors. High-throughput screening has been used to identify a family of saccharin derivatives which inhibit LmPYK (Leishmania mexicana PYK) activity in a time- (and dose-) dependent manner, a characteristic of irreversible inhibition. The crystal structure of DBS {4-[(1,1-dioxo-1,2-benzothiazol-3-yl)sulfanyl]benzoic acid} complexed with LmPYK shows that the saccharin moiety reacts with an active-site lysine residue (Lys335), forming a covalent bond and sterically hindering the binding of ADP/ATP. Mutation of the lysine residue to an arginine residue eliminated the effect of the inhibitor molecule, providing confirmation of the proposed inhibitor mechanism. This lysine residue is conserved in the active sites of the four human PYK isoenzymes, which were also found to be irreversibly inhibited by DBS. X-ray structures of PYK isoforms show structural differences at the DBS-binding pocket, and this covalent inhibitor of PYK provides a chemical scaffold for the design of new families of potentially isoform-specific irreversible inhibitors.

  2. New highly luminescent hybrid materials: terbium pyridine-picolinate covalently grafted on kaolinite.

    Science.gov (United States)

    de Faria, Emerson H; Nassar, Eduardo J; Ciuffi, Katia J; Vicente, Miguel A; Trujillano, Raquel; Rives, Vicente; Calefi, Paulo S

    2011-04-01

    Luminescent hybrid materials derived from kaolinite appear as promising materials for optical applications due to their specific properties. The spectroscopic behavior of terbium picolinate complexes covalently grafted on kaolinite and the influence of the secondary ligand and thermal treatment on luminescence are reported. The resulting materials were characterized by thermal analysis, element analysis, X-ray diffraction, infrared absorption spectroscopy, and photoluminescence. The thermogravimetric curves indicated an enhancement in the thermal stability up to 300 °C for the lanthanide complexes covalently grafted on kaolinite, with respect to the isolated complexes. The increase in the basal spacing observed by X-ray diffraction confirmed the insertion of the organic ligands into the basal space of kaolinite, involving the formation of a bond between Al-OH and the carboxylate groups, as evidenced by infrared spectroscopy. The luminescent hybrid material exhibited a stronger characteristic emission of Tb(3+) compared to the isolated complex. The excitation spectra displayed a broad band at 277 nm, assigned to a ligand-to-metal charge transfer, while the emission spectra presented bands related to the electronic transitions characteristic of the Tb(3+) ion from the excited state (5)D(4) to the states (7)F(J) (J=5, 4, and 3), with the 4→5 transition having high intensity with green emission. © 2011 American Chemical Society

  3. Nonvolatile memory device using gold nanoparticles covalently bound to reduced graphene oxide.

    Science.gov (United States)

    Cui, Peng; Seo, Sohyeon; Lee, Junghyun; Wang, Luyang; Lee, Eunkyo; Min, Misook; Lee, Hyoyoung

    2011-09-27

    Nonvolatile memory devices using gold nanoparticles (AuNPs) and reduced graphene oxide (rGO) sheets were fabricated in both horizontal and vertical structures. The horizontal memory device, in which a singly and doubly overlayered semiconducting rGO channel was formed by simply using a spin-casting technique to connect two gold electrodes, was designed for understanding the origin of charging effects. AuNPs were chemically bound to the rGO channel through a π-conjugated molecular linker. The π-conjugated bifunctional molecular linker, 4-mercapto-benzenediazonium tetrafluoroborate (MBDT) salt, was newly synthesized and used as a molecular bridge to connect the AuNPs and rGOs. By using a self-assembly technique, the diazonium functional group of the MBDT molecular linker was spontaneously immobilized on the rGOs. Then, the monolayered AuNPs working as capacitors were covalently connected to the thiol groups of the MBDT molecules, which were attached to rGOs (AuNP-frGO). These covalent bonds were confirmed by XPS analyses. The current-voltage characteristics of both the horizontal and vertical AuNP-frGO memory devices showed noticeable nonlinear hysteresis, stable write-multiple read-erase-multiple read cycles over 1000 s, and a long retention time over 700 s. In addition, the vertical AuNP-frGO memory device showed a large current ON/OFF ratio and high stability. © 2011 American Chemical Society

  4. Local Electronic Structure of a Single-Layer Porphyrin-Containing Covalent Organic Framework

    KAUST Repository

    Chen, Chen

    2017-12-20

    We have characterized the local electronic structure of a porphyrin-containing single-layer covalent organic framework (COF) exhibiting a square lattice. The COF monolayer was obtained by the deposition of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMA) and 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) onto a Au(111) surface in ultrahigh vacuum followed by annealing to facilitate Schiff-base condensations between monomers. Scanning tunneling spectroscopy (STS) experiments conducted on isolated TAPP precursor molecules and the covalently linked COF networks yield similar transport (HOMO-LUMO) gaps of 1.85 ± 0.05 eV and 1.98 ± 0.04 eV, respectively. The COF orbital energy alignment, however, undergoes a significant downward shift compared to isolated TAPP molecules due to the electron-withdrawing nature of the imine bond formed during COF synthesis. Direct imaging of the COF local density of states (LDOS) via dI/dV mapping reveals that the COF HOMO and LUMO states are localized mainly on the porphyrin cores and that the HOMO displays reduced symmetry. DFT calculations reproduce the imine-induced negative shift in orbital energies and reveal that the origin of the reduced COF wave function symmetry is a saddle-like structure adopted by the porphyrin macrocycle due to its interactions with the Au(111) substrate.

  5. Are Stock and Corporate Bond Markets Integrated?

    OpenAIRE

    van Zundert, J.; Driessen, Joost

    2017-01-01

    This study explores the cross-sectional integration of stock and corporate bond markets by comparing a firm’s expected stock return, as implied by corporate bond spreads, to its realized stock return. We compute expected corporate bond returns by correcting credit spreads for expected losses due to default, which are then transformed into expected stock returns. We find, surprisingly, a strong negative cross-sectional relation between these expected and realized stock returns over the period ...

  6. Scanning tunneling spectroscopy of CdSe nanocrystals covalently bound to GaAs

    DEFF Research Database (Denmark)

    Walzer, K.; Marx, E.; Greenham, N.C.

    2003-01-01

    We present scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) measurements of CdSe nanocrystals covalently attached to doped GaAs substrates using monolayers of 1,6-hexanedithiol. STM measurements showed the formation of stable, densely packed, homogeneous monolayers...... and the bands in the substrate which are bent under the influence of the strong electric field between the closely separated semiconductor substrate and STM tip. The polarity of the forward bias direction is determined by the alignment of the CdSe electronic states with the semiconductor bands. (C) 2003...

  7. Extra-electron induced covalent strengthening and generalization of intrinsic ductile-to-brittle criterion

    Science.gov (United States)

    Niu, Haiyang; Chen, Xing-Qiu; Liu, Peitao; Xing, Weiwei; Cheng, Xiyue; Li, Dianzhong; Li, Yiyi

    2012-10-01

    Traditional strengthening ways, such as strain, precipitation, and solid-solution, come into effect by pinning the motion of dislocation. Here, through first-principles calculations we report on an extra-electron induced covalent strengthening mechanism, which alters chemical bonding upon the introduction of extra-valence electrons in the matrix of parent materials. It is responsible for the brittle and high-strength properties of Al12W-type compounds featured by the typical fivefold icosahedral cages, which are common for quasicrystals and bulk metallic glasses (BMGs). In combination with this mechanism, we generalize ductile-to-brittle criterion in a universal hyperbolic form by integrating the classical Pettifor's Cauchy pressure with Pugh's modulus ratio for a wide variety of materials with cubic lattices. This study provides compelling evidence to correlate Pugh's modulus ratio with hardness of materials and may have implication for understanding the intrinsic brittleness of quasicrystals and BMGs.

  8. Diffusionless bonding of aluminum to type 304 stainless steel

    International Nuclear Information System (INIS)

    Watson, R.D.

    1963-03-01

    High strength diffusionless bonds can be produced between 1S aluminum and oxidized 304 stainless steel by hot pressing and extrusion bonding. Both the hot pressing and extrusion bonding techniques have been developed to a point where consistently good bonds can be obtained. Although the bonding is performed at elevated temperatures (about 510 o C) a protective atmosphere is not required to produce strong bonds. The aluminum-stainless steel bonded specimens can be used to join aluminum and stainless steel by conventional welding. Welding close to the bond zone does not appear to affect the integrity of the bond. The extrusion bonding technique is covered by Canadian patent 702,438 January 26, 1965 and the hot press bonding technique by Canadian patent application 904,548 June 6, 1964. (author)

  9. Understanding Bonds - Denmark

    DEFF Research Database (Denmark)

    Rimmer, Nina Røhr

    2016-01-01

    a specified rate of interest during the life of the bond and to repay the face value of the bond (the principal) when it “matures,” or comes due. Among the types of bonds you can choose from are: Government securities, municipal bonds, corporate bonds, mortgage and asset-backed securities, federal agency...

  10. Robustly Engineering Thermal Conductivity of Bilayer Graphene by Interlayer Bonding

    Science.gov (United States)

    Zhang, Xiaoliang; Gao, Yufei; Chen, Yuli; Hu, Ming

    2016-01-01

    Graphene and its bilayer structure are the two-dimensional crystalline form of carbon, whose extraordinary electron mobility and other unique features hold great promise for nanoscale electronics and photonics. Their realistic applications in emerging nanoelectronics usually call for thermal transport manipulation in a controllable and precise manner. In this paper we systematically studied the effect of interlayer covalent bonding, in particular different interlay bonding arrangement, on the thermal conductivity of bilayer graphene using equilibrium molecular dynamics simulations. It is revealed that, the thermal conductivity of randomly bonded bilayer graphene decreases monotonically with the increase of interlayer bonding density, however, for the regularly bonded bilayer graphene structure the thermal conductivity possesses unexpectedly non-monotonic dependence on the interlayer bonding density. The results suggest that the thermal conductivity of bilayer graphene depends not only on the interlayer bonding density, but also on the detailed topological configuration of the interlayer bonding. The underlying mechanism for this abnormal phenomenon is identified by means of phonon spectral energy density, participation ratio and mode weight factor analysis. The large tunability of thermal conductivity of bilayer graphene through rational interlayer bonding arrangement paves the way to achieve other desired properties for potential nanoelectronics applications involving graphene layers. PMID:26911859

  11. K- and L-edge X-ray Absorption Spectroscopy (XAS) and Resonant Inelastic X-ray Scattering (RIXS) Determination of Differential Orbital Covalency (DOC) of Transition Metal Sites.

    Science.gov (United States)

    Baker, Michael L; Mara, Michael W; Yan, James J; Hodgson, Keith O; Hedman, Britt; Solomon, Edward I

    2017-08-15

    Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as K resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3d orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of and donor bonding and back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. The application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.

  12. Characterization of the Bonds Developed between Calcium Silicate Hydrate and Polycarboxylate-Based Superplasticizers with Silyl Functionalities

    KAUST Repository

    Orozco, Carlos A.

    2017-03-24

    Major developments in concrete technology have been achieved with the use of polycarboxylate-based superplasticizers (PCEs) to improve the concrete rheology without increasing the mix water content. Currently, it is possible to control the fluidity of the fresh concrete and obtain stronger and more durable structures. Therefore, there is a strong incentive to understand the interactions between PCEs and cement hydrates at the atomic scale to design new customized functional PCEs according to the ever-increasing requirements of the concrete industry. Here, the bonding types generated between a PCE with silyl functionalities (PCE-Sil) and a synthetic calcium silicate hydrate (C-S-H) are analyzed using XRD, 29Si NMR spectroscopy, and synchrotron-based techniques, such as NEXAFS and EXAFS. The results indicated that the carboxylic groups present in PCE-Sil interact by a ligand-type bond with calcium, which modified not only the symmetry and coordination number of the calcium located at the surface of C-S-H but also the neighboring silicon atoms of the C-S-H. In addition, the silyl functionalities of the PCE-Sil generated covalent bonds through siloxane bridges between the silanol groups of PCE-Sil and the nonbonding oxygen located at the dimeric sites in C-S-H, forming new bridging silicon sites and subsequently increasing the silicate polymerization.

  13. Structure and bonding in cubic IV-VI crystals. 1

    International Nuclear Information System (INIS)

    Enders, P.

    1983-01-01

    The inherent instability of the cubic structure of IV-VI compounds is considered. Alternatively to the work of Littlewood, the treatment bases on the LCAO method and relates to Harrison's approach as Littlewood's papers do to Phillips'-Van Vechten's one. First Harrison's polarity is calculated from Slater-Koster parameters due to Volkov and coworkers. It indicates predominantly covalent bonding character for the cubic IV-VI compounds. A comparison is given with Littlewood's treatment. The method of special points is used to calculate integral bonding properties. Chadi and Cohen's two point set is shown to be often equivalent to a ligand-field theoretical treatment. (author)

  14. Construction of covalently coupled, concatameric dimers of 7TM receptors

    DEFF Research Database (Denmark)

    Terpager, Marie; Scholl, D Jason; Kubale, Valentina

    2009-01-01

    -Ala repeats flanked by flexible spacers and positively charged residues to ensure correct inside-out orientation plus an extracellular HA-tag to construct covalently coupled dimers of 7TM receptors. Such 15 TM concatameric homo- and heterodimers of the beta(2)-adrenergic and the NK(1) receptors, which...... for either of the protomers, which was not observed upon simple coexpression of the two receptors. It is concluded that covalently joined 7TM receptor dimers with surprisingly normal receptor properties can be constructed with use of an artificial transmembrane connector, which perhaps can be used to fuse...

  15. Assay of covalent intermediate of 5'-nucleotide phosphodiesterase

    International Nuclear Information System (INIS)

    Blytt, H.J.; Brotherton, J.E.; Butler, L.

    1985-01-01

    A new procedure is reported for isolating a covalent phosphoryl enzyme (diester) intermediate of bovine intestinal 5'-nucleotide phosphodiesterase. The convenience of the procedure makes it possible to determine effects of reaction conditions on the yield of covalent intermediate. Under optimum conditions, using [methyl- 3 H]deoxythymidine 5'-triphosphate as substrate, more than 50% of the enzyme is recovered as thymidylyl enzyme, a 10-fold increase in yield over the previous procedure. Yields of thymidylyl enzyme were maximal at pH 4, whereas optimum catalytic activity is observed at pH greater than 9

  16. Acid Hydrolysis and Molecular Density of Phytoglycogen and Liver Glycogen Helps Understand the Bonding in Glycogen α (Composite) Particles

    Science.gov (United States)

    Powell, Prudence O.; Sullivan, Mitchell A.; Sheehy, Joshua J.; Schulz, Benjamin L.; Warren, Frederick J.; Gilbert, Robert G.

    2015-01-01

    Phytoglycogen (from certain mutant plants) and animal glycogen are highly branched glucose polymers with similarities in structural features and molecular size range. Both appear to form composite α particles from smaller β particles. The molecular size distribution of liver glycogen is bimodal, with distinct α and β components, while that of phytoglycogen is monomodal. This study aims to enhance our understanding of the nature of the link between liver-glycogen β particles resulting in the formation of large α particles. It examines the time evolution of the size distribution of these molecules during acid hydrolysis, and the size dependence of the molecular density of both glucans. The monomodal distribution of phytoglycogen decreases uniformly in time with hydrolysis, while with glycogen, the large particles degrade significantly more quickly. The size dependence of the molecular density shows qualitatively different shapes for these two types of molecules. The data, combined with a quantitative model for the evolution of the distribution during degradation, suggest that the bonding between β into α particles is different between phytoglycogen and liver glycogen, with the formation of a glycosidic linkage for phytoglycogen and a covalent or strong non-covalent linkage, most probably involving a protein, for glycogen as most likely. This finding is of importance for diabetes, where α-particle structure is impaired. PMID:25799321

  17. Acid hydrolysis and molecular density of phytoglycogen and liver glycogen helps understand the bonding in glycogen α (composite particles.

    Directory of Open Access Journals (Sweden)

    Prudence O Powell

    Full Text Available Phytoglycogen (from certain mutant plants and animal glycogen are highly branched glucose polymers with similarities in structural features and molecular size range. Both appear to form composite α particles from smaller β particles. The molecular size distribution of liver glycogen is bimodal, with distinct α and β components, while that of phytoglycogen is monomodal. This study aims to enhance our understanding of the nature of the link between liver-glycogen β particles resulting in the formation of large α particles. It examines the time evolution of the size distribution of these molecules during acid hydrolysis, and the size dependence of the molecular density of both glucans. The monomodal distribution of phytoglycogen decreases uniformly in time with hydrolysis, while with glycogen, the large particles degrade significantly more quickly. The size dependence of the molecular density shows qualitatively different shapes for these two types of molecules. The data, combined with a quantitative model for the evolution of the distribution during degradation, suggest that the bonding between β into α particles is different between phytoglycogen and liver glycogen, with the formation of a glycosidic linkage for phytoglycogen and a covalent or strong non-covalent linkage, most probably involving a protein, for glycogen as most likely. This finding is of importance for diabetes, where α-particle structure is impaired.

  18. A single molecule assay to probe monovalent and multivalent bonds between hyaluronan and its key leukocyte receptor CD44 under force

    Science.gov (United States)

    Bano, Fouzia; Banerji, Suneale; Howarth, Mark; Jackson, David G.; Richter, Ralf P.

    2016-09-01

    Glycosaminoglycans (GAGs), a category of linear, anionic polysaccharides, are ubiquitous in the extracellular space, and important extrinsic regulators of cell function. Despite the recognized significance of mechanical stimuli in cellular communication, however, only few single molecule methods are currently available to study how monovalent and multivalent GAG·protein bonds respond to directed mechanical forces. Here, we have devised such a method, by combining purpose-designed surfaces that afford immobilization of GAGs and receptors at controlled nanoscale organizations with single molecule force spectroscopy (SMFS). We apply the method to study the interaction of the GAG polymer hyaluronan (HA) with CD44, its receptor in vascular endothelium. Individual bonds between HA and CD44 are remarkably resistant to rupture under force in comparison to their low binding affinity. Multiple bonds along a single HA chain rupture sequentially and independently under load. We also demonstrate how strong non-covalent bonds, which are versatile for controlled protein and GAG immobilization, can be effectively used as molecular anchors in SMFS. We thus establish a versatile method for analyzing the nanomechanics of GAG·protein interactions at the level of single GAG chains, which provides new molecular-level insight into the role of mechanical forces in the assembly and function of GAG-rich extracellular matrices.

  19. Chemical bonding in view of electron charge density and kinetic energy density descriptors.

    Science.gov (United States)

    Jacobsen, Heiko

    2009-05-01

    Stalke's dilemma, stating that different chemical interpretations are obtained when one and the same density is interpreted either by means of natural bond orbital (NBO) and subsequent natural resonance theory (NRT) application or by the quantum theory of atoms in molecules (QTAIM), is reinvestigated. It is shown that within the framework of QTAIM, the question as to whether for a given molecule two atoms are bonded or not is only meaningful in the context of a well-defined reference geometry. The localized-orbital-locator (LOL) is applied to map out patterns in covalent bonding interaction, and produces results that are consistent for a variety of reference geometries. Furthermore, LOL interpretations are in accord with NBO/NRT, and assist in an interpretation in terms of covalent bonding. 2008 Wiley Periodicals, Inc.

  20. Hydrazide-Derivatized Microgels Bond to Wet, Oxidized Cellulose Giving Adhesion Without Drying or Curing.

    Science.gov (United States)

    Yang, Dong; Gustafsson, Emil; Stimpson, Taylor C; Esser, Anton; Pelton, Robert H

    2017-06-21

    Hydrazide-derivatized poly(N-isopropylacrylamide-co-acrylic acid) microgels gave strong adhesion to wet, TEMPO oxidized, regenerated cellulose membranes without a drying or heating step. Adhesion was attributed to hydrazone covalent bond formation with aldehyde groups present on the cellulose surfaces. This is one of only three chemistries we have found that gives significant never-dried adhesion between wet cellulose surfaces. By contrast, for cellulose joints that have been dried and heated before wet testing, the hydrazide-hydrazone chemistry offers no advantages over standard paper industry wet strength resins. The design rules for the hydrazide-microgel adhesives include: cationic microgels are superior to anionic gels; the lower the microgel cross-link density, the higher the adhesion; longer PEG-based hydrazide tethers offer no advantage over shorter attachments; and, adhesion is independent of microgel diameter. Many of these rules were in agreement with predictions of a simple adhesion model where the microgels were assumed to be ideal springs. We propose that the unexpected, high cohesion between neighboring microgels in multilayer films was a result of bond formation between hydrazide groups and residual NHS-carboxyl esters from the preparation of the hydrazide microgels.

  1. Gas phase hydration of halogenated benzene cations. Is it hydrogen or halogen bonding?

    Science.gov (United States)

    Mason, Kyle A; Pearcy, Adam C; Attah, Isaac K; Platt, Sean P; Aziz, Saadullah G; El-Shall, M Samy

    2017-07-19

    Halogen bonding (XB) non-covalent interactions can be observed in compounds containing chlorine, bromine, or iodine which can form directed close contacts of the type R1-XY-R2, where the halogen X acts as a Lewis acid and Y can be any electron donor moiety including electron lone pairs on hetero atoms such as O and N, or π electrons in olefin double bonds and aromatic conjugated systems. In this work, we present the first evidence for the formation of ionic halogen bonds (IXBs) in the hydration of bromobenzene and iodobenzene radical cations in the gas phase. We present a combined thermochemical investigation using the mass-selected ion mobility (MSIM) technique and density functional theory (DFT) calculations of the stepwise hydration of the fluoro, chloro, bromo, and iodobenzene radical cations. The binding energy associated with the formation of an IXB in the hydration of the iodobenzene cation (11.2 kcal mol -1 ) is about 20% higher than the typical unconventional ionic hydrogen bond (IHB) of the CH δ+ OH 2 interaction. The formation of an IXB in the hydration of the iodobenzene cation involves a significant entropy loss (29 cal mol -1 K -1 ) resulting from the formation of a more ordered structure and a highly directional interaction between the oxygen lone pair of electrons of water and the electropositive region around the iodine atom of the iodobenzene cation. In comparison, the hydration of the fluorobenzene and chlorobenzene cations where IHBs are formed, -ΔS° = 18-21 cal mol -1 K -1 consistent with the formation of less ordered structures and loose interactions. The electrostatic potentials on the lowest energy structures of the hydrated halogenated benzene radical cations show clearly that the formation of an IXB is driven by a positively charged σ-hole on the external side of the halogen atom X along the C-X bond axis. The size of the σ-hole increases significantly in bromobenzene and iodobenzene radical cations which results in strong

  2. 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...

  3. Covalent magnetism, exchange interactions and anisotropy of the high temperature layered antiferromagnet MnB₂.

    Science.gov (United States)

    Khmelevskyi, S; Mohn, P

    2012-01-11

    The investigation of the electronic structure and magnetism for the compound MnB(2) with crystal structure type AlB(2) has been revisited to resolve contradictions between various experimental and theoretical results present in the literature. We find that MnB(2) exhibits an interesting example of a Kübler's covalent magnetism (Williams et al 1981 J. Appl. Phys. 52 2069). The covalent magnetism also appears to be the source of some disagreement between the calculated values of the magnetic moments and those given by neutron diffraction experiments. We show that this shortcoming is due to the atomic sphere approximation applied in earlier calculations. The application of the disordered local moment approach and the calculation of the inter-atomic exchange interactions within the Liechtenstein formalism reveal strong local moment antiferromagnetism with a high Néel temperature predicted from Monte Carlo simulations. A fully relativistic band structure calculation and then the application of the torque method yields a strong in-plane anisotropy of the Mn magnetic moments. The agreement of these results with neutron diffraction studies rules out any possible weak itinerant electron magnetism scenarios as proposed earlier for MnB(2).

  4. Hydrogen Bonding to Alkanes: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen; Olesen, Solveig Gaarn

    2009-01-01

    The structural, vibrational, and energetic properties of adducts of alkanes and strong cationic proton donors were studied with composite ab initio calculations. Hydrogen bonding in [D-H+ H-alkyl] adducts contributes to a significant degree to the interactions between the two components, which...... are stronger in adducts of isobutane and in adducts of stronger acids. Intramolecular hydrogen bonding in protonated long-chain alcohols manifests itself in the same manner as intermolecular hydrogen bonding and can be equally strong. Udgivelsesdato: 12 juni 2009...

  5. Thermal solid-state Z/E isomerization of 2-alkylidene-4-oxothiazolidines: effects of non-covalent interactions

    Directory of Open Access Journals (Sweden)

    ZDRAVKO DŽAMBASKI

    2011-03-01

    Full Text Available Configurational isomerization of stereo-defined 5-substituted and unsubstituted 2-alkylidene-4-oxothiazolidines (1 in the solid state, giving the Z/E mixtures in various ratios, was investigated by 1H-NMR spectroscopy, X-ray powder crystallography and differential scanning calorimetry (DSC. The Z/E composition can be rationalized in terms of non-covalent interactions, involving intermolecular and intramolecular hydrogen bonding and directional non-bonded 1,5-type S×××O interactions. X-Ray powder crystallography, using selected crystalline (Z-4-oxothiazolidine substrates, revealed transformation to the amorphous state during the irreversible Z®E process. A correlation between previous results on the Z/E isomerization in solution and now in the solid state was established.

  6. DETERMINANTS OF ORI001 TYPE GOVERNMENT BOND

    Directory of Open Access Journals (Sweden)

    Yosandi Yulius

    2011-09-01

    Full Text Available The need to build a strong bond market is amenable, especially after the 1997 crises. This paper analyzes the influence of deposit interest rate, foreign exchange rates, and Composite Stock Price Index on yield-to-maturity of Bond Series Retail ORI001, employing monthly data from Bloomberg information service, 2006(8 to 2008(12, using Generalized Autoregressive Conditional Heteroscedasticity type models. It finds the evidence that deposit interest rate and exchange rate have positive significant influence on the bond, and that stock index has a negative significant influence on the bond. It also finds that Deposit Interest Rate, exchange rate, and the stock index significantly influence the bond altogether.Keywords: Interest rate, exchange rate, composite stock price index, yield-to-maturity, bondJEL classification numbers: G12, G15

  7. Supramolecular catalysis. Part 1: non-covalent interactions as a tool for building and modifying homogeneous catalysts.

    Science.gov (United States)

    Raynal, Matthieu; Ballester, Pablo; Vidal-Ferran, Anton; van Leeuwen, Piet W N M

    2014-03-07

    Supramolecular catalysis is a rapidly expanding discipline which has benefited from the development of both homogeneous catalysis and supramolecular chemistry. The properties of classical metal and organic catalysts can now be carefully tailored by means of several suitable approaches and the choice of reversible interactions such as hydrogen bond, metal-ligand, electrostatic and hydrophobic interactions. The first part of these two subsequent reviews will be dedicated to catalytic systems for which non-covalent interactions between the partners of the reaction have been designed although mimicking enzyme properties has not been intended. Ligand, metal, organocatalyst, substrate, additive, and metal counterion are reaction partners that can be held together by non-covalent interactions. The resulting catalysts possess unique properties compared to analogues lacking the assembling properties. Depending on the nature of the reaction partners involved in the interactions, distinct applications have been accomplished, mainly (i) the building of bidentate ligand libraries (intra ligand-ligand), (ii) the building of di- or oligonuclear complexes (inter ligand-ligand), (iii) the alteration of the coordination spheres of a metal catalyst (ligand-ligand additive), and (iv) the control of the substrate reactivity (catalyst-substrate). More complex systems that involve the cooperative action of three reaction partners have also been disclosed. In this review, special attention will be given to supramolecular catalysts for which the observed catalytic activity and/or selectivity have been imputed to non-covalent interaction between the reaction partners. Additional features of these catalysts are the easy modulation of the catalytic performance by modifying one of their building blocks and the development of new catalytic pathways/reactions not achievable with classical covalent catalysts.

  8. Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds.

    Science.gov (United States)

    Alkorta, Ibon; Legon, Anthony C

    2017-10-23

    It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N₂, CO, HC≡CH, CH₂=CH₂, C₃H₆, PH₃, H₂S, HCN, H₂O, H₂CO and NH₃) and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H₂O, F₂, Cl₂, Br₂, ClF, BrCl, H₃SiF, H₃GeF, F₂CO, CO₂, N₂O, NO₂F, PH₂F, AsH₂F, SO₂, SeO₂, SF₂, and SeF₂) can be represented to good approximation by means of the equation D e = c ' N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ' is a constant, conveniently chosen to have the value 1.00 kJ mol -1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1) the hydrogen bond; (2) the halogen bond; (3) the tetrel bond; (4) the pnictogen bond; and (5) the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

  9. Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds

    Directory of Open Access Journals (Sweden)

    Ibon Alkorta

    2017-10-01

    Full Text Available It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N2, CO, HC≡CH, CH2=CH2, C3H6, PH3, H2S, HCN, H2O, H2CO and NH3 and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H2O, F2, Cl2, Br2, ClF, BrCl, H3SiF, H3GeF, F2CO, CO2, N2O, NO2F, PH2F, AsH2F, SO2, SeO2, SF2, and SeF2 can be represented to good approximation by means of the equation D e = c ′ N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ′ is a constant, conveniently chosen to have the value 1.00 kJ mol−1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1 the hydrogen bond; (2 the halogen bond; (3 the tetrel bond; (4 the pnictogen bond; and (5 the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

  10. X hydrogen bonds

    Indian Academy of Sciences (India)

    sigma electrons, can be hydrogen bond acceptors.11–14. The recent IUPAC report and recommendation on hydro gen bond have recognised the diverse nature of hydro- gen bond donors and acceptors.13,14. Unlike methane, hydrogen bonding by higher alkanes has not received much attention. One of the earlier works.

  11. Enhancement of the performance of covalently immobilized lipase ...

    African Journals Online (AJOL)

    STORAGESEVER

    2010-06-07

    Jun 7, 2010 ... FT-IR, fourier transform infrared. the enzyme towards organic media (Xie et al., ... characterized by FT-IR spectroscopy (Zeiss, Specord M 80) using. KBr method. Covalent immobilization of lipase in the ... and kcat, interpreted from the Lineweaver-Burk plots, were shown in Table 1. The data indicate that the ...

  12. Covalent bindings in proteins following UV-C irradiation

    International Nuclear Information System (INIS)

    Diezel, W.; Meffert, H.; Soennichsen, N.; Reinicke, C.

    1980-01-01

    Following a UV-C irradiation of catalase cross-linked catalase subunits could be detected by sodium dodecylsulfate gel electrophoresis. The subunits of aldolase were not cross-linked. The origin of covalent bindings in the catalase molecule is suggested to be effected by a free radical chain reaction induced by the heme component of catalase after UV-C irradiation. (author)

  13. Covalent microcontact printing of proteins fro cell patterning

    NARCIS (Netherlands)

    Rozkiewicz, D.I.; Kraan, Yvonne M.; Werten, Marc W.T.; de Wolf, Frits A.; Subramaniam, Vinod; Ravoo, B.J.; Reinhoudt, David

    2006-01-01

    We describe a straightforward approach to the covalent immobilization of cytophilic proteins by microcontact printing, which can be used to pattern cells on substrates. Cytophilic proteins are printed in micropatterns on reactive self-assembled monolayers by using imine chemistry. An

  14. Hybridization characteristics of biomolecular adaptors, covalent DNA streptavidin conjugates

    NARCIS (Netherlands)

    Niemeyer, CM; Burger, W; Hoedemakers, RMJ

    1998-01-01

    Semisynthetic, covalent streptavidin-DNA adducts are versatile molecular connectors for the fabrication of both nano-and microstructured protein arrays by use of DNA hybridization. In this study, the hybridization characteristics of six adduct species, each containing a different DNA sequence of 21

  15. Covalently cross-linked polyetheretherketone proton exchange membrane for DMFC

    CSIR Research Space (South Africa)

    Luo, H

    2009-05-01

    Full Text Available The proton exchange membrane was prepared by covalent cross-linking sulfonated-sulfinated polyetheretherketone. The cross-linked membrane showed high proton conductivity (0.04 S/cm) with suitable water uptake, low methanol permeability (2.21 × 10...

  16. Evidence for covalent binding of epicocconone with proteins from ...

    Indian Academy of Sciences (India)

    TECS

    Evidence for covalent binding of epicocconone with proteins from synchronous fluorescence spectra ... the interaction of epicocconone with human serum albumin is significantly different from its interaction with surfactant assemblies. .... at 620 nm is collected at right angles to the direction of the excitation beam, at magic ...

  17. Macrophage migration inhibitory factor covalently complexed with phenethyl isothiocyanate

    OpenAIRE

    Tyndall, Joel D. A.; Lue, Hongqi; Rutledge, Malcolm T.; Bernhagen, Jurgen; Hampton, Mark B.; Wilbanks, Sigurd M.

    2012-01-01

    Macrophage migration inhibitory factor undergoes a localized conformational shift in response to covalent modification by phenethyl isothiocyanate, a natural compound with anti-inflammatory and anticancer properties. The inhibitor sits within a deep hydrophobic pocket and defines a potential target for the development of improved inhibitors.

  18. Improved covalent functionalization of multi-walled carbon ...

    Indian Academy of Sciences (India)

    Abstract. Ascorbic acid has been covalently linked to multi-walled carbon nanotubes (MWCNTs). The structures of the functionalized MWCNTs were characterized with Fourier-transform infrared spectroscopy. Thermogravi- metric analysis results also demonstrated the presence of organic portions of the functionalized ...

  19. Characterization of Hydrogen Bonds by IR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Vojta, D.

    2012-05-01

    Full Text Available In the identification and quantification of hydrogen bond, as one of the most abundant non-covalent interactions in phenomena like self-assembly and molecular recognition, IR spectrosopy has been employed as the most sensitive method. The performance of the high dilution method enables determination of the stability constant of hydrogen-bonded complex as one of the most important thermodynamic quantities used in their characterization. However, the alleged experimental simplicity of the mentioned method is loaded with errors originating not only from researcher intervention but also independent from it. The second source of error is particularly emphasized and elaborated in this paper, which is designed as the recipe for the successful characterization of hydrogen bonds. Besides the enumeration of all steps in the determination of hydrogen-bonded stability constants, the reader can be acquainted with the most important ex perimental conditions that should be fulfilled in order to minimize the naturally occurring errors in this type of investigation. In the spectral analysis, the application of both uni- and multivariate approach has been discussed. Some computer packages, considering the latter, are mentioned, described, and recommended. KUI -10/2012Received August 1, 2011Accepted October 24, 2011

  20. H-Bonding Cooperativity Effects in Amyloids: Quantum Mechanical and Molecular Mechanics Study

    Czech Academy of Sciences Publication Activity Database

    Přenosil, Ondřej; Pitoňák, Michal; Sedlák, Robert; Kabeláč, Martin; Hobza, Pavel

    2011-01-01

    Roč. 225, č. 5 (2011), s. 553-574 ISSN 0942-9352 R&D Projects: GA MŠk LC512 Institutional research plan: CEZ:AV0Z40550506 Keywords : non-covalent interaction * hydrogen bond * amyloids * DFT Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.568, year: 2011

  1. Evolution of the chemical bonding nature and electrode activity of indium selenide upon the composite formation with graphene nanosheets

    International Nuclear Information System (INIS)

    Oh, Seung Mi; Lee, Eunsil; Adpakpang, Kanyaporn; Patil, Sharad B.; Park, Mi Jin; Lim, Young Soo; Lee, Kyu Hyoung; Kim, Jong-Young; Hwang, Seong-Ju

    2015-01-01

    Graphical abstract: Display Omitted -- Highlights: • In 4 Se 2.85 @graphene nanocomposite is easily prepared by high energy mechanical milling process. • The bond covalency of In 4 Se 2.85 is notably changed upon the composite formation with graphene. • In 4 Se 2.85 @graphene nanocomposite shows promising anode performance for lithium ion battery. -- Abstract: Evolution of the chemical bonding nature and electrochemical activity of indium selenide upon the composite formation with carbon species is systematically investigated. Nanocomposites of In 4 Se 2.85 @graphene and In 4 Se 2.85 @carbon-black are synthesized via a solid state reaction between In and Se elements, and the following high energy mechanical milling of In 4 Se 2.85 with graphene and carbon-black, respectively. The high energy mechanical milling (HEMM) of In 4 Se 2.85 with carbon species gives rise to a decrease of particle size with a significant depression of the crystallinity of In 4 Se 2.85 phase. In contrast to the composite formation with carbon-black, that with graphene induces a notable decrease of (In−Se) bond covalency, underscoring significant chemical interaction between graphene and In 4 Se 2.85 . Both the nanocomposites of In 4 Se 2.85 @graphene and In 4 Se 2.85 @carbon-black show much better anode performance for lithium ion batteries with larger discharge capacity and better cyclability than does the pristine In 4 Se 2.85 material, indicating the beneficial effect of composite formation on the electrochemical activity of indium selenide. Between the present nanocomposites, the electrode performance of the In 4 Se 2.85 @graphene nanocomposite is superior to that of the In 4 Se 2.85 @carbon-black nanocomposite, which is attributable to the weakening of (In−Se) bonds upon the composite formation with graphene as well as to the better mixing between In 4 Se 2.85 and graphene. The present study clearly demonstrates that the composite formation with graphene has strong influence

  2. Adhesive wafer bonding

    Science.gov (United States)

    Niklaus, F.; Stemme, G.; Lu, J.-Q.; Gutmann, R. J.

    2006-02-01

    Wafer bonding with intermediate polymer adhesives is an important fabrication technique for advanced microelectronic and microelectromechanical systems, such as three-dimensional integrated circuits, advanced packaging, and microfluidics. In adhesive wafer bonding, the polymer adhesive bears the forces involved to hold the surfaces together. The main advantages of adhesive wafer bonding include the insensitivity to surface topography, the low bonding temperatures, the compatibility with standard integrated circuit wafer processing, and the ability to join different types of wafers. Compared to alternative wafer bonding techniques, adhesive wafer bonding is simple, robust, and low cost. This article reviews the state-of-the-art polymer adhesive wafer bonding technologies, materials, and applications.

  3. Optimized assembly and covalent coupling of single-molecule DNA origami nanoarrays.

    Science.gov (United States)

    Gopinath, Ashwin; Rothemund, Paul W K

    2014-12-23

    Artificial DNA nanostructures, such as DNA origami, have great potential as templates for the bottom-up fabrication of both biological and nonbiological nanodevices at a resolution unachievable by conventional top-down approaches. However, because origami are synthesized in solution, origami-templated devices cannot easily be studied or integrated into larger on-chip architectures. Electrostatic self-assembly of origami onto lithographically defined binding sites on Si/SiO2 substrates has been achieved, but conditions for optimal assembly have not been characterized, and the method requires high Mg2+ concentrations at which most devices aggregate. We present a quantitative study of parameters affecting origami placement, reproducibly achieving single-origami binding at 94±4% of sites, with 90% of these origami having an orientation within ±10° of their target orientation. Further, we introduce two techniques for converting electrostatic DNA-surface bonds to covalent bonds, allowing origami arrays to be used under a wide variety of Mg2+-free solution conditions.

  4. Formation of a covalent complex between the terminal protein of pneumococcal bacteriophage Cp-1 and 5'-dAMP

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, P.; Hermoso, J.M.; Garcia, J.A.; Garcia, E.; Lopez, R.; Salas, M.

    1986-04-01

    Incubation of extracts of Cp-1-infected Streptococcus pneumoniae with (..cap alpha..-/sup 32/P)dATP produced a labeled protein with the electrophoretic mobility of the Cp-1 terminal protein. The reaction product was resistant to treatment with micrococcal nuclease and sensitive to treatment with proteinase K. Incubation of the /sup 32/P-labeled protein with 5 M piperidine for 4 h at 50/sup 0/C released 5'-dAMP, indicating that a covalent complex between the terminal protein and 5'-dAMP was formed in vitro. When the four deoxynucleoside triphosphates were included in the reaction mixture, a labeled complex of slower electrophoretic mobility in sodium dodecyl sulfate-polyacrylamide gels than the terminal protein-dAMP complex was also found, indicating that the Cp-1 terminal protein-dAMP complex can be elongated and, therefore, that it is an initiation complex. Treatment of the /sup 32/P-labeled terminal protein-dAMP complex with 5.8 M HCl at 110/sup 0/C for 2 h yielded phosphothreonine. These results, together with the resistance of the terminal protein-DNA linkage to hydroxylamine, suggest that the Cp-1 terminal protein is covalently linked to the DNA through a phosphoester bond between L-threonine and 5'-dAMP, namely, a O-5'-deoxyadenylyl-L-threonine bond.

  5. Formation of a covalent complex between the terminal protein of pneumococcal bacteriophage Cp-1 and 5'-dAMP

    International Nuclear Information System (INIS)

    Garcia, P.; Hermoso, J.M.; Garcia, J.A.; Garcia, E.; Lopez, R.; Salas, M.

    1986-01-01

    Incubation of extracts of Cp-1-infected Streptococcus pneumoniae with [α- 32 P]dATP produced a labeled protein with the electrophoretic mobility of the Cp-1 terminal protein. The reaction product was resistant to treatment with micrococcal nuclease and sensitive to treatment with proteinase K. Incubation of the 32 P-labeled protein with 5 M piperidine for 4 h at 50 0 C released 5'-dAMP, indicating that a covalent complex between the terminal protein and 5'-dAMP was formed in vitro. When the four deoxynucleoside triphosphates were included in the reaction mixture, a labeled complex of slower electrophoretic mobility in sodium dodecyl sulfate-polyacrylamide gels than the terminal protein-dAMP complex was also found, indicating that the Cp-1 terminal protein-dAMP complex can be elongated and, therefore, that it is an initiation complex. Treatment of the 32 P-labeled terminal protein-dAMP complex with 5.8 M HCl at 110 0 C for 2 h yielded phosphothreonine. These results, together with the resistance of the terminal protein-DNA linkage to hydroxylamine, suggest that the Cp-1 terminal protein is covalently linked to the DNA through a phosphoester bond between L-threonine and 5'-dAMP, namely, a O-5'-deoxyadenylyl-L-threonine bond

  6. Advances in oral controlled drug delivery: the role of drug-polymer and interpolymer non-covalent interactions.

    Science.gov (United States)

    De Robertis, Simona; Bonferoni, Maria Cristina; Elviri, Lisa; Sandri, Giuseppina; Caramella, Carla; Bettini, Ruggero

    2015-03-01

    After more than four decades of intense research, oral controlled drug delivery systems (DDSs) still represent a topic of major interest for pharmaceutical scientist and formulators. This can be explained in part by considering the economic value of oral DDSs whose market accounts for more than half of the overall drug delivery market. Polymeric systems based on drug-polymer non-covalent interaction represent a limited, but growing part of the field. Despite the large amount of literature and published reviews covering specific aspects, there is still need for a review of the relevant literature providing a general picture of the topic. The present review aims at presenting the latest findings in drug-polymer and interpolymer non-covalent interactions in oral controlled delivery while providing a specific perspective and a critical point of view, particularly on the tools and methods used for the study of these DDSs. Four main sections are considered: i) ionic interactions between drugs and polymers; ii) interpolymer complexes; iii) hydrogen bond; and iv) hydrophobic interactions. The largest part of the scientific literature deals with systems based on drug-polymer ionic interactions while hydrogen bonding and hydrophobic interaction though, very promising, are more difficult to exploit, and therefore less studied. An accurate and exhaustive representation of the specific role of the chemical functions in establishing predictable interactions between drug and polymers is still required.

  7. Hydrogen bonding characterization in water and small molecules

    Science.gov (United States)

    Silvestrelli, Pier Luigi

    2017-06-01

    The prototypical hydrogen bond in water dimer and hydrogen bonds in the protonated water dimer, in other small molecules, in water cyclic clusters, and in ice, covering a wide range of bond strengths, are theoretically investigated by first-principles calculations based on density functional theory, considering not only a standard generalized gradient approximation functional but also, for the water dimer, hybrid and van der Waals corrected functionals. We compute structural, energetic, and electrostatic (induced molecular dipole moments) properties. In particular, hydrogen bonds are characterized in terms of differential electron density distributions and profiles, and of the shifts of the centres of maximally localized Wannier functions. The information from the latter quantities can be conveyed to a single geometric bonding parameter that appears to be correlated with the Mayer bond order parameter and can be taken as an estimate of the covalent contribution to the hydrogen bond. By considering the water trimer, the cyclic water hexamer, and the hexagonal phase of ice, we also elucidate the importance of cooperative/anticooperative effects in hydrogen-bonding formation.

  8. Native lignin for bonding fiber boards - evaluation of bonding mechanisms in boards made from laccase-treated fibers of beech (Fagus sylvatica)

    DEFF Research Database (Denmark)

    Felby, Claus; Thygesen, Lisbeth Garbrecht; Sanadi, Anand

    2004-01-01

    The auto-adhesion of beech wood (Fagus sylvatica) fibers can be enhanced by a pretreatment of the fibers with a phenol oxidase enzyme. The mechanism of enzymatic catalyzed bonding is linked to the generation of stable radicals in lignin by oxidation. Fiberboards made from laccase-treated fibers...... indicate that lignin extractives are precipitated on the fiber surfaces. The improved bonding may be related to several factors, linked to a more lignin rich fiber surface, such as surface molecular entanglements and covalent bonding between fibers through cross-linking of radicals. (C) 2004 Published...

  9. Real space in situ bond energies: toward a consistent energetic definition of bond strength.

    Science.gov (United States)

    Menéndez-Crespo, Daniel; Costales, Aurora; Francisco, Evelio; Martin Pendas, Angel

    2018-04-14

    A rigorous definition of intrinsic bond strength based on the partitioning of a molecule into real space fragments is presented. Using the domains provided by the quantum theory of atoms in molecules (QTAIM) together with the interacting quantum atoms (IQA) energetic decomposition, we show how an in situ bond strength, matching all the requirements of an intrinsic bond energy, can be defined between each pair of fragments. Total atomization or fragmentation energies are shown to be equal to the sum of these in situ bond energies (ISBEs) if the energies of the fragments are measured with respect to their in-the-molecule state. These energies usually lie above the ground state of the isolated fragments by quantities identified with the standard fragment relaxation or deformation energies, which are also provided by the protocol. Deformation energies bridge dissociation energies with ISBEs, and can be dissected using well-known tools of real space theories of chemical bonding. Similarly, ISBEs can be partitioned into ionic and covalent contributions, and this feature adds to the chemical appeal of the procedure. All the energetic quantities examined are observable and amenable, in principle, to experimental determination. Several systems, exemplifying the role of each energetic term herein presented are used to show the power of the approach. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Quantitative Measurement of GPCR Endocytosis via Pulse-Chase Covalent Labeling.

    Science.gov (United States)

    Kumagai, Hidetoshi; Ikeda, Yuichi; Motozawa, Yoshihiro; Fujishiro, Mitsuhiro; Okamura, Tomohisa; Fujio, Keishi; Okazaki, Hiroaki; Nomura, Seitaro; Takeda, Norifumi; Harada, Mutsuo; Toko, Haruhiro; Takimoto, Eiki; Akazawa, Hiroshi; Morita, Hiroyuki; Suzuki, Jun-ichi; Yamazaki, Tsutomu; Yamamoto, Kazuhiko; Komuro, Issei; Yanagisawa, Masashi

    2015-01-01

    G protein-coupled receptors (GPCRs) play a critical role in many physiological systems and represent one of the largest families of signal-transducing receptors. The number of GPCRs at the cell surface regulates cellular responsiveness to their cognate ligands, and the number of GPCRs, in turn, is dynamically controlled by receptor endocytosis. Recent studies have demonstrated that GPCR endocytosis, in addition to affecting receptor desensitization and resensitization, contributes to acute G protein-mediated signaling. Thus, endocytic GPCR behavior has a significant impact on various aspects of physiology. In this study, we developed a novel GPCR internalization assay to facilitate characterization of endocytic GPCR behavior. We genetically engineered chimeric GPCRs by fusing HaloTag (a catalytically inactive derivative of a bacterial hydrolase) to the N-terminal end of the receptor (HT-GPCR). HaloTag has the ability to form a stable covalent bond with synthetic HaloTag ligands that contain fluorophores or a high-affinity handle (such as biotin) and the HaloTag reactive linker. We selectively labeled HT-GPCRs at the cell surface with a HaloTag PEG ligand, and this pulse-chase covalent labeling allowed us to directly monitor the relative number of internalized GPCRs after agonist stimulation. Because the endocytic activities of GPCR ligands are not necessarily correlated with their agonistic activities, applying this novel methodology to orphan GPCRs, or even to already characterized GPCRs, will increase the likelihood of identifying currently unknown ligands that have been missed by conventional pharmacological assays.

  11. Covalent immobilisation of VEGF on plasma-coated electrospun scaffolds for tissue engineering applications.

    Science.gov (United States)

    Guex, A G; Hegemann, D; Giraud, M N; Tevaearai, H T; Popa, A M; Rossi, R M; Fortunato, G

    2014-11-01

    Recent findings in the field of biomaterials and tissue engineering provide evidence that surface immobilised growth factors display enhanced stability and induce prolonged function. Cell response can be regulated by material properties and at the site of interest. To this end, we developed scaffolds with covalently bound vascular endothelial growth factor (VEGF) and evaluated their mitogenic effect on endothelial cells in vitro. Nano- (254±133 nm) or micro-fibrous (4.0±0.4 μm) poly(ɛ-caprolactone) (PCL) non-wovens were produced by electrospinning and coated in a radio frequency (RF) plasma process to induce an oxygen functional hydrocarbon layer. Implemented carboxylic acid groups were converted into amine-reactive esters and covalently coupled to VEGF by forming stable amide bonds (standard EDC/NHS chemistry). Substrates were analysed by X-ray photoelectron spectroscopy (XPS), enzyme-linked immuno-assays (ELISA) and immunohistochemistry (anti-VEGF antibody and VEGF-R2 binding). Depending on the reaction conditions, immobilised VEGF was present at 127±47 ng to 941±199 ng per substrate (6mm diameter; concentrations of 4.5 ng mm(-2) or 33.3 ng mm(-2), respectively). Immunohistochemistry provided evidence for biological integrity of immobilised VEGF. Endothelial cell number of primary endothelial cells or immortalised endothelial cells were significantly enhanced on VEGF-functionalised scaffolds compared to native PCL scaffolds. This indicates a sustained activity of immobilised VEGF over a culture period of nine days. We present a versatile method for the fabrication of growth factor-loaded scaffolds at specific concentrations. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Spectroscopic and DFT Studies of Second Sphere Variants of the Type 1 Copper Site in Azurin: Covalent and Non-Local Electrostatic Contributions to Reduction Potentials

    Science.gov (United States)

    Hadt, Ryan G.; Sun, Ning; Marshall, Nicholas M.; Hodgson, Keith O.; Hedman, Britt; Lu, Yi; Solomon, Edward I.

    2012-01-01

    The reduction potentials (E0) of type 1 (T1) or blue copper (BC) sites in proteins and enzymes with identical first coordination spheres around the redox active copper ion can vary by ~400 mV. Here, we use a combination of low temperature electronic absorption and magnetic circular dichroism, electron paramagnetic resonance, resonance Raman, and S K-edge X-ray absorption spectroscopies to investigate a series of second sphere variants—F114P, N47S, and F114N in Pseudomonas aeruginosa azurin (Az)—which modulate hydrogen bonding to and protein derived dipoles nearby the Cu-S(Cys) bond. Density functional theory (DFT) calculations correlated to the experimental data allow for the fractionation of the contributions to tuning E0 into covalent and non-local electrostatic components. These are found to be significant, comparable in magnitude, and additive for active H-bonds, while passive H-bonds are mostly non-local electrostatic in nature. For dipoles, these terms can be additive to or oppose one another. This study provides a methodology for uncoupling covalency from non-local electrostatics, which, when coupled to X-ray crystallographic data, distinguishes specific local interactions from more long range protein/active interactions, while affording further insight into the second sphere mechanisms available to the protein to tune the E0 of electron transfer sites in biology. PMID:22985400

  13. A covalent PIN1 inhibitor selectively targets cancer cells by a dual mechanism of action

    Science.gov (United States)

    Campaner, Elena; Rustighi, Alessandra; Zannini, Alessandro; Cristiani, Alberto; Piazza, Silvano; Ciani, Yari; Kalid, Ori; Golan, Gali; Baloglu, Erkan; Shacham, Sharon; Valsasina, Barbara; Cucchi, Ulisse; Pippione, Agnese Chiara; Lolli, Marco Lucio; Giabbai, Barbara; Storici, Paola; Carloni, Paolo; Rossetti, Giulia; Benvenuti, Federica; Bello, Ezia; D'Incalci, Maurizio; Cappuzzello, Elisa; Rosato, Antonio; Del Sal, Giannino

    2017-06-01

    The prolyl isomerase PIN1, a critical modifier of multiple signalling pathways, is overexpressed in the majority of cancers and its activity strongly contributes to tumour initiation and progression. Inactivation of PIN1 function conversely curbs tumour growth and cancer stem cell expansion, restores chemosensitivity and blocks metastatic spread, thus providing the rationale for a therapeutic strategy based on PIN1 inhibition. Notwithstanding, potent PIN1 inhibitors are still missing from the arsenal of anti-cancer drugs. By a mechanism-based screening, we have identified a novel covalent PIN1 inhibitor, KPT-6566, able to selectively inhibit PIN1 and target it for degradation. We demonstrate that KPT-6566 covalently binds to the catalytic site of PIN1. This interaction results in the release of a quinone-mimicking drug that generates reactive oxygen species and DNA damage, inducing cell death specifically in cancer cells. Accordingly, KPT-6566 treatment impairs PIN1-dependent cancer phenotypes in vitro and growth of lung metastasis in vivo.

  14. Highly Elastic and Ultratough Hybrid Ionic-Covalent Hydrogels with Tunable Structures and Mechanics.

    Science.gov (United States)

    Yang, Yanyu; Wang, Xing; Yang, Fei; Wang, Luning; Wu, Decheng

    2018-03-25

    Hybrid ionically-covalently crosslinked double-network (DN) hydrogels are attracting increasing attention on account of their self-recovery ability and fatigue resistance, but their relative low mechanical strength and tedious performance adjustment severely limit their applications. Herein, a new strategy to concurrently fabricate hybrid ionic-covalent DN hydrogels and modulate their structures and mechanics is reported, in which an in situ formed chitosan ionic network is incorporated by post-crosslinking the chitosan-based composite hydrogel using multivalent anions solutions. The obtained hybrid DN hydrogels exhibit predominant mechanical properties including superior elastic modulus, high tensile strength, and ultrahigh fracture energy because of the more efficient energy dissipation of rigid short-chain chitosan network. Notably, the swollen hydrogels still remain mechanically strong and tough even after immersion in water for 24 h. More significantly, simply changing the post-crosslinking time can vary the compactness and rigidity of the chitosan network in situ, achieving flexible and efficient modulation of the structures and mechanics of the hybrid DN hydrogels. This study opens up a new horizon in the preparation and regulation of DN hydrogels for promising applications in tissue scaffolds, actuators, and wearable devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Covalent linkage of nanodiamond-paclitaxel for drug delivery and cancer therapy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Kuang-Kai; Wang, Chi-Ching; Chao, Jui-I [Department of Biological Science and Technology, National Chiao Tung University, Hsinchu 30013, Taiwan (China); Zheng, Wen-Wei; Lo, Yu-Shiu; Chen, Chinpiao [Department of Chemistry, National Dong Hwa University, Hualien 97401, Taiwan (China); Chiu, Yu-Chung; Cheng, Chia-Liang, E-mail: clcheng@mail.ndhu.edu.tw, E-mail: chinpiao@mail.ndhu.edu.tw, E-mail: jichao@faculty.nctu.edu.tw [Department of Physics, National Dong Hwa University, Hualien 97401, Taiwan (China)

    2010-08-06

    A nanoparticle-conjugated cancer drug provides a novel strategy for cancer therapy. In this study, we manipulated nanodiamond (ND), a carbon nanomaterial, to covalently link paclitaxel for cancer drug delivery and therapy. Paclitaxel was bound to the surface of 3-5 nm sized ND through a succession of chemical modifications. The ND-paclitaxel conjugation was measured by atomic force microscope and nuclear magnetic resonance spectroscopy, and confirmed with infrared spectroscopy by the detection of deuterated paclitaxel. Treatment with 0.1-50 {mu}g ml{sup -1} ND-paclitaxel for 48 h significantly reduced the cell viability in the A549 human lung carcinoma cells. ND-paclitaxel induced both mitotic arrest and apoptosis in A549 cells. However, ND alone or denatured ND-paclitaxel (after treatment with strong alkaline solution, 1 M NaOH) did not induce the damage effects on A549 cells. ND-paclitaxel was taken into lung cancer cells in a concentration-dependent manner using flow cytometer analysis. The ND-paclitaxel particles were located in the microtubules and cytoplasm of A549 cells observed by confocal microscopy. Furthermore, ND-paclitaxel markedly blocked the tumor growth and formation of lung cancer cells in xenograft SCID mice. Together, we provide a functional covalent conjugation of ND-paclitaxel, which can be delivered into lung carcinoma cells and preserves the anticancer activities on the induction of mitotic blockage, apoptosis and anti-tumorigenesis.

  16. S-nitrosoglutathione covalently modifies cysteine residues of human carbonyl reductase 1 and affects its activity.

    Science.gov (United States)

    Hartmanová, Tereza; Tambor, Vojtěch; Lenčo, Juraj; Staab-Weijnitz, Claudia A; Maser, Edmund; Wsól, Vladimír

    2013-02-25

    Carbonyl reductase 1 (CBR1 or SDR21C1) is a ubiquitously-expressed, cytosolic, monomeric, and NADPH-dependent enzyme. CBR1 participates in apoptosis, carcinogenesis and drug resistance, and has a protective role in oxidative stress, cancer and neurodegeneration. S-Nitrosoglutathione (GSNO) represents the newest addition to its diverse substrate spectrum, which includes a wide range of xenobiotics and endogenous substances. GSNO has also been shown to covalently modify and inhibit CBR1. The aim of the present study was to quantify and characterize the resulting modifications. Of five candidate cysteines for modification by 2 mM GSNO (positions 26, 122, 150, 226, 227), the last four were analyzed using MALDI-TOF/TOF mass spectrometry and then quantified using the Selected Reaction Monitoring Approach on hyphenated HPLC with a triple quadrupole mass spectrometer. The analysis confirmed GSNO concentration-dependent S-glutathionylation of cysteines at positions 122, 150, 226, 227 which was 2-700 times higher compared to wild-type CBR1 (WT-CBR1). Moreover, a disulfide bond between neighboring Cys-226 and Cys-227 was detected. We suggest a role of these two cysteines as a redox-sensitive cysteine pair. The catalytic properties of wild-type and enzyme modified with 2 mM GSNO were also investigated by steady state kinetic experiments with various substrates. GSNO treatment of CBR1 resulted in a 2-5-fold decrease in kcat with menadione, 4-benzoylpyridine, 2,3-hexanedione, daunorubicin and 1,4-naphthoquinone. In contrast, the same treatment increased kcat for substrates containing a 1,2-diketo group in a ring structure (1,2-naphthoquinone, 9,10-phenanthrenequinone, isatin). Except for 9,10-phenanthrenequinone, all changes in kcat were at least in part compensated for by a similar change in Km, overall yielding no drastic changes in catalytic efficiency. The findings indicate that GSNO-induced covalent modification of cysteine residues affects the kinetic mechanism of CBR1

  17. Shear bond strength of four commercial bonding systems to cp Ti.

    Science.gov (United States)

    Fujishima, A; Fujishima, Y; Ferracane, J L

    1995-03-01

    The purpose of this study was to evaluate the bond strength of veneering composite to commercially pure titanium (cp Ti) using several different bonding systems and a post-cure heat treatment. Four commercial bonding systems (Cesead, Kuraray; New Metacolor, Sun Medical; Silicaoater MD, Kulzer; Termoresin LC II, GC) were evaluated. Bonding was attempted with the opaque resin provided by each bonding system as well as with the New Metacolor opaque resin. New Metacolor resin composite was used for the veneering composite. Half of the specimens were subjected to a post-cure heat treatment at 100 degrees C for 30 min. The shear bond strengths were tested after aging the specimens in water at 37 degrees C for 1 d and also after thermocycling for 16.5 d (20,000 cycles). Strong bonds, exceeding 20 MPa, were achieved with all of the bonding systems with the exception of Thermoresin LC II, which is designed for noble metals. Bond strengths were only increased by the post-cure heat treatment for the New Metacolor system. Thermocycling caused a significant reduction in bond strength for the New Metacolor adn the Thermoresin LC II systems. The use of the New Metacolor opaque resin produced increased bonding for the Silicoater MD and the opaque resin produced increased bonding for the Silicoater MD and the Cesead systems, but the effect was eliminated after thermocycling. Strong, durable bonds can be achieved between composite and sandblasted cp Ti, thus enhancing the usefulness of this metal for esthetic resin-veneered crowns and other fixed prosthetics.

  18. Applications of reversible covalent chemistry in analytical sample preparation.

    Science.gov (United States)

    Siegel, David

    2012-12-07

    Reversible covalent chemistry (RCC) adds another dimension to commonly used sample preparation techniques like solid-phase extraction (SPE), solid-phase microextraction (SPME), molecular imprinted polymers (MIPs) or immuno-affinity cleanup (IAC): chemical selectivity. By selecting analytes according to their covalent reactivity, sample complexity can be reduced significantly, resulting in enhanced analytical performance for low-abundance target analytes. This review gives a comprehensive overview of the applications of RCC in analytical sample preparation. The major reactions covered include reversible boronic ester formation, thiol-disulfide exchange and reversible hydrazone formation, targeting analyte groups like diols (sugars, glycoproteins and glycopeptides, catechols), thiols (cysteinyl-proteins and cysteinyl-peptides) and carbonyls (carbonylated proteins, mycotoxins). Their applications range from low abundance proteomics to reversible protein/peptide labelling to antibody chromatography to quantitative and qualitative food analysis. In discussing the potential of RCC, a special focus is on the conditions and restrictions of the utilized reaction chemistry.

  19. Covalent interactions of acetaldehyde with the actin/microfilament system.

    Science.gov (United States)

    Xu, D S; Jennett, R B; Smith, S L; Sorrell, M F; Tuma, D J

    1989-01-01

    The covalent binding of [14C]acetaldehyde to purified rabbit skeletal muscle actin was characterized. As we have found for other cytoskeletal proteins, actin formed stable covalent adducts under reductive and non-reductive conditions. Under non-reductive conditions, individual and competition binding studies versus albumin both showed that the G-form of actin is more reactive toward acetaldehyde than the F-form. When proteins were compared on an 'equi-lysine' basis under non-reducing conditions, G-actin was found to preferentially compete with albumin for binding to acetaldehyde. Time-course dialysis studies indicated that acetaldehyde-actin adducts become more stable with prolonged incubation at 37 degrees C. These data raise the possibility that actin could be a preferential target for adduct formation in cellular systems and will serve as the basis for ongoing studies aimed at defining the role of acetaldehyde-protein adducts in ethanol-induced cell injury.

  20. Covalent binding of aniline to humic substances. 1. Kinetic studies

    Science.gov (United States)

    Weber, E.J.; Spidle, D.L.; Thorn, K.A.

    1996-01-01

    The reaction kinetics for the covalent binding of aniline with reconstituted IHSS humic and fulvic acids, unfractionated DOM isolated from Suwannee River water, and whole samples of Suwannee River water have been investigated. The reaction kinetics in each of these systems can be adequately described by a simple second-order rate expression. The effect of varying the initial concentration of aniline on reaction kinetics suggested that approximately 10% of the covalent binding sites associated with Suwannee River fulvic acid are highly reactive sites that are quickly saturated. Based on the kinetic parameters determined for the binding of aniline with the Suwannee River fulvic and humic acid isolates, it was estimated that 50% of the aniline concentration decrease in a Suwannee River water sample could be attributed to reaction with the fulvic and humic acid components of the whole water sample. Studies with Suwannee River fulvic acid demonstrated that the rate of binding decreased with decreasing pH, which parallels the decrease in the effective concentration of the neutral form, or reactive nucleophilic species of aniline. The covalent binding of aniline with Suwannee River fulvic acid was inhibited by prior treatment of the fulvic acid with hydrogen sulfide, sodium borohydride, or hydroxylamine. These observations are consistent with a reaction pathway involving nucleophilic addition of aniline to carbonyl moieties present in the fulvic acid.

  1. Photophysics of covalently functionalized single wall carbon nanotubes with verteporfin

    Science.gov (United States)

    Staicu, Angela; Smarandache, Adriana; Pascu, Alexandru; Pascu, Mihail Lucian

    2017-09-01

    Covalently functionalized single wall carbon nanotubes (SWCNT) with the photosensitizer verteporfin (VP) were synthesized and studied. Photophysical properties of the obtained compounds like optical absorption, laser-induced fluorescence and generated singlet oxygen were investigated. In order to highlight the features of the conjugated compound, its photophysical characteristics were compared with those of the mixtures of the initial components. The optical absorption data evidenced a compound that combines features of the primary SWCNTs and VP. This is the also the case of the laser induced fluorescence of the synthesized product. Moreover, fluorescence quantum yield (Φf) of the compound (Φf = 2.4%) is smaller than for the mixture of SWCNT and VP in (Φf = 3.2%). The behavior is expected, because linked VP (carrying the fluorescent moiety) transfers easier a part of its excitation energy to the SWCNT in the covalent structure. Relative to the quantum yield of singlet oxygen generation (ΦΔ) by Methylene Blue, it was found that the ΦΔ for the conjugated VP-SWCNT is 51% while for the mixture ΦΔ is 23%. The results indicate covalently functionalized single walled carbon nanotubes with verteporfin as potential compounds of interest in targeted drug delivery and photodynamic therapy.

  2. Covalent assembly of gold nanoparticles for nonvolatile memory applications.

    Science.gov (United States)

    Gupta, Raju Kumar; Kusuma, Damar Yoga; Lee, P S; Srinivasan, M P

    2011-12-01

    This work reports a versatile approach for enhancing the stability of nonvolatile memory devices through covalent assembly of functionalized gold nanoparticles. 11-mercapto-1-undecanol functionalized gold nanoparticles (AuNPs) with a narrow size distribution and particle size of about 5 nm were synthesized. Then, the AuNPs were immobilized on a SiO(2) substrate using a functionalized polymer as a surface modifier. Microscopic and spectroscopic techniques were used to characterize the AuNPs and their morphology before and after immobilization. Finally, a metal-insulator-semiconductor (MIS) type memory device with such covalently anchored AuNPs as a charge trapping layer was fabricated. The MIS structure showed well-defined counterclockwise C-V hysteresis curves indicating a good memory effect. The flat band voltage shift was 1.64 V at a swapping voltage between ±7 V. Furthermore, the MIS structure showed a good retention characteristic up to 20,000 s. The present synthetic route to covalently immobilize gold nanoparticles system will be a step towards realization for the nanoparticle-based electronic devices and related applications. © 2011 American Chemical Society

  3. Characteristics of chemical bond and vacancy formation in chalcopyrite-type CuInSe2 and related compounds

    International Nuclear Information System (INIS)

    Maeda, Tsuyoshi; Wada, Takahiro

    2009-01-01

    We studied characteristics of chemical bond and vacancy formation in chalcopyrite-type CuInSe 2 (CIS) by first principles calculations. The chalcopyrite-type CIS has two kinds of chemical bonds, Cu-Se and In-Se. The Cu-Se bond is a weak covalent bonding because electrons occupy both bonding and antibonding orbitals of Cu 3d and Se 4p and occupy only the bonding orbital (a 1 ) of Cu 4s and Se 4p and do not occupy the antibonding orbital (a 1 * ) of Cu 4s and Se 4p. On the other hand, the In-Se bond has a partially covalent and partially ionic character because the In 5s orbital covalently interacts with Se 4p; the In 5p orbital is higher than Se 4p and so the electron in the In 5p orbital moves to the Se 4p orbital. The average bond order of the Cu-Se and In-Se bonds can be calculated to be 1/4 and 1, respectively. The bond order of Cu-Se is smaller than that of In-Se. The characteristics of these two chemical bonds are related to the formation of Cu and In vacancies in CIS. The formation energy of the Cu vacancy is smaller than that of the In vacancy under both Cu-poor and In-poor conditions. The displacement (Δl) of the surrounding Se atoms after the formation of the Cu vacancy is smaller than the Δl after the formation of the In vacancy. The interesting and unique characteristics of CIS are discussed on the basis of the characteristics of the chemical bond. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  4. Australia's Bond Home Bias

    OpenAIRE

    Anil V. Mishra; 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 ...

  5. Variance Risk Premia on Stocks and Bonds

    DEFF Research Database (Denmark)

    Mueller, Philippe; Sabtchevsky, Petar; Vedolin, Andrea

    Investors in fixed income markets are willing to pay a very large premium to be hedged against shocks in expected volatility and the size of this premium can be studied through variance swaps. Using thirty years of option and high-frequency data, we document the following novel stylized facts......: First, exposure to bond market volatility is strongly priced with a Sharpe ratio of -1.8, 20% higher than what is observed in the equity market. Second, while there is strong co-movement between equity and bond market variance risk, there are distinct periods when the bond variance risk premium...... is different from the equity variance risk premium. Third, the conditional correlation between stock and bond market variance risk premium switches sign often and ranges between -60% and +90%. We then show that these stylized facts pose a challenge to standard consumption-based asset pricing models....

  6. Thermal Conductance in Cross-linked Polymers: Effects of Non-Bonding Interactions.

    Science.gov (United States)

    Rashidi, Vahid; Coyle, Eleanor J; Sebeck, Katherine; Kieffer, John; Pipe, Kevin P

    2017-05-04

    Weak interchain interactions have been considered to be a bottleneck for heat transfer in polymers, while covalent bonds are believed to give a high thermal conductivity to polymer chains. For this reason, cross-linkers have been explored as a means to enhance polymer thermal conductivity; however, results have been inconsistent. Some studies show an enhancement in the thermal conductivity for polymers upon cross-linking, while others show the opposite trend. In this work we study the mechanisms of heat transfer in cross-linked polymers in order to understand the reasons for these discrepancies, in particular examining the relative contributions of covalent (referred to here as "bonding") and nonbonding (e.g., van der Waals and electrostatic) interactions. Our results indicate cross-linkers enhance thermal conductivity primarily when they are short in length and thereby bring polymer chains closer to each other, leading to increased interchain heat transfer by enhanced nonbonding interactions between the chains (nonbonding interactions being highly dependent on interchain distance). This suggests that enhanced nonbonding interactions, rather than thermal pathways through cross-linker covalent bonds, are the primary transport mechanism by which thermal conductivity is increased. We further illustrate this by showing that energy from THz acoustic waves travels significantly faster in polymers when nonbonding interactions are included versus when only covalent interactions are present. These results help to explain prior studies that measure differing trends in thermal conductivity for polymers upon cross-linking with various species.

  7. 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

  8. Determinants Of Ori001 Type Government Bond

    OpenAIRE

    Yulius, Yosandi

    2011-01-01

    The need to build a strong bond market is amenable, especially after the 1997 crises. This paper analyzes the influence of deposit interest rate, foreign exchange rates, and Composite Stock Price Index on yield-to-maturity of Bond Series Retail ORI001, employing monthly data from Bloomberg information service, 2006(8) to 2008(12), using Generalized Autoregressive Conditional Heteroscedasticity type models. It finds the evidence that deposit interest rate and exchange rate have positive signif...

  9. Atomic Charges and Chemical Bonding in Y-Ga Compounds

    Directory of Open Access Journals (Sweden)

    Yuri Grin

    2018-02-01

    Full Text Available A negative deviation from Vegard rule for the average atomic volume versus yttrium content was found from experimental crystallographic information about the binary compounds of yttrium with gallium. Analysis of the electron density (DFT calculations employing the quantum theory of atoms in molecules revealed an increase in the atomic volumes of both Y and Ga with the increase in yttrium content. The non-linear increase is caused by the strengthening of covalent Y-Ga interactions with stronger participation of genuine penultimate shell electrons (4d electrons of yttrium in the valence region. Summing the calculated individual atomic volumes for a unit cell allows understanding of the experimental trend. With increasing yttrium content, the polarity of the Y-Ga bonding and, thus its ionicity, rises. The covalency of the atomic interactions in Y-Ga compounds is consistent with their delocalization from two-center to multi-center ones.

  10. Shear bond strength evaluation of resin composite bonded to glass-ionomer cement using self-etching bonding agents with different pH: In vitro study

    Science.gov (United States)

    Kandaswamy, Deivanayagam; Rajan, Karunamoorthy Jeyavel; Venkateshbabu, Nagendrababu; Porkodi, Ilango

    2012-01-01

    Aim: To evaluate the bonding ability of composite to unset glass-ionomer cement (GIC) using different self-etching bonding systems. Materials and Methods: One hundred samples of composite bonded to unset GIC were prepared and were divided into four groups. In Group A, composite was bonded to unset GIC employing a strong (pH 1) self-etch primer was used. In Group B, intermediary strong (pH 1.4) self-etch primer was employed. In Group C and D, mild (pH 2) and (pH 2.2) self-etch primer was employed. Shear bond strength analysis was performed at a cross-head speed of 0.5 mm/min. Results: Statistical analysis performed with one way analysis of variance and Tukey's test showed that the bond strength of composite to unset GIC was significantly higher for the mild self-etch primer group. In addition, energy dispersive x-ray (EDX) analysis was used to determine the composition of various structural phases identified by FE-SEM along the GIC-bonding agent interfaces. Conclusion: Hence this present study concludes that clinically the use of mild self-etching bonding agent over unset GIC has improved bond strength compared to the use of strong and intermediate self-etching bonding agent. PMID:22368331

  11. Stable Covalent Organic Frameworks for Exceptional Mercury Removal from Aqueous Solutions.

    Science.gov (United States)

    Huang, Ning; Zhai, Lipeng; Xu, Hong; Jiang, Donglin

    2017-02-15

    The pre-designable porous structures found in covalent organic frameworks (COFs) render them attractive as a molecular platform for addressing environmental issues such as removal of toxic heavy metal ions from water. However, a rational structural design of COFs in this aspect has not been explored. Here we report the rational design of stable COFs for Hg(II) removal through elaborate structural design and control over skeleton, pore size, and pore walls. The resulting framework is stable under strong acid and base conditions, possesses high surface area, has large mesopores, and contains dense sulfide functional termini on the pore walls. These structural features work together in removing Hg(II) from water and achieve a benchmark system that combines capacity, efficiency, effectivity, applicability, selectivity, and reusability. These results suggest that COFs offer a powerful platform for tailor-made structural design to cope with various types of pollution.

  12. β-Ketoenamine-linked covalent organic frameworks capable of pseudocapacitive energy storage.

    Science.gov (United States)

    DeBlase, Catherine R; Silberstein, Katharine E; Truong, Thanh-Tam; Abruña, Héctor D; Dichtel, William R

    2013-11-13

    Two-dimensional covalent organic frameworks (2D COFs) are candidate materials for charge storage devices because of their micro- or mesoporosity, high surface area, and ability to predictably organize redox-active groups. The limited chemical and oxidative stability of established COF linkages, such as boroxines and boronate esters, precludes these applications, and no 2D COF has demonstrated reversible redox behavior. Here we describe a β-ketoenamine-linked 2D COF that exhibits reversible electrochemical processes of its anthraquinone subunits, excellent chemical stability to a strongly acidic electrolyte, and one of the highest surface areas of the imine- or enamine-linked 2D COFs. Electrodes modified with the redox-active COF show higher capacitance than those modified with a similar non-redox-active COF, even after 5000 charge-discharge cycles. These findings demonstrate the promise of using 2D COFs for capacitive storage.

  13. Removal U(VI) from artificial seawater using facilely and covalently grafted polyacrylonitrile fibers with lysine

    Science.gov (United States)

    Li, Wenting; Liu, Qi; Liu, Jingyuan; Zhang, Hongsen; Li, Rumin; Li, Zhanshuang; Jing, Xiaoyan; Wang, Jun

    2017-05-01

    Polyacrylonitrile fibers (PANF) covalently modified with lysine (PAN-Lys) was facilely synthesized and carefully characterized. The critical factors affecting U(VI) adsorption from aqueous solution were exploited, such as initial pH, contact time, concentration and temperature. The adsorption process is strongly dependent on solution pH. With excellent adsorption capacity and high affinity toward U(VI), the process for U(VI) is extremely rapid and the equilibrium can be reached within 20 min. The thermodynamics and kinetics were strictly evaluated. In addition, the hypothetical adsorption mechanisms were proposed. Moreover, the adsorption behavior at low concentrations (3-30 μg L-1) in simulated seawater was also investigated. Therefore, PAN-Lys can be potentially utilized for the efficient removal of U(VI) from seawater.

  14. Porous Hydrogen-Bonded Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Yi-Fei Han

    2017-02-01

    Full Text Available Ordered porous solid-state architectures constructed via non-covalent supramolecular self-assembly have attracted increasing interest due to their unique advantages and potential applications. Porous metal-coordination organic frameworks (MOFs are generated by the assembly of metal coordination centers and organic linkers. Compared to MOFs, porous hydrogen-bonded organic frameworks (HOFs are readily purified and recovered via simple recrystallization. However, due to lacking of sufficiently ability to orientate self-aggregation of building motifs in predictable manners, rational design and preparation of porous HOFs are still challenging. Herein, we summarize recent developments about porous HOFs and attempt to gain deeper insights into the design strategies of basic building motifs.

  15. Testing strong interaction theories

    International Nuclear Information System (INIS)

    Ellis, J.

    1979-01-01

    The author discusses possible tests of the current theories of the strong interaction, in particular, quantum chromodynamics. High energy e + e - interactions should provide an excellent means of studying the strong force. (W.D.L.)

  16. Green and social bonds - A promising tool

    International Nuclear Information System (INIS)

    Blanc, Dominique; Barochez, Aurelie de; Cozic, Aela

    2013-11-01

    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

  17. Investigation of thermal expansion and compressibility of rare-earth orthovanadates using a dielectric chemical bond method.

    Science.gov (United States)

    Zhang, Siyuan; Zhou, Shihong; Li, Huaiyong; Li, Ling

    2008-09-01

    The chemical bond properties, lattice energies, linear expansion coefficients, and mechanical properties of ReVO 4 (Re = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y) are investigated systematically by the dielectric chemical bond theory. The calculated results show that the covalencies of Re-O bonds are increasing slightly from La to Lu and that the covalencies of V-O bonds in crystals are decreasing slightly from La to Lu. The linear expansion coefficients decrease progressively from LaVO 4 to LuVO 4; on the contrary, the bulk moduli increase progressively. Our calculated results are in good agreement with some experimental values for linear expansion coefficients and bulk moduli.

  18. Eriocalyxin B Inhibits STAT3 Signaling by Covalently Targeting STAT3 and Blocking Phosphorylation and Activation of STAT3.

    Directory of Open Access Journals (Sweden)

    Xiaokui Yu

    Full Text Available Activated STAT3 plays an important role in oncogenesis by stimulating cell proliferation and resisting apoptosis. STAT3 therefore is an attractive target for cancer therapy. We have screened a traditional Chinese herb medicine compound library and found Eriocalyxin B (EB, a diterpenoid from Isodon eriocalyx, as a specific inhibitor of STAT3. EB selectively inhibited constitutive as well as IL-6-induced phosphorylation of STAT3 and induced apoptosis of STAT3-dependent tumor cells. EB did not affect the upstream protein tyrosine kinases or the phosphatase (PTPase of STAT3, but rather interacted directly with STAT3. The effects of EB could be abolished by DTT or GSH, suggesting a thiol-mediated covalent linkage between EB and STAT3. Site mutagenesis of cysteine in and near the SH2 domain of STAT3 identified Cys712 to be the critical amino acid for the EB-induced inactivation of STAT3. Furthermore, LC/MS/MS analyses demonstrated that an α, β-unsaturated carbonyl of EB covalently interacted with the Cys712 of STAT3. Computational modeling analyses also supported a direct interaction between EB and the Cys712 of STAT3. These data strongly suggest that EB directly targets STAT3 through a covalent linkage to inhibit the phosphorylation and activation of STAT3 and induces apoptosis of STAT3-dependent tumor cells.

  19. Enhancement of localization phenomena driven by covalency in the SrBiMn{sub 1.75}Ti{sub 0.25}O{sub 6} manganite

    Energy Technology Data Exchange (ETDEWEB)

    Asensio de Lucas, E.; Alvarez-Serrano, I. [Depto. Quimica Inorganica I, Facultad Ciencias Quimicas, Universidad Complutense de Madrid, E-28040 Madrid (Spain); Cuello, G.J. [Institut Laue-Langevin, 6 rue Jules Horowitz, F-38042 Grenoble (France); Garcia-Hernandez, M. [Instituto de Ciencia de Materiales de Madrid, CSIC, E-28049 Cantoblanco, Madrid (Spain); Lopez, M.L., E-mail: marisal@quim.ucm.es [Depto. Quimica Inorganica I, Facultad Ciencias Quimicas, Universidad Complutense de Madrid, E-28040 Madrid (Spain); Pico, C.; Veiga, M.L. [Depto. Quimica Inorganica I, Facultad Ciencias Quimicas, Universidad Complutense de Madrid, E-28040 Madrid (Spain)

    2012-05-05

    Graphical abstract: Enhancement of localization phenomena driven by covalency in the BiSrMn{sub 1.75}Ti{sub 0.25}O{sub 6} manganite. The CO/OO phenomena and magnetic clusters (Mn{sub 4}) stabilization at temperatures up to 520 K in BiSrMn{sub 1.75}Ti{sub 0.25}O{sub 6} are connected to a structural transition. The observed enhancement of electronic localization is interpreted considering covalent effects of Ti{sup 4+} and Bi{sup 3+} cations as the main driving force. Highlights: Black-Right-Pointing-Pointer The structural, electronic and magnetic behaviour of the new SrBiMn{sub 1.75}Ti{sub 0.25}O{sub 6} manganite is reported. Black-Right-Pointing-Pointer A structural transition above 520 K takes place, coinciding with relevant changes in the transport properties. Black-Right-Pointing-Pointer The electronic behavior is interpreted in terms of a remarkably high orbital and charge ordering temperature and cluster models. Black-Right-Pointing-Pointer The observed features are explained considering a scenario in which bonds covalence is enhanced by the Bi{sup 3+} and Ti{sup 4+} cations. - Abstract: Manganites are materials that show remarkable phenomena related to charge orbital ordering (CO/OO) and it is extremely important to understand the fundamental nature of this behaviour. This paper reports on the structural, electronic and magnetic behaviour of the new SrBiMn{sub 1.75}Ti{sub 0.25}O{sub 6} manganite and the dependence of these properties with temperature. A detailed structural analysis has been carried out by electron, X-ray, neutron diffraction between 4 and 700 K. The electron diffraction patterns obtained at room temperature (RT) evidence that the average structure (a{approx}b{approx}{radical}(2)a{sub p} and c {approx} 2a{sub p}) presents a modulation that doubles the a and c lattice parameters. A very high charge ordering (CO) transition temperature of 510 K, similar to that found for the non-doped material, SrBiMn{sub 2}O{sub 6}, is observed. Above this

  20. Bonding in phase change materials: concepts and misconceptions.

    Science.gov (United States)

    Jones, R O

    2018-04-18

    Bonding concepts originating in chemistry are surveyed from a condensed matter perspective, beginning around 1850 with 'valence' and the word 'bond' itself. The analysis of chemical data in the 19th century resulted in astonishing progress in understanding the connectivity and stereochemistry of molecules, almost without input from physicists until the development of quantum mechanics in 1925 and afterwards. The valence bond method popularized by Pauling and the molecular orbital methods of Hund, Mulliken, Bloch, and Hückel play major roles in the subsequent development, as does the central part played by the kinetic energy in covalent bonding (Ruedenberg and others). 'Metallic' (free electron) and related approaches, including pseudopotential and density functional theories, have been remarkably successful in understanding structures and bonding in molecules and solids. We discuss these concepts in the context of phase change materials, which involve the rapid and reversible transition between amorphous and crystalline states, and note the confusion that some have caused, in particular 'resonance' and 'resonant bonding'.

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

    Science.gov (United States)

    Li, Rui; Zhou, Hui; Wei, Wei; Wang, Chen; Sun, Ying Chun; Gao, Ping

    2015-01-01

    The bonding strength between resin cement and posts is important for post and core restorations. An important method of improving the bonding strength is the use of various surface pretreatments of the post. In this study, the surfaces of zirconia (fiber) posts were treated by mechanical and/or chemical methods such as sandblasting and silanization. The bonding strength between the zirconia (fiber) post and the resin cement was measured by a push-out method after thermocycling based on the adhesion to Panavia F 2.0 resin cement. The zirconia and fiber posts exhibited different bonding strengths after sandblasting and/or silanization because of the different strengths and chemical structures. The zirconia post showed a high bonding strength of up to 17.1 MPa after a combined treatment of sandblasting and silanization because of the rough surface and covalent bonds at the interface. This effect was also enhanced by using 1,2-bis(trimethoxysilyl)ethane for the formation of a flexible layer at the interface. In contrast, a high bonding strength of 13.9 MPa was obtained for the fiber post treated by silane agents because the sandblasting treatment resulted in damage to the fiber post, as observed by scanning electron microscopy. The results indicated that the improvement in the bonding strength between the post and the resin cement could be controlled by different chemical and/or mechanical treatments. Enhanced bonding strength depended on covalent bonding and the surface roughness. A zirconia post with high bonding strength could potentially be used for the restoration of teeth in the future. PMID:26066349

  2. Reaction mechanisms for on-surface synthesis of covalent nanostructures

    International Nuclear Information System (INIS)

    Björk, J

    2016-01-01

    In recent years, on-surface synthesis has become an increasingly popular strategy to form covalent nanostructures. The approach has great prospects for facilitating the manufacture of a range of fascinating materials with atomic precision. However, the on-surface reactions are enigmatic to control, currently restricting its bright perspectives and there is a great need to explore how the reactions are governed. The objective of this topical review is to summarize theoretical work that has focused on comprehending on-surface synthesis protocols through studies of reaction mechanisms. (topical review)

  3. The Search for Covalently Ligandable Proteins in Biological Systems

    Directory of Open Access Journals (Sweden)

    Syed Lal Badshah

    2016-09-01

    Full Text Available This commentary highlights the recent article published in Nature, June 2016, titled: “Proteome-wide covalent ligand discovery in native biological systems”. They screened the whole proteome of different human cell lines and cell lysates. Around 700 druggable cysteines in the whole proteome were found to bind the electrophilic fragments in both active and inactive states of the proteins. Their experiment and computational docking results agreed with one another. The usefulness of this study in terms of bringing a change in medicinal chemistry is highlighted here.

  4. Structural, dynamical, electronic, and bonding properties of laser-heated silicon: An ab initio molecular-dynamics study

    NARCIS (Netherlands)

    Silvestrelli, P.-L.; Alavi, A.; Parrinello, M.; Frenkel, D.

    1997-01-01

    The method of ab initio molecular dynamics, based on finite-temperature density-functional theory, is used to simulate laser heating of crystalline silicon. We found that a high concentration of excited electrons dramatically weakens the covalent bonding. As a result the system undergoes a melting

  5. The road to the first, fully active and more stable human insulin variant with an additional disulfide bond

    DEFF Research Database (Denmark)

    Vinther, Tine N.; Kjeldsen, Thomas B.; Jensen, Knud Jørgen

    2015-01-01

    Insulin, a small peptide hormone, is crucial in maintaining blood glucose homeostasis. The stability and activity of the protein is directed by an intricate system involving disulfide bonds to stabilize the active monomeric species and by their non-covalent oligomerization. All known insulin vari...

  6. A solution-state NMR approach to elucidating pMDI-wood bonding mechanisms in loblolly pine

    Science.gov (United States)

    Daniel Joseph Yelle

    2009-01-01

    Solution-state NMR spectroscopy is a powerful tool for unambiguously determining the existence or absence of covalent chemical bonds between wood components and adhesives. Finely ground wood cell wall material dissolves in a solvent system containing DMSO-d6 and NMI-d6, keeping wood component polymers intact and in a near-...

  7. Enantioselective Synthesis of Various Cyanohydrins Using Covalently Immobilized Preparations of Hydroxynitrile Lyase from Prunus dulcis.

    Science.gov (United States)

    Alagöz, Dilek; Tükel, S Seyhan; Yildirim, Deniz

    2015-11-01

    The carrier-based and carrier-free (cross-linked enzyme aggregate) covalent immobilizations of Prunus dulcis hydroxynitrile lyase were investigated. The immobilized preparations were tested for enantioselective carbon-carbon bond formation activity in the biphasic medium. Of the tested preparations, only cross-linked enzyme aggregate of P. dulcis hydroxynitrile lyase (PdHNL-CLEA) achieved the synthesis of (R)-mandelonitrile with 93% yield and 99% enantiopurity. PdHNL-CLEA was also used in the synthesis of various (R)-cyanohydrins from corresponding aldehydes/ketones and hydrocyanic acid. When 4-methoxybenzaldehyde, 4-methyl benzaldehyde, and 4-hydroxybenzaldehyde were used as substrates, the yield-enantiomeric excess of corresponding (R)-cyanohydrins were obtained as 95-95, 85-79, and 2-25%, respectively, after 96 h at pH 4.0 and 5 °C. For acetophenone, 4-fluoroacetophenone, 4-chloroacetophenone, 4-bromoacetophenone, and 4-iodoacetophenone, the yield-enantiomeric excess of corresponding (R)-cyanohydrins were 1-99, 20-84, 11-95, 5-99, and 3-24%, respectively at the same conditions. The results demonstrate PdHNL-CLEA can be effectively used in the synthesis of (R)-mandelonitrile.

  8. Immobilization of Candida antarctica Lipase B by Covalent Attachment to Green Coconut Fiber

    Science.gov (United States)

    Brígida, Ana I. S.; Pinheiro, Álvaro D. T.; Ferreira, Andrea L. O.; Pinto, Gustavo A. S.; Gonçalves, Luciana R. B.

    The objective of this study was to covalently immobilize Candida antarctica type B lipase (CALB) onto silanized green coconut fibers. Variables known to control the number of bonds between enzyme and support were evaluated including contact time, pH, and final reduction with sodium borohydride. Optimal conditions for lipase immobilization were found to be 2h incubation at both pH 7.0 and 10.0. Thermal stability studies at 60°C showed that the immobilized lipase prepared at pH 10.0 (CALB-10) was 363-fold more stable than the soluble enzyme and 5.4-fold more stable than the biocatalyst prepared at pH 7.0 (CALB-7). CALB-7 was found to have higher specific activity and better stability when stored at 5°C. When sodium borohydride was used as reducing agent on CALB-10 there were no improvement in storage stability and at 60°C stability was reduced for both CALB-7 and CALB-10.

  9. Ultrasensitive detection of clenbuterol by a covalent imprinted polymer as a biomimetic antibody.

    Science.gov (United States)

    Tang, Yiwei; Gao, Jingwen; Liu, Xiuying; Gao, Xue; Ma, Tao; Lu, Xiaonan; Li, Jianrong

    2017-08-01

    As an ideal biomimetic antibody, molecularly imprinted polymer (MIP) has shown great promise in immunoassays. Here, we developed a covalent imprinting method to prepare MIP artificial antibody towards clenbuterol on the well surface of a microtiter plate. Template molecule (clenbuterol) was splited by hydrolysis with functional monomer and removed by methanol/acetic acid solution, and then three-dimensional cavities were fabricated in the MIP, which can rebind template molecule via hydrogen bond interaction. Using this artificial antibody, we developed a novel biomimetic enzyme-linked immunosorbent assay (ELISA) with excellent sensitivity and specificity. The linear range for clenbuterol was 10 -5 to 1000μgL -1 , with a detection limit of 10 -7 μgL -1 . Cross reactivity of this MIP artificial antibody to other four structural analogs was less than 0.93%. This method was applied to determine clenbuterol in real samples with satisfactory result, suggesting a promising application of the biomimetic ELISA in food and environmental analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Covalent Triazine-Based Frameworks with Ultramicropores and High Nitrogen Contents for Highly Selective CO2 Capture.

    Science.gov (United States)

    Wang, Keke; Huang, Hongliang; Liu, Dahuan; Wang, Chang; Li, Jinping; Zhong, Chongli

    2016-05-03

    Porous organic frameworks (POFs) are a class of porous materials composed of organic precursors linked by covalent bonds. The objective of this work is to develop POFs with both ultramicropores and high nitrogen contents for CO2 capture. Specifically, two covalent triazine-based frameworks (CTFs) with ultramicropores (pores of width selectively capture CO2 due to ultramicroporous nature. Especially, CTF-FUM-350 has the highest nitrogen content (27.64%) and thus the highest CO2 adsorption capacity (57.2 cc/g at 298 K) and selectivities for CO2 over N2 and CH4 (102.4 and 20.5 at 298 K, respectively) among all CTF-FUM and CTF-DCN. More impressively, as far as we know, the CO2/CH4 selectivity is larger than that of all reported CTFs and ranks in top 10 among all reported POFs. Dynamic breakthrough curves indicate that both CTFs could indeed separate gas mixtures of CO2/N2 and CO2/CH4 completely.

  11. Green coconut fiber: a novel carrier for the immobilization of commercial laccase by covalent attachment for textile dyes decolourization.

    Science.gov (United States)

    Cristóvão, Raquel O; Silvério, Sara C; Tavares, Ana P M; Brígida, Ana Iraidy S; Loureiro, José M; Boaventura, Rui A R; Macedo, Eugénia A; Coelho, Maria Alice Z

    2012-09-01

    Commercial laccase formulation was immobilized on modified green coconut fiber silanized with 3-glycidoxypropyltrimethoxysilane, aiming to achieve a cheap and effective biocatalyst. Two different strategies were followed: one point (pH 7.0) and multipoint (pH 10.0) covalent attachment. The influence of immobilization time on enzymatic activity and the final reduction with sodium borohydride were evaluated. The highest activities were achieved after 2 h of contact time in all situations. Commercial laccase immobilized at pH 7.0 was found to have higher activity and higher affinity to the substrate. However, the immobilization by multipoint covalent attachment improved the biocatalyst thermal stability at 50 °C, when compared to soluble enzyme and to the immobilized enzyme at pH 7.0. The Schiff's bases reduction by sodium borohydride, in spite of causing a decrease in enzyme activity, showed to contribute to the increase of operational stability through bonds stabilization. Finally, these immobilized enzymes showed high efficiency in the continuous decolourization of reactive textile dyes. In the first cycle, the decolourization is mainly due to dyes adsorption on the support. However, when working in successive cycles, the adsorption capacity of the support decreases (saturation) and the enzymatic action increases, indicating the applicability of this biocatalyst for textile wastewater treatment.

  12. Chemical Mapping of Nano-defects within 2D Covalent Monolayers by Tip-enhanced Raman Spectroscopy.

    Science.gov (United States)

    Shao, Feng; Dai, Wenyang; Zhang, Yao; Zhang, Wei; Schlüter, A Dieter; Zenobi, Renato

    2018-04-16

    Nanoscale defects in monolayers (MLs) of two-dimensional (2D) materials, such as graphene, transition metal dichalcogenides (TMDCs), and 2D polymers (2DPs), can alter their physical, mechanical, optoelectronic, and chemical properties. However, detailed information about nano-defects within 2D covalent monolayers is difficult to obtain because it requires highly selective and sensitive techniques that can provide chemical information at the nanoscale. Here, we report a 2D imine-linked ML prepared from two custom-designed building blocks by dynamic imine chemistry at the air/water interface, in which an acetylenic moiety in one of the blocks was used as a spectroscopic reporter for nano-defects. Combined with density functional theory (DFT) calculations that take into account surface selection rules, tip-enhanced Raman spectroscopy (TERS) imaging provides information of the chemical bonds, molecular orientation, as well as nano-defects in the resulting ML. Additionally, TERS imaging visualizes the topography and integrity of the ML at Au(111) terrace edges, suggesting possible ductility of the ML. Furthermore, edge-induced molecular tilting and a stronger signal enhancement were observed at the terrace edges, from which a spatial resolution around 8 nm could be deduced. The present work can be used to study covalent 2D materials at the nanoscale, which are expected to be of use when engineering their properties for specific device applications.

  13. Photogeneration of singlet oxygen by the phenothiazine derivatives covalently bound to the surface-modified glassy carbon

    Energy Technology Data Exchange (ETDEWEB)

    Blacha-Grzechnik, Agata, E-mail: agata.blacha@polsl.pl [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland); Piwowar, Katarzyna; Krukiewicz, Katarzyna [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland); Koscielniak, Piotr; Szuber, Jacek [Institute of Electronics, Silesian University of Technology, Akademicka 16, 44-100 Gliwice (Poland); Zak, Jerzy K. [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland)

    2016-05-15

    Highlights: • The selected group of four NH{sub 2}-derivatives of phenothiazine was grafted to Glassy Carbon (GC) surface. • The grafted phenothiazines are able to generate {sup 1}O{sub 2} when activated by the radiation. • Such modified solid surfaces may find their application in the wastewater treatment. - Abstract: The selected group of four amine-derivatives of phenothiazine was covalently grafted to the glassy carbon surface in the four-step procedure consisting of the electrochemical reduction of the diazonium salt followed by the electrochemical and chemical post-modification steps. The proposed strategy involves the bonding of linker molecule to which the photosensitizer is attached. The synthesized organic layers were characterized by means of cyclic voltammetry, XPS and Raman Spectroscopy. It was shown that the phenothiazines immobilized via proposed strategy retain their photochemical properties and are able to generate {sup 1}O{sub 2} when activated by the laser radiation. The effectiveness of in situ singlet oxygen generation by those new solid photoactive materials was determined by means of UVVis spectroscopy. The reported, covalently modified solid surfaces may find their application as the singlet oxygen photogenerators in the fine chemicals’ synthesis or in the wastewater treatment.

  14. The effect of hydrochloric acid addition to increase carbon nanotubes dispersibility as drug delivery system by covalent functionalization

    Science.gov (United States)

    Wulan, P. P. D. K.; Ulwani, S. H.; Wulandari, H.; Purwanto, W. W.; Mulia, K.

    2018-03-01

    This study is to obtain the effect of adding hydrochloric acid (HCl) to the mixture of sulfuric acid (H2SO4) and HNO3 in CNT covalent functionalization. HCl expected to increase the dispersibility of functionalized CNT by improving the dispersion time period done with H2SO4 or HNO3. Functionalization used mixture of H2SO4 and HNO3 with volume ratio of 3:1. Covalent functionalization used 0.5 grams of MWCNT ultra sonicated in 50mL HNO3 with and mixture of H2SO4 and HNO3. Additions of 200 mL HCl used variation of molarity from 1M, 2M, 3M, 4M, 5M to 6M. CNT were oxidized to form carboxylic and hydroxyl bonds on the surface that increase dispersibility of CNT. FTIR spectrums showed the existences of carboxyl and hydroxyl group on spectra of 2600-3700 cm-1 and 900-1400 cm-1. Dispersion tests, which showed functionalized CNT (f-CNT) dispersion capabilities, were done by dissolving f-CNT in water. The study resulted that 6M f-CNT (NSC6) gave the best dispersion with zeta potential value of -37.1mV. NSC6 gave the longest dispersion time which was 20 days until f-CNT settle again. SEM-EDS micrographs showed the surface structure of 6M f-CNT without significant damage and no longer contain impurities of Fe, Ni, and Cl.

  15. 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.

  16. Synthesis of Sub-10 nm Two-Dimensional Covalent Organic Thin Film with Sharp Molecular Sieving Nanofiltration

    KAUST Repository

    Gadwal, Ikhlas

    2018-04-06

    We demonstrated here a novel and facile synthesis of two-dimensional (2D) covalent organic thin film with pore size around 1.5 nm using a planar, amphiphilic and substituted heptacyclic truxene based triamine and a simple dialdehyde as building blocks by dynamic imine bond formation at the air/water interface using Langmuir–Blodgett (LB) method. Optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM), all unanimously showed the formation of large, molecularly thin and free-standing membrane that can be easily transferred on different substrate surfaces. The 2D membrane supported on a porous polysulfone showed a rejection rate of 64 and 71% for NaCl and MgSO4, respectively, and a clear molecular sieving at molecular size around 1.3 nm, which demonstrated a great potential in the application of pretreatment of seawater desalination and separation of organic molecules.

  17. Direct observation of covalency between O and disordered Pb in cubic PbZrO sub 3

    CERN Document Server

    Aoyagi, S; Sawada, A; Tanaka, H; Harada, J; Nishibori, E; Takata, M; Sakata, M

    2002-01-01

    In cubic PbZrO sub 3 , which undergoes an antiferroelectric phase transition, the distinct disorder of Pb at twelve sites toward the neighboring O is detected for the first time by analyzing high-energy X-ray powder diffraction data. In the charge density distributions, the covalent nature of the Pb-O bond is also revealed, which proves the existence of electron hybridization between O and disordered Pb in cubic PbZrO sub 3. None of these structural characteristics of PbZrO sub 3 were found in the previously studied cubic PbTiO sub 3 structure [Y. Kuroiwa et al.: Phys. Rev. Lett. 87 (2001) 217601], which undergoes a ferroelectric phase transition. This may be a clue to understanding why PbTiO sub 3 and PbZrO sub 3 respectively show ferroelectric and antiferroelectric phase transitions.

  18. Structure and bonding of transition metal-boryl compounds. Theoretical study of [(PH3)2(CO)ClOs-BR2] and [(PH3)2(CO)2ClOs-BR2] (BR2 = BH2, BF2, B(OH)2, B(OCH=CHO), Bcat).

    Science.gov (United States)

    Giju, K T; Bickelhaupt, F M; Frenking, G

    2000-10-16

    Quantum chemical DFT calculations using the B3LYP functionals have been carried out for the electronically unsaturated 16 VE five-coordinate osmium boryl-complexes [(PH3)2(CO)ClOs-BR2] and the 18 VE six-coordinate complexes [(PH3)2(CO)2ClOs-BR2] with BR2 = BH2, BF2, B(OH)2, B(OHC=CHO), and Bcat (cat = catecholate O2C6H4). The bonding situation of the Os-BR2 bond was analyzed with the help of the NBO partitioning scheme. The Os-B bond dissociation energies of the 16 VE complexes are very high, and they do not change very much for the different boryl ligands. The 18 VE complexes have only slightly lower bond energies than the 16 VE species. The Os-B bond in both classes of compounds is provided by a covalent sigma-bond which is polarized toward osmium and by strong charge attraction. Os-->B pi-donation is not important for the Os-B binding interactions, except for the Os-BH2 complexes. The stability of the boryl complexes [Os]-BR2 comes mainly from BB pi-donation. The intraligand charge distribution of the BR2 group changes little when the Os-B bond is formed, except for BH2. The CO ligand in [(PH3)2(CO)2ClOs-BR2] which is trans to BR2 has a relatively weak bond to the osmium atom.

  19. 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...

  20. Bifunctional avidin with covalently modifiable ligand binding site.

    Directory of Open Access Journals (Sweden)

    Jenni Leppiniemi

    Full Text Available The extensive use of avidin and streptavidin in life sciences originates from the extraordinary tight biotin-binding affinity of these tetrameric proteins. Numerous studies have been performed to modify the biotin-binding affinity of (streptavidin to improve the existing applications. Even so, (streptavidin greatly favours its natural ligand, biotin. Here we engineered the biotin-binding pocket of avidin with a single point mutation S16C and thus introduced a chemically active thiol group, which could be covalently coupled with thiol-reactive molecules. This approach was applied to the previously reported bivalent dual chain avidin by modifying one binding site while preserving the other one intact. Maleimide was then coupled to the modified binding site resulting in a decrease in biotin affinity. Furthermore, we showed that this thiol could be covalently coupled to other maleimide derivatives, for instance fluorescent labels, allowing intratetrameric FRET. The bifunctional avidins described here provide improved and novel tools for applications such as the biofunctionalization of surfaces.

  1. Neural mechanisms of mother-infant bonding and pair bonding: Similarities, differences, and broader implications

    Science.gov (United States)

    Numan, Michael; Young, Larry J.

    2015-01-01

    Mother-infant bonding is a characteristic of virtually all mammals. The maternal neural system may have provided the scaffold upon which other types of social bonds in mammals have been built. For example, most mammals exhibit a polygamous mating system, but monogamy and pair bonding between mating partners occurs in ∼5% of mammalian species. In mammals, it is plausible that the neural mechanisms that promote mother-infant bonding have been modified by natural selection to establish the capacity to develop a selective bond with a mate during the evolution of monogamous mating strategies. Here we compare the details of the neural mechanisms that promote mother-infant bonding in rats and other mammals with those that underpin pair bond formation in the monogamous prairie vole. Although details remain to be resolved, remarkable similarities and a few differences between the mechanisms underlying these two types of bond formation are revealed. For example, amygdala and nucleus accumbens-ventral pallidum (NA-VP) circuits are involved in both types of bond formation, and dopamine and oxytocin action within NA appears to promote the synaptic plasticity that allows either infant or mating partner stimuli to persistently activate NA-VP attraction circuits, leading to an enduring social attraction and bonding. Further, although the medial preoptic area is essential for maternal behavior, its role in pair bonding remains to be determined. Our review concludes by examining the broader implications of this comparative analysis, and evidence is provided that the maternal care system may have also provided the basic neural foundation for other types of strong social relationships, beyond pair bonding, in mammals, including humans. PMID:26062432

  2. Destination bonding: Hybrid cognition using Instagram

    Directory of Open Access Journals (Sweden)

    Arup Kumar Baksi

    2015-01-01

    Full Text Available Empirical research has identified the phenomenon of destination bonding as a result of summated physical and emotional values associated with the destination. Physical values, namely natural landscape & other physical settings and emotional values, namely the enculturation processes, have a significant role to play in portraying visitors’ cognitive framework for destination preference. The physical values seemed to be the stimulator for bonding that embodies action or behavior tendencies in imagery. The emotional values were the conditions that lead to affective bonding and are reflected in attitudes for a place which were evident in text narratives. Social networking on virtual platforms offers the scope for hybrid cognitive expression using imagery and text to the visitors. Instagram has emerged as an application-window to capture these hybrid cognitions of visitors. This study focuses on assessing the relationship between hybrid cognition of visitors expressed via Instagram and their bond with the destination. Further to this, the study attempts to examine the impact of hybrid cognition of visitors on the behavioral pattern of prospective visitors to the destination. The study revealed that sharing of visual imageries and related text by the visitors is an expression of the physico-emotional bonding with the destination. It was further established that hybrid cognition strongly asserts destination bonding and has been also found to have moderating impact on the link between destination bonding and electronic-word-of-mouth.

  3. Covalent and density-controlled surface immobilization of E-cadherin for adhesion force spectroscopy.

    Directory of Open Access Journals (Sweden)

    Dagmar Fichtner

    Full Text Available E-cadherin is a key cell-cell adhesion molecule but the impact of receptor density and the precise contribution of individual cadherin ectodomains in promoting cell adhesion are only incompletely understood. Investigating these mechanisms would benefit from artificial adhesion substrates carrying different cadherin ectodomains at defined surface density. We therefore developed a quantitative E-cadherin surface immobilization protocol based on the SNAP-tag technique. Extracellular (EC fragments of E-cadherin fused to the SNAP-tag were covalently bound to self-assembled monolayers (SAM of thiols carrying benzylguanine (BG head groups. The adhesive functionality of the different E-cadherin surfaces was then assessed using cell spreading assays and single-cell (SCSF and single-molecule (SMSF force spectroscopy. We demonstrate that an E-cadherin construct containing only the first and second outmost EC domain (E1-2 is not sufficient for mediating cell adhesion and yields only low single cadherin-cadherin adhesion forces. In contrast, a construct containing all five EC domains (E1-5 efficiently promotes cell spreading and generates strong single cadherin and cell adhesion forces. By varying the concentration of BG head groups within the SAM we determined a lateral distance of 5-11 nm for optimal E-cadherin functionality. Integrating the results from SCMS and SMSF experiments furthermore demonstrated that the dissolution of E-cadherin adhesion contacts involves a sequential unbinding of individual cadherin receptors rather than the sudden rupture of larger cadherin receptor clusters. Our method of covalent, oriented and density-controlled E-cadherin immobilization thus provides a novel and versatile platform to study molecular mechanisms underlying cadherin-mediated cell adhesion under defined experimental conditions.

  4. Isolation and characterization of a uranium(VI)-nitride triple bond

    Science.gov (United States)

    King, David M.; Tuna, Floriana; McInnes, Eric J. L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

    2013-06-01

    The nature and extent of covalency in uranium bonding is still unclear compared with that of transition metals, and there is great interest in studying uranium-ligand multiple bonds. Although U=O and U=NR double bonds (where R is an alkyl group) are well-known analogues to transition-metal oxo and imido complexes, the uranium(VI)-nitride triple bond has long remained a synthetic target in actinide chemistry. Here, we report the preparation of a uranium(VI)-nitride triple bond. We highlight the importance of (1) ancillary ligand design, (2) employing mild redox reactions instead of harsh photochemical methods that decompose transiently formed uranium(VI) nitrides, (3) an electrostatically stabilizing sodium ion during nitride installation, (4) selecting the right sodium sequestering reagent, (5) inner versus outer sphere oxidation and (6) stability with respect to the uranium oxidation state. Computational analyses suggest covalent contributions to U≡N triple bonds that are surprisingly comparable to those of their group 6 transition-metal nitride counterparts.

  5. Quantification of Hydrogen Bond Strength Based on Interaction Coordinates: A New Approach.

    Science.gov (United States)

    Pandey, Sarvesh Kumar; Manogaran, Dhivya; Manogaran, Sadasivam; Schaefer, Henry F

    2017-08-17

    A new approach to quantify hydrogen bond strengths based on interaction coordinates (HBSBIC) is proposed and is very promising. In this research, it is assumed that the projected force field of the fictitious three atoms fragment (DHA) where D is the proton donor and A is the proton acceptor from the full molecular force field of the H-bonded complex characterizes the hydrogen bond. The "interaction coordinate (IC)" derived from the internal compliance matrix elements of this three-atom fragment measures how the DH covalent bond (its electron density) responds to constrained optimization when the HA hydrogen bond is stretched by a known amount (its electron density is perturbed by a specified amount). This response of the DH bond, based on how the IC depends on the electron density along the HA bond, is a measure of the hydrogen bond strength. The inter- and intramolecular hydrogen bond strengths for a variety of chemical and biological systems are reported. When defined and evaluated using the IC approach, the HBSBIC index leads to satisfactory results. Because this involves only a three-atom fragment for each hydrogen bond, the approach should open up new directions in the study of "appropriate small fragments" in large biomolecules.

  6. Boride ceramics covalent functionalization and its effect on the thermal conductivity of epoxy composites

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Zhi-Qiang, E-mail: yuzhiqiang@fudan.edu.cn [Department of Materials Science, Fudan University, 200433 Shanghai (China); Wu, Yicheng [Department of Materials Science, Fudan University, 200433 Shanghai (China); Wei, Bin; Baier, Horst [Institute of Lightweight Structures, Technical University Munich (TUM), Boltzmannstr. 15, D-85747 Garching (Germany)

    2015-08-15

    Zirconium diboride/aluminium oxide (ZrB{sub 2}/Al{sub 2}O{sub 3}) composite particles were functionalized with epoxide functionalized γ-glycidoxypropyltrimethoxysilane by the covalent bonding approach to improve the interfacial compatibility of composite particles in epoxy matrix. The composites of epoxy resin filled with functionalized ZrB{sub 2}/Al{sub 2}O{sub 3} were prepared by in situ bulk condensation polymerization of bisphenol A and epichlorohydrin in the presence of ZrB{sub 2}/Al{sub 2}O{sub 3}. The heat-conducting properties of composites were investigated by the finite element method (FEM) and the thermal conductivity test. The finite-element program ANSYS was used for this numerical analysis, and three-dimensional spheres-in-cube lattice array models were built to simulate the microstructure of composite materials for different filler contents. The thermal conductivity of composites was determined by laser flash method (LFA447 Nanoflash), using the measured heat capacity and thermal diffusivity, with separately entered density data. The results show that the effective chemical bonds are formed between ZrB{sub 2}/Al{sub 2}O{sub 3} and γ-glycidoxypropyltrimethoxysilane after the surface functionalization. The interfacial compatibility and bonding of modified particles with the epoxy matrix are improved. The thermal conductivities of functionalized composites with 3 vol% and 5 vol% loading are increased by 8.3% and 12.5% relative to the unmodified composites, respectively. Comparison of experimental values and calculated values of the thermal conductivity, the average relative differences are under 5%. The predictive values of thermal conductivity of epoxy composites are in reasonable agreement with the experimental values. - Highlights: • The surfaces of ZrB{sub 2}/Al{sub 2}O{sub 3} were functionalized by silane coupling agents. • The thermal conductivity (TC) of modified epoxy composites is improved significantly. • The FEM values of TC are in

  7. Note: Anodic bonding with cooling of heat-sensitive areas

    DEFF Research Database (Denmark)

    Vesborg, Peter Christian Kjærgaard; Olsen, Jakob Lind; Henriksen, Toke Riishøj

    2010-01-01

    Anodic bonding of silicon to glass always involves heating the glass and device to high temperatures so that cations become mobile in the electric field. We present a simple way of bonding thin silicon samples to borosilicate glass by means of heating from the glass side while locally cooling heat......-sensitive areas from the silicon side. Despite the high thermal conductivity of silicon, this method allows a strong anodic bond to form just millimeters away from areas essentially at room temperature....

  8. Shape Bonding method

    Science.gov (United States)

    Pontius, James T. (Inventor)

    2010-01-01

    The present invention is directed to a method of bonding at least two surfaces together. The methods step of the present invention include applying a strip of adhesive to a first surface along a predefined outer boundary of a bond area and thereby defining a remaining open area there within. A second surface, or gusset plate, is affixed onto the adhesive before the adhesive cures. The strip of adhesive is allowed to cure and then a second amount of adhesive is applied to cover the remaining open area and substantially fill a void between said first and second surfaces about said bond area. A stencil may be used to precisely apply the strip of adhesive. When the strip cures, it acts as a dam to prevent overflow of the subsequent application of adhesive to undesired areas. The method results in a precise bond area free of undesired shapes and of a preferred profile which eliminate the drawbacks of the prior art bonds.

  9. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    Corporate financing is the choice between capital generated by the corporation and capital from external investors. However, since the financial crisis shook the markets in 2007–2008, financing opportunities through the classical means of financing have decreased. As a result, corporations have...... 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...... markets. However, NASDAQ OMX has introduced the First North Bond Market in December 2012 and new regulatory framework came into place in 2014, which may contribute to a Danish based corporate bond market. The purpose of this article is to present the regulatory changes in Denmark in relation to corporate...

  10. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    Corporate financing is the choice between capital generated by the corporation and capital from external investors. However, since the financial crisis shook the markets in 2007–2008, financing opportunities through the classical means of financing have decreased. As a result, corporations have...... markets. However, NASDAQ OMX has introduced the First North Bond Market in December 2012 and new regulatory framework came into place in 2014, which may contribute to a Danish based corporate bond market. The purpose of this article is to present the regulatory changes in Denmark in relation to corporate...... bonds. The purpose is further to analyse the tax consequences of issuing bonds in both a direct issue of bonds and through securitization....

  11. The role of hydrogen bonds in the melting points of sulfonate-based protic organic salts

    DEFF Research Database (Denmark)

    Luo, Jiangshui

    2016-01-01

    there is evidence of bond formation [6]. Hydrogen bonds in the solid state fall into the classification of strong, moderate, and weak hydrogen bonds [7]. In molecular systems like H2O (vs. H2S) or NH3 (vs. PH3), strong hydrogen bonds lead to higher melting points. However, in organic salts, the situation may......There are three main types of interactions inside organic salts - electrostatic interaction, hydrogen bonding and van der Waals force [1-4]. While van der Waals force is relatively weak, it is hydrogen bonding and particularly electrostatic interaction that determine the lattice energies of ionic...

  12. Mechanism-based labeling defines the free energy change for formation of the covalent glycosyl-enzyme intermediate in a xyloglucan endo-transglycosylase.

    Science.gov (United States)

    Piens, Kathleen; Fauré, Régis; Sundqvist, Gustav; Baumann, Martin J; Saura-Valls, Marc; Teeri, Tuula T; Cottaz, Sylvain; Planas, Antoni; Driguez, Hugues; Brumer, Harry

    2008-08-08

    Xyloglucan endo-transglycosylases (XETs) are key enzymes involved in the restructuring of plant cell walls during morphogenesis. As members of glycoside hydrolase family 16 (GH16), XETs are predicted to employ the canonical retaining mechanism of glycosyl transfer involving a covalent glycosyl-enzyme intermediate. Here, we report the accumulation and direct observation of such intermediates of PttXET16-34 from hybrid aspen by electrospray mass spectrometry in combination with synthetic "blocked" substrates, which function as glycosyl donors but are incapable of acting as glycosyl acceptors. Thus, GalGXXXGGG and GalGXXXGXXXG react with the wild-type enzyme to yield relatively stable, kinetically competent, covalent GalG-enzyme and GalGXXXG-enzyme complexes, respectively (Gal=Galbeta(1-->4), G=Glcbeta(1-->4), and X=Xylalpha(1-->6)Glcbeta(1-->4)). Quantitation of ratios of protein and saccharide species at pseudo-equilibrium allowed us to estimate the free energy change (DeltaG(0)) for the formation of the covalent GalGXXXG-enzyme as 6.3-8.5 kJ/mol (1.5-2.0 kcal/mol). The data indicate that the free energy of the beta(1-->4) glucosidic bond in xyloglucans is preserved in the glycosyl-enzyme intermediate and harnessed for religation of the polysaccharide in vivo.

  13. The Bonding Situation in Metalated Ylides.

    Science.gov (United States)

    Scharf, Lennart T; Andrada, Diego M; Frenking, Gernot; Gessner, Viktoria H

    2017-03-28

    Quantum chemical calculations have been carried out to study the electronic structure of metalated ylides particularly in comparison to their neutral analogues, the bisylides. A series of compounds of the general composition Ph 3 P-C-L with L being either a neutral or an anionic ligand were analyzed and the impact of the nature of the substituent L and the total charge on the electronics and bonding situation was studied. The charge at the carbon atom as well as the dissociation energies, bond lengths, and Wiberg bond indices strongly depend on the nature of L. Here, not only the charge of the ligand but also the position of the charge within the ligand backbone plays an important role. Independent of the substitution pattern, the NBO analysis reveals the preference of unsymmetrical bonding situations (P=C-L or P-C=L) for almost all compounds. However, Lewis structures with two lone-pair orbitals at the central carbon atom are equally valid for the description of the bonding situation. This is confirmed by the pronounced lone-pair character of the frontier orbitals. Energy decomposition analysis mostly reveals the preference of several bonding situations, mostly with dative and ylidic electron-sharing bonds (e.g., P→C - -L). In general, the anionic systems show a higher preference of the ylidic bonding situations compared to the neutral analogues. However, in most of the cases different resonance structures have to be considered for the description of the "real" bonding situation. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  14. Strongly Correlated Topological Insulators

    Science.gov (United States)

    2016-02-03

    Strongly Correlated Topological Insulators In the past year, the grant was used for work in the field of topological phases, with emphasis on finding...surface of topological insulators. In the past 3 years, we have started a new direction, that of fractional topological insulators. These are materials...in which a topologically nontrivial quasi-flat band is fractionally filled and then subject to strong interactions. The views, opinions and/or

  15. Strong Cosmic Censorship

    Science.gov (United States)

    Isenberg, James

    2017-01-01

    The Hawking-Penrose theorems tell us that solutions of Einstein's equations are generally singular, in the sense of the incompleteness of causal geodesics (the paths of physical observers). These singularities might be marked by the blowup of curvature and therefore crushing tidal forces, or by the breakdown of physical determinism. Penrose has conjectured (in his `Strong Cosmic Censorship Conjecture`) that it is generically unbounded curvature that causes singularities, rather than causal breakdown. The verification that ``AVTD behavior'' (marked by the domination of time derivatives over space derivatives) is generically present in a family of solutions has proven to be a useful tool for studying model versions of Strong Cosmic Censorship in that family. I discuss some of the history of Strong Cosmic Censorship, and then discuss what is known about AVTD behavior and Strong Cosmic Censorship in families of solutions defined by varying degrees of isometry, and discuss recent results which we believe will extend this knowledge and provide new support for Strong Cosmic Censorship. I also comment on some of the recent work on ``Weak Null Singularities'', and how this relates to Strong Cosmic Censorship.

  16. The Effect of Intermolecular Halogen Bond on 19F DNP Enhancement in 1, 4-Diiodotetrafluorobenzene/4-OH-TEMPO Supramolecular Assembly

    Directory of Open Access Journals (Sweden)

    GAO Shan

    2017-12-01

    Full Text Available Halogen bond, as hydrogen bond, is a non-covalent bond. Dynamic nuclear polarization (DNP technique has been used previously to study hydrogen bonds-mediated intermolecular interactions. However, no study has been carried out so far to study the halogen bond-mediated intermolecular interactions with DNP. In this work, 19F DNP polarization efficiency of the halogen bonds existing in supramolecular assembling by 4-OH-TEMPO and 1,4-diiodotetrafluorobenzene (DITFB was studied on a home-made DNP system. The formation of intermolecular halogen bonds appeared to increase 19F DNP polarization efficiency, suggesting that the spin-spin interactions among electrons were weakened by the halogen bonds, resulting in an increased T2e and a larger saturation factor.

  17. Covalent immobilization of Pseudomonas cepacia lipase on semiconducting materials

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, Renny Edwin [Microelectronics and MEMS Laboratory, Department of Electrical Engineering, Indian Institute of Technology Madras, Chennai (India)], E-mail: rennyedwin@gmail.com; Bhattacharya, Enakshi [Microelectronics and MEMS Laboratory, Department of Electrical Engineering, Indian Institute of Technology Madras, Chennai (India)], E-mail: enakshi@ee.iitm.ac.in; Chadha, Anju [Department of Biotechnology, National Centre for Catalysis Research, Indian Institute of Technology Madras, Chennai (India)], E-mail: anjuc@iitm.ac.in

    2008-05-30

    Lipase from Pseudomonas cepacia was covalently immobilized on crystalline silicon, porous silicon and silicon nitride surfaces. The various stages of immobilization were characterized using FTIR (Fourier transform infrared) spectroscopy. The surface topography of the enzyme immobilized surfaces was investigated using scanning electron microscopy (SEM). The quantity of the immobilized active enzyme was estimated by the para-nitrophenyl palmitate (pNPP) assay. The immobilized lipase was used for triglyceride hydrolysis and the acid produced was detected by a pH sensitive silicon nitride surface as a shift in the C-V (capacitance-voltage) characteristics of an electrolyte-insulator-semiconductor capacitor (EISCAP) thus validating the immobilization method for use as a biosensor.

  18. Covalent Organic Framework Electrocatalysts for Clean Energy Conversion.

    Science.gov (United States)

    Lin, Chun-Yu; Zhang, Detao; Zhao, Zhenghang; Xia, Zhenhai

    2018-02-01

    Covalent organic frameworks (COFs) are promising for catalysis, sensing, gas storage, adsorption, optoelectricity, etc. owning to the unprecedented combination of large surface area, high crystallinity, tunable pore size, and unique molecular architecture. Although COFs are in their initial research stage, progress has been made in the design and synthesis of COF-based electrocatalysis for the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, and CO 2 reduction in energy conversion and fuel generation. Design principles are also established for some of the COF materials toward rational design and rapid screening of the best electrocatalysts for a specific application. Herein, the recent advances in the design and synthesis of COF-based catalysts for clean energy conversion and storage are presented. Future research directions and perspectives are also being discussed for the development of efficient COF-based electrocatalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Near universal support for covalent immobilisation of enzymes for biotechnology

    International Nuclear Information System (INIS)

    Elnashar, M.M.; Millner, P.A.; Gibson, T.D.

    2005-01-01

    Carrageenan [1], natural polymer, has been modified to be used as a universal/near universal support to immobilise enzymes, where the gel remained stable at 70 degree C for 24 h at a wide range of buffers and ph s and its mechanical strength was 400% greater than the unmodified gel. The new matrix successfully immobilised covalently eight commercially used enzymes including hydrolases, Upases, oxidoreductases, proteases and dehydrogenases. It also acted as a self buffering system in case of hydrolases and stopped enzyme's product inhibition. The apparent Km values of immobilised enzymes were found in many cases to be much less than those of the free enzymes. Another interesting correlation was observed where the great lowering of the apparent Km with immobilised enzymes was directly proportional to the substrate molecular weight. In economic terms, the new matrix is at least two orders of magnitude cheaper than supports such as Eupergit C

  20. Non-Covalent Organocatalyzed Domino Reactions Involving Oxindoles: Recent Advances

    Directory of Open Access Journals (Sweden)

    Tecla Gasperi

    2017-09-01

    Full Text Available The ubiquitous presence of spirooxindole architectures with several functionalities and stereogenic centers in bioactive molecules has been appealing for the development of novel methodologies seeking their preparation in high yields and selectivities. Expansion and refinement in the field of asymmetric organocatalysis have made possible the development of straightforward strategies that address these two requisites. In this review, we illustrate the current state-of-the-art in the field of spirooxindole synthesis through the use of non-covalent organocatalysis. We aim to provide a concise overview of very recent methods that allow to the isolation of unique, densely and diversified spirocyclic oxindole derivatives with high structural diversity via the use of cascade, tandem and domino processes.

  1. Prolonged and tunable residence time using reversible covalent kinase inhibitors.

    Science.gov (United States)

    Bradshaw, J Michael; McFarland, Jesse M; Paavilainen, Ville O; Bisconte, Angelina; Tam, Danny; Phan, Vernon T; Romanov, Sergei; Finkle, David; Shu, Jin; Patel, Vaishali; Ton, Tony; Li, Xiaoyan; Loughhead, David G; Nunn, Philip A; Karr, Dane E; Gerritsen, Mary E; Funk, Jens Oliver; Owens, Timothy D; Verner, Erik; Brameld, Ken A; Hill, Ronald J; Goldstein, David M; Taunton, Jack

    2015-07-01

    Drugs with prolonged on-target residence times often show superior efficacy, yet general strategies for optimizing drug-target residence time are lacking. Here we made progress toward this elusive goal by targeting a noncatalytic cysteine in Bruton's tyrosine kinase (BTK) with reversible covalent inhibitors. Using an inverted orientation of the cysteine-reactive cyanoacrylamide electrophile, we identified potent and selective BTK inhibitors that demonstrated biochemical residence times spanning from minutes to 7 d. An inverted cyanoacrylamide with prolonged residence time in vivo remained bound to BTK for more than 18 h after clearance from the circulation. The inverted cyanoacrylamide strategy was further used to discover fibroblast growth factor receptor (FGFR) kinase inhibitors with residence times of several days, demonstrating the generalizability of the approach. Targeting of noncatalytic cysteines with inverted cyanoacrylamides may serve as a broadly applicable platform that facilitates 'residence time by design', the ability to modulate and improve the duration of target engagement in vivo.

  2. Spin Labeling ESR Investigation of Covalently Bound Residues in Soil

    Science.gov (United States)

    Aleksandrova, Olga; Steinhoff, Heinz-Juergen; Klasmeier, Joerg; Schulz, Marcus; Matthies, Michael

    2013-04-01

    Organic xenobiotic chemicals, such as pesticides, biocides and veterinary pharmaceuticals, interact with soil, which results in the simultaneous formations of metabolites, mineralization products, and bound or non-extractable residues (NER). Substances or metabolites with reactive functional groups, such as aniline or phenol, have a tendency to give a larger proportion of NER. Despite numerous studies on NER, the majority of their chemical structures is still unknown. Reversible sequestration and irreversible formation of NER were also observed for veterinary antibiotic pharmaceuticals, after their application to soil with and without manure. For this purpose, we hypothesized a key role of specific functional groups of soil contaminants, via which contaminants are covalently bound to soil constituents, and advance a method of spin labeling ESR investigation of reaction products using a membrane method. Spin labels (SL) represent chemically stable paramagnetic molecules used as molecular labels and molecular probes for testing the covalent binding, structural properties, and molecular mobility of different physical, chemical, and biological systems. In the case of covalent binding of SL, their ESR spectra become broadened. We used stable nitroxide radicals (NR) as SL. These radicals modeled organic chemical contaminants and differed only in one functional group. The paramagnetic SL 4-Amino Tempo (4-amino-2,2,6,6-tetramethyl-1-piperidinylox) differed from Tempo (2,2,6,6-Tetramethylpiperidinooxy) in a substituent at the para-position of the piperidine ring, whereas Aniline Tempo (1-Piperidinyloxy, 2,2,6,-tetramethyl, 6-Aniline) differed from Tempo in an Aniline substituting one CH3 functional group. Before experimental analysis, we tested temporal changes in the concentration of both NR incubated with soil and found that the life-times of them in soil exceeded 3 days. We contaminated and labeled soil samples with NR, adding to soil the aqueous solution, which already

  3. Characterization of actinide bonding in Th(S2PMe2)4 by synchrotron X-ray diffraction

    International Nuclear Information System (INIS)

    Iversen, B.B.; Larsen, F.K.; Pinkerton, A.A.; Martin, A.; Darovsky, A.; Reynolds, P.A.

    1998-01-01

    Extensive synchrotron (28 K) and conventional sealed-tube (9 K) X-ray diffraction data have been collected on Th(S 2 PMe 2 ) 4 . Modeling of the electron density of the complex shows the bonding is quite ionic with little diffuse f or d type bonding density. Furthermore a large polarization of the Th core is observed revealing some 5d-like involvement in the bonding. High-quality ab initio density functional calculations are not able to reproduce these features and instead predict rather covalent bonding with considerable 6d-5f mixing. The study suggests that this theoretical method exaggerates the covalent nature of actinide bonds. It is shown that the most direct measure of covalence -- charge transfer and electron distributions -- can be usefully estimated by X-ray diffraction even in this most unfavorable of cases, where many actinide core electrons are present. The use of very low temperature data is crucial in the study of heavy metal complexes in order to minimize systematic errors such as thermal diffuse scattering and anharmonicity. The fact that accurate synchrotron radiation diffraction data can be measured within days makes studies of compounds beyond the first transition series more frequently within reach

  4. Covalency Trends in Group IV Metallocene Dichlorides. Chlorine K-Edge X-Ray Absorption Spectroscopy And Time Dependent-Density Functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Kozimor, S.A.; Yang, P.; Batista, E.R.; Boland, K.S.; Burns, C.J.; Christensen, C.N.; Clark, D.L.; Conradson, S.D.; Hay, P.J.; Lezama, J.S.; Martin, R.L.; Schwarz, D.E.; Wilkerson, M.P.; Wolfsberg, L.E.

    2009-05-20

    For 3-5d transition-metal ions, the (C{sub 5}R{sub 5}){sub 2}MCl{sub 2} (R = H, Me for M = Ti, Zr, Hf) bent metallocenes represent a series of compounds that have been central in the development of organometallic chemistry and homogeneous catalysis. Here, we evaluate how changes in the principal quantum number for the group IV (C{sub 5}H{sub 5}){sub 2}MCl{sub 2} (M = Ti, Zr, Hf; 1-3, respectively) complexes affects the covalency of M-Cl bonds through application of Cl K-edge X-ray Absorption Spectroscopy (XAS). Spectra were recorded on solid samples dispersed as a thin film and encapsulated in polystyrene matrices to reliably minimize problems associated with X-ray self-absorption. The data show that XAS pre-edge intensities can be quantitatively reproduced when analytes are encapsulated in polystyrene. Cl K-edge XAS data show that covalency in M-Cl bonding changes in the order Ti > Zr > Hf and demonstrates that covalency slightly decreases with increasing principal quantum number in 1-3. The percent Cl 3p character was experimentally determined to be 26, 23, and 18% per M-Cl bond in the thin-film samples for 1-3 respectively and was indistinguishable from the polystyrene samples, which analyzed as 25, 25, and 19% for 1-3, respectively. To aid in interpretation of Cl K-edge XAS, 1-3 were also analyzed by ground-state and time-dependent density functional theory (TD-DFT) calculations. The calculated spectra and percent chlorine character are in close agreement with the experimental observations, and show 20, 18, and 17% Cl 3p character per M-Cl bond for 1-3, respectively. Polystyrene matrix encapsulation affords a convenient method to safely contain radioactive samples to extend our studies to include actinide elements, where both 5f and 6d orbitals are expected to play a role in M-Cl bonding and where transition assignments must rely on accurate theoretical calculations.

  5. Restricting rotation of triple bond through π-stacking interactions in ...

    Indian Academy of Sciences (India)

    SANKARARAMAN

    E. Bosch, et. al., J. Org. Chem. 2008, 73, 3931-3934. Covalent bond mediated restriction of conformational mobility. Page 10. π π π π. Why not use weak ... Page 22. 0. 0.2. 0.4. 0.6. 0.8. 1. 1.2. 200. 250. 300. 350. 400. 450. 500. Wavelength (nm). A b s o rb a n c e. CH. MeOH. 10-5 M. Page 23. 250. 350. 450. 550. 650.

  6. Titanium Alloy Strong Back for IXO Mirror Segments

    Science.gov (United States)

    Byron, Glenn P.; Kai-Wang, Chan

    2011-01-01

    A titanium-alloy mirror-holding fixture called a strong back allows the temporary and permanent bonding of a 50 degree D263 glass x-ray mirror (IXO here stands for International X-ray Observatory). The strong back is used to hold and position a mirror segment so that mounting tabs may be bonded to the mirror with ultra-low distortion of the optical surface. Ti-15%Mo alloy was the material of choice for the strong back and tabs because the coefficient of thermal expansion closely matches that of the D263 glass and the material is relatively easy to machine. This invention has the ability to transfer bonded mounting points from a temporary location on the strong back to a permanent location on the strong back with minimal distortion. Secondly, it converts a single mirror segment into a rigid body with an acceptable amount of distortion of the mirror, and then maneuvers that rigid body into optical alignment such that the mirror segment can be bonded into a housing simulator or mirror module. Key problems are that the mirrors are 0.4-mm thick and have a very low coefficient of thermal expansion (CTE). Because the mirrors are so thin, they are very flexible and are easily distorted. When permanently bonding the mirror, the goal is to achieve a less than 1-micron distortion. Temperature deviations in the lab, which have been measured to be around 1 C, have caused significant distortions in the mirror segment.

  7. 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....

  8. Strong Arcwise Connectedness

    OpenAIRE

    Espinoza, Benjamin; Gartside, Paul; Kovan-Bakan, Merve; Mamatelashvili, Ana

    2012-01-01

    A space is `n-strong arc connected' (n-sac) if for any n points in the space there is an arc in the space visiting them in order. A space is omega-strong arc connected (omega-sac) if it is n-sac for all n. We study these properties in finite graphs, regular continua, and rational continua. There are no 4-sac graphs, but there are 3-sac graphs and graphs which are 2-sac but not 3-sac. For every n there is an n-sac regular continuum, but no regular continuum is omega-sac. There is an omega-sac ...

  9. Abortion: Strong's counterexamples fail

    DEFF Research Database (Denmark)

    Di Nucci, Ezio

    2009-01-01

    This paper shows that the counterexamples proposed by Strong in 2008 in the Journal of Medical Ethics to Marquis's argument against abortion fail. Strong's basic idea is that there are cases--for example, terminally ill patients--where killing an adult human being is prima facie seriously morally......'s scenarios have some valuable future or admitted that killing them is not seriously morally wrong. Finally, if "valuable future" is interpreted as referring to objective standards, one ends up with implausible and unpalatable moral claims....

  10. Covalently bound conjugates of albumin and heparin: Synthesis, fractionation and characterization

    NARCIS (Netherlands)

    Hennink, Wim E.; Feijen, Jan; Ebert, Charles D.; Kim, Sung Wan

    1983-01-01

    Covalently bound conjugates of human serum albumin and heparin were prepared as compounds which could improve the blood-compatibility of polymer surfaces either by preadsorption or by covalent coupling of the conjugates onto blood contacting surfaces. The conjugates (10–16 weight % of heparin) were

  11. Covalently Immobilised Cytochrome C Imaged by In Situ Scanning Tunnelling Microscopy

    DEFF Research Database (Denmark)

    Andersen, Jens Enevold Thaulov; Olesen, Klaus G.; Danilov, Alexey I.

    1997-01-01

    In situ scanning tunnelling microscopy (STM) imaging of cytochrome c (cyt c) on polycrystalline Pt surfaces and on Au(lll) was achieved first by covalent immobilisation of 3-aminopropyltriethoxysilane (3-APTS) brought to react with oxide present on the Pt surfaces. Covalently bound 3-APTS forms...

  12. Covalent-ionically cross-linked polyetheretherketone proton exchange membrane for direct methanol fuel cell

    CSIR Research Space (South Africa)

    Luo, H

    2010-08-01

    Full Text Available In this paper, the proton exchange membrane prepared by covalent-ionically crosslinking water soluble sulfonated-sulfinated poly(oxa-p-phenylene-3,3-phthalido-pphenylene- oxa-p-phenylene-oxy-phenylene) (SsPEEK-WC) is reported. Compared with covalent...

  13. Organogel-derived Covalent-Noncovalent Hybrid Polymers as Alkali Metal Ion Scavengers for Partial Deionization of Water.

    Science.gov (United States)

    Prathap, Annamalai; Raju, Cijil; Sureshan, Kana M

    2018-04-12

    We show that crown ethers (CEs) 1-5 congeal both polar and non-polar solvents via their self-assembly through weak non-covalent interactions (NCI) such as CH...O and CH...π interactions. Di-isopropylidene-mannitol (6) is a known gelator that self-assembles through stronger OH...O H-bonding. These two gelators together also congeal non-polar solvents via their individual self-assembly. The gelator 6 self-assembles swiftly to fibers, which act as templates and attract CE to their surface through H-bonding and thereby facilitate their self-assembly through weak NCI. Polymerization of styrene gels made from CE and 6 followed by the washing off of the sacrificial gelator 6 yields robust porous polystyrene-crown ether hybrid matrices (PCH), having pore-exposed CEs. These PCHs were not only efficient in sequestering alkali metal ions from aqueous solutions but also can be recycled. This novel use of organogels for making solid sorbents for metal ion scavenging might be of great interest.

  14. Recognition of anions using urea and thiourea substituted calixarenes: A density functional theory study of non-covalent interactions

    Science.gov (United States)

    Athar, Mohd; Lone, Mohsin Y.; Jha, Prakash C.

    2018-02-01

    Designing of new calixarene receptors for the selective binding of anions is an age-old concept; even though expected outcomes from this field are at premature stage. Herein, we have performed quantum chemical calculations to provide structural basis of anion binding with urea and thiourea substituted calixarenes (1, 2, and 3). In particular, spherical halides (F-, Cl-, Br-) and linear anions (CN-, N3-, SCN-) were modelled for calculating binding energies with receptor 1, 2 and 3 followed by their marked IR vibrations; taking the available experimental information into account. We found that the thiourea substitutions have better capability to stabilize the anions. Results have suggested that the structural behaviour of macrocyclic motifs were responsible for displaying the anion binding potentials. Moreover, second order "charge transfer" interactions of n-σ∗NH and n-σ∗OH type along the H-bond axis played critical role in developing hydrogen bonds. The present work also examines the role of non-covalent interactions (NCI) and their effects on thermodynamic and chemical-reactivity descriptors.

  15. Chemisorption bonding and catalysis

    International Nuclear Information System (INIS)

    Danese, J.B.; Schrieffer, J.R.

    1976-01-01

    The general features of the LCAO--MO, Green's function, and multiple-scattering chi α methods and their applications to surfaces and surface-related problems are discussed. Emphasis is placed on the localization of bonding in surface complexes

  16. Tile-bonding tool

    Science.gov (United States)

    Haynie, C. C.; Holt, J. W.

    1978-01-01

    Device applies uniform, constant, precise pressure to hold tiles in place during bonding. Tool consists of pressure bladders supported by adjustable pole. Pole can accomodate single or multiple bladders. Tiles can be flat or contoured.

  17. Bond markets in Africa

    Directory of Open Access Journals (Sweden)

    Yibin Mu

    2013-07-01

    Full Text Available African bond markets have been steadily growing in recent years, but nonetheless remain undeveloped. African countries would benefit from greater access to financing and deeper financial markets. This paper compiles a unique set of data on government securities and corporate bond markets in Africa. It then applies an econometric model to analyze the key determinants of African government securities market and corporate bond market capitalization. Government securities market capitalization is directly related to better institutions and interest rate volatility, and inversely related to smaller fiscal deficits, higher interest rate spreads, exchange rate volatility, and current and capital account openness. Corporate bond market capitalization is directly linked to economic size, the level of development of the economy and financial markets, better institutions, and interest rate volatility, and inversely related to higher interest rate spreads and current account openness. Policy implications follow.

  18. Towards 4th generation biomaterials: a covalent hybrid polymer-ormoglass architecture

    Science.gov (United States)

    Sachot, N.; Mateos-Timoneda, M. A.; Planell, J. A.; Velders, A. H.; Lewandowska, M.; Engel, E.; Castaño, O.

    2015-09-01

    Hybrid materials are being extensively investigated with the aim of mimicking the ECM microenvironment to develop effective solutions for bone tissue engineering. However, the common drawbacks of a hybrid material are the lack of interactions between the scaffold's constituents and the masking of its bioactive phase. Conventional hybrids often degrade in a non-homogeneous manner and the biological response is far from optimal. We have developed a novel material with strong interactions between constituents. The bioactive phase is directly exposed on its surface mimicking the structure of the ECM of bone. Here, polylactic acid electrospun fibers have been successfully and reproducibly coated with a bioactive organically modified glass (ormoglass, Si-Ca-P2 system) covalently. In comparison with the pure polymeric mats, the fibers obtained showed improved hydrophilicity and mechanical properties, bioactive ion release, exhibited a nanoroughness and enabled good cell adhesion and spreading after just one day of culture (rMSCs and rEPCs). The fibers were coated with different ormoglass compositions to tailor their surface properties (roughness, stiffness, and morphology) by modifying the experimental parameters. Knowing that cells modulate their behavior according to the exposed physical and chemical signals, the development of this instructive material is a valuable advance in the design of functional regenerative biomaterials.Hybrid materials are being extensively investigated with the aim of mimicking the ECM microenvironment to develop effective solutions for bone tissue engineering. However, the common drawbacks of a hybrid material are the lack of interactions between the scaffold's constituents and the masking of its bioactive phase. Conventional hybrids often degrade in a non-homogeneous manner and the biological response is far from optimal. We have developed a novel material with strong interactions between constituents. The bioactive phase is directly exposed

  19. Unexpected covalency from actinide 5f orbital interactions (An = Th, U, Np, Pu) determined from chlorine K-edge X-ray absorption spectroscopy and electronic structure theory

    International Nuclear Information System (INIS)

    Clark, D.L.; Batista, E.R.; Boland, K.S.

    2010-01-01

    We have employed Cl K-edge XAS and multiple levels of sophisticated electronic structure calculations on a series of simple octahedral light actinide (Th, U, Np, Pu) chloride salts, AnCl 6 n- in order to assess the relative roles of the valence 5f and 6d orbitals in chemical bonding. Chlorine K-edge X-ray absorption spectroscopy on AnCl 6 n- (An = Th, U, Np, Pu) systems indicates the presence of covalent interactions between both Cl 3p and An 5f and 6d orbitals, with the relative contributions changing across the series. Electronic structure calculations indicate the predominant covalent interactions are expected to occur through An-Cl bonding via t 1u and t 2u interactions with the An 5f orbitals, and through t 2g and e g interactions with An 6d orbitals. For the Cl K-edge data therefore, we expect bound state transitions from Cl 1s → e g (σ), t 2g (π), and t 1u (σ + π) orbitals. Qualitatively, the Cl K-edge data fulfills these expectations

  20. Comparison of covalent and noncovalent immobilization of Malatya apricot pectinesterase (Prunus armeniaca L.).

    Science.gov (United States)

    Karakuş, Emine; Pekyardımcı, Sule

    2012-02-01

    Pectinesterase isolated from Malatya apricot pulp was noncovalently and covalently immobilized onto bentonite and glutaraldehyde-containing amino group functionalized porous glass beads surface at pH 8.0 and pH 9.0, respectively. The effect of various parameters such as pH, temperature, activation energy, heat and storage stability on immobilized enzyme were investigated. The optimum temperature of covalently and noncovalently immobilized PE was 50°C. This value was 60°C for free PE. Although optimum pH of covalently-immobilized PE was 8.0, this parameter was 9.0 for free and covalently-immobilized PE. The noncovalently immobilized enzyme exhibited better thermostability than the free and covalently immobilized PE.

  1. A strong comeback

    International Nuclear Information System (INIS)

    Marier, D.

    1992-01-01

    This article presents the results of a financial rankings survey which show a strong economic activity in the independent energy industry. The topics of the article include advisor turnover, overseas banks, and the increase in public offerings. The article identifies the top project finance investors for new projects and restructurings and rankings for lenders

  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. Diffusion bonding techniques

    International Nuclear Information System (INIS)

    Peters, R.D.

    1978-01-01

    The applications of diffusion bonding at the General Electric Neutron Devices Department are briefly discussed, with particular emphasis on the gold/gold or gold/indium joints made between metallized alumina ceramic parts in the vacuum switch tube and the crystal resonator programs. Fixtures which use the differential expansion of dissimilar metals are described and compared to one that uses hydraulic pressure to apply the necessary bonding force

  4. Protein samples for NMR: expression and analysis without purification, and stabilization by covalent cyclization

    International Nuclear Information System (INIS)

    Otting, G.; Ozawa, K.; Prosselkov, P.; Williams, N.K.; Dixon, N.E.; Liepinsh, E.

    2002-01-01

    Full text: A modified cell-free in vitro expression system was established for the expression of milligram quantities of protein per mL reaction medium. Expression levels of the E coli cytoplasmic peptidyl-prolyl cis-trans isomerase, PpiB, in 0 6 mL reaction medium were sufficient for the direct recording of clean 15N-HSQC spectra without chromatographic purification or sample concentration steps, using a 600 MHz NMR spectrometer with cryoprobe. Besides providing a route to high-throughput sample preparation, in vitro expression systems are known to be highly economic in their utilization of selectively labelled ammo acids. Using dual-selective labelling with 15N- and 13C-labelled amino acids, the 15N-HSQC cross peaks of strategically selected ammo acids can readily be identified and monitored for their response to the presence of ligand molecules, again without sample purification. 2) The N-terminal domain of E coli DnaB is a protein of ca 110 residues with a structured core composed of 6 helices. Additional segments of 10 residues each at the N- and C-termini are highly mobile. Both ends are close in space and can be linked together in a covalent peptide bond using intern technology. The core structures of linear (lin-DnaB-N) and cyclized (cz-DnaB-N) protein are conserved, as evidenced by superimposable NOESY spectra and chemical shifts. The linker segment in cz-DnaB-N is mobile as shown by 1H-15N NOEs. Yet, the cyclic protein melts about 10 degrees higher than the linear version. A stabilization free energy of ca 2 kcal/mol is in agreement with predictions based on the reduced entropy in the unfolded state. Amide proton exchange rates are much slower in the cyclic protein and reveal cooperative exchange through total, global unfolding at a rate of once every 100 minutes in the linear protein

  5. The role of the 5f valence orbitals of early actinides in chemical bonding

    Science.gov (United States)

    Vitova, T.; Pidchenko, I.; Fellhauer, D.; Bagus, P. S.; Joly, Y.; Pruessmann, T.; Bahl, S.; Gonzalez-Robles, E.; Rothe, J.; Altmaier, M.; Denecke, M. A.; Geckeis, H.

    2017-01-01

    One of the long standing debates in actinide chemistry is the level of localization and participation of the actinide 5f valence orbitals in covalent bonds across the actinide series. Here we illuminate the role of the 5f valence orbitals of uranium, neptunium and plutonium in chemical bonding using advanced spectroscopies: actinide M4,5 HR-XANES and 3d4f RIXS. Results reveal that the 5f orbitals are active in the chemical bonding for uranium and neptunium, shown by significant variations in the level of their localization evidenced in the spectra. In contrast, the 5f orbitals of plutonium appear localized and surprisingly insensitive to different bonding environments. We envisage that this report of using relative energy differences between the 5fδ/ϕ and 5fπ*/5fσ* orbitals as a qualitative measure of overlap-driven actinyl bond covalency will spark activity, and extend to numerous applications of RIXS and HR-XANES to gain new insights into the electronic structures of the actinide elements. PMID:28681848

  6. Mott Transition In Strongly Correlated Materials: Many-Body Methods And Realistic Materials Simulations

    Science.gov (United States)

    Lee, Tsung-Han

    improved DMFT to describe a Mott insulator containing spin-propagating and chargeless fermionic excitations, spinons. We found the spinon Fermi-liquid, in the Mott insulating phase, is immiscible to the electron Fermi-liquid, in the metallic phase, due to the strong scattering between spinons in a metal. Third, we proposed a new approach within the slave-boson (Gutzwiller) framework that allows to describe both the low energy quasiparticle excitation and the high energy Hubbard excitation, which cannot be captured within the original slave-boson framework. In the second part, we applied LDA+RISB to realistic materials modeling. First, we tested the accuracy of LDA+RISB on predicting the structure of transition metal compounds, CrO, MnO, FeO, CoO, CoS, and CoSe. Our results display remarkable agreements with the experimental observations. Second, we applied LDA+RISB to analyze the nature of the Am-O chemical bonding in the CsAm(CrO 4)2 crystal. Our results indicate the Am-O bonding has strongly covalent character, and they also address the importance of the correlation effects to describe the experimentally observed electronic structure. In summary, we proposed three extensions within DMFT and RISB framework, which allow to investigate the domain wall structure in metal-Mott insulator coexistence regime, the metal-to-Mott-insulator transition with spinons excitation in the Mott-insulating phase, and the Hubbard excitation within RISB approach. Furthermore, we demonstrated that LDA+RISB is a reliable approximation to the strongly correlated materials by applying it to the transition metal compounds and the Americian chromate compounds.

  7. Comparison of Ab initio low-energy models for LaFePO, LaFeAsO, BaFe2As2, LiFeAs, FeSe, and FeTe. Electron correlation and covalency

    International Nuclear Information System (INIS)

    Miyake, Takashi; Nakamura, Kazuma; Arita, Ryotaro; Imada, Masatoshi

    2010-01-01

    Effective low-energy Hamiltonians for several different families of iron-based superconductors are compared after deriving them from the downfolding scheme based on first-principles calculations. Systematic dependences of the derived model parameters on the families are elucidated, many of which are understood from the systematic variation of the covalency between Fe-3d and pnictogen-/chalcogen-p orbitals. First, LaFePO, LaFeAsO (1111), BaFe 2 As 2 (122), LiFeAs (111), FeSe, and FeTe (11) have overall similar band structures near the Fermi level, where the total widths of 10-fold Fe-3d bands are mostly around 4.5 eV. However, the derived effective models of the 10-fold Fe-3d bands (d model) for FeSe and FeTe have substantially larger effective onsite Coulomb interactions U - 4.2 and 3.4 eV, respectively, after the screening by electrons on other bands and after averaging over orbitals, as compared to ∼2.5 eV for LaFeAsO. The difference is similar in the effective models containing p orbitals of As, Se or Te (dp or dpp model), where U ranges from ∼4 eV for the 1111 family to ∼7 eV for the 11 family. The exchange interaction J has a similar tendency. The family dependence of models indicates a wide variation ranging from weak correlation regime (LaFePO) to substantially strong correlation regime (FeSe). The origin of the larger effective interaction in the 11 family is ascribed to smaller spread of the Wannier orbitals generating larger bare interaction, and to fewer screening channels by the other bands. This variation is primarily derived from the distance h between the pnictogen/chalcogen position and the Fe layer: The longer h for the 11 family generates more ionic character of the bonding between iron and anion atoms, while the shorter h for the 1111 family leads to more covalent-bonding character, the larger spread of the Wannier orbitals, and more efficient screening by the anion p orbitals. The screened interaction of the d model is strongly orbital

  8. Surface activated room-temperature bonding in Ar gas ambient for MEMS encapsulation

    Science.gov (United States)

    Takagi, Hideki; Kurashima, Yuichi; Takamizawa, Akifumi; Ikegami, Takeshi; Yanagimachi, Shinya

    2018-02-01

    Surface activated room-temperature bonding of Si and sapphire wafers in high-purity inert gas ambient was examined. Although surface activated bonding has been mainly performed in high vacuum, Si and sapphire wafers were successfully bonded in Ar gas ambient up to 90 kPa, which is almost atmospheric pressure. The dicing test proved that the bonding prepared in Ar gas ambient was strong enough for MEMS packaging, although the bonding strength was slightly decreased compared with that prepared in vacuum. Transmission electron microscope observation revealed that the bonding interface prepared in Ar gas ambient is almost the same as that prepared in vacuum. It means that Ar atoms in the bonding ambient do not hamper the interatomic bond formation at the bonding interface. Room-temperature bonding in gas ambient enables hermetic packaging of MEMS devices, such as inertia sensors, MEMS switches, and Cs vapor cells for MEMS atomic clocks at various pressures.

  9. Strong Electroweak Symmetry Breaking

    CERN Document Server

    Grinstein, Benjamin

    2011-01-01

    Models of spontaneous breaking of electroweak symmetry by a strong interaction do not have fine tuning/hierarchy problem. They are conceptually elegant and use the only mechanism of spontaneous breaking of a gauge symmetry that is known to occur in nature. The simplest model, minimal technicolor with extended technicolor interactions, is appealing because one can calculate by scaling up from QCD. But it is ruled out on many counts: inappropriately low quark and lepton masses (or excessive FCNC), bad electroweak data fits, light scalar and vector states, etc. However, nature may not choose the minimal model and then we are stuck: except possibly through lattice simulations, we are unable to compute and test the models. In the LHC era it therefore makes sense to abandon specific models (of strong EW breaking) and concentrate on generic features that may indicate discovery. The Technicolor Straw Man is not a model but a parametrized search strategy inspired by a remarkable generic feature of walking technicolor,...

  10. Unusual H-Bond Topology and Bifurcated H-bonds in the 2-Fluoroethanol Trimer.

    Science.gov (United States)

    Thomas, Javix; Liu, Xunchen; Jäger, Wolfgang; Xu, Yunjie

    2015-09-28

    By using a combination of rotational spectroscopy and ab initio calculations, an unusual H-bond topology was revealed for the 2-fluoroethanol trimer. The trimer exhibits a strong heterochiral preference and adopts an open OH⋅⋅⋅OH H-bond topology while utilizing two types of bifurcated H-bonds involving organic fluorine. This is in stark contrast to the cyclic OH⋅⋅⋅OH H-bond topology adopted by trimers of water and other simple alcohols. The strengths of different H-bonds in the trimer were analyzed by using the quantum theory of atoms in molecules. The study showcases a remarkable example of a chirality-induced switch in H-bond topology in a simple transient chiral fluoroalcohol. It provides important insight into the H-bond topologies of small fluoroalcohol aggregates, which are proposed to play a key role in protein folding and in enantioselective reactions and separations where fluoroalcohols serve as a (co)solvent. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Plasmons in strong superconductors

    International Nuclear Information System (INIS)

    Baldo, M.; Ducoin, C.

    2011-01-01

    We present a study of the possible plasmon excitations that can occur in systems where strong superconductivity is present. In these systems the plasmon energy is comparable to or smaller than the pairing gap. As a prototype of these systems we consider the proton component of Neutron Star matter just below the crust when electron screening is not taken into account. For the realistic case we consider in detail the different aspects of the elementary excitations when the proton, electron components are considered within the Random-Phase Approximation generalized to the superfluid case, while the influence of the neutron component is considered only at qualitative level. Electron screening plays a major role in modifying the proton spectrum and spectral function. At the same time the electron plasmon is strongly modified and damped by the indirect coupling with the superfluid proton component, even at moderately low values of the gap. The excitation spectrum shows the interplay of the different components and their relevance for each excitation modes. The results are relevant for neutrino physics and thermodynamical processes in neutron stars. If electron screening is neglected, the spectral properties of the proton component show some resemblance with the physical situation in high-T c superconductors, and we briefly discuss similarities and differences in this connection. In a general prospect, the results of the study emphasize the role of Coulomb interaction in strong superconductors.

  12. Topological Properties of Chemical Bonds from Static and Dynamic Electron Densities

    Science.gov (United States)

    Jagannatha Prathapa, Siriyara; Held, Jeanette; van Smaalen, Sander

    2013-01-01

    Dynamic and static electron densities (EDs) based on the independent spherical atom model (IAM) and multipole (MP) models of crambin were successfully computed, holding no series-termination effects. The densities are compared to EDs of small biological molecules at diverse temperatures. It is outlined that proteins exhibit an intrinsic flexibility, present as frozen disorder at 100 K, in contrast to small molecules. The flexibility of the proteins is reflected by atomic displacement parameters (B-factors), which are considerably larger than for small molecules at 298 K. Thus, an optimal deconvolution of deformation density and thermal motion is not guaranteed, which prevents a free refinement of MP parameters but allows an application of transferable, fixed MP parameters. The analysis of the topological properties, such as the density at bond critical points (BCPs) and the Laplacian, reveals systematic differences between static and dynamic EDs. Zero-point-vibrations, yet present in dynamic EDs at low temperature, affect but marginally the EDs of small molecules. The zero-point-vibrations cause a smearing of the ED, which becomes more pronounced with increasing temperature. Topological properties, primarily the Laplacian, of covalent bonds appear to be more sensitive to effects by temperature and the polarity of the bonds. However, dynamic EDs at ca. 20 K based on MP models provide a good characterization of chemical bonding. Both the density at BCPs and the Laplacian of hydrogen bonds constitute similar values from static and dynamic EDs for all studied temperatures. Deformation densities demonstrate the necessity of the employment of MP parameters in order to comprise the nature of covalent bonds. The character of hydrogen bonds can be roughly pictured by IAM, whereas MP parameters are recommended for a classification of hydrogen bonds beyond a solely interpretation of topological properties. PMID:25995522

  13. 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.

  14. Lanthanide and actinide extractions with anionic ligands based on cobalt bis(dicarbollide) ions with covalently bonded CMPO functions

    Czech Academy of Sciences Publication Activity Database

    Selucký, P.; Rais, J.; Lučaníková, M.; Grüner, Bohumír; Kvíčalová, Magdalena; Fejfarová, Karla; Císařová, I.

    2008-01-01

    Roč. 96, 4-5 (2008), s. 273-284 ISSN 0033-8230 R&D Projects: GA MŠk LC523 Grant - others:GA ČR(CZ) GA104/08/0006 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z10100521 Keywords : carboranes * metallaboranes * dicarbollides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.084, year: 2008

  15. Anionic alkyl diglycoldiamides with covalently bonded cobalt bis(dicarbollide)(1-) ions for lanthanide and actinide extractions

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Kvíčalová, Magdalena; Selucký, P.; Lučaníková, M.

    2010-01-01

    Roč. 695, č. 9 (2010), s. 1261-1264 ISSN 0022-328X R&D Projects: GA MŠk LC523; GA ČR GA104/09/0668 Grant - others:European Commision(XE) F16W-CT-2003-508854 Institutional research plan: CEZ:AV0Z40320502 Keywords : carboranes * metallaboranes * dicarbollides * TODGA Subject RIV: CA - Inorganic Chemistry Impact factor: 2.205, year: 2010

  16. Bifacial dye-sensitized solar cells from covalent-bonded polyaniline-multiwalled carbon nanotube complex counter electrodes

    Science.gov (United States)

    Zhang, Huihui; He, Benlin; Tang, Qunwei; Yu, Liangmin

    2015-02-01

    Exploration of cost-effective counter electrodes (CEs) and enhancement of power conversion efficiency have been two persistent objectives for dye-sensitized solar cells (DSSCs). In the current work, polyaniline-multiwalled carbon nanotube (PANi-MWCNT) complexes are synthesized by a reflux method and employed as CE materials for bifacial DSSCs. Owing to the high optical transparency of PANi-MWCNT complex CE, the incident light from rear side can compensate for the incident light from TiO2 anode. The charge-transfer ability and electrochemical behaviors demonstrate the potential utilization of PANi-MWCNT complex CEs in robust bifacial DSSCs. The electrochemical properties as well as photovoltaic performances are optimized by adjusting MWCNT dosages. A maximum power conversion efficiency of 9.24% is recorded from the bifacial DSSC employing PANi-8 wt‰ MWCNT complex CE for both irradiation, which is better than 8.08% from pure PANi CE.

  17. Development of fiber reactive, non-halogenated flame retardant on cotton fabrics and the enhanced flame retardancy by covalent bonding

    Science.gov (United States)

    The US law requires flame resistant properties on apparel or house hold items to prevent or minimize the fire damage. The objective of this research was to develop a non-halogenated flame retardant for application onto cotton fabrics. These treated fabrics can then be used in clothes or beddings to ...

  18. Efficient Covalent Bond Formation in Gas-Phase Peptide-Peptide Ion Complexes with the Photoleucine Stapler

    Czech Academy of Sciences Publication Activity Database

    Shaffer, C. J.; Andrikopoulos, Prokopis C.; Řezáč, Jan; Rulíšek, Lubomír; Tureček, F.

    2016-01-01

    Roč. 27, č. 4 (2016), s. 633-645 ISSN 1044-0305 R&D Projects: GA ČR(CZ) GA14-31419S; GA ČR GP13-01214P Institutional support: RVO:61388963 Keywords : peptide-peptide ion complexes * laser photodissociation * diazirine chromophores * photoleucine * Born-Oppenheimer molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.786, year: 2016

  19. Lanthanide and actinide extractions with anionic ligands based on cobalt bis(dicarbollide) ions with covalently bonded CMPO functions

    Energy Technology Data Exchange (ETDEWEB)

    Selucky, P.; Rais, J.; Lucanikova, M. [Nuclear Research Inst. plc., Rez near Prague (Czech Republic); Gruener, B.; Kvicalova, M. [Inst. of Inorganic Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Husinec-Rez near Prague (Czech Republic); Fejfarova, K. [Inst. of Physics, Academy of Sciences of the Czech Republic, Prague (Czech Republic); Cisarova, I. [Charles Univ., Prague (Czech Republic). Dept. of Chemistry

    2008-07-01

    Compounds were synthesized with the aim to develop efficient extraction agents for liquid-liquid extraction of polyvalent cations, i.e. lanthanides and actinides from high-level activity nuclear waste. Compounds of general formulation [(8-CMPO-(CH{sub 2}-CH{sub 2}O){sub 2}-1,2-C{sub 2}B{sub 9}H{sub 10})(1',2'-C{sub 2}B{sub 9}H{sub 11})-3.3'-Co(III)] with different phosphorus and nitrogen substitution (CMPO={sup 2}R,{sup 3}R P(O)-(CH{sub 2}){sub n}C(O)N{sup 1}R, {sup 1}R = t-octyl, H, Ph, {sup 2}R=Ph, n-octyl, {sup 3}R=Ph, n = 1,2)-(4a to 4e), were prepared and characterized by combination of {sup 11}B NMR, {sup 1}H high field NMR, ESI-M.S., HPLC and other techniques. Molecular structure of the sodium complex of ligand 4a ({sup 1}R = t-octyl, {sup 2}R = {sup 3}R = Ph, n = 1) was determined by single crystal X-ray diffraction analysis. Effect of several modifications in the structure of 4a-4e on the extraction properties was outlined. The study resulted in the definition of ionic ligand with enhanced extraction efficiency for 4a,b (t-octyl and H on the amidic nitrogen atom) and a better solubility of 4a and 4d ({sup 1}R = t-octyl, {sup 2}R = n-Oct, {sup 1}R=Ph, n = 1) in less polar solvents. Low polar mixtures of hydrogenated tetrapropylene (TPH) hexyl methyl ketone (HMK) can be applied as an auxiliary solvent for 4a, selected for detailed studies, replacing thus the polar and less environmentally friendly nitro-, fluoro- and chloro- solvents used in the current dicarbollide liquid-liquid extraction process. Results of the fission products separation from the simulated PUREX feed using 4a are presented inclusive procedures for Eu{sup 3+} stripping. (orig.)

  20. Luminescent hybrid materials of lanthanide β-diketonate and mesoporous host through covalent and ionic bonding with anion metathesis.

    Science.gov (United States)

    Li, Qiu-Ping; Yan, Bing

    2012-07-28

    Luminescent mesoporous materials were prepared by performing an anion metathesis reaction on ionic liquid modified SBA15, which has imidazolium chloride bridging units. The lanthanide β-diketonate complex anion was successfully anchored onto the SBA15 framework after the anion metathesis reaction. The resulting materials were characterized by FTIR, TEM, TGA, small-angle X-ray powder diffraction (SAXRD) and nitrogen adsorption-desorption isotherms. The photoluminescent properties of these materials were investigated in detail, and the results reveal that these hybrid mesoporous SBA15, prepared through this preparation approach, present favorable photoluminescent behavior such as high luminescent quantum efficiencies and long luminescent lifetimes.

  1. Lanthanide and actinide extractions with cobalt bis(dicarbollide) ion derivatives covalently bonded to diglycolyl diamide platform

    Czech Academy of Sciences Publication Activity Database

    Lučaníková, M.; Selucký, P.; Rais, J.; Grüner, Bohumír; Kvíčalová, Magdalena

    2011-01-01

    Roč. 1, č. 1 (2011), s. 89-95 ISSN 2193-2875 R&D Projects: GA ČR GA104/09/0668; GA MŠk LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : Dicarbollides derivatives * TODGA * Liquid-liquid extraction * Lanthanides * Actinides Subject RIV: CA - Inorganic Chemistry

  2. Iridium and ruthenium complexes covalently bonded to carbon surfaces by means of electrochemical oxidation of aromatic amines

    Czech Academy of Sciences Publication Activity Database

    Sandroni, M.; Volpi, G.; Fiedler, Jan; Buscaino, R.; Viscardi, G.; Milone, L.; Gobetto, R.; Nervi, C.

    2010-01-01

    Roč. 158, 1-2 (2010), s. 22-28 ISSN 0920-5861 R&D Projects: GA ČR GA203/09/0705 Institutional research plan: CEZ:AV0Z40400503 Keywords : functionalization * glassy carbon electrode * metallorganic complexes * cyclic voltammetry Subject RIV: CG - Electrochemistry Impact factor: 2.993, year: 2010

  3. 46 CFR Sec. 10 - Bonds.

    Science.gov (United States)

    2010-10-01

    ... open penalty type. (e) No repair voucher (progress or final) where bond coverage is required shall be... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA...) shall be used. (b) In compliance with the perform- ance bond and payment bond requirements of Article 14...

  4. Electrophilicities and Protein Covalent Binding of Demethylation Metabolites of Colchicine.

    Science.gov (United States)

    Guo, Xiucai; Lin, Dongju; Li, Weiwei; Wang, Kai; Peng, Ying; Zheng, Jiang

    2016-03-21

    Colchicine, an alkaloid existing in plants of Liliaceous colchicum, has been widely used in the treatment of gout and familial Mediterranean fever. The administration of colchicine was found to cause liver injury in humans. The mechanisms of colchicine-induced liver toxicity remain unknown. The objectives of this study were to determine the electrophilicities of demethylation metabolites of colchicine and investigate the protein adductions derived from the reactive metabolites of colchicine. Four demethylated colchicine (1-, 2-, 3-, and 10-DMCs), namely, M1-M4, were detected in colchicine-fortified microsomal incubations. Four N-acetyl cysteine (NAC) conjugates (M5-M8) derived from colchicine were detected in the microsomes in the presence of NAC. M5 and M6 were derived from 10-DMC. M7 resulted from the reaction of 2-DMC or 3-DMC with NAC, and M8 originated from 10-DMC. Microsomal protein covalent binding was observed after exposure to colchicine. Two cysteine adducts (CA-1 and CA-2) derived from 10-DMC were found in proteolytically digested microsomal protein samples after incubation with colchicine. The findings allow us to define the chemical property of demethylation metabolites of colchicine and the interaction between protein and the reactive metabolites of colchicine generated in situ.

  5. Functionalization of silicone rubber for the covalent immobilization of fibronectin.

    Science.gov (United States)

    Völcker, N; Klee, D; Höcker, H; Langefeld, S

    2001-02-01

    Surface modification techniques were employed in order to provide functionalized silicone rubber with enhanced cytocompatibility. Acrylic acid (AAc), methacrylic acid (MAAc) and glycidylmethacrylate (GMA) were graft-co-polymerized onto the surface of silicone induced by an argon plasma and thermal initiation. The polymerizations were carried out in solution, in the case of acrylic acid a vapor phase graft-co-polymerization subsequent to argon plasma activation was carried out as well. Human fibronectin (hFn), which acts as a cell adhesion mediator for fibroblasts, was immobilized by making use of the generated carboxylic or epoxy groups, respectively. Surface analysis was accomplished by means of X-ray photoelectron spectroscopy (XPS), infrared spectroscopy in attenuated total reflection mode (IR-ATR), scanning electron microscopy (SEM), atomic force microscopy (AFM) and dynamic contact angle measurements using the Wilhelmy-plate method. The amount of immobilized active hFn was semiquantified by enzyme-linked immunosorbent assay (ELISA) using a structure-specific antibody against the cell-binding domain of hFn. In vitro testing showed a remarkable difference between surfaces exposing adsorbed-only and surfaces with covalently immobilized hFn. Copyright 2001 Kluwer Academic Publishers

  6. Graphene magnetism induced by covalent adsorption of aromatic radicals.

    Science.gov (United States)

    Lin, He; Fratesi, Guido; Brivio, Gian Paolo

    2015-01-21

    We report a computational study of adsorption of aromatic radicals onto graphene, with the aim of understanding the effect of covalent molecular functionalization on the magnetic and structural properties of graphene. Our results show that the adsorption of an aromatic radical like phenyl also functionalized with donor or acceptor groups generates a band gap and two spin-dependent midgap states, one located above and the other below the Fermi energy of pristine graphene, which cause a net magnetic moment. Due to the interaction between the radical and graphene, we find that the carbon atom on the adsorption site is lifted out of the graphene plane, and its pz orbital is removed from the π band system, leaving the electrons in the other sublattice unpaired, which results in nonzero magnetism. But the band gap of the full system is insensitive to the different attached species and the midgap states are independent of the alignment of the molecular orbitals, so that the magnetic moment is the same for the various radicals studied. The net result of the radical adsorption is to have almost the same aromatic species as those in the gas phase but anchored on a surface.

  7. Anion binding in covalent and self-assembled molecular capsules.

    Science.gov (United States)

    Ballester, Pablo

    2010-10-01

    This critical review describes selected examples extracted from the extensive literature generated during the past 42 years on the topic of anion binding in molecular capsules. The goal of including anions in molecular capsules emerges from the idea of incorporating the traits exhibited by biological receptors into synthetic ones. At the outset of this research area the capsules were unimolecular. The scaffold of the receptor was designed to covalently link a series of functional groups that could converge into a cavity and to avoid its collapse. The initial examples involved the encapsulation of one monoatomic spherical anion. With time, the cavity size of the receptor was increased and encapsulation of polyatomic anions and co-encapsulation became a reality. Synthetic economy fueled the use of aggregates of self-complementary molecules rather than one large molecule as capsules. The main purpose of this review is to give a general overview of the topic which might be of interest to supramolecular or non supramolecular chemists alike (149 references).

  8. COVALENT IMMOBILIZATION OF INVERTASE ON EPOXY-ACTIVATED POLYANILINE FILMS

    Directory of Open Access Journals (Sweden)

    Loredana Vacareanu

    2013-08-01

    Full Text Available The growing interest in manufacturing and use of biosensors is their rapid and selective detection of the target analyte. The immobilization of the enzymes, onto the appropriate matrix is the key-step in the construction of biosensing devices, considerably affecting its performance. In this study, new polyaniline bearing epoxy groups was synthesized by electrochemical polymerization reactions, as adherent, green film deposited on electrode surface, and was further used as immobilization matrix for invertase enzyme. The immobilization was carried out by condensation reactions between the amino groups of the enzyme molecules and the epoxy groups of polyaniline film. The covalent attachment was achieved by simple immersing the epoxy-activated polyaniline in acetate buffer solution (10 mM, pH 6.0 containing 2mg/mL invertase, for 24 h at 4 ºC, by continuous stirring. The polyaniline films thus obtained were analyzed before and after the invertase attachment, by using FT-IR spectroscopy and SEM microscopy. The presence of the invertase was evaluated by measuring their activity, using UV-Vis spectroscopy, in the presence of a known amount of sucrose as a substrate. These tests, performed for three times under the same conditions, revealed that even after five washes of the polyaniline /invertase electrode to remove the unbounded enzyme, the enzyme remain attached on the polyaniline film, being able to hydrolyze the sucrose presented in the assay solutions.

  9. Self-Suspended Suspensions of Covalently Grafted Hairy Nanoparticles

    KAUST Repository

    Choudhury, Snehashis

    2015-03-17

    © 2015 American Chemical Society. Dispersions of small particles in liquids have been studied continuously for almost two centuries for their ability to simultaneously advance understanding of physical properties of fluids and their widespread use in applications. In both settings, the suspending (liquid) and suspended (solid) phases are normally distinct and uncoupled on long length and time scales. In this study, we report on the synthesis and physical properties of a novel family of covalently grafted nanoparticles that exist as self-suspended suspensions with high particle loadings. In such suspensions, we find that the grafted polymer chains exhibit unusual multiscale structural transitions and enhanced conformational stability on subnanometer and nanometer length scales. On mesoscopic length scales, the suspensions display exceptional homogeneity and colloidal stability. We attribute this feature to steric repulsions between grafted chains and the space-filling constraint on the tethered chains in the single-component self-suspended materials, which inhibits phase segregation. On macroscopic length scales, the suspensions exist as neat fluids that exhibit soft glassy rheology and, counterintuitively, enhanced elasticity with increasing temperature. This feature is discussed in terms of increased interpenetration of the grafted chains and jamming of the nanoparticles. (Chemical Presented).

  10. Bonding in phase change materials: concepts and misconceptions

    Science.gov (United States)

    Jones, R. O.

    2018-04-01

    Bonding concepts originating in chemistry are surveyed from a condensed matter perspective, beginning around 1850 with ‘valence’ and the word ‘bond’ itself. The analysis of chemical data in the 19th century resulted in astonishing progress in understanding the connectivity and stereochemistry of molecules, almost without input from physicists until the development of quantum mechanics in 1925 and afterwards. The valence bond method popularized by Pauling and the molecular orbital methods of Hund, Mulliken, Bloch, and Hückel play major roles in the subsequent development, as does the central part played by the kinetic energy in covalent bonding (Ruedenberg and others). ‘Metallic’ (free electron) and related approaches, including pseudopotential and density functional theories, have been remarkably successful in understanding structures and bonding in molecules and solids. We discuss these concepts in the context of phase change materials, which involve the rapid and reversible transition between amorphous and crystalline states, and note the confusion that some have caused, in particular ‘resonance’ and ‘resonant bonding’.

  11. Structural, electronic properties, and chemical bonding in quaternary layered titanium pnictide-oxides Na2Ti2Pn2O and BaTi2Pn2O (Pn = As, Sb) from FLAPW–GGA calculations

    International Nuclear Information System (INIS)

    Suetin, D.V.; Ivanovskii, A.L.

    2013-01-01

    Highlights: •Layered Na 2 Ti 2 Pn 2 O and BaTi 2 Pn 2 O (Pn = As, Sb) are probed from first principles. •Structural, electronic properties and Fermi surfaces are evaluated. •Chemical bonding is analyzed. -- Abstract: By means of the first-principles FLAPW–GGA calculations, we have investigated the main trends in structural, electronic properties, and chemical bonding for a series of quaternary titanium pnictide-oxides: Na 2 Ti 2 As 2 O, Na 2 Ti 2 Sb 2 O, BaTi 2 As 2 O, and BaTi 2 Sb 2 O, which attracted now much attention as parent phases for a novel group of layered Fe-free superconducting materials. Our results cover the optimized lattice parameters and atomic positions, electronic bands, Fermi surface topology, total and partial density of electronic states. Besides, Bader analysis and the charge density maps are used to discuss the chemical bonding for the examined materials. We find that the atomic substitutions lead to anisotropic deformation of the crystal structure; this effect is related to strong anisotropy of inter-atomic bonds, which are of a mixed (covalent-ionic-metallic) type – in blocks [Ti 2 Pn 2 O], whereas the bonding between blocks [Ti 2 Pn 2 O] and atomic sheets of Na, Ba ions is of an ionic type. The actual effective atomic charges differ from the formal ionic charges due to covalency in blocks [Ti 2 Pn 2 O]. The near-Fermi electronic bands, which are responsible for metallic-like behavior of these materials and will be involved in the formation of superconducting state, arise mainly from the Ti 3d xy , d x2−y2 , and d z2 states of the blocks [Ti 2 Pn 2 O], which define also the anisotropic character of conduction happening mainly in these blocks. The differences in the topology of the multi-sheet Fermi surfaces of these materials are discussed

  12. Structure, properties and wear behaviour of multilayer coatings consisting of metallic and covalent hard materials, prepared by magnetron sputtering

    International Nuclear Information System (INIS)

    Schier, V.

    1995-12-01

    Novel multilayer coatings with metallic and covalent layer materials were prepared by magnetron sputtering and characterised concerning structure, properties and application behaviour. At first single layer coatings were deposited for the determination of the material properties. To evaluate relations between structure and properties of the multilayer coatings, different multilayer concepts were realised: - coatings consisting of at most 7 layers of metallic hard materials, - 100-layer coatings consisting of metallic and covalent hard materials, - TiN-TiC multilayer coatings with different numbers of layers (between 10 and 1000), - 150-layer coatings, based on TiN-TiC multilayers, with thin ( 4 C, AlN, SiC, a:C, Si 3 N 4 , SiAlON). X-rays and electron microscopic analysis indicate in spite of nonstoichiometric compositions single phase crystalline structures for nonreactively and reactively sputtered metastable single layer Ti(B,C)-, Ti(B,N)- and Ti(B,C,N)-coatings. These single layer coatings show excellent mechanical properties (e.g. hardness values up to 6000 HV0,05), caused by lattice stresses as well as by atomic bonding conditions similar to those in c:BN and B 4 C. The good tribological properties shown in pin-on-disk-tests can be attributed to the very high hardness of the coatings. The coatings consisting of at most 7 layers of metallic hard materials show good results mainly for the cutting of steel Ck45, due to the improved mechanical properties (e.g. hardness, toughness) of the multilayers compared to the single layer coatings. This improvement is caused by inserting the hard layer materials and the coherent reinforcement of the coatings. (orig.)

  13. Ab Initio Ligand-Field Theory Analysis and Covalency Trends in Actinide and Lanthanide Free Ions and Octahedral Complexes.

    Science.gov (United States)

    Jung, Julie; Atanasov, Mihail; Neese, Frank

    2017-08-07

    Actinide chemistry is gaining increased focus in modern research, particularly in the fields of energy research and molecular magnetism. However, the structure-function and structure-property relationships of actinides have still not been studied as intensely as those for transition metals. In this work, we report a detailed ab initio study of the spectroscopic, magnetic, and bonding properties of the trivalent actinide free ions and their associated hexachloride complexes in octahedral symmetry. The electronic structures of these systems are examined using complete active-space self-consistent-field calculations followed by second-order N-electron valence perturbation theory, including both scalar relativistic and spin-orbit-coupling effects. The computed energies and wave functions are further analyzed by means of ab initio ligand-field theory (AILFT) and finally chemically interpreted by means of the angular overlap model (AOM). The derived Slater-Condon and spin-orbit parameters have allowed us to systematically rationalize the spectroscopic and magnetic properties of the investigated free ions and complexes along the entire actinide series. Overall, the AILFT- and AOM-derived parameters accurately reproduce the multireference electronic structure calculations. The small observed discrepancies with respect to experimentally derived ligand-field parameters are essentially due to an underestimation of the electronic correlation, which arises from both the constrained size of the active space (restricted to the f orbitals) and the limit of the perturbation approach to account for dynamical correlation. Our analysis also provides insight into the metal-ligand covalency trends along the series. Consistent with natural population analysis, the nephelauxetic (Slater-Condon parameters) and relativistic nephelauxetic (spin-orbit-coupling) reductions determined for these complexes indicate a decrease in the covalency along the series. These trends also hold, to varying

  14. Science and technology of plasma activated direct wafer bonding

    Science.gov (United States)

    Roberds, Brian Edward

    This dissertation studied the kinetics of silicon direct wafer bonding with emphasis on low temperature bonding mechanisms. The project goals were to understand the topological requirements for initial bonding, develop a tensile test to measure the bond strength as a function of time and temperature and, using the kinetic information obtained, develop lower temperature methods of bonding. A reproducible surface metrology metric for bonding was best described by power spectral density derived from atomic force microscopy measurements. From the tensile strength kinetics study it was found that low annealing temperatures could be used to obtain strong bonds, but at the expense of longer annealing times. Three models were developed to describe the kinetics. A diffusion controlled model and a reaction rate controlled model were developed for the higher temperature regimes (T > 600sp°C), and an electric field assisted oxidation model was proposed for the low temperature range. An in situ oxygen plasma treatment was used to further enhance the field-controlled mechanism which resulted in dramatic increases in the low temperature bonding kinetics. Multiple internal transmission Fourier transform infrared spectroscopy (MIT-FTIR) was used to monitor species evolution at the bonded interface and a capacitance-voltage (CV) study was undertaken to investigate charge distribution and surface states resulting from plasma activation. A short, less than a minute, plasma exposure prior to contacting the wafers was found to obtain very strong bonds for hydrophobic silicon wafers at very low temperatures (100sp°C). This novel bonding method may enable new technologies involving heterogeneous material systems or bonding partially fabricated devices to become realities.

  15. Coval: improving alignment quality and variant calling accuracy for next-generation sequencing data.

    Directory of Open Access Journals (Sweden)

    Shunichi Kosugi

    Full Text Available Accurate identification of DNA polymorphisms using next-generation sequencing technology is challenging because of a high rate of sequencing error and incorrect mapping of reads to reference genomes. Currently available short read aligners and DNA variant callers suffer from these problems. We developed the Coval software to improve the quality of short read alignments. Coval is designed to minimize the incidence of spurious alignment of short reads, by filtering mismatched reads that remained in alignments after local realignment and error correction of mismatched reads. The error correction is executed based on the base quality and allele frequency at the non-reference positions for an individual or pooled sample. We demonstrated the utility of Coval by applying it to simulated genomes and experimentally obtained short-read data of rice, nematode, and mouse. Moreover, we found an unexpectedly large number of incorrectly mapped reads in 'targeted' alignments, where the whole genome sequencing reads had been aligned to a local genomic segment, and showed that Coval effectively eliminated such spurious alignments. We conclude that Coval significantly improves the quality of short-read sequence alignments, thereby increasing the calling accuracy of currently available tools for SNP and indel identification. Coval is available at http://sourceforge.net/projects/coval105/.

  16. The covalence effect of energy levels of ZnS:Mn2+

    International Nuclear Information System (INIS)

    Dong-Yang, Li; Mao-Lu, Du; Yi, Huang

    2013-01-01

    The contribution of the different covalence for t 2 and e orbitals must be considered in the investigation of the optical and magnetic properties of the transition metal ion in II–VI and III–V semiconductors. In present paper, two covalent parameters N t and N e associated with t 2 and e orbitals have been adopted to describe the covalence. The energy matrices considering the different covalence for t 2 and e orbitals have been provided for d 5 ions in crystal. These matrices show that the contribution from the Racah parameter A cannot be neglected in calculation of energy-level of d 5 ions in covalent crystal. The calculated results using the matrix show that the energy levels of 4 E and 4 A 1 states split, and the energy-level difference between 4 E and 4 A 1 states increases with increase of the different covalence between t 2 and e orbitals. These energy levels are always degenerate, when the different covalence for t 2 and e orbitals is neglected. By using the energy matrices, the energy-level of ZnS:Mn 2+ has been calculated. The calculated energy levels of ZnS:Mn 2+ are in good agreement with the experiments

  17. New biofuel integrating glycerol into its composition through the use of covalent immobilized pig pancreatic lipase.

    Science.gov (United States)

    Luna, Diego; Posadillo, Alejandro; Caballero, Verónica; Verdugo, Cristóbal; Bautista, Felipa M; Romero, Antonio A; Sancho, Enrique D; Luna, Carlos; Calero, Juan

    2012-01-01

    By using 1,3-specific Pig Pancreatic lipase (EC 3.1.1.3 or PPL), covalently immobilized on AlPO(4)/Sepiolite support as biocatalyst, a new second-generation biodiesel was obtained in the transesterification reaction of sunflower oil with ethanol and other alcohols of low molecular weight. The resulting biofuel is composed of fatty acid ethyl esters and monoglycerides (FAEE/MG) blended in a molar relation 2/1. This novel product, which integrates glycerol as monoacylglycerols (MG) into the biofuel composition, has similar physicochemical properties compared to those of conventional biodiesel and also avoids the removal step of this by-product. The biocatalyst was found to be strongly fixed to the inorganic support (75%). Nevertheless, the efficiency of the immobilized enzyme was reduced to half (49.1%) compared to that of the free PPL. The immobilized enzyme showed a remarkable stability as well as a great reusability (more than 40 successive reuses) without a significant loss of its initial catalytic activity. Immobilized and free enzymes exhibited different reaction mechanisms, according to the different results in the Arrhenius parameters (Ln A and Ea). However, the use of supported PPL was found to be very suitable for the repetitive production of biofuel due to its facile recyclability from the reaction mixture.

  18. New Biofuel Integrating Glycerol into Its Composition Through the Use of Covalent Immobilized Pig Pancreatic Lipase

    Directory of Open Access Journals (Sweden)

    Carlos Luna

    2012-08-01

    Full Text Available By using 1,3-specific Pig Pancreatic lipase (EC 3.1.1.3 or PPL, covalently immobilized on AlPO4/Sepiolite support as biocatalyst, a new second-generation biodiesel was obtained in the transesterification reaction of sunflower oil with ethanol and other alcohols of low molecular weight. The resulting biofuel is composed of fatty acid ethyl esters and monoglycerides (FAEE/MG blended in a molar relation 2/1. This novel product, which integrates glycerol as monoacylglycerols (MG into the biofuel composition, has similar physicochemical properties compared to those of conventional biodiesel and also avoids the removal step of this by-product. The biocatalyst was found to be strongly fixed to the inorganic support (75%. Nevertheless, the efficiency of the immobilized enzyme was reduced to half (49.1% compared to that of the free PPL. The immobilized enzyme showed a remarkable stability as well as a great reusability (more than 40 successive reuses without a significant loss of its initial catalytic activity. Immobilized and free enzymes exhibited different reaction mechanisms, according to the different results in the Arrhenius parameters (Ln A and Ea. However, the use of supported PPL was found to be very suitable for the repetitive production of biofuel due to its facile recyclability from the reaction mixture.

  19. Removal U(VI) from artificial seawater using facilely and covalently grafted polyacrylonitrile fibers with lysine

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wenting; Liu, Qi; Liu, Jingyuan; Zhang, Hongsen; Li, Rumin; Li, Zhanshuang; Jing, Xiaoyan [Key Laboratory of Superlight Material and Surface Technology, Ministry of Education, Harbin Engineering University, Harbin 150001 (China); Wang, Jun, E-mail: zhqw1888@sohu.com [Key Laboratory of Superlight Material and Surface Technology, Ministry of Education, Harbin Engineering University, Harbin 150001 (China); Institute of Advanced Marine Materials, Harbin Engineering University, 150001 (China)

    2017-05-01

    Highlights: • Novel lysine modified fibrous adsorbents were prepared using a facile and green method. • PAN-Lys exhibited high adsorption activity and fast adsorption rate. • PAN-Lys significantly remove U(VI) from simulated seawater. - Abstract: Polyacrylonitrile fibers (PANF) covalently modified with lysine (PAN-Lys) was facilely synthesized and carefully characterized. The critical factors affecting U(VI) adsorption from aqueous solution were exploited, such as initial pH, contact time, concentration and temperature. The adsorption process is strongly dependent on solution pH. With excellent adsorption capacity and high affinity toward U(VI), the process for U(VI) is extremely rapid and the equilibrium can be reached within 20 min. The thermodynamics and kinetics were strictly evaluated. In addition, the hypothetical adsorption mechanisms were proposed. Moreover, the adsorption behavior at low concentrations (3–30 μg L{sup −1}) in simulated seawater was also investigated. Therefore, PAN-Lys can be potentially utilized for the efficient removal of U(VI) from seawater.

  20. Removal U(VI) from artificial seawater using facilely and covalently grafted polyacrylonitrile fibers with lysine

    International Nuclear Information System (INIS)

    Li, Wenting; Liu, Qi; Liu, Jingyuan; Zhang, Hongsen; Li, Rumin; Li, Zhanshuang; Jing, Xiaoyan; Wang, Jun

    2017-01-01

    Highlights: • Novel lysine modified fibrous adsorbents were prepared using a facile and green method. • PAN-Lys exhibited high adsorption activity and fast adsorption rate. • PAN-Lys significantly remove U(VI) from simulated seawater. - Abstract: Polyacrylonitrile fibers (PANF) covalently modified with lysine (PAN-Lys) was facilely synthesized and carefully characterized. The critical factors affecting U(VI) adsorption from aqueous solution were exploited, such as initial pH, contact time, concentration and temperature. The adsorption process is strongly dependent on solution pH. With excellent adsorption capacity and high affinity toward U(VI), the process for U(VI) is extremely rapid and the equilibrium can be reached within 20 min. The thermodynamics and kinetics were strictly evaluated. In addition, the hypothetical adsorption mechanisms were proposed. Moreover, the adsorption behavior at low concentrations (3–30 μg L −1 ) in simulated seawater was also investigated. Therefore, PAN-Lys can be potentially utilized for the efficient removal of U(VI) from seawater.

  1. Evidence for covalent attachment of phospholipid to the capsular polysaccharide of Haemophilus influenzae type b

    Energy Technology Data Exchange (ETDEWEB)

    Kuo, J.S.; Doelling, V.W.; Graveline, J.F.; McCoy, D.W.

    1985-08-01

    Cells of Haemophilus influenzae type b were grown in a liquid medium containing (TH)palmitate or ( UC)ribose or both for two generations of exponential growth. Radiolabeled type-specific capsular polysaccharide, polyribosyl ribitol phosphate (PRP), was purified from the culture supernatant by Cetavlon precipitation, ethanol fractionation, and hydroxylapatite and Sepharose 4B chromatography. The doubly labeled ( (TH)palmitate and ( UC)ribose) PRP preparation was found to coelute in a single peak from a Sepharose 4B column, suggesting that both precursors were incorporated into the purified PRP. A singly labeled ( (TH)palmitate) purified PRP preparation was found to be quantitatively immune precipitated by human serum containing antibody against PRP. Only after acid, alkaline, or phospholipase A2 treatment of PRP labeled with (TH)palmitate or (TH)palmitate and ( UC)ribose followed by chloroform-methanol extraction could most of the TH-radioactivity be recovered in the organic phase. The chloroform-soluble acid-hydrolyzed or phospholipase A2-treated product was identified as palmitic acid after thin-layer chromatography. These results strongly suggest that a phospholipid moiety is covalently associated with the H. influenzae type b polysaccharide PRP.

  2. New Biofuel Integrating Glycerol into Its Composition Through the Use of Covalent Immobilized Pig Pancreatic Lipase

    Science.gov (United States)

    Luna, Diego; Posadillo, Alejandro; Caballero, Verónica; Verdugo, Cristóbal; Bautista, Felipa M.; Romero, Antonio A.; Sancho, Enrique D.; Luna, Carlos; Calero, Juan

    2012-01-01

    By using 1,3-specific Pig Pancreatic lipase (EC 3.1.1.3 or PPL), covalently immobilized on AlPO4/Sepiolite support as biocatalyst, a new second-generation biodiesel was obtained in the transesterification reaction of sunflower oil with ethanol and other alcohols of low molecular weight. The resulting biofuel is composed of fatty acid ethyl esters and monoglycerides (FAEE/MG) blended in a molar relation 2/1. This novel product, which integrates glycerol as monoacylglycerols (MG) into the biofuel composition, has similar physicochemical properties compared to those of conventional biodiesel and also avoids the removal step of this by-product. The biocatalyst was found to be strongly fixed to the inorganic support (75%). Nevertheless, the efficiency of the immobilized enzyme was reduced to half (49.1%) compared to that of the free PPL. The immobilized enzyme showed a remarkable stability as well as a great reusability (more than 40 successive reuses) without a significant loss of its initial catalytic activity. Immobilized and free enzymes exhibited different reaction mechanisms, according to the different results in the Arrhenius parameters (Ln A and Ea). However, the use of supported PPL was found to be very suitable for the repetitive production of biofuel due to its facile recyclability from the reaction mixture. PMID:22949849

  3. Non-covalent interactions of cadmium sulphide and gold nanoparticles with DNA

    Science.gov (United States)

    Atay, Z.; Biver, T.; Corti, A.; Eltugral, N.; Lorenzini, E.; Masini, M.; Paolicchi, A.; Pucci, A.; Ruggeri, G.; Secco, F.; Venturini, M.

    2010-08-01

    Mercaptoethanol-capped CdS nanoparticles (CdSnp) and monohydroxy-(1-mercaptoundec-11-yl)tetraethylene-glycol-capped Au nanoparticles (Aunp) were synthesised, characterised and their interactions with DNA were investigated. Aunp are stable in different aqueous solvents, whereas CdSnp do precipitate in 0.1 M NaCl and form two different cluster types in 0.1 M NaNO3. As regards the CdSnp/DNA interaction, absorbance and fluorescence titrations, ethidium bromide displacement assays and gel electrophoresis experiments indicate that a non-covalent interaction between DNA and the CdSnp external surface does take place. The binding constant was evaluated to be equal to (2.2 ± 0.5) × 105 M-1. On the contrary, concerning Aunp, no direct interaction with DNA could be observed. Possible interaction with serum albumin was also checked, but no effects could be observed for either CdSnp or Aunp. Finally, short-time exposure of cultured cells to nanoparticles revealed the ability of CdSnp to enter the cells and allocate both in cytosol and nucleus, thus promoting cell proliferation at low concentration ( p resulted in a significant inhibition of cell growth, accompanied by apoptotic cell death. Aunp neither enter the cells, nor do affect cell proliferation. In conclusion, our data indicate that CdSnp can strongly interact with living cells and nucleic acid while no effects or interactions were observed for Aunp.

  4. Strong-coupling approximations

    International Nuclear Information System (INIS)

    Abbott, R.B.

    1984-03-01

    Standard path-integral techniques such as instanton calculations give good answers for weak-coupling problems, but become unreliable for strong-coupling. Here we consider a method of replacing the original potential by a suitably chosen harmonic oscillator potential. Physically this is motivated by the fact that potential barriers below the level of the ground-state energy of a quantum-mechanical system have little effect. Numerically, results are good, both for quantum-mechanical problems and for massive phi 4 field theory in 1 + 1 dimensions. 9 references, 6 figures

  5. Strong interaction and QFD

    International Nuclear Information System (INIS)

    Ebata, T.

    1981-01-01

    With an assumed weak multiplet structure for bosonic hadrons, which is consistent with the ΔI = 1/2 rule, it is shown that the strong interaction effective hamiltonian is compatible with the weak SU(2) x U(1) gauge transformation. Especially the rho-meson transforms as a triplet under SU(2)sub(w), and this is the origin of the rho-photon analogy. It is also shown that the existence of the non-vanishing Cabibbo angle is a necessary condition for the absence of the exotic hadrons. (orig.)

  6. Strong Coupling Holography

    CERN Document Server

    Dvali, Gia

    2009-01-01

    We show that whenever a 4-dimensional theory with N particle species emerges as a consistent low energy description of a 3-brane embedded in an asymptotically-flat (4+d)-dimensional space, the holographic scale of high-dimensional gravity sets the strong coupling scale of the 4D theory. This connection persists in the limit in which gravity can be consistently decoupled. We demonstrate this effect for orbifold planes, as well as for the solitonic branes and string theoretic D-branes. In all cases the emergence of a 4D strong coupling scale from bulk holography is a persistent phenomenon. The effect turns out to be insensitive even to such extreme deformations of the brane action that seemingly shield 4D theory from the bulk gravity effects. A well understood example of such deformation is given by large 4D Einstein term in the 3-brane action, which is known to suppress the strength of 5D gravity at short distances and change the 5D Newton's law into the four-dimensional one. Nevertheless, we observe that the ...

  7. Role of covalent defects on phonon softening in metallic carbon nanotubes.

    Science.gov (United States)

    Nguyen, Khoi T; Shim, Moonsub

    2009-05-27

    We have examined how electrical characteristics and charging dependent Raman G-band phonon softening in individual metallic carbon nanotubes are influenced by covalent defects. In addition to decreasing electrical conductance with increasing on/off current ratio eventually leading to semiconducting behavior, adding covalent defects reduces the degree of softening and broadening of longitudinal optical (LO) phonon mode of the G-band near the charge neutrality point where the bands cross. On the other hand, the transverse optical (TO) mode softening is enhanced by defects. Implications on the interpretation of Raman G-band phonon softening and on utilizing Raman spectroscopy to examine covalent functionalization are discussed.

  8. Native lignin for bonding fiber boards - evaluation of bonding mechanisms in boards made from laccase-treated fibers of beech (Fagus sylvatica)

    DEFF Research Database (Denmark)

    Felby, Claus; Thygesen, Lisbeth Garbrecht; Sanadi, Anand

    2004-01-01

    The auto-adhesion of beech wood (Fagus sylvatica) fibers can be enhanced by a pretreatment of the fibers with a phenol oxidase enzyme. The mechanism of enzymatic catalyzed bonding is linked to the generation of stable radicals in lignin by oxidation. Fiberboards made from laccase-treated fibers...... have a high wet strength compared to boards made from untreated fibers. This indicates better fiber-fiber interactions and improved fiber-fiber stress transfer. The surface of laccase-treated fibers shows a markedly increased hydrophobicity as well as a change in the chemical composition, which...... indicate that lignin extractives are precipitated on the fiber surfaces. The improved bonding may be related to several factors, linked to a more lignin rich fiber surface, such as surface molecular entanglements and covalent bonding between fibers through cross-linking of radicals. (C) 2004 Published...

  9. Hydrogen bonded supramolecular materials

    CERN Document Server

    Li, Zhan-Ting

    2015-01-01

    This book is an up-to-date text covering topics in utilizing hydrogen bonding for constructing functional architectures and supramolecular materials. The first chapter addresses the control of photo-induced electron and energy transfer. The second chapter summarizes the formation of nano-porous materials. The following two chapters introduce self-assembled gels, many of which exhibit unique functions. Other chapters cover the advances in supramolecular liquid crystals and the versatility of hydrogen bonding in tuning/improving the properties and performance of materials. This book is designed

  10. Amorphous chalcogenides as random octahedrally bonded solids: I. Implications for the first sharp diffraction peak, photodarkening, and Boson peak

    Science.gov (United States)

    Lukyanov, Alexey; Lubchenko, Vassiliy

    2017-09-01

    We develop a computationally efficient algorithm for generating high-quality structures for amorphous materials exhibiting distorted octahedral coordination. The computationally costly step of equilibrating the simulated melt is relegated to a much more efficient procedure, viz., generation of a random close-packed structure, which is subsequently used to generate parent structures for octahedrally bonded amorphous solids. The sites of the so-obtained lattice are populated by atoms and vacancies according to the desired stoichiometry while allowing one to control the number of homo-nuclear and hetero-nuclear bonds and, hence, effects of the mixing entropy. The resulting parent structure is geometrically optimized using quantum-chemical force fields; by varying the extent of geometric optimization of the parent structure, one can partially control the degree of octahedrality in local coordination and the strength of secondary bonding. The present methodology is applied to the archetypal chalcogenide alloys AsxSe1-x. We find that local coordination in these alloys interpolates between octahedral and tetrahedral bonding but in a non-obvious way; it exhibits bonding motifs that are not characteristic of either extreme. We consistently recover the first sharp diffraction peak (FSDP) in our structures and argue that the corresponding mid-range order stems from the charge density wave formed by regions housing covalent and weak, secondary interactions. The number of secondary interactions is determined by a delicate interplay between octahedrality and tetrahedrality in the covalent bonding; many of these interactions are homonuclear. The present results are consistent with the experimentally observed dependence of the FSDP on arsenic content, pressure, and temperature and its correlation with photodarkening and the Boson peak. They also suggest that the position of the FSDP can be used to infer the effective particle size relevant for the configurational equilibration in

  11. LIGO: The strong belief

    CERN Multimedia

    Antonella Del Rosso

    2016-01-01

    Twenty years of designing, building and testing a number of innovative technologies, with the strong belief that the endeavour would lead to a historic breakthrough. The Bulletin publishes an abstract of the Courier’s interview with Barry Barish, one of the founding fathers of LIGO.   The plots show the signals of gravitational waves detected by the twin LIGO observatories at Livingston, Louisiana, and Hanford, Washington. (Image: Caltech/MIT/LIGO Lab) On 11 February, the Laser Interferometer Gravitational-Wave Observatory (LIGO) and Virgo collaborations published a historic paper in which they showed a gravitational signal emitted by the merger of two black holes. These results come after 20 years of hard work by a large collaboration of scientists operating the two LIGO observatories in the US. Barry Barish, Linde Professor of Physics, Emeritus at the California Institute of Technology and former Director of the Global Design Effort for the Internat...

  12. Covalent Crosslinking of Carbon Nanotube Materials for Improved Tensile Strength

    Science.gov (United States)

    Baker, James S.; Miller, Sandi G.; Williams, Tiffany A.; Meador, Michael A.

    2013-01-01

    Carbon nanotubes have attracted much interest in recent years due to their exceptional mechanical properties. Currently, the tensile properties of bulk carbon nanotube-based materials (yarns, sheets, etc.) fall far short of those of the individual nanotube elements. The premature failure in these materials under tensile load has been attributed to inter-tube sliding, which requires far less force than that needed to fracture individual nanotubes.1,2 In order for nanotube materials to achieve their full potential, methods are needed to restrict this tube-tube shear and increase inter-tube forces.Our group is examining covalent crosslinking between the nanotubes as a means to increase the tensile properties of carbon nanotube materials. We are working with multi-walled carbon nanotube (MWCNT) sheet and yarn materials obtained from commercial sources. Several routes to functionalize the nanotubes have been examined including nitrene, aryl diazonium, and epoxide chemistries. The functional nanotubes were crosslinked through small molecule or polymeric bridges. Additionally, electron beam irradiation induced crosslinking of the non-functional and functional nanotube materials was conducted. For example, a nanotube sheet material containing approximately 3.5 mol amine functional groups exhibited a tensile strength of 75 MPa and a tensile modulus of 1.16 GPa, compared to 49 MPa and 0.57 GPa, respectively, for the as-received material. Electron beam irradiation (2.2x 1017 ecm2) of the same amine-functional sheet material further increased the tensile strength to 120 MPa and the modulus to 2.61 GPa. This represents approximately a 150 increase in tensile strength and a 360 increase in tensile modulus over the as-received material with only a 25 increase in material mass. Once we have optimized the nanotube crosslinking methods, the performance of these materials in polymer matrix composites will be evaluated.

  13. Covalent immobilization of antimicrobial peptides (AMPs) onto biomaterial surfaces.

    Science.gov (United States)

    Costa, Fabíola; Carvalho, Isabel F; Montelaro, Ronald C; Gomes, P; Martins, M Cristina L

    2011-04-01

    Bacterial adhesion to biomaterials remains a major problem in the medical devices field. Antimicrobial peptides (AMPs) are well-known components of the innate immune system that can be applied to overcome biofilm-associated infections. Their relevance has been increasing as a practical alternative to conventional antibiotics, which are declining in effectiveness. The recent interest focused on these peptides can be explained by a group of special features, including a wide spectrum of activity, high efficacy at very low concentrations, target specificity, anti-endotoxin activity, synergistic action with classical antibiotics, and low propensity for developing resistance. Therefore, the development of an antimicrobial coating with such properties would be worthwhile. The immobilization of AMPs onto a biomaterial surface has further advantages as it also helps to circumvent AMPs' potential limitations, such as short half-life and cytotoxicity associated with higher concentrations of soluble peptides. The studies discussed in the current review report on the impact of covalent immobilization of AMPs onto surfaces through different chemical coupling strategies, length of spacers, and peptide orientation and concentration. The overall results suggest that immobilized AMPs may be effective in the prevention of biofilm formation by reduction of microorganism survival post-contact with the coated biomaterial. Minimal cytotoxicity and long-term stability profiles were obtained by optimizing immobilization parameters, indicating a promising potential for the use of immobilized AMPs in clinical applications. On the other hand, the effects of tethering on mechanisms of action of AMPs have not yet been fully elucidated. Therefore, further studies are recommended to explore the real potential of immobilized AMPs in health applications as antimicrobial coatings of medical devices. Copyright © 2010 Acta Materialia Inc. All rights reserved.

  14. Spin Labeling ESR Investigation of a Role of Humic Acids at Covalent Binding of Xenobiotics to Soil

    Science.gov (United States)

    Aleksandrova, Olga

    2014-05-01

    The environmental risk of organic xenobiotic chemicals released into soils is controlled by their sorption and binding processes. However, the molecular mechanisms of reversible and irreversible interactions of xenobiotics with soil constituents and an influence of humic substances on this interaction are only partly understood. New methods and approaches aimed at understanding of molecular mechanisms in the soil environment and a role of humic substances in the sorption and binding processes are today required to manage and keep the quality of soil used and fertilized in agricultural industry. The paper presents a new approach of using stable ESR spin labels to investigate a role of humic substances in the interactions of organic xenobiotic chemicals with constituents of natural soil via the typical functional groups of xenobiotics, such as Amines. At the experiment, the nitroxide spin labels, such as TEMPO (2,2,6,6-Tetramethylpiperidin-1-oxyl), Amino-TEMPO (4-amino-2,2,6,6-Tetramethylpiperidin-1-oxyl) and Aniline spin labels (2,5,5-Trimethyl-2-(3-aminophenyl)pyrrolidin-1-oxyl), were added to samples of different natural soils, such luvisol, cambisol and chernozem. Amino-TEMPO and Aniline spin labels include the aliphatic amino and aromatic amino functional groups, respectively. A significant broadening of the ESR spectrum of Aniline spin labels incubated in different soils indicated a stable effect of covalent binding of the spin labels to soil constituents via the aromatic amino, whereas the ESR spectra of the other two spin labels were not broadened that pointed at the absence of covalent binding of spin labels via the aliphatic amino. As shown, a part of bound spin labels via the aromatic amino increased with increasing of the concentration of humic acids in soil. The same broadened signals were also be detected with the humic acids extracted from the investigated soils. A strong covalent binding of spin labels to humic substances via the aromatic amines was

  15. Cytotoxicity of dentin bonding agents.

    Science.gov (United States)

    Cal, Ebru; Guneri, Pelin; Atay, Ayse; Cetintas, Vildan Bozok

    2014-01-01

    This study sought to evaluate the cytotoxicity of 5 dentin bonding agents (Admira Bond, Adper Single Bond Plus, Clearfil SE Bond, Clearfil S3 Bond, and Heliobond) by XTT assay using human gingival fibroblast cells. Samples of dentin bonding agents were prepared on a black 96-well microplate, and the cytotoxicity of each bonding material was measured every 24 hours for 7 days, then on Days 14, 21, and 28. One-way ANOVA and Bonferroni post hoc tests were used for statistical analyses. All 5 materials were evaluated as severely cytotoxic (P agents showed severe cytotoxicity with viability results exception of Adper Single Bond Plus, toxicity continued to Day 28 for all compounds. The utmost care must be considered during the clinical utilization of dentin bonding agents to keep them within the area of restoration and prevent their contact with adjacent tissues.

  16. Photochemical tissue bonding

    Science.gov (United States)

    Redmond, Robert W [Brookline, MA; Kochevar, Irene E [Charlestown, MA

    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.

  17. Use of Functionalized Carbon Nanotubes for Covalent Attachment of Nanotubes to Silicon

    Science.gov (United States)

    Tour, James M.; Dyke, Christopher A.; Maya, Francisco; Stewart, Michael P.; Chen, Bo; Flatt, Austen K.

    2012-01-01

    The purpose of the invention is to covalently attach functionalized carbon nanotubes to silicon. This step allows for the introduction of carbon nanotubes onto all manner of silicon surfaces, and thereby introduction of carbon nano - tubes covalently into silicon-based devices, onto silicon particles, and onto silicon surfaces. Single-walled carbon nanotubes (SWNTs) dispersed as individuals in surfactant were functionalized. The nano - tube was first treated with 4-t-butylbenzenediazonium tetrafluoroborate to give increased solubility to the carbon nanotube; the second group attached to the sidewall of the nanotube has a silyl-protected terminal alkyne that is de-protected in situ. This gives a soluble carbon nanotube that has functional groups appended to the sidewall that can be attached covalently to silicon. This reaction was monitored by UV/vis/NJR to assure direct covalent functionalization.

  18. Construction and repair of highly ordered 2D covalent networks by chemical equilibrium regulation.

    Science.gov (United States)

    Guan, Cui-Zhong; Wang, Dong; Wan, Li-Jun

    2012-03-21

    The construction of well-ordered 2D covalent networks via the dehydration of di-borate aromatic molecules was successfully realized through introducing a small amount of water into a closed reaction system to regulate the chemical equilibrium.

  19. Covalent organic polymer functionalization of activated carbon surfaces through acyl chloride for environmental clean-up

    DEFF Research Database (Denmark)

    Mines, Paul D.; Thirion, Damien; Uthuppu, Basil

    2017-01-01

    Nanoporous networks of covalent organic polymers (COPs) are successfully grafted on the surfaces of activated carbons, through a series of surface modification techniques, including acyl chloride formation by thionyl chloride. Hybrid composites of activated carbon functionalized with COPs exhibit...

  20. SbcCD-Mediated Processing of Covalent Gyrase-DNA Complex in Escherichia coli

    OpenAIRE

    Aedo, Sandra; Tse-Dinh, Yuk-Ching

    2013-01-01

    Quinolones trap the covalent gyrase-DNA complex in Escherichia coli, leading to cell death. Processing activities for trapped covalent complex have not been characterized. A mutant strain lacking SbcCD nuclease activity was examined for both accumulation of gyrase-DNA complex and viability after quinolone treatment. Higher complex levels were found in ΔsbcCD cells than in wild-type cells after incubation with nalidixic acid and ciprofloxacin. However, SbcCD activity protected cells against th...