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Sample records for stable covalent bonds

  1. Covalent bonding in heavy metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S.; Nelin, Connie J.; Hrovat, Dave A.; Ilton, Eugene S.

    2017-04-07

    Novel theoretical methods were used to quantify the magnitude and the energetic contributions of 4f/5f-O2p and 5d/6d-O2p interactions to covalent bonding in lanthanide and actinide oxides. Although many analyses have neglected the involvement of the frontier d orbitals, the present study shows that f and d covalency are of comparable importance. Two trends are identified. As is expected, the covalent mixing is larger when the nominal oxidation state is higher. More subtly, the importance of the nf covalent mixing decreases sharply relative to (n+1)d as the nf occupation increases. Atomic properties of the metal cations that drive these trends are identified.

  2. Evidence of significant covalent bonding in Au(CN)(2)(-).

    Science.gov (United States)

    Wang, Xue-Bin; Wang, Yi-Lei; Yang, Jie; Xing, Xiao-Peng; Li, Jun; Wang, Lai-Sheng

    2009-11-18

    The Au(CN)(2)(-) ion is the most stable Au compound known for centuries, yet a detailed understanding of its chemical bonding is still lacking. Here we report direct experimental evidence of significant covalent bonding character in the Au-C bonds in Au(CN)(2)(-) using photoelectron spectroscopy and comparisons with its lighter congeners, Ag(CN)(2)(-) and Cu(CN)(2)(-). Vibrational progressions in the Au-C stretching mode were observed for all detachment transitions for Au(CN)(2)(-), in contrast to the atomic-like transitions for Cu(CN)(2)(-), revealing the Au-C covalent bonding character. In addition, rich electronic structural information was obtained for Au(CN)(2)(-) by employing 118 nm detachment photons. Density functional theory and high-level ab initio calculations were carried out to understand the photoelectron spectra and obtain insight into the nature of the chemical bonding in the M(CN)(2)(-) complexes. Significant covalent character in the Au-C bonding due to the strong relativistic effects was revealed in Au(CN)(2)(-), consistent with its high stability.

  3. Binding matter with antimatter: the covalent positron bond.

    Science.gov (United States)

    Charry, Jorge Alfonso; Varella, Marcio T Do N; Reyes, Andrés

    2018-05-16

    We report sufficient theoretical evidence of the energy stability of the e⁺H₂²⁻ molecule, formed by two H⁻ anions and one positron. Analysis of the electronic and positronic densities of the latter compound undoubtedly points out the formation of a positronic covalent bond between the otherwise repelling hydride anions. The lower limit for the bonding energy of the e⁺H₂²⁻ molecule is 74 kJ/mol (0.77 eV), accounting for the zero-point vibrational correction. The formation of a non electronic covalent bond is fundamentally distinct from positron attachment to stable molecules, as the latter process is characterized by a positron affinity, analogous to the electron affinity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Covalent versus ionic bonding in alkalimetal fluoride oligomers

    NARCIS (Netherlands)

    Bickelhaupt, F.M.; Sola, M.; Fonseca Guerra, C.

    2007-01-01

    The most polar bond in chemistry is that between a fluorine and an alkalimetal atom. Inspired by our recent finding that other polar bonds (C - M and H - M) have important covalent contributions (i.e., stabilization due to bond overlap), we herein address the question if covalency is also essential

  5. Dislocations in materials with mixed covalent and metallic bonding

    International Nuclear Information System (INIS)

    Nguyen-Manh, D.; Cawkwell, M.J.; Groeger, R.; Mrovec, M.; Porizek, R.; Pettifor, D.G.; Vitek, V.

    2005-01-01

    Environment-dependent bond-order potentials have been developed for L1 0 TiAl, bcc Mo and fcc Ir. They comprise both the angular character of bonding and the screening effect of nearly free electrons. These potentials have been employed in atomistic studies of screw dislocations that revealed the non-planar character of their cores. It is argued that both covalent as well as metallic character of bonding govern these structures, which in turn control the mechanical behaviour

  6. Design of a covalently bonded glycosphingolipid microarray

    DEFF Research Database (Denmark)

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

    2012-01-01

    , 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...... of the fatty acyl moiety of the ceramide aglycone of selected mammalian GSLs with sphingolipid N-deacylase (SCDase). Derivatization of the free amino group of a typical lyso-GSL, lyso-G(M1), with a prototype linker assembled from succinimidyl-[(N-maleimidopropionamido)-diethyleneglycol] ester and 2...

  7. Covalent bond force profile and cleavage in a single polymer chain

    Science.gov (United States)

    Garnier, Lionel; Gauthier-Manuel, Bernard; van der Vegte, Eric W.; Snijders, Jaap; Hadziioannou, Georges

    2000-08-01

    We present here the measurement of the single-polymer entropic elasticity and the single covalent bond force profile, probed with two types of atomic force microscopes (AFM) on a synthetic polymer molecule: polymethacrylic acid in water. The conventional AFM allowed us to distinguish two types of interactions present in this system when doing force spectroscopic measurements: the first interaction is associated with adsorption sites of the polymer chains onto a bare gold surface, the second interaction is directly correlated to the rupture process of a single covalent bond. All these bridging interactions allowed us to stretch the single polymer chain and to determine the various factors playing a role in the elasticity of these molecules. To obtain a closer insight into the bond rupture process, we moved to a force sensor stable in position when measuring attractive forces. By optimizing the polymer length so as to fulfill the elastic stability conditions, we were able for the first time to map out the entire force profile associated with the cleavage of a single covalent bond. Experimental data coupled with molecular quantum mechanical calculations strongly suggest that the breaking bond is located at one end of the polymer chain.

  8. Covalent bond orders and atomic valences from correlated wavefunctions

    Science.gov (United States)

    Ángyán, János G.; Rosta, Edina; Surján, Péter R.

    1999-01-01

    A comparison is made between two alternative definitions for covalent bond orders: one derived from the exchange part of the two-particle density matrix and the other expressed as the correlation of fluctuations (covariance) of the number of electrons between the atomic centers. Although these definitions lead to identical formulae for mono-determinantal SCF wavefunctions, they predict different bond orders for correlated wavefunctions. It is shown that, in this case, the fluctuation-based definition leads to slightly lower values of the bond order than does the exchange-based definition, provided one uses an appropriate space-partitioning technique like that of Bader's topological theory of atoms in a molecule; however, use of Mulliken partitioning in this context leads to unphysical behaviour. The example of H 2 is discussed in detail.

  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

    Directory of Open Access Journals (Sweden)

    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

    Science.gov (United States)

    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. 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.

  13. Unsynchronized resonance of covalent bonds in the superconducting state

    International Nuclear Information System (INIS)

    Costa, Marconi B.S.; Bastos, Cristiano C.; Pavao, Antonio C.

    2012-01-01

    Daft calculations performed on different cluster models of cuprates (LaBa 2 Cu 3 O 6.7 , La 1.85 Sr 0.15 CuO 4 , YBa 2 Cu 3 O 7 , TlBa 2 Ca 2 Cu 3 O 8.78 , HgBa 2 Ca 2 Cu 3 O 8.27 ), metallic systems (Nb 3 Ge, MgB 2 ) and the pnictide LaO 0.92 F 0.08 FeAs made evident the occurrence of un synchronized resonance of covalent bonds in the superconducting state, as predicted by Paling's resonating valence bond Rb) theory. For cuprates, the un synchronized resonance involves electron transfer between Cu atoms accompanied by a decrease in the charge of the La, Sr, Y and Ca atoms. For MgB 2 , electron transfer occurs in the Mg layer, while the B layer behaves as charge reservoir. For Nb 3 Ge, unsynchronized resonance occurs among the Ge atoms, which should be responsible for charge transfer. For LaO 0.92 F 0.08 FeAs, the results suggest that both La-O and Fe-As layers are involved in the mechanism of superconductivity. The identification of unsynchronized resonances in these systems provides evidence which supports RVB as a suitable theory for high-temperature superconductivity (high-TC). (author)

  14. 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

  15. Adaptive polymeric nanomaterials utilizing reversible covalent and hydrogen bonding

    Science.gov (United States)

    Neikirk, Colin

    Adaptive materials based on stimuli responsive and reversible bonding moieties are a rapidly developing area of materials research. Advances in supramolecular chemistry are now being adapted to novel molecular architectures including supramolecular polymers to allow small, reversible changes in molecular and nanoscale structure to affect large changes in macroscale properties. Meanwhile, dynamic covalent chemistry provides a complementary approach that will also play a role in the development of smart adaptive materials. In this thesis, we present several advances to the field of adaptive materials and also provide relevant insight to the areas of polymer nanocomposites and polymer nanoparticles. First, we have utilized the innate molecular recognition and binding capabilities of the quadruple hydrogen bonding group ureidopyrimidinone (UPy) to prepare supramolecular polymer nanocomposites based on supramolecular poly(caprolactone) which show improved mechanical properties, but also an increase in particle aggregation with nanoparticle UPy functionalization. We also present further insight into the relative effects of filler-filler, filler-matrix, and matrix-matrix interactions using a UPy side-chain functional poly(butyl acrylate). These nanocomposites have markedly different behavior depending on the amount of UPy sidechain functionality. Meanwhile, our investigations of reversible photo-response showed that coumarin functionality in polymer nanoparticles not only facilitates light mediated aggregation/dissociation behavior, but also provides a substantial overall reduction in particle size and improvement in nanoparticle stability for particles prepared by Flash NanoPrecipitation. Finally, we have combined these stimuli responsive motifs as a starting point for the development of multiresponsive adaptive materials. The synthesis of a library of multifunctional materials has provided a strong base for future research in this area, although our initial

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

    Science.gov (United States)

    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.

  17. Oriented growth of magnetite along the carbon nanotubes via covalently bonded method in a simple solvothermal system

    Energy Technology Data Exchange (ETDEWEB)

    Zhan Yingqing; Zhao Rui; Meng Fanbing; Lei Yajie; Zhong Jiachun; Yang Xulin [Research Branch of Functional Materials, Institute of Microelectronic and Solid State Electronic, University of Electronic Science and Technology of China, Chengdu 610054 (China); Liu Xiaobo, E-mail: liuxb@uestc.edu.cn [Research Branch of Functional Materials, Institute of Microelectronic and Solid State Electronic, University of Electronic Science and Technology of China, Chengdu 610054 (China)

    2011-06-15

    Highlights: > Novel CNTs/magnetite hybrid materials were prepared via covalently bonded method. > Stable interaction between nitriles and iron ion promoted the oriented growth of magnetite. > The hybrid material exhibited higher magnetism and electromagnetic properties - Abstract: A new type of CNTs/magnetite hybrid material was prepared via covalently bonded method in a simple solvothermal system using FeCl{sub 3} as iron source, ethylene glycol as the reducing agent, and 4-aminophenoxyphthalonitrile-grafted CNTs as templates. The magnetite nanoparticles, with the diameters of 70-80 nm, were self-assembled along the CNTs. The FTIR, UV-vis and DSC revealed that a stable covalent bond between nitriles group and iron ion promoted the oriented growth of magnetite nanoparticles along the CNTs, resulting in good dispersibility and solution storage stability. The magnetic properties measurements indicated that a higher saturated magnetization (70.7 emu g{sup -1}) existed in the CNTs/magnetite hybrid material, which further enhanced the electromagnetic properties. The magnetic loss was caused mainly by natural resonance, which is in good agreement with the Kittel equation results. The novel electromagnetic hybrid material is believed to have potential applications in the microwave absorbing performances.

  18. Oriented growth of magnetite along the carbon nanotubes via covalently bonded method in a simple solvothermal system

    International Nuclear Information System (INIS)

    Zhan Yingqing; Zhao Rui; Meng Fanbing; Lei Yajie; Zhong Jiachun; Yang Xulin; Liu Xiaobo

    2011-01-01

    Highlights: → Novel CNTs/magnetite hybrid materials were prepared via covalently bonded method. → Stable interaction between nitriles and iron ion promoted the oriented growth of magnetite. → The hybrid material exhibited higher magnetism and electromagnetic properties - Abstract: A new type of CNTs/magnetite hybrid material was prepared via covalently bonded method in a simple solvothermal system using FeCl 3 as iron source, ethylene glycol as the reducing agent, and 4-aminophenoxyphthalonitrile-grafted CNTs as templates. The magnetite nanoparticles, with the diameters of 70-80 nm, were self-assembled along the CNTs. The FTIR, UV-vis and DSC revealed that a stable covalent bond between nitriles group and iron ion promoted the oriented growth of magnetite nanoparticles along the CNTs, resulting in good dispersibility and solution storage stability. The magnetic properties measurements indicated that a higher saturated magnetization (70.7 emu g -1 ) existed in the CNTs/magnetite hybrid material, which further enhanced the electromagnetic properties. The magnetic loss was caused mainly by natural resonance, which is in good agreement with the Kittel equation results. The novel electromagnetic hybrid material is believed to have potential applications in the microwave absorbing performances.

  19. Molecular-dynamics simulation of crystalline 18-crown-6: thermal shortening of covalent bonds

    NARCIS (Netherlands)

    van Eerden, J.; Harkema, Sybolt; Feil, D.

    1990-01-01

    Molecular-dynamics simulations of crystalline 18-crown-6 have been performed in a study of the apparent thermal shortening of covalent bonds observed in crystal structures. At 100 K, a shortening of 0.006 _+ 0.001 A for C----C and C----O bonds was obtained. This result was found to be independent of

  20. A Cost-Effective Physical Modeling Exercise to Develop Students' Understanding of Covalent Bonding

    Science.gov (United States)

    Turner, Kristy L.

    2016-01-01

    Chemical bonding is one of the basic concepts in chemistry, and the topic of covalent bonding forms an important core of knowledge for the high school chemistry student. For many teachers it is a challenging concept to teach, not least because it relies mainly on traditional instruction and written work. Similarly, many students find the topic…

  1. 共价键的离子化%Ionization of Covalent Bond

    Institute of Scientific and Technical Information of China (English)

    王稼国; 荆西平

    2017-01-01

    本文用化学键理论分析和推导了共价键离子化的几种方式,包括金属和非金属单质中共价键的诱导离子化、化合物中共价键的降温和自诱导离子化以及含氢化合物和金属化合物的诱导离子化.从能量角度分析了离子化趋势的规律性,并且讨论了共价键的离子化的一些重要应用.%Several ionization patterns of covalent bond,including induced-ionization of covalent bond in metals and nonmetals,induced-ionization of covalent bond in hydrogen compounds and metal compounds,lowering temperature and self-induced ionization of compound,and so on,were dedueed and analyzed by using chemical bond theory.The trend of ionization was also analyzed on energy changing and several important applications of the ionization of covalent bond were discussed.

  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. Covalent Bonding of Chlorogenic Acid Induces Structural Modifications on Sunflower Proteins

    NARCIS (Netherlands)

    Karefyllakis, D.; Salakou, Stavroula; Bitter, J.H.; Goot, van der A.J.; Nikiforidis, K.

    2018-01-01

    Proteins and phenols coexist in the confined space of plant cells leading to reactions between them, which result in new covalently bonded complex molecules. This kind of reactions has been widely observed during storage and processing of plant materials. However, the nature of the new complex

  4. 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

  5. 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...

  6. 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.

  7. 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.

  8. Preparation and fluorescent recognition properties for fluoride of a nanostructured covalently bonded europium hybrid material

    Institute of Scientific and Technical Information of China (English)

    余旭东; 李景印; 李亚娟; 耿丽君; 甄小丽; 于涛

    2015-01-01

    A novel covalently bonded Eu3+-based silica hybrid material was designed and its spectrophotometric anion sensing prop-erty was studied. The fluorescent receptor (europium complex) was covalently grafted to the silica matrix via a sol-gel approach. FTIR, UV-vis spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescent spectra were characterized, and the results revealed that the hybrid material with nanosphere structure displayed excellent photophysical property. In addition, the selective anion sensing property of the hybrid material was studied by UV-vis and fluorescence spectra. The results showed that the hybrid material exhibited a smart response with fluoride anions.

  9. Preventing disulfide bond formation weakens non-covalent forces among lysozyme aggregates.

    Directory of Open Access Journals (Sweden)

    Vijay Kumar Ravi

    Full Text Available Nonnative disulfide bonds have been observed among protein aggregates in several diseases like amyotrophic lateral sclerosis, cataract and so on. The molecular mechanism by which formation of such bonds promotes protein aggregation is poorly understood. Here in this work we employ previously well characterized aggregation of hen eggwhite lysozyme (HEWL at alkaline pH to dissect the molecular role of nonnative disulfide bonds on growth of HEWL aggregates. We employed time-resolved fluorescence anisotropy, atomic force microscopy and single-molecule force spectroscopy to quantify the size, morphology and non-covalent interaction forces among the aggregates, respectively. These measurements were performed under conditions when disulfide bond formation was allowed (control and alternatively when it was prevented by alkylation of free thiols using iodoacetamide. Blocking disulfide bond formation affected growth but not growth kinetics of aggregates which were ∼50% reduced in volume, flatter in vertical dimension and non-fibrillar in comparison to control. Interestingly, single-molecule force spectroscopy data revealed that preventing disulfide bond formation weakened the non-covalent interaction forces among monomers in the aggregate by at least ten fold, thereby stalling their growth and yielding smaller aggregates in comparison to control. We conclude that while constrained protein chain dynamics in correctly disulfide bonded amyloidogenic proteins may protect them from venturing into partial folded conformations that can trigger entry into aggregation pathways, aberrant disulfide bonds in non-amyloidogenic proteins (like HEWL on the other hand, may strengthen non-covalent intermolecular forces among monomers and promote their aggregation.

  10. Unanticipated C=C bonds in covalent monolayers on silicon revealed by NEXAFS.

    Science.gov (United States)

    Lee, Michael V; Lee, Jonathan R I; Brehmer, Daniel E; Linford, Matthew R; Willey, Trevor M

    2010-02-02

    Interfaces are crucial to material properties. In the case of covalent organic monolayers on silicon, molecular structure at the interface controls the self-assembly of the monolayers, which in turn influences the optical properties and electrical transport. These properties intrinsically affect their application in biology, tribology, optics, and electronics. We use near-edge X-ray absorption fine structure spectroscopy to show that the most basic covalent monolayers formed from 1-alkenes on silicon retain a double bond in one-fifth to two-fifths of the resultant molecules. Unsaturation in the predominantly saturated monolayers will perturb the regular order and affect the dependent properties. The presence of unsaturation in monolayers produced by two different methods also prompts the re-evaluation of other radical-based mechanisms for forming covalent monolayers on silicon.

  11. From Coordination Cages to a Stable Crystalline Porous Hydrogen-Bonded Framework

    Energy Technology Data Exchange (ETDEWEB)

    Ju, Zhanfeng [State Key Lab of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou 350002 P. R. China; Liu, Guoliang [State Key Lab of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou 350002 P. R. China; Chen, Yu-Sheng [ChemMatCARS, Center for Advanced Radiation Sources, The University of Chicago, Argonne Illinois 60439 USA; Yuan, Daqiang [State Key Lab of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou 350002 P. R. China; Chen, Banglin [Department of Chemistry, University of Texas at San Antonio, San Antonio Texas 78249-0698 USA

    2017-03-20

    A stable framework has been constructed through multiple charge-assisted H-bonds between cationic coordination cages and chloride ions. The framework maintained its original structure upon desolvation, which has been established by single-crystal structure analysis. This is the first fully characterized stable porous framework based on coordination cages after desolvation, with a moderately high Brunauer–Emmett–Teller (BET) surface area of 1201 m2 g-1. This work will not only give a light to construct stable porous frameworks based on coordination cages and thus broaden their applications, but will also provide a new avenue to the assembly of other porous materials such as porous organic cages and hydrogen-bonded organic frameworks (HOFs) through non covalent bonds.

  12. A chiroptical switch based on supramolecular chirality transfer through alkyl chain entanglement and dynamic covalent bonding.

    Science.gov (United States)

    Lv, Kai; Qin, Long; Wang, Xiufeng; Zhang, Li; Liu, Minghua

    2013-12-14

    Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.

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

    Science.gov (United States)

    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.

  14. Covalent bonds and their crucial effects on pseudogap formation in α-Al(Mn,Re)Si icosahedral quasicrystalline approximant

    International Nuclear Information System (INIS)

    Kirihara, K.; Nagata, T.; Kimura, K.; Kato, K.; Takata, M.; Nishibori, E.; Sakata, M.

    2003-01-01

    X-ray charge densities of Al-based icosahedral quasicrystalline approximant crystals α-AlReSi, α-AlMnSi, and Al 12 Re were observed by a combination of the maximum entropy method with the Rietveld method. We successfully obtained the clear images of interatomic covalent bonds between Al and transition metals (Mn, Re) and those in the Al (or Si) icosahedron in Mackay icosahedral clusters of both α-AlReSi and α-AlMnSi approximant crystals. The bonding nature of the three kinds of glue atom sites connecting Mackay icosahedral clusters was also clarified. This covalent bonding nature should strongly relate with the enhancement of the electron density-of-states pseudogap near the Fermi level. In addition, the interatomic covalent bonds of α-AlReSi are stronger than those of α-AlMnSi. This fact leads to the low effective carrier density of α-AlReSi in comparison with that of α-AlMnSi. Unlike the covalent bonding nature of an icosahedron in α-AlReSi and α-AlMnSi crystals, the Al icosahedron with an Re center atom exhibits no Al-Al interatomic covalent bonds in the Al 12 Re crystal. The tendency for metallic-covalent bonding conversion in the Al icosahedron, which is related to the atom site occupancy of the icosahedral cluster center, is also strongly supported

  15. Covalent Bonding of Pyrrolobenzodiazepines (PBDs) to Terminal Guanine Residues within Duplex and Hairpin DNA Fragments

    Science.gov (United States)

    Mantaj, Julia; Jackson, Paul J. M.; Karu, Kersti; Rahman, Khondaker M.; Thurston, David E.

    2016-01-01

    Pyrrolobenzodiazepines (PBDs) are covalent-binding DNA-interactive agents with growing importance as payloads in Antibody Drug Conjugates (ADCs). Until now, PBDs were thought to covalently bond to C2-NH2 groups of guanines in the DNA-minor groove across a three-base-pair recognition sequence. Using HPLC/MS methodology with designed hairpin and duplex oligonucleotides, we have now demonstrated that the PBD Dimer SJG-136 and the C8-conjugated PBD Monomer GWL-78 can covalently bond to a terminal guanine of DNA, with the PBD skeleton spanning only two base pairs. Control experiments with the non-C8-conjugated anthramycin along with molecular dynamics simulations suggest that the C8-substituent of a PBD Monomer, or one-half of a PBD Dimer, may provide stability for the adduct. This observation highlights the importance of PBD C8-substituents, and also suggests that PBDs may bind to terminal guanines within stretches of DNA in cells, thus representing a potentially novel mechanism of action at the end of DNA strand breaks. PMID:27055050

  16. 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.

  17. Effect of covalently bonded polysiloxane multilayers on the electrochemical behavior of graphite electrode in lithium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Qinmin; Jiang, Yinghua [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China)

    2008-03-15

    Polysiloxane multilayers were covalently bonded to the surface of natural graphite particles via diazonium chemistry and silylation reaction. The as-prepared graphite exhibited excellent discharge-charge behavior as negative electrode materials in lithium ion batteries. The improvement in the electrochemical performance of the graphite electrodes was attributed to the formation of a stable and flexible passive film on their surfaces. It was also revealed that the chemical compositions of the multilayers exerted influence on the electrochemical behavior of the graphite electrodes. The result of this study presents a new strategy to the formation of elastic and strong passive film on the graphite electrode via molecular design. Owing to the diversity of polysilxoane multilayers, this method also enables researchers to control the surface chemistries of carbonaceous materials with flexibility. (author)

  18. Improved Procedure for Preparation of Covalently Bonded Cellulose Tris-phenylcarbamate Chiral Stationary Phases

    Institute of Scientific and Technical Information of China (English)

    秦峰; 陈小明; 刘月启; 邹汉法; 王俊德

    2005-01-01

    The classical method for preparation of covalently boned cellulose derivative chiral stationary phases (CSP) with diisocyanate as spacer was improved. Diisocyanate was firstly allowed to react with 3-aminopropyltriethoxysilane, and the resulting product was then applied as the spacer reagent to immobilize cellulose derivatives onto silica gel. Influences of the amount and the length of the spacer on the optical resolution ability of the CSP were investigated. Comparing improved procedure to classical diisocyanate method, the cross-linking between the glucose units of the cellulose derivatives was avoided to the most extent. With the improved procedure, regio-nonselective ways could be adooted to prepare covalently bonded CSP, which showed an advantage for the rapid preparation.

  19. Structural modification of covalent-bonded networks: on some methodological resolutions for binary chalcogenide glasses

    Energy Technology Data Exchange (ETDEWEB)

    Shpotyuk, M; Shpotyuk, Ya; Shpotyuk, O, E-mail: shpotyukmy@yahoo.com [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 212, Stryjska str., Lviv, 79031 (Ukraine)

    2011-04-01

    New methodology to estimate efficiency of externally-induced structural modification in chalcogenide glasses is developed. This approach is grounded on the assumption that externally-induced structural modification is fully associated with destruction-polymerization transformations, which reveal themselves as local misbalances in covalent bond distribution, normal atomic coordination and intrinsic electrical fields. The input of each of these components into the total value of structural modification efficiency was probed for quasibinary (As{sub 2}S{sub 3}){sub 100-x}(Sb{sub 2}S{sub 3}){sub x} ChG.

  20. Structural modification of covalent-bonded networks: on some methodological resolutions for binary chalcogenide glasses

    International Nuclear Information System (INIS)

    Shpotyuk, M; Shpotyuk, Ya; Shpotyuk, O

    2011-01-01

    New methodology to estimate efficiency of externally-induced structural modification in chalcogenide glasses is developed. This approach is grounded on the assumption that externally-induced structural modification is fully associated with destruction-polymerization transformations, which reveal themselves as local misbalances in covalent bond distribution, normal atomic coordination and intrinsic electrical fields. The input of each of these components into the total value of structural modification efficiency was probed for quasibinary (As 2 S 3 ) 100-x (Sb 2 S 3 ) x ChG.

  1. Methacrylate-bonded covalent-organic framework monolithic columns for high performance liquid chromatography.

    Science.gov (United States)

    Liu, Li-Hua; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2017-01-06

    Covalent-organic frameworks (COFs) are a newfangled class of intriguing microporous materials. Considering their unique properties, COFs should be promising as packing materials for high performance liquid chromatography (HPLC). However, the irregular shape and sub-micrometer size of COFs synthesized via the traditional methods render the main obstacles for the application of COFs in HPLC. Herein, we report the preparation of methacrylate-bonded COF monolithic columns for HPLC to overcome the above obstacles. The prepared COF bonded monolithic columns not only show good homogeneity and permeability, but also give high column efficiency, good resolution and precision for HPLC separation of small molecules including polycyclic aromatic hydrocarbons, phenols, anilines, nonsteroidal anti-inflammatory drugs and benzothiophenes. Compared with the bare polymer monolithic column, the COF bonded monolithic columns show enhanced hydrophobic, π-π and hydrogen bond interactions in reverse phase HPLC. The results reveal the great potential of COF bonded monoliths for HPLC and COFs in separation sciences. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Chemically Stable Covalent Organic Framework (COF)-Polybenzimidazole Hybrid Membranes: Enhanced Gas Separation through Pore Modulation.

    Science.gov (United States)

    Biswal, Bishnu P; Chaudhari, Harshal D; Banerjee, Rahul; Kharul, Ulhas K

    2016-03-24

    Highly flexible, TpPa-1@PBI-BuI and TpBD@PBI-BuI hybrid membranes based on chemically stable covalent organic frameworks (COFs) could be obtained with the polymer. The loading obtained was substantially higher (50 %) than generally observed with MOFs. These hybrid membranes show an exciting enhancement in permeability (about sevenfold) with appreciable separation factors for CO2/N2 and CO2/CH4. Further, we found that with COF pore modulation, the gas permeability can be systematically enhanced. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. 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

  4. 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.

  5. The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol

    International Nuclear Information System (INIS)

    Liriano, Melissa L.; Lewis, Emily A.; Murphy, Colin J.; Lawton, Timothy J.; Marcinkowski, Matthew D.; Therrien, Andrew J.; Sykes, E. Charles H.; Carrasco, Javier; Michaelides, Angelos

    2016-01-01

    The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule’s intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our

  6. The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol

    Energy Technology Data Exchange (ETDEWEB)

    Liriano, Melissa L.; Lewis, Emily A.; Murphy, Colin J.; Lawton, Timothy J.; Marcinkowski, Matthew D.; Therrien, Andrew J.; Sykes, E. Charles H., E-mail: charles.sykes@tufts.edu [Department of Chemistry, Tufts University, Medford, Massachusetts 02155 (United States); Carrasco, Javier [CIC Energigune, Albert Einstein 48, 01510 Miñano, Álava (Spain); Michaelides, Angelos [Thomas Young Centre, London Centre for Nanotechnology and Department of Physics and Astronomy, University College London, London WC1E 6BT (United Kingdom)

    2016-03-07

    The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule’s intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our

  7. Role of direct covalent bonding in enhanced heat dissipation property of flexible graphene oxide–carbon nanotube hybrid film

    International Nuclear Information System (INIS)

    Hwang, Yongseon; Kim, Myeongjin; Kim, Jooheon

    2013-01-01

    The thermal conductivity of graphene oxide/multiwalled carbon nanotube (GO/MWCNT) hybrid films with and without covalent bonding is examined in this study. To fabricate chemically bonded GO/MWCNT hybrid films, chlorinated GO and amino-functionalized MWCNTs are bonded covalently. The mixtures of surface modified GO and MWCNT were filtered and then subjected to hot pressing to fabricate stacked films. Examination of these chemically bonded hybrid films reveal that chlorine-doped GO exhibits enhanced electrical properties because it creates hole charge carriers by attracting the electrons in GO towards chlorine. Enhanced electrical conductivity and low sheet resistance are observed also with increasing MWCNT loadings. On comparing the through-plane thermal properties, the chemically bonded hybrid films were found to exhibit higher thermal conductivity than do the physically bonded hybrid films because of the synergetic interaction of functional groups in GO and MWCNTs in the former films. However, excess addition of MWCNTs to the films leads to an increasing phonon scattering density and a decreased thermal conductivity. - Highlights: • Graphene oxide/carbon nanotube (GO/CNT) films are bonded covalently. • GO/CNT hybrid films are prepared through filtering and hot-pressing method. • Chemically bonded hybrid films exhibit enhanced electrical and thermal properties. • Enhanced thermal conductivity is explained according to increasing CNT contents

  8. 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.

  9. 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.

  10. Molecular assembly of materials with covalent bonding: Path to robust structures

    International Nuclear Information System (INIS)

    Puniredd, Sreenivasa Reddy; Zhang Fengxiang; Srinivasan, M.P.

    2006-01-01

    Ultrathin films were fabricated using synthesized polyimide (HPI) with hydroxyl pendant groups in a layer-by-layer fashion on amine-terminated substrates of silicon, quartz and gold. The interlayer linkages were established by using terephthaloyl chloride as a bridging agent to form ester groups between HPI layers. Furthermore, when working on the nanometer scale in liquid solvents, necessity of a solvent rinse after each deposition step and the presence of residual solvent are problematic. To avoid the problems related to residual solvent we have fabricated an ultrathin film of oligoimide on amine-modified substrates of silicon and quartz through alternate layer-by-layer (LBL) assembly of pyromellitic dianhydride (PMDA) and diaminodiphenylether (DDE), with inter-layer links established by covalent bonds. The assembly was formed in supercritical carbon dioxide (SCCO 2 ), and in solution (N,N-dimethylacetamide, DMAc), and the imidization reaction was performed by thermal and chemical methods, in benzene and in the supercritical medium. We have compared these films with those assembled in a conventional solvent medium. The comparison is further extended to carrying out the imidization reaction by various methods. The films show excellent stability and strength, which can be attributed to the covalent interlayer linkage

  11. The effective fragment molecular orbital method for fragments connected by covalent bonds.

    Directory of Open Access Journals (Sweden)

    Casper Steinmann

    Full Text Available We extend the effective fragment molecular orbital method (EFMO into treating fragments connected by covalent bonds. The accuracy of EFMO is compared to FMO and conventional ab initio electronic structure methods for polypeptides including proteins. Errors in energy for RHF and MP2 are within 2 kcal/mol for neutral polypeptides and 6 kcal/mol for charged polypeptides similar to FMO but obtained two to five times faster. For proteins, the errors are also within a few kcal/mol of the FMO results. We developed both the RHF and MP2 gradient for EFMO. Compared to ab initio, the EFMO optimized structures had an RMSD of 0.40 and 0.44 Å for RHF and MP2, respectively.

  12. 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

    The remarkable thermal properties of graphene and carbon nanotubes (CNTs) have been the subject of intensive investigations for the thermal management of integrated circuits. However, the small contact area of CNTs and the large anisotropic heat conduction of graphene have hindered...... 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...... extraction. Through computer simulations, it is demonstrated that the G-CNT outperforms few-layer graphene by more than 2 orders of magnitude for the c-axis heat transfer, while its thermal resistance is 3 orders of magnitude lower than the state-of-the-art TIMs. We show that heat can be removed from the G...

  13. Electrochromic Behaviors of Water-Soluble Polyaniline with Covalently Bonded Acetyl Ferrocene

    Science.gov (United States)

    Xiong, Shanxin; Wang, Ru; Li, Shuaishuai; Wu, Bohua; Chu, Jia; Wang, Xiaoqin; Zhang, Runlan; Gong, Ming

    2018-04-01

    A novel ferrocene-containing hybrid electrochromic material was synthesized via copolymerization of aniline with p-phenylenediamine functionalized acetyl ferrocene in the presence of poly (styrene sulfonate) dopant in an aqueous medium, and neat polyaniline (PANI) was prepared for comparison. The polymerization characteristics and the structure of the copolymer were systematically studied by Fourier-transform infrared, meanwhile, their electrochromic properties and electrochemical behaviors were tested by UV-vis spectra, cyclic voltammetry and electrochemical impedance spectroscopy (EIS). It was found that the strong covalent bond and large conjugated system between PANI and ferrocene enhance the electron transfer rate and electron delocalization in the ferrocene-polyaniline (Fc-PANI) hybrid. In particular, the electrochromic device with Fc-PANI as the active layer shows significant enhancement in optical contrast over the PANI-based device.

  14. ESI-MS study on non-covalent bond complex of rhFKBP12 and new neurogrowth promoter

    Institute of Scientific and Technical Information of China (English)

    WANG; Hongxia; (王红霞); ZHANG; Xuemin; (张学敏); YANG; Songcheng; (杨松成); XIAO; Junhai; (肖军海); NIE; Aihua; (聂爱华); ZHAO; Liqin; (赵丽琴); LI; Song; (李松)

    2003-01-01

    An ESI-MS method for studying the non-covalent bond complex of rhFKBP12 with its nonimmunosuppressive ligands was developed. The method was used to screen out three compounds capable of binding to rhFKBP12 non-covalently from 52 compounds. By competing binding experiment, the binding site and the relative binding strength of these three compounds 000107, 000308 and A2B12 with rhFKBP12 were measured. All of them have the same binding site as FK506 does. X-ray crystalline diffraction experiment of non-covalent bond complex of 000107, 000308 with rhFKBP12 by Tsinghua University showed the same results. Among them 000308 has good effect on stimulating neurite to grow in chicken sensory neuronal cultures.

  15. A Comprehensive Analysis in Terms of Molecule-Intrinsic, Quasi-Atomic Orbitals. III. The Covalent Bonding Structure of Urea.

    Science.gov (United States)

    West, Aaron C; Schmidt, Michael W; Gordon, Mark S; Ruedenberg, Klaus

    2015-10-15

    The analysis of molecular electron density matrices in terms of quasi-atomic orbitals, which was developed in previous investigations, is quantitatively exemplified by a detailed application to the urea molecule. The analysis is found to identify strong and weak covalent bonding interactions as well as intramolecular charge transfers. It yields a qualitative as well as quantitative ab initio description of the bonding structure of this molecule, which raises questions regarding some traditional rationalizations.

  16. 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

  17. 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.

  18. 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

  19. Electrocatalytic reduction of H2O2 by Pt nanoparticles covalently bonded to thiolated carbon nanostructures

    International Nuclear Information System (INIS)

    You, Jung-Min; Kim, Daekun; Jeon, Seungwon

    2012-01-01

    Highlights: ► Novel thiolated carbon nanostructures – platinum nanoparticles [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] have been synthesized, and [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] denotes as t-GO-pt and t-MWCNT-Pt in manuscript, respectively. ► The modified electrode denoted as PDDA/t-GO-pt/GCE was used for the electrochemical determination of H 2 O 2 for the first time. ► The results show that PDDA/t-GO-pt nanoparticles have the promising potential as the basic unit of the electrochemical biosensors for the detection of H 2 O 2 . ► The proposed H 2 O 2 biosensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s. - Abstract: Glassy carbon electrodes were coated with thiolated carbon nanostructures – multi-walled carbon nanotubes and graphene oxide. The subsequent covalent addition of platinum nanoparticles and coating with poly(diallydimethylammonium chloride) resulted in biosensors that detected hydrogen peroxide through its electrocatalytic reduction. The sensors were easily and quickly prepared and showed improved sensitivity to the electrocatalytic reduction of H 2 O 2 . The Pt nanoparticles covalently bonded to the thiolated carbon nanostructures were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectroscopy. Cyclic voltammetry and amperometry were used to characterize the biosensors’ performances. The sensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s, thus demonstrating their potential for use in H 2 O 2 analysis.

  20. Dynamic Covalent Chemistry within Biphenyl Scaffolds: Reversible Covalent Bonding, Control of Selectivity, and Chirality Sensing with a Single System.

    Science.gov (United States)

    Ni, Cailing; Zha, Daijun; Ye, Hebo; Hai, Yu; Zhou, Yuntao; Anslyn, Eric V; You, Lei

    2018-01-26

    Axial chirality is a prevalent and important phenomenon in chemistry. Herein we report a combination of dynamic covalent chemistry and axial chirality for the development of a versatile platform for the binding and chirality sensing of multiple classes of mononucleophiles. An equilibrium between an open aldehyde and its cyclic hemiaminal within biphenyl derivatives enabled the dynamic incorporation of a broad range of alcohols, thiols, primary amines, and secondary amines with high efficiency. Selectivity toward different classes of nucleophiles was also achieved by regulating the distinct reactivity of the system with external stimuli. Through induced helicity as a result of central-to-axial chirality transfer, the handedness and ee values of chiral monoalcohol and monoamine analytes were reported by circular dichroism. The strategies introduced herein should find application in many contexts, including assembly, sensing, and labeling. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Covalent bonding and band-gap formation in ternary transition-metal di-aluminides: Al4MnCo and related compounds

    International Nuclear Information System (INIS)

    Krajci, M.; Hafner, J.

    2002-01-01

    In this paper we extend our previous study of the electronic structure of and bonding mechanism in transition-metal (TM) di-aluminides to ternary systems. We have studied the character of the bonding in Al 4 MnCo and related TM di-aluminides in the C11 b (MoSi 2 ) and C54 (TiSi 2 ) crystal structures. A peculiar feature of the electronic structure of these TM di-aluminides is the existence of a semiconducting gap at the Fermi level. In our previous work we predicted a gap in Al 2 TM compounds where the TM atoms have eight valence electrons. Here we demonstrate that the semiconducting gap does not disappear if the TM sites are occupied by two different TMs, provided that the electron-per-atom ratio is conserved. Such a replacement substantially increases the class of possibly semiconducting TM di-aluminides. Substitution for 3d TMs of 4d or 5d TMs enhances the width of the gap. From the analysis of the charge density distribution and the crystal orbital overlap population, we conclude that the bonding between atoms has dominantly covalent character. This is confirmed not only by the enhanced charge density halfway between atoms, but also by the clear bonding-antibonding splitting of the electronic states. If the gaps between split states that correspond to all bonding configurations in the crystal have a common overlap at the Fermi level, the intermetallic compound becomes a semiconductor. However, the results of the total-energy calculations suggest that the existence of a band gap does not necessarily imply a stable structure. Strong covalent bonds can exist also in Al-TM structures where no band gap is observed. (author)

  2. 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

  3. Review: peripheral nerve regeneration using non-tubular alginate gel crosslinked with covalent bonds.

    Science.gov (United States)

    Hashimoto, Tadashi; Suzuki, Yoshihisa; Suzuki, Kyoko; Nakashima, Toshihide; Tanihara, Masao; Ide, Chizuka

    2005-06-01

    We have developed a nerve regeneration material consisting of alginate gel crosslinked with covalent bonds. in the first part of this study, we attempted to analyze nerve regeneration through alginate gel in the early stages within 2 weeks. in the second part, we tried to regenerate cat peripheral nerve by using alginate tubular or non-tubular nerve regeneration devices, and compared their efficacies. Four days after surgery, regenerating axons grew without Schwann cell investment through the partially degraded alginate gel, being in direct contact with the alginate without a basal lamina covering. One to 2 weeks after surgery, regenerating axons were surrounded by common Schwann cells, forming small bundles, with some axons at the periphery being partly in direct contact with alginate. At the distal stump, numerous Schwann cells had migrated into the alginate 8-14 days after surgery. Remarkable restorations of the 50-mm gap in cat sciatic nerve were obtained after a long term by using tubular or non-tubular nerve regeneration material consisting mainly of alginate gel. However, there was no significant difference between both groups at electrophysiological and morphological evaluation. Although, nowadays, nerve regeneration materials being marketed mostly have a tubular structure, our results suggest that the tubular structure is not indispensable for peripheral nerve regeneration.

  4. Films of covalently bonded gold nanoparticles synthesized by a sol–gel process

    International Nuclear Information System (INIS)

    Dell’Erba, Ignacio E.; Hoppe, Cristina E.; Williams, Roberto J. J.

    2012-01-01

    Gold nanoparticles (NPs) with a size close to 1.5 nm, coated with organic ligands bearing Si(OEt) 3 groups, were synthesized and used to obtain self-standing films by a sol–gel process catalyzed by formic acid. Using FESEM images, FTIR, and UV–visible spectra, it was observed that very small gold NPs self-assembled by Si–O–Si covalent bonds forming crosslinked clusters with sizes up to about 50 nm in which NPs preserve their individuality. The possibility of fixing very small gold NPs in a crosslinked film opens a variety of potential applications based on the specific properties of small-size particles. As an example, we illustrated the way in which one can take advantage of the low melting temperature of these NPs to generate tiny gold crystals partially embedded at the surface, a process that might be used for the development of catalysts or sensors. Besides, the shift and change in the intensity of the plasmon band produced by heating to 100 °C may be employed to develop an irreversible sensor of undesirable temperature excursions during the life-time of a specific product.

  5. Stable non-covalent labeling of layered silicate nanoparticles for biological imaging.

    Science.gov (United States)

    Mortimer, Gysell M; Jack, Kevin S; Musumeci, Anthony W; Martin, Darren J; Minchin, Rodney F

    2016-04-01

    Layered silicate nanoparticles (LSN) are widely used in industrial applications and consumer products. They also have potential benefits in biomedical applications such as implantable devices and for drug delivery. To study how nanomaterials interact with cells and tissues, techniques to track and quantify their movement through different biological compartments are essential. While radiolabels can be very sensitive, particularly for in vivo studies, fluorescent labeling has been preferred in recent years because of the array of methods available to image and quantify fluorescent nanoparticles. However, labeling can be problematic, especially if it alters the physical properties of the nanomaterial. Herein is described a novel non-covalent labeling technique for LSN using readily available fluorescent dimeric cyanine dyes without the need to use excess amounts of dye to achieve labeling, or the need for removal of unbound dye. The approach utilizes the cationic binding properties of layered silicate clays and the multiple quaternary nitrogens associated with the dyes. Preparation of YOYO-1 labeled LSN with optimal dispersion in aqueous media is presented. The utilization of the labeled particles is then demonstrated in cell binding and uptake studies using flow cytometry and confocal microscopy. The labeled LSN are highly fluorescent, stable and exhibit identical physical properties with respect to the unlabeled nanoparticles. The general approach described here is applicable to other cyanine dyes and may be utilized more widely for labeling nanoparticles that comprise a crystalline plate structure with a high binding capacity. Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.

  6. An effective hierarchical model for the biomolecular covalent bond: an approach integrating artificial chemistry and an actual terrestrial life system.

    Science.gov (United States)

    Oohashi, Tsutomu; Ueno, Osamu; Maekawa, Tadao; Kawai, Norie; Nishina, Emi; Honda, Manabu

    2009-01-01

    Under the AChem paradigm and the programmed self-decomposition (PSD) model, we propose a hierarchical model for the biomolecular covalent bond (HBCB model). This model assumes that terrestrial organisms arrange their biomolecules in a hierarchical structure according to the energy strength of their covalent bonds. It also assumes that they have evolutionarily selected the PSD mechanism of turning biological polymers (BPs) into biological monomers (BMs) as an efficient biomolecular recycling strategy We have examined the validity and effectiveness of the HBCB model by coordinating two complementary approaches: biological experiments using existent terrestrial life, and simulation experiments using an AChem system. Biological experiments have shown that terrestrial life possesses a PSD mechanism as an endergonic, genetically regulated process and that hydrolysis, which decomposes a BP into BMs, is one of the main processes of such a mechanism. In simulation experiments, we compared different virtual self-decomposition processes. The virtual species in which the self-decomposition process mainly involved covalent bond cleavage from a BP to BMs showed evolutionary superiority over other species in which the self-decomposition process involved cleavage from BP to classes lower than BM. These converging findings strongly support the existence of PSD and the validity and effectiveness of the HBCB model.

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

    Directory of Open Access Journals (Sweden)

    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.

  8. 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

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

    Science.gov (United States)

    García-Sánchez, M A; Serratos, I N; Sosa, R; Tapia-Esquivel, T; González-García, F; Rojas-González, F; Tello-Solís, S R; Palacios-Enriquez, A Y; Esparza Schulz, J M; Arrieta, A

    2016-07-22

    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 physicochemical

  10. 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.

  11. 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 ether linkages between lignin and titanium coupling agent. In the present work, changes were found in the attenuated total reflectance-Fourier transform IR (ATR-FTIR) spectra of lignin and wood mixed with silane, and titanium coupling agents, and to a lesser extent for a zirconium coupling agent...

  12. Dynamic Covalent Self-Assembly of Mono-, Bi- and Trimacro-cycles from Hydrogen Bonded Preorganized Templates

    Institute of Scientific and Technical Information of China (English)

    LIN Jianbin; WU Jing; JIANG Xikui; LI Zhanting

    2009-01-01

    This paper describes the dynamic covalent assembly of three mono-, bi- and trimacrocycles by utilizing hydro-gen bonding-driven zigzag anthranilamides as "leading" components. The monomacrocycle, a tetraamino molecule, was prepared from the [24+2] coupling reaction of a "'U"-shaped dialdehyde and a porphyrin diamine, followed by the reduction of the macrocyclic tetraimine by NaBH3CN, while the bi-and trimacrocycles were obtained through two six-component coupling reactions with rigid tri- and tetraamino-appended oligomers as templates.

  13. Hydrides of Alkaline Earth–Tetrel (AeTt) Zintl Phases: Covalent Tt–H Bonds from Silicon to Tin

    Energy Technology Data Exchange (ETDEWEB)

    Auer, Henry; Guehne, Robin; Bertmer, Marko; Weber, Sebastian; Wenderoth, Patrick; Hansen, Thomas Christian; Haase, Jürgen; Kohlmann, Holger (Leipzig); (Saarland-MED); (ILL)

    2017-01-18

    Zintl phases form hydrides either by incorporating hydride anions (interstitial hydrides) or by covalent bonding of H to the polyanion (polyanionic hydrides), which yields a variety of different compositions and bonding situations. Hydrides (deuterides) of SrGe, BaSi, and BaSn were prepared by hydrogenation (deuteration) of the CrB-type Zintl phases AeTt and characterized by laboratory X-ray, synchrotron, and neutron diffraction, NMR spectroscopy, and quantum-chemical calculations. SrGeD4/3–x and BaSnD4/3–x show condensed boatlike six-membered rings of Tt atoms, formed by joining three of the zigzag chains contained in the Zintl phase. These new polyanionic motifs are terminated by covalently bound H atoms with d(Ge–D) = 1.521(9) Å and d(Sn–D) = 1.858(8) Å. Additional hydride anions are located in Ae4 tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD2–x retains the zigzag Si chain as in the parent Zintl phase, but in the hydride (deuteride), it is terminated by H (D) atoms, thus forming a linear (SiD) chain with d(Si–D) = 1.641(5) Å.

  14. 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.

  15. 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.

  16. Self-healing polymer gels based on dynamic covalent bonds%基于动态共价键的可自愈合聚合物凝胶

    Institute of Scientific and Technical Information of China (English)

    张云飞; 邓国华

    2012-01-01

    简要介绍了动态共价键既具有普通共价键的高强度和稳定性,又能像分子间作用力(如氢键)那样可逆地断裂和重组的特点,以及基于动态共价键构筑智能凝胶材料的优势。综述了多种动态共价键,如芳香基苯并呋喃酮二聚体(diarylbibenzo furanone,DABBF)、三硫酯(trithiocarbonate,TTC)、芳基硼酸酯、酰腙键(acylhydrazone bond)、双硫键(disulfide bond)等的结构及其动态化学,以及应用它们合成聚合物凝胶的方法、凝胶的自愈合机理和性能。提出了发现和采用多种动态共价键构筑可自愈合聚合物凝胶的趋势,为此须解决多种动态共价键的相容性、凝胶自愈合机理与性能的光谱表征等问题,并加强应用研究。%Dynamic covalent bonds have high mechanical strength and stability like ordinary covalent bonds and can reversibly break and rebuild like intermolecular forces(such as hydrogen bonding).The properties of dynamic covalent bonds are introduced.The advantages of building smart gels based on dynamic covalent bonds are described.Specifically,the structure and dynamic chemistry of diarylbibenzo furanone(DABBF),trithiocarbonate(TTC),phenylboronic aciddiol ester bond,acylhydrazone bond and disulfide bond are reviewed.The methods of utilizing those dynamic covalent bonds to construct dynamic gels with self-healing properties,including the healing mechanisms,are presented.Combining two or more covalent bonds to construct dynamic gels with more complex responsiveness are proposed.Problems,such as compatibility of the dynamic covalent bonds,spectroscopic methods for characterizing self-healing mechanisms and capabilities,and application-oriented systems need to be further investigated.

  17. Hydrogen-bond acidic functionalized carbon nanotubes (CNTs) with covalently-bound hexafluoroisopropanol groups

    Energy Technology Data Exchange (ETDEWEB)

    Fifield, Leonard S.; Grate, Jay W.

    2010-06-01

    Fluorinated hydrogen-bond acidic groups are directly attached to the backbone of single walled carbon nanotubes (SWCNTs) without the introduction of intermediate electron donating surface groups. Hexafluoroalcohol functional groups are exceptionally strong hydrogen bond acids, and are added to the nanotube surface using the aryl diazonium approach to create hydrogen-bond acidic carbon nanotube (CNT) surfaces. These groups can promote strong hydrogen-bonding interactions with matrix materials in composites or with molecular species to be concentrated and sensed. In the latter case, this newly developed material is expected to find useful application in chemical sensors and in CNT-based preconcentrator devices for the detection of pesticides, chemical warfare agents and explosives.

  18. Synthesis, characterization, and near-infrared luminescent properties of the ternary thulium complex covalently bonded to mesoporous MCM-41

    International Nuclear Information System (INIS)

    Feng Jing; Song Shuyan; Xing Yan; Zhang Hongjie; Li Zhefeng; Sun Lining; Guo Xianmin; Fan Weiqiang

    2009-01-01

    The crystal structure of a ternary Tm(DBM) 3 phen complex (DBM=dibenzoylmethane; phen=1, 10-phenanthroline) and the synthesis of hybrid mesoporous material in which the complex covalently bonded to mesoporous MCM-41 are reported. Crystal data: Tm(DBM) 3 phen C 59 H 47 N 2 O 7 Tm, monoclinic, P21/c, a=19.3216(12) A, b=10.6691(7) A, c=23.0165(15) A, α=90 deg., β=91.6330(10) deg., γ=90 deg., V=4742.8(5) A 3 , Z=4. The properties of the Tm(DBM) 3 phen complex and the corresponding hybrid mesoporous material [Tm(DBM) 3 phen-MCM-41] have been studied. The results reveal that the Tm(DBM) 3 phen complex is successfully covalently bonded to MCM-41. Both Tm(DBM) 3 phen complex and Tm(DBM) 3 phen-MCM-41 display typical near-infrared (NIR) luminescence upon excitation at the maximum absorption of the ligands, which contributes to the efficient energy transfer from the ligands to the Tm 3+ ion, an antenna effect. The full width at half maximum (FWHM) centered at 1474 nm in the emission spectrum of Tm(DBM) 3 phen-MCM-41 is 110 nm, which is the potential candidate of broadening amplification band from C band (1530-1560 nm) to S + band (1450-1480 nm) in optical area. - Graphical abstract: The crystal structure of Tm(DBM) 3 phen complex (DBM=dibenzoylmethane; phen=1, 10-phenanthroline). The complex is successfully covalently bonded to MCM-41 (Tm(DBM) 3 phen-MCM-41). After ligand-mediated excitation, the emission spectrum of Tm(DBM) 3 phen-MCM-41 shows the bands 802 and 1474 nm. The FWHM of the 1474-nm band for Tm(DBM) 3 phen-MCM-41 is 110 nm, such a broad spectrum enables a wide gain bandwidth for optical amplification

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

    OpenAIRE

    Camelia Florela Voinea

    2015-01-01

    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 ...

  20. Photo-induced cooperative covalent-bond switching in amorphous arsenic selenide

    Energy Technology Data Exchange (ETDEWEB)

    Shpotyuk, O [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202, Stryjska str., Lviv, UA-290031 (Ukraine); Balitska, V [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202, Stryjska str., Lviv, UA-290031 (Ukraine); Filipecki, J [Institute of Physics of Jan Dlugosz University, 13/15, Al. Armii Krajowej, Czestochowa, PL-42201 (Poland)

    2005-01-01

    A microstructural mechanism of photoinduced transformations in amorphous arsenic selenide films was studied with IR Fourier-spectroscopy technique in 300-100 cm{sup -1} region. It was shown that stage of irreversible photostructural changes was connected with cooperative process of coordination defect formation accompanied by homopolar chemical bonds switching in heteropolar ones. On the contrary, reversible photoinduced effects were caused by heteropolar chemical bonds switching in homopolar ones, as well as additional channel of bridge heteropolar bonds switching in short-layer ones. The both processes were associated with formation of anomalously coordinated defect pairs and accompanying atomic displacements at the level of medium-range ordering. The developed mathematical simulation procedure testified in a favour of defect-related origin of the reversible photo-thermallyinduced transformations, since their kinetics corresponded to known stretched-exponential dependence, tending to bimolecular behaviour rather then to single-exponential one.

  1. Immobilization of collagen peptide on dialdehyde bacterial cellulose nanofibers via covalent bonds for tissue engineering and regeneration

    Directory of Open Access Journals (Sweden)

    Wen XX

    2015-07-01

    Full Text Available Xiaoxiao Wen,1 Yudong Zheng,1 Jian Wu,2 Lu-Ning Wang,1 Zhenya Yuan,1 Jiang Peng,3 Haoye Meng3 1School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing, People’s Republic of China; 2Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Soochow, People’s Republic of China; 3Institute of Orthopedics, Chinese PLA General Hospital, Beijing, People’s Republic of China Abstract: Bacterial cellulose (BC is an alternative nanostructured biomaterial to be utilized for a wide range of biomedical applications. Because of its low bioactivity, which restricted its practical application, collagen and collagen hydrolysate were usually composited into BC. It is necessary to develop a new method to generate covalent bonds between collagen and cellulose to improve the immobilization of collagen on BC. This study describes a facile dialdehyde BC/collagen peptide nanocomposite. BC was oxidized into dialdehyde bacterial cellulose (DBC by regioselective oxidation, and then composited with collagen peptide (Col-p via covalent bonds to form Schiff’s base type compounds, which was demonstrated by the results of microstructures, contact angle, Col-p content, and peptide-binding ratio. The peptide-binding ratio was further affected by the degree of oxidation, pH value, and zeta potential. In vitro desorption measurement of Col-p suggested a controlled release mechanism of the nanocomposite. Cell tests indicated that the prepared DBC/Col-p composite was bioactive and suitable for cell adhesion and attachment. This work demonstrates that the DBC/Col-p composite is a promising material for tissue engineering and regeneration. Keywords: bacterial cellulose, dialdehyde cellulose, collagen peptide, composite materials, cytoactivity 

  2. Reconstitution of Qbeta RNA replicase from a covalently bonded elongation factor Tu-Ts complex

    DEFF Research Database (Denmark)

    Brown, S; Blumenthal, T

    1976-01-01

    of these polypeptides, protein synthesis elongation factors EF-Tu and EF-Ts, can be covalently crosslinked with dimethyl suberimidate to form a complex which lacks the ability to catalyze the known host functions catalyzed by the individual elongation factors. Using a previously developed reconstitution system we have...... examined the effects of crosslinking the EF-Tu-Ts complex on reconstituted replicase activity. Renaturation is significantly more efficient when exogenously added native EF-Tu-Ts is crosslinked than when it is not. Crosslinked EF-Tu-Ts can be purified from a crude crosslinked postribosomal supernatant...... by its ability to replace EF-Tu and EF-Ts in the renaturation of denatured Qbeta replicase. A sample of Qbeta replicase with crosslinked EF-Tu-Ts replacing the individual elongation factors was prepared. Although it lacked EF-Tu and EF-Ts activities, it could initiate transcription of both poly...

  3. 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…

  4. Intrinsic self-healing thermoset through covalent and hydrogen bonding interactions

    NARCIS (Netherlands)

    Araya-Hermosilla, R.; Lima, G. M. R.; Raffa, P.; Fortunato, G.; Pucci, A.; Flores, Mario E.; Moreno-Villoslada, I.; Broekhuis, A. A.; Picchioni, F.

    The intrinsic self-healing ability of polyketone (PK) chemically modified into furan and/or OH groups containing derivatives is presented. Polymers bearing different ratios of both functional groups were cross-linked via furan/bis-maleimide (Diels-Alder adducts) and hydrogen bonding interactions

  5. 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

    by codeposition of Pb and Sn. Our surface X-ray diffraction measurements prove that the alloy structure is closely related to the low-temperature reconstruction. The interatomic distances reveal the nature of the chemical bonding in the surface layer and provide insight into the mechanism stabilizing...

  6. High-energy, stable and recycled molecular solar thermal storage materials using AZO/graphene hybrids by optimizing hydrogen bonds.

    Science.gov (United States)

    Luo, Wen; Feng, Yiyu; Qin, Chengqun; Li, Man; Li, Shipei; Cao, Chen; Long, Peng; Liu, Enzuo; Hu, Wenping; Yoshino, Katsumi; Feng, Wei

    2015-10-21

    An important method for establishing a high-energy, stable and recycled molecular solar heat system is by designing and preparing novel photo-isomerizable molecules with a high enthalpy and a long thermal life by controlling molecular interactions. A meta- and ortho-bis-substituted azobenzene chromophore (AZO) is covalently grafted onto reduced graphene oxide (RGO) for solar thermal storage materials. High grafting degree and close-packed molecules enable intermolecular hydrogen bonds (H-bonds) for both trans-(E) and cis-(Z) isomers of AZO on the surface of nanosheets, resulting in a dramatic increase in enthalpy and lifetime. The metastable Z-form of AZO on RGO is thermally stabilized with a half-life of 52 days by steric hindrance and intermolecular H-bonds calculated using density functional theory (DFT). The AZO-RGO fuel shows a high storage capacity of 138 Wh kg(-1) by optimizing intermolecular H-bonds with a good cycling stability for 50 cycles induced by visible light at 520 nm. Our work opens up a new method for making advanced molecular solar thermal storage materials by tuning molecular interactions on a nano-template.

  7. 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.

  8. 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.

  9. Covalent lanthanide(III) macrocyclic complexes: the bonding nature and optical properties of a promising single antenna molecule.

    Science.gov (United States)

    Rabanal-León, Walter A; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

    2014-12-21

    The present work is focused on the elucidation of the electronic structure, bonding nature and optical properties of a series of low symmetry (C2) coordination compounds of type [Ln(III)HAM](3+), where "Ln(III)" are the trivalent lanthanide ions: La(3+), Ce(3+), Eu(3+) and Lu(3+), while "HAM" is the neutral six-nitrogen donor macrocyclic ligand [C22N6H26]. This systematic study has been performed in the framework of the Relativistic Density Functional Theory (R-DFT) and also using a multi-reference approach via the Complete Active Space (CAS) wavefunction treatment with the aim of analyzing their ground state and excited state electronic structures as well as electronic correlation. Furthermore, the use of the energy decomposition scheme proposed by Morokuma-Ziegler and the electron localization function (ELF) allows us to characterize the bonding between the lanthanide ions and the macrocyclic ligand, obtaining as a result a dative-covalent interaction. Due to a great deal of lanthanide optical properties and their technological applications, the absorption spectra of this set of coordination compounds were calculated using the time-dependent density functional theory (TD-DFT), where the presence of the intense Ligand to Metal Charge Transfer (LMCT) bands in the ultraviolet and visible region and the inherent f-f electronic transitions in the Near-Infra Red (NIR) region for some lanthanide ions allow us to propose these systems as "single antenna molecules" with potential applications in NIR technologies.

  10. Covalent and stable CuAAC modification of silicon surfaces for control of cell adhesion

    DEFF Research Database (Denmark)

    Vutti, Surendra; Buch-Månson, Nina; Schoffelen, Sanne

    2015-01-01

    in the vapor or liquid phase. In this work, we compared these two methods for oxidized silicon surfaces and thoroughly characterized the functionalization steps by tagging and fluorescence imaging. We demonstrate that the vapor-phase functionalization only provided transient surface modification that was lost...... on extensive washing. For stable surface modification, a liquid-phase method was developed. In this method, silicon wafers were decorated with azides, either by silanization with (3-azidopropyl)triethoxysilane or by conversion of the amine groups of an aminopropylated surface by means of the azido...

  11. Electrocatalytic reduction of H{sub 2}O{sub 2} by Pt nanoparticles covalently bonded to thiolated carbon nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    You, Jung-Min; Kim, Daekun [Department of Chemistry and Institute of Basic Science, Chonnam National University, Gwangju 500-757 (Korea, Republic of); Jeon, Seungwon [Department of Chemistry and Institute of Basic Science, Chonnam National University, Gwangju 500-757 (Korea, Republic of)

    2012-03-30

    Highlights: Black-Right-Pointing-Pointer Novel thiolated carbon nanostructures - platinum nanoparticles [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] have been synthesized, and [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] denotes as t-GO-pt and t-MWCNT-Pt in manuscript, respectively. Black-Right-Pointing-Pointer The modified electrode denoted as PDDA/t-GO-pt/GCE was used for the electrochemical determination of H{sub 2}O{sub 2} for the first time. Black-Right-Pointing-Pointer The results show that PDDA/t-GO-pt nanoparticles have the promising potential as the basic unit of the electrochemical biosensors for the detection of H{sub 2}O{sub 2}. Black-Right-Pointing-Pointer The proposed H{sub 2}O{sub 2} biosensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s. - Abstract: Glassy carbon electrodes were coated with thiolated carbon nanostructures - multi-walled carbon nanotubes and graphene oxide. The subsequent covalent addition of platinum nanoparticles and coating with poly(diallydimethylammonium chloride) resulted in biosensors that detected hydrogen peroxide through its electrocatalytic reduction. The sensors were easily and quickly prepared and showed improved sensitivity to the electrocatalytic reduction of H{sub 2}O{sub 2}. The Pt nanoparticles covalently bonded to the thiolated carbon nanostructures were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectroscopy. Cyclic voltammetry and amperometry were used to characterize the biosensors' performances. The sensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s, thus demonstrating their potential for use in H{sub 2}O{sub 2} analysis.

  12. 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.

  13. 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).

  14. Chemically fixed p-n heterojunctions for polymer electronics by means of covalent B-F bond formation

    Science.gov (United States)

    Hoven, Corey V.; Wang, Huiping; Elbing, Mark; Garner, Logan; Winkelhaus, Daniel; Bazan, Guillermo C.

    2010-03-01

    Widely used solid-state devices fabricated with inorganic semiconductors, including light-emitting diodes and solar cells, derive much of their function from the p-n junction. Such junctions lead to diode characteristics and are attained when p-doped and n-doped materials come into contact with each other. Achieving bilayer p-n junctions with semiconducting polymers has been hindered by difficulties in the deposition of thin films with independent p-doped and n-doped layers. Here we report on how to achieve permanently fixed organic p-n heterojunctions by using a cationic conjugated polyelectrolyte with fluoride counteranions and an underlayer composed of a neutral conjugated polymer bearing anion-trapping functional groups. Application of a bias leads to charge injection and fluoride migration into the neutral layer, where irreversible covalent bond formation takes place. After the initial charging and doping, one obtains devices with no delay in the turn on of light-emitting electrochemical behaviour and excellent current rectification. Such devices highlight how mobile ions in organic media can open opportunities to realize device structures in ways that do not have analogies in the world of silicon and promise new opportunities for integrating organic materials within technologies now dominated by inorganic semiconductors.

  15. 共价键长的变化规律及计算%Variation Rule of Covalent Bond Length and Its Calculation Method

    Institute of Scientific and Technical Information of China (English)

    徐永群; 陈年友

    2001-01-01

    研究了共价键长的变化规律,提出了两个影响键长的参数,即配位体的半径与中心原子半径之比Rratio和由中心原子组成的基团的拓扑指数F2,用BP神经网络法逼近了50个、预测了11个简单无机分子中非含氢原子键的键长,其计算误差基本上在2pm以内。%The variation rule of covalent bond lengths is investigated.Two parameters which influence covalent bond lengths are presented: the radius ratio of the ligand to the centre atom and the topological index of the group of centre atom.With BP neural networks, 50 bond lengths have been approached and other 11 bond lengths have been forecasted. Errors of calculated bond lengths is almost within 2pm.

  16. 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

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

    Science.gov (United States)

    Correia, Manuel; Neves-Petersen, Maria Teresa; Jeppesen, Per Bendix; Gregersen, Søren; Petersen, Steffen B

    2012-01-01

    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 in protein

  18. A Highly Stable Microporous Covalent Imine Network Adsorbent for Natural Gas Upgrading and Flue Gas CO2 Capture

    KAUST Repository

    Das, Swapan Kumar; Wang, Xinbo; Ostwal, Mayur; Lai, Zhiping

    2016-01-01

    The feasible capture and separation of CO2 and N2 from CH4 is an important task for natural gas upgrading and the control of greenhouse gas emissions. Here, we studied the microporous covalent imine networks (CIN) material prepared through Schiff

  19. Vanillyl alcohol oxidases produced in Komagataella phaffii contain a highly stable non-covalently bound anionic FAD semiquinone

    NARCIS (Netherlands)

    Gygli, G.A.; Berkel, van W.J.H.

    2017-01-01

    Vanillyl alcohol oxidase (VAO) from Penicillium simplicissimum is a covalent flavoprotein that has emerged as a promising biocatalyst for the production of aromatic fine chemicals such as vanillin, coniferyl alcohol and enantiopure 1-(4’-hydroxyphenyl) alcohols. The largescale production of this

  20. EPR-spin probe studies of model polymers: separation of covalent cross-linking effects from hydrogen bonding effects in swelled Argonne Premium Coal samples

    Energy Technology Data Exchange (ETDEWEB)

    Spears, D.R.; Sady, W.; Tucker, D.; Kispert, L.D. (University of Alabama, Tuscaloosa, AL (United States). Chemistry Dept.)

    The swelling behaviour of 2-12% cross-linked polystyrene-divinylbenzene (PSDVB) copolymers was examined by an EPR-spin probe technique. It was observed that the mechanism of spin probe inclusion was the intercalation into the matrix rather than diffusion into the pores. The disruption of van der Waals forces between adjacent aromatic rings appeared to be the primary mechanism for pyridine swelling of PSDVB. By comparing the data to results from coal swelling studies it was also inferred that the extent of hydrogen bonding in coal will have a much greater impact on its swelling properties than its covalently cross-linked character. 24 refs., 6 figs.

  1. A new approach for enhancement of the corrosion protection properties and interfacial adhesion bonds between the epoxy coating and steel substrate through surface treatment by covalently modified amino functionalized graphene oxide film

    International Nuclear Information System (INIS)

    Parhizkar, N.; Shahrabi, T.; Ramezanzadeh, B.

    2017-01-01

    Highlights: •The steel substrate was treated by a covalently modified amino functionalized graphene oxide (fGO) film. •Deposition of fGO film at the interface of steel and epoxy could effectively improve the adhesion strength and corrosion protection properties. •More stable and stronger interfacial bonds was obtained when treating the interface by fGO film. -- Abstract: This study introduces a novel surface treatment approach of steel substrate by covalent modification of graphene oxide (fGO) nanosheets with 3-aminopropyltriethoxysilane to improve the adhesion and corrosion protection properties of an epoxy coating. The effect of fGO film on the epoxy coating performance was studied by field-emission scanning electron microscopy (FE-SEM), X-Ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), Pull-off adhesion, salt spray and cathodic delamination tests. Results revealed that deposition of fGO film on steel surface can effectively improve the adhesion strength and corrosion protection properties and reduce the cathodic delamination rate of the epoxy coating.

  2. Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry.

    Science.gov (United States)

    Seber, Gonca; Rudnev, Alexander V; Droghetti, Andrea; Rungger, Ivan; Veciana, Jaume; Mas-Torrent, Marta; Rovira, Concepció; Crivillers, Núria

    2017-01-26

    A novel, persistent, electrochemically active perchlorinated triphenylmethyl (PTM) radical with a diazonium functionality has been covalently attached to highly ordered pyrolytic graphite (HOPG) by electrografting in a single-step process. Electrochemical scanning tunneling microscopy (EC-STM) and Raman spectroscopy measurements revealed that PTM molecules had a higher tendency to covalently react at the HOPG step edges. The cross-section profiles from EC-STM images showed that there was current enhancement at the functionalized areas, which could be explained by redox-mediated electron tunneling through surface-confined redox-active molecules. Cyclic voltammetry clearly demonstrated that the intrinsic properties of the organic radical were preserved upon grafting and DFT calculations also revealed that the magnetic character of the PTM radical was preserved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Highly stable ionic-covalent cross-linked sulfonated poly(ether ether ketone) for direct methanol fuel cells

    Science.gov (United States)

    Lei, Linfeng; Zhu, Xingye; Xu, Jianfeng; Qian, Huidong; Zou, Zhiqing; Yang, Hui

    2017-05-01

    A novel ionic cross-linked sulfonated poly(ether ether ketone) containing equal content of sulfonic acid and pendant tertiary amine groups (TA-SPEEK) has been initially synthesized for the application in direct methanol fuel cells (DMFCs). By adjusting the ratio of p-xylene dibromide to tertiary amine groups of TA-SPEEK, a series of ionic-covalent cross-linked membranes (C-SPEEK-x) with tunable degree of cross-linking are prepared. Compared with the pristine membrane, the ionic and ionic-covalent cross-linked proton exchange membranes (PEMs) exhibit reduced methanol permeability and improved mechanical properties, dimensional and oxidative stability. The proton conductivity and methanol selectivity of protonated TA-SPEEK and C-SPEEK-x at 25 °C is up to 0.109 S cm-1 and 3.88 × 105 S s cm-3, respectively, which are higher than that of Nafion 115. The DMFC incorporating C-SPEEK-25 exhibits a maximum power density as high as 35.3 mW cm-2 with 4 M MeOH at 25 °C (31.8 mW cm-2 for Nafion 115). Due to the highly oxidative stability of the membrane, no obvious performance degradation of the DMFC is observed after more than 400 h operation, indicating such cost-effective ionic-covalent cross-linked membranes have substantial potential as alternative PEMs for DMFC applications.

  4. 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...... variants in vertebrates consist of two peptide chains and have six cysteine residues, which form three disulfide bonds, two of them link the two chains and a third is an intra-chain bond in the A-chain. This classical insulin fold appears to have been conserved over half a billion years of evolution. We...... addressed the question whether a human insulin variant with four disulfide bonds could exist and be fully functional. In this review, we give an overview of the road to engineering four-disulfide bonded insulin analogs. During our journey, we discovered several active four disulfide bonded insulin analogs...

  5. Functionalized Cobalt Triarylcorrole Covalently Bonded with Graphene Oxide: A Selective Catalyst for the Two- or Four-Electron Reduction of Oxygen.

    Science.gov (United States)

    Tang, Jijun; Ou, Zhongping; Guo, Rui; Fang, Yuanyuan; Huang, Dong; Zhang, Jing; Zhang, Jiaoxia; Guo, Song; McFarland, Frederick M; Kadish, Karl M

    2017-08-07

    A cobalt triphenylcorrole (CorCo) was covalently bonded to graphene oxide (GO), and the resulting product, represented as GO-CorCo, was characterized by UV-vis, FT-IR, and micro-Raman spectroscopy as well as by HRTEM, TGA, XRD, XPS, and AFM. The electrocatalytic activity of GO-CorCo toward the oxygen reduction reaction (ORR) was then examined in air-saturated 0.1 M KOH and 0.5 M H 2 SO 4 solutions by cyclic voltammetry and linear sweep voltammetry using a rotating disk electrode and/or a rotating ring-disk electrode. An overall 4-electron reduction of O 2 is obtained in alkaline media while under acidic conditions a 2-electron process is seen. The ORR results thus indicate that covalently bonded GO-CoCor can be used as a selective catalyst for either the 2- or 4-electron reduction of oxygen, the prevailing reaction depending upon the acidity of the solution.

  6. Nanostructured organic electrode materials grown on graphene with covalent-bond interaction for high-rate and ultra-long-life lithium-ion batteries

    Institute of Scientific and Technical Information of China (English)

    Qing Zhao; Jianbin Wang; Chengcheng Chen; Ting Ma; Jun Chen

    2017-01-01

    Nanostructured organic tetralithium salts of 2,5-dihydroxyterephthalic acid (Li4C8H2O6) supported on graphene were prepared via a facile recrystallization method.The optimized composite with 75 wt.% Li4C8H2O6 was evaluated as an anode with redox couples of Li4C8H2OdLi6C8H2O6 and as a cathode with redox couples of Li4C8H2O6/Li2C8H2O6 for Li-ion batteries,exhibiting a high-rate capability (10 C) and long cycling life (1,000 cycles).Moreover,in an all-organic symmetric Li-ion battery,this dual-function electrode retained capacities of 191 and 121 mA.h·g-1 after 100 and 500 cycles,respectively.Density functional theory calculations indicated the presence of covalent bonds between Li4C8H2O6 and graphene,which affected both the morphology and electronic structure of the composite.The special nanostructures,high electronic conductivity of graphene,and covalent-bond interaction between Li4C8H2O6 and graphene contributed to the superior electrochemical properties.Our results indicate that the combination of organic salt molecules with graphene is useful for obtaining high-performance organic batteries.

  7. Morphological effects of single-layer graphene oxide in the formation of covalently bonded polypyrrole composites using intermediate diisocyanate chemistry

    International Nuclear Information System (INIS)

    Whitby, Raymond L. D.; Korobeinyk, Alina; Mikhalovsky, Sergey V.; Fukuda, Takahiro; Maekawa, Toru

    2011-01-01

    Single-layer graphene oxide (SLGO) possesses carboxylic and hydroxyl groups suitable for reactions with aliphatic or aromatic diisocyanate molecules. TEM analysis reveals that aliphatic diisocyanate molecules caused SLGO to scroll into star-like formations, whereas aromatic diisocyanate molecules retained SGLO in a flat-sheet morphology. TGA confirms the stabilisation of the formed urea and urethane groups on SLGO, but the onset of sheet pyrolysis occurs at a lower temperature due to isocyanate reactions with anhydride and epoxide groups embedded in the sheet. Pendant isocyanate groups act as bridging units to facilitate the attachment of pyrrole molecules, which are then used as anchor sites for the covalent polymerisation of pyrrole to polypyrrole (PPy). The use of FeCl 3 as the polymerisation catalyst generated both covalent and free PPy, but also iron hydroxide nanoparticles were observed decorating the SLGO surface. When using ammonium persulfate as a catalyst and dodecylbenzenesulfonate as a dopant, free PPy could be removed under treatment with solvents to leave a purely covalent system. Discrete regions of SLGO were observed decorated with nanoparticles of PPy along the edge or across the surface of individual sheets. It was found that the flexibility of the SLGO sheet and the type of diisocyanate used directly affected the electrical resistance of the final composite.

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

    KAUST Repository

    Minenkov, Yury; Chermak, Edrisse; Cavallo, Luigi

    2015-01-01

    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.

  9. 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.

  10. Ionic ASi{sub 2}N{sub 3} (A=Li, Na, K and Rb) stabilized by the covalent Si–N bonding: First-principles calculations

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Huijun [College of Information Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Ren, Jiadong, E-mail: jdren@ysu.edu.cn [College of Information Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Wu, Lailei [Key Laboratory of Metastable Materials Science and Technology, College of Material Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zhang, Jingwu, E-mail: zjw@ysu.edu.cn [Key Laboratory of Metastable Materials Science and Technology, College of Material Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

    2017-01-15

    The structural, elastic and electronic properties of LiSi{sub 2}N{sub 3} and its substitutions by Na, K and Rb were investigated through first-principles computations. The expansion of lattice parameters of ASi{sub 2}N{sub 3} from Li, Na, K to Rb is found to be determined by the bond angle of Si–N1–Si, which suggests a possible way to improve the lithium ionic conductivity by substitutions. ASi{sub 2}N{sub 3} (A=Li, Na, K and Rb) shows the similar elastic behaviors, while the electronic band gap gradually decreases from 5.1 to 3.4 eV from LiSi{sub 2}N{sub 3} to RbSi{sub 2}N{sub 3}. Interestingly, the analysis of electronic structure, crystal orbital Hamiltonian populations and Bader charges shows that the covalence of Si–N bonding is critical for the stability of ASi{sub 2}N{sub 3} phase. Among ASi{sub 2}N{sub 3} phases, there is a relatively high ionicity in NaSi{sub 2}N{sub 3}; the Si–N bond strength in [Si{sub 2}N{sub 3}]{sup −} net for KSi{sub 2}N{sub 3} and RbSi{sub 2}N{sub 3} is comparable to LiSi{sub 2}N{sub 3}, but stronger than NaSi{sub 2}N{sub 3}. - Graphic abstract: Universal trend of structural and electronic properties in alkaline metal silicon nitrides, ASi{sub 2}N{sub 3}, A=Li, Na, K and Rb. - Highlights: • Trend in structure, electronic and mechanical properties of ASi{sub 2}N{sub 3} (A=Li-Rb) were predicted. • Lattice expansion of ASi{sub 2}N{sub 3} induced by the bond angle of Si–N1–Si was found. • Calculated band gap decreases from 5.1 to 3.4 eV from LiSi{sub 2}N{sub 3} to RbSi{sub 2}N{sub 3}. • Covalent Si–N bonding is critical for the stability of ASi{sub 2}N{sub 3}.

  11. Covalent bonding and J-J mixing effects on the EPR parameters of Er3+ions in GaN crystal

    Institute of Scientific and Technical Information of China (English)

    柴瑞鹏; 李隆; 梁良; 庞庆

    2016-01-01

    The EPR parameters of trivalent Er3+ ions doped in hexagonal GaN crystal have been studied by diagonalizing the 364×364 complete energy matrices. The results indicate that the resonance ground states may be derived from the Kramers doubletΓ6. The EPR g-factors may be ascribed to the stronger covalent bonding and nephelauxetic effects compared with other rare-earth doped complexes, as a result of the mismatch of ionic radii of the impurity Er3+ion and the replaced Ga3+ion apart from the intrinsic covalency of host GaN. Furthermore, the J–J mixing effects on the EPR parameters from the high-lying manifolds have been evaluated. It is found that the dominant J–J mixing contribution is from the manifold 2K15/2, which accounts for about 2.5%. The next important J–J contribution arises from the crystal–field mixture between the ground state 4I15/2 and the first excited state 4I13/2, and is usually less than 0.2%. The contributions from the rest states may be ignored.

  12. Sol-gel approach to the novel organic-inorganic hybrid composite films with ternary europium complex covalently bonded with silica matrix

    International Nuclear Information System (INIS)

    Dong Dewen; Yang Yongsheng; Jiang Bingzheng

    2006-01-01

    Novel organic-inorganic hybrid composite films with ternary lanthanide complex covalently bonded with silica matrix were prepared in situ via co-ordination of N-(3-propyltriethoxysilane)-4-carboxyphthalimide (TAT) and 1,10-phenanthroline (Phen) with europium ion (Eu 3+ ) during a sol-gel approach and characterized by the means of spectrofluorimeter, phosphorimeter and infrared spectrophotometer (FTIR). The resulting transparent films showed improved photophysical properties, i.e. increased luminescence intensity and longer luminescence lifetime, compared with the corresponding binary composite films without Phen. All the results revealed that the intense luminescence of the composite film was attributed to the efficient energy transfer from ligands, especially Phen, to chelated Eu 3+ and the reduced non-radiation through the rigid silica matrix and 'site isolation'

  13. Fluorescence properties of dansyl groups covalently bonded to the surface of oxidatively functionalized low-density polyethylene film

    Science.gov (United States)

    Holmes-Farley, S. R.; Whitesides, G. M.

    1985-12-01

    Brief oxidation of low-density polyethylene film with chromic acid in aqueous sulfuric acid introduced carboxylic acid and ketone and/or aldehyde groups onto the surface of the film. The carboxylic acid moieties can be used to attach more complex functionality to the polymer surface. We are developing this surface-functionalized polyethylene (named polyethylene carboxylic acid, PE-CO2H, to emphasize the functional group that dominates its surface properties) as a substrate with which to study problems in organic surface chemistry--especially wetting, polymer surface reconstruction, and adhesion--using physical-organic techniques. This document describes the preparation, characterization, and fluorescence properties of derivatives of PE-CO2H in which the Dansyl (5-dimethylaminonaphthalene-1-sulfonyl) group has been covalently attached by amide links to the surface carbonyl moieties.

  14. Stable Dispersions of Covalently Tethered Polymer Improved Graphene Oxide Nanoconjugates as an Effective Vector for siRNA Delivery.

    Science.gov (United States)

    Yadav, Nisha; Kumar, Naveen; Prasad, Peeyush; Shirbhate, Shivani; Sehrawat, Seema; Lochab, Bimlesh

    2018-05-02

    Conjugates of poly(amidoamine) (PAMAM) with modified graphene oxide (GO) are attractive nonviral vectors for gene-based cancer therapeutics. GO protects siRNA from enzymatic cleavage and showed reasonable transfection efficiency along with simultaneous benefits of low cost and large scale production. PAMAM is highly effective in siRNA delivery but suffers from high toxicity with poor in vivo efficacy. Co-reaction of GO and PAMAM led to aggregation and more importantly, have detrimental effect on stability of dispersion at physiological pH preventing their exploration at clinical level. In the current work, we have designed, synthesized, characterized and explored a new type of hybrid vector (GPD), using GO synthesized via improved method which was covalently tethered with poly(ethylene glycol) (PEG) and PAMAM. The existence of covalent linkage, relative structural changes and properties of GPD is well supported by Fourier transform infrared (FTIR), UV-visible (UV-vis), Raman, X-ray photoelectron (XPS), elemental analysis, powder X-ray diffraction (XRD), thermogravimetry analysis (TGA), dynamic light scattering (DLS), and zeta potential. Scanning electron microscopy (SEM), and transmission electron microscopy (TEM) of GPD showed longitudinally aligned columnar self-assembled ∼10 nm thick polymeric nanoarchitectures onto the GO surface accounting to an average size reduction to ∼20 nm. GPD revealed an outstanding stability in both phosphate buffer saline (PBS) and serum containing cell medium. The binding efficiency of EPAC1 siRNA to GPD was supported by gel retardation assay, DLS, zeta potential and photoluminescence (PL) studies. A lower cytotoxicity with enhanced cellular uptake and homogeneous intracellular distribution of GPD/siRNA complex is confirmed by imaging studies. GPD exhibited a higher transfection efficiency with remarkable inhibition of cell migration and lower invasion than PAMAM and Lipofectamine 2000 suggesting its role in prevention of breast

  15. Covalently Connecting Crystal Grains with Polyvinylammonium Carbochain Backbone To Suppress Grain Boundaries for Long-Term Stable Perovskite Solar Cells.

    Science.gov (United States)

    Li, Han; Liang, Chao; Liu, Yingliang; Zhang, Yiqiang; Tong, Jincheng; Zuo, Weiwei; Xu, Shengang; Shao, Guosheng; Cao, Shaokui

    2017-02-22

    Grain boundaries act as rapid pathways for nonradiative carrier recombination, anion migration, and water corrosion, leading to low efficiency and poor stability of organometal halide perovskite solar cells (PSCs). In this work, the strategy suppressing the crystal grain boundaries is applied to improve the photovoltaic performance, especially moisture-resistant stability, with polyvinylammonium carbochain backbone covalently connecting the perovskite crystal grains. This cationic polyelectrolyte additive serves as nucleation sites and template for crystal growth of MAPbI 3 and afterward the immobilized adjacent crystal grains grow into the continuous compact, pinhole-free perovskite layer. As a result, the unsealed PSC devices, which are fabricated under low-temperature fabrication protocol with a proper content of polymer additive PVAm·HI, currently exhibit the maximum efficiency of 16.3%. Remarkably, these unsealed devices follow an "outside-in" corrosion mechanism and respectively retain 92% and 80% of the initial PCE value after being exposed under ambient environment for 50 days and 100 days, indicating the superiority of carbochain polymer additives in solving the long-term stability problem of PSCs.

  16. Highly Stable Porous Covalent Triazine-Piperazine Linked Nanoflower as a Feasible Adsorbent for Flue Gas CO2 Capture

    KAUST Repository

    Das, Swapan Kumar

    2016-02-11

    Here, we report a porous covalent triazine-piperazine linked polymer (CTPP) featuring 3D nanoflower morphology and enhanced capture/removal of CO2, CH4 from air (N2), essential to control greenhouse gas emission and natural gas upgrading. 13C solid-state NMR and FTIR analyses and CHN and X-ray photoelectron spectroscopy (XPS) elemental analyses confirmed the integration of triazine and piperazine components in the network. Scanning electron microscopic (SEM) and transmission electron microscopic (TEM) analyses revealed a relatively uniform particle size of approximately 400 to 500 nm with 3D nanoflower microstructure, which was formed by the self-assembly of interwoven and slight bent nanoflake components. The material exhibited outstanding chemical robustness under acidic and basic medium and high thermal stability up to 773 K. The CTPP possess high surface area (779 m2/g) and single-component gas adsorption study exhibited enhanced CO2 and CH4 uptake of 3.48 mmol/g, 1.09 mmol/g, respectively at 273 K, 1 bar; coupled with high sorption selectivities for CO2/N2 and CH4/N2 of 128 and 17, respectively. The enriched Lewis basicity of the CTPP favors the interaction with CO2, which results in an enhanced CO2 adsorption capacity and high CO2/N2 selectivity. The binary mixture breakthrough study for the flue gas composition at 298 K showed a high CO2/N2 selectivity of 82. CO2 heats of adsorption for the CTPP (34 kJ mol−1) were realized at the borderline between strong physisorption and weak chemisorption (QstCO2; 25−50 kJ mol−1) and low Qst value for N2 (22.09 kJ mol−1), providing the ultimate validation for the high selectivity of CO2 over N2.

  17. A Highly Stable Microporous Covalent Imine Network Adsorbent for Natural Gas Upgrading and Flue Gas CO2 Capture

    KAUST Repository

    Das, Swapan Kumar

    2016-06-06

    The feasible capture and separation of CO2 and N2 from CH4 is an important task for natural gas upgrading and the control of greenhouse gas emissions. Here, we studied the microporous covalent imine networks (CIN) material prepared through Schiff base condensation and exhibited superior chemical robustness under both acidic and basic conditions and high thermal stability. The material possesses a relatively uniform nanoparticle size of approximately 70 to 100 nm. This network featured permanent porosity with a high surface area (722 m2g-1) and micropores. A single-component gas adsorption study showed enhanced CO2 and CH4 uptakes of 3.32 mmol/g and 1.14 mmol/g, respectively, at 273 K and 1 bar, coupled with high separation selectivities for CO2/CH4, CH4/N2, and CO2/N2 of 23, 11.8 and 211, respectively. The enriched Lewis basicity in the porous skeletons favours the interaction of quadrupolar CO2 and polarizable CH4, resulting in enhanced CH4 and CO2 uptake and high CH4/N2, CO2/CH4 and CO2/N2 selectivities. Breakthrough experiments showed high CO2/CH4, CH4/N2 and CO2/N2 selectivities of 7.29, 40 and 125, respectively, at 298 K and 1 bar. High heats of adsorption for CH4 and CO2 (QstCH4; 32.61 kJ mol-1 and QstCO2; 42.42 kJ mol-1) provide the ultimate validation for the high selectivity. To the best of our knowledge, such a versatile adsorbent material that displays both enhanced uptake and selectivity for a variety of binary gas mixtures, including CO2/ CH4, CO2/N2 and CH4/N2, has not been extensively explored.

  18. 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

  19. Covalent Bonding of Thermoplastics to Rubbers for Printable, Reel-to-Reel Processing in Soft Robotics and Microfluidics.

    Science.gov (United States)

    Taylor, Jay M; Perez-Toralla, Karla; Aispuro, Ruby; Morin, Stephen A

    2018-02-01

    The lamination of mechanically stiff structures to elastic materials is prevalent in biological systems and popular in many emerging synthetic systems, such as soft robotics, microfluidics, stretchable electronics, and pop-up assemblies. The disparate mechanical and chemical properties of these materials have made it challenging to develop universal synthetic procedures capable of reliably adhering to these classes of materials together. Herein, a simple and scalable procedure is described that is capable of covalently laminating a variety of commodity ("off-the-shelf") thermoplastic sheets to silicone rubber films. When combined with laser printing, the nonbonding sites can be "printed" onto the thermoplastic sheets, enabling the direct fabrication of microfluidic systems for actuation and liquid handling applications. The versatility of this approach in generating thin, multifunctional laminates is demonstrated through the fabrication of milliscale soft actuators and grippers with hinged articulation and microfluidic channels with built-in optical filtering and pressure-dependent geometries. This method of fabrication offers several advantages, including technical simplicity, process scalability, design versatility, and material diversity. The concepts and strategies presented herein are broadly applicable to the soft robotics, microfluidics, and advanced and additive manufacturing communities where hybrid rubber/plastic structures are prevalent. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Kinetics of rapid covalent bond formation of aniline with humic acid: ESR investigations with nitroxide spin labels

    Science.gov (United States)

    Glinka, Kevin; Matthies, Michael; Theiling, Marius; Hideg, Kalman; Steinhoff, Heinz-Jürgen

    2016-04-01

    Sulfonamide antibiotics used in livestock farming are distributed to farmland by application of slurry as fertilizer. Previous work suggests rapid covalent binding of the aniline moiety to humic acids found in soil. In the current work, kinetics of this binding were measured in X-band EPR spectroscopy by incubating Leonardite humic acid (LHA) with a paramagnetic aniline spin label (anilino-NO (2,5,5-Trimethyl-2-(3-aminophenyl)pyrrolidin-1-oxyl)). Binding was detected by a pronounced broadening of the spectral lines after incubation of LHA with anilino-NO. The time evolution of the amplitude of this feature was used for determining the reaction kinetics. Single- and double-exponential models were fitted to the data obtained for modelling one or two first-order reactions. Reaction rates of 0.16 min-1 and 0.012 min-1, were found respectively. Addition of laccase peroxidase did not change the kinetics but significantly enhanced the reacting fraction of anilino-NO. This EPR-based method provides a technically simple and effective method for following rapid binding processes of a xenobiotic substance to humic acids.

  1. Preparation of catalytically active, covalent α-polylysine-enzyme conjugates via UV/vis-quantifiable bis-aryl hydrazone bond formation.

    Science.gov (United States)

    Grotzky, Andrea; Manaka, Yuichi; Kojima, Taisuke; Walde, Peter

    2011-01-10

    Covalent UV/vis-quantifiable bis-aryl hydrazone bond formation was investigated for the preparation of conjugates between α-poly-d-lysine (PDL) and either α-chymotrypsin (α-CT) or horseradish peroxidase (HRP). PDL and the enzymes were first modified via free amino groups with the linking reagents succinimidyl 6-hydrazinonicotinate acetone hydrazone (S-HyNic, at pH 7.6) and succinimidyl 4-formylbenzoate (S-4FB, at pH 7.2), respectively. The modified PDL and enzymes were then conjugated at pH 4.7, whereby polymer chains carrying several enzymes were obtained. Kinetics of the bis-aryl hydrazone bond formation was investigated spectrophotometrically at 354 nm. Retention of the enzymatic activity after conjugate formation was confirmed by using the substrates N-succinimidyl-l-Ala-l-Ala-l-Pro-l-Phe-p-nitroanilide (for α-CT) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS, for HRP). Thus, not only a mild and efficient preparation and convenient quantification of a conjugate between the polycationic α-polylysine and enzymes could be shown, but also the complete preservation of the enzymatic activity.

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

    International Nuclear Information System (INIS)

    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(C4α)-OOH intermediate. Strikingly, the 8α 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.

  3. 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.

  4. Direct Covalent Grafting of Phytate to Titanium Surfaces through Ti-O-P Bonding Shows Bone Stimulating Surface Properties and Decreased Bacterial Adhesion.

    Science.gov (United States)

    Córdoba, Alba; Hierro-Oliva, Margarita; Pacha-Olivenza, Miguel Ángel; Fernández-Calderón, María Coronada; Perelló, Joan; Isern, Bernat; González-Martín, María Luisa; Monjo, Marta; Ramis, Joana M

    2016-05-11

    Myo-inositol hexaphosphate, also called phytic acid or phytate (IP6), is a natural molecule abundant in vegetable seeds and legumes. Among other functions, IP6 inhibits bone resorption. It is adsorbed on the surface of hydroxyapatite, inhibiting its dissolution and decreasing the progressive loss of bone mass. We present here a method to directly functionalize Ti surfaces covalently with IP6, without using a cross-linker molecule, through the reaction of the phosphate groups of IP6 with the TiO2 layer of Ti substrates. The grafting reaction consisted of an immersion in an IP6 solution to allow the physisorption of the molecules onto the substrate, followed by a heating step to obtain its chemisorption, in an adaptation of the T-Bag method. The reaction was highly dependent on the IP6 solution pH, only achieving a covalent Ti-O-P bond at pH 0. We evaluated two acidic pretreatments of the Ti surface, to increase its hydroxylic content, HNO3 30% and HF 0.2%. The structure of the coated surfaces was characterized by X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and ellipsometry. The stability of the IP6 coating after three months of storage and after sterilization with γ-irradiation was also determined. Then, we evaluated the biological effect of Ti-IP6 surfaces in vitro on MC3T3-E1 osteoblastic cells, showing an osteogenic effect. Finally, the effect of the surfaces on the adhesion and biofilm viability of oral microorganisms S. mutans and S. sanguinis was also studied, and we found that Ti-IP6 surfaces decreased the adhesion of S. sanguinis. A surface that actively improves osseointegration while decreasing the bacterial adhesion could be suitable for use in bone implants.

  5. Synthesis and Crystal Structure of a Three—dimensionla Manganese(Ⅱ)Complex COnstructed via Covalent and Hydrogen Bonds

    Institute of Scientific and Technical Information of China (English)

    WANGRui-Hu; ChenLi-Hua; 等

    2003-01-01

    The assembly of 1,4-benzenedicarboxylic acid (H2bdc),4,4′-bipyridine (4,4′-bipy),trimethyltin chloride and MnBr2.4H2O in hydrothermal conditions gave rise to a hydrogen-bonded three-dimensional complex {Mn(4,4′-bipy).4H2O](bdc}nwhich has been characterized by single-crystal X-ray diffraction.The complex crystallizes in the monoclinic system,space group,P2/n with a=7.0001(2),b=11.5540(3),c=11.4192(1)°↑A,β=101.754(2)°,V=904.21(4)°↑A3,Z=2,C18H20MnN2O8,Mr=447.30,Dc=1.643 g/cm3,F(000)=462 and μ(Mokα)=0.783mm1,The final R and wR are 0.0499 and 0.1301,respectively for 1335 observed reflctions with I≥2σ(I).The Mn(Ⅱ)is six-coordinated in a distorted octahedral geometry,4,4′-Bipyridine in a μ-bridge mode links [Mn(H2O)4]2+ into a linear cation chain.bdc acts as a counter anion and links the linear chains into a three-dimensional structure through hydrogen bonds.

  6. 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

  7. Stable Failure-Inducing Micro-Silica Aqua Epoxy Bonding Material for Floating Concrete Module Connection

    Directory of Open Access Journals (Sweden)

    Jang-Ho Jay Kim

    2015-11-01

    Full Text Available Many recent studies in the development of floating concrete structures focused on a connection system made of modules. In the connection system, the modules are designed to be attached by pre-stressing (PS while floating on the water, which exposes them to loads on the surface of the water. Therefore, the development of a pre-connection material becomes critical to ensure successful bonding of floating concrete modules. Micro-silica mixed aqua-epoxy (MSAE was developed for this task. To find the proper MSAE mix proportion, 0% to 4% micro-silica was mixed in a standard mixture of aqua-epoxy for material testing. Also, the effect of micro-silica on the viscosity of the aqua epoxy was evaluated by controlling the epoxy silane at proportions of 0%, ±5%, and ±10%. After completion of the performance tests of the MSAE, we evaluated the effect of MSAE in a connected structure. The plain unreinforced concrete module joint specimens applied with MSAE at thicknesses of 5, 10, and 20 mm were prepared to be tested. Finally, we evaluated the performance of MSAE-applied reinforced concrete (RC module specimens connected by PS tendons, and these were compared with those of continuous RC and non-MSAE-applied beams. The results showed that the mix of micro-silica in the aqua-epoxy changed the performance of the aqua-epoxy and the mix ratio of 2% micro-silica gave a stable failure behavior. The flexural capacity of concrete blocks bonded with MSAE changed according to the bond thickness and was better than that of concrete blocks bonded with aqua-epoxy without micro-silica. Even though MSAE insignificantly increases the load-carrying capacity of the attached concrete module structure, the stress concentration reduction effect stabilized the failure of the structure.

  8. Toward "stable-on-the-table" enzymes: improving key properties of catalase by covalent conjugation with poly(acrylic acid).

    Science.gov (United States)

    Riccardi, Caterina M; Cole, Kyle S; Benson, Kyle R; Ward, Jessamyn R; Bassett, Kayla M; Zhang, Yiren; Zore, Omkar V; Stromer, Bobbi; Kasi, Rajeswari M; Kumar, Challa V

    2014-08-20

    Several key properties of catalase such as thermal stability, resistance to protease degradation, and resistance to ascorbate inhibition were improved, while retaining its structure and activity, by conjugation to poly(acrylic acid) (PAA, Mw 8000) via carbodiimide chemistry where the amine groups on the protein are appended to the carboxyl groups of the polymer. Catalase conjugation was examined at three different pH values (pH 5.0, 6.0, and 7.0) and at three distinct mole ratios (1:100, 1:500, and 1:1000) of catalase to PAA at each reaction pH. The corresponding products are labeled as Cat-PAA(x)-y, where x is the protein to polymer mole ratio and y is the pH used for the synthesis. The coupling reaction consumed about 60-70% of the primary amines on the catalase; all samples were completely water-soluble and formed nanogels, as evidenced by gel electrophoresis and electron microscopy. The UV circular dichroism (CD) spectra indicated substantial retention of protein secondary structure for all samples, which increased to 100% with increasing pH of the synthesis and polymer mole fraction. Soret CD bands of all samples indicated loss of ∼50% of band intensities, independent of the reaction pH. Catalytic activities of the conjugates increased with increasing synthesis pH, where 55-80% and 90-100% activity was retained for all samples synthesized at pH 5.0 and pH 7.0, respectively, and the Km or Vmax values of Cat-PAA(100)-7 did not differ significantly from those of the free enzyme. All conjugates synthesized at pH 7.0 were thermally stable even when heated to ∼85-90 °C, while native catalase denatured between 55 and 65 °C. All conjugates retained 40-90% of their original activities even after storing for 10 weeks at 8 °C, while unmodified catalase lost all of its activity within 2 weeks, under similar storage conditions. Interestingly, PAA surrounding catalase limited access to the enzyme from large molecules like proteases and significantly increased

  9. In-situ determination of amine/epoxy and carboxylic/epoxy exothermic heat of reaction on surface of modified carbon nanotubes and structural verification of covalent bond formation

    Science.gov (United States)

    Neves, Juliana C.; de Castro, Vinícius G.; Assis, Ana L. S.; Veiga, Amanda G.; Rocco, Maria Luiza M.; Silva, Glaura G.

    2018-04-01

    An effective nanofiller-matrix interaction is considered crucial to produce enhanced nanocomposites. Nevertheless, there is lack of experiments focused in the direct measurement of possible filler-matrix covalent linkage, which was the main goal of this work for a carbon nanotube (CNT)/epoxy system. CNT were functionalized with oxygenated (ox) functions and further with triethylenetetramine (TETA). An in-situ determination methodology of epoxy-CNTs heat of reaction was developed by Differential Scanning Calorimetry (DSC). Values of -(8.7 ± 0.4) and -(6.0 ± 0.6) J/g were observed for epoxy with CNT-ox and CNT-TETA, respectively. These results confirm the occurrence of covalent bonds for both functionalized CNTs, a very important information due to the literature generally disregard this possibility for oxygenated functions. The higher value obtained for CNT-ox can be attributed to a not complete amidation and to steric impediments in the CNT-TETA structure. The modified CNTs produced by DSC experiments were then characterized by X-Ray Photoelectron Spectroscopy, Transmission Electron Microscopy and Thermogravimetry, which confirmed the covalent linkage. This characterization methodology can be used to verify the occurrence of covalent bonds in various nanocomposites with a quantitative evaluation, providing data for better understanding of the role of CNT functional groups and for tailoring its interface with polymers.

  10. 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

    Science.gov (United States)

    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.

  11. Stable Au–C bonds to the substrate for fullerene-based nanostructures

    Directory of Open Access Journals (Sweden)

    Taras Chutora

    2017-05-01

    Full Text Available We report on the formation of fullerene-derived nanostructures on Au(111 at room temperature and under UHV conditions. After low-energy ion sputtering of fullerene films deposited on Au(111, bright spots appear at the herringbone corner sites when measured using a scanning tunneling microscope. These features are stable at room temperature against diffusion on the surface. We carry out DFT calculations of fullerene molecules having one missing carbon atom to simulate the vacancies in the molecules resulting from the sputtering process. These modified fullerenes have an adsorption energy on the Au(111 surface that is 1.6 eV higher than that of C60 molecules. This increased binding energy arises from the saturation by the Au surface of the bonds around the molecular vacancy defect. We therefore interpret the observed features as adsorbed fullerene-derived molecules with C vacancies. This provides a pathway for the formation of fullerene-based nanostructures on Au at room temperature.

  12. 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

  13. Dynamic covalent gels assembled from small molecules:from discrete gelators to dynamic covalent polymers

    Institute of Scientific and Technical Information of China (English)

    Jian-Yong Zhang; Li-Hua Zeng; Juan Feng

    2017-01-01

    Dynamic covalent chemistry has emerged recently to be a powerful tool to construct functional materials.This article reviews the progress in the research and development of dynamic covalent chemistry in gels assembled from small molecules.First dynamic covalent reactions used in gels are reviewed to understand the dynamic covalent bonding.Afterwards the catalogues of dynamic covalent gels are reviewed according to the nature of gelators and the interactions between gelators.Dynamic covalent bonding can be involved to form low molecular weight gelators.Low molecular weight molecules with multiple functional groups react to form dynamic covalent cross-linked polymers and act as gelators.Two catalogues of gels show different properties arising from their different structures.This review aims to illustrate the structure-property relationships of these dynamic covalent gels.

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

    International Nuclear Information System (INIS)

    Xiong, Shanxin; Li, Zhufeng; Gong, Ming; Wang, Xiaoqin; Fu, Jialun; Shi, Yujing; Wu, Bohua; Chu, Jia

    2014-01-01

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

  15. 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...

  16. The propeptide is required for in vivo formation of stable active yeast proteinase A and can function even when not covalently linked to the mature region

    DEFF Research Database (Denmark)

    van den Hazel, H B; Kielland-Brandt, Morten; Winther, Jakob R.

    1993-01-01

    The PEP4-encoded aspartate protease proteinase A from Saccharomyces cerevisiae is synthesized as a zymogen (Ammerer, G., Hunter, C. P., Rothman, J. H., Saari, G. C., Valls, L. A., and Stevens, T. H. (1986) Mol. Cell. Biol. 6, 2490-2499; Woolford, C. A., Daniels, L. B., Park, F. J., Jones, E. W., ...... folding of the mature region, even when the propeptide and the mature region are not covalently linked....

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

    Institute of Scientific and Technical Information of China (English)

    WANG; Bingwu; XU; Guangxian; CHEN; Zhida

    2004-01-01

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

  18. On the calculation and interpretation of covalency in the intensity parameters of 4f–4f transitions in Eu{sup 3+} complexes based on the chemical bond overlap polarizability

    Energy Technology Data Exchange (ETDEWEB)

    Moura, Renaldo T., E-mail: renaldotmjr@gmail.com; Carneiro Neto, Albano N.; Longo, Ricardo L.; Malta, Oscar L.

    2016-02-15

    The concepts of chemical bond overlap polarizability (α{sub OP}) and of specific ionic valence (υ) were used to characterize the Eu{sup 3+}–ligating atom bonds in complexes. The underlying chemical bond properties, namely, bond distance, overlap integral, force constant, and the energy excitation, were successfully calculated for the Eu{sup 3+}–ligating atom diatomic-like species under the influence of the molecular environment. The quantities α{sub OP} and υ were used to reshape and reinterpret the expressions of the forced electric dipole (FED) and the dynamic coupling (DC) mechanisms responsible for the intensity parameters of 4f–4f transitions. These parameters were calculated with this new approach for a series of Eu{sup 3+} complexes: [EuL{sub 3}L′] with L=AIND, BIND, TTA, BTFA, FOD, ABSe, ABSeCl, DPM and L′=(H{sub 2}O){sub 2}, NO{sub 3}, DPbpy, DBSO, TPPO, Phen, for which the experimental intensity parameters and some E{sub 00} (={sup 5}D{sub 0}→{sup 7}F{sub 0}) energies are available. Comparisons between the theoretical and experimental results suggest that this new methodology is reliable and an important step toward an approach to calculate the 4f–4f intensities free of adjustable parameters, which has been accomplished for complexes without aquo ligand. - Highlights: • New methodology to calculate intensity parameters of f–f transitions. • Inclusion of overlap polarizability (covalency) on dynamic coupling mechanism. • Analytical calculation of the charge factors in the ligand field Hamiltonian. • Step towards a parameter-free computational method for f–f intensities. • Interpretation and quantification of the intensity parameters in terms of covalency.

  19. System in biology leading to cell pathology: stable protein-protein interactions after covalent modifications by small molecules or in transgenic cells.

    Science.gov (United States)

    Malina, Halina Z

    2011-01-19

    The physiological processes in the cell are regulated by reversible, electrostatic protein-protein interactions. Apoptosis is such a regulated process, which is critically important in tissue homeostasis and development and leads to complete disintegration of the cell. Pathological apoptosis, a process similar to apoptosis, is associated with aging and infection. The current study shows that pathological apoptosis is a process caused by the covalent interactions between the signaling proteins, and a characteristic of this pathological network is the covalent binding of calmodulin to regulatory sequences. Small molecules able to bind covalently to the amino group of lysine, histidine, arginine, or glutamine modify the regulatory sequences of the proteins. The present study analyzed the interaction of calmodulin with the BH3 sequence of Bax, and the calmodulin-binding sequence of myristoylated alanine-rich C-kinase substrate in the presence of xanthurenic acid in primary retinal epithelium cell cultures and murine epithelial fibroblast cell lines transformed with SV40 (wild type [WT], Bid knockout [Bid-/-], and Bax-/-/Bak-/- double knockout [DKO]). Cell death was observed to be associated with the covalent binding of calmodulin, in parallel, to the regulatory sequences of proteins. Xanthurenic acid is known to activate caspase-3 in primary cell cultures, and the results showed that this activation is also observed in WT and Bid-/- cells, but not in DKO cells. However, DKO cells were not protected against death, but high rates of cell death occurred by detachment. The results showed that small molecules modify the basic amino acids in the regulatory sequences of proteins leading to covalent interactions between the modified sequences (e.g., calmodulin to calmodulin-binding sites). The formation of these polymers (aggregates) leads to an unregulated and, consequently, pathological protein network. The results suggest a mechanism for the involvement of small molecules

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

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

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

  1. 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

  2. Hydrogen spillover in Pt-single-walled carbon nanotube composites: formation of stable C-H bonds.

    Science.gov (United States)

    Bhowmick, Ranadeep; Rajasekaran, Srivats; Friebel, Daniel; Beasley, Cara; Jiao, Liying; Ogasawara, Hirohito; Dai, Hongjie; Clemens, Bruce; Nilsson, Anders

    2011-04-13

    Using in situ electrical conductivity and ex situ X-ray photoelectron spectroscopy (XPS) measurements, we have examined how the hydrogen uptake of single-walled carbon nanotubes (SWNTs) is influenced by the addition of Pt nanoparticles. The conductivity of platinum-sputtered single-walled carbon nanotubes (Pt-SWNTs) during molecular hydrogen exposure decreased more rapidly than that of the corresponding pure SWNTs, which supports a hydrogenation mechanism facilitated by "spillover" of dissociated hydrogen from the Pt nanoparticles. C 1s XPS spectra indicate that the Pt-SWNTs store hydrogen by means of chemisorption, that is, covalent C-H bond formation: molecular hydrogen charging at elevated pressure (8.27 bar) and room temperature yielded Pt-SWNTs with up to 16 ± 1.5 at. % sp(3)-hybridized carbon atoms, which corresponds to a hydrogen-storage capacity of 1.2 wt % (excluding the weight of Pt nanoparticles). Pt-SWNTs prepared by the Langmuir-Blodgett (LB) technique exhibited the highest Pt/SWNT ratio and also the best hydrogen uptake. © 2011 American Chemical Society

  3. Stable Au-C bonds to the substrate for fullerene-based nanostructures

    Czech Academy of Sciences Publication Activity Database

    Chutora, Taras; López, Roso Redondo Jesús R.; De La Torre Cerdeño, Bruno; Švec, Martin; Jelínek, Pavel; Vázquez, Héctor

    2017-01-01

    Roč. 8, č. 1 (2017), s. 1073-1079 ISSN 2190-4286 R&D Projects: GA ČR GA15-19672S Institutional support: RVO:68378271 Keywords : Au-C bonds * density functional theory (DFT) * fullerenes * scanning tunneling microscopy (STM) * sputtering Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.127, year: 2016

  4. Hybrid materials of SBA-16 functionalized by rare earth (Eu3+, Tb3+) complexes of modified β-diketone (TTA and DBM): Covalently bonding assembly and photophysical properties

    International Nuclear Information System (INIS)

    Li Yajuan; Yan Bing; Li Ying

    2010-01-01

    Novel mesoporous SBA-16 type of hybrids TTA-S16 and DBM-S16 were synthesized by co-condensation of modified β-diketone (TTA-Si and DBM-Si, DBM=1,3-diphenyl-1,3- propanepione, TTA=2-thenoyltrifluoroacetone) and tetraethoxysilane (TEOS) in the presence of Pluronic F127 as template, which were confirmed by FTIR, XRD, 29 Si CP-MAS NMR, and N 2 adsorption measurements. Novel organic-inorganic mesoporous luminescent hybrid containing RE 3+ (Eu 3+ , Tb 3+ ) complexes covalently attached to the functionalized ordered mesoporous SBA-16 (TTA-S16 and DBM-S16), which were designated as bpy-RE-TTA-S16 and bpy-RE-DBM-S16, were obtained by sol-gel process. The luminescence properties of these resulting materials were characterized in detail, and the results reveal that mesoporous hybrid material bpy-Eu-TTA-S16 present stronger luminescent intensities, longer lifetimes, and higher luminescent quantum efficiencies than the corresponding DBM-containing materials bpy-Eu-DBM-S16, while bpy-Tb-DBM-S16 exhibit the stronger characteristic emission of Tb 3+ and longer lifetime than the corresponding TTA-containing materials bpy-Tb-TTA-S16. - Graphical abstract: Novel organic-inorganic mesoporous luminescent hybrids containing RE 3+ complex covalently attached to the β-diketone-functionalized ordered mesoporous SBA-16, which were designated as bpy-RE-TTA-S16 and bpy-RE-DBM-S16, were obtained by sol-gel process.

  5. 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.

  6. 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

  7. Understanding the stable boron clusters: A bond model and first-principles calculations based on high-throughput screening

    International Nuclear Information System (INIS)

    Xu, Shao-Gang; Liao, Ji-Hai; Zhao, Yu-Jun; Yang, Xiao-Bao

    2015-01-01

    The unique electronic property induced diversified structure of boron (B) cluster has attracted much interest from experimentalists and theorists. B 30–40 were reported to be planar fragments of triangular lattice with proper concentrations of vacancies recently. Here, we have performed high-throughput screening for possible B clusters through the first-principles calculations, including various shapes and distributions of vacancies. As a result, we have determined the structures of B n clusters with n = 30–51 and found a stable planar cluster of B 49 with a double-hexagon vacancy. Considering the 8-electron rule and the electron delocalization, a concise model for the distribution of the 2c–2e and 3c–2e bonds has been proposed to explain the stability of B planar clusters, as well as the reported B cages

  8. Hydrophobic and electrostatic interactions between cell penetrating peptides and plasmid DNA are important for stable non-covalent complexation and intracellular delivery.

    Science.gov (United States)

    Upadhya, Archana; Sangave, Preeti C

    2016-10-01

    Cell penetrating peptides are useful tools for intracellular delivery of nucleic acids. Delivery of plasmid DNA, a large nucleic acid, poses a challenge for peptide mediated transport. The paper investigates and compares efficacy of five novel peptide designs for complexation of plasmid DNA and subsequent delivery into cells. The peptides were designed to contain reported DNA condensing agents and basic cell penetrating sequences, octa-arginine (R 8 ) and CHK 6 HC coupled to cell penetration accelerating peptides such as Bax inhibitory mutant peptide (KLPVM) and a peptide derived from the Kaposi fibroblast growth factor (kFGF) membrane translocating sequence. A tryptophan rich peptide, an analogue of Pep-3, flanked with CH 3 on either ends was also a part of the study. The peptides were analysed for plasmid DNA complexation, protection of peptide-plasmid DNA complexes against DNase I, serum components and competitive ligands by simple agarose gel electrophoresis techniques. Hemolysis of rat red blood corpuscles (RBCs) in the presence of the peptides was used as a measure of peptide cytotoxicity. Plasmid DNA delivery through the designed peptides was evaluated in two cell lines, human cervical cancer cell line (HeLa) and (NIH/3 T3) mouse embryonic fibroblasts via expression of the secreted alkaline phosphatase (SEAP) reporter gene. The importance of hydrophobic sequences in addition to cationic sequences in peptides for non-covalent plasmid DNA complexation and delivery has been illustrated. An alternative to the employment of fatty acid moieties for enhanced gene transfer has been proposed. Comparison of peptides for plasmid DNA complexation and delivery of peptide-plasmid DNA complexes to cells estimated by expression of a reporter gene, SEAP. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd.

  9. 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.

  10. K2 ZnSn3 Se8 : A Non-Centrosymmetric Zinc Selenidostannate(IV) Featuring Interesting Covalently Bonded [ZnSn3 Se8 ]2- Layer and Exhibiting Intriguing Second Harmonic Generation Activity.

    Science.gov (United States)

    Zhou, Molin; Jiang, Xingxing; Yang, Yi; Guo, Yangwu; Lin, Zheshuai; Yao, JJiyong; Wu, Yicheng

    2017-06-19

    Non-centrosymmetric zinc selenidostannate(IV) K 2 ZnSn 3 Se 8 was synthesized. It features interesting covalently bonded [ZnSn 3 Se 8 ] 2- layers with K + cations filling in the interlayer voids. The phonon spectrum was calculated to clarify its structural stability. Based on the X-ray diffraction data along with the Raman spectrum, the major bonding features of the title compound were identified. According to the UV/vis-NIR spectroscopy, K 2 ZnSn 3 Se 8 possesses a typical direct band gap of 2.10 eV, which is in good agreement with the band structure calculations. Moreover, our experimental measurements and detailed theoretical calculations reveal that K 2 ZnSn 3 Se 8 is a new phase-matchable nonlinear optical material with a powder second harmonic generation (SHG) signal about 0.6 times of that of AgGaS 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 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

  12. 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

  13. Hydrogen-bonded Three-Dimensional Networks Encapsulating One-dimensional Covalent Chains: [Cu(3-ampy)(H2O)4](SO4)·(H2O) (3-ampy = 3-Aminopyridine)

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A three-dimensional complex [Cu(3-ampy)(H2O)4](SO4)·(H2O) (3-ampy = 3-aminopyridine) has been synthesized. Crystallographic data: C5H16CuN2O9S, Mr = 343.80, triclinic, space group P, a = 7.675(2), b = 8.225(3), c = 10.845(3) (A), α= 86.996(4), β = 76.292(4),γ = 68.890(4)°, V = 620.0(3) (A)3, Z = 2, Dc = 1.841 g/cm3, F(000) = 354 and μ = 1.971 mm-1. The structure was refined to R = 0.0269 and wR = 0.0659 for 1838 observed reflections (I > 2σ(Ⅰ)). The structure consists of [Cu(3-ampy)(H2O)4]2+ cations, SO42- anions and lattice water molecules. 3-Ampy acting as a bidentate bridging ligand generates a 1D covalent chain. A supramolecular 2D framework is formed through π-π stacking of pyridine rings. The lattice water molecules and SO42- anions are located between the adjacent 2D frameworks. The hydrogen bonding interactions from lattice water molecules and SO42- anions to coordinate water extend the 2D framework into a 3D network.

  14. 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)

  15. 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.

  16. Molecular electrostatic potential analysis of non-covalent complexes

    Indian Academy of Sciences (India)

    Chemical Sciences and Technology Division and Academy of Scientific & Innovative Research (AcSIR), ... workers proposed the electrostatic-covalent model of hydrogen bonding. ..... tain degree of electron donation and acceptance occurs.

  17. Biofriendly bonding processes for nanoporous implantable SU-8 microcapsules for encapsulated cell therapy.

    Science.gov (United States)

    Nemani, Krishnamurthy; Kwon, Joonbum; Trivedi, Krutarth; Hu, Walter; Lee, Jeong-Bong; Gimi, Barjor

    2011-01-01

    Mechanically robust, cell encapsulating microdevices fabricated using photolithographic methods can lead to more efficient immunoisolation in comparison to cell encapsulating hydrogels. There is a need to develop adhesive bonding methods which can seal such microdevices under physiologically friendly conditions. We report the bonding of SU-8 based substrates through (i) magnetic self assembly, (ii) using medical grade photocured adhesive and (iii) moisture and photochemical cured polymerization. Magnetic self-assembly, carried out in biofriendly aqueous buffers, provides weak bonding not suitable for long term applications. Moisture cured bonding of covalently modified SU-8 substrates, based on silanol condensation, resulted in weak and inconsistent bonding. Photocured bonding using a medical grade adhesive and of acrylate modified substrates provided stable bonding. Of the methods evaluated, photocured adhesion provided the strongest and most stable adhesion.

  18. Remendable Polymeric Materials Using Reversible Covalent Bonds

    Science.gov (United States)

    2008-12-01

    response in poly(ethylene-co-methacrylic acid ) copolymers. Journal of The Royal Society Interface, 4, 405-411. Kavitha, A. A., and N. K. Singha...2007: A tailor-made polymethacrylate bearing a reactive diene in reversible diels-alder reaction. J. Polym. Sci. A Polym. Chem., 45, 4441-4449

  19. 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

  20. Covalent immobilization of lipase from Candida rugosa on Eupergit®

    Directory of Open Access Journals (Sweden)

    Bezbradica Dejan I.

    2005-01-01

    Full Text Available An approach is presented for the stable covalent immobilization of Upase from Candida rugosa on Eupergit® with a high retention of hydrolytic activity. It comprises covalent bonding via lipase carbohydrate moiety previously modified by periodate oxidation, allowing a reduction in the involvement of the enzyme functional groups that are probably important in the catalytic mechanism. The hydrolytic activities of the lipase immobilized on Eupergif1 by two conventional methods (via oxirane group and via glutaralde-hyde and with periodate method were compared. Results of lipase assays suggest that periodate method is superior for lipase immobilization on Eupergit® among methods applied in this study with respect to both, yield of immobilization and hydrolytic activity of the immobilized enzyme.

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

    Directory of Open Access Journals (Sweden)

    Tine N Vinther

    Full Text Available 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 in the circulation, and it is stabilized by hexamer formation in the presence of zinc ions during storage in the pancreatic β-cell. Due to the transient nature of insulin dimer, direct investigation of this important form is inherently difficult. To address the relationship between insulin oligomerization 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 to form the structural equivalent of the classical hexamer. The covalently linked dimer neither bound to the insulin receptor, nor induced a metabolic response in vitro. However, it was extremely thermodynamically stable and did not form amyloid fibrils when subjected to mechanical stress, underlining the importance of oligomerization for insulin stability.

  2. Structural and catalytic characterization of a thermally stable and acid-stable variant of human carbonic anhydrase II containing an engineered disulfide bond

    Energy Technology Data Exchange (ETDEWEB)

    Boone, Christopher D.; Habibzadegan, Andrew [University of Florida, PO Box 100245, Gainesville, FL 32610 (United States); Tu, Chingkuang; Silverman, David N. [University of Florida, PO Box 100267, Gainesville, FL 32610 (United States); McKenna, Robert, E-mail: rmckenna@ufl.edu [University of Florida, PO Box 100245, Gainesville, FL 32610 (United States)

    2013-08-01

    The X-ray crystallographic structure of the disulfide-containing HCAII (dsHCAII) has been solved to 1.77 Å resolution and revealed that successful oxidation of the cysteine bond was achieved while also retaining desirable active-site geometry. The carbonic anhydrases (CAs) are a family of mostly zinc metalloenzymes that catalyze the reversible hydration of CO{sub 2} to bicarbonate and a proton. Recently, there has been industrial interest in utilizing CAs as biocatalysts for carbon sequestration and biofuel production. The conditions used in these processes, however, result in high temperatures and acidic pH. This unfavorable environment results in rapid destabilization and loss of catalytic activity in CAs, ultimately resulting in cost-inefficient high-maintenance operation of the system. In order to negate these detrimental industrial conditions, cysteines at residues 23 (Ala23Cys) and 203 (Leu203Cys) were engineered into a wild-type variant of human CA II (HCAII) containing the mutation Cys206Ser. The X-ray crystallographic structure of the disulfide-containing HCAII (dsHCAII) was solved to 1.77 Å resolution and revealed that successful oxidation of the cysteine bond was achieved while also retaining desirable active-site geometry. Kinetic studies utilizing the measurement of {sup 18}O-labeled CO{sub 2} by mass spectrometry revealed that dsHCAII retained high catalytic efficiency, and differential scanning calorimetry showed acid stability and thermal stability that was enhanced by up to 14 K compared with native HCAII. Together, these studies have shown that dsHCAII has properties that could be used in an industrial setting to help to lower costs and improve the overall reaction efficiency.

  3. Covalent Functionalization of Carbon Nanotube by Tetrasubtituted Amino Manganese Phthalocyanine

    Institute of Scientific and Technical Information of China (English)

    Zheng Long YANG; Hong Zheng CHEN; Lei CAO; Han Yin LI; Mang WANG

    2004-01-01

    The multiwall carbon nanotube (MWCNT) bonded to 2, 9, 16, 23-tetraamino manganese phthalocyanine (TAMnPc) was obtained by covalent functionalization, and its chemical structure was characterized by TEM. The photoconductivity of single-layered photoreceptors, where MWCNT bonded by TAMnPc (MWCNT-b-TAMnPc) served as the charge generation material (CGM), was also studied.

  4. 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

    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......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...

  5. 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.

  6. α-Actinin/titin interaction: A dynamic and mechanically stable cluster of bonds in the muscle Z-disk.

    Science.gov (United States)

    Grison, Marco; Merkel, Ulrich; Kostan, Julius; Djinović-Carugo, Kristina; Rief, Matthias

    2017-01-31

    Stable anchoring of titin within the muscle Z-disk is essential for preserving muscle integrity during passive stretching. One of the main candidates for anchoring titin in the Z-disk is the actin cross-linker α-actinin. The calmodulin-like domain of α-actinin binds to the Z-repeats of titin. However, the mechanical and kinetic properties of this important interaction are still unknown. Here, we use a dual-beam optical tweezers assay to study the mechanics of this interaction at the single-molecule level. A single interaction of α-actinin and titin turns out to be surprisingly weak if force is applied. Depending on the direction of force application, the unbinding forces can more than triple. Our results suggest a model where multiple α-actinin/Z-repeat interactions cooperate to ensure long-term stable titin anchoring while allowing the individual components to exchange dynamically.

  7. Computational study of the signature of hydrogen-bond strength on the infrared spectra of a hydrogen-bonded complex dissolved in a polar liquid

    International Nuclear Information System (INIS)

    Hanna, Gabriel; Geva, Eitan

    2010-01-01

    The signature of hydrogen-bond strength on the one- and two-dimensional infrared spectra of the hydrogen-stretch in a hydrogen-bonded complex dissolved in a polar liquid was investigated via mixed quantum-classical molecular dynamics simulations. Non-Condon effects were found to intensify with increasing hydrogen-bond strength and to shift oscillator strength from the stable configurations that correspond to the ionic and covalent tautomers into unstable configurations that correspond to the transition-state between them. The transition-state peak is observed to blue shift and increase in intensity with increasing hydrogen-bond strength, and to dominate the spectra in the case of a strong hydrogen-bond. It is argued that the application of multidimensional infrared spectroscopy in the region of the transition-state peak can provide a uniquely direct probe of the molecular events underlying breaking and forming of hydrogen-bonds in the condensed phase.

  8. Electronic basis of hardness and phase transformations (covalent crystals)

    International Nuclear Information System (INIS)

    Gilman, J J

    2008-01-01

    Several electronic parameters measure the stabilities of covalent crystals, including minimum energy band-gap densities, inverse polarizabilities, plasma frequencies, transverse vibrational frequencies and elastic shear moduli. Convenient is the band-gap density (energy/volume; called the 'bond modulus'). For a given bonding type, the indentation hardness is proportional to the bond modulus. Examples are the group IV elements, III-V compounds; and II-VI compounds. The motion of dislocation kinks requires the excitation of bonding electrons into anti-bonding states. The bond modulus measures this together with the work done by the applied stress when a kink moves. In addition to hardness, the bond modulus measures the compressive strain (pressure) needed to transform an ambient structure into a more dense structure. Activation of such transformations also requires the excitation of bonding electrons into anti-bonding states together with the work done by the compressive stress

  9. A covalent attraction between two molecular cation TTF·~+

    Institute of Scientific and Technical Information of China (English)

    WANG FangFang; WANG Yi; WANG BingQiang; WANG YinFeng; MA Fang; Li ZhiRu

    2009-01-01

    The optimized structure of the tetrathiafulvalence radical-cation dimer (TTF·~+-TTF·~+) with all-real frequencies is obtained at MP2/6-311G level,which exhibits the attraction between two molecular cation TTF·~+.The new attraction interaction is a 20-center-2-electron intermolecular covalent π/π bonding with a telescope shape.The covalent π/π bonding has the bonding energy of about-21 kcal·mol~(-1) and is concealed by the Coulombic repulsion between two TTF·~+ cations.This intermolecular covalent attraction also influences the structure of the TTF·~+ subunit,I.e.,its molecular plane is bent by an angle θ=5.6°.This work provides new knowledge on intermolecular interaction.

  10. A covalent attraction between two molecular cation TTF·~+

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The optimized structure of the tetrathiafulvalence radical-cation dimer(TTF·+-TTF·+) with all-real frequencies is obtained at MP2/6-311G level,which exhibits the attraction between two molecular cation TTF·+.The new attraction interaction is a 20-center-2-electron intermolecular covalent π /π bonding with a telescope shape.The covalent π /π bonding has the bonding energy of about -21 kcal·mol-1 and is concealed by the Coulombic repulsion between two TTF·+ cations.This intermolecular covalent attraction also influences the structure of the TTF·+ subunit,i.e.,its molecular plane is bent by an angle θ=5.6°.This work provides new knowledge on intermolecular interaction.

  11. 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)

  12. Evaluation of a novel enzyme-linked immunosorbent assay for detection of antibodies against Salmonella, employing a stable coating of lipopolysaccharide-derived antigens covalently attached to polystyrene microwells

    DEFF Research Database (Denmark)

    Wiuff, C.; Jauho, E. S.; Stryhn, H.

    2000-01-01

    to microtiter polystyrene plates by ultraviolet irradiation. Both polysaccharide antigens could be coupled simultaneously to the same microtiter plate. The coated surface was used in indirect ELISA for the determination of serum antibodies from pigs infected with bacteria of the two Salmonella groups and from......Polysaccharides derived from Salmonella typhimurium lipopolysaccharide (LPS) representing the O-antigen factors 1, 4, 5, and 12 and the O-antigen factors 6 and 7 from Salmonella choleraesuis LPS were derivatized with the photoreactive compound anthraquinone and subsequently covalently coupled...

  13. Surface passivation for tight-binding calculations of covalent solids

    International Nuclear Information System (INIS)

    Bernstein, N

    2007-01-01

    Simulation of a cluster representing a finite portion of a larger covalently bonded system requires the passivation of the cluster surface. We compute the effects of an explicit hybrid orbital passivation (EHOP) on the atomic structure in a model bulk, three-dimensional, narrow gap semiconductor, which is very different from the wide gap, quasi-one-dimensional organic molecules where most passivation schemes have been studied in detail. The EHOP approach is directly applicable to minimal atomic orbital basis methods such as tight-binding. Each broken bond is passivated by a hybrid created from an explicitly expressed linear combination of basis orbitals, chosen to represent the contribution of the missing neighbour, e.g. a sp 3 hybrid for a single bond. The method is tested by computing the forces on atoms near a point defect as a function of cluster geometry. We show that, compared to alternatives such as pseudo-hydrogen passivation, the force on an atom converges to the correct bulk limit more quickly as a function of cluster radius, and that the force is more stable with respect to perturbations in the position of the cluster centre. The EHOP method also obviates the need for parameterizing the interactions between the system atoms and the passivating atoms. The method is useful for cluster calculations of non-periodic defects in large systems and for hybrid schemes that simulate large systems by treating finite regions with a quantum-mechanical model, coupled to an interatomic potential description of the rest of the system

  14. Magnesium and cadmium in covalently-bonded Lonsdaleite networks: Synthesis, structure, and conding of AETMg{sub 2} and SrTCd{sub 2} (AE = Ca, Sr; T = Pd, Ag, Pt, Au)

    Energy Technology Data Exchange (ETDEWEB)

    Kersting, Marcel; Johnscher, Michael; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster, Corrensstrasse 30, 48149 Muenster (Germany); Matar, Samir F. [Universite Bordeaux, ICMCB, UPR 9048, 33600 Pessac (France)

    2013-04-15

    The alkaline earth metal compounds AETMg{sub 2} and AETCd{sub 2} (AE = Ca, Sr; T = Pd, Ag, Pt, Au) were synthesized by induction-melting (or in muffle furnaces) of the elements in sealed niobium ampoules. The new phases were characterized by powder X-ray diffraction. The structures of SrPdMg{sub 2} and SrPdCd{sub 2} were investigated by X-ray diffraction on single crystals: MgCuAl{sub 2} type, Cmcm, a = 436.42(4), b = 1130.1(1), c = 820.54(7) pm, wR{sub 2} = 0.0115, 511 F{sup 2} values for SrPdMg{sub 2} and a = 443.5(2), b = 1063.0(2), c = 810.2(2) pm, wR{sub 2} = 0.0296, 386 F{sup 2} values for SrPdCd{sub 2} with 16 variables for each refinement. The magnesium and cadmium atoms build up [TMg{sub 2}] and [TCd{sub 2}] polyanionic networks, which leave cavities for the calcium and strontium atoms. The bonding variations within the polyanions, which are mainly influenced by the length of the b axis are discussed. Ab initio calculations of electronic structure, charge densities, and chemical bonding, characterize SrPdMg{sub 2} with a larger cohesive energy than SrPdCd{sub 2}. This is illustrated by larger bonding Pd-Mg interactions, opposite to compensating Pd-Cd between bonding and antibonding states. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Water-Stable Metal-Organic Framework with Three Hydrogen-Bond Acceptors: Versatile Theoretical and Experimental Insights into Adsorption Ability and Thermo-Hydrolytic Stability.

    Science.gov (United States)

    Roztocki, Kornel; Lupa, Magdalena; Sławek, Andrzej; Makowski, Wacław; Senkovska, Irena; Kaskel, Stefan; Matoga, Dariusz

    2018-03-19

    A new microporous cadmium metal-organic framework was synthesized both mechanochemically and in solution by using a sulfonyl-functionalized dicarboxylate linker and an acylhydrazone colinker. The three-dimensional framework is highly stable upon heating to 300 °C as well as in aqueous solutions at elevated temperatures or acidic conditions. The thermally activated material exhibits steep water vapor uptake at low relative pressures at 298 K and excellent recyclability up to 260 °C as confirmed by both quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) method as well as adsorption isotherm measurements. Reversible isotherms and hysteretic isobars recorded for the desorption-adsorption cycles indicate the maximum uptake of 0.19 g/g (at 298 K, up to p/p 0 = 1) or 0.18 g/g (at 1 bar, within 295-375 K range), respectively. The experimental isosteric heat of adsorption (48.9 kJ/mol) indicates noncoordinative interactions of water molecules with the framework. Exchange of the solvent molecules in the as-made material with water, performed in the single-crystal to single-crystal manner, allows direct comparison of both X-ray crystal structures. The single-crystal X-ray diffraction for the water-loaded framework demonstrates the orientation of water clusters in the framework cavities and reveals their strong hydrogen bonding with sulfonyl, acyl, and carboxylate groups of the two linkers. The grand canonical Monte Carlo (GCMC) simulations of H 2 O adsorption corroborate the experimental findings and reveal preferable locations of guest molecules in the framework voids at various pressures. Additionally, both experimental and GCMC simulation insights into the adsorption of CO 2 (at 195 K) on the activated framework are presented.

  16. 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.

  17. Tough Self-Healing Elastomers by Molecular Enforced Integration of Covalent and Reversible Networks.

    Science.gov (United States)

    Wu, Jinrong; Cai, Li-Heng; Weitz, David A

    2017-10-01

    Self-healing polymers crosslinked by solely reversible bonds are intrinsically weaker than common covalently crosslinked networks. Introducing covalent crosslinks into a reversible network would improve mechanical strength. It is challenging, however, to apply this concept to "dry" elastomers, largely because reversible crosslinks such as hydrogen bonds are often polar motifs, whereas covalent crosslinks are nonpolar motifs. These two types of bonds are intrinsically immiscible without cosolvents. Here, we design and fabricate a hybrid polymer network by crosslinking randomly branched polymers carrying motifs that can form both reversible hydrogen bonds and permanent covalent crosslinks. The randomly branched polymer links such two types of bonds and forces them to mix on the molecular level without cosolvents. This enables a hybrid "dry" elastomer that is very tough with fracture energy 13500 Jm -2 comparable to that of natural rubber. Moreover, the elastomer can self-heal at room temperature with a recovered tensile strength 4 MPa, which is 30% of its original value, yet comparable to the pristine strength of existing self-healing polymers. The concept of forcing covalent and reversible bonds to mix at molecular scale to create a homogenous network is quite general and should enable development of tough, self-healing polymers of practical usage. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. COVALENTLY ATTACHED MULTILAYER ULTRA-THIN FILMS FROM DIAZORESIN AND CALIXARENES

    Institute of Scientific and Technical Information of China (English)

    Zhao-hui Yang; Wei-xiao Cao

    2003-01-01

    A kind of photosensitive ultra-thin film was fabricated from diazoresin (DR) and various calixarenes by using the self-assembly technique. Under UV irradiation both the ionic- and hydrogen bonds between the layers of the film will convert into covalent bonds. As a result, the stability of the film toward polar solvents increases dramatically.

  19. Nitroxide stable radicals interacting as Lewis bases in hydrogen bonds: A search in the Cambridge structural data base for intermolecular contacts

    Science.gov (United States)

    Alkorta, Ibon; Elguero, José; Elguero, Eric

    2017-11-01

    1125 X-ray structures of nitroxide free radicals presenting intermolecular hydrogen bonds have been reported in the Cambridge Structural Database. We will report in this paper a qualitative and quantitative analysis of these bonds. The observation in some plots of an excluded region was statistically analyzed using convex hull and kernel smooting methodologies. A theoretical study at the MP2 level with different basis has been carried out indicating that the nitronyl nitroxide radicals (five electrons) lie just in between nitroso compounds (four electrons) and amine N-oxides (six electrons) as far as hydrogen-bond basicity is concerned.

  20. Novel hydroxyapatite biomaterial covalently linked to raloxifene.

    Science.gov (United States)

    Meme, L; Santarelli, A; Marzo, G; Emanuelli, M; Nocini, P F; Bertossi, D; Putignano, A; Dioguardi, M; Lo Muzio, L; Bambini, F

    2014-01-01

    Since raloxifene, a drug used in osteoporosis therapy, inhibits osteoclast, but not osteoblast functions, it has been suggested to improve recovery during implant surgery. The present paper describes an effective method to link raloxifene, through a covalent bond, to a nano-Hydroxyapatite-based biomaterial by interfacing with (3-aminopropyl)-Triethoxysilane as assessed by Infra Red-Fourier Transformed (IR-FT) spectroscopy and Scanning Electron Microscope (SEM). To evaluate the safety of this modified new material, the vitality of osteoblast-like cells cultured with the new biomaterial was then investigated. Raloxifene-conjugated HAbiomaterial has been shown to be a safe material easy to obtain which could be an interesting starting point for the use of a new functional biomaterial suitable in bone regeneration procedures.

  1. A tensegrity model for hydrogen bond networks in proteins

    Directory of Open Access Journals (Sweden)

    Robert P. Bywater

    2017-05-01

    Full Text Available Hydrogen-bonding networks in proteins considered as structural tensile elements are in balance separately from any other stabilising interactions that may be in operation. The hydrogen bond arrangement in the network is reminiscent of tensegrity structures in architecture and sculpture. Tensegrity has been discussed before in cells and tissues and in proteins. In contrast to previous work only hydrogen bonds are studied here. The other interactions within proteins are either much stronger − covalent bonds connecting the atoms in the molecular skeleton or weaker forces like the so-called hydrophobic interactions. It has been demonstrated that the latter operate independently from hydrogen bonds. Each category of interaction must, if the protein is to have a stable structure, balance out. The hypothesis here is that the entire hydrogen bond network is in balance without any compensating contributions from other types of interaction. For sidechain-sidechain, sidechain-backbone and backbone-backbone hydrogen bonds in proteins, tensegrity balance (“closure” is required over the entire length of the polypeptide chain that defines individually folding units in globular proteins (“domains” as well as within the repeating elements in fibrous proteins that consist of extended chain structures. There is no closure to be found in extended structures that do not have repeating elements. This suggests an explanation as to why globular domains, as well as the repeat units in fibrous proteins, have to have a defined number of residues. Apart from networks of sidechain-sidechain hydrogen bonds there are certain key points at which this closure is achieved in the sidechain-backbone hydrogen bonds and these are associated with demarcation points at the start or end of stretches of secondary structure. Together, these three categories of hydrogen bond achieve the closure that is necessary for the stability of globular protein domains as well as repeating

  2. A tensegrity model for hydrogen bond networks in proteins.

    Science.gov (United States)

    Bywater, Robert P

    2017-05-01

    Hydrogen-bonding networks in proteins considered as structural tensile elements are in balance separately from any other stabilising interactions that may be in operation. The hydrogen bond arrangement in the network is reminiscent of tensegrity structures in architecture and sculpture. Tensegrity has been discussed before in cells and tissues and in proteins. In contrast to previous work only hydrogen bonds are studied here. The other interactions within proteins are either much stronger - covalent bonds connecting the atoms in the molecular skeleton or weaker forces like the so-called hydrophobic interactions. It has been demonstrated that the latter operate independently from hydrogen bonds. Each category of interaction must, if the protein is to have a stable structure, balance out. The hypothesis here is that the entire hydrogen bond network is in balance without any compensating contributions from other types of interaction. For sidechain-sidechain, sidechain-backbone and backbone-backbone hydrogen bonds in proteins, tensegrity balance ("closure") is required over the entire length of the polypeptide chain that defines individually folding units in globular proteins ("domains") as well as within the repeating elements in fibrous proteins that consist of extended chain structures. There is no closure to be found in extended structures that do not have repeating elements. This suggests an explanation as to why globular domains, as well as the repeat units in fibrous proteins, have to have a defined number of residues. Apart from networks of sidechain-sidechain hydrogen bonds there are certain key points at which this closure is achieved in the sidechain-backbone hydrogen bonds and these are associated with demarcation points at the start or end of stretches of secondary structure. Together, these three categories of hydrogen bond achieve the closure that is necessary for the stability of globular protein domains as well as repeating elements in fibrous proteins.

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

    Indian Academy of Sciences (India)

    Wintec

    photographs of the dispersions of amide-functio- nalized DWNTs in dichloromethane and tetrahydro- furan. In figure 3b, we show a TEM image of DWNTs after covalent functionalization. The images are not as sharp after functionalization as in the case of pris- tine nanotubes (figure 3a), and the bundles seem to be intact.

  4. A novel amperometric biosensor based on covalently attached multilayer assemblies of gold nanoparticles, diazo-resins and acetylcholinesterase for the detection of organophosphorus pesticides.

    Science.gov (United States)

    Jiang, Bin; Dong, Pei; Zheng, Jianbin

    2018-06-01

    Using an ionic layer-by-layer self-assembly technique, colloidal gold nanoparticles (AuNPs) and diazo-resins (DAR) were immobilised on the surface of a p-aminobenzenesulfonic acid-modified glassy carbon electrode to form a matrix composite membrane for acetylcholinesterase (AChE) immobilisation. Photo-sensitive DAR was used as the assembly interlayer to convert the ionic bond into a covalent bond to improve the biosensor stability. These fabrication processes were followed by electrochemical impedance spectroscopy and cyclic voltammetry to verify the membrane formation. Because of the introduction of AuNPs/DAR/AChE biofilms, the modified electrode exhibited excellent electron transfer mediation and electrical conductivity. In addition, it exhibited high sensitivity in the range of linear concentration from 1.0 × 10 -8 to 1.0 × 10 -12 g L -1 with the detection limit of 5.12 × 10 -13 and 5.85 × 10 -13 g L -1 for malathion and methyl parathion, respectively. More importantly, the presented biosensor considerably improved stability because the electrostatic interaction was converted into covalent bonds by UV irradiation. It is a simple, cheap and stable method for quantitative detection of organophosphorus pesticides, and this method may pave a way for the sensitive, simple detection of different analytes without the need of expensive instrumentation. Copyright © 2018 Elsevier B.V. All rights reserved.

  5. Two supramolecular complexes based on polyoxometalates and Co-EDTA units via covalent connection or non-covalent interaction

    Energy Technology Data Exchange (ETDEWEB)

    Teng, Chunlin; Xiao, Hanxi [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China); Cai, Qing [Chemistry Department, City University of New York, New York, NY 10016 (United States); Tang, Jianting; Cai, Tiejun [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China); Deng, Qian, E-mail: dengqian10502@163.com [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China)

    2016-11-15

    Two new 3D network organic-inorganic hybrid supramolecular complexes ([Na{sub 6}(CoEDTA){sub 2}(H{sub 2}O){sub 13}]·(H{sub 2}SiW{sub 12}O{sub 40})·xH{sub 2}O)n (1) and [CoH{sub 4}EDTA(H{sub 2}O)]{sub 2}(SiW{sub 12}O{sub 40})·15H{sub 2}O (2) (H{sub 4}EDTA=Ethylenediamine tetraacetic acid) have been successfully synthesized by solution method, and characterized by infrared spectrum (IR), thermogravimetric-differential thermal analysis (TG-DTA), cyclic voltammetry (CV) and single{sup −}crystal X-ray diffraction (XRD). Both of the complexes are the supramolecules, but with different liking mode, they are two representative models of supramolecule. complex (1) is a 3D infinite network supramolecular coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through coordinate-covalent bonds. While complex (2) is normal supramolecule, which linked by non-covalent interactions, such as H-bonding interaction, electrostatic interaction and van der waals force. Both of complex (1) and (2) exhibit good catalytic activities for catalytic oxidation of methanol, when the initial concentration of methanol is 3.0 g m{sup −3}, flow rate is 10 mL min{sup −1}, and the quality of catalyst is 0.2 g, for complex (1) and complex (2) the maximum elimination rates of methanol are 85% (150 °C) and 92% (120 °C), respectively. - Graphical abstract: Two new organic-inorganic hybrid supramolecular complexes based on Co-EDTA, and Keggin polyanions have been successfully synthesized with different pH value by solution method. They are attributed to two representative models of supramolecule. Complex(1) is an infinite coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through covalent bonds. Complex (2) is a normal supramolecule, which linked by non-covalent interactions of H-bonding interaction, electrostatic interaction and van der waals force. - Highlights: • Two supramolecules

  6. Comparative TEM study of bonded silicon/silicon interfaces fabricated by hydrophilic, hydrophobic and UHV wafer bonding

    International Nuclear Information System (INIS)

    Reznicek, A.; Scholz, R.; Senz, S.; Goesele, U.

    2003-01-01

    Wafers of Czochralski-grown silicon were bonded hydrophilically, hydrophobically and in ultrahigh vacuum (UHV) at room temperature. Wafers bonded hydrophilically adhere together by hydrogen bonds, those bonded hydrophobically by van der Waals forces and UHV-bonded ones by covalent bonds. Annealing the pre-bonded hydrophilic and hydrophobic wafer pairs in argon for 2 h at different temperatures increases the initially low bonding energy. UHV-bonded wafer pairs were also annealed to compare the results. Transmission electron microscopy (TEM) investigations show nano-voids at the interface. The void density depends on the initial bonding strength. During annealing the shape, coverage and density of the voids change significantly

  7. 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.

  8. 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

  9. Biofunctional Paper via Covalent Modification of Cellulose

    Science.gov (United States)

    Yu, Arthur; Shang, Jing; Cheng, Fang; Paik, Bradford A.; Kaplan, Justin M.; Andrade, Rodrigo B.; Ratner, Daniel M.

    2012-01-01

    Paper-based analytical devices are the subject of growing interest for the development of low-cost point-of-care diagnostics, environmental monitoring technologies and research tools for limited-resource settings. However, there are limited chemistries available for the conjugation of biomolecules to cellulose for use in biomedical applications. Herein, divinyl sulfone (DVS) chemistry was demonstrated to covalently immobilize small molecules, proteins and DNA onto the hydroxyl groups of cellulose membranes through nucleophilic addition. Assays on modified cellulose using protein-carbohydrate and protein-glycoprotein interactions as well as oligonucleotide hybridization showed that the membrane’s bioactivity was specific, dose-dependent, and stable over a long period of time. Use of an inkjet printer to form patterns of biomolecules on DVS-activated cellulose illustrates the adaptability of the DVS functionalization technique to pattern sophisticated designs, with potential applications in cellulose-based lateral flow devices. PMID:22708701

  10. The Covalent Binding of Photosensitive Dyes to Monocrystalline Silicon Surface and Their Spectral Response

    Institute of Scientific and Technical Information of China (English)

    郭志新; 郝纪祥; 张祖训; 曹子祥

    1993-01-01

    A chemical method is proposed to bond photo-sensitive dyes directly to the surface of polished monocrystalline silicon. A methincyanine dye and a trimethincyanine dye have been bonded covalently onto silicon surface through Si—N bond, which are characterized by XPS technique and laser Raman spectra. Photovoltaic effect has been observed with the In/dye/n-Si sandwich devices composed of the dye-bonded n-Si wafers. Significant spectral response shows the characteristic absorptance maxima of the bonded dyes.

  11. Optimising hydrogen bonding in solid wood

    DEFF Research Database (Denmark)

    Engelund, Emil Tang

    2009-01-01

    The chemical bonds of wood are both covalent bonds within the wood polymers and hydrogen bonds within and between the polymers. Both types of bonds are responsible for the coherence, strength and stiffness of the material. The hydrogen bonds are more easily modified by changes in load, moisture...... and temperature distorting the internal bonding state. A problem arises when studying hydrogen bonding in wood since matched wood specimens of the same species will have very different internal bonding states. Thus, possible changes in the bonding state due to some applied treatment such as conditioning...... maintaining 100 % moisture content of the wood. The hypothesis was that this would enable a fast stress relaxation as a result of reorganization of bonds, since moisture plasticizes the material and temperature promotes faster kinetics. Hereby, all past bond distortions caused by various moisture, temperature...

  12. Protein covalent immobilization via its scarce thiol versus abundant amine groups: Effect on orientation, cell binding domain exposure and conformational lability.

    Science.gov (United States)

    Ba, O M; Hindie, M; Marmey, P; Gallet, O; Anselme, K; Ponche, A; Duncan, A C

    2015-10-01

    Quantity, orientation, conformation and covalent linkage of naturally cell adhesive proteins adsorbed or covalently linked to a surface, are known to influence the preservation of their subsequent long term cell adhesion properties and bioactivity. In the present work, we explore two different strategies for the covalent linking of plasma fibronectin (pFN) - used as a cell adhesive model protein, onto a polystyrene (PS) surface. One is aimed at tethering the protein to the surface in a semi-oriented fashion (via one of the 4 free thiol reactive groups on the protein) with a heterofunctional coupling agent (SSMPB method). The other aims to immobilize the protein in a more random fashion by reaction between the abundant pendant primary amine bearing amino acids of the pFN and activated carboxylic surface functions obtained after glutaric anhydride surface treatment (GA method). The overall goal will be to verify the hypothesis of a correlation between covalent immobilization of a model cell adhesive protein to a PS surface in a semi-oriented configuration (versus randomly oriented) with promotion of enhanced exposure of the protein's cell binding domain. This in turn would lead to enhanced cell adhesion. Ideally the goal is to elaborate substrates exhibiting a long term stable protein monolayer with preserved cell adhesive properties and bioactivity for biomaterial and/or cell adhesion commercial plate applications. However, the initial restrictive objective of this paper is to first quantitatively and qualitatively investigate the reversibly (merely adsorbed) versus covalently irreversibly bound protein to the surface after the immobilization procedure. Although immobilized surface amounts were similar (close to the monolayer range) for all immobilization approaches, covalent grafting showed improved retention and stronger "tethering" of the pFN protein to the surface (roughly 40%) after SDS rinsing compared to that for mere adsorption (0%) suggesting an added value

  13. 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.

  14. Reversible polymer networks containing covalent and hydrogen bonding interactions

    NARCIS (Netherlands)

    Araya-Hermosilla, R.; Broekhuis, A.A.; Picchioni, F.

    Thermally reversible polymers with relatively high glass transition temperatures (T-g) are difficult to prepare but very interesting from an application point of view. In this work we present a novel reversible thermoset with tunable T-g based on chemical modification of aliphatic polyketones (PM)

  15. 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.

  16. Theoretical study of ZnO adsorption and bonding on Al2O3 (0001) surface

    Institute of Scientific and Technical Information of China (English)

    LI Yanrong; YANG Chun; XUE Weidong; LI Jinshan; LIU Yonghua

    2004-01-01

    ZnO adsorption on sapphire (0001) surface is theoretically calculated by using a plane wave ultrasoft pseudo-potential method based on ab initio molecular dynamics. The results reveal that the surface relaxation in the first layer Al-O is reduced, even eliminated after the surface adsorption of ZnO, and the chemical bonding energy is 434.3(±38.6) kJ·mol-1. The chemical bond of ZnO (0.185 ± 0.01 nm) has a 30° angle away from the adjacent Al-O bond, and the stable chemical adsorption position of the Zn is deflected from the surface O-hexagonal symmetry with an angle of about 30°. The analysis of the atomic populations, density of state and bonding electronic density before and after the adsorption indicates that the chemical bond formed by the O2- of the ZnO and the surface Al3+ has a strong ionic bonding characteristic, while the chemical bond formed by the Zn2+ and the surface O2- has an obvious covalent characteristic, which comes mainly from the hybridization of the Zn 4s and the O 2p and partially from that of the Zn 3d and the O 2p.

  17. Stable electroluminescence from passivated nano-crystalline porous silicon using undecylenic acid

    Science.gov (United States)

    Gelloz, B.; Sano, H.; Boukherroub, R.; Wayner, D. D. M.; Lockwood, D. J.; Koshida, N.

    2005-06-01

    Stabilization of electroluminescence from nanocrystalline porous silicon diodes has been achieved by replacing silicon-hydrogen bonds terminating the surface of nanocrystalline silicon with more stable silicon-carbon (Si-C) bonds. Hydrosilylation of the surface of partially and anodically oxidized porous silicon samples was thermally induced at about 90 °C using various different organic molecules. Devices whose surface have been modified with stable covalent bonds shows no degradation in the EL efficiency and EL output intensity under DC operation for several hours. The enhanced stability can be attributed to the high chemical resistance of Si-C bonds against current-induced surface oxidation associated with the generation of nonradiative defects. Although devices treated with 1-decene exhibit reduced EL efficiency and brightness compared to untreatred devices, other molecules, such as ethyl-undecylenate and particularly undecylenic acid provide stable and more efficient visible electroluminescence at room temperature. Undecylenic acid provides EL brightness as high as that of an untreated device.

  18. Stable electroluminescence from passivated nano-crystalline porous silicon using undecylenic acid

    Energy Technology Data Exchange (ETDEWEB)

    Gelloz, B.; Sano, H.; Koshida, N. [Dept. Elec. and Elec. Eng., Tokyo Univ. of A and T, Koganei, Tokyo 184-8588 (Japan); Boukherroub, R. [Laboratoire de Physique de la Matiere Condensee, Ecole Polytechnique, Route de Saclay, 91128 Palaiseau (France); Wayner, D.D.M.; Lockwood, D.J. [National Research Council, Ottawa (Canada)

    2005-06-01

    Stabilization of electroluminescence from nanocrystalline porous silicon diodes has been achieved by replacing silicon-hydrogen bonds terminating the surface of nanocrystalline silicon with more stable silicon-carbon (Si-C) bonds. Hydrosilylation of the surface of partially and anodically oxidized porous silicon samples was thermally induced at about 90 C using various different organic molecules. Devices whose surface have been modified with stable covalent bonds shows no degradation in the EL efficiency and EL output intensity under DC operation for several hours. The enhanced stability can be attributed to the high chemical resistance of Si-C bonds against current-induced surface oxidation associated with the generation of nonradiative defects. Although devices treated with 1-decene exhibit reduced EL efficiency and brightness compared to untreated devices, other molecules, such as ethyl-undecylenate and particularly undecylenic acid provide stable and more efficient visible electroluminescence at room temperature. Undecylenic acid provides EL brightness as high as that of an untreated device. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  19. Quantitative Measurement of GPCR Endocytosis via Pulse-Chase Covalent Labeling.

    Directory of Open Access Journals (Sweden)

    Hidetoshi Kumagai

    Full Text Available 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.

  20. Electron Beam Modification and Functionalization of MWNT for Covalent Dispersion into Polymeric Systems

    International Nuclear Information System (INIS)

    Palmese, G. R.

    2006-01-01

    The discovery of multiwalled carbon nanotubes (MWNT) and singlewalled nanotubes (SWNT) has allowed for the development of structural and conductive reinforcement fillers for polymers and electronic systems. Due to their small diameter, high aspect ratio, strength, and conductive and semi-conductive properties, nanotubes are excellent reinforcing fillers for systems requiring enhanced electrical or material properties and may disperse into such systems at low percolation concentrations. However, despite their potential for enhanced composites properties, van der Waals interactions between nanotubes as well as their highly stable graphitic structure render them insoluble in water, organic solvents and most monomers. As a result, nanotubes separate from solution, and their excellent material properties are not realized on a macroscopic scale. Furthermore, in order for nanotube-reinforced systems to be structurally enhanced (allowing for load transfer from the bulk material to the nanotube filler), covalent interactions between nanotubes and the polymer chains are preferred. Therefore, the development of nanotube-based polymer composites with improved mechanical properties and electrical conductivity requires the covalent dispersion of carbon nanotubes. In this work, we have developed a novel method of nanotube surface modification in which dry MWNT are irradiated with a high-energy electron-beam (EB) in ambient air environment. Raman spectroscopy was performed to characterize the influence of EB irradiation on nanotubes, namely, variance of the disorder, or D band (∼1360 cm - 1) with respect to the graphitic, or G, peak (∼1580 cm - 1). Spectra show increased deformation to the graphitic structure, as well as increased strain on the carbon-carbon bonds, weakening the nanotube. Transmission Electron Microscopy (TEM) confirms that nanotubes remain intact despite high EB dose. In addition, minimal surface deformation and length reduction occurred on irradiated MWNT

  1. On-surface synthesis of covalent coordination polymers on micrometer scale

    Institute of Scientific and Technical Information of China (English)

    Mathieu Koudia; Elena Nardi; Olivier Siri; Mathieu Abel

    2017-01-01

    On-surface synthesis under ultrahigh vacuum provides a promising strategy to control matter at the atomic level,with important implications for the design of new two-dimensional materials having remarkable electronic,magnetic,or catalytic properties.This strategy must address the problem of limited extension of the domains due to the irreversible nature of covalent bonds,which prevents the ripening of defects.We show here that extended materials can be produced by a controlled co-deposition process.In particular,co-deposition of quinoid zwitterion molecules with iron atoms on a Ag(111) surface held at 570 K allows the formation of micrometer-sized domains based on covalent coordination bonds.This work opens up the construction of micrometer-scale single-layer covalent coordination materials under vacuum conditions.

  2. A method for synthesis and functionalization of ultrasmall superparamagnetic covalent carriers based on maghemite and dextran

    International Nuclear Information System (INIS)

    Mornet, Stephane; Portier, Josik; Duguet, Etienne

    2005-01-01

    A new generation of susceptibility contrast agents for MRI and based on maghemite cores covalently bonded to dextran stabilizing macromolecules was investigated. The multistep preparation of these versatile ultrasmall superparamagnetic iron oxides (VUSPIO) consisted of colloidal maghemite synthesis, surface modification by aminopropylsilane groups, and coupling of partially oxidized dextran via Schiff's bases and secondary amine bonds. The dextran corona might be easily derivatized, e.g. by PEGylation

  3. Visualized Bond Scission in Mechanically Activated Polymers

    Institute of Scientific and Technical Information of China (English)

    Yuan Yuan; Yu-lan Chen

    2017-01-01

    Visualization and quantitative evaluation of covalent bond scission in polymeric materials are critical in understanding their failure mechanisms and improving the toughness and reliability of the materials.Mechano-responsive polymers with the ability of molecular-level transduction of force into chromism and luminescence have evoked major interest and experienced significant progress.In the current review,we highlight the recent achievements in covalent mechanochromic and mechanoluminescent polymers,leading to a bridge between macroscopic mechanical properties and microscopic bond scission events.After a general introduction concerning polymer mechanochemistry,various examples that illustrate the strategies of design and incorporation of functional and weak covalent bonds in polymers were presented,the mechanisms underlying the optical phenomenon were introduced and their potential applications as stress sensors were discussed.This review concludes with a comment on the opportunities and challenges of the field.

  4. Control of O-H bonds at a-IGZO/SiO2 interface by long time thermal annealing for highly stable oxide TFT

    Directory of Open Access Journals (Sweden)

    Jae Kwon Jeon

    2017-12-01

    Full Text Available We report two-step annealing, high temperature and sequent low temperature, for amorphous indium-gallium-zinc-oxide (a-IGZO thin-film transistor (TFT to improve its stability and device performance. The annealing is carried out at 300 oC in N2 ambient for 1 h (1st step annealing and then at 250 oC in vacuum for 10 h (2nd step annealing. It is found that the threshold voltage (VTH changes from 0.4 V to -2.0 V by the 1st step annealing and to +0.6 V by 2nd step annealing. The mobility changes from 18 cm2V-1s-1 to 25 cm2V-1s-1 by 1st step and decreases to 20 cm2V-1s-1 by 2nd step annealing. The VTH shift by positive bias temperature stress (PBTS is 3.7 V for the as-prepared TFT, and 1.7 V for the 1st step annealed TFT, and 1.3 V for the 2nd step annealed TFT. The XPS (X-ray photoelectron spectroscopy depth analysis indicates that the reduction in O-H bonds at the top interface (SiO2/a-IGZO by 2nd step annealing appears, which is related to the positive VTH shift and smaller VTH shift by PBTS.

  5. Control of O-H bonds at a-IGZO/SiO2 interface by long time thermal annealing for highly stable oxide TFT

    Science.gov (United States)

    Jeon, Jae Kwon; Um, Jae Gwang; Lee, Suhui; Jang, Jin

    2017-12-01

    We report two-step annealing, high temperature and sequent low temperature, for amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film transistor (TFT) to improve its stability and device performance. The annealing is carried out at 300 oC in N2 ambient for 1 h (1st step annealing) and then at 250 oC in vacuum for 10 h (2nd step annealing). It is found that the threshold voltage (VTH) changes from 0.4 V to -2.0 V by the 1st step annealing and to +0.6 V by 2nd step annealing. The mobility changes from 18 cm2V-1s-1 to 25 cm2V-1s-1 by 1st step and decreases to 20 cm2V-1s-1 by 2nd step annealing. The VTH shift by positive bias temperature stress (PBTS) is 3.7 V for the as-prepared TFT, and 1.7 V for the 1st step annealed TFT, and 1.3 V for the 2nd step annealed TFT. The XPS (X-ray photoelectron spectroscopy) depth analysis indicates that the reduction in O-H bonds at the top interface (SiO2/a-IGZO) by 2nd step annealing appears, which is related to the positive VTH shift and smaller VTH shift by PBTS.

  6. 1D and 2D NMR Spectroscopy of Bonding Interactions within Stable and Phase-Separating Organic Electrolyte-Cellulose Solutions.

    Science.gov (United States)

    Clough, Matthew T; Farès, Christophe; Rinaldi, Roberto

    2017-09-11

    Organic electrolyte solutions (i.e. mixtures containing an ionic liquid and a polar, molecular co-solvent) are highly versatile solvents for cellulose. However, the underlying solvent-solvent and solvent-solute interactions are not yet fully understood. Herein, mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate, the co-solvent 1,3-dimethyl-2-imidazolidinone, and cellulose are investigated using 1D and 2D NMR spectroscopy. The use of a triply- 13 C-labelled ionic liquid enhances the signal-to-noise ratio for 13 C NMR spectroscopy, enabling changes in bonding interactions to be accurately pinpointed. Current observations reveal an additional degree of complexity regarding the distinct roles of cation, anion, and co-solvent toward maintaining cellulose solubility and phase stability. Unexpectedly, the interactions between the dialkylimidazolium ring C 2 -H substituent and cellulose become more pronounced at high temperatures, counteracted by a net weakening of acetate-cellulose interactions. Moreover, for mixtures that exhibit critical solution behavior, phase separation is accompanied by the apparent recombination of cation-anion pairs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Preparation and characterization of uranium-iron triple-bonded UFe(CO){sub 3}{sup -} and OUFe(CO){sub 3}{sup -} complexes

    Energy Technology Data Exchange (ETDEWEB)

    Chi, Chaoxian; Meng, Luyan; Luo, Mingbiao [School of Chemistry, Biological and Materials Sciences, State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China University of Technology, Nanchang (China); Wang, Jia-Qi; Li, Wan-Lu; Li, Jun [Department of Chemistry and Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University, Beijing (China); Qu, Hui; Zhou, Mingfei [Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai (China)

    2017-06-06

    We report the preparation of UFe(CO){sub 3}{sup -} and OUFe(CO){sub 3}{sup -} complexes using a laser-vaporization supersonic ion source in the gas phase. These compounds were mass-selected and characterized by infrared photodissociation spectroscopy and state-of-the-art quantum chemical studies. There are unprecedented triple bonds between U 6d/5f and Fe 3d orbitals, featuring one covalent σ bond and two Fe-to-U dative π bonds in both complexes. The uranium and iron elements are found to exist in unique formal U(I or III) and Fe(-II) oxidation states, respectively. These findings suggest that there may exist a whole family of stable df-d multiple-bonded f-element-transition-metal compounds that have not been fully recognized to date. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Experimental Realisation of Elusive Multiple-bonded Aluminium Compounds: A New Horizon in the Aluminium Chemistry.

    Science.gov (United States)

    Inoue, Shigeyoshi; Bag, Prasenjit; Weetman, Catherine

    2018-05-23

    Synthesis and isolation of stable main group compounds featuring multiple bonds has been of keen interest for the last several decades. Multiply bonded complexes were obtained using sterically demanding substituents that provide kinetic and thermodynamic stability. Many of these compounds have unusual structural and electronic properties that challenges the classical concept of covalent multiple bonding. In contrast, analogous aluminium compounds are scarce in spite of its high natural abundance. The parent dialumene (Al2H2) has been calculated to be extremely weak, thus making Al multiple bonds a challenging synthetic target. This review provides an overview of these recent advances in the cutting edge synthetic approaches used to obtain aluminium homo- and heterodiatomic multiply bonded complexes. Additionally, the reactivity of these novel compounds towards various small molecules and reagents will be discussed herein. This review provides an overview on the current progress in aluminium multiple bond chemistry and the careful ligand design required to stabilise these reactive species. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Building high-coverage monolayers of covalently bound magnetic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Williams, Mackenzie G.; Teplyakov, Andrew V., E-mail: andrewt@udel.edu

    2016-12-01

    Graphical abstract: - Highlights: • A method for forming a layer of covalently bound nanoparticles is offered. • A nearly perfect monolayer of covalently bound magnetic nanoparticles was formed on gold. • Spectroscopic techniques confirmed covalent binding by the “click” reaction. • The influence of the functionalization scheme on surface coverage was investigated. - Abstract: This work presents an approach for producing a high-coverage single monolayer of magnetic nanoparticles using “click chemistry” between complementarily functionalized nanoparticles and a flat substrate. This method highlights essential aspects of the functionalization scheme for substrate surface and nanoparticles to produce exceptionally high surface coverage without sacrificing selectivity or control over the layer produced. The deposition of one single layer of magnetic particles without agglomeration, over a large area, with a nearly 100% coverage is confirmed by electron microscopy. Spectroscopic techniques, supplemented by computational predictions, are used to interrogate the chemistry of the attachment and to confirm covalent binding, rather than attachment through self-assembly or weak van der Waals bonding. Density functional theory calculations for the surface intermediate of this copper-catalyzed process provide mechanistic insight into the effects of the functionalization scheme on surface coverage. Based on this analysis, it appears that steric limitations of the intermediate structure affect nanoparticle coverage on a flat solid substrate; however, this can be overcome by designing a functionalization scheme in such a way that the copper-based intermediate is formed on the spherical nanoparticles instead. This observation can be carried over to other approaches for creating highly controlled single- or multilayered nanostructures of a wide range of materials to result in high coverage and possibly, conformal filling.

  10. 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

  11. Covalently coupled hybrid of graphitic carbon nitride with reduced graphene oxide as a superior performance lithium-ion battery anode

    Science.gov (United States)

    Fu, Yongsheng; Zhu, Junwu; Hu, Chong; Wu, Xiaodong; Wang, Xin

    2014-10-01

    An in situ chemical synthetic approach has been designed for the fabrication of a covalently coupled hybrid consisting of graphitic carbon nitride (g-C3N4) with reduced graphene oxide (rGO) with differing g-C3N4/rGO ratio. The epoxy groups of graphene oxide (GO) undergo a nucleophilic substitution reaction with dicyandiamide (C2H4N4) to form the C2H4N4-GO composite via a covalent C-N bond, and then both the in situ polymerization of C2H4N4 and the thermal reduction of GO can be achieved at higher temperatures, forming the covalently coupled g-C3N4-rGO. FT-IR, CP-MAS NMR and XPS analyses, clearly revealed a covalent interaction between the g-C3N4 and rGO sheets. The g-C3N4-rGO exhibits an unprecedented high, stable and reversible capacity of 1525 mA h g-1 at a current density of 100 mA g-1 after 50 cycles. Even at a large current density of 1000 mA g-1, a reversible capacity of 943 mA h g-1 can still be retained. The superior electrochemical performance of g-C3N4-rGO is attributed to the specific characteristics of the unique nanostructure of g-C3N4-rGO and the concerted effects of g-C3N4 and rGO, including covalent interactions between the two moieties, the good conductivity and high special surface area of the nanocomposite, as well as the template effect of the planar amino group of g-C3N4 for the dispersed decoration of Li+ ions.An in situ chemical synthetic approach has been designed for the fabrication of a covalently coupled hybrid consisting of graphitic carbon nitride (g-C3N4) with reduced graphene oxide (rGO) with differing g-C3N4/rGO ratio. The epoxy groups of graphene oxide (GO) undergo a nucleophilic substitution reaction with dicyandiamide (C2H4N4) to form the C2H4N4-GO composite via a covalent C-N bond, and then both the in situ polymerization of C2H4N4 and the thermal reduction of GO can be achieved at higher temperatures, forming the covalently coupled g-C3N4-rGO. FT-IR, CP-MAS NMR and XPS analyses, clearly revealed a covalent interaction between

  12. 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.

  13. Hydrothermally stable molecular separation membranes from organically linked silica

    Energy Technology Data Exchange (ETDEWEB)

    Castricum, H.L.; Sah, A; Blank, D.H.A.; Ten Elshof, J.E. [Inorganic Materials Science, MESA Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Kreiter, R.; Vente, J.F. [ECN Energy Efficiency in the Industry, Petten (Netherlands)

    2008-06-15

    A highly hydrothermally stable microporous network material has been developed that can be applied in energy-efficient molecular sieving. The material was synthesized by employing organically bridged monomers in acid-catalysed sol-gel hydrolysis and condensation, and is composed of covalently bonded organic and inorganic moieties. Due to its hybrid nature, it withstands higher temperatures than organic polymers and exhibits high solvolytical and acid stability. A thin film membrane that was prepared with the hybrid material was found to be stable in the dehydration of n-butanol at 150C for almost two years. This membrane is the first that combines a high resistance against water at elevated temperatures with a high separation factor and permeance. It therefore has high potential for energy-efficient molecular separation under industrial conditions, including the dehydration of organic solvents. The organically bridged monomers induce increased toughness in the thin film layer. This suppresses hydrolysis of Si-O-Si network bonds and results in a high resistance towards stress-induced cracking. The large non-hydrolysable units thus remain well incorporated in the surrounding matrix such that the material combines high (pore) structural and mechanical stability. The sol mean particle size was found to be a viable parameter to tune the thickness of the membrane layer and thus optimize the separation performance. We anticipate that other hybrid organosilicas can be made in a similar fashion, to yield a whole new class of materials with superior molecular sieving properties and high hydrothermal stability.

  14. Molecular characterization of covalent complexes between tissue transglutaminase and gliadin peptides

    DEFF Research Database (Denmark)

    Fleckenstein, Burkhard; Qiao, Shuo-Wang; Larsen, Martin Røssel

    2004-01-01

    recognized by intestinal T cells from patients. Incubation of TG2 with gliadin peptides also results in the formation of covalent TG2-peptide complexes. Here we report the characterization of complexes between TG2 and two immunodominant gliadin peptides. Two types of covalent complexes were found......; the peptides are either linked via a thioester bond to the active site cysteine of TG2 or via isopeptide bonds to particular lysine residues of the enzyme. We quantified the number of gliadin peptides bound to TG2 under different conditions. After 30 min of incubation of TG2 at 1 microm with an equimolar ratio...... of peptides to TG2, approximately equal amounts of peptides were bound by thioester and isopeptide linkage. At higher peptide to TG2 ratios, more than one peptide was linked to TG2, and isopeptide bond formation dominated. The lysine residues in TG2 that act as acyl acceptors were identified by matrix...

  15. Additional disulfide bonds in insulin

    DEFF Research Database (Denmark)

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

    2015-01-01

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

  16. Conformational analysis of a covalently cross-linked Watson-Crick base pair model.

    Science.gov (United States)

    Jensen, Erik A; Allen, Benjamin D; Kishi, Yoshito; O'Leary, Daniel J

    2008-11-15

    Low-temperature NMR experiments and molecular modeling have been used to characterize the conformational behavior of a covalently cross-linked DNA base pair model. The data suggest that Watson-Crick or reverse Watson-Crick hydrogen bonding geometries have similar energies and can interconvert at low temperatures. This low-temperature process involves rotation about the crosslink CH(2)C(5') (psi) carbon-carbon bond, which is energetically preferred over the alternate CH(2)N(3) (phi) carbon-nitrogen bond rotation.

  17. Halogen bonding in solution: thermodynamics and applications.

    Science.gov (United States)

    Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

    2013-02-21

    Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

  18. Dynamic covalent chemistry of bisimines at the solid/liquid interface monitored by scanning tunnelling microscopy.

    Science.gov (United States)

    Ciesielski, Artur; El Garah, Mohamed; Haar, Sébastien; Kovaříček, Petr; Lehn, Jean-Marie; Samorì, Paolo

    2014-11-01

    Dynamic covalent chemistry relies on the formation of reversible covalent bonds under thermodynamic control to generate dynamic combinatorial libraries. It provides access to numerous types of complex functional architectures, and thereby targets several technologically relevant applications, such as in drug discovery, (bio)sensing and dynamic materials. In liquid media it was proved that by taking advantage of the reversible nature of the bond formation it is possible to combine the error-correction capacity of supramolecular chemistry with the robustness of covalent bonding to generate adaptive systems. Here we show that double imine formation between 4-(hexadecyloxy)benzaldehyde and different α,ω-diamines as well as reversible bistransimination reactions can be achieved at the solid/liquid interface, as monitored on the submolecular scale by in situ scanning tunnelling microscopy imaging. Our modular approach enables the structurally controlled reversible incorporation of various molecular components to form sophisticated covalent architectures, which opens up perspectives towards responsive multicomponent two-dimensional materials and devices.

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

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

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

  20. Characterising non-covalent interactions with the Cambridge Structural Database.

    Science.gov (United States)

    Lommerse, J P; Taylor, R

    1997-02-01

    This review describes how the CSD can be used to study non-covalent interactions. Several different types of information may be obtained. First, the relative frequencies of various interactions can be studied; for example, we have shown that the terminal oxygen atoms of phosphate groups accept hydrogen bonds far more often than the linkage oxygens. Secondly, information can be obtained about the geometries of nonbonded contacts; for example, hydrogen bonds to P-O groups rarely form along the extension of the P-O bond, whereas short contacts between oxygen and carbon-bound iodine show a strong preference for linear C-I ... O angles. Thirdly, the CSD can be searched for novel interactions which may be exploited in inhibitor design; for example, the I ... O contacts just mentioned, and N-H ... pi hydrogen bonds. Finally, the CSD can suggest synthetic targets for medicinal chemistry; for example, molecules containing delocalised electron deficient groups such as trimethylammonium, pyridinium, thaizolium and dinitrophenyl have a good chance of binding to an active-site tryptophan. Although the CSD contains small-molecule crystal structures, not protein-ligand complexes, there is considerable evidence that the contacts seen in the two types of structures are similar. We have illustrated this a number of times in the present review and additional evidence has been given previously by Klebe. The major advantages of the CSD are its size, diversity and experimental accuracy. For these reasons, it is a useful tool for modellers engaged in rational inhibitor design.

  1. Hydrogen bonding in ionic liquids.

    Science.gov (United States)

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

    2015-03-07

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

  2. Targeting of [[sup 111]In]biocytin to cultured ovarian adenocarcinoma cells using covalent monoclonal antibody -streptavidin conjugates

    Energy Technology Data Exchange (ETDEWEB)

    Sheldon, K.; Marks, A. (Toronto Univ., ON (Canada). Banting and Best Dept. of Medical Research); Baumal, R. (Hospital for Sick Children, Toronto, ON (Canada). Dept. of Pathology)

    1992-11-01

    Three monoclonal antibodies (mAb) directed against the human ovarian adenocarcinoma cell line HEY, were substituted with maleimide and covalently bonded to thiolated streptavidin. The conjugates were separated from unreacted reagents by successive affinity chromatography on protein A-Sepharose and iminobiotin columns. Purified conjugates consisted of an immunoglobulin (Ig) monomer bound to a streptavidin tetramer through a covalent bond between the Ig molecule and one of the streptavidin subunits. The conjugates were able to specifically target [[sup 111]In]biocytin to HEY cells in vitro in the presence of human serum and ascitic fluid from ovarian cancer patients. (Author).

  3. Protein tetrazinylation via diazonium coupling for covalent and catalyst-free bioconjugation.

    Science.gov (United States)

    Zhang, Jie; Men, Yuwen; Lv, Shanshan; Yi, Long; Chen, Jian-Feng

    2015-12-21

    An efficient and bench-stable reagent was synthesized for direct and covalent introduction of tetrazines onto target protein or virus surfaces, which can be further modified based on tetrazine-ene ligation to achieve fluorescence labelling or PEGylation under mild conditions.

  4. 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 : cyclodextrins * disulfide bond * dynamic covalent bond Subject RIV: CC - Organic Chemistry Impact factor: 2.631, year: 2010

  5. Covalently linked bisporphyrins bearing tetraphenylporphyrin and ...

    Indian Academy of Sciences (India)

    Covalently linked bisporphyrins bearing tetraphenylporphyrin and perbromoporphyrin units: Synthesis and their properties. Puttaiah Bhyrappa V Krishnan ... yields of the TPP moiety. Electrochemical redox and fluorescence data seem to suggest the possible existence of intramolecular interactions in these bisporphyrins.

  6. Applications of covalent organic frameworks (COFs): From gas storage and separation to drug delivery

    Institute of Scientific and Technical Information of China (English)

    Ming-Xue Wu; Ying-Wei Yang

    2017-01-01

    Covalent organic frameworks (COFs) are an emerging class of porous covalent organic structures whose backbones were composed of light elements (B,C,N,O,Si) and linked by robust covalent bonds to endow such material with desirable properties,i.e.,inherent porosity,well-defined pore aperture,ordered channel structure,large surface area,high stability,and multi-dimension.As expected,the abovementioned properties of COFs broaden the applications of this class of materials in various fields such as gas storage and separation,catalysis,optoelectronics,sensing,small molecules adsorption,and drug delivery.In this review,we outlined the synthesis of COFs and highlighted their applications ranging from the initial gas storage and separation to drug delivery.

  7. 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...... in the circulation, and it is stabilized by hexamer formation in the presence of zinc ions during storage in the pancreatic ß-cell. Due to the transient nature of insulin dimer, direct investigation of this important form is inherently difficult. To address the relationship between insulin oligomerization...... 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...

  8. 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.

  9. Merging constitutional and motional covalent dynamics in reversible imine formation and exchange processes.

    Science.gov (United States)

    Kovaříček, Petr; Lehn, Jean-Marie

    2012-06-06

    The formation and exchange processes of imines of salicylaldehyde, pyridine-2-carboxaldehyde, and benzaldehyde have been studied, showing that the former has features of particular interest for dynamic covalent chemistry, displaying high efficiency and fast rates. The monoimines formed with aliphatic α,ω-diamines display an internal exchange process of self-transimination type, inducing a local motion of either "stepping-in-place" or "single-step" type by bond interchange, whose rate decreases rapidly with the distance of the terminal amino groups. Control of the speed of the process over a wide range may be achieved by substituents, solvent composition, and temperature. These monoimines also undergo intermolecular exchange, thus merging motional and constitutional covalent behavior within the same molecule. With polyamines, the monoimines formed execute internal motions that have been characterized by extensive one-dimensional, two-dimensional, and EXSY proton NMR studies. In particular, with linear polyamines, nondirectional displacement occurs by shifting of the aldehyde residue along the polyamine chain serving as molecular track. Imines thus behave as simple prototypes of systems displaying relative motions of molecular moieties, a subject of high current interest in the investigation of synthetic and biological molecular motors. The motional processes described are of dynamic covalent nature and take place without change in molecular constitution. They thus represent a category of dynamic covalent motions, resulting from reversible covalent bond formation and dissociation. They extend dynamic covalent chemistry into the area of molecular motions. A major further step will be to achieve control of directionality. The results reported here for imines open wide perspectives, together with other chemical groups, for the implementation of such features in multifunctional molecules toward the design of molecular devices presenting a complex combination of

  10. 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

  11. The yeast cell fusion protein Prm1p requires covalent dimerization to promote membrane fusion.

    Directory of Open Access Journals (Sweden)

    Alex Engel

    2010-05-01

    Full Text Available Prm1p is a multipass membrane protein that promotes plasma membrane fusion during yeast mating. The mechanism by which Prm1p and other putative regulators of developmentally controlled cell-cell fusion events facilitate membrane fusion has remained largely elusive. Here, we report that Prm1p forms covalently linked homodimers. Covalent Prm1p dimer formation occurs via intermolecular disulfide bonds of two cysteines, Cys-120 and Cys-545. PRM1 mutants in which these cysteines have been substituted are fusion defective. These PRM1 mutants are normally expressed, retain homotypic interaction and can traffic to the fusion zone. Because prm1-C120S and prm1-C545S mutants can form covalent dimers when coexpressed with wild-type PRM1, an intermolecular C120-C545 disulfide linkage is inferred. Cys-120 is adjacent to a highly conserved hydrophobic domain. Mutation of a charged residue within this hydrophobic domain abrogates formation of covalent dimers, trafficking to the fusion zone, and fusion-promoting activity. The importance of intermolecular disulfide bonding informs models regarding the mechanism of Prm1-mediated cell-cell fusion.

  12. Atomic bonding of precipitate and phase transformation of Al-Cu-Mg alloy

    International Nuclear Information System (INIS)

    Gao Yingjun; Hou Xianhua; Mo Qifeng; Wei Chengyang; Qin Xiaobing

    2007-01-01

    Atomic bonding of the GPB zone and S'' phase of Al-Cu-Mg alloys in early aging stage are calculated using the empirical electron theory (EET) in solid. The results show that not only the covalence bond-network is very strong in GPB zone, but the whole covalence bond energy of S'' phase is also very large, and all the primary bond-net framework of these precipitates can consolidate the matrix of alloy. Phase transformation from GPB zone to S'' phase is explained reasonably based on atomic bonding and total binding capacity of Al and Cu atoms in these precipitates

  13. Covalent Organic Frameworks: From Materials Design to Biomedical Application

    Directory of Open Access Journals (Sweden)

    Fuli Zhao

    2017-12-01

    Full Text Available Covalent organic frameworks (COFs are newly emerged crystalline porous polymers with well-defined skeletons and nanopores mainly consisted of light-weight elements (H, B, C, N and O linked by dynamic covalent bonds. Compared with conventional materials, COFs possess some unique and attractive features, such as large surface area, pre-designable pore geometry, excellent crystallinity, inherent adaptability and high flexibility in structural and functional design, thus exhibiting great potential for various applications. Especially, their large surface area and tunable porosity and π conjugation with unique photoelectric properties will enable COFs to serve as a promising platform for drug delivery, bioimaging, biosensing and theranostic applications. In this review, we trace the evolution of COFs in terms of linkages and highlight the important issues on synthetic method, structural design, morphological control and functionalization. And then we summarize the recent advances of COFs in the biomedical and pharmaceutical sectors and conclude with a discussion of the challenges and opportunities of COFs for biomedical purposes. Although currently still at its infancy stage, COFs as an innovative source have paved a new way to meet future challenges in human healthcare and disease theranostic.

  14. 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.

  15. 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.

  16. Structure and chemical bond characteristics of LaB6

    International Nuclear Information System (INIS)

    Bai Lina; Ma Ning; Liu Fengli

    2009-01-01

    The structure and chemical bond characteristics of LaB 6 have been achieved by means of the density functional theory using the state-of-the-art full-potential linearized augmented plane wave (FPLAPW) method, which are implemented within the EXCITING code. The results show our optimized lattice constant a (4.158 A), parameter z (0.1981) and bulk modulus B (170.4 GPa) are in good agreement with the corresponding experimental data. Electron localization function (ELF) shows the La-La bond mainly is ionic bond, La-B bond is between ionic and covalent bond while the covalent bond between the nearest neighbor B atoms (B2 and B3) is a little stronger than that between the nearer neighbor B atoms (B1 and B4).

  17. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

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

  18. A new bonded catalyst for safe lithium-thionyl chloride batteries

    Science.gov (United States)

    Walsh, F.; Hopewood, J.

    1982-08-01

    The goal of the research effort was to demonstrate that a new class of organometallic cathode catalysts, the TAAs, are stable in thionyl chloride and that they significantly improve the power performance of lithium-thionyl chloride primary batteries. A number of TAAs were evaluated and shown to be active catalysts. Included in this evaluation were TAAs which were covalently bonded to the supporting carbon electrode material; a covalently bonded catalyst has the potential advantage that it will not dissolve into the electrolyte and negatively affect anode performance. During the six month research program, the TAAS were shown to: significantly improve cathode performance in Li/SOCl2 cells; improve cathode capacity; improve cathode performance throughout long-term tests; and not affect anode performance. Further work is needed to develop data in cell studies on temperature range, shelf life, voltage delay effects, energy/power density as a function of rate, and factors affecting electrode capacity. Battery performance in stress tests to develop safety and cost data is also needed.

  19. Theoretical investigation of compounds with triple bonds

    International Nuclear Information System (INIS)

    Devarajan, Deepa

    2011-01-01

    In this thesis, compounds with potential triple-bonding character involving the heavier main-group elements, Group 4 transition metals, and the actinides uranium and thorium were studied by using molecular quantum mechanics. The triple bonds are described in terms of the individual orbital contributions (σ, π parallel , and π perpendicular to ), involving electron-sharing covalent or donor-acceptor interactions between the orbitals of two atoms or fragments. Energy decomposition, natural bond orbital, and atoms in molecules analyses were used for the bonding analysis of the triple bonds. The results of this thesis suggest that the triple-bonding character between the heavier elements of the periodic table is important and worth further study and exploration.

  20. Unusual bond paths in organolithium compounds

    International Nuclear Information System (INIS)

    Bachrach, S.M.; Ritchie, J.P.

    1986-01-01

    We have applied the topological method to a number of organolithium compounds. The wavefunctions were determined with GAUSSIAN-82 using 3-21G basis set and fully optimized geometries. Gradient paths were obtained using the RHODER package and critical points were located using EXTREME. These results indicate the unusual nature of organolithium compounds. The strange bond paths arise mainly from the ionic nature of the C-Li interaction. We suggest that the term ''bond path'' may best be suited for covalent bonds. 4 figs., 1 tab

  1. 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

  2. CovalentDock Cloud: a web server for automated covalent docking.

    Science.gov (United States)

    Ouyang, Xuchang; Zhou, Shuo; Ge, Zemei; Li, Runtao; Kwoh, Chee Keong

    2013-07-01

    Covalent binding is an important mechanism for many drugs to gain its function. We developed a computational algorithm to model this chemical event and extended it to a web server, the CovalentDock Cloud, to make it accessible directly online without any local installation and configuration. It provides a simple yet user-friendly web interface to perform covalent docking experiments and analysis online. The web server accepts the structures of both the ligand and the receptor uploaded by the user or retrieved from online databases with valid access id. It identifies the potential covalent binding patterns, carries out the covalent docking experiments and provides visualization of the result for user analysis. This web server is free and open to all users at http://docking.sce.ntu.edu.sg/.

  3. 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

  4. Living Polymerization for the Introduction of Tailored Hydrogen Bonding

    OpenAIRE

    Elkins, Casey Lynn

    2005-01-01

    In an effort to synthesize macromolecules comprising both covalent and non-covalent bonding to tune ultimate physical properties, a variety of methodologies and functionalization strategies were employed. First, protected functional initiation, namely 3-[(N-benzyl-N-methyl)amino]-1-propyllithium and 3-(t-butyldimethylsilyloxy)-1-propyllithium, in living anionic polymerization of isoprene was used to yield well-defined chain end functional macromolecules. Using both initiating systems, polym...

  5. Crystallographic studies evidencing the high energy tolerance to disrupting the interface disulfide bond of thioredoxin 1 from white leg shrimp Litopenaeus vannamei.

    Science.gov (United States)

    Campos-Acevedo, Adam A; Rudiño-Piñera, Enrique

    2014-12-15

    Thioredoxin (Trx) is a small 12-kDa redox protein that catalyzes the reduction of disulfide bonds in proteins from different biological systems. A recent study of the crystal structure of white leg shrimp thioredoxin 1 from Litopenaeus vannamei (LvTrx) revealed a dimeric form of the protein mediated by a covalent link through a disulfide bond between Cys73 from each monomer. In the present study, X-ray-induced damage in the catalytic and the interface disulfide bond of LvTrx was studied at atomic resolution at different transmission energies of 8% and 27%, 12.8 keV at 100 K in the beamline I-24 at Diamond Light Source. We found that at an absorbed dose of 32 MGy, the X-ray induces the cleavage of the disulfide bond of each catalytic site; however, the interface disulfide bond was cleaved at an X-ray adsorbed dose of 85 MGy; despite being the most solvent-exposed disulfide bond in LvTrx (~50 Å2). This result clearly established that the interface disulfide bond is very stable and, therefore, less susceptible to being reduced by X-rays. In fact, these studies open the possibility of the existence in solution of a dimeric LvTrx.

  6. Crystallographic Studies Evidencing the High Energy Tolerance to Disrupting the Interface Disulfide Bond of Thioredoxin 1 from White Leg Shrimp Litopenaeus vannamei

    Directory of Open Access Journals (Sweden)

    Adam A. Campos-Acevedo

    2014-12-01

    Full Text Available Thioredoxin (Trx is a small 12-kDa redox protein that catalyzes the reduction of disulfide bonds in proteins from different biological systems. A recent study of the crystal structure of white leg shrimp thioredoxin 1 from Litopenaeus vannamei (LvTrx revealed a dimeric form of the protein mediated by a covalent link through a disulfide bond between Cys73 from each monomer. In the present study, X-ray-induced damage in the catalytic and the interface disulfide bond of LvTrx was studied at atomic resolution at different transmission energies of 8% and 27%, 12.8 keV at 100 K in the beamline I-24 at Diamond Light Source. We found that at an absorbed dose of 32 MGy, the X-ray induces the cleavage of the disulfide bond of each catalytic site; however, the interface disulfide bond was cleaved at an X-ray adsorbed dose of 85 MGy; despite being the most solvent-exposed disulfide bond in LvTrx (~50 Å2. This result clearly established that the interface disulfide bond is very stable and, therefore, less susceptible to being reduced by X-rays. In fact, these studies open the possibility of the existence in solution of a dimeric LvTrx.

  7. Conformational Analysis of a Covalently Cross-Linked Watson-Crick Base Pair Model

    OpenAIRE

    Jensen, Erik A.; Allen, Benjamin D.; Kishi, Yoshito; O'Leary, Daniel J.

    2008-01-01

    Low temperature NMR experiments and molecular modeling have been used to characterize the conformational behavior of a covalently cross-linked DNA base pair model. The data suggest that Watson-Crick or reverse Watson-Crick hydrogen bonding geometries have similar energies and can interconvert at low temperatures. This low-temperature process involves rotation about the crosslink CH2–C(5′) (ψ) carbon-carbon bond, which is energetically preferred over the alternate CH2–N(3) (ϕ) carbon-nitrogen ...

  8. 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.

  9. Chemial Bond and Stability of Adsorption of[Au(AsS3)]2- on the Surface of Kaolinite

    Institute of Scientific and Technical Information of China (English)

    MIN Xin-min; CHEN Yun; HONG Han-lie

    2004-01-01

    Density function theory and discrete variation method (DFT-DVM) were used to study the adsorption of [Au(AsS3 ) ]2- on the surface of kaolinite. The correlation among structure, chemical bond and stability was discussed. Several models were selected with [ Au( AsS3 ) ]2- in different directions and sites. The resultsshow that the models with gold on the edge of kaolinite basal layer contain pincerlike bond among gold and severaloxygen atoms and form strong Au - O covalent bond, so these models are more stable than those with gold aboveor under the layer. The models with gold near to [ AlO2(OH)4 ] octahedra are more stable than those with goldnear to the vacancy without aluminium. These two stable tendencies in kaolinite- [ Au( AsS3 ) ]2- are stronger thanthat in kaolinite-Au systems. The interaction between [ Au( AsS3 ) ]2- and kaolinite is stronger than that betweengold and kaolinite, and this interaction is strong enough to form the surface complexes.

  10. Analysis of Halogen and Other σ-Hole Bonds in Crystals

    Directory of Open Access Journals (Sweden)

    Peter Politzer

    2018-01-01

    Full Text Available Schneider has observed that [1]: “ . . . the chemistry of the last century was largely the chemistry of covalent bonding, whereas that of the present century is more likely to be the chemistry of noncovalent binding.”[...

  11. 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.

  12. 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

  13. Biofunctional paper via the covalent modification of cellulose.

    Science.gov (United States)

    Yu, Arthur; Shang, Jing; Cheng, Fang; Paik, Bradford A; Kaplan, Justin M; Andrade, Rodrigo B; Ratner, Daniel M

    2012-07-31

    Paper-based analytical devices are the subject of growing interest for the development of low-cost point-of-care diagnostics, environmental monitoring technologies, and research tools for limited-resource settings. However, there are limited chemistries available for the conjugation of biomolecules to cellulose for use in biomedical applications. Herein, divinyl sulfone (DVS) chemistry was demonstrated to immobilize small molecules, proteins, and DNA covalently onto the hydroxyl groups of cellulose membranes through nucleophilic addition. Assays on modified cellulose using protein-carbohydrate and protein-glycoprotein interactions as well as oligonucleotide hybridization showed that the membrane's bioactivity was specific, dose-dependent, and stable over a long period of time. The use of an inkjet printer to form patterns of biomolecules on DVS-activated cellulose illustrates the adaptability of the DVS functionalization technique to pattern sophisticated designs, with potential applications in cellulose-based lateral flow devices.

  14. 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

    2018-05-01

    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.

  15. Improving the Thermostability and Optimal Temperature of a Lipase from the Hyperthermophilic Archaeon Pyrococcus furiosus by Covalent Immobilization

    Directory of Open Access Journals (Sweden)

    Roberta V. Branco

    2015-01-01

    Full Text Available A recombinant thermostable lipase (Pf2001Δ60 from the hyperthermophilic Archaeon Pyrococcus furiosus (PFUL was immobilized by hydrophobic interaction on octyl-agarose (octyl PFUL and by covalent bond on aldehyde activated-agarose in the presence of DTT at pH = 7.0 (one-point covalent attachment (glyoxyl-DTT PFUL and on glyoxyl-agarose at pH 10.2 (multipoint covalent attachment (glyoxyl PFUL. The enzyme’s properties, such as optimal temperature and pH, thermostability, and selectivity, were improved by covalent immobilization. The highest enzyme stability at 70°C for 48 h incubation was achieved for glyoxyl PFUL (around 82% of residual activity, whereas glyoxyl-DTT PFUL maintained around 69% activity, followed by octyl PFUL (27% remaining activity. Immobilization on glyoxyl-agarose improved the optimal temperature to 90°C, while the optimal temperature of octyl PFUL was 70°C. Also, very significant changes in activity with different substrates were found. In general, the covalent bond derivatives were more active than octyl PFUL. The E value also depended substantially on the derivative and the conditions used. It was observed that the reaction of glyoxyl-DTT PFUL using methyl mandelate as a substrate at pH 7 presented the best results for enantioselectivity E=22 and enantiomeric excess (ee (% = 91.

  16. 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.

  17. Covalent biofunctionalization of silicon nitride surfaces

    NARCIS (Netherlands)

    Arafat, A.; Giesbers, M.; Rosso, M.; Sudhölter, E.J.R.; Schroën, C.G.P.H.; White, R.G.; Li Yang,; Linford, M.R.; Zuilhof, H.

    2007-01-01

    Covalently attached organic monolayers on etched silicon nitride (SixN4; x 3) surfaces were prepared by reaction of SixN4-coated wafers with neat or solutions of 1-alkenes and 1-alkynes in refluxing mesitylene. The surface modification was monitored by measurement of the static water contact angle,

  18. Anisotropic Covalency Contributions to Superexchange Pathways in Type One Copper Active Sites

    Science.gov (United States)

    2015-01-01

    Type one (T1) Cu sites deliver electrons to catalytic Cu active sites: the mononuclear type two (T2) Cu site in nitrite reductases (NiRs) and the trinuclear Cu cluster in the multicopper oxidases (MCOs). The T1 Cu and the remote catalytic sites are connected via a Cys-His intramolecular electron-transfer (ET) bridge, which contains two potential ET pathways: P1 through the protein backbone and P2 through the H-bond between the Cys and the His. The high covalency of the T1 Cu–S(Cys) bond is shown here to activate the T1 Cu site for hole superexchange via occupied valence orbitals of the bridge. This covalency-activated electronic coupling (HDA) facilitates long-range ET through both pathways. These pathways can be selectively activated depending on the geometric and electronic structure of the T1 Cu site and thus the anisotropic covalency of the T1 Cu–S(Cys) bond. In NiRs, blue (π-type) T1 sites utilize P1 and green (σ-type) T1 sites utilize P2, with P2 being more efficient. Comparing the MCOs to NiRs, the second-sphere environment changes the conformation of the Cys-His pathway, which selectively activates HDA for superexchange by blue π sites for efficient turnover in catalysis. These studies show that a given protein bridge, here Cys-His, provides different superexchange pathways and electronic couplings depending on the anisotropic covalencies of the donor and acceptor metal sites. PMID:25310460

  19. Stable isotopes

    International Nuclear Information System (INIS)

    Evans, D.K.

    1986-01-01

    Seventy-five percent of the world's stable isotope supply comes from one producer, Oak Ridge Nuclear Laboratory (ORNL) in the US. Canadian concern is that foreign needs will be met only after domestic needs, thus creating a shortage of stable isotopes in Canada. This article describes the present situation in Canada (availability and cost) of stable isotopes, the isotope enrichment techniques, and related research programs at Chalk River Nuclear Laboratories (CRNL)

  20. Covalent functionalization of graphene with reactive intermediates.

    Science.gov (United States)

    Park, Jaehyeung; Yan, Mingdi

    2013-01-15

    Graphene, a material made exclusively of sp(2) carbon atoms with its π electrons delocalized over the entire 2D network, is somewhat chemically inert. Covalent functionalization can enhance graphene's properties including opening its band gap, tuning conductivity, and improving solubility and stability. Covalent functionalization of pristine graphene typically requires reactive species that can form covalent adducts with the sp(2) carbon structures in graphene. In this Account, we describe graphene functionalization reactions using reactive intermediates of radicals, nitrenes, carbenes, and arynes. These reactive species covalently modify graphene through free radical addition, CH insertion, or cycloaddition reactions. Free radical additions are among the most common reaction, and these radicals can be generated from diazonium salts and benzoyl peroxide. Electron transfer from graphene to aryl diazonium ion or photoactivation of benzoyl peroxide yields aryl radicals that subsequently add to graphene to form covalent adducts. Nitrenes, electron-deficient species generated by thermal or photochemical activation of organic azides, can functionalize graphene very efficiently. Because perfluorophenyl nitrenes show enhanced bimolecular reactions compared with alkyl or phenyl nitrenes, perfluorophenyl azides are especially effective. Carbenes are used less frequently than nitrenes, but they undergo CH insertion and C═C cycloaddition reactions with graphene. In addition, arynes can serve as a dienophile in a Diels-Alder type reaction with graphene. Further study is needed to understand and exploit the chemistry of graphene. The generation of highly reactive intermediates in these reactions leads to side products that complicate the product composition and analysis. Fundamental questions remain about the reactivity and regioselectivity of graphene. The differences in the basal plane and the undercoordinated edges of graphene and the zigzag versus arm-chair configurations

  1. Theoretical Insights into Monometallofullerene Th@C76: Strong Covalent Interaction between Thorium and the Carbon Cage.

    Science.gov (United States)

    Zhao, Pei; Zhao, Xiang; Ehara, Masahiro

    2018-03-19

    Th@C 76 has been studied by density functional theory combined with statistical mechanics calculations. The results reveal that Th@ T d (19151)-C 76 satisfying the isolated pentagon rule possesses the lowest energy. Nevertheless, considering the enthalpy-entropy interplay, Th@ C 1 (17418)-C 76 with one pair of adjacent pentagons is thermodynamically favorable at elevated temperatures, which is reported for the first time. The bonding critical points in both isomers were analyzed to disclose covalent interactions between the inner Th and cages. In addition, the Wiberg bond orders of M-C bonding in different endohedral metallofullerenes (EMFs) were investigated to prove stronger covalent interactions of Th-C in Th-based EMFs.

  2. Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Reece Beekmeyer

    2015-11-01

    Full Text Available The electronic structure of a series of uranium and cerium hexachlorides in a variety of oxidation states was evaluated at both the correlated wavefunction and density functional (DFT levels of theory. Following recent experimental observations of covalency in tetravalent cerium hexachlorides, bonding character was studied using topological and integrated analysis based on the quantum theory of atoms in molecules (QTAIM. This analysis revealed that M–Cl covalency was strongly dependent on oxidation state, with greater covalency found in higher oxidation state complexes. Comparison of M–Cl delocalisation indices revealed a discrepancy between correlated wavefunction and DFT-derived values. Decomposition of these delocalisation indices demonstrated that the origin of this discrepancy lay in ungerade contributions associated with the f-manifold which we suggest is due to self-interaction error inherent to DFT-based methods. By all measures used in this study, extremely similar levels of covalency between complexes of U and Ce in the same oxidation state was found.

  3. 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.

  4. 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.

  5. Interstellar hydrogen bonding

    Science.gov (United States)

    Etim, Emmanuel E.; Gorai, Prasanta; Das, Ankan; Chakrabarti, Sandip K.; Arunan, Elangannan

    2018-06-01

    This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.

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

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Hang [College of Water Resources and Architectural Engineering, Northwest A& F University, Yangling 712100 (China); Cai, Kun, E-mail: caikun1978@163.com [College of Water Resources and Architectural Engineering, Northwest A& F University, Yangling 712100 (China); Wan, Jing [College of Water Resources and Architectural Engineering, Northwest A& F University, Yangling 712100 (China); Gao, Zhaoliang, E-mail: coopcg@163.com [Institute of Soil and Water Conservation, Northwest A& F University, Yangling, 712100 (China); Chen, Zhen [State Key Laboratory of Structural Analysis for Industrial Equipment, Department of Engineering Mechanics, Faculty of Vehicle Engineering and Mechanics, Dalian University of Technology, Dalian 116024 (China)

    2016-03-01

    Graphical abstract: - Highlights: • The rotational transmission performance of a rotational transmission system (RTS) with different types of C−H bonding layouts on the edge of motor and rotor is investigated using MD simulation method. • The L–J interaction between covalently bonded hydrogen atoms and sp1 carbon atoms is too weak to support a stable rotational transmission when only the motor or rotor has bonded hydrogen atoms. • When both the motor and rotor have the same C−H bonding layout on their adjacent ends, a stable output rotational speed of rotor can be obtained. • A low input rotational speed (e.g., 100 GHz) would lead to a synchronous rotational transmission if the system has (+0.5H) C−H bonding layout. - Abstract: In a nano rotational transmission system (RTS) which consists of a single walled carbon nanotube (SWCNT) as the motor and a coaxially arranged double walled carbon nanotube (DWCNT) as a bearing, the interaction between the motor and the rotor in bearing, which has great effects on the response of the RTS, is determined by their adjacent edges. Using molecular dynamics (MD) simulation, the interaction is analyzed when the adjacent edges have different carbon-hydrogen (C−H) bonding layouts. In the computational models, the rotor in bearing and the motor with a specific input rotational speed are made from the same armchair SWCNT. Simulation results demonstrate that a perfect rotational transmission could happen when the motor and rotor have the same C−H bonding layout on their adjacent ends. If only half or less of the carbon atoms on the adjacent ends are bonded with hydrogen atoms, the strong attraction between the lower speed (100 GHz) motor and rotor leads to a synchronous rotational transmission. If only the motor or the rotor has C−H bonds on their adjacent ends, no rotational transmission happens due to weak interaction between the bonded hydrogen atoms on one end with the sp{sup 1} bonded carbon atoms on the other

  7. 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...

  8. Bonding in [CuNRR′]4 type clusters

    Institute of Scientific and Technical Information of China (English)

    WANG Bingwu; XU Guangxian; CHEN Zhida

    2004-01-01

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

  9. Conditional repair by locally switching the thermal healing capability of dynamic covalent polymers with light

    Science.gov (United States)

    Fuhrmann, Anne; Göstl, Robert; Wendt, Robert; Kötteritzsch, Julia; Hager, Martin D.; Schubert, Ulrich S.; Brademann-Jock, Kerstin; Thünemann, Andreas F.; Nöchel, Ulrich; Behl, Marc; Hecht, Stefan

    2016-12-01

    Healable materials could play an important role in reducing the environmental footprint of our modern technological society through extending the life cycles of consumer products and constructions. However, as most healing processes are carried out by heat alone, the ability to heal damage generally kills the parent material's thermal and mechanical properties. Here we present a dynamic covalent polymer network whose thermal healing ability can be switched `on' and `off' on demand by light, thereby providing local control over repair while retaining the advantageous macroscopic properties of static polymer networks. We employ a photoswitchable furan-based crosslinker, which reacts with short and mobile maleimide-substituted poly(lauryl methacrylate) chains forming strong covalent bonds while simultaneously allowing the reversible, spatiotemporally resolved control over thermally induced de- and re-crosslinking. We reason that our system can be adapted to more complex materials and has the potential to impact applications in responsive coatings, photolithography and microfabrication.

  10. Tribology study of reduced graphene oxide sheets on silicon substrate synthesized via covalent assembly.

    Science.gov (United States)

    Ou, Junfei; Wang, Jinqing; Liu, Sheng; Mu, Bo; Ren, Junfang; Wang, Honggang; Yang, Shengrong

    2010-10-19

    Reduced graphene oxide (RGO) sheets were covalently assembled onto silicon wafers via a multistep route based on the chemical adsorption and thermal reduction of graphene oxide (GO). The formation and microstructure of RGO were analyzed by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, Raman spectroscopy, and water contact angle (WCA) measurements. Characterization by atomic force microscopy (AFM) was performed to evaluate the morphology and microtribological behaviors of the samples. Macrotribological performance was tested on a ball-on-plate tribometer. Results show that the assembled RGO possesses good friction reduction and antiwear ability, properties ascribed to its intrinsic structure, that is, the covalent bonding to the substrate and self-lubricating property of RGO.

  11. Dynamic Multi-Component Covalent Assembly for the Reversible Binding of Secondary Alcohols and Chirality Sensing

    Science.gov (United States)

    You, Lei; Berman, Jeffrey S.; Anslyn, Eric V.

    2011-01-01

    Reversible covalent bonding is often employed for the creation of novel supramolecular structures, multi-component assemblies, and sensing ensembles. In spite of remarkable success of dynamic covalent systems, the reversible binding of a mono-alcohol with high strength is challenging. Here we show that a strategy of carbonyl activation and hemiaminal ether stabilization can be embodied in a four-component reversible assembly that creates a tetradentate ligand and incorporates secondary alcohols with exceptionally high affinity. Evidence is presented that the intermediate leading to binding and exchange of alcohols is an iminium ion. Further, to demonstrate the use of this assembly process we explored chirality sensing and enantiomeric excess determinations. An induced twist in the ligand by a chiral mono-ol results in large Cotton effects in the circular dichroism spectra indicative of the alcohol’s handedness. The strategy revealed in this study should prove broadly applicable for the incorporation of alcohols into supramolecular architecture construction. PMID:22109274

  12. The role of uranium-arene bonding in H2O reduction catalysis

    Science.gov (United States)

    Halter, Dominik P.; Heinemann, Frank W.; Maron, Laurent; Meyer, Karsten

    2018-03-01

    The reactivity of uranium compounds towards small molecules typically occurs through stoichiometric rather than catalytic processes. Examples of uranium catalysts reacting with water are particularly scarce, because stable uranyl groups form that preclude the recovery of the uranium compound. Recently, however, an arene-anchored, electron-rich uranium complex has been shown to facilitate the electrocatalytic formation of H2 from H2O. Here, we present the precise role of uranium-arene δ bonding in intermediates of the catalytic cycle, as well as details of the atypical two-electron oxidative addition of H2O to the trivalent uranium catalyst. Both aspects were explored by synthesizing mid- and high-valent uranium-oxo intermediates and by performing comparative studies with a structurally related complex that cannot engage in δ bonding. The redox activity of the arene anchor and a covalent δ-bonding interaction with the uranium ion during H2 formation were supported by density functional theory analysis. Detailed insight into this catalytic system may inspire the design of ligands for new uranium catalysts.

  13. Formation of reflective and conductive silver film on ABS surface via covalent grafting and solution spray

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Dexin; Zhang, Yan [School of Mechanical and Automotive Engineering, South China University of Technology, 381 Wushan, Guangzhou 510640 (China); Bessho, Takeshi [Higashifuji Technical Center, Toyota Motor Corporation, 1200 Mishuku, Susono, Shizuoka 410-1193 (Japan); Kudo, Takahiro; Sang, Jing; Hirahara, Hidetoshi; Mori, Kunio [Faculty of Engineering, Iwate University, 4-3-5 Ueda, Morioka 020-8551 (Japan); Kang, Zhixin, E-mail: zxkang@scut.edu.cn [School of Mechanical and Automotive Engineering, South China University of Technology, 381 Wushan, Guangzhou 510640 (China)

    2015-09-15

    Highlights: • A pure and homogenous silver film was deposited by spray-style plating technique. • The mechanism of covalent bonding between coating and substrate was studied. • The silver coating is highly reflective and conductive. • UV light was used to activate the ABS surface with triazine azide derivative. - Abstract: Conductive and reflective silver layers on acrylonitrile butadiene styrene (ABS) plastics have been prepared by photo grafting of triazine azides upon ultraviolet activation, self-assembling of triazine dithiols and silver electroless plating by solution spray based on silver mirror reaction. The as-prepared silver film exhibited excellent adhesion with ABS owing to covalent bonds between coating and substrate, and the detailed bonding mechanism have been investigated by X-ray photoelectron spectroscopy (XPS). X-ray diffraction (XRD) result revealed that silver film on ABS was pure and with a nanocrystalline structure. Atomic force microscope (AFM) analysis demonstrated that massive silver particles with sizes varying from 80 to 120 nm were deposited on ABS and formed a homogenous and smooth coating, resulting in highly reflective surface. Furthermore, silver maintained its unique conductivity even as film on ABS surface in term of four-point probe method.

  14. Formation of reflective and conductive silver film on ABS surface via covalent grafting and solution spray

    International Nuclear Information System (INIS)

    Chen, Dexin; Zhang, Yan; Bessho, Takeshi; Kudo, Takahiro; Sang, Jing; Hirahara, Hidetoshi; Mori, Kunio; Kang, Zhixin

    2015-01-01

    Highlights: • A pure and homogenous silver film was deposited by spray-style plating technique. • The mechanism of covalent bonding between coating and substrate was studied. • The silver coating is highly reflective and conductive. • UV light was used to activate the ABS surface with triazine azide derivative. - Abstract: Conductive and reflective silver layers on acrylonitrile butadiene styrene (ABS) plastics have been prepared by photo grafting of triazine azides upon ultraviolet activation, self-assembling of triazine dithiols and silver electroless plating by solution spray based on silver mirror reaction. The as-prepared silver film exhibited excellent adhesion with ABS owing to covalent bonds between coating and substrate, and the detailed bonding mechanism have been investigated by X-ray photoelectron spectroscopy (XPS). X-ray diffraction (XRD) result revealed that silver film on ABS was pure and with a nanocrystalline structure. Atomic force microscope (AFM) analysis demonstrated that massive silver particles with sizes varying from 80 to 120 nm were deposited on ABS and formed a homogenous and smooth coating, resulting in highly reflective surface. Furthermore, silver maintained its unique conductivity even as film on ABS surface in term of four-point probe method

  15. Determination of the major tautomeric form of the covalently modified adenine in the (+)-CC-1065-DNA adduct by 1H and 15N NMR studies

    International Nuclear Information System (INIS)

    Lin, Chin Hsiung; Hurley, L.H.

    1990-01-01

    (+)-CC-1065 is an extremely potent antitumor antibiotic produced by Streptomyces zelensis. The potent cytotoxic effects of the drug are thought to be due to the formation of a covalent adduct with DNA through N3 of adenine. Although the covalent linkage sites between (+)-CC-1065 and DNA have been determined, the tautomeric form of the covalently modified adenine in the (+)-CC-1065-DNA duplex adduct was not defined. The [6- 15 N]deoxyadenosine-labeled 12-mer duplex adduct was then studied by 1 H and 15 N NMR. One-dimensional NOE difference and two-dimensional NOESY 1 H NMR experiments on the nonisotopically labeled 12-mer duplex adduct demonstrate that the 6-amino protons of the covalently modified adenine exhibit two signals at 9.19 and 9.08 ppm. Proton NMR experiments on the [6- 15 N]deoxyadenosine-labeled 12-mer duplex adduct show that the two resonance signals for adenine H6 observed on the nonisotopically labeled duplex adduct were split into doublets by the 15 N nucleus with coupling constants of 91.3 Hz for non-hydrogen-bonded and 86.8 Hz for hydrogen-bonded amino protons. The authors conclude that the covalently modified adenine N6 of the (+)-CC-1065-12-mer duplex adduct is predominantly in the doubly protonated form, in which calculations predict that the C6-N6 bond is shortened and the positive charge is delocalized over the entire adenine molecule

  16. Reversible and formaldehyde-mediated covalent binding of a bis-amino mitoxantrone analogue to DNA.

    Science.gov (United States)

    Konda, Shyam K; Kelso, Celine; Pumuye, Paul P; Medan, Jelena; Sleebs, Brad E; Cutts, Suzanne M; Phillips, Don R; Collins, J Grant

    2016-05-18

    The ability of a bis-amino mitoxantrone anticancer drug (named WEHI-150) to form covalent adducts with DNA, after activation by formaldehyde, has been studied by electrospray ionisation mass spectrometry and HPLC. Mass spectrometry results showed that WEHI-150 could form covalent adducts with d(ACGCGCGT)2 that contained one, two or three covalent links to the octanucleotide, whereas the control drugs (daunorubicin and the anthracenediones mitoxantrone and pixantrone) only formed adducts with one covalent link to the octanucleotide. HPLC was used to examine the extent of covalent bond formation of WEHI-150 with d(CGCGCG)2 and d(CG(5Me)CGCG)2. Incubation of WEHI-150 with d(CG(5Me)CGCG)2 in the presence of formaldehyde resulted in the formation of significantly greater amounts of covalent adducts than was observed with d(CGCGCG)2. In order to understand the observed increase of covalent adducts with d(CG(5Me)CGCG)2, an NMR study of the reversible interaction of WEHI-150 at both CpG and (5Me)CpG sites was undertaken. Intermolecular NOEs were observed in the NOESY spectra of d(ACGGCCGT)2 with added WEHI-150 that indicated that the drug selectively intercalated at the CpG sites and from the major groove. In particular, NOEs were observed from the WEHI-150 H2,3 protons to the H1' protons of G3 and G7 and from the H6,7 protons to the H5 protons of C2 and C6. By contrast, intermolecular NOEs were observed between the WEHI-150 H2,3 protons to the H2'' proton of the (5Me)C3 in d(CG(5Me)CGCG)2, and between the drug aliphatic protons and the H1' proton of G4. This demonstrated that WEHI-150 preferentially intercalates at (5Me)CpG sites, compared to CpG sequences, and predominantly via the minor groove at the (5Me)CpG site. The results of this study demonstrate that WEHI-150 is likely to form interstrand DNA cross-links, upon activation by formaldehyde, and consequently exhibit greater cytotoxicity than other current anthracenedione drugs.

  17. Transition from metal-ligand bonding to halogen bonding involving a metal as halogen acceptor a study of Cu, Ag, Au, Pt, and Hg complexes

    Science.gov (United States)

    Oliveira, Vytor; Cremer, Dieter

    2017-08-01

    Utilizing all-electron Dirac-exact relativistic calculations with the Normalized Elimination of the Small Component (NESC) method and the local vibrational mode approach, the transition from metal-halide to metal halogen bonding is determined for Au-complexes interacting with halogen-donors. The local stretching force constants of the metal-halogen interactions reveal a smooth transition from weak non-covalent halogen bonding to non-classical 3-center-4-electron bonding and finally covalent metal-halide bonding. The strongest halogen bonds are found for dialkylaurates interacting with Cl2 or FCl. Differing trends in the intrinsic halogen-metal bond strength, the binding energy, and the electrostatic potential are explained.

  18. Hydrogen Bonds and Life in the Universe

    Directory of Open Access Journals (Sweden)

    Giovanni Vladilo

    2018-01-01

    Full Text Available 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.

  19. 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

  20. 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.

  1. Iron(II) phthalocyanine covalently functionalized graphene as a highly efficient non-precious-metal catalyst for the oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Liu, Ying; Wu, Yan-Ying; Lv, Guo-Jun; Pu, Tao; He, Xing-Quan; Cui, Li-Li

    2013-01-01

    Graphical abstract: The fabricated FePc-Gr catalyst for ORR exhibited high activity, favoring a direct 4-electron process, good stability and selectivity, all of which should be attributed to its high conductivity, the synergistic effect between FePc and graphene, as well as the formation of stable FePc-Gr composite through covalent bonding and π–π interaction. - Abstract: A novel iron(II) phthalocyanine covalently modified graphene (FePc-Gr) was synthesized by reduction of the product obtained through an amidation reaction between carboxyl-functionalized graphene oxide (CFGO) and iron(II) tetra-aminophthalocyanine (FeTAPc). The FePc-Gr hybird was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS), respectively. The electrocatalytic properties of FePc-Gr toward the oxygen reduction reaction (ORR) were evaluated using cyclic voltammetry (CV) and linear sweep voltammetry methods. The peak potential of the ORR on the FePc-Gr catalyst was found to be about −0.12 V vs. SCE in 0.1 M NaOH solution, which was 180 and 360 mV more positive than that on FeTAPc and bare GCE, respectively. The rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) measurements revealed that the ORR mechanism was nearly via a direct four-electron pathway to water on FePc-Gr. The current still remained 83.5% of its initial after chronoamperometric test for 10,000 s. Nevertheless, Pt/C catalyst only retained 40.5% of its initial current. The peak potential and peak current changed slightly when 3 M methanol was introduced. So the FePc-Gr composite catalyst for ORR exhibited high activity, good stability and methanol-tolerance, which could be used as a promising Pt-free catalyst for ORR in alkaline direct methanol fuel cell (DMFC)

  2. 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

  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. Bonding Strength of Ni/Ni3Al Interface with Different Lattice Misfit

    Institute of Scientific and Technical Information of China (English)

    Ping PENG; Caixing ZHENG; Shaochang HAN; Zhaohui JIN; Rui YANG; Zhuangqi HU

    2003-01-01

    The interfacial binding covalent bond density (CBD) and the local environmental total bond order (LTBO) of the Ni/Ni3Alinterface with different lattice misfits (δ) were calculated by using first-principles discrete variation Xα method. It was foundthat

  5. High Charge Mobility of a Perylene Bisimide Dye with Hydrogen-bond Formation Group

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    A perylene bisimide dye covalently bonded with a hydrogen-bond formation group of 1,3, 5-triazine-2, 4-diamine has been synthesized. Its casting films show a charge carrier mobility over 10-3 cm2/Vs, which is in the range of the highest values found for other promising charge transport materials suitable for solution processable technique.

  6. Shielding and mediating of hydrogen bonding in amide-based (macro)molecules

    NARCIS (Netherlands)

    Harings, J.A.W.

    2009-01-01

    Polymers are long chain molecules comprising continuously repeating building blocks, monomers, which are chemically linked via covalent bonds, for example the C-C bond in polyethylene. A distinction can be made in biopolymers that are made in nature and synthetic polymers that are produced by the

  7. Unpredictably Stable

    DEFF Research Database (Denmark)

    Failla, Virgilio; Melillo, Francesca; Reichstein, Toke

    2014-01-01

    Is entrepreneurship a more stable career choice for high employment turnover individuals? We find that a transition to entrepreneurship induces a shift towards stayer behavior and identify job matching, job satisfaction and lock-in effects as main drivers. These findings have major implications...

  8. 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.

  9. Bonds Boom.

    Science.gov (United States)

    Reynolds, Cathryn

    1989-01-01

    The combined effect of the "Serrano" decision and Proposition 13 left California school districts with aging, overcrowded facilities. Chico schools won a $18.5 million general obligation bond election for facilities construction. With $11 billion needed for new school construction, California will need to tap local sources. A sidebar…

  10. 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....

  11. Molecular marriage through partner preferences in covalent cage formation and cage-to-cage transformation.

    Science.gov (United States)

    Acharyya, Koushik; Mukherjee, Sandip; Mukherjee, Partha Sarathi

    2013-01-16

    Unprecedented self-sorting of three-dimensional purely organic cages driven by dynamic covalent bonds is described. Four different cages were first synthesized by condensation of two triamines and two dialdehydes separately. When a mixture of all the components was allowed to react, only two cages were formed, which suggests a high-fidelity self-recognition. The issue of the preference of one triamine for a particular dialdehyde was further probed by transforming a non-preferred combination to either of the two preferred combinations by reacting it with the appropriate triamine or dialdehyde.

  12. 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

  13. 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,

  14. Covalently attached multilayer assemblies of diazo-resins and binuclear cobalt phthalocyanines

    International Nuclear Information System (INIS)

    Li Xiaofang; Zhao Shuang; Yang Min; Sun Changqing; Guo, Liping

    2005-01-01

    By using the ionic self-assembly technique, ordered multilayer thin films composed of diazo-resin (DAR) as polycation and water-soluble binuclear cobalt phthalocyaninehexasulfonate (Bi-CoPc) as polyanion were alternately fabricated on quartz, CaF 2 and glassy carbon electrodes (GCEs). Upon ultraviolet irradiation, the adjacent interface of the multilayer films reacted to form a covalently cross-linking structure. The obtained thin films were characterized by ultraviolet (UV)-vis, Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), atomic force microscope (AFM), surface photovoltage spectra (SPS), and cyclic voltammetry. The results show that the uniform, highly stable and ordered multilayer thin films were formed. The linkage nature between the adjacent interface of the multilayer films converts from ionic to covalent, and, as a result, the stability of the multilayer thin films dramatically improved. The multilayer thin films on GCEs also exhibited excellent electrochemical behavior

  15. Covalently attached multilayer assemblies of diazo-resins and binuclear cobalt phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Li Xiaofang [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Zhao Shuang [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Yang Min [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Sun Changqing [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China)]. E-mail: sunchq@mail.jlu.edu.cn; Guo, Liping [Department of Chemistry, Northeast Normal University, Changchun 130024 (China)

    2005-05-01

    By using the ionic self-assembly technique, ordered multilayer thin films composed of diazo-resin (DAR) as polycation and water-soluble binuclear cobalt phthalocyaninehexasulfonate (Bi-CoPc) as polyanion were alternately fabricated on quartz, CaF{sub 2} and glassy carbon electrodes (GCEs). Upon ultraviolet irradiation, the adjacent interface of the multilayer films reacted to form a covalently cross-linking structure. The obtained thin films were characterized by ultraviolet (UV)-vis, Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), atomic force microscope (AFM), surface photovoltage spectra (SPS), and cyclic voltammetry. The results show that the uniform, highly stable and ordered multilayer thin films were formed. The linkage nature between the adjacent interface of the multilayer films converts from ionic to covalent, and, as a result, the stability of the multilayer thin films dramatically improved. The multilayer thin films on GCEs also exhibited excellent electrochemical behavior.

  16. Three-dimensional metal-intercalated covalent organic frameworks for near-ambient energy storage

    Science.gov (United States)

    Gao, Fei; Ding, Zijing; Meng, Sheng

    2013-01-01

    A new form of nanoporous material, metal intercalated covalent organic framework (MCOF) is proposed and its energy storage property revealed. Employing density functional and thermodynamical analysis, we find that stable, chemically active, porous materials could form by stacking covalent organic framework (COF) layers with metals as a gluing agent. Metal acts as active sites, while its aggregation is suppressed by a binding energy significantly larger than the corresponding cohesive energy of bulk metals. Two important parameters, metal binding and metal-metal separation, are tuned by selecting suitable building blocks and linkers when constructing COF layers. Systematic searches among a variety of elements and organic molecules identify Ca-intercalated COF with diphenylethyne units as optimal material for H2 storage, reaching a striking gravimetric density ~ 5 wt% at near-ambient conditions (300 K, 20 bar), in comparison to < 0.1 wt% for bare COF-1 under the same condition. PMID:23698018

  17. Stable particles

    International Nuclear Information System (INIS)

    Samios, N.P.

    1993-01-01

    I have been asked to review the subject of stable particles, essentially the particles that eventually comprised the meson and baryon octets. with a few more additions -- with an emphasis on the contributions made by experiments utilizing the bubble chamber technique. In this activity, much work had been done by the photographic emulsion technique and cloud chambers-exposed to cosmic rays as well as accelerator based beams. In fact, many if not most of the stable particles were found by these latter two techniques, however, the forte of the bubble chamber (coupled with the newer and more powerful accelerators) was to verify, and reinforce with large statistics, the existence of these states, to find some of the more difficult ones, mainly neutrals and further to elucidate their properties, i.e., spin, parity, lifetimes, decay parameters, etc

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

    Directory of Open Access Journals (Sweden)

    Damien Thirion

    2016-10-01

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

  19. Nitrogen-tuned bonding mechanism of Li and Ti adatom embedded graphene

    International Nuclear Information System (INIS)

    Lee, Sangho; Chung, Yong-Chae

    2013-01-01

    The effects of nitrogen defects on the bonding mechanism and resultant binding energy between the metal and graphene layer were investigated using density functional theory (DFT) calculations. For the graphitic N-doped graphene, Li adatom exhibited ionic bonding character, while Ti adatom showed features of covalent bonding similar to that of pristine graphene. However, in the cases of pyridinic and pyrrolic structures, partially covalent bonding characteristic occurred around N atoms in the process of binding with metals, and this particular bond formation enhanced the bond strength of metal on the graphene layer as much as it exceeded the cohesive energy of the metal bulk. Thus, Li and Ti metals are expected to be dispersed with atomic accuracy on the pyridinic and pyrrolic N-doped graphene layers. These results demonstrate that the bonding mechanism of metal–graphene complex can change according to the type of N defect, and this also affects the binding results. - Graphical abstract: Display Omitted - Highlights: • Nitrogen defects changed the bonding mechanism between metal and graphene. • Bonding character and binding results were investigated using DFT calculations. • Covalent bonding character occurred around pyridinic and pyrrolic N-doped graphene. • Pyridinic and pyrrolic N atoms are effective for metal dispersion on the graphene

  20. Alignment of non-covalent interactions at protein-protein interfaces.

    Directory of Open Access Journals (Sweden)

    Hongbo Zhu

    Full Text Available BACKGROUND: The study and comparison of protein-protein interfaces is essential for the understanding of the mechanisms of interaction between proteins. While there are many methods for comparing protein structures and protein binding sites, so far no methods have been reported for comparing the geometry of non-covalent interactions occurring at protein-protein interfaces. METHODOLOGY/PRINCIPAL FINDINGS: Here we present a method for aligning non-covalent interactions between different protein-protein interfaces. The method aligns the vector representations of van der Waals interactions and hydrogen bonds based on their geometry. The method has been applied to a dataset which comprises a variety of protein-protein interfaces. The alignments are consistent to a large extent with the results obtained using two other complementary approaches. In addition, we apply the method to three examples of protein mimicry. The method successfully aligns respective interfaces and allows for recognizing conserved interface regions. CONCLUSIONS/SIGNIFICANCE: The Galinter method has been validated in the comparison of interfaces in which homologous subunits are involved, including cases of mimicry. The method is also applicable to comparing interfaces involving non-peptidic compounds. Galinter assists users in identifying local interface regions with similar patterns of non-covalent interactions. This is particularly relevant to the investigation of the molecular basis of interaction mimicry.

  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. Encapsulation and covalent binding of molecular payload in enzymatically activated micellar nanocarriers.

    Science.gov (United States)

    Rosenbaum, Ido; Harnoy, Assaf J; Tirosh, Einat; Buzhor, Marina; Segal, Merav; Frid, Liat; Shaharabani, Rona; Avinery, Ram; Beck, Roy; Amir, Roey J

    2015-02-18

    The high selectivity and often-observed overexpression of specific disease-associated enzymes make them extremely attractive for triggering the release of hydrophobic drug or probe molecules from stimuli-responsive micellar nanocarriers. Here we utilized highly modular amphiphilic polymeric hybrids, composed of a linear hydrophilic polyethylene glycol (PEG) and an esterase-responsive hydrophobic dendron, to prepare and study two diverse strategies for loading of enzyme-responsive micelles. In the first type of micelles, hydrophobic coumarin-derived dyes were encapsulated noncovalently inside the hydrophobic core of the micelle, which was composed of lipophilic enzyme-responsive dendrons. In the second type of micellar nanocarrier the hydrophobic molecular cargo was covalently linked to the end-groups of the dendron through enzyme-cleavable bonds. These amphiphilic hybrids self-assembled into micellar nanocarriers with their cargo covalently encapsulated within the hydrophobic core. Both types of micelles were highly responsive toward the activating enzyme and released their molecular cargo upon enzymatic stimulus. Importantly, while faster release was observed with noncovalent encapsulation, higher loading capacity and slower release rate were achieved with covalent encapsulation. Our results clearly indicate the great potential of enzyme-responsive micellar delivery platforms due to the ability to tune their payload capacities and release rates by adjusting the loading strategy.

  3. 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

  4. Covalently functionalized graphene sheets with biocompatible natural amino acids

    International Nuclear Information System (INIS)

    Mallakpour, Shadpour; Abdolmaleki, Amir; Borandeh, Sedigheh

    2014-01-01

    Graphene sheets were covalently functionalized with aromatic–aliphatic amino acids (phenylalanine and tyrosine) and aliphatic amino acids (alanine, isoleucine, leucine, methionine and valine) by simple and green procedure. For this aim, at first natural graphite was converted into graphene oxide (GO) through strong oxidation procedure; then, based on the surface-exposed epoxy and carboxylic acid groups in GO solid, its surface modification with naturally occurring amino acids, occurred easily throughout the corresponding nucleophilic substitution and condensation reactions. Amino acid functionalized graphene demonstrates stable dispersion in water and common organic solvents. Fourier transform infrared, Raman and X-ray photoelectron spectroscopies, X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy were used to investigate the nanostructures and properties of prepared materials. Each amino acid has different considerable effects on the structure and morphology of the pure graphite, from increasing the layer spacing to layer scrolling, based on their structures, functional groups and chain length. In addition, therogravimetric analysis was used for demonstrating a successful grafting of amino acid molecules to the surface of graphene.

  5. Density functional theory study of the structural and bonding mechanism of molecular oxygen (O2) with C3Si

    Science.gov (United States)

    Parida, Saroj K.; Behera, C.; Sahu, Sridhar

    2018-07-01

    The investigations of pure and heteroatom doped carbon clusters have created great interest because of their enormous prospective applications in various research zones, for example, optoelectronics, semiconductors, material science, energy storage devices, astro-science and so on. In this article, the interaction of molecular oxygen (O2) with C3Si has explored within a density functional theory (DFT). Different possible types of structure for C3SiO2 have collected. Among five different kinds of structure, the structure-1a, 1A1 is more energetically stable. The nature of the bonding of O2 and C3Si, in C3SiO2 has been studied by using Bader's topological analysis of the electron charge density distribution ρ(r) , Laplacian ∇2 ρ(r) and total energy density H(r) at the bond critical points (BCPs) of the structures within the framework of the atoms in molecules theory (AIM). The bonding mechanism of O2 and C3Si in C3SiO2 prompts to the fundamental understanding of the interaction of C3Si with oxygen molecule. It is interesting to note that, two types of bonding mechanism are established in same C3SiO2 system such as (i) shared-kind interactions (ii) closed-shell interactions. From various kinds of structure, Csbnd C bonds in all structures are shown as shared-kind interactions whereas Csbnd Si, Osbnd O bonds are classified as closed-shell type interactions with a certain degree of covalent character.

  6. 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.

  7. Stable isotopes

    International Nuclear Information System (INIS)

    Brazier, J.L.; Guinamant, J.L.

    1995-01-01

    According to the progress which has been realised in the technology of separating and measuring isotopes, the stable isotopes are used as preferable 'labelling elements' for big number of applications. The isotopic composition of natural products shows significant variations as a result of different reasons like the climate, the seasons, or their geographic origins. So, it was proved that the same product has a different isotopic composition of alimentary and agriculture products. It is also important in detecting the pharmacological and medical chemicals. This review article deals with the technology, like chromatography and spectrophotometry, adapted to this aim, and some important applications. 17 refs. 6 figs

  8. Stable Tetraquarks

    Energy Technology Data Exchange (ETDEWEB)

    Quigg, Chris [Fermilab

    2018-04-13

    For very heavy quarks, relations derived from heavy-quark symmetry imply novel narrow doubly heavy tetraquark states containing two heavy quarks and two light antiquarks. We predict that double-beauty states will be stable against strong decays, whereas the double-charm states and mixed beauty+charm states will dissociate into pairs of heavy-light mesons. Observing a new double-beauty state through its weak decays would establish the existence of tetraquarks and illuminate the role of heavy color-antitriplet diquarks as hadron constituents.

  9. 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.

  10. Non-covalent associative structure of coal

    Energy Technology Data Exchange (ETDEWEB)

    Shui, H. [Anhui University of Technology, Maanshan (China). School of Chemistry and Chemical Engineering

    2004-06-01

    The recent progress of non-covalent associative structure of coal and the mechanisms of the carbon disulphide-N-methyl-2-pyrrolidone (CS{sub 2}/NMP) are mixed solvent and the additive addition enhancing the extraction yield of coals are reviewed, and the aggregation behaviour of coal in solid and solution states are presented, and the aggregation behavior of coal in solid and solution states are introduced in this paper. Coal extraction and swelling in organic solvents at room temperature were the most useful methods to understand the associative structure of coal. CS{sub 2}/NMP is a unique solvent to give high extraction yields for some bituminous coals. Some additives such as tetracyanoethylene (TCNE) can dissociate the stronger interactions among coal molecules and enhance the extraction yields of coal in the mixed solvent. 37 refs., 1 fig.

  11. Revisiting nitrogen species in covalent triazine frameworks

    KAUST Repository

    Osadchii, Dmitrii Yu.; Olivos Suarez, Alma Itzel; Bavykina, Anastasiya V.; Gascon, Jorge

    2017-01-01

    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.

  12. Pore surface engineering in covalent organic frameworks.

    Science.gov (United States)

    Nagai, Atsushi; Guo, Zhaoqi; Feng, Xiao; Jin, Shangbin; Chen, Xiong; Ding, Xuesong; Jiang, Donglin

    2011-11-15

    Covalent organic frameworks (COFs) are a class of important porous materials that allow atomically precise integration of building blocks to achieve pre-designable pore size and geometry; however, pore surface engineering in COFs remains challenging. Here we introduce pore surface engineering to COF chemistry, which allows the controlled functionalization of COF pore walls with organic groups. This functionalization is made possible by the use of azide-appended building blocks for the synthesis of COFs with walls to which a designable content of azide units is anchored. The azide units can then undergo a quantitative click reaction with alkynes to produce pore surfaces with desired groups and preferred densities. The diversity of click reactions performed shows that the protocol is compatible with the development of various specific surfaces in COFs. Therefore, this methodology constitutes a step in the pore surface engineering of COFs to realize pre-designed compositions, components and functions.

  13. Cell Signalling Through Covalent Modification and Allostery

    Science.gov (United States)

    Johnson, Louise N.

    Phosphorylation plays essential roles in nearly every aspect of cell life. Protein kinases catalyze the transfer of the γ-phosphate of ATP to a serine, threonine or tyrosine residue in protein substrates. This covalent modification allows activation or inhibition of enzyme activity, creates recognition sites for other proteins and promotes order/disorder or disorder/order transitions. These properties regulate ­signalling pathways and cellular processes that mediate metabolism, transcription, cell cycle progression, differentiation, cytoskeleton arrangement and cell movement, apoptosis, intercellular communication, and neuronal and immunological functions. In this lecture I shall review the structural consequences of protein phosphorylation using our work on glycogen phosphorylase and the cell cycle cyclin dependent protein kinases as illustrations. Regulation of protein phosphorylation may be disrupted in the diseased state and protein kinases have become high profile targets for drug development. To date there are 11 compounds that have been approved for clinical use in the treatment of cancer.

  14. The Nature of Bonding in WC and WN

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The nature of bonding in the title compounds has been studied by using CASSCF and FOCl techniques. The ground states of WC and WN are found to be 3Δ and 4∑- state arising primarily from:...1σ2σ21π41δ13σ1 and ...1σ2σ21π41δ23σ1 configuration respectively. WC shows a strong character of covalent bond while WN have obvious character of ionic bond and the dissociation energy of WN is larger than that of WC (6.15 and 5.41 eV respective).

  15. Functionalization of multiwalled carbon nanotubes by microwave irradiation for lysozyme attachment: comparison of covalent and adsorption methods by kinetics of thermal inactivation

    Science.gov (United States)

    Puentes-Camacho, Daniel; Velázquez, Enrique F.; Rodríguez-Félix, Dora E.; Castillo-Ortega, Mónica; Sotelo-Mundo, Rogerio R.; del Castillo-Castro, Teresa

    2017-12-01

    Proteins suffer changes in their tertiary structure when they are immobilized, and enzymatic activity is affected due to the low biocompatibility of some supporting materials. In this work immobilization of lysozyme on carbon nanotubes previously functionalized by microwave irradiation was studied. The effectiveness of the microwave-assisted acid treatment of carbon nanotubes was evaluated by XPS, TEM, Raman and FTIR spectroscopy. The carboxylic modification of nanotube surfaces by this fast, simple and feasible method allowed the physical adsorption and covalent linking of active lysozyme onto the carbonaceous material. Thermal inactivation kinetics, thermodynamic parameters and storage stability were studied for adsorbed and covalent enzyme complexes. A major stability was found for lysozyme immobilized by the covalent method, the activation energy for inactivation of the enzyme was higher for the covalent method and it was stable after 50 d of storage at 4 °C. The current study highlights the effect of protein immobilization method on the biotechnological potential of nanostructured biocatalysts.

  16. Stable beams

    CERN Multimedia

    2015-01-01

    Stable beams: two simple words that carry so much meaning at CERN. When LHC page one switched from "squeeze" to "stable beams" at 10.40 a.m. on Wednesday, 3 June, it triggered scenes of jubilation in control rooms around the CERN sites, as the LHC experiments started to record physics data for the first time in 27 months. This is what CERN is here for, and it’s great to be back in business after such a long period of preparation for the next stage in the LHC adventure.   I’ve said it before, but I’ll say it again. This was a great achievement, and testimony to the hard and dedicated work of so many people in the global CERN community. I could start to list the teams that have contributed, but that would be a mistake. Instead, I’d simply like to say that an achievement as impressive as running the LHC – a machine of superlatives in every respect – takes the combined effort and enthusiasm of everyone ...

  17. One hundred years of Lewis Chemical Bond!

    Indian Academy of Sciences (India)

    2016-09-20

    Sep 20, 2016 ... Chemists knew how many electrons are there in each element and were also aware of stable electronic configurations. For example, 'inert gases' having. 8 electrons in the valence shell (now known as s and p orbitals) were very stable. Bonding in polar molecules, called electrovalent those days, such as ...

  18. 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.

  19. Covalent modification of calcium hydroxyapatite surface by grafting phenyl phosphonate moieties

    International Nuclear Information System (INIS)

    Aissa, Abdallah; Debbabi, Mongi; Gruselle, Michel; Thouvenot, Rene; Gredin, Patrick; Traksmaa, Rainer; Tonsuaadu, Kaia

    2007-01-01

    The reaction between phenyl phosphonic dichloride (C 6 H 5 P(O)Cl 2 ) and synthetic calcium hydroxy- and fluorapatite has been investigated. The presence of mono- or polymeric (C 6 H 5 PO) fragment bound to hydroxyapatite was evidenced by IR, and solid-state 31 P NMR spectroscopy. X-ray powder analysis has shown that the apatitic structure remains unchanged during the reaction. In contrast, no reaction was found using fluorapatite. According to the results found for these two different apatites a mechanism was proposed for the formation of covalent P-O-P bonds as the result of a reaction between the C 6 H 5 P(O)Cl 2 organic reagent and (HPO 4 ) - and/or OH - ions of the hydroxyapatite. - Graphical abstract: Representation of the first step of the reaction between the phenyl phosphonic dichloride and the hydroxyl groups on the surface of the apatite, leading to covalent P-O-P bond with elimination of HCl

  20. Superior H2 production by hydrophilic ultrafine Ta2O5 engineered covalently on graphene

    International Nuclear Information System (INIS)

    Mao, Lin; Zhu, Shenmin; Shi, Dian; Chen, Yixin; Yin, Chao; Li, Yao; Zhang, Di; Ma, Jun; Chen, Zhixin

    2014-01-01

    A H 2 O 2 -mediated hydrothermal method was developed for the fabrication of hydrophilic Ta 2 O 5 /graphene composite. The composite shows a superior H 2 productivity, up to 30 mmol g −1 h −1 when used as a photocatalyst for water splitting, corresponding to an apparent quantum efficiency of 33.8% at 254 nm. This superior performance is due to the hydrophilic nature of the composite and more importantly due to the ultrafine Ta 2 O 5 nanoparticles (about 4.0 ± 1.5 nm) which are covalently bonded with the conductive graphene. The hydrophilic property of the composite is attributed to the use of H 2 O 2 in the hydrothermal process. The ultrafine size of the Ta 2 O 5 particles which are covalently bonded with the graphene sheets is attributed to the use of sonication in the synthesis process. Furthermore, the hydrophilic Ta 2 O 5 /Gr composite is durable, which is beneficial to long term photocatalysis. The strategy reported here provides a new approach to designing photocatalysts with superior performance for H 2 production. (papers)

  1. Holistic Approach to Partial Covalent Interactions in Protein Structure Prediction and Design with Rosetta.

    Science.gov (United States)

    Combs, Steven A; Mueller, Benjamin K; Meiler, Jens

    2018-05-29

    Partial covalent interactions (PCIs) in proteins, which include hydrogen bonds, salt bridges, cation-π, and π-π interactions, contribute to thermodynamic stability and facilitate interactions with other biomolecules. Several score functions have been developed within the Rosetta protein modeling framework that identify and evaluate these PCIs through analyzing the geometry between participating atoms. However, we hypothesize that PCIs can be unified through a simplified electron orbital representation. To test this hypothesis, we have introduced orbital based chemical descriptors for PCIs into Rosetta, called the PCI score function. Optimal geometries for the PCIs are derived from a statistical analysis of high-quality protein structures obtained from the Protein Data Bank (PDB), and the relative orientation of electron deficient hydrogen atoms and electron-rich lone pair or π orbitals are evaluated. We demonstrate that nativelike geometries of hydrogen bonds, salt bridges, cation-π, and π-π interactions are recapitulated during minimization of protein conformation. The packing density of tested protein structures increased from the standard score function from 0.62 to 0.64, closer to the native value of 0.70. Overall, rotamer recovery improved when using the PCI score function (75%) as compared to the standard Rosetta score function (74%). The PCI score function represents an improvement over the standard Rosetta score function for protein model scoring; in addition, it provides a platform for future directions in the analysis of small molecule to protein interactions, which depend on partial covalent interactions.

  2. 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.

  3. 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...... of nanocrystals. STS measurements showed rectifying behaviour, with high currents at the opposite sample bias to that previously observed for CdSe nanocrystals adsorbed on Si substrates. We explain the rectifying behaviour by considering the interaction between the electronic states of the nanocrystals...

  4. Valence electron structure and bonding features of RuB2 and OSB2: The empirical electron theory calculations

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The valence electron structure (VES) of RuB2 and OsB2 were calculated by the empirical electron theory (EET) of solids and molecules and compared with the results derived from the first-principles calculations. The distributions of covalent electrons in different bonds indicate that B-B and B-Me have remarkably covalent bonding characters. Lattice electrons cruising around Me-Me layers are found to have great influences on electronic conductivity and high temperature plasticity. The ultra-high values of elastic constant Cn in the two compounds originate from close-packed covalent bonding along the c axis. Uneven bond strengths and distributions of covalent bonds, especially for B-Afe bonds, yield significant anisotropy. Low ratios of lattice electrons to covalent electrons suggest the intrinsic embrittlement in crystals. The fact that the calculated cohesive energies well agree with experimental results demonstrates the good suitability of the EET calculations in estimating cohesive energy for transition-metal borides.

  5. 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.

  6. 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.

  7. Protein covalent modification by biologically active quinones

    Directory of Open Access Journals (Sweden)

    MIROSLAV J. GASIC

    2004-11-01

    Full Text Available The avarone/avarol quinone/hydroquinone couple shows considerable antitumor activity. In this work, covalent modification of b-lactoglobulin by avarone and its derivatives as well as by the synthetic steroidal quinone 2,5(10-estradiene-1,4,17-trione and its derivatives were studied. The techniques for studying chemical modification of b-lactoglobulin by quinones were: UV/Vis spectrophotometry, SDS PAGE and isoelectrofocusing. SDS PAGE results suggest that polymerization of the protein occurs. It could be seen that the protein of 18 kD gives the bands of 20 kD, 36 kD, 40 kD, 45 kD, 64 kD and 128 kD depending on modification agent. The shift of the pI of the protein (5.4 upon modification toward lower values (from pI 5.0 to 5.3 indicated that lysine amino groups are the principal site of the reaction of b-lactoglobulin with the quinones.

  8. 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.

  9. Effects of Magnetic Field on the Valence Bond Property of the Double-Quantum-Dot Molecule

    Institute of Scientific and Technical Information of China (English)

    王立民; 罗莹; 马本堃

    2002-01-01

    The effects of the magnetic field on the valence bond property of the double-quantum-dot molecule are numerically studied by the finite element method and perturbation approach because of the absence of cylindrical symmetry in the horizontally coupled dots. The calculation results show that the energy value of the ground state changes differently from that of the first excited state with increasing magnetic field strength, and they cross under a certain magnetic field. The increasing magnetic field makes the covalent bond state change into an ionic bond state, which agrees qualitatively with experimental results and makes ionic bond states remain. The oscillator strength of transition between covalent bond states decreases distinctly with the increasing magnetic field strength, when the molecule is irradiated by polarized light. Such a phenomenon is possibly useful for actual applications.

  10. Study on immobilization enzyme using radiation grafting and condensation covalent

    International Nuclear Information System (INIS)

    Cao Jin; Su Zongxian; Gao Jianfeng

    1989-01-01

    The immobilization of gluecose oxidase (GOD) on polyethylene and F 46 is described by radiation grafting and condensation covalent. The GOD on polyethylene film is characterized with IR-spectrum. The results show that the enzyme activity on F 46 film is high when dose rate and covalent yield are low. When covalent yield is 4.3% the enzyme relative activity achieves the greatest value for F 46 film. The experiment also demonstrates that acrylic acid affects the relative activity of enzyme and the method of IR-pectrum character is convenient and efficient for GOD on polyethylene film

  11. Strategies to balance covalent and non-covalent biomolecule attachment within collagen-GAG biomaterials.

    Science.gov (United States)

    Pence, Jacquelyn C; Gonnerman, Emily A; Bailey, Ryan C; Harley, Brendan A C

    2014-09-01

    Strategies to integrate instructive biomolecular signals into a biomaterial are becoming increasingly complex and bioinspired. While a large majority of reports still use repeated treatments with soluble factors, this approach can be prohibitively costly and difficult to translate in vivo for applications where spatial control over signal presentation is necessary. Recent efforts have explored the use of covalent immobilization of biomolecules to the biomaterial, via both bulk (ubiquitous) as well as spatially-selective light-based crosslinking, as a means to both enhance stability and bioactivity. However, little is known about how processing conditions during immobilization impact the degree of unintended non-covalent interactions, or fouling, that takes place between the biomaterial and the biomolecule of interest. Here we demonstrate the impact of processing conditions for bulk carbodiimide (EDC) and photolithography-based benzophenone (BP) crosslinking on specific attachment vs. fouling of a model protein (Concanavalin A, ConA) within collagen-glycosaminoglycan (CG) scaffolds. Collagen source significantly impacts the selectivity of biomolecule immobilization. EDC crosslinking intensity and ligand concentration significantly impacted selective immobilization. For benzophenone photoimmobilization we observed that increased UV exposure time leads to increased ConA immobilization. Immobilization efficiency for both EDC and BP strategies was maximal at physiological pH. Increasing ligand concentration during immobilization process led to enhanced immobilization for EDC chemistry, no impact on BP immobilization, but significant increases in non-specific fouling. Given recent efforts to covalently immobilize biomolecules to a biomaterial surface to enhance bioactivity, improved understanding of the impact of crosslinking conditions on selective attachment versus non-specific fouling will inform the design of instructive biomaterials for applications across tissue

  12. Self-generated covalent cross-links in the cell-surface adhesins of Gram-positive bacteria.

    Science.gov (United States)

    Baker, Edward N; Squire, Christopher J; Young, Paul G

    2015-10-01

    The ability of bacteria to adhere to other cells or to surfaces depends on long, thin adhesive structures that are anchored to their cell walls. These structures include extended protein oligomers known as pili and single, multi-domain polypeptides, mostly based on multiple tandem Ig-like domains. Recent structural studies have revealed the widespread presence of covalent cross-links, not previously seen within proteins, which stabilize these domains. The cross-links discovered so far are either isopeptide bonds that link lysine side chains to the side chains of asparagine or aspartic acid residues or ester bonds between threonine and glutamine side chains. These bonds appear to be formed by spontaneous intramolecular reactions as the proteins fold and are strategically placed so as to impart considerable mechanical strength. © 2015 Authors; published by Portland Press Limited.

  13. Stable Chloro- and Bromoxenate Cage Anions; [X3(XeO3)3]3- and [X4(XeO3)4]4- (X = Cl or Br).

    Science.gov (United States)

    Goettel, James T; Haensch, Veit G; Schrobilgen, Gary J

    2017-06-28

    The number of isolable compounds which contain different noble-gas-element bonds is limited for xenon and even more so for krypton. Examples of Xe-Cl bonds are rare, and prior to this work, no Xe-Br bonded compound had been isolated in macroscopic quantities. The syntheses, isolation, and characterization of the first compounds to contain Xe-Br bonds and their chlorine analogues are described in the present work. The reactions of XeO 3 with [N(CH 3 ) 4 ]Br and [N(C 2 H 5 ) 4 ]Br have provided two bromoxenate salts, [N(C 2 H 5 ) 4 ] 3 [Br 3 (XeO 3 ) 3 ] and [N(CH 3 ) 4 ] 4 [Br 4 (XeO 3 ) 4 ], in which the cage anions have Xe-Br bond lengths that range from 3.0838(3) to 3.3181(8) Å. The isostructural chloroxenate anions (Xe-Cl bond lengths, 2.9316(2) to 3.101(4) Å) were synthesized by analogy with their bromine analogues. The bromo- and chloroxenate salts are stable in the atmosphere at room temperature and were characterized in the solid state by Raman spectroscopy and low-temperature single-crystal X-ray diffraction, and in the gas phase by quantum-chemical calculations. They are the only known examples of cage anions that contain a noble-gas element. The Xe-Br and Xe-Cl bonds are very weakly covalent and can be viewed as σ-hole interactions, similar to those encountered in halogen bonding. However, the halogen atoms in these cases are valence electron lone pair donors, and the σ* Xe-O orbitals are lone pair acceptors.

  14. Noble gas bond and the behaviour of XeO3 under pressure.

    Science.gov (United States)

    Hou, Chunju; Wang, Xianlong; Botana, Jorge; Miao, Maosheng

    2017-10-18

    Over the past few decades, the concept of hydrogen bonds, in which hydrogen is electrophilic, has been extended to halogen bonds, chalcogen bonds and pnicogen bonds. Herein, we show that such a non-covalent bonding also exists in noble gas compounds. Using first principles calculations, we illustrate the OXe-O bond in molecular crystal XeO 3 and its effect on the behavior of this compound under pressure. Our calculations show that the covalent Xe-O bond lengths were elongated with increasing pressure and correspondingly the Xe-O stretching vibration frequencies were red shifted, which is similar to the change of H-bonds under pressure. The OXe-O bond and related hopping of O between neighboring Xe sites also correspond to the structural changes in the XeO 3 compounds at about 2 GPa. Our study extends the concept of hydrogen bonding to include all p-block elements and show a new bonding type for Noble gas elements in which it acts as an electrophilic species.

  15. Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases.

    Science.gov (United States)

    Alkorta, Ibon; Blanco, Fernando; Solimannejad, Mohammad; Elguero, Jose

    2008-10-30

    A theoretical study of the complexes formed by hypohalous acids (HOX, X = F, Cl, Br, I, and At) with three nitrogenated bases (NH 3, N 2, and NCH) has been carried out by means of ab initio methods, up to MP2/aug-cc-pVTZ computational method. In general, two minima complexes are found, one with an OH...N hydrogen bond and the other one with a X...N halogen bond. While the first one is more stable for the smallest halogen derivatives, the two complexes present similar stabilities for the iodine case and the halogen-bonded structure is the most stable one for the hypoastatous acid complexes.

  16. Sodium bicarbonate-gelled chitosan beads as mechanically stable carriers for the covalent immobilization of enzymes.

    Science.gov (United States)

    Wahba, Marwa I

    2018-03-01

    The poor mechanical stability of chitosan has long impeded its industrial utilization as an immobilization carrier. In this study, the mechanical properties of chitosan beads were greatly improved through utilizing the slow rate of the sodium bicarbonate-induced chitosan gelation and combining it with the chemical cross-linking action of glutaraldehyde (GA). The GA-treated sodium bicarbonate-gelled chitosan beads exhibited much better mechanical properties and up to 2.45-fold higher observed activity of the immobilized enzyme (β-D-galactosidase (β-gal)) when compared to the GA-treated sodium tripolyphosphate (TPP)-gelled chitosan beads. The differences between the sodium bicarbonate-gelled and the TPP-gelled chitosan beads were proven visually and also via scanning electron microscopy, elemental analysis, and differential scanning calorimetry. Moreover, the optimum pH, the optimum temperature, the apparent K m , and the apparent V max of the β-gals immobilized onto the two aforementioned types of chitosan beads were determined and compared. A reusability study was also performed. This study proved the superiority of the sodium bicarbonate-gelled chitosan beads as they retained 72.22 ± 4.57% of their initial observed activity during the 13 th reusability cycle whereas the TPP-gelled beads lost their activity during the first four reusability cycles, owing to their fragmentation. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 34:347-361, 2018. © 2017 American Institute of Chemical Engineers.

  17. Bond strength of masonry

    NARCIS (Netherlands)

    Pluijm, van der R.; Vermeltfoort, A.Th.

    1992-01-01

    Bond strength is not a well defined property of masonry. Normally three types of bond strength can be distinguished: - tensile bond strength, - shear (and torsional) bond strength, - flexural bond strength. In this contribution the behaviour and strength of masonry in deformation controlled uniaxial

  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. Predominantly ligand guided non-covalently linked assemblies of ...

    Indian Academy of Sciences (India)

    JUBARAJ B BARUAH

    2018-05-12

    May 12, 2018 ... Abstract. Various non-covalently linked inorganic self-assemblies formed by the supramolecular interacting .... metal-organic frameworks.59 Inorganic chemists rou- ...... two-dimensional organic–inorganic layered perovskite.

  20. Preparation and characterization of malonic acid cross-linked chitosan and collagen 3D scaffolds: an approach on non-covalent interactions.

    Science.gov (United States)

    Mitra, Tapas; Sailakshmi, G; Gnanamani, A; Mandal, A B

    2012-05-01

    The present study emphasizes the influence of non-covalent interactions on the mechanical and thermal properties of the scaffolds of chitosan/collagen origin. Malonic acid (MA), a bifuncitonal diacid was chosen to offer non-covalent cross-linking. Three dimensional scaffolds was prepared using chitosan at 1.0% (w/v) and MA at 0.2% (w/v), similarly collagen 0.5% (w/v) and MA 0.2% (w/v) and characterized. Results on FT-IR, TGA, DSC, SEM and mechanical properties (tensile strength, stiffness, Young's modulus, etc.) assessment demonstrated the existence of non-covalent interaction between MA and chitosan/collagen, which offered flexibility and high strength to the scaffolds suitable for tissue engineering research. Studies using NIH 3T3 fibroblast cells suggested biocompatibility nature of the scaffolds. Docking simulation study further supports the intermolecular hydrogen bonding interactions between MA and chitosan/collagen.

  1. Covalent and non-covalent chemical engineering of actin for biotechnological applications.

    Science.gov (United States)

    Kumar, Saroj; Mansson, Alf

    2017-11-15

    The cytoskeletal filaments are self-assembled protein polymers with 8-25nm diameters and up to several tens of micrometres length. They have a range of pivotal roles in eukaryotic cells, including transportation of intracellular cargoes (primarily microtubules with dynein and kinesin motors) and cell motility (primarily actin and myosin) where muscle contraction is one example. For two decades, the cytoskeletal filaments and their associated motor systems have been explored for nanotechnological applications including miniaturized sensor systems and lab-on-a-chip devices. Several developments have also revolved around possible exploitation of the filaments alone without their motor partners. Efforts to use the cytoskeletal filaments for applications often require chemical or genetic engineering of the filaments such as specific conjugation with fluorophores, antibodies, oligonucleotides or various macromolecular complexes e.g. nanoparticles. Similar conjugation methods are also instrumental for a range of fundamental biophysical studies. Here we review methods for non-covalent and covalent chemical modifications of actin filaments with focus on critical advantages and challenges of different methods as well as critical steps in the conjugation procedures. We also review potential uses of the engineered actin filaments in nanotechnological applications and in some key fundamental studies of actin and myosin function. Finally, we consider possible future lines of investigation that may be addressed by applying chemical conjugation of actin in new ways. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  2. 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.

  3. Role of interatomic bonding in the mechanical anisotropy and interlayer cohesion of CSH crystals

    Energy Technology Data Exchange (ETDEWEB)

    Dharmawardhana, C.C. [Department of Physics and Astronomy, University of Missouri—Kansas City, Kansas City, MO 64110 (United States); Misra, A. [Department of Civil, Environmental, and Architectural Engineering, University of Kansas, Lawrence, KS 66045 (United States); Aryal, S.; Rulis, P. [Department of Physics and Astronomy, University of Missouri—Kansas City, Kansas City, MO 64110 (United States); Ching, W.Y., E-mail: ccdxz8@mail.umkc.edu [Department of Physics and Astronomy, University of Missouri—Kansas City, Kansas City, MO 64110 (United States)

    2013-10-15

    Atomic scale properties of calcium silicate hydrate (CSH), the main binding phase of hardened Portland cement, are not well understood. Over a century of intense research has identified almost 50 different crystalline CSH minerals which are mainly categorized by their Ca/Si ratio. The electronic structure and interatomic bonding in four major CSH crystalline phases with structures close to those found in hardened cement are investigated via ab initio methods. Our result reveals the critical role of hydrogen bonding and importance of specifying precise locations for water molecules. Quantitative analysis of contributions from different bond types to the overall cohesion shows that while the Si-O covalent bonds dominate, the hydrogen bonding and Ca-O bonding are also very significant. Calculated results reveal the correlation between bond topology and interlayer cohesion. The overall bond order density (BOD) is found to be a more critical measure than the Ca/Si ratio in classifying different CSH crystals.

  4. Behavior of the E-E' Bonds (E, E' = S and Se) in Glutathione Disulfide and Derivatives Elucidated by Quantum Chemical Calculations with the Quantum Theory of Atoms-in-Molecules Approach.

    Science.gov (United States)

    Hayashi, Satoko; Tsubomoto, Yutaka; Nakanishi, Waro

    2018-02-17

    The nature of the E-E' bonds (E, E' = S and Se) in glutathione disulfide ( 1 ) and derivatives 2 - 3 , respectively, was elucidated by applying quantum theory of atoms-in-molecules (QTAIM) dual functional analysis (QTAIM-DFA), to clarify the basic contribution of E-E' in the biological redox process, such as the glutathione peroxidase process. Five most stable conformers a - e were obtained, after applying the Monte-Carlo method then structural optimizations. In QTAIM-DFA, total electron energy densities H b ( r c ) are plotted versus H b ( r c ) - V b ( r c )/2 at bond critical points (BCPs), where V b ( r c ) are potential energy densities at BCPs. Data from the fully optimized structures correspond to the static nature. Those containing perturbed structures around the fully optimized one in the plot represent the dynamic nature of interactions. The behavior of E-E' was examined carefully. Whereas E-E' in 1a - 3e were all predicted to have the weak covalent nature of the shared shell interactions, two different types of S-S were detected in 1 , depending on the conformational properties. Contributions from the intramolecular non-covalent interactions to stabilize the conformers were evaluated. An inverse relationship was observed between the stability of a conformer and the strength of E-E' in the conformer, of which reason was discussed.

  5. Behavior of the E–E’ Bonds (E, E’ = S and Se in Glutathione Disulfide and Derivatives Elucidated by Quantum Chemical Calculations with the Quantum Theory of Atoms-in-Molecules Approach

    Directory of Open Access Journals (Sweden)

    Satoko Hayashi

    2018-02-01

    Full Text Available The nature of the E–E’ bonds (E, E’ = S and Se in glutathione disulfide (1 and derivatives 2–3, respectively, was elucidated by applying quantum theory of atoms-in-molecules (QTAIM dual functional analysis (QTAIM-DFA, to clarify the basic contribution of E–E’ in the biological redox process, such as the glutathione peroxidase process. Five most stable conformers a–e were obtained, after applying the Monte-Carlo method then structural optimizations. In QTAIM-DFA, total electron energy densities Hb(rc are plotted versus Hb(rc − Vb(rc/2 at bond critical points (BCPs, where Vb(rc are potential energy densities at BCPs. Data from the fully optimized structures correspond to the static nature. Those containing perturbed structures around the fully optimized one in the plot represent the dynamic nature of interactions. The behavior of E–E’ was examined carefully. Whereas E–E’ in 1a–3e were all predicted to have the weak covalent nature of the shared shell interactions, two different types of S–S were detected in 1, depending on the conformational properties. Contributions from the intramolecular non-covalent interactions to stabilize the conformers were evaluated. An inverse relationship was observed between the stability of a conformer and the strength of E–E’ in the conformer, of which reason was discussed.

  6. 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…

  7. 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)

  8. Modeling of thin films growth processes in the early stage for atoms with covalent bonds

    International Nuclear Information System (INIS)

    Tupik, V A; Margolin, V I; Su, Chu Trong

    2017-01-01

    Computer simulation for obtaining thin film’s growth process at an early stage with the proposed model of atoms with isotropic and anisotropic interactions been considered. Carrying out the procedure for analyzing the problem on the basis of the program being implemented, computer simulation of thin film growth processes has been carried out on several examples. The results of computer simulation of the growth process of thin film on a given substrate and an aggregate in a vacuum condition are shown. Some characteristic distributions of the obtained structure have been carried out to evaluate the proposed adequate model and to reflect the high complexity of thin films growth process. (paper)

  9. Tetramethylguanidine covalently bonded onto silica gel as catalyst for the addition of nitromethane to cyclopentenone

    International Nuclear Information System (INIS)

    Oliveira, Edimar de; Torres, Jocilene D.; Silva, Carlos C.; Luz, Afranio A.M.; Bakuzis, Peter; Prado, Alexandre G.S.

    2006-01-01

    A catalyst based on silica chemically modified with tetramethylguanidine (TMG) was synthesized by the co-condensation of tetraethyl orthosilicate with a new silylant agent derived from the reaction between the TMG molecule and (3-chloropropyl)trimethoxysilane. A neutral n-dodecylamine template was used to organize the polymerization of the inorganic-organic catalyst. Thermogravimetry showed that the number of active pendant groups in the catalyst was 1.35 mmol g -1 , with a surface area of 811±75 m 2 g -1 . Infrared spectroscopy and 13 C and 29 Si nuclear magnetic resonance data are in agreement with the proposed structure. This material has been used to catalyse the addition of nitromethane to cyclopentenone. The catalytic efficiency was followed and the nitromethylcyclopentanone conversion presented a yield of 98% at 3 h of reaction. The catalyst was recovered and reused 14 times, maintaining about 98% of its catalytic efficiency. (author)

  10. Tetramethylguanidine covalently bonded onto silica gel as catalyst for the addition of nitromethane to cyclopentenone

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Edimar de; Torres, Jocilene D.; Silva, Carlos C.; Luz, Afranio A.M.; Bakuzis, Peter; Prado, Alexandre G.S. [Brasilia Univ., DF (Brazil). Inst. de Quimica]. E-mail: agspradus@gmail.com

    2006-09-15

    A catalyst based on silica chemically modified with tetramethylguanidine (TMG) was synthesized by the co-condensation of tetraethyl orthosilicate with a new silylant agent derived from the reaction between the TMG molecule and (3-chloropropyl)trimethoxysilane. A neutral n-dodecylamine template was used to organize the polymerization of the inorganic-organic catalyst. Thermogravimetry showed that the number of active pendant groups in the catalyst was 1.35 mmol g{sup -1}, with a surface area of 811{+-}75 m{sup 2} g{sup -1}. Infrared spectroscopy and {sup 13}C and {sup 29}Si nuclear magnetic resonance data are in agreement with the proposed structure. This material has been used to catalyse the addition of nitromethane to cyclopentenone. The catalytic efficiency was followed and the nitromethylcyclopentanone conversion presented a yield of 98% at 3 h of reaction. The catalyst was recovered and reused 14 times, maintaining about 98% of its catalytic efficiency. (author)

  11. 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

  12. Spin state transition and covalent bonding in LaCoO.sub.3./sub..

    Czech Academy of Sciences Publication Activity Database

    Křápek, Vlastimil; Novák, Pavel; Kuneš, Jan; Novoselov, D.; Vorotin, D.M.; Anisimov, V.I.

    2012-01-01

    Roč. 86, č. 19 (2012), "195104-1"-"195104-9" ISSN 1098-0121 R&D Projects: GA ČR GAP204/10/0284 Institutional research plan: CEZ:AV0Z10100521 Keywords : LaCoO 3 * dynamical mean-field theory Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.767, year: 2012

  13. Local structure of Iridium organometallic catalysts covalently bonded to carbon nanotubes.

    Science.gov (United States)

    Blasco, J.; Cuartero, V.; Subías, G.; Jiménez, M. V.; Pérez-Torrente, J. J.; Oro, L. A.; Blanco, M.; Álvarez, P.; Blanco, C.; Menéndez, R.

    2016-05-01

    Hybrid catalysts based on Iridium N-heterocyclic carbenes anchored to carbon nanotubes (CNT) have been studied by XAFS spectroscopy. Oxidation of CNT yields a large amount of functional groups, mainly hydroxyl groups at the walls and carboxylic groups at the tips, defects and edges. Different kinds of esterification reactions were performed to functionalize oxidized CNT with imidazolium salts. Then, the resulting products were reacted with an Ir organometallic compound to form hybrid catalysts efficient in hydrogen transfer processes. XANES spectroscopy agree with the presence of Ir(I) in these catalysts and the EXAFS spectra detected differences in the local structure of Ir atoms between the initial Ir organometallic compound and the Ir complexes anchored to the CNT. Our results confirm that the halide atom, present in the Ir precursor, was replaced by oxygen from -OH groups at the CNT wall in the first coordination shell of Ir. The lability of this group accounts for the good recyclability and the good efficiency shown by these hybrid catalysts.

  14. 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

  15. Covalently coating dextran on macroporous polyglycidyl methacrylate microsphere enabled rapid protein chromatographic separation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Rongyue; Li, Qiang; Li, Juan; Zhou, Weiqing; Ye, Peili; Gao, Yang; Ma, Guanghui, E-mail: ghma@home.ipe.ac.cn; Su, Zhiguo

    2012-12-01

    Protein denaturation and nonspecific adsorption on polymer media as a chromatographic support have been a problem which needs to be overcome. Macroporous poly(glycidyl methacrylate-divinylbezene) (PGMA-DVB) microspheres prepared in this study were firstly covalently coated with dextran through a three-step method. The dextran was firstly adsorbed onto the microspheres and then covalently bound to the PGMA-DVB microsphere through ether bonds which were formed by hydroxyl group reacting with epoxy group at the presence of 4-(Dimethylamino) pyridine. Finally, the coating dextran layer was crosslinked by ethylene glycol diglycidyl ether to form the continuous network coating. The coated microspheres were characterized by Fourier transform infrared spectra, scanning electron microscope, mercury porosimetry measurements, laser scanning confocal microscope, and protein adsorption experiments. Results showed that PGMA-DVB microspheres coated with dextran successfully maintained the macroporous structure and high permeability. The backpressure was only 1.69 MPa at a high flow rate of 2891 cm/h. Consequently, the hydrophilicity and biocompatibility of modified microspheres were greatly improved, and the contact angle decreased from 184 Degree-Sign to 13 Degree-Sign , and nonspecific adsorption of proteins was decreased to little or none. The clad dextran coating with large amounts of hydroxyl group was easily derived to be various functional groups. The derived media have great potential applications in rapid protein chromatography. - Highlights: Black-Right-Pointing-Pointer Macroporous PGMA-DVB microspheres were covalently coated with dextran. Black-Right-Pointing-Pointer The hydrophilicity of the coated microspheres was significantly improved. Black-Right-Pointing-Pointer The irreversible adsorption of proteins was reduced to zero. Black-Right-Pointing-Pointer The coated microspheres can maintain the macropore structure. Black-Right-Pointing-Pointer The coated microspheres

  16. Covalently coating dextran on macroporous polyglycidyl methacrylate microsphere enabled rapid protein chromatographic separation

    International Nuclear Information System (INIS)

    Zhang, Rongyue; Li, Qiang; Li, Juan; Zhou, Weiqing; Ye, Peili; Gao, Yang; Ma, Guanghui; Su, Zhiguo

    2012-01-01

    Protein denaturation and nonspecific adsorption on polymer media as a chromatographic support have been a problem which needs to be overcome. Macroporous poly(glycidyl methacrylate–divinylbezene) (PGMA–DVB) microspheres prepared in this study were firstly covalently coated with dextran through a three-step method. The dextran was firstly adsorbed onto the microspheres and then covalently bound to the PGMA–DVB microsphere through ether bonds which were formed by hydroxyl group reacting with epoxy group at the presence of 4-(Dimethylamino) pyridine. Finally, the coating dextran layer was crosslinked by ethylene glycol diglycidyl ether to form the continuous network coating. The coated microspheres were characterized by Fourier transform infrared spectra, scanning electron microscope, mercury porosimetry measurements, laser scanning confocal microscope, and protein adsorption experiments. Results showed that PGMA–DVB microspheres coated with dextran successfully maintained the macroporous structure and high permeability. The backpressure was only 1.69 MPa at a high flow rate of 2891 cm/h. Consequently, the hydrophilicity and biocompatibility of modified microspheres were greatly improved, and the contact angle decreased from 184° to 13°, and nonspecific adsorption of proteins was decreased to little or none. The clad dextran coating with large amounts of hydroxyl group was easily derived to be various functional groups. The derived media have great potential applications in rapid protein chromatography. - Highlights: ► Macroporous PGMA–DVB microspheres were covalently coated with dextran. ► The hydrophilicity of the coated microspheres was significantly improved. ► The irreversible adsorption of proteins was reduced to zero. ► The coated microspheres can maintain the macropore structure. ► The coated microspheres were applied to rapid protein separation.

  17. The Role of Wheat and Egg Constituents in the Formation of a Covalent and Non-covalent Protein Network in Fresh and Cooked Egg Noodles.

    Science.gov (United States)

    Lambrecht, Marlies A; Rombouts, Ine; Nivelle, Mieke A; Delcour, Jan A

    2017-01-01

    Noodles of constant protein content and flour-to-egg protein ratio were made with whole egg, egg white, or egg yolk. The optimal cooking time, water absorption, and cooking loss of salted whole egg noodles was respectively lower and higher than of egg white and egg yolk noodles. However, cooked whole egg noodles showed the best Kieffer-rig extensibility. Differences in noodle properties were linked to protein network formation. Disulfide bonds in whole egg noodles developed faster and to a larger extent during cooking than in egg yolk noodles but slower and to a lower extent than in egg white noodles. The balance between the rate of protein cross-linking and starch swelling determines cooked noodle properties. Ionic and hydrophobic protein interactions increase the optimum cooking time and total work in Kieffer-rig extensibility testing of fresh noodles. Hydrogen bonds and covalent cross-links are probably the main determinants of the extensibility of cooked noodles. © 2016 Institute of Food Technologists®.

  18. Muon-oxygen bonding in V2O3

    International Nuclear Information System (INIS)

    Chan, K.C.B.; Lichti, R.L.; Boekema, C.

    1986-01-01

    A muon site search using calculated internal fields has been performed for V 2 O 3 , where purely dipolar fields allow a site determination free from covalent complications. The obtained sites are a subset of the Rodriguez and Bates sites found in α-Fe 2 O 3 and indicate muon oxygen bond formation. The sites missing at low temperatures are consistent with the vanadium pairing mechanism for the metal-to-insulator (corundum-to-monoclinic) phase transition. (orig.)

  19. Understanding Bonds - Denmark

    DEFF Research Database (Denmark)

    Rimmer, Nina Røhr

    2016-01-01

    Undervisningsmateriale. A bond is a debt security, similar to an ”I Owe You document” (IOU). When you purchase a bond, you are lending money to a government, municipality, corporation, federal agency or other entity known as the issuer. In return for the loan, the issuer promises to pay you...... 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...... securities and foreign government bonds....

  20. 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.

  1. 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

  2. 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.

  3. The effect of non-covalent functionalization on the thermal conductance of graphene/organic interfaces

    International Nuclear Information System (INIS)

    Lin Shangchao; Buehler, Markus J

    2013-01-01

    The intrinsic interfacial thermal resistance at graphene/organic interfaces, as a result of mismatches in the phonon vibrational spectra of the two materials, diminishes the overall heat transfer performance of graphene/organic nanocomposites. In this paper, we use molecular dynamics (MD) simulations to design alkyl-pyrene molecules that can non-covalently functionalize graphene surfaces in contact with a model organic phase composed of octane. The alkyl-pyrene molecules possess phonon-spectra features of both graphene and octane and, therefore, can serve as phonon-spectra linkers to bridge the vibrational mismatch at the graphene/octane interface. In support of this hypothesis, we find that the best linker candidate can enhance the out-of-plane graphene/organic interfacial thermal conductance by ∼22%, attributed to its capability to compensate the low-frequency phonon mode of graphene. We also find that the length of the alkyl chain indirectly affects the interfacial thermal conductance through different orientations of these chains because they dictate the contribution of the out-of-plane high-frequency carbon–hydrogen bond vibrations to the overall phonon transport. This study advances our understanding of the less destructive non-covalent functionalization method and design principles of suitable linker molecules to enhance the thermal performance of graphene/organic nanocomposites while retaining the intrinsic chemical, thermal, and mechanical properties of pristine graphene. (paper)

  4. Theory of Covalent Adsorbate Frontier Orbital Energies on Functionalized Light-Absorbing Semiconductor Surfaces.

    Science.gov (United States)

    Yu, Min; Doak, Peter; Tamblyn, Isaac; Neaton, Jeffrey B

    2013-05-16

    Functional hybrid interfaces between organic molecules and semiconductors are central to many emerging information and solar energy conversion technologies. Here we demonstrate a general, empirical parameter-free approach for computing and understanding frontier orbital energies - or redox levels - of a broad class of covalently bonded organic-semiconductor surfaces. We develop this framework in the context of specific density functional theory (DFT) and many-body perturbation theory calculations, within the GW approximation, of an exemplar interface, thiophene-functionalized silicon (111). Through detailed calculations taking into account structural and binding energetics of mixed-monolayers consisting of both covalently attached thiophene and hydrogen, chlorine, methyl, and other passivating groups, we quantify the impact of coverage, nonlocal polarization, and interface dipole effects on the alignment of the thiophene frontier orbital energies with the silicon band edges. For thiophene adsorbate frontier orbital energies, we observe significant corrections to standard DFT (∼1 eV), including large nonlocal electrostatic polarization effects (∼1.6 eV). Importantly, both results can be rationalized from knowledge of the electronic structure of the isolated thiophene molecule and silicon substrate systems. Silicon band edge energies are predicted to vary by more than 2.5 eV, while molecular orbital energies stay similar, with the different functional groups studied, suggesting the prospect of tuning energy alignment over a wide range for photoelectrochemistry and other applications.

  5. A novel, eco-friendly technique for covalent functionalization of graphene nanoplatelets and the potential of their nanofluids for heat transfer applications

    Science.gov (United States)

    Sadri, Rad; Hosseini, Maryam; Kazi, S. N.; Bagheri, Samira; Zubir, Nashrul; Ahmadi, Goodarz; Dahari, Mahidzal; Zaharinie, Tuan

    2017-05-01

    In this study, a facile and eco-friendly covalent functionalization technique is developed to synthesize highly stable graphene nanoplatelets (GNPs) in aqueous media. This technique involves free radical grafting of gallic acid onto the surface of GNPs rather than corrosive inorganic acids. Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy are used to confirm the covalent functionalization of GNPs with gallic acid (GAGNPs). The solubility of the GAGNPs in aqueous media is verified using zeta potential and UV-vis spectra measurements. The nanofluid shows significant improvement in thermo-physical properties, indicating its superb potential for various thermal applications.

  6. 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...

  7. Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry

    Science.gov (United States)

    Ryder, Christopher R.; Wood, Joshua D.; Wells, Spencer A.; Yang, Yang; Jariwala, Deep; Marks, Tobin J.; Schatz, George C.; Hersam, Mark C.

    2016-06-01

    Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)—a layered two-dimensional semiconductor—exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

  8. Luminescent hybrid films obtained by covalent grafting of terbium complex to silica network

    International Nuclear Information System (INIS)

    Liu Fengyi; Fu Lianshe; Wang Jun; Liu Ze; Li Huanrong; Zhang Hongjie

    2002-01-01

    Luminescent hybrid thin films consisting of terbium complex covalently bonded to a silica-based network have been obtained in situ via a sol-gel approach. A new monomer, N-(4-benzoic acid-yl), N'-(propyltriethoxysilyl)urea (PABI), has been synthesized by grafting isocyanatopropyltriethoxysilane (ICPTES) to p-aminobenzoic acid and characterized by 1 H NMR, IR and MS. The monomer acts as a ligand for Tb 3+ ion and as a sol-gel precursor. Band emission from Tb 3+ ion due to an efficient ligand-to-metal energy transfer was observed by UV excitation. The decay curves of Tb 3+ in the hybrid films were measured. The energy difference between the triplet state energy of PABI and the 5 D 4 level of Tb 3+ ion falls in the exciting range to sensitize Tb 3+ ion fluorescence

  9. 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

    2012-01-01

    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 Al(12)W-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.

  10. Solitons on H bonds in proteins

    DEFF Research Database (Denmark)

    d'Ovidio, F.; Bohr, H.G.; Lindgård, Per-Anker

    2003-01-01

    system shows that the solitons are spontaneously created and are stable and moving along the helix axis. A perturbation on one of the three H-bond lines forms solitons on the other H bonds as well. The robust solitary wave may explain very long-lived modes in the frequency range of 100 cm(-1) which...... are found in recent x-ray laser experiments. The dynamics parameters of the Toda lattice are in accordance with the usual Lennard-Jones parameters used for realistic H-bond potentials in proteins....

  11. 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.

  12. Bonding and M?ssbauer Isomer Shifts in (Tl,Pb) - 1223 Cuprate

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    By using the chemical bond theory of dielectric description,the chemical bond parameters of (Tl,Pb) - 1223 was calculated.The results show that the Sr-O,Tl-O,and Ca-O types of bond have higher ionic character and the Cu-O types of bond have more covalent character.M?ssbauer isomer shifts of 57Fe and 119Sn doped in (Tl,Pb) -1223 were calculated by using the chemical environmental factor,he,defined by covalency and electronic polarizability.Four valence state tin and three valence iron sites were identified in 57Fe,and 119Sn doped (Tl,Pb) -1223 superconductor.We conclude that all of the Fe atoms substitute the Cu at square planar Cu (1) site,whereas Sn prefers to substitute the square pyramidal Cu (2) site.

  13. Bonding and Moessbauer Isomer Shifts in (Hg,Pb)—1223 Cuprate

    Institute of Scientific and Technical Information of China (English)

    高发明; 田永君; 谌岩; 李东春; 董海峰; 张思远

    2003-01-01

    By using the chemical bond theory of dielectric description,the chemical bond parameters of(Hg,Pb)-1223 were calculated.The results show that the(Ba,Sr)-O and Ca-0 types of bond have higher ionic character,while the Cu-O and(Hg,Pb)-0 types of bond have more covalent character.Moessbauer isomer shifts of 57Fe and 119Sn doped in(Hg,Pb)-1223 were calculated by using the chemical environmental factor,he,defined by covalency and electronic polarizability.Four valence state tin and three valence iron sites were identified in 57Fe and 119Sn doped(Hg,Pb)-1223 superconductor.It can be concluded that all of the Fe atoms substitute the Cu at square planar Cu(1) site,Whereas Sn prefers to substitute the square pyramidal Cu(2) site.

  14. 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...... a low toxicity of the conjugates in the THP-1 cells. The low toxicity and the cellular uptake of single-walled carbon nanotube–folic acid by cancer cells suggest their potential use in carbon nanotube-based drug delivery systems and in the diagnosis of cancer or tropical diseases such as leishmaniasis....

  15. 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.

  16. Substituent Effects on the Hydrogen Bonding Between Phenolate and HF, H2O and NH3

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    B3LYP/6-31+g(d) calculations were performed on the hydrogen bonded complexes between substituted phenolates and HF, H2O as well as NH3. It was found that some properties of the non-covalent complexes, including the interaction energies, donor-acceptor (host-guest) distances, bond lengths, and vibration frequencies, could show well-defined substituent effects. Thus, from the substituent studies we can not only understand the mechanism of a particular non-covalent interaction better, but also easily predict the interaction energies and structures of a particular non-covalent complex, which might otherwise be very hard or resource-consuming to be known. This means that substituent effect is indeed a useful tool to be used in supramolecular chemistry and therefore, many valuable studies remain to be carried out.

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

    Institute of Scientific and Technical Information of China (English)

    高发明; 李东春; 张思远

    2003-01-01

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

  18. Effects of a donor on the bond property of quantum-dot molecules

    Institute of Scientific and Technical Information of China (English)

    Wang Li-Min; Luo Ying; Ma Ben-Kun; Duan Su-Qing; Zhao Xian-Geng

    2004-01-01

    Within the framework of effective mass approximation, we have calculated the electronic structure of the two laterally coupled quantum dots with a donor by the finite element method. The calculated results show that the bond states of quantum-dot molecules are quite sensitive to the donor positions. By varying the donor position, the transition from covalent to ionic bond state is realized for some electronic states. Some extreme cases are also discussed for comparison.

  19. Theory and Applications of Covalent Docking in Drug Discovery: Merits and Pitfalls

    Directory of Open Access Journals (Sweden)

    Hezekiel Mathambo Kumalo

    2015-01-01

    Full Text Available he present art of drug discovery and design of new drugs is based on suicidal irreversible inhibitors. Covalent inhibition is the strategy that is used to achieve irreversible inhibition. Irreversible inhibitors interact with their targets in a time-dependent fashion, and the reaction proceeds to completion rather than to equilibrium. Covalent inhibitors possessed some significant advantages over non-covalent inhibitors such as covalent warheads can target rare, non-conserved residue of a particular target protein and thus led to development of highly selective inhibitors, covalent inhibitors can be effective in targeting proteins with shallow binding cleavage which will led to development of novel inhibitors with increased potency than non-covalent inhibitors. Several computational approaches have been developed to simulate covalent interactions; however, this is still a challenging area to explore. Covalent molecular docking has been recently implemented in the computer-aided drug design workflows to describe covalent interactions between inhibitors and biological targets. In this review we highlight: (i covalent interactions in biomolecular systems; (ii the mathematical framework of covalent molecular docking; (iii implementation of covalent docking protocol in drug design workflows; (iv applications covalent docking: case studies and (v shortcomings and future perspectives of covalent docking. To the best of our knowledge; this review is the first account that highlights different aspects of covalent docking with its merits and pitfalls. We believe that the method and applications highlighted in this study will help future efforts towards the design of irreversible inhibitors.

  20. 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.

  1. 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.

  2. 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.

  3. 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

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

    Science.gov (United States)

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

    2017-03-01

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

  5. 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

  6. 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.

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

    International Nuclear Information System (INIS)

    Lipińska, Monika E.; Rebelo, Susana L.H.; Pereira, M. Fernando R.; Figueiredo, José L.; Freire, Cristina

    2013-01-01

    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 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

  8. 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.

  9. Covalent modification and exfoliation of graphene oxide using ferrocene

    Science.gov (United States)

    Avinash, M. B.; Subrahmanyam, K. S.; Sundarayya, Y.; Govindaraju, T.

    2010-09-01

    Large scale preparation of single-layer graphene and graphene oxide is of great importance due to their potential applications. We report a simple room temperature method for the exfoliation of graphene oxide using covalent modification of graphene oxide with ferrocene to obtain single-layer graphene oxide sheets. The samples were characterized by FESEM, HRTEM, AFM, EDAX, FT-IR, Raman and Mössbauer spectroscopic studies. HRTEM micrograph of the covalently modified graphene oxide showed increased interlayer spacing of ~2.4 nm due to ferrocene intercalation. The presence of single-layer graphene oxide sheets were confirmed by AFM studies. The covalently modified ferrocene-graphene oxide composite showed interesting magnetic behavior.Large scale preparation of single-layer graphene and graphene oxide is of great importance due to their potential applications. We report a simple room temperature method for the exfoliation of graphene oxide using covalent modification of graphene oxide with ferrocene to obtain single-layer graphene oxide sheets. The samples were characterized by FESEM, HRTEM, AFM, EDAX, FT-IR, Raman and Mössbauer spectroscopic studies. HRTEM micrograph of the covalently modified graphene oxide showed increased interlayer spacing of ~2.4 nm due to ferrocene intercalation. The presence of single-layer graphene oxide sheets were confirmed by AFM studies. The covalently modified ferrocene-graphene oxide composite showed interesting magnetic behavior. Electronic supplementary information (ESI) available: Magnetic data; AFM images; TEM micrographs; and Mössbauer spectroscopic data. See DOI: 10.1039/c0nr00024h

  10. Covalent and non-covalent curcumin loading in acid-responsive polymeric micellar nanocarriers

    Science.gov (United States)

    Gao, Min; Chen, Chao; Fan, Aiping; Zhang, Ju; Kong, Deling; Wang, Zheng; Zhao, Yanjun

    2015-07-01

    Poor aqueous solubility, potential degradation, rapid metabolism and elimination lead to low bioavailability of pleiotropic impotent curcumin. Herein, we report two types of acid-responsive polymeric micelles where curcumin was encapsulated via both covalent and non-covalent modes for enhanced loading capacity and on-demand release. Biodegradable methoxy poly(ethylene glycol)-poly(lactic acid) copolymer (mPEG-PLA) was conjugated with curcumin via a hydrazone linker, generating two conjugates differing in architecture (single-tail versus double-tail) and free curcumin was encapsulated therein. The two micelles exhibited similar hydrodynamic size at 95 ± 3 nm (single-tail) and 96 ± 3 nm (double-tail), but their loading capacities differed significantly at 15.0 ± 0.5% (w/w) (single-tail) and 4.8 ± 0.5% (w/w) (double-tail). Under acidic sink conditions (pH 5.0 and 6.0), curcumin displayed a faster release from the single-tail nanocarrier, which was correlated to a low IC50 of 14.7 ± 1.6 (μg mL-1) compared to the value of double-tail micelle (24.9 ± 1.3 μg mL-1) in HeLa cells. The confocal imaging and flow cytometry analysis demonstrated a superior capability of single-tail micelle for intracellular curcumin delivery, which was a consequence of the higher loading capacity and lower degree of mPEG surface coverage. In conclusion, the dual loading mode is an effective means to increase the drug content in the micellar nanocarriers whose delivery efficiency is highly dependent on its polymer-drug conjugate architecture. This strategy offers an alternative nanoplatform for intracellularly delivering impotent hydrophobic agents (i.e. curcumin) in an efficient stimuli-triggered way, which is valuable for the enhancement of curcumin’s efficacy in managing a diverse range of disorders.

  11. Covalent and non-covalent curcumin loading in acid-responsive polymeric micellar nanocarriers

    International Nuclear Information System (INIS)

    Gao, Min; Chen, Chao; Fan, Aiping; Wang, Zheng; Zhao, Yanjun; Zhang, Ju; Kong, Deling

    2015-01-01

    Poor aqueous solubility, potential degradation, rapid metabolism and elimination lead to low bioavailability of pleiotropic impotent curcumin. Herein, we report two types of acid-responsive polymeric micelles where curcumin was encapsulated via both covalent and non-covalent modes for enhanced loading capacity and on-demand release. Biodegradable methoxy poly(ethylene glycol)-poly(lactic acid) copolymer (mPEG-PLA) was conjugated with curcumin via a hydrazone linker, generating two conjugates differing in architecture (single-tail versus double-tail) and free curcumin was encapsulated therein. The two micelles exhibited similar hydrodynamic size at 95 ± 3 nm (single-tail) and 96 ± 3 nm (double-tail), but their loading capacities differed significantly at 15.0 ± 0.5% (w/w) (single-tail) and 4.8 ± 0.5% (w/w) (double-tail). Under acidic sink conditions (pH 5.0 and 6.0), curcumin displayed a faster release from the single-tail nanocarrier, which was correlated to a low IC_5_0 of 14.7 ± 1.6 (μg mL"−"1) compared to the value of double-tail micelle (24.9 ± 1.3 μg mL"−"1) in HeLa cells. The confocal imaging and flow cytometry analysis demonstrated a superior capability of single-tail micelle for intracellular curcumin delivery, which was a consequence of the higher loading capacity and lower degree of mPEG surface coverage. In conclusion, the dual loading mode is an effective means to increase the drug content in the micellar nanocarriers whose delivery efficiency is highly dependent on its polymer–drug conjugate architecture. This strategy offers an alternative nanoplatform for intracellularly delivering impotent hydrophobic agents (i.e. curcumin) in an efficient stimuli-triggered way, which is valuable for the enhancement of curcumin’s efficacy in managing a diverse range of disorders. (paper)

  12. 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.

  13. Stable Isotope Data

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Tissue samples (skin, bone, blood, muscle) are analyzed for stable carbon, stable nitrogen, and stable sulfur analysis. Many samples are used in their entirety for...

  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. Direct covalent coupling of proteins to nanostructured plasma polymers: a route to tunable cell adhesion

    International Nuclear Information System (INIS)

    Melnichuk, Iurii; Choukourov, Andrei; Bilek, Marcela; Weiss, Anthony; Vandrovcová, Marta; Bačáková, Lucie; Hanuš, Jan; Kousal, Jaroslav; Shelemin, Artem; Solař, Pavel

    2015-01-01

    Highlights: • Flat and nanostructured interfaces were overcoated by hydrocarbon plasma polymer. • Linker-free covalent attachment of proteins to resultant surfaces was validated. • Ultra-thin hydrocarbon overcoat (<2 nm) secured prolonged effective binding. • Pre-adsorbed tropoelastin promoted proliferation of osteoblast-like MG-63 cells. • Nanostructured films were multi-affine and impeded cell adhesion. - Abstract: Flat and nanostructured thin films were fabricated by deposition of ultra-thin (<2 nm) layer of hydrocarbon plasma polymer over polished silicon and over a pattern of 8 nm-thick poly(ethylene) islands on silicon. Linker-free radical-based covalent binding of bovine serum albumin and tropoelastin was confirmed for both types of films. The binding capability of albumin was found to be stable over many days of ambient air storage time. Tropoelastin-mediated flat plasma polymers favored adhesion and proliferation of osteoblast-like MG-63 cells. Nanostructured plasma polymers were multi-affine and their hierarchical surface represented an additional barrier for cell attachment

  16. Tailorable thiolated trimethyl chitosans for covalently stabilized nanoparticles.

    Science.gov (United States)

    Verheul, Rolf J; van der Wal, Steffen; Hennink, Wim E

    2010-08-09

    A novel four-step method is presented to synthesize partially thiolated trimethylated chitosan (TMC) with a tailorable degree of quaternization and thiolation. First, chitosan was partially N-carboxylated with glyoxylic acid and sodium borohydride. Next, the remaining amines were quantitatively dimethylated with formaldehyde and sodium borohydride and then quaternized with iodomethane in NMP. Subsequently, these partially carboxylated TMCs dissolved in water were reacted with cystamine at pH 5.5 using EDC as coupling agent. After addition of DTT and dialysis, thiolated TMCs were obtained, varying in degree of quaternization (25-54%) and degree of thiolation (5-7%), as determined with (1)H NMR and Ellman's assay. Gel permeation chromatography with light scattering detection indicated limited intermolecular cross-linking. All thiolated TMCs showed rapid oxidation to yield disulfide cross-linked TMC at pH 7.4, while the thiolated polymers were rather stable at pH 4.0. When Calu-3 cells were used, XTT and LDH cell viability tests showed a slight reduction in cytotoxicity for thiolated TMCs as compared to the nonthiolated polymers with similar DQs. Positively charged nanoparticles loaded with fluorescently labeled ovalbumin were made from thiolated TMCs and thiolated hyaluronic acid. The stability of these particles was confirmed in 0.8 M NaCl, in contrast to particles made from nonthiolated polymers that dissociated under these conditions, demonstrating that the particles were held together by intermolecular disulfide bonds.

  17. 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.

  18. Exploring the Nature of Silicon-Noble Gas Bonds in H3SiNgNSi and HSiNgNSi Compounds (Ng = Xe, Rn

    Directory of Open Access Journals (Sweden)

    Sudip Pan

    2015-03-01

    Full Text Available Ab initio and density functional theory-based computations are performed to investigate the structure and stability of H3SiNgNSi and HSiNgNSi compounds (Ng = Xe, Rn. They are thermochemically unstable with respect to the dissociation channel producing Ng and H3SiNSi or HSiNSi. However, they are kinetically stable with respect to this dissociation channel having activation free energy barriers of 19.3 and 23.3 kcal/mol for H3SiXeNSi and H3SiRnNSi, respectively, and 9.2 and 12.8 kcal/mol for HSiXeNSi and HSiRnNSi, respectively. The rest of the possible dissociation channels are endergonic in nature at room temperature for Rn analogues. However, one three-body dissociation channel for H3SiXeNSi and one two-body and one three-body dissociation channels for HSiXeNSi are slightly exergonic in nature at room temperature. They become endergonic at slightly lower temperature. The nature of bonding between Ng and Si/N is analyzed by natural bond order, electron density and energy decomposition analyses. Natural population analysis indicates that they could be best represented as (H3SiNg+(NSi− and (HSiNg+(NSi−. Energy decomposition analysis further reveals that the contribution from the orbital term (ΔEorb is dominant (ca. 67%–75% towards the total attraction energy associated with the Si-Ng bond, whereas the electrostatic term (ΔEelstat contributes the maximum (ca. 66%–68% for the same in the Ng–N bond, implying the covalent nature of the former bond and the ionic nature of the latter.

  19. Dangling bonds and crystalline inclusions in amorphous materials

    Energy Technology Data Exchange (ETDEWEB)

    Ferrari, L [Ferrara Univ. (Italy). Ist. di Matematica; Russo, G [Bologna Univ. (Italy). Ist. di Fisica

    1981-02-07

    It is suggested that on the surface of crystalline inclusions dangling bond formation is favoured due to unbalanced local stresses. The energy for bond tearings is probably originated from the exothermic process leading to the crystalline inclusion configuration which is more stable than the original amorphous one. A thermodynamical calculation is performed giving the ratio nsub(k) of crystalline inclusions having k dangling bonds on their surface.

  20. Construction of porous covalent organic polymer as photocatalysts for RhB degradation under visible light

    Institute of Scientific and Technical Information of China (English)

    Pingxiao Liu; Lingbao Xing; Hongtao Lin; Haining Wang; Ziyan Zhou; Zhongmin Su

    2017-01-01

    In the present work,a novel porous,and chemically stable amine-based covalent organic polymer (POP-1) was designed and synthesized under solvothermal conditions.The porosity,crystallinity,chemical stability,electrochemical properties,and diffuse reflectance of POP-1 were investigated via N2 sorption experiment,power X-ray diffraction,thermogravimetric analysis,cyclic voltammetry,and ultraviolet visible near infrared spectrometry,respectively.POP-1 exhibits good chemical stability in both acidic and alkaline aqueous solutions,as well as in organic solvents.Undoped POP-1 can be directly used as a photocatalyst for rhodamine B irradiation degradation under light-emitting diode and natural light.The Ea of POP-1 for RhB degradation is 82.37 kJ/mol.Furthermore,POP-1 can be reused as a catalyst in RhB degradation without degraded catalytic activity.

  1. Multiply fully recyclable carbon fibre reinforced heat-resistant covalent thermosetting advanced composites.

    Science.gov (United States)

    Yuan, Yanchao; Sun, Yanxiao; Yan, Shijing; Zhao, Jianqing; Liu, Shumei; Zhang, Mingqiu; Zheng, Xiaoxing; Jia, Lei

    2017-03-02

    Nondestructive retrieval of expensive carbon fibres (CFs) from CF-reinforced thermosetting advanced composites widely applied in high-tech fields has remained inaccessible as the harsh conditions required to recycle high-performance resin matrices unavoidably damage the structure and properties of CFs. Degradable thermosetting resins with stable covalent structures offer a potential solution to this conflict. Here we design a new synthesis scheme and prepare a recyclable CF-reinforced poly(hexahydrotriazine) resin matrix advanced composite. The multiple recycling experiments and characterization data establish that this composite demonstrates performance comparable to those of its commercial counterparts, and more importantly, it realizes multiple intact recoveries of CFs and near-total recycling of the principal raw materials through gentle depolymerization in certain dilute acid solution. To our best knowledge, this study demonstrates for the first time a feasible and environment-friendly preparation-recycle-regeneration strategy for multiple CF-recycling from CF-reinforced advanced composites.

  2. 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

  3. 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.

  4. Scaled MP3 non-covalent interaction energies agree closely with accurate CCSD(T) benchmark data.

    Science.gov (United States)

    Pitonák, Michal; Neogrády, Pavel; Cerný, Jirí; Grimme, Stefan; Hobza, Pavel

    2009-01-12

    Scaled MP3 interaction energies calculated as a sum of MP2/CBS (complete basis set limit) interaction energies and scaled third-order energy contributions obtained in small or medium size basis sets agree very closely with the estimated CCSD(T)/CBS interaction energies for the 22 H-bonded, dispersion-controlled and mixed non-covalent complexes from the S22 data set. Performance of this so-called MP2.5 (third-order scaling factor of 0.5) method has also been tested for 33 nucleic acid base pairs and two stacked conformers of porphine dimer. In all the test cases, performance of the MP2.5 method was shown to be superior to the scaled spin-component MP2 based methods, e.g. SCS-MP2, SCSN-MP2 and SCS(MI)-MP2. In particular, a very balanced treatment of hydrogen-bonded compared to stacked complexes is achieved with MP2.5. The main advantage of the approach is that it employs only a single empirical parameter and is thus biased by two rigorously defined, asymptotically correct ab-initio methods, MP2 and MP3. The method is proposed as an accurate but computationally feasible alternative to CCSD(T) for the computation of the properties of various kinds of non-covalently bound systems.

  5. Covalent heme attachment to the protein in human heme oxygenase-1 with selenocysteine replacing the His25 proximal iron ligand.

    Science.gov (United States)

    Jiang, Yongying; Trnka, Michael J; Medzihradszky, Katalin F; Ouellet, Hugues; Wang, Yongqiang; Ortiz de Montellano, Paul R

    2009-03-01

    To characterize heme oxygenase with a selenocysteine (SeCys) as the proximal iron ligand, we have expressed truncated human heme oxygenase-1 (hHO-1) His25Cys, in which Cys-25 is the only cysteine, in the Escherichia coli cysteine auxotroph strain BL21(DE3)cys. Selenocysteine incorporation into the protein was demonstrated by both intact protein mass measurement and mass spectrometric identification of the selenocysteine-containing tryptic peptide. One selenocysteine was incorporated into approximately 95% of the expressed protein. Formation of an adduct with Ellman's reagent (DTNB) indicated that the selenocysteine in the expressed protein was in the reduced state. The heme-His25SeCys hHO-1 complex could be prepared by either (a) supplementing the overexpression medium with heme, or (b) reconstituting the purified apoprotein with heme. Under reducing conditions in the presence of imidazole, a covalent bond is formed by addition of the selenocysteine residue to one of the heme vinyl groups. No covalent bond is formed when the heme is replaced by mesoheme, in which the vinyls are replaced by ethyl groups. These results, together with our earlier demonstration that external selenolate ligands can transfer an electron to the iron [Y. Jiang, P.R. Ortiz de Montellano, Inorg. Chem. 47 (2008) 3480-3482 ], indicate that a selenyl radical is formed in the hHO-1 His25SeCys mutant that adds to a heme vinyl group.

  6. Photodissociative Cross-Linking of Non-covalent Peptide-Peptide Ion Complexes in the Gas Phase

    Science.gov (United States)

    Nguyen, Huong T. H.; Andrikopoulos, Prokopis C.; Rulíšek, Lubomír; Shaffer, Christopher J.; Tureček, František

    2018-05-01

    We report a gas-phase UV photodissociation study investigating non-covalent interactions between neutral hydrophobic pentapeptides and peptide ions incorporating a diazirine-tagged photoleucine residue. Phenylalanine (Phe) and proline (Pro) were chosen as the conformation-affecting residues that were incorporated into a small library of neutral pentapeptides. Gas-phase ion-molecule complexes of these peptides with photo-labeled pentapeptides were subjected to photodissociation. Selective photocleavage of the diazirine ring at 355 nm formed short-lived carbene intermediates that underwent cross-linking by insertion into H-X bonds of the target peptide. The cross-link positions were established from collision-induced dissociation tandem mass spectra (CID-MS3) providing sequence information on the covalent adducts. Effects of the amino acid residue (Pro or Phe) and its position in the target peptide sequence were evaluated. For proline-containing peptides, interactions resulting in covalent cross-links in these complexes became more prominent as proline was moved towards the C-terminus of the target peptide sequence. The photocross-linking yields of phenylalanine-containing peptides depended on the position of both phenylalanine and photoleucine. Density functional theory calculations were used to assign structures of low-energy conformers of the (GLPMG + GLL*LK + H)+ complex. Born-Oppenheimer molecular dynamics trajectory calculations were used to capture the thermal motion in the complexes within 100 ps and determine close contacts between the incipient carbene and the H-X bonds in the target peptide. This provided atomic-level resolution of potential cross-links that aided spectra interpretation and was in agreement with experimental data. [Figure not available: see fulltext.

  7. Determination of the number of and classification of two-component ionic-covalent chemical compounds

    International Nuclear Information System (INIS)

    Vigdorovich, V.N.; Dzhuraev, T.D.; Khanin, V.A.

    1989-01-01

    The aim of this work was to determine the number of and to classify two-component compounds corresponding to the four-electron and full-valence concepts and characterized by the ionic-covalent type of bond, on which the metallic bond is superimposed to a greater lesser degree. At the same time it was proposed to verify the position of the axes in the periodic system. The presence of numerous compound analogs for the element prototypes of one axis of the Mendeleev periodic system [the group of noble (inert) gases] was confirmed by computer experiments. However, the other axis (the carbon group) is not so obvious and is evidently due, on account of the superimposition of the effect of noncharacteristic (possible) valences, to the elements of various groups (boron, aluminum, germanium, antimony, bismuth). In addition, the compound analogs for the element prototypes of the d block are numerous, i.e., the copper-silver-gold, manganese-technetium-rhenium, and iron and platinum families

  8. 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.

  9. 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

  10. 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.

  11. COVAL, Compound Probability Distribution for Function of Probability Distribution

    International Nuclear Information System (INIS)

    Astolfi, M.; Elbaz, J.

    1979-01-01

    1 - Nature of the physical problem solved: Computation of the probability distribution of a function of variables, given the probability distribution of the variables themselves. 'COVAL' has been applied to reliability analysis of a structure subject to random loads. 2 - Method of solution: Numerical transformation of probability distributions

  12. Covalent Attachment of Bent-Core Mesogens to Silicon Surfaces

    NARCIS (Netherlands)

    Scheres, L.; Achten, R.; Giesbers, M.; Smet, de L.; Arafat, A.; Sudhölter, E.J.R.; Marcelis, A.T.M.; Zuilhof, H.

    2009-01-01

    Two vinyl-terminated bent core-shaped liquid crystalline molecules that exhibit thermotropic antiferroelectric SmCPA phases have been covalently attached onto a hydrogen-terminated silicon(111) surface. The surface attachment was achieved via a mild procedure from a mesitylene solution, using

  13. Multi-step non-covalent pathways to supramolecular systems

    NARCIS (Netherlands)

    Hermans, T.M.

    2010-01-01

    The spontaneous organization of building blocks into ordered structures governed by non-covalent interactions, or self-assembly, is a commonly encountered pathway in nature to obtain functional materials. These materials often consist of many different components ordered into intricate structures.

  14. Double Dynamic Supramolecular Polymers of Covalent Oligo-Dynamers

    NARCIS (Netherlands)

    Schaeffer, Gaël; Buhler, Eric; Candau, Sauveur Jean; Lehn, Jean-Marie

    2013-01-01

    Double-dynamic polymers, incorporating both molecular and supramolecular dynamic features (“double dynamers”) have been generated, where these functions are present in a nonstoichiometric ratio in the main chain of the polymer. It has been achieved by (1) the formation of covalent oligo-dynamers in

  15. 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)

  16. Bonding with Your Baby

    Science.gov (United States)

    ... the future bonding of the child and parent. Adoptive parents may be concerned about bonding with their ... general emotional support. And it's OK to ask family members and friends for help in the days — ...

  17. 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 ...

  18. Bonding Properties of a Novel Inorganometallic Complex, Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) (iPr-DAB = N,N'-Diisopropyl-1,4-diaza-1,3-butadiene), and its Stable Radical-Anion, Studied by UV-Vis, IR, and EPR Spectroscopy, (Spectro-) Electrochemistry, and Density Functional Calculations.

    Science.gov (United States)

    Aarnts, Maxim P.; Wilms, Maikel P.; Peelen, Karin; Fraanje, Jan; Goubitz, Kees; Hartl, Frantisek; Stufkens, Derk J.; Baerends, Evert Jan; Vlcek, Antonín

    1996-09-11

    Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) was synthesized and characterized by UV-vis, IR, (1)H NMR, (13)C NMR, (119)Sn NMR, and mass (FAB(+)) spectroscopies and by single-crystal X-ray diffraction, which proved the presence of a nearly linear Sn-Ru-Sn unit. Crystals of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB).3.5C(6)H(6) form in the triclinic space group P&onemacr; in a unit cell of dimensions a = 11.662(6) Å, b = 13.902(3) Å, c = 19.643(2) Å, alpha = 71.24(2) degrees, beta = 86.91(4) degrees, gamma = 77.89(3) degrees, and V = 2946(3) Å(3). One-electron reduction of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) produces the stable radical-anion [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)](*-) that was characterized by IR, and UV-vis spectroelectrochemistry. Its EPR spectrum shows a signal at g = 1.9960 with well resolved Sn, Ru, and iPr-DAB (H, N) hyperfine couplings. DFT-MO calculations on the model compound Ru(SnH(3))(2)(CO)(2)(H-DAB) reveal that the HOMO is mainly of sigma(Sn-Ru-Sn) character mixed strongly with the lowest pi orbital of the H-DAB ligand. The LUMO (SOMO in the reduced complex) should be viewed as predominantly pi(H-DAB) with an admixture of the sigma(Sn-Ru-Sn) orbital. Accordingly, the lowest-energy absorption band of the neutral species will mainly belong to the sigma(Sn-Ru-Sn)-->pi(iPr-DAB) charge transfer transition. The intrinsic strength of the Ru-Sn bond and the delocalized character of the three-center four-electron Sn-Ru-Sn sigma-bond account for the inherent stability of the radical anion.

  19. Phenylacetylene and H bond

    Indian Academy of Sciences (India)

    ... all resembling H bonds. Non-linear H bonds due to secondary interactions. C-H stretching frequency shows blue shift. Heavy atom distances are longer than the sum of van der Waals radii. Formed a task group through IUPAC to come up with a modern definition of H bond. 15 international experts including Desiraju.

  20. Stable convergence and stable limit theorems

    CERN Document Server

    Häusler, Erich

    2015-01-01

    The authors present a concise but complete exposition of the mathematical theory of stable convergence and give various applications in different areas of probability theory and mathematical statistics to illustrate the usefulness of this concept. Stable convergence holds in many limit theorems of probability theory and statistics – such as the classical central limit theorem – which are usually formulated in terms of convergence in distribution. Originated by Alfred Rényi, the notion of stable convergence is stronger than the classical weak convergence of probability measures. A variety of methods is described which can be used to establish this stronger stable convergence in many limit theorems which were originally formulated only in terms of weak convergence. Naturally, these stronger limit theorems have new and stronger consequences which should not be missed by neglecting the notion of stable convergence. The presentation will be accessible to researchers and advanced students at the master's level...

  1. 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

  2. Super-pnicogen bonding in the radical anion of the fluorophosphine dimer

    Science.gov (United States)

    Setiawan, Dani; Cremer, Dieter

    2016-10-01

    The LUMO of the pnicogen-bonded fluoro-phosphine dimer has PP bonding character. Radical anion and dianion form relatively strong pnicogen bonds with some covalent character where however the dianion turns out to be a second order transition state. The binding energy of (FPH 2)2- is 30.4 kcal/mol (CCSD(T)/aug-cc-pVTZ; CASPT2(5,8): 30.7 kcal/mol) and the bond strength order measured with the local PP bond stretching force constant increases from 0.055 for the neutral dimer to 0.187 thus revealing that the stabilization of the radical anion is to a large extend a result of one-electron six-center delocalization. Pnicogen-bonded complexes have a stabilizing electron affinity.

  3. The pseudohydrogen bond structures between 2-F-epoxy-butane and three kinds of bimolecular

    International Nuclear Information System (INIS)

    Liu Yanzhi; Yuan Kun; Lu Lingling; Zhu Yuancheng; Dong Xiaoning

    2012-01-01

    The weak intermolecular interactions between 2-F-epoxy-butane and Iminazole, Thiazole and Oxazole were theoretically discussed by using density functional B3LYP (Becke, three-parameter, Lee- Yang-Parr)/6-311++G ** and HF (Hartree Fock)/6-311++G ** methods. The results showed that both the N…H conventional hydrogen bond and C-F…H-C pseudohydrogen bond (PHB) structures are coexisting in the three complexes. The weak intermolecular interactions energies indicate the relative stabilities of the three complexes are proportionable. The calculated results showed that the stretch vibrational frequency of C-H bond (electronic acceptor) presents blue shift, but that of C-F bond, which is intensely related to F group (electronic donor), presents red shift. Electron density topological properties demonstrates that the covalent and ionic characteristics of the C-F…H-C pseudohydrogen bond are proportional to that of convention hydrogen bond. (authors)

  4. 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.)

  5. Bone bonding at natural and biomaterial surfaces.

    Science.gov (United States)

    Davies, John E

    2007-12-01

    Bone bonding is occurring in each of us and all other terrestrial vertebrates throughout life at bony remodeling sites. The surface created by the bone-resorbing osteoclast provides a three-dimensionally complex surface with which the cement line, the first matrix elaborated during de novo bone formation, interdigitates and is interlocked. The structure and composition of this interfacial bony matrix has been conserved during evolution across species; and we have known for over a decade that this interfacial matrix can be recapitulated at a biomaterial surface implanted in bone, given appropriate healing conditions. No evidence has emerged to suggest that bone bonding to artificial materials is any different from this natural biological process. Given this understanding it is now possible to explain why bone-bonding biomaterials are not restricted to the calcium-phosphate-based bioactive materials as was once thought. Indeed, in the absence of surface porosity, calcium phosphate biomaterials are not bone bonding. On the contrary, non-bonding materials can be rendered bone bonding by modifying their surface topography. This paper argues that the driving force for bone bonding is bone formation by contact osteogenesis, but that this has to occur on a sufficiently stable recipient surface which has micron-scale surface topography with undercuts in the sub-micron scale-range.

  6. Characterization of the regions from E. coli 16 S RNA covalently linked to ribosomal proteins S4 and S20 after ultraviolet irradiation

    International Nuclear Information System (INIS)

    Ehresmann, B.; Backendorf, C.; Ehresmann, C.; Ebel, J.P.

    1977-01-01

    The use of ultraviolet irradiation to form photochemical covalent bonds between the 16 S RNA and a ribosomal protein is a reliable method to check RNA regions which are interacting with the protein. This technique was successfully used to covalently link RNA or DNA and specific proteins in several cases. In the case of ribosome, it has been shown that the irradiation of 30 S and 50 S subunits using high doses of ultraviolet light allowed the covalent binding of almost all of the ribosomal proteins to the 16 S or 23 S RNAs. Using mild conditions, only proteins S7 and L4 could be covalently linked to the 16 S and 23 S RNAs, respectively, and the 16 S RNA region linked to protein S7 has now been characterized. The specificity of the photoreaction was demonstrated earlier and the tryptic peptides from proteins S4 and S7, photochemically linked to the 16 S RNA complexes, were identified. A report is presented on the sequences of the RNA regions which can be photochemically linked to proteins S4 and S7 after ultraviolet irradiation of the specific S4-16 S RNA and 20 S-16 S RNA complexes

  7. Benchmarking lithium amide versus amine bonding by charge density and energy decomposition analysis arguments.

    Science.gov (United States)

    Engelhardt, Felix; Maaß, Christian; Andrada, Diego M; Herbst-Irmer, Regine; Stalke, Dietmar

    2018-03-28

    Lithium amides are versatile C-H metallation reagents with vast industrial demand because of their high basicity combined with their weak nucleophilicity, and they are applied in kilotons worldwide annually. The nuclearity of lithium amides, however, modifies and steers reactivity, region- and stereo-selectivity and product diversification in organic syntheses. In this regard, it is vital to understand Li-N bonding as it causes the aggregation of lithium amides to form cubes or ladders from the polar Li-N covalent metal amide bond along the ring stacking and laddering principle. Deaggregation, however, is more governed by the Li←N donor bond to form amine adducts. The geometry of the solid state structures already suggests that there is σ- and π-contribution to the covalent bond. To quantify the mutual influence, we investigated [{(Me 2 NCH 2 ) 2 (C 4 H 2 N)}Li] 2 ( 1 ) by means of experimental charge density calculations based on the quantum theory of atoms in molecules (QTAIM) and DFT calculations using energy decomposition analysis (EDA). This new approach allows for the grading of electrostatic Li + N - , covalent Li-N and donating Li←N bonding, and provides a way to modify traditional widely-used heuristic concepts such as the -I and +I inductive effects. The electron density ρ ( r ) and its second derivative, the Laplacian ∇ 2 ρ ( r ), mirror the various types of bonding. Most remarkably, from the topological descriptors, there is no clear separation of the lithium amide bonds from the lithium amine donor bonds. The computed natural partial charges for lithium are only +0.58, indicating an optimal density supply from the four nitrogen atoms, while the Wiberg bond orders of about 0.14 au suggest very weak bonding. The interaction energy between the two pincer molecules, (C 4 H 2 N) 2 2- , with the Li 2 2+ moiety is very strong ( ca. -628 kcal mol -1 ), followed by the bond dissociation energy (-420.9 kcal mol -1 ). Partitioning the interaction energy

  8. 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

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

    Science.gov (United States)

    Zhang, Suling; Du, Zhuo; Li, Gongke

    2011-10-01

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

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

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

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

  12. 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.

  13. Effects of Electric Field on the Valence-Bond Property of an Electron in a Quantum-Dot Molecule

    Institute of Scientific and Technical Information of China (English)

    王立民; 罗莹; 马本堃

    2002-01-01

    The electronic structure of the quantum-dot molecules in an electric field is investigated by the finite element method with the effective mass approximation. The numerical calculation results show that the valence bond of the quantum-dot molecule alternates between covalent bonds and ionic bonds as the electric field increases. The valence-bond property can be reflected by the oscillator strength of the intraband transition. The bound state with the highest energy level in the quantum-dot molecule gradually changes into a quasibound state when the electric field increases.

  14. Structural, elastic, electronic, bonding, and optical properties of BeAZ2 (A = Si, Ge, Sn; Z = P, As) chalcopyrites

    International Nuclear Information System (INIS)

    Fahad, Shah; Murtaza, G.; Ouahrani, T.; Khenata, R.; Yousaf, Masood; Omran, S.Bin; Mohammad, Saleh

    2015-01-01

    A first principles density functional theory (DFT) technique is used to study the structural, chemical bonding, electronic and optical properties of BeAZ 2 (A = Si, Ge, Sn; Z = P, As) chalcopyrite materials. The calculated parameters are in good agreement with the available experimental results. The lattice constants and the equilibrium volume increased as we moved from Si to Ge to Sn, whereas the c/a and internal parameters u decreased by shifting the cation from P to As. These compounds are elastically stable. An investigation of the band gap using the WC-GGA, EV-GGA, PBE-GGA and mBJ-metaGGA potentials suggested that BeSiP 2 and BeSiAs 2 are direct band gap compounds, whereas BeGeP 2, BeGeAs 2, BeSnP 2, BeSnAs 2 are indirect band gap compounds. The energy band gaps decreased by changing B from Si to Sn and increased by changing the anion C from P to As. The bonding among the cations and anions is primarily ionic. In the optical properties, the real and imaginary parts of the dielectric functions, reflectivity and optical conductivity have been studied over a wide energy range. - Highlights: • The compounds are studied by FP-LAPW method within mBJ approximation. • All of the studied materials show isotropic behaviour. • All the compounds show direct band gap nature. • Bonding nature is mostly covalent among the studied compounds. • High absorption peaks and reflectivity ensures there utility in optoelectronic devices

  15. Exploring Covalent Allosteric Inhibition of Antigen 85C from Mycobacterium tuberculosis by Ebselen Derivatives.

    Science.gov (United States)

    Goins, Christopher M; Dajnowicz, Steven; Thanna, Sandeep; Sucheck, Steven J; Parks, Jerry M; Ronning, Donald R

    2017-05-12

    Previous studies identified ebselen as a potent in vitro and in vivo inhibitor of the Mycobacterium tuberculosis (Mtb) antigen 85 (Ag85) complex, comprising three homologous enzymes required for the biosynthesis of the mycobacterial cell wall. In this study, the Mtb Ag85C enzyme was cocrystallized with azido and adamantyl ebselen derivatives, resulting in two crystallographic structures of 2.01 and 1.30 Å resolution, respectively. Both structures displayed the anticipated covalent modification of the solvent accessible, noncatalytic Cys209 residue forming a selenenylsulfide bond. Continuous difference density for both thiol modifiers allowed for the assessment of interactions that influence ebselen binding and inhibitor orientation that were unobserved in previous Ag85C ebselen structures. The k inact /K I values for ebselen, adamantyl ebselen, and azido ebselen support the importance of observed constructive chemical interactions with Arg239 for increased in vitro efficacy toward Ag85C. To better understand the in vitro kinetic properties of these ebselen derivatives, the energetics of specific protein-inhibitor interactions and relative reaction free energies were calculated for ebselen and both derivatives using density functional theory. These studies further support the different in vitro properties of ebselen and two select ebselen derivatives from our previously published ebselen library with respect to kinetics and protein-inhibitor interactions. In both structures, the α9 helix was displaced farther from the enzyme active site than the previous Ag85C ebselen structure, resulting in the restructuring of a connecting loop and imparting a conformational change to residues believed to play a role in substrate binding specific to Ag85C. These notable structural changes directly affect protein stability, reducing the overall melting temperature by up to 14.5 °C, resulting in the unfolding of protein at physiological temperatures. Additionally, this structural

  16. 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.

  17. stableGP

    Data.gov (United States)

    National Aeronautics and Space Administration — The code in the stableGP package implements Gaussian process calculations using efficient and numerically stable algorithms. Description of the algorithms is in the...

  18. Angina Pectoris (Stable Angina)

    Science.gov (United States)

    ... Peripheral Artery Disease Venous Thromboembolism Aortic Aneurysm More Angina Pectoris (Stable Angina) Updated:Aug 21,2017 You may have heard the term “angina pectoris” or “stable angina” in your doctor’s office, ...

  19. Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger.

    Science.gov (United States)

    Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L

    2015-11-15

    The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX TEMPO EEQQQTEDELQDK. The X TEMPO residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-C α backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b H ) and y + H (y H ) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long

  20. Preparation and characterization of two types of covalently immobilized amyloglucosidase

    Directory of Open Access Journals (Sweden)

    ZORAN VUJCIC

    2005-05-01

    Full Text Available Amyloglucosidase from A. niger was covalently immobilized onto poly (GMA-co-EGDMA by the glutaraldehyde and periodate method. The immobilization of amyloglucosidase after periodate oxidation gave a preparate with the highest specific activity reported so far on similar polymers. The obtained immobilized preparates show the same pH optimum, but a higher temperature optimum compared with the soluble enzyme. The kinetic parameters for the hydrolysis of soluble starch by free and both immobilized enzymes were determined.

  1. Covalently bound molecular states in beryllium and carbon isotopes

    International Nuclear Information System (INIS)

    Wolfram von, Oertzen; Hans-Gerhard, Bohlen; Wolfram von, Oertzen

    2003-01-01

    Nuclear clustering in N=Z nuclei has been studied since many decades. States close to the decay thresholds, as described by the Ikeda diagram, are of particular interest. Recent studies in loosely bound systems, as observed with neutron-rich nuclei has revived the interest in cluster structures in nuclei, with additional valence neutrons, which give rise to pronounced covalent molecular structures. The Beryllium isotopes represent the first example of such unique states in nuclear physics with extreme deformations. In the deformed shell model these are referred to as super- and hyper-deformation. These states can be described explicitly by molecular concepts, with neutrons in covalent binding orbits. Examples of recent experiments performed at the HMI-Berlin demonstrating the molecular structure of the rotational bands in Beryllium isotopes are presented. Further work on chain states (nuclear polymers) in the carbon isotopes is in progress, these are the first examples of deformed structures in nuclei with an axis ratio of 3:1. A threshold diagram with clusters bound via neutrons in covalent molecular configurations can be established, which can serve as a guideline for future work. (authors)

  2. Substituent Effects on the Hydrogen Bonding between 4-Substituted Phenols and HF, H2O, NH3

    Institute of Scientific and Technical Information of China (English)

    程宇辉; 傅尧; 刘磊; 郭庆祥

    2003-01-01

    Density function theory UB3LYP/6-31+g(d) calculations were performed to study the hydrogen bonds between para-substituted phenols and HF, H2O, or NH3. It revealed that many properties of the non-covalent complexes, such as the interaction energies, donor-acceptor distances, bond lengths and vibration frequencies, showed well-defined substituent effects. Therefore, from the substituent effects not only the mechanism of a certain non-covalent interaction can be better understood, but also the interaction energies and structures of a certain non-covalent complex, which otherwise might be very hard or resource-consuming to estimate, can be easily predicted.

  3. BONDING ALUMINUM METALS

    Science.gov (United States)

    Noland, R.A.; Walker, D.E.

    1961-06-13

    A process is given for bonding aluminum to aluminum. Silicon powder is applied to at least one of the two surfaces of the two elements to be bonded, the two elements are assembled and rubbed against each other at room temperature whereby any oxide film is ruptured by the silicon crystals in the interface; thereafter heat and pressure are applied whereby an aluminum-silicon alloy is formed, squeezed out from the interface together with any oxide film, and the elements are bonded.

  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. 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-...

  6. 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...

  7. Application of infrared spectroscopy for study of chemical bonds in complexes of rare earth nitrates with alkylammonium nitrates

    International Nuclear Information System (INIS)

    Klimov, V.D.; Chudinov, Eh.G.

    1974-01-01

    The IR absorption spectra for the tri-n-octylamine, methyl-di-n-octylamine, their nitrates and complexes with the rare element nitrates are obtained. The IR spectra analysis of the complexes has suggested that the degree of covalent character bond of a nitrate with a metal grows with the atomic number of the element. Based on the comparison of the obtained data with those available in literature for various rare-earth complexes a conclusion is made that the bond character of a metal with nitrate groups is influenced by all ligands constituting the inner coordinating sphere. As the donor capacity of a ligand grows the covalent character of the metal-nitrate bond is enhanced. The replacement of the outer-sphere cations (trioctylammonium or methyldioctylammonium) only slightly affects the bond character of a metal with the nitrate group. The distribution coefficients in the rare-earth series are shown to decrease as the electrostatic part in the metal-nitrate declines. The phenomenon is attributed to the competition between nitrate and water for the metal bond as concurrently with the intensification of metal-nitrate covalent bond in the organic phase the strength of metal hydrates in aqueous phase grows much faster. (author)

  8. Highly sensitive covalently functionalized light-addressable potentiometric sensor for determination of biomarker

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Jintao [School of Life and Environmental Sciences, Guilin University of Electronic Technology, Guilin, Guangxi 541004 (China); Guangxi Experiment Center of Information Sciences, Guilin University of Electronic Technology, Guilin, Guangxi 541004 (China); Guan, Mingyuan; Huang, Guoyin; Qiu, Hengming; Chen, Zhengcheng [School of Life and Environmental Sciences, Guilin University of Electronic Technology, Guilin, Guangxi 541004 (China); Li, Guiyin, E-mail: liguiyin01@163.com [School of Life and Environmental Sciences, Guilin University of Electronic Technology, Guilin, Guangxi 541004 (China); Guangxi Experiment Center of Information Sciences, Guilin University of Electronic Technology, Guilin, Guangxi 541004 (China); Huang, Yong, E-mail: huangyong503@126.com [School of Life and Environmental Sciences, Guilin University of Electronic Technology, Guilin, Guangxi 541004 (China); Guangxi Experiment Center of Information Sciences, Guilin University of Electronic Technology, Guilin, Guangxi 541004 (China)

    2016-06-01

    A biomarker is related to the biological status of a living organism and shows great promise for the early prediction of a related disease. Herein we presented a novel structured light-addressable potentiometric sensor (LAPS) for the determination of a model biomarker, human immunoglobulin G (hIgG). In this system, the goat anti-human immunoglobulin G antibody was used as recognition element and covalently immobilized on the surface of light-addressable potentiometric sensor chip to capture human immunoglobulin G. Due to the light addressable capability of light-addressable potentiometric sensor, human immunoglobulin G dissolved in the supporting electrolyte solution can be detected by monitoring the potential shifts of the sensor. In order to produce a stable photocurrent, the laser diode controlled by field-programmable gate array was used as the light emitter to drive the light-addressable potentiometric sensor. A linear correlation between the potential shift response and the concentration of human immunoglobulin G was achieved and the corresponding regression equation was ΔV (V) = 0.00714C{sub hIgG} (μg/mL)–0.0147 with a correlation coefficient of 0.9968 over a range 0–150 μg/mL. Moreover, the light-addressable potentiometric sensor system also showed acceptable stability and reproducibility. All the results demonstrated that the system was more applicable to detection of disease biomarkers with simple operation, multiple-sample format and might hold great promise in various environmental, food, and clinical applications. - Highlights: • A novel structured light-addressable potentiometric sensor (LAPS) based on covalently functionalized membrane was designed. • The composition of the surface of LAPS chip was investigated by X-ray photoelectron spectroscopy (XPS). • hIgG dissolved in the supporting electrolyte solution can be detected by monitoring the potential shifts of LAPS.

  9. Catalytic mechanism and inhibition of tRNA (Uracil-5-)methyltransferase: evidence for covalent catalysis

    International Nuclear Information System (INIS)

    Santi, D.V.; Hardy, L.W.

    1987-01-01

    tRNA (Ura-5-) methyltransferase catalyzes the transfer of a methyl group from S-adenosylmethionine (AdoMet) to the 5-carbon of a specific Urd residue in tRNA. This results in stoichiometric release of tritium from [5- 3 H] Urd-labeled substrate tRNA isolated from methyltransferase-deficient Escherichia coli. The enzyme also catalyzes an AdoMet-independent exchange reaction between [5- 3 H]-Urd-labeled substrate tRNA and protons of water at a rate that is about 1% that of the normal methylation reaction, but with identical stoichiometry. S-Adenosylhomocysteine inhibits the rate of the exchange reaction by 2-3-fold, whereas an analog having the sulfur of AdoMet replaced by nitrogen accelerates the exchange reaction 9-fold. In the presence (but not absence) of AdoMet, 5-fluorouracil-substituted tRNA (FUra-tRNA) leads to the first-order inactivation of the enzyme. This is accompanied by the formation of a stable covalent complex containing the enzyme, FUra-tRNA, and the methyl group AdoMet. A mechanism for catalysis is proposed that explains both the 5-H exchange reaction and the inhibition by FUra-tRNA: the enzyme forms a covalent Michael adduct with substrate or inhibitor tRNA by attack of a nucleophilic group of the enzyme at carbon 6 of the pyrimidine residue to be modified. As a result, an anion equivalent is generated at carbon 5 that is sufficiently reactive to be methylated by AdoMet. Preliminary experiments and precedents suggest that the nucleophilic catalyst of the enzyme is a thiol group of cysteine. The potent irreversible inhibition by FUra-tRNA suggest that a mechanism for the RNA effects of FUra may also involve irreversible inhibition of RNA-modifying enzymes

  10. 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.

  11. Hydrogen bond disruption in DNA base pairs from (14)C transmutation.

    Science.gov (United States)

    Sassi, Michel; Carter, Damien J; Uberuaga, Blas P; Stanek, Christopher R; Mancera, Ricardo L; Marks, Nigel A

    2014-09-04

    Recent ab initio molecular dynamics simulations have shown that radioactive carbon does not normally fragment DNA bases when it decays. Motivated by this finding, density functional theory and Bader analysis have been used to quantify the effect of C → N transmutation on hydrogen bonding in DNA base pairs. We find that (14)C decay has the potential to significantly alter hydrogen bonds in a variety of ways including direct proton shuttling (thymine and cytosine), thermally activated proton shuttling (guanine), and hydrogen bond breaking (cytosine). Transmutation substantially modifies both the absolute and relative strengths of the hydrogen bonding pattern, and in two instances (adenine and cytosine), the density at the critical point indicates development of mild covalent character. Since hydrogen bonding is an important component of Watson-Crick pairing, these (14)C-induced modifications, while infrequent, may trigger errors in DNA transcription and replication.

  12. Influence of crystallography and bonding on the structure and migration of irrational interphase boundaries

    Science.gov (United States)

    Aaronson, H. I.

    2006-03-01

    Interphase boundary structure developed during precipitation from solid solution and during massive transformations is considered in diverse alloy systems in the presence of differences in stacking sequence across interphase boundaries. Linear misfit compensating defects, including misfit dislocations, structural disconnections, and misfit disconnections, are present over a wide range of crystallographie when both phases have metallic bonding. Misfit dislocations have also been observed when both phases have covalent bonding ( e.g., US: β US2 by Sole and van der Walt). These defects are also found when one phase is ionic and the other is metallic (Nb∶Al2O3 by Rühle et al.), albeit when the latter is formed by vapor deposition. However, when bonding is metallic in one phase but significantly covalent in the other, the structure of the interphase boundary appears to depend upon the strength of the covalent bonding relative to that in the metallically bonded phase. When this difference is large, growth can take place as if it were occurring at a free surface, resulting in orientation relationships that are irrational and conjugate habit planes that are ill matched ( e.g., ZrN: α Zr-N by Li et al. and Xe(solid):Al-Xe by Kishida and Yamaguchi). At lower levels of bonding directionality and strength, crystallography is again irrational, but now edge-to-edge-based low-energy structures can replace linear misfit compensating defects (γm:TiAl:αTi-Al by Reynolds et al.). In the perhaps still smaller difference case of Widmanstätten cementite precipitated from austenite, one orientation relationship yields plates with linear misfit compensating defects at their broad faces whereas another (presumably nucleated at different types of site) produces laths with poorly defined shapes and interfacial structures. Hence, Hume-Rothery-type bonding considerations can markedly affect interphase boundary structure and thus the mechanisms, kinetics, and morphology of growth.

  13. 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...

  14. 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...

  15. Effect of Interfacial Bonding on Interphase Properties in SiO2/Epoxy Nanocomposite: A Molecular Dynamics Simulation Study.

    Science.gov (United States)

    Wang, Zhikun; Lv, Qiang; Chen, Shenghui; Li, Chunling; Sun, Shuangqing; Hu, Songqing

    2016-03-23

    Atomistic molecular dynamics simulations have been performed to explore the effect of interfacial bonding on the interphase properties of a nanocomposite system that consists of a silica nanoparticle and the highly cross-linked epoxy matrix. For the structural properties, results show that interfacial covalent bonding can broaden the interphase region by increasing the radial effect range of fluctuated mass density and oriented chains, as well as strengthen the interphase region by improving the thermal stability of interfacial van der Waals excluded volume and reducing the proportion of cis conformers of epoxy segments. The improved thermal stability of the interphase region in the covalently bonded model results in an increase of ∼21 K in the glass transition temperature (Tg) compared to that of the pure epoxy. It is also found that interfacial covalent bonding mainly restricts the volume thermal expansion of the model at temperatures near or larger than Tg. Furthermore, investigations from mean-square displacement and fraction of immobile atoms point out that interfacial covalent and noncovalent bonding induces lower and higher mobility of interphase atoms than that of the pure epoxy, respectively. The obtained critical interfacial bonding ratio when the interphase and matrix atoms have the same mobility is 5.8%. These results demonstrate that the glass transitions of the interphase and matrix will be asynchronous when the interfacial bonding ratio is not 5.8%. Specifically, the interphase region will trigger the glass transition of the matrix when the ratio is larger than 5.8%, whereas it restrains the glass transition of the matrix when the ratio is smaller than 5.8%.

  16. 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.

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

    Science.gov (United States)

    Qiu, Hanxun; Han, Xuebin; Qiu, Feilong; Yang, Junhe

    2016-07-01

    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-1 at 0.5 A g-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.

  18. 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.

  19. Non-Covalent Fluorescent Labeling of Hairpin DNA Probe Coupled with Hybridization Chain Reaction for Sensitive DNA Detection.

    Science.gov (United States)

    Song, Luna; Zhang, Yonghua; Li, Junling; Gao, Qiang; Qi, Honglan; Zhang, Chengxiao

    2016-04-01

    An enzyme-free signal amplification-based assay for DNA detection was developed using fluorescent hairpin DNA probes coupled with hybridization chain reaction (HCR). The hairpin DNAs were designed to contain abasic sites in the stem moiety. Non-covalent labeling of the hairpin DNAs was achieved when a fluorescent ligand was bound to the abasic sites through hydrogen bonding with the orphan cytosine present on the complementary strand, accompanied by quench of ligand fluorescence. As a result, the resultant probes, the complex formed between the hairpin DNA and ligand, showed almost no fluorescence. Upon hybridization with target DNA, the probe underwent a dehybridization of the stem moiety containing an abasic site. The release of ligand from the abasic site to the solution resulted in an effective fluorescent enhancement, which can be used as a signal. Compared with a sensing system without HCR, a 20-fold increase in the sensitivity was achieved using the sensing system with HCR. The fluorescent intensity of the sensing system increased with the increase in target DNA concentration from 0.5 nM to 100 nM. A single mismatched target ss-DNA could be effectively discriminated from complementary target DNA. Genotyping of a G/C single-nucleotide polymorphism of polymerase chain reaction (PCR) products was successfully demonstrated with the sensing system. Therefore, integrating HCR strategy with non-covalent labeling of fluorescent hairpin DNA probes provides a sensitive and cost-effective DNA assay. © The Author(s) 2016.

  20. A binderless, covalently bulk modified electrochemical sensor: Application to simultaneous determination of lead and cadmium at trace level

    Energy Technology Data Exchange (ETDEWEB)

    Gunigollahalli Kempegowda, Raghu [Department of Studies in Chemistry, Bangalore University, Central College Campus, Bangalore 560001 (India); Malingappa, Pandurangappa, E-mail: mprangachem@gmail.com [Department of Studies in Chemistry, Bangalore University, Central College Campus, Bangalore 560001 (India)

    2012-05-30

    Highlights: Black-Right-Pointing-Pointer Proposed sensor is a new type of binderless covalent bulk modified electrode. Black-Right-Pointing-Pointer Surface can be easily renewed by simple mechanical polishing using emery sheets. Black-Right-Pointing-Pointer Free from modifier leaching during electrochemical measurements. Black-Right-Pointing-Pointer Provides long term storage stability with good reproducibility. Black-Right-Pointing-Pointer Nanomolar level detection limit achieved with selectivity. - Abstract: A new type of covalent binderless bulk modified electrode has been fabricated and used in the simultaneous determination of lead and cadmium ions at nanomolar level. The modification of graphitic carbon with 4-amino salicylic acid was carried out under microwave irradiation through the amide bond formation. The electrochemical behavior of the fabricated electrode has been carried out to decipher the interacting ability of the functional moieties present on the modifier molecules toward the simultaneous determination of Pb{sup 2+} and Cd{sup 2+} ions using cyclic and differential pulse anodic stripping voltammetry. The possible mode of interaction of functional groups with metal ions is proposed based on the pKa values of the modifier functionalities present on the surface of graphitic carbon particles. The analytical utility of the proposed sensor has been validated by measuring the lead and cadmium content from pretreated waste water samples of lead acid batteries.

  1. 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.

  2. Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings.

    Science.gov (United States)

    Wooles, Ashley J; Mills, David P; Tuna, Floriana; McInnes, Eric J L; Law, Gareth T W; Fuller, Adam J; Kremer, Felipe; Ridgway, Mark; Lewis, William; Gagliardi, Laura; Vlaisavljevich, Bess; Liddle, Stephen T

    2018-05-29

    Despite the fact that non-aqueous uranium chemistry is over 60 years old, most polarised-covalent uranium-element multiple bonds involve formal uranium oxidation states IV, V, and VI. The paucity of uranium(III) congeners is because, in common with metal-ligand multiple bonding generally, such linkages involve strongly donating, charge-loaded ligands that bind best to electron-poor metals and inherently promote disproportionation of uranium(III). Here, we report the synthesis of hexauranium-methanediide nanometre-scale rings. Combined experimental and computational studies suggest overall the presence of formal uranium(III) and (IV) ions, though electron delocalisation in this Kramers system cannot be definitively ruled out, and the resulting polarised-covalent U = C bonds are supported by iodide and δ-bonded arene bridges. The arenes provide reservoirs that accommodate charge, thus avoiding inter-electronic repulsion that would destabilise these low oxidation state metal-ligand multiple bonds. Using arenes as electronic buffers could constitute a general synthetic strategy by which to stabilise otherwise inherently unstable metal-ligand linkages.

  3. Stable Boundary Layer Issues

    OpenAIRE

    Steeneveld, G.J.

    2012-01-01

    Understanding and prediction of the stable atmospheric boundary layer is a challenging task. Many physical processes are relevant in the stable boundary layer, i.e. turbulence, radiation, land surface coupling, orographic turbulent and gravity wave drag, and land surface heterogeneity. The development of robust stable boundary layer parameterizations for use in NWP and climate models is hampered by the multiplicity of processes and their unknown interactions. As a result, these models suffer ...

  4. NOVEL APPLICATION OF POROUS AND CELLULAR MATERIALS FOR COVALENT IMMOBILIZATION OF PEPSIN

    Directory of Open Access Journals (Sweden)

    K. Szałapata

    Full Text Available Abstract Pepsin was immobilized via covalent bonds on different carriers: a silica gel carrier, acrylic beads, and a cellulose-based carrier - Granocel. All carriers were functionalized through the presence of -OH, -COOH, -NH2, or glycidyl groups on their surfaces. Three different cross-linkers were used for activation thereof. The results showed that Granocel activated by glutaraldehyde or carbodiimide and silica gel activated by glutaraldehyde were suitable carriers for the expression of enzyme activity. The optimum pH range for the native enzyme was 2.5-3.5 and this range was extended to the value 6.5 in the case of enzyme immobilized on the silica gel carrier and on Granocel. The optimum temperature values for the native and immobilized enzyme were in the range 37-40 °C and 40-50 °C, respectively. The activity of the immobilized pepsin at different values of pH and temperature was higher in comparison with the activity of the free enzyme.

  5. Surface functionalization of polyethylene via covalent immobilization of O-stearoyl-chitosan

    International Nuclear Information System (INIS)

    Xin, Zhirong; Hou, Juan; Ding, Jiaotong; Yang, Zongfeng; Yan, Shunjie; Liu, Chan

    2013-01-01

    When used in blood-contacting field, the hemocompatibility of polyethylene (PE) needs further to be improved. In this article, O-stearoyl-chitosans (OSC) with different esterification degrees were successfully prepared via changing the ratios of chitosan and stearoyl chloride for decreasing the cationic and hydrogen bond strength, thus improving the solubility of chitosan. The PE film was grafted with carboxyl groups of acrylic acid (AA) (PE-g-PAA) by means of O 2 plasma pre-treatment and UV-induced graft polymerization, and then PE-g-PAA was used for covalent immobilization of OSC. The above surface modification was confirmed by ATR-FTIR and XPS. Effect of the UV-irradiated graft polymerization parameters, i.e., the discharge power, the plasma pretreatment time, the UV irradiation time and the monomer concentration on the grafting density of AA was investigated. Relative to the value of about 107° for the virgin sample, the water contact angle (WCA) of the PAA-grafted film was about 50°. After the further immobilization of OSC onto the PAA-grafted film, the strength of negative charge of the PAA-grafted surface was decreased by the electropositive OSC, thus presenting a WCA value of about 62° and the excellent performance of anti-platelet adhesion with respect to the virgin and PAA-grafted samples.

  6. 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.

  7. Subtle differences in the hydrogen bonding of alcohol to divalent oxygen and sulfur

    DEFF Research Database (Denmark)

    Du, Lin; Tang, Shanshan; Hansen, Anne Schou

    2017-01-01

    complexes are more stable and form stronger hydrogen bonds compared to complexes with MeOH and EtOH, which are comparable, and only for the stronger hydrogen bond donor (TFE) are the small differences in acceptor molecules highlighted. The equilibrium constant for complex formation was determined from......The Osingle bondH⋯O and Osingle bondH⋯S hydrogen bonds were investigated by gas phase FTIR spectroscopy of alcohol–dimethylether and alcohol–dimethylsulfide complexes, with alcohols of increasing hydrogen bond donor strength; methanol (MeOH), ethanol (EtOH) and 2,2,2-trifluoroethanol (TFE). The TFE...

  8. Macromolecular weight specificity in covalent binding of bromobenzene

    International Nuclear Information System (INIS)

    Sun, J.D.; Dent, J.G.

    1984-01-01

    Bromobenzene is a hepatotoxicant that causes centrilobular necrosis. Pretreatment of animals with 3-methylcholanthrene decreases and phenobarbital pretreatment enhances the hepatotoxic action of this compound. We have investigated the macromolecular weight specificity of the covalent interactions of bromobenzene with liver macromolecules following incubation of [ 14 C]bromobenzene in isolated hepatocytes. Hepatocytes were prepared from Fischer-344 rats treated for 3 days with 3-methylcholanthrene, phenobarbital, or normal saline. After a 1-hr incubation, total covalent binding, as measured by sodium dodecyl sulfate-equilibrium dialysis, was twofold less in hepatocytes from 3-methylcholanthrene-treated rats and sixfold greater in hepatocytes from phenobarbital-treated rats, as compared to hepatocytes from control animals. Analysis of the arylated macromolecules by electrophoresis on 15% sodium dodecyl sulfate-polyacrylamide disc gels indicated that in the first 1 to 3 min of incubation substantial amounts of covalently bound radiolabel were associated with macromolecules of between 20,000 and 40,000. The amount of radioactivity associated with these macromolecules rapidly diminished in hepatocytes from control and 3-methylcholanthrene-treated animals. In hepatocytes from phenobarbital-treated animals, the amount of radioactivity associated with macromolecules, 20,000, increased throughout the incubation. The amount of radiolabel associated with macromolecules, 20,000, increased in all incubations. When nontoxic doses of phenylmethylsulfonyl fluoride, a specific inhibitor of serine proteases, were added to control hepatocytes incubated with [ 14 C]-bromobenzene, the decrease in radioactivity associated with larger (greater than 20,000) macromolecules was inhibited and a corresponding lack of increase in radioactivity associated with smaller macromolecules was observed

  9. Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).

    Science.gov (United States)

    Löble, Matthias W; Keith, Jason M; Altman, Alison B; Stieber, S Chantal E; Batista, Enrique R; Boland, Kevin S; Conradson, Steven D; Clark, David L; Lezama Pacheco, Juan; Kozimor, Stosh A; Martin, Richard L; Minasian, Stefan G; Olson, Angela C; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Zehnder, Ralph A

    2015-02-25

    Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln = Ce(III), Nd(III), Sm(III), Eu(III), Gd(III); x = 2 for Ln = Ce(IV)) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L3,2-edge and M5,4-edge XAS were also used to characterize CeCl6(x-) (x = 2, 3). The M5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce(III) and Ce(IV)). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t2g* and eg*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce(III) to Ce(IV) had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl6(3-) (formally Ln(III)), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce(IV) 4f-orbital mixing (t1u* + t2u*) in CeCl6(2-). This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).

  10. 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.

  11. Covalent functionalization of carbon nanotubes with tetramanganese complexes

    International Nuclear Information System (INIS)

    Meyer, Carola; Frielinghaus, Robert; Saelhoff, Anna-Katharina; Schneider, Claus M.; Besson, Claire; Floetotto, Henrik; Koegerler, Paul; Houben, Lothar

    2012-01-01

    We present first results on the covalent chemical functionalization of single-walled carbon nanotubes with polynuclear {Mn 4 } coordination complexes. Raman spectra prove that the reaction can only be achieved for tubes which have been oxidized to create carboxylic groups. HRTEM is used to show that the reaction can be carried out directly on a substrate as well. Analysis of the D/G intensity ratio for different oxidation times shows that it is possible to reduce the amount of defects created. This is important for the future application of this material in transport devices. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. 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)

  13. Gas-phase ion/ion reactions of peptides and proteins: acid/base, redox, and covalent chemistries.

    Science.gov (United States)

    Prentice, Boone M; McLuckey, Scott A

    2013-02-01

    Gas-phase ion/ion reactions are emerging as useful and flexible means for the manipulation and characterization of peptide and protein biopolymers. Acid/base-like chemical reactions (i.e., proton transfer reactions) and reduction/oxidation (redox) reactions (i.e., electron transfer reactions) represent relatively mature classes of gas-phase chemical reactions. Even so, especially in regards to redox chemistry, the widespread utility of these two types of chemistries is undergoing rapid growth and development. Additionally, a relatively new class of gas-phase ion/ion transformations is emerging which involves the selective formation of functional-group-specific covalent bonds. This feature details our current work and perspective on the developments and current capabilities of these three areas of ion/ion chemistry with an eye towards possible future directions of the field.

  14. 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.

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

    KAUST Repository

    Li, Huifang; Li, Haoyuan; Dai, Qingqing; Li, Hong; Bredas, Jean-Luc

    2018-01-01

    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

  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. Stable isotopes labelled compounds

    International Nuclear Information System (INIS)

    1982-09-01

    The catalogue on stable isotopes labelled compounds offers deuterium, nitrogen-15, and multiply labelled compounds. It includes: (1) conditions of sale and delivery, (2) the application of stable isotopes, (3) technical information, (4) product specifications, and (5) the complete delivery programme

  18. Evolutionary Stable Strategy

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 21; Issue 9. Evolutionary Stable Strategy: Application of Nash Equilibrium in Biology. General Article Volume 21 Issue 9 September 2016 pp 803- ... Keywords. Evolutionary game theory, evolutionary stable state, conflict, cooperation, biological games.

  19. Stable Boundary Layer Issues

    NARCIS (Netherlands)

    Steeneveld, G.J.

    2012-01-01

    Understanding and prediction of the stable atmospheric boundary layer is a challenging task. Many physical processes are relevant in the stable boundary layer, i.e. turbulence, radiation, land surface coupling, orographic turbulent and gravity wave drag, and land surface heterogeneity. The

  20. Non-covalent and reversible functionalization of carbon nanotubes

    Directory of Open Access Journals (Sweden)

    Antonello Di Crescenzo

    2014-09-01

    Full Text Available Carbon nanotubes (CNTs have been proposed and actively explored as multipurpose innovative nanoscaffolds for applications in fields such as material science, drug delivery and diagnostic applications. Their versatile physicochemical features are nonetheless limited by their scarce solubilization in both aqueous and organic solvents. In order to overcome this drawback CNTs can be easily non-covalently functionalized with different dispersants. In the present review we focus on the peculiar hydrophobic character of pristine CNTs that prevent them to easily disperse in organic solvents. We report some interesting examples of CNTs dispersants with the aim to highlight the essential features a molecule should possess in order to act as a good carbon nanotube dispersant both in water and in organic solvents. The review pinpoints also a few examples of dispersant design. The last section is devoted to the exploitation of the major quality of non-covalent functionalization that is its reversibility and the possibility to obtain stimuli-responsive precipitation or dispersion of CNTs.

  1. 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.

  2. Privileged Electrophile Sensors: A Resource for Covalent Drug Development.

    Science.gov (United States)

    Long, Marcus John Curtis; Aye, Yimon

    2017-07-20

    This Perspective delineates how redox signaling affects the activity of specific enzyme isoforms and how this property may be harnessed for rational drug design. Covalent drugs have resurged in recent years and several reports have extolled the general virtues of developing irreversible inhibitors. Indeed, many modern pharmaceuticals contain electrophilic appendages. Several invoke a warhead that hijacks active-site nucleophiles whereas others take advantage of spectator nucleophilic side chains that do not participate in enzymatic chemistry, but are poised to bind/react with electrophiles. The latest data suggest that innate electrophile sensing-which enables rapid reaction with an endogenous signaling electrophile-is a quintessential resource for the development of covalent drugs. For instance, based on recent work documenting isoform-specific electrophile sensing, isozyme non-specific drugs may be converted to isozyme-specific analogs by hijacking privileged first-responder electrophile-sensing cysteines. Because this approach targets functionally relevant cysteines, we can simultaneously harness previously untapped moonlighting roles of enzymes linked to redox sensing. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Effect of Reaction Temperature on Structure, Appearance and Bonding Type of Functionalized Graphene Oxide Modified P-Phenylene Diamine

    Directory of Open Access Journals (Sweden)

    Hong-Juan Sun

    2018-04-01

    Full Text Available In this study, graphene oxides with different functionalization degrees were prepared by a facile one-step hydrothermal reflux method at various reaction temperatures using graphene oxide (GO as starting material and p-phenylenediamine (PPD as the modifier. The effects of reaction temperature on structure, appearance and bonding type of the obtained materials were investigated by X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR, X-ray photoelectron spectroscopy (XPS, and scanning electron microscopy (SEM. The results showed that when the reaction temperature was 10–70 °C, the GO reacted with PPD through non-covalent ionic bonds (–COO−H3+N–R and hydrogen bonds (C–OH…H2N–X. When the reaction temperature reached 90 °C, the GO was functionalized with PPD through covalent bonds of C–N. The crystal structure of products became more ordered and regular, and the interlayer spacing (d value and surface roughness increased as the temperature increased. Furthermore, the results suggested that PPD was grafted on the surface of GO through covalent bonding by first attacking the carboxyl groups and then the epoxy groups of GO.

  4. Description of pnicogen bonding with the help of vibrational spectroscopy-The missing link between theory and experiment

    Science.gov (United States)

    Setiawan, D.; Kraka, E.; Cremer, D.

    2014-10-01

    The nature of the E⋯E‧ pnicogen bond (E = N, P, As) in dimers such as H2FP⋯PH2F (1) and H3N⋯PHNO2 (2) can be described using vibrational spectroscopy in form of the calculated infrared and depolarized Raman scattering spectra. Utilizing the six calculated intermonomer frequencies, the corresponding local mode E⋯E‧ stretching frequency and force constant are obtained, where the latter provides a unique measure of the E⋯E‧ bond strength. Pnicogen bonding in 1 is relative strong (bond strength order n = 0.151) and covalent whereas pnicogen bonding in 2 is electrostatic (n = 0.047) because of a different bonding mechanism.

  5. Superconductivity and the magnetic electron bond

    International Nuclear Information System (INIS)

    Szurek, P.

    1989-01-01

    The concept of the magnetic electron bond as the fundamental characteristic of superconductivity was first introduced during a presentation at the 1988 Winter Annual Meeting of the American Society of Mechanical Engineers. Postulates describing the role of the electron and the magnetic bond were suggested to explain in a consistent manner known observations. What may becoming clear is that a boundary set of conditions may exist above and below the transition temperature at which a material superconducts. Prior to recent history, scientists have concentrated on postulating, experimenting, and learning about the set of conditions that exist above the transition temperature, which has set the standard for todays quantum theory. Above the transition temperature they have learned about the interrelationships that exist between the electron, a small magnetic and negatively charged body, and the nucleus, a large positively charged body. By grouping common general characteristics due to the interaction between the outer shell electrons and the nucleus of different elements, three bond types have been established, covalent, ionic, and metallic. They may now be in the process of determining those conditions that lie below the transition temperature, a realm where charge effects may no longer dominate magnetic effects. This may involve updating the quantum theory to reflect those conditions that exist above and below the transition temperature. The following discussion reviews, updates, and attempts to answer some preliminary questions regarding postulates that may define some of the conditions that lie below the transition temperature. As an introduction, figure 1 depicts what may occur to loosely held outer shell electrons below the transition temperature due to increased inner electron shielding. 7 refs., 9 figs

  6. Unusually short chalcogen bonds involving organoselenium: insights into the Se-N bond cleavage mechanism of the antioxidant ebselen and analogues.

    Science.gov (United States)

    Thomas, Sajesh P; Satheeshkumar, K; Mugesh, Govindasamy; Guru Row, T N

    2015-04-27

    Structural studies on the polymorphs of the organoselenium antioxidant ebselen and its derivative show the potential of organic selenium to form unusually short Se⋅⋅⋅O chalcogen bonds that lead to conserved supramolecular recognition units. Se⋅⋅⋅O interactions observed in these polymorphs are the shortest such chalcogen bonds known for organoselenium compounds. The FTIR spectral evolution characteristics of this interaction from solution state to solid crystalline state further validates the robustness of this class of supramolecular recognition units. The strength and electronic nature of the Se⋅⋅⋅O chalcogen bonds were explored using high-resolution X-ray charge density analysis and atons-in-molecules (AIM) theoretical analysis. A charge density study unravels the strong electrostatic nature of Se⋅⋅⋅O chalcogen bonding and soft-metal-like behavior of organoselenium. An analysis of the charge density around Se-N and Se-C covalent bonds in conjunction with the Se⋅⋅⋅O chalcogen bonding modes in ebselen and its analogues provides insights into the mechanism of drug action in this class of organoselenium antioxidants. The potential role of the intermolecular Se⋅⋅⋅O chalcogen bonding in forming the intermediate supramolecular assembly that leads to the bond cleavage mechanism has been proposed in terms of electron density topological parameters in a series of molecular complexes of ebselen with reactive oxygen species (ROS). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Dimeric DNA Aptamer Complexes for High-capacity–targeted Drug Delivery Using pH-sensitive Covalent Linkages

    Directory of Open Access Journals (Sweden)

    Olcay Boyacioglu

    2013-01-01

    Full Text Available Treatment with doxorubicin (Dox results in serious systemic toxicities that limit effectiveness for cancer treatment and cause long-term health issues for cancer patients. We identified a new DNA aptamer to prostate-specific membrane antigen (PSMA using fixed sequences to promote Dox binding and developed dimeric aptamer complexes (DACs for specific delivery of Dox to PSMA+ cancer cells. DACs are stable under physiological conditions and are internalized specifically into PSMA+ C4-2 cells with minimal uptake into PSMA-null PC3 cells. Cellular internalization of DAC was demonstrated by confocal microscopy and flow cytometry. Covalent modification of DAC with Dox (DAC-D resulted in a complex with stoichiometry ~4:1. Dox was covalently bound in DAC-D using a reversible linker that promotes covalent attachment of Dox to genomic DNA following cell internalization. Dox was released from the DAC-D under physiological conditions with a half-life of 8 hours, sufficient for in vivo targeting. DAC-D was used to selectively deliver Dox to C4-2 cells with endosomal release and nuclear localization of Dox. DAC-D was selectively cytotoxic to C4-2 cells with similar cytotoxicity as the molar equivalent of free-Dox. In contrast, DAC-D displayed minimal cytotoxicity to PC3 cells, demonstrating the complex displays a high degree of selectivity for PSMA+ cells. DAC-D displays specificity and stability features that may be useful for improved delivery of Dox selectively to malignant tissue in vivo.

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. Epoxy-functionalized mesostructured cellular foams as effective support for covalent immobilization of penicillin G acylase

    Science.gov (United States)

    Xue, Ping; Xu, Fang; Xu, Lidong

    2008-12-01

    The epoxy-functionalized mesoporous cellular foams (G-MCFs) with high specific surface area (˜400 m 2/g) and large-size mesopores (˜17 nm) were obtained by condensation of 3-glycidoxypropyltriethoxysilane (GPTS) and the surface silanol groups of mesoporous cellular foams (MCFs) and used as the support for immobilization of penicillin G acylase (PGA). The structural properties of G-MCF were characterized by FT-IR, N 2 adsorption, TG-DTA and 29Si MAS NMR. The studies indicated that the glycidoxypropyl groups were chemically bonded to the silicon atoms on the surface of MCF. The epoxy-functionalized mesoporous cellular foams can provide the microenvironments suitable for the immobilization of PGA, and the enzyme molecules could be immobilized covalently onto the G-MCF under mild conditions by reaction between the amino groups of the enzyme molecules and the epoxy groups on the surface of G-MCF. The PGA immobilized on G-MCF (PGA/G-MCF) exhibited the apparent activity of 1782 IU/g and 46.6% of activity recovery for hydrolyzing penicillin G potassium to produce 6-aminopenicillanic acid at 37 °C which were higher than that of PGA on pure silica MCF (1521 IU/g and 39.8%, respectively). The kinetic study also indicated that PGA immobilized on G-MCF has a Km of 2.1 × 10 -2 mol/L lower than that of PGA immobilized on the pure silica MCF (5.0 × 10 -2 mol/L). These may be attributed to the enhanced surface affinity between G-MCF support and the substrate molecules. Due to the covalent immobilization of PGA molecules on the surface of G-MCF, the immobilized PGA with considerable operational stability was achieved. The activity of PGA/G-MCF is still about 91.4% of its initial activity at the 10th cycle reuse while that of PGA/MCF only remains 41.5% of its initial activity at the same reuse numbers. In addition, the investigation results show the thermal stability and durability on acid or basic medium of PGA immobilized on G-MCF were improved remarkably.

  13. Epoxy-functionalized mesostructured cellular foams as effective support for covalent immobilization of penicillin G acylase

    International Nuclear Information System (INIS)

    Xue Ping; Xu Fang; Xu Lidong

    2008-01-01

    The epoxy-functionalized mesoporous cellular foams (G-MCFs) with high specific surface area (∼400 m 2 /g) and large-size mesopores (∼17 nm) were obtained by condensation of 3-glycidoxypropyltriethoxysilane (GPTS) and the surface silanol groups of mesoporous cellular foams (MCFs) and used as the support for immobilization of penicillin G acylase (PGA). The structural properties of G-MCF were characterized by FT-IR, N 2 adsorption, TG-DTA and 29 Si MAS NMR. The studies indicated that the glycidoxypropyl groups were chemically bonded to the silicon atoms on the surface of MCF. The epoxy-functionalized mesoporous cellular foams can provide the microenvironments suitable for the immobilization of PGA, and the enzyme molecules could be immobilized covalently onto the G-MCF under mild conditions by reaction between the amino groups of the enzyme molecules and the epoxy groups on the surface of G-MCF. The PGA immobilized on G-MCF (PGA/G-MCF) exhibited the apparent activity of 1782 IU/g and 46.6% of activity recovery for hydrolyzing penicillin G potassium to produce 6-aminopenicillanic acid at 37 o C which were higher than that of PGA on pure silica MCF (1521 IU/g and 39.8%, respectively). The kinetic study also indicated that PGA immobilized on G-MCF has a K m of 2.1 x 10 -2 mol/L lower than that of PGA immobilized on the pure silica MCF (5.0 x 10 -2 mol/L). These may be attributed to the enhanced surface affinity between G-MCF support and the substrate molecules. Due to the covalent immobilization of PGA molecules on the surface of G-MCF, the immobilized PGA with considerable operational stability was achieved. The activity of PGA/G-MCF is still about 91.4% of its initial activity at the 10th cycle reuse while that of PGA/MCF only remains 41.5% of its initial activity at the same reuse numbers. In addition, the investigation results show the thermal stability and durability on acid or basic medium of PGA immobilized on G-MCF were improved remarkably.

  14. Epoxy-functionalized mesostructured cellular foams as effective support for covalent immobilization of penicillin G acylase

    Energy Technology Data Exchange (ETDEWEB)

    Xue Ping [Key Laboratory of Energy Resources and Chemical Engineering, Ningxia University, Yinchuan 750021 (China)], E-mail: Ping@nxu.edu.cn; Xu Fang [Department of Molecule Biology, Ningxia Medical College, Yinchuan 750021 (China); Xu Lidong [Key Laboratory of Energy Resources and Chemical Engineering, Ningxia University, Yinchuan 750021 (China)

    2008-12-30

    The epoxy-functionalized mesoporous cellular foams (G-MCFs) with high specific surface area ({approx}400 m{sup 2}/g) and large-size mesopores ({approx}17 nm) were obtained by condensation of 3-glycidoxypropyltriethoxysilane (GPTS) and the surface silanol groups of mesoporous cellular foams (MCFs) and used as the support for immobilization of penicillin G acylase (PGA). The structural properties of G-MCF were characterized by FT-IR, N{sub 2} adsorption, TG-DTA and {sup 29}Si MAS NMR. The studies indicated that the glycidoxypropyl groups were chemically bonded to the silicon atoms on the surface of MCF. The epoxy-functionalized mesoporous cellular foams can provide the microenvironments suitable for the immobilization of PGA, and the enzyme molecules could be immobilized covalently onto the G-MCF under mild conditions by reaction between the amino groups of the enzyme molecules and the epoxy groups on the surface of G-MCF. The PGA immobilized on G-MCF (PGA/G-MCF) exhibited the apparent activity of 1782 IU/g and 46.6% of activity recovery for hydrolyzing penicillin G potassium to produce 6-aminopenicillanic acid at 37 {sup o}C which were higher than that of PGA on pure silica MCF (1521 IU/g and 39.8%, respectively). The kinetic study also indicated that PGA immobilized on G-MCF has a K{sub m} of 2.1 x 10{sup -2} mol/L lower than that of PGA immobilized on the pure silica MCF (5.0 x 10{sup -2} mol/L). These may be attributed to the enhanced surface affinity between G-MCF support and the substrate molecules. Due to the covalent immobilization of PGA molecules on the surface of G-MCF, the immobilized PGA with considerable operational stability was achieved. The activity of PGA/G-MCF is still about 91.4% of its initial activity at the 10th cycle reuse while that of PGA/MCF only remains 41.5% of its initial activity at the same reuse numbers. In addition, the investigation results show the thermal stability and durability on acid or basic medium of PGA immobilized on G

  15. Thermally assisted peeling of an elastic strip in adhesion with a substrate via molecular bonds

    Science.gov (United States)

    Qian, Jin; Lin, Ji; Xu, Guang-Kui; Lin, Yuan; Gao, Huajian

    A statistical model is proposed to describe the peeling of an elastic strip in adhesion with a flat substrate via an array of non-covalent molecular bonds. Under an imposed tensile peeling force, the interfacial bonds undergo diffusion-type transition in their bonding state, a process governed by a set of probabilistic equations coupled to the stretching, bending and shearing of the elastic strip. Because of the low characteristic energy scale associated with molecular bonding, thermal excitations are found to play an important role in assisting the escape of individual molecular bonds from their bonding energy well, leading to propagation of the peeling front well below the threshold peel-off force predicted by the classical theories. Our study establishes a link between the deformation of the strip and the spatiotemporal evolution of interfacial bonds, and delineates how factors like the peeling force, bending rigidity of the strip and binding energy of bonds influence the resultant peeling velocity and dimensions of the process zone. In terms of the apparent adhesion strength and dissipated energy, the bond-mediated interface is found to resist peeling in a strongly rate-dependent manner.

  16. Atomic bonding and mechanical properties of Al-Mg-Zr-Sc alloy

    Institute of Scientific and Technical Information of China (English)

    高英俊; 班冬梅; 韩永剑; 钟夏平; 刘慧

    2004-01-01

    The valence electron structures of Al-Mg alloy with minor Sc and Zr were calculated according to the empirical electron theory(EET) in solid. The results show that because of the strong interaction of Al atom with Zr and Sc atom in melting during solidification, the Al3 Sc and Al3 (Sc1-xZrx) particles which act as heterogeneous nuclear are firstly crystallized in alloy to make grains refine. In progress of solidification, the Al-Sc, Al-Zr-Sc segregation regions are formed in solid solution matrix of Al-Mg alloy owing to the strong interaction of Al atom with Zr, Scatoms in bulk of alloy, so in the following homogenization treatment, the finer dispersed Al3 Sc and Al3 (Sc1-x Zrx) second-particles which are coherence with the matrix are precipitated in the segregation region. These finer second particles with the strong Al-Zr, Al-Sc covalent bonds can strengthen the covalent bonds in matrix of the alloy, and also enhance the hardness and strength of Al-Mg alloy. Those finer second-particles precipitated in interface of sub-grains can also strengthen the covalence bonds there, and effectively hinder the interface of sub-grains from migrating and restrain the sub-grains from growing, and cause better thermal stability of Al-Mg alloy.

  17. Normal modified stable processes

    DEFF Research Database (Denmark)

    Barndorff-Nielsen, Ole Eiler; Shephard, N.

    2002-01-01

    Gaussian (NGIG) laws. The wider framework thus established provides, in particular, for added flexibility in the modelling of the dynamics of financial time series, of importance especially as regards OU based stochastic volatility models for equities. In the special case of the tempered stable OU process......This paper discusses two classes of distributions, and stochastic processes derived from them: modified stable (MS) laws and normal modified stable (NMS) laws. This extends corresponding results for the generalised inverse Gaussian (GIG) and generalised hyperbolic (GH) or normal generalised inverse...

  18. Applications of stable isotopes

    International Nuclear Information System (INIS)

    Letolle, R.; Mariotti, A.; Bariac, T.

    1991-06-01

    This report reviews the historical background and the properties of stable isotopes, the methods used for their measurement (mass spectrometry and others), the present technics for isotope enrichment and separation, and at last the various present and foreseeable application (in nuclear energy, physical and chemical research, materials industry and research; tracing in industrial, medical and agronomical tests; the use of natural isotope variations for environmental studies, agronomy, natural resources appraising: water, minerals, energy). Some new possibilities in the use of stable isotope are offered. A last chapter gives the present state and forecast development of stable isotope uses in France and Europe

  19. Catalytic-site mapping of pyruvate formate lyase. Hypophosphite reaction on the acetyl-enzyme intermediate affords carbon-phosphorus bond synthesis (1-hydroxyethylphosphonate).

    Science.gov (United States)

    Plaga, W; Frank, R; Knappe, J

    1988-12-15

    Pyruvate formate-lyase of Escherichia coli cells, a homodimeric protein of 2 x 85 kDa, is distinguished by the property of containing a stable organic free radical (g = 2.0037) in its resting state. The enzyme (E-SH) achieves pyruvate conversion to acetyl-CoA via two distinct half-reactions (E-SH + pyruvate in equilibrium E-S-acetyl + formate; E-S-acetyl + CoA in equilibrium E-SH + acetyl-CoA), the first of which has been proposed to involve reversible homolytic carbon-carbon bond cleavage [J. Knappe et al. (1984) Proc. Natl Acad. Sci. USA 81, 1332-1335]. Present studies identified Cys-419 as the covalent-catalytic cysteinyl residue via CNBr fragmentation of E-S-[14C]acetyl and radio-sequencing of the isolated peptide CB-Ac (amino acid residues 406-423). Reaction of the formate analogue hypophosphite with E-S-acetyl was investigated and found to produce 1-hydroxyethylphosphonate with a thioester linkage to the adjacent Cys-418. The structure was determined from the chymotryptic peptide CH-P (amino acid residues 415-425), using 31P-NMR spectroscopy (delta = 44 ppm) and by chemical characterisation through degradation into 1-hydroxyethylphosphonate with phosphodiesterase or bromine. This novel P-C-bond synthesis involves the enzyme-based free radical and is proposed to resemble the physiological C-C-bond synthesis (pyruvate production) from formate and E-S-acetyl. These findings are interpreted as proof of a radical mechanism for the action of pyruvate formate-lyase. The central Cys-418/Cys-419 pair of the active site shows a distinctive thiolate property even in the inactive (nonradical) form of the enzyme, as determined using an iodoacetate probe.

  20. Structural, elastic, electronic, bonding, and optical properties of BeAZ{sub 2} (A = Si, Ge, Sn; Z = P, As) chalcopyrites

    Energy Technology Data Exchange (ETDEWEB)

    Fahad, Shah [Department of Physics, Hazara University Mansehra, KPK, Mansehra (Pakistan); Murtaza, G., E-mail: murtaza@icp.edu.pk [Materials Modeling Laboratory, Department of Physics, Islamia College University, Peshawar (Pakistan); Ouahrani, T. [Laboratoire de Physique Théorique, B.P. 230, Université de Tlemcen, Tlemcen 13000 (Algeria); Ecole Préparatoire en Sciences et Techniques, BP 165 R.P., 13000 Tlemcen (Algeria); Khenata, R., E-mail: khenata_rabah@yahoo.fr [Laboratoire de Physique Quantique et de Modélisation Mathématique, Université de Mascara, 29000 (Algeria); Yousaf, Masood [Center for Multidimensional Carbon Materials, Institute for Basic Science, Department of Physics, Ulsan National Institute of Science and Technology, Ulsan 689-798 (Korea, Republic of); Omran, S.Bin [Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451 (Saudi Arabia); Mohammad, Saleh [Department of Physics, Hazara University Mansehra, KPK, Mansehra (Pakistan)

    2015-10-15

    A first principles density functional theory (DFT) technique is used to study the structural, chemical bonding, electronic and optical properties of BeAZ{sub 2} (A = Si, Ge, Sn; Z = P, As) chalcopyrite materials. The calculated parameters are in good agreement with the available experimental results. The lattice constants and the equilibrium volume increased as we moved from Si to Ge to Sn, whereas the c/a and internal parameters u decreased by shifting the cation from P to As. These compounds are elastically stable. An investigation of the band gap using the WC-GGA, EV-GGA, PBE-GGA and mBJ-metaGGA potentials suggested that BeSiP{sub 2} and BeSiAs{sub 2} are direct band gap compounds, whereas BeGeP{sub 2,} BeGeAs{sub 2,} BeSnP{sub 2,} BeSnAs{sub 2} are indirect band gap compounds. The energy band gaps decreased by changing B from Si to Sn and increased by changing the anion C from P to As. The bonding among the cations and anions is primarily ionic. In the optical properties, the real and imaginary parts of the dielectric functions, reflectivity and optical conductivity have been studied over a wide energy range. - Highlights: • The compounds are studied by FP-LAPW method within mBJ approximation. • All of the studied materials show isotropic behaviour. • All the compounds show direct band gap nature. • Bonding nature is mostly covalent among the studied compounds. • High absorption peaks and reflectivity ensures there utility in optoelectronic devices.