Science.gov

Sample records for activated bonding method

  1. Room-temperature bonding method for polymer substrate of flexible electronics by surface activation using nano-adhesion layers

    NASA Astrophysics Data System (ADS)

    Matsumae, Takashi; Fujino, Masahisa; Suga, Tadatomo

    2015-10-01

    A sealing method for polymer substrates to be used in flexible electronics is studied. For this application, a low-temperature sealing method that achieves flexible bonding of inorganic bonding material is required, but no conventional technique satisfies these requirements simultaneously. In this study, a new polymer bonding method using thin Si and Fe layers and the surface activated bonding (SAB) method are applied to bond poly(ethylene naphthalate) (PEN) films to each other. PEN films can be bonded via the proposed method without voids at room temperature, and the bonded samples are bendable. The adhesion strength of the bonded samples is so strong that fracture occurs in the polymer bulk rather than at the bond interface. Investigations of the bonded samples by transmission electron microscopy (TEM) and Fourier-transform infrared spectroscopy (FTIR) reveal that bonding is achieved by chemical interactions between the polymer surface and deposited atoms.

  2. Shape Bonding method

    NASA Technical Reports Server (NTRS)

    Pontius, James T. (Inventor)

    2010-01-01

    The present invention is directed to a method of bonding at least two surfaces together. The methods step of the present invention include applying a strip of adhesive to a first surface along a predefined outer boundary of a bond area and thereby defining a remaining open area there within. A second surface, or gusset plate, is affixed onto the adhesive before the adhesive cures. The strip of adhesive is allowed to cure and then a second amount of adhesive is applied to cover the remaining open area and substantially fill a void between said first and second surfaces about said bond area. A stencil may be used to precisely apply the strip of adhesive. When the strip cures, it acts as a dam to prevent overflow of the subsequent application of adhesive to undesired areas. The method results in a precise bond area free of undesired shapes and of a preferred profile which eliminate the drawbacks of the prior art bonds.

  3. Method of bonding

    DOEpatents

    Saller, deceased, Henry A.; Hodge, Edwin S.; Paprocki, Stanley J.; Dayton, Russell W.

    1987-12-01

    1. A method of making a fuel-containing structure for nuclear reactors, comprising providing an assembly comprising a plurality of fuel units; each fuel unit consisting of a core plate containing thermal-neutron-fissionable material, sheets of cladding metal on its bottom and top surfaces, said cladding sheets being of greater width and length than said core plates whereby recesses are formed at the ends and sides of said core plate, and end pieces and first side pieces of cladding metal of the same thickness as the core plate positioned in said recesses, the assembly further comprising a plurality of second side pieces of cladding metal engaging the cladding sheets so as to space the fuel units from one another, and a plurality of filler plates of an acid-dissolvable nonresilient material whose melting point is above 2000.degree. F., each filler plate being arranged between a pair of said second side pieces and the cladding plates of two adjacent fuel units, the filler plates having the same thickness as the second side pieces; the method further comprising enclosing the entire assembly in an envelope; evacuating the interior of the entire assembly through said envelope; applying inert gas under a pressure of about 10,000 psi to the outside of said envelope while at the same time heating the assembly to a temperature above the flow point of the cladding metal but below the melting point of any material of the assembly, whereby the envelope is pressed against the assembly and integral bonds are formed between plates, sheets, first side pieces, and end pieces and between the sheets and the second side pieces; slowly cooling the assembly to room temperature; removing the envelope; and dissolving the filler plates without attacking the cladding metal.

  4. Intermolecular hydrogen bonds in hetero-complexes of biologically active aromatic molecules probed by the methods of vibrational spectroscopy.

    PubMed

    Semenov, M A; Blyzniuk, Iu N; Bolbukh, T V; Shestopalova, A V; Evstigneev, M P; Maleev, V Ya

    2012-09-01

    By the methods of vibrational spectroscopy (Infrared and Raman) the investigation of the hetero-association of biologically active aromatic compounds: flavin-mononucleotide (FMN), ethidium bromide (EB) and proflavine (PRF) was performed in aqueous solutions. It was shown that between the functional groups (CO and NH(2)) the intermolecular hydrogen bonds are formed in the hetero-complexes FMN-EB and FMN-PRF, additionally stabilizing these structures. An estimation of the enthalpy of Н-bonding obtained from experimental shifts of carbonyl vibrational frequencies has shown that the H-bonds do not dominate in the magnitude of experimentally measured total enthalpy of the hetero-association reactions. The main stabilization is likely due to intermolecular interactions of the molecules in these complexes and their interaction with water environment.

  5. Intermolecular hydrogen bonds in hetero-complexes of biologically active aromatic molecules probed by the methods of vibrational spectroscopy

    NASA Astrophysics Data System (ADS)

    Semenov, M. A.; Blyzniuk, Iu. N.; Bolbukh, T. V.; Shestopalova, A. V.; Evstigneev, M. P.; Maleev, V. Ya.

    2012-09-01

    By the methods of vibrational spectroscopy (Infrared and Raman) the investigation of the hetero-association of biologically active aromatic compounds: flavin-mononucleotide (FMN), ethidium bromide (EB) and proflavine (PRF) was performed in aqueous solutions. It was shown that between the functional groups (Cdbnd O and NH2) the intermolecular hydrogen bonds are formed in the hetero-complexes FMN-EB and FMN-PRF, additionally stabilizing these structures. An estimation of the enthalpy of Н-bonding obtained from experimental shifts of carbonyl vibrational frequencies has shown that the H-bonds do not dominate in the magnitude of experimentally measured total enthalpy of the hetero-association reactions. The main stabilization is likely due to intermolecular interactions of the molecules in these complexes and their interaction with water environment.

  6. GRAPHITE BONDING METHOD

    DOEpatents

    King, L.D.P.

    1964-02-25

    A process for bonding or joining graphite members together in which a thin platinum foil is placed between the members, heated in an inert atmosphere to a temperature of 1800 deg C, and then cooled to room temperature is described. (AEC)

  7. IMPROVED BONDING METHOD

    DOEpatents

    Padgett, E.V. Jr.; Warf, D.H.

    1964-04-28

    An improved process of bonding aluminum to aluminum without fusion by ultrasonic vibrations plus pressure is described. The surfaces to be bonded are coated with an aqueous solution of alkali metal stearate prior to assembling for bonding. (AEC) O H19504 Present information is reviewed on steady state proliferation, differentiation, and maturation of blood cells in mammals. Data are cited from metabolic tracer studies, autoradiographic studies, cytologic studies, studies of hematopoietic response to radiation injuries, and computer analyses of blood cell production. A 3-step model for erythropoiesis and a model for granulocyte kinetics are presented. New approaches to the study of lymphocytopoiesis described include extracorporeal blood irradiation to deplete lymphocytic tissue without direct injury to the formative tissues as a means to study the stressed system, function control, and rates of proliferation. It is pointed out that present knowledge indicates that lymphocytes comprise a mixed family, with diverse life spans, functions, and migration patterns with apparent aimless recycling from modes to lymph to blood to nodes that has not yet been quantitated. Areas of future research are postulated. (70 references.) (C.H.)

  8. The selective activation of a C-F bond with an auxiliary strong Lewis acid: a method to change the activation preference of C-F and C-H bonds.

    PubMed

    Wang, Lin; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter

    2016-11-15

    The selective activation of the C-F bonds in substituted (2,6-difluorophenyl)phenylimines (2,6-F2H3C6-(C[double bond, length as m-dash]NH)-n'-R-C6H4 (n' = 2, R = H (1); n' = 2, R = Me (2); n' = 4, R = tBu (3))) by Fe(PMe3)4 with an auxiliary strong Lewis acid (LiBr, LiI, or ZnCl2) was explored. As a result, iron(ii) halides ((H5C6-(C[double bond, length as m-dash]NH)-2-FH3C6)FeX(PMe3)3 (X = Br (8); Cl (9)) and (n-RH4C6-(C[double bond, length as m-dash]NH)-2'-FH3C6)FeX(PMe3)3 (n = 2, R = Me, X = Br (11); n = 4, R = tBu, X = I (12))) were obtained. Under similar reaction conditions, using LiBF4 instead of LiBr or ZnCl2, the reaction of (2,6-difluorophenyl)phenylimine with Fe(PMe3)4 afforded an ionic complex [(2,6-F2H3C6-(C[double bond, length as m-dash]NH)-H4C6)Fe(PMe3)4](BF4) (10) via the activation of a C-H bond. The method of C-F bond activation with an auxiliary strong Lewis acid is appropriate for monofluoroarylmethanimines. Without the Lewis acid, iron(ii) hydrides ((2-RH4C6-(C[double bond, length as m-dash]NH)-2'-FH3C6)FeH(PMe3)3 (R = H (13); Me (14))) were generated from the reactions of Fe(PMe3)4 with the monofluoroarylmethanimines (2-FH4C6-(C[double bond, length as m-dash]NH)-2'-RC6H4 (R = H (4); Me (5))); however, in the presence of ZnCl2 or LiBr, iron(ii) halides ((2-RH4C6-(C[double bond, length as m-dash]NH)-H4C6)FeX(PMe3)3 (R = H, X = Cl (15); R = Me, X = Br (16))) could be obtained through the activation of a C-F bond. Furthermore, a C-F bond activation with good regioselectivity in (pentafluorophenyl)arylmethanimines (F5C6-(C[double bond, length as m-dash]NH)-2,6-Y2C6H3 (Y = F (6); H (7))) could be realized in the presence of ZnCl2 to produce iron(ii) chlorides ((2,6-Y2H3C6-(C[double bond, length as m-dash]NH)-F4C6)FeCl(PMe3)3 (Y = F (17); H (18))). This series of iron(ii) halides could be used to catalyze the hydrosilylation reaction of aldehydes. Due to the stability of iron(ii) halides to high temperature, the reaction mixture was allowed to be

  9. Method to improve commercial bonded SOI material

    DOEpatents

    Maris, Humphrey John; Sadana, Devendra Kumar

    2000-07-11

    A method of improving the bonding characteristics of a previously bonded silicon on insulator (SOI) structure is provided. The improvement in the bonding characteristics is achieved in the present invention by, optionally, forming an oxide cap layer on the silicon surface of the bonded SOI structure and then annealing either the uncapped or oxide capped structure in a slightly oxidizing ambient at temperatures greater than 1200.degree. C. Also provided herein is a method for detecting the bonding characteristics of previously bonded SOI structures. According to this aspect of the present invention, a pico-second laser pulse technique is employed to determine the bonding imperfections of previously bonded SOI structures.

  10. Three methods to measure RH bond energies

    NASA Astrophysics Data System (ADS)

    Berkowitz, Joseph; Ellison, G. Barney; Gutman, David

    1993-03-01

    In this paper, the authors compare and contrast three powerful methods for experimentally measuring bond energies in polyatomic molecules. The methods are: radical kinetics; gas phase acidity cycles; and photoionization mass spectroscopy. The knowledge of the values of bond energies are a basic piece of information to a chemist. Chemical reactions involve the making and breaking of chemical bonds. It has been shown that comparable bonds in polyatomic molecules, compared to the same bonds in radicals, can be significantly different. These bond energies can be measured in terms of bond dissociation energies.

  11. Three methods to measure RH bond energies

    SciTech Connect

    Berkowitz, J.; Ellison, G.B.; Gutman, D.

    1993-03-21

    In this paper the authors compare and contrast three powerful methods for experimentally measuring bond energies in polyatomic molecules. The methods are: radical kinetics; gas phase acidity cycles; and photoionization mass spectroscopy. The knowledge of the values of bond energies are a basic piece of information to a chemist. Chemical reactions involve the making and breaking of chemical bonds. It has been shown that comparable bonds in polyatomic molecules, compared to the same bonds in radicals, can be significantly different. These bond energies can be measured in terms of bond dissociation energies.

  12. Method of bond strength evaluation for silicon direct wafer bonding

    NASA Astrophysics Data System (ADS)

    Spivak, Alexander; Avagyan, Avag; Davies, Brady R.

    2001-09-01

    A crack-opening method used for characterization of silicon direct wafer bonding (DWB) techniques was analyzed. Mathematical model describing the influence of the pattern shape on the wafer pair resistance curve, so-called the R-curve, was developed. Two-dimensional patterns were created on a mirror-polished silicon wafer surface by a combination of photolithography, deposition and etching steps. Experimental observations did show that structured wafers can be used for large bond energy measurements. We propose utilization of structured wafers for bond energy measurements. It allows R-curve shape manipulation, increases the method sensitivity, and reduces probability of wafer failure. The resulting theory can also be used for developing new experimental methods for large bond energy measurements.

  13. Ultra precision and reliable bonding method

    NASA Technical Reports Server (NTRS)

    Gwo, Dz-Hung (Inventor)

    2001-01-01

    The bonding of two materials through hydroxide-catalyzed hydration/dehydration is achieved at room temperature by applying hydroxide ions to at least one of the two bonding surfaces and by placing the surfaces sufficiently close to each other to form a chemical bond between them. The surfaces may be placed sufficiently close to each other by simply placing one surface on top of the other. A silicate material may also be used as a filling material to help fill gaps between the surfaces caused by surface figure mismatches. A powder of a silica-based or silica-containing material may also be used as an additional filling material. The hydroxide-catalyzed bonding method forms bonds which are not only as precise and transparent as optical contact bonds, but also as strong and reliable as high-temperature frit bonds. The hydroxide-catalyzed bonding method is also simple and inexpensive.

  14. Method for vacuum fusion bonding

    DOEpatents

    Ackler, Harold D.; Swierkowski, Stefan P.; Tarte, Lisa A.; Hicks, Randall K.

    2001-01-01

    An improved vacuum fusion bonding structure and process for aligned bonding of large area glass plates, patterned with microchannels and access holes and slots, for elevated glass fusion temperatures. Vacuum pumpout of all components is through the bottom platform which yields an untouched, defect free top surface which greatly improves optical access through this smooth surface. Also, a completely non-adherent interlayer, such as graphite, with alignment and location features is located between the main steel platform and the glass plate pair, which makes large improvements in quality, yield, and ease of use, and enables aligned bonding of very large glass structures.

  15. Bond additivity corrections for quantum chemistry methods

    SciTech Connect

    C. F. Melius; M. D. Allendorf

    1999-04-01

    In the 1980's, the authors developed a bond-additivity correction procedure for quantum chemical calculations called BAC-MP4, which has proven reliable in calculating the thermochemical properties of molecular species, including radicals as well as stable closed-shell species. New Bond Additivity Correction (BAC) methods have been developed for the G2 method, BAC-G2, as well as for a hybrid DFT/MP2 method, BAC-Hybrid. These BAC methods use a new form of BAC corrections, involving atomic, molecular, and bond-wise additive terms. These terms enable one to treat positive and negative ions as well as neutrals. The BAC-G2 method reduces errors in the G2 method due to nearest-neighbor bonds. The parameters within the BAC-G2 method only depend on atom types. Thus the BAC-G2 method can be used to determine the parameters needed by BAC methods involving lower levels of theory, such as BAC-Hybrid and BAC-MP4. The BAC-Hybrid method should scale well for large molecules. The BAC-Hybrid method uses the differences between the DFT and MP2 as an indicator of the method's accuracy, while the BAC-G2 method uses its internal methods (G1 and G2MP2) to provide an indicator of its accuracy. Indications of the average error as well as worst cases are provided for each of the BAC methods.

  16. Understanding acoustic methods for cement bond logging.

    PubMed

    Wang, Hua; Tao, Guo; Shang, Xuefeng

    2016-05-01

    Well cementation is important for oil/gas production, underground gas storage, and CO2 storage, since it isolates the reservoir layers from aquifers to increase well integrity and reduce environmental footprint. This paper analyzes wave modes of different sonic/ultrasonic methods for cement bonding evaluation. A Two dimensional finite difference method is then used to simulate the wavefield for the ultrasonic methods in the cased-hole models. Waveforms of pulse-echo method from different interfaces in a good bonded well are analyzed. Wavefield of the pitch-catch method for free casing, partial or full bonded models with ultra-low density cement are studied. Based on the studies, the modes in different methods are considered as follows: the zero-order symmetric Leaky-Lamb mode (S0) for sonic method, the first-order symmetric Leaky-Lamb mode (S1) for the pulse-echo method, and the zero-order anti-symmetric Leaky-Lamb mode (A0) for the pitch-catch method. For the sonic method, a directional transmitter in both the azimuth and axial directions can generate energy with a large incidence angle and azimuth resolution, which can effectively generate S0 and break out the azimuth limitation of the conventional sonic method. Although combination of pulse-echo and pitch-catch methods can determine the bonding condition of the third interface for the ultra-low density cement case, the pitch-catch cannot tell the fluid annulus thickness behind casing for the partial bonded cased-hole.

  17. Bond additivity corrections for quantum chemistry methods

    SciTech Connect

    Melius, C.F.; Allendorf, M.D.

    2000-03-23

    New bond additivity correction (BAC) methods have been developed for the G2 method, BAC-G2, as well as for a hybrid density functional theory (DFT) Moller-Plesset (MP)2 method, BAC-hybrid. These BAC methods use a new form of BAC corrections, involving atomic, molecular, and bond-wise additive terms. These terms enable one to treat positive and negative ions as well as neutrals. The BAC-G2 method reduces errors in the G2 method due to nearest-neighbor bonds. The parameters within the BAC-G2 method only depend on atom types. Thus the BAC-G2 method can be used to determine the parameters needed by BAC methods involving lower levels of theory, such as BAC-hybrid and BAC-MP4. The BAC-hybrid method is expected to scale well for large molecules. The BAC-hybrid method uses the differences between the DFT and MP2 predictions as an indication of the method's accuracy, whereas the BAC-G2 method uses its internal methods (G1 and G2MP2) to accomplish this. A statistical analysis of the error in each of the methods is presented on the basis of calculations performed for large sets (more than 120) of molecules.

  18. DISSOLUTION METHOD OF REMOVING BONDING AGENTS

    DOEpatents

    Hyman, H.H.

    1960-04-19

    A method is given for removing residual aluminumsilicon bonding agents from uranium slugs after the removal of aluminum coatings. To accomplish this the slug is immersed in an aqueous solution about 0.75 N in hydrofluoric acid and about 7 N in nitric acid.

  19. The variational subspace valence bond method.

    PubMed

    Fletcher, Graham D

    2015-04-07

    The variational subspace valence bond (VSVB) method based on overlapping orbitals is introduced. VSVB provides variational support against collapse for the optimization of overlapping linear combinations of atomic orbitals (OLCAOs) using modified orbital expansions, without recourse to orthogonalization. OLCAO have the advantage of being naturally localized, chemically intuitive (to individually model bonds and lone pairs, for example), and transferrable between different molecular systems. Such features are exploited to avoid key computational bottlenecks. Since the OLCAO can be doubly occupied, VSVB can access very large problems, and calculations on systems with several hundred atoms are presented.

  20. The variational subspace valence bond method

    SciTech Connect

    Fletcher, Graham D.

    2015-04-07

    The variational subspace valence bond (VSVB) method based on overlapping orbitals is introduced. VSVB provides variational support against collapse for the optimization of overlapping linear combinations of atomic orbitals (OLCAOs) using modified orbital expansions, without recourse to orthogonalization. OLCAO have the advantage of being naturally localized, chemically intuitive (to individually model bonds and lone pairs, for example), and transferrable between different molecular systems. Such features are exploited to avoid key computational bottlenecks. Since the OLCAO can be doubly occupied, VSVB can access very large problems, and calculations on systems with several hundred atoms are presented.

  1. Epoxy bond and stop etch fabrication method

    DOEpatents

    Simmons, Jerry A.; Weckwerth, Mark V.; Baca, Wes E.

    2000-01-01

    A class of epoxy bond and stop etch (EBASE) microelectronic fabrication techniques is disclosed. The essence of such techniques is to grow circuit components on top of a stop etch layer grown on a first substrate. The first substrate and a host substrate are then bonded together so that the circuit components are attached to the host substrate by the bonding agent. The first substrate is then removed, e.g., by a chemical or physical etching process to which the stop etch layer is resistant. EBASE fabrication methods allow access to regions of a device structure which are usually blocked by the presence of a substrate, and are of particular utility in the fabrication of ultrafast electronic and optoelectronic devices and circuits.

  2. Method of bonding metals to ceramics

    DOEpatents

    Maroni, Victor A.

    1992-01-01

    A method of forming a composite by providing a ceramic capable of having zero electrical resistance and complete diamagnetism at superconducting temperatures, bonding a thin layer of Ag, Au or alloys thereof with the ceramic. Thereafter, there is bonded a first metal to the ceramic surface at a temperature less than about 400.degree. C., and then a second metal is bonded to the first metal at a temperature less than about 400.degree. C. to form a composite wherein the first metal is selected from the class consisting of In, Ga, Sn, Bi, Zn, Cd, Pb, Ti and alloys thereof and wherein the second metal is selected from the class consisting of Al, Cu, Pb and Zn and alloys thereof.

  3. Catalytic activation of carbon-carbon bonds in cyclopentanones.

    PubMed

    Xia, Ying; Lu, Gang; Liu, Peng; Dong, Guangbin

    2016-11-24

    In the chemical industry, molecules of interest are based primarily on carbon skeletons. When synthesizing such molecules, the activation of carbon-carbon single bonds (C-C bonds) in simple substrates is strategically important: it offers a way of disconnecting such inert bonds, forming more active linkages (for example, between carbon and a transition metal) and eventually producing more versatile scaffolds. The challenge in achieving such activation is the kinetic inertness of C-C bonds and the relative weakness of newly formed carbon-metal bonds. The most common tactic starts with a three- or four-membered carbon-ring system, in which strain release provides a crucial thermodynamic driving force. However, broadly useful methods that are based on catalytic activation of unstrained C-C bonds have proven elusive, because the cleavage process is much less energetically favourable. Here we report a general approach to the catalytic activation of C-C bonds in simple cyclopentanones and some cyclohexanones. The key to our success is the combination of a rhodium pre-catalyst, an N-heterocyclic carbene ligand and an amino-pyridine co-catalyst. When an aryl group is present in the C3 position of cyclopentanone, the less strained C-C bond can be activated; this is followed by activation of a carbon-hydrogen bond in the aryl group, leading to efficient synthesis of functionalized α-tetralones-a common structural motif and versatile building block in organic synthesis. Furthermore, this method can substantially enhance the efficiency of the enantioselective synthesis of some natural products of terpenoids. Density functional theory calculations reveal a mechanism involving an intriguing rhodium-bridged bicyclic intermediate.

  4. 76 FR 12364 - Agency Information Collection Activities: Bonded Warehouse Regulations

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-07

    ... SECURITY U.S. Customs and Border Protection Agency Information Collection Activities: Bonded Warehouse... Bonded Warehouse Regulations. This request for comment is being made pursuant to the Paperwork Reduction... concerning the following information collection: Title: Bonded Warehouse Regulations. OMB Number:...

  5. METHOD OF MAKING METAL BONDED CARBON BODIES

    DOEpatents

    Goeddel, W.V.; Simnad, M.T.

    1961-09-26

    A method of producing carbon bodies having high structural strength and low permeability is described. The method comprises mixing less than 10 wt.% of a diffusional bonding material selected from the group consisting of zirconium, niobium, molybdenum, titanium, nickel, chromium, silicon, and decomposable compounds thereof with finely divided particles of carbon or graphite. While being maintained at a mechanical pressure over 3,000 psi, the mixture is then heated uniformly to a temperature of 1500 deg C or higher, usually for less than one hour. The resulting carbon bodies have a low diffusion constant, high dimensional stability, and high mechanical strength.

  6. Facile and Promising Method for Michael Addition of Indole and Pyrrole to Electron-Deficient trans-β-Nitroolefins Catalyzed by a Hydrogen Bond Donor Catalyst Feist's Acid and Preliminary Study of Antimicrobial Activity

    PubMed Central

    Al Majid, Abdullah M. A.; Islam, Mohammad Shahidul; Barakat, Assem; Al-Agamy, Mohamed H. M.; Naushad, Mu.

    2014-01-01

    The importance of cooperative hydrogen-bonding effects has been demonstrated using novel 3-methylenecyclopropane-1,2-dicarboxylic acid (Feist's acid (FA)) as hydrogen bond donor catalysts for the addition of indole and pyrrole to trans-β-nitrostyrene derivatives. Because of the hydrogen bond donor (HBD) ability, Feist's acid (FA) has been introduced as a new class of hydrogen bond donor catalysts for the activation of nitroolefin towards nucleophilic substitution reaction. It has effectively catalyzed the Michael addition of indoles and pyrrole to β-nitroolefins under optimum reaction condition to furnish the corresponding Michael adducts in good to excellent yields (up to 98%). The method is general, atom-economical, convenient, and eco-friendly and could provide excellent yields and regioselectivities. Some newly synthesized compounds were for examined in vitro antimicrobial activity and their preliminary results are reported. PMID:24574906

  7. Facile and promising method for michael addition of indole and pyrrole to electron-deficient trans-β-nitroolefins catalyzed by a hydrogen bond donor catalyst Feist's acid and preliminary study of antimicrobial activity.

    PubMed

    Al Majid, Abdullah M A; Islam, Mohammad Shahidul; Barakat, Assem; Al-Agamy, Mohamed H M; Naushad, Mu

    2014-01-01

    The importance of cooperative hydrogen-bonding effects has been demonstrated using novel 3-methylenecyclopropane-1,2-dicarboxylic acid (Feist's acid (FA)) as hydrogen bond donor catalysts for the addition of indole and pyrrole to trans-β-nitrostyrene derivatives. Because of the hydrogen bond donor (HBD) ability, Feist's acid (FA) has been introduced as a new class of hydrogen bond donor catalysts for the activation of nitroolefin towards nucleophilic substitution reaction. It has effectively catalyzed the Michael addition of indoles and pyrrole to β-nitroolefins under optimum reaction condition to furnish the corresponding Michael adducts in good to excellent yields (up to 98%). The method is general, atom-economical, convenient, and eco-friendly and could provide excellent yields and regioselectivities. Some newly synthesized compounds were for examined in vitro antimicrobial activity and their preliminary results are reported.

  8. Disulfide Bond Requirements for Active Wnt Ligands*

    PubMed Central

    MacDonald, Bryan T.; Hien, Annie; Zhang, Xinjun; Iranloye, Oladoyin; Virshup, David M.; Waterman, Marian L.; He, Xi

    2014-01-01

    Secreted Wnt lipoproteins are cysteine-rich and lipid-modified morphogens that bind to the Frizzled (FZD) receptor and LDL receptor-related protein 6 (LRP6). Wnt engages FZD through protruding thumb and index finger domains, which are each assembled from paired β strands secured by disulfide bonds and grasp two sides of the FZD ectodomain. The importance of Wnt disulfide bonds has been assumed but uncharacterized. We systematically analyzed cysteines and associated disulfide bonds in the prototypic Wnt3a. Our data show that mutation of any individual cysteine of Wnt3a results in covalent Wnt oligomers through ectopic intermolecular disulfide bond formation and diminishes/abolishes Wnt signaling. Although individual cysteine mutations in the amino part of the saposin-like domain and in the base of the index finger are better tolerated and permit residual Wnt3a secretion/activity, those in the amino terminus, the thumb, and at the tip of the index finger are incompatible with secretion and/or activity. A few select double cysteine mutants based on the disulfide bond pattern restore Wnt secretion/activity. Further, a double cysteine mutation at the index finger tip results in a Wnt3a with normal secretion but minimal FZD binding and dominant negative properties. Our results experimentally validate predictions from the Wnt crystal structure and highlight critical but different roles of the saposin-like and cytokine-like domains, including the thumb and the index finger in Wnt folding/secretion and FZD binding. Finally, we modified existing expression vectors for 19 epitope-tagged human WNT proteins by removal of a tag-supplied ectopic cysteine, thereby generating tagged WNT ligands active in canonical and non-canonical signaling. PMID:24841207

  9. A covalent method of gentamicin bonding to silica supports.

    PubMed

    Ginalska, Grazyna; Osińska, Monika; Uryniak, Adam

    2004-04-01

    Results of a novel method of covalent bonding of an antibiotic (gentamicin) to silica bead supports are shown. Gentamicin was immobilized to four types of matrix: silica gel and porous glass beads activated by either silanization (APTES) or by adhesively bound keratin (with immobilization yield ranging from 36.5 to 91%). Gentamicin was immobilized to the supports after opening its carbohydrate ring in the molecule. This method of gentamicin activation before the immobilization process did not inhibit its antibiotic activity. The four gentamicin-containing immobilized preparations were stable, meaning that they did not release the antibiotic into the solution during the 30 days of incubation, not even during shaking experiments.

  10. 75 FR 68809 - Agency Information Collection Activities: Importation Bond Structure

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-09

    ... Information Collection Activities: Importation Bond Structure AGENCY: U.S. Customs and Border Protection...: Importation Bond Structure. This is a proposed extension and revision of an information collection that was...: Importation Bond Structure. OMB Number: 1651-0050. Form Numbers: 301 and 5297. Abstract: Bonds are used...

  11. Novel methods of bonding solar cells

    NASA Astrophysics Data System (ADS)

    Thomaier, Rob

    2011-09-01

    Messy liquid adhesives, short work times, long cure times, difficult clean-up of stray adhesive - all of these are associated with liquid adhesives for bonding solar cells. Current adhesion methods have been in place since the '70s: mix a two-part liquid silicone adhesive, coat a portion of adhesive onto a section of substrate, place the cells in a vacuum bag and wait for the adhesive to cure. Alternatively, one can use a fairly complicated robotic procedure to apply adhesive then fix a cell down and, again, wait for the adhesive to cure. Some difficulties that need to be overcome include balancing the amount adhesive to spread out with the available worktime in order to get all the cells onto the substrate with good adhesion; controlling the bondline; ensuring that the adhesive cures correctly after application; and, finally, if there is any re-work, removing the part from the adhesive without damaging everything around it.

  12. Chemical Bond Activation Observed with an X-ray Laser.

    PubMed

    Beye, Martin; Öberg, Henrik; Xin, Hongliang; Dakovski, Georgi L; Dell'Angela, Martina; Föhlisch, Alexander; Gladh, Jörgen; Hantschmann, Markus; Hieke, Florian; Kaya, Sarp; Kühn, Danilo; LaRue, Jerry; Mercurio, Giuseppe; Minitti, Michael P; Mitra, Ankush; Moeller, Stefan P; Ng, May Ling; Nilsson, Anders; Nordlund, Dennis; Nørskov, Jens; Öström, Henrik; Ogasawara, Hirohito; Persson, Mats; Schlotter, William F; Sellberg, Jonas A; Wolf, Martin; Abild-Pedersen, Frank; Pettersson, Lars G M; Wurth, Wilfried

    2016-09-15

    The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free-electron laser to directly observe the decreased bonding-antibonding splitting following bond-activation using an ultrashort optical laser pulse.

  13. Spontaneous and specific activation of chemical bonds in macromolecular fluids.

    PubMed

    Park, Insun; Shirvanyants, David; Nese, Alper; Matyjaszewski, Krzysztof; Rubinstein, Michael; Sheiko, Sergei S

    2010-09-08

    Mechanical activation of chemical bonds typically involves the application of external forces, which implies a broad distribution of bond tensions. We demonstrate that controlling the flow profile of a macromolecular fluid generates and delineates mechanical force concentration, enabling a hierarchical activation of chemical bonds on different length scales from the macroscopic to the molecular. Bond tension is spontaneously generated within brushlike macromolecules as they spread on a solid substrate. The molecular architecture creates an uneven distribution of tension in the covalent bonds, leading to spatially controlled bond scission. By controlling the flow rate and the gradient of the film pressure, one can sever the flowing macromolecules with high precision. Specific chemical bonds are activated within distinct macromolecules located in a defined area of a thin film. Furthermore, the flow-controlled loading rate enables quantitative analysis of the bond activation parameters.

  14. Bonding, Achievement, and Activities: School Bonding, Academic Achievement, and Participation in Extracurricular Activities

    ERIC Educational Resources Information Center

    Howard, Anissa K.; Ziomek-Daigle, Jolie

    2009-01-01

    Utilizing a single-group interrupted time series design (Creswell, 2003), this pilot study examined the relationship between academic achievement, school bonding, and the extracurricular activity participation of "uninvolved" students (n=11) who participated in a voluntary support group at a suburban high school in the southeast. Results…

  15. Method of bonding metals to ceramics

    DOEpatents

    Maroni, V.A.

    1991-04-23

    A ceramic or glass having a thin layer of silver, gold or alloys thereof at the surface thereof is disclosed. A first metal is bonded to the thin layer and a second metal is bonded to the first metal. The first metal is selected from the class consisting of In, Ga, Sn, Bi, Zn, Cd, Pb, Tl and alloys thereof, and the second metal is selected from the class consisting of Cu, Al, Pb, Au and alloys thereof. 3 figures.

  16. Method of bonding metals to ceramics

    DOEpatents

    Maroni, Victor A.

    1991-01-01

    A ceramic or glass having a thin layer of silver, gold or alloys thereof at the surface thereof. A first metal is bonded to the thin layer and a second metal is bonded to the first metal. The first metal is selected from the class consisting of In, Ga, Sn, Bi, Zn, Cd, Pb, Tl and alloys thereof, and the second metal is selected from the class consisting of Cu, Al, Pb, An and alloys thereof.

  17. Cu-Cu direct bonding achieved by surface method at room temperature

    SciTech Connect

    Utsumi, Jun; Ichiyanagi, Yuko

    2014-02-20

    The metal bonding is a key technology in the processes for the microelectromechanical systems (MEMS) devices and the semiconductor devices to improve functionality and higher density integration. Strong adhesion between surfaces at the atomic level is crucial; however, it is difficult to achieve close bonding in such a system. Cu films were deposited on Si substrates by vacuum deposition, and then, two Cu films were bonded directly by means of surface activated bonding (SAB) at room temperature. The two Cu films, with the surface roughness Ra about 1.3nm, were bonded by using SAB at room temperature, however, the bonding strength was very weak in this method. In order to improve the bonding strength between the Cu films, samples were annealed at low temperatures, between 323 and 473 K, in air. As the result, the Cu-Cu bonding strength was 10 times higher than that of the original samples without annealing.

  18. Method for bonding a transmission line to a downhole tool

    DOEpatents

    Hall, David R.; Fox, Joe

    2007-11-06

    An apparatus for bonding a transmission line to the central bore of a downhole tool includes a pre-formed interface for bonding a transmission line to the inside diameter of a downhole tool. The pre-formed interface includes a first surface that substantially conforms to the outside contour of a transmission line and a second surface that substantially conforms to the inside diameter of a downhole tool. In another aspect of the invention, a method for bonding a transmission line to the inside diameter of a downhole tool includes positioning a transmission line near the inside wall of a downhole tool and placing a mold near the transmission line and the inside wall. The method further includes injecting a bonding material into the mold and curing the bonding material such that the bonding material bonds the transmission line to the inside wall.

  19. On the activation of σ-bonds by electric fields: A Valence Bond perspective

    NASA Astrophysics Data System (ADS)

    Rincón, Luis; Mora, Jose R.; Torres, F. Javier; Almeida, Rafael

    2016-09-01

    The activation of non-polar σ -bonds induced by an electric field is studied from the perspective of the Valence Bond theory. As representative examples we study the dissociation of the H-H and C-H bonds of molecular hydrogen and methane, respectively, under the experience of an homogeneous as well as an heterogeneous field oriented along the bond axis. For all cases, the increase in the electric field have similar effects: (i) the stabilization of the potential energy, (ii) an increment of the equilibrium bond length and (iii) the transition from an homolytic dissociation mechanism to an heterolytic one when the bond is subjected under a strong enough field. These general observations are thoroughly explained using a simple Valence Bond model that involve the increment of the resonance energy between the covalent and the ionic structures, and the curve crossing between the two structures after some field strength.

  20. Bonded ultrasonic transducer and method for making

    DOEpatents

    Dixon, Raymond D.; Roe, Lawrence H.; Migliori, Albert

    1995-01-01

    An ultrasonic transducer is formed as a diffusion bonded assembly of piezoelectric crystal, backing material, and, optionally, a ceramic wear surface. The mating surfaces of each component are silver films that are diffusion bonded together under the application of pressure and heat. Each mating surface may also be coated with a reactive metal, such as hafnium, to increase the adhesion of the silver films to the component surfaces. Only thin silver films are deposited, e.g., a thickness of about 0.00635 mm, to form a substantially non-compliant bond between surfaces. The resulting transducer assembly is substantially free of self-resonances over normal operating ranges for taking resonant ultrasound measurements.

  1. Bonded ultrasonic transducer and method for making

    DOEpatents

    Dixon, R.D.; Roe, L.H.; Migliori, A.

    1995-11-14

    An ultrasonic transducer is formed as a diffusion bonded assembly of piezoelectric crystal, backing material, and, optionally, a ceramic wear surface. The mating surfaces of each component are silver films that are diffusion bonded together under the application of pressure and heat. Each mating surface may also be coated with a reactive metal, such as hafnium, to increase the adhesion of the silver films to the component surfaces. Only thin silver films are deposited, e.g., a thickness of about 0.00635 mm, to form a substantially non-compliant bond between surfaces. The resulting transducer assembly is substantially free of self-resonances over normal operating ranges for taking resonant ultrasound measurements. 12 figs.

  2. 76 FR 28801 - Agency Information Collection Activities: Bonded Warehouse Regulations

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-05-18

    ... SECURITY U.S. Customs and Border Protection Agency Information Collection Activities: Bonded Warehouse... approval in accordance with the Paperwork Reduction Act: Bonded Warehouse Regulations. This is a proposed..., mechanical, or other technological techniques or other forms of information. Title: Bonded...

  3. METHOD AND ALLOY FOR BONDING TO ZIRCONIUM

    DOEpatents

    McCuaig, F.D.; Misch, R.D.

    1960-04-19

    A brazing alloy can be used for bonding zirconium and its alloys to other metals, ceramics, and cermets, and consists of 6 to 9 wt.% Ni, 6 to 9 wn~.% Cr, Mo, or W, 0 to 7.5 wt.% Fe, and the balance Zr.

  4. Calculation of activation energies for hydrogen-atom abstractions by radicals containing carbon triple bonds

    NASA Technical Reports Server (NTRS)

    Brown, R. L.; Laufer, A. H.

    1981-01-01

    Activation energies are calculated by the bond-energy-bond-order (BEBO) and the bond-strength-bond-length (BSBL) methods for the reactions of C2H radicals with H2, CH4, and C2H6 and for the reactions of CN radicals with H2 and CH4. The BSBL technique accurately predicts the activation energies for these reactions while the BEBO method yields energies averaging 9 kcal higher than those observed. A possible reason for the disagreement is considered.

  5. A glass microfluidic chip adhesive bonding method at room temperature

    NASA Astrophysics Data System (ADS)

    Pan, Yu-Jen; Yang, Ruey-Jen

    2006-12-01

    This paper presents a novel method using UV epoxy resin for the bonding of glass blanks and patterned plates at room temperature. There is no need to use a high-temperature thermal fusion process and therefore avoid damaging temperature-sensitive metals in a microchip. The proposed technique has the further advantage that the sealed glass blanks and patterned plates can be separated by the application of adequate heat. In this way, the microchip can be opened, the fouling microchannels may be easily cleaned-up and the plates then re-bonded to recycle the microchip. The proposed sealing method is used to bond a microfluidic device, and the bonding strength is then investigated in a series of chemical resistance tests conducted in various chemicals. Leakage of solution was evaluated in a microfluidic chip using pressure testing to 1.792 × 102 kPa (26 psi), and the microchannel had no observable leak. Electrical leakage between channels was tested by comparing the resistances of two bonding methods, and the result shows no significant electrical leakage. The performance of the device obtained from the proposed bonding method is compared with that of the thermal fusion bonding technique for an identical microfluidic device. It is found that identical results are obtained under the same operating conditions. The proposed method provides a simple, quick and inexpensive method for sealing glass microfluidic chips.

  6. Investigation of Adhesive Bond Cure Conditions using Nonlinear Ultrasonic Methods

    NASA Technical Reports Server (NTRS)

    Berndt, Tobias P.; Green, Robert E., Jr.

    1999-01-01

    The objective of this presentation is to investigate various cure conditions of adhesive bonds using nonlinear ultrasonic methods with water coupling. Several samples were used to obtain normal incidence, oblique incidence, and wave mixing.

  7. A novel bonding method for fabrication of PET planar nanofluidic chip with low dimension loss and high bonding strength

    NASA Astrophysics Data System (ADS)

    Yin, Zhifu; Qi, Liping; Zou, Helin; Sun, Lei; Xu, Shenbo

    2015-08-01

    Plastic planar nanofluidic chips are becoming increasingly important for biological and chemical applications. However, the majority of the present bonding methods for planar nanofluidic chips suffer from high dimension loss and low bonding strength. In this work, a novel thermal bonding technique based on O2 plasma and ethanol treatment was proposed. With the assistance of O2 plasma and ethanol, the PET (polyethylene terephthalate) planar nanofluidic chip can be bonded at a low bonding temperature of 50 °C. To increase the bonding rate and bonding strength, the O2 plasma parameters and thermal bonding parameters were optimized during the bonding process. The tensile test indicates that the bonding strength of the PET planar nanofluidic chip can reach 0.954 MPa, while the auto-fluorescence test demonstrates that there is no leakage or blockage in any of the bonded micro- or nanochannels.

  8. Electrically conductive resinous bond and method of manufacture

    DOEpatents

    Snowden, Jr., Thomas M.; Wells, Barbara J.

    1987-01-01

    A method of bonding elements together with a bond of high strength and good electrical conductivity which comprises: applying an unfilled polyimide resin between surfaces of the elements to be bonded, heat treating said unfilled polyimide resin in stages between a temperature range of about 40.degree. to 365.degree. C. to form a strong adhesive bond between said elements, applying a metal-filled polyimide resin overcoat between said elements so as to provide electrical connection therebetween, and heat treating said metal-filled polyimide resin with substantially the same temperature profile as the unfilled polyimide resin. The present invention is also concerned with an adhesive, resilient, substantially void free bonding combination for providing a high strength, electrically conductive adhesive attachment between electrically conductive elements which comprises a major amount of an unfilled polyimide resin and a minor amount of a metal-filled polyimide resin.

  9. Electrically conductive resinous bond and method of manufacture

    DOEpatents

    Snowden, T.M. Jr.; Wells, B.J.

    1985-01-01

    A method of bonding elements together with a bond of high strength and good electrical conductivity which comprises: applying an unfilled polyimide resin between surfaces of the elements to be bonded, heat treating said unfilled polyimide resin in stages between a temperature range of about 40 to 365/sup 0/C to form a strong adhesive bond between said elements, applying a metal-filled polyimide resin overcoat between said elements so as to provide electrical connection therebetween, and heat treating said metal-filled polyimide resin with substantially the same temperature profile as the unfilled polyimide resin. The present invention is also concerned with an adhesive, resilient, substantially void free bonding combination for providing a high strength, electrically conductive adhesive attachment between electrically conductive elements which comprises a major amount of an unfilled polyimide resin and a minor amount of a metal-filled polyimide resin.

  10. Method for joining metal by solid-state bonding

    DOEpatents

    Burkhart, L. Elkin; Fultz, Chester R.; Maulden, Kerry A.

    1979-01-01

    The present development is directed to a method for joining metal at relatively low temperatures by solid-state bonding. Planar surfaces of the metal workpieces are placed in a parallel abutting relationship with one another. A load is applied to at least one of the workpieces for forcing the workpieces together while one of the workpieces is relatively slowly oscillated in a rotary motion over a distance of about 1.degree.. After a preselected number of oscillations, the rotary motion is terminated and the bond between the abutting surfaces is effected. An additional load may be applied to facilitate the bond after terminating the rotary motion.

  11. Hydrogen bonds and antiviral activity of benzaldehyde derivatives

    NASA Astrophysics Data System (ADS)

    Tolstorozhev, G. B.; Skornyakov, I. V.; Belkov, M. V.; Shadyro, O. I.; Brinkevich, S. D.; Samovich, S. N.

    2012-09-01

    We have obtained the Fourier transform IR spectra of solutions of benzaldehyde derivatives having different antiviral activities against a herpes virus. We observe a correlation between the presence of hydrogen bonds in the benzaldehyde molecules and the appearance of antiviral properties in the compounds. For compounds having antiviral activity, we have obtained spectral data suggesting the existence of hydrogen bonds of the type C=OṡṡṡH-O and O-HṡṡṡO in the molecules. When the hydrogen atom in the hydroxyl groups are replaced by a methyl group, no intramolecular hydrogen bonds are formed and the compounds lose their antiviral activity.

  12. Vacuum pull down method for an enhanced bonding process

    DOEpatents

    Davidson, James C.; Balch, Joseph W.

    1999-01-01

    A process for effectively bonding arbitrary size or shape substrates. The process incorporates vacuum pull down techniques to ensure uniform surface contact during the bonding process. The essence of the process for bonding substrates, such as glass, plastic, or alloys, etc., which have a moderate melting point with a gradual softening point curve, involves the application of an active vacuum source to evacuate interstices between the substrates while at the same time providing a positive force to hold the parts to be bonded in contact. This enables increasing the temperature of the bonding process to ensure that the softening point has been reached and small void areas are filled and come in contact with the opposing substrate. The process is most effective where at least one of the two plates or substrates contain channels or grooves that can be used to apply vacuum between the plates or substrates during the thermal bonding cycle. Also, it is beneficial to provide a vacuum groove or channel near the perimeter of the plates or substrates to ensure bonding of the perimeter of the plates or substrates and reduce the unbonded regions inside the interior region of the plates or substrates.

  13. BN Bonded BN fiber article and method of manufacture

    DOEpatents

    Hamilton, Robert S.

    1981-08-18

    A boron nitride bonded boron nitride fiber article and the method for its manufacture which comprises forming a shaped article with a composition comprising a bonding compound selected from boron oxide and boric acid and a structural fiber selected from the group consisting of boron oxide, boron nitride and partially nitrided boron oxide fibers, heating the composition in an anhydrous gas to a temperature above the melting point of the compound and nitriding the resulting article in ammonia gas.

  14. Review of methods for fusion bonding thermoplastic composites

    SciTech Connect

    Benatar, A.; Gutowski, T.G.

    1987-02-01

    Bonding of thermoplastic composites is a critical step in the manufacture of aerospace structures. The objective of this project is to investigate different methods for fusion bonding thermoplastic composites quickly, with a good bond strength, and without warping and deconsolidation. This is best accomplished by heating and melting the thermoplastic on the bond surface only, and then pressing the parts together for a fusion bond. For this purpose, a variety of surface heating techniques were examined for bonding of PEEK and J Polymer composites. These included: resistance heating, infrared heating, induction heating, dielectric/microwave heating, and ultrasonic welding. In resistance heating, a single prepreg ply was placed between the composites and heated by passing electric current through the graphite fibers. With induction heating, a single ply of nickel coated graphite fibers was placed between the composites and heated. Ultrasonic welding was done by molding thermoplastic-only energy directors into the composites; the ultrasonic vibration melted these energy directors thereby fusion bonding the parts. 20 references.

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

    SciTech Connect

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

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

  16. A Simplified Diagnostic Method for Elastomer Bond Durability

    NASA Technical Reports Server (NTRS)

    White, Paul

    2009-01-01

    A simplified method has been developed for determining bond durability under exposure to water or high humidity conditions. It uses a small number of test specimens with relatively short times of water exposure at elevated temperature. The method is also gravimetric; the only equipment being required is an oven, specimen jars, and a conventional laboratory balance.

  17. Effect of UVA-activated riboflavin on dentin bonding.

    PubMed

    Cova, A; Breschi, L; Nato, F; Ruggeri, A; Carrilho, M; Tjäderhane, L; Prati, C; Di Lenarda, R; Tay, F R; Pashley, D H; Mazzoni, A

    2011-12-01

    Recent studies have reported collagen cross-linking after exposure to riboflavin followed by ultraviolet-A (UVA) exposure. This study is the first to investigate the effect of a riboflavin-containing primer on adhesive interface stability and dentinal matrix metalloproteinase activity. Human dentin was etched with 35% phosphoric acid, treated with 0.1% riboflavin, exposed to UVA for 2 min, and bonded with a two-step etch-and-rinse adhesive. Adhesive was applied to control specimens without riboflavin/UVA. Specimens were subjected to microtensile bond strength tests and pulled to failure after storage for 24 hrs, 6 mos, or 1 yr. Interfacial nanoleakage was evaluated by light and transmission electron microscopy. To investigate dentinal matrix metalloproteinase activity, we performed correlative zymographic assays on protein extracts obtained from phosphoric-acid-etched dentin powder with or without riboflavin/UVA treatment and XP Bond. Ultraviolet-activated riboflavin treatment increased the immediate bond strength to dentin at all aging intervals (p < 0.05 vs. control) and decreased interfacial nanoleakage in aged specimens (1 yr; p < 0.05). Zymograms revealed that riboflavin/UVA pre-treatment inhibited dentinal matrix metalloproteinase activity (especially MMP-9). In conclusion, dentinal collagen cross-linking induced by riboflavin/UVA increased immediate bond strength, stabilized the adhesive interface, and inhibited dentin matrix metalloproteinases, thereby increasing the durability of resin-dentin bonds.

  18. Effect of UVA-activated Riboflavin on Dentin Bonding

    PubMed Central

    Cova, A.; Breschi, L.; Nato, F.; Ruggeri, A.; Carrilho, M.; Tjäderhane, L.; Prati, C.; Di Lenarda, R.; Tay, F.R.; Pashley, D.H.; Mazzoni, A.

    2011-01-01

    Recent studies have reported collagen cross-linking after exposure to riboflavin followed by ultraviolet-A (UVA) exposure. This study is the first to investigate the effect of a riboflavin-containing primer on adhesive interface stability and dentinal matrix metalloproteinase activity. Human dentin was etched with 35% phosphoric acid, treated with 0.1% riboflavin, exposed to UVA for 2 min, and bonded with a two-step etch-and-rinse adhesive. Adhesive was applied to control specimens without riboflavin/UVA. Specimens were subjected to microtensile bond strength tests and pulled to failure after storage for 24 hrs, 6 mos, or 1 yr. Interfacial nanoleakage was evaluated by light and transmission electron microscopy. To investigate dentinal matrix metalloproteinase activity, we performed correlative zymographic assays on protein extracts obtained from phosphoric-acid-etched dentin powder with or without riboflavin/UVA treatment and XP Bond. Ultraviolet-activated riboflavin treatment increased the immediate bond strength to dentin at all aging intervals (p < 0.05 vs. control) and decreased interfacial nanoleakage in aged specimens (1 yr; p < 0.05). Zymograms revealed that riboflavin/UVA pre-treatment inhibited dentinal matrix metalloproteinase activity (especially MMP-9). In conclusion, dentinal collagen cross-linking induced by riboflavin/UVA increased immediate bond strength, stabilized the adhesive interface, and inhibited dentin matrix metalloproteinases, thereby increasing the durability of resin-dentin bonds. PMID:21940521

  19. Changes in active site histidine hydrogen bonding trigger cryptochrome activation.

    PubMed

    Ganguly, Abir; Manahan, Craig C; Top, Deniz; Yee, Estella F; Lin, Changfan; Young, Michael W; Thiel, Walter; Crane, Brian R

    2016-09-06

    Cryptochrome (CRY) is the principal light sensor of the insect circadian clock. Photoreduction of the Drosophila CRY (dCRY) flavin cofactor to the anionic semiquinone (ASQ) restructures a C-terminal tail helix (CTT) that otherwise inhibits interactions with targets that include the clock protein Timeless (TIM). All-atom molecular dynamics (MD) simulations indicate that flavin reduction destabilizes the CTT, which undergoes large-scale conformational changes (the CTT release) on short (25 ns) timescales. The CTT release correlates with the conformation and protonation state of conserved His378, which resides between the CTT and the flavin cofactor. Poisson-Boltzmann calculations indicate that flavin reduction substantially increases the His378 pKa Consistent with coupling between ASQ formation and His378 protonation, dCRY displays reduced photoreduction rates with increasing pH; however, His378Asn/Arg variants show no such pH dependence. Replica-exchange MD simulations also support CTT release mediated by changes in His378 hydrogen bonding and verify other responsive regions of the protein previously identified by proteolytic sensitivity assays. His378 dCRY variants show varying abilities to light-activate TIM and undergo self-degradation in cellular assays. Surprisingly, His378Arg/Lys variants do not degrade in light despite maintaining reactivity toward TIM, thereby implicating different conformational responses in these two functions. Thus, the dCRY photosensory mechanism involves flavin photoreduction coupled to protonation of His378, whose perturbed hydrogen-bonding pattern alters the CTT and surrounding regions.

  20. Changes in active site histidine hydrogen bonding trigger cryptochrome activation

    PubMed Central

    Ganguly, Abir; Manahan, Craig C.; Top, Deniz; Yee, Estella F.; Lin, Changfan; Young, Michael W.; Thiel, Walter; Crane, Brian R.

    2016-01-01

    Cryptochrome (CRY) is the principal light sensor of the insect circadian clock. Photoreduction of the Drosophila CRY (dCRY) flavin cofactor to the anionic semiquinone (ASQ) restructures a C-terminal tail helix (CTT) that otherwise inhibits interactions with targets that include the clock protein Timeless (TIM). All-atom molecular dynamics (MD) simulations indicate that flavin reduction destabilizes the CTT, which undergoes large-scale conformational changes (the CTT release) on short (25 ns) timescales. The CTT release correlates with the conformation and protonation state of conserved His378, which resides between the CTT and the flavin cofactor. Poisson-Boltzmann calculations indicate that flavin reduction substantially increases the His378 pKa. Consistent with coupling between ASQ formation and His378 protonation, dCRY displays reduced photoreduction rates with increasing pH; however, His378Asn/Arg variants show no such pH dependence. Replica-exchange MD simulations also support CTT release mediated by changes in His378 hydrogen bonding and verify other responsive regions of the protein previously identified by proteolytic sensitivity assays. His378 dCRY variants show varying abilities to light-activate TIM and undergo self-degradation in cellular assays. Surprisingly, His378Arg/Lys variants do not degrade in light despite maintaining reactivity toward TIM, thereby implicating different conformational responses in these two functions. Thus, the dCRY photosensory mechanism involves flavin photoreduction coupled to protonation of His378, whose perturbed hydrogen-bonding pattern alters the CTT and surrounding regions. PMID:27551082

  1. Ultrasonically Activated Diffusion Bonding for Fluidic Control Assembly

    DTIC Science & Technology

    1979-02-01

    commercially available vacuum bell jar. Provisions for elevated temperature operation included an induction heating coil surrounding the welding and...Ultrasonic bonding times of 2 to 4 seconds are orders of magnitude faster than thermally activated bonding and require no furnaces or high vacuum ...sonic spot welding system appropriately modified for use under high vacuum conditions, with a shortened reed member for containment within a

  2. Brazing method produces solid-solution bond between refractory metals

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Brazing two refractory metals by diffusion bonding minimizes distortion and avoids excessive grain growth in the metals. This method requires the selection of an interface metal that forms intermediate low-melting eutectics or solid solutions with the metals to be brazed.

  3. Hybrid correlation models based on active-space partitioning: seeking accurate O(N5) ab initio methods for bond breaking.

    PubMed

    Bochevarov, Arteum D; Temelso, Berhane; Sherrill, C David

    2006-08-07

    Moller-Plesset second-order (MP2) perturbation theory remains the least expensive standard ab initio method that includes electron correlation, scaling as O(N5) with the number of molecular orbitals N. Unfortunately, when restricted Hartree-Fock orbitals are employed, the potential energy curves calculated with this method are of little use at large interatomic separations because of the divergent behavior of MP2 in these regions. In our previous study [J. Chem. Phys. 122, 234110 (2005)] we combined the MP2 method with the singles and doubles coupled cluster (CCSD) method to produce a hybrid method that retains the computational scaling of MP2 and improves dramatically the shape of the MP2 curves. In this work we expand the hybrid methodology to several other schemes. We investigate a new, improved MP2-CCSD method as well as a few other O(N5) methods related to the Epstein-Nesbet pair correlation theory. Nonparallelity errors across the dissociation curve as well as several spectroscopic constants are computed for BH, HF, H2O, CH+, CH4, and Li2 molecules with the 6-31G* basis set and compared with the corresponding full configuration interaction results. We show that among the O(N5) methods considered, our new hybrid MP2-CCSD method is the most accurate and significantly outperforms MP2 not only at large interatomic separations, but also near equilibrium geometries.

  4. Porcelain laminate veneer restorations bonded with a three-liquid silane bonding agent and a dual-activated luting composite.

    PubMed

    Matsumura, Hideo; Aida, Yukiko; Ishikawa, Yumi; Tanoue, Naomi

    2006-12-01

    This clinical report describes the fabrication and bonding of porcelain laminate veneer restorations in a patient with anterior open spaces. Laminate veneer restorations made of feldspathic porcelain were etched with 5% hydrofluoric acid, rinsed under tap water, ultrasonically cleaned with methanol, and primed with a chemically activated three-liquid silane bonding agent (Clearfil Porcelain Bond). The enamel surfaces were etched with 40% phosphoric acid, rinsed with water, and primed with a two-liquid bonding agent (Clearfil New Bond) that contained a hydrophobic phosphate (10-methacryloyloxydecyl dihydrogen phosphate; MDP). The restorations were bonded with a dual-activated luting composite (Clapearl DC). The veneers have been functioning satisfactorily for an observation period of one year. Combined use of the Clearfil bonding agents and Clapearl DC luting composite is an alternative to conventional materials for seating porcelain laminate veneer restorations, although the system is inapplicable to dentin bonding.

  5. Method of bonding single crystal quartz by field-assisted bonding

    DOEpatents

    Curlee, Richard M.; Tuthill, Clinton D.; Watkins, Randall D.

    1991-01-01

    The method of producing a hermetic stable structural bond between quartz crystals includes providing first and second quartz crystals and depositing thin films of borosilicate glass and silicon on portions of the first and second crystals, respectively. The portions of the first and second crystals are then juxtaposed in a surface contact relationship and heated to a temperature for a period sufficient to cause the glass and silicon films to become electrically conductive. An electrical potential is then applied across the first and second crystals for creating an electrostatic field between the adjoining surfaces and causing the juxtaposed portions to be attracted into an intimate contact and form a bond for joining the adjoining surfaces of the crystals.

  6. Method of bonding single crystal quartz by field-assisted bonding

    DOEpatents

    Curlee, R.M.; Tuthill, C.D.; Watkins, R.D.

    1991-04-23

    The method of producing a hermetic stable structural bond between quartz crystals includes providing first and second quartz crystals and depositing thin films of borosilicate glass and silicon on portions of the first and second crystals, respectively. The portions of the first and second crystals are then juxtaposed in a surface contact relationship and heated to a temperature for a period sufficient to cause the glass and silicon films to become electrically conductive. An electrical potential is then applied across the first and second crystals for creating an electrostatic field between the adjoining surfaces and causing the juxtaposed portions to be attracted into an intimate contact and form a bond for joining the adjoining surfaces of the crystals. 2 figures.

  7. Transition-metal-catalyzed additions of C-H bonds to C-X (X = N, O) multiple bonds via C-H bond activation.

    PubMed

    Yan, Guobing; Wu, Xiangmei; Yang, Minghua

    2013-09-14

    Chemical transformations via catalytic C-H bond activation have been established as one of the most powerful tools in organic synthetic chemistry. Transition-metal-catalyzed addition reactions of C-H bonds to polar C-X (X = N, O) multiple bonds, such as aldehydes, ketones, imines, isocyanates, nitriles, isocyanides, carbon monoxide and carbon dioxide, have undergone a rapid development in recent years. In this review, recent advances in this active area have been highlighted and their mechanisms have been discussed.

  8. Selenium bond decreases ON resistance of light-activated switch

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Vitrified amorphous selenium bond decreases the ON resistance of a gallium arsenide-silicon light-activated, low-level switch. The switch is used under a pulse condition to prolong switch life and minimize errors due to heating, devitrification, and overdrawing.

  9. Assessment of Proper Bonding Methods and Mechanical Characterization FPGA CQFPs

    NASA Technical Reports Server (NTRS)

    Davis, Milton C.

    2008-01-01

    This presentation discusses fractured leads on field-programmable gate array (FPGA) during flight vibration. Actions taken to determine root cause and resolution of the failure include finite element analysis (FEA) and vibration testing and scanning electron microscopy (with X-ray microanalysis) and energy dispersive spectrometry (SEM/EDS) failure assessment. Bonding methods for surface mount parts is assessed, including critical analysis and assessment of random fatigue damage. Regarding ceramic quad flat pack (CQFP) lead fracture, after disassembling the attitude control electronics (ACE) configuration, photographs showed six leads cracked on FPGA RTSX72SU-1 CQ208B package located on the RWIC card. An identical package (FPGA RTSX32SU-1 CQ208B) mounted on the RWIC did not results in cracked pins due to vibration. FPGA lead failure theories include workmanship issues in the lead-forming, material defect in the leads of the FPGA packages, and the insecure mounting of the board in the card guides, among other theories. Studies were conducted using simple calculations to determine the response and fatigue life of the package. Shorter packages exhibited more response when loaded by out-of-plane displacement of PCB while taller packages exhibit more response when loaded by in-plane acceleration of PCB. Additionally, under-fill did not contribute to reducing stress in leads due to out-of-plane PCB loading or from component twisting, as much as corner bonding. The combination of corner bond and under-fill is best to address mechanical and thermal S/C environment. Test results of bonded parts showed reduced (dampened) amplitude and slightly shifted peaks at the un-bonded natural frequency and an additional response at the bonded frequency. Stress due to PCBB out-of-plane loading was decreased on in the corners when only a corner bond was used. Future work may address CQFP fatigue assessment, including the investigation of discrepancy in predicted fatigue damage, as well as

  10. Methods for Using Durable Adhesively Bonded Joints for Sandwich Structures

    NASA Technical Reports Server (NTRS)

    Smeltzer, Stanley S., III (Inventor); Lundgren, Eric C. (Inventor)

    2016-01-01

    Systems, methods, and apparatus for increasing durability of adhesively bonded joints in a sandwich structure. Such systems, methods, and apparatus includes an first face sheet and an second face sheet as well as an insert structure, the insert structure having a first insert face sheet, a second insert face sheet, and an insert core material. In addition, sandwich core material is arranged between the first face sheet and the second face sheet. A primary bondline may be coupled to the face sheet(s) and the splice. Further, systems, methods, and apparatus of the present disclosure advantageously reduce the load, provide a redundant path, reduce structural fatigue, and/or increase fatigue life.

  11. 77 FR 6814 - Agency Information Collection Activities: Bonded Warehouse Proprietor's Submission

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-02-09

    ... SECURITY U.S. Customs and Border Protection Agency Information Collection Activities: Bonded Warehouse... the Bonded Warehouse Proprietor's Submission (CBP Form 300). This request for comment is being made... CBP is soliciting comments concerning the following information collection: Title: Bonded...

  12. Friedel-Crafts reaction of benzyl fluorides: selective activation of C-F bonds as enabled by hydrogen bonding.

    PubMed

    Champagne, Pier Alexandre; Benhassine, Yasmine; Desroches, Justine; Paquin, Jean-François

    2014-12-08

    A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups.

  13. Effect of water-ageing on dentine bond strength and anti-biofilm activity of bonding agent containing new monomer dimethylaminododecyl methacrylate

    PubMed Central

    Zhang, Ke; Cheng, Lei; Wu, Eric J.; Weir, Michael D.; Bai, Yuxing; Xu, Hockin H. K.

    2013-01-01

    Objectives The objectives of this study were to develop bonding agent containing a new antibacterial monomer dimethylaminododecyl methacrylate (DMADDM) as well as nanoparticles of silver (NAg) and nanoparticles of amorphous calcium phosphate (NACP), and to investigate the effects of water-ageing for 6 months on dentine bond strength and anti-biofilm properties for the first time. Methods Four bonding agents were tested: Scotchbond Multi-Purpose (SBMP) Primer and Adhesive control; SBMP + 5% DMADDM; SBMP + 5% DMADDM + 0.1% NAg; and SBMP + 5% DMADDM + 0.1% NAg with 20% NACP in adhesive. Specimens were water-aged for 1 d and 6 months at 37 °C. Then the dentine shear bond strengths were measured. A dental plaque microcosm biofilm model was used to inoculate bacteria on water-aged specimens and to measure metabolic activity, colony-forming units (CFUs), and lactic acid production. Results Dentine bond strength showed a 35% loss in 6 months of water-ageing for SBMP control (mean ± sd; n = 10); in contrast, the new antibacterial bonding agents showed no strength loss. The DMADDM–NAg–NACP containing bonding agent imparted a strong antibacterial effect by greatly reducing biofilm viability, metabolic activity and acid production. The biofilm CFU was reduced by more than two orders of magnitude, compared to SBMP control. Furthermore, the DMADDM–NAg–NACP bonding agent exhibited a long-term antibacterial performance, with no significant difference between 1 d and 6 months (p > 0.1). Conclusions Incorporating DMADDM–NAg–NACP in bonding agent yielded potent and long-lasting antibacterial properties, and much stronger bond strength after 6 months of water-ageing than a commercial control. The new antibacterial bonding agent is promising to inhibit biofilms and caries at the margins. The method of DMADDM–NAg–NACP incorporation may have a wide applicability to other adhesives, cements and composites. PMID:23583528

  14. C-H bond activation by f-block complexes.

    PubMed

    Arnold, Polly L; McMullon, Max W; Rieb, Julia; Kühn, Fritz E

    2015-01-02

    Most homogeneous catalysis relies on the design of metal complexes to trap and convert substrates or small molecules to value-added products. Organometallic lanthanide compounds first gave a tantalizing glimpse of their potential for catalytic C-H bond transformations with the selective cleavage of one C-H bond in methane by bis(permethylcyclopentadienyl)lanthanide methyl [(η(5) -C5 Me5 )2 Ln(CH3 )] complexes some 25 years ago. Since then, numerous metal complexes from across the periodic table have been shown to selectively activate hydrocarbon C-H bonds, but the challenges of closing catalytic cycles still remain; many f-block complexes show great potential in this important area of chemistry.

  15. Transition Metals Catalyzed Element-Cyano Bonds Activations

    PubMed Central

    Wang, Rui; Falck, John R.

    2014-01-01

    Cyano group as a versatile functionalized intermediate has been explored for several decades, as it readily transfers to many useful functionalization groups such as amine, amide, acid, etc., which make it possess high popularization and use value in organic synthesis. Reactions involved with element-cyano bond cleavage can provide not only a new cyano group but also a freshly functionalized skeleton in one-pot, consequently making it of high importance. The highlights reviewed herein include H-CN, Si-CN, C-CN, B-CN, Sn-CN, Ge-CN, S-CN, Halo-CN, N-CN, and O-CN bonds cleavages and will summarize progress in such an important research area. This review article will focus on transition metal catalyzed reactions involving element-cyano bond activation. PMID:25558119

  16. Effect of bonding on the performance of a piezoactuator-based active control system

    NASA Technical Reports Server (NTRS)

    Baz, A.; Poh, S.

    1987-01-01

    The utilization of piezoelectric actuators in controlling the structural vibrations of flexible beams is studied. A Modified Independent Modal Space Control (MIMSC) method is devised to select the optimal location, control gains and excitation voltage of the piezoelectric actuators in a way that would minimize the amplitudes of vibrations of beams to which these actuators are bonded, as well as the input control energy necessary to suppress these vibrations. The presented method accounts for the effects that the piezoelectric actuators and the bonding layers have on changing the elastic and inertial properties of the flexible beams. Numerical examples are presented to illustrate the application of the MIMSC method and to demonstrate the effect of the physical and geometrical properties of the bonding layer on the dynamic performance of the actively controlled beams. The obtained results emphasize the importance of the devised method in designing more realistic active control systems for flexible beams, in particular, and large flexible structures in general.

  17. Method of Bonding Optical Elements with Near-Zero Displacement

    NASA Technical Reports Server (NTRS)

    Robinson, David; McClelland, Ryan; Byron, Glenn; Evans, Tyler

    2012-01-01

    The International X-ray Project seeks to build an x-ray telescope using thousands of pieces of thin and flexible glass mirror segments. Each mirror segment must be bonded into a housing in nearly perfect optical alignment without distortion. Forces greater than 0.001 Newton, or displacements greater than 0.5 m of the glass, cause unacceptable optical distortion. All known epoxies shrink as they cure. Even the epoxies with the least amount of shrinkage (<0.01%) cause unacceptable optical distortion and misalignment by pulling the mirror segments towards the housing as it cures. A related problem is that the shrinkage is not consistent or predictable so that it cannot be accounted for in the setup (i.e., if all of the bonds shrunk an equal amount, there would be no problem). A method has been developed that allows two components to be joined with epoxy in such a way that reduces the displacement caused by epoxy shrinking as it cures to less than 200 nm. The method involves using ultraviolet-cured epoxy with a displacement sensor and a nanoactuator in a control loop. The epoxy is cured by short-duration exposures to UV light. In between each exposure, the nano-actuator zeroes out the displacement caused by epoxy shrinkage and thermal expansion. After a few exposures, the epoxy has cured sufficiently to prevent further displacement of the two components. Bonding of optical elements has been done for many years, but most optics are thick and rigid elements that resist micro-Newton-level forces without causing distortion. When bonding thin glass optics such as the 0.40-mm thick IXO X-ray mirrors, forces in the micro- and milli-Newton levels cause unacceptable optical figure error. This innovation can now repeatedly and reliably bond a thin glass mirror to a metal housing with less than 0.2 m of displacement (<200 nm). This is an enabling technology that allows the installation of virtually stress-free, undistorted thin optics onto structures. This innovation is

  18. Wafer bonded virtual substrate and method for forming the same

    DOEpatents

    Atwater, Jr., Harry A.; Zahler, James M.; Morral, Anna Fontcuberta i

    2007-07-03

    A method of forming a virtual substrate comprised of an optoelectronic device substrate and handle substrate comprises the steps of initiating bonding of the device substrate to the handle substrate, improving or increasing the mechanical strength of the device and handle substrates, and thinning the device substrate to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. The handle substrate is typically Si or other inexpensive common substrate material, while the optoelectronic device substrate is formed of more expensive and specialized electro-optic material. Using the methodology of the invention a wide variety of thin film electro-optic materials of high quality can be bonded to inexpensive substrates which serve as the mechanical support for an optoelectronic device layer fabricated in the thin film electro-optic material.

  19. Wafer bonded virtual substrate and method for forming the same

    NASA Technical Reports Server (NTRS)

    Atwater, Jr., Harry A. (Inventor); Zahler, James M. (Inventor); Morral, Anna Fontcuberta i (Inventor)

    2007-01-01

    A method of forming a virtual substrate comprised of an optoelectronic device substrate and handle substrate comprises the steps of initiating bonding of the device substrate to the handle substrate, improving or increasing the mechanical strength of the device and handle substrates, and thinning the device substrate to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. The handle substrate is typically Si or other inexpensive common substrate material, while the optoelectronic device substrate is formed of more expensive and specialized electro-optic material. Using the methodology of the invention a wide variety of thin film electro-optic materials of high quality can be bonded to inexpensive substrates which serve as the mechanical support for an optoelectronic device layer fabricated in the thin film electro-optic material.

  20. Transition-state metal aryl bond stability determines regioselectivity in palladium acetate mediated C-H bond activation of heteroarenes.

    PubMed

    Petit, Alban; Flygare, Josh; Miller, Alex T; Winkel, Gerrit; Ess, Daniel H

    2012-07-20

    Density functional calculations reveal that the stability of developing metal aryl bonds in Pd(II)-acetate C-H activation transition states determines regioselectivity in arene and heteroarene compounds. This kinetic-thermodynamic connection explains the general preference for activation of the strongest C-H bond and provides the possibility for regioselectivity prediction.

  1. Investigation of adhesive bond cure conditions using nonlinear ultrasonic methods

    NASA Astrophysics Data System (ADS)

    Berndt, Tobias Paul

    2000-09-01

    Various linear and nonlinear ultrasonic methods with water coupling have been used to study aluminum-adhesive- aluminum laminates, prepared under different adhesive curing conditions, for possible nondestructive bond strength determination. Although our improperly cured adhesive bonds are expected to exhibit a reduced adhesion strength, ultrasonic characterization of all samples using small-amplitude techniques did not reveal differences between the various samples. The ill-cured bonds appear to differ from the well-cured ones only in their acoustic velocities in the adhesive. Thus, the ill-cured adhesives exhibit longitudinal and shear wave velocities that are several percent higher than in the normal-cured adhesives. Therefore, in the course of a larger research effort, we have investigated a variety of finite-amplitude experimental methods for the acquisition of data that would possibly allow to differentiate the various cure conditions as well as the degree of adhesion. For example, we have explored numerous normal and oblique incidence approaches, that are based on nonlinear harmonic generation, and we have explored several non- collinear two-wave interaction approaches. In this dissertation, we report on theoretical aspects and experimental results obtained so far using different normal incidence setups. First, we discuss an approach in which the sample is mechanically scanned in various ways with respect to the focus of a transmitting transducer that is operated at one frequency and one excitation level. Subsequently, we discuss several variable excitation frequency and variable excitation level setups. Due to a combination of complicating factors, even if powerful sample-related resonances via a frequency scanning approach are exploited, it is extremely difficult to isolate the nonlinear characteristics of an adhesive bond. However, a multi-frequency multi-power approach has been quite successful in acquiring nonlinear ultrasonic data that appears to be

  2. A comparison of bond strength between direct- and indirect-bonding methods.

    PubMed

    Linn, Brandon James; Berzins, David W; Dhuru, Virendra B; Bradley, Thomas Gerard

    2006-03-01

    The purpose of this study was to evaluate and compare the shear bond strength and the sites of bond failure for brackets bonded to teeth, using two indirect-bonding material protocols and a direct-bonding technique. Sixty extracted human premolars were collected and randomly divided into three groups. The direct-bonded group (group 1) used a light-cured adhesive and primer (Transbond XT). One indirect-bonded group (group 2) consisted of a chemical-cured primer (Sondhi Rapid Set) and light-cured adhesive (Transbond XT), whereas the other group (group 3) used a light-cured primer (Orthosolo) and adhesive (Enlight LV). Forty hours after bonding, the samples were debonded. Mean shear bond strengths were 16.27, 13.83, and 14.76 MPa for groups 1, 2, and 3, respectively. A one-way analysis of variance showed no significant difference in mean bond strength between groups (P = .21). Furthermore, a Weibull analysis showed all three groups tested provided over a 90% survival rate at normal masticatory and orthodontic force levels. For each tooth, an Adhesive Remnant Index (ARI) score was determined. Group 2 was found to have a significantly lower ARI score (P < .05) compared with groups 1 and 3. In addition, Pearson correlation coefficients indicated no strong correlation between bond strength and ARI score within or across all groups.

  3. Microshear bond strength according to dentin cleansing methods before recementation

    PubMed Central

    Taşar, Simge; Ulusoy, Mutahhar Muhammed

    2014-01-01

    PURPOSE The aim of this study was to determine the efficiency of Erbium, Chromium: Yttrium-Scandium-Gallium-Garnet laser in different output powers for removing permanent resin cement residues and therefore its influence on microshear bond strength compared to other cleaning methods. MATERIALS AND METHODS 90 extracted human molars were sectioned in 1 mm thickness. Resin cement was applied to surface of sliced teeth. After the removal of initial cement, 6 test groups were prepared by various dentin surface treatment methods as follows: no treatment (Group 1), ethylene diamine tetra acetic acid application (Group 2), Endosolv R application (Group 3), 1.25 W Erbium, Chromium:Yttrium-Scandium-Gallium-Garnet laser irradiation (Group 4), 2 W Erbium, Chromium:Yttrium-Scandium-Gallium-Garnet laser irradiation (Group 5) and 3.5 W Erbium, Chromium:Yttrium-Scandium-Gallium-Garnet laser irradiation (Group 6). The topography and morphology of the treated dentin surfaces were investigated by scanning electron microscopy (n=2 for each group). Following the repetitive cementation, microshear bond strength between dentin and cement (n=26 in per group) were measured with universal testing machine and the data were analyzed by Kruskal Wallis H Test with Bonferroni correction (P<.05). Fracture patterns were investigated by light microscope. RESULTS Mean microshear bond strength ± SD (MPa) for each group was 34.9 ± 17.7, 32.1 ± 15.8, 37.8 ± 19.3, 31.3 ± 12.7, 44.4 ± 13.6, 40.2 ± 13.2 respectively. Group 5 showed significantly difference from Group 1, Group 2 and Group 4. Also, Group 6 was found statistically different from Group 4. CONCLUSION 2 W and 3.5 W Erbium, Chromium: Yttrium-Scandium-Gallium-Garnet laser application were found efficient in removing resin residues. PMID:24843391

  4. Catastrophic fault diagnosis in dynamic systems using bond graph methods

    SciTech Connect

    Yarom, Tamar.

    1990-01-01

    Detection and diagnosis of faults has become a critical issue in high performance engineering systems as well as in mass-produced equipment. It is particularly helpful when the diagnosis can be made at the initial design level with respect to a prospective fault list. A number of powerful methods have been developed for aiding in the general fault analysis of designs. Catastrophic faults represent the limit case of complete local failure of connections or components. They result in the interruption of energy transfer between corresponding points in the system. In this work the conventional approach to fault detection and diagnosis is extended by means of bond-graph methods to a wide variety of engineering systems. Attention is focused on catastrophic fault diagnosis. A catastrophic fault dictionary is generated from the system model based on topological properties of the bond graph. The dictionary is processed by existing methods to extract a catastrophic fault report to aid the engineer in performing a design analysis.

  5. α-Halogenoacetanilides as hydrogen-bonding organocatalysts that activate carbonyl bonds: fluorine versus chlorine and bromine.

    PubMed

    Koeller, Sylvain; Thomas, Coralie; Peruch, Fréderic; Deffieux, Alain; Massip, Stéphane; Léger, Jean-Michel; Desvergne, Jean-Pierre; Milet, Anne; Bibal, Brigitte

    2014-03-03

    α-Halogenoacetanilides (X=F, Cl, Br) were examined as H-bonding organocatalysts designed for the double activation of CO bonds through NH and CH donor groups. Depending on the halide substituents, the double H-bond involved a nonconventional CH⋅⋅⋅O interaction with either a HCXn (n=1-2, X=Cl, Br) or a HCAr bond (X=F), as shown in the solid-state crystal structures and by molecular modeling. In addition, the catalytic properties of α-halogenoacetanilides were evaluated in the ring-opening polymerization of lactide, in the presence of a tertiary amine as cocatalyst. The α-dichloro- and α-dibromoacetanilides containing electron-deficient aromatic groups afforded the most attractive double H-bonding properties towards CO bonds, with a NH⋅⋅⋅O⋅⋅⋅HCX2 interaction.

  6. Analysis Method for Inelastic, Adhesively Bonded Joints with Anisotropic Adherends

    NASA Technical Reports Server (NTRS)

    Smeltzer, Stanley S., III; Klang, Eric C.

    2003-01-01

    A one-dimensional analysis method for evaluating adhesively bonded joints composed of anisotropic adherends and adhesives with nonlinear material behavior is presented in the proposed paper. The strain and resulting stress field in a general, bonded joint overlap are determined by using a variable-step, finite-difference solution algorithm to iteratively solve a system of first-order differential equations. Applied loading is given by a system of combined extensional, bending, and shear forces that are applied to the edge of the joint overlap. Adherends are assumed to behave as linear, cylindrically bent plates using classical laminated plate theory that includes the effects of first-order transverse shear deformation. Using the deformation theory of plasticity and a modified von-Mises yield criterion, inelastic material behavior is modeled in the adhesive layer. Results for the proposed method are verified against previous results from the literature and shown to be in excellent agreement. An additional case that highlights the effects of transverse shear deformation between similar adherends is also presented.

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

    PubMed

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

    2015-04-14

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

  8. Electrical Bonding: A Survey of Requirement, Methods, and Specifications

    NASA Technical Reports Server (NTRS)

    Evans, R. W.

    1998-01-01

    This document provides information helpful to engineers imposing electrical bonding requirements, reviewing waiver requests, or modifying specifications on various space programs. Electrical bonding specifications and some of the processes used in the United States have been reviewed. This document discusses the specifications, the types of bonds, the intent of each, and the basic requirements where possible. Additional topics discussed are resistance versus impedance, bond straps, corrosion, finishes, and special applications.

  9. 26 CFR 1.103(n)-2T - Private activity bond defined (temporary).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... activity bond” means any industrial development bond or student loan bond the interest on which is exempt... definition of the term “industrial development bond.” See A-17 of this § 1.103(n)-2T for the definition of..., Governmental Unit M issues industrial development bonds to provide an airport, as described in section...

  10. 26 CFR 1.103(n)-2T - Private activity bond defined (temporary).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... activity bond” means any industrial development bond or student loan bond the interest on which is exempt... definition of the term “industrial development bond.” See A-17 of this § 1.103(n)-2T for the definition of..., Governmental Unit M issues industrial development bonds to provide an airport, as described in section...

  11. Transition metal activation and functionalization of carbon-hydrogen bonds

    SciTech Connect

    Jones, W.D.

    1992-06-01

    We are investigating the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers and the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. Advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds or arenes upon photolysis. The mechanism of these reactions was found to proceed by way of initial phosphine dissociation, followed by C-H activation and isonitrile insertion. We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. The effects of resonance, specifically the differences in the Hueckel energies of the bound vs free ligand, are now believed to fully control the C-H activation/{eta}{sup 2}-coordination equilibria. We have begun to examine the reactions of rhodium isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more facilely than thermal reductive elimination of H{sub 2}. We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion.

  12. Bond-valence methods for p Ka prediction. II. Bond-valence, electrostatic, molecular geometry, and solvation effects

    NASA Astrophysics Data System (ADS)

    Bickmore, Barry R.; Rosso, Kevin M.; Tadanier, Christopher J.; Bylaska, Eric J.; Doud, Darrin

    2006-08-01

    In a previous contribution, we outlined a method for predicting (hydr)oxy-acid and oxide surface acidity constants based on three main factors: bond valence, Me-O bond ionicity, and molecular shape. Here, electrostatics calculations and ab initio molecular dynamics simulations are used to qualitatively show that Me-O bond ionicity controls the extent to which the electrostatic work of proton removal departs from ideality, bond valence controls the extent of solvation of individual functional groups, and bond valence and molecular shape control local dielectric response. These results are consistent with our model of acidity, but completely at odds with other methods of predicting acidity constants for use in multisite complexation models. In particular, our ab initio molecular dynamics simulations of solvated monomers clearly indicate that hydrogen bonding between (hydr)oxo-groups and water molecules adjusts to obey the valence sum rule, rather than maintaining a fixed valence based on the coordination of the oxygen atom as predicted by the standard MUSIC model. However, we also show how our method for p Ka prediction could be improved using ab initio molecular dynamics simulations of solvated surfaces.

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

    DOEpatents

    Wagh, Arun; Maloney, Martin D.

    2010-06-29

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

  14. Thermal assisted ultrasonic bonding method for poly(methyl methacrylate) (PMMA) microfluidic devices.

    PubMed

    Zhang, Zongbo; Wang, Xiaodong; Luo, Yi; He, Shengqiang; Wang, Liding

    2010-06-15

    A thermal assisted ultrasonic bonding method for poly(methyl methacrylate) (PMMA) microfluidic devices has been presented. The substrates were preheated to 20-30 degrees C lower than glass transition temperature (T(g)) of the polymer. Then low amplitude ultrasonic vibration was employed to generate facial heat at the interface of PMMA substrates. PMMA microfluidic chips were successfully bonded with bulk temperature well below T(g) of the material and with pressure two orders lower than conventional thermal bonding, which was of great benefit to reduce the deformation of microstructures. The bonding process was optimized by Taguchi method. This bonding technique showed numerous superiorities including high bonding strength (0.95MPa), low dimension loss (0.3-0.8%) and short bonding time. Finally, a micromixer was successfully bonded by this method and its performance was demonstrated.

  15. Bond-valence methods for pKa prediction. II. Bond-valence, electrostatic, molecular geometry, and solvation effects

    SciTech Connect

    Bickmore, Barry R.; Rosso, Kevin M.; Tadanier, Christopher J.; Bylaska, Eric J.; Doud, Darrin

    2006-08-15

    In a previous contribution, we outlined a method for predicting (hydr)oxy-acid and oxide surface acidity constants based on three main factors: bond valence, Me?O bond ionicity, and molecular shape. Here electrostatics calculations and ab initio molecular dynamics simulations are used to qualitatively show that Me?O bond ionicity controls the extent to which the electrostatic work of proton removal departs from ideality, bond valence controls the extent of solvation of individual functional groups, and bond valence and molecular shape controls local dielectric response. These results are consistent with our model of acidity, but completely at odds with other methods of predicting acidity constants for use in multisite complexation models. In particular, our ab initio molecular dynamics simulations of solvated monomers clearly indicate that hydrogen bonding between (hydr)oxo-groups and water molecules adjusts to obey the valence sum rule, rather than maintaining a fixed valence based on the coordination of the oxygen atom as predicted by the standard MUSIC model.

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

    ERIC Educational Resources Information Center

    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…

  17. Caul and method for bonding and curing intricate composite structures

    NASA Technical Reports Server (NTRS)

    Willden, Kurtis S. (Inventor); Goodno, Kenneth N. (Inventor)

    1993-01-01

    The invention disclosed here is a method for forming and curing an intricate structure of criss-crossing composite stringers and frames that are bonded to a skin panel. A structure constructed in accordance with the invention would be well-suited for use as a portion of an aircraft fuselage, a boat hull, or the like. The method is preferably practiced by applying uncured composite stringers to an uncured composite sheet panel. This is followed by placing cured frames crosswise over the stringers. The frames have openings at the locations where they intersect with the stringers which enables the frames to come into direct contact with the skin along most of their length. During the forming and curing process, the stringers are covered with a plurality of cauls, and the entire assembly of skin panel, stringers, frames and cauls is subjected to a vacuum bagging and curing process. The cauls serve to maintain both part shape and to control the flow of resin within the stringers as they are cured. Further, they probably eliminate the need for intermediate protective materials between the vacuum bag and the stringers.

  18. Method for bonding thin film thermocouples to ceramics

    DOEpatents

    Kreider, Kenneth G.

    1993-01-01

    A method is provided for adhering a thin film metal thermocouple to a ceramic substrate used in an environment up to 700 degrees Centigrade, such as at a cylinder of an internal combustion engine. The method includes the steps of: depositing a thin layer of a reactive metal on a clean ceramic substrate; and depositing thin layers of platinum and a platinum-10% rhodium alloy forming the respective legs of the thermocouple on the reactive metal layer. The reactive metal layer serves as a bond coat between the thin noble metal thermocouple layers and the ceramic substrate. The thin layers of noble metal are in the range of 1-4 micrometers thick. Preferably, the ceramic substrate is selected from the group consisting of alumina and partially stabilized zirconia. Preferably, the thin layer of reactive metal is in the range of 0.015-0.030 micrometers (15-30 nanometers) thick. The preferred reactive metal is chromium. Other reactive metals may be titanium or zirconium. The thin layer of reactive metal may be deposited by sputtering in ultra high purity argon in a vacuum of approximately 2 milliTorr (0.3 Pascals).

  19. New surface-active comonomer for adhesive bonding.

    PubMed

    Bowen, R L; Bennett, P S; Groh, R J; Farahani, M; Eichmiller, F C

    1996-01-01

    Previous studies have indicated that chemical and physical characteristics of aromatic amines can be influenced by the nature of their substituents. The experimental question examined in the present study relates to the effects of replacing specific hydrogen atoms with methyl groups in a surface-active comonomer utilized in adhesive bonding protocols. N-2-propionic acid-N-3-(2-hydroxy-1-methacryloxy)propyl-3,5-dimethylaniline sodium salt (N35A) was synthesized by an addition reaction of glycidyl methacrylate with the sodium salt of N-reaction of glycidyl methacrylate with the sodium salt of N-(3,5-dimethylphenyl)alanine, which was formed by alkaline hydrolysis of ethyl-N-(3,5-dimethylphenyl)alanate that was prepared by condensation of ethyl-2-bromopropionate with 3,5-dimethylaniline. 1H and 13C NMR spectra and analysis by mass spectroscopy were consistent with N35A after it had been recrystallized from acetone. Color stability and adhesion-promoting capability of N35A were compared with those of N-2-acetic acid-N-3-(2-hydroxy-1-methacryloxy)propyl-4-methylanaline sodium salt (Na-NTG-GMA), the latter being widely used in commercial bonding formulations. Both N35A and Na-NTG-GMA polymerized within a few minutes at 23 degrees C when dissolved in aliquots from a stock solution containing benzene 85 wt%, ethanol 14 wt%, and benzoyl peroxide 1.0 wt%; but with each at 0.018 molal concentration, the N35A suspension was more color-stable than that of the Na-NTG-GMA. In the protocol used, shear bond strengths of a hybrid composite to human dentin with N35A were 30.2 MPa, SD = 7.5 MPa, and with Na-NTG-GMA, 29.7 MPa, SD = 11.8 MPa(n = 7 each; t test, p = 0.93).

  20. A study on Zr-Ir multiple bonding active for C-H bond cleavage.

    PubMed

    Oishi, Masataka; Oshima, Masato; Suzuki, Hiroharu

    2014-07-07

    Zr-Ir hydrido complexes with ansa-(cyclopentadienyl)(amide) as the supporting ligand in the zirconium fragment, e.g., (L(1)ZrR)(Cp*Ir)(μ-H)3 [L(1) = Me2Si(η(5)-C5Me4)(N(t)Bu), R = Cl (5), Ph (7), Me (10), alkyl, and aryl] were designed, synthesized, and isolated as tractable early-late heterodinuclear complexes. Despite the presence of the three supporting hydride ligands, Zr-Ir distances in the crystal structures of 5, alkyl, and aryl complexes [2.74-2.76 Å] were slightly longer than the sum of the element radii of Zr and Ir [2.719 Å]. These hydrocarbyl complexes displayed the thermolytic C-H activation of a variety of aromatic compounds and several organometallic compounds. Also, the substrate scope and limitation in the Zr-Ir system were studied. The regiochemical outcomes during the C-H activation of pyridine derivatives and methoxyarenes suggested the in situ generation of a Lewis acidic active intermediate, i.e., (L(1)Zr)(Cp*IrH2) (III). The existence of III and relevant σ-complex intermediates {L(1)Zr(η(2)-R-H)}(Cp*IrH2) (IIR) (R = Me, Ph) in the ligand exchange was demonstrated by the direct isolation of a Et3PO-adduct of III (39b) from 7 and kinetic studies. The structure of the direct Zr-Ir bonds in IIPh, IIMe, III, and 39b were probed using computational studies. The unprecedented strong M-M' interactions in the early-late heterobimetallic (ELHB) complexes have been proposed herein.

  1. Highly dispersed buckybowls as model carbocatalysts for C–H bond activation

    DOE PAGES

    Soykal, I. Ilgaz; Wang, Hui; Park, Jewook; ...

    2015-03-19

    Buckybowl fractions dispersed on mesoporous silica constitute an ideal model for studying the catalysis of graphitic forms of carbon since the dispersed carbon nanostructures contain a high ratio of edge defects and curvature induced by non-six-membered rings. Dispersion of the active centers on an easily accessible high surface area material allowed for high density of surface active sites associated with oxygenated structures. This report illustrates a facile method of creating model polycyclic aromatic nano-structures that are not only active for alkane C-H bond activation and oxidative dehydrogenation but also can be practical catalysts to be eventually used in industry.

  2. Methodologies to analyze surface bonding properties using parametric and density functional methods

    NASA Astrophysics Data System (ADS)

    Ruette, Fernando; Sánchez, Morella; Castellano, Olga; Soscún, Humberto

    This work presents two general methodologies to calculate bond adsorption energy (BAE) between surface and adsorbate using parametric quantum (PQM) and density functional (DFM) methods. The first one corresponds to the bond partition energy technique that is directly applied to PQMs by using energy partition approach and considering diatomic and monoatomic energy changes. The second methodology to evaluate BAE, as well as for PQMs and DFMs, is by means of the following equation: {BAE} = E_{ads} - Delta E_{s} - Delta E_{a'} where Eads is the adsorption energy and ΔEs and ΔEa correspond to energy changes in the surface and substrate due to adsorption, respectively. Applications to radical adsorption: H°, CH2°, and CH3° is performed on a grafitic grain model, using a polyaromatic hydrocarbon (PAH), such as coronene. The methods employed are a PQM (CATIVIC program) and DFMs (GAUSSIAN and DMol software packages). Results show that Eads is completely different of BAE, because of distortion of surface and adsorbate. There is a strong destabilization in the region adjacent to the adsorption site and stabilization in the rest of the surface. Two terms for BAE are reported: one that corresponds to direct bonding interaction (BAEb) and other to long range ones, due to electrostatic interaction (BAEe). Owing to the important effects of bond strength adsorbate-surface interaction, results suggest that BAE is fundamental for understanding bond activation in adsorbate and surface, cooperative effects, diffusion, reaction, and desorption process. In general, similar results were found for both CATIVIC and DFMs, by using the second methodology.

  3. Bond slip detection of concrete-encased composite structure using shear wave based active sensing approach

    NASA Astrophysics Data System (ADS)

    Zeng, Lei; Parvasi, Seyed Mohammad; Kong, Qingzhao; Huo, Linsheng; Lim, Ing; Li, Mo; Song, Gangbing

    2015-12-01

    Concrete-encased composite structure exhibits improved strength, ductility and fire resistance compared to traditional reinforced concrete, by incorporating the advantages of both steel and concrete materials. A major drawback of this type of structure is the bond slip introduced between steel and concrete, which directly reduces the load capacity of the structure. In this paper, an active sensing approach using shear waves to provide monitoring and early warning of the development of bond slip in the concrete-encased composite structure is proposed. A specimen of concrete-encased composite structure was investigated. In this active sensing approach, shear mode smart aggregates (SAs) embedded in the concrete act as actuators and generate desired shear stress waves. Distributed piezoceramic transducers installed in the cavities of steel plates act as sensors and detect the wave response from shear mode SAs. Bond slip acts as a form of stress relief and attenuates the wave propagation energy. Experimental results from the time domain analysis clearly indicate that the amplitudes of received signal by lead zirconate titanate sensors decreased when bond slip occurred. In addition, a wavelet packet-based analysis was developed to compute the received signal energy values, which can be used to determine the initiation and development of bond slip in concrete-encased composite structure. In order to establish the validity of the proposed method, a 3D finite element analysis of the concrete-steel bond model is further performed with the aid of the commercial finite element package, Abaqus, and the numerical results are compared with the results obtained in experimental study.

  4. Nickel-catalyzed Csp2-Csp3 bond formation by carbon-fluorine activation.

    PubMed

    Sun, Alex D; Leung, Kaylyn; Restivo, Anita D; LaBerge, Nicole A; Takasaki, Harumi; Love, Jennifer A

    2014-03-10

    We report herein a general catalytic method for Csp(2)-Csp(3) bond formation through C-F activation. The process uses an inexpensive nickel complex with either diorganozinc or alkylzinc halide reagents, including those with β-hydrogen atoms. A variety of fluorine substitution patterns and functional groups can be readily incorporated. Sequential reactions involving different precatalysts and coupling partners permit the synthesis of densely functionalized fluorinated building blocks.

  5. Nondestructive tests of regenerative chambers. [evaluating nondestructive methods of determining metal bond integrity

    NASA Technical Reports Server (NTRS)

    Malone, G. A.; Vecchies, L.; Wood, R.

    1974-01-01

    The capabilities and limitations of nondestructive evaluation methods were studied to detect and locate bond deficiencies in regeneratively cooled thrust chambers for rocket engines. Flat test panels and a cylinder were produced to simulate regeneratively cooled thrust chamber walls. Planned defects with various bond integrities were produced in the panels to evaluate the sensitivity, accuracy, and limitations of nondestructive methods to define and locate bond anomalies. Holography, acoustic emission, and ultrasonic scan were found to yield sufficient data to discern bond quality when used in combination and in selected sequences. Bonding techniques included electroforming and brazing. Materials of construction included electroformed nickel bonded to Nickel 200 and OFHC copper, electroformed copper bonded to OFHC copper, and 300 series stainless steel brazed to OFHC copper. Variations in outer wall strength, wall thickness, and defect size were evaluated for nondestructive test response.

  6. Antibacterial activity and ion release of bonding agent containing amorphous calcium phosphate nanoparticles

    PubMed Central

    Chen, Chen; Weir, Michael D.; Cheng, Lei; Lin, Nancy; Lin-Gibson, Sheng; Chow, Laurence C.; Zhou, Xuedong; Xu, Hockin H. K.

    2015-01-01

    Objectives Recurrent caries at the margins is a primary reason for restoration failure. The objectives of this study were to develop bonding agent with the double benefits of antibacterial and remineralizing capabilities, to investigate the effects of NACP filler level and solution pH on Ca and P ion release from adhesive, and to examine the antibacterial and dentin bond properties. Methods Nanoparticles of amorphous calcium phosphate (NACP) and a quaternary ammonium monomer (dimethylaminododecyl methacrylate, DMADDM) were synthesized. Scotchbond Multi-Purpose (SBMP) primer and adhesive served as control. DMADDM was incorporated into primer and adhesive at 5% by mass. NACP was incorporated into adhesive at filler mass fractions of 10%, 20%, 30% and 40%. A dental plaque microcosm biofilm model was used to test the antibacterial bonding agents. Calcium (Ca) and phosphate (P) ion releases from the cured adhesive samples were measured vs. filler level and solution pH of 7, 5.5 and 4. Results Adding 5% DMADDM and 10–40% NACP into bonding agent, and water-aging for 28 days, did not affect dentin bond strength, compared to SBMP control at 1 day (p > 0.1). Adding DMADDM into bonding agent substantially decreased the biofilm metabolic activity and lactic acid production. Total microorganisms, total streptococci, and mutans streptococci were greatly reduced for bonding agents containing DMADDM. Increasing NACP filler level from 10% to 40% in adhesive increased the Ca and P ion release by an order of magnitude. Decreasing solution pH from 7 to 4 increased the ion release from adhesive by 6–10 folds. Significance Bonding agents containing antibacterial DMADDM and remineralizer NACP were formulated to have Ca and P ion release, which increased with NACP filler level from 10% to 40% in adhesive. NACP adhesive was “smart” and dramatically increased the ion release at cariogenic pH 4, when these ions would be most-needed to inhibit caries. Therefore, bonding agent

  7. Methods and system for controlled laser-driven explosive bonding

    SciTech Connect

    Rubenchik, Alexander M.; Farmer, Joseph C.; Hackel, Lloyd; Rankin, Jon

    2015-11-19

    A technique for bonding two dissimilar materials includes positioning a second material over a first material at an oblique angle and applying a tamping layer over the second martial. A laser beam is directed at the second material that generates a plasma at the location of impact on the second material. The plasma generates pressure that accelerates a portion of the second material to a very high velocity and towards the first material. The second material impacts the first material causing bonding of the two materials.

  8. Method of densifying an article formed of reaction bonded silicon nitride

    NASA Technical Reports Server (NTRS)

    Mangels, John A. (Inventor)

    1982-01-01

    A method of densifying an article formed of reaction bonded silicon nitride is disclosed. The reaction bonded silicon nitride article is packed in a packing mixture consisting of silicon nitride powder and a densification aid. The reaction bonded silicon nitride article and packing powder are sujected to a positive, low pressure nitrogen gas treatment while being heated to a treatment temperature and for a treatment time to cause any open porosity originally found in the reaction bonded silicon nitride article to be substantially closed. Thereafter, the reaction bonded silicon nitride article and packing powder are subjected to a positive high pressure nitrogen gas treatment while being heated to a treatment temperature and for a treatment time to cause a sintering of the reaction bonded silicon nitride article whereby the strength of the reaction bonded silicon nitride article is increased.

  9. Mild Catalytic methods for Alkyl-Alkyl Bond Formation

    SciTech Connect

    Vicic, David A

    2009-08-10

    Overview of Research Goals and Accomplishments for the Period 07/01/06 – 06/30/07: Our overall research goal is to transform the rapidly emerging synthetic chemistry involving alkyl-alkyl cross-couplings into more of a mechanism-based field so that that new, rationally-designed catalysts can be performed under energy efficient conditions. Our specific objectives for the previous year were 1) to obtain a proper electronic description of an active catalyst for alkyl-alkyl cross-coupling reactions and 2) to determine the effect of ligand structure on the rate, scope, selectivity, and functional group compatibility of C(sp3)-C(sp3) cross-coupling catalysis. We have completed both of these initial objectives and established a firm base for further studies. The specific significant achievements of the current grant period include: 1) we have performed magnetic and computational studies on (terpyridine)NiMe, an active catalyst for alkyl-alkyl cross couplings, and have discovered that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand; 2) we have for the first time shown that alkyl halide reduction by terpyridyl nickel catalysts is substantially ligand based; 3) we have shown by isotopic labeling studies that the active catalyst (terpyridine)NiMe is not produced via a mechanism that involves the formation of methyl radicals when (TMEDA)NiMe2 is used as the catalyst precursor; 4) we have performed an extensive ligand survey for the alkyl-alkyl cross-coupling reactions and have found that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors; 5) we have found that the use of bis(dialkylphosphino)methanes as ligands for nickel does not produce active catalysts for cross-coupling but rather leads to bridging hydride

  10. Method of preparation of bonded polyimide fuel cell package

    DOEpatents

    Morse, Jeffrey D [Martinez, CA; Jankowski, Alan [Livermore, CA; Graff, Robert T [Modesto, CA; Bettencourt, Kerry [Dublin, CA

    2011-04-26

    Described herein are processes for fabricating microfluidic fuel cell systems with embedded components in which micron-scale features are formed by bonding layers of DuPont Kapton.TM. polyimide laminate. A microfluidic fuel cell system fabricated using this process is also described.

  11. Bonded polyimide fuel cell package and method thereof

    DOEpatents

    Morse, Jeffrey D.; Jankowski, Alan; Graff, Robert T.; Bettencourt, Kerry

    2005-11-01

    Described herein are processes for fabricating microfluidic fuel cell systems with embedded components in which micron-scale features are formed by bonding layers of DuPont Kapton.TM. polyimide laminate. A microfluidic fuel cell system fabricated using this process is also described.

  12. Carbon–carbon bond activation of cyclobutenones enabled by the addition of chiral organocatalyst to ketone

    PubMed Central

    Li, Bao-Sheng; Wang, Yuhuang; Jin, Zhichao; Zheng, Pengcheng; Ganguly, Rakesh; Chi, Yonggui Robin

    2015-01-01

    The activation of carbon–carbon (C–C) bonds is an effective strategy in building functional molecules. The C–C bond activation is typically accomplished via metal catalysis, with which high levels of enantioselectivity are difficult to achieve due to high reactivity of metal catalysts and the metal-bound intermediates. It remains largely unexplored to use organocatalysis for C–C bond activation. Here we describe an organocatalytic activation of C–C bonds through the addition of an NHC to a ketone moiety that initiates a C–C single bond cleavage as a key step to generate an NHC-bound intermediate for chemo- and stereo-selective reactions. This reaction constitutes an asymmetric functionalization of cyclobutenones using organocatalysts via a C–C bond activation process. Structurally diverse and multicyclic compounds could be obtained with high optical purities via an atom and redox economic process. PMID:25652912

  13. 75 FR 50772 - Agency Information Collection Activities: Importation Bond Structure

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-17

    ... Structure AGENCY: U.S. Customs and Border Protection, Department of Homeland Security. ] ACTION: 60-Day... concerning the: Importation Bond Structure. This request for comment is being made pursuant to the Paperwork...: Title: Importation Bond Structure. OMB Number: 1651-0050. Form Numbers: 301 and 5297. Abstract:...

  14. 78 FR 75576 - Agency Information Collection Activities: Importation Bond Structure

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-12-12

    ... Structure AGENCY: U.S. Customs and Border Protection (CBP), Department of Homeland Security. ACTION: 60-day... Importation Bond Structure. This request for comment is being made pursuant to the Paperwork Reduction Act of... Structure. OMB Number: 1651-0050. Form Number: CBP Forms 301 and 5297. Abstract: Bonds are used to...

  15. Emerging concepts of laser-activated nanoparticles for tissue bonding

    NASA Astrophysics Data System (ADS)

    Matteini, Paolo; Ratto, Fulvio; Rossi, Francesca; Pini, Roberto

    2012-01-01

    We report recent achievements and future perspectives of minimally invasive bonding of biological tissues triggered by laser light. In particular, we review new advancements in the biomedical exploitation of near-infrared absorbing gold nanoparticles as an original solution for the photothermal closure of surgical incisions. Advanced concepts of laser tissue bonding involving the application of hybrid nanocomposites obtained by inclusion of nanochromophores into biopolymer scaffolds are also introduced. The perspectives of tissue bonding are discussed in the following aspects: (1) tissue bonding with highly-stabilized nanochromophores, (2) enhanced tissue bonding with patterned nanocomposites, (3) real-time monitoring of temperature distributions, (4) tracking of tissue regeneration based on the optical resonances of gold nanoparticles.

  16. Photodiodes integration on a suspended ridge structure VOA using 2-step flip-chip bonding method

    NASA Astrophysics Data System (ADS)

    Kim, Seon Hoon; Kim, Tae Un; Ki, Hyun Chul; Kim, Doo Gun; Kim, Hwe Jong; Lim, Jung Woon; Lee, Dong Yeol; Park, Chul Hee

    2015-01-01

    In this works, we have demonstrated a VOA integrated with mPDs, based on silica-on-silicon PLC and flip-chip bonding technologies. The suspended ridge structure was applied to reduce the power consumption. It achieves the attenuation of 30dB in open loop operation with the power consumption of below 30W. We have applied two-step flipchip bonding method using passive alignment to perform high density multi-chip integration on a VOA with eutectic AuSn solder bumps. The average bonding strength of the two-step flip-chip bonding method was about 90gf.

  17. Reactivity of mononuclear alkylperoxo copper(II) complex. O-O bond cleavage and C-H bond activation.

    PubMed

    Kunishita, Atsushi; Ishimaru, Hirohito; Nakashima, Satoru; Ogura, Takashi; Itoh, Shinobu

    2008-04-02

    A detailed reactivity study has been carried out for the first time on a new mononuclear alkylperoxo copper(II) complex, which is generated by the reaction of copper(II) complex supported by the bis(pyridylmethyl)amine tridentate ligand containing a phenyl group at the 6-position of the pyridine donor groups and cumene hydroperoxide (CmOOH) in CH3CN. The cumylperoxo copper(II) complex thus obtained has been found to undergo homolytic cleavage of the O-O bond and induce C-H bond activation of exogenous substrates, providing important insights into the catalytic mechanism of copper monooxygenases.

  18. Method of bonding silver to glass and mirrors produced according to this method

    DOEpatents

    Pitts, John R.; Thomas, Terence M.; Czanderna, Alvin W.

    1985-01-01

    A method for adhering silver to a glass substrate for producing mirrors includes attaining a silicon enriched substrate surface by reducing the oxygen therein in a vacuum and then vacuum depositing a silver layer onto the silicon enriched surface. The silicon enrichment can be attained by electron beam bombardment, ion beam bombardment, or neutral beam bombardment. It can also be attained by depositing a metal, such as aluminum, on the substrate surface, allowing the metal to oxidize by pulling oxygen from the substrate surface, thereby leaving a silicon enriched surface, and then etching or eroding the metal oxide layer away to expose the silicon enriched surface. Ultraviolet rays can be used to maintain dangling silicon bonds on the enriched surface until covalent bonding with the silver can occur. This disclosure also includes encapsulated mirrors with diffusion layers built therein. One of these mirrors is assembled on a polymer substrate.

  19. Method of bonding silver to glass and mirrors produced according to this method

    DOEpatents

    Pitts, J.R.; Thomas, T.M.; Czanderna, A.W.

    1984-07-31

    A method for adhering silver to a glass substrate for producing mirrors includes attaining a silicon enriched substrate surface by reducing the oxygen therein in a vacuum and then vacuum depositing a silver layer onto the silicon enriched surface. The silicon enrichment can be attained by electron beam bombardment, ion beam bombardment, or neutral beam bombardment. It can also be attained by depositing a metal, such as aluminum, on the substrate surface, allowing the metal to oxidize by pulling oxygen from the substrate surface, thereby leaving a silicon enriched surface, and then etching or eroding the metal oxide layer away to expose the silicon enriched surface. Ultraviolet rays can be used to maintain dangling silicon bonds on the enriched surface until covalent bonding with the silver can occur. This disclosure also includes encapsulated mirrors with diffusion layers built therein. One of these mirrors is assembled on a polymer substrate.

  20. Method and device for secure, high-density tritium bonded with carbon

    DOEpatents

    Wertsching, Alan Kevin; Trantor, Troy Joseph; Ebner, Matthias Anthony; Norby, Brad Curtis

    2016-04-05

    A method and device for producing secure, high-density tritium bonded with carbon. A substrate comprising carbon is provided. A precursor is intercalated between carbon in the substrate. The precursor intercalated in the substrate is irradiated until at least a portion of the precursor, preferably a majority of the precursor, is transmutated into tritium and bonds with carbon of the substrate forming bonded tritium. The resulting bonded tritium, tritium bonded with carbon, produces electrons via beta decay. The substrate is preferably a substrate from the list of substrates consisting of highly-ordered pyrolytic graphite, carbon fibers, carbon nanotunes, buckministerfullerenes, and combinations thereof. The precursor is preferably boron-10, more preferably lithium-6. Preferably, thermal neutrons are used to irradiate the precursor. The resulting bonded tritium is preferably used to generate electricity either directly or indirectly.

  1. Molecular mechanics-valence bond method for planar conjugated hydrocarbon cations.

    PubMed

    Hall, Katherine F; Tokmachev, Andrei M; Bearpark, Michael J; Boggio-Pasqua, Martial; Robb, Michael A

    2007-10-07

    We present an extension of the molecular mechanics-valence bond (MMVB) hybrid method to study ground and excited states of planar conjugated hydrocarbon cations. Currently, accurate excited state calculations on these systems are limited to expensive ab initio studies of smaller systems: up to 15 active electrons in 16 pi orbitals with complete active space self-consistent field (CASSCF) theory using high symmetry. The new MMVB extension provides a faster, cheaper treatment to investigate larger cation systems with more than 24 active orbitals. Extension requires both new matrix elements and new parameters: In this paper we present both, for the limited planar case. The scheme is tested for the planar radical cations of benzene, naphthalene, anthracene, and phenanthrene. Calculated MMVB relative energies are in good agreement with CASSCF results for equilibrium geometries on the ground and first excited states, and conical intersections.

  2. Female Adolescents' Delinquent Activity: The Intersection of Bonds to Parents and Reputation Enhancement

    ERIC Educational Resources Information Center

    Kerpelman, Jennifer L.; Smith-Adcock, Sondra

    2005-01-01

    According to the reputation enhancement theory, social bonds influence adolescents' delinquent activity indirectly through the reputations they select. Findings from the current study of a school-based sample of female adolescents indicate that bonds to parents affect reputation enhancement beliefs, which, in turn, predict delinquent activity.…

  3. 26 CFR 1.103(n)-3T - Private activity bond limit (temporary).

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 26 Internal Revenue 2 2014-04-01 2014-04-01 false Private activity bond limit (temporary). 1.103(n)-3T Section 1.103(n)-3T Internal Revenue INTERNAL REVENUE SERVICE, DEPARTMENT OF THE TREASURY....103(n)-3T Private activity bond limit (temporary). Q-1: What is the “State ceiling”? A-1: In...

  4. Effects of surface-conditioning methods on shear bond strength of brackets bonded to different all-ceramic materials.

    PubMed

    Saraç, Y Şinasi; Külünk, Tolga; Elekdağ-Türk, Selma; Saraç, Duygu; Türk, Tamer

    2011-12-01

    The aims of this study were to investigate the effects of two surface-conditioning methods on the shear bond strength (SBS) of metal brackets bonded to three different all-ceramic materials, and to evaluate the mode of failure after debonding. Twenty feldspathic, 20 fluoro-apatite, and 20 leucite-reinforced ceramic specimens were examined following two surface-conditioning methods: air-particle abrasion (APA) with 25 μm Al(2)O(3) and silica coating with 30 μm Al(2)O(3) particles modified by silica. After silane application, metal brackets were bonded with light cure composite and then stored in distilled water for 1 week and thermocycled (×1000 at 5-55°C for 30 seconds). The SBS of the brackets was measured on a universal testing machine. The ceramic surfaces were examined with a stereomicroscope to determine the amount of composite resin remaining using the adhesive remnant index. Two-way analysis of variance, Tukey's multiple comparison test, and Weibull analysis were used for evaluation of SBS. The lowest SBS was with APA for the fluoro-apatite ceramic (11.82 MPa), which was not significantly different from APA for the feldspathic ceramic (13.58 MPa). The SBS for the fluoro-apatite ceramic was significantly lower than that of leucite-reinforced ceramic with APA (14.82 MPa). The highest SBS value was obtained with silica coating of the leucite-reinforced ceramic (24.17 MPa), but this was not significantly different from the SBS for feldspathic and fluoro-apatite ceramic (23.51 and 22.18 MPa, respectively). The SBS values with silica coating showed significant differences from those of APA. For all samples, the adhesive failures were between the ceramic and composite resin. No ceramic fractures or cracks were observed. Chairside tribochemical silica coating significantly increased the mean bond strength values.

  5. Ribosomal crystallography: peptide bond formation, chaperone assistance and antibiotics activity.

    PubMed

    Yonath, Ada

    2005-08-31

    The peptidyl transferase center (PTC) is located in a protein free environment, thus confirming that the ribosome is a ribozyme. This arched void has dimensions suitable for accommodating the 3' ends of the A-and the P-site tRNAs, and is situated within a universal sizable symmetry-related region that connects all ribosomal functional centers involved in amino-acid polymerization. The linkage between the elaborate PTC architecture and the A-site tRNA position revealed that the A- to P-site passage of the tRNA 3' end is performed by a rotatory motion, which leads to stereochemistry suitable for peptide bond formation and for substrate mediated catalysis, thus suggesting that the PTC evolved by gene-fusion. Adjacent to the PTC is the entrance of the protein exit tunnel, shown to play active roles in sequence-specific gating of nascent chains and in responding to cellular signals. This tunnel also provides a site that may be exploited for local co-translational folding and seems to assist in nascent chain trafficking into the hydrophobic space formed by the first bacterial chaperone, the trigger factor. Many antibiotics target ribosomes. Although the ribosome is highly conserved, subtle sequence and/or conformational variations enable drug selectivity, thus facilitating clinical usage. Comparisons of high-resolution structures of complexes of antibiotics bound to ribosomes from eubacteria resembling pathogens, to an archaeon that shares properties with eukaryotes and to its mutant that allows antibiotics binding, demonstrated the unambiguous difference between mere binding and therapeutical effectiveness. The observed variability in antibiotics inhibitory modes, accompanied by the elucidation of the structural basis to antibiotics mechanism justifies expectations for structural based improved properties of existing compounds as well as for the development of novel drugs.

  6. Is the peptide bond formation activated by Cu(2+) interactions? Insights from density functional calculations.

    PubMed

    Rimola, A; Rodríguez-Santiago, L; Ugliengo, P; Sodupe, M

    2007-05-24

    The catalytic role that Cu(2+) cations play in the peptide bond formation has been addressed by means of density functional calculations. First, the Cu(2+)-(glycine)2 --> Cu(2+)-(glycylglycine) + H2O reaction was investigated since mass spectrometry low collision activated dissociation (CAD) spectra of Cu(2+)-(glycine)2 led to the elimination of a water molecule, which suggested that an intracomplex peptide bond formation might have occurred. Results show that this intracomplex condensation is associated to a very high free energy barrier (97 kcal mol(-1)) and reaction free energy (66 kcal mol(-1)) because of the loss of metal coordination during the reaction. Second, on the basis of the salt-induced peptide formation theory, the condensation reaction between two glycines was studied in aqueous solution using discrete water molecules and the conductor polarized continuum model (CPCM) continuous method. It is found that the synergy between the interaction of glycines with Cu(2+) and the presence of water molecules acting as proton-transfer helpers significantly lower the activation barrier (from 55 kcal/mol for the uncatalyzed system to 20 kcal/mol for the Cu(2+) solvated system) which largely favors the formation of the peptide bond.

  7. In vitro evaluation of an alternative method to bond molar tubes

    PubMed Central

    PINZAN-VERCELINO, Célia Regina Maio; PINZAN, Arnaldo; GURGEL, Júlio de Araújo; BRAMANTE, Fausto Silva; PINZAN, Luciana Maio

    2011-01-01

    Despite the advances in bonding materials, many clinicians today still prefer to place bands on molar teeth. Molar bonding procedures need improvement to be widely accepted clinically. Objective The purpose of this study was to evaluate the shear bond strength when an additional adhesive layer was applied on the occlusal tooth/tube interface to provide reinforcement to molar tubes. Material and methods Sixty third molars were selected and allocated to the 3 groups: group 1 received a conventional direct bond followed by the application of an additional layer of adhesive on the occlusal tooth/tube interface, group 2 received a conventional direct bond, and group 3 received a conventional direct bond and an additional cure time of 10 s. The specimens were debonded in a universal testing machine. The results were analyzed statistically by ANOVA and Tukey’s test (α=0.05). Results Group 1 had a significantly higher (p<0.05) shear bond strength compared to groups 2 and 3. No difference was detected between groups 2 and 3 (p>0.05). Conclusions The present in vitro findings indicate that the application of an additional layer of adhesive on the tooth/tube interface increased the shear bond strength of the bonded molar tubes. PMID:21437468

  8. Surface-Controlled Mono/Diselective ortho C-H Bond Activation.

    PubMed

    Li, Qing; Yang, Biao; Lin, Haiping; Aghdassi, Nabi; Miao, Kangjian; Zhang, Junjie; Zhang, Haiming; Li, Youyong; Duhm, Steffen; Fan, Jian; Chi, Lifeng

    2016-03-02

    One of the most charming and challenging topics in organic chemistry is the selective C-H bond activation. The difficulty arises not only from the relatively large bond-dissociation enthalpy, but also from the poor reaction selectivity. In this work, Au(111) and Ag(111) surfaces were used to address ortho C-H functionalization and ortho-ortho couplings of phenol derivatives. More importantly, the competition between dehydrogenation and deoxygenation drove the diversity of reaction pathways of phenols on surfaces, that is, diselective ortho C-H bond activation on Au(111) surfaces and monoselective ortho C-H bond activation on Ag(111) surfaces. The mechanism of this unprecedented phenomenon was extensively explored by scanning tunneling microscopy, density function theory, and X-ray photoelectron spectroscopy. Our findings provide new pathways for surface-assisted organic synthesis via the mono/diselective C-H bond activation.

  9. Bonding thermoplastic polymers

    DOEpatents

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

    2008-06-24

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

  10. Method to produce catalytically active nanocomposite coatings

    DOEpatents

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

    2016-02-09

    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  11. Method of making bonded or sintered permanent magnets

    DOEpatents

    McCallum, R.W.; Dennis, K.W.; Lograsso, B.K.; Anderson, I.E.

    1993-08-31

    An isotropic permanent magnet is made by mixing a thermally responsive, low viscosity binder and atomized rare earth-transition metal (e.g., iron) alloy powder having a carbon-bearing (e.g., graphite) layer thereon that facilitates wetting and bonding of the powder particles by the binder. Prior to mixing with the binder, the atomized alloy powder may be sized or classified to provide a particular particle size fraction having a grain size within a given relatively narrow range. A selected particle size fraction is mixed with the binder and the mixture is molded to a desired complex magnet shape. A molded isotropic permanent magnet is thereby formed. A sintered isotropic permanent magnet can be formed by removing the binder from the molded mixture and thereafter sintering to full density.

  12. Method of making bonded or sintered permanent magnets

    DOEpatents

    McCallum, R.W.; Dennis, K.W.; Lograsso, B.K.; Anderson, I.E.

    1995-11-28

    An isotropic permanent magnet is made by mixing a thermally responsive, low viscosity binder and atomized rare earth-transition metal (e.g., iron) alloy powder having a carbon-bearing (e.g., graphite) layer thereon that facilitates wetting and bonding of the powder particles by the binder. Prior to mixing with the binder, the atomized alloy powder may be sized or classified to provide a particular particle size fraction having a grain size within a given relatively narrow range. A selected particle size fraction is mixed with the binder and the mixture is molded to a desired complex magnet shape. A molded isotropic permanent magnet is thereby formed. A sintered isotropic permanent magnet can be formed by removing the binder from the molded mixture and thereafter sintering to full density. 14 figs.

  13. Method of making bonded or sintered permanent magnets

    DOEpatents

    McCallum, R. William; Dennis, Kevin W.; Lograsso, Barbara K.; Anderson, Iver E.

    1995-11-28

    An isotropic permanent magnet is made by mixing a thermally responsive, low viscosity binder and atomized rare earth-transition metal (e.g., iron) alloy powder having a carbon-bearing (e.g., graphite) layer thereon that facilitates wetting and bonding of the powder particles by the binder. Prior to mixing with the binder, the atomized alloy powder may be sized or classified to provide a particular particle size fraction having a grain size within a given relatively narrow range. A selected particle size fraction is mixed with the binder and the mixture is molded to a desired complex magnet shape. A molded isotropic permanent magnet is thereby formed. A sintered isotropic permanent magnet can be formed by removing the binder from the molded mixture and thereafter sintering to full density.

  14. Two-dimensional gold nanostructures with high activity for selective oxidation of carbon-hydrogen bonds

    NASA Astrophysics Data System (ADS)

    Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

    2015-04-01

    Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold-gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon-hydrogen bonds with molecular oxygen.

  15. Two-dimensional gold nanostructures with high activity for selective oxidation of carbon–hydrogen bonds

    PubMed Central

    Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

    2015-01-01

    Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold–gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon–hydrogen bonds with molecular oxygen. PMID:25902034

  16. Effect of cleaning methods on bond strength of self-etching adhesive to dentin

    PubMed Central

    Bronzato, Juliana Delatorre; Cecchin, Doglas; Miyagaki, Daniela Cristina; de Almeida, José Flávio Affonso; Ferraz, Caio Cezar Randi

    2016-01-01

    Aim: The aim of this study was to investigate the influence of cleaning methods to remove zinc oxide-eugenol-based root canal sealer (Endomethasone) on the bond strength of the self-etching adhesive to dentin. Materials and Methods: Twenty crowns of bovine incisors were cut to expose the pulp chamber. A zinc oxide- and eugenol-based sealer was placed for 10 min in contact with the pulp chamber dentin. Specimens were divided into four groups according to the cleaning method of dentin used: G1, no root canal sealer (control); G2, 0.9% sodium chlorite (NaCl); G3, ethanol; and G4, followed by diamond drill. After cleaning, the teeth were restored with composite resin and Clearfil SE Bond. All specimens were sectioned to produce rectangular sticks and dentin/resin interface was submitted to microtensile bond testing. The mean bond strengths were analyzed using ANOVA/Tukey (α = 0.05). Results: G3 and G4 showed bond strengths similar to the G1 (P > 0.05). A significant decrease in the bond strength in the G2 was observed (P < 0.05). G1, G3, and G4, the predominant failure mode was the mixed type. The prevalence of adhesive failure mode was verified in the G2. Conclusion: The cleaning methods affected the bond strength of the self-etching adhesive to dentin differently. PMID:26957789

  17. Battery equalization active methods

    NASA Astrophysics Data System (ADS)

    Gallardo-Lozano, Javier; Romero-Cadaval, Enrique; Milanes-Montero, M. Isabel; Guerrero-Martinez, Miguel A.

    2014-01-01

    Many different battery technologies are available for the applications which need energy storage. New researches are being focused on Lithium-based batteries, since they are becoming the most viable option for portable energy storage applications. As most of the applications need series battery strings to meet voltage requirements, battery imbalance is an important matter to be taken into account, since it leads the individual battery voltages to drift apart over time, and premature cells degradation, safety hazards, and capacity reduction will occur. A large number of battery equalization methods can be found, which present different advantages/disadvantages and are suitable for different applications. The present paper presents a summary, comparison and evaluation of the different active battery equalization methods, providing a table that compares them, which is helpful to select the suitable equalization method depending on the application. By applying the same weight to the different parameters of comparison, switch capacitor and double-tiered switching capacitor have the highest ratio. Cell bypass methods are cheap and cell to cell ones are efficient. Cell to pack, pack to cell and cell to pack to cell methods present a higher cost, size, and control complexity, but relatively low voltage and current stress in high-power applications.

  18. Rhodium mediated bond activation: from synthesis to catalysis

    SciTech Connect

    Ho, Hung-An

    2012-01-01

    Recently, our lab has developed monoanionic tridentate ligand, ToR, showing the corresponding coordination chemistry and catalyst reactivity of magnesium, zirconium, zinc and iridium complexes. This thesis details synthetic chemistry, structural study and catalytic reactivity of the ToR-supported rhodium compounds. Tl[ToR] has been proved to be a superior ligand transfer agent for synthesizing rhodium complexes. The salt metathesis route of Tl[ToM] with [Rh(μ-Cl)(CO)]2 and [Rh(μ- Cl)(COE)]2 gives ToMRh(CO)2 (2.2) and ToMRhH(β3-C8H13) (3.1) respectively while Tl[ToM] with [Rh(μ-Cl)(CO)]2 affords ToPRh(CO)2 (2.3). 2.2 reacts with both strong and weak electrophiles, resulting in the oxazoline N-attacked and the metal center-attacked compounds correspondingly. Using one of the metal center-attacked electrophiles, 2.3 was demonstrated to give high diastereoselectivity. Parallel to COE allylic C-H activation complex 3.1, the propene and allylbenzene allylic C-H activation products have also been synthesized. The subsequent functionalization attempts have been examined by treating with Brønsted acids, Lewis acids, electrophiles, nucleophiles, 1,3-dipolar reagents and reagents containing multiple bonds able to be inserted. Various related complexes have been obtained under these conditions, in which one of the azide insertion compounds reductively eliminates to give an allylic functionalization product stoichiometrically. 3.1 reacts with various primary alcohols to give the decarbonylation dihydride complex ToMRh(H)2CO (4.1). 4.1 shows catalytic reactivity for primary alcohol decarbonylation under a photolytic condition. Meanwhile, 2.2 has been found to be more reactive than 4.1 for catalytic alcohol decarbonylation under the same condition. Various complexes and primary

  19. Electrochemical reduction of carbon fluorine bond in 4-fluorobenzonitrile Mechanistic analysis employing Marcus Hush quadratic activation-driving force relation

    NASA Astrophysics Data System (ADS)

    Muthukrishnan, A.; Sangaranarayanan, M. V.

    2007-10-01

    The reduction of carbon-fluorine bond in 4-fluorobenzonitrile in acetonitrile as the solvent, is analyzed using convolution potential sweep voltammetry and the dependence of the transfer coefficient on potential is investigated within the framework of Marcus-Hush quadratic activation-driving force theory. The validity of stepwise mechanism is inferred from solvent reorganization energy estimates as well as bond length calculations using B3LYP/6-31g(d) method. A novel method of estimating the standard reduction potential of the 4-fluorobenzonitrile in acetonitrile is proposed.

  20. Activation of C-H bond in methane by Pd atom from the bonding evolution theory perspective.

    PubMed

    Nizovtsev, Anton S

    2013-08-15

    We report detailed study focused on the electron density redistribution during the simple oxidative addition reaction being the crucial stage of various catalytic processes. The bonding evolution theory based on the electron localization function and Thom's catastrophe theory shows that activation of methane's C-H bond by Pd atom consist of six elementary steps. The important feature revealed is the pronounced reorganization of Pd's outer core maxima corresponding to N-shell electrons of metal. Electronic rearrangements identified in this model reaction are likely to be the case in the more complex reactions of the same type involving transition metal compounds and, in principle, can be observed by modern ultrafast spectroscopy and diffraction techniques.

  1. Revealing the nature of the active site on the carbon catalyst for C-H bond activation.

    PubMed

    Sun, XiaoYing; Li, Bo; Su, Dangsheng

    2014-09-28

    A reactivity descriptor for the C-H bond activation on the nanostructured carbon catalyst is proposed. Furthermore the calculations reveal that the single ketone group can be an active site in ODH reaction.

  2. Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation.

    PubMed

    Gong, Liang; Xing, Li-Juan; Xu, Tong; Zhu, Xue-Ping; Zhou, Wen; Kang, Ning; Wang, Bin

    2014-09-14

    An oxidative olefination reaction between aliphatic primary amines and benzylic sp(3) C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration.

  3. Effect of photo-activated disinfection on bond strength of three different root canal sealers

    PubMed Central

    Ok, Evren; Ertas, Huseyin; Saygili, Gokhan; Gok, Tuba

    2014-01-01

    Introduction: The aim of this in vitro study was to evaluate the bond strength of Photo-Activated Disinfection (PAD) system to dentin with different root canal sealers by using a push-out test design. Materials and Methods: A total of 30 extracted mandibular premolar teeth with single and straight roots were used. The crowns were removed and the root canals were prepared by using ProTaper rotary files. The smear layer was removed and the roots were randomly divided into two groups (n = 15) according to the use of PAD system as the final disinfecting agent. Each group was then divided into 6 (n = 5) subgroups and obturated with gutta-percha and 3 different root canal sealers. The groups were Group 1: Sodium hypochlorite (NaOCl) + ethylenediaminetetraacetic acid (EDTA)-AH Plus sealer; Group 2: NaOCl + EDTA + PAD-AH Plus; Group 3: NaOCl + EDTA-Sealapex; Group 4: NaOCl + EDTA + PAD-Sealapex; Group 5: NaOCl + EDTA-mineral trioxide aggregate (MTA)-Fiallapex; and Group 6: NaOCl + EDTA + PAD-MTA-Fillapex. 1-mm thickness horizontal sections (n: 5 × 4 = 20) were sliced for the push-out bond strength measurement. Results: Group 3 and 4 showed significantly lower bond strengths compared with all the other groups (P < 0.05). No statistically significant difference was found among Groups 1, 2 and 5, but there was statistically significant difference between Group 5 and 6 (P < 0.05). Conclusion: This in vitro study indicated that the PAD system adversely affected the bond strength of the MTA Fillapex root canal sealer. PMID:24966752

  4. Benchmarking DFT methods with small basis sets for the calculation of halogen-bond strengths.

    PubMed

    Siiskonen, Antti; Priimagi, Arri

    2017-02-01

    In recent years, halogen bonding has become an important design tool in crystal engineering, supramolecular chemistry and biosciences. The fundamentals of halogen bonding have been studied extensively with high-accuracy computational methods. Due to its non-covalency, the use of triple-zeta (or larger) basis sets is often recommended when studying halogen bonding. However, in the large systems often encountered in supramolecular chemistry and biosciences, large basis sets can make the calculations far too slow. Therefore, small basis sets, which would combine high computational speed and high accuracy, are in great demand. This study focuses on comparing how well density functional theory (DFT) methods employing small, double-zeta basis sets can estimate halogen-bond strengths. Several methods with triple-zeta basis sets are included for comparison. Altogether, 46 DFT methods were tested using two data sets of 18 and 33 halogen-bonded complexes for which the complexation energies have been previously calculated with the high-accuracy CCSD(T)/CBS method. The DGDZVP basis set performed far better than other double-zeta basis sets, and it even outperformed the triple-zeta basis sets. Due to its small size, it is well-suited to studying halogen bonding in large systems.

  5. 29 CFR 2580.412-8 - The nature of the duties or activities to which the bonding requirement relates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 9 2010-07-01 2010-07-01 false The nature of the duties or activities to which the bonding... BENEFITS SECURITY ADMINISTRATION, DEPARTMENT OF LABOR TEMPORARY BONDING RULES UNDER THE EMPLOYEE RETIREMENT INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-8 The nature...

  6. 29 CFR 2580.412-8 - The nature of the duties or activities to which the bonding requirement relates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 29 Labor 9 2011-07-01 2011-07-01 false The nature of the duties or activities to which the bonding... BENEFITS SECURITY ADMINISTRATION, DEPARTMENT OF LABOR TEMPORARY BONDING RULES UNDER THE EMPLOYEE RETIREMENT INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-8 The nature...

  7. Bond strength evaluation in adhesive joints using NDE and DIC methods

    NASA Astrophysics Data System (ADS)

    Poudel, Anish

    Adhesive bonding of graphite epoxy composite laminates to itself or traditional metal alloys in modern aerospace and aircraft structural applications offers an excellent opportunity to use the most efficient and intelligent combination of materials available thus providing an attractive package for efficient structural designs. However, one of the major issues of adhesive bonding is the occasional formation of interfacial defects such as kissing or weak bonds in the bondline interface. Also, there are shortcomings of existing non-destructive evaluation (NDE) methods to non-destructively detect/characterize these interfacial defects and reliably predicting the bond shear strength. As a result, adhesive bonding technology is still not solely implemented in primary structures of an aircraft. Therefore, there is a greater demand for a novel NDE tool that can meet the existing aerospace requirement for adhesive bondline characterization. This research implemented a novel Acoustography ultrasonic imaging and digital image correlation (DIC) technique to detect and characterize interfacial defects in the bondline and determine bond shear strength in adhesively bonded composite-metal joints. Adhesively bonded Carbon Fiber Reinforced Plastic (CFRP) laminate and 2024-T3 Aluminum single lap shear panels subjected to various implanted kissing/weak bond defects were the primary focus of this study. Kissing/weak bonds were prepared by controlled surface contamination in the composite bonding surface and also by improperly mixing the adhesive constituent. SEM analyses were also conducted to understand the surface morphology of substrates and their interaction with the contaminants. Morphological changes were observed in the microscopic scale and the chemical analysis confirmed the stability of the contaminant at or very close to the interface. In addition, it was also demonstrated that contaminants migrated during the curing of the adhesive from CFRP substrate which caused a

  8. An activated triple bond linker enables 'click' attachment of peptides to oligonucleotides on solid support.

    PubMed

    Wenska, Malgorzata; Alvira, Margarita; Steunenberg, Peter; Stenberg, Asa; Murtola, Merita; Strömberg, Roger

    2011-11-01

    A general procedure, based on a new activated alkyne linker, for the preparation of peptide-oligonucleotide conjugates (POCs) on solid support has been developed. With this linker, conjugation is effective at room temperature (RT) in millimolar concentration and submicromolar amounts. This is made possible since the use of a readily attachable activated triple bond linker enhances the Cu(I) catalyzed 1,3-dipolar cycloaddition ('click' reaction). The preferred scheme for conjugate preparation involves sequential conjugation to oligonucleotides on solid support of (i) an H-phosphonate-based aminolinker; (ii) the triple bond donor p-(N-propynoylamino)toluic acid (PATA); and (iii) azido-functionalized peptides. The method gives conversion of oligonucleotide to the POC on solid support, and only involves a single purification step after complete assembly. The synthesis is flexible and can be carried out without the need for specific automated synthesizers since it has been designed to utilize commercially available oligonucleotide and peptide derivatives on solid support or in solution. Methodology for the ready conversion of peptides into 'clickable' azidopeptides with the possibility of selecting either N-terminus or C-terminus connection also adds to the flexibility and usability of the method. Examples of synthesis of POCs include conjugates of oligonucleotides with peptides known to be membrane penetrating and nuclear localization signals.

  9. A theoretical view on CrO2+-mediated C-H bond activation in ethane

    NASA Astrophysics Data System (ADS)

    Tong, YongChun; Zhang, XiaoYong; Wang, QingYun; Xu, XinJian; Wang, YongCheng

    2015-06-01

    The gas-phase reaction of C-H bond activation in ethane by CrO2+ has been investigated using density functional theory (DFT) at the UB3LYP/6-311G(2d,p) level. Our results reveal that the activation process is actually a spin-forbidden reaction. The involved crossing point between the doublet and quartet potential energy surfaces (PES) has been discussed by two well-known methods, i.e., intrinsic reaction coordinate (IRC) approach for crossing point (CP) and Harvey's algorithm for minimum energy crossing point (MECP). The obtained single ( P1ISC = 2.48 × 10-3) and double ( P1ISC = 4.95 × 10-3) passes estimated at MECP show that the intersystem crossing (ISC) occurs with a little probability. The C-H bond activation processes should proceed to be endothermic by 73.16 kJ/mol on the doublet surface without any spin change.

  10. Identification of active sites in amidase: Evolutionary relationship between amide bond- and peptide bond-cleaving enzymes

    PubMed Central

    Kobayashi, Michihiko; Fujiwara, Yoshie; Goda, Masahiko; Komeda, Hidenobu; Shimizu, Sakayu

    1997-01-01

    Mainly based on various inhibitor studies previously performed, amidases came to be regarded as sulfhydryl enzymes. Not completely satisfied with this generally accepted interpretation, we performed a series of site-directed mutagenesis studies on one particular amidase of Rhodococcus rhodochrous J1 that was involved in its nitrile metabolism. For these experiments, the recombinant amidase was produced as the inclusion body in Escherichia coli to greatly facilitate its recovery and subsequent purification. With regard to the presumptive active site residue Cys203, a Cys203 → Ala mutant enzyme still retained 11.5% of the original specific activity. In sharp contrast, substitutions in certain other positions in the neighborhood of Cys203 had a far more dramatic effect on the amidase. Glutamic acid substitution of Asp191 reduced the specific activity of the mutant enzyme to 1.33% of the wild-type activity. Furthermore, Asp191 → Asn substitution as well as Ser195 → Ala substitution completely abolished the specific activity. It would thus appear that, among various conserved residues residing within the so-called signature sequence common to all amidases, the real active site residues are Asp191 and Ser195 rather than Cys203. Inasmuch as an amide bond (CO-NH2) in the amide substrate is not too far structurally removed from a peptide bond (CO-NH-), the signature sequences of various amidases were compared with the active site sequences of various types of proteases. It was found that aspartic acid and serine residues corresponding to Asp191 and Ser195 of the Rhodococcus amidase are present within the active site sequences of aspartic proteinases, thus suggesting the evolutionary relationship between the two. PMID:9342349

  11. 26 CFR 1.103(n)-1T - Limitation on aggregrate amount of private activity bonds (temporary).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... activity bonds (temporary). 1.103(n)-1T Section 1.103(n)-1T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-1T Limitation on aggregrate amount of private activity bonds (temporary). Q-1: What does section 103(n) provide? A-1: Interest on an issue of private activity bonds...

  12. 26 CFR 1.103(n)-1T - Limitation on aggregrate amount of private activity bonds (temporary).

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... activity bonds (temporary). 1.103(n)-1T Section 1.103(n)-1T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-1T Limitation on aggregrate amount of private activity bonds (temporary). Q-1: What does section 103(n) provide? A-1: Interest on an issue of private activity bonds...

  13. 26 CFR 1.103(n)-1T - Limitation on aggregrate amount of private activity bonds (temporary).

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... activity bonds (temporary). 1.103(n)-1T Section 1.103(n)-1T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-1T Limitation on aggregrate amount of private activity bonds (temporary). Q-1: What does section 103(n) provide? A-1: Interest on an issue of private activity bonds...

  14. 26 CFR 1.103(n)-1T - Limitation on aggregrate amount of private activity bonds (temporary).

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... activity bonds (temporary). 1.103(n)-1T Section 1.103(n)-1T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-1T Limitation on aggregrate amount of private activity bonds (temporary). Q-1: What does section 103(n) provide? A-1: Interest on an issue of private activity bonds...

  15. 26 CFR 1.103(n)-1T - Limitation on aggregrate amount of private activity bonds (temporary).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... activity bonds (temporary). 1.103(n)-1T Section 1.103(n)-1T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-1T Limitation on aggregrate amount of private activity bonds (temporary). Q-1: What does section 103(n) provide? A-1: Interest on an issue of private activity bonds...

  16. 26 CFR 1.147-1 - Other requirements applicable to certain private activity bonds.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...) Overview. Interest on a private activity bond is not excludable from gross income under section 103(a... the rules limiting use of proceeds to acquire land or existing property under sections 147(c) (1)...

  17. Method of fluxless brazing and diffusion bonding of aluminum containing components

    NASA Technical Reports Server (NTRS)

    Featherston, A. B.; Okelly, K. P. (Inventor)

    1976-01-01

    A method of diffusion bonding and fluxless brazing of aluminum containing components is reported. The aluminum surfaces are freed of any aluminum oxide coating and are coated with a polymeric sealer which can be thermally removed leaving essentially no residue. The polymeric sealer is being removed in a substantially oxygen free environment, and the aluminum components are then being brazed or diffusion bonded without the use of a flux to remove oxide coating.

  18. Activation of C-H bonds in nitrones leads to iridium hydrides with antitumor activity.

    PubMed

    Song, Xiaoda; Qian, Yong; Ben, Rong; Lu, Xiang; Zhu, Hai-Liang; Chao, Hui; Zhao, Jing

    2013-08-22

    We report the design and synthesis of a series of new cyclometalated iridium hydrides derived from the C-H bond activation of aromatic nitrones and the biological evaluation of these iridium hydrides as antitumor agents. The nitrone ligands are based on the structure of a popular antioxidant, α-phenyl-N-tert-butylnitrone (PBN). Compared to cisplatin, the iridium hydrides exhibit excellent antitumor activity on HepG2 cells. The metal-coordinated compound with the most potent anticancer activity, 2f, was selected for further analysis because of its ability to induce apoptosis and interact with DNA. During in vitro studies and in vivo efficacy analysis with tumor xenograft models in Institute of Cancer Research (ICR) mice, complex 2f exhibited antitumor activity that was markedly superior to that of cisplatin. Our results suggest, for the first time, that metal hydrides could be a new type of metal-based antitumor agent.

  19. Surface-Bonded Antimicrobial Activity of an Organosilicon Quaternary Ammonium Chloride

    PubMed Central

    Isquith, A. J.; Abbott, E. A.; Walters, P. A.

    1972-01-01

    The hydrolysis product of 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride exhibited antimicrobial activity against a broad range of microorganisms while chemically bonded to a variety of surfaces. The chemical was not removed from surfaces by repeated washing with water, and its antimicrobial activity could not be attributed to a slow release of the chemical, but rather to the surface-bonded chemical. Images PMID:4650597

  20. Method of bonding metals to ceramics and other materials

    DOEpatents

    Gruen, Dieter M.; Krauss, Alan R.; DeWald, A. Bruce; Ju, Chien-Ping; Rigsbee, James M.

    1993-01-01

    A composite and method of forming same wherein the composite has a non-metallic portion and an alloy portion wherein the alloy comprises an alkali metal and a metal which is an electrical conductor such as Cu, Ag, Al, Sn or Au and forms an alloy with the alkali metal. A cable of superconductors and composite is also disclosed.

  1. Method of bonding metals to ceramics and other materials

    DOEpatents

    Gruen, D.M.; Krauss, A.R.; DeWald, A.P.; Chienping Ju; Rigsbee, J.M.

    1993-01-05

    A composite and method of forming same wherein the composite has a non-metallic portion and an alloy portion wherein the alloy comprises an alkali metal and a metal which is an electrical conductor such as Cu, Ag, Al, Sn or Au and forms an alloy with the alkali metal. A cable of superconductors and composite is also disclosed.

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

    PubMed Central

    2016-01-01

    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. PMID:28144357

  3. Method of waste stabilization via chemically bonded phosphate ceramics

    DOEpatents

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

    1998-01-01

    A method for regulating the reaction temperature of a ceramic formulation process is provided comprising supplying a solution containing a monovalent alkali metal; mixing said solution with an oxide powder to create a binder; contacting said binder with bulk material to form a slurry; and allowing the slurry to cure. A highly crystalline waste form is also provided consisting of a binder containing potassium and waste substrate encapsulated by the binder.

  4. Method of waste stabilization via chemically bonded phosphate ceramics

    DOEpatents

    Wagh, A.S.; Singh, D.; Jeong, S.Y.

    1998-11-03

    A method for regulating the reaction temperature of a ceramic formulation process is provided comprising supplying a solution containing a monovalent alkali metal; mixing said solution with an oxide powder to create a binder; contacting said binder with bulk material to form a slurry; and allowing the slurry to cure. A highly crystalline waste form is also provided consisting of a binder containing potassium and waste substrate encapsulated by the binder. 3 figs.

  5. Automated Modeling and Simulation Using the Bond Graph Method for the Aerospace Industry

    NASA Technical Reports Server (NTRS)

    Granda, Jose J.; Montgomery, Raymond C.

    2003-01-01

    Bond graph modeling was originally developed in the late 1950s by the late Prof. Henry M. Paynter of M.I.T. Prof. Paynter acted well before his time as the main advantage of his creation, other than the modeling insight that it provides and the ability of effectively dealing with Mechatronics, came into fruition only with the recent advent of modern computer technology and the tools derived as a result of it, including symbolic manipulation, MATLAB, and SIMULINK and the Computer Aided Modeling Program (CAMPG). Thus, only recently have these tools been available allowing one to fully utilize the advantages that the bond graph method has to offer. The purpose of this paper is to help fill the knowledge void concerning its use of bond graphs in the aerospace industry. The paper first presents simple examples to serve as a tutorial on bond graphs for those not familiar with the technique. The reader is given the basic understanding needed to appreciate the applications that follow. After that, several aerospace applications are developed such as modeling of an arresting system for aircraft carrier landings, suspension models used for landing gears and multibody dynamics. The paper presents also an update on NASA's progress in modeling the International Space Station (ISS) using bond graph techniques, and an advanced actuation system utilizing shape memory alloys. The later covers the Mechatronics advantages of the bond graph method, applications that simultaneously involves mechanical, hydraulic, thermal, and electrical subsystem modeling.

  6. Time resolved studies of bond activation by organometallic complexes

    SciTech Connect

    Wilkens, Matthew J.

    1998-05-01

    In 1971, Jetz and Graham discovered that the silicon-hydrogen bond in silanes could be broken under mild photochemical conditions in the presence of certain transition metal carbonyls. Such reactions fall within the class of oxidative addition. A decade later, similar reactivity was discovered in alkanes. In these cases a C-H bond in non-functionalized alkanes was broken through the oxidative addition of Cp*Ir(H)2L (Cp* = (CH3)5C5, L = PPh3, Ph = C6H5) to form Cp*ML(R)(H) or of Cp*Ir(CO)2 to form Cp*Ir(CO)(R)(H). These discoveries opened an entirely new field of research, one which naturally included mechanistic studies aimed at elucidating the various paths involved in these and related reactions. Much was learned from these experiments but they shared the disadvantage of studying under highly non-standard conditions a system which is of interest largely because of its characteristics under standard conditions. Ultrafast time-resolved IR spectroscopy provides an ideal solution to this problem; because it allows the resolution of chemical events taking place on the femto-through picosecond time scale, it is possible to study this important class of reactions under the ambient conditions which are most of interest to the practicing synthetic chemist. Certain of the molecules in question are particularly well-suited to study using the ultrafast IR spectrophotometer described in the experimental section because they contain one or more carbonyl ligands.

  7. Antioxidant activity of phenolic and related compounds: a density functional theory study on the O-H bond dissociation enthalpy.

    PubMed

    Giacomelli, Cristiano; Miranda, Fabio da Silva; Gonçalves, Norberto Sanches; Spinelli, Almir

    2004-01-01

    We report here on calculations at the hybrid DFT/HF (B3-LYP/6-31G(d, p)) level of the O-H bond dissociation enthalpy (O-H BDE) of phenylpropenoic acids (caffeic, ferulic, p-coumaric and cinnamic) and phenolic acids and related compounds (gallic, methylgallate, vanillic and gentisic) in order to gain insight into the understanding of structure-antioxidant activity relationships. The results were correlated and discussed mainly on the basis of experimental data in a companion work (Galato D, Giacomelli C, Ckless K, Susin MF, Vale RMR, Spinelli A. Antioxidant capacity of phenolic and related compounds: correlation among electrochemical, visible spectroscopy methods and structure-antioxidant activity. Redox Report 2001; 6: 243-250). The O-H BDE values showed remarkable dependence on the hydroxyl position in the benzene ring and the existence of additional interaction due to hydrogen bonding. For parent molecules, the experimental antioxidant activity (AA) order was properly obeyed only when intramolecular hydrogen bonding was present in the radicalized structures of o-dihydroxyl moieties. In structurally related compounds, excellent correlation with experimental data was in general observed (0.64 < rho < 0.99). However, it is shown that excellent correlation can also be obtained for this series of compounds considering p-radicalized structures which were not stabilized by intramolecular hydrogen bonding, but this had no physical meaning. These findings suggested that the antioxidant activity evaluation of phenolic and related compounds must take into consideration the characteristics of each particular compound.

  8. Weaving and bonding method to prevent warp and fill distortion

    NASA Technical Reports Server (NTRS)

    Farley, Gary L. (Inventor)

    1997-01-01

    A method to prevent fiber distortion in textile materials employed in a modified weaving process. In a first embodiment, a tacifier in powder form is applied to the yarn and melted while on the fabric. Cool air is then supplied after the tacifier has melted to expedite the solidification of the tacifier. In a second embodiment, a solution form of a tacifier is used by dissolving the tacifier into a solvent that has a high evaporation rate. The solution is then sprayed onto the fabric or fill yarn as each fill yarn is inserted into a shed of the fabric. A third embodiment applies the tacifier in a liquid form that has not been dissolved in a solvent. That is, the tacifier is melted and is sprayed as a liquid onto the fabric or fill yarn as it is being extracted from a fill yarn spool prior to the fill yarn being inserted into the shed of the fabric. A fourth embodiment employs adhesive yarns contained as an integral part of the warp or fill yarn. Additional tacifier material is not required because a matrix is used as the tacifier. The matrix is then locally melted using heating elements on clamping bars or take-up rollers, is cooled, if necessary, and solidified.

  9. MZI optical isolator with Si-wire waveguides by surface-activated direct bonding.

    PubMed

    Shoji, Yuya; Ito, Masatoshi; Shirato, Yuya; Mizumoto, Tetsuya

    2012-07-30

    We fabricate a Mach-Zehnder interferometer-based optical isolator using a silicon-wire waveguide with magneto-optic garnet cladding using direct bonding techniques. Using Si-wire waveguides, the size of the device is greatly reduced from that of our previous device. We investigate surface-activated direct bonding with nitrogen plasma treatment, which shows better bonding results than oxygen plasma treatment. A large magneto-optic phase shift of 0.8π and an optical isolation of 18 dB are obtained at a wavelength of 1322 nm.

  10. Method of bonding functional surface materials to substrates and applications in microtechnology and anti-fouling

    DOEpatents

    Feng, Xiangdong; Liu, Jun; Liang, Liang

    2001-01-01

    A simple and effective method to bond a thin coating of poly(N-isopropylacylamide) (NIPAAm) on a glass surface by UV photopolymerization, and the use of such a coated surface in nano and micro technology applications. A silane coupling agent with a dithiocarbamate group is provided as a photosensitizer preferably, (N,N'-diethylamine) dithiocarbamoylpropyl-(trimethoxy) silane (DATMS). The thiocarbamate group of the sensitizer is then bonded to the glass surface by coupling the silane agent with the hydroxyl groups on the glass surface. The modified surface is then exposed to a solution of NIPAAm and a crosslinking agent which may be any organic molecule having an acrylamide group and at least two double bonds in its structure, such as N, N'-methylenebisacrylamide, and a polar solvent which may be any polar liquid which will dissolve the monomer and the crosslinking agent such as acetone, water, ethanol, or combinations thereof. By exposing the glass surface to a UV light, free radicals are generated in the thiocarbamate group which then bonds to the crosslinking agent and the NIPAAm. Upon bonding, the crosslinking agent and the NIPAAm polymerize to form a thin coating of PNIPAAm bonded to the glass. Depending upon the particular configuration of the glass, the properties of the PNIPAAm allow applications in micro and nano technology.

  11. Method of bonding functional surface materials to substrates and applications in microtechnology and antifouling

    DOEpatents

    Feng, Xiangdong; Liu, Jun; Liang, Liang

    1999-01-01

    A simple and effective method to bond a thin coating of poly(N-isopropylacylamide) (NIPAAm) on a glass surface by UV photopolymerization, and the use of such a coated surface in nano and micro technology applications. A silane coupling agent with a dithiocarbamate group is provided as a photosensitizer, preferably, (N,N'-diethylamine)dithiocarbamoylpropyl-(trimethoxy)silane (DATMS). The thiocarbamate group of the sensitizer is then bonded to the glass surface by coupling the silane agent with the hydroxyl groups on the glass surface. The modified surface is then exposed to a solution of NIPAAm and a crosslinking agent which may be any organic molecule having an acrylamide group and at least two double bonds in its structure, such as N,N'-methylenebisacrylamide, and a polar solvent which may be any polar liquid which will dissolve the monomer and the crosslinking agent such as acetone, water, ethanol, or combinations thereof. By exposing the glass surface to a UV light, free radicals are generated in the thiocarbamate group which then bonds to the crosslinking agent and the NIPAAm. Upon bonding, the crosslinking agent and the NIPAAm polymerize to form a thin coating of PNIPAAm bonded to the glass. Depending upon the particular configuration of the glass, the properties of the PNIPAAm allow applications in micro and nano technology.

  12. Evaluation of nonrinse conditioning solution and a compomer as an alternative method of bonding orthodontic bracket.

    PubMed

    Bishara, S E; Laffoon, J F; VonWald, L; Warren, J J

    2001-12-01

    Damage to the enamel surface during bonding and debonding of orthodontic brackets is a clinical concern. Alternative bonding methods that minimize enamel surface damage while maintaining a clinically useful bond strength are an aim of current research. The purpose of this study was to compare the effects of using two enamel conditioners and adhesives on the shear bond strength and bracket failure location. Forty freshly extracted human molars were pumiced and randomly divided into two groups of 20 teeth. Metal orthodontic brackets were bonded to the enamel surface by one of two protocols: 37% phosphoric acid with a composite adhesive (Transbond XT) or a nonrinse conditioner with a compomer adhesive (Dyract flow). The teeth were mounted in phenolic rings and stored in deionized water at 37 degrees C for 24 hours. A Zwick Universal Testing Machine was used to determine shear bond strengths in MegaPascals. The residual adhesive on the enamel surface was evaluated using the Adhesive Remnant Index. Student t-test and chi2-test were used to compare the two groups. Significance was predetermined at P < or = .05. The results of the t-tests indicated that there were significant differences between the two adhesive systems (t = 11.18 and P = .001) with the nonrinse conditioner/compomer system having lower shear bond strength (X = 1.7 +/- 0.9 MPa) than the phosphoric acid/composite adhesive (X = 10.4 +/- 2.8 MPa). The results of the Chi Square test evaluating the residual adhesives on the enamel surfaces also revealed significant differences between the two groups (chi2 = 7.62, P = .022). In conclusion, a nonrinse conditioner used with a compomer adhesive had significantly lower shear bond strength than a phosphoric acid/composite adhesive system.

  13. Shear Bond Strength of Orthodontic Brackets to Tooth Enamel After Treatment With Different Tooth Bleaching Methods

    PubMed Central

    Vahid Dastjerdi, Elahe; Khaloo, Negar; Mojahedi, Seyed Masoud; Azarsina, Mohadese

    2015-01-01

    Background: Bleaching treatments decrease shear bond strength between orthodontic brackets and teeth; although definite results have not been reported in this regard. Objectives: This study determined the effects of different bleaching protocols on the shear bond strength of orthodontic brackets to teeth. Materials and Methods: This experimental study was performed in Iran. Forty-eight extracted human premolars were randomly assigned into four groups. In the control group, no bleaching treatment was performed. In groups 2 - 4, the bleaching procedures were performed using carbamide peroxide 45%, carbamide peroxide 20% and diode laser, respectively. Two weeks later, brackets were bonded to teeth and thermocycled. The shear bond strengths of the brackets to the teeth were measured. Data was analyzed by one-way ANOVA and Dunnett post-hoc test. Results: Shear bond strength of the brackets to the teeth were 10.54 ± 1.51, 6.37 ± 0.92, 7.67 ± 1.01 and 7.49 ± 1.19 MPa, in groups 1 - 4, respectively. Significant differences were found between control group and all other groups (P < 0.001); and also between groups 2 and 3 (P < 0.05). No significant differences were found between the other groups. Conclusions: The bleaching procedures using 20% carbamide peroxide and 45% carbamide peroxide and diode laser significantly decreased shear bond strength of brackets to the teeth. 45% carbamide peroxide had a more significant effect on bond strength compared to 20% carbamide peroxide. The difference in bond strength was not significant between laser group and either carbamide peroxide groups. PMID:26734481

  14. Low-cost bump bonding activities at CERN

    NASA Astrophysics Data System (ADS)

    Vähänen, S.; Tick, T.; Campbell, M.

    2010-11-01

    Conventional bumping processes used in the fabrication of hybrid pixel detectors for High Energy Physics (HEP) experiments use electroplating for Under Bump Metallization (UBM) and solder bump deposition. This process is laborious, involves time consuming photolithography and can only be performed using whole wafers. Electroplating has been found to be expensive when used for the low volumes which are typical of HEP experiments. In the low-cost bump bonding development work, electroless deposition technology of UBM is studied as an alternative to the electroplating process in the bump size / pitch window beginning from 20 μm / 50 μm. Electroless UBM deposition used in combination with solder transfer techniques has the potential to significantly lower the cost of wafer bumping without requiring increased wafer volumes. A test vehicle design of sensor and readout chip, having daisy chains and Kelvin bump structures, was created to characterize the flip chip process with electroless UBM. Two batches of test vehicle wafers were manufactured with different bump pad metallization. Batch #1 had AlSi(1%) metallization, which is similar to the one used on sensor wafers, and Batch #2 had AlSi(2%)Cu(1%) metallization, which is very similar to the one used on readout wafers. Electroless UBMs were deposited on both wafer batches. In addition, electroplated Ni UBM and SnPb solder bumps were grown on the test sensor wafers. Test assemblies were made by flip chip bonding the solder-bumped test sensors against the test readout chips with electroless UBMs. Electrical yields and individual joint resistances were measured from assemblies, and the results were compared to a well known reference technique based on electroplated solder bumps structures on both chips. The electroless UBMs deposited on AlSi(2%)Cu(1%) metallization showed excellent electrical yields and small tolerances in individual joint resistance. The results from the UBMs deposited on AlSi(1%) metallization were non

  15. On the Relative Merits of Non-Orthogonal and Orthogonal Valence Bond Methods Illustrated on the Hydrogen Molecule

    ERIC Educational Resources Information Center

    Angeli, Celestino; Cimiraglia, Renzo; Malrieu, Jean-Paul

    2008-01-01

    Valence bond (VB) is one of the cornerstone theories of quantum chemistry. Even if in practical applications the molecular orbital (MO) approach has obtained more attention, some basic chemical concepts (such as the nature of the chemical bond and the failure of the single determinant-based MO methods in describing the bond cleavage) are normally…

  16. Oxygen activation and intramolecular C-H bond activation by an amidate-bridged diiron(II) complex.

    PubMed

    Jones, Matthew B; Hardcastle, Kenneth I; Hagen, Karl S; MacBeth, Cora E

    2011-07-18

    A diiron(II) complex containing two μ-1,3-(κN:κO)-amidate linkages has been synthesized using the 2,2',2''-tris(isobutyrylamido)triphenylamine (H(3)L(iPr)) ligand. The resulting diiron complex, 1, reacts with dioxygen (or iodosylbenzene) to effect intramolecular C-H bond activation at the methine position of the ligand isopropyl group. The ligand-activated product, 2, has been isolated and characterized by a variety of methods including X-ray crystallography. Electrospray ionization mass spectroscopy of 2 prepared from(18)O(2) was used to confirm that the oxygen atom incorporated into the ligand framework is derived from molecular oxygen.

  17. Role of peptide bond in the realization of biological activity of short peptides.

    PubMed

    Khavinson, V Kh; Tarnovskaya, S I; Lin'kova, N S; Chervyakova, N A; Nichik, T E; Elashkina, E V; Chalisova, N I

    2015-02-01

    We performed a comparative analysis of biological activity of Lys-Glu peptide and its amino acid constituents. It was established that Lys-Glu stimulated proliferation of splenic cells in organotypic culture, while the mixture of glutamic acid and lysine inhibited culture growth. Using the method of molecular docking, we showed that glutamic acid, lysine, and Lys-Glu peptide can interact with different DNA sequences. The energy of interaction and the most beneficial localization of glutamic acid, lysine, and Lys-Glu peptide in DNA molecule was calculated. We demonstrated the interaction of the peptide and amino acids with DNA along the minor groove. The energy of DNA interaction with the peptide is higher than with individual amino acids. The peptide bonds increase the interaction of Lys-Glu peptide with DNA, which potentiates the biological effect on cell proliferation in organotypic culture of splenic cells.

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

    PubMed Central

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

    2015-01-01

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

  19. Cu-catalyzed cross-dehydrogenative coupling: A versatile strategy for C-C bond formations via the oxidative activation of sp3 C-H bonds

    NASA Astrophysics Data System (ADS)

    Li, Zhiping; Bohle, D. Scott; Li, Chao-Jun

    2006-06-01

    Cu-catalyzed cross-dehydrogenative coupling (CDC) methodologies were developed based on the oxidative activation of sp3 C-H bonds adjacent to a nitrogen atom. Various sp, sp2, and sp3 C-H bonds of pronucleophiles were used in the Cu-catalyzed CDC reactions. Based on these results, the mechanisms of the CDC reactions also are discussed. C-H activation | catalysis | Baylis-Hillman reaction | Mannich reaction | Friedel-Crafts reaction

  20. Active Learning Methods

    ERIC Educational Resources Information Center

    Zayapragassarazan, Z.; Kumar, Santosh

    2012-01-01

    Present generation students are primarily active learners with varied learning experiences and lecture courses may not suit all their learning needs. Effective learning involves providing students with a sense of progress and control over their own learning. This requires creating a situation where learners have a chance to try out or test their…

  1. Carbon-Hydrogen (C-H) Bond Activation at PdIV: A Frontier in C–H Functionalization Catalysis

    PubMed Central

    Topczewski, Joseph J.; Sanford, Melanie S.

    2014-01-01

    The direct functionalization of carbon-hydrogen (C-H) bonds has emerged as a versatile strategy for the synthesis and derivatization of organic molecules. Among the methods for C-H bond activation, catalytic processes that utilize a PdII/PdIV redox cycle are increasingly common. The C-H activation step in most of these catalytic cycles is thought to occur at a PdII centre. However, a number of recent reports have suggested the feasibility of C-H cleavage occurring at PdIV complexes. Importantly, these latter processes often result in complementary reactivity and selectivity relative to analogous transformations at PdII. This Mini Review highlights proposed examples of C-H activation at PdIV centres. Applications of this transformation in catalysis as well as mechanistic details obtained from stoichiometric model studies are discussed. Furthermore, challenges and future perspectives for the field are reviewed. PMID:25544882

  2. A Highly Reactive Mononuclear Non-Heme Manganese(IV)-Oxo Complex That Can Activate the Strong C-H Bonds of Alkanes

    SciTech Connect

    Wu, Xiujuan; Seo, Mi Sook; Davis, Katherine M; Lee, Yong-Min; Chen, Junying; Cho, Kyung-Bin; Pushkar, Yulia N; Nam, Wonwoo

    2012-03-15

    A mononuclear non-heme manganese(IV)-oxo complex has been synthesized and characterized using various spectroscopic methods. The Mn(IV)-oxo complex shows high reactivity in oxidation reactions, such as C-H bond activation, oxidations of olefins, alcohols, sulfides, and aromatic compounds, and N-dealkylation. In C-H bond activation, the Mn(IV)-oxo complex can activate C-H bonds as strong as those in cyclohexane. It is proposed that C-H bond activation by the non-heme Mn(IV)-oxo complex does not occur via an oxygen-rebound mechanism. The electrophilic character of the non-heme Mn(IV)-oxo complex is demonstrated by a large negative ρ value of ~4.4 in the oxidation of para-substituted thioanisoles.

  3. Computational study on the mechanism and selectivity of C-H bond activation and dehydrogenative functionalization in the synthesis of rhazinilam.

    PubMed

    Ellis, Corey S; Ess, Daniel H

    2011-09-02

    The key platinum mediated C-H bond activation and functionalization steps in the synthesis of (-)-rhazinilam (Johnson, J. A.; Li, N.; Sames, D. J. Am. Chem. Soc. 2002, 124, 6900) were investigated using the M06 and B3LYP density functional approximation methods. This computational study reveals that ethyl group dehydrogenation begins with activation of a primary C-H bond in preference to a secondary C-H bond in an insertion/methane elimination pathway. The C-H activation step is found to be reversible while the methane elimination (reductive elimination) transition state controls rate and diastereoselectivity. The chiral oxazolinyl ligand induces ethyl group selectivity through stabilizing weak interactions between its phenyl group (or cyclohexyl group) and the carboxylate group. After C-H activation and methane elimination steps, Pt-C bond functionalization occurs through β-hydride elimination to give the alkene platinum hydride complex.

  4. The effects of hydrogen bonds on metal-mediated O2 activation and related processes

    PubMed Central

    Shook, Ryan L.; Borovik, A. S.

    2009-01-01

    Hydrogen bonds stabilize and direct chemistry performed by metalloenzymes. With inspiration from enzymes, we will utilize an approach that incorporates intramolecular hydrogen bond donors to determine their effects on the stability and reactivity of metal complexes. Our premise is that control of secondary coordination sphere interactions will promote new function in synthetic metal complexes. Multidentate ligands have been developed that create rigid organic structures around metal ions. These ligands place hydrogen bond (H-bond) donors proximal to the metal centers, forming specific microenvironments. One distinguishing attribute of these systems is that site-specific modulations in structure can be readily accomplished, in order to evaluate correlations with reactivity. A focus of this research is consideration of dioxygen binding and activation by metal complexes, including developing structure–function relationships in metal-assisted oxidative catalysis. PMID:19082087

  5. Functionalization of non-activated C-H bonds in the synthesis of vitamin D metabolites and analogs.

    PubMed

    Moman, Edelmiro

    2014-01-01

    The development of non-microbial methods for the selective functionalization of non-activated C-H bonds has constituted a challenge, with important economical and environmental implications, for chemists for over a century. The present review provides a comprehensive and current compendium that illustrates the power of C-H functionalization and, namely, of remote functionalization strategies, to expeditiously access vitamin D analogs with intricate structures.

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

    PubMed

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

    2013-10-16

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

  7. Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH₄ Reactions on Pd Catalysts

    SciTech Connect

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

    2013-10-01

    Mechanistic assessments based on kinetic and isotopic methods combined with density functional theory are used to probe the diverse pathways by which C-H bonds in CH₄ react on bare Pd clusters, Pd cluster surfaces saturated with chemisorbed oxygen (O*), and PdO clusters. C-H activation routes change from oxidative addition to Habstraction and then to σ-bond metathesis with increasing O-content, as active sites evolve from metal atom pairs (*-*) to oxygen atom (O*-O*) pairs and ultimately to Pd cationlattice oxygen pairs (Pd2+-O2-) in PdO. The charges in the CH₃ and H moieties along the reaction coordinate depend on the accessibility and chemical state of the Pd and O centers involved. Homolytic C-H dissociation prevails on bare (*-*) and O*- covered surfaces (O*-O*), while C-H bonds cleave heterolytically on Pd2+-O2- pairs at PdO surfaces. On bare surfaces, C-H bonds cleave via oxidative addition, involving Pd atom insertion into the C-H bond with electron backdonation from Pd to C-H antibonding states and the formation of tight three-center (H₃C···Pd···H)‡ transition states. On O*-saturated Pd surfaces, C-H bonds cleave homolytically on O*-O* pairs to form radical-like CH3 species and nearly formed O-H bonds at a transition state (O*···CH3 •···*OH)‡ that is looser and higher in enthalpy than on bare Pd surfaces. On PdO surfaces, site pairs consisting of exposed Pd2+ and vicinal O2-, Pdox-Oox, cleave C-H bonds heterolytically via σ-bond metathesis, with Pd2+ adding to the C-H bond, while O2- abstracts the H-atom to form a four-center (H3Cδ-···Pdox···Hδ+···Oox) transition state without detectable Pdox reduction. The latter is much more stable than transition states on *-* and O*-O* pairs and give rise to a large increase in CH₄ oxidation turnover rates at oxygen chemical

  8. Sticker Bonding.

    ERIC Educational Resources Information Center

    Frazier, Laura Corbin

    2000-01-01

    Introduces a science activity on the bonding of chemical compounds. Assigns students the role of either a cation or anion and asks them to write the ions they may bond with. Assesses students' understanding of charge, bonding, and other concepts. (YDS)

  9. Method of making cascaded die mountings with springs-loaded contact-bond options

    DOEpatents

    Hsu, John S.; Adams, Donald J.; Su, Gui-Jia; Marlino, Laura D.; Ayers, Curtis W.; Coomer, Chester

    2007-06-19

    A cascaded die mounting device and method using spring contacts for die attachment, with or without metallic bonds between the contacts and the dies, is disclosed. One embodiment is for the direct refrigerant cooling of an inverter/converter carrying higher power levels than most of the low power circuits previously taught, and does not require using a heat sink.

  10. Activation of remote meta-C-H bonds assisted by an end-on template.

    PubMed

    Leow, Dasheng; Li, Gang; Mei, Tian-Sheng; Yu, Jin-Quan

    2012-06-27

    Functionalization of unactivated carbon-hydrogen (C-H) single bonds is an efficient strategy for rapid generation of complex molecules from simpler ones. However, it is difficult to achieve selectivity when multiple inequivalent C-H bonds are present in the target molecule. The usual approach is to use σ-chelating directing groups, which lead to ortho-selectivity through the formation of a conformationally rigid six- or seven-membered cyclic pre-transition state. Despite the broad utility of this approach, proximity-driven reactivity prevents the activation of remote C-H bonds. Here we report a class of easily removable nitrile-containing templates that direct the activation of distal meta-C-H bonds (more than ten bonds away) of a tethered arene. We attribute this new mode of C-H activation to a weak 'end-on' interaction between the linear nitrile group and the metal centre. The 'end-on' coordination geometry relieves the strain of the cyclophane-like pre-transition state of the meta-C-H activation event. In addition, this template overrides the intrinsic electronic and steric biases as well as ortho-directing effects with two broadly useful classes of arene substrates (toluene derivatives and hydrocinnamic acids).

  11. Method and apparatus for combined cement bond and acoustic well logging

    SciTech Connect

    Smith, J. R. E.

    1985-01-22

    Method and apparatus are provided for measuring acoustic signals having amplitudes of widely varying magnitude during one traversal of the borehole corresponding to indications of cement bonding along a casing as well as acoustic travel time through an increment of the formation. Variable attenuators are provided associated with acoustic receivers disposed within the logging sonde wherein attenuation may be automatically adjusted as a function of acoustic transmitter-receiver trigger pulses transmitted downhole, depending upon whether a cement bond or other log of acoustic signal information having a substantially different magnitude is desired.

  12. Biological Activity Predictions and Hydrogen Bonding Analysis in Quinolines

    NASA Astrophysics Data System (ADS)

    Gupta, Palvi; Kamni

    The paper has been designed to make a comprehensive review of a particular series of organic molecular assembly in the form of compendium. An overview of general description of fifteen quinoline derivatives has been given. The biological activity spectra of quinoline derivatives have been correlated on structure activity relationships base which provides the different Pa (possibility of activity) and Pi (possibility of inactivity) values. Expositions of the role of intermolecular interactions in the identified derivatives have been discussed with the standard distance and angle cut-off criteria criteria as proposed by Desiraju and Steiner (1999) in an International monogram on crystallography. Distance-angle scatter plots for intermolecular interactions are presented for a better understanding of the packing interactions which exist in quinoline derivatives.

  13. Novel method for the prediction of an interface bonding species at alumina/metal interfaces

    SciTech Connect

    Yoshitake, Michiko Yagyu, Shinjiro; Chikyow, Toyohiro

    2014-03-15

    Interface bonding between alumina and various metals is discussed from the viewpoint of chemical thermodynamics. A method to predict the interface bonding species at an alumina/metal interface under equilibrium conditions is proposed by using the concept of chemical equilibrium for interface termination. The originality of this method is in the way a simple estimation of the interface binding energy, which is generally applicable to most metals, is developed. The effectiveness of this method is confirmed by careful examination of the experimental results. Comparison of the predicted and experimentally observed interface terminations reveals that the proposed method agrees well with the reported results. The method uses only basic quantities of pure elements and the formation enthalpy of oxides. Therefore, it can be applied to most metals in the periodic table and is useful for screening materials in the quest to develop interfaces with particular functions.

  14. Calculations of bond dissociation energies. New select applications of an old method.

    PubMed

    Boudreaux, Edward A

    2011-03-10

    Application of Sanderson's definition of electronegativity as stability ratios (SRs), which BE = [E(i) + E(DA)] (IC) + E(cov) had been applied in the past to a wide variety of organic and nontransitional metal inorganic compounds with very good success, has been revived, modified so as to be applied to any types of molecules, including those containing transition metals, lanthanides, and actinides. This paper is limited to a demonstration of the method which is applied to a few metal cyclopentadienyl compounds, plus specific emphasis on the U(III) metallocene (CpSiMe(3))(3)U-AlCp* recently prepared by Arnold and co-workers having no experimental bond energies available. It is shown that computed bond energies of pertinent metallocyclopentadieneyls are in excellent agreement with the available experimental data. Calculated bond energies for all essential bonds in the uranium metallocene cited above are provided together with a further analysis of the bonding and magnetic properties of this unique compound.

  15. Wound healing studies of skin incisions in animal models: laser soldering versus other bonding methods

    NASA Astrophysics Data System (ADS)

    Simhon, David; Vasilyev, Tamar; Brosh, Tamar; Nevo, Zvi; Tennenbaum, Tamar; Kariv, Naam; Katzir, Abraham

    2003-06-01

    In the past, we have successfully used laser soldering for bonding cuts in the skin of medium and large size animal models. In this work, we have used the same method for bonding cuts on the backs of rabbits and mature pigs model. Cuts were created in dorsally depilated skins of rabbits and mature pigs. 47% bovine serum albumin (BSA) solder was applied onto the approximated edges of each cut, using a special approximation device. An infrared fiberoptic CO2 laser system was used to heat a spot on the cut, under good temperature control, to 65°C for 10 seconds. Other glued or sutured cuts, served as controls. Immediate tensile strength measurements were done on bonded incisions in rabbit skins. We found that laser soldered incisions exhibited similar strength to one bonded by cayanoacrylate glue. No dehiscence of wound edges was found in both treatments. The laser soldering procedure was 25% faster then suturing. A 14-day follow up of the bonded pig skin incisions was carried out, using punch biopsies. We found better aesthetic appearance of the soldered incisions. We observed better and faster wound repair in the laser-soldered scars, using histological and molecular staining. The temperature controlled laser soldering offers immediate strength similar to that of cyanoacrylate glues and better aesthetic and wound healing properties, in comparison to suturing techniques. We have clearly demonstrated the potential of this novel technique, which will pave thw way for clinical studies.

  16. Bonding brackets on white spot lesions pretreated by means of two methods

    PubMed Central

    Vianna, Julia Sotero; Marquezan, Mariana; Lau, Thiago Chon Leon; Sant'Anna, Eduardo Franzotti

    2016-01-01

    Abstract Objective: The aim of this study was to evaluate the shear bond strength (SBS) of brackets bonded to demineralized enamel pretreated with low viscosity Icon Infiltrant resin (DMG) and glass ionomer cement (Clinpro XT Varnish, 3M Unitek) with and without aging. Methods: A total of 75 bovine enamel specimens were allocated into five groups (n = 15). Group 1 was the control group in which the enamel surface was not demineralized. In the other four groups, the surfaces were submitted to cariogenic challenge and white spot lesions were treated. Groups 2 and 3 were treated with Icon Infiltrant resin; Groups 4 and 5, with Clinpro XT Varnish. After treatment, Groups 3 and 5 were artificially aged. Brackets were bonded with Transbond XT adhesive system and SBS was evaluated by means of a universal testing machine. Statistical analysis was performed by one-way analysis of variance followed by Tukey post-hoc test. Results: All groups tested presented shear bond strengths similar to or higher than the control group. Specimens of Group 4 had significantly higher shear bond strength values (p < 0.05) than the others. Conclusion: Pretreatment of white spot lesions, with or without aging, did not decrease the SBS of brackets. PMID:27275613

  17. Chemical methods for producing disulfide bonds in peptides and proteins to study folding regulation.

    PubMed

    Okumura, Masaki; Shimamoto, Shigeru; Hidaka, Yuji

    2014-04-01

    Disulfide bonds play a critical role in the folding of secretory and membrane proteins. Oxidative folding reactions of disulfide bond-containing proteins typically require several hours or days, and numerous misbridged disulfide isomers are often observed as intermediates. The rate-determining step in refolding is thought to be the disulfide-exchange reaction from nonnative to native disulfide bonds in folding intermediates, which often precipitate during the refolding process because of their hydrophobic properties. To overcome this, chemical additives or a disulfide catalyst, protein disulfide isomerase (PDI), are generally used in refolding experiments to regulate disulfide-coupled peptide and protein folding. This unit describes such methods in the context of the thermodynamic and kinetic control of peptide and protein folding, including (1) regulation of disulfide-coupled peptides and protein folding assisted by chemical additives, (2) reductive unfolding of disulfide-containing peptides and proteins, and (3) regulation of disulfide-coupled peptide and protein folding using PDI.

  18. 29 CFR 2580.412-8 - The nature of the duties or activities to which the bonding requirement relates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 29 Labor 9 2012-07-01 2012-07-01 false The nature of the duties or activities to which the bonding requirement relates. 2580.412-8 Section 2580.412-8 Labor Regulations Relating to Labor (Continued) EMPLOYEE... INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-8 The nature...

  19. 29 CFR 2580.412-8 - The nature of the duties or activities to which the bonding requirement relates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 29 Labor 9 2014-07-01 2014-07-01 false The nature of the duties or activities to which the bonding requirement relates. 2580.412-8 Section 2580.412-8 Labor Regulations Relating to Labor (Continued) EMPLOYEE... INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-8 The nature...

  20. 29 CFR 2580.412-8 - The nature of the duties or activities to which the bonding requirement relates.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 29 Labor 9 2013-07-01 2013-07-01 false The nature of the duties or activities to which the bonding requirement relates. 2580.412-8 Section 2580.412-8 Labor Regulations Relating to Labor (Continued) EMPLOYEE... INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-8 The nature...

  1. Biological activity predictions, crystallographic comparison and hydrogen bonding analysis of cholane derivatives.

    PubMed

    Rajnikant; Dinesh; Chand, Bhavnaish

    2007-12-01

    A total of eighteen molecules of cholane derivatives (I-XVIII) (a series of steroids) have been included to predict their pharmacological effects, specific mechanisms of action, known toxicities, drug-likeness, etc, by using the statistics of multilevel neighbourhoods of atoms (MNA) descriptors for active and inactive fragments. The biological activity spectra for substances have been correlated on SAR base (structure-activity relationships data and knowledge base), which provides the different P(a) (possibility of activity) and P(i) (possibility of inactivity). Most of the probable activities have been characterized by P(a) and P(i) values, which depict that all the molecules have high value of teratogen activity. The Lipinski's thumb rule predicts that all the cholane derivatives have stronger preponderance for "cancer-like-drug" molecules and some of their related analogous have entered in the ANCI (American National Cancer Institute) database. Some selected bond distances and bond angles of interest have been taken into account and deviation of bond distances/bond angles, vis-a-vis the substitutional group and X-H...A intra/intermolecular hydrogen bonds has been discussed in detail. X-H...A intra and intermolecular hydrogen bonds in the molecules have been described with the standard distance and angle cut-off criteria. D-theta and d-theta. scatter plots for intra- and intermolecular interactions are presented for better understanding of packing interactions existing among these derivatives. There exists only one C-H...O intramolecular bifurcated hydrogen bond. while high tendency of intermolecular bifurcated hydrogen bonds based on a defined O-H...O has been observed, in which O atom acts as a prototype donor as well as acceptor. The frequency of occurrence of C-H...O hydrogen bonds is predominant (i.e. 85.7%) in intramolecular interactions, whereas in intermolecular interactions, frequency of occurrence for O-H...O interactions is 62.9%. Solvent

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

    SciTech Connect

    Raupach, Marc; Tonner, Ralf

    2015-05-21

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

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

    PubMed

    Raupach, Marc; Tonner, Ralf

    2015-05-21

    The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the bonding energy between two fragments (e.g., the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic, Pauli repulsion, and orbital relaxation energies. This is complemented by consideration of dispersion interactions via a pairwise scheme. One major extension toward a previous implementation [Philipsen and Baerends, J. Phys. Chem. B 110, 12470 (2006)] lies in the separate discussion of electrostatic and Pauli and the addition of a dispersion term. The pEDA presented here for an implementation based on atomic orbitals can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy, and k-space sampling. Four typical bonding scenarios for surface-adsorbate complexes were chosen to highlight the performance of the method representing insulating (CO on MgO(001)), metallic (H2 on M(001), M = Pd, Cu), and semiconducting (CO and C2H2 on Si(001)) substrates. These examples cover diverse substrates as well as bonding scenarios ranging from weakly interacting to covalent (shared electron and donor acceptor) bonding. The results presented lend confidence that the pEDA will be a powerful tool for the analysis of surface-adsorbate bonding in the future, enabling the transfer of concepts like ionic and covalent bonding, donor-acceptor interaction, steric repulsion, and others to extended systems.

  4. Comparative Assessment of DFT Performances in Ru- and Rh-Promoted σ-Bond Activations.

    PubMed

    Sun, Yuanyuan; Hu, Lianrui; Chen, Hui

    2015-04-14

    In this work, the performances of 19 density functional theory (DFT) methods are calibrated comparatively on Ru- and Rh-promoted σ-bond (C-H, O-H, and H-H) activations. DFT calibration reference is generated from explicitly correlated coupled cluster CCSD(T)-F12 calculations, and the 4s4p core-valence correlation effect of the two 4d platinum group transition metals is also included. Generally, the errors of DFT methods for calculating energetics of Ru-/Rh-mediated reactions appear to correlate more with the magnitude of energetics itself than other factors such as metal identity. For activation energy calculations, the best performing functionals for both Ru and Rh systems are MN12SX < CAM-B3LYP < M06-L < MN12L < M06 < ωB97X < B3LYP < LC-ωPBE (in the order of increasing mean unsigned deviations, MUDs, of less than 2 kcal/mol). For reaction energy calculations, best functionals with MUDs less than 2 kcal/mol are PBE0 < CAM-B3LYP ≈ N12SX. The effect of the DFT empirical dispersion correction on the performance of the DFT methods is beneficial for most density functionals tested in this work, reducing their MUDs to different extents. After including empirical dispersion correction, ωB97XD, B3LYP-D3, and CAM-B3LYP-D3 (PBE0-D3, B3LYP-D3, and ωB97XD) are the three best performing DFs for activation energy (reaction energy) calculations, from which B3LYP-D3 and ωB97XD can notably be recommended uniformly for both the reaction energy and reaction barrier calculations. The good performance of B3LYP-D3 in quantitative description of the energetic trends further adds value to B3LYP-D3 and singles this functional out as a reasonable choice in the Ru/Rh-promoted σ-bond activation processes.

  5. [Hydrogen induced C-C, C-N, and C-S bond activities on Pi and Ni surfaces]: Summary

    SciTech Connect

    Gland, J.L.

    1994-12-31

    This document summarizes research applied to chemical bond activation studies. Topics summarized include: Carbon nitrogen bonds experimentation with aniline on Ni(111), Mi(100), and Pt(111) surfaces; carbon sulfur bonds experimentation with methanethiol, phenylthiol, and dimethyl disulfide on Pt(111) and Ni(111) surfaces; carbon-carbon bonds experimentation on Ni(100), Ni(111) and Pt(111) surfaces; and in-situ fluorescence yield near edge spectroscopy.

  6. Development of a method to accurately calculate the Dpb and quickly predict the strength of a chemical bond

    NASA Astrophysics Data System (ADS)

    Du, Xia; Zhao, Dong-Xia; Yang, Zhong-Zhi

    2013-02-01

    A new approach to characterize and measure bond strength has been developed. First, we propose a method to accurately calculate the potential acting on an electron in a molecule (PAEM) at the saddle point along a chemical bond in situ, denoted by Dpb. Then, a direct method to quickly evaluate bond strength is established. We choose some familiar molecules as models for benchmarking this method. As a practical application, the Dpb of base pairs in DNA along C-H and N-H bonds are obtained for the first time. All results show that C7-H of A-T and C8-H of G-C are the relatively weak bonds that are the injured positions in DNA damage. The significance of this work is twofold: (i) A method is developed to calculate Dpb of various sizable molecules in situ quickly and accurately; (ii) This work demonstrates the feasibility to quickly predict the bond strength in macromolecules.

  7. A new simple and fast thermally-solvent assisted method to bond PMMA-PMMA in micro-fluidics devices

    NASA Astrophysics Data System (ADS)

    Bamshad, Arshya; Nikfarjam, Alireza; Khaleghi, Hossein

    2016-06-01

    A rapid and simple thermally-solvent assisted method of bonding was introduced for poly(methyl methacrylate) (PMMA) based microfluidic substrates. The technique is a low-temperature (68 {}^\\circ \\text{C} ), and rapid (15 \\min ) bonding technique; in addition, only a fan-assisted oven with some paper clamps are used. Two different solvents (ethanol and isopropyl alcohol) with two different methods of cooling (one-step and three steps) were employed to determine the best solvent and method of cooling (residual stresses may be released in different cooling methods) by considering bonding strength and quality. In this bonding technique, a thin film of solvent between two PMMA sheets disperses tends to dissolve a thin film of PMMA sheet surface, then evaporate, and finally reconnect monomers of the PMMA sheets at the specific operating temperature. The operating temperature of this method comes from the coincidence of the solubility parameter graph of PMMA with the solubility parameter graph of the solvents. Different tests such as tensile strength test, deformation test, leakage tests, and surface characteristics tests were performed to find the optimum conditions for this bonding strategy. The best bonding quality and the highest bonding strength (28.47 \\text{MPa} ) occurred when 70% isopropyl alcohol solution was employed with the one-step cooling method. Furthermore, the bonding reversibility was taken into account and critical percentages for irreversible bonding were obtained for both of the solvents and methods. This method provides a perfect bonding quality for PMMA substrates, and can be used in laboratories without needing any expensive and special instruments, because of its merits such as lower bonding time, lower-cost, and higher strength etc in comparison with the majority of other common bonding techniques.

  8. Mechanism of a C-H bond activation reaction in room-temperature alkane solution

    SciTech Connect

    Bromberg, S.E.; Yang, H.; Asplund, M.C.

    1997-10-10

    Chemical reactions that break alkane carbon-hydrogen (C-H) bonds are normally carried out under conditions of high temperature and pressure because these bonds are extremely strong ({approx} 100 kilocalories per mole), but certain metal complexes can activate C-H bonds in alkane solution under the mild conditions of room temperature and pressure. Time-resolved infrared experiments probing the initial femtosecond dynamics through the nano- and microsecond kinetics to the final stable products have been used to generate a detailed picture of the C-H activation reaction. Structures of all of the intermediates involved in the reaction of Tp*Rh(CO){sub 2} (Tp* = HB-Pz{sub 3}*, Pz* = 3,5-di-methylpyrazolyl) in alkane solution have been identified and assigned, and energy barriers for each reaction step from solvation to formation of the final alkyl hydride product have been estimated from transient lifetimes. 27 refs., 6 figs.

  9. The mechanism of a C-H Bond Activation reaction in roomtemperature alkane solution

    SciTech Connect

    Bromberg, Steven E.; Yang, Haw; Asplund, Matthew C.; Lian, T.; McNamara, B.K.; Kotz, K.T.; Yeston, J.S.; Wilkens, M.; Frei, H.; Bergman,Robert G.; Harris, C.B.

    1997-07-31

    Chemical reactions that break alkane carbon-hydrogen (C-H) bonds are normally carried out under conditions of high temperature and pressure because these bonds are extremely strong ({approx}100 kilocalories per mole), but certain metal complexes can activate C-H bonds in alkane solution under the mild conditions of room temperature and pressure. Time-resolved infrared experiments probing the initial femtosecond dynamics through the nano- and microsecond kinetics to the final stable products have been used to generate a detailed picture of the C-H activation reaction. Structures of all of the intermediates involved in the reaction of Tp*Rh(CO)2 (Tp* = HB-Pz3*, Pz* = 3,5-dimethylpyrazolyl) in alkane solution have been identified and assigned, and energy barriers for each reaction step from solvation to formation of the final alkylhydride product have been estimated from transient lifetimes.

  10. Disulfide Bond Formation and Activation of Escherichia coli β-Galactosidase under Oxidizing Conditions

    PubMed Central

    Seras-Franzoso, Joaquin; Affentranger, Roman; Ferrer-Navarro, Mario; Daura, Xavier; Villaverde, Antonio

    2012-01-01

    Escherichia coli β-galactosidase is probably the most widely used reporter enzyme in molecular biology, cell biology, and biotechnology because of the easy detection of its activity. Its large size and tetrameric structure make this bacterial protein an interesting model for crystallographic studies and atomic mapping. In the present study, we investigate a version of Escherichia coli β-galactosidase produced under oxidizing conditions, in the cytoplasm of an Origami strain. Our data prove the activation of this microbial enzyme under oxidizing conditions and clearly show the occurrence of a disulfide bond in the β-galactosidase structure. Additionally, the formation of this disulfide bond is supported by the analysis of a homology model of the protein that indicates that two cysteines located in the vicinity of the catalytic center are sufficiently close for disulfide bond formation. PMID:22286993

  11. Adhesion to tooth structure: a critical review of "micro" bond strength test methods.

    PubMed

    Armstrong, Steve; Geraldeli, Saulo; Maia, Rodrigo; Raposo, Luís Henrique Araújo; Soares, Carlos José; Yamagawa, Junichiro

    2010-02-01

    The objective of this paper is to critically review the literature regarding the mechanics, geometry, load application and other testing parameters of "micro" shear and tensile adhesion tests, and to outline their advantages and limitations. The testing of multiple specimens from a single tooth conserves teeth and allows research designs not possible using conventional 'macro' methods. Specimen fabrication, gripping and load application methods, in addition to material properties of the various components comprising the resin-tooth adhesive bond, will influence the stress distribution and consequently, the nominal bond strength and failure mode. These issues must be understood; as should the limitations inherent to strength-based testing of a complicated adhesive bond joining dissimilar substrates, for proper test selection, conduct and interpretation. Finite element analysis and comprehensive reporting of test conduct and results will further our efforts towards a standardization of test procedures. For the foreseeable future, both "micro" and "macro" bond strength tests will, as well as various morphological and spectroscopic investigative techniques, continue to be important tools for improving resin-tooth adhesion to increase the service life of dental resin-based composite restorations.

  12. Ultrasonic bonding method for heterogeneous microstructures using self-balancing jig.

    PubMed

    Lee, Kyoung G; Shin, Sujeong; Kim, Byeong Il; Bae, Nam Ho; Lee, Moon-Keun; Lee, Seok Jae; Lee, Tae Jae

    2015-03-21

    Perfect sealing of heterogeneous microstructures in plastic-based microfluidic devices is a significant and urgent challenge to be able to apply them in various microfluidic-based applications, including biosensing, biofiltering, chemical reactors and lab-on-a-chip. In this study we report a simple but practical and effective method to bond a microstructure-incorporated microfluidic device using an ultrasonic bonding method. The specially designed hemisphere-shaped jig, which is called a self-balancing jig, provides a free motion in all x, y, and z directions. These unique properties of the jig allow us to precisely adjust and bond the heterogeneous microstructures in the device. A conventional jig shows in solution leakages around the heterogeneous microstructures while the self-balancing jig did not show any leakages in devices. Furthermore, the bonding performance was also confirmed by using a black ink and fluorescent dye solution. The micro-pillar arrays in the device also demonstrated its capability for selective filtering of microbeads. We believe that this technique would be a useful tool for producing microfluidic devices with heterogeneous microstructures.

  13. Merging allylic C-H bond activation and C-C bond cleavage en route to the formation of a quaternary carbon stereocenter in acyclic systems.

    PubMed

    Vasseur, Alexandre; Marek, Ilan

    2017-01-01

    This protocol describes a diastereoselective approach for the synthesis of complex molecular architectures containing two stereogenic centers in a 1,4 relationship, one of which being an all-carbon quaternary stereogenic center. Such molecules could be intermediates in the synthesis of steroids, for example. Conceived as a single-flask synthetic sequence from ω-ene cyclopropanes, the protocol involves a concerted allylic C-H and C-C bond activation promoted by the Negishi reagent (Cp2Zr(η(2)-butene)). This zirconium-promenade-based procedure affords bifunctionalized products in high diastereomeric ratios after reaction of ω-ene cyclopropanes with the Negishi complex, followed by a thermal treatment and sequential addition of two different electrophiles. The method proves to be particularly efficient when carbonyl compounds are used as first electrophiles and hydrogen or elemental halides are used as second electrophiles. In addition, it offers the opportunity to create new C-C bonds via remote functionalization of a (sp(3))-C-H bond, a result of a copper or copper/palladium transmetalation step that extends the scope of the process to alkyl, acyl and aromatic halide compounds as second electrophiles. The typical described protocol allows the synthesis of the highly diastereo-enriched 2-((1R*,2S*)-2-butyl-2 propylcyclopropyl)ethanol and may provide a new entry to access complex molecular segments of natural products such as steroids or C30 botryococcene. It requires a simple reaction setup and takes ∼18.5 h to run the reaction and 2 h for isolation and purification.

  14. Palladium(II)-Catalyzed C-H Bond Activation/C-C and C-O Bond Formation Reaction Cascade: Direct Synthesis of Coumestans.

    PubMed

    Neog, Kashmiri; Borah, Ashwini; Gogoi, Pranjal

    2016-12-02

    A palladium catalyzed cascade reaction of 4-hydroxycoumarins and in situ generated arynes has been developed for the direct synthesis of coumestans. This cascade strategy proceeds via C-H bond activation/C-O and C-C bond formations in a single reaction vessel. This methodology affords moderate to good yields of coumestans and is tolerant of a variety of functional groups including halide. The methodology was applied to the synthesis of natural product flemichapparin C.

  15. Diffusion Bonding Beryllium to Reduced Activation Ferritic Martensitic Steel: Development of Processes and Techniques

    NASA Astrophysics Data System (ADS)

    Hunt, Ryan Matthew

    Only a few materials are suitable to act as armor layers against the thermal and particle loads produced by magnetically confined fusion. These candidates include beryllium, tungsten, and carbon fiber composites. The armor layers must be joined to the plasma facing components with high strength bonds that can withstand the thermal stresses resulting from differential thermal expansion. While specific joints have been developed for use in ITER (an experimental reactor in France), including beryllium to CuCrZr as well as tungsten to stainless steel interfaces, joints specific to commercially relevant fusion reactors are not as well established. Commercial first wall components will likely be constructed front Reduced Activation Ferritic Martensitic (RAFM) steel, which will need to be coating with one of the three candidate materials. Of the candidates, beryllium is particularly difficult to bond, because it reacts during bonding with most elements to form brittle intermetallic compounds. This brittleness is unacceptable, as it can lead to interface crack propagation and delamination of the armor layer. I have attempted to overcome the brittle behavior of beryllium bonds by developing a diffusion bonding process of beryllium to RAFM steel that achieves a higher degree of ductility. This process utilized two bonding aids to achieve a robust bond: a. copper interlayer to add ductility to the joint, and a titanium interlayer to prevent beryllium from forming unwanted Be-Cu intermetallics. In addition, I conducted a series of numerical simulations to predict the effect of these bonding aids on the residual stress in the interface. Lastly, I fabricated and characterized beryllium to ferritic steel diffusion bonds using various bonding parameters and bonding aids. Through the above research, I developed a process to diffusion bond beryllium to ferritic steel with a 150 M Pa tensile strength and 168 M Pa shear strength. This strength was achieved using a Hot Isostatic

  16. An electrical test method for quality detecting of wafer level eutectic bonding

    NASA Astrophysics Data System (ADS)

    Zhang, Lemin; Jiao, Binbin; Ku, Will; Tseng, Li-Tien; Kong, Yanmei; Chien, Yu-Hao; Yun, Shichang; Chen, Dapeng

    2017-01-01

    As the costs of packaging and testing account for a substantial portion of microelectromechanical system (MEMS) devices, an effective and convenient characterization method is urgent to be investigated to lower the cost. In this paper, an electrical test method was utilized, and the test key used for a four-probe current-voltage test was designed to monitor the quality of the AuSn eutectic bonding. The electrical test can directly detect whether or not voids existed in the bonding layer. The difference in alloy state, for example, the existence of the (Au, Ni) 3Sn2 phase confirmed by the scanning electron microscope and energy dispersive x-ray spectroscopy test, can also be reflected by resistivity variation. The electrical test can be implemented automatically and conveniently unlike other characterization methods. Therefore, it is suitable to be applied in quality inspection in industrial production.

  17. Algebraic method of determining bond length of perovskite compounds doped with Mn 2+

    NASA Astrophysics Data System (ADS)

    Shuen, Wei-Li; Li, Zhao-Min

    1999-10-01

    An algebraic method is proposed for calculating the exponent n and constant K in the power law 10Dq= KR- n. By using this method, the values of n and K for the cubic perovskites KMnF 3 and RbMnF 3 are derived and then used to determine the true Mn 2+-F - bond length R in crystals of KMgF 3, KZnF 3, RbCdF 3, and CsCaF 3 doped with Mn 2+ from the reported optical spectra. The results obtained are in good agreement with those derived from the electron paramagnetic resonance data and the extended X-ray absorption fine structure techniques. Thus, as a new theoretical method, it is valuable and convenient for the determination of the bond lengths.

  18. 78 FR 66038 - Agency Information Collection Activities: Application for Exportation of Articles Under Special Bond

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-11-04

    ... SECURITY U. S. Customs and Border Protection Agency Information Collection Activities: Application for Exportation of Articles Under Special Bond AGENCY: U.S. Customs and Border Protection, Department of Homeland...: 1651-0004. SUMMARY: U.S. Customs and Border Protection (CBP) of the Department of Homeland...

  19. 77 FR 26024 - Agency Information Collection Activities: Bonded Warehouse Proprietor's Submission

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-05-02

    ... Management and Budget. Comments should be addressed to the OMB Desk Officer for U.S. Customs and Border... Doc No: 2012-10522] DEPARTMENT OF HOMELAND SECURITY U.S. Customs and Border Protection Agency Information Collection Activities: Bonded Warehouse Proprietor's Submission AGENCY: U.S. Customs and...

  20. 26 CFR 1.103(n)-3T - Private activity bond limit (temporary).

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... City Q in any prior year made a carryforward election for the pollution control facility, (v) The... containing constitutional home rule cities. Q-2: What is the private activity bond limit for a State agency... create an issuing authority empowered to issue obligations to provide pollution control facilities...

  1. 26 CFR 1.103(n)-3T - Private activity bond limit (temporary).

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... City Q in any prior year made a carryforward election for the pollution control facility, (v) The... containing constitutional home rule cities. Q-2: What is the private activity bond limit for a State agency... create an issuing authority empowered to issue obligations to provide pollution control facilities...

  2. Effect of Four Methods of Surface Treatment on Shear Bond Strength of Orthodontic Brackets to Zirconium

    PubMed Central

    Yassaei, Soghra; Aghili, Hossein Agha; Davari, Abdolrahim

    2015-01-01

    Objectives: Providing reliable attachment between bracket base and zirconia surface is a prerequisite for exertion of orthodontic force. The purpose of the present study was to evaluate the effect of four zirconium surface treatment methods on shear bond strength (SBS) of orthodontic brackets. Materials and Methods: One block of zirconium was trimmed into four zirconium surfaces, which served as our four study groups and each had 18 metal brackets bonded to them. Once the glazed layer was removed, the first group was etched with 9.6% hydrofluoric acid (HF), and the remaining three groups were prepared by means of sandblasting and 1W, and 2W Er: YAG laser, respectively. After application of silane, central incisor brackets were bonded to the zirconium surfaces. The SBS values were measured by a Dartec testing machine with a crosshead speed of 1 mm/min. Data were analyzed using one-way ANOVA and Tukey’s HSD for multiple comparisons. Results: The highest SBS was achieved in the sandblasted group (7.81±1.02 MPa) followed in a descending order by 2W laser group (6.95±0.87 MPa), 1W laser group (6.87±0.92 MPa) and HF acid etched group (5.84±0.78 MPa). The differences between the study groups were statistically significant except between the laser groups (P<0.05). Conclusion: In terms of higher bond strength and safety, sandblasting and Er: YAG laser irradiation with power output of 1W and 2W can be considered more appropriate alternatives to HF acid etching for zirconium surface treatment prior to bracket bonding. PMID:26622283

  3. A fusion of the closed-shell coupled cluster singles and doubles method and valence-bond theory for bond breaking.

    PubMed

    Small, David W; Head-Gordon, Martin

    2012-09-21

    Closed-shell coupled cluster singles and doubles (CCSD) is among the most important of electronic-structure methods. However, it fails qualitatively when applied to molecular systems with more than two strongly correlated electrons, such as those with stretched or broken covalent bonds. We show that it is possible to modify the doubles amplitudes to obtain a closed-shell CCSD method that retains the computational cost and desirable features of standard closed-shell CCSD, e.g., correct spin symmetry, size extensivity, orbital invariance, etc., but produces greatly improved energies upon bond dissociation of multiple electron pairs; indeed, under certain conditions the dissociation energies are exact.

  4. Investigation of the hydrogen bonding in ice Ih by first-principles density function methods.

    PubMed

    Zhang, P; Tian, L; Zhang, Z P; Shao, G; Li, J C

    2012-07-28

    It is a well recognized difficult task to simulate the vibrational dynamics of ices using the density functional theory (DFT), and there has thus been rather limited success in modelling the inelastic neutron scattering (INS) spectra for even the simplest structure of ice, ice Ih, particularly in the translational region below 400 cm(-1). The reason is partly due to the complex nature of hydrogen bonding (H-bond) among water-water molecules which require considerable improvement of the quantum mechanical simulation methods, and partly owing to the randomness of protons in ice structures which often requires simulation of large super-lattices. In this report, we present the first series of successful simulation results for ice Ih using DFT methods. On the basis of the recent advancement in the DFT programs, we have achieved for the first time theoretical outcomes that not only reproduce the rotational frequencies between 500 to 1200 cm(-1) for ice Ih, but also the two optic peaks at ∼240 and 320 cm(-1) in the translational region of the INS spectra [J. C. Li, J. Chem. Phys 105, 6733 (1996)]. Besides, we have also investigated the impact of pairwise configurations of H(2)O molecules on the H-bond and found that different proton arrangements of pairwise H(2)O in the ice Ih crystal lattice could not alter the nature of H-bond as significantly as suggested in an early paper [J. C. Li and D. K. Ross, Nature (London) 365, 327 (1993)], i.e., reproducing the two experimental optic peaks do not need to invoke the two H-bonds as proposed in the previous model which led to considerable debates. The results of this work suggest that the observed optic peaks may be attributed to the coupling between the two bands of H-O stretching modes in H(2)O. The current computational work is expected to shed new light on the nature of the H-bonds in water, and in addition to offer a new approach towards probing the interaction between water and biomaterials for which H-bond is essential.

  5. Hydrogen-bond-assisted activation of allylic alcohols for palladium-catalyzed coupling reactions.

    PubMed

    Gumrukcu, Yasemin; de Bruin, Bas; Reek, Joost N H

    2014-03-01

    We report direct activation of allylic alcohols using a hydrogen-bond-assisted palladium catalyst and use this for alkylation and amination reactions. The novel catalyst comprises a palladium complex based on a functionalized monodentate phosphoramidite ligand in combination with urea additives and affords linear alkylated and aminated allylic products selectively. Detailed kinetic analysis show that oxidative addition of the allyl alcohol is the rate-determining step, which is facilitated by hydrogen bonds between the alcohol, the ligand functional group, and the additional urea additive.

  6. Effect of activation mode on shear bond strength of metallic brackets.

    PubMed

    Correr, Américo Bortolazzo; Costa, Ana Rosa; Lucato, Adriana Simoni; Vedovello, Silvia Amélia; Valdrighi, Heloísa Cristina; Vedovello Filho, Mário; Correr-Sobrinho, Lourenço

    2013-01-01

    The aim of this study was to evaluate the shear bond strength (SBS) of metallic orthodontic brackets bonded to bovine teeth using light-activated or chemically activated composite resins. One hundred and twenty bovine mandibular incisors were divided into 6 groups (n=20), according to the bonding materials: Transbond XT (T); Enforce Dual (ED); Enforce chemical (EC); Enforce Light-activated (EL); Concise Orthodontic (C); and RelyX Unicem Capsule (UN). Metallic brackets were positioned and firmly bonded to the teeth. Light-activation for T, ED, EL and UN was carried out with four exposures on each side of the bracket with 20 s total exposure times using XL2500 (3M ESPE). EC and C were chemically cured. Next, all specimens were stored in deionized water at 37 °C for 24 h. The shear bond strength was carried out at a crosshead speed of 1.0 mm/min. Data were subjected to one-way ANOVA and Tukey's test (α=0.05). The adhesive remnant index (ARI) was evaluated at 8× magnification. C (17.72 ± 4.45) presented significantly higher SBS means (in MPa) than the other groups (p<0.05), followed by EC (11.97 ± 5.77) and ED (10.57 ± 1.32). EL (5.39 ± 1.06) and UN (4.32 ± 1.98) showed the lowest SBS means, while T (9.09 ± 2.56) showed intermediate values. For ARI, there was a predominance of score 0 for EC, C and UN, and score 3 for T, ED and EL. In conclusion, the activation mode influenced the SBS.

  7. The effect of methyl-donated hydrogen bonding on active site conformations of hyaluronate lyase

    NASA Astrophysics Data System (ADS)

    Migues, Angela N.; Vergenz, Robert A.; Moore, Kevin B.

    2010-03-01

    Geometric evidence shows a val-A252 methyl-donated (MD) hydrogen bond (HB) in hyaluronate lyase (Streptococcus pneumoniae) interacts with nearby NH--O and OH--O HBs, distorting active-site helical structure. Results for model fragment A248-254 are based on experimental heavy atom positions with ab initio hydrogen atoms. The MDHB, with (H-O distance, donor-H-O angle) = (2.3å; 174^o), exhibits more favorable geometry than thr-A253 OH--O HB (1.8å; 170^o) to the same ala-249 C=O. Consequently, thr-253 N-H--O interaction is forced closer to lys-250 C=O than ala-249 C=O(2.6 versus 2.7å). A novel method has been developed to quantify the effects of atomic diplacements on motions of neighboring helices. A coordinate system was established to track the movement of specific residues and to ascertain the effect of such motions on active site conformations.

  8. Bond of acrylic teeth to different denture base resins after various surface-conditioning methods.

    PubMed

    Lang, Reinhold; Kolbeck, Carola; Bergmann, Rainer; Handel, Gerhard; Rosentritt, Martin

    2012-02-01

    The study examined the bond between different denture base resins and highly cross-linked acrylic denture teeth with different base surface-conditioning methods. One hundred fifty highly cross-linked resin denture teeth (SR-Antaris, No. 11, Ivoclar-Vivadent, FL) were divided into five groups with different surface-conditioning methods of the base surfaces of the teeth (C = control, no surface conditioning, MM = application of methyl methacrylate monomer, SB = sand blasting, SBB = sand blasting + bonding agent, TSS = tribochemical silica coating + silanization). Teeth were bonded to either a cold-cured denture base resin (ProBase Cold, Ivoclar-Vivadent, FL) or heat-cured denture base resins (SR Ivocap Plus, Ivoclar-Vivadent, FL and Lucitone 199, Dentsply, USA). After 24 h of storage in distilled water, compressive load was applied at 90° on the palatal surface of each tooth until fracture. Median failure load ranged between 103 and 257 N for Probase Cold groups, 91 to 261 N for Lucitone 199, and 149 to 320 N for SR Ivocap Plus. For Probase Cold, significant highest failure loads resulted when teeth were treated with SB, SBB, or TSS. For Lucitone 199, significant highest failure loads has been found with MM and TSS treatment. For SR Ivocap Plus, highest failure loads resulted using SBB and TSS. Conditioning of the base surfaces of the teeth prior to denture base processing is highly recommended. Tooth bond is significantly affected by the surface-conditioning method and applied denture base resin. Tribochemical silica coating + silanization method can be recommended for pre-treatment of teeth applying either heat-cured or cold-cured denture base resin.

  9. Joint strength measurements of individual fiber-fiber bonds: An atomic force microscopy based method

    NASA Astrophysics Data System (ADS)

    Schmied, Franz J.; Teichert, Christian; Kappel, Lisbeth; Hirn, Ulrich; Schennach, Robert

    2012-07-01

    We are introducing a method to measure tensile strength of individual fiber-fiber bonds within a breaking force range of 0.01 mN-1 mN as well as the energy consumed during breaking. Until now, such a method was not available. Using a conventional atomic force microscope and a specifically designed sample holder, the desired force and the breaking behavior can be analyzed by two different approaches. First, dynamic loading can be applied, where force-versus-distance curves are employed to determine the proportions of elastic energy and energy dissipated in the bond. Second, static loading is utilized to study viscoelastic behavior and calculate viscoelastic energy contributions. To demonstrate the capability of the proposed method, we are presenting results for breaking strength of kraft pulp fiber-fiber bonds in tensile opening mode. The procedure is by no means restricted to cellulose fibers, it has the potential to quantify joint strength of micrometer-sized fibers in general.

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

    SciTech Connect

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan

    2008-02-04

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

  11. 26 CFR 1.103(n)-2T - Private activity bond defined (temporary).

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...(n)-2T Section 1.103(n)-2T Internal Revenue INTERNAL REVENUE SERVICE, DEPARTMENT OF THE TREASURY....103(n)-2T Private activity bond defined (temporary). Q-1: What is the definition of the term “private activity bond”? A-1: In general, for purposes of §§ 1.103(n)-1T through 1.103(n)-6T, the term...

  12. Comparison of DFT with Traditional Methods for the Calculation of Vibrational Frequencies and Bond Energies

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W.; Arnold, James O. (Technical Monitor)

    1997-01-01

    The vibrational frequencies of MO2 are computed at many levels of theory, including HF, B3LYP, BP86, CASSCF, MP2, and CCSD(T). The computed results are compared with the available experimental results. Most of the methods fail for at least one state of the systems considered. The accuracy of the results and the origin of the observed failures are discussed. The B3LYP bond energies are compared with traditional methods for a variety of systems, ranging from FeCOn+ to SiCln and its positive ions. The cases where B3LYP differs from the traditional methods are discussed.

  13. Systems, Apparatuses, and Methods for Using Durable Adhesively Bonded Joints for Sandwich Structures

    NASA Technical Reports Server (NTRS)

    Smeltzer, III, Stanley S. (Inventor); Lundgren, Eric C. (Inventor)

    2014-01-01

    Systems, methods, and apparatus for increasing durability of adhesively bonded joints in a sandwich structure. Such systems, methods, and apparatus includes an first face sheet and an second face sheet as well as an insert structure, the insert structure having a first insert face sheet, a second insert face sheet, and an insert core material. In addition, sandwich core material is arranged between the first face sheet and the second face sheet. A primary bondline may be coupled to the face sheet(s) and the splice. Further, systems, methods, and apparatus of the present disclosure advantageously reduce the load, provide a redundant path, reduce structural fatigue, and/or increase fatigue life.

  14. A Single-Lap Joint Adhesive Bonding Optimization Method Using Gradient and Genetic Algorithms

    NASA Technical Reports Server (NTRS)

    Smeltzer, Stanley S., III; Finckenor, Jeffrey L.

    1999-01-01

    A natural process for any engineer, scientist, educator, etc. is to seek the most efficient method for accomplishing a given task. In the case of structural design, an area that has a significant impact on the structural efficiency is joint design. Unless the structure is machined from a solid block of material, the individual components which compose the overall structure must be joined together. The method for joining a structure varies depending on the applied loads, material, assembly and disassembly requirements, service life, environment, etc. Using both metallic and fiber reinforced plastic materials limits the user to two methods or a combination of these methods for joining the components into one structure. The first is mechanical fastening and the second is adhesive bonding. Mechanical fastening is by far the most popular joining technique; however, in terms of structural efficiency, adhesive bonding provides a superior joint since the load is distributed uniformly across the joint. The purpose of this paper is to develop a method for optimizing single-lap joint adhesive bonded structures using both gradient and genetic algorithms and comparing the solution process for each method. The goal of the single-lap joint optimization is to find the most efficient structure that meets the imposed requirements while still remaining as lightweight, economical, and reliable as possible. For the single-lap joint, an optimum joint is determined by minimizing the weight of the overall joint based on constraints from adhesive strengths as well as empirically derived rules. The analytical solution of the sin-le-lap joint is determined using the classical Goland-Reissner technique for case 2 type adhesive joints. Joint weight minimization is achieved using a commercially available routine, Design Optimization Tool (DOT), for the gradient solution while an author developed method is used for the genetic algorithm solution. Results illustrate the critical design variables

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

    SciTech Connect

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

    2008-05-30

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

  16. Pi Bond Orders and Bond Lengths

    ERIC Educational Resources Information Center

    Herndon, William C.; Parkanyi, Cyril

    1976-01-01

    Discusses three methods of correlating bond orders and bond lengths in unsaturated hydrocarbons: the Pauling theory, the Huckel molecular orbital technique, and self-consistent-field techniques. (MLH)

  17. HAp/Ti2Ni coatings of high bonding strength on Ti-6Al-4V prepared by the eutectic melting bonding method.

    PubMed

    Ye, Ya-Jing; Wang, Peng-Yan; Li, Ya-Peng; Yin, Da-Chuan

    2015-02-01

    Eutectic melting bonding (EMB) method is a useful technique for fabricating bioactive coatings with relatively high crystallinity and bonding strength with substrate on titanium substrates. Using the EMB method, hydroxyapatite/Ti2Ni coatings were prepared on the surface of Ti-6Al-4V at a relatively low temperature (1,050 °C) in a vacuum furnace. The coatings were then characterized in terms of phase components, microstructure, bonding strength and cytotoxicity. The results showed that the coatings were mainly composed of HAp and Ti2Ni, and the thickness of the coatings was approximately 300 μm. X-ray diffraction analysis showed that the coatings exhibited relatively high crystallinity. The tensile bonding strength between the coatings and the substrates was 69.68±5.15 MPa. The coatings had a porous and rough surface which is suitable for cell attachment and filopodia growth. The cell culture study showed that the number of MG-63 cells increased, and the cell morphology changed with the incubation time. This study showed that the EMB method can be utilized as a potentially powerful method to obtain high quality hydroxyapatite coatings with desired mechanical and biocompatibility properties on Ti-alloy substrates.

  18. The active site of hen egg-white lysozyme: flexibility and chemical bonding

    SciTech Connect

    Held, Jeanette Smaalen, Sander van

    2014-04-01

    Chemical bonding at the active site of lysozyme is analyzed on the basis of a multipole model employing transferable multipole parameters from a database. Large B factors at low temperatures reflect frozen-in disorder, but therefore prevent a meaningful free refinement of multipole parameters. Chemical bonding at the active site of hen egg-white lysozyme (HEWL) is analyzed on the basis of Bader’s quantum theory of atoms in molecules [QTAIM; Bader (1994 ▶), Atoms in Molecules: A Quantum Theory. Oxford University Press] applied to electron-density maps derived from a multipole model. The observation is made that the atomic displacement parameters (ADPs) of HEWL at a temperature of 100 K are larger than ADPs in crystals of small biological molecules at 298 K. This feature shows that the ADPs in the cold crystals of HEWL reflect frozen-in disorder rather than thermal vibrations of the atoms. Directly generalizing the results of multipole studies on small-molecule crystals, the important consequence for electron-density analysis of protein crystals is that multipole parameters cannot be independently varied in a meaningful way in structure refinements. Instead, a multipole model for HEWL has been developed by refinement of atomic coordinates and ADPs against the X-ray diffraction data of Wang and coworkers [Wang et al. (2007), Acta Cryst. D63, 1254–1268], while multipole parameters were fixed to the values for transferable multipole parameters from the ELMAM2 database [Domagala et al. (2012), Acta Cryst. A68, 337–351] . Static and dynamic electron densities based on this multipole model are presented. Analysis of their topological properties according to the QTAIM shows that the covalent bonds possess similar properties to the covalent bonds of small molecules. Hydrogen bonds of intermediate strength are identified for the Glu35 and Asp52 residues, which are considered to be essential parts of the active site of HEWL. Furthermore, a series of weak C

  19. Chitosan-Copper (II) complex as antibacterial agent: synthesis, characterization and coordinating bond- activity correlation study

    NASA Astrophysics Data System (ADS)

    Mekahlia, S.; Bouzid, B.

    2009-11-01

    The antimicrobial activity of chitosan is unstable and sensitive to many factors such as molecular weight. Recent investigations showed that low molecular weight chitosan exhibited strong bactericidal activities compared to chitosan with high molecular weight. Since chitosan degradation can be caused by the coordinating bond, we attempt to synthesize and characterize the chitosan-Cu (II) complex, and thereafter study the coordinating bond effect on its antibacterial activity against Salmonella enteritidis. Seven chitosan-copper complexes with different copper contents were prepared and characterized by FT-IR, UV-vis, XRD and atomic absorption spectrophotometry (AAS). Results indicated that for chitosan-Cu (II) complexes with molar ratio close to 1:1, the inhibition rate reached 100%.

  20. Influence of Adhesives and Methods of Enamel Pretreatment on the Shear Bond Strength of Orthodontic Brackets

    PubMed Central

    Jurišić, Sanja; Jurišić, Gordan

    2015-01-01

    Aim The objective of present study was to examine influence of adhesives and methods of enamel pretreatment on the shear bond strength (SBS) of orthodontic brackets. The adhesives used were resin-reinforced glass ionomer cements-GIC (Fuji Ortho LC) and composite resin (Transbond XT). Material and Methods The experimental sample consisted of 80 extracted human first premolars. The sample was divided into four equal groups, and the metal brackets were bonded with different enamel pretreatments by using two adhesives: group A-10% polyacrylic acid; Fuji Ortho LC, group B–37% phosphoric acid; Fuji Ortho LC, group C–self etching primer; Transbond XT, group D–37% phosphoric acid, primer; Transbond XT. SBS of brackets was measured. After debonding of brackets, the adhesive remnant index (ARI) was evaluated. Results After the statistical analysis of the collected data was performed (ANOVA; Sheffe post-hoc test), the results showed that significantly lower SBS of the group B was found in relation to the groups C (p=0.031) and D (p=0.026). The results of ARI were similar in all testing groups and it was not possible to determine any statistically significant difference of the ARI (Chi- square test) between all four experimental groups. Conclusion The conclusion is that the use of composite resins material with appropriate enamel pretreatment according to manufacturer’s recommendation is the “gold standard” for brackets bonding for fixed orthodontic appliances. PMID:27688410

  1. Chemical methods and approaches to the regioselective formation of multiple disulfide bonds.

    PubMed

    Shimamoto, Shigeru; Katayama, Hidekazu; Okumura, Masaki; Hidaka, Yuji

    2014-04-01

    Disulfide-bond formation plays an important role in the stabilization of the native conformation of peptides and proteins. In the case of multidisulfide-containing peptides and proteins, numerous folding intermediates are produced, including molecules that contain non-native and native disulfide bonds during in vitro folding. These intermediates can frequently be trapped covalently during folding and subsequently analyzed. The structural characterization of these kinetically trapped disulfide intermediates provides a clue to understanding the oxidative folding pathway. To investigate the folding of disulfide-containing peptides and proteins, in this unit, chemical methods are described for regulating regioselective disulfide formation (1) by using a combination of several types of thiol protecting groups, (2) by incorporating unique SeCys residues into a protein or peptide molecule, and (3) by combining with post-translational modification.

  2. A Valence-Bond/Hartree Fock method to determine the Hubbard transfer integrals in organic conductors

    NASA Astrophysics Data System (ADS)

    Castet, F.; Ducasse, L.; Fritsch, A.

    1998-06-01

    In previous reports [F. Castet, A. Fritsch, L. Ducasse, J. Phys. (Paris) I, 6 (1996) 583; L. Ducasse, A. Fritsch, F. Castet, Synth. Metals 85 (1997) 1627], we presented a new mixed Valence-Bond/Hartree-Fock (VB/HF) method to extract the Extended Hubbard Coulombic parameters in organic conductors. In our approach, calculations (restricted to all valence electrons) are performed on finite size clusters using crystal data and molecular orbitals (MOs) localised on fragments. The optimized MOs depend on the charge of the fragment. The present paper describes the calculation scheme for matrix elements between distinct Valence-Bond configurations involved in charge transfer processes, i.e. the transfer integrals. Calculations were performed for different representative salts with either quasi one-dimensional or two-dimensional character, using different semi-empirical hamiltonians.

  3. Method of applying a bond coating and a thermal barrier coating on a metal substrate, and related articles

    DOEpatents

    Hasz, Wayne Charles; Borom, Marcus Preston

    2002-01-01

    A method for applying at least one bond coating on a surface of a metal-based substrate is described. A foil of the bond coating material is first attached to the substrate surface and then fused thereto, e.g., by brazing. The foil is often initially prepared by thermally spraying the bond coating material onto a removable support sheet, and then detaching the support sheet. Optionally, the foil may also include a thermal barrier coating applied over the bond coating. The substrate can be a turbine engine component.

  4. Method for applying a high-temperature bond coat on a metal substrate, and related compositions and articles

    DOEpatents

    Hasz, Wayne Charles; Sangeeta, D

    2002-01-01

    A method for applying a bond coat on a metal-based substrate is described. A slurry which contains braze material and a volatile component is deposited on the substrate. The slurry can also include bond coat material. Alternatively, the bond coat material can be applied afterward, in solid form or in the form of a second slurry. The slurry and bond coat are then dried and fused to the substrate. A repair technique using this slurry is also described, along with related compositions and articles.

  5. Method for applying a high-temperature bond coat on a metal substrate, and related compositions and articles

    DOEpatents

    Hasz, Wayne Charles; Sangeeta, D

    2006-04-18

    A method for applying a bond coat on a metal-based substrate is described. A slurry which contains braze material and a volatile component is deposited on the substrate. The slurry can also include bond coat material. Alternatively, the bond coat material can be applied afterward, in solid form or in the form of a second slurry. The slurry and bond coat are then dried and fused to the substrate. A repair technique using this slurry is also described, along with related compositions and articles.

  6. Solution structure and activity of the synthetic four-disulfide bond Mediterranean mussel defensin (MGD-1).

    PubMed

    Yang, Y S; Mitta, G; Chavanieu, A; Calas, B; Sanchez, J F; Roch, P; Aumelas, A

    2000-11-28

    MGD-1 is a 39-residue defensin-like peptide isolated from the edible Mediterranean mussel, Mytilus galloprovincialis. This peptide is characterized by the presence of four disulfide bonds. We report here its solid-phase synthesis and an easy way to improve the yield of the four native disulfide bonds. Synthetic and native MGD-1 display similar antibacterial activity, suggesting that the hydroxylation of Trp28 observed in native MGD-1 is not involved in the antimicrobial effect. The three-dimensional solution structure of MGD-1 has been established using (1)H NMR and mainly consists of a helical part (Asn7-Ser16) and two antiparallel beta-strands (Arg20-Cys25 and Cys33-Arg37), together giving rise to the common cystine-stabilized alpha-beta motif frequently observed in scorpion toxins. In MGD-1, the cystine-stabilized alpha-beta motif is stabilized by four disulfide bonds (Cys4-Cys25, Cys10-Cys33, Cys14-Cys35, and Cys21-Cys38), instead of by the three disulfide bonds commonly found in arthropod defensins. Except for the Cys21-Cys38 disulfide bond which is solvent-exposed, the three others belong to the particularly hydrophobic core of the highly constrained structure. Moreover, the C4-P5 amide bond in the cis conformation characterizes the MGD-1 structure. MGD-1 and insect defensin A possess similar bactericidal anti-Gram-positive activity, suggesting that the fourth disulfide bond of MGD-1 is not essential for the biological activity. In agreement with the general features of antibacterial peptides, the MGD-1 and defensin A structures display a typical distribution of positively charged and hydrophobic side chains. The positively charged residues of MGD-1 are located in three clusters. For these two defensin peptides isolated from insects and mollusks, it appears that the rather well conserved location of certain positively charged residues and of the large hydrophobic cluster are enough to generate the bactericidal potency and the Gram-positive specificity.

  7. Photochemistry of hydrogen bonded heterocycles probed by photodissociation experiments and ab initio methods.

    PubMed

    Slavíček, Petr; Fárník, Michal

    2011-07-14

    In this perspective article, we focus on the photochemistry of five-membered nitrogen containing heterocycles (pyrrole, imidazole and pyrazole) in clusters. These heterocycles represent paradigmatic structures for larger biologically active heterocyclic molecules and complexes. The dimers of the three molecules are also archetypes of different bonding patterns: N-H···π interaction, N-H···N hydrogen bond and double hydrogen bond. We briefly review available data on photochemistry of the title molecules in the gas phase, but primarily we focus on the new reaction channels opened upon the complexation with other heterocycles or solvent molecules. Based on ab initio calculations we discuss various possible reactions in the excited states of the clusters: (1) hydrogen dissociation, (2) hydrogen transfer between the heterocyclic units, (3) molecular ring distortion, and (4) coupled electron-proton transfer. The increasing photostability with complexity of the system can be inferred from experiments with photodissociation in these clusters. A unified view on photoinduced processes in five-membered N-heterocycles is provided. We show that even though different deactivation channels are energetically possible for the complexed heterocycles, in most cases the major result is a fast reconstruction of the ground state. The complexed or solvated heterocycles are thus inherently photostable although the stability can in principle be achieved via different reaction routes.

  8. Papain-catalyzed peptide bond formation: enzyme-specific activation with guanidinophenyl esters.

    PubMed

    de Beer, Roseri J A C; Zarzycka, Barbara; Amatdjais-Groenen, Helene I V; Jans, Sander C B; Nuijens, Timo; Quaedflieg, Peter J L M; van Delft, Floris L; Nabuurs, Sander B; Rutjes, Floris P J T

    2011-09-19

    The substrate mimetics approach is a versatile method for small-scale enzymatic peptide-bond synthesis in aqueous systems. The protease-recognized amino acid side chain is incorporated in an ester leaving group, the substrate mimetic. This shift of the specific moiety enables the acceptance of amino acids and peptide sequences that are normally not recognized by the enzyme. The guanidinophenyl group (OGp), a known substrate mimetic for the serine proteases trypsin and chymotrypsin, has now been applied for the first time in combination with papain, a cheap and commercially available cysteine protease. To provide insight in the binding mode of various Z-X(AA)-OGp esters, computational docking studies were performed. The results strongly point at enzyme-specific activation of the OGp esters in papain through a novel mode of action, rather than their functioning as mimetics. Furthermore, the scope of a model dipeptide synthesis was investigated with respect to both the amino acid donor and the nucleophile. Molecular dynamics simulations were carried out to prioritize 22 natural and unnatural amino acid donors for synthesis. Experimental results correlate well with the predicted ranking and show that nearly all amino acids are accepted by papain.

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

    SciTech Connect

    LICHTENBERGER, DENNIS L.

    2002-03-26

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

  10. Electrostatic and Charge-Induced Methane Activation by a Concerted Double C-H Bond Insertion.

    PubMed

    Geng, Caiyun; Li, Jilai; Weiske, Thomas; Schlangen, Maria; Shaik, Sason; Schwarz, Helmut

    2017-02-01

    A mechanistically unique, simultaneous activation of two C-H bonds of methane has been identified during the course of its reaction with the cationic copper carbide, [Cu-C](+). Detailed high-level quantum chemical calculations support the experimental findings obtained in the highly diluted gas phase using FT-ICR mass spectrometry. The behavior of [Cu-C](+)/CH4 contrasts that of [Au-C](+)/CH4, for which a stepwise bond-activation scenario prevails. An explanation for the distinct mechanistic differences of the two coinage metal complexes is given. It is demonstrated that the coupling of [Cu-C](+) with methane to form ethylene and Cu(+) is modeled very well by the reaction of a carbon atom with methane mediated by an oriented external electric field of a positive point charge.

  11. Catalytic intermolecular amination of C-H bonds: method development and mechanistic insights.

    PubMed

    Fiori, Kristin Williams; Du Bois, J

    2007-01-24

    Reaction methodology for intermolecular C-H amination of benzylic and 3 degrees C-H bonds is described. This process uses the starting alkane as the limiting reagent, gives optically pure tetrasubstituted amines through stereospecific insertion into enantiomeric 3 degrees centers, displays high chemoselectivity for benzylic oxidation, and enables the facile preparation of isotopically enriched 15N-labeled compounds. Access to substituted amines, amino alcohols, and diamines is thereby made possible in a single transformation. Important information relevant to understanding the initial steps in the catalytic cycle, reaction chemoselectivity, the nature of the active oxidant, and pathways for catalyst inactivation has been gained through mechanistic analysis; these studies are also presented.

  12. Carbon-Carbon Bond Cleavage in Activation of the Prodrug Nabumetone

    PubMed Central

    Varfaj, Fatbardha; Zulkifli, Siti N. A.; Park, Hyoung-Goo; Challinor, Victoria L.; De Voss, James J.

    2014-01-01

    Carbon-carbon bond cleavage reactions are catalyzed by, among others, lanosterol 14-demethylase (CYP51), cholesterol side-chain cleavage enzyme (CYP11), sterol 17β-lyase (CYP17), and aromatase (CYP19). Because of the high substrate specificities of these enzymes and the complex nature of their substrates, these reactions have been difficult to characterize. A CYP1A2-catalyzed carbon-carbon bond cleavage reaction is required for conversion of the prodrug nabumetone to its active form, 6-methoxy-2-naphthylacetic acid (6-MNA). Despite worldwide use of nabumetone as an anti-inflammatory agent, the mechanism of its carbon-carbon bond cleavage reaction remains obscure. With the help of authentic synthetic standards, we report here that the reaction involves 3-hydroxylation, carbon-carbon cleavage to the aldehyde, and oxidation of the aldehyde to the acid, all catalyzed by CYP1A2 or, less effectively, by other P450 enzymes. The data indicate that the carbon-carbon bond cleavage is mediated by the ferric peroxo anion rather than the ferryl species in the P450 catalytic cycle. CYP1A2 also catalyzes O-demethylation and alcohol to ketone transformations of nabumetone and its analogs. PMID:24584631

  13. Carbon-carbon bond cleavage in activation of the prodrug nabumetone.

    PubMed

    Varfaj, Fatbardha; Zulkifli, Siti N A; Park, Hyoung-Goo; Challinor, Victoria L; De Voss, James J; Ortiz de Montellano, Paul R

    2014-05-01

    Carbon-carbon bond cleavage reactions are catalyzed by, among others, lanosterol 14-demethylase (CYP51), cholesterol side-chain cleavage enzyme (CYP11), sterol 17β-lyase (CYP17), and aromatase (CYP19). Because of the high substrate specificities of these enzymes and the complex nature of their substrates, these reactions have been difficult to characterize. A CYP1A2-catalyzed carbon-carbon bond cleavage reaction is required for conversion of the prodrug nabumetone to its active form, 6-methoxy-2-naphthylacetic acid (6-MNA). Despite worldwide use of nabumetone as an anti-inflammatory agent, the mechanism of its carbon-carbon bond cleavage reaction remains obscure. With the help of authentic synthetic standards, we report here that the reaction involves 3-hydroxylation, carbon-carbon cleavage to the aldehyde, and oxidation of the aldehyde to the acid, all catalyzed by CYP1A2 or, less effectively, by other P450 enzymes. The data indicate that the carbon-carbon bond cleavage is mediated by the ferric peroxo anion rather than the ferryl species in the P450 catalytic cycle. CYP1A2 also catalyzes O-demethylation and alcohol to ketone transformations of nabumetone and its analogs.

  14. Method and system for evaluating integrity of adherence of a conductor bond to a mating surface of a substrate

    DOEpatents

    Telschow, K.L.; Siu, B.K.

    1996-07-09

    A method of evaluating integrity of adherence of a conductor bond to a substrate includes: (a) impinging a plurality of light sources onto a substrate; (b) detecting optical reflective signatures emanating from the substrate from the impinged light; (c) determining location of a selected conductor bond on the substrate from the detected reflective signatures; (d) determining a target site on the selected conductor bond from the detected reflective signatures; (e) optically imparting an elastic wave at the target site through the selected conductor bond and into the substrate; (f) optically detecting an elastic wave signature emanating from the substrate resulting from the optically imparting step; and (g) determining integrity of adherence of the selected conductor bond to the substrate from the detected elastic wave signature emanating from the substrate. A system is disclosed which is capable of conducting the method. 13 figs.

  15. Palladium-Catalyzed Dearomative Cyclocarbonylation by C-N Bond Activation.

    PubMed

    Yu, Hui; Zhang, Guoying; Huang, Hanmin

    2015-09-07

    A fundamentally novel approach to bioactive quinolizinones is based on the palladium-catalyzed intramolecular cyclocarbonylation of allylamines. [Pd(Xantphos)I2 ], which features a very large bite angle, has been found to facilitate the rapid carbonylation of azaarene-substituted allylamines into bioactive quinolizinones in good to excellent yields. This transformation represents the first dearomative carbonylation and is proposed to proceed by palladium-catalyzed CN bond activation, dearomatization, CO insertion, and a Heck reaction.

  16. Asymmetric Intramolecular Alkylation of Chiral Aromatic Imines via Catalytic C-H Bond Activation

    SciTech Connect

    Watzke, Anja; Wilson, Rebecca; O'Malley, Steven; Bergman, Robert; Ellman, Jonathan

    2007-04-16

    The asymmetric intramolecular alkylation of chiral aromatic aldimines, in which differentially substituted alkenes are tethered meta to the imine, was investigated. High enantioselectivities were obtained for imines prepared from aminoindane derivatives, which function as directing groups for the rhodium-catalyzed C-H bond activation. Initial demonstration of catalytic asymmetric intramolecular alkylation also was achieved by employing a sterically hindered achiral imine substrate and catalytic amounts of a chiral amine.

  17. Synthesis of Active Hexafluoroisopropyl Benzoates through a Hydrogen-Bond-Enabled Palladium(II)-Catalyzed C-H Alkoxycarbonylation Reaction.

    PubMed

    Wang, Yang; Gevorgyan, Vladimir

    2017-03-13

    A Pd(II) -catalyzed ortho C-H alkoxycarbonylation reaction of aryl silanes toward active hexafluoroisopropyl (HFIP) benzoate esters has been developed. This efficient reaction features high selectivity and good functional-group tolerance. Notably, given the general nature of the silyl-tethered directing group, this method delivers products bearing two independently modifiable sites. NMR studies reveal the presence of hydrogen bonding between HFIP and a pyrimidine nitrogen atom of the directing group, and it is thought to be crucial for the success of this alkoxycarbonylation reaction.

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

    PubMed

    Xu, Zheng; Xu, Li-Wen

    2015-07-08

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

  19. Effects of different surface conditioning methods on the bond strength of composite resin to amalgam.

    PubMed

    Ozcan, M; Koolman, C; Aladag, A; Dündar, M

    2011-01-01

    Repairing amalgam restorations with composite resins using surface conditioning methods is a conservative treatment approach. This study investigated the effects of different conditioning methods that could be used for repair of amalgam fractures. Amalgam (N=96) was condensed into cavities within autopolymerizing polymethylmethacrylate (PMMA), and the exposed surface of each specimen (diameter, 6 mm; thickness, 2 mm) was ground finished. The specimens were randomly divided into nine experimental groups (n=12 per group), depending on the conditioning method used. The control group had natural central incisors with amalgam (n=12). The combination of the following conditioning methods was tested: silicacoating (Sc), sandblasting (Sb), metal primers, coupling agents, fiber (Fb) application, and opaquers (O). Five types of silanes, metal primers, or adhesives (Visiobond [V], Porcelain Photobond [PP], Alloy Primer [AP], Unibond sealer [Us], ESPE-Sil [ES]), and four opaquers, namely, Clearfil St Opaquer (CstO), Sinfony (S), Miris (M), and an experimental Opaquer (EO-Cavex), were used. The groups were as follows: group 1, Sc+ES+S+V; group 2, Sc+ES+CstO+V; group 3, Sc+ES+M+V; group 4, Sc+ES+EO+V; group 5, Sb+AP+S; group 6, Sb+AP+PP+CstO; group 7, Sc+ES+S+Fb+V+Fb; group 8-control, SC+ES+V; and group 9, Etch+Sc+ES+S+Us. One repair composite was used for all groups (Clearfil Photo Bond Posterior, Kuraray, Tokyo, Japan). Shear bond strengths (SBSs) (MPa ± SD) were evaluated after 5 weeks of water storage (analysis of variance [ANOVA], Tukey honestly significant differences [HSD], α=0.05). Group 1 exhibited significantly higher values (35.5 ± 4.1) than were seen in group 4 (19.4 ± 8.9), group 6 (19.1 ± 7.8), and group 8 (20.1 ± 4.1) (p<0.05). Group 9 exhibited significantly lower values (8.3 ± 3.4) than were noted in groups 1 to 3 (35.5 ± 4.1; 27 ± 12.5; 24.4 ± 5.1, respectively) (p<0.05). Group 7 (16.4 ± 5.9) showed significantly lower values than were observed in

  20. C-H bond activation enables the rapid construction and late-stage diversification of functional molecules

    NASA Astrophysics Data System (ADS)

    Wencel-Delord, Joanna; Glorius, Frank

    2013-05-01

    The beginning of the twenty-first century has witnessed significant advances in the field of C-H bond activation, and this transformation is now an established piece in the synthetic chemists' toolbox. This methodology has the potential to be used in many different areas of chemistry, for example it provides a perfect opportunity for the late-stage diversification of various kinds of organic scaffolds, ranging from relatively small molecules like drug candidates, to complex polydisperse organic compounds such as polymers. In this way, C-H activation approaches enable relatively straightforward access to a plethora of analogues or can help to streamline the lead-optimization phase. Furthermore, synthetic pathways for the construction of complex organic materials can now be designed that are more atom- and step-economical than previous methods and, in some cases, can be based on synthetic disconnections that are just not possible without C-H activation. This Perspective highlights the potential of metal-catalysed C-H bond activation reactions, which now extend beyond the field of traditional synthetic organic chemistry.

  1. 26 CFR 1.103(n)-4T - Elective carryforward of unused private activity bond limit (temporary).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... bond limit (temporary). 1.103(n)-4T Section 1.103(n)-4T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-4T Elective carryforward of unused private activity bond limit... carryforward for any one or more projects described in A-5 of this § 1.103(n)-4T (carryforward projects)....

  2. 26 CFR 1.103(n)-4T - Elective carryforward of unused private activity bond limit (temporary).

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... bond limit (temporary). 1.103(n)-4T Section 1.103(n)-4T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-4T Elective carryforward of unused private activity bond limit... carryforward for any one or more projects described in A-5 of this § 1.103(n)-4T (carryforward projects)....

  3. B-H activation and H-H formation: two consecutive heterolytic processes on an osmium-hydrogensulfide bond.

    PubMed

    Esteruelas, Miguel A; López, Ana M; Mora, Malka; Oñate, Enrique

    2013-09-04

    Heterolytic B-H activation and H-H formation on an Os-SH bond give borylthiolate-dihydrogen derivatives. These species exchange borylthiol by borane to afford σ-borane derivatives or release H2 and undergo a hydride-boryl exchange to yield boryl-hydrogensulfide complexes depending on the boryl group bonded to the sulfur atom.

  4. 26 CFR 1.103(n)-4T - Elective carryforward of unused private activity bond limit (temporary).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... bond limit (temporary). 1.103(n)-4T Section 1.103(n)-4T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-4T Elective carryforward of unused private activity bond limit... carryforward for any one or more projects described in A-5 of this § 1.103(n)-4T (carryforward projects)....

  5. Method for producing components with internal architectures, such as micro-channel reactors, via diffusion bonding sheets

    DOEpatents

    Alman, David E.; Wilson, Rick D.; Davis, Daniel L.

    2011-03-08

    This invention relates to a method for producing components with internal architectures, and more particularly, this invention relates to a method for producing structures with microchannels via the use of diffusion bonding of stacked laminates. Specifically, the method involves weakly bonding a stack of laminates forming internal voids and channels with a first generally low uniaxial pressure and first temperature such that bonding at least between the asperites of opposing laminates occurs and pores are isolated in interfacial contact areas, followed by a second generally higher isostatic pressure and second temperature for final bonding. The method thereby allows fabrication of micro-channel devices such as heat exchangers, recuperators, heat-pumps, chemical separators, chemical reactors, fuel processing units, and combustors without limitation on the fin aspect ratio.

  6. A theoretical study of molecular structure, optical properties and bond activation of energetic compound FOX-7 under intense electric fields

    NASA Astrophysics Data System (ADS)

    Tao, Zhiqiang; Wang, Xin; Wei, Yuan; Lv, Li; Wu, Deyin; Yang, Mingli

    2017-02-01

    Molecular structure, vibrational and electronic absorption spectra, chemical reactivity of energetic compound FOX-7, one of the most widely used explosives, were studied computationally in presence of an electrostatic field of 0.01-0.05 a.u. The Csbnd N bond, which usually triggers the decomposition of FOX-7, is shortened/elongated under a parallel/antiparallel field. The Csbnd N bond activation energy varies with the external electric field, decreasing remarkably with the field strength in regardless of the field direction. This is attributed to two aspects: the bond weakening by the field parallel to the Csbnd N bond and the stabilization effect on the transition-state structure by the field antiparallel to the bond. The variations in the structure and property of FOX-7 under the electric fields were further analyzed with its distributional polarizability, which is dependent on the charge transfer characteristics through the Csbnd N bond.

  7. Time resolved infrared studies of C-H bond activation by organometallics

    SciTech Connect

    Asplund, M.C. |

    1998-06-01

    This work describes how step-scan Fourier Transform Infrared spectroscopy and visible and near infrared ultrafast lasers have been applied to the study of the photochemical activation of C-H bonds in organometallic systems, which allow for the selective breaking of C-H bonds in alkanes. The author has established the photochemical mechanism of C-H activation by Tp{sup *}Rh(CO){sub 2}(Tp{sup *} = HB-Pz{sup *}{sub 3}, Pz = 3,5-dimethylpyrazolyl) in alkane solution. The initially formed monocarbonyl forms a weak solvent complex, which undergoes a change in Tp{sup *} ligand connectivity. The final C-H bond breaking step occurs at different time scales depending on the structure of the alkane. In linear solvents, the time scale is <50 ns and cyclic alkanes is {approximately}200 ps. The reactivity of the Tp{sup *}Rh(CO){sub 2} system has also been studied in aromatic solvents. Here the reaction proceeds through two different pathways, with very different time scales. The first proceeds in a manner analogous to alkanes and takes <50 ns. The second proceeds through a Rh-C-C complex, and takes place on a time scale of 1.8 {micro}s.

  8. Full CI benchmark calculations on N2, NO, and O2 - A comparison of methods for describing multiple bonds

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1987-01-01

    Full configuration interaction (CI) calculations on the ground states of N2, NO, and O2 using a DZP Gaussian basis are compared with single-reference SDCI and coupled pair approaches (CPF), as well as with CASSCF multireference CI approaches. The CASSCF/MRCI technique is found to describe multiple bonds as well as single bonds. Although the coupled pair functional approach gave chemical accuracy (1 kcal/mol) for bonds involving hydrogen, larger errors occur in the CPF approach for the multiple bonded systems considered here. CI studies on the 1Sigma(g +) state of N2, including all single, double, triple, and quadruple excitations show that triple excitations are very important for the multiple bond case, and accounts for most of the deficiency in the coupled pair functional methods.

  9. Mercury Detoxification by Bacteria: Simulations of Transcription Activation and Mercury-Carbon Bond Cleavage

    SciTech Connect

    Guo, Hao-Bo; Parks, Jerry M; Johs, Alexander; Smith, Jeremy C

    2011-01-01

    In this chapter, we summarize recent work from our laboratory and provide new perspective on two important aspects of bacterial mercury resistance: the molecular mechanism of transcriptional regulation by MerR, and the enzymatic cleavage of the Hg-C bond in methylmercury by the organomercurial lyase, MerB. Molecular dynamics (MD) simulations of MerR reveal an opening-and-closing dynamics, which may be involved in initiating transcription of mercury resistance genes upon Hg(II) binding. Density functional theory (DFT) calculations on an active-site model of the enzyme reveal how MerB catalyzes the Hg-C bond cleavage using cysteine coordination and acid-base chemistry. These studies provide insight into the detailed mechanisms of microbial gene regulation and defense against mercury toxicity.

  10. Hydrogen induced C-C, C-N, and C-S bond activation on Pt and Ni surfaces

    SciTech Connect

    Gland, J.L.

    1992-12-01

    The work has focussed on hydrogen induced bond activation in adsorbed organic molecules and intermediates containin C-S and C-N and C-C bonds on Ni(100), Ni(111), and Pt(111) surfaces. Fluorescence Yield Near Edge Spectroscopy (FYNES) above the carbon K edge was used for adsorbed organic reactants and in-situ kinetic studies of bond activation. Results indicate that the activation is enhanced on Ni relative to Pt. Methylthiolate and methylamine adsorbed on Pt(111) were studied.

  11. Hydrogen induced C-C, C-N, and C-S bond activation on Pt and Ni surfaces

    SciTech Connect

    Gland, J.L.

    1992-01-01

    The work has focussed on hydrogen induced bond activation in adsorbed organic molecules and intermediates containin C-S and C-N and C-C bonds on Ni(100), Ni(111), and Pt(111) surfaces. Fluorescence Yield Near Edge Spectroscopy (FYNES) above the carbon K edge was used for adsorbed organic reactants and in-situ kinetic studies of bond activation. Results indicate that the activation is enhanced on Ni relative to Pt. Methylthiolate and methylamine adsorbed on Pt(111) were studied.

  12. Energetics of tert-butoxyl addition reaction to norbornadiene: a method for estimating the pi-bond strength of a carbon-carbon double bond.

    PubMed

    Nunes, Paulo M; Estácio, Sílvia G; Lopes, Gustavo T; Agapito, Filipe; Santos, Rui C; Costa Cabral, Benedito J; Borges dos Santos, Rui M; Martinho Simões, José A

    2009-06-11

    The energetics of tert-butoxyl radical addition reaction to norbornadiene was investigated by time-resolved photoacoustic calorimetry (TR-PAC). The result, together with the C-O bond dissociation enthalpy (BDE) in the addition product, allowed us to calculate the pi-bond dissociation enthalpy in norbornadiene. Quantum chemistry (QC) methods were also used to obtain several enthalpies of reaction of the addition of oxygen-centered radicals to alkenes. The pi-bond dissociation enthalpies in these molecules were calculated by a procedure similar to that used in the case of norbornadiene and were compared with the pi-BDE values obtained by the method proposed by Benson. These two different approaches yield similar values for the pi-BDEs in alkenes, indicating that the addition method proposed in the present study is a valid way to derive that quantity. The influence of strain in the pi-BDEs of cyclic alkenes was investigated and allowed us to justify the difference between the pi-BDE in norbornene and norbornadiene. Finally, the thermochemistry of the addition and abstraction reactions involving these two molecules and tert-butoxyl radical was analyzed.

  13. C-H Bond Activation/Arylation Catalyzed by Arene-Ruthenium-Aniline Complexes in Water.

    PubMed

    Binnani, Chinky; Tyagi, Deepika; Rai, Rohit K; Mobin, Shaikh M; Singh, Sanjay K

    2016-11-07

    Water-soluble arene-ruthenium complexes coordinated with readily available aniline-based ligands were successfully employed as highly active catalysts in the C-H bond activation and arylation of 2-phenylpyridine with aryl halides in water. A variety of (hetero)aryl halides were also used for the ortho-C-H bond arylation of 2-phenylpyridine to afford the corresponding ortho- monoarylated products as major products in moderate to good yields. Our investigations, including time-scaled NMR spectroscopy and mass spectrometry studies, evidenced that the coordinating aniline-based ligands, having varying electronic and steric properties, had a significant influence on the catalytic activity of the resulting arene-ruthenium-aniline-based complexes. Moreover, mass spectrometry identification of the cycloruthenated species, {(η(6) -arene)Ru(κ(2) -C,N-phenylpyridine)}(+) , and several ligand-coordinated cycloruthenated species, such as [(η(6) -arene)Ru(4-methylaniline)(κ(2) -C,N-phenylpyridine)](+) , found during the reaction of 2-phenylpyridine with the arene-ruthenium-aniline complexes further authenticated the crucial roles of these species in the observed highly active and tuned catalyst. At last, the structures of a few of the active catalysts were also confirmed by single-crystal X-ray diffraction studies.

  14. [Determination of double bonds in olive and sunflower oils by ozonize method].

    PubMed

    Evteeva, N M

    2007-01-01

    Kinetics of spending double bonds of tocotherol and accumulation of peroxides during oxidation of olive and sunflower oils were investigated. Date on spending double bonds during oxidation of commercial oils were measured for the first time.

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

    SciTech Connect

    Bromberg, S.E.

    1998-05-01

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

  16. Transparent and electrically conductive GaSb/Si direct wafer bonding at low temperatures by argon-beam surface activation

    NASA Astrophysics Data System (ADS)

    Predan, F.; Reinwand, D.; Klinger, V.; Dimroth, F.

    2015-10-01

    Direct wafer bonds of the material system n-GaSb/n-Si have been achieved by means of a low-temperature direct wafer bonding process, enabling an optical transparency of the bonds along with a high electrical conductivity of the boundary layer. In the used technique, the surfaces are activated by sputter-etching with an argon fast-atom-beam (FAB) and bonded in ultra-high vacuum. The bonds were annealed at temperatures between 300 and 400 °C, followed by an optical, mechanical and electrical characterization of the interface. Additionally, the influence of the sputtering on the surface topography of the GaSb was explicitly investigated. Fully bonded wafer pairs with high bonding strengths were found, as no blade could be inserted into the bonds without destroying the samples. The interfacial resistivities of the bonded wafers were significantly reduced by optimizing the process parameters, by which Ohmic interfacial resistivities of less than 5 mΩ cm2 were reached reproducibly. These promising results make the monolithic integration of GaSb on Si attractive for various applications.

  17. The Effective Fragment Molecular Orbital Method for Fragments Connected by Covalent Bonds

    PubMed Central

    Steinmann, Casper; Fedorov, Dmitri G.; Jensen, Jan H.

    2012-01-01

    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. PMID:22844433

  18. Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry.

    PubMed

    Ruscic, Branko

    2015-07-16

    Active Thermochemical Tables (ATcT) thermochemistry for the sequential bond dissociations of methane, ethane, and methanol systems were obtained by analyzing and solving a very large thermochemical network (TN). Values for all possible C-H, C-C, C-O, and O-H bond dissociation enthalpies at 298.15 K (BDE298) and bond dissociation energies at 0 K (D0) are presented. The corresponding ATcT standard gas-phase enthalpies of formation of the resulting CHn, n = 4-0 species (methane, methyl, methylene, methylidyne, and carbon atom), C2Hn, n = 6-0 species (ethane, ethyl, ethylene, ethylidene, vinyl, ethylidyne, acetylene, vinylidene, ethynyl, and ethynylene), and COHn, n = 4-0 species (methanol, hydroxymethyl, methoxy, formaldehyde, hydroxymethylene, formyl, isoformyl, and carbon monoxide) are also presented. The ATcT thermochemistry of carbon dioxide, water, hydroxyl, and carbon, oxygen, and hydrogen atoms is also included, together with the sequential BDEs of CO2 and H2O. The provenances of the ATcT enthalpies of formation, which are quite distributed and involve a large number of relevant determinations, are analyzed by variance decomposition and discussed in terms of principal contributions. The underlying reasons for periodic appearances of remarkably low and/or unusually high BDEs, alternating along the dissociation sequences, are analyzed and quantitatively rationalized. The present ATcT results are the most accurate thermochemical values currently available for these species.

  19. C-C Bond Activation and Coupling of Propene Induced by la Atom

    NASA Astrophysics Data System (ADS)

    Hewage, Dilrukshi; Tao, Hong; Silva, Ruchira; Kumari, Sudesh; Yang, Dong-Sheng

    2013-06-01

    A series of La(C_nH_m) complexes with n ≤ 6 and m ≤ 12 were produced by the reactions between propene and La in a supersonic molecular beam source. Their formation and structures were investigated using mass-analyzed threshold ionization (MATI) spectroscopy in combination with theoretical calculations. Previously, we identified the formation of La(C_3H_4) and H-La(C_3H_5) through dehydrogenation and metal insertion mechanisms. In this work, we will discuss the formation of La(CH_2) and La(C_4H_6) by La induced C-C bond activation and coupling. La(CH_2) is formed by the C-C bond breakage and 1,2-hydride shift of propene and is a Schrock-type carbene complex. This complex is then coupled with the C=C bond of a second propene molecule to form La(C_4H_6) by removing two hydrogen atoms. The resultant La(C_4H_6) complex was idetified in two low-energy isomeric forms: one was a metallacycle (isomer A) and the other was lanthanum trimethylenemethane (isomer B). Both La(C_4H_6) isomers are in a doublet ground state, with isomer A in C_s point group and isomer B in C_3_v. Adiabatic ionization energies and several vibrational frequencies of the two complexes were obtained from the sharp MATI spectra.

  20. Active site remodelling accompanies thioester bond formation in the SUMO E1

    SciTech Connect

    Olsen, Shaun K.; Capili, Allan D.; Lu, Xuequan; Tan, Derek S.; Lima, Christopher D.

    2010-03-30

    E1 enzymes activate ubiquitin (Ub) and ubiquitin-like (Ubl) proteins in two steps by carboxy-terminal adenylation and thioester bond formation to a conserved catalytic cysteine in the E1 Cys domain. The structural basis for these intermediates remains unknown. Here we report crystal structures for human SUMO E1 in complex with SUMO adenylate and tetrahedral intermediate analogues at 2.45 and 2.6 {angstrom}, respectively. These structures show that side chain contacts to ATP-Mg are released after adenylation to facilitate a 130 degree rotation of the Cys domain during thioester bond formation that is accompanied by remodelling of key structural elements including the helix that contains the E1 catalytic cysteine, the crossover and re-entry loops, and refolding of two helices that are required for adenylation. These changes displace side chains required for adenylation with side chains required for thioester bond formation. Mutational and biochemical analyses indicate these mechanisms are conserved in other E1s.

  1. Active site remodelling accompanies thioester bond formation in the SUMO E1.

    PubMed

    Olsen, Shaun K; Capili, Allan D; Lu, Xuequan; Tan, Derek S; Lima, Christopher D

    2010-02-18

    E1 enzymes activate ubiquitin (Ub) and ubiquitin-like (Ubl) proteins in two steps by carboxy-terminal adenylation and thioester bond formation to a conserved catalytic cysteine in the E1 Cys domain. The structural basis for these intermediates remains unknown. Here we report crystal structures for human SUMO E1 in complex with SUMO adenylate and tetrahedral intermediate analogues at 2.45 and 2.6 A, respectively. These structures show that side chain contacts to ATP.Mg are released after adenylation to facilitate a 130 degree rotation of the Cys domain during thioester bond formation that is accompanied by remodelling of key structural elements including the helix that contains the E1 catalytic cysteine, the crossover and re-entry loops, and refolding of two helices that are required for adenylation. These changes displace side chains required for adenylation with side chains required for thioester bond formation. Mutational and biochemical analyses indicate these mechanisms are conserved in other E1s.

  2. Water-containing hydrogen-bonding network in the active center of channelrhodopsin.

    PubMed

    Ito, Shota; Kato, Hideaki E; Taniguchi, Reiya; Iwata, Tatsuya; Nureki, Osamu; Kandori, Hideki

    2014-03-05

    Channelrhodopsin (ChR) functions as a light-gated ion channel in Chlamydomonas reinhardtii. Passive transport of cations by ChR is fundamentally different from the active transport by light-driven ion pumps such as archaerhodopsin, bacteriorhodopsin, and halorhodopsin. These microbial rhodopsins are important tools for optogenetics, where ChR is used to activate neurons by light, while the ion pumps are used for neural silencing. Ion-transport functions by these rhodopsins strongly depend on the specific hydrogen-bonding networks containing water near the retinal chromophore. In this work, we measured protein-bound water molecules in a chimeric ChR protein of ChR1 (helices A to E) and ChR2 (helices F and G) of Chlamydomonas reinhardtii using low-temperature FTIR spectroscopy at 77 K. We found that the active center of ChR possesses more water molecules (9 water vibrations) than those of other microbial (2-6 water vibrations) and animal (6-8 water vibrations) rhodopsins. We conclude that the protonated retinal Schiff base interacts with the counterion (Glu162) directly, without the intervening water molecule found in proton-pumping microbial rhodopsins. The present FTIR results and the recent X-ray structure of ChR reveal a unique hydrogen-bonding network around the active center of this light-gated ion channel.

  3. Sacrificial adhesive bonding: a powerful method for fabrication of glass microchips.

    PubMed

    Lima, Renato S; Leão, Paulo A G C; Piazzetta, Maria H O; Monteiro, Alessandra M; Shiroma, Leandro Y; Gobbi, Angelo L; Carrilho, Emanuel

    2015-08-21

    A new protocol for fabrication of glass microchips is addressed in this research paper. Initially, the method involves the use of an uncured SU-8 intermediate to seal two glass slides irreversibly as in conventional adhesive bonding-based approaches. Subsequently, an additional step removes the adhesive layer from the channels. This step relies on a selective development to remove the SU-8 only inside the microchannel, generating glass-like surface properties as demonstrated by specific tests. Named sacrificial adhesive layer (SAB), the protocol meets the requirements of an ideal microfabrication technique such as throughput, relatively low cost, feasibility for ultra large-scale integration (ULSI), and high adhesion strength, supporting pressures on the order of 5 MPa. Furthermore, SAB eliminates the use of high temperature, pressure, or potential, enabling the deposition of thin films for electrical or electrochemical experiments. Finally, the SAB protocol is an improvement on SU-8-based bondings described in the literature. Aspects such as substrate/resist adherence, formation of bubbles, and thermal stress were effectively solved by using simple and inexpensive alternatives.

  4. Sacrificial adhesive bonding: a powerful method for fabrication of glass microchips

    PubMed Central

    Lima, Renato S.; Leão, Paulo A. G. C.; Piazzetta, Maria H. O.; Monteiro, Alessandra M.; Shiroma, Leandro Y.; Gobbi, Angelo L.; Carrilho, Emanuel

    2015-01-01

    A new protocol for fabrication of glass microchips is addressed in this research paper. Initially, the method involves the use of an uncured SU-8 intermediate to seal two glass slides irreversibly as in conventional adhesive bonding-based approaches. Subsequently, an additional step removes the adhesive layer from the channels. This step relies on a selective development to remove the SU-8 only inside the microchannel, generating glass-like surface properties as demonstrated by specific tests. Named sacrificial adhesive layer (SAB), the protocol meets the requirements of an ideal microfabrication technique such as throughput, relatively low cost, feasibility for ultra large-scale integration (ULSI), and high adhesion strength, supporting pressures on the order of 5 MPa. Furthermore, SAB eliminates the use of high temperature, pressure, or potential, enabling the deposition of thin films for electrical or electrochemical experiments. Finally, the SAB protocol is an improvement on SU-8-based bondings described in the literature. Aspects such as substrate/resist adherence, formation of bubbles, and thermal stress were effectively solved by using simple and inexpensive alternatives. PMID:26293346

  5. New light on the Co-C bond activation in B 12-dependent enzymes from density functional theory

    NASA Astrophysics Data System (ADS)

    Andruniow, Tadeusz; Zgierski, Marek Z.; Kozlowski, Pawel M.

    2000-12-01

    Density functional theory (DFT) is applied to the calculation of activation of the Co-C R bond in models of vitamin B 12, B-[Co III(corrin)]-R. It is shown that there is a positive correlation of the bond lengths between the Co atom and the two axial ligands, B and R. The electron donation from axial ligands to the cobalt atom either by electron donating substituents or by a properly oriented external electric field caused by external electric charges is argued to be the main trigger for the activation of the Co-C R bond.

  6. Synthesis of new class of alkyl azarene pyridinium zwitterions via iodine mediated sp3 C-H bond activation.

    PubMed

    Kumar, Atul; Gupta, Garima; Srivastava, Suman

    2011-12-16

    An efficient and conceptually different approach toward C-H bond activation by using iodine mediated sp(3) C-H functionalization for the synthesis of alkyl azaarene pyridinium zwitterions is described. This work has the interesting distinction of being the first synthesis of a new class of alkyl azaarene pyridinium zwitterion via transition-metal-free sp(3) C-H bond activation of an alkyl azaarene.

  7. Highly Active Gold(I)-Silver(I) Oxo Cluster Activating sp³ C-H Bonds of Methyl Ketones under Mild Conditions.

    PubMed

    Pei, Xiao-Li; Yang, Yang; Lei, Zhen; Chang, Shan-Shan; Guan, Zong-Jie; Wan, Xian-Kai; Wen, Ting-Bin; Wang, Quan-Ming

    2015-04-29

    The activation of C(sp(3))-H bonds is challenging, due to their high bond dissociation energy, low proton acidity, and highly nonpolar character. Herein we report a unique gold(I)-silver(I) oxo cluster protected by hemilabile phosphine ligands [OAu3Ag3(PPhpy2)3](BF4)4 (1), which can activate C(sp(3))-H bonds under mild conditions for a broad scope of methyl ketones (RCOCH3, R = methyl, phenyl, 2-methylphenyl, 2-aminophenyl, 2-hydroxylphenyl, 2-pyridyl, 2-thiazolyl, tert-butyl, ethyl, isopropyl). Activation happens via triple deprotonation of the methyl group, leading to formation of heterometallic Au(I)-Ag(I) clusters with formula RCOCAu4Ag4(PPhpy2)4(BF4)5 (PPhpy2 = bis(2-pyridyl)phenylphosphine). Cluster 1 can be generated in situ via the reaction of [OAu3Ag(PPhpy2)3](BF4)2 with 2 equiv of AgBF4. The oxo ion and the metal centers are found to be essential in the cleavage of sp(3) C-H bonds of methyl ketones. Interestingly, cluster 1 selectively activates the C-H bonds in -CH3 rather than the N-H bonds in -NH2 or the O-H bond in -OH which is traditionally thought to be more reactive than C-H bonds. Control experiments with butanone, 3-methylbutanone, and cyclopentanone as substrates show that the auration of the C-H bond of the terminal methyl group is preferred over secondary or tertiary sp(3) C-H bonds; in other words, the C-H bond activation is influenced by steric effect. This work highlights the powerful reactivity of metal clusters toward C-H activation and sheds new light on gold(I)-mediated catalysis.

  8. Evaluating interaction energies of weakly bonded systems using the Buckingham-Hirshfeld method

    SciTech Connect

    Krishtal, A.; Van Alsenoy, C.; Geerlings, P.

    2014-05-14

    We present the finalized Buckingham-Hirshfeld method (BHD-DFT) for the evaluation of interaction energies of non-bonded dimers with Density Functional Theory (DFT). In the method, dispersion energies are evaluated from static multipole polarizabilities, obtained on-the-fly from Coupled Perturbed Kohn-Sham calculations and partitioned into diatomic contributions using the iterative Hirshfeld partitioning method. The dispersion energy expression is distributed over four atoms and has therefore a higher delocalized character compared to the standard pairwise expressions. Additionally, full multipolar polarizability tensors are used as opposed to effective polarizabilities, allowing to retain the anisotropic character at no additional computational cost. A density dependent damping function for the BLYP, PBE, BP86, B3LYP, and PBE0 functionals has been implemented, containing two global parameters which were fitted to interaction energies and geometries of a selected number of dimers using a bi-variate RMS fit. The method is benchmarked against the S22 and S66 data sets for equilibrium geometries and the S22x5 and S66x8 data sets for interaction energies around the equilibrium geometry. Best results are achieved using the B3LYP functional with mean average deviation values of 0.30 and 0.24 kcal/mol for the S22 and S66 data sets, respectively. This situates the BHD-DFT method among the best performing dispersion inclusive DFT methods. Effect of counterpoise correction on DFT energies is discussed.

  9. Effect of cleansing methods on saliva-contaminated zirconia--an evaluation of resin bond durability.

    PubMed

    Feitosa, S A; Patel, D; Borges, A L S; Alshehri, E Z; Bottino, M A; Özcan, M; Valandro, L F; Bottino, M C

    2015-01-01

    The aims of this study were to investigate 1) the influence of cleansing methods after saliva contamination and 2) aging conditions (thermocycling and water storage) on zirconia shear bond strength (SBS) with a resin cement. One hundred and eighty zirconia specimens were sandblasted with 50 μm aluminum oxide particles, immersed in saliva for one minute (with the exception of the control group, [C]), and divided into groups according to the cleansing method, as follows: water rinse (W); 37% phosphoric acid gel (PA); cleaning paste (ie, Ivoclean®) containing mainly zirconium oxide (IC); and 70% isopropanol (AL). Scanning electron microscopy was done to qualitatively evaluate the zirconia surface after each cleansing method. For the SBS test, resin cement buttons were bonded to the specimens using a dedicated jig. SBS was evaluated according to standard protocols after 24 hours, 5000 thermal cycles (TC), or 150 days of water storage. Statistical analysis was performed using two-way analysis of variance and Tukey test (p<0.05). Data showed a significant effect for the 150 days of water storage, TC, and 24 hours of water storage (150 days < TC < 24 hours). Group comparisons showed that PA < AL and W < IC and C. SBS ranged from 10.4 to 21.9 MPa (24 hours), from 6.4 to 14.8 MPa (TC), and from 2.9 to 7.0 MPa (150 days). Failure analysis revealed a greater percentage of mixed failures for the majority of the specimens and a smaller percentage of adhesive failures at the ceramic-resin cement interface. Our findings suggest that Ivoclean® was able to maintain adequate SBS values after TC and 150 days of storage, comparable to the uncontaminated zirconia.

  10. Annulation of Aromatic Imines via Directed C-H BondActivation

    SciTech Connect

    Thalji, Reema K.; Ahrendt, Kateri A.; Bergman, Robert G.; Ellman,Jonathan A.

    2005-04-14

    A directed C-H bond activation approach to the synthesis of indans, tetralins, dihydrofurans, dihydroindoles, and other polycyclic aromatic compounds is presented. Cyclization of aromatic ketimines and aldimines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using (PPh{sub 3}){sub 3}RhCl (Wilkinson's catalyst). The cyclization of a range of aromatic ketimines and aldimines provides bi- and tricyclic ring systems with good regioselectivity. Different ring sizes and substitution patterns can be accessed through the coupling of monosubstituted, 1,1- or 1,2-disubstituted, and trisubstituted alkenes bearing both electron-rich and electron-deficient functionality.

  11. Selective molecular recognition, C-H bond activation, and catalysis in nanoscale reaction vessels

    SciTech Connect

    Fiedler, Dorothea; Leung, Dennis H.; Raymond, Kenneth N.; Bergman, Robert G.

    2004-11-27

    Supramolecular chemistry represents a way to mimic enzyme reactivity by using specially designed container molecules. We have shown that a chiral self-assembled M{sub 4}L{sub 6} supramolecular tetrahedron can encapsulate a variety of cationic guests, with varying degrees of stereoselectivity. Reactive iridium guests can be encapsulated and the C-H bond activation of aldehydes occurs, with the host cavity controlling the ability of substrates to interact with the metal center based upon size and shape. In addition, the host container can act as a catalyst by itself. By restricting reaction space and preorganizing the substrates into reactive conformations, it accelerates the sigmatropic rearrangement of enammonium cations.

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

    PubMed

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

    2011-01-07

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

  13. Activation of carboxyl group with cyanate: peptide bond formation from dicarboxylic acids.

    PubMed

    Danger, Grégoire; Charlot, Solenne; Boiteau, Laurent; Pascal, Robert

    2012-06-01

    The reaction of cyanate with C-terminal carboxyl groups of peptides in aqueous solution was considered as a potential pathway for the abiotic formation of peptide bonds under the condition of the primitive Earth. The catalytic effect of dicarboxylic acids on cyanate hydrolysis was definitely attributed to intramolecular nucleophilic catalysis by the observation of the 1H-NMR signal of succinic anhydride when reacting succinic acid with KOCN in aqueous solution (pH 2.2-5.5). The formation of amide bonds was noticed when adding amino acids or amino acid derivatives into the solution. The reaction of N-acyl aspartic acid derivatives was observed to proceed similarly and the scope of the cyanate-promoted reaction was analyzed from the standpoint of prebiotic peptide formation. The role of cyanate in activating peptide C-terminus constitutes a proof of principle that intramolecular reactions of adducts of peptides C-terminal carboxyl groups with activating agents represent a pathway for peptide activation in aqueous solution, the relevance of which is discussed in connexion with the issue of the emergence of homochirality.

  14. Femtosecond time resolved infrared studies of Si-H bond activation

    SciTech Connect

    Yang, H.; Kotz, K.T.; Asplund, M.; Bromberg, S.E. |

    1997-12-31

    We report the first time-resolved IR studies of the silane Si-H bond activation mechansim on time-scales from sub-picosecond to nanosecond. It has been accepted that the primary photochemical process following UV irradiation of {eta}{sup 5}-CpMn(CO){sub 3} [A] in room temperature solution is the loss of a CO ligand. By monitoring the time evolution of the CO stretching frequencies, we have observed three distinct pathways for the formation of the activated hydridosilyl complex {eta}{sup 5}-CpMn(CO){sub 2}(H)(SiEt{sub 3}) [B]: (1) direct formation after CO dissociation; (2) formation through an intermediate [C] whose lifetime is about 90 ps; and (3) formation through another intermediate [D] which can be assigned as a solvated dicarbonyl species that eventually rearranges to form B on a time-scale of > 1 ns. Considering possible chemical processes, we have tentatively assigned C as a ring-slipped {eta}{sup 3} species which changes its hapticity from {eta}{sup 3} to {eta}{sup 5} in {approximately}90 ps. Detailed structures of the intermediates are being studied using ab initio electronic structure calculations. Experiments that extend beyond 1 ns and those on Si-H bond activation by other metal complexes such as {eta}{sup 5}-CpRe (CO){sub 3} are underway.

  15. Simulation of the effect of hydrogen bonds on water activity of glucose and dextran using the Veytsman model.

    PubMed

    De Vito, Francesca; Veytsman, Boris; Painter, Paul; Kokini, Jozef L

    2015-03-06

    Carbohydrates exhibit either van der Waals and ionic interactions or strong hydrogen bonding interactions. The prominence and large number of hydrogen bonds results in major contributions to phase behavior. A thermodynamic framework that accounts for hydrogen bonding interactions is therefore necessary. We have developed an extension of the thermodynamic model based on the Veytsman association theory to predict the contribution of hydrogen bonds to the behavior of glucose-water and dextran-water systems and we have calculated the free energy of mixing and its derivative leading to chemical potential and water activity. We compared our calculations with experimental data of water activity for glucose and dextran and found excellent agreement far superior to the Flory-Huggins theory. The validation of our calculations using experimental data demonstrated the validity of the Veytsman model in properly accounting for the hydrogen bonding interactions and successfully predicting water activity of glucose and dextran. Our calculations of the concentration of hydrogen bonds using the Veytsman model were instrumental in our ability to explain the difference between glucose and dextran and the role that hydrogen bonds play in contributing to these differences. The miscibility predictions showed that the Veytsman model is also able to correctly describe the phase behavior of glucose and dextran.

  16. The Effect of Four Surface Treatment Methods on the Shear Bond Strength of Metallic Brackets to the Fluorosed Enamel

    PubMed Central

    Zarif Najafi, Hooman; Moshkelgosha, Vahid; Khanchemehr, Atefeh; Alizade, Akram; Mokhtar, Ali

    2015-01-01

    Statement of the Problem Some studies have reported the bond strength to be significantly lower in fluorotic enamels than the non-fluorosed. Purpose The purpose of this study was to evaluate the shear bond streongth of metallic brackets to non-fluorosed and fluorosed teeth after different enamel conditioning. Materials and Method A total of 176 freshly extracted human premolars (88 non-fluorosed and 88 fluorosed teeth) were used in this study for bonding the metallic brackets. Teeth with moderate fluorosis were used according to Thylstrup and Fejereskov index (TFI). Eighty non-fluorosed and 80 fluorosed teeth (TFI=4-6) were randomly divided into 8 equal groups of 20 teeth each. The remaining 16 teeth were used for scanning electron microscopy observation. The enamel surface was conditioned by 4 methods: acid etching  for 30 sec, acid etching for 120 sec, air abrasion followed by acid etching, and Er: YAG laser etching followed by acid etching. The morphology of etching patterns in different groups was studied under scanning electron microscope. Results The shear bond strength of fluorosed teeth to the brackets was significantly lower than non-fluorosed ones (p= 0.003). The shear bond strength of laser-acid groups in both non-fluorosed and fluorosed teeth was significantly lower than other groups (p< 0.001). Weibull analysis indicated that the chance of failure under the applied force was different between fluorosed and non-fluorosed group. The scanning electron microscope observations revealed that the fluorosed teeth treated with phosphoric acid had fewer irregularities compared to non-fluorosed teeth. The most irregularities were detected in the teeth conditioned with phosphoric acid for 120 seconds. Conclusion Fluorotic enamel adversely affects the bond strength of orthodontic brackets. None of the conditioning methods tested in this study could significantly improve shear bond strength of metallic brackets. Er: YAG laser conditioning followed by acid further

  17. Effect of surface treatment methods on the shear bond strength of auto-polymerized resin to thermoplastic denture base polymer

    PubMed Central

    Koodaryan, Roodabeh

    2016-01-01

    PURPOSE Polyamide polymers do not provide sufficient bond strength to auto-polymerized resins for repairing fractured denture or replacing dislodged denture teeth. Limited treatment methods have been developed to improve the bond strength between auto-polymerized reline resins and polyamide denture base materials. The objective of the present study was to evaluate the effect of surface modification by acetic acid on surface characteristics and bond strength of reline resin to polyamide denture base. MATERIALS AND METHODS 84 polyamide specimens were divided into three surface treatment groups (n=28): control (N), silica-coated (S), and acid-treated (A). Two different auto-polymerized reline resins GC and Triplex resins were bonded to the samples (subgroups T and G, respectively, n=14). The specimens were subjected to shear bond strength test after they were stored in distilled water for 1 week and thermo-cycled for 5000 cycles. Data were analyzed with independent t-test, two-way analysis of variance (ANOVA), and Tukey's post hoc multiple comparison test (α=.05). RESULTS The bond strength values of A and S were significantly higher than those of N (P<.001 for both). However, statistically significant difference was not observed between group A and group S. According to the independent Student's t-test, the shear bond strength values of AT were significantly higher than those of AG (P<.001). CONCLUSION The surface treatment of polyamide denture base materials with acetic acid may be an efficient and cost-effective method for increasing the shear bond strength to auto-polymerized reline resin. PMID:28018569

  18. Activation of carbon-hydrogen bonds in alkanes and other organic molecules using organotransition metal complexes

    SciTech Connect

    Bergman, R.G.

    1991-10-01

    We have recently begun to investigate the interaction of C-H activating iridium and rhodium complexes with functionalized organic molecules, to determine the effect of functional groups on the process, as well as to investigate the propensity of Ir and Rh to insert into C-H versus other types of X-H bonds. Recent experiments have demonstrated that xenon liquefied at -70{degrees}C and 10 atm pressure serves as an inert solvent for the C-H oxidative addition reaction. We have been able to prepare and isolate, for the first time, C-H oxidative addition products formed from high-melting solid substrates such as naphthalene, adamantane, and even cubane; the latter case represents the first observation of C-H oxidative addition at a tertiary C-H bond. Liquid xenon has also allowed us to carry out more conveniently the C-H oxidative addition reactions of low-boiling gases that are difficult to liquefy, such as methane. Recently we have also been able to carry out analogous studies in the gas phase. Under these conditions, naked'' rather than solvated Cp*Rh(CO) is formed, and this species reacts with cyclohexane at nearly gas-kinetic rates. Under the conditions, collision between Cp*Rh(CO) and cyclohexane is the slowest step in the overall C-H activation process. In contrast, in solution association of solvent with free Cp*Rh(CO) is so rapid that the step involving C-H bond cleavage in the coordinated alkane complex becomes rate-determining. 3 refs., 5 figs.

  19. Activation of carbon-hydrogen bonds in alkanes and other organic molecules using organotransition metal complexes

    SciTech Connect

    Bergman, R.G.

    1991-10-01

    We have recently begun to investigate the interaction of C-H activating iridium and rhodium complexes with functionalized organic molecules, to determine the effect of functional groups on the process, as well as to investigate the propensity of Ir and Rh to insert into C-H versus other types of X-H bonds. Recent experiments have demonstrated that xenon liquefied at -70{degrees}C and 10 atm pressure serves as an inert solvent for the C-H oxidative addition reaction. We have been able to prepare and isolate, for the first time, C-H oxidative addition products formed from high-melting solid substrates such as naphthalene, adamantane, and even cubane; the latter case represents the first observation of C-H oxidative addition at a tertiary C-H bond. Liquid xenon has also allowed us to carry out more conveniently the C-H oxidative addition reactions of low-boiling gases that are difficult to liquefy, such as methane. Recently we have also been able to carry out analogous studies in the gas phase. Under these conditions, ``naked`` rather than solvated Cp*Rh(CO) is formed, and this species reacts with cyclohexane at nearly gas-kinetic rates. Under the conditions, collision between Cp*Rh(CO) and cyclohexane is the slowest step in the overall C-H activation process. In contrast, in solution association of solvent with free Cp*Rh(CO) is so rapid that the step involving C-H bond cleavage in the coordinated alkane complex becomes rate-determining. 3 refs., 5 figs.

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

    PubMed

    Kumar, Rahul; Jagirdar, Balaji R

    2013-01-07

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

  1. Active Site Formation, Not Bond Kinetics, Limits Adhesion Rate between Human Neutrophils and Immobilized Vascular Cell Adhesion Molecule 1

    PubMed Central

    Waugh, Richard E.; Lomakina, Elena B.

    2009-01-01

    Abstract The formation of receptor ligand bonds at the interface between different cells and between cells and substrates is a widespread phenomenon in biological systems. Physical measurements of bond formation rates between cells and substrates have been exploited to increase our understanding of the biophysical mechanisms that regulate bond formation at interfaces. Heretofore, these measurements have been interpreted in terms of simple bimolecular reaction kinetics. Discrepancies between this simple framework and the behavior of neutrophils adhering to surfaces expressing vascular cell adhesion molecule 1 (VCAM-1) motivated the development of a new kinetic framework in which the explicit formation of active bond formation sites (reaction zones) are a prerequisite for bond formation to occur. Measurements of cells interacting with surfaces having a wide range of VCAM-1 concentrations, and for different durations of contact, enabled the determination of novel kinetic rate constants for the formation of reaction zones and for the intrinsic bond kinetics. Comparison of these rates with rates determined previously for other receptor-ligand pairs points to a predominant role of extrinsic factors such as surface topography and accessibility of active molecules to regions of close contact in determining forward rates of bond formation at cell interfaces. PMID:19134479

  2. LEAP-1, a novel highly disulfide-bonded human peptide, exhibits antimicrobial activity.

    PubMed

    Krause, A; Neitz, S; Mägert, H J; Schulz, A; Forssmann, W G; Schulz-Knappe, P; Adermann, K

    2000-09-01

    We report the isolation and characterization of a novel human peptide with antimicrobial activity, termed LEAP-1 (liver-expressed antimicrobial peptide). Using a mass spectrometric assay detecting cysteine-rich peptides, a 25-residue peptide containing four disulfide bonds was identified in human blood ultrafiltrate. LEAP-1 expression was predominantly detected in the liver, and, to a much lower extent, in the heart. In radial diffusion assays, Gram-positive Bacillus megaterium, Bacillus subtilis, Micrococcus luteus, Staphylococcus carnosus, and Gram-negative Neisseria cinerea as well as the yeast Saccharomyces cerevisiae dose-dependently exhibited sensitivity upon treatment with synthetic LEAP-1. The discovery of LEAP-1 extends the known families of mammalian peptides with antimicrobial activity by its novel disulfide motif and distinct expression pattern.

  3. Screening possible solid electrolytes by calculating the conduction pathways using Bond Valence method

    NASA Astrophysics Data System (ADS)

    Gao, Jian; Chu, Geng; He, Meng; Zhang, Shu; Xiao, RuiJuan; Li, Hong; Chen, LiQuan

    2014-08-01

    Inorganic solid electrolytes have distinguished advantages in terms of safety and stability, and are promising to substitute for conventional organic liquid electrolytes. However, low ionic conductivity of typical candidates is the key problem. As connective diffusion path is the prerequisite for high performance, we screen for possible solid electrolytes from the 2004 International Centre for Diffraction Data (ICDD) database by calculating conduction pathways using Bond Valence (BV) method. There are 109846 inorganic crystals in the 2004 ICDD database, and 5295 of them contain lithium. Except for those with toxic, radioactive, rare, or variable valence elements, 1380 materials are candidates for solid electrolytes. The rationality of the BV method is approved by comparing the existing solid electrolytes' conduction pathways we had calculated with those from experiments or first principle calculations. The implication for doping and substitution, two important ways to improve the conductivity, is also discussed. Among them Li2CO3 is selected for a detailed comparison, and the pathway is reproduced well with that based on the density functional studies. To reveal the correlation between connectivity of pathways and conductivity, α/ γ-LiAlO2 and Li2CO3 are investigated by the impedance spectrum as an example, and many experimental and theoretical studies are in process to indicate the relationship between property and structure. The BV method can calculate one material within a few minutes, providing an efficient way to lock onto targets from abundant data, and to investigate the structure-property relationship systematically.

  4. 78 FR 49761 - Agency Information Collection Activities: Application for Exportation of Articles Under Special Bond

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-08-15

    ... Exportation of Articles Under Special Bond AGENCY: U.S. Customs and Border Protection, Department of Homeland... information collection requirement concerning the Application for Exportation of Articles under Special Bond... Articles Under Special Bond. OMB Number: 1651-0004. Form Number: CBP Form 3495. Abstract: CBP Form...

  5. 75 FR 61162 - Agency Information Collection Activities: Application for Exportation of Articles Under Special Bond

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-10-04

    ... Exportation of Articles Under Special Bond AGENCY: U.S. Customs and Border Protection, Department of Homeland... Exportation of Articles under Special Bond (CBP Form 3495). This is a proposed extension of an information... Exportation of Articles under Special Bond. OMB Number: 1651-0004. Form Number: Form 3495. Abstract:...

  6. 75 FR 47608 - Agency Information Collection Activities: Application for Exportation of Articles under Special Bond

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-06

    ... Exportation of Articles under Special Bond AGENCY: U.S. Customs and Border Protection, Department of Homeland... requirement concerning the: Application for Exportation of Articles under Special Bond. This request for...: Title: Application for Exportation of Articles under Special Bond. OMB Number: 1651-0004. Form...

  7. 26 CFR 1.103(n)-3T - Private activity bond limit (temporary).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... V empowered Authority Z to issue industrial development bonds on behalf of the three States and to... industrial development bonds to provide a pollution control facility described in section 103(b)(4)(F) for... the County to issue $25 million of industrial development bonds for its project during calendar...

  8. 26 CFR 1.103(n)-3T - Private activity bond limit (temporary).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... V empowered Authority Z to issue industrial development bonds on behalf of the three States and to... industrial development bonds to provide a pollution control facility described in section 103(b)(4)(F) for... the County to issue $25 million of industrial development bonds for its project during calendar...

  9. Mass spectrometry method to identify aging pathways of Sp- and Rp-tabun adducts on human butyrylcholinesterase based on the acid labile P-N bond.

    PubMed

    Jiang, Wei; Cashman, John R; Nachon, Florian; Masson, Patrick; Schopfer, Lawrence M; Lockridge, Oksana

    2013-04-01

    The phosphoramidate nerve agent tabun inhibits butyrylcholinesterase (BChE) and acetylcholinesterase by making a covalent bond on the active site serine. The adduct loses an alkyl group in a process called aging. The mechanism of aging of the tabun adduct is controversial. Some studies claim that aging proceeds through deamination, whereas crystal structure studies show aging by O-dealkylation. Our goal was to develop a method that clearly distinguishes between deamination and O-dealkylation. We began by studying the tetraisopropyl pyrophosphoramide adduct of BChE because this adduct has two P-N bonds. Mass spectra showed that the P-N bonds were stable during trypsin digestion at pH 8 but were cleaved during pepsin digestion at pH 2. The P-N bond in tabun was also acid labile, whereas the P-O bond was stable. A scheme to distinguish aging by deamination from aging by O-dealkylation was based on the acid labile P-N bond. BChE was inhibited with Sp- and Rp-tabun thiocholine nerve agent model compounds to make adducts identical to those of tabun with known stereochemistry. After aging and digestion with pepsin at pH 2, peptide FGES198AGAAS from Sp-tabun thiocholine had a mass of 902.2 m/z in negative mode, indicating that it had aged by deamination, whereas peptide FGES198AGAAS from Rp-tabun thiocholine had a mass of 874.2 m/z in negative mode, indicating that it had aged by O-dealkylation. BChE inhibited by authentic, racemic tabun yielded both 902.2 and 874.2 m/z peptides, indicating that both stereoisomers reacted with BChE and aged either by deamination or dealkylation.

  10. Mass Spectrometry Method to Identify Aging Pathways of Sp- and Rp-Tabun Adducts on Human Butyrylcholinesterase Based on the Acid Labile P-N Bond

    PubMed Central

    Lockridge, Oksana

    2013-01-01

    The phosphoramidate nerve agent tabun inhibits butyrylcholinesterase (BChE) and acetylcholinesterase by making a covalent bond on the active site serine. The adduct loses an alkyl group in a process called aging. The mechanism of aging of the tabun adduct is controversial. Some studies claim that aging proceeds through deamination, whereas crystal structure studies show aging by O-dealkylation. Our goal was to develop a method that clearly distinguishes between deamination and O-dealkylation. We began by studying the tetraisopropyl pyrophosphoramide adduct of BChE because this adduct has two P-N bonds. Mass spectra showed that the P-N bonds were stable during trypsin digestion at pH 8 but were cleaved during pepsin digestion at pH 2. The P-N bond in tabun was also acid labile, whereas the P-O bond was stable. A scheme to distinguish aging by deamination from aging by O-dealkylation was based on the acid labile P-N bond. BChE was inhibited with Sp- and Rp-tabun thiocholine nerve agent model compounds to make adducts identical to those of tabun with known stereochemistry. After aging and digestion with pepsin at pH 2, peptide FGES198AGAAS from Sp-tabun thiocholine had a mass of 902.2 m/z in negative mode, indicating that it had aged by deamination, whereas peptide FGES198AGAAS from Rp-tabun thiocholine had a mass of 874.2 m/z in negative mode, indicating that it had aged by O-dealkylation. BChE inhibited by authentic, racemic tabun yielded both 902.2 and 874.2 m/z peptides, indicating that both stereoisomers reacted with BChE and aged either by deamination or dealkylation. PMID:23345579

  11. The Effect of Artificial Aging on The Bond Strength of Heat-activated Acrylic Resin to Surface-treated Nickel-chromium-beryllium Alloy

    PubMed Central

    Al Jabbari, Youssef S.; Zinelis, Spiros; Al Taweel, Sara M.; Nagy, William W.

    2016-01-01

    Purpose The debonding load of heat-activated polymethylmethacrylate (PMMA) denture base resin material to a nickel-chromium-beryllium (Ni-Cr-Be) alloy conditioned by three different surface treatments and utilizing two different commercial bonding systems was investigated. Materials and Methods Denture resin (Lucitone-199) was bonded to Ni-Cr-Be alloy specimens treated with Metal Primer II, the Rocatec system with opaquer and the Rocatec system without opaquer. Denture base resin specimens bonded to non-treated sandblasted Ni-Cr-Be alloy were used as controls. Twenty samples for each treatment condition (80 specimens) were tested. The 80 specimens were divided into two categories, thermocycled and non-thermocycled, containing four groups of ten specimens each. The non-thermocycled specimens were tested after 48 hours’ storage in room temperature water. The thermocycled specimens were tested after 2,000 cycles in 4°C and 55°C water baths. The debonding load was calculated in Newtons (N), and collected data were subjected by non parametric test Kruskal-Wallis One Way Analysis of Variance on Ranks and Dunn’s post hoc test at the α = 0.05. Results The Metal Primer II and Rocatec system without opaquer groups produced significantly higher bond strengths (119.9 and 67.6 N), respectively, than did the sandblasted and Rocatec system with opaquer groups, where the bond strengths were 2.6 N and 0 N, respectively. The Metal Primer II was significantly different from all other groups (P<0.05). The bond strengths of all groups were significantly decreased (P<0.05) after thermocycling. Conclusions Although thermocycling had a detrimental effect on the debonding load of all surface treatments tested, the Metal Primer II system provided higher values among all bonding systems tested, before and after thermocycling. PMID:27335613

  12. Surface activated bonding of GaAs and SiC wafers at room temperature for improved heat dissipation in high-power semiconductor lasers

    NASA Astrophysics Data System (ADS)

    Higurashi, Eiji; Okumura, Ken; Nakasuji, Kaori; Suga, Tadatomo

    2015-03-01

    Thermal management of high-power semiconductor lasers is of great importance since the output power and beam quality are affected by the temperature rise of the gain region. Thermal simulations of a vertical-external-cavity surface-emitting laser by a finite-element method showed that the solder layer between the semiconductor thin film consisting of the gain region and a heat sink has a strong influence on the thermal resistance and direct bonding is preferred to achieve effective heat dissipation. To realize thin-film semiconductor lasers directly bonded on a high-thermal-conductivity substrate, surface-activated bonding using an argon fast atom beam was applied to the bonding of gallium arsenide (GaAs) and silicon carbide (SiC) wafers. The GaAs/SiC structure was demonstrated in the wafer scale (2 in. in diameter) at room temperature. The cross-sectional transmission electron microscopy observations showed that void-free bonding interfaces were achieved.

  13. Activation of CO and CO2 on homonuclear boron bonds of fullerene-like BN cages: first principles study

    PubMed Central

    Sinthika, S.; Kumar, E. Mathan; Surya, V. J.; Kawazoe, Y.; Park, Noejung; Iyakutti, K.; Thapa, Ranjit

    2015-01-01

    Using density functional theory we investigate the electronic and atomic structure of fullerene-like boron nitride cage structures. The pentagonal ring leads to the formation of homonuclear bonds. The homonuclear bonds are also found in other BN structures having pentagon line defect. The calculated thermodynamics and vibrational spectra indicated that, among various stable configurations of BN-60 cages, the higher number of homonuclear N-N bonds and lower B:N ratio can result in the more stable structure. The homonuclear bonds bestow the system with salient catalytic properties that can be tuned by modifying the B atom bonding environment. We show that homonuclear B-B (B2) bonds can anchor both oxygen and CO molecules making the cage to be potential candidates as catalyst for CO oxidation via Langmuir–Hinshelwood (LH) mechanism. Moreover, the B-B-B (B3) bonds are reactive enough to capture, activate and hydrogenate CO2 molecules to formic acid. The observed trend in reactivity, viz B3 > B2 > B1 is explained in terms of the position of the boron defect state relative to the Fermi level. PMID:26626147

  14. Effect of root canal rinsing protocol on dentin bond strength of two resin cements using three different method of test

    PubMed Central

    Khoroushi, Maryam; Sheikhi, Mohammadreza; Soleimani, Bahram

    2016-01-01

    Background Different studies have used different tests to evaluate bond strength of resin cements to root dentin. In this in vitrostudy, three different tests were used to evaluate the bond strength of two resin cements to root dentin using two root dentin irrigation protocols. Material and Methods Ninety-six intact single-rooted teeth were selected for this study. Forty-eight teeth, with a root length of 15mm, were randomly divided into two groups and irrigated with normal saline or 2.5% sodium hypochlorite solutions during root canal preparation, respectively. For each 12 specimens from each group, fiber post #1 was bonded using an etch-and-rinse (Duo-Link) and a self-adhesive (BisCem) resin cement, respectively. After incubation, two specimens were prepared for the push-out test from the middle thirds of the roots. In another 24 teeth, after two 1.5-mm sections were prepared from the middle thirds of the prepared roots, sections of the post were bonded in two subgroups with each of the cements mentioned above and the samples were prepared for the pull-out test. For shear test, the crowns of 48 teeth were cut away, the dentin surfaces were prepared, the two irrigation solutions were used, and the resin cements were bonded. Data collected from the three tests were evaluated by ANOVA, post-hoc Tukey and Weibull tests (α=0.05). Results There were significant differences in the mean bond strength values between the three bond strength tests (P<0.001). Rinsing protocol and cement type resulted in similar variations in the mean bond strength in all tests (P>0.05). Conclusions Under the limitations of the present study, the method of the test used had an effect on the recorded bond strength between the resin cement and root dentin. Cement type and irrigation protocol resulted in similar variations with all the tests. Push-out and shear tests exhibited more coherent results. Key words:Bond strength, endodontically treated tooth, fiber post, resin cement, sodium

  15. Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation

    PubMed Central

    Tian, Panpan; Feng, Chao; Loh, Teck-Peng

    2015-01-01

    Fluoroalkenes represent a class of privileged structural motifs, which found widespread use in medicinal chemistry. However, the synthetic access to fluoroalkenes was much underdeveloped with previous reported methods suffering from either low step economy or harsh reaction conditions. Here we present a RhIII-catalysed tandem C–H/C–F activation for the synthesis of (hetero)arylated monofluoroalkenes. The use of readily available gem-difluoroalkenes as electrophiles provides a highly efficient and operationally simple method for the introduction of α-fluoroalkenyl motifs onto (hetero)arenes under oxidant-free conditions. Furthermore, the employment of alcoholic solvent and the in-situ generated hydrogen fluoride are found to be beneficial in this transformation, indicating the possibility of the involvement of hydrogen bond activation mode with regards to the C–F bond cleavage step. PMID:26081837

  16. Probing the nature of chemical bonding in uranyl(VI) complexes with quantum chemical methods.

    PubMed

    Vallet, Valérie; Wahlgren, Ulf; Grenthe, Ingmar

    2012-12-20

    To assess the nature of chemical bonds in uranyl(VI) complexes with Lewis base ligands, such as F(-), Cl(-), OH(-), CO(3)(2-), and O(2)(2-), we have used quantum chemical observables, such as the bond distances, the internal symmetric/asymmetric uranyl stretch frequencies, and the electron density with its topology analyzed using the quantum theory of atoms-in-molecules. This analysis confirms that complex formation induces a weakening of the uranium-axial oxygen bond, reflected by the longer U-O(yl) bond distance and reduced uranyl-stretching frequencies. The strength of the ligand-induced effect increases in the order H(2)O < Cl(-) < F(-) < OH(-) < CO(3)(2-) < O(2)(2-). In-depth analysis reveals that the trend across the series does not always reflect an increasing covalent character of the uranyl-ligand bond. By using a point-charge model for the uranyl tetra-fluoride and tetra-chloride complexes, we show that a significant part of the uranyl bond destabilization arises from purely electrostatic interactions, the remaining part corresponding either to charge-transfer from the negatively charged ligands to the uranyl unit or a covalent interaction. The charge-transfer and the covalent interaction are qualitatively different due to the absence of a charge build up in the uranyl-halide bond region in the latter case. In all the charged complexes, the uranyl-ligand bond is best described as an ionic interaction. However, there are covalent contributions in the very stable peroxide complex and, to some extent, also in the carbonate complex. This study demonstrates that it is possible to describe the nature of chemical bond by observables rather than by ad hoc quantities such as atomic populations or molecular orbitals.

  17. Annealing effects on recombinative activity of nickel at direct silicon bonded interface

    SciTech Connect

    Kojima, Takuto Ohshita, Yoshio; Yamaguchi, Masafumi

    2015-09-15

    By performing capacitance transient analyses, the recombination activity at a (110)/(100) direct silicon bonded (DSB) interface contaminated with nickel diffused at different temperatures, as a model of grain boundaries in multicrystalline silicon, was studied. The trap level depth from the valence band, trap density of states, and hole capture cross section peaked at an annealing temperature of 300 °C. At temperatures ⩾400 °C, the hole capture cross section increased with temperature, but the density of states remained unchanged. Further, synchrotron-based X-ray analyses, microprobe X-ray fluorescence (μ-XRF), and X-ray absorption near edge structure (XANES) analyses were performed. The analysis results indicated that the chemical phase after the sample was annealed at 200 °C was a mixture of NiO and NiSi{sub 2}.

  18. Polyhydrides of Platinum Group Metals: Nonclassical Interactions and σ-Bond Activation Reactions.

    PubMed

    Esteruelas, Miguel A; López, Ana M; Oliván, Montserrat

    2016-08-10

    The preparation, structure, dynamic behavior in solution, and reactivity of polyhydride complexes of platinum group metals, described during the last three decades, are contextualized from both organometallic and coordination chemistry points of view. These compounds, which contain dihydrogen, elongated dihydrogen, compressed dihydride, and classical dihydride ligands promote the activation of B-H, C-H, Si-H, N-H, O-H, C-C, C-N, and C-F, among other σ-bonds. In this review, it is shown that, unlike other more mature areas, the chemistry of polyhydrides offers new exciting conceptual challenges and at the same time the possibility of interacting with other fields including the conversion and storage of regenerative energy, organic synthetic chemistry, drug design, and material science. This wide range of possible interactions foresees promising advances in the near future.

  19. Annealing effects on recombinative activity of nickel at direct silicon bonded interface

    NASA Astrophysics Data System (ADS)

    Kojima, Takuto; Ohshita, Yoshio; Yamaguchi, Masafumi

    2015-09-01

    By performing capacitance transient analyses, the recombination activity at a (110)/(100) direct silicon bonded (DSB) interface contaminated with nickel diffused at different temperatures, as a model of grain boundaries in multicrystalline silicon, was studied. The trap level depth from the valence band, trap density of states, and hole capture cross section peaked at an annealing temperature of 300 °C. At temperatures ⩾400 °C, the hole capture cross section increased with temperature, but the density of states remained unchanged. Further, synchrotron-based X-ray analyses, microprobe X-ray fluorescence (μ-XRF), and X-ray absorption near edge structure (XANES) analyses were performed. The analysis results indicated that the chemical phase after the sample was annealed at 200 °C was a mixture of NiO and NiSi2.

  20. Using Unnatural Amino Acids to Probe the Energetics of Oxyanion Hole Hydrogen Bonds in the Ketosteroid Isomerase Active Site

    PubMed Central

    2015-01-01

    Hydrogen bonds are ubiquitous in enzyme active sites, providing binding interactions and stabilizing charge rearrangements on substrate groups over the course of a reaction. But understanding the origin and magnitude of their catalytic contributions relative to hydrogen bonds made in aqueous solution remains difficult, in part because of complexities encountered in energetic interpretation of traditional site-directed mutagenesis experiments. It has been proposed for ketosteroid isomerase and other enzymes that active site hydrogen bonding groups provide energetic stabilization via “short, strong” or “low-barrier” hydrogen bonds that are formed due to matching of their pKa or proton affinity to that of the transition state. It has also been proposed that the ketosteroid isomerase and other enzyme active sites provide electrostatic environments that result in larger energetic responses (i.e., greater “sensitivity”) to ground-state to transition-state charge rearrangement, relative to aqueous solution, thereby providing catalysis relative to the corresponding reaction in water. To test these models, we substituted tyrosine with fluorotyrosines (F-Tyr’s) in the ketosteroid isomerase (KSI) oxyanion hole to systematically vary the proton affinity of an active site hydrogen bond donor while minimizing steric or structural effects. We found that a 40-fold increase in intrinsic F-Tyr acidity caused no significant change in activity for reactions with three different substrates. F-Tyr substitution did not change the solvent or primary kinetic isotope effect for proton abstraction, consistent with no change in mechanism arising from these substitutions. The observed shallow dependence of activity on the pKa of the substituted Tyr residues suggests that the KSI oxyanion hole does not provide catalysis by forming an energetically exceptional pKa-matched hydrogen bond. In addition, the shallow dependence provides no indication of an active site electrostatic

  1. Electrocrystallization: A Synthetic Method for Intermetallic Phases with Polar Metal-Metal Bonding.

    PubMed

    Tambornino, Frank; Sappl, Jonathan; Pultar, Felix; Cong, Trung Minh; Hübner, Sabine; Giftthaler, Tobias; Hoch, Constantin

    2016-11-07

    Isothermal electrolysis is a convenient preparation technique for a large number of intermetallic phases. A solution of the salt of a less-noble metal is electrolyzed on a cathode consisting of a liquid metal or intermetallic system. This yields crystalline products at mild reaction conditions in a few hours. We show the aptness and the limitations of this approach. First, we give an introduction into the relevance of electrolytic synthesis for chemistry. Then we present materials and techniques our group has developed for electrocrystallization that are useful for electrochemical syntheses in general. Subsequently, we discuss different phase formation eventualities and propose basic rationalization concepts, illustrated with examples from our work. The scope of this report is to present electrocrystallization as a well-known yet underestimated synthetic process, especially in intermetallic chemistry. For this purpose we adduce literature examples (Li3Ga14, NaGa4, K8Ga8Sn38), technical advice, basic concepts, and new crystal structures only available by this method: Li3Ga13Sn and CsIn12. Electrocrystallization has recently proven especially helpful in our work concerning synthesis of intermetallic phases with polar metal-metal bonding, especially Hg-rich amalgams of less-noble metals. With the term "polar metal-metal bonding" we describe phases where the constituting elements have large electronegativity difference and yet show incomplete electron transfer from the less-noble to the nobler metal. This distinguishes polar intermetallic phases from classical Zintl phases where the electron transfer is virtually complete. Polar metallic phases can show "bad metal behavior" and interesting combinations of ionic and metallic properties. Amalgams of less-noble metals are preeminent representatives for this class of intermetallic phases as Hg is the only noble metal with endothermic electron affinity and thus a very low tendency toward anion formation. To illustrate both

  2. Method and device for determining bond separation strength using induction heating

    NASA Technical Reports Server (NTRS)

    Coultrip, Robert H. (Inventor); Johnson, Samuel D. (Inventor); Copeland, Carl E. (Inventor); Phillips, W. Morris (Inventor); Fox, Robert L. (Inventor)

    1994-01-01

    An induction heating device includes an induction heating gun which includes a housing, a U-shaped pole piece having two spaced apart opposite ends defining a gap there between, the U-shaped pole piece being mounted in one end of the housing, and a tank circuit including an induction coil wrapped around the pole piece and a capacitor connected to the induction coil. A power source is connected to the tank circuit. A pull test machine is provided having a stationary chuck and a movable chuck, the two chucks holding two test pieces bonded together at a bond region. The heating gun is mounted on the pull test machine in close proximity to the bond region of the two test pieces, whereby when the tank circuit is energized, the two test pieces are heated by induction heating while a tension load is applied to the two test pieces by the pull test machine to determine separation strength of the bond region.

  3. Steel bonded dense silicon nitride compositions and method for their fabrication

    DOEpatents

    Landingham, Richard L.; Shell, Thomas E.

    1987-01-01

    A two-stage bonding technique for bonding high density silicon nitride and other ceramic materials to stainless steel and other hard metals, and multilayered ceramic-metal composites prepared by the technique are disclosed. The technique involves initially slurry coating a surface of the ceramic material at about 1500.degree. C. in a vacuum with a refractory material and the stainless steel is then pressure bonded to the metallic coated surface by brazing it with nickel-copper-silver or nickel-copper-manganese alloys at a temperature in the range of about 850.degree. to 950.degree. C. in a vacuum. The two-stage bonding technique minimizes the temperature-expansion mismatch between the dissimilar materials.

  4. Steel bonded dense silicon nitride compositions and method for their fabrication

    DOEpatents

    Landingham, R.L.; Shell, T.E.

    1985-05-20

    A two-stage bonding technique for bonding high density silicon nitride and other ceramic materials to stainless steel and other hard metals, and multilayered ceramic-metal composites prepared by the technique are disclosed. The technique involves initially slurry coating a surface of the ceramic material at about 1500/sup 0/C in a vacuum with a refractory material and the stainless steel is then pressure bonded to the metallic coated surface by brazing it with nickel-copper-silver or nickel-copper-manganese alloys at a temperature in the range of about 850/sup 0/ to 950/sup 0/C in a vacuum. The two-stage bonding technique minimizes the temperature-expansion mismatch between the dissimilar materials.

  5. In vitro evaluation of a moisture-active adhesive for indirect bonding.

    PubMed

    Klocke, Arndt; Shi, Jianmin; Kahl-Nieke, Bärbel; Bismayer, Ulrich

    2003-12-01

    The aim of this in vitro investigation was to evaluate bond strength for a cyanoacrylate adhesive in combination with an indirect bonding technique. Eighty bovine permanent mandibular incisors were randomly divided into four groups of 20 teeth each. The influence of two factors on shear bond strength was investigated: (1) type of adhesive (Smartbond cyanoacrylate, Sondhi Rapid Set composite sealant) and (2) time of debonding (30 minutes and 24 hours after bonding). Stainless steel mesh-based brackets were used. Although, bond strength was not significantly different for the two debonding time periods, significantly lower bond strength measurements were found for the cyanoacrylate adhesive (P < .001). The mean bond strength for the cyanoacrylate adhesive group was 5.44 +/- 1.65 MPa for debonding 30 minutes and 6.92 +/- 1.48 MPa for debonding 24 hours after the bonding procedure vs 16.16 +/- 5.25 MPa and 14.98 +/- 2.85 MPa for the composite adhesive groups debonded at 30 minutes and 24 hours, respectively. The Weibull analysis indicated that there was an increased risk of bond failure at clinically relevant levels of stress for indirect bonding with the cyanoacrylate adhesive.

  6. Nsbnd H⋯O hydrogen bonded novel nonlinear optical semiorganic crystal (4-methoxyanilinium trifluoroacetate) studied through theoretical and experimental methods

    NASA Astrophysics Data System (ADS)

    Siva, V.; Suresh Kumar, S.; Suresh, M.; Raja, M.; Athimoolam, S.; Asath Bahadur, S.

    2017-04-01

    The new semi-organic crystal of 4-methoxyanilinium trifluoroacetate (4MATFA) was designed through strong Nsbnd H⋯O hydrogen bonds in the perspective of its nonlinear optical (NLO) properties. The crystalline state of 4MATFA was successfully attained by slow evaporation solution growth method at room temperature. The molecular structure of the grown crystal was determined by single crystal X-ray diffraction technique which confirms the importance of Nsbnd H⋯O hydrogen bonds in the molecular assembly. The amino group of the cation and carboxylate group of the anion are hydrogen bonded through two primary chains C12(4) and C22(6) motifs and a secondary ring R44(12) motif leading to alternate hydrophobic and hydrophilic layers at z = 0 or 1 and at z = 1/2, respectively. The molecular geometry was optimized theoretically by Hartree-Fock (HF) and Density Functional Theory (DFT) methods with 6-311++G(d,p) basis set. The optimized molecular geometrical parameters and computed vibrational spectra demonstrated the presence of Nsbnd H⋯O hydrogen bonds and the absence of expected Nsbnd H⋯F hydrogen bonds. The strong Nsbnd H⋯O tendency between the ions are observed as strong intensity isolated peak in computed IR spectra and strong intensity broad peak in experimental IR spectrum. Further, the calculated first (β) and second order hyperpolarizability (γ) values showed that the compound is good candidate for NLO applications. The chemical hardness, electro-negativity and chemical potential of the molecule were computed by HOMO - LUMO plot. The frontier orbital has lower band gap value, which indicate the possible optical activity of the molecule. The thermal stability of the grown crystals were confirmed by TG/DTA which showed the thermal stability of the compound upto 150 °C.

  7. A Review of Chemical Bonding Studies: Needs, Aims, Methods of Exploring Students' Conceptions, General Knowledge Claims and Students' Alternative Conceptions

    ERIC Educational Resources Information Center

    Unal, Suat; Calik, Muammer; Ayas, Alipasa; Coll, Richard K.

    2006-01-01

    The present paper presents a detailed thematic review of chemical bonding studies. To achieve this, a matrix is developed to summarize and present the findings by focusing on insights derived from the related studies. The matrix incorporates the following themes: needs, aims, methods of exploring students' conceptions, general knowledge claims,…

  8. GaInAsP/silicon-on-insulator hybrid laser with ring-resonator-type reflector fabricated by N2 plasma-activated bonding

    NASA Astrophysics Data System (ADS)

    Hayashi, Yusuke; Suzuki, Junichi; Inoue, Satoshi; Tanvir Hasan, Shovon Muhammad; Kuno, Yuki; Itoh, Kazuto; Amemiya, Tomohiro; Nishiyama, Nobuhiko; Arai, Shigehisa

    2016-08-01

    III-V/Si hybrid integration with direct bonding is an attractive method of realizing an electrophotonic convergence router with a small size and a low power consumption. Plasma-activated bonding (PAB) is an effective approach for reducing thermal stress during the bonding process because PAB achieves a high bonding strength with low-temperature annealing. This time, the fabrication of a GaInAsP/silicon-on-insulator (SOI) hybrid laser with Si ring-resonator-type reflectors was demonstrated by N2 PAB. By measuring the lasing spectra, we confirmed the reflective characteristics resulting from the cascaded Si ring resonators. We also investigated kink characteristics, which occur around the threshold current, of the current-light output (I-L) characteristics, and successfully approximated the kink characteristics by considering saturable absorption occurring at the III-V/Si taper tip. The taper structure was investigated in terms of a passive device as well as an active device, and a structure for eliminating saturable absorption was proposed.

  9. Platinum(0)-mediated C-O bond activation of ethers via an SN2 mechanism.

    PubMed

    Ortuño, Manuel A; Jasim, Nasarella A; Whitwood, Adrian C; Lledós, Agustí; Perutz, Robin N

    2016-11-29

    A computational study of the C(methyl)-O bond activation of fluorinated aryl methyl ethers by a platinum(0) complex Pt(PCyp3)2 (Cyp = cyclopentyl) (N. A. Jasim, R. N. Perutz, B. Procacci and A. C. Whitwood, Chem. Commun., 2014, 50, 3914) demonstrates that the reaction proceeds via an SN2 mechanism. Nucleophilic attack of Pt(0) generates an ion pair consisting of a T-shaped platinum cation with an agostic interaction with a cyclopentyl group and a fluoroaryloxy anion. This ion-pair is converted to a 4-coordinate Pt(ii) product trans-[PtMe(OAr(F))(PCyp3)2]. Structure-reactivity correlations are fully consistent with this mechanism. The Gibbs energy of activation is calculated to be substantially higher for aryl methyl ethers without fluorine substituents and higher still for alkyl methyl ethers. These conclusions are in accord with the experimental results. Further support was obtained in an experimental study of the reaction of Pt(PCy3)2 with 2,3,5,6-tetrafluoro-4-allyloxypyridine yielding the salt of the Pt(η(3)-allyl) cation and the tetrafluoropyridinolate anion [Pt(PCy3)2(η(3)-allyl)][OC5NF4]. The calculated activation energy for this reaction is significantly lower than that for fluorinated aryl methyl ethers.

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

    SciTech Connect

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

    2016-02-24

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

  11. Simple, Automated, High Resolution Mass Spectrometry Method to Determine the Disulfide Bond and Glycosylation Patterns of a Complex Protein

    PubMed Central

    Pike, Gennett M.; Madden, Benjamin J.; Melder, Deborah C.; Charlesworth, M. Cristine; Federspiel, Mark J.

    2011-01-01

    Enveloped viruses must fuse the viral and cellular membranes to enter the cell. Understanding how viral fusion proteins mediate entry will provide valuable information for antiviral intervention to combat associated disease. The avian sarcoma and leukosis virus envelope glycoproteins, trimers composed of surface (SU) and transmembrane heterodimers, break the fusion process into several steps. First, interactions between SU and a cell surface receptor at neutral pH trigger an initial conformational change in the viral glycoprotein trimer followed by exposure to low pH enabling additional conformational changes to complete the fusion of the viral and cellular membranes. Here, we describe the structural characterization of the extracellular region of the subgroup A avian sarcoma and leukosis viruses envelope glycoproteins, SUATM129 produced in chicken DF-1 cells. We developed a simple, automated method for acquiring high resolution mass spectrometry data using electron capture dissociation conditions that preferentially cleave the disulfide bond more readily than the peptide backbone amide bonds that enabled the identification of disulfide-linked peptides. Seven of nine disulfide bonds were definitively assigned; the remaining two bonds were assigned to an adjacent pair of cysteine residues. The first cysteine of surface and the last cysteine of the transmembrane form a disulfide bond linking the heterodimer. The surface glycoprotein contains a free cysteine at residue 38 previously reported to be critical for virus entry. Eleven of 13 possible SUATM129 N-linked glycosylation sites were modified with carbohydrate. This study demonstrates the utility of this simple yet powerful method for assigning disulfide bonds in a complex glycoprotein. PMID:21454567

  12. Effect of three adhesive primers on the bond strengths of four light-activated opaque resins to noble alloy.

    PubMed

    Yoshida, K; Kamada, K; Taira, Y; Atsuta, M

    2001-02-01

    The effect of commercial adhesive primers for noble metals on the bond strength of light-activated opaque resin has not been determined. This study evaluated the effect of three adhesive primers on the shear bond strengths of each of the four light-activated opaque resins to silver--palladium--copper--gold (Ag--Pd--Cu--Au) alloy. The adhesive primers Alloy Primer (AP), Metal Primer II (MPII) and Metaltite(MT) were used. Four commercial light-activated opaque resins (Axis (AX), Cesead II (CEII), Dentacolor(DE) and Solidex (SO) were used to bond a light-activated resin-veneered composite to Ag--Pd--Cu--Au alloy. The specimens were stored in water at 37 degrees C for 24 h and then immersed alternatively in water baths at 4 and 60 degrees C for 1 min each for up to 20,000 thermal cycles before shear mode testing at a cross-head speed of 0.5 mm min(-1). All the primers examined improved the shear bond strength between opaque resin and Ag--Pd--Cu--Au alloy compared with non-primed specimens prior to thermal cycling. After 20,000 thermal cycles, the bond strengths of combined use of AP and DE and that of MT and each of AX, CE or DE were significantly greater than any other groups. Significant difference was observed between the bond strengths at thermal cycles 0 and 20,000, with the combined use of MT and DE. With the combination of appropriate adhesive metal primers and light-activated opaque resins, complicated surface preparations of metal frameworks of resin-veneered prostheses that are composed of casting Ag-Pd-Cu-Au alloy may be negligible.

  13. Application of the bond valence method in the non-isovalent semiconductor alloy (GaN)1-x(ZnO)x

    NASA Astrophysics Data System (ADS)

    Liu, Jian

    2016-10-01

    This paper studies the bond valence method (BVM) and its application in the non-isovalent semiconductor alloy (GaN)1-x(ZnO)x. Particular attention is paid to the role of short-range order (SRO). The theoretical standing of the BVM is examined by density-functional theory (DFT) calculations. Combining the BVM with Monte-Carlo simulations and a DFT-based cluster expansion model, bond-length distributions and bond-angle variations are predicted. The connection between bond valence and bond stiffness is also discussed. Finally the BVM is extended to the modelling of an interatomic potential.

  14. Effect of testing methods on the bond strength of resin to zirconia-alumina ceramic: microtensile versus shear test.

    PubMed

    Valandro, Luiz F; Ozcan, Mutlu; Amaral, Regina; Vanderlei, Aleska; Bottino, Marco A

    2008-11-01

    This study tested the bond strength of a resin cement to a glass-infiltrated zirconia-alumina ceramic after three conditioning methods and using two test methods (shear-SBS versus microtensile-MTBS). Ceramic blocks for MTBS and ceramic disks for SBS were fabricated. Three surface conditioning (SC) methods were evaluated: (1) 110-microm Al2O3+silanization; (2) Chairside silica coating+silanization; (3) Laboratory silica coating+silanization. Following surface conditioning, the resin cement (Panavia F) was bonded to the conditioned ceramics. Although no statistically significant differences (p = 0.1076) were seen between the test methods, results yielded with the different surface conditioning methods showed statistically significant differences (p < 0.0001) (SC2 = SC3 > SC1). As for the interaction between the factors, two-way ANOVA showed that it was not statistically significant (p = 0.1443). MTBS test resulted in predominantly mixed failure (85%), but SBS test resulted in exclusively adhesive failure. On the effects of different surface conditioning methods, chairside and laboratory tribochemical silica coating followed by silanization showed higher bond strength results compared to those of aluminum oxide abrasion and silanization, independent of the test method employed.

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  16. Unexpected intermediates and products in the C-F bond activation of tetrafluorobenzenes with a bis(triethylphosphine)nickel synthon: direct evidence of a rapid and reversible C-H bond activation by Ni(0).

    PubMed

    Johnson, Samuel A; Huff, Carla W; Mustafa, Ferheen; Saliba, Mark

    2008-12-24

    The reaction of (PEt(3))(2)Ni(eta(2)-C(14)H(10)), a source of the reactive Ni(PEt(3))(2) moiety, with 1,2,4,5-F(4)C(6)H(2) yields a mixture of three C-F bond activation products that include the unexpected products (PEt(3))(2)NiF-2,3,5,6-F(4)C(6)H and (PEt(3))(2)NiF-2,3,5-F(3)C(6)H(2). Monitoring the reaction mixture via (19)F and (1)H NMR also reveals the presence of the C-H bond activation product, (PEt(3))(2)NiH-2,3,5,6-F(4)C(6)H which is produced in a rapid equilibrium reaction. This observation provides insight into the steps necessary to modify nickel complexes for selective C-F bond activation in a variety of polyfluorinated aromatic substrates, but also expands the potential of simple nickel compounds for C-H bond activation and functionalization reactions.

  17. The role of short-range Cys171-Cys178 disulfide bond in maintaining cutinase active site integrity: A molecular dynamics simulation

    SciTech Connect

    Matak, Mehdi Youssefi; Moghaddam, Majid Erfani

    2009-12-11

    Understanding structural determinants in enzyme active site integrity can provide a good knowledge to design efficient novel catalytic machineries. Fusarium solani pisi cutinase with classic triad Ser-His-Asp is a promising enzyme to scrutinize these structural determinants. We performed two MD simulations: one, with the native structure, and the other with the broken Cys171-Cys178 disulfide bond. This disulfide bond stabilizes a turn in active site on which catalytic Asp175 is located. Functionally important H-bonds and atomic fluctuations in catalytic pocket have been changed. We proposed that this disulfide bond within active site can be considered as an important determinant of cutinase active site structural integrity.

  18. Native disulfide bonds in plasma retinol-binding protein are not essential for all-trans-retinol-binding activity.

    PubMed

    Reznik, Gabriel O; Yu, Yong; Tarr, George E; Cantor, Charles R

    2003-01-01

    A human plasma retinol-binding protein (RBP) mutant, named RBP-S, has been designed and produced in which the six native cysteine residues, involved in the formation of three disulfide bonds, have been replaced with serine. A hexa-histidine tag was also added to the C-terminus of RBP for ease of purification. The removal of the disulfide bonds led to a decrease in the affinity of RBP for all trans-retinol. Data indicates all-trans-retinol binds RBP and RBP-S with Kd = 4 x 10(-8) M and 1 x 10(-7) M, respectively, at approximately 20 degrees C. RBP-S has reduced stability as compared to natural RBP below pH 8.0 and at room temperature. Circular dichroism in the far-UV shows that there is a relaxation of the RBP structure upon the removal of its disulfide bonds. Circular dichroism in the near-UV shows that in the absence of the disulfide bonds, the optical activity of RBP is higher in the 310-330 nm than in the 280-290 nm range. This work suggests that the three native disulfide bonds aid in the folding of RBP but are not essential to produce a soluble, active protein.

  19. Approach to In- Situ Producing Reinforcing Phase Within an Active-Transient Liquid Phase Bond Seam for Aluminum Matrix Composite

    NASA Astrophysics Data System (ADS)

    Zhang, Guifeng; Liao, Xianjin; Chen, Bo; Zhang, Linjie; Zhang, Jianxun

    2015-06-01

    To optimize the braze composition design route for aluminum matrix composite, the feasibility of in situ producing reinforcing phase within the transient liquid phase bond seam matrix, by adding active melting point increaser (MPI, e.g., Ti) together with general melting point depressant (MPD, e.g., Cu) into the interlayer, was demonstrated. For SiC p /A356 composite, by comparing the wettability, joint microstructure, joint shear strength, and fracture path for the developed Al-19Cu-1Ti, Al-19Cu, Al-33Cu-1Ti, Al-33Cu (wt pct), and commercial Cu foils as interlayer, the feasibility of in situ producing reinforcing phase within the bond seam by adding Ti was demonstrated. Especially for Al-19Cu-1Ti active braze, small and dispersed ternary aluminide of Al-Si-Ti phase was obtained within the bond seam as in situ reinforcement, leading to a favorable fracture path within SiC p /A356, not along the initial interface or within the bond seam. For the formation mechanism of the in situ reinforcing phase of MPI-containing intermetallic compound within the bond seam, a model of repeating concentration-precipitation-termination-engulfment during isothermal solidification is proposed.

  20. Theoretical study of optical activity of 1:1 hydrogen bond complexes of water with S-warfarin

    NASA Astrophysics Data System (ADS)

    Dadsetani, Mehrdad; Abdolmaleki, Ahmad; Zabardasti, Abedin

    2016-11-01

    The molecular interaction between S-warfarin (SW) and a single water molecule was investigated using the B3LYP method at 6-311 ++G(d,p) basis set. The vibrational spectra of the optimized complexes have been investigated for stabilization checking. Quantum theories of atoms in molecules, natural bond orbitals, molecular electrostatic potentials and energy decomposition analysis methods have been applied to analyze the intermolecular interactions. The intermolecular charge transfer in the most stable complex is in the opposite direction from those in the other complexes. The optical spectra and the hyperpolarizabilities of SW-water hydrogen bond complexes have been computed.

  1. Systems and methods for using a boehmite bond-coat with polyimide membranes for gas separation

    DOEpatents

    Polishchuk, Kimberly Ann

    2013-03-05

    The subject matter disclosed herein relates to gas separation membranes and, more specifically, to polyimide gas separation membranes. In an embodiment, a gas separation membrane includes a porous substrate, a substantially continuous polyimide membrane layer, and one or more layers of boehmite nanoparticles disposed between the porous substrate and the polyimide membrane layer to form a bond-coat layer. The bond-coat layer is configured to improve the adhesion of the polyimide membrane layer to the porous substrate, and the polyimide membrane layer has a thickness approximately 100 nm or less.

  2. A Novel Method to Quantify Soil Aggregate Stability by Measuring Aggregate Bond Energies

    NASA Astrophysics Data System (ADS)

    Efrat, Rachel; Rawlins, Barry G.; Quinton, John N.; Watts, Chris W.; Whitmore, Andy P.

    2016-04-01

    Soil aggregate stability is a key indicator of soil quality because it controls physical, biological and chemical functions important in cultivated soils. Micro-aggregates are responsible for the long term sequestration of carbon in soil, therefore determine soils role in the carbon cycle. It is thus vital that techniques to measure aggregate stability are accurate, consistent and reliable, in order to appropriately manage and monitor soil quality, and to develop our understanding and estimates of soil as a carbon store to appropriately incorporate in carbon cycle models. Practices used to assess the stability of aggregates vary in sample preparation, operational technique and unit of results. They use proxies and lack quantification. Conflicting results are therefore drawn between projects that do not provide methodological or resultant comparability. Typical modern stability tests suspend aggregates in water and monitor fragmentation upon exposure to an un-quantified amount of ultrasonic energy, utilising a laser granulometer to measure the change in mean weight diameter. In this project a novel approach has been developed based on that of Zhu et al., (2009), to accurately quantify the stability of aggregates by specifically measuring their bond energies. The bond energies are measured operating a combination of calorimetry and a high powered ultrasonic probe, with computable output function. Temperature change during sonication is monitored by an array of probes which enables calculation of the energy spent heating the system (Ph). Our novel technique suspends aggregates in heavy liquid lithium heteropolytungstate, as opposed to water, to avoid exposing aggregates to an immeasurable disruptive energy source, due to cavitation, collisions and clay swelling. Mean weight diameter is measured by a laser granulometer to monitor aggregate breakdown after successive periods of calculated ultrasonic energy input (Pi), until complete dispersion is achieved and bond

  3. C-H bond activation of methane in aqueous solution: a hybrid quantum mechanical/effective fragment potential study.

    PubMed

    Da Silva, Júlio C S; Rocha, Willian R

    2011-12-01

    In this study, we investigated the C-H bond activation of methane catalyzed by the complex [PtCl(4)](2-), using the hybrid quantum mechanical/effective fragment potential (EFP) approach. We analyzed the structures, energetic properties, and reaction mechanism involved in the elementary steps that compose the catalytic cycle of the Shilov reaction. Our B3LYP/SBKJC/cc-pVDZ/EFP results show that the methane activation may proceed through two pathways: (i) electrophilic addition or (ii) direct oxidative addition of the C-H bond of the alkane. The electrophilic addition pathway proceeds in two steps with formation of a σ-methane complex, with a Gibbs free energy barrier of 24.6 kcal mol(-1), followed by the cleavage of the C-H bond, with an energy barrier of 4.3 kcal mol(-1) . The activation Gibbs free energy, calculated for the methane uptake step was 24.6 kcal mol(-1), which is in good agreement with experimental value of 23.1 kcal mol(-1) obtained for a related system. The results shows that the activation of the C-H bond promoted by the [PtCl(4)](2-) catalyst in aqueous solution occurs through a direct oxidative addition of the C-H bond, in a single step, with an activation free energy of 25.2 kcal mol(-1), as the electrophilic addition pathway leads to the formation of a σ-methane intermediate that rapidly undergoes decomposition. The inclusion of long-range solvent effects with polarizable continuum model does not change the activation energies computed at the B3LYP/SBKJC/cc-pVDZ/EFP level of theory significantly, indicating that the large EFP water cluster used, obtained from Monte Carlo simulations and analysis of the center-of-mass radial pair distribution function, captures the most important solvent effects.

  4. Palladium-catalyzed cross-coupling of aryl fluorides with N-tosylhydrazones via C-F bond activation.

    PubMed

    Luo, Haiqing; Wu, Guojiao; Xu, Shuai; Wang, Kang; Wu, Chaoqiang; Zhang, Yan; Wang, Jianbo

    2015-09-04

    A palladium-catalyzed cross-coupling reaction of electron-deficient aryl fluorides with aryl N-tosylhydrazones has been reported. Mechanistically, this approach involves C-F bond activation and migratory insertion of palladium carbene as the two key steps.

  5. Palladium-catalyzed oxidative arylalkylation of activated alkenes: dual C-H bond cleavage of an arene and acetonitrile.

    PubMed

    Wu, Tao; Mu, Xin; Liu, Guosheng

    2011-12-23

    Not one but two: The title reaction proceeds through the dual C-H bond cleavage of both aniline and acetonitrile. The reaction affords a variety of cyano-bearing indolinones in excellent yield. Mechanistic studies demonstrate that this reaction involves a fast arylation of the olefin and a rate-determining C-H activation of the acetonitrile.

  6. Carbon-hydrogen bond activation of aromatic imines by (Cp{sup *}{sub 2}SmH){sub 2}

    SciTech Connect

    Radu, N.S.; Buchwald, S.L.; Scott, B.; Burns, C.J.

    1996-09-17

    Treatment of (Cp{sup *}{sub 2}SmH){sub 2} with 2-phenyl-1-pyrroline forms product 1, via ortho-metalation. Complex 1 was characterized spectroscopically and by single-crystal X-ray diffraction. The C-H bond activation reaction also occurs for acyclic aromatic ketimines and aldimines. 30 refs., 1 fig.

  7. Method of bonding diamonds in a matrix and articles thus produced

    DOEpatents

    Taylor, G.W.

    1981-01-27

    By fluorinating diamond grit, the grit may be readily bonded into a fluorocarbon resin matrix. The matrix is formed by simple hot pressing techniques. Diamond grinding wheels may advantageously be manufactured using such a matrix. Teflon fluorocarbon resins are particularly well suited for using in forming the matrix.

  8. Neutral redox-active hydrogen- and halogen-bonding [2]rotaxanes for the electrochemical sensing of chloride.

    PubMed

    Lim, Jason Y C; Cunningham, Matthew J; Davis, Jason J; Beer, Paul D

    2014-12-14

    The first examples of redox-active ferrocene-functionalised neutral [2]rotaxanes have been synthesised via chloride anion templation. (1)H NMR spectroscopic titrations reveal that these [2]rotaxane host systems recognize chloride selectively over other halides and oxoanions in highly-competitive aqueous media. By replacing the hydrogen bonding prototriazole units of the rotaxane axle component with iodotriazole halogen bond-donor groups, the degree of chloride selectivity of the [2]rotaxanes is modulated. Electrochemical voltammetric experiments demonstrate that the rotaxanes can sense chloride via cathodic perturbations of the respective rotaxanes' ferrocene-ferrocenium redox-couple upon anion addition.

  9. Hydroxide-catalyzed bonding

    NASA Technical Reports Server (NTRS)

    Gwo, Dz-Hung (Inventor)

    2003-01-01

    A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

  10. Interatomic Potential for Hydrocarbons on the Basis of the Modified Embedded-Atom Method with Bond Order (MEAM-BO).

    PubMed

    Mun, Sungkwang; Bowman, Andrew L; Nouranian, Sasan; Gwaltney, Steven R; Baskes, Michael I; Horstemeyer, Mark F

    2017-02-23

    In this paper, we develop a new modified embedded atom method (MEAM) potential that includes the bond order (MEAM-BO) to describe the energetics of unsaturated hydrocarbons (double and triple carbon bonds) and also develop improved parameters for saturated hydrocarbons from those of our previous work. Such quantities like bond lengths, bond angles, and atomization energies at 0 K, dimer molecule interactions, rotational barriers, and the pressure-volume-temperature relationships of dense systems of small molecules give a comparable or more accurate property relative to experimental and first-principles data than the classical reactive force fields REBO and ReaxFF. Our extension of the MEAM potential for unsaturated hydrocarbons (MEAM-BO) is a step toward developing more reliable and accurate polymer simulations with their associated structure-property relationships, such as reactive multicomponent (organic/metal) systems, polymer-metal interfaces, and nanocomposites. When the constants for the BO are zero, MEAM-BO reduces to the original MEAM potential. As such, this MEAM-BO potential describing the interaction of organic materials with metals within the same MEAM formalism is a significant advancement for computational materials science.

  11. Active vibration reduction of a flexible structure bonded with optimised piezoelectric pairs using half and quarter chromosomes in genetic algorithms

    NASA Astrophysics Data System (ADS)

    Daraji, A. H.; Hale, J. M.

    2012-08-01

    The optimal placement of sensors and actuators in active vibration control is limited by the number of candidates in the search space. The search space of a small structure discretized to one hundred elements for optimising the location of ten actuators gives 1.73 × 1013 possible solutions, one of which is the global optimum. In this work, a new quarter and half chromosome technique based on symmetry is developed, by which the search space for optimisation of sensor/actuator locations in active vibration control of flexible structures may be greatly reduced. The technique is applied to the optimisation for eight and ten actuators located on a 500×500mm square plate, in which the search space is reduced by up to 99.99%. This technique helps for updating genetic algorithm program by updating natural frequencies and mode shapes in each generation to find the global optimal solution in a greatly reduced number of generations. An isotropic plate with piezoelectric sensor/actuator pairs bonded to its surface was investigated using the finite element method and Hamilton's principle based on first order shear deformation theory. The placement and feedback gain of ten and eight sensor/actuator pairs was optimised for a cantilever and clamped-clamped plate to attenuate the first six modes of vibration, using minimization of linear quadratic index as an objective function.

  12. Comprehensive investigation of sequential plasma activated Si/Si bonded interfaces for nano-integration on the wafer scale.

    PubMed

    Kibria, M G; Zhang, F; Lee, T H; Kim, M J; Howlader, M M R

    2010-04-02

    The sequentially plasma activated bonding of silicon wafers has been investigated to facilitate the development of chemical free, room temperature and spontaneous bonding required for nanostructure integration on the wafer scale. The contact angle of the surface and the electrical and nanostructural behavior of the interface have been studied. The contact angle measurements show that the sequentially plasma (reactive ion etching plasma followed by microwave radicals) treated surfaces offer highly reactive and hydrophilic surfaces. These highly reactive surfaces allow spontaneous integration at the nanometer scale without any chemicals, external pressure or heating. Electrical characteristics show that the current transportation across the nanobonded interface is dependent on the plasma parameters. High resolution transmission electron microscopy results confirm nanometer scale bonding which is needed for the integration of nanostructures. The findings can be applied in spontaneous integration of nanostructures such as nanowires/nanotubes/quantum dots on the wafer scale.

  13. Locking covalent organic frameworks with hydrogen bonds: general and remarkable effects on crystalline structure, physical properties, and photochemical activity.

    PubMed

    Chen, Xiong; Addicoat, Matthew; Jin, Enquan; Zhai, Lipeng; Xu, Hong; Huang, Ning; Guo, Zhaoqi; Liu, Lili; Irle, Stephan; Jiang, Donglin

    2015-03-11

    A series of two-dimensional covalent organic frameworks (2D COFs) locked with intralayer hydrogen-bonding (H-bonding) interactions were synthesized. The H-bonding interaction sites were located on the edge units of the imine-linked tetragonal porphyrin COFs, and the contents of the H-bonding sites in the COFs were synthetically tuned using a three-component condensation system. The intralayer H-bonding interactions suppress the torsion of the edge units and lock the tetragonal sheets in a planar conformation. This planarization enhances the interlayer interactions and triggers extended π-cloud delocalization over the 2D sheets. Upon AA stacking, the resulting COFs with layered 2D sheets amplify these effects and strongly affect the physical properties of the material, including improving their crystallinity, enhancing their porosity, increasing their light-harvesting capability, reducing their band gap, and enhancing their photocatalytic activity toward the generation of singlet oxygen. These remarkable effects on the structure and properties of the material were observed for both freebase and metalloporphyin COFs. These results imply that exploration of supramolecular ensembles would open a new approach to the structural and functional design of COFs.

  14. C-H fluorination: U can fluorinate unactivated bonds

    NASA Astrophysics Data System (ADS)

    Neumann, Constanze N.; Ritter, Tobias

    2016-09-01

    Introducing C-F bonds into organic molecules is a challenging task, particularly through C-H activation methods. Now, a uranium-based photocatalyst turns traditional selectivity rules on their heads and fluorinates unfunctionalized alkane Csp3-H bonds, even in the presence of C-H bonds that are typically more reactive.

  15. 77 FR 15378 - Agency Information Collection Activities: Application for Withdrawal of Bonded Stores for Fishing...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-15

    ... permission of the CBP port director for the withdrawal and lading of bonded merchandise (especially alcoholic beverages) for use on board fishing vessels involved in international trade. The applicant must certify...

  16. Methandiide as a non-innocent ligand in carbene complexes: from the electronic structure to bond activation reactions and cooperative catalysis.

    PubMed

    Becker, Julia; Modl, Tanja; Gessner, Viktoria H

    2014-09-01

    The synthesis of a ruthenium carbene complex based on a sulfonyl-substituted methandiide and its application in bond activation reactions and cooperative catalysis is reported. In the complex, the metal-carbon interaction can be tuned between a Ru-C single bond with additional electrostatic interactions and a Ru=C double bond, thus allowing the control of the stability and reactivity of the complex. Hence, activation of polar and non-polar bonds (O-H, H-H) as well as dehydrogenation reactions become possible. In these reactions the carbene acts as a non-innocent ligand supporting the bond activation as nucleophilic center in the 1,2-addition across the metal-carbon double bond. This metal-ligand cooperativity can be applied in the catalytic transfer hydrogenation for the reduction of ketones. This concept opens new ways for the application of carbene complexes in catalysis.

  17. Apparatus and method for explosive bonding to edge of flyer plate

    NASA Technical Reports Server (NTRS)

    Bement, Laurence J. (Inventor); Kushnick, Anne C. (Inventor)

    1991-01-01

    The invention is an apparatus and a process for the explosive joining of a flyer plate and a base plate. The apparatus consists of a flyer plate positioned over a base plate. The flyer plate has a notch containing a filler material in intimate contact with the flyer plate. An adhesive means holds a ribbon explosive partially overlapping the notch in the flyer plate. A detonating means initiates the ribbon explosive that drives the flyer plate to accomplish a high velocity, angular collision between the mating surfaces. This collision creates surface melts and effacing bonding, resulting in electron sharing linkups between the plates. An unbonded tab fractures at a base of the notch leaving a bond to an edge of the attached flyer plate.

  18. Bond Activation by Metal-Carbene Complexes in the Gas Phase.

    PubMed

    Zhou, Shaodong; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2016-03-15

    "Bare" metal-carbene complexes, when generated in the gas phase and exposed to thermal reactions under (near) single-collision conditions, exhibit rather unique reactivities in addition to the well-known metathesis and cyclopropanation processes. For example, at room temperature the unligated [AuCH2](+) complex brings about efficient C-C coupling with methane to produce C2Hx (x = 4, 6), and the couple [TaCH2](+)/CO2 gives rise to the generation of the acetic acid equivalent CH2═C═O. Entirely unprecedented is the thermal extrusion of a carbon atom from halobenzenes (X = F, Cl, Br, I) by [MCH2](+) (M = La, Hf, Ta, W, Re, Os) and its coupling with the methylene ligand to deliver C2H2 and [M(X)(C5H5)](+). Among the many noteworthy C-N bond-forming processes, the formation of CH3NH2 from [RhCH2](+)/NH3, the generation of CH2═NH2(+) from [MCH2](+)/NH3 (M = Pt, Au), and the production of [PtCH═NH2](+) from [PtCH2](+)/NH3 are of particular interest. The latter species are likely to be involved as intermediates in the platinum-mediated large-scale production of HCN from CH4/NH3 (the DEGUSSA process). In this context, a few examples are presented that point to the operation of co-operative effects even at a molecular level. For instance, in the coupling of CH4 with NH3 by the heteronuclear clusters [MPt](+) (M = coinage metal), platinum is crucial for the activation of methane, while the coinage metal M controls the branching ratio between the C-N bond-forming step and unwanted soot formation. For most of the gas-phase reactions described in this Account, detailed mechanistic insight has been derived from extensive computational work in conjunction with time-honored labeling and advanced mass-spectrometry-based experiments, and often a coherent description of the experimental findings has been achieved. As for some transition metals, in particular those from the third row, the metal-carbene complexes can be formed directly from methane, coupling of the so

  19. Activation of Propane C-H and C-C Bonds by Gas-Phase Pt Atom: A Theoretical Study

    PubMed Central

    Li, Fang-Ming; Yang, Hua-Qing; Ju, Ting-Yong; Li, Xiang-Yuan; Hu, Chang-Wei

    2012-01-01

    The reaction mechanism of the gas-phase Pt atom with C3H8 has been systematically investigated on the singlet and triplet potential energy surfaces at CCSD(T)//BPW91/6-311++G(d, p), Lanl2dz level. Pt atom prefers the attack of primary over secondary C-H bonds in propane. For the Pt + C3H8 reaction, the major and minor reaction channels lead to PtC3H6 + H2 and PtCH2 + C2H6, respectively, whereas the possibility to form products PtC2H4 + CH4 is so small that it can be neglected. The minimal energy reaction pathway for the formation of PtC3H6 + H2, involving one spin inversion, prefers to start at the triplet state and afterward proceed along the singlet state. The optimal C-C bond cleavages are assigned to C-H bond activation as the first step, followed by cleavage of a C-C bond. The C-H insertion intermediates are kinetically favored over the C-C insertion intermediates. From C-C to C-H oxidative insertion, the lowering of activation barrier is mainly caused by the more stabilizing transition state interaction ΔE≠int, which is the actual interaction energy between the deformed reactants in the transition state. PMID:22942766

  20. The Nature of Activated Non-classical Hydrogen Bonds: A Case Study on Acetylcholinesterase-Ligand Complexes.

    PubMed

    Berg, Lotta; Mishra, Brijesh Kumar; Andersson, C David; Ekström, Fredrik; Linusson, Anna

    2016-02-18

    Molecular recognition events in biological systems are driven by non-covalent interactions between interacting species. Here, we have studied hydrogen bonds of the CH⋅⋅⋅Y type involving electron-deficient CH donors using dispersion-corrected density functional theory (DFT) calculations applied to acetylcholinesterase-ligand complexes. The strengths of CH⋅⋅⋅Y interactions activated by a proximal cation were considerably strong; comparable to or greater than those of classical hydrogen bonds. Significant differences in the energetic components compared to classical hydrogen bonds and non-activated CH⋅⋅⋅Y interactions were observed. Comparison between DFT and molecular mechanics calculations showed that common force fields could not reproduce the interaction energy values of the studied hydrogen bonds. The presented results highlight the importance of considering CH⋅⋅⋅Y interactions when analysing protein-ligand complexes, call for a review of current force fields, and opens up possibilities for the development of improved design tools for drug discovery.

  1. Effects of hydrogen peroxide pretreatment and heat activation of silane on the shear bond strength of fiber-reinforced composite posts to resin cement

    PubMed Central

    Shin, Tae-Bong; Lee, Joo-Hee; Ahn, Kang-Min; Kim, Tae-Hyung

    2016-01-01

    PURPOSE To evaluate the effects of hydrogen peroxide pretreatment and heat activation of silane on the shear bond strength of fiber-reinforced composite posts to resin cement. MATERIALS AND METHODS The specimens were prepared to evaluate the bond strength of epoxy resin-based fiber posts (D.T. Light-Post) to dual-curing resin cement (RelyX U200). The specimens were divided into four groups (n=18) according to different surface treatments: group 1, no treatment; group 2, silanization; group 3, silanization after hydrogen peroxide etching; group 4, silanization with warm drying at 80℃ after hydrogen peroxide etching. After storage of the specimens in distilled water at 37℃ for 24 hours, the shear bond strength (in MPa) between the fiber post and resin cement was measured using a universal testing machine. The fractured surface of the fiber post was examined using scanning electron microscopy. Data were analyzed using one-way ANOVA and post-hoc analysis with Tukey's HSD test (α=0.05). RESULTS Silanization of the fiber post (Group 2) significantly increased the bond strength in comparison with the non treated control (Group 1) (P<.05). Heat drying after silanization also significantly increased the bond strength (Group 3 and 4) (P<.05). However, no effect was determined for hydrogen peroxide etching before applying silane agent (Group 2 and 3) (P>.05). CONCLUSION Fiber post silanization and subsequent heat treatment (80℃) with warm air blower can be beneficial in clinical post cementation. However, hydrogen peroxide etching prior to silanization was not effective in this study. PMID:27141252

  2. A calorimetric method to determine water activity

    NASA Astrophysics Data System (ADS)

    Björklund, Sebastian; Wadsö, Lars

    2011-11-01

    A calorimetric method to determine water activity covering the full range of the water activity scale is presented. A dry stream of nitrogen gas is passed either over the solution whose activity should be determined or left dry before it is saturated by bubbling through water in an isothermal calorimeter. The unknown activity is in principle determined by comparing the thermal power of vaporization related to the gas stream with unknown activity to that with zero activity. Except for three minor corrections (for pressure drop, non-perfect humidification, and evaporative cooling) the unknown water activity is calculated solely based on the water activity end-points zero and unity. Thus, there is no need for calibration with references with known water activities. The method has been evaluated at 30 °C by measuring the water activity of seven aqueous sodium chloride solutions ranging from 0.1 mol kg-1 to 3 mol kg-1 and seven saturated aqueous salt solutions (LiCl, MgCl2, NaBr, NaCl, KCl, KNO3, and K2SO4) with known water activities. The performance of the method was adequate over the complete water activity scale. At high water activities the performance was excellent, which is encouraging as many other methods used for water activity determination have limited performance at high water activities.

  3. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

    SciTech Connect

    Lichtenberger, D.L.

    1991-10-01

    The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies has been developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. This relationship has been used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. We have been able to obtain a direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal. The ionization energies have also been used to correlate the rates of carbonyl substitution reactions of ({eta}{sup 5}-C{sub 5}H{sub 4}X)Rh(CO){sub 2} complexes, and to reveal the electronic factors that control the stability of the transition state. The extent that the electronic features of these bonding interactions transfer to other chemical systems is being investigated in terms of the principle of additivity of ligand electronic effects. Specific examples under study include metal- phosphines, metal-halides, and metallocenes. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C{sub 60} molecule, buckminsterfullerene, and its interaction with a metal surface. The high-resolution valence ionizations in the gas phase reveal the high symmetry of the molecule, and studies of thin films of C{sub 60} reveal weak intermolecular interactions. Scanning tunneling and atomic force microscopy reveal the arrangement of spherical molecules on gold substrates, with significant delocalization of charge from the metal surface. 21 refs.

  4. Effects of polymerization method on flexural and shear bond strengths of a fiber-reinforced composite resin.

    PubMed

    Yanagida, Hiroaki; Tanoue, Naomi; Minesaki, Yoshito; Kamasaki, Yoko; Fujiwara, Taku; Minami, Hiroyuki

    2017-03-31

    This study investigated the effects of indirect composite polymerization on the postcuring mechanical properties of a fiber-reinforced composite. An indirect composite seated on glass fibers preimpregnated with polymerized monomer was polymerized by 1) photoirradiation using a halogen-fluorescent polymerizing unit for 5 min, 2) method 1 plus secondary heating at 100°C for 15 min, 3) photoirradiation using a metal halide light unit for 60 s, or 4) preliminary polymerization using a halogen light unit for 20 s followed by method 3. After polymerization, the flexural and shear bond strengths of the fiber-reinforced composite were examined, as was the flexural strength of non-fiber-reinforced composite specimens polymerized using the same methods. Among non-fiber-reinforced composite specimens, flexural strength was lower for method 1 than for the other three methods; however, among fiberreinforced composite specimens, the four methods did not significantly differ in flexural strength or shear bond strength. Composite-fiber interface separation without breakage of the fiber after flexural strength testing was not observed in specimens polymerized by methods 2 or 4. In conclusion, use of a conventional unit for high-intensity light irradiation after preliminary irradiation, or light irradiation followed by secondary heating, is recommended for polymerization of composite material seated on polymerized glass fiber.

  5. C-O and O-H Bond Activation of Methanole by Lanthanum

    NASA Astrophysics Data System (ADS)

    Silva, Ruchira; Hewage, Dilrukshi; Yang, Dong-Sheng

    2012-06-01

    The interaction between methanol (CH_3OH) molecules and laser-vaporized La atoms resulted in the cleavage of C-O and O-H bonds and the formation of three major products, LaH_2O_2, LaCH_4O_2 and LaC_2H_6O_2, in a supersonic molecular beam. These products were identified by time-of-flight mass spectrometry, and their electronic spectra were obtained using mass-analyzed threshold ionization (MATI) spectroscopy. From the MATI spectra, adiabatic ionization energies of the three complexes were measured to be 40136 (5), 39366 (5) and 38685 (5) cm-1 for LaH_2O_2, LaCH_4O_2 and LaC_2H_6O_2, respectively. The ionization energies of these complexes decrease as the size of the coordinated organic fragments increases. The most active vibrational transitions of all three complexes were observed to be the M-O stretches in the ionic state. A metal-ligand bending mode with a frequency of 127 cm-1 was also observed for [LaH_2O_2]^+. However, the spectra of the other two complexes were less resolved, due to the existence of a large number of low frequency modes, which could be thermally excited even in the supersonic molecular beams, and of multiple rotational isomers formed by the free rotation of the methyl group in these systems. The electronic transitions responsible for the observed spectra were identified as ^1A_1 (C2v) ← ^2A_1 (C2v) for LaH_2O_2 and ^1A (C_1) ← ^2A (C_1) for LaCH_4O_2 and LaC_2H_6O_2.

  6. Electrophilic, Ambiphilic, and Nucleophilic C-H bond Activation. Understanding the electronic continuum of C-H bond activation through transition-state and reaction pathway interaction energy decompositions

    SciTech Connect

    Ess, Daniel H.; Goddard, William A.; Periana, Roy A.

    2010-10-29

    The potential energy and interaction energy profiles for metal- and metal-ligand-mediated alkane C-H bond activation were explored using B3LYP density functional theory (DFT) and the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA). The set of complexes explored range from late transition metal group 10 (Pt and Pd) and group 11 (Au) metal centers to group 7-9 (Ir, Rh, Ru, and W) metal centers as well as a group 3 Sc complex. The coordination geometries, electron metal count (d8, d6, d4, and d0), and ligands (N-heterocycles, O-donor, phosphine, and Cp*) are also diverse. Quantitative analysis using ALMO-EDA of both directions of charge-transfer stabilization (occupied to unoccupied orbital stabilization) energies between the metal-ligand fragment and the coordinated C-H bond in the transition state for cleavage of the C-H bond allows classification of C-H activation reactions as electrophilic, ambiphilic, or nucleophilic on the basis of the net direction of charge-transfer energy stabilization. This bonding pattern transcends any specific mechanistic or bonding paradigm, such as oxidative addition, σ-bond metathesis, or substitution. Late transition metals such as Au(III), Pt(II), Pd(II), and Rh(III) metal centers with N-heterocycle, halide, or O-donor ligands show electrophilically dominated reaction profiles with forward charge-transfer from the C-H bond to the metal, leading to more stabilization than reverse charge transfer from the metal to the C-H bond. Transition states and reaction profiles for d6 Ru(II) and Ir(III) metals with Tp and acac ligands were found to have nearly equal forward and reverse charge-transfer energy stabilization. This ambiphilic region also includes the classically labeled electrophilic cationic species Cp*(PMe3)Ir(Me). Nucleophilic character, where the metal to C-H bond charge-transfer interaction is most stabilizing, was found in

  7. Bent Bonds and Multiple Bonds.

    ERIC Educational Resources Information Center

    Robinson, Edward A.; Gillespie, Ronald J.

    1980-01-01

    Considers carbon-carbon multiple bonds in terms of Pauling's bent bond model, which allows direct calculation of double and triple bonds from the length of a CC single bond. Lengths of these multiple bonds are estimated from direct measurements on "bent-bond" models constructed of plastic tubing and standard kits. (CS)

  8. Non-innocent additives in a palladium(II)-catalyzed C-H bond activation reaction: insights into multimetallic active catalysts.

    PubMed

    Anand, Megha; Sunoj, Raghavan B; Schaefer, Henry F

    2014-04-16

    The role of a widely employed additive (AgOAc) in a palladium acetate-catalyzed ortho-C-H bond activation reaction has been examined using the M06 density functional theory. A new hetero-bimetallic Pd-(μ-OAc)3-Ag is identified as the most likely active species. This finding could have far-reaching implications with respect to the notion of the active species in palladium catalysis in the presence of other metal salt additives.

  9. Active Hydrogen Bond Network (AHBN) and Applications for Improvement of Thermal Stability and pH-Sensitivity of Pullulanase from Bacillus naganoensis

    PubMed Central

    Du, Qi-Shi; Qin, Yan; Li, Jian-Xiu; Meng, Jian-Zong; Huang, Ri-Bo

    2017-01-01

    A method, so called “active hydrogen bond network” (AHBN), is proposed for site-directed mutations of hydrolytic enzymes. In an enzyme the AHBN consists of the active residues, functional residues, and conservative water molecules, which are connected by hydrogen bonds, forming a three dimensional network. In the catalysis hydrolytic reactions of hydrolytic enzymes AHBN is responsible for the transportation of protons and water molecules, and maintaining the active and dynamic structures of enzymes. The AHBN of pullulanase BNPulA324 from Bacillus naganoensis was constructed based on a homologous model structure using Swiss Model Protein-modeling Server according to the template structure of pullulanase BAPulA (2WAN). The pullulanase BNPulA324 are mutated at the mutation sites selected by means of the AHBN method. Both thermal stability and pH-sensitivity of pullulanase BNPulA324 were successfully improved. The mutations at the residues located at the out edge of AHBN may yield positive effects. On the other hand the mutations at the residues inside the AHBN may deprive the bioactivity of enzymes. The AHBN method, proposed in this study, may provide an assistant and alternate tool for protein rational design and protein engineering. PMID:28103251

  10. Active Hydrogen Bond Network (AHBN) and Applications for Improvement of Thermal Stability and pH-Sensitivity of Pullulanase from Bacillus naganoensis.

    PubMed

    Wang, Qing-Yan; Xie, Neng-Zhong; Du, Qi-Shi; Qin, Yan; Li, Jian-Xiu; Meng, Jian-Zong; Huang, Ri-Bo

    2017-01-01

    A method, so called "active hydrogen bond network" (AHBN), is proposed for site-directed mutations of hydrolytic enzymes. In an enzyme the AHBN consists of the active residues, functional residues, and conservative water molecules, which are connected by hydrogen bonds, forming a three dimensional network. In the catalysis hydrolytic reactions of hydrolytic enzymes AHBN is responsible for the transportation of protons and water molecules, and maintaining the active and dynamic structures of enzymes. The AHBN of pullulanase BNPulA324 from Bacillus naganoensis was constructed based on a homologous model structure using Swiss Model Protein-modeling Server according to the template structure of pullulanase BAPulA (2WAN). The pullulanase BNPulA324 are mutated at the mutation sites selected by means of the AHBN method. Both thermal stability and pH-sensitivity of pullulanase BNPulA324 were successfully improved. The mutations at the residues located at the out edge of AHBN may yield positive effects. On the other hand the mutations at the residues inside the AHBN may deprive the bioactivity of enzymes. The AHBN method, proposed in this study, may provide an assistant and alternate tool for protein rational design and protein engineering.

  11. Method of bonding plasticized elastomer to metal and articles produced thereby

    NASA Technical Reports Server (NTRS)

    White, W. T.; Clemons, J. M.; Ledbetter, F. E., III (Inventor)

    1982-01-01

    Plasticized elastomer was securely bonded to a metal surface by interposing between the adhesive-coated metal surface and the elastomer sheet of material obtained by combining adhesive with a portion of the elastomer that was treated to remove plasticizers therefrom and heating the assembly in a mold under pressure. The sheet material is made up by dissolving a portion of the plasticized elastomer in an organic solvent, casting the solution, exposing it to a vacuum to remove the solvent and plasticizers, dissolving the deplasticized material in liquid adhesive and casting and drying the resulting liquid.

  12. The effect of prophylaxis method on microtensile bond strength of indirect restorations to dentin.

    PubMed

    Soares, C J; Pereira, J C; Souza, S J B; Menezes, M S; Armstrong, S R

    2012-01-01

    The aim of this study was to evaluate the effect of different materials used for dentin prophylaxis on the microtensile bond strengths (μTBS) of adhesively cemented indirect composite restorations. Sixty bovine incisors had the buccal surface ground with wet #600-grit silicon carbide abrasive paper to obtain a flat exposed superficial dentin and were submitted to different prophylaxis protocols, as follows: 3% hydrogen peroxide (HydP); 0.12% chlorhexidine (Chlo); sodium bicarbonate jet (SodB); 50-μm aluminum oxide air abrasion (AirA); pumice paste (PumP), and control group-water spray (Cont). After prophylaxis protocols a resin composite block (3.0 mm × 5.0 mm × 5.0 mm) was adhesively cemented using dual resin cement (Rely X ARC). After 24 hours of water storage, specimens were serially sectioned perpendicular to the bonded interface into 1-mm-thick slices. Each specimen was trimmed with a diamond bur to an hourglass shape with a cross-sectional area of approximately 1.0 mm(2) at the bonded area. Specimens were tested (μTBS) at 0.5 mm/min using a universal testing machine. Scanning electron microscopy was used to examine the effects of prophylaxis techniques on dentin. Bond strength data (MPa) were analyzed by one-way analysis of variance and failure mode by Fisher test (α=0.05). μTBS data, means (SD), were (different superscripted letters indicate statistically significant differences): AirA, 25.2 (7.2)(a); PumP, 24.1 (7.8)(a); Chlo, 21.5 (5.6)(a); Cont, 20.6 (8.1)(a); HydP(,) 15.5 (7.6)(b); and SodB(,) 11.5 (4.4)(c). The use of aluminum oxide air abrasion, pumice paste, and chlorhexidine before acid etching did not significantly affect μTBS to dentin; however, the use of hydrogen peroxide and sodium bicarbonate jet significantly reduced μTBS.

  13. Lamb wave based active damage identification in adhesively bonded composite lap joints

    NASA Astrophysics Data System (ADS)

    Jolly, Prateek

    Bonding composite structures using adhesives offers several advantages over mechanical fastening such as better flow stress, weight saving, improved fatigue resistance and the ability to join dissimilar structures. The hesitation to adopt adhesively bonded composite joints stems from the lack of knowledge regarding damage initiation and propagation mechanisms within the joint. A means of overcoming this hesitation is to continuously monitor damage in the joint. This study proposes a methodology to conduct structural health monitoring (SHM) of an adhesively bonded composite lap joint using acoustic, guided Lamb waves by detecting, locating and predicting the size of damage. Finite element modeling of a joint in both 2D and 3D is used to test the feasibility of the proposed damage triangulation technique. Experimental validation of the methodology is conducted by detecting the presence, location and size of inflicted damage with the use of tuned guided Lamb waves.

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

    PubMed Central

    Vinther, Tine N; Norrman, Mathias; Ribel, Ulla; Huus, Kasper; Schlein, Morten; Steensgaard, Dorte B; Pedersen, Thomas Å; Pettersson, Ingrid; Ludvigsen, Svend; Kjeldsen, Thomas; Jensen, Knud J; Hubálek, František

    2013-01-01

    Insulin is a key hormone controlling glucose homeostasis. All known vertebrate insulin analogs have a classical structure with three 100% conserved disulfide bonds that are essential for structural stability and thus the function of insulin. It might be hypothesized that an additional disulfide bond may enhance insulin structural stability which would be highly desirable in a pharmaceutical use. To address this hypothesis, we designed insulin with an additional interchain disulfide bond in positions A10/B4 based on Cα-Cα distances, solvent exposure, and side-chain orientation in human insulin (HI) structure. This insulin analog had increased affinity for the insulin receptor and apparently augmented glucodynamic potency in a normal rat model compared with HI. Addition of the disulfide bond also resulted in a 34.6°C increase in melting temperature and prevented insulin fibril formation under high physical stress even though the C-terminus of the B-chain thought to be directly involved in fibril formation was not modified. Importantly, this analog was capable of forming hexamer upon Zn addition as typical for wild-type insulin and its crystal structure showed only minor deviations from the classical insulin structure. Furthermore, the additional disulfide bond prevented this insulin analog from adopting the R-state conformation and thus showing that the R-state conformation is not a prerequisite for binding to insulin receptor as previously suggested. In summary, this is the first example of an insulin analog featuring a fourth disulfide bond with increased structural stability and retained function. PMID:23281053

  15. Chemically Non-Innocent Cyclic (Alkyl)(Amino)Carbenes: Ligand Rearrangement, C-H and C-F Bond Activation.

    PubMed

    Turner, Zoë R

    2016-08-01

    A cyclic (alkyl)(amino)carbene (CAAC) was found to undergo unprecedented rearrangements and transformations of its core structure in the presence of Group 1 and 2 metals. Although the carbene was also found to be prone to intramolecular C-H activation, it was competent for intermolecular activation of a variety of sp-, sp(2) -, and sp(3) -hybridized C-H bonds. Double C-F activation of hexafluorobenzene was also observed in this work. These processes all hold relevance to the role of these carbenes in catalysis, as well as to their use in the synthesis of new and unusual main group or transition metal complexes.

  16. Diffusion bonding aeroengine components

    NASA Astrophysics Data System (ADS)

    Fitzpatrick, G. A.; Broughton, T.

    1988-10-01

    The use of diffusion bonding processes at Rolls-Royce for the manufacture of titanium-alloy aircraft engine components and structures is described. A liquid-phase diffusion bonding process called activated diffusion bonding has been developed for the manufacture of the hollow titanium wide chord fan blade. In addition, solid-state diffusion bonding is being used in the manufacture of hollow vane/blade airfoil constructions mainly in conjunction with superplastic forming and hot forming techniques.

  17. Conversion of amides to esters by the nickel-catalysed activation of amide C-N bonds

    NASA Astrophysics Data System (ADS)

    Hie, Liana; Fine Nathel, Noah F.; Shah, Tejas K.; Baker, Emma L.; Hong, Xin; Yang, Yun-Fang; Liu, Peng; Houk, K. N.; Garg, Neil K.

    2015-08-01

    Amides are common functional groups that have been studied for more than a century. They are the key building blocks of proteins and are present in a broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to the resonance stability of the amide bond. Although amides can readily be cleaved by enzymes such as proteases, it is difficult to selectively break the carbon-nitrogen bond of an amide using synthetic chemistry. Here we demonstrate that amide carbon-nitrogen bonds can be activated and cleaved using nickel catalysts. We use this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory calculations provide insight into the thermodynamics and catalytic cycle of the amide-to-ester transformation. Our results provide a way to harness amide functional groups as synthetic building blocks and are expected to lead to the further use of amides in the construction of carbon-heteroatom or carbon-carbon bonds using non-precious-metal catalysis.

  18. Method of bonding a conductive layer on an electrode of an electrochemical cell

    DOEpatents

    Bowker, Jeffrey C.; Singh, Prabhakar

    1989-01-01

    A dense, electronically conductive interconnection layer 26 is bonded onto a porous, tubular, electronically conductive air electrode structure 16, optionally supported by a ceramic support 22, by (A) providing an air electrode surface, (B) forming on a selected portion of the electrode surface 24, without the use of pressure, particles of LaCrO.sub.3 doped with an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the particles have a deposit on their surface comprising calcium oxide and chromium oxide; (C) heating the particles with the oxide surface deposit in an oxidizing atmosphere at from 1,300.degree. C. to 1,550.degree. C., without the application of pressure, to provide a dense, sintered, interconnection material 26 bonded to the air electrode 16, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO.sub.3. A solid electrolyte layer 18 can be applied to the uncovered portion of the air electrode, and a fuel electrode 20 can be applied to the solid electrolyte, to provide an electrochemical cell 10.

  19. Method of bonding a conductive layer on an electrode of an electrochemical cell

    DOEpatents

    Bowker, J.C.; Singh, P.

    1989-08-29

    A dense, electronically conductive interconnection layer is bonded onto a porous, tubular, electronically conductive air electrode structure, optionally supported by a ceramic support, by (A) providing an air electrode surface, (B) forming on a selected portion of the electrode surface, without the use of pressure, particles of LaCrO[sub 3] doped with an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the particles have a deposit on their surface comprising calcium oxide and chromium oxide; (C) heating the particles with the oxide surface deposit in an oxidizing atmosphere at from 1,300 C to 1,550 C, without the application of pressure, to provide a dense, sintered, interconnection material bonded to the air electrode, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO[sub 3]. A solid electrolyte layer can be applied to the uncovered portion of the air electrode, and a fuel electrode can be applied to the solid electrolyte, to provide an electrochemical cell. 4 figs.

  20. Carbon-tuned bonding method significantly enhanced the hydrogen storage of BN-Li complexes.

    PubMed

    Deng, Qing-ming; Zhao, Lina; Luo, You-hua; Zhang, Meng; Zhao, Li-xia; Zhao, Yuliang

    2011-11-01

    Through first-principles calculations, we found doping carbon atoms onto BN monolayers (BNC) could significantly strengthen the Li bond on this material. Unlike the weak bond strength between Li atoms and the pristine BN layer, it is observed that Li atoms are strongly hybridized and donate their electrons to the doped substrate, which is responsible for the enhanced binding energy. Li adsorbed on the BNC layer can serve as a high-capacity hydrogen storage medium, without forming clusters, which can be recycled at room temperature. Eight polarized H(2) molecules are attached to two Li atoms with an optimal binding energy of 0.16-0.28 eV/H(2), which results from the electrostatic interaction of the polarized charge of hydrogen molecules with the electric field induced by positive Li atoms. This practical carbon-tuned BN-Li complex can work as a very high-capacity hydrogen storage medium with a gravimetric density of hydrogen of 12.2 wt%, which is much higher than the gravimetric goal of 5.5 wt % hydrogen set by the U.S. Department of Energy for 2015.

  1. New seven membered palladacycles: C-Br bond activation of 2-bromo-pyridine derivative by Pd(II).

    PubMed

    Nicasio-Collazo, Juan; Álvarez, Eleuterio; Alvarado-Monzón, José C; Andreu-de-Riquer, Gabriel; Jimenez-Halla, J Oscar C; De León-Rodríguez, Luis M; Merino, Gabriel; Morales, Ubaldo; Serrano, Oracio; López, Jorge A

    2011-12-14

    C-Br bond activation followed by a C-C coupling reaction of the 2-bromo-pyridyl unit of [1-phenyl-2-(6-bromopyridin-2-yl)-benzoimidazole] was performed by Pd(CH(2)CMe(2)-o-C(6)H(4))(η(4)-COD). Two new seven membered palladacycles were obtained. A combined experimental and theoretical DFT study elucidates the mechanism for this reaction.

  2. The biologically active form of the sea urchin egg receptor for sperm is a disulfide-bonded homo-multimer

    PubMed Central

    1994-01-01

    Since many cell surface receptors exist in their active form as oligomeric complexes, we have investigated the subunit composition of the biologically active sperm receptor in egg plasma membranes from Strongylocentrotus purpuratus. Electrophoretic analysis of the receptor without prior reduction of disulfide bonds revealed that the surface receptor exists in the form of a disulfide-bonded multimer, estimated to be a tetramer. These findings are in excellent agreement with the fact that the NH2-terminus of the extracellular domain of the sperm receptor is rich in cysteine residues. Studies with cross-linking agents of various length and hydrophobicity suggest that no other major protein is tightly associated with the receptor. Given the multimeric structure of the receptor, we investigated the effect of disulfide bond reduction on its biological activity. Because in quantitative bioassays fertilization was found to be inhibited by treatment of eggs with 5 mM dithiothreitol, we undertook more direct studies of the effect of reduction on properties of the receptor. First, we studied the effect of addition of isolated, pure receptor on fertilization. Whereas the non-reduced, native receptor complex inhibited fertilization in a dose- dependent manner, the reduced and alkylated receptor was inactive. Second, we tested the ability of the isolated receptor to mediate binding of acrosome-reacted sperm to polystyrene beads. Whereas beads coated with native receptor bound sperm, those containing reduced and alkylated receptor did not. Thus, these results demonstrate that the biologically active form of the sea urchin sperm receptor consists only of 350 kD subunits and that these must be linked as a multimer via disulfide bonds to produce a complex that is functional in sperm recognition and binding. PMID:8188748

  3. Enantioselective Aminomethylamination of Conjugated Dienes with Aminals Enabled by Chiral Palladium Complex-Catalyzed C-N Bond Activation.

    PubMed

    Liu, Yang; Xie, Yinjun; Wang, Hongli; Huang, Hanmin

    2016-04-06

    A novel highly enantioselective aminomethylamination of conjugated dienes with aminals catalyzed by a chiral palladium complex ligated with BINOL-derived chiral diphosphinite has been successfully developed. This reaction proceeds via a Pd-catalyzed cascade C-N bond activation, aminomethylation, and asymmetric allylic amination reaction under mild reaction conditions, providing a unique and efficient strategy for the synthesis of enantiomerically pure allylic 1,3-diamines.

  4. Easy activation of two C-H bonds of an N-heterocyclic carbene N-methyl group.

    PubMed

    Cabeza, Javier A; del Río, Ignacio; Miguel, Daniel; Sánchez-Vega, M Gabriela

    2005-08-21

    The first trinuclear clusters containing NHC ligands are described; the compound [Ru3(Me2Im)(CO)11](Me2Im=1,3-dimethylimidazol-2-ylidene) is easily converted into [Ru3(mu-H)2(mu3-MeImCH)(CO)9] by a process involving the activation of two C-H bonds of a methyl group that is an example of degradation of a metal-coordinated NHC ligand under mild conditions.

  5. Vapour-induced solid-state C-H bond activation for the clean synthesis of an organopalladium biothiol sensor.

    PubMed

    Monas, Andrea; Užarević, Krunoslav; Halasz, Ivan; Kulcsár, Marina Juribašić; Ćurić, Manda

    2016-10-27

    Room-temperature accelerated aging in the solid state has been applied for atom- and energy-efficient activation of either one or two C-H bonds of azobenzene and methyl orange by palladium(ii) acetate. Organopalladium complexes are prepared in quantitative reactions without potentially harmful side products. Dicyclopalladated methyl orange is water-soluble and is a selective chromogenic biothiol sensor at physiologically-relevant micromolar concentrations in buffered aqueous media.

  6. Influence of Laser Activated Irrigation with two Erbium Lasers on Bond Strength of Inidividually Formed Fiber Reinforced Composite Posts to Root Canal Dentin

    PubMed Central

    Parčina, Ivana; Miletić, Ivana; Ionescu, Andrei C.; Brambilla, Eugenio; Gabrić, Dragana; Baraba, Anja

    2016-01-01

    Objective The aim of this in vitro study was to investigate the effect of laser activated irrigation (LAI) using two erbium lasers on bond strength of individually formed fiber-reinforced composite (FRC) posts to root canal dentin. Materials and methods Twenty-seven single-rooted human teeth were endodontically treated and after post space preparation divided into three groups (n=9 per group), according to the pre-treatment of post space preparation: 1) Conventional syringe irrigation (CSI) and saline; 2) Er.YAG photon-induced photoacoustic streaming (PIPS) technique and saline; 3) Er,Cr:YSGG activated irrigation with RFT2 tip. Two specimens from each group were used for SEM analysis. The remaining specimens (n=7 per group) received individually formed FRC post, everStick POST, luted with self-adhesive cement, G-CEM LinkAce. After cementation, the roots were perpendicularly sectioned into 1 mm thin sections and a push-out test was carried out (0.5 mm/min). The data were calculated as megapascals and were log transformed and statistically analysed using one-way ANOVA at the level of significance set at 5%. Results In the control group, the smear layer was still present. In the Er:YAG group, the smear layer was removed. In the Er,Cr:YSGG group, the smear layer was partially removed. The Er,Cr:YSGG group achieved the highest bond strength values, followed by the control group and then the Er:YAG group, but no statistically significant difference was found in bond strength values in the tested group of post space pretreatment (p=0.564). Conclusions LAI using two erbium lasers, with PIPS or RFT2 tip, did not affect the bond strength of individually formed FRC posts to root canal dentin. PMID:28275279

  7. [The influence of the difference of caries detective methods on the bond strength for caries affected root canal dentin].

    PubMed

    Otake, Shiho

    2010-03-01

    Firm adhesion of composite resin and dentin is the basic premise for building up resin composite cores successfully. To assess the efficacy of several caries detective methods (stained with Caries Detector and probing with sharp probe) for caries affected root canal dentin, microtensile bond strengths of resin composite to caries-affected root canal dentin and failure mode distribution were analyzed in this study. Color and hardness were used for assessment of root caries as follows: Dye stain group (pale pink stained with Caries Detector), Probing group (probing with sharp probe) and Sound dentin group (Control). The bond strengths (mean +/- standard deviation) of the Probing group (64.6 +/- 11.9 MPa) and the Sound dentin group (68.7 +/- 11.1 MPa) were significantly higher than those of the Dye stain group (46.9 +/- 7.9 MPa, p<0.05). However, there is no significant difference in fracture mode between the Dye stain group and the Probing group (p<0.05). This could be attributed to that the thick smear layer caused a loss of hybrid layer strength. In conclusion, the caries removal technique of the root canal dentin affected the bond strength of the resin composite.

  8. Regional push-out bond strength and coronal microleakage of Resilon after different light-curing methods.

    PubMed

    Nagas, Emre; Cehreli, Zafer C; Durmaz, Veli; Vallittu, Pekka K; Lassila, Lippo V J

    2007-12-01

    The purpose of this study was to assess the push-out bond strength and coronal microleakage of the Epiphany (Pentron Clinical Technologies, Wallingford, CT) + Resilon (Resilon Research LLC, Madison, CT) obturation system with respect to different photoactivation methods used. Roots of human maxillary central incisors (n = 60) were prepared with 0.06 taper nickel-titanum rotary files to size 30. After application of the Epiphany sealer, the roots were obturated with Resilon cones. The specimens were randomly assigned into three groups (n = 10/group) according to the light-curing unit (LCU) used from the coronal aspect: (1) quartz-tungsten-halogen/40 seconds, (2) light-emitting diode/20 seconds, and (3) plasma arc/6 seconds. Thereafter, 2-mm thick horizontal sections (n = 3) were obtained from each specimen from the coronal to apical direction and subjected to push-out test at a crosshead-speed of 1mm/min. Failure modes were assessed quantitatively under a stereomicroscope and morphologically under a scanning electron microscope. The remaining 30 roots were used for the dye-leakage assessments. Both the type of LCU and the level of sectioning had significant effects on bond strength. The following statistical ranking was obtained for bond strength values: quartz-tungsten-halogen > light-emitting diode > plasma arc. Coronal microleakage of specimens cured with the plasma arc was significantly greater than those of other groups (p < 0.05).

  9. Interdigitated hydrogen bonds: electrophile activation for covalent capture and fluorescence turn-on detection of cyanide.

    PubMed

    Jo, Junyong; Olasz, András; Chen, Chun-Hsing; Lee, Dongwhan

    2013-03-06

    Hydrogen-bonding promoted covalent modifications are finding useful applications in small-molecule chemical synthesis and detection. We have designed a xanthene-based fluorescent probe 1, in which tightly held acylguanidine and aldehyde groups engage in multiple intramolecular hydrogen bonds within the concave side of the molecule. Such an interdigitated hydrogen bond donor-acceptor (HBD-HBA) array imposes significant energy barriers (ΔG(‡) = 10-16 kcal mol(-1)) for internal bond rotations to assist structural preorganization and effectively polarizes the electrophilic carbonyl group toward a nucleophilic attack by CN(-) in aqueous environment. This covalent modification redirects the de-excitation pathways of the cyanohydrin adduct 2 to elicit a large (>7-fold) enhancement in the fluorescence intensity at λmax = 440 nm. A remarkably faster (> 60-fold) response kinetics of 1, relative to its N-substituted (and therefore "loosely held") analogue 9, provided compelling experimental evidence for the functional role of HBD-HBA interactions in the "remote" control of chemical reactivity, the electronic and steric origins of which were investigated by DFT computational and X-ray crystallographic studies.

  10. Comparative evaluation of microshear bond strength of the caries-affected dentinal surface treated with conventional method and chemomechanical method (papain)

    PubMed Central

    Chittem, Jyothi; Sajjan, Girija S.; Varma, Kanumuri Madhu

    2015-01-01

    Background: There is a growing interest in chemomechanical excavation (papain) in permanent molar teeth. There are several studies dealing with primary molar teeth. Aim: The aim of this study was to evaluate the influence of conventional method and Carie-care (chemomechanical method) on the microshear bond strength (μSBS) and the type of failure of an adhesive system to caries-affected dentin of permanent molar teeth. Materials and Methods: Twenty permanent molar teeth with carious lesions extending into the dentin were selected. Through the center of the carious lesion, teeth were sectioned mesiodistally and divided into two groups based on the method of caries excavation (conventional and chemomechanical method). The time required for the completion of excavation procedure was noted. Samples were again divided into two subgroups in each according to the method of restoration (Ketac N100 and Filtek Z350 composite). The bonded interface was subjected to μSBS testing in a universal testing machine. Fractured surfaces were examined under a stereomicroscope, and representative specimens were examined under scanning electron microscope for the type of failure. Statistical Analysis: It was achieved with unpaired t-test and Kruskal-Wallis H-test at 5% level of significance. Results: The μSBS values of Carie-care groups were similar to that of the conventional method. The μSBSs of resin composite were significantly (P < 0.001) more than that of resin glass ionomer bonded irrespective of the method of caries excavation. Conclusion: A papain-based chemomechanical agent can be used safely as a method for caries removal when employing conventional adhesive systems. PMID:26430299

  11. Performance of wave function and density functional methods for water hydrogen bond spin-spin coupling constants.

    PubMed

    García de la Vega, J M; Omar, S; San Fabián, J

    2017-04-01

    Spin-spin coupling constants in water monomer and dimer have been calculated using several wave function and density functional-based methods. CCSD, MCSCF, and SOPPA wave functions methods yield similar results, specially when an additive approach is used with the MCSCF. Several functionals have been used to analyze their performance with the Jacob's ladder and a set of functionals with different HF exchange were tested. Functionals with large HF exchange appropriately predict (1) J O H , (2) J H H and (2h) J O O couplings, while (1h) J O H is better calculated with functionals that include a reduced fraction of HF exchange. Accurate functionals for (1) J O H and (2) J H H have been tested in a tetramer water model. The hydrogen bond effects on these intramolecular couplings are additive when they are calculated by SOPPA(CCSD) wave function and DFT methods. Graphical Abstract Evaluation of the additive effect of the hydrogen bond on spin-spin coupling constants of water using WF and DFT methods.

  12. The role of group 14 element hydrides in the activation of C-H bonds in cyclic olefins.

    PubMed

    Summerscales, Owen T; Caputo, Christine A; Knapp, Caroline E; Fettinger, James C; Power, Philip P

    2012-09-05

    Formally, triple-bonded dimetallynes ArEEAr [E = Ge (1), Sn (2); Ar = C(6)H(3)-2,6-(C(6)H(3)-2,6-(i)Pr(2))(2)] have been previously shown to activate aliphatic, allylic C-H bonds in cyclic olefins, cyclopentadiene (CpH), cyclopentene (c-C(5)H(8)) and 1,4-cyclohexadiene, with intriguing selectivity. In the case of the five-membered carbocycles, cyclopentadienyl species ArECp [E = Ge (3), Sn (4)] are formed. In this study, we examine the mechanisms for activation of CpH and c-C(5)H(8) using experimental methods and describe a new product found from the reaction between 1 and c-C(5)H(8), an asymmetrically substituted digermene ArGe(H)Ge(c-C(5)H(9))Ar (5), crystallized in 46% yield. This compound contains a hydrogenated cyclopentyl moiety and is found to be produced in a 3:2 ratio with 3, explaining the fate of the liberated H atoms following triple C-H activation. We show that when these C-H activation reactions are carried out in the presence of tert-butyl ethylene (excess), compounds {ArE(CH(2)CH(2)tBu)}(2) [E = Ge(8), Sn(9)] are obtained in addition to ArECp; in the case of CpH, the neohexyl complexes replace the production of H(2) gas, and for c-C(5)H(8) they displace cyclopentyl product 5 and account for all the hydrogen removed in the dehydroaromatization reactions. To confirm the source of 8 and 9, it was demonstrated that these molecules are formed cleanly between the reaction of (ArEH)(2) [E = Ge(6), Sn(7)] and tert-butyl ethylene, new examples of noncatalyzed hydro-germylation and -stannylation. Therefore, the presence of transient hydrides of the type 6 and 7 can be surmised to be reactive intermediates in the production of 3 and 4, along with H(2), from 1 and 2 and CpH (respectively), or the formation of 3 and 5 from 1. The reaction of 6 or 7 with CpH gave 3 or 4, respectively, with concomitant H(2) evolution, demonstrating the basic nature of these low-valent group 14 element hydrides and their key role in the 'cascade' of C-H activation steps

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

    SciTech Connect

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

    1999-05-05

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

  14. Substituted naphthalenes: Stability, conformational flexibility and description of bonding based on ETS-NOCV method

    NASA Astrophysics Data System (ADS)

    Stanković, B.; Ostojić, B. D.; Gruden, M.; Popović, A.; Đorđević, D. S.

    2016-09-01

    For all dimethylnaphthalenes (DMNs) the transition from a planar ring conformation to a nonplanar one results in energy increase in the range 1.7-2.4 kcal/mol. There is a linear relationship between averaged rigidity constant and relative energy of DMNs. The relative stability of DMNs does not follow the aromatic stabilization based on NICS values. The ETS-NOCV analysis shows that more efficient bonding in the π-electron system is the origin of enhanced stability in laterally substituted (CH3, Cl and NO2) naphthalenes. The results for Caryl-CH3 system indicate more steric repulsion in going from 2,7-DMN to 1,8-DMN following the increase of relative energies.

  15. Method for fabricating light weight carbon-bonded carbon fiber composites

    DOEpatents

    Wrenn, G.E. Jr.; Abbatiello, L.A.; Lewis, J. Jr.

    1987-06-17

    The invention is directed to the fabrication of ultralight carbon- bonded carbon fiber composites of densities in the range of about 0. 04 to 0.10 grams per cubic centimeter. The composites are fabricated by forming an aqueous slurry of carbonaceous fibers which include carbonized fibers and 0-50 weight percent fugitive fibers and a particulate thermosetting resin precursor. The slurry is brought into contact with a perforated mandrel and the water is drained from the slurry through the perforations at a controlled flow rate of about 0. 03 to 0.30 liters per minutes per square inch of a mandrel surface. The deposited billet of fibers and resin precursor is heated to cure the resin precursor to bind the fibers together, removed from the mandrel, and then the resin and fugitive fibers, if any, are carbonized.

  16. Method for producing chemically bonded phosphate ceramics and for stabilizing contaminants encapsulated therein utilizing reducing agents

    DOEpatents

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

    2000-01-01

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

  17. Method for fabricating light weight carbon-bonded carbon fiber composites

    SciTech Connect

    Wrenn, Jr., George E.; Abbatiello, Leonard A.; Lewis, Jr., John

    1989-01-01

    Ultralight carbon-bonded carbon fiber composites of densities in the range of about 0.04 to 0.10 grams per cubic centimeter are fabricated by forming an aqueous slurry of carbonaceous fibers which include carbonized fibers and 0-50 weight percent fugitive fibers and a particulate thermosetting resin precursor. The slurry is brought into contact with a perforated mandrel and the water is drained from the slurry through the perforations at a controlled flow rate of about 0.03 to 0.30 liters per minutes per square inch of mandrel surface. The deposited billet of fibers and resin precursor is heated to cure the resin precursor to bind the fibers together, removed from the mandrel, and then the resin and fugitive fibers, if any, are carbonized.

  18. A method for determining local elastoplastic stress and strain in metallurgically bonded notched laminates subjected to a loading cycle

    NASA Technical Reports Server (NTRS)

    Sova, J. A.; Crews, J. H., Jr.

    1974-01-01

    A semianalytical method was developed for determining elastoplastic cyclic stresses and strains at notch roots in metallurgically bonded metal laminates. The method is based on the Neuber equation, which was used with an effective stress-strain curve for the laminate. It was applied to laminates containing a circular hole which were subjected to one cycle of reversed loading. The laminates consisted of two elasto-perfectly-plastic materials with different yield strengths and with either equal or different Young's moduli. A laminate of high-strength titanium alloy with alternate layers of commercially pure titanium was also analyzed. The accuracy of the method was evaluated by comparing the stresses and strains with those calculated from a finite-element analysis. The results estimated by the simple method based on the Neuber equation agreed closely with the results computed from the more elaborate finite-element analysis.

  19. Preferential activation of primary C-H bonds in the reactions of small alkanes with the diatomic MgO(+*) cation.

    PubMed

    Schröder, Detlef; Roithová, Jana; Alikhani, Esmail; Kwapien, Karolina; Sauer, Joachim

    2010-04-06

    The C-H bond activation of small alkanes by the gaseous MgO(+*) cation is probed by mass spectrometric means. In addition to H-atom abstraction from methane, the MgO(+*) cation reacts with ethane, propane, n- and iso-butane through several pathways, which can all be assigned to the occurrence of initial C-H bond activations. Specifically, the formal C-C bond cleavages observed are assigned to C-H bond activation as the first step, followed by cleavage of a beta-C-C bond concomitant with release of the corresponding alkyl radical. Kinetic modeling of the observed product distributions reveals a high preference of MgO(+*) for the attack of primary C-H bonds. This feature represents a notable distinction of the main-group metal oxide MgO(+*) from various transition-metal oxide cations, which show a clear preference for the attack of secondary C-H bonds. The results of complementary theoretical calculations indicate that the C-H bond activation of larger alkanes by the MgO(+*) cation is subject to pronounced kinetic control.

  20. Exploring the Nature of the H[subscript 2] Bond. 1. Using Spreadsheet Calculations to Examine the Valence Bond and Molecular Orbital Methods

    ERIC Educational Resources Information Center

    Halpern, Arthur M.; Glendening, Eric D.

    2013-01-01

    A three-part project for students in physical chemistry, computational chemistry, or independent study is described in which they explore applications of valence bond (VB) and molecular orbital-configuration interaction (MO-CI) treatments of H[subscript 2]. Using a scientific spreadsheet, students construct potential-energy (PE) curves for several…

  1. Mechanism and Stereoselectivity in an Asymmetric N-Heterocyclic Carbene-Catalyzed Carbon-Carbon Bond Activation Reaction.

    PubMed

    Pareek, Monika; Sunoj, Raghavan B

    2016-11-18

    The mechanism and origin of stereoinduction in a chiral N-heterocyclic carbene (NHC) catalyzed C-C bond activation of cyclobutenone has been established using B3LYP-D3 density functional theory computations. The activation of cyclobutenone as an NHC-bound vinyl enolate and subsequent reaction with the electrophilic sulfonyl imine leads to the lactam product. The most preferred stereocontrolling transition state exhibits a number of noncovalent interactions rendering additional stabilization. The computed enantio- and diastereoselectivities are in good agreement with the previous experimental observations.

  2. Foster mother-infant bonding: associations between foster mothers' oxytocin production, electrophysiological brain activity, feelings of commitment, and caregiving quality.

    PubMed

    Bick, Johanna; Dozier, Mary; Bernard, Kristin; Grasso, Damion; Simons, Robert

    2013-01-01

    This study examined the biological processes associated with foster mother-infant bonding. In an examination of foster mother-infant dyads (N = 41, mean infant age = 8.5 months), foster mothers' oxytocin production was associated with their expressions of behavioral delight toward their foster infant and their average P3 response to images of all infant faces in the first 2 months of the relationship. Three months later, foster mothers' oxytocin production was still associated with delight toward their foster infant and was also specifically associated with their P3 response to an image of their foster infant. Similar to biologically related mothers and infants, oxytocin appears to be associated with foster mothers' brain activity and caregiving behavior, with patterns suggestive of bond formation.

  3. Aniline hydrogenolysis on the Pt(111) single crystal surface: Mechanisms for C-N bond activation

    SciTech Connect

    Huang, S.X.; Gland, J.L.; Fischer, D.A. |

    1993-12-31

    Hydrogenolysis of C-N bond on transition metals is a crucial step in hydrodenitrogenation (HDN) reactions. Despite the overall complexity of HDN processes, the details of important surface reactions can be characterized using model reactions of organonitrogen compounds on single crystal model catalysts. The structure and reactivity of well characterized aniline monolayers on the Pt(111) surface both in vacuum and in the presence of hydrogen is discussed here. Adsorption and reactions of aniline were studied by Gland and Somorjai on the Pt(111) and Pt(100) surfaces, and more recently by Benziger`s group on the Ni(111) and Ni(100) surfaces. On both Pt and Ni surfaces, aniline {pi} bonds through the aromatic ring with its ring parallel to the substrate surface.

  4. METHOD OF SUPPRESSING GASTROINTESTINAL UREASE ACTIVITY

    DOEpatents

    Visek, W.J.

    1963-04-23

    This patent shows a method of increasing the growth rate of chicks. Certain diacyl substituted ureas such as alloxan, murexide, and barbituric acid are added to their feed, thereby suppressing gastrointestinal urease activity and thus promoting growth. (AEC)

  5. Diffusion bonding

    DOEpatents

    Anderson, Robert C.

    1976-06-22

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

  6. Insight into the general rule for the activation of the X-H bonds (X = C, N, O, S) induced by chemisorbed oxygen atoms.

    PubMed

    Xing, Bin; Wang, Gui-Chang

    2014-02-14

    Density functional theory calculations are presented for adsorption and dissociation of NH3, H2O, CH3OH, H2S and C2H4 on clean and oxygen atom pre-adsorbed metal surfaces (Cu, Ag, Au, Ni, Pd, Pt, Rh, Ru, Os and Ir). The calculation results indicated that the oxygen-promotion effect depends both on the metallic activity and the character of the X-H bond. On the one hand, for a given reaction on a series metals, a good linear correlation was found between the energy barrier difference of X-H bond breaking on clean and oxygen-covered metals and the binding strength of oxygen on metals, namely an oxygen-promotion effect was favorable to the less active metals but unfavorable to the more active metals. On the other hand, for a series of X-H bond breaking reactions on a given metal, it was found that the promotion effect follows the trend of O-H > N-H > C-H, that is, the O-H bond is most promoted by the oxygen atom. The possible reason is the O-H bond forms the strongest hydrogen bond in the transition state among the X-H bonds investigated in this work. Additionally, it was found that the oxygen coverage has little effect on the X-H bond scission.

  7. Encapsulation method for maintaining biodecontamination activity

    DOEpatents

    Rogers, Robert D.; Hamilton, Melinda A.; Nelson, Lee O.; Benson, Jennifer; Green, Martin J.; Milner, Timothy N.

    2006-04-11

    A method for maintaining the viability and subsequent activity of microorganisms utilized in a variety of environments to promote biodecontamination of surfaces. One application involves the decontamination of concrete surfaces. Encapsulation of microbial influenced degradation (MID) microorganisms has shown that MID activity is effectively maintained under passive conditions, that is, without manual addition of moisture or nutrients, for an extended period of time.

  8. Encapsulation method for maintaining biodecontamination activity

    DOEpatents

    Rogers, Robert D.; Hamilton, Melinda A.; Nelson, Lee O.; Benson, Jennifer; Green, Martin J.; Milner, Timothy N.

    2002-01-01

    A method for maintaining the viability and subsequent activity of microorganisms utilized in a variety of environments to promote biodecontamination of surfaces. One application involves the decontamination of concrete surfaces. Encapsulation of microbial influenced degradation (MID) microorganisms has shown that MID activity is effectively maintained under passive conditions, that is, without manual addition of moisture or nutrients, for an extended period of time.

  9. Heterolytic Activation of C-H Bonds on Cr(III)-O Surface Sites Is a Key Step in Catalytic Polymerization of Ethylene and Dehydrogenation of Propane.

    PubMed

    Conley, Matthew P; Delley, Murielle F; Núñez-Zarur, Francisco; Comas-Vives, Aleix; Copéret, Christophe

    2015-06-01

    We describe the reactivity of well-defined chromium silicates toward ethylene and propane. The initial motivation for this study was to obtain a molecular understanding of the Phillips polymerization catalyst. The Phillips catalyst contains reduced chromium sites on silica and catalyzes the polymerization of ethylene without activators or a preformed Cr-C bond. Cr(II) sites are commonly proposed active sites in this catalyst. We synthesized and characterized well-defined chromium(II) silicates and found that these materials, slightly contaminated with a minor amount of Cr(III) sites, have poor polymerization activity and few active sites. In contrast, chromium(III) silicates have 1 order of magnitude higher activity. The chromium(III) silicates initiate polymerization by the activation of a C-H bond of ethylene. Density functional theory analysis of this process showed that the C-H bond activation step is heterolytic and corresponds to a σ-bond metathesis type process. The same well-defined chromium(III) silicate catalyzes the dehydrogenation of propane at elevated temperatures with activities similar to those of a related industrial chromium-based catalyst. This reaction also involves a key heterolytic C-H bond activation step similar to that described for ethylene but with a significantly higher energy barrier. The higher energy barrier is consistent with the higher pKa of the C-H bond in propane compared to the C-H bond in ethylene. In both cases, the rate-determining step is the heterolytic C-H bond activation.

  10. Methods to produce B-C, B-P, B-N and B-S bonds in boron clusters.

    PubMed

    Olid, David; Núñez, Rosario; Viñas, Clara; Teixidor, Francesc

    2013-04-21

    Boranes, heteroboranes and metallacarboranes, all named as boron clusters, offer an alternative to typical organic molecules or organic molecular materials. Carbon and boron share the important property of self-catenation thus these elements can produce individually large and sophisticated molecules. Boron clusters and organic molecules display electronic, physical, chemical and geometrical characteristics manifestly different. These differences highlight the complementarity of organic molecules and boron clusters, and therefore the feasibility or necessity to produce hybrid molecules incorporating both types of fragments. To join these two types of fragments, or alternatively these two types of molecular compounds, tools are needed. In this review the current methods of producing boron clusters with carbon, B-C, nitrogen, B-N, phosphorus, B-P and sulphur bonds, B-S, are indicated. As there are many existing borane clusters of different sizes, heteroboranes and metallacarboranes, the revision of methods to generate the B-C, B-P, B-S, and B-N bonds has been restricted to the most widely used boron clusters; [B12H12](2-), dianionic and an example of a borane, 1,2-C2B10H12, neutral and an example of a heteroborane, and [Co(C2B9H11)2](-), monoanionic and an example of a metallacarborane.

  11. Comparison of hydrogen bonds, halogen bonds, Csbnd H⋯π interactions, and Csbnd X⋯π interactions using high-level ab initio methods

    NASA Astrophysics Data System (ADS)

    Riley, Kevin E.; Ford, Carey L.; Demouchet, Kamirah

    2015-02-01

    High quality CCSD(T) and DFT-SAPT potential energy curves were generated for complexes of HCN, BrCN, and HBr donors with formaldehyde and benzene acceptors in order to compare the strengths and properties of hydrogen bonds, halogen bonds, Csbnd H⋯π interactions, and Csbnd Br⋯π interactions. It is found that interactions involving BrCN, which has a large region of positive charge, are similar in strength to interactions involving HCN. Dispersion plays a pronounced role in Ysbnd Br⋯π complexes, accounting for about two thirds of attraction in the HBr⋯C6H6 complex. As might be expected, interactions involving halogens have stronger contributions from dispersion.

  12. Transition metal activation and functionalization of carbon-hydrogen bonds. Progress report, December 1, 1989--November 30, 1992

    SciTech Connect

    Jones, W.D.

    1992-06-01

    We are investigating the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers and the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. Advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds or arenes upon photolysis. The mechanism of these reactions was found to proceed by way of initial phosphine dissociation, followed by C-H activation and isonitrile insertion. We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. The effects of resonance, specifically the differences in the Hueckel energies of the bound vs free ligand, are now believed to fully control the C-H activation/{eta}{sup 2}-coordination equilibria. We have begun to examine the reactions of rhodium isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more facilely than thermal reductive elimination of H{sub 2}. We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion.

  13. Zero-point tunneling splittings in compounds with multiple hydrogen bonds calculated by the rainbow instanton method.

    PubMed

    Smedarchina, Zorka; Siebrand, Willem; Fernández-Ramos, Antonio

    2013-10-31

    Zero-point tunneling splittings are calculated, and the values are compared with the experimentally observed values for four compounds in which the splittings are due to multiple-proton transfer along hydrogen bonds. These compounds are three binary complexes, namely, the formic acid and benzoic acid dimer and the 2-pyridone-2-hydroxypyridine complex, in which the protons move in pairs, and the calix[4]arene molecule, in which they move as a quartet. The calculations make use of and provide a test for the newly developed rainbow approximation for the zero-temperature instanton action which governs the tunneling splitting (as well as the transfer rate). This approximation proved to be much less drastic than the conventional adiabatic and sudden approximations, leading to a new general approach to approximate the instanton action directly. As input parameters the method requires standard electronic-structure data and the Hessians of the molecule or complex at the stationary configurations only; the same parameters also yield isotope effects. Compared to our earlier approximate instanton method, the rainbow approximation offers an improved treatment of the coupling of the tunneling mode to the other vibrations. Contrary to the conventional instanton approach based on explicit evaluation of the instanton trajectory, both methods bypass this laborious procedure, which renders them very efficient and capable of handling systems that thus far have not been handled by other theoretical methods. Past results for model systems have shown that the method should be valid for a wide range of couplings. The present results for real compounds show that it gives a satisfactory account of tunneling splittings and isotope effects in systems with strong coupling that enhances tunneling, thus demonstrating its applicability to low-temperature proton dynamics in systems with multiple hydrogen bonds.

  14. Uranium azide photolysis results in C-H bond activation and provides evidence for a terminal uranium nitride

    NASA Astrophysics Data System (ADS)

    Thomson, Robert K.; Cantat, Thibault; Scott, Brian L.; Morris, David E.; Batista, Enrique R.; Kiplinger, Jaqueline L.

    2010-09-01

    Uranium nitride [U≡N]x is an alternative nuclear fuel that has great potential in the expanding future of nuclear power; however, very little is known about the U≡N functionality. We show, for the first time, that a terminal uranium nitride complex can be generated by photolysis of an azide (U-N=N=N) precursor. The transient U≡N fragment is reactive and undergoes insertion into a ligand C-H bond to generate new N-H and N-C bonds. The mechanism of this unprecedented reaction has been evaluated through computational and spectroscopic studies, which reveal that the photochemical azide activation pathway can be shut down through coordination of the terminal azide ligand to the Lewis acid B(C6F5)3. These studies demonstrate that photochemistry can be a powerful tool for inducing redox transformations for organometallic actinide complexes, and that the terminal uranium nitride fragment is reactive, cleaving strong C-H bonds.

  15. Structure-activity relationships of the intramolecular disulfide bonds in coprisin, a defensin from the dung beetle

    PubMed Central

    Lee, Daeun; Choi, Hyemin; Kim, Ha Hyung; Kim, Ho; Hwang, Jae Sam; Lee, Dong Gun; Kim, Jae Il

    2014-01-01

    Defensins, which are small cationic molecules produced by organisms as part of their innate immune response, share a common structural scaffold that is stabilized by three disulfide bridges. Coprisin is a 43-amino acid defensin-like peptide from Copris tripartitus. Here, we report the intramolecular disulfide connectivity of cysteine-rich coprisin, and show that it is the same as in other insect defensins. The disulfide bond pairings of coprisin were determined by combining the enzymatic cleavage and mass analysis. We found that the loss of any single disulfide bond in coprisin eliminated all antibacterial, but not antifungal, activity. Circular dichroism (CD) analysis showed that two disulfide bonds, Cys20-Cys39 and Cys24-Cys41, stabilize coprisin’s α-helical region. Moreover, a BLAST search against UniProtKB database revealed that coprisin’s α-helical region is highly homologous to those of other insect defensins. [BMB Reports 2014; 47(11): 625-630] PMID:24393527

  16. The Stereoselective Formation of Bicyclic Enamines with Bridgehead Unsaturation via Tandem C-H Bond Activation/Alkenylation/Electrocyclization

    SciTech Connect

    Ellman, Jonathan A.; Yotphan, Sirilata; Bergman, Robert

    2007-12-10

    Rhodium-catalyzed intermolecular C-H activation of {alpha}, {beta}-unsaturated imines in the presence of alkynes leads to a tandem process in which coupling to the alkyne occurs at the {beta}-C-H bond of the imine, followed by electrocyclization of the resulting azatriene intermediates to give dihydropyridines (eq 1). Consideration of the intramolecular version of this overall transformation (Scheme 1) raises interesting regiochemical issues. For example in a compound such as 1, where the nitrogen and alkyne are connected by a 4-carbon tether, the presumed first-formed hydrido(vinyl)rhodium function can add to the triple bond in a 1,2-fashion, producing complex 2 with a new endocyclic double bond. Alternatively, addition might occur in a 2,1-fashion, leading to product 4 with an exocyclic double bond. We now wish to report that this intramolecular cyclization occurs smoothly at 100 C, and the exocyclic double bond route is exclusively followed. Remarkably, products such as 4 do not resist further cyclization. Even though both the transition state for this process and the resulting product are presumably strained, the overall transformation leads to good yields of unusual bridgehead doubly-bonded enamines such as 5. The unique chemistry of conjugated enamine 5 is consistent with the increased strain of this molecule as well as with inhibited conjugation between the nitrogen lone pair and the adjacent double bond (vida infra). We began our investigation into the C-H activation/cyclization of alkyne-tethered imine 1 by extensive screening of transition metal catalysts for this process. Rhodium-based catalysts were found to be the most efficient (Table 1), leading exclusively to the bridgehead dienamine; none of the catalysts that were employed in the screening led to quinolizidine 3 or to the product of intramolecular Diels-Alder reaction. The optimized reaction conditions employ the electron-rich monophosphine ligand (p-NMe{sub 2})PhPEt{sub 2} in 1:1 ratio relative

  17. Simple Bond Cleavage

    SciTech Connect

    Gary S. Groenewold

    2005-08-01

    Simple bond cleavage is a class of fragmentation reactions in which a single bond is broken, without formation of new bonds between previously unconnected atoms. Because no bond making is involved, simple bond cleavages are endothermic, and activation energies are generally higher than for rearrangement eliminations. The rate of simple bond cleavage reactions is a strong function of the internal energy of the molecular ion, which reflects a loose transition state that resembles reaction products, and has a high density of accessible states. For this reason, simple bond cleavages tend to dominate fragmentation reactions for highly energized molecular ions. Simple bond cleavages have negligible reverse activation energy, and hence they are used as valuable probes of ion thermochemistry, since the energy dependence of the reactions can be related to the bond energy. In organic mass spectrometry, simple bond cleavages of odd electron ions can be either homolytic or heterolytic, depending on whether the fragmentation is driven by the radical site or the charge site. Simple bond cleavages of even electron ions tend to be heterolytic, producing even electron product ions and neutrals.

  18. Ce-PROMOTED Bond Activation of Propene Probed by Mass-Analyzed Threshold Ionization Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Yuchen; Kumari, Sudesh; Yang, Dong-Sheng

    2016-06-01

    The reaction of Ce + propene (CH2=CH-CH3) was carried out in a laser-ablation supersonic molecular beam source. CeC_2H_2, CeC_3H_4, CeC_3H_6, CeC_4H_6, CeC_6H10, and CeC_6H12 were identified by photoionization time-of-flight mass spectrometric measurements, and their structures and electronic states were investigated with mass-analyzed threshold ionization (MATI) spectroscopy and theoretical calculations. The metal complexes containing two or three carbon atoms were formed by the C-C bond breakage (CeC_2H_2), dehydrogenation (CeC_3H_4), or metal insertion into a C-H bond (CeC_3H_6) of a propene molecule. The larger complexes with four to six carbons are formed through secondary reactions involving C-C bond coupling and dehydrogenation. The ground electronic states of the neutral CeC_2H_2, CeC_3H_4, CeC_3H_6, and CeC_4H_6 complexes are triplets with a 4f16s1 electron configuration on the Ce center, and those of the corresponding ions are doublet with a 4f1 configuration. Their MATI spectra are much more complex than those of the corresponding La species formed in the La + propene reaction previously observed by our group. The spectral complexity arises from possibly multiple electronic transitions due to the existence of a 4f electron of the Ce atom which could be located in any one of the seven f-atomic orbitals or involved in considerable spin-orbit interactions.

  19. Wafer level vacuum packaging of scanning micro-mirrors using glass-frit and anodic bonding methods

    NASA Astrophysics Data System (ADS)

    Langa, S.; Drabe, C.; Kunath, C.; Dreyhaupt, A.; Schenk, H.

    2013-03-01

    In this paper the authors report about the six inch wafer level vacuum packaging of electro-statically driven two dimensional micro-mirrors. The packaging was done by means of two types of wafer bonding methods: anodic and glass frit. The resulting chips after dicing are 4 mm wide, 6 mm long and 1.6 mm high and the residual pressure inside the package after dicing was estimated to be between 2 and 20 mbar. This allowed us to reduce the driving voltage of the micro-mirrors by more than 40% compared to the driving voltage without vacuum packaging. The vacuum stability after 5 months was verified by measurement using the so called "membrane method". Persistence of the vacuum was proven. No getter materials were used for packaging.

  20. Activation of Aromatic C-C Bonds of 2,2'-Bipyridine Ligands.

    PubMed

    Fombona, Sergio; Espinal-Viguri, Maialen; Huertos, Miguel A; Díaz, Jesús; López, Ramón; Menéndez, M Isabel; Pérez, Julio; Riera, Lucía

    2016-11-21

    4,4'-Disubstituted-2,2'-bipyridine ligands coordinated to Mo(II) and Re(I) cationic fragments become dearomatized by an intramolecular nucleophilic attack from a deprotonated N-alkylimidazole ligand in cis disposition. The subsequent protonation of these neutral complexes takes place on a pyridine carbon atom rather than at nitrogen, weakening an aromatic C-C bond and affording a dihydropyridyl moiety. Computational calculations allowed for the rationalization of the formation of the experimentally obtained products over other plausible alternatives.

  1. The significance of disulfide bonding in biological activity of HB-EGF, a mutagenesis approach

    SciTech Connect

    Hoskins, J.T.; Zhou, Z.; Harding, P.A.

    2008-10-31

    A site-directed mutagenesis approach was taken to disrupt each of 3 disulfide bonds within human HB-EGF by substituting serine for both cysteine residues that contribute to disulfide bonding. Each HB-EGF disulfide analogue (HB-EGF-Cys/Ser{sub 108/121}, HB-EGF-Cys/Ser{sub 116/132}, and HB-EGF-Cys/Ser{sub 134/143}) was cloned under the regulation of the mouse metallothionein (MT) promoter and stably expressed in mouse fibroblasts. HB-EGF immunoreactive proteins with M{sub r} of 6.5, 21 and 24 kDa were observed from lysates of HB-EGF and each HB-EGF disulfide analogue. HB-EGF immunohistochemical analyses of each HB-EGF stable cell line demonstrated ubiquitous protein expression except HB-EGF-Cys/Ser{sub 108/121} and HB-EGF-Cys/Ser{sub 116/132} stable cell lines which exhibited accumulated expression immediately outside the nucleus. rHB-EGF, HB-EGF, and HB-EGF{sub 134/143} proteins competed with {sup 125}I-EGF in an A431 competitive binding assay, whereas HB-EGF-Cys/Ser{sub 108/121} and HB-EGF-Cys/Ser{sub 116/132} failed to compete. Each HB-EGF disulfide analogue lacked the ability to stimulate tyrosine phosphorylation of the 170 kDa EGFR. These results suggest that HB-EGF-Cys/Ser{sub 134/143} antagonizes EGFRs.

  2. Methods of measuring Protein Disulfide Isomerase activity: a critical overview

    NASA Astrophysics Data System (ADS)

    Watanabe, Monica; Laurindo, Francisco; Fernandes, Denise

    2014-09-01

    Protein disulfide isomerase is an essential redox chaperone from the endoplasmic reticulum (ER) and is responsible for correct disulfide bond formation in nascent proteins. PDI is also found in other cellular locations in the cell, particularly the cell surface. Overall, PDI contributes to ER and global cell redox homeostasis and signaling. The knowledge about PDI structure and function progressed substantially based on in vitro studies using recombinant PDI and chimeric proteins. In these experimental scenarios, PDI reductase and chaperone activities are readily approachable. In contrast, assays to measure PDI isomerase activity, the hallmark of PDI family, are more complex. Assessment of PDI roles in cells and tissues mainly relies on gain- or loss-of-function studies. However, there is limited information regarding correlation of experimental readouts with the distinct types of PDI activities. In this mini-review, we evaluate the main methods described for measuring the different kinds of PDI activity: thiol reductase, thiol oxidase, thiol isomerase and chaperone. We emphasize the need to use appropriate controls and the role of critical interferents (e.g., detergent, presence of reducing agents). We also discuss the translation of results from in vitro studies with purified recombinant PDI to cellular and tissue samples, with critical comments on the interpretation of results.

  3. The electronic structure and chemical bonding of vitamin B12

    NASA Astrophysics Data System (ADS)

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

    2003-05-01

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

  4. Transesterification of PHA to Oligomers Covalently Bonded with (Bio)Active Compounds Containing Either Carboxyl or Hydroxyl Functionalities

    PubMed Central

    Kwiecień, Iwona; Radecka, Iza; Kowalczuk, Marek; Adamus, Grażyna

    2015-01-01

    This manuscript presents the synthesis and structural characterisation of novel biodegradable polymeric controlled-release systems of pesticides with potentially higher resistance to weather conditions in comparison to conventional forms of pesticides. Two methods for the preparation of pesticide-oligomer conjugates using the transesterification reaction were developed. The first method of obtaining conjugates, which consist of bioactive compounds with the carboxyl group and polyhydroxyalkanoates (PHAs) oligomers, is "one-pot" transesterification. In the second method, conjugates of bioactive compounds with hydroxyl group and polyhydroxyalkanoates oligomers were obtained in two-step method, through cyclic poly(3-hydroxybutyrate) oligomers. The obtained pesticide-PHA conjugates were comprehensively characterised using GPC, 1H NMR and mass spectrometry techniques. The structural characterisation of the obtained products at the molecular level with the aid of mass spectrometry confirmed that both of the synthetic strategies employed led to the formation of conjugates in which selected pesticides were covalently bonded to PHA oligomers via a hydrolysable ester bond. PMID:25781908

  5. C-H bond activation of benzene by unsaturated η2-cyclopropene and η2-benzyne complexes of niobium.

    PubMed

    Boulho, Cédric; Oulié, Pascal; Vendier, Laure; Etienne, Michel; Pimienta, Véronique; Locati, Abel; Bessac, Fabienne; Maseras, Feliu; Pantazis, Dimitrios A; McGrady, John E

    2010-10-13

    We report the synthesis of a niobium cyclopropyl complex, Tp(Me2)NbMe(c-C(3)H(5))(MeCCMe), and show that thermal loss of methane from this compound generates an intermediate that is capable of activating both aliphatic and aromatic C-H bonds. Isotopic labeling, trapping studies, a detailed kinetic analysis, and density functional theory all suggest that the active intermediate is an η(2)-cyclopropene complex formed via β-hydrogen abstraction rather than an isomeric cyclopropylidene species. C-H activation chemistry of this type represents a rather unusual reactivity pattern for η(2)-alkene complexes but is favored in this case by the strain in the C(3) ring which prevents the decomposition of the key intermediate via loss of cyclopropene.

  6. Method and apparatus for forming a carbon-silicon bond in a silane

    DOEpatents

    Schattenmann, Florian Johannes

    2002-01-01

    A method for forming at least one product silane, comprising reacting a transition metal hydride with a starting silane in a presence of a catalyst and at a temperature that exceeds a threshold temperature associated with said reacting.

  7. Study of bonding methods of aluminum beam leaded devices on microcircuit ceramic substrates

    NASA Technical Reports Server (NTRS)

    1973-01-01

    The use of aluminum beam lead devices in hybrid circuits is described by modification of existing processing equipment. Principles, procedures, and methods of application of Al beam lead devices are discussed in terms of processing the devices onto hybrids.

  8. Complementary MS Methods Assist Conformational Characterization of Antibodies with Altered S-S Bonding Networks

    NASA Astrophysics Data System (ADS)

    Jones, Lisa M.; Zhang, Hao; Cui, Weidong; Kumar, Sandeep; Sperry, Justin B.; Carroll, James A.; Gross, Michael L.

    2013-06-01

    As therapeutic monoclonal antibodies (mAbs) become a major focus in biotechnology and a source of the next-generation drugs, new analytical methods or combination methods are needed for monitoring changes in higher order structure and effects of post-translational modifications. The complexity of these molecules and their vulnerability to structural change provide a serious challenge. We describe here the use of complementary mass spectrometry methods that not only characterize mutant mAbs but also may provide a general framework for characterizing higher order structure of other protein therapeutics and biosimilars. To frame the challenge, we selected members of the IgG2 subclass that have distinct disulfide isomeric structures as a model to evaluate an overall approach that uses ion mobility, top-down MS sequencing, and protein footprinting in the form of fast photochemical oxidation of proteins (FPOP). These three methods are rapid, sensitive, respond to subtle changes in conformation of Cys → Ser mutants of an IgG2, each representing a single disulfide isoform, and may be used in series to probe higher order structure. The outcome suggests that this approach of using various methods in combination can assist the development and quality control of protein therapeutics.

  9. Complementary MS Methods Assist Conformational Characterization of Antibodies with Altered S–S Bonding Networks

    PubMed Central

    Jones, Lisa M.; Zhang, Hao; Cui, Weidong; Kumar, Sandeep; Sperry, Justin B.; Carroll, James A.; Gross, Michael L.

    2013-01-01

    As therapeutic monoclonal antibodies (mAbs) become a major focus in biotechnology and a source of the next-generation drugs, new analytical methods or combination methods are needed for monitoring changes in higher order structure and effects of post-translational modifications. The complexity of these molecules and their vulnerability to structural change provide a serious challenge. We describe here the use of complementary mass spectrometry methods that not only characterize mutant mAbs but also may provide a general framework for characterizing higher order structure of other protein therapeutics and biosimilars. To frame the challenge, we selected members of the IgG2 subclass that have distinct disulfide isomeric structures as a model to evaluate an overall approach that uses ion mobility, top-down MS sequencing, and protein footprinting in the form of fast photochemical oxidation of proteins (FPOP). These three methods are rapid, sensitive, respond to subtle changes in conformation of Cys→Ser mutants of an IgG2, each representing a single disulfide isoform, and may be used in series to probe higher order structure. The outcome suggests that this approach of using various methods in combination can assist the development and quality control of protein therapeutics. PMID:23483515

  10. Methods of making non-covalently bonded carbon-titania nanocomposite thin films and applications of the same

    DOEpatents

    Liang, Yu Teng; Vijayan, Baiju K.; Gray, Kimberly A.; Hersam, Mark C.

    2016-07-19

    In one aspect, a method of making non-covalently bonded carbon-titania nanocomposite thin films includes: forming a carbon-based ink; forming a titania (TiO.sub.2) solution; blade-coating a mechanical mixture of the carbon-based ink and the titania solution onto a substrate; and annealing the blade-coated substrate at a first temperature for a first period of time to obtain the carbon-based titania nanocomposite thin films. In certain embodiments, the carbon-based titania nanocomposite thin films may include solvent-exfoliated graphene titania (SEG-TiO.sub.2) nanocomposite thin films, or single walled carbon nanotube titania (SWCNT-TiO.sub.2) nanocomposite thin films.

  11. Interactively Applying the Variational Method to the Dihydrogen Molecule: Exploring Bonding and Antibonding

    ERIC Educational Resources Information Center

    Cruzeiro, Vinícius Wilian D.; Roitberg, Adrian; Polfer, Nicolas C.

    2016-01-01

    In this work we are going to present how an interactive platform can be used as a powerful tool to allow students to better explore a foundational problem in quantum chemistry: the application of the variational method to the dihydrogen molecule using simple Gaussian trial functions. The theoretical approach for the hydrogen atom is quite…

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

    PubMed

    Putz, Mihai V; Dudaş, Nicoleta A

    2013-07-30

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

  13. Subsurface defect detection in first layer of pavement structure and reinforced civil engineering structure by FRP bonding using active infrared thermography

    NASA Astrophysics Data System (ADS)

    Dumoulin, Jean; Ibos, Laurent

    2010-05-01

    In many countries road network ages while road traffic and maintenance costs increase. Nowadays, thousand and thousand kilometers of roads are each year submitted to surface distress survey. They generally lean on pavement surface imaging measurement techniques, mainly in the visible spectrum, coupled with visual inspection or image processing detection of emergent distresses. Nevertheless, optimisation of maintenance works and costs requires an early detection of defects within the pavement structure when they still are hidden from surface. Accordingly, alternative measurement techniques for pavement monitoring are currently under investigation (seismic methods, step frequency radar). On the other hand, strengthening or retrofitting of reinforced concrete structures by externally bonded Fiber Reinforced Polymer (FRP) systems is now a commonly accepted and widespread technique. However, the use of bonding techniques always implies following rigorous installing procedures. To ensure the durability and long-term performance of the FRP reinforcements, conformance checking through an in situ auscultation of the bonded FRP systems is then highly suitable. The quality-control program should involve a set of adequate inspections and tests. Visual inspection and acoustic sounding (hammer tap) are commonly used to detect delaminations (disbonds) but are unable to provide sufficient information about the depth (in case of multilayered composite) and width of debonded areas. Consequently, rapid and efficient inspection methods are also required. Among the non destructive methods under study, active infrared thermography was investigated both for pavement and civil engineering structures through experiments in laboratory and numerical simulations, because of its ability to be also used on field. Pulse Thermography (PT), Pulse Phase Thermography (PPT) and Principal Component Thermography (PCT) approaches have been tested onto pavement samples and CFRP bonding on concrete

  14. Reactivity of oxygen radical anions bound to scandia nanoparticles in the gas phase: C-H bond activation.

    PubMed

    Tian, Li-Hua; Meng, Jing-Heng; Wu, Xiao-Nan; Zhao, Yan-Xia; Ding, Xun-Lei; He, Sheng-Gui; Ma, Tong-Mei

    2014-01-20

    The activation of C-H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O(-·)) is an important species in C-H activation. The mechanistic details of C-H activation by O(-·) radicals can be well understood by studying the reactions between O(-·) containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n-butane was studied by using a high-resolution time-of-flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n-butane by (Sc2O3)(N)O(-) (N=1-18) clusters was observed. The reactivity of (Sc2O3)(N)O(-) (N=1-18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc8O13(-)) and 12 (Sc24O37(-)). Larger (Sc2O3)(N)O(-) clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc2O3)(N)O(-) (N=1-5) clusters, which were found to contain the O(-·) radicals as the active sites. The local charge environment around the O(-·) radicals was demonstrated to control the experimentally observed size-dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O(-·) containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C-H bond activation.

  15. Methods for using polypeptides having cellobiohydrolase activity

    DOEpatents

    Morant, Marc D; Harris, Paul

    2016-08-23

    The present invention relates to isolated polypeptides having cellobiohydrolase activity and isolated polynucleotides encoding the polypeptides. The invention also relates to nucleic acid constructs, vectors, and host cells comprising the polynucleotides as well as methods of producing and using the polypeptides.

  16. Strength of pitch-bonded coal briquets as influenced by the preparation method

    SciTech Connect

    Zorina, E.I.; Romanov, Yu.A.; Glushankov, S.L.

    1992-05-20

    Briquetting technology is widely used in metallurgical production, fuel-based energetic, coal-tar chemistry, and commercial production of activated carbons. Strong, dense molded materials with comparatively low contents of molden binder can be obtained by pressing at relatively low pressures. As objects of investigation the authors selected coals from the Kuznetsk Basin, representing different stages of metamorphism and a medium-temperature coal-tar pitch (MTP) from the Nizhnii Tagil Metallurgical Combine (ring-and-ball softening point 72{degrees}C). 6 refs., 4 figs., 1 tab.

  17. Application of "hydrogen bonding interaction" in new drug development: design, synthesis, antiviral activity, and SARs of thiourea derivatives.

    PubMed

    Lu, Aidang; Wang, Ziwen; Zhou, Zhenghong; Chen, Jianxin; Wang, Qingmin

    2015-02-11

    A series of simple thiourea derivatives were designed based on the structure of natural product harmine and lead compound and synthesized from amines in one step. The antiviral activity of these thiourea derivatives was evaluated. Most of them exhibited significantly higher anti-TMV activity than commercial plant virucides ribavirin, harmine, and lead compound. The hydrogen bond was found to be important but not the more the better. The optimal compound (R,R)-20 showed the best anti-TMV activity in vitro and in vivo (in vitro activity, 75%/500 μg/mL and 39%/100 μg/mL; inactivation activity, 71%/500 μg/mL and 35%/100 μg/mL; curative activity, 73%/500 μg/mL and 37%/100 μg/mL; protection activity, 69%/500 μg/mL and 33%/100 μg/mL), which is significantly higher than that of Ningnanmycin. The systematic study provides strong evidence that these simple thiourea derivatives could become potential TMV inhibitors.

  18. Collision-activated cleavage of a peptide/antibiotic disulfide linkage: possible evidence for intramolecular disulfide bond rearrangement upon collisional activation.

    PubMed

    Fagerquist, Clifton K

    2004-01-01

    Ceftiofur is an important veterinary beta-lactam antibiotic whose bioactive metabolite, desfuroylceftiofur, has a free thiol group. Desfuroylceftiofur (DFC) was reacted with two peptides, [Arg8]-vasopressin and reduced glutathione, both of which have cysteine residues to form disulfide-linked peptide/antibiotic complexes. The products of the reaction, [vasopressin + (DFC-H) + (DFC-H) + H]+, [(vasopressin+H) + (DFC-H) + H]+ and [(glutathione-H) + (DFC-H) + H]+, were analyzed using collision-activated dissociation (CAD) with a quadrupole ion trap tandem mass spectrometer. MS/MS of [vasopressin + (DFC-H) + (DFC-H) + H]+ resulted in facile dissociative loss of one and two covalently bound DFC moieties. Loss of one DFC resulted from either homolytic or heterolytic dissociation of the peptide/antibiotic disulfide bond with equal or unequal partitioning of the two sulfur atoms between the fragment ion and neutral loss. Hydrogen migration preceded heterolytic dissociation. Loss of two DFC moieties from [vasopressin + (DFC-H) + (DFC-H) + H]+ appears to result from collision-activated intramolecular disulfide bond rearrangement (IDBR) to produce cyclic [vasopressin + H]+ (at m/z 1084) as well as other cyclic fragment ions at m/z 1084 +/- 32 and +64. The cyclic structure of these ions could only be inferred as MS/MS may result in rearrangement to non-cyclic structures prior to dissociative loss. IDBR was also detected from MS(3) experiments of [vasopressin + (DFC-H) + (DFC-H) + H]+ fragment ions. MS/MS of [(glutathione-H) + (DFC-H) + H]+ resulted in cleavage of the peptide backbone with retention of the DFC moiety as well as heterolytic cleavage of the peptide/antibiotic disulfide bond to produce the fragment ion: [(DFC-2H) + H]+. These results demonstrate the facile dissociative loss by CAD of DFC moieties covalently attached to peptides through disulfide bonds. Published in 2004 by John Wiley & Sons, Ltd.

  19. The Comparative Studies of Binding Activity of Curcumin and Didemethylated Curcumin with Selenite: Hydrogen Bonding vs Acid-Base Interactions

    NASA Astrophysics Data System (ADS)

    Liao, Jiahn-Haur; Wu, Tzu-Hua; Chen, Ming-Yi; Chen, Wei-Ting; Lu, Shou-Yun; Wang, Yi-Hsuan; Wang, Shao-Pin; Hsu, Yen-Min; Huang, Yi-Shiang; Huang, Zih-You; Lin, Yu-Ching; Chang, Ching-Ming; Huang, Fu-Yung; Wu, Shih-Hsiung

    2015-12-01

    In this report, the in vitro relative capabilities of curcumin (CCM) and didemethylated curcumin (DCCM) in preventing the selenite-induced crystallin aggregation were investigated by turbidity tests and isothermal titration calorimetry (ITC). DCCM showed better activity than CCM. The conformers of CCM/SeO32- and DCCM/SeO32- complexes were optimized by molecular orbital calculations. Results reveal that the selenite anion surrounded by CCM through the H-bonding between CCM and selenite, which is also observed via IR and NMR studied. For DCCM, the primary driving force is the formation of an acid-base adduct with selenite showing that the phenolic OH group of DCCM was responsible for forming major conformer of DCCM. The formation mechanisms of selenite complexes with CCM or DCCM explain why DCCM has greater activity than CCM in extenuating the toxicity of selenite as to prevent selenite-induced lens protein aggregation.

  20. The Comparative Studies of Binding Activity of Curcumin and Didemethylated Curcumin with Selenite: Hydrogen Bonding vs Acid-Base Interactions

    PubMed Central

    Liao, Jiahn-Haur; Wu, Tzu-Hua; Chen, Ming-Yi; Chen, Wei-Ting; Lu, Shou-Yun; Wang, Yi-Hsuan; Wang, Shao-Pin; Hsu, Yen-Min; Huang, Yi-Shiang; Huang, Zih-You; Lin, Yu-Ching; Chang, Ching-Ming; Huang, Fu-Yung; Wu, Shih-Hsiung

    2015-01-01

    In this report, the in vitro relative capabilities of curcumin (CCM) and didemethylated curcumin (DCCM) in preventing the selenite-induced crystallin aggregation were investigated by turbidity tests and isothermal titration calorimetry (ITC). DCCM showed better activity than CCM. The conformers of CCM/SeO32− and DCCM/SeO32− complexes were optimized by molecular orbital calculations. Results reveal that the selenite anion surrounded by CCM through the H-bonding between CCM and selenite, which is also observed via IR and NMR studied. For DCCM, the primary driving force is the formation of an acid-base adduct with selenite showing that the phenolic OH group of DCCM was responsible for forming major conformer of DCCM. The formation mechanisms of selenite complexes with CCM or DCCM explain why DCCM has greater activity than CCM in extenuating the toxicity of selenite as to prevent selenite-induced lens protein aggregation. PMID:26635113

  1. The Comparative Studies of Binding Activity of Curcumin and Didemethylated Curcumin with Selenite: Hydrogen Bonding vs Acid-Base Interactions.

    PubMed

    Liao, Jiahn-Haur; Wu, Tzu-Hua; Chen, Ming-Yi; Chen, Wei-Ting; Lu, Shou-Yun; Wang, Yi-Hsuan; Wang, Shao-Pin; Hsu, Yen-Min; Huang, Yi-Shiang; Huang, Zih-You; Lin, Yu-Ching; Chang, Ching-Ming; Huang, Fu-Yung; Wu, Shih-Hsiung

    2015-12-04

    In this report, the in vitro relative capabilities of curcumin (CCM) and didemethylated curcumin (DCCM) in preventing the selenite-induced crystallin aggregation were investigated by turbidity tests and isothermal titration calorimetry (ITC). DCCM showed better activity than CCM. The conformers of CCM/SeO3(2-) and DCCM/SeO3(2-) complexes were optimized by molecular orbital calculations. Results reveal that the selenite anion surrounded by CCM through the H-bonding between CCM and selenite, which is also observed via IR and NMR studied. For DCCM, the primary driving force is the formation of an acid-base adduct with selenite showing that the phenolic OH group of DCCM was responsible for forming major conformer of DCCM. The formation mechanisms of selenite complexes with CCM or DCCM explain why DCCM has greater activity than CCM in extenuating the toxicity of selenite as to prevent selenite-induced lens protein aggregation.

  2. Evaluation of methods to assess physical activity

    NASA Astrophysics Data System (ADS)

    Leenders, Nicole Y. J. M.

    Epidemiological evidence has accumulated that demonstrates that the amount of physical activity-related energy expenditure during a week reduces the incidence of cardiovascular disease, diabetes, obesity, and all-cause mortality. To further understand the amount of daily physical activity and related energy expenditure that are necessary to maintain or improve the functional health status and quality of life, instruments that estimate total (TDEE) and physical activity-related energy expenditure (PAEE) under free-living conditions should be determined to be valid and reliable. Without evaluation of the various methods that estimate TDEE and PAEE with the doubly labeled water (DLW) method in females there will be eventual significant limitations on assessing the efficacy of physical activity interventions on health status in this population. A triaxial accelerometer (Tritrac-R3D, (TT)), an uniaxial (Computer Science and Applications Inc., (CSA)) activity monitor, a Yamax-Digiwalker-500sp°ler , (YX-stepcounter), by measuring heart rate responses (HR method) and a 7-d Physical Activity Recall questionnaire (7-d PAR) were compared with the "criterion method" of DLW during a 7-d period in female adults. The DLW-TDEE was underestimated on average 9, 11 and 15% using 7-d PAR, HR method and TT. The underestimation of DLW-PAEE by 7-d PAR was 21% compared to 47% and 67% for TT and YX-stepcounter. Approximately 56% of the variance in DLW-PAEE*kgsp{-1} is explained by the registration of body movement with accelerometry. A larger proportion of the variance in DLW-PAEE*kgsp{-1} was explained by jointly incorporating information from the vertical and horizontal movement measured with the CSA and Tritrac-R3D (rsp2 = 0.87). Although only a small amount of variance in DLW-PAEE*kgsp{-1} is explained by the number of steps taken per day, because of its low cost and ease of use, the Yamax-stepcounter is useful in studies promoting daily walking. Thus, studies involving the

  3. Increased Back-Bonding Explains Step-Edge Reactivity and Particle Size Effect for CO Activation on Ru Nanoparticles.

    PubMed

    Foppa, Lucas; Copéret, Christophe; Comas-Vives, Aleix

    2016-12-28

    Carbon monoxide is a ubiquitous molecule, a key feedstock and intermediate in chemical processes. Its adsorption and activation, typically carried out on metallic nanoparticles (NPs), are strongly dependent on the particle size. In particular, small NPs, which in principle contain more corner and step-edge atoms, are surprisingly less reactive than larger ones. Hereby, first-principles calculations on explicit Ru NP models (1-2 nm) show that both small and large NPs can present step-edge sites (e.g., B5 and B6 sites). However, such sites display strong particle-size-dependent reactivity because of very subtle differences in local chemical bonding. State-of-the-art crystal orbital Hamilton population analysis allows a detailed molecular orbital picture of adsorbed CO on step-edges, which can be classified as flat (η(1) coordination) and concave (η(2) coordination) sites. Our analysis shows that the CO π-metal dπ hybrid band responsible for the electron back-donation is better represented by an oxygen lone pair on flat sites, whereas it is delocalized on both C and O atoms on concave sites, increasing the back-bonding on these sites compared to flat step-edges or low-index surface sites. The bonding analysis also rationalizes why CO cleavage is easier on step-edge sites of large NPs compared to small ones irrespective of the site geometry. The lower reactivity of small NPs is due to the smaller extent of the Ru-O interaction in the η(2) adsorption mode, which destabilizes the η(2) transition-state structure for CO direct cleavage. Our findings provide a molecular understanding of the reactivity of CO on NPs, which is consistent with the observed particle size effect.

  4. Dynamic modeling and analysis of the PZT-bonded composite Timoshenko beams: Spectral element method

    NASA Astrophysics Data System (ADS)

    Lee, Usik; Kim, Daehwan; Park, Ilwook

    2013-03-01

    The health of thin laminated composite beams is often monitored using the ultrasonic guided waves excited by wafer-type piezoelectric transducers (PZTs). Thus, for the smart composite beams which consist of a laminated composite base beam and PZT layers, it is very important to develop a very reliable mathematical model and to use a very accurate computational method to predict accurate dynamic characteristics at very high ultrasonic frequency. In this paper, the axial-bending-shear-lateral contraction coupled differential equations of motion are derived first by the Hamilton's principle with Lagrange multipliers. The smart composite beam is represented by a Timoshenko beam model by adopting the first-order shear deformation theory (FSDT) for the laminated composite base beam. The axial deformation of smart composite beam is improved by taking into account the effects of lateral contraction by adopting the concept of Mindlin-Herrmann rod theory. The spectral element model is then formulated by the variation approach from coupled differential equations of motion transformed into the frequency domain via the discrete Fourier transform. The high accuracy of the present spectral element model is verified by comparing with other solution methods: the finite element model developed in this paper and the commercial FEA package ANSYS. Finally the dynamics and wave characteristics of some example smart composite beams are investigated through the numerical studies.

  5. Prediction of inhomogeneous texture in clad sheet metals by hot roll bond method

    NASA Astrophysics Data System (ADS)

    Choi, Shi-Hoon; Kwon, Jae Wook; Oh, Kyu Hwan

    1996-06-01

    A finite element analysis was applied to analyze the evolution of an inhomogeneity of rolling texture in hot rolled clad metal with Taylor-Bishop-Hill model and Renourd-Winterberger method. The shear texture has been developed in the surface layer of the aluminum and plane strain texture has been developed in the center layer. The calculated texture variations through thickness direction could simulate experimental texture using deformation gradient from FEM. The ratio of shear strain to rolling strain, x, which represents the degree of rotation about transverse direction could give the degree of development of shear texture. The larger value of x gives the larger crystal rotation about transverse direction and subsequently the development of shear texture. The calculated (111) pole figures were in good agreement with experimentally measured pole figures.

  6. Active music therapy and Parkinson's disease: methods.

    PubMed

    Pacchetti, C; Aglieri, R; Mancini, F; Martignoni, E; Nappi, G

    1998-01-01

    Music therapy (MT) is an unconventional, multisensorial therapy poorly assessed in medical care but widely used to different ends in a variety of settings. MT has two branches: active and passive. In active MT the utilisation of instruments is structured to correspond to all sensory organs so as to obtain suitable motor and emotional responses. We conducted a prospective study to evaluate the effects of MT in the neurorehabilitation of patients with Parkinson's Disease (PD), a common degenerative disorder involving movement and emotional impairment. Sixteen PD patients took part in 13 weekly sessions of MT each lasting 2 hours. At the beginning and at the end of the session, every 2 weeks, the patients were evaluated by a neurologist, who assessed PD severity with UPDRS, emotional functions with Happiness Measures (HM) and quality of life using the Parkinson's Disease Quality of Life Questionnaire (PDQL). After every session a significant improvement in motor function, particularly in relation to hypokinesia, was observed both in the overall and in the pre-post session evaluations. HM, UPDRS-ADL and PDQL changes confirmed an improving effect of MT on emotional functions, activities of daily living and quality of life. In conclusion, active MT, operating at a multisensorial level, stimulates motor, affective and behavioural functions. Finally, we propose active MT as new method to include in PD rehabilitation programmes. This article describes the methods adopted during MT sessions with PD patients.

  7. Ce-PROMOTED Bond Activation of Ethylene Probed by Mass-Analyzed Threshold Ionization Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Yuchen; Kumari, Sudesh; Cao, Wenjin; Yang, Dong-Sheng

    2015-06-01

    Ce(C_2H_2) and Ce(C_4H_6) complexes were observed in the reaction of Ce atom with ethylene in a supersonic molecular beam source and investigated by mass-analyzed threshold ionization spectroscopy (MATI) and theoretical calculations. Preliminary data analysis shows that Ce(C_2H_2) has a triangle structure (C2v) with Ce binding to C_2H_2 in a two-fold mode and Ce(C_4H_6) has a five-membered metallacyclic structure (Cs) with Ce binding to the two terminal carbon atoms of butadiene. The ground states of both species are triplets with a 4f16s1 Ce-based electron configuration and those of the corresponding ions are doublets from the removal of the 6s1 electron. The Ce(C_2H_2) complex is formed by ethylene dehydrogenation, whereas Ce(C_4H_6) by ethylene dehydrogenation and carbon-carbon bond coupling. The MATI spectra of Ce(C_2H_2) and Ce(C_4H_6) are rather similar to those of the corresponding La complexes previously observed by our group, except that the spectra of the Ce complexes exhibit two electronic transitions with almost identical vibrational intervals. This observation suggests that the existence of a 4f electron results in an increased complexity of the electronic spectra and states of the lanthanide hydrocarbons.

  8. Defluorination of perfluoroolefins by divalent lanthanoid reagents: Activating C-F bonds

    SciTech Connect

    Watson, P.L.; Tulip, T.H.; Williams, I. )

    1990-07-01

    Divalent lanthanoid complexes MCp*{sub 2} {times} L (M = Yb, Eu, Sm; L = diethyl ether or THF; Cp* = {eta}{sup 5}-pentamethylcyclopetadienyl) and YbCp{prime}{sub 2} {times} L (Cp{prime} = {eta}{sup 5}-methylcyclopentadienyl; L = tetrahydrofuran) rapidly abstract fluorine atoms from a variety of perfluoroolefins including perfluoro-2,4-dimethyl-3-ethylpent-2-ene, perfluoro-2,3-dimethylpent-2-ene, and perfluorocyclohexene. Qualitative observation shows that the relative fluorine abstraction reactivity of the four lanthanoid complexes increases with increasingly negative reduction potential for reasonably unhindered fluoroolefin substrates. The Yb(III)/Yb(II) reduction potential of YbCp{prime}{sub 2} solvated in acetonitrile is determined here to be {minus}1.65 V (relative to ferrocene) by cyclic voltammetry. The fully characterized organometallic products from the fluorine atom abstraction reactions are solvated trivalent lanthanoid fluorides MCp*{sub 2}F {times} L (M = Yb, Eu, Sm; L = diethyl ether or THF) and YbCp{prime}{sub 2}F {times} THF. The molecular structures of YbCp*{sub 2}F {times} OEt{sub 2} and YbCp*{sub 2}F {times} THF determined by X-ray crystallography reveal the first terminal lanthanoid-fluoride bonds.

  9. Cooperativity between Al Sites Promotes Hydrogen Transfer and Carbon–Carbon Bond Formation upon Dimethyl Ether Activation on Alumina

    PubMed Central

    2015-01-01

    The methanol-to-olefin (MTO) process allows the conversion of methanol/dimethyl ether into olefins on acidic zeolites via the so-called hydrocarbon pool mechanism. However, the site and mechanism of formation of the first carbon–carbon bond are still a matter of debate. Here, we show that the Lewis acidic Al sites on the 110 facet of γ-Al2O3 can readily activate dimethyl ether to yield CH4, alkenes, and surface formate species according to spectroscopic studies combined with a computational approach. The carbon–carbon forming step as well as the formation of methane and surface formate involves a transient oxonium ion intermediate, generated by a hydrogen transfer between surface methoxy species and coordinated methanol on adjacent Al sites. These results indicate that extra framework Al centers in acidic zeolites, which are associated with alumina, can play a key role in the formation of the first carbon–carbon bond, the initiation step of the industrial MTO process. PMID:27162986

  10. [Bioluminescent method of determining antiprotease activity].

    PubMed

    Gitel'zon, I I; Rykov, S A; Kratasiuk, G A; Petushkov, V N; Shvetskiĭ, A G

    1985-11-01

    A method for antiprotease activity measurement based on the use of luminous bacteria luciferase as protein substrate of proteases is suggested. Antiprotease is incubated with protease for 1 to 2 min at 30 degrees C and then it is added to the reaction mixture containing luciferase, NADH: FMN-oxidoreductase and their substrates--myristic aldehyde, FMN and NADH. Biofluorescence is measured in a temperature-controlled cuvette for 1 min. The total time of the measurement is 3 min. The method can be applied both in fine biochemical assays and in medical rapid diagnosis.

  11. A method of coupling the Paternò-Büchi reaction with direct infusion ESI-MS/MS for locating the C[double bond, length as m-dash]C bond in glycerophospholipids.

    PubMed

    Stinson, Craig A; Xia, Yu

    2016-06-21

    Tandem mass spectrometry (MS/MS) coupled with soft ionization is established as an essential platform for lipid analysis; however, determining high order structural information, such as the carbon-carbon double bond (C[double bond, length as m-dash]C) location, remains challenging. Recently, our group demonstrated a method for sensitive and confident lipid C[double bond, length as m-dash]C location determination by coupling online the Paternò-Büchi (PB) reaction with nanoelectrospray ionization (nanoESI) and MS/MS. Herein, we aimed to expand the scope of the PB reaction for lipid analysis by enabling the reaction with infusion ESI-MS/MS at much higher flow rates than demonstrated in the nanoESI setup (∼20 nL min(-1)). In the new design, the PB reaction was effected in a fused silica capillary solution transfer line, which also served as a microflow UV reactor, prior to ESI. This setup allowed PB reaction optimization and kinetics studies. Under optimized conditions, a maximum of 50% PB reaction yield could be achieved for a standard glycerophosphocholine (PC) within 6 s of UV exposure over a wide flow rate range (0.1-10 μL min(-1)). A solvent composition of 7 : 3 acetone : H2O (with 1% acid or base modifier) allowed the highest PB yields and good lipid ionization, while lower yields were obtained with an addition of a variety of organic solvents. Radical induced lipid peroxidation was identified to induce undesirable side reactions, which could be effectively suppressed by eliminating trace oxygen in the solution via N2 purge. Finally, the utility of coupling the PB reaction with infusion ESI-MS/MS was demonstrated by analyzing a yeast polar lipid extract where C[double bond, length as m-dash]C bond locations were revealed for 35 glycerophospholipids (GPs).

  12. Testing Geometrical Discrimination within an Enzyme Active Site: Constrained Hydrogen Bonding in the Ketosteroid Isomerase Oxyanion Hole

    PubMed Central

    Sigala, Paul A.; Kraut, Daniel A.; Caaveiro, Jose M. M.; Pybus, Brandon; Ruben, Eliza A.; Ringe, Dagmar; Petsko, Gregory A.; Herschlag, Daniel

    2009-01-01

    Enzymes are classically proposed to accelerate reactions by binding substrates within active site environments that are structurally preorganized to optimize binding interactions with reaction transition states rather than ground states. This is a remarkably formidable task considering the limited 0.1 – 1 Å scale of most substrate rearrangements. The flexibility of active site functional groups along the coordinate of substrate rearrangement, the distance scale on which enzymes can distinguish structural rearrangement, and the energetic significance of discrimination on that scale remain open questions that are fundamental to a basic physical understanding of enzyme active sites and catalysis. We bring together high resolution X-ray crystallography, 1H and 19F NMR spectroscopy, quantum mechanical calculations, and transition state analog binding measurements to test the distance scale on which non-covalent forces can constrain side chain and ligand relaxation or translation along a specific coordinate and the energetic consequences of such geometric constraints within the active site of bacterial ketosteroid isomerase (KSI). Our results strongly suggest that packing and binding interactions within the KSI active site can constrain local side chain reorientation and prevent hydrogen bond shortening by 0.1 Å or less. Further, this constraint has substantial energetic effects on ligand binding and stabilization of negative charge within the oxyanion hole. These results provide evidence that subtle geometric effects, indistinguishable in most X-ray crystallographic structures, can have significant energetic consequences and highlight the importance of using synergistic experimental approaches to dissect enzyme function. PMID:18808119

  13. N-Methylphthalimide-substituted benzimidazolium salts and PEPPSI Pd–NHC complexes: synthesis, characterization and catalytic activity in carbon–carbon bond-forming reactions

    PubMed Central

    Gök, Yetkin; İlhan, İlhan Özer

    2016-01-01

    Summary A series of novel benzimidazolium salts (1–4) and their pyridine enhanced precatalyst preparation stabilization and initiation (PEPPSI) themed palladium N-heterocyclic carbene complexes [PdCl2(NHC)(Py)] (5–8), where NHC = 1-(N-methylphthalimide)-3-alkylbenzimidazolin-2-ylidene and Py = 3-chloropyridine, were synthesized and characterized by means of 1H and 13C{1H} NMR, UV–vis (for 5–8), ESI-FTICR-MS (for 2, 4, 6–8) and FTIR spectroscopic methods and elemental analysis. The synthesized compounds were tested in Suzuki–Miyaura cross-coupling (for 1–8) and arylation (for 5–8) reactions. As catalysts, they demonstrated a highly efficient route for the formation of asymmetric biaryl compounds even though they were used in very low loading. For example, all compounds displayed good catalytic activity for the C–C bond formation of 4-tert-butylphenylboronic acid with 4-chlorotoluene. PMID:26877810

  14. Interaction between the antibiotic spiramycin and a ribosomal complex active in peptide bond formation.

    PubMed

    Dinos, G; Synetos, D; Coutsogeorgopoulos, C

    1993-10-12

    The inhibition of peptide bond formation by spiramycin was studied in an in vitro system derived from Escherichia coli. Peptide bonds are formed between puromycin (S) and Ac-Phe-tRNA, which is a component of complex C, i.e., of the [Ac-Phe-tRNA-70S ribosome-poly(U)] complex, according to the puromycin reaction: C+S (Ks)<==>CS (k3)==>C'+P [Synetos, D., & Coutsogeorgopoulos, C. (1987) Biochim. Biophys. Acta 923, 275-285]. It is shown that spiramycin (A) reacts with complex C and forms the spiramycin complex C*A, which is inactive toward puromycin. C*A is the tightest complex formed between complex C and any of a number of antibiotics, such as chloramphenicol, blasticidin S, lincomycin, or sparsomycin. C*A remains stable following gel chromatography on Sephadex G-200 and sucrose gradient ultracentrifugation. Detailed kinetic study suggests that C*A is formed in a variation of a two-step mechanism in which the initial encounter complex CA is kinetically insignificant and C*A is the product of a conformational change of complex CA according to the equation, C+A (kassoc)<==>(kdissoc) C*A. The rate constants of this reaction (spiramycin reaction) are kassoc = 3.0 x 10(4) M-1 s-1 and kdissoc = 5.0 x 10(-5) s-1. Such values allow the classification of spiramycin as a slow-binding, slowly reversible inhibitor; they also lead to the calculation of an apparent overall dissociation constant equal to 1.8 nM for the C*A complex. Furthermore, they render spiramycin a useful tool in the study of antibiotic action on protein synthesis in vitro. Thus, the spiramycin reaction, in conjunction with the puromycin reaction, is applied (i) to detect a strong preincubation effect exerted by chloramphenicol and lincomycin (this effect constitutes further evidence that these two antibiotics combine with complex C as slow-binding inhibitors) and (ii) to determine the rate constant for the regeneration (k7 = 2.0 x 10(-3) s-1) of complex C from the sparsomycin complex C*I [Theocharis, D. A

  15. Method for photon activation positron annihilation analysis

    DOEpatents

    Akers, Douglas W.

    2006-06-06

    A non-destructive testing method comprises providing a specimen having at least one positron emitter therein; determining a threshold energy for activating the positron emitter; and determining whether a half-life of the positron emitter is less than a selected half-life. If the half-life of the positron emitter is greater than or equal to the selected half-life, then activating the positron emitter by bombarding the specimen with photons having energies greater than the threshold energy and detecting gamma rays produced by annihilation of positrons in the specimen. If the half-life of the positron emitter is less then the selected half-life, then alternately activating the positron emitter by bombarding the specimen with photons having energies greater then the threshold energy and detecting gamma rays produced by positron annihilation within the specimen.

  16. A theoretical study of the structures and chemical bonds of neptunium (III) molecules by a density functional method

    NASA Astrophysics Data System (ADS)

    Yin, Yao-Peng; Dong, Chen-Zhong; Du, Lei-Qiang; Wu, Fang-Xian; Ding, Xiao-Bin

    2014-10-01

    In this paper, equilibrium structures and chemical bond characteristics of neptunium trihalide molecules NpX3 (X = F, Cl, Br and I) have been investigated by using density functional theory (DFT). The influences of the size of the relativistic effective core potential (RECP) have been examined on the molecular structures. The chemical bond characteristics have also been systematically studied by calculating the density of states (DOS), bond length differences and electronic charge distributions. We have determined that the chemical bonds are mainly ionic in those molecules, and the covalency is enhancing while ionicity decreases from NpF3 to NpI3. The calculated bond energies show that the interaction strength in NpX3 molecules becomes weaker as the halogen atoms becoming heavier.

  17. Understanding trends in C-H bond activation in heterogeneous catalysis.

    PubMed

    Latimer, Allegra A; Kulkarni, Ambarish R; Aljama, Hassan; Montoya, Joseph H; Yoo, Jong Suk; Tsai, Charlie; Abild-Pedersen, Frank; Studt, Felix; Nørskov, Jens K

    2017-02-01

    While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.

  18. Understanding trends in C-H bond activation in heterogeneous catalysis

    NASA Astrophysics Data System (ADS)

    Latimer, Allegra A.; Kulkarni, Ambarish R.; Aljama, Hassan; Montoya, Joseph H.; Yoo, Jong Suk; Tsai, Charlie; Abild-Pedersen, Frank; Studt, Felix; Nørskov, Jens K.

    2016-10-01

    While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.

  19. The Unexpected Reactivity of the Carbon Sites on the Nanostructured Carbon Catalysts towards the C-H Bond Activation from the Analysis of the Aromaticity.

    PubMed

    Sun, XiaoYing; Li, Bo; Su, DangSheng

    2016-06-06

    It is believed that the oxygen groups on the carbon catalysts are responsible for the observed reactivity for C-H bond activations. On the other hand, the oxygen groups also reduce the aromaticity of the host. The loss of the aromaticity increases reactivities of the carbon atoms and they become the active sites for the C-H bond activation. The newly identified C-C site exhibits the comparable catalytic performance in the oxidative dehydrogenation (ODH) of propane compared with the conventional oxygen groups like quinone and ketone. A series of calculations indicate that the aromaticity might be a useful descriptor for the carbon catalysts.

  20. A Palladium-Catalyzed Method for the Synthesis of Carbazoles via Tandem C-H Functionalization and C-N Bond Formation

    PubMed Central

    Tsang, W. C. Peter; Munday, Rachel H.; Brasche, Gordon; Zheng, Nan; Buchwald, Stephen L.

    2009-01-01

    The development of a new method for the assembly of unsymmetrical carbazoles is reported. The strategy involves the selective intramolecular functionalization of an arene C-H bond and the formation of a new arene C-N bond. The substitution pattern of the carbazole product can be controlled by the design of the biaryl amide substrate, and the method is compatible with a variety of functional groups. The utility of the new protocol was demonstrated by the concise synthesis of three natural products from commercially available materials. PMID:18761437

  1. Investigations on the dynamic coupling in AUV-manipulator system and the manipulator trajectory errors using bond graph method

    NASA Astrophysics Data System (ADS)

    Periasamy, T.; Asokan, T.; Singaperumal, M.

    2012-06-01

    This article presents the modelling and simulation of the dynamic coupling in an autonomous underwater vehicle (AUV)-manipulator system, used for subsea intervention tasks. Bond graph, a powerful tool in multi-domain dynamic system modelling, is used for the first time to model the coupled dynamics of the AUV-manipulator system. This method enables the development of the system model in a modular form by creating sub-system models and connecting these models together at energy interactions ports, thus overcoming many of the computational difficulties encountered in conventional modelling methods. The effects of gravity, buoyancy, added mass and fluid drag on the dynamics of a 3 degrees of freedom (DoF) manipulator mounted on a 6 DoF AUV are analysed. The manipulator trajectory errors due to the interaction forces and moments between the vehicle and the manipulator have also been investigated and the results are presented. The dynamic model predicts the reaction forces on the vehicle under various operating conditions of the manipulator and their influence on the manipulator trajectory. The percentage errors of manipulator tip trajectory for different initial configurations and operating conditions are analysed. The estimation of resulting errors in the manipulator path due to dynamic coupling effect on the manipulator trajectory helps in the design of suitable trajectory controller for the system. Cartesian space transpose Jacobian controller for trajectory control of manipulator has been implemented and results are presented.

  2. Accurate prediction of polarised high order electrostatic interactions for hydrogen bonded complexes using the machine learning method kriging

    NASA Astrophysics Data System (ADS)

    Hughes, Timothy J.; Kandathil, Shaun M.; Popelier, Paul L. A.

    2015-02-01

    As intermolecular interactions such as the hydrogen bond are electrostatic in origin, rigorous treatment of this term within force field methodologies should be mandatory. We present a method able of accurately reproducing such interactions for seven van der Waals complexes. It uses atomic multipole moments up to hexadecupole moment mapped to the positions of the nuclear coordinates by the machine learning method kriging. Models were built at three levels of theory: HF/6-31G**, B3LYP/aug-cc-pVDZ and M06-2X/aug-cc-pVDZ. The quality of the kriging models was measured by their ability to predict the electrostatic interaction energy between atoms in external test examples for which the true energies are known. At all levels of theory, >90% of test cases for small van der Waals complexes were predicted within 1 kJ mol-1, decreasing to 60-70% of test cases for larger base pair complexes. Models built on moments obtained at B3LYP and M06-2X level generally outperformed those at HF level. For all systems the individual interactions were predicted with a mean unsigned error of less than 1 kJ mol-1.

  3. Accurate prediction of polarised high order electrostatic interactions for hydrogen bonded complexes using the machine learning method kriging.

    PubMed

    Hughes, Timothy J; Kandathil, Shaun M; Popelier, Paul L A

    2015-02-05

    As intermolecular interactions such as the hydrogen bond are electrostatic in origin, rigorous treatment of this term within force field methodologies should be mandatory. We present a method able of accurately reproducing such interactions for seven van der Waals complexes. It uses atomic multipole moments up to hexadecupole moment mapped to the positions of the nuclear coordinates by the machine learning method kriging. Models were built at three levels of theory: HF/6-31G(**), B3LYP/aug-cc-pVDZ and M06-2X/aug-cc-pVDZ. The quality of the kriging models was measured by their ability to predict the electrostatic interaction energy between atoms in external test examples for which the true energies are known. At all levels of theory, >90% of test cases for small van der Waals complexes were predicted within 1 kJ mol(-1), decreasing to 60-70% of test cases for larger base pair complexes. Models built on moments obtained at B3LYP and M06-2X level generally outperformed those at HF level. For all systems the individual interactions were predicted with a mean unsigned error of less than 1 kJ mol(-1).

  4. Oxidation-promoted activation of a ferrocene C-H bond by a rhodium complex.

    PubMed

    Labande, Agnès; Debono, Nathalie; Sournia-Saquet, Alix; Daran, Jean-Claude; Poli, Rinaldo

    2013-05-14

    The oxidation of a rhodium(I) complex containing a ferrocene-based heterodifunctional phosphine N-heterocyclic carbene (NHC) ligand produces a stable, planar chiral rhodium(III) complex with an unexpected C-H activation on ferrocene. The oxidation of rhodium(I) to rhodium(III) may be accomplished by initial oxidation of ferrocene to ferrocenium and subsequent electron transfer from rhodium to ferrocenium. Preliminary catalytic tests showed that the rhodium(III) complex is active for the Grignard-type arylation of 4-nitrobenzaldehyde via C-H activation of 2-phenylpyridine.

  5. Hydrolysis activities of the particle of agarose-Ce4+ complex for compounds containing phosphodiester or peptide bonds

    NASA Astrophysics Data System (ADS)

    Yu, Lina; Wang, Dongfeng; Su, Lin; Luo, Yi; Sun, Liping; Xue, Changhu

    2005-07-01

    Hydrolysis activities of PACC (particle of agarose-Ce4+ complex, newly made through double emulsification) for compounds containing phosphodiester or peptide bonds were studied. The results showed that PACC could hydrolyze organophosphorous pesticides not only in water but also in vegetable juice or tea extract. Hydrolysis rates of methamidophos, omethoate and chlorpyrifos in water are 32.39%, 27.12% and 46.62% respectively, those of chlorpyrifos and methamidophos in mung sprout juice 38.28% and 35.45% respectively, and that of chlorpyrifos in tea extract 59.76%. Hydrolysis rates of BSA (bovine serum albumin) in water and protein in tea extract by PACC increase by 54.30% and 86.46% respectively as compared with the control.

  6. P-P bond activation of P4 tetrahedron by group 13 carbenoid and its bis molybdenum pentacarbonyl adduct.

    PubMed

    Prabusankar, Ganesan; Doddi, Adinarayana; Gemel, Christian; Winter, Manuela; Fischer, Roland A

    2010-09-06

    Activation of white phosphorus with Ga(DDP) (DDP = 2-diiso-propylphenylamino-4-diiso-propylphenylimino-2-pentene) afforded [(DDP)Ga(P(4))] (1) by insertion of the Ga(I) center at one of the six P-P bonded edges of the P(4) tetrahedron. Further reaction of 1 with three equivalents of Mo(CO)(6) results in the formation of [(DDP)Ga(eta(2:1:1)-P(4)){Mo(CO)(5)}(2)] x 2 toluene (2). Compounds 1 and 2 are characterized by (1)H, (13)C, and (31)P NMR spectroscopy, elemental analysis, and single crystal X-ray structural analysis. The solid-state structure of molecule 1 reveals the first example of a structurally characterized GaP(4) core stabilized by a beta-diketiminate ligand. Compound 2 represents a rare type of coordination mode of a gallium supported P(4) butterfly structure.

  7. Modifications on the hydrogen bond network by mutations of Escherichia coli copper efflux oxidase affect the process of proton transfer to dioxygen leading to alterations of enzymatic activities

    SciTech Connect

    Kajikawa, Takao; Kataoka, Kunishige; Sakurai, Takeshi

    2012-05-25

    Highlights: Black-Right-Pointing-Pointer Proton transfer pathway to dioxygen in CueO was identified. Black-Right-Pointing-Pointer Glu506 is the key amino acid to transport proton. Black-Right-Pointing-Pointer The Ala mutation at Glu506 formed a compensatory proton transfer pathway. Black-Right-Pointing-Pointer The Ile mutation at Glu506 shut down the hydrogen bond network. -- Abstract: CueO has a branched hydrogen bond network leading from the exterior of the protein molecule to the trinuclear copper center. This network transports protons in the four-electron reduction of dioxygen. We replaced the acidic Glu506 and Asp507 residues with the charged and uncharged amino acid residues. Peculiar changes in the enzyme activity of the mutants relative to the native enzyme indicate that an acidic amino acid residue at position 506 is essential for effective proton transport. The Ala mutation resulted in the formation of a compensatory hydrogen bond network with one or two extra water molecules. On the other hand, the Ile mutation resulted in the complete shutdown of the hydrogen bond network leading to loss of enzymatic activities of CueO. In contrast, the hydrogen bond network without the proton transport function was constructed by the Gln mutation. These results exerted on the hydrogen bond network in CueO are discussed in comparison with proton transfers in cytochrome oxidase.

  8. Hydroxy functionalization of non-activated C-H and C=C bonds: new perspectives for the synthesis of alcohols through biocatalytic processes.

    PubMed

    Gröger, Harald

    2014-03-17

    New perspectives through enzymes: Recent breakthroughs have been achieved in the selective hydroxy functionalization of non-activated C-H and C=C bonds. Enzymes turned out to be suitable catalysts for the ω-hydroxylation of (substituted) alkanes and regioselective hydroxylation of aromatic hydrocarbons with atmospheric oxygen as the oxidant, and the asymmetric addition of water to non-activated alkenes.

  9. Spectroscopic insights into axial ligation and active-site H-bonding in substrate-bound human heme oxygenase-2.

    PubMed

    Gardner, Jessica D; Yi, Li; Ragsdale, Stephen W; Brunold, Thomas C

    2010-09-01

    Heme oxygenases (HOs) are monooxygenases that catalyze the first step in heme degradation, converting heme to biliverdin with concomitant release of Fe(II) and CO from the porphyrin macrocycle. Two heme oxygenase isoforms, HO-1 and HO-2, exist that differ in several ways, including a complete lack of Cys residues in HO-1 and the presence of three Cys residues as part of heme-regulatory motifs (HRMs) in HO-2. HRMs in other heme proteins are thought to directly bind heme, or to otherwise regulate protein stability or activity; however, it is not currently known how the HRMs exert these effects on HO-2 function. To better understand the properties of this vital enzyme and to elucidate possible roles of its HRMs, various forms of HO-2 possessing distinct alterations to the HRMs were prepared. In this study, variants with Cys265 in a thiol form are compared with those with this residue in an oxidized (part of a disulfide bond or existing as a sulfenate moiety) form. Absorption and magnetic circular dichroism spectroscopic data of these HO-2 variants clearly demonstrate that a new low-spin Fe(III) heme species characteristic of thiolate ligation is formed when Cys265 is reduced. Additionally, absorption, magnetic circular dichroism, and resonance Raman data collected at different temperatures reveal an intriguing temperature dependence of the iron spin state in the heme-HO-2 complex. These findings are consistent with the presence of a hydrogen-bonding network at the heme's distal side within the active site of HO-2 with potentially significant differences from that observed in HO-1.

  10. James Webb Space Telescope (JWST) Integrated Science Instruments Module (ISIM) Electronics Compartment (IEC) Conformal Shields Composite Bond Structure Qualification Test Method

    NASA Technical Reports Server (NTRS)

    Yew, Calinda; Stephens, Matt

    2015-01-01

    The JWST IEC conformal shields are mounted onto a composite frame structure that must undergo qualification testing to satisfy mission assurance requirements. The composite frame segments are bonded together at the joints using epoxy, EA 9394. The development of a test method to verify the integrity of the bonded structure at its operating environment introduces challenges in terms of requirements definition and the attainment of success criteria. Even though protoflight thermal requirements were not achieved, the first attempt in exposing the structure to cryogenic operating conditions in a thermal vacuum environment resulted in approximately 1 bonded joints failure during mechanical pull tests performed at 1.25 times the flight loads. Failure analysis concluded that the failure mode was due to adhesive cracks that formed and propagated along stress concentrated fillets as a result of poor bond squeeze-out control during fabrication. Bond repairs were made and the structures successfully re-tested with an improved LN2 immersion test method to achieve protoflight thermal requirements.

  11. A new method for FMRI activation detection

    NASA Astrophysics Data System (ADS)

    Wei, Jianing; Talavage, Thomas M.; Pollak, Ilya

    2009-02-01

    The objective of fMRI data analysis is to detect the region of the brain that gets activated in response to a specific stimulus presented to the subject. We develop a new algorithm for activation detection in event-related fMRI data. We utilize a forward model for fMRI data acquisition which explicitly incorporates physiological noise, scanner noise and the spatial blurring introduced by the scanner. After slice-by-slice image restoration procedure that independently restores each data slice corresponding to each time index, we estimate the parameters of the hemodynamic response function (HRF) model for each pixel of the restored data. In order to enforce spatial regularity in our estimates, we model the prior distribution of the HRF parameters as a generalized Gaussian Markov random field (GGMRF) model. We develop an algorithm to compute the maximum a posteriori (MAP) estimates of the parameters. We then threshold the amplitude parameters to obtain the final activation map. We illustrate our algorithm by comparing it with the widely used general linear model (GLM) method. In synthetic data experiments, under the same probability of false alarm, the probability of correct detection for our method is up to 15% higher than GLM. In real data experiments, through anatomical analysis and benchmark testing using block paradigm results, we demonstrate that our algorithm produces fewer false alarms than GLM.

  12. Comparison of standard methods and gas chromatography method in determination of formaldehyde emission from MDF bonded with formaldehyde-based resins.

    PubMed

    Kim, Sumin; Kim, Hyun-Joong

    2005-09-01

    Formaldehyde emissions from MDF bonded with urea-formaldehyde resin (UF), melamine-formaldehyde resin (MF) and the co-polycondensation resin of urea-melamine-formaldehyde (UMF) and melamine-formaldehyde, measured by the Japanese standard method of determining formaldehyde emission with a desiccator (JIS A 5908) and the DIN EN 120 (European Committee For Standardization, 1991) method using the perforator value, were used as the typical standard methods. While the UF resin showed a desiccator value of 7.05 ppm and a perforator value of 12.1 mg/100 g panel, the MF resin exhibited a desiccator value of 0.6 ppm and a perforator value of 2.88 mg/100 g panel. According to the Japanese industrial standard and the European standard, the formaldehyde emission level of the MDF panels made with UF resin in this study was E(2) grade. The formaldehyde emission level was dramatically reduced by the addition of MF resin. This is because the addition of formaldehyde to melamine occurs more easily and completely than its addition to urea, even though the condensation reaction of melamine with formaldehyde is similar to that between urea and formaldehyde. These two methods, the desiccator method and the perforator method, produced proportionally equivalent results. Gas chromatography, a more sensitive and advanced method, was also used. The samples used for gas chromatography were gathered during the experiment involving the perforator method. The formaldehyde emission levels obtained from gas chromatography were similar to those obtained from the perforator method. The formaldehyde contents measured by gas chromatography were directly proportional to the perforator values.

  13. Carbon–Hydrogen Bond Activation, C–N Bond Coupling, and Cycloaddition Reactivity of a Three-Coordinate Nickel Complex Featuring a Terminal Imido Ligand

    PubMed Central

    2015-01-01

    The three-coordinate imidos (dtbpe)Ni=NR (dtbpe = tBu2PCH2CH2PtBu2, R = 2,6-iPr2C6H3, 2,4,6-Me3C6H2 (Mes), and 1-adamantyl (Ad)), which contain a legitimate Ni–N double bond as well as basic imido nitrogen based on theoretical analysis, readily deprotonate HC≡CPh to form the amide acetylide species (dtbpe)Ni{NH(Ar)}(C≡CPh). In the case of R = 2,6-iPr2C6H3, reductive carbonylation results in formation of the (dtbpe)Ni(CO)2 along with the N–C coupled product keteneimine PhCH=C=N(2,6- iPr2C6H3). Given the ability of the Ni=N bond to have biradical character as suggested by theoretical analysis, H atom abstraction can also occur in (dtbpe)Ni=N{2,6-iPr2C6H3} when this species is treated with HSn(nBu)3. Likewise, the microscopic reverse reaction—conversion of the Ni(I) anilide (dtbpe)Ni{NH(2,6-iPr2C6H3)} to the imido (dtbpe)Ni=N{2,6-iPr2C6H3}—is promoted when using the radical Mes*O• (Mes* = 2,4,6-tBu3C6H2). Reactivity studies involving the imido complexes, in particular (dtbpe)Ni=N{2,6-iPr2C6H3}, are also reported with small, unsaturated molecules such as diphenylketene, benzylisocyanate, benzaldehyde, and carbon dioxide, including the formation of C–N and N–N bonds by coupling reactions. In addition to NMR spectroscopic data and combustion analysis, we also report structural studies for all the cycloaddition reactions involving the imido (dtbpe)Ni=N{2,6-iPr2C6H3}. PMID:25437507

  14. System and method for monitoring cellular activity

    NASA Technical Reports Server (NTRS)

    Bearman, Gregory H. (Inventor); Fraser, Scott E. (Inventor); Lansford, Russell D. (Inventor)

    2004-01-01

    A system and method for monitoring cellular activity in a cellular specimen. According to one embodiment, a plurality of excitable markers are applied to the specimen. A multi-photon laser microscope is provided to excite a region of the specimen and cause fluorescence to be radiated from the region. The radiating fluorescence is processed by a spectral analyzer to separate the fluorescence into respective wavelength bands. The respective bands of fluorescence are then collected by an array of detectors, with each detector receiving a corresponding one of the wavelength bands.

  15. System and method for monitoring cellular activity

    NASA Technical Reports Server (NTRS)

    Bearman, Gregory H. (Inventor); Fraser, Scott E. (Inventor); Lansford, Russell D. (Inventor)

    2002-01-01

    A system and method for monitoring cellular activity in a cellular specimen. According to one embodiment, a plurality of excitable markers are applied to the specimen. A multi-photon laser microscope is provided to excite a region of the specimen and cause fluorescence to be radiated from the region. The radiating fluorescence is processed by a spectral analyzer to separate the fluorescence into respective wavelength bands. The respective bands of fluorescence are then collected by an array of detectors, with each detector receiving a corresponding one of the wavelength bands.

  16. Dual stage active magnetic regenerator and method

    DOEpatents

    Pecharsky, Vitalij K.; Gschneidner, Jr., Karl A.

    1999-03-30

    A dual stage active magnetic regenerator refrigerator as well as method using the Joule-Brayton thermodynamic cycle includes a high temperature stage refrigerant comprising DyAl.sub.2 or (Dy.sub.1-x Er.sub.x)Al.sub.2 where x is selected to be greater than 0 and less than about 0.3 in combination with a low temperature stage comprising (Dy.sub.1-x Er.sub.x)Al.sub.2 where x is selected to be greater than about 0.5 and less than 1 to provide significantly improved refrigeration efficiency in the liquefaction of gaseous hydrogen.

  17. Dual stage active magnetic regenerator and method

    DOEpatents

    Pecharsky, V.K.; Gschneidner, K.A. Jr.

    1999-03-30

    A dual stage active magnetic regenerator refrigerator as well as method using the Joule-Brayton thermodynamic cycle includes a high temperature stage refrigerant comprising DyAl{sub 2} or (Dy{sub 1{minus}x}Er{sub x})Al{sub 2} where x is selected to be greater than 0 and less than about 0.3 in combination with a low temperature stage comprising (Dy{sub 1{minus}x}Er{sub x})Al{sub 2} where x is selected to be greater than about 0.5 and less than 1 to provide significantly improved refrigeration efficiency in the liquefaction of gaseous hydrogen. 17 figs.

  18. A Series of Diamagnetic Pyridine Monoimine Rhenium Complexes with Different Degrees of Metal-to-Ligand Charge Transfer: Correlating (13) C NMR Chemical Shifts with Bond Lengths in Redox-Active Ligands.

    PubMed

    Sieh, Daniel; Kubiak, Clifford P

    2016-07-18

    A set of pyridine monoimine (PMI) rhenium(I) tricarbonyl chlorido complexes with substituents of different steric and electronic properties was synthesized and fully characterized. Spectroscopic (NMR and IR) and single-crystal X-ray diffraction analyses of these complexes showed that the redox-active PMI ligands are neutral and that the overall electronic structure is little affected by the choices of the substituent at the ligand backbone. One- and two-electron reduction products were prepared from selected starting compounds and could also be characterized by multiple spectroscopic methods and X-ray diffraction. The final product of a one-electron reduction in THF is a diamagnetic metal-metal-bonded dimer after loss of the chlorido ligand. Bond lengths in and NMR chemical shifts of the PMI ligand backbone indicate partial electron transfer to the ligand. Two-electron reduction in THF also leads to the loss of the chlorido ligand and a pentacoordinate complex is obtained. The comparison with reported bond lengths and (13) C NMR chemical shifts of doubly reduced free pyridine monoaldimine ligands indicates that both redox equivalents in the doubly reduced rhenium complex investigated here are located in the PMI ligand. With diamagnetic complexes varying over three formal reduction stages at the PMI ligand we were, for the first time, able to establish correlations of the (13) C NMR chemical shifts with the relevant bond lengths in redox-active ligands over a full redox series.

  19. Role of the intra-A-chain disulfide bond of insulin-like peptide 3 in binding and activation of its receptor, RXFP2.

    PubMed

    Zhang, Suode; Hughes, Richard A; Bathgate, Ross A D; Shabanpoor, Fazel; Hossain, M Akhter; Lin, Feng; van Lierop, Bianca; Robinson, Andrea J; Wade, John D

    2010-09-01

    INSL3 is a member of the insulin-IGF-relaxin superfamily and plays a key role in male fetal development and in adult germ cell maturation. It is the cognate ligand for RXFP2, a leucine-rich repeat containing G-protein coupled receptor. To date, and in contrast to our current knowledge of the key structural features that are required for the binding of INSL3 to RXFP2, comparatively little is known about the key residues that are required to elicit receptor activation and downstream cell signaling. Early evidence suggests that these are contained principally within the A-chain. To further explore this hypothesis, we have undertaken an examination of the functional role of the intra-A-chain disulfide bond. Using solid-phase peptide synthesis together with regioselective disulfide bond formation, two analogs of human INSL3 were prepared in which the intra-chain disulfide bond was replaced, one in which the corresponding Cys residues were substituted with the isosteric Ser and the other in which the Cys were removed altogether. Both of these peptides retained nearly full RXFP2 receptor binding but were devoid of cAMP activity (receptor activation), indicating that the intra-A-chain disulfide bond makes a significant contribution to the ability of INSL3 to act as an RXFP2 agonist. Replacement of the disulfide bond with a metabolically stable dicarba bond yielded two isomers of INSL3 that each exhibited bioactivity similar to native INSL3. This study highlights the critical structural role played by the intra-A-chain disulfide bond of INSL3 in mediating agonist actions through the RXFP2 receptor.

  20. Catalysis of hydrolysis and nucleophilic substitution at the P-N bond of phosphoimidazolide-activated nucleotides in phosphate buffers

    NASA Technical Reports Server (NTRS)

    Kanavarioti, A.; Rosenbach, M. T.

    1991-01-01

    Phosphoimidazolide-activated derivatives of guanosine and cytidine 5'-monophosphates, henceforth called ImpN's, exhibit enhanced rates of degradation in the presence of aqueous inorganic phosphate in the range 4.0 < or = pH < or = 8.6. This degradation is been attributed to (i) nucleophilic substitution of the imidazolide and (ii) catalysis of the P-N bond hydrolysis by phosphate. The first reaction results in the formation of nucleoside 5'-diphosphate and the second in nucleoside 5'-monophosphate. Analysis of the observed rates as well as the product ratios as a function of pH and phosphate concentration allow distinction between various mechanistic possibilities. The results show that both H2PO4- and HPO4(2-) participate in both hydrolysis and nucleophilic substitution. Statistically corrected biomolecular rate constants indicate that the dianion is 4 times more effective as a general base than the monoanion, and 8 times more effective as nucleophile. The low Bronsted value beta = 0.15 calculated for these phosphate species, presumed to act as general bases in facilitating water attack, is consistent with the fact that catalysis of the hydrolysis of the P-N bond in ImpN's has not been detected before. The beta nuc = 0.35 calculated for water, H2PO4-, HPO4(2-), and hydroxide acting as nucleophiles indicates a more associative transition state for nucleotidyl (O2POR- with R = nucleoside) transfers than that observed for phosphoryl (PO3(2-)) transfers (beta nuc = 0.25). With respect to the stability/reactivity of ImpN's under prebiotic conditions, our study shows that these materials would not suffer additional degradation due to inorganic phosphate, assuming the concentrations of phosphate, Pi, on prebiotic Earth were similar to those in the present oceans ([Pi] approximately 2.25 micromoles).

  1. Synthesis of a Benzodiazepine-derived Rhodium NHC Complex by C-H Bond Activation

    SciTech Connect

    Bergman, Roberg G.; Gribble, Jr., Michael W.; Ellman, Jonathan A.

    2008-01-30

    The synthesis and characterization of a Rh(I)-NHC complex generated by C-H activation of 1,4-benzodiazepine heterocycle are reported. This complex constitutes a rare example of a carbene tautomer of a 1,4-benzodiazepine aldimine stabilized by transition metal coordination and demonstrates the ability of the catalytically relevant RhCl(PCy{sub 3}){sub 2} fragment to induce NHC-forming tautomerization of heterocycles possessing a single carbene-stabilizing heteroatom. Implications for the synthesis of benzodiazepines and related pharmacophores via C-H functionalization are discussed.

  2. Evidence for disulfide bonds in SR Protein Kinase 1 (SRPK1) that are required for activity and nuclear localization

    PubMed Central

    Koutroumani, Maria; Papadopoulos, Georgios E.; Vlassi, Metaxia; Nikolakaki, Eleni; Giannakouros, Thomas

    2017-01-01

    Serine/arginine protein kinases (SRPKs) phosphorylate Arg/Ser dipeptide-containing proteins that play crucial roles in a broad spectrum of basic cellular processes. The existence of a large internal spacer sequence that separates the bipartite kinase catalytic core is a unique structural feature of SRPKs. Previous structural studies on a catalytically active fragment of SRPK1, which lacks the main part of the spacer domain, revealed that SRPK1 remains in an active state without any post-translational modifications or specific intra-protein interactions, while the spacer domain is depicted as a loop structure, outside the kinase core. Using systematic mutagenesis we now provide evidence that replacement of any individual cysteine residue in the spacer, apart from Cys414, or in its proximal flaking ends of the two kinase catalytic domains has an impact on kinase activity. Furthermore, the cysteine residues are critical for nuclear translocation of SRPK1 in response to genotoxic stress and SRPK1-dependent splicing of a reporter gene. While replacement of Cys207, Cys502 and Cys539 of the catalytic domains is predicted to distort the kinase active structure, our findings suggest that Cys356, Cys386, Cys427 and Cys455 of the spacer domain and Cys188 of the first catalytic domain are engaged in disulfide bridging. We propose that such a network of intramolecular disulfide bonds mediates the bending of the spacer region thus allowing the proximal positioning of the two catalytic subunits which is a prerequisite for SRPK1 activity. PMID:28166275

  3. Glutamic Acid Selective Chemical Cleavage of Peptide Bonds.

    PubMed

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

    2016-03-04

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

  4. Asymmetric Desymmetrization via Metal-Free C-F Bond Activation: Synthesis of 3,5-Diaryl-5-fluoromethyloxazolidin-2-ones with Quaternary Carbon Centers.

    PubMed

    Tanaka, Junki; Suzuki, Satoru; Tokunaga, Etsuko; Haufe, Günter; Shibata, Norio

    2016-08-01

    We disclose the first asymmetric activation of a non-activated aliphatic C-F bond in which a conceptually new desymmetrization of 1,3-difluorides by silicon-induced selective C-F bond scission is a key step. The combination of a cinchona alkaloid based chiral ammonium bifluoride catalyst and N,O-bis(trimethylsilyl)acetoamide (BSA) as the silicon reagent enabled the efficient catalytic cycle of asymmetric Csp3 -F bond cleavage under mild conditions with high enantioselectivities. The ortho effect of the aryl group at the prostereogenic center is remarkable. This concept was applied for the asymmetric synthesis of promising agrochemical compounds, 3,5-diaryl-5-fluoromethyloxazolidin-2-ones bearing a quaternary carbon center.

  5. Theoretical study of lanthanide mono cation-mediated C-F bond activation

    NASA Astrophysics Data System (ADS)

    Matsuda, Aya; Mori, Hirotoshi

    2011-02-01

    The potential energy surface corresponding to the reaction of lanthanide mono-cations (Ln +; Ln = Ce-Yb) with CH 3F has been investigated using density functional theory calculations. In the initial step of the C-F activation reaction, Ln + directly coordinates to the F atom of CH 3F, and forms same [Ln⋯F⋯CH 3] + type transition state structures with an accompanying electron-transfer from the Ln + to the F atom. Performing intrinsic reaction coordinate calculations from the transition states, we found that all Ln + reactions can be classified into one of two different reaction mechanisms, "harpoon-like" and "insertion-elimination", which were experimentally proposed by Cohrnel et al. and Konayagi et al., respectively. The two mechanisms have been proposed exclusive to each other. Our results show that both reaction mechanisms are possible in Ln + reaction systems.

  6. Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures.

    PubMed

    Christopher, Phillip; Xin, Hongliang; Marimuthu, Andiappan; Linic, Suljo

    2012-12-01

    The field of heterogeneous photocatalysis has almost exclusively focused on semiconductor photocatalysts. Herein, we show that plasmonic metallic nanostructures represent a new family of photocatalysts. We demonstrate that these photocatalysts exhibit fundamentally different behaviour compared with semiconductors. First, we show that photocatalytic reaction rates on excited plasmonic metallic nanostructures exhibit a super-linear power law dependence on light intensity (rate ∝ intensity(n), with n > 1), at significantly lower intensity than required for super-linear behaviour on extended metal surfaces. We also demonstrate that, in sharp contrast to semiconductor photocatalysts, photocatalytic quantum efficiencies on plasmonic metallic nanostructures increase with light intensity and operating temperature. These unique characteristics of plasmonic metallic nanostructures suggest that this new family of photocatalysts could prove useful for many heterogeneous catalytic processes that cannot be activated using conventional thermal processes on metals or photocatalytic processes on semiconductors.

  7. Intramolecular hydroalkoxylation of non-activated C=C bonds catalysed by zeolites: an experimental and theoretical study.

    PubMed

    Pérez-Mayoral, Elena; Matos, Ines; Nachtigall, Petr; Položij, Miroslav; Fonseca, Isabel; Vitvarová-Procházková, Dana; Čejka, Jiří

    2013-06-01

    The high activity and selectivity of zeolites in the cyclisation of unsaturated alcohols is reported for the first time; the details of a reaction mechanism based on quantum chemical calculations are also provided. The high efficiency of zeolites MFI, BEA and FAU in the cyclisation of unsaturated alcohols (cis-decen-1-ol, 6-methylhept-5-en-2-ol and 2-allylphenol) to afford oxygen-containing heterocyclic rings is demonstrated. The best catalytic performance is found for zeolites with the optimum concentration of Brønsted acid sites (ca. 0.2 mmol g(-1)) and the minimum number of Lewis acid sites. It is proposed that the efficiency of the catalysts is reduced by the existence of the so-called dual site, at which a molecule of unsaturated alcohol can simultaneously interact with two acid sites (an OH group with one and the double bond with the other Brønsted site), which increases the interaction strength. The formation of such adsorption complexes leads to a decrease in the catalyst activity because of (i) an increase in the reaction barrier, (ii) an unfavourable conformation and (iii) diffusion limitations. A new procedure for the preparation of tetrahydrofurans and pyrans over zeolite catalysts provides important oxygen-containing heterocycles with numerous applications.

  8. Synthesis of hybrid cellulose nanocomposite bonded with dopamine SiO2/TiO2 and its antimicrobial activity

    NASA Astrophysics Data System (ADS)

    Ramesh, Sivalingam; Kim, Gwang-Hoon; Kim, Jaehwan; Kim, Joo-Hyung

    2015-04-01

    Organic-inorganic hybrid material based cellulose was synthesized by the sol-gel approach. The explosion of activity in this area in the past decade has made tremendous progress in industry or academic both fundamental understanding of sol-gel process and applications of new functionalized hybrid materials. In this present research work, we focused on cellulose-dopamine functionalized SiO2/TiO2 hybrid nanocomposite by sol-gel process. The cellulose-dopamine hybrid nanocomposite was synthesized via γ-aminopropyltriethoxysilane (γ-APTES) coupling agent by in-situ sol-gel process. The chemical structure of cellulose-amine functionalized dopamine bonding to cellulose structure with covalent cross linking hybrids was confirmed by FTIR spectral analysis. The morphological analysis of cellulose-dopamine nanoSiO2/TiO2 hybrid nanocomposite materials was characterized by XRD, SEM and TEM. From this different analysis results indicate that the optical transparency, thermal stability, control morphology of cellulose-dopamine-SiO2/TiO2 hybrid nanocomposite. Furthermore cellulose-dopamine-SiO2/TiO2 hybrid nanocomposite was tested against pathogenic bacteria for antimicrobial activity.

  9. Effect of addition of chitosan to self-etching primer: antibacterial activity and push-out bond strength to radicular dentin

    PubMed Central

    Elsaka, Shaymaa; Elnaghy, Amr

    2012-01-01

    The purpose of this study was to evaluate the antibacterial activity of a modified self-etching primer incorporating chitosan and whether this modification affected the bond strength to radicular dentin. A modified self-etching primer was prepared by adding chitosan solutions at 0.03%, 0.06%, 0.12% and 0.25% (W/W) to RealSeal selfe-tching primer. RealSeal primer without chitosan was used as the control. The antibacterial activity of the modified self-etching primer was evaluated using the direct contact test against Enterococcus faecalis. The bonding ability of the RealSeal system to radicular dentin was evaluated using the push-out bond strength test. The modes of failure were examined under a stereomicroscope. Data were analyzed using analysis of variance (ANOVA) and Tukey's test, with a P-value < 0.05 indicating statistical significance. The results showed that the antibacterial properties of the freshly prepared and aged modified self-etching primer incorporating chitosan exhibited potent antibacterial effect against Enterococcus faecalis compared with the unmodified primer. The RealSeal system with the aged modified self-etching primer incorporating chitosan showed no significant differences in the bond strength as compared with the control (P = 0.99). The findings suggest that modified self-etching primer incorporating chitosan is a promising antibacterial primer which does not adversely affect the bond strength of the RealSeal system to radicular dentin. PMID:23554762

  10. Intramolecular C-N bond activation and ring-expansion reactions of N-heterocyclic carbenes.

    PubMed

    Hemberger, Patrick; Bodi, Andras; Berthel, Johannes H J; Radius, Udo

    2015-01-19

    Intramolecular ring-expansion reactions (RER) of the N-heterocyclic carbene 1,3-dimethylimidazolin-2-ylidene were observed upon vacuum ultraviolet (VUV) photoexcitation. Similarly to RERs reported in the solvent phase, for the reaction of NHCs with main-group-element hydrides, hydrogen transfer to the NHC carbon atom is the crucial initial step. In an ionization-mediated protonation, 1,3-dimethylimidazolin-2-ylidene forms an imidazolium ion, which is the rate-limiting step on the pathway to two six-membered ring products, namely, methylpyrimidinium and -pyrazinium ions. To unravel the reaction path, we have used imaging photoelectron photoion coincidence spectroscopy with VUV synchrotron radiation, as well as high-level composite method calculations. Similarities and differences between the mechanism in the gas phase and in the condensed phase are discussed.

  11. Influence of temporary cement remnant and surface cleaning method on bond strength to dentin of a composite luting system.

    PubMed

    Kanakuri, Katsuhito; Kawamoto, Yoshikazu; Matsumura, Hideo

    2005-03-01

    The aim of the current study was to evaluate the influence of polycarboxylate temporary cement remaining on the dentin surface on the bond strength of a composite luting system. An acrylic resin plate was luted to bovine dentin with a polycarboxylate temporary cement (HY-Bond Temporary Cement Hard, HYB). The temporary cement was not used for the control groups. After removing the temporary cement with an excavator, dentin specimens were divided into five groups; 1) no subsequent treatment, 2) cleaning with a rotational brush (RTB), 3) cleaning with a rotational brush and non-fluoridated flour of pumice, 4) sweeping with an air scaler, and 5) treated with a sonic toothbrush. A silane-treated ceramic disk (IPS Empress) was bonded to each dentin specimen with a composite luting system (Panavia F). Shear testing results showed that the RTB groups exhibited the highest bond strength regardless of the use of temporary cement (P < 0.05). The use of a rotational brush with water coolant is recommended to achieve ideal bond strength between the Panavia F luting system and dentin to which HYB temporary cement was primarily applied.

  12. Structure-activity relation of human beta-defensin 3: influence of disulfide bonds and cysteine substitution on antimicrobial activity and cytotoxicity.

    PubMed

    Klüver, Enno; Schulz-Maronde, Sandra; Scheid, Svenja; Meyer, Bernd; Forssmann, Wolf-Georg; Adermann, Knut

    2005-07-19

    Human beta-defensins form a group of cysteine-rich antimicrobial peptides which have been found in epithelial tissue and, more recently, in the male genital tract. They play a role in the defense against microbial pathogens in innate immunity and display additional chemotactic functions in the adaptive immune system. An important characteristic of antimicrobial peptides is that they also exhibit toxic potential on eukaryotic cells. Very little is known about the structure dependence of antimicrobial and cytotoxic effects. We investigated human beta-defensin 3 (hBD-3), a potent broad-spectrum antimicrobial effector peptide, regarding the influence of structural parameters on the antimicrobial and cytotoxic activity. We have established a structure-activity relation of the hBD-3 using synthetic derivatives differing in length, charge, disulfide connectivity, and overall hydrophobicity. The antimicrobial activity of the peptides was compared to the cyctotoxic effects on monocytic THP-1 cells and the hemolytic activity on human erythrocytes. We found that it is not important for antimicrobial and cytotoxic activity whether and how cysteine residues are arranged to form disulfide bonds. Substitution of half-cystinyl residues by tryptophan resulted in increased activities, while other substitutions did not change activity. Correlation of activities with the structural changes demonstrates that the activity on eukaryotic cells appears to depend strongly on the overall hydrophobicity. In contrast, the antimicrobial potency of hBD-3 peptides is determined by the distribution of positively charged amino acid residues and hydrophobic side chains. The results facilitate the understanding of beta-defensin interaction with different cell types and guide the design of antimicrobially active peptides.

  13. Microstructural evolution at the bonding interface during the early-stage infrared active brazing of alumina

    NASA Astrophysics Data System (ADS)

    Shiue, R. K.; Wu, S. K.; O, J. M.; Wang, J. Y.

    2000-10-01

    Infrared brazing of Al2O3 and alloy 42 using a silver-base active braze alloy was investigated at 900 °C for 0 to 300 seconds, with a heating rate of 3000 °C/min. Experimental results show that Ti3(Cu, Al)3O intermetallic with various amounts of Al is observed in the reaction layer and plays an important role in the early stage of reactive wetting. A two-layer structure is observed at the reaction interface brazed at 900 °C for 5 seconds. The reaction layer close to the alumina contains large amounts of Al, so the mass balance of the system is maintained. The growth of the reaction layer is not rate controlled by diffusion within the first 120 seconds. After 120 seconds, the rate controlling mechanism of the reaction layer becomes the diffusion control, satisfying the parabolic law. Dynamic wetting angle measurements using a traditional vacuum furnace at the heating rate of 10 °C/min demonstrate that the wetting angle rapidly decreases within the first 150 seconds, especially 0 to 80 seconds, and eventually stabilizes after 600 seconds.

  14. Actively controlled vibration welding system and method

    DOEpatents

    Cai, Wayne W.; Kang, Bongsu; Tan, Chin-An

    2013-04-02

    A vibration welding system includes a controller, welding horn, an active material element, and anvil assembly. The assembly may include an anvil body connected to a back plate and support member. The element, e.g., a piezoelectric stack or shape memory alloy, is positioned with respect to the assembly. The horn vibrates in a desirable first direction to form a weld on a work piece. The element controls any vibrations in a second direction by applying calibrated response to the anvil body in the second direction. A method for controlling undesirable vibrations in the system includes positioning the element with respect to the anvil assembly, connecting the anvil body to the support member through the back plate, vibrating the horn in a desirable first direction, and transmitting an input signal to the element to control vibration in an undesirable second direction.

  15. Activation of a Covalent Enzyme-Substrate Bond by Noncovalent Interaction with an Effector

    PubMed Central

    Malhotra, O. P.; Bernhard, Sidney A.

    1973-01-01

    The absorption spectrum of an activesite specific chromophoric acyl enzyme, sturgeon β-(2-furyl)-acryloyl-glyceraldehyde-3-phosphate dehydrogenase, is reported. This acyl enzyme undergoes all of the catalyzed reactions characteristic of the intermediate of the physiological acyl enzyme, 3-phospho-D-glyceroyl-glyceraldehyde-3-phosphate dehydrogenease. The rates of reactions of both these acyl enzymes depend strongly on the extent of interaction of the acyl enzyme with the oxidized coenzyme, NAD+, even where the “redox” properties of the coenzyme are not required. Likewise, the spectral properties of chromophoric acyl enzyme are affected by the extent of bound NAD. Under the pseudophysiological conditions reported herein, there is a stoichiometric limitation of two furylacryloyl-acyl groups per enzyme molecule containing four covalently-equivalent subunits. The binding of NAD both to the apoenzyme and to the diacyl enzyme is heterogeneous: at low extents of NAD occupancy, NAD binding is stronger. The binding to acyl enzyme can be quantitatively described by an enzyme model involving a tetramer with 2-fold symmetry, and consequently containing equal numbers of two classes of sites. NAD binding to difurylacryloyl-enzyme occurs virtually discretely, first to the two unmodified (tight-binding) sites, followed by looser binding to the two acyl-sites. NAD occupancy at these latter sites transforms the chromophoric acyl spectrum from that characteristic of a model furylacryloyl-thiol ester in H2O to a highly perturbed furylacryloyl spectrum characteristic of monomeric native “active-thiol” furylacryloyl-enzymes. Likewise the acyl reactivity towards arsenolysis depends on the extent of NAD bound to the loose sites. Elimination of the tight binding of NAD to the difurylacryloyl enzyme tetramer by alkylation of the remaining two free SH groups with iodoacetate has no apparent influence on the NAD-dependent furylacryloyl-spectral perturbation at the “two equivalent

  16. A Fluorometric Method of Measuring Carboxypeptidase Activities for Angiotensin II and Apelin-13

    PubMed Central

    Liu, Pan; Wysocki, Jan; Serfozo, Peter; Ye, Minghao; Souma, Tomokazu; Batlle, Daniel; Jin, Jing

    2017-01-01

    Degradation of the biologically potent octapeptide angiotensin Ang II-(1-8) is mediated by the activities of several peptidases. The conversion of Ang II to the septapeptide Ang-(1-7) is of particular interest as the latter also confers organ protection. The conversion is catalyzed by angiotensin-converting enzyme 2 and other enzymes that selectively cleave the peptide bond between the proline and the phenylalanine at the carboxyl terminus of Ang II. The contribution of various enzyme activities that collectively lead to the formation of Ang-(1-7) from Ang II, in both normal conditions and in disease states, remains only partially understood. This is largely due to the lack of a reliable and sensitive method to detect these converting activities in complex samples, such as blood and tissues. Here, we report a fluorometric method to measure carboxypeptidase activities that cleave the proline-phenylalanine dipeptide bond in Ang II. This method is also suitable for measuring the conversion of apelin-13. The assay detects the release of phenylalanine amino acid in a reaction with the yeast enzyme of phenylalanine ammonia lyase (PAL). When used in cell and mouse organs, the assay can robustly measure endogenous Ang II and apelin-13-converting activities involved in the renin-angiotensin and the apelinergic systems, respectively. PMID:28378780

  17. Photodegradation of organic contamination in wastewaters by bonding TiO2/single-walled carbon nanotube composites with enhanced photocatalytic activity.

    PubMed

    Zhou, Wei; Pan, Kai; Qu, Yang; Sun, Fanfei; Tian, Chungui; Ren, Zhiyu; Tian, Guohui; Fu, Honggang

    2010-10-01

    Bonding TiO(2)/single-walled carbon nanotube (SWCNT) composites have been successfully synthesized through a facile sol-solvothermal technique. The obtained materials were characterized in detail by XRD, FT-IR, Raman and TEM. The results revealed that TiO(2) and SWNCT linked compactly through ester bonds and thus improved their interfaces. Therefore, the recombination of photogenerated electron-hole pairs was inhibited efficiently, which improved the photocatalytic activity. A reasonable mechanism was proposed to explain its formation. The photocatalytic activity was investigated utilizing rhodamine B and nitrobenzene (NB) as models for organic contamination in wastewaters. Experimental results indicated that this bonding composite exhibited higher photocatalytic activity than that of Degussa P25. The excellent photocatalytic activity could be attributed to larger surface area, smaller crystalline size, and especially the ester bonds, which was further confirmed by surface photovoltage spectroscopy. Furthermore, by adding ()OH scavenger tert-butanol, the obvious decrease of NB photodegradation indicated that NB was oxidized primarily by ()OH. The photodegradation products were identified by GC/MS, further indicating that the degradation proceeded via ()OH oxidation. A possible reaction pathway for the degradation of NB was suggested by the evidence presented in this study.

  18. Energy-efficient green catalysis: supported gold nanoparticle-catalyzed aminolysis of esters with inert tertiary amines by C-O and C-N bond activations.

    PubMed

    Bao, Yong-Sheng; Baiyin, Menghe; Agula, Bao; Jia, Meilin; Zhaorigetu, Bao

    2014-07-18

    Catalyzed by supported gold nanoparticles, an aminolysis reaction between various aryl esters and inert tertiary amines by C-O and C-N bond activations has been developed for the selective synthesis of tertiary amides. Comparison studies indicated that the gold nanoparticles could perform energy-efficient green catalysis at room temperature, whereas Pd(OAc)2 could not.

  19. Discovery of molluscicidal and cercaricidal activities of 3-substituted quinazolinone derivatives by a scaffold hopping approach using a pseudo-ring based on the intramolecular hydrogen bond formation.

    PubMed

    Guo, Wei; Zheng, Lv-Yin; Li, Yong-Dong; Wu, Ren-Miao; Chen, Qiang; Yang, Ding-Qiao; Fan, Xiao-Lin

    2016-06-10

    Discovery of novel topological agents against Oncomelania hupensis snails and cercariae remains a significant challenge in current Schistosomiasis control. A pseudo-ring formed from salicylanilide by an intramolecular hydrogen bond led to the discovery of 3-substituted quinazolinone derivatives which showed a potent molluscicidal and cercaricidal activities.

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

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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