Mullite/Mo interfaces formed by Intrusion bonding

Energy Technology Data Exchange (ETDEWEB)

Bartolome, Jose F.; Diaz, Marcos; Moya, Jose S.; Saiz, Eduardo; Tomsia, Antoni P.

2003-04-30

The microstructure and strength of Mo/mullite interfaces formed by diffusion bonding at 1650 C has been analyzed. Interfacial metal-ceramic interlocking contributes to flexural strength of approx. 140 MPa as measured by 3 point bending. Saturation of mullite with MoO2 does not affect the interfacial strength.

Mullite/Mo interfaces formed by Intrusion bonding

OpenAIRE

Bartolome, Jose F.; Diaz, Marcos; Moya, Jose S.; Saiz, Eduardo; Tomsia, Antoni P.

2003-01-01

The microstructure and strength of Mo/mullite interfaces formed by diffusion bonding at 1650oC has been analyzed. Interfacial metal-ceramic interlocking contributes to flexural strength of approx. 140 MPa as measured by 3 point bending. Saturation of mullite with MoO2 does not affect the interfacial strength.

Evidence for single metal two electron oxidative addition and reductive elimination at uranium.

Science.gov (United States)

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; McInnes, Eric J L; Tuna, Floriana; Wooles, Ashley J; Maron, Laurent; Liddle, Stephen T

2017-12-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis.

75 FR 55849 - Proposed Collection; Comment Request for Form 1097-BTC, Bond Tax Credit

Science.gov (United States)

2010-09-14

... 1097-BTC, Bond Tax Credit AGENCY: Internal Revenue Service (IRS), Treasury. ACTION: Notice and request... comments concerning Form 1097-BTC, Bond Tax Credit. DATES: Written comments should be received on or before... INFORMATION: Title: Form 1097-BTC, Bond Tax Credit. Abstract: This is an information return for reporting tax...

Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium

OpenAIRE

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; Mcinnes, Eric; Tuna, Floriana; Wooles, Ashley; Maron, Laurent; Liddle, Stephen

2017-01-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here, we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido compl...

Superplastic forming and diffusion bonding: Progress and trends

Directory of Open Access Journals (Sweden)

Zhiqiang Li

2015-01-01

Full Text Available This paper summarized recent progress in metal superplasticity and the application of Superplastic Forming/Diffusion Bonding (SPF/DB or SPF/Welding in typical structures. Various aerospace components such as three dimensional lattice structures made by SPF/DB have been demonstrated. In addition, some newly developed technologies, such as melt droplet spreading/thermo-mechanical forming (MDS/TMF, were also included. Finally, the future potential of SPF/DB technology was predicted.

The Convention on the Elimination of All Forms of Discrimination Against Women (CEDAW): Congressional Issues

National Research Council Canada - National Science Library

Blanchfield, Luisa

2008-01-01

The U.N. Convention on the Elimination of All Forms of Discrimination Against Women calls for Parties to eliminate discrimination against women in all areas of life, including healthcare, education...

The Convention on the Elimination of All Forms of Discrimination Against Women (CEDAW): Congressional Issues

National Research Council Canada - National Science Library

Blanchfield, Luisa

2006-01-01

The U.N. Convention on the Elimination of All Forms of Discrimination against Women calls for Parties to eliminate discrimination against women in all areas of life, including healthcare, education...

FT-IR spectroelectrochemical study of the reduction of 1,4-dinitrobenzene on Au electrode: Hydrogen bonding and protonation in proton donor mixed media

International Nuclear Information System (INIS)

Tian Dexiang; Jin Baokang

2011-01-01

Highlights: → 1,4-Dinitrobenzene electrochemical reduction on the Au electrode is explored. → Radical anion (PNB· - ) is found both in aprotic media and in proton donors mixed media. → The H-bonding forming between PNB· - , PNB 2- and proton donors in low donors concentration. → The protonation of PNB 2- occurs in high concentration proton donor mixed media. - Abstract: The electrochemical behavior of 1,4-dinitrobenzene (1,4-PNB) on the Au electrode was investigated by cyclic voltammetry (CV), in situ FT-IR spectroelectrochemistry, cyclic voltabsorptometry (CVA) and derivative cyclic voltabsorptometry (DCVA) techniques. In aprotic media, 1,4-dinitrobenzene is reversibly reduced in two-step one-electron transfer. A series of IR absorption bands at 1056, 1210, 1341, 1356, 1464 and 1549 cm -1 , tracing to PNB; PNB· - and PNB 2- are observed. In the presence of proton donors mixed media, with increasing concentrations of proton donors, hydrogen-bonding and protonation process are found successively. The values of combining proton donors with per PNB 2- to form hydrogen-bonding are estimated by using electrochemical parameters. The result of forming aromatic nitroso compound is supported by tracing the change of IR absorption bands at 1149 and 1587 cm -1 at high concentration of proton donors. Based on CVA and DCVA techniques, it is clearly distinguished that the mechanisms of electrochemical reduction of PNB are elaborated in different systems.

Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

KAUST Repository

Liu, Xiangqian; Hsiao, Chien-Chi; Kalvet, Indrek; Leiendecker, Matthias; Guo, Lin; Schoenebeck, Franziska; Rueping, Magnus

2016-01-01

In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel

Identification and prevention of antibody disulfide bond reduction during cell culture manufacturing.

Science.gov (United States)

Trexler-Schmidt, Melody; Sargis, Sandy; Chiu, Jason; Sze-Khoo, Stefanie; Mun, Melissa; Kao, Yung-Hsiang; Laird, Michael W

2010-06-15

In the biopharmaceutical industry, therapeutic monoclonal antibodies are primarily produced in mammalian cell culture systems. During the scale-up of a monoclonal antibody production process, we observed excessive mechanical cell shear as well as significant reduction of the antibody's interchain disulfide bonds during harvest operations. This antibody reduction event was catastrophic as the product failed to meet the drug substance specifications and the bulk product was lost. Subsequent laboratory studies have demonstrated that cells subjected to mechanical shear release cellular enzymes that contribute to this antibody reduction phenomenon (manuscript submitted; Kao et al., 2009). Several methods to prevent this antibody reduction event were developed using a lab-scale model to reproduce the lysis and reduction events. These methods included modifications to the cell culture media with chemicals (e.g., cupric sulfate (CuSO(4))), pre- and post-harvest chemical additions to the cell culture fluid (CCF) (e.g., CuSO(4), EDTA, L-cystine), as well as lowering the pH and air sparging of the harvested CCF (HCCF). These methods were evaluated for their effectiveness in preventing disulfide bond reduction and their impact to product quality. Effective prevention methods, which yielded acceptable product quality were evaluated for their potential to be implemented at manufacturing-scale. The work described here identifies numerous effective reduction prevention measures from lab-scale studies; several of these methods were then successfully translated into manufacturing processes. 2010 Wiley Periodicals, Inc.

Elimination of C3 as the Bond-Neff depression opacity source in Hr 774

International Nuclear Information System (INIS)

Baird, S.R.

1982-01-01

The pseudocontinuum of C 3 has been proposed by Fix as the source of the Bond-Neff depression in HR 774. In such a case the strongest rotational lines of the 4050 A vibrational band of C 3 should be clearly evident at high dispersion. A 2.2 A mm -1 plate of HR 774 is examined in the 4050--4060 A region where the strongest lines should form. The absence of C 3 rotational lines indicates that C 3 cannot be the major contributor to the Bond-Neff depression in HR 774

Glass binder development for a glass-bonded sodalite ceramic waste form

International Nuclear Information System (INIS)

Riley, Brian J.; Vienna, John D.; Frank, Steven M.; Kroll, Jared O.; Peterson, Jacob A.

2017-01-01

This paper discusses work to develop Na_2O-B_2O_3-SiO_2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. In this paper, five new glasses with ~20 mass% Na_2O were designed to generate waste forms with high sodalite. The glasses were then used to produce ceramic waste forms with a surrogate salt waste. The waste forms made using these new glasses were formulated to generate more sodalite than those made with previous baseline glasses for this type of waste. The coefficients of thermal expansion for the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature than previous binder glasses used. Finally, these improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability.

The pricing of firm bonds with extendable maturity by the reduced form approach

Directory of Open Access Journals (Sweden)

REN Xuemin

2012-10-01

Full Text Available We associate credit events with market rates to price firm bonds with extendable maturity.We deal with the credit risk by the reduced form approach and obtain the pricing formula for firm bonds with extendable maturity by the PDE approach under the assumption of stochastic interest rate and compare its return rate with that of ordinary firm bonds.

32 CFR Appendix E to Part 623 - Surety Bond (DA Form 4881-3-R)

Science.gov (United States)

2010-07-01

... 32 National Defense 3 2010-07-01 2010-07-01 true Surety Bond (DA Form 4881-3-R) E Appendix E to Part 623 National Defense Department of Defense (Continued) DEPARTMENT OF THE ARMY SUPPLIES AND EQUIPMENT LOAN OF ARMY MATERIEL Pt. 623, App. E Appendix E to Part 623—Surety Bond (DA Form 4881-3-R...

The E1 mechanism in photo-induced beta-elimination reactions for green-to-red conversion of fluorescent proteins.

Science.gov (United States)

Tsutsui, Hidekazu; Shimizu, Hideaki; Mizuno, Hideaki; Nukina, Nobuyuki; Furuta, Toshiaki; Miyawaki, Atsushi

2009-11-25

KikGR is a fluorescent protein engineered to display green-to-red photoconvertibility that is induced by irradiation with ultraviolet or violet light. Similar to Kaede and EosFP, two naturally occurring photoconvertible proteins, KikGR contains a His(62)-Tyr(63)-Gly(64) tripeptide sequence, which forms a green chromophore that can be photoconverted to a red one via formal beta-elimination and subsequent extension of a pi-conjugated system. Using a crystallizable variant of KikGR, we determined the structures of both the green and red state at 1.55 A resolution. The double bond between His(62)-C(alpha) and His(62)-C(beta) in the red chromophore is in a cis configuration, indicating that rotation along the His(62) C(alpha)-C(beta) bond occurs following cleavage of the His(62) N(alpha)-C(alpha) bond. This structural rearrangement provides evidence that the beta-elimination reaction governing the green-to-red photoconversion of KikGR follows an E1 (elimination, unimolecular) mechanism.

Relating structural parameters to leachability in a glass-bonded ceramic waste form

International Nuclear Information System (INIS)

Frank, S. M.; Johnson, S. G.; Moschetti, T. L.

1998-01-01

Lattice parameters for a crystalline material can be obtained by several methods, notably by analyzing x-ray powder diffraction patterns. By utilizing a computer program to fit a pattern, one can follow the evolution or subtle changes in a structure of a crystalline species in different environments. This work involves such a study for an essential component of the ceramic waste form that is under development at Argonne National Laboratory. Zeolite 4A and zeolite 5A are used to produce two different types of waste forms: a glass-bonded sodalite and a glass-bonded zeolite, respectively. Changes in structure during production of the waste forms are discussed. Specific salt-loadings in the sodalite waste form are related to relative peak intensities of certain reflections in the XRD patterns. Structural parameters for the final waste forms will also be given and related to leachability under standard conditions

Translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I

Science.gov (United States)

Takahashi, Masae; Ishikawa, Yoichi

2013-06-01

We perform dispersion-corrected first-principles calculations, and far-infrared (terahertz) spectroscopic experiments at 4 K, to examine translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I. The calculated frequencies and relative intensities reproduce the observed spectrum to accuracy of 11 cm-1 or less. The stronger one of the two peaks assigned to the translational mode includes the stretching vibration of the weak hydrogen bond between the acetyl groups of a neighboring one-dimensional chain. The calculation of aspirin form II performed for comparison gives the stretching vibration of the weak hydrogen bond in one-dimensional chain.

Rhodium(I)-catalyzed cyclization of allenynes with a carbonyl group through unusual insertion of a C-O bond into a rhodacycle intermediate.

Science.gov (United States)

Oonishi, Yoshihiro; Yokoe, Takayuki; Hosotani, Akihito; Sato, Yoshihiro

2014-01-20

Rhodium(I)-catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp(2) )-rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8-oxabicyclo[3.2.1]octane skeleton, while β-hydride elimination from the same intermediate gives products that contain fused five- and seven-membered rings in high yields. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel metal-to-metal bonding process through in-situ formation of Ag nanoparticles using Ag2O microparticles

International Nuclear Information System (INIS)

Hirose, Akio; Tatsumi, Hiroaki; Takeda, Naoya; Akada, Yusuke; Ogura, Tomo; Ide, Eiichi; Morita, Toshiaki

2009-01-01

The metal-to-metal bonding has been successfully achieved via the bonding process using Ag metallo-organic nanoparticles at a bonding temperature of around 300-, which can be alternative to the current microsoldering in electronics assembly using high-temperature solders. However, further reduction of bonding temperature and/or bonding pressure is needed. In the present research, a novel bonding process through in-situ formation of Ag nanoparticles instead of the filler material of the Ag metallo-organic nanoparticles has been developed. The Ag nanoparticles can form by the reduction of Ag 2 O particles. In this study, the Ag 2 O particles were mixed with triethylene glycol as a reducing agent to form a paste for bonding. The Au coated cylindrical specimens were bonded using the paste. The Ag nanoparticles formed at around 130 to 160 through the reduction process of Ag2O particles with triethylene glycol. The Ag nanoparticles were immediately sintered each other due to a great surface energy per volume. A transmission electron microscope observation revealed that the sintered Ag metallurgically bonded to the Au substrate at around 160 and a dense Ag layer formed after further heating. The tensile strength of the joint bonded at 250 under a bonding pressure of 5MPa was around 60MPa

MLKL forms disulfide bond-dependent amyloid-like polymers to induce necroptosis.

Science.gov (United States)

Liu, Shuzhen; Liu, Hua; Johnston, Andrea; Hanna-Addams, Sarah; Reynoso, Eduardo; Xiang, Yougui; Wang, Zhigao

2017-09-05

Mixed-lineage kinase domain-like protein (MLKL) is essential for TNF-α-induced necroptosis. How MLKL promotes cell death is still under debate. Here we report that MLKL forms SDS-resistant, disulfide bond-dependent polymers during necroptosis in both human and mouse cells. MLKL polymers are independent of receptor-interacting protein kinase 1 and 3 (RIPK1/RIPK3) fibers. Large MLKL polymers are more than 2 million Da and are resistant to proteinase K digestion. MLKL polymers are fibers 5 nm in diameter under electron microscopy. Furthermore, the recombinant N-terminal domain of MLKL forms amyloid-like fibers and binds Congo red dye. MLKL mutants that cannot form polymers also fail to induce necroptosis efficiently. Finally, the compound necrosulfonamide conjugates cysteine 86 of human MLKL and blocks MLKL polymer formation and subsequent cell death. These results demonstrate that disulfide bond-dependent, amyloid-like MLKL polymers are necessary and sufficient to induce necroptosis.

Superplastic Forming/Adhesive Bonding of Aluminum (SPF/AB) Multi-Sheet Structures

Science.gov (United States)

Wagner, John A. (Technical Monitor); Will, Jeff D.; Cotton, James D.

2003-01-01

A significant fraction of airframe structure consists of stiffened panels that are costly and difficult to fabricate. This program explored a potentially lower-cost processing route for producing such panels. The alternative process sought to apply concurrent superplastic forming and adhesive bonding of aluminum alloy sheets. Processing conditions were chosen to balance adequate superplasticity of the alloy with thermal stability of the adhesive. As a first objective, an air-quenchable, superplastic aluminum-lithium alloy and a low-volatile content, low-viscosity adhesive with compatible forming/curing cycles were identified. A four-sheet forming pack was assembled which consisted of a welded two-sheet core separated from the face sheets by a layer of adhesive. Despite some preliminary success, of over 30 forming trials none was completely successful. The main problem was inadequate superplasticity in the heat-affected zones of the rib welds, which generally fractured prior to completion of the forming cycle. The welds are a necessary component in producing internal ribs by the 'four-sheet' process. Other challenges, such as surface preparation and adhesive bonding, were adequately solved. But without the larger issue of tearing at the weld locations, complex panel fabrication by SPF/AB does not appear viable.

Plastic scintillators based on polymers with eliminated excimer forming

Energy Technology Data Exchange (ETDEWEB)

Adadurov, A.F., E-mail: adadurov@isma.kharkov.u [Institute for Scintillating Materials NAN of Ukraine, 60 Lenin Ave, 61001 Kharkov (Ukraine); Yelyseev, D.A.; Titskaya, V.D.; Lebedev, V.N.; Zhmurin, P.N. [Institute for Scintillating Materials NAN of Ukraine, 60 Lenin Ave, 61001 Kharkov (Ukraine)

2011-05-15

Plastic scintillators (PS) were made based on benzyl methacrylate and methyl-methacrylate P(BzMA + MMA) copolymer in which the excimer forming rate is by two order lesser than that in polystyrene-based polymer matrix. Studying of these PS light yield demonstrates the importance of migration processes comparing to excimer formation. It is found that to obtain PS with high scintillation efficiency it is necessary to use the polymer base (matrix) in which excimer forming is eliminated but the migration process along the chromophores is maximally favored. To explain the accelerated energy transfer between phenyl chromophores it is proposed to use a mechanism of exchange of that virtual excitons that can propagate along a one-dimensional back-bone of polymer molecule. Clearing the details of mechanism of interaction between chromophores of polymer molecules which is responsible for accelerated radiationless energy transfer enable will determine in future the way of effective plastic scintillators designing.

Effect of the aluminum flow pattern on the bonding of aluminum to oxidized Zircaloy-2

International Nuclear Information System (INIS)

Watson, R.D.; Lambert, J.P.

1965-04-01

The bonds produced when hot aluminum is allowed to flow smoothly from an extrusion die to the oxidized surface of a heated tube of Zircaloy-2 are consistently inferior to those produced with back-extruded flow. The difference is believed to be due to the reduction in, or elimination of, the oxide layer on the aluminum that comes in contact with the surface of the Zircaloy-2. This method of bonding aluminum to Zircaloy-2 is covered by Canadian patent 702,438 January 1965. (author)

Catalytic diastereoselective tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts by C-C bond cleavage

KAUST Repository

Yang, Wenguo

2012-02-08

Through the cleavage of the C-C bond, the first catalytic tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts has been presented. Various S N2′-like C-, S-, and P-allylic compounds could be obtained with exclusive E configuration in good to excellent yields. The Michael product could also be easily prepared by tuning the β-C-substituent group of the α-methylene ester under the same reaction conditions. Calculated relative energies of various transition states by DFT methods strongly support the observed chemoselectivity and diastereoselectivity. © 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

Improved variable reduction in partial least squares modelling by Global-Minimum Error Uninformative-Variable Elimination.

Science.gov (United States)

Andries, Jan P M; Vander Heyden, Yvan; Buydens, Lutgarde M C

2017-08-22

The calibration performance of Partial Least Squares regression (PLS) can be improved by eliminating uninformative variables. For PLS, many variable elimination methods have been developed. One is the Uninformative-Variable Elimination for PLS (UVE-PLS). However, the number of variables retained by UVE-PLS is usually still large. In UVE-PLS, variable elimination is repeated as long as the root mean squared error of cross validation (RMSECV) is decreasing. The set of variables in this first local minimum is retained. In this paper, a modification of UVE-PLS is proposed and investigated, in which UVE is repeated until no further reduction in variables is possible, followed by a search for the global RMSECV minimum. The method is called Global-Minimum Error Uninformative-Variable Elimination for PLS, denoted as GME-UVE-PLS or simply GME-UVE. After each iteration, the predictive ability of the PLS model, built with the remaining variable set, is assessed by RMSECV. The variable set with the global RMSECV minimum is then finally selected. The goal is to obtain smaller sets of variables with similar or improved predictability than those from the classical UVE-PLS method. The performance of the GME-UVE-PLS method is investigated using four data sets, i.e. a simulated set, NIR and NMR spectra, and a theoretical molecular descriptors set, resulting in twelve profile-response (X-y) calibrations. The selective and predictive performances of the models resulting from GME-UVE-PLS are statistically compared to those from UVE-PLS and 1-step UVE, one-sided paired t-tests. The results demonstrate that variable reduction with the proposed GME-UVE-PLS method, usually eliminates significantly more variables than the classical UVE-PLS, while the predictive abilities of the resulting models are better. With GME-UVE-PLS, a lower number of uninformative variables, without a chemical meaning for the response, may be retained than with UVE-PLS. The selectivity of the classical UVE method

Leaching behavior of phosphate-bonded ceramic waste forms

International Nuclear Information System (INIS)

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

1996-04-01

Over the last few years, Argonne National Laboratory has been developing room-temperature-setting chemically bonded phosphate ceramics for solidifying and stabilizing low-level mixed wastes. This technology is crucial for stabilizing waste streams that contain volatile species and off-gas secondary waste streams generated by high-temperature treatment of such wastes. We have developed a magnesium phosphate ceramic to treat mixed wastes such as ash, salts, and cement sludges. Waste forms of surrogate waste streams were fabricated by acid-base reactions between the mixtures of magnesium oxide powders and the wastes, and phosphoric acid or acid phosphate solutions. Dense and hard ceramic waste forms are produced in this process. The principal advantage of this technology is that the contaminants are immobilized by both chemical stabilization and subsequent microencapsulation of the reaction products. This paper reports the results of durability studies conducted on waste forms made with ash waste streams spiked with hazardous and radioactive surrogates. Standard leaching tests such as ANS 16.1 and TCLP were conducted on the final waste forms. Fates of the contaminants in the final waste forms were established by electron microscopy. In addition, stability of the waste forms in aqueous environments was evaluated with long-term water-immersion tests

Safe and Liquid Mortgage Bonds

DEFF Research Database (Denmark)

Dick-Nielsen, Jens; Gyntelberg, Jacob; Lund, Jesper

This paper shows that strict match pass-through funding of covered bonds provides safe and liquid mortgage bonds. Despite a 30% drop in house prices during the 2008 global crisis Danish mortgage bonds remained as liquid as most European government bonds. The Danish pass-through system effectively...... eliminates credit risk from the investor's perspective. Similar to other safe bonds, funding liquidity becomes the main driver of mortgage bond liquidity and this creates commonality in liquidity across markets and countries. These findings have implications for how to design a robust mortgage bond system...

Theoretical investigation on hydrogen bond interaction of diketo/keto-enol form uracil and thymine tautomers with intercalators.

Science.gov (United States)

Anithaa, V S; Vijayakumar, S; Sudha, M; Shankar, R

2017-11-06

The interaction of diketo and keto-enol form of thymine and uracil tautomers with acridine (Acr), phenazine (Phen), benzo[c]cinnoline (Ben), 1,10-phenanthroline (1,10-Phe), and 4,7-phenenthroline (4,7-Phe) intercalating drug molecules was studied using density functional theory at B3LYP/6-311++G** and M05-2×/6-311++G** levels of theory. From the interaction energy, it is found that keto-enol form tautomers have stronger interaction with intercalators than diketone form tautomers. On complex formation of thymine and uracil tautomers with benzo[c]cinnoline the drug molecules have high interaction energy values of -20.14 (BenT3) and -20.55 (BenU3) kcal mol -1 , while phenazine has the least interaction energy values of -6.52 (PhenT2) and -6.67 (PhenU2) kcal mol -1 . The closed shell intermolecular type interaction between the molecules with minimum elliptical value of 0.018 and 0.019 a.u at both levels of theory has been found from topological analysis. The benzo[c]cinnoline drug molecule with thymine and uracil tautomers has short range intermolecular N-H…N, C-H…O, and O-H...N hydrogen bonds (H-bonds) resulting in higher stability than other drug molecules. The proper hydrogen bonds N-H..N and O-H..N have the frequency shifted toward the lower side (red shifted) with the elongation in their bond length while the improper hydrogen bond C-H...O has the frequency shifted toward the higher side (blue shifted) of the spectral region with the contraction in their bond length. Further, the charge transfer between proton acceptor and donor along with stability of the bond is studied using natural bond orbital (NBO) analysis. Graphical abstract Hydrogen bond interaction of diketo/keto-enol form uracil and thymine tautomers with intercalators.

Elimination of NO/sub x/ by selective reduction with NH3

International Nuclear Information System (INIS)

Bruggeman, A.; Meynendonckx, L.; Gossens, W.R.A.

1979-01-01

In nuclear reprocessing plants the nitrogen oxides generated during the dissolution of the fuel are only partially removed in the primary off-gas treatments. Further reduction to the ppM level is necessary as a preliminary step to the cryogenic retention and separation of the noble gases. If simultaneous oxygen removal is not required, selective reduction of NO (and NO 2 ) to N 2 and H 2 O by NH 3 is a preferable method. Laboratory experiments have confrmed the feasibility of eliminating NO from air beyond the ppM level by adding NH 3 over a hydrogen mordenite catalyst. At atmospheric pressure and with air (water content 0.5% V/V) as a carrier gas selective catalytic reduction of NO to N 2 is easily achieved at temperatures up to 500 0 C. Under the same conditions dimensioning of the reactor for destruction of the excess NH 3 by the O 2 of the air is made possible. The activity of the catalyst remains rather constant even when large concentrations of I 2 are present. On the basis of the laboratory results a pilot installation has been designed and constructed which will demonstrate the process in an integrated gas purification loop at a pressure of 8 x 10 5 Pa during the next months

Simulating progressive social transfers. Gas subsidies and solidarity bonds in Ecuador

International Nuclear Information System (INIS)

Cuesta, J.; Ponce, J.; Leon, M.

2004-02-01

After two decades of neglect, social expending has become a cornerstone in the current fight against poverty in Ecuador. Ecuador is presently considering the elimination of regressive gas subsidies and the shift of these resources into pro-poor targeted Solidarity Bonds. Great distributive gains are expected from this reform. There are, however, a number of considerations that may prevent this policy shift from obtaining substantial poverty and equality gains. Despite their regressivity, implicit gas subsidies still represent a considerable proportion of total household consumption among poor households. Also, solidarity bonds siphon off a substantial share of their total benefits to middle income groups. This paper estimates the redistributive consequences of policy reforms on gas subsidies and solidarity bonds in Ecuador. A simulation methodology estimates both direct and indirect (labour-driven) distributive effects of four alternative scenarios: (1) total elimination of gas subsidies; (2) selective elimination of gas subsidies among non-poor households; (3) total elimination of gas subsidies and shift of resources to solidarity bonds targeted to the poor; (4) selective elimination of gas subsidies and shift of resources to solidarity bonds targeted to the poor. Estimates confirm that the redistributive gains from these reforms are rather small both for poverty and inequality. Incentives to work following the elimination of subsidies compensate, or even outdo, immediate poverty rises. Also, the elimination of gas subsidies without further expansion of subsidy bonds will unambiguously increase poverty in Ecuador between one and one and a half percent points

Experimental analysis of two-layered dissimilar metals by roll bonding

Science.gov (United States)

Zhao, Guanghui; Li, Yugui; Li, Juan; Huang, Qingxue; Ma, Lifeng

2018-02-01

Rolling reduction and base layers thickness have important implications for rolling compounding. A two-layered 304 stainless steel/Q345R low alloyed steel was roll bonded. The roll bonding was performed at the three thickness reductions of 25%, 40% and 55% with base layers of various thicknesses (Q345R). The microstructures of the composite were investigated by the ultra-deep microscope (OM) and scanning electron microscope (SEM) and Transmission electron microscope (TEM). Simultaneously, the mechanical properties of the composite were experimentally measured and the tensile fracture surfaces were observed by SEM. The interfaces were successfully bonded without any cracking or voids, which indicated a good fabrication of the 304/Q345R composite. The rolling reduction rate and thinning increase of the substrate contributed to the bonding effects appearance of the roll bonded sheet. The Cr and Ni enriched diffusion layer was formed by the interface elements diffusion. The Cr and Ni diffusion led to the formation of ˜10 μm wide Cr and Ni layers on the carbon steel side.

Elimination of maintenance outage and cost reduction by development of outage-free maintenance techniques

International Nuclear Information System (INIS)

Jakabe, Hideo; Maruyama, Yoshinaga

1996-01-01

The development program of KEPCO on outage-free maintenance techniques for distribution line work since 1984 is overviewed. It has succeeded in eliminating maintenance outages since 1989. The original aim was to improve customer satisfaction. However, in all, four benefits were realised through the development. These are cost reduction, securing of worker safety, improvement of customer service, and advancement of distribution techniques and morale in KEPCO. The introduction of robotic techniques for maintenance work and manipulator techniques for repair work is planned for further modernization. These new techniques are helping in both work safety and work efficiency improvement. Cost reduction and advancement of distribution line work techniques is also considered. (R.P.)

Application of Elimination Voltammetry to the Study of Electrochemical Reduction and Determination of the Herbicide Metribuzin

Czech Academy of Sciences Publication Activity Database

Skopalová, J.; Navrátil, Tomáš

2007-01-01

Roč. 52, č. 6 (2007), s. 961-977 ISSN 0009-2223 R&D Projects: GA ČR GA203/07/1195 Institutional research plan: CEZ:AV0Z40400503 Keywords : Elimination voltammetry with linear scan (EVLS) * metribuzin * electrochemical reduction * mercury electrodes Subject RIV: CG - Electrochemistry Impact factor: 0.529, year: 2007

Elimination reactions. V. Steric effects in Hofmann elimination

International Nuclear Information System (INIS)

Coke, J.L.; Smith, G.D.; Britton, G.H. Jr.

1975-01-01

Earlier Hofmann elimination studies were extended, and the percent syn eliminations in several ring systems have been correlated using cis-d 1 and trans-d 1 models. The measurements of several syn and anti k/sub H//k/sub D/ kinetic isotope effects are reported. Results indicate that Hofmann elimination of N,N,N-trimethyl-3,3-dimethylcyclopentylammonium hydroxide goes by 97 percent syn mechanism to give 3,3-dimethylcyclopentene and by 70 + - 6 percent syn mechanism to give 4,4-dimethylcyclopentene. There appears to be severe steric interactions in the anti mechanism in the 3,3-dimethylcyclopentyl system. Results indicate that, for Hofmann pyrolysis of trimethylammonium hydroxides, cyclopentene is formed by a 39 +- 7 percent syn mechanism, cyclohexene is formed by a 2 + - 2 percent syn mechanism, and cycloheptene is formed by a 30 +- 2 percent syn mechanism. Steric effects on isotope effects and mechanisms are discussed. (U.S.)

Characterization and durability testing of a glass-bonded ceramic waste form

International Nuclear Information System (INIS)

Johnson, S. G.

1998-01-01

Argonne National Laboratory is developing a glass bonded ceramic waste form for encapsulating the fission products and transuranics from the conditioning of metallic reactor fuel. This waste form is currently being scaled to the multi-kilogram size for encapsulation of actual high level waste. This paper will present characterization and durability testing of the ceramic waste form. An emphasis on results from application of glass durability tests such as the Product Consistency Test and characterization methods such as X-ray diffraction and scanning electron microscopy. The information presented is based on a suite of tests utilized for assessing product quality during scale-up and parametric testing

Pharmacodynamically optimized erythropoietin treatment combined with phlebotomy reduction predicted to eliminate blood transfusions in selected preterm infants.

Science.gov (United States)

Rosebraugh, Matthew R; Widness, John A; Nalbant, Demet; Cress, Gretchen; Veng-Pedersen, Peter

2014-02-01

Preterm very-low-birth-weight (VLBW) infants weighing eliminated by reducing laboratory blood loss in combination with pharmacodynamically optimized erythropoietin (Epo) treatment. Twenty-six VLBW ventilated infants receiving RBCTx were studied during the first month of life. RBCTx simulations were based on previously published RBCTx criteria and data-driven Epo pharmacodynamic optimization of literature-derived RBC life span and blood volume data corrected for phlebotomy loss. Simulated pharmacodynamic optimization of Epo administration and reduction in phlebotomy by ≥ 55% predicted a complete elimination of RBCTx in 1.0-1.5 kg infants. In infants 1.0 kg.

Unlocking the Electrocatalytic Activity of Chemically Inert Amorphous Carbon-Nitrogen for Oxygen Reduction: Discerning and Refactoring Chaotic Bonds

DEFF Research Database (Denmark)

Zhang, Caihong; Zhang, Wei; Wang, Dong

2017-01-01

Mild annealing enables inactive nitrogen (N)-doped amorphous carbon (a-C) films abundant with chaotic bonds prepared by magnetron sputtering to become effective for the oxygen reduction reaction (ORR) by virtue of generating pyridinic N. The rhythmic variation of ORR activity elaborates well...... on the subtle evolution of the amorphous C−N bonds conferred by spectroscopic analysis....

Quantum Devices Bonded Beneath a Superconducting Shield: Part 2

Science.gov (United States)

McRae, Corey Rae; Abdallah, Adel; Bejanin, Jeremy; Earnest, Carolyn; McConkey, Thomas; Pagel, Zachary; Mariantoni, Matteo

The next-generation quantum computer will rely on physical quantum bits (qubits) organized into arrays to form error-robust logical qubits. In the superconducting quantum circuit implementation, this architecture will require the use of larger and larger chip sizes. In order for on-chip superconducting quantum computers to be scalable, various issues found in large chips must be addressed, including the suppression of box modes (due to the sample holder) and the suppression of slot modes (due to fractured ground planes). By bonding a metallized shield layer over a superconducting circuit using thin-film indium as a bonding agent, we have demonstrated proof of concept of an extensible circuit architecture that holds the key to the suppression of spurious modes. Microwave characterization of shielded transmission lines and measurement of superconducting resonators were compared to identical unshielded devices. The elimination of box modes was investigated, as well as bond characteristics including bond homogeneity and the presence of a superconducting connection.

ATP-Dependent C–F Bond Cleavage Allows the Complete Degradation of 4-Fluoroaromatics without Oxygen

Directory of Open Access Journals (Sweden)

Oliver Tiedt

2016-08-01

Full Text Available Complete biodegradation of the abundant and persistent fluoroaromatics requires enzymatic cleavage of an arylic C–F bond, probably the most stable single bond of a biodegradable organic molecule. While in aerobic microorganisms defluorination of fluoroaromatics is initiated by oxygenases, arylic C–F bond cleavage has never been observed in the absence of oxygen. Here, an oxygen-independent enzymatic aryl fluoride bond cleavage is described during the complete degradation of 4-fluorobenzoate or 4-fluorotoluene to CO2 and HF in the denitrifying Thauera aromatica: the ATP-dependent defluorination of 4-fluorobenzoyl-coenzyme A (4-F-BzCoA to benzoyl-coenzyme A (BzCoA and HF, catalyzed by class I BzCoA reductase (BCR. Adaptation to growth with the fluoroaromatics was accomplished by the downregulation of a promiscuous benzoate-CoA ligase and the concomitant upregulation of 4-F-BzCoA-defluorinating/dearomatizing BCR on the transcriptional level. We propose an unprecedented mechanism for reductive arylic C–F bond cleavage via a Birch reduction-like mechanism resulting in a formal nucleophilic aromatic substitution. In the proposed anionic 4-fluorodienoyl-CoA transition state, fluoride elimination to BzCoA is favored over protonation to a fluorinated cyclic dienoyl-CoA.

Reversible Photoinduced Reductive Elimination of H2 from the Nitrogenase Dihydride State, the E4(4H) Janus Intermediate

OpenAIRE

Lukoyanov, Dmitriy; Khadka, Nimesh; Yang, Zhi-Yong; Dean, Dennis R.; Seefeldt, Lance C.; Hoffman, Brian M.

2016-01-01

We recently demonstrated that N2 reduction by nitrogenase involves the obligatory release of one H2 per N2 reduced. These studies focused on the E4(4H) ‘Janus intermediate’, which has accumulated four reducing equivalents as two [Fe-H-Fe] bridging hydrides. E4(4H) is poised to bind and reduce N2 through reductive elimination (re) of the two hydrides as H2, coupled to the binding/reduction of N2. To obtain atomic-level details of the re activation process, we carried out in situ 450 nm photoly...

Cyclopentadiene-mediated hydride transfer from rhodium complexes.

Science.gov (United States)

Pitman, C L; Finster, O N L; Miller, A J M

2016-07-12

Attempts to generate a proposed rhodium hydride catalytic intermediate instead resulted in isolation of (Cp*H)Rh(bpy)Cl (1), a pentamethylcyclopentadiene complex, formed by C-H bond-forming reductive elimination from the fleeting rhodium hydride. The hydride transfer ability of diene 1 was explored through thermochemistry and hydride transfer reactions, including the reduction of NAD(+).

Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

KAUST Repository

Liu, Xiangqian

2016-04-10

In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel-catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process.

Evidence for a Proton Transfer Network and a Required Persulfide-Bond-Forming Cysteine Residue in Ni-Containing Carbon Monoxide Dehydrogenases

International Nuclear Information System (INIS)

Eun Jin Kim; Jian Feng; Bramlett, Matthew R.; Lindahl, Paul A.

2004-01-01

OAK-B135 Carbon monoxide dehydrogenase from Moorella thermoacetica catalyzes the reversible oxidation of CO to CO2 at a nickel-iron-sulfur active-site called the C-cluster. Mutants of a proposed proton transfer pathway and of a cysteine residue recently found to form a persulfide bond with the C-cluster were characterized. Four semi-conserved histidine residues were individually mutated to alanine. His116 and His122 were essential to catalysis, while His113 and His119 attenuated catalysis but were not essential. Significant activity was ''rescued'' by a double mutant where His116 was replaced by Ala and His was also introduced at position 115. Activity was also rescued in double mutants where His122 was replaced by Ala and His was simultaneously introduced at either position 121 or 123. Activity was also ''rescued'' by replacing His with Cys at position 116. Mutation of conserved Lys587 near the C-cluster attenuated activity but did not eliminate it. Activity was virtually abolished in a double mutant where Lys587 and His113 were both changed to Ala. Mutations of conserved Asn284 also attenuated activity. These effects suggest the presence of a network of amino acid residues responsible for proton transfer rather than a single linear pathway. The Ser mutant of the persulfide-forming Cys316 was essentially inactive and displayed no EPR signals originating from the C-cluster. Electronic absorption and metal analysis suggests that the C-cluster is absent in this mutant. The persulfide bond appears to be essential for either the assembly or stability of the C-cluster, and/or for eliciting the redox chemistry of the C-cluster required for catalytic activity

The role of uranium-arene bonding in H2O reduction catalysis

Science.gov (United States)

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

2018-03-01

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

Cleavage of sp3 C-O bonds via oxidative addition of C-H bonds.

Science.gov (United States)

Choi, Jongwook; Choliy, Yuriy; Zhang, Xiawei; Emge, Thomas J; Krogh-Jespersen, Karsten; Goldman, Alan S

2009-11-04

(PCP)Ir (PCP = kappa(3)-C(6)H(3)-2,6-[CH(2)P(t-Bu)(2)](2)) is found to undergo oxidative addition of the methyl-oxygen bond of electron-poor methyl aryl ethers, including methoxy-3,5-bis(trifluoromethyl)benzene and methoxypentafluorobenzene, to give the corresponding aryloxide complexes (PCP)Ir(CH(3))(OAr). Although the net reaction is insertion of the Ir center into the C-O bond, density functional theory (DFT) calculations and a significant kinetic isotope effect [k(CH(3))(OAr)/k(CD(3))(OAr) = 4.3(3)] strongly argue against a simple insertion mechanism and in favor of a pathway involving C-H addition and alpha-migration of the OAr group to give a methylene complex followed by hydride-to-methylene migration to give the observed product. Ethoxy aryl ethers, including ethoxybenzene, also undergo C-O bond cleavage by (PCP)Ir, but the net reaction in this case is 1,2-elimination of ArO-H to give (PCP)Ir(H)(OAr) and ethylene. DFT calculations point to a low-barrier pathway for this reaction that proceeds through C-H addition of the ethoxy methyl group followed by beta-aryl oxide elimination and loss of ethylene. Thus, both of these distinct C-O cleavage reactions proceed via initial addition of a C(sp(3))-H bond, despite the fact that such bonds are typically considered inert and are much stronger than C-O bonds.

Glass-bonded iodosodalite waste form for immobilization of 129I

Science.gov (United States)

Chong, Saehwa; Peterson, Jacob A.; Riley, Brian J.; Tabada, Diana; Wall, Donald; Corkhill, Claire L.; McCloy, John S.

2018-06-01

Immobilization of radioiodine is an important requirement for current and future nuclear fuel cycles. Iodosodalite [Na8(AlSiO4)6I2] was synthesized hydrothermally from metakaolin, NaI, and NaOH. Dried unwashed sodalite powders were used to synthesize glass-bonded iodosodalite waste forms (glass composite materials) by heating pressed pellets at 650, 750, or 850 °C with two types of sodium borosilicate glass binders. These heat-treated specimens were characterized with X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal analysis, porosity and density measurements, neutron activation analysis, and inductively-coupled plasma mass spectrometry. For the best waste form produced (pellets mixed with 10 mass% of glass binder and heat-treated at 750 °C), the maximum possible elemental iodine loading was 19.8 mass%, but only ∼8-9 mass% waste loading of iodine was retained in the waste form after thermal processing. Other pellets with higher iodine retention either contained higher porosity or were incompletely sintered. ASTM C1308 and C1285 (product consistency test, PCT) experiments were performed to understand chemical durability under diffusive and static conditions. The C1308 test resulted in significantly higher normalized loss compared to the C1285 test, most likely because of the strong effect of neutral pH solution renewal and prevention of ion saturation in solution. Both experiments indicated that release rates of Na and Si were higher than for Al and I, probably due to a poorly durable Na-Si-O phase from the glass bonding matrix or from initial sodalite synthesis; however the C1308 test result indicated that congruent dissolution of iodosodalite occurred. The average release rates of iodine obtained from C1308 were 0.17 and 1.29 g m-2 d-1 for 80 or 8 m-1, respectively, and the C1285 analysis gave a value of 2 × 10-5 g m-2 d-1, which is comparable to or better than the durability of

The effectiveness of riboflavin and ultraviolet light pathogen reduction technology in eliminating Trypanosoma cruzi from leukoreduced whole blood.

Science.gov (United States)

Jimenez-Marco, Teresa; Cancino-Faure, Beatriz; Girona-Llobera, Enrique; Alcover, M Magdalena; Riera, Cristina; Fisa, Roser

2017-06-01

The parasitic Chagas disease is caused by the protozoan Trypanosoma cruzi, which is mainly transmitted by insect vectors. Other infection routes, both in endemic and in nonendemic areas, include organ and marrow transplantation, congenital transmission, and blood transfusion. Asymptomatic chronic chagasic individuals may have a low and transient parasitemia in peripheral blood and, consequently, they can unknowingly transmit the disease via blood transfusion. Riboflavin and ultraviolet (UV) light pathogen reduction is a method to reduce pathogen transfusion transmission risk based on damage to the pathogen nucleic acids. In this study, we tested the effectiveness of this technology for the elimination of T. cruzi parasites in artificially contaminated whole blood units (WBUs) and thus for decreasing the risk of T. cruzi transfusion transmission. The contaminated WBUs were leukoreduced by filtration and treated with riboflavin and UV light. The level of pathogen reduction was quantified by a real-time polymerase chain reaction (qPCR) and a real-time reverse transcription-polymerase chain reaction (RT-qPCR) as a viability assay. The RNA (cDNA) quantification of the parasites showed a more than 99% reduction of viable T. cruzi parasites after leukoreduction and a complete reduction (100%) after the riboflavin and UV light treatment. Riboflavin and UV light treatment and leukoreduction used in conjunction appears to eliminate significant amounts of viable T. cruzi in whole blood. Both strategies could complement other blood bank measures already implemented to prevent the transmission of T. cruzi via blood transfusion. © 2017 AABB.

Reduction of canine plasminogen leads to an expanded molecule which precipitates.

Directory of Open Access Journals (Sweden)

Jack A Kornblatt

Full Text Available Canine plasminogen is made up of seven domains. In each domain there are several cysteines that are linked by disulfide bonds. Reduction of a limited number of the cystines destabilizes the protein such that it precipitates. The bond or bonds that are broken provide about 14 kcal of stabilization energy. Circular dichroism and dynamic light scattering indicate that there is probably an intermediate that is formed prior to precipitation and that the intermediate is somewhat larger than the compact form of plasminogen.

Nickel-Catalyzed Alkoxy-Alkyl Interconversion with Alkylborane Reagents through C−O Bond Activation of Aryl and Enol Ethers

KAUST Repository

Guo, Lin

2016-11-07

A nickel-catalyzed alkylation of polycyclic aromatic methyl ethers as well as methyl enol ethers with B-alkyl 9-BBN and trialkylborane reagents that involves the cleavage of stable C(sp2)−OMe bonds is described. The transformation has a wide substrate scope and good chemoselectivity profile while proceeding under mild reaction conditions; it provides a versatile way to form C(sp2)−C(sp3) bonds that does not suffer from β-hydride elimination. Furthermore, a selective and sequential alkylation process by cleavage of inert C−O bonds is presented to demonstrate the advantage of this method.

Modeling on-column reduction of trisulfide bonds in monoclonal antibodies during protein A chromatography.

Science.gov (United States)

Ghose, Sanchayita; Rajshekaran, Rupshika; Labanca, Marisa; Conley, Lynn

2017-01-06

Trisulfides can be a common post-translational modification in many recombinant monoclonal antibodies. These are a source of product heterogeneity that add to the complexity of product characterization and hence, need to be reduced for consistent product quality. Trisulfide bonds can be converted to the regular disulfide bonds by incorporating a novel cysteine wash step during Protein A affinity chromatography. An empirical model is developed for this on-column reduction reaction to compare the reaction rates as a function of typical operating parameters such as temperature, cysteine concentration, reaction time and starting level of trisulfides. The model presented here is anticipated to assist in the development of optimal wash conditions for the Protein A step to effectively reduce trisulfides to desired levels. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Institute of Scientific and Technical Information of China (English)

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

2004-01-01

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

Influence of heat-pretreatments on the microstructural and mechanical properties of galfan-coated metal bonds

Science.gov (United States)

Hordych, Illia; Rodman, Dmytro; Nürnberger, Florian; Schmidt, Hans Christian; Orive, Alejandro Gonzalez; Homberg, Werner; Grundmeier, Guido; Maier, Hans Jürgen

2018-05-01

In the present study, heat-treatment assisted bonding of galfan-coated low-carbon steel sheets was investigated. Steel sheets were bonded by cold rolling subsequently to a heat treatment in the temperature range from 400 °C to 550°C. The reduction ratio during cold rolling was varied in the range from 50% to 80%. Such high reduction ratios were achieved by splitting the bonding process into three stages. By employing heat-treatments, the mechanical properties of the bonds were improved. The heat-pretreatment allowed the formation of brittle intermetallic phases that were easily fractured in the rolling gap during the bonding process. Thus, juvenile non-oxidized surfaces were formed, which facilitated the bonding between the steel layers, and thus increased the bond strength. The intermetallic phases were actively formed at temperatures of 450 °C and above; however increasing temperatures resulted in decreasing mechanical properties due to oxidation processes. The local microstructure was analyzed by scanning electron microscopy in order to characterize the contact zone on the micro level with a focus on the formation of intermetallic phases. The mechanical properties were determined in tensile shear tests. Interestingly, it was found that the galfan coating allowed for bonding at room temperature, and the aluminum fraction was primarily responsible for the enhanced oxide formation during the heat-pretreatment.

Bonding Properties of Basalt Fiber and Strength Reduction According to Fiber Orientation

Directory of Open Access Journals (Sweden)

Jeong-Il Choi

2015-09-01

Full Text Available The basalt fiber is a promising reinforcing fiber because it has a relatively higher tensile strength and a density similar to that of a concrete matrix as well as no corrosion possibility. This study investigated experimentally the bonding properties of basalt fiber with cementitious material as well as the effect of fiber orientation on the tensile strength of basalt fiber for evaluating basalt fiber’s suitability as a reinforcing fiber. Single fiber pullout tests were performed and then the tensile strength of fiber was measured according to fiber orientation. The test results showed that basalt fiber has a strong chemical bond with the cementitious matrix, 1.88 times higher than that of polyvinyl alcohol fibers with it. However, other properties of basalt fiber such as slip-hardening coefficient and strength reduction coefficient were worse than PVA and polyethylene fibers in terms of fiber bridging capacity. Theoretical fiber-bridging curves showed that the basalt fiber reinforcing system has a higher cracking strength than the PVA fiber reinforcing system, but the reinforcing system showed softening behavior after cracking.

Bonding Properties of Basalt Fiber and Strength Reduction According to Fiber Orientation.

Science.gov (United States)

Choi, Jeong-Il; Lee, Bang Yeon

2015-09-30

The basalt fiber is a promising reinforcing fiber because it has a relatively higher tensile strength and a density similar to that of a concrete matrix as well as no corrosion possibility. This study investigated experimentally the bonding properties of basalt fiber with cementitious material as well as the effect of fiber orientation on the tensile strength of basalt fiber for evaluating basalt fiber's suitability as a reinforcing fiber. Single fiber pullout tests were performed and then the tensile strength of fiber was measured according to fiber orientation. The test results showed that basalt fiber has a strong chemical bond with the cementitious matrix, 1.88 times higher than that of polyvinyl alcohol fibers with it. However, other properties of basalt fiber such as slip-hardening coefficient and strength reduction coefficient were worse than PVA and polyethylene fibers in terms of fiber bridging capacity. Theoretical fiber-bridging curves showed that the basalt fiber reinforcing system has a higher cracking strength than the PVA fiber reinforcing system, but the reinforcing system showed softening behavior after cracking.

Br2 elimination in 248-nm photolysis of CF2Br2 probed by using cavity ring-down absorption spectroscopy.

Science.gov (United States)

Hsu, Ching-Yi; Huang, Hong-Yi; Lin, King-Chuen

2005-10-01

By using cavity ring-down absorption spectroscopy technique, we have observed the channel of Br2 molecular elimination following photodissociation of CF2Br2 at 248 nm. A tunable laser beam, which is crossed perpendicular to the photolyzing laser beam in a ring-down cell, is used to probe the Br2 fragment in the B 3Piou+-X1Sigmag+ transition. The vibrational population is obtained in a nascent state, despite ring-down time as long as 500-1000 ns. The population ratio of Br2(v=1)/Br2(v=0) is determined to be 0.4+/-0.2, slightly larger than the value of 0.22 evaluated by Boltzmann distribution at room temperature. The quantum yield of the Br2 elimination reaction is also measured to be 0.04+/-0.01. This work provides direct evidence to support molecular elimination occurring in the CF2Br2 photodissociation and proposes a plausible pathway with the aid of ab initio potential-energy calculations. CF2Br2 is excited probably to the 1B1 and 3B2 states at 248 nm. As the C-Br bond is elongated upon excitation, the coupling of the 1A'(1B1) state to the high vibrational levels of the ground state X 1A'(1A1) may be enhanced to facilitate the process of internal conversion. After transition, the highly vibrationally excited CF2Br2 feasibly surpasses a transition barrier prior to decomposition. According to the ab initio calculations, the transition state structure tends to correlate with the intermediate state CF2Br+Br(CF2Br...Br) and the products CF2+Br2. A sequential photodissociation pathway is thus favored. That is, a single C-Br bond breaks, and then the free-Br atom moves to form a Br-Br bond, followed by the Br2 elimination. The formed Br-Br bond distance in the transition state tends to approach equilibrium such that the Br2 fragment may be populated in cold vibrational distribution. Observation of a small vibrational population ratio of Br2(v=1)Br2(v=0) agrees with the proposed mechanism.

Nicotinamidase/pyrazinamidase of Mycobacterium tuberculosis forms homo-dimers stabilized by disulfide bonds.

Science.gov (United States)

Rueda, Daniel; Sheen, Patricia; Gilman, Robert H; Bueno, Carlos; Santos, Marco; Pando-Robles, Victoria; Batista, Cesar V; Zimic, Mirko

2014-12-01

Recombinant wild-pyrazinamidase from H37Rv Mycobacterium tuberculosis was analyzed by gel electrophoresis under differential reducing conditions to evaluate its quaternary structure. PZAse was fractionated by size exclusion chromatography under non-reducing conditions. PZAse activity was measured and mass spectrometry analysis was performed to determine the identity of proteins by de novo sequencing and to determine the presence of disulfide bonds. This study confirmed that M. tuberculosis wild type PZAse was able to form homo-dimers in vitro. Homo-dimers showed a slightly lower specific PZAse activity compared to monomeric PZAse. PZAse dimers were dissociated into monomers in response to reducing conditions. Mass spectrometry analysis confirmed the existence of disulfide bonds (C72-C138 and C138-C138) stabilizing the quaternary structure of the PZAse homo-dimer. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sn interaction with the CeO.sub.2./sub.(111) system: bimetallic bonding and ceria reduction

Czech Academy of Sciences Publication Activity Database

Škoda, M.; Cabala, M.; Cháb, Vladimír; Prince, K. C.; Sedláček, L.; Skála, T.; Šutara, F.; Matolín, V.

2008-01-01

Roč. 254, č. 14 (2008), 4375-4379 ISSN 0169-4332 R&D Projects: GA MŠk(CZ) LC06058 Institutional research plan: CEZ:AV0Z10100521 Keywords : resonant photoemission * RPES * XPS * LEED * ceria * tin * reduction * bimetallic interaction * bimetallic bonding Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.576, year: 2008

Fracture toughness measurements on a glass bonded sodalite high-level waste form

International Nuclear Information System (INIS)

DiSanto, T.; Goff, K. M.; Johnson, S. G.; O'Holleran, T. P.

1999-01-01

The electrometallurgical treatment of metallic spent nuclear fuel produces two high-level waste streams; cladding hulls and chloride salt. Argonne National Laboratory is developing a glass bonded sodalite waste form to immobilize the salt waste stream. The waste form consists of 75 Vol.% crystalline sodalite (containing the salt) with 25 Vol.% of an ''intergranular'' glassy phase. Microindentation fracture toughness measurements were performed on representative samples of this material using a Vickers indenter. Palmqvist cracking was confirmed by post-indentation polishing of a test sample. Young's modulus was measured by an acoustic technique. Fracture toughness, microhardness, and Young's modulus values are reported, along with results from scanning electron microscopy studies

Reversible Photoinduced Reductive Elimination of H2 from the Nitrogenase Dihydride State, the E(4)(4H) Janus Intermediate.

Science.gov (United States)

Lukoyanov, Dmitriy; Khadka, Nimesh; Yang, Zhi-Yong; Dean, Dennis R; Seefeldt, Lance C; Hoffman, Brian M

2016-02-03

We recently demonstrated that N2 reduction by nitrogenase involves the obligatory release of one H2 per N2 reduced. These studies focus on the E4(4H) "Janus intermediate", which has accumulated four reducing equivalents as two [Fe-H-Fe] bridging hydrides. E4(4H) is poised to bind and reduce N2 through reductive elimination (re) of the two hydrides as H2, coupled to the binding/reduction of N2. To obtain atomic-level details of the re activation process, we carried out in situ 450 nm photolysis of E4(4H) in an EPR cavity at temperatures below 20 K. ENDOR and EPR measurements show that photolysis generates a new FeMo-co state, denoted E4(2H)*, through the photoinduced re of the two bridging hydrides of E4(4H) as H2. During cryoannealing at temperatures above 175 K, E4(2H)* reverts to E4(4H) through the oxidative addition (oa) of the H2. The photolysis quantum yield is temperature invariant at liquid helium temperatures and shows a rather large kinetic isotope effect, KIE = 10. These observations imply that photoinduced release of H2 involves a barrier to the combination of the two nascent H atoms, in contrast to a barrierless process for monometallic inorganic complexes, and further suggest that H2 formation involves nuclear tunneling through that barrier. The oa recombination of E4(2H)* with the liberated H2 offers compelling evidence for the Janus intermediate as the point at which H2 is necessarily lost during N2 reduction; this mechanistically coupled loss must be gated by N2 addition that drives the re/oa equilibrium toward reductive elimination of H2 with N2 binding/reduction.

77 FR 12594 - Agency Forms Undergoing Paperwork Reduction Act Review

Science.gov (United States)

2012-03-01

... Script. Refusal Questions Form.. 62 1 2/60 Individual Consent Form. 250 1 3/60 Contact Information Form... Screening 92 1 5/60 Survey. Informed Consent........ 50 1 1/60 Interview Questionnaire. 50 1 1 Network Size...-12-12BL] Agency Forms Undergoing Paperwork Reduction Act Review The Agency for Toxic Substances and...

Editing disulphide bonds: error correction using redox currencies.

Science.gov (United States)

Ito, Koreaki

2010-01-01

The disulphide bond-introducing enzyme of bacteria, DsbA, sometimes oxidizes non-native cysteine pairs. DsbC should rearrange the resulting incorrect disulphide bonds into those with correct connectivity. DsbA and DsbC receive oxidizing and reducing equivalents, respectively, from respective redox components (quinones and NADPH) of the cell. Two mechanisms of disulphide bond rearrangement have been proposed. In the redox-neutral 'shuffling' mechanism, the nucleophilic cysteine in the DsbC active site forms a mixed disulphide with a substrate and induces disulphide shuffling within the substrate part of the enzyme-substrate complex, followed by resolution into a reduced enzyme and a disulphide-rearranged substrate. In the 'reduction-oxidation' mechanism, DsbC reduces those substrates with wrong disulphides so that DsbA can oxidize them again. In this issue of Molecular Microbiology, Berkmen and his collaborators show that a disulphide reductase, TrxP, from an anaerobic bacterium can substitute for DsbC in Escherichia coli. They propose that the reduction-oxidation mechanism of disulphide rearrangement can indeed operate in vivo. An implication of this work is that correcting errors in disulphide bonds can be coupled to cellular metabolism and is conceptually similar to the proofreading processes observed with numerous synthesis and maturation reactions of biological macromolecules.

75 FR 6671 - Agency Forms Undergoing Paperwork Reduction Act Review

Science.gov (United States)

2010-02-10

... programs implemented a new consent form. This form asked participants for permission for CDC to contact...] Agency Forms Undergoing Paperwork Reduction Act Review The Centers for Disease Control and Prevention... prevention behaviors, CDC will conduct telephone interviews of 425 Matter of Balance program participants six...

Investigation of ball bond integrity for 0.8 mil (20 microns) diameter gold bonding wire on low k die in wire bonding technology

Science.gov (United States)

Kudtarkar, Santosh Anil

Microelectronics technology has been undergoing continuous scaling to accommodate customer driven demand for smaller, faster and cheaper products. This demand has been satisfied by using novel materials, design techniques and processes. This results in challenges for the chip connection technology and also the package technology. The focus of this research endeavor was restricted to wire bond interconnect technology using gold bonding wires. Wire bond technology is often regarded as a simple first level interconnection technique. In reality, however, this is a complex process that requires a thorough understanding of the interactions between the design, material and process variables, and their impact on the reliability of the bond formed during this process. This research endeavor primarily focused on low diameter, 0.8 mil thick (20 mum) diameter gold bonding wire. Within the scope of this research, the integrity of the ball bond formed by 1.0 mil (25 mum) and 0.8 mil (20 mum) diameter wires was compared. This was followed by the evaluation of bonds formed on bond pads having doped SiO2 (low k) as underlying structures. In addition, the effect of varying the percentage of the wire dopant, palladium and bonding process parameters (bonding force, bond time, ultrasonic energy) for 0.8 mil (20 mum) bonding wire was also evaluated. Finally, a degradation empirical model was developed to understand the decrease in the wire strength. This research effort helped to develop a fundamental understanding of the various factors affecting the reliability of a ball bond from a design (low diameter bonding wire), material (low k and bonding wire dopants), and process (wire bonding process parameters) perspective for a first level interconnection technique, namely wire bonding. The significance of this research endeavor was the systematic investigation of the ball bonds formed using 0.8 mil (20 microm) gold bonding wire within the wire bonding arena. This research addressed low k

NiTi bonded space regainer/maintainer

Directory of Open Access Journals (Sweden)

Negi K

2010-06-01

Full Text Available Early orthodontic interventions are often initiated in the developing dentition to promote favorable developmental changes. Interceptive orthodontic can eliminate or reduce the severity of a developing malocclusion, the complexity of orthodontic treatment, overall treatment time and cost. Premature loss of deciduous tooth or teeth can often destroy the integrity of normal occlusion. There are many space regaining and maintaining devices mentioned in literature. In this article, I present a simple space regaining method by a piece of nickel titanium (NiTi wire bonded between the teeth in active loop form, and the unique shape memory property of NiTi wire will upright or move the teeth and the lost space can be regained easily.

An approach to eliminate stepped features in multistage incremental sheet forming process: Experimental and FEA analysis

Energy Technology Data Exchange (ETDEWEB)

Nirala, Harish Kumar; Jain, Prashant K.; Tandon, Puneet [PDPM Indian Institute of Information Technology, Design and Manufacturing Jabalpur Jabalpur-482005, Madhya Pradesh (India); Roy, J. J.; Samal, M. K. [Bhabha Atomic Research Centre, Mumbai (India)

2017-02-15

Incremental sheet forming (ISF) is a recently developed manufacturing technique. In ISF, forming is done by applying deformation force through the motion of Numerically controlled (NC) single point forming tool on the clamped sheet metal blank. Single Point Incremental sheet forming (SPISF) is also known as a die-less forming process because no die is required to fabricate any component by using this process. Now a day it is widely accepted for rapid manufacturing of sheet metal components. The formability of SPISF process improves by adding some intermediate stages into it, which is known as Multi-stage SPISF (MSPISF) process. However during forming in MSPISF process because of intermediate stages stepped features are generated. This paper investigates the generation of stepped features with simulation and experimental results. An effective MSPISF strategy is proposed to remove or eliminate this generated undesirable stepped features.

Reduction of disulfide bonds in peptides and proteins. Reduction des groupes disulfure dans les peptides et proteines

Energy Technology Data Exchange (ETDEWEB)

Conte, D [Institut Curie, 75 - Paris (France); Houee-Levin, C [Paris-5 Univ., 75 (France)

1993-04-01

We have re-examined the mechanism of disulfide bond reduction in oxidized glutathione by C0[sub 2][sup .-] free radicals. The process appears to be a chain reaction whose initial yield depends on pH and on both peptide and formate ion concentrations, but remains independent on the radiation dose rate. Kinetic schemes drawn from studies on dithiothreitol are unable to account for the results obtained with glutathione and proteins, although the disulfide radical anion is the primary intermediate found with all compounds. The rate constant for its formation from C0[sub 2][sup .-] and glutathione is in the same range as those found using proteins, while decay pathways are somewhat different. Hypotheses are proposed to account for these differences. 6 figs., 2 tabs.

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

Science.gov (United States)

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

2017-08-07

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

Surface characterization by X-ray photoelectron spectroscopy and cyclic voltammetry of products formed during the potentiostatic reduction of chalcopyrite

International Nuclear Information System (INIS)

Nava, Dora; Gonzalez, Ignacio; Leinen, Dietmar; Ramos-Barrado, Jose R.

2008-01-01

Surface characterization of the transient products that precede chalcocite formation during chalcopyrite reduction was carried out. The experimental strategy employed in the present work consisted of the application of different potential pulses (fixed energetic conditions) on the surface of chalcopyrite electrodes in 1.7 M H 2 SO 4 . The chemical products formed at different potential pulses were characterized by cyclic voltammetry (CV) and XPS. Each electrogenerated species presented a specific voltammetric behavior and an XPS spectrum, in which the values of principal photoelectronic peak bond energies for Cu 2p 3/2 , Fe 2p 3/2 and S 2p 3/2 and the atomic concentrations were considered. Several potential intervals could be identified: in 0.115 ≥ E cat ≥ -0.085 V vs. SHE, an intermediate copper sulfide is formed whose composition is between those of chalcopyrite and bornite, such as talnakhite. The reduction of this product occurs slowly, giving bornite at potentials less than -0.085 V. In the applied potential region -0.085 ≥ E cat > -0.185 V, the bornite gradually decomposes causing the incomplete conversion to chalcocite. In the potential interval -0.185 > E cat ≥ -0.285 V, energetic conditions are large enough to allow the immediate decomposition of bornite, forming chalcocite in a more quantitative manner

Photo-reduction on the rupture of disulfide bonds and the related protein assembling

Science.gov (United States)

Wang, Wei

It has been found that many proteins can self-assemble into nanoscale assemblies when they unfold or partially unfold under harsh conditions, such as low pH, high temperature, or the presence of denaturants, and so on. These nanoscale assemblies can have some applications such as the drug-delivery systems (DDSs). Here we report a study that a very physical way, the UV illumination, can be used to facilitate the formation of protein fibrils and nanoparticles under native conditions by breaking disulfide bonds in some disulfide-containing proteins. By controlling the intensity of UV light and the illumination time, we realized the preparation of self-assembly nanoparticles which encapsulate the anticancer drug doxorubicin (DOX) and can be used as the DDS for inhibiting the growth of tumor. The formation of fibrillary assemblies was also observed. The rupture of disulfide bonds through photo-reduction process due to the effect of tryptophan and tyrosine was studied, and the physical mechanism of the assembling of the related disulfide-containing proteins was also discussed. We thank the financial support from NSF of China and the 973 project.

Robust fault detection in bond graph framework using interval analysis and Fourier-Motzkin elimination technique

Science.gov (United States)

Jha, Mayank Shekhar; Chatti, Nizar; Declerck, Philippe

2017-09-01

This paper addresses the fault diagnosis problem of uncertain systems in the context of Bond Graph modelling technique. The main objective is to enhance the fault detection step based on Interval valued Analytical Redundancy Relations (named I-ARR) in order to overcome the problems related to false alarms, missed alarms and robustness issues. These I-ARRs are a set of fault indicators that generate the interval bounds called thresholds. A fault is detected once the nominal residuals (point valued part of I-ARRs) exceed the thresholds. However, the existing fault detection method is limited to parametric faults and it presents various limitations with regards to estimation of measurement signal derivatives, to which I-ARRs are sensitive. The novelties and scientific interest of the proposed methodology are: (1) to improve the accuracy of the measurements derivatives estimation by using a dedicated sliding mode differentiator proposed in this work, (2) to suitably integrate the Fourier-Motzkin Elimination (FME) technique within the I-ARRs based diagnosis so that measurements faults can be detected successfully. The latter provides interval bounds over the derivatives which are included in the thresholds. The proposed methodology is studied under various scenarios (parametric and measurement faults) via simulations over a mechatronic torsion bar system.

Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

Science.gov (United States)

Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

2011-01-18

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

A computational mechanistic study of Pd(ii)-catalyzed γ-C(sp3)-H olefination/cyclization of amines: the roles of bicarbonate and ligand effect.

Science.gov (United States)

Liu, Jian-Biao; Tian, Ying-Ying; Zhang, Xin; Wang, Lu-Lin; Chen, De-Zhan

2018-04-03

The detailed mechanism of palladium-catalyzed γ-C(sp3)-H olefination/cyclization of triflyl-protected amines was investigated by density functional theory (DFT) calculations. The olefinated intermediate was initially formed in the first catalytic cycle involving ligand exchange, bicarbonate-assisted C(sp3)-H bond cleavage, alkene insertion and 'reductive β-hydride elimination'. The following syn-addition and reductive elimination furnish the aza-Wacker product. The first step of reductive elimination is the rate-determining step. The mechanism unveils the important roles of bicarbonate: aiding the C-H activation and abstracting the β-proton in the second step of reductive elimination. The parallel bridging mode in the metal-olefin intermediate facilitates the syn-addition, explaining the experimentally observed stereoselectivity. The effect of the monodentate pyridine-based ligands is also discussed.

Elimination device for metal impurities

International Nuclear Information System (INIS)

Yanagisawa, Ko.

1982-01-01

Purpose: To enable reuse of adsorbing materials by eliminating Fe 3 O 4 films reduced with adsorbing performance by way of electrolytic polishing and then forming fresh membranes using high temperature steams. Constitution: An elimination device is provided to a coolant clean-up system of a reactor for eliminating impurities such as cobalt. The elimination device comprises adsorbing materials made of stainless steel tips or the likes having Fe 3 O 4 films. The adsorbing materials are regenerated by applying an electric current between grid-like cathode plates and anode plates to leach out the Fe 3 O 4 films, washing out the electrolytic solution by cleaning water and then applying steams at high temperature onto the adsorbing materials to thereby form fresh Fe 3 O 4 films again thereon. The regeneration of the adsorbing materials enables to eliminate Co 60 and the like in the primary coolant efficiently. (Moriyama, K.)

Si-to-Si wafer bonding using evaporated glass

DEFF Research Database (Denmark)

Reus, Roger De; Lindahl, M.

1997-01-01

Anodic bonding of Si to Si four inch wafers using evaporated glass was performed in air at temperatures ranging from 300°C to 450°C. Although annealing of Si/glass structures around 340°C for 15 minutes eliminates stress, the bonded wafer pairs exhibit compressive stress. Pull testing revealed...

Cost-estimate and proposal for a development impact bond for canine rabies elimination by mass vaccination in Chad.

Science.gov (United States)

Anyiam, Franziska; Lechenne, Monique; Mindekem, Rolande; Oussigéré, Assandi; Naissengar, Service; Alfaroukh, Idriss Oumar; Mbilo, Celine; Moto, Daugla Doumagoum; Coleman, Paul G; Probst-Hensch, Nicole; Zinsstag, Jakob

2017-11-01

Close to 69,000 humans die of rabies each year, most of them in Africa and Asia. Clinical rabies can be prevented by post-exposure prophylaxis (PEP). However, PEP is commonly not available or not affordable in developing countries. Another strategy besides treating exposed humans is the vaccination of vector species. In developing countries, the main vector is the domestic dog, that, once infected, is a serious threat to humans. After a successful mass vaccination of 70% of the dogs in N'Djaména, we report here a cost-estimate for a national rabies elimination campaign for Chad. In a cross-sectional survey in four rural zones, we established the canine : human ratio at the household level. Based on human census data and the prevailing socio-cultural composition of rural zones of Chad, the total canine population was estimated at 1,205,361 dogs (95% Confidence interval 1,128,008-1,736,774 dogs). Cost data were collected from government sources and the recent canine mass vaccination campaign in N'Djaména. A Monte Carlo simulation was used for the simulation of the average cost and its variability, using probability distributions for dog numbers and cost items. Assuming the vaccination of 100 dogs on average per vaccination post and a duration of one year, the total cost for the vaccination of the national Chadian canine population is estimated at 2,716,359 Euros (95% CI 2,417,353-3,035,081) for one vaccination round. A development impact bond (DIB) organizational structure and cash flow scenario were then developed for the elimination of canine rabies in Chad. Cumulative discounted cost of 28.3 million Euros over ten years would be shared between the government of Chad, private investors and institutional donors as outcome funders. In this way, the risk of the investment could be shared and the necessary investment could be made available upfront - a key element for the elimination of canine rabies in Chad. Copyright © 2016 The Authors. Published by Elsevier B

Mechanism of reductive elimination. Reaction of alkylpalladium(II) complexes with tetraorganotin, organolithium, and Grignard reagents. Evidence for palladium(IV) intermediacy

International Nuclear Information System (INIS)

Milstein, D.; Stille, J.K.

1979-01-01

Coupling products are obtained in good yields from the reaction of tetraorganotin compounds or Grignard reagents and organohalogenopalladium(II) complexes provided that a benzyl bromide is present. Low yields are obtained in the absence of the benzyl bromides, in which case other decomposition pathways (e.g., α elimination) take place, even in the presence of electron acceptors (e.g., oxygen, m-dinitrobenzene). The first step in the reaction of benzylhalogenobis(triphenylphosphine)-palladium(II) complexes with MeM (M = SnMe 3 , MgBr) is metathesis of the benzyl ligand rather than the halogen. This unique carbon-for-carbon transmetalation takes place at 25 0 C and is facilitated by electron-donating substituents on the benzyl ligand. The products of this reaction subsequently react at higher temperature in the presence of a benzyl bromide to afford ethylbenzene. Optically active chloro-(α-deuteriobenzyl)bis(triphenylphosphine)palladium yields, upon reaction with tetramethyltin in the presence of p-nitrobenzyl bromide, optically active α-deuterioethylbenzene in which overall retention of configuration at carbon has resulted. cis-dimethylbis(triphenylphosphine)palladium(II) reacts with benzyl bromide at 25 0 C to afford ethylbenzene and bromomethylbis(triphenylphosphine)palladium(II) rather than ethane. When optically active α-deuteriobenzyl bromide is used in this reaction, optically active α-deuterioethylbenzene is formed, and inversion of configuration at carbon takes place. The reductive elimination process is proposed to take place preferentially from a palladium(IV) intermediate with retention of configuration at carbon

Proceedings: Instrumentation and control test reduction workshop

International Nuclear Information System (INIS)

1991-09-01

Instrumentation and control (I ampersand C) surveillance and testing is a significant contributor to operations and management costs. Several techniques to eliminate or reduce manual testing requirements could reduce costs while improving plant safety and performance. I ampersand C test reduction was the subject of this 1991 workshop. The workshop covered test elimination, test reduction, test automation, and relevant standards and benefits. The conclusions of the workshop were the following: More utility information sharing is important. There is a significant amount of information available throughout the industry, but it is not available in a concise, useable form. An I ampersand C utility users group is needed to address items such as instrument calibration reduction, set-point methodologies, and other current I ampersand C issues. The workshop was well received. The timing is right to initiate actions to reduce testing

76 FR 55915 - Agency Forms Undergoing Paperwork Reduction Act Review

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2011-09-09

... type 2 diabetes DPRP Application Form........ 120 1 1 prevention programs. DPRP Evaluation Data... mechanism for recognizing organizations that deliver effective, community-based type 2 diabetes prevention...] Agency Forms Undergoing Paperwork Reduction Act Review The Centers for Disease Control and Prevention...

Pulse radiolysis study of the reduction mechanism of an antitumor antibiotic, mitomycin C

International Nuclear Information System (INIS)

Machtalere, G.; Houee-Levin, C.; Gardes-Albert, M.; Ferradini, C.; Hickel, B.

1988-01-01

Mitomycin C is a quinonic antitumor metabolized in vivo by one-electron reduction. We have studied the mechanism of the one-electron reduction of this drug by pulse radiolysis using C00 .- free radicals as reductants. Semiquinonic and hydroquinonic intermediates are formed. The hydroquinonic form undergoes a methanol elimination leading to a transient which can disappear in one of two ways: by either internal redox reaction or hydrolysis of the aziridine. 17 refs [fr

Cut elimination in multifocused linear logic

DEFF Research Database (Denmark)

Guenot, Nicolas; Brock-Nannestad, Taus

2015-01-01

We study cut elimination for a multifocused variant of full linear logic in the sequent calculus. The multifocused normal form of proofs yields problems that do not appear in a standard focused system, related to the constraints in grouping rule instances in focusing phases. We show that cut...... elimination can be performed in a sensible way even though the proof requires some specific lemmas to deal with multifocusing phases, and discuss the difficulties arising with cut elimination when considering normal forms of proofs in linear logic....

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

Science.gov (United States)

Fernandez, Julio M.

2008-03-01

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

Simultaneous bond degradation and bond formation during phenol-formaldehyde curing with wood

Science.gov (United States)

Daniel J. Yelle; John Ralph

2016-01-01

Bonding of wood using phenol–formaldehyde adhesive develops highly durable bonds. Phenol– formaldehyde is believed to form primary bonds with wood cell wall polymers (e.g., lignin). However, it is unclear how this adhesive interacts and bonds to lignin. Through wood solubilisation methodologies, earlywood and latewood bonded assemblies were characterized using two-...

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2012-02-09

... pregnant during Health Questionnaire/ 750 1 20/60 NHANES 1999-2010. Consent Form. 3. State/local vital...-11CE] Agency Forms Undergoing Paperwork Reduction Act Review The Centers for Disease Control and... about the pregnant women at the time of interview. Having information on their children's birth...

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2013-07-03

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Selective elimination of intracortically projecting neurons of the rat neocortex by prenatal x-irradiation

International Nuclear Information System (INIS)

Jensen, K.F.

1981-01-01

The development of new racing methods has suggested that there are species differences in the extent of the contribution of the different layers of the neocortex to the callosal projection. The present investigation has utilized prenatal x-irradiation to selectively eliminate the late forming neurons of the supragranular layers of the rat neocortex. The reduction in the neuronal population of the supragranular layers closely parallels the reduction in the corpus callosum. These results indicate that the primary source of neurons of the callosal projection, are the late forming neurons of the supragranular layers. Thus, the current results suggest that low dose prenatal x-irradiation may be used to evaluate important developmental events in the formation of neocortical circuitry

Methods for Reducing Normal Tissue Complication Probabilities in Oropharyngeal Cancer: Dose Reduction or Planning Target Volume Elimination

Energy Technology Data Exchange (ETDEWEB)

Samuels, Stuart E.; Eisbruch, Avraham; Vineberg, Karen; Lee, Jae; Lee, Choonik; Matuszak, Martha M.; Ten Haken, Randall K.; Brock, Kristy K., E-mail: kbrock@med.umich.edu

2016-11-01

Purpose: Strategies to reduce the toxicities of head and neck radiation (ie, dysphagia [difficulty swallowing] and xerostomia [dry mouth]) are currently underway. However, the predicted benefit of dose and planning target volume (PTV) reduction strategies is unknown. The purpose of the present study was to compare the normal tissue complication probabilities (NTCP) for swallowing and salivary structures in standard plans (70 Gy [P70]), dose-reduced plans (60 Gy [P60]), and plans eliminating the PTV margin. Methods and Materials: A total of 38 oropharyngeal cancer (OPC) plans were analyzed. Standard organ-sparing volumetric modulated arc therapy plans (P70) were created and then modified by eliminating the PTVs and treating the clinical tumor volumes (CTVs) only (C70) or maintaining the PTV but reducing the dose to 60 Gy (P60). NTCP dose models for the pharyngeal constrictors, glottis/supraglottic larynx, parotid glands (PGs), and submandibular glands (SMGs) were analyzed. The minimal clinically important benefit was defined as a mean change in NTCP of >5%. The P70 NTCP thresholds and overlap percentages of the organs at risk with the PTVs (56-59 Gy, vPTV{sub 56}) were evaluated to identify the predictors for NTCP improvement. Results: With the P60 plans, only the ipsilateral PG (iPG) benefited (23.9% vs 16.2%; P<.01). With the C70 plans, only the iPG (23.9% vs 17.5%; P<.01) and contralateral SMG (cSMG) (NTCP 32.1% vs 22.9%; P<.01) benefited. An iPG NTCP threshold of 20% and 30% predicted NTCP benefits for the P60 and C70 plans, respectively (P<.001). A cSMG NTCP threshold of 30% predicted for an NTCP benefit with the C70 plans (P<.001). Furthermore, for the iPG, a vPTV{sub 56} >13% predicted benefit with P60 (P<.001) and C70 (P=.002). For the cSMG, a vPTV{sub 56} >22% predicted benefit with C70 (P<.01). Conclusions: PTV elimination and dose-reduction lowered the NTCP of the iPG, and PTV elimination lowered the NTCP of the cSMG. NTCP thresholds and the

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2010-05-05

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2011-07-01

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Reaction sintering of a clay-containing silicon nitride bonded silicon carbide refractory

International Nuclear Information System (INIS)

Swenser, S.P.; Cheng, Y.B.

1998-01-01

Aspects of the reaction sequence for the reaction bonding of a cast refractory, which in the green state was composed of 79 wt-% SiC grit, 16 wt-% Si powder and 5 wt-% clay were established. As it was fired up to 1600 deg C in flowing N 2 (g), weight gains were noted and phase evolution was monitored by X-ray diffraction. However, details of the reaction sequence were not determined directly from this material because several reaction-bonding processes occurred simultaneously. Reaction features were ascertained by contrasting the weight changes and phase evolution in the refractory with those observed during reaction-bonding of (a) Si and clay without the SiC and (b) SiC and clay without the Si. In addition to silicon nitridation and the development of sialon phases by silicothermal and carbothermal reduction-nitridation processes, indirect evidence suggested that α-Si 3 N 4 formed by the carbothermal reduction-nitridation (CRN) of SiO(g). Copyright (1998) Australasian Ceramic Society

Oxidation study on as-bonded intermetallic of copper wire–aluminum bond pad metallization for electronic microchip

International Nuclear Information System (INIS)

Joseph Sahaya Anand, T.; Yau, Chua Kok; Huat, Lim Boon

2012-01-01

In this work, influence of Copper free air ball (FAB) oxidation towards Intermetallic Compound (IMC) at Copper wire–Aluminum bond pad metallization (Cu/Al) is studied. Samples are synthesized with different Copper FAB oxidation condition by turning Forming Gas supply ON and OFF. Studies are performed using Optical Microscope (OM), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and line-scan Energy Dispersive X-ray (EDX). SEM result shows there is a cross-sectional position offset from center in sample synthesized with Forming Gas OFF. This is due to difficulty of determining the position of cross-section in manual grinding/polishing process and high occurrence rate of golf-clubbed shape of oxidized Copper ball bond. TEM inspection reveals that the Copper ball bond on sample synthesized with Forming Gas OFF is having intermediate oxidation. Besides, the presence of IMC at the bonding interface of Cu/Al for both samples is seen. TEM study shows voids form at the bonding interface of Forming Gas ON sample belongs to unbonded area; while that in Forming Gas OFF sample is due to volume shrinkage of IMC growth. Line-scan EDX shows the phases present in the interfaces of as-bonded samples are Al 4 Cu 9 (∼3 nm) for sample with Forming Gas ON and mixed CuAl and CuAl 2 (∼15 nm) for sample with Forming Gas OFF. Thicker IMC in sample with Forming Gas OFF is due to cross-section is positioned at high stress area that is close to edge of ball bond. Mechanical ball shear test shows that shear strength of sample with Forming Gas OFF is about 19% lower than that of sample with Forming Gas ON. Interface temperature is estimated at 437 °C for as-bonded sample with Forming Gas ON by using empirical parabolic law of volume diffusion. -- Highlights: ► 3 nm Al 4 Cu 9 are found in sample prepared with Forming Gas ON. ► 15 nm mixed CuAl + CuAl 2 are found in sample prepared with Forming Gas OFF. ► Voids are present at the bonding interfaces of both

Oxidation study on as-bonded intermetallic of copper wire-aluminum bond pad metallization for electronic microchip

Energy Technology Data Exchange (ETDEWEB)

Joseph Sahaya Anand, T., E-mail: anand@utem.edu.my [Faculty of Manufacturing Engineering, University Technical Malaysia Melaka, Hang Tuah Jaya, 76100 Durian Tunggal, Melaka (Malaysia); Yau, Chua Kok [Faculty of Manufacturing Engineering, University Technical Malaysia Melaka, Hang Tuah Jaya, 76100 Durian Tunggal, Melaka (Malaysia); University of Technical Malaysia Supported by Infineon Technology - Malaysia - Sdn. Bhd., Melaka (Malaysia); Huat, Lim Boon [Department of Innovation, Infineon Technology - Malaysia - Sdn. Bhd., FTZ Batu Berendam, 75350 Melaka (Malaysia)

2012-10-15

In this work, influence of Copper free air ball (FAB) oxidation towards Intermetallic Compound (IMC) at Copper wire-Aluminum bond pad metallization (Cu/Al) is studied. Samples are synthesized with different Copper FAB oxidation condition by turning Forming Gas supply ON and OFF. Studies are performed using Optical Microscope (OM), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and line-scan Energy Dispersive X-ray (EDX). SEM result shows there is a cross-sectional position offset from center in sample synthesized with Forming Gas OFF. This is due to difficulty of determining the position of cross-section in manual grinding/polishing process and high occurrence rate of golf-clubbed shape of oxidized Copper ball bond. TEM inspection reveals that the Copper ball bond on sample synthesized with Forming Gas OFF is having intermediate oxidation. Besides, the presence of IMC at the bonding interface of Cu/Al for both samples is seen. TEM study shows voids form at the bonding interface of Forming Gas ON sample belongs to unbonded area; while that in Forming Gas OFF sample is due to volume shrinkage of IMC growth. Line-scan EDX shows the phases present in the interfaces of as-bonded samples are Al{sub 4}Cu{sub 9} ({approx}3 nm) for sample with Forming Gas ON and mixed CuAl and CuAl{sub 2} ({approx}15 nm) for sample with Forming Gas OFF. Thicker IMC in sample with Forming Gas OFF is due to cross-section is positioned at high stress area that is close to edge of ball bond. Mechanical ball shear test shows that shear strength of sample with Forming Gas OFF is about 19% lower than that of sample with Forming Gas ON. Interface temperature is estimated at 437 Degree-Sign C for as-bonded sample with Forming Gas ON by using empirical parabolic law of volume diffusion. -- Highlights: Black-Right-Pointing-Pointer 3 nm Al{sub 4}Cu{sub 9} are found in sample prepared with Forming Gas ON. Black-Right-Pointing-Pointer 15 nm mixed CuAl + CuAl{sub 2} are found

46 CFR Sec. 10 - Bonds.

Science.gov (United States)

2010-10-01

... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form 25...

Nonperfect synchronization of bond-forming and bond-rupturing processes in the reaction H + H2 → H2 + H

International Nuclear Information System (INIS)

Chandra, A.K.; Rao, V.S.

1996-01-01

The simplest prototypical hydrogen transfer reaction, i.e., H + H 2 → H 2 + H, is studied by the quantum-mechanical ab initio methods. Results reveal that during this reaction free valence which almost equals the square of the spin density develops on the migrating hydrogen atom. Bond orders are calculated using Mayer's formalism. Both the variations of bond orders and bond lengths along the reaction path are examined. This analysis reveals that the bond formation and bond cleavage processes in this reaction are not perfectly synchronous. The bond clevage process is slightly more advanced on the reaction path. 38 refs., 6 figs., 2 tabs

Hydrogenation of graphene nanoflakes and C-H bond dissociation of hydrogenated graphene nanoflakes: a density functional theory study

Institute of Scientific and Technical Information of China (English)

Sheng Tao; Hui-Ting Liu; Liu-Ming Yan; Bao-Hua Yue; Ai-Jun Li

2017-01-01

The Gibbs free energy change for the hydrogenation of graphene nanoflakes Cn (n =24,28,30 and 32) and the C-H bond dissociation energy of hydrogenated graphene nanoflakes CnHm (n =24,28,30 and 32;and m =1,2 and 3) are evaluated using density functional theory calculations.It is concluded that the graphene nanoflakes and hydrogenated graphene nanoflakes accept the ortharyne structure with peripheral carbon atoms bonded via the most triple bonds and leaving the least unpaired dangling electrons.Five-membered rings are formed at the deep bay sites attributing to the stabilization effect from the pairing of dangling electrons.The hydrogenation reactions which eliminate one unpaired dangling electron and thus decrease the overall multiplicity of the graphene nanoflakes or hydrogenated graphene nanoflakes are spontaneous with negative or near zero Gibbs free energy change.And the resulting C-H bonds are stable with bond dissociation energy in the same range as those of aromatic compounds.The other C-H bonds are not as stable attributing to the excessive unpaired dangling electrons being filled into the C-H anti-bond orbital.

Corrosion behaviors of a glass-bonded sodalite ceramic waste form and its constituents

International Nuclear Information System (INIS)

Lewis, M. A.; Ebert, W. L.; Morss, L.

1999-01-01

A ceramic waste form (CWF) of glass bonded sodalite is being developed as a waste form for the long-term immobilization of fission products and transuranic elements from the U.S. Department of Energy's activities on spent nuclear fuel conditioning. A durable waste form was prepared by hot isostatic pressing (HIP) a mixture of salt-loaded zeolite powders and glass frit. During HIP the zeolite is converted to sodalite, and the resultant CWF is been completed for durations of up to 182 days. Four dissolution modes were identified: dissolution of free salt, dissolution of the aluminosilicate matrix of sodalite and the accompanying dissolution of occluded salt, dissolution of the boroaluminosilicate matrix of the glass, and ion exchange. Synergies inherent to the CWF were identified by comparing the results of the tests with pure glass and sodalite with those of the composite CWF

7 CFR 1726.27 - Contractor's bonds.

Science.gov (United States)

2010-01-01

... 7 Agriculture 11 2010-01-01 2010-01-01 false Contractor's bonds. 1726.27 Section 1726.27... AGRICULTURE ELECTRIC SYSTEM CONSTRUCTION POLICIES AND PROCEDURES General § 1726.27 Contractor's bonds. (a) RUS Form 168b, Contractor's Bond, shall be used when a contractor's bond is required by RUS Forms 200, 257...

Bond Strength of Resin Cements to Dentin Using New Universal Bonding Agents

Science.gov (United States)

2015-06-30

and acidic simplified adhesives is a well-studied phenomenon (Kanehira et al., 2006). A chemical incompatibility may occur in the oxygen-inhibited...not completely eliminate this incompatibility (Tay et al., 2003). Recently, new “universal adhesives ” have been introduced. These universal...potential incompatibilities with self-curing resin materials. Low bond strength between self-curing resin materials and acidic simplified adhesives is

Voltage-assisted polymer wafer bonding

International Nuclear Information System (INIS)

Varsanik, J S; Bernstein, J J

2012-01-01

Polymer wafer bonding is a widely used process for fabrication of microfluidic devices. However, best practices for polymer bonds do not achieve sufficient bond strength for many applications. By applying a voltage to a polymer bond in a process called voltage-assisted bonding, bond strength is shown to improve dramatically for two polymers (Cytop™ and poly(methyl methacrylate)). Several experiments were performed to provide a starting point for further exploration of this technique. An optimal voltage range is experimentally observed with a reduction in bonding strength at higher voltages. Additionally, voltage-assisted bonding is shown to reduce void diameter due to bond defects. An electrostatic force model is proposed to explain the improved bond characteristics. This process can be used to improve bond strength for most polymers. (paper)

Thiocarbamate-Directed Tandem Olefination-Intramolecular Sulfuration of Two Ortho C-H Bonds: Application to Synthesis of a COX-2 Inhibitor.

Science.gov (United States)

Li, Wendong; Zhao, Yingwei; Mai, Shaoyu; Song, Qiuling

2018-02-16

A palladium-catalyzed dual ortho C-H bond activation of aryl thiocarbamates is developed. This tandem reaction initiates by thiocarbamate-directed ortho C-H palladation, which leads to favorable olefin insertion rather than reductive elimination. The oxidative Heck reaction followed by another C-H activation and sulfuration affords the dual-functionalized products. This reaction provides a concise route to the S,O,C multisubstituted benzene skeleton which could be successfully applied for the synthesis of a COX-2 inhibitor.

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

Science.gov (United States)

Oliveira, Vytor; Cremer, Dieter

2017-08-01

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

77 FR 37051 - Agency Forms Undergoing Paperwork Reduction Act Review

Science.gov (United States)

2012-06-20

... Year 1 and Year 2. Informed Consent Form... 4,404 1 2/60 Non-Responder Interview. 792 1 5/60 Kimberly S...] Agency Forms Undergoing Paperwork Reduction Act Review The Centers for Disease Control and Prevention...-minute interview will be conducted with a 10% sample of non-responders (up to 792 individuals). In order...

The chemical bond in inorganic chemistry the bond valence model

CERN Document Server

Brown, I David

2016-01-01

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

New type of bonding formed from an overlap between pi aromatic and pi C=O molecular orbitals stabilizes the coexistence in one molecule of the ionic and neutral meso-ionic forms of imidazopyridine.

Science.gov (United States)

Hoffmann, Marcin; Plutecka, Agnieszka; Rychlewska, Urszula; Kucybala, Zdzislaw; Paczkowski, Jerzy; Pyszka, Ilona

2005-05-26

New bis(imidazo)pyridine dye has been synthesized and tested as a potential photoinitaitor for free-radical polymerization induced with the visible emission of an argon ion laser. The X-ray analysis based on data collected at 170 and 130 K, as well as density functional theory (DFT) calculations, revealed the presence of two different forms of imidazopyridine rings within the same molecule. These two forms of the same moiety had not only different geometries but different electronic structures as well. One of the imidazopyridine rings was in the ionic form, while the other was in the meso-ionic form. DFT calculations provided an explanation for such an observed phenomena. The averaging of ionic and meso-ionic forms of imidazopyridine rings within the same molecule is hindered because of an attractive interaction between them. Analysis of electronic density revealed that, indeed, a new type of bonding is formed as the result of an overlap between pi aromatic and pi C=O molecular orbitals. This bonding, like the hydrogen bond, is primarily of electrostatic character, and its energy was estimated at 3.5 kcal/mol.

Mechanism of forming interfacial intermetallic compounds at interface for solid state diffusion bonding of dissimilar materials

International Nuclear Information System (INIS)

He, P.; Liu, D.

2006-01-01

The formation of brittle intermetallic compounds at the interfaces of diffusion bonds is the main cause which leads to poor bond strength. Therefore, it is very important to study and establish the formation and growth model of intermetallic compounds at the interfaces for the control process of diffusion bonding. In this paper, according to the diffusion kinetics and the thermodynamics, the principle of formation of intermetallic compounds at interfaces in the multi-component diffusion couple, the flux-energy principle, is put forward. In the light of diffusion theory, the formation capacity of the phase at the interfaces is determined by specific properties of the composition in the diffusion couple and the composition ratio of the formed phase is in agreement with the diffusion flux. In accordance with the flux-energy principle, the microstructure of the Ni/TC4 interface is Ni/TiNi 3 /TiNi/Ti 2 Ni/TC4, the microstructure of the TC4/00Cr18Ni9Ti interface is 00Cr18Ni9Ti/TiFe 2 /TiFe/Ti 2 Fe/TC4, and the microstructure of the TiAl/40Cr interface is 40Cr/TiC/Ti 3 Al + FeAl + FeAl 2 /TiAl. Multi-intermetallic compounds with the equivalent flux-energy can be formed at the interfaces at the same time

77 FR 72999 - Small Brewers Bond Reduction

Science.gov (United States)

2012-12-07

... 1986 (IRC), pertains to the taxation of distilled spirits, wines, and beer (see title 26 of the United... qualification of breweries, bonds and taxation, removals without payment of tax, and records and reporting..., including the increased number of small (``craft'') brewers. In an advance notice of proposed rulemaking...

A slow-forming isopeptide bond in the structure of the major pilin SpaD from Corynebacterium diphtheriae has implications for pilus assembly

Energy Technology Data Exchange (ETDEWEB)

Kang, Hae Joo; Paterson, Neil G. [University of Auckland, Private Bag 92019, Auckland 1142 (New Zealand); Kim, Chae Un [Cornell University, Ithaca, NY 14853 (United States); Middleditch, Martin [University of Auckland, Private Bag 92019, Auckland 1142 (New Zealand); Chang, Chungyu; Ton-That, Hung [University of Texas–Houston Medical School, Houston, TX 77030 (United States); Baker, Edward N., E-mail: ted.baker@auckland.ac.nz [University of Auckland, Private Bag 92019, Auckland 1142 (New Zealand)

2014-05-01

Two crystal structures of the major pilin SpaD from C. diphtheriae have been determined at 1.87 and 2.5 Å resolution. The N-terminal domain is found to contain an isopeptide bond that forms slowly over time in the recombinant protein. Given its structural context, this provides insight into the relationship between internal isopeptide-bond formation and pilus assembly. The Gram-positive organism Corynebacterium diphtheriae, the cause of diphtheria in humans, expresses pili on its surface which it uses for adhesion and colonization of its host. These pili are covalent protein polymers composed of three types of pilin subunit that are assembled by specific sortase enzymes. A structural analysis of the major pilin SpaD, which forms the polymeric backbone of one of the three types of pilus expressed by C. diphtheriae, is reported. Mass-spectral and crystallographic analysis shows that SpaD contains three internal Lys–Asn isopeptide bonds. One of these, shown by mass spectrometry to be located in the N-terminal D1 domain of the protein, only forms slowly, implying an energy barrier to bond formation. Two crystal structures, of the full-length three-domain protein at 2.5 Å resolution and of a two-domain (D2-D3) construct at 1.87 Å resolution, show that each of the three Ig-like domains contains a single Lys–Asn isopeptide-bond cross-link, assumed to give mechanical stability as in other such pili. Additional stabilizing features include a disulfide bond in the D3 domain and a calcium-binding loop in D2. The N-terminal D1 domain is more flexible than the others and, by analogy with other major pilins of this type, the slow formation of its isopeptide bond can be attributed to its location adjacent to the lysine used in sortase-mediated polymerization during pilus assembly.

A Disulfide Bond-forming Machine Is Linked to the Sortase-mediated Pilus Assembly Pathway in the Gram-positive Bacterium Actinomyces oris*

Science.gov (United States)

Reardon-Robinson, Melissa E.; Osipiuk, Jerzy; Chang, Chungyu; Wu, Chenggang; Jooya, Neda; Joachimiak, Andrzej; Das, Asis; Ton-That, Hung

2015-01-01

Export of cell surface pilins in Gram-positive bacteria likely occurs by the translocation of unfolded precursor polypeptides; however, how the unfolded pilins gain their native conformation is presently unknown. Here, we present physiological studies to demonstrate that the FimA pilin of Actinomyces oris contains two disulfide bonds. Alanine substitution of cysteine residues forming the C-terminal disulfide bridge abrogates pilus assembly, in turn eliminating biofilm formation and polymicrobial interaction. Transposon mutagenesis of A. oris yielded a mutant defective in adherence to Streptococcus oralis, and revealed the essential role of a vitamin K epoxide reductase (VKOR) gene in pilus assembly. Targeted deletion of vkor results in the same defects, which are rescued by ectopic expression of VKOR, but not a mutant containing an alanine substitution in its conserved CXXC motif. Depletion of mdbA, which encodes a membrane-bound thiol-disulfide oxidoreductase, abrogates pilus assembly and alters cell morphology. Remarkably, overexpression of MdbA or a counterpart from Corynebacterium diphtheriae, rescues the Δvkor mutant. By alkylation assays, we demonstrate that VKOR is required for MdbA reoxidation. Furthermore, crystallographic studies reveal that A. oris MdbA harbors a thioredoxin-like fold with the conserved CXXC active site. Consistently, each MdbA enzyme catalyzes proper disulfide bond formation within FimA in vitro that requires the catalytic CXXC motif. Because the majority of signal peptide-containing proteins encoded by A. oris possess multiple Cys residues, we propose that MdbA and VKOR constitute a major folding machine for the secretome of this organism. This oxidative protein folding pathway may be a common feature in Actinobacteria. PMID:26170452

A Disulfide Bond-forming Machine Is Linked to the Sortase-mediated Pilus Assembly Pathway in the Gram-positive Bacterium Actinomyces oris.

Science.gov (United States)

Reardon-Robinson, Melissa E; Osipiuk, Jerzy; Chang, Chungyu; Wu, Chenggang; Jooya, Neda; Joachimiak, Andrzej; Das, Asis; Ton-That, Hung

2015-08-28

Export of cell surface pilins in Gram-positive bacteria likely occurs by the translocation of unfolded precursor polypeptides; however, how the unfolded pilins gain their native conformation is presently unknown. Here, we present physiological studies to demonstrate that the FimA pilin of Actinomyces oris contains two disulfide bonds. Alanine substitution of cysteine residues forming the C-terminal disulfide bridge abrogates pilus assembly, in turn eliminating biofilm formation and polymicrobial interaction. Transposon mutagenesis of A. oris yielded a mutant defective in adherence to Streptococcus oralis, and revealed the essential role of a vitamin K epoxide reductase (VKOR) gene in pilus assembly. Targeted deletion of vkor results in the same defects, which are rescued by ectopic expression of VKOR, but not a mutant containing an alanine substitution in its conserved CXXC motif. Depletion of mdbA, which encodes a membrane-bound thiol-disulfide oxidoreductase, abrogates pilus assembly and alters cell morphology. Remarkably, overexpression of MdbA or a counterpart from Corynebacterium diphtheriae, rescues the Δvkor mutant. By alkylation assays, we demonstrate that VKOR is required for MdbA reoxidation. Furthermore, crystallographic studies reveal that A. oris MdbA harbors a thioredoxin-like fold with the conserved CXXC active site. Consistently, each MdbA enzyme catalyzes proper disulfide bond formation within FimA in vitro that requires the catalytic CXXC motif. Because the majority of signal peptide-containing proteins encoded by A. oris possess multiple Cys residues, we propose that MdbA and VKOR constitute a major folding machine for the secretome of this organism. This oxidative protein folding pathway may be a common feature in Actinobacteria. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Hydrogen bonding in ionic liquids.

Science.gov (United States)

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

2015-03-07

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

Using Canonical Forms for Isomorphism Reduction in Graph-based Model Checking

NARCIS (Netherlands)

Kant, Gijs

Graph isomorphism checking can be used in graph-based model checking to achieve symmetry reduction. Instead of one-to-one comparing the graph representations of states, canonical forms of state graphs can be computed. These canonical forms can be used to store and compare states. However, computing

27 CFR 70.281 - Form of bond and security required.

Science.gov (United States)

2010-04-01

..., express or telegraph money order; (v) Secured by corporate bonds or stocks, or by bonds issued by a State... of business or legal residence of the primary obligor is located; (ii) The surety must have property... which the principal place of business or legal residence of the primary obligor is located; (iv) The...

Microstructure of Reaction Zone Formed During Diffusion Bonding of TiAl with Ni/Al Multilayer

Science.gov (United States)

Simões, Sónia; Viana, Filomena; Koçak, Mustafa; Ramos, A. Sofia; Vieira, M. Teresa; Vieira, Manuel F.

2012-05-01

In this article, the characterization of the interfacial structure of diffusion bonding a TiAl alloy is presented. The joining surfaces were modified by Ni/Al reactive multilayer deposition as an alternative approach to conventional diffusion bonding. TiAl substrates were coated with alternated Ni and Al nanolayers. The nanolayers were deposited by dc magnetron sputtering with 14 nm of period (bilayer thickness). Joining experiments were performed at 900 °C for 30 and 60 min with a pressure of 5 MPa. Cross sections of the joints were prepared for characterization of their interfaces by scanning electron microscopy (SEM), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), high resolution TEM (HRTEM), energy dispersive x-ray spectroscopy (EDS), and electron backscatter diffraction (EBSD). Several intermetallic compounds form at the interface, assuring the bonding of the TiAl. The interface can be divided into three distinct zones: zone 1 exhibits elongated nanograins, very small equiaxed grains are observed in zone 2, while zone 3 has larger equiaxed grains. EBSD analysis reveals that zone 1 corresponds to the intermetallic Al2NiTi and AlNiTi, and zones 2 and 3 to NiAl.

Form factors of descendant operators: reduction to perturbed M(2,2s+1) models

International Nuclear Information System (INIS)

Lashkevich, Michael; Pugai, Yaroslav

2015-01-01

In the framework of the algebraic approach to form factors in two-dimensional integrable models of quantum field theory we consider the reduction of the sine-Gordon model to the Φ 13 -perturbation of minimal conformal models of the M(2,2s+1) series. We find in an algebraic form the condition of compatibility of local operators with the reduction. We propose a construction that make it possible to obtain reduction compatible local operators in terms of screening currents. As an application we obtain exact multiparticle form factors for the compatible with the reduction conserved currents T ±2k , Θ ±(2k−2) , which correspond to the spin ±(2k−1) integrals of motion, for any positive integer k. Furthermore, we obtain all form factors of the operators T 2k T −2l , which generalize the famous TT̄ operator. The construction is analytic in the s parameter and, therefore, makes sense in the sine-Gordon theory.

Method of eliminating undesirable gaseous products resulting in underground uranium ore leaching

International Nuclear Information System (INIS)

Krizek, J.; Dedic, K.; Johann, J.; Haas, F.; Sokola, K.

1980-01-01

The method described is characteristic of the fact that gases being formed or dissolved are oxidized using a combined oxidation-reduction system consisting of airborne oxygen, oxygen carriers and a strong irreversible oxidant. The oxygen carrier system consists of a mixture of Fe 2+ and Fe 3+ cations or of Cu + and Cu 2+ cations introduced in solutions in form of iron salts at a concentration of 0.0001 to 0.003 M, or copper salts maximally of 0.0003 M. The irreversible oxidant shows a standard redox potential of at least +1.0 V. In addition to undesirable product elimination, the method allows increasing the leaching process yield. (J.B.)

Criteria to form a > of thyroid gland diseases appearance in those who took part in elimination of the Chernobyl accident aftereffects

International Nuclear Information System (INIS)

Afanas'jeva, N.Yi.; Tkachenko, G.Yi.; Astap'jeva, O.M.; Lozins'ka, Yi.M.; Rozdyil's'kij, S.Yi.; Vasil'jev, L.Ya.

1994-01-01

The authors report and discuss the results of clinical study of the thyroid gland and hormonal thyroid state in 100 male patients who had taken part in elimination of the Chernobyl accident aftereffects. The revealed changes in the thyroid homeostasis state depending the terms of observation and enlargement of the thyroid gland (stage 1 - 2) in 32% of the patients suggest of appearance of predisposing factors to development of the thyroid gland pathologic conditions. Criteria to form a > of thyropathy appearance in those who took part in elimination of the Chernobyl accident aftereffects were determined

Pricing catastrophic bonds for earthquakes in Mexico

OpenAIRE

Cabrera, Brenda López

2006-01-01

After the occurrence of a natural disaster, the reconstruction can be financed with catastrophic bonds (CAT bonds) or reinsurance. For insurers, reinsurers and other corporations CAT bonds provide multi year protection without the credit risk present in reinsurance. For investors CAT bonds offer attractive returns and reduction of portfolio risk, since CAT bonds defaults are uncorrelated with defaults of other securities. As the study of natural catastrophe models plays an important role in t...

Characterization of bulk-micromachined direct-bonded silicon nanofilters

Science.gov (United States)

Tu, Jay K.; Huen, Tony; Szema, Robert; Ferrari, Mauro

1998-03-01

The ability to separate 30-100 nm particles - nanofiltration - is critical for many biomedical applications. Where this filtration needs to be absolute, such as for viral elimination in the blood fractionation process, the large variations in pore size found with conventional polymeric filters can lead to the unwanted presence of viruses in the filtrate. To overcome this problem, we have developed a filter with micromachined channels sandwiched between two bonded silicon wafers. These channels are formed through the selective deposition and then removal of a thermally-grown oxide, the thickness of which can be controlled to +/- 4 percent for 30 nm pores. In this paper, we will present both the gas and liquid characterization, and the filtration studies done on 44 and 100 nm beads.

Spectroscopic Identification of the Au-C Bond Formation upon Electroreduction of an Aryl Diazonium Salt on Gold.

Science.gov (United States)

Guo, Limin; Ma, Lipo; Zhang, Yelong; Cheng, Xun; Xu, Ye; Wang, Jin; Wang, Erkang; Peng, Zhangquan

2016-11-08

Electroreduction of aryl diazonium salts on gold can produce organic films that are more robust than their analogous self-assembled monolayers formed from chemical adsorption of organic thiols on gold. However, whether the enhanced stability is due to the Au-C bond formation remains debated. In this work, we report the electroreduction of an aryl diazonium salt of 4,4'-disulfanediyldibenzenediazonium on gold forming a multilayer of Au-(Ar-S-S-Ar) n , which can be further degraded to a monolayer of Au-Ar-S - by electrochemical cleavage of the S-S moieties within the multilayer. By conducting an in situ surface-enhanced Raman spectroscopic study of both the multilayer formation/degradation and the monolayer reduction/oxidation processes, coupled to density functional theory calculations, we provide compelling evidence that an Au-C bond does form upon electroreduction of aryl diazonium salts on gold and that the enhanced stability of the electrografted organic films is due to the Au-C bond being intrinsically stronger than the Au-S bond for a given phenylthiolate compound by ca. 0.4 eV.

Oxidation and reduction kinetics of eutectic SnPb, InSn, and AuSn: a knowledge base for fluxless solder bonding applications

DEFF Research Database (Denmark)

Kuhmann, Jochen Friedrich; Preuss, A.; Adolphi, B.

1998-01-01

: (1) SnPb; (2) InSn; (3) AuSn. The studies of the oxidation kinetics show that the growth of the native oxide, which covers the solder surfaces from the start of all soldering operations is self-limiting. The rate of oxidation on the molten, metallic solder surfaces is significantly reduced...... and reduction kinetics, are applied to flip-chip (FC) bonding experiments in vacuum with and without the injection of H2. Wetting in vacuum is excellent but the self-alignment during flip-chip soldering is restricted. The desired, perfectly self-aligned FC-bonds have been only achieved, using evaporated...

Reaction pathways for reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes

International Nuclear Information System (INIS)

Cunha, M.C.P.M. da; De Souza, J.P.I.; Nart, F.C.

2000-01-01

The reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes has been investigated using differential electrochemical mass spectrometry and in situ FTIR measurements. For 3 M HNO 3 concentration it has been found that nitrate starts the reduction with partial N-O bond dissociation and N-N bond formation generating NO and N 2 O. At potentials lower than 0.2 V the reaction proceeds forming dissolved NH 4 + . For potentials lower than 0 V the reduction continues via a multiple pathway reaction leading to the nonselective production of N 2 , NH 2 OH, and N 2 H 2 . On the alloyed electrodes, the production of NO and N 2 O has been observed in both cathodic and anodic scans, while on pure platinum and rhodium electrodes the reaction has been observed only during the cathodic scan. Contrasting with the pure platinum and rhodium alloys, where the N-O bond break starts forming NO and N 2 O, on the alloys HNO 2 has been observed as the first reaction step. For alloys with higher rhodium composition, like Pt 75 Rh 25 , no N 2 has been detected for potentials lower than 0 V

75 FR 52459 - Regulations Governing Agencies for Issue of United States Savings Bonds; Offering of United...

Science.gov (United States)

2010-08-26

... eliminate the option to purchase paper savings bonds through payroll deductions for United States government... savings bonds purchased through payroll sales; individuals will still be able to purchase paper savings bonds at financial institutions for themselves and as gifts. Payroll savers will be encouraged to...

Click polymerization for the synthesis of reduction-responsive polymeric prodrug

Science.gov (United States)

Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

2018-05-01

Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

Phenylacetylene and H bond

Indian Academy of Sciences (India)

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

Physical mechanisms of Cu-Cu wafer bonding

International Nuclear Information System (INIS)

Rebhan, B.

2014-01-01

Modern manufacturing processes of complex integrated semiconductor devices are based on wafer-level manufacturing of components which are subsequently interconnected. When compared with classical monolithic bi-dimensional integrated circuits (2D ICs), the new approach of three-dimensional integrated circuits (3D ICs) exhibits significant benefits in terms of signal propagation delay and power consumption due to the reduced metal interconnection length and allows high integration levels with reduced form factor. Metal thermo-compression bonding is a process suitable for 3D interconnects applications at wafer level, which facilitates the electrical and mechanical connection of two wafers even processed in different technologies, such as complementary metal oxide semiconductor (CMOS) and microelectromechanical systems (MEMS). Due to its high electrical conductivity, copper is a very attractive material for electrical interconnects. For Cu-Cu wafer bonding the process requires typically bonding for around 1 h at 400°C and high contact pressure applied during bonding. Temperature reduction below such values is required in order to solve issues regarding (i) throughput in the wafer bonder, (ii) wafer-to-wafer misalignment after bonding and (iii) to minimise thermo-mechanical stresses or device degradation. The aim of this work was to study the physical mechanisms of Cu-Cu bonding and based on this study to further optimise the bonding process for low temperatures. The critical sample parameters (roughness, oxide, crystallinity) were identified using selected analytical techniques and correlated with the characteristics of the bonded Cu-Cu interfaces. Based on the results of this study the impact of several materials and process specifications on the bonding result were theoretically defined and experimentally proven. These fundamental findings subsequently facilitated low temperature (LT) metal thermo-compression Cu-Cu wafer bonding and even room temperature direct

Underestimated Halogen Bonds Forming with Protein Backbone in Protein Data Bank.

Science.gov (United States)

Zhang, Qian; Xu, Zhijian; Shi, Jiye; Zhu, Weiliang

2017-07-24

Halogen bonds (XBs) are attracting increasing attention in biological systems. Protein Data Bank (PDB) archives experimentally determined XBs in biological macromolecules. However, no software for structure refinement in X-ray crystallography takes into account XBs, which might result in the weakening or even vanishing of experimentally determined XBs in PDB. In our previous study, we showed that side-chain XBs forming with protein side chains are underestimated in PDB on the basis of the phenomenon that the proportion of side-chain XBs to overall XBs decreases as structural resolution becomes lower and lower. However, whether the dominant backbone XBs forming with protein backbone are overlooked is still a mystery. Here, with the help of the ratio (R F ) of the observed XBs' frequency of occurrence to their frequency expected at random, we demonstrated that backbone XBs are largely overlooked in PDB, too. Furthermore, three cases were discovered possessing backbone XBs in high resolution structures while losing the XBs in low resolution structures. In the last two cases, even at 1.80 Å resolution, the backbone XBs were lost, manifesting the urgent need to consider XBs in the refinement process during X-ray crystallography study.

Anisotropic electrical conduction and reduction in dangling-bond density for polycrystalline Si films prepared by catalytic chemical vapor deposition

Science.gov (United States)

Niikura, Chisato; Masuda, Atsushi; Matsumura, Hideki

1999-07-01

Polycrystalline Si (poly-Si) films with high crystalline fraction and low dangling-bond density were prepared by catalytic chemical vapor deposition (Cat-CVD), often called hot-wire CVD. Directional anisotropy in electrical conduction, probably due to structural anisotropy, was observed for Cat-CVD poly-Si films. A novel method to separately characterize both crystalline and amorphous phases in poly-Si films using anisotropic electrical conduction was proposed. On the basis of results obtained by the proposed method and electron spin resonance measurements, reduction in dangling-bond density for Cat-CVD poly-Si films was achieved using the condition to make the quality of the included amorphous phase high. The properties of Cat-CVD poly-Si films are found to be promising in solar-cell applications.

A Method Based on Semi-Solid Forming for Eliminating Coarse Dendrites and Shrinkage Porosity of H13 Tool Steel

Directory of Open Access Journals (Sweden)

Yifeng Guo

2018-04-01

Full Text Available A method called forging solidifying metal (FSM, which is applied for eliminating coarse dendrites and shrinkage porosity defects of ferrous alloys was proposed based on semi-solid forming technology (SSF. To verify its feasibility, the effects of liquid fraction (FL on the microstructure of the deformed H13 steel were investigated experimentally. The coarse dendrites structure still existed and cracks appeared when the 0.1/s 50% FSM method was carried out at ~20% FL. What is significantly different from that is, the elimination of the coarse dendrites structure and shrinkage porosity defects became more significant, when this method was conducted at the end of solidification (FL < 10%. The microstructure of H13 steel was significantly refined and also became dense in such condition.

Graphical reduction of reaction networks by linear elimination of species

DEFF Research Database (Denmark)

Saez Cornellana, Meritxell; Wiuf, Carsten; Feliu, Elisenda

2017-01-01

We give a graphically based procedure to reduce a reaction network to a smaller reaction network with fewer species after linear elimination of a set of noninteracting species. We give a description of the reduced reaction network, its kinetics and conservations laws, and explore properties...

75 FR 68360 - Agency Forms Undergoing Paperwork Reduction Act Review

Science.gov (United States)

2010-11-05

...] Agency Forms Undergoing Paperwork Reduction Act Review The Centers for Disease Control and Prevention... screener questionnaire will be used to determine participation eligibility and obtain oral consent. Approximately 7,000 individuals will be approached and screened (through a 2-minute interview) for eligibility...

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2012-12-26

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2012-07-09

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FE modeling of Cu wire bond process and reliability

NARCIS (Netherlands)

Yuan, C.A.; Weltevreden, E.R.; Akker, P. van den; Kregting, R.; Vreugd, J. de; Zhang, G.Q.

2011-01-01

Copper based wire bonding technology is widely accepted by electronic packaging industry due to the world-wide cost reduction actions (compared to gold wire bond). However, the mechanical characterization of copper wire differs from the gold wire; hence the new wire bond process setting and new bond

Competition of electron transfer, dissociation, and bond-forming reactions in collisions of CO22+ with neutral CO2

Czech Academy of Sciences Publication Activity Database

Ricketts, Claire; Schröder, Detlef; Roithová, Jana; Schwarz, H.; Thissen, R.; Dutuit, O.; Žabka, Ján; Herman, Zdeněk; Price, S. D.

2008-01-01

Roč. 10, č. 33 (2008), s. 5135-5143 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : carbon dioxide * bond -forming reactions * dications Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.064, year: 2008

75 FR 65489 - Agency Forms Undergoing Paperwork Reduction Act Review

Science.gov (United States)

2010-10-25

... children. The three environmental chemicals, Bisphenol A (BPA), phthalates, and mercury have been selected...] Agency Forms Undergoing Paperwork Reduction Act Review The Centers for Disease Control and Prevention (CDC) publishes a list of information collection requests under review by the Office of Management and...

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Science.gov (United States)

2010-04-20

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78 FR 24422 - Agency Forms Undergoing Paperwork Reduction Act Review

Science.gov (United States)

2013-04-25

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Glass-bonded iodosodalite waste form for immobilization of 129 I

Energy Technology Data Exchange (ETDEWEB)

Chong, Saehwa; Peterson, Jacob A.; Riley, Brian J.; Tabada, Diana; Wall, Donald; Corkhill, Claire L.; McCloy, John S.

2018-06-01

Immobilization of radioiodine (e.g., 129I, 131I) is an important need for current and future nuclear fuel cycles. For the current work, iodosodalite [Na8(AlSiO4)6I2] was synthesized hydrothermally from metakaolin, NaI, and NaOH. Following hydrothermal treatment, dried unwashed powders were used to make glass-bonded iodosodalite waste forms by heating pressed pellets at 650, 750, or 850 °C with two different types of sodium borosilicate glass binders, i.e., NBS-4 and SA-800. These heat-treated specimens were characterized with X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal analysis, porosity and density measurements, neutron activation analysis, and inductively-coupled plasma mass spectrometry. The pellets mixed with 10 mass% of NBS-4 or SA-800 and heat-treated at 750 °C contained relatively high percentage iodine retention (~44-47 % of the maximum iodine loading) with relatively low porosities, while other pellets with higher percentages iodine retention either contained higher porosity or were not completely sintered. ASTM C1308 chemical durability tests of monolithic specimens showed a large initial release of Na, Al, Si, and I on the first day, possibly from water-soluble salt crystals or non-durable amorphous phases. Release rates of Na and Si were higher than for Al and I, probably due to a poorly durable Na-Si-O phase from the glass bonding matrix. The cumulative normalized release of iodine was 12.5 g m-2 for the first 10 1-d exchanges, suggestive of coherent dissolution. The average release rate from 10-24 days during the 7-d exchange intervals was 0.2336 g m-2 d-1.

Using graphitic foam as the bonding material in metal fuel pins for sodium fast reactors

International Nuclear Information System (INIS)

Karahan, Aydın; Kazimi, Mujid S.

2013-01-01

The study evaluates the possible use of graphite foam as the bonding material between U–Pu–Zr metallic fuel and steel clad for sodium fast reactor applications using FEAST-METAL fuel performance code. Furthermore, the applicability of FEAST-METAL to the advanced fuel designs is demonstrated. Replacing the sodium bond with a chemically stable foam material would eliminate fuel clad metallurgical interactions, and allow for fuel swelling under low external stress. Hence, a significant improvement is expected for the steady state and transient performance. FEAST-METAL was used to assess the thermo-mechanical behavior of the new fuel form and a reference metallic fuel pin. Nearly unity conversion ratio, 75% smear density U–15Pu–6Zr metallic fuel pin with sodium bond, and T91 cladding was selected as a reference case. It was found that operating the reference case at high clad temperatures (600–660 °C) results in (1) excessive clad wastage formation/clad thinning due to lanthanide migration and formation of brittle phases at clad inner surface, and (2) excessive clad hoop strain at the upper axial section due mainly to the occurrence of thermal creep. The combination of these two factors may lead to cladding breach. The work concludes that replacing the sodium bond with 80% porous graphite foam and reducing the fuel smear density to 70%, it is likely that the fuel clad metallurgical interaction would be eliminated while the fuel swelling is allowed without excessive fuel clad mechanical interaction. The suggested design appears as an alternative for a high performance metallic fuel design for sodium fast reactors

Using graphitic foam as the bonding material in metal fuel pins for sodium fast reactors

Energy Technology Data Exchange (ETDEWEB)

Karahan, Aydın, E-mail: karahan@alum.mit.edu; Kazimi, Mujid S.

2013-10-15

The study evaluates the possible use of graphite foam as the bonding material between U–Pu–Zr metallic fuel and steel clad for sodium fast reactor applications using FEAST-METAL fuel performance code. Furthermore, the applicability of FEAST-METAL to the advanced fuel designs is demonstrated. Replacing the sodium bond with a chemically stable foam material would eliminate fuel clad metallurgical interactions, and allow for fuel swelling under low external stress. Hence, a significant improvement is expected for the steady state and transient performance. FEAST-METAL was used to assess the thermo-mechanical behavior of the new fuel form and a reference metallic fuel pin. Nearly unity conversion ratio, 75% smear density U–15Pu–6Zr metallic fuel pin with sodium bond, and T91 cladding was selected as a reference case. It was found that operating the reference case at high clad temperatures (600–660 °C) results in (1) excessive clad wastage formation/clad thinning due to lanthanide migration and formation of brittle phases at clad inner surface, and (2) excessive clad hoop strain at the upper axial section due mainly to the occurrence of thermal creep. The combination of these two factors may lead to cladding breach. The work concludes that replacing the sodium bond with 80% porous graphite foam and reducing the fuel smear density to 70%, it is likely that the fuel clad metallurgical interaction would be eliminated while the fuel swelling is allowed without excessive fuel clad mechanical interaction. The suggested design appears as an alternative for a high performance metallic fuel design for sodium fast reactors.

Crystallochemical transformations at low temperature reduction of molybdenum trioxide

International Nuclear Information System (INIS)

Solonin, Yu.M.

1979-01-01

Results are given of studying development of reaction products morphology at different stages of reduction of molybdenum trioxide separate crystals. It is determined that character of MoO 3 macrocrystals destruction at the first stage (MoO 3 -MoO 2 ) is determined by anisotropy of the chemical bond at the original crystal. MoO 2 nuclei are formed as intensively branched dendrite-like single crystals regularly oriented with respect to MoO 3 crystal. The degree of branching is determined by the reduction temperature and increases with its decrease. Formation of MoO 2 nuclei is proceeded by appearance of crystallographic shear planes in MoO 3 crystal. At the stage of MoO 2 -Mo transition no additional development of the reduction products surface takes place. The forming molybdenum crystals are strongly textured

Effects of aqueous environment on long-term durability of phosphate-bonded ceramic waste forms

International Nuclear Information System (INIS)

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

1996-01-01

Over the last few years, Argonne National Laboratory has been developing room-temperature-setting chemically-bonded phosphate ceramics for solidifying and stabilizing low-level mixed wastes. This technology is crucial for stabilizing waste streams that contain volatile species and off-gas secondary waste streams generated by high-temperature treatment of such wastes. Magnesium phosphate ceramic has been developed to treat mixed wastes such as ash, salts, and cement sludges. Waste forms of surrogate waste streams were fabricated by acid-base reactions between the mixtures of magnesium oxide powders and the wastes, and phosphoric acid or acid phosphate solutions. Dense and hard ceramic waste forms are produced in this process. The principal advantage of this technology is that the contaminants are immobilized by both chemical stabilization and subsequent microencapsulation of the reaction products. This paper reports the results of durability studies conducted on waste forms made with ash waste streams spiked with hazardous and radioactive surrogates. Standard leaching tests such as ANS 16.1 and TCLP were conducted on the final waste forms. Fates of the contaminants in the final waste forms were established by electron microscopy. In addition, stability of the waste forms in aqueous environments was evaluated with long-term water-immersion tests

Reductive dehalogenase structure suggests a mechanism for B12-dependent dehalogenation.

Science.gov (United States)

Payne, Karl Ap; Quezada, Carolina P; Fisher, Karl; Dunstan, Mark S; Collins, Fraser A; Sjuts, Hanno; Levy, Colin; Hay, Sam; Rigby, Stephen Ej; Leys, David

2015-01-22

Organohalide chemistry underpins many industrial and agricultural processes, and a large proportion of environmental pollutants are organohalides. Nevertheless, organohalide chemistry is not exclusively of anthropogenic origin, with natural abiotic and biological processes contributing to the global halide cycle. Reductive dehalogenases are responsible for biological dehalogenation in organohalide respiring bacteria, with substrates including polychlorinated biphenyls or dioxins. Reductive dehalogenases form a distinct subfamily of cobalamin (B12)-dependent enzymes that are usually membrane associated and oxygen sensitive, hindering detailed studies. Here we report the characterization of a soluble, oxygen-tolerant reductive dehalogenase and, by combining structure determination with EPR (electron paramagnetic resonance) spectroscopy and simulation, show that a direct interaction between the cobalamin cobalt and the substrate halogen underpins catalysis. In contrast to the carbon-cobalt bond chemistry catalysed by the other cobalamin-dependent subfamilies, we propose that reductive dehalogenases achieve reduction of the organohalide substrate via halogen-cobalt bond formation. This presents a new model in both organohalide and cobalamin (bio)chemistry that will guide future exploitation of these enzymes in bioremediation or biocatalysis.

Smear layer-deproteinizing improves bonding of one-step self-etch adhesives to dentin.

Science.gov (United States)

Thanatvarakorn, Ornnicha; Prasansuttiporn, Taweesak; Thittaweerat, Suppason; Foxton, Richard M; Ichinose, Shizuko; Tagami, Junji; Hosaka, Keiichi; Nakajima, Masatoshi

2018-03-01

Smear layer deproteinizing was proved to reduce the organic phase of smear layer covered on dentin surface. It was shown to eliminate hybridized smear layer and nanoleakage expression in resin-dentin bonding interface of two-step self-etch adhesive. This study aimed to investigate those effects on various one-step self-etch adhesives. Four different one-step self-etch adhesives were used in this study; SE One (SE), Scotchbond™ Universal (SU), BeautiBond Multi (BB), and Bond Force (BF). Flat human dentin surfaces with standardized smear layer were prepared. Smear layer deproteinizing was carried out by the application of 50ppm hypochlorous acid (HOCl) on dentin surface for 15s followed by Accel ® (p-toluenesulfinic acid salt) for 5s prior to adhesive application. No surface pretreatment was used as control. Microtensile bond strength (μTBS) and nanoleakage under TEM observation were investigated. The data were analyzed by two-way ANOVA and Tukey's post-hoc test and t-test at the significant level of 0.05. Smear layer deproteinizing significantly improved μTBS of SE, SU, and BB (player observed in control groups of SE, BB, and BF, and reticular nanoleakage presented throughout the hybridized complex in control groups of BB and BF were eliminated upon the smear layer deproteinizing. Smear layer deproteinizing by HOCl and Accel ® application could enhance the quality of dentin for bonding to one-step self-etch adhesives, resulting in the improving μTBS, eliminating hybridized smear layer and preventing reticular nanoleakage formation in resin-dentin bonding interface. Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Research on Soft Reduction Amount Distribution to Eliminate Typical Inter-dendritic Crack in Continuous Casting Slab of X70 Pipeline Steel by Numerical Model

Science.gov (United States)

Liu, Ke; Wang, Chang; Liu, Guo-liang; Ding, Ning; Sun, Qi-song; Tian, Zhi-hong

2017-04-01

To investigate the formation of one kind of typical inter-dendritic crack around triple point region in continuous casting(CC) slab during the operation of soft reduction, fully coupled 3D thermo-mechanical finite element models was developed, also plant trials were carried out in a domestic continuous casting machine. Three possible types of soft reduction amount distribution (SRAD) in the soft reduction region were analyzed. The relationship between the typical inter-dendritic cracks and soft reduction conditions is presented and demonstrated in production practice. Considering the critical strain of internal crack formation, a critical tolerance for the soft reduction amount distribution and related casing parameters have been proposed for better contribution of soft reduction to the internal quality of slabs. The typical inter-dendritic crack around the triple point region had been eliminated effectively through the application of proposed suggestions for continuous casting of X70 pipeline steel in industrial practice.

26 CFR 301.7101-1 - Form of bond and security required.

Science.gov (United States)

2010-04-01

..., bank, express or telegraph money order; (v) Secured by corporate bonds or stocks, or by bonds issued by... legal residence of the primary obligor is located; (ii) He must have property subject to execution of a... or legal residence of the primary obligor is located; (iv) He must agree not to mortgage, or...

Strength of Al and Al-Mg/alumina bonds prepared using ultrahigh vacuum diffusion bonding

International Nuclear Information System (INIS)

King, W.E.; Campbell, G.H.; Wien, W.L.; Stoner, S.L.

1994-01-01

The authors have measured the cross-breaking strength of Al and Al-Mg alloys bonded with alumina. Diffusion bonding of Al and Al-Mg alloys requires significantly more bonding time than previously thought to obtain complete bonding. In contrast to previous diffusion bonding studies, fracture morphologies are similar to those obtained in bonds formed by liquid phase reaction; i.e., bonds are as strong or stronger than the ceramic; and fracture tends to propagate in the metal for pure Al and near the interface in the ceramic for the alloys. There are indications that the fracture morphology depends on Mg content and therefore on plasticity in the metal

[Effect of sandblasting particle sizes on bonding strength between porcelain and titanium fabricated by rapid laser forming].

Science.gov (United States)

Zhang, Li-jun; Wang, Zhong-yi; Gao, Bo; Gao, Yang; Zhang, Chun-bao

2009-11-01

To evaluate the effect of sandblasting particle sizes of Al2O3 on the bonding strength between porcelain and titanium fabricated by laser rapid forming (LRF). The thermal expansion coefficient, roughness (Ra), contact angle, surface morphology of titanium surface and the bonding strength between titanium and porcelain were evaluated after the titanium surface being sandblasted using different sizes of Al2O3 (50 microm, 120 microm, 250 microm) at a pressure of 0.5 MPa. The cast titanium specimens were used as control, and were sandblasted with 50 microm Al2O3 at the same pressure. The thermal expansion coefficient of cast titanium [(9.84 +/- 0.42) x 10(-6)/ degrees C] and LRF Ti [(9.79 +/- 0.31) x 10(-6)/ degrees C) matched that of Noritake Ti-22 dentin porcelain [(8.93 +/- 0.36) x 10(-6)/ degrees C). When larger size of Al2O3 was used, the value of Ra and contact angle increased as well. There was no significant difference in bonding strength between the LRF Ti-50 microm [(25.91 +/- 1.02) MPa] and cast titanium [(26.42 +/- 1.65) MPa]. Significantly lower bonding strength was found in LRF Ti-120 microm [(21.86 +/- 1.64) MPa] and LRF Ti-250 microm [(19.96 +/- 1.03) MPa]. The bond strength between LRF Ti and Noritake Ti-22 dentin porcelain was above the lower limit value in the ISO 9693 (25 MPa) after using 50 microm Al2O3 sandblasting in 0.5MPa air pressure.

BONDING ALUMINUM METALS

Science.gov (United States)

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

1961-06-13

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

Extreme population inversion in the fragments formed by UV photoinduced S-H bond fission in 2-thiophenethiol.

Science.gov (United States)

Ingle, Rebecca A; Karsili, Tolga N V; Dennis, Gregg J; Staniforth, Michael; Stavros, Vasilios G; Ashfold, Michael N R

2016-04-28

H atom loss following near ultraviolet photoexcitation of gas phase 2-thiophenethiol molecules has been studied experimentally, by photofragment translational spectroscopy (PTS) methods, and computationally, by ab initio electronic structure calculations. The long wavelength (277.5 ≥ λ(phot) ≥ 240 nm) PTS data are consistent with S-H bond fission after population of the first (1)πσ* state. The partner thiophenethiyl (R) radicals are formed predominantly in their first excited Ã(2)A' state, but assignment of a weak signal attributable to H + R(X˜(2)A'') products allows determination of the S-H bond strength, D0 = 27,800 ± 100 cm(-1) and the Ã-X˜ state splitting in the thiophenethiyl radical (ΔE = 3580 ± 100 cm(-1)). The deduced population inversion between the à and X˜ states of the radical reflects the non-planar ground state geometry (wherein the S-H bond is directed near orthogonal to the ring plane) which, post-photoexcitation, is unable to planarise sufficiently prior to bond fission. This dictates that the dissociating molecules follow the adiabatic fragmentation pathway to electronically excited radical products. π* ← π absorption dominates at shorter excitation wavelengths. Coupling to the same (1)πσ* potential energy surface (PES) remains the dominant dissociation route, but a minor yield of H atoms attributable to a rival fragmentation pathway is identified. These products are deduced to arise via unimolecular decay following internal conversion to the ground (S0) state PES via a conical intersection accessed by intra-ring C-S bond extension. The measured translational energy disposal shows a more striking change once λ(phot) ≤ 220 nm. Once again, however, the dominant decay pathway is deduced to be S-H bond fission following coupling to the (1)πσ* PES but, in this case, many of the evolving molecules are deduced to have sufficiently near-planar geometries to allow passage through the conical intersection at extended S-H bond

Quadruple metal-metal bonds with strong donor ligands. Ultraviolet photoelectron spectroscopy of M{sub 2}(form){sub 4} (M = Cr, Mo, W; form = N,N{prime}-diphenylformamidinate)

Energy Technology Data Exchange (ETDEWEB)

Lichtenberger, D.L.; Lynn, M.A.; Chisholm, M.H.

1999-12-29

The He I photoelectron spectra of M{sub 2}(form){sub 4}(M = Cr, Mo, W; form - N,N{prime}-diphenylformamidinate) and Mo{sub 2}(cyform){sub 4} (cyform = N,N{prime}-dicyclohexylformamidinate) are presented. For comparison, the Ne I, He I, and He II photoelectron spectra of Mo{sub 2}(p-CH{sub 3}-form){sub 4} have also been obtained. The valence ionization features of these molecules are interpreted based on (1) the changes that occur with the metal and ligand substitutions, (2) the changes in photoelectron cross sections with excitation source, and (3) the changes from previously studied dimetal complexes. These photoelectron spectra are useful for revealing the effects that better electron donor ligands have on the valence electronic structure of M{sub 2}(L-L){sub 4} systems. Comparison with the He I spectra of the isoelectronic M{sub 2}(O{sub 2}CCH{sub 3}){sub 4} compounds is particularly revealing. Unlike with the more electron-withdrawing acetate ligand, several formamidinate-based ionizations derived from the nitrogen p{sub {pi}} orbitals occur among the metal-metal {sigma}, {pi}, and {delta} ionization bands. Although these formamidinate-based levels are close in energy to the occupied metal-metal bonds, they have little direct mixing interaction with them. The shift of the metal-metal bond ionizations to lower ionization energies for the formamidinate systems is primarily a consequence of the lower electronegativity of the ligand and the better {pi} donation into empty metal levels. The metal-metal {delta} orbital experiences some additional net bonding interaction with ligand orbitals of the same symmetry. Also, an additional bonding interaction from ligand-to-metal electron donation to the {delta}* orbital is identified. These spectra suggest a greater degree of metal-ligand covalency than in the related M{sub 2}(O{sub 2}CCH{sub 3}){sub 4} systems. Fenske-Hall molecular orbital and density functional (ADF) calculations agree with the assignment and

Mechanical properties of intermetallics formed during thermal aging of Cu-Al ball bonds

NARCIS (Netherlands)

Kouters, M.H.M.; Gubbels, G.H.M.; O'Halloran, O.; Rongen, R.; Weltevreden, E.R.

2011-01-01

In high power automotive electronics copper wire bonding is regarded as most promising alternative for gold wire bonding in 1st level interconnects and therefore subjected to severe functional requirements. In the Cu-Al ball bond interface the growth of intermetallic compounds may deteriorate the

Radiation-induced cleavage of disulfide bonds in proteins. Clivage radiolytique des ponts disulfure des proteines

Energy Technology Data Exchange (ETDEWEB)

Favaudon, V; Tourbez, H; Lhoste, J M [Paris-11 Univ., 91 - Orsay (FR); Houee-Levin, C [Paris-5 Univ., 75 (FR)

1991-06-01

The reduction of the disulfide bonds in apo-Riboflavin-Binding Protein (apoRBP) by the CO{sub 2}{sup -}{center dot} radical occurred under {gamma}-ray irradiation as a chain reaction whose efficiency increased upon acidification of the medium. Pulse-radiolysis analysis showed a rapid one-electron oxidation of the disulfide bonds yielding the anionic or protonated form of the disulfide radical. The main decay path of this radical under acidic conditions consisted of the rapid formation of a thiyl radical intermediate in equilibrium with the closed, cyclic form. At pH 8 the disulfide radical anion decayed via intramolecular and/or intermolecular routes including disproportionation, protein-protein crosslinking, non-dismutative recombination processes, and reaction with sulfhydryl groups in pre-reduced systems.

Experiment and simulation analysis of roll-bonded Q235 steel plate

International Nuclear Information System (INIS)

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

2016-01-01

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

Dual hydrogen-bonding motifs in complexes formed between tropolone and formic acid

Science.gov (United States)

Nemchick, Deacon J.; Cohen, Michael K.; Vaccaro, Patrick H.

2016-11-01

The near-ultraviolet π*←π absorption system of weakly bound complexes formed between tropolone (TrOH) and formic acid (FA) under cryogenic free-jet expansion conditions has been interrogated by exploiting a variety of fluorescence-based laser-spectroscopic probes, with synergistic quantum-chemical calculations built upon diverse model chemistries being enlisted to unravel the structural and dynamical properties of the pertinent ground [X˜ 1A'] and excited [A˜ 1A'(" separators="π*π )] electronic states. For binary TrOH ṡ FA adducts, the presence of dual hydrogen-bond linkages gives rise to three low-lying isomers designated (in relative energy order) as INT, EXT1, and EXT2 depending on whether docking of the FA ligand to the TrOH substrate takes place internal or external to the five-membered reaction cleft of tropolone. While the symmetric double-minimum topography predicted for the INT potential surface mediates an intermolecular double proton-transfer event, the EXT1 and EXT2 structures are interconverted by an asymmetric single proton-transfer process that is TrOH-centric in nature. The A ˜ -X ˜ origin of TrOH ṡ FA at ν˜ 00=27 484 .45 cm-1 is displaced by δ ν˜ 00=+466 .76 cm-1 with respect to the analogous feature for bare tropolone and displays a hybrid type - a/b rotational contour that reflects the configuration of binding. A comprehensive analysis of vibrational landscapes supported by the optically connected X˜ 1A' and A˜ 1A'(" separators="π*π ) manifolds, including the characteristic isotopic shifts incurred by partial deuteration of the labile TrOH and FA protons, has been performed leading to the uniform assignment of numerous intermolecular (viz., modulating hydrogen-bond linkages) and intramolecular (viz., localized on monomer subunits) degrees of freedom. The holistic interpretation of all experimental and computational findings affords compelling evidence that an external-binding motif (attributed to EXT1), rather than the

Bonding pathways of high-pressure chemical transformations

International Nuclear Information System (INIS)

Hu Anguang; Zhang Fan

2013-01-01

A three-stage bonding pathway towards high-pressure chemical transformations from molecular precursors or intermediate states has been identified by first-principles simulations. With the evolution of principal stress tensor components in the response of chemical bonding to compressive loading, the three stages can be defined as the van der Waals bonding destruction, a bond breaking and forming reaction, and equilibrium of new bonds. The three-stage bonding pathway leads to the establishment of a fundamental principle of chemical bonding under compression. It reveals that during high-pressure chemical transformation, electrons moving away from functional groups follow anti-addition, collision-free paths to form new bonds in counteracting the local stress confinement. In applying this principle, a large number of molecular precursors were identified for high-pressure chemical transformations, resulting in new materials. (fast track communication)

Reductive amination of glutaraldehyde 2,4-dinitrophenylhydrazone using 2-picoline borane and high-performance liquid chromatographic analysis.

Science.gov (United States)

Uchiyama, Shigehisa; Sakamoto, Hironari; Ohno, Akiko; Inaba, Yohei; Nakagome, Hideki; Kunugita, Naoki

2012-09-21

A typical method for the measurement of glutaraldehyde (GLA) employs 2,4-dinitrophenylhydrazine (DNPH) to form GLA-DNPhydrazone derivatives. However, this method is subject to analytical errors because GLA-DNPhydrazone is a quaternary bis-derivative and forms three geometric isomers (E-E, E-Z and Z-Z) as a result of the two C[double bond, length as m-dash]N double bonds. To overcome this issue, a method for transforming the C[double bond, length as m-dash]N double bond into a C-N single bond, using reductive amination of DNPhydrazone derivatives, has been applied. The amination reaction of GLA-DNPhydrazones with 2-picoline borane is accelerated with catalytic amounts of acid and is completed within 10 minutes in the presence of 100 mmol L(-1) phosphoric acid. Reduction of GLA-DNPhydrazone by 2-picoline borane is unique and results in the formation of N-(2,4-dinitrophenyl)-1-piperidinamine (DNPPA). NMR and LC-APCI-MS data confirmed the product identification. DNPPA is very stable and did not change when stored for at least four weeks at room temperature. DNPPA has excellent solubility of 14.6 g L(-1) at 20 °C in acetonitrile. The absorption maximum wavelength and the molar absorptivity of DNPPA were 351 nm and 4.2 × 10(4) L mol(-1) cm(-1) respectively. Complete separation between the reduced forms of C1-C10 aldehyde DNPhydrazones, including DNPPA, can be achieved by operating the reversed-phase high-performance liquid chromatograph at 351 nm in gradient mode using a C18 amide column. The reductive amination method for GLA overcomes analytical errors caused by E-E, E-Z and Z-Z geometrical isomers.

Modification of dentin surface to enamel-like structure: A potential strategy for improving dentin bonding durability, desensitizing and self-repairing

Directory of Open Access Journals (Sweden)

Hongye Yang

2014-01-01

Full Text Available Introduction: Current theories of dentin bonding are based on the concept of "hybrid layer". However, the histological complexity of dentin, as well as the vulnerability of the hybrid layer, goes against the long-term effect of dentin bonding. At the same time, post-operative sensitivity is more likely to occur after traditional adhesive restoration. The Hypothesis: Compared to dentin bonding, enamel bonding exhibits a more optimal immediate and long-term performance, owing to its higher degree of mineralization, well-arranged enamel crystals and the porous structure after etching. Moreover, "enamel hypersensitivity" is never going to happen due to the lack of tubules existing in dentin. In light of this phenomenon, we brought up the concept and the proposal method to form an "enamel-like" dentin, simulating enamel structure to achieve satisfying durability of dentin bonding and obtain good performance for preventing post-operative sensitivity. With the application of mesoporous silicon bi-directionally binding to hydroxyapatite of dentin itself and hydroxyapatite nanorods synthetized in vitro, we may be able to form an enamel-like "functional layer" via ion-regulating self-assembly. Evaluation of Hypothesis: This paper explains how to achieve dentin enamel-like modification by chemical methods, especially, details the strategies and possible mechanisms of the hypothesis. Validation of the hypothesis is more likely to eliminate the adverse effect of dentinal fluid, improve long-term performance of dentin bonding, offer strategies for desensitizing treatment and self-repairing carious-affected dentin, and furthermore, provide the possibility to introduce new theories of dentin bonding.

In Situ Study of Reduction Process of CuO Paste and Its Effect on Bondability of Cu-to-Cu Joints

Science.gov (United States)

Yao, Takafumi; Matsuda, Tomoki; Sano, Tomokazu; Morikawa, Chiaki; Ohbuchi, Atsushi; Yashiro, Hisashi; Hirose, Akio

2018-04-01

A bonding method utilizing redox reactions of metallic oxide microparticles achieves metal-to-metal bonding in air, which can be alternative to lead-rich high-melting point solder. However, it is known that the degree of the reduction of metallic oxide microparticles have an influence on the joint strength using this bonding method. In this paper, the reduction behavior of CuO paste and its effect on Cu-to-Cu joints were investigated through simultaneous microstructure-related x-ray diffraction and differential scanning calorimetry measurements. The CuO microparticles in the paste were gradually reduced to submicron Cu2O particles at 210-250°C. Subsequently, Cu nanoparticles were generated instantaneously at 300-315°C. There was a marked difference in the strengths of the joints formed at 300°C and 350°C. Thus, the Cu nanoparticles play a critical role in sintering-based bonding using CuO paste. Furthermore, once the Cu nanoparticles have formed, the joint strength increases with higher bonding temperature (from 350°C to 500°C) and pressure (5-15 MPa), which can exceed the strength of Pb-5Sn solder at higher temperature and pressure.

Elimination Voltammetry with Linear Scan as a New Detection Method for DNA Sensors

Directory of Open Access Journals (Sweden)

Rene Kizek

2005-11-01

Full Text Available The paper describes successful coupling of adsorptive transfer stripping (AdTS andelimination voltammetry with linear scan (EVLS for the resolution of reduction signals of cytosine (Cand adenine (A residues in hetero-oligodeoxynucleotides (ODNs. Short ODNs (9-mers and 20-merswere adsorbed from a small volume on a hanging mercury drop electrode (HMDE. After washing ofthe ODN-modified electrode by water and its transferring to an electrochemical cell, voltammetric curves were measured. The AdTS EVLS was able to determine of C/A ratio of ODNs through theelimination function conserving the diffusion current component and eliminating kinetic and chargingcurrent components. This function, which provides the elimination signal in a peak-counterpeak form,increased the current sensitivity for A and C resolution, and for the recognition of bases sequences inODN chains. Optimal conditions of elimination experiments such as pH, time of adsorption, and scanrate were found. The combination of EVLS with AdTS procedure can be considered as a newdetection method in a DNA sensor.

N₂reduction and hydrogenation to ammonia by a molecular iron-potassium complex.

Science.gov (United States)

Rodriguez, Meghan M; Bill, Eckhard; Brennessel, William W; Holland, Patrick L

2011-11-11

The most common catalyst in the Haber-Bosch process for the hydrogenation of dinitrogen (N(2)) to ammonia (NH(3)) is an iron surface promoted with potassium cations (K(+)), but soluble iron complexes have neither reduced the N-N bond of N(2) to nitride (N(3-)) nor produced large amounts of NH(3) from N(2). We report a molecular iron complex that reacts with N(2) and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations. The product has a Fe(3)N(2) core, implying that three iron atoms cooperate to break the N-N triple bond through a six-electron reduction. The nitride complex reacts with acid and with H(2) to give substantial yields of N(2)-derived ammonia. These reactions, although not yet catalytic, give structural and spectroscopic insight into N(2) cleavage and N-H bond-forming reactions of iron.

Analysis of factors influencing the bond strength in roll bonding processes

Science.gov (United States)

Khaledi, Kavan; Wulfinghoff, Stephan; Reese, Stefanie

2018-05-01

Cold Roll Bonding (CRB) is recognized as an industrial technique in which the metal sheets are joined together in order to produce laminate metal composites. In this technique, a metallurgical bond resulting from severe plastic deformation is formed between the rolled metallic layers. The main objective of this paper is to analyse different factors which may affect the bond formation in rolling processes. To achieve this goal, first, an interface model is employed which describes both the bonding and debonding. In this model, the bond strength evolution between the metallic layers is calculated based on the film theory of bonding. On the other hand, the debonding process is modelled by means of a bilinear cohesive zone model. In the numerical section, different scenarios are taken into account to model the roll bonding process of metal sheets. The numerical simulation includes the modelling of joining during the roll bonding process followed by debonding in a Double Cantilever Beam (DCB) peeling test. In all simulations, the metallic layers are regarded as elastoplastic materials subjected to large plastic deformations. Finally, the effects of some important factors on the bond formation are numerically investigated.

Bond-Slip Relationship for CFRP Sheets Externally Bonded to Concrete under Cyclic Loading.

Science.gov (United States)

Li, Ke; Cao, Shuangyin; Yang, Yue; Zhu, Juntao

2018-02-26

The objective of this paper was to explore the bond-slip relationship between carbon fiber-reinforced polymer (CFRP) sheets and concrete under cyclic loading through experimental and analytical approaches. Modified beam tests were performed in order to gain insight into the bond-slip relationship under static and cyclic loading. The test variables are the CFRP-to-concrete width ratio, and the bond length of the CFRP sheets. An analysis of the test results in this paper and existing test results indicated that the slope of the ascending segment of the bond-slip curve decreased with an increase in the number of load cycles, but the slip corresponding to the maximum shear stress was almost invariable as the number of load cycles increased. In addition, the rate of reduction in the slope of the ascending range of the bond-slip curve during cyclic loading decreased as the concrete strength increased, and increased as the load level or CFRP-to-concrete width ratio enhanced. However, these were not affected by variations in bond length if the residual bond length was longer than the effective bond length. A bilinear bond-slip model for CFRP sheets that are externally bonded to concrete under cyclic loading, which considered the effects of the cyclic load level, concrete strength, and CFRP-to-concrete ratio, was developed based on the existing static bond-slip model. The accuracy of this proposed model was verified by a comparison between this proposed model and test results.

Human movement data for malaria control and elimination strategic planning.

Science.gov (United States)

Pindolia, Deepa K; Garcia, Andres J; Wesolowski, Amy; Smith, David L; Buckee, Caroline O; Noor, Abdisalan M; Snow, Robert W; Tatem, Andrew J

2012-06-18

Recent increases in funding for malaria control have led to the reduction in transmission in many malaria endemic countries, prompting the national control programmes of 36 malaria endemic countries to set elimination targets. Accounting for human population movement (HPM) in planning for control, elimination and post-elimination surveillance is important, as evidenced by previous elimination attempts that were undermined by the reintroduction of malaria through HPM. Strategic control and elimination planning, therefore, requires quantitative information on HPM patterns and the translation of these into parasite dispersion. HPM patterns and the risk of malaria vary substantially across spatial and temporal scales, demographic and socioeconomic sub-groups, and motivation for travel, so multiple data sets are likely required for quantification of movement. While existing studies based on mobile phone call record data combined with malaria transmission maps have begun to address within-country HPM patterns, other aspects remain poorly quantified despite their importance in accurately gauging malaria movement patterns and building control and detection strategies, such as cross-border HPM, demographic and socioeconomic stratification of HPM patterns, forms of transport, personal malaria protection and other factors that modify malaria risk. A wealth of data exist to aid filling these gaps, which, when combined with spatial data on transport infrastructure, traffic and malaria transmission, can answer relevant questions to guide strategic planning. This review aims to (i) discuss relevant types of HPM across spatial and temporal scales, (ii) document where datasets exist to quantify HPM, (iii) highlight where data gaps remain and (iv) briefly put forward methods for integrating these datasets in a Geographic Information System (GIS) framework for analysing and modelling human population and Plasmodium falciparum malaria infection movements.

Studies toward the oxidative and reductive activation of C-S bonds in 2'-S-aryl-2'-thiouridine derivatives.

Science.gov (United States)

Rayala, Ramanjaneyulu; Giuglio-Tonolo, Alain; Broggi, Julie; Terme, Thierry; Vanelle, Patrice; Theard, Patricia; Médebielle, Maurice; Wnuk, Stanislaw F

2016-04-21

Studies directed toward the oxidative and reductive desulfurization of readily available 2'- S -aryl-2'-thiouridine derivatives were investigated with the prospect to functionalize the C2'-position of nucleosides. The oxidative desulfurization-difluorination strategy was successful on 2-(arylthio)alkanoate surrogates, while extension of the combination of oxidants and fluoride sources was not an efficient fluorination protocol when applied to 2'- S -aryl-2'-thiouridine derivatives, resulting mainly in C5-halogenation of the pyrimidine ring and C2'-monofluorination without desulfurization. Cyclic voltammetry of 2'-arylsulfonyl-2'-deoxyuridines and their 2'-fluorinated analogues showed that cleavage of the arylsulfone moiety could occur, although at relatively high cathodic potentials. While reductive-desulfonylation of 2'-arylsulfonyl-2'-deoxyuridines with organic electron donors (OEDs) gave predominantly base-induced furan type products, chemical (OED) and electrochemical reductive-desulfonylation of the α-fluorosulfone derivatives yielded the 2'-deoxy-2'-fluorouridine and 2',3'-didehydro-2',3'-dideoxy-2'-fluorouridine derivatives. These results provided good evidence of the generation of a C2'-anion through carbon-sulfur bond cleavage, opening new horizons for the reductive-functionalization approaches in nucleosides.

Studies toward the oxidative and reductive activation of C-S bonds in 2'-S-aryl-2'-thiouridine derivatives

Science.gov (United States)

Rayala, Ramanjaneyulu; Giuglio-Tonolo, Alain; Broggi, Julie; Terme, Thierry; Vanelle, Patrice; Theard, Patricia; Médebielle, Maurice; Wnuk, Stanislaw F.

2016-01-01

Studies directed toward the oxidative and reductive desulfurization of readily available 2'-S-aryl-2'-thiouridine derivatives were investigated with the prospect to functionalize the C2'-position of nucleosides. The oxidative desulfurization-difluorination strategy was successful on 2-(arylthio)alkanoate surrogates, while extension of the combination of oxidants and fluoride sources was not an efficient fluorination protocol when applied to 2'-S-aryl-2'-thiouridine derivatives, resulting mainly in C5-halogenation of the pyrimidine ring and C2'-monofluorination without desulfurization. Cyclic voltammetry of 2'-arylsulfonyl-2'-deoxyuridines and their 2'-fluorinated analogues showed that cleavage of the arylsulfone moiety could occur, although at relatively high cathodic potentials. While reductive-desulfonylation of 2'-arylsulfonyl-2'-deoxyuridines with organic electron donors (OEDs) gave predominantly base-induced furan type products, chemical (OED) and electrochemical reductive-desulfonylation of the α-fluorosulfone derivatives yielded the 2'-deoxy-2'-fluorouridine and 2',3'-didehydro-2',3'-dideoxy-2'-fluorouridine derivatives. These results provided good evidence of the generation of a C2'-anion through carbon-sulfur bond cleavage, opening new horizons for the reductive-functionalization approaches in nucleosides. PMID:27019535

Screw-vector bond graphs for kinetic-static modelling and analysis of mechanisms

International Nuclear Information System (INIS)

Bidard, Catherine

1994-01-01

This dissertation deals with the kinetic-static modelling and analysis of spatial mechanisms used in robotics systems. A framework is proposed, which embodies a geometrical and a network approach for kinetic-static modelling. For this purpose we use screw theory and bond graphs. A new form of bond graphs is introduced: the screw-vector bond graph, whose power variables are defined to be wrenches and twists expressed as intrinsic screw-vectors. The mechanism is then identified as a network, whose components are kinematic pairs and whose topology is described by a directed graph. A screw-vector Simple Junction Structure represents the topological constraints. Kinematic pairs are represented by one-port elements, defined by two reciprocal screw-vector spaces. Using dual bases of screw-vectors, a generic decomposition of kinematic pair elements is given. The reduction of kinetic-static models of series and parallel kinematic chains is used in order to derive kinetic-static functional models in geometric form. Thereupon, the computational causality assignment is adapted for the graphical analysis of the mobility and the functioning of spatial mechanisms, based on completely or incompletely specified models. (author) [fr

48 CFR 53.301-25 - Performance Bond.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 2 2010-10-01 2010-10-01 false Performance Bond. 53.301-25 Section 53.301-25 Federal Acquisition Regulations System FEDERAL ACQUISITION REGULATION (CONTINUED) CLAUSES AND FORMS FORMS Illustrations of Forms 53.301-25 Performance Bond. ER18DE98.007 ER18DE98.008 [63...

Reductive amination of aldehyde 2,4-dinitorophenylhydrazones using 2-picoline borane and high-performance liquid chromatographic analysis.

Science.gov (United States)

Uchiyama, Shigehisa; Inaba, Yohei; Matsumoto, Mariko; Suzuki, Gen

2009-01-01

A new method for the determination of carbonyls in air using 2,4-dinitrophenylhydrazine (DNPH) has been developed. The traditional method for the measurement of carbonyl compounds, using DNPH to form the corresponding 2,4-dinitrophenylhydrazone (DNPhydrazone) derivatives, is subject to analytical errors because DNPhydrazones form both E- and Z-geometrical isomers as a result of the C=N double bond. To overcome this issue, a method for transforming the C=N double bond into a C-N single bond, using reductive amination of DNPhydrazone derivatives, has been developed. Reductive amination of aldehyde DNPhydrazones was carried out by adding 2-picoline borane acetonitrile solution in eluate through the DNPH-cartridge. The amination reactions of C(1)-C(10) aldehyde DNPhydrazones were completely converted into the reduced forms within 40 min in the presence of 1 mmol/L 2-picoline borane and 20 mmol/L of phosphoric acid. These reduced forms were very stable and did not change when stored for 2 weeks at room temperature. The absorption maximum wavelengths of the reduced forms from C(1)-C(10) aldehyde DNPhydrazones were 351-352 nm and shifted 6-7 nm toward shorter wavelengths when compared to the corresponding DNPhydrazones, and the molar absorption coefficients were 1.5 x 10(4) (C(1)) to 2.2 x 10(4) L/mol/cm (C(10)). Complete separation between C(1)-C(10) aldehyde DNPhydrazones and the corresponding reduced forms can be achieved by operating the HPLC in gradient mode using an Ascentis RP-Amide column (150 mm x 4.6 mm i.d.). The RSDs of DNPhydrazone (Z + E) peak areas ranged from 0.40-0.66 and those of the corresponding reduced forms ranged from 0.26-0.41. It was shown that the reductive amination method gave improved HPLC analytical precision because of the absence of isomers.

Efektivitas Implementasi Convention On The Elimination Of All Forms Of Discrimination Against Woman (CEDAW) Terhadap Penurunan diskriminasi perempuan di Pakistan

OpenAIRE

MURSALIN, FAHIRA ULFA

2017-01-01

2017 FAHIRA ULFA MURSALIN, E 131 13 514. Skripsi yang berjudul ???Efektivitas Implementasi Convention On The Elimination Of All Form Of Discrimination Against Woman (Cedaw) Terhadap Penurunan Diskriminasi Perempuan Di Pakistan???. Di bawah bimbingan bapak H. Darwis, MA, Ph.D selaku pembimbing I dan bapak Burhanuddin, S.IP. M.SI selaku pembimbing II, pada Jurusan Ilmu Hubungan Internasional, Fakultas Ilmu Sosial dan Ilmu Politik, ...

Interface bonding of SA508-3 steel under deformation and high temperature diffusion

Science.gov (United States)

Xu, Bin; Shao, Chunjuan; Sun, Mingyue

2018-05-01

There are mainly two parameters affecting high temperature interface bonding: deformation and diffusion. To study these two parameters, interface bonding of SA508-3 bainitic steel at 1100°C are simulated by gleeble3500 thermal simulator. The results show that interface of SA508-3 steel can be bonded under deformation and high temperature. For a specimen pressed at 1100°C without further high temperature diffusion, a reduction ratio of 30% can make the interface begun to bond, but the interface is still part of the grain boundary and small grains exist near the interface. When reduction ratio reaches 50%, the interface can be completely bonded and the microstructure near the interface is the same as that of the base material. When deformation is small, long time diffusion can also help the interface bonding. The results show that when the diffusion time is long enough, the interface under small deformation can also be bonded. For a specimen holding for 24h at 1100°C, only 13% reduction ratio is enough for interface bonding.

Mucositis reduction by selective elimination of oral flora in irradiated cancers of the head and neck: a placebo-controlled double-blind randomized study

International Nuclear Information System (INIS)

Wijers, Oda B.; Levendag, Peter C.; Harms, Erik; Gan-Teng, A.M.; Schmitz, Paul I.M.; Hendriks, W.D.H.; Wilms, Erik B.; Est, Henri van der; Visch, Leo L.

2001-01-01

Purpose: The aim of the study was to test the hypothesis that aerobic Gram-negative bacteria (AGNB) play a crucial role in the pathogenesis of radiation-induced mucositis; consequently, selective elimination of these bacteria from the oral flora should result in a reduction of the mucositis. Methods and Materials: Head-and-neck cancer patients, when scheduled for treatment by external beam radiation therapy (EBRT), were randomized for prophylactic treatment with an oral paste containing either a placebo or a combination of the antibiotics polymyxin E, tobramycin, and amphotericin B (PTA group). Weekly, the objective and subjective mucositis scores and microbiologic counts of the oral flora were noted. The primary study endpoint was the mucositis grade after 3 weeks of EBRT. Results: Seventy-seven patients were evaluable. No statistically significant difference for the objective and subjective mucositis scores was observed between the two study arms (p=0.33). The percentage of patients with positive cultures of AGNB was significantly reduced in the PTA group (p=0.01). However, complete eradication of AGNB was not achieved. Conclusions: Selective elimination of AGNB of the oral flora did not result in a reduction of radiation-induced mucositis and therefore does not support the hypothesis that these bacteria play a crucial role in the pathogenesis of mucositis

N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex

Science.gov (United States)

Rodriguez, Meghan M.; Bill, Eckhard; Brennessel, William W.; Holland, Patrick L.

2011-01-01

The most common catalyst in the Haber-Bosch process for the hydrogenation of dinitrogen (N2) to ammonia is an iron surface promoted with K+, but soluble iron complexes have neither reduced the N-N bond of N2 to nitride nor produced large amounts of NH3 from N2. We report a molecular iron complex that reacts with N2 and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations. The product has a Fe3N2 core, implying that three iron atoms cooperate to break the N-N triple bond through a six-electron reduction. The nitride complex reacts with acid and with H2 to give substantial yields of N2-derived ammonia. These reactions, though not yet catalytic, give structural and spectroscopic insight into N2 cleavage and N-H bond-forming reactions of iron. PMID:22076372

Preparation of low valent technetium metal-metal bonded species via solvothermal reduction of pertechnetate salts

International Nuclear Information System (INIS)

Kerlin, W.M.; Poineau, F.; Forster, P.M.; Czerwinski, K.R.; Sattelberger, A.P.

2013-01-01

A new one-step solvothermal synthesis route for reduction of pertechnetate salts to low valent technetium metal-metal bonded dimers will be presented. The reaction of potassium pertechnetate with glacial acetic acid plus either halo acids or halo salts under in-situ hydrogen production by sodium borohydride at various temperatures yields multiple products consisting of tetraacetate Tc-Tc (II,III) and Tc-Tc (III,III) paddle wheel dimers. Solid products isolated and analyzed via Single Crystal X-ray Diffraction (SC-XRD) in these reactions consist of polymeric chains Tc 2 +5 core: Tc 2 (μ-O 2 CCH 3 ) 4 (O 2 CCH 3 ), Tc 2 (μ-O 2 CCH 3 ) 4 Cl, Tc 2 (μ-O 2 CCH 3 ) 4 Br, Tc 2 (μ-O 2 CCH 3 ) 4 I, molecular Tc 2 +5 core: Tc 2 (μ-O 2 CCH 3 ) 3 Cl 2 (H 2 O) 2 ·H 2 O, K[Tc 2 (μ-O 2 CCH 3 ) 4 Br 2 ], and molecular Tc 2 +6 core: Tc 2 (μ-O 2 CCH 3 ) 4 Cl 2 , Tc 2 (μ-O 2 CCH 3 ) 4 Br 2 . Of the compounds listed, four are newly discovered using the one-step technique and two more additions to crystal database. Additional spectroscopic (X-ray Absorbance Fine Structure, UV-Vis, and FT-IR) characterization of the new compounds will be shown and used to propose a mechanism. Analysis of the mother liquor of each reaction by UV-Vis and formation of crystals over time due to oxidation of solutions affords a possible insight into mechanism of the Tc 2 +5 to Tc 2 +6 core formation. The oxidation states of Tc-Tc dimers formed is also dependent on temperature and pH of the starting solutions and will be explained in extensive detail. These one step reactions of reducing Tc(VII) to low valent technetium provides high yield intermediates for potential waste forms, use in nuclear fuel cycle separations, and radiopharmaceuticals. (author)

Solid-state Water-mediated Transport Reduction of Nanostructured Iron Oxides

International Nuclear Information System (INIS)

Smirnov, Vladimir M.; Povarov, Vladimir G.; Voronkov, Gennadii P.; Semenov, Valentin G.; Murin, Igor' V.; Gittsovich, Viktor N.; Sinel'nikov, Boris M.

2001-01-01

The Fe 2+ /Fe 3+ ratio in two-dimensional iron oxide nanosructures (nanolayers with a thickness of 0.3-1.5 nm on silica surface) may be precisely controlled using the transport reduction (TR) technique. The species ≡-O-Fe(OH) 2 and (≡Si-O-) 2 -FeOH forming the surface monolayer are not reduced at 400-600 deg. C because of their covalent bonding to the silica surface, as demonstrated by Moessbauer spectroscopy. Iron oxide microparticles (microstructures) obtained by the impregnation technique, being chemically unbound to silica, are subjected to reduction at T ≥ 500 deg. C with formation of metallic iron in the form of α-Fe. Transport reduction of supported nanostructures (consisting of 1 or 4 monolayers) at T ≥ 600 deg. C produces bulk iron(II) silicate and metallic iron phases. The structural-chemical transformations occurring in transport reduction of supported iron oxide nanolayers are proved to be governed by specific phase processes in the nanostructures themselves

Effect of different glasses in glass bonded zeolite

International Nuclear Information System (INIS)

Lewis, M.A.; Ackerman, J.P.; Verma, S.

1995-01-01

A mineral waste form has been developed for chloride waste salt generated during the pyrochemical treatment of spent nuclear fuel. The waste form consists of salt-occluded zeolite powders bound within a glass matrix. The zeolite contains the salt and immobilizes the fission products. The zeolite powders are hot pressed to form a mechanically stable, durable glass bonded zeolite. Further development of glass bonded zeolite as a waste form requires an understanding of the interaction between the glass and the zeolite. Properties of the glass that enhance binding and durability of the glass bonded zeolite need to be identified. Three types of glass, boroaluminosilicate, soda-lime silicate, and high silica glasses, have a range of properties and are now being investigated. Each glass was hot pressed by itself and with an equal amount of zeolite. MCC-1 leach tests were run on both. Soda-lime silicate and high silica glasses did not give a durable glass bonded zeolite. Boroaluminosilicate glasses rich in alkaline earths did bind the zeolite and gave a durable glass bonded zeolite. Scanning electron micrographs suggest that the boroaluminosilicate glasses wetted the zeolite powders better than the other glasses. Development of the glass bonded zeolite as a waste form for chloride waste salt is continuing

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

Science.gov (United States)

Münchow, Eliseu A; Bottino, Marco C

2017-09-01

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

Effect of confinement on bond strength of hot-dip galvanized lap splices in concrete structures

International Nuclear Information System (INIS)

Fakhran, Mazen

2004-01-01

Galvanizing the reinforcing steel is one of the methods used to protect bars against corrosion. Galvanizing is a hot dip process where the reinforcing bars are immersed in an aqueous pre flux solution of zinc ammonium chloride at a controlled temperature between 840 and 850 degrees F. In 2001, a research program was started at AUB to evaluate experimentally the effect of hot dip galvanizing on the bond capacity of tension lap splices anchored in full-scale beam specimens designed to fail in bond splitting mode. The test results indicated that the use of galvanized bars had a negligible effect on bond strength of reinforcement in normal strength. However, galvanizing caused an average of 20 percent decrease in bond strength of reinforcement in high strength concrete. The primary objective of research reported in this thesis, is the need to find a solution to eliminate the bond reduction of galvanized bars in high strength concrete. It is significant to evaluate the positive effect of the addition of transverse reinforcement in the splice region. The hypothesis to be tested is that such transverse reinforcement will insure uniform bond stress distribution over the entire splice region, thus mobilizing all bar lugs along the splice in the stress transfer mechanism between the bar and the surrounding concrete. Such mechanism might reduce the significant decrease in bond strength in high strength concrete due to galvanizing. To achieve this objective, eighteen full-scale beam specimens were tested in positive bending. Each beam was reinforced with bars spliced in a constant moment region at midspam. The splice length was chosen in such a way that the beams failed in bond splitting of the concrete cover in the splice region. The main variables were type of coating (black or galvanized bars), bar size (20, 25 and 32 mm), and amount of transverse reinforcement in the splice region (0, 2 or 4 stirrups). The test results indicated that confinement did not have a significant

Human movement data for malaria control and elimination strategic planning

Directory of Open Access Journals (Sweden)

Pindolia Deepa K

2012-06-01

Full Text Available Abstract Recent increases in funding for malaria control have led to the reduction in transmission in many malaria endemic countries, prompting the national control programmes of 36 malaria endemic countries to set elimination targets. Accounting for human population movement (HPM in planning for control, elimination and post-elimination surveillance is important, as evidenced by previous elimination attempts that were undermined by the reintroduction of malaria through HPM. Strategic control and elimination planning, therefore, requires quantitative information on HPM patterns and the translation of these into parasite dispersion. HPM patterns and the risk of malaria vary substantially across spatial and temporal scales, demographic and socioeconomic sub-groups, and motivation for travel, so multiple data sets are likely required for quantification of movement. While existing studies based on mobile phone call record data combined with malaria transmission maps have begun to address within-country HPM patterns, other aspects remain poorly quantified despite their importance in accurately gauging malaria movement patterns and building control and detection strategies, such as cross-border HPM, demographic and socioeconomic stratification of HPM patterns, forms of transport, personal malaria protection and other factors that modify malaria risk. A wealth of data exist to aid filling these gaps, which, when combined with spatial data on transport infrastructure, traffic and malaria transmission, can answer relevant questions to guide strategic planning. This review aims to (i discuss relevant types of HPM across spatial and temporal scales, (ii document where datasets exist to quantify HPM, (iii highlight where data gaps remain and (iv briefly put forward methods for integrating these datasets in a Geographic Information System (GIS framework for analysing and modelling human population and Plasmodium falciparum malaria infection movements.

Morphology, topography, and hardness of diffusion bonded sialon to AISI 420 at different bonding time

Science.gov (United States)

Ibrahim, Nor Nurulhuda Md.; Hussain, Patthi; Awang, Mokhtar

2015-07-01

Sialon and AISI 420 martensitic stainless steel were diffusion bonded in order to study the effect of bonding time on reaction layer's growth. Joining of these materials was conducted at 1200°C under a uniaxial pressure of 17 MPa in a vacuum ranging from 5.0 to 8.0×10-6 Torr with bonding time varied for 0.5, 2, and 3 h. Thicker reaction layer was formed in longer bonded sample since the elements from sialon could diffuse further into the steel. Sialon retained its microstructure but it was affected at the initial contact with the steel to form the new interface layer. Diffusion layer grew toward the steel and it was segregated with the parent steel as a result of the difference in properties between these regions. The segregation formed a stream-like structure and its depth decreased when the bonding time was increased. The microstructure of the steel transformed into large grain size with precipitates. Prolonging the bonding time produced more precipitates in the steel and reduced the steel thickness as well. Interdiffusions of elements occurred between the joined materials and the concentrations were decreasing toward the steel and vice versa. Silicon easily diffused into the steel because it possessed lower ionization potential compared to nitrogen. Formation of silicide and other compounds such as carbides were detected in the interface layer and steel grain boundary, respectively. These compounds were harmful due to silicide brittleness and precipitation of carbides in the grain boundary might cause intergranular corrosion cracking. Sialon retained its hardness but it dropped very low at the interface layer. The absence of crack at the joint in all samples could be contributed from the ductility characteristic of the reaction layer which compensated the residual stress that was formed upon the cooling process.

Cerium, uranium, and plutonium behavior in glass-bonded sodalite, a ceramic nuclear waste form

International Nuclear Information System (INIS)

Lewis, M. A.; Lexa, D.; Morss, L. R.; Richmann, M. K.

1999-01-01

Glass-bonded sodalite is being developed as a ceramic waste form (CWF) to immobilize radioactive fission products, actinides, and salt residues from electrometallurgical treatment of spent nuclear reactor fuel. The CWF consists of about 75 mass % sodalite, 25 mass % glass, and small amounts of other phases. This paper presents some results and interpretation of physical measurements to characterize the CWF structure, and dissolution tests to measure the release of matrix components and radionuclides from the waste form. Tests have been carried out with specimens of the CWF that contain rare earths at concentrations similar to those expected in the waste form. Parallel tests have been carried out on specimens that have uranium or plutonium as well as the rare earths at concentrations similar to those expected in the waste forms; in these specimens UCl 3 forms UO 2 and PuCl 3 forms PuO 2 . The normalized releases of rare earths in dissolution tests were found to be much lower than those of matrix elements (B, Si, Al, Na). When there is no uranium in the CWF, the release of cerium is two to ten times lower than the release of the other rare earths. The low release of cerium may be due to its tetravalent state in uranium-free CWF. However, when there is uranium in the CWF, the release of cerium is similar to that of the other rare earths. This trivalent behavior of cerium is attributed to charge transfer or covalent interactions among cerium, uranium, and oxygen in (U,Ce)O 2

Mechanism of bonding and debonding using surface activated bonding method with Si intermediate layer

Science.gov (United States)

Takeuchi, Kai; Fujino, Masahisa; Matsumoto, Yoshiie; Suga, Tadatomo

2018-04-01

Techniques of handling thin and fragile substrates in a high-temperature process are highly required for the fabrication of semiconductor devices including thin film transistors (TFTs). In our previous study, we proposed applying the surface activated bonding (SAB) method using Si intermediate layers to the bonding and debonding of glass substrates. The SAB method has successfully bonded glass substrates at room temperature, and the substrates have been debonded after heating at 450 °C, in which TFTs are fabricated on thin glass substrates for LC display devices. In this study, we conducted the bonding and debonding of Si and glass in order to understand the mechanism in the proposed process. Si substrates are also successfully bonded to glass substrates at room temperature and debonded after heating at 450 °C using the proposed bonding process. By the composition analysis of bonding interfaces, it is clarified that the absorbed water on the glass forms interfacial voids and cause the decrease in bond strength.

Influence of Laser Activated Irrigation with Erbium Lasers on Bond Strength of Inidividually Formed Fiber Reinforced Composite Posts to Root Canal Dentin

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Ivana Miletić

2016-01-01

Full Text Available 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.

Comparison of the effect of hydrogel and solution forms of sodium ascorbate on orthodontic bracket-enamel shear bond strength immediately after bleaching: An in vitro study

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Kimyai Soodabeh

2010-01-01

Full Text Available Aim: This study compared the effects of hydrogel and solution forms of sodium ascorbate (SA with two different application times on bracket bond strength subsequent to bleaching. Materials and Methods: A total of 72 sound premolars were randomly divided into six groups (n = 12: An unbleached control group (group one and five experimental groups of carbamide peroxide. Specimens in group two were bonded immediately after bleaching; specimens in groups three and four were bleached, then treated with SA solution for ten minutes and three hours, respectively, and then bonded. In groups five and six, SA hydrogel was used and the specimens were prepared similar to groups three and four, respectively. Following debonding, bond strengths were recorded in MPa. To evaluate the amount of resin left on the enamel surfaces, adhesive remnant index (ARI scores were used. Statistical Analysis: The bond strength data were analyzed with ANOVA and pairwise comparisons were made by Tukey test. The ARI data were subjected to Kruskal-Wallis test and two-by-two comparisons were made by the Mann-Whitney U test. Results: There were significant differences in bond strengths between the groups ( P < 0.0005. However, the differences between groups three, four, five and six were not significant. Furthermore, there were no significant differences between group one and groups four and six, whereas the differences between the other groups were significant ( P < 0.05. Regarding ARI, there were significant differences among the groups ( P = 0.004. Conclusion: Bleaching significantly decreased the bracket bond strength. Compromised bonding was reversed with a three-hour application of both forms of SA.

The study of forms of bonding marshmallow moisture with different composition by method of thermal analysis

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G. O. Magomedov

2017-01-01

Full Text Available Marshmallow is a sugar confectionary product with increased sugar content and energy value because of the significant content of carbohydrates, in particular sugar-sand. The main drawback of marshmallow is the rapid process of its drying during storage due to the crystallization of sucrose and the gradual removal of moisture from the product. A method for obtaining marshmallow without sugar on the basis of high-conversion glucose syrup. In the work, experimental studies were carried out to determine the content and ratio of free and bound forms of moisture in marshmallow on the basis of sugars and on the basis of  high-conversion glucose syrup by Differential Scanning Calorimetry (DSC and Thermogravimetry (TG. To study the patterns of thermal effects on the properties of marshmallow samples, the non-isothermal analysis method and the synchronous thermal analysis instrument (TG-DTA / DSC of the STA 449 F3 Jupiter were used. In the process of thermal exposure, the samples decompose sugars and other organic compounds, as a result of which the sample weight decreases due to evaporation of moisture. The process of dehydration in a control sample of marshmallow using sugar occurs in a less wide temperature range than in a sample of marshmallow on the basis of  high-conversion glucose syrup, which indicates a greater degree of moisture bonding in the developed sample. A quantitative evaluation of the forms of moisture bonding in the samples was carried out using the experimental curves obtained by the TG method. From the temperature curves, the endothermic effects were determined, which correspond to the release of moisture with different forms and energies. Substitution of sugar for treacle in the formula of marshmallow reduces the share of free moisture and increases the safety of the product without signs of staling.

Bond strength and stress measurements in thermal barrier coatings

Energy Technology Data Exchange (ETDEWEB)

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

1995-10-01

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

Organometallic Methods for Forming and Cleaving Carbon-Carbon Bonds

DEFF Research Database (Denmark)

Christensen, Stig Holden

with concomitant C-C bond formation was studied with a number of Grignard reagents. The transformation was performed in a sealed vial by heating to about 160 °C in an aluminum block or at 180 °C in a microwave oven. Good yields of the product alcohols were obtained with allyl- and benzylmagnesium halides when...

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

Science.gov (United States)

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

2011-05-24

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

Effect of cariogenic challenge on the stability of dentin bonds

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Fernanda Blos BORGES

2014-01-01

Full Text Available Objective: The oral environment is subject to biofilm accumulation and cariogenic challenge, and few studies exist on the effect of these factors on the bond strength of adhesive systems. The aim of this study was to test if the exposure of adhesive interfaces to cariogenic challenge under biofilm accumulation could promote higher degradation than the exposure to biofilm accumulation alone. Material And Methods: Five molars were ground until exposure of medium dentin and then restored (Single Bond 2 and Z250 3M ESPE. The tooth/resin sets were cut to obtain beam-shaped specimens, which were distributed according to the aging conditions (n=20: water for 24 h (control; biofilm under cariogenic challenge for 3, 5 or 10 days; biofilm without cariogenic challenge for 10 days; and water for 3 months. Microcosm biofilms were formed from human saliva and grown in a saliva analogue medium, supplemented or not with sucrose to promote cariogenic challenge. Specimens were tested for microtensile bond strength, and failure modes were classified using light microscopy. Bond strength data were analyzed using ANOVA and failure modes were analyzed using ANOVA on ranks (α=0.05. Results: No significant differences in bond strength were detected among the aging methods (P=0.248. The aging period was associated with an increase in the frequency of adhesive failures for the groups aged for 10 days or longer (P<0.001. Conclusion: Aging leads to a higher prevalence of interfacial adhesive failures, although this effect is not associated with cariogenic challenge or reduction in bond strengths.

Role of dissimilatory sulfate reduction in wetlands constructed for acid coal mine drainage (AMD) treatment. Master's thesis

International Nuclear Information System (INIS)

Taddeo, F.J.

1991-01-01

Five constructed wetlands with different organic substrates were exposed to the same quantity/quality of acid mine drainage (AMD). During the 16-month exposure to AMD, all wetlands accumulated S in the forms of organic and reduced inorganic S and Fe in the form of iron sulfides. Iron sulfide and probably most of the organic S(C-bonded S) accumulation were end products of bacterial dissimilatory sulfate reduction. Results of study support the notion that sulfate reduction and accumulation of Fe sulfides contribute to Fe retention in wetlands exposed to AMD. Detailed information is provided

Method to improve commercial bonded SOI material

Science.gov (United States)

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.

Synthesis, Anti-HCV, Antioxidant and Reduction of Intracellular Reactive Oxygen Species Generation of a Chlorogenic Acid Analogue with an Amide Bond Replacing the Ester Bond.

Science.gov (United States)

Wang, Ling-Na; Wang, Wei; Hattori, Masao; Daneshtalab, Mohsen; Ma, Chao-Mei

2016-06-08

Chlorogenic acid is a well known natural product with important bioactivities. It contains an ester bond formed between the COOH of caffeic acid and the 3-OH of quinic acid. We synthesized a chlorogenic acid analogue, 3α-caffeoylquinic acid amide, using caffeic and quinic acids as starting materials. The caffeoylquinc acid amide was found to be much more stable than chlorogenic acid and showed anti-Hepatitis C virus (anti-HCV) activity with a potency similar to chlorogenic acid. The caffeoylquinc acid amide potently protected HepG2 cells against oxidative stress induced by tert-butyl hydroperoxide.

Interstellar hydrogen bonding

Science.gov (United States)

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

2018-06-01

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

Elimination device for decontaminated surface layers

International Nuclear Information System (INIS)

Yoshikawa, Kozo.

1983-01-01

Purpose: To conduct efficient decontamination injecting solid carbon dioxide particles at a high speed by using a simple and compact device. Constitution: Liquid carbon dioxide is injected from a first vessel containing liquid carbon dioxide by way of a carbon dioxide supply tube to a solid carbon dioxide particle jetting device. The liquid carbon dioxide is partially converted into fine solid carbon dioxide particles due to the temperature reduction caused by adiabatic expansion of the gaseous carbon dioxide in an expansion space for the gaseous carbon dioxide formed in the jetting device and arrives at a solid carbon dioxide injection nozzle in communication with the expansion space. Then, the fine solid carbon dioxide particles are further cooled and accelerated by the nitrogen gas jetted out from a nitrogen gas nozzle at the top of a nitrogen gas supply tube in communication with a second vessel containing liquid nitrogen disposed within the nozzle, and jetted out from the solid carbon dioxide injection nozzle to collide against the surface to be decontaminated and eliminate the surface contamination. (Seki, T.)

Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

Science.gov (United States)

Grigg, R David; Van Hoveln, Ryan; Schomaker, Jennifer M

2012-10-03

A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.

Hot Roll Bonding of Aluminum to Twin-Roll Cast (TRC) Magnesium and Its Subsequent Deformation Behavior

Science.gov (United States)

Saleh, H.; Schmidtchen, M.; Kawalla, R.

2018-02-01

In an experiment in which twin-roll cast AZ31 magnesium alloy and commercial purity aluminum (AA 1050) sheets were bonded by hot rolling as Al/Mg/Al laminate composites, it was found that increasing the preheating temperatures up to 400 °C enhances the bonding strength of composites. Further increases in the preheating temperatures accelerate the magnesium oxide growth and thus reduce the bonding strength. The influence of the reduction ratio on the bonding properties was also studied, whereby it was observed that increasing the rolling reduction led to an increase in the bonding strength. The experimental results show that the optimum bonding strength can be obtained at rolling temperatures of 375-400 °C with a 50-60% reduction in thickness. On the other hand, the subsequent deformation behavior of composite was assessed using plane strain compression and deep drawing tests. We demonstrate that the composites produced using the optimum roll bonding conditions exhibited sufficient bonding during subsequent deformation and did not reveal any debonding at the bonding interface.

Bond Potential of Lithium Disilicate to Heat-Cured Polymethylmethacrylate (PMMA)

Science.gov (United States)

2015-06-01

system eliminates the need for flasking, boil-out, and long processing times. Instead, the base is light-cured while the teeth are placed with a VLC set...component of previous studies causing failure can be challenged . The stronger ceramic may be durable enough to more accurately measure the bond strength

Single-crystal micromachining using multiple fusion-bonded layers

Science.gov (United States)

Brown, Alan; O'Neill, Garry; Blackstone, Scott C.

2000-08-01

Multi-layer structures have been fabricated using Fusion bonding. The paper shows void free layers of between 2 and 100 microns that have been bonded to form multi-layer structures. Silicon layers have been bonded both with and without interfacial oxide layers.

CD44 Binding to Hyaluronic Acid Is Redox Regulated by a Labile Disulfide Bond in the Hyaluronic Acid Binding Site.

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Helena Kellett-Clarke

Full Text Available CD44 is the primary leukocyte cell surface receptor for hyaluronic acid (HA, a component of the extracellular matrix. Enzymatic post translational cleavage of labile disulfide bonds is a mechanism by which proteins are structurally regulated by imparting an allosteric change and altering activity. We have identified one such disulfide bond in CD44 formed by Cys77 and Cys97 that stabilises the HA binding groove. This bond is labile on the surface of leukocytes treated with chemical and enzymatic reducing agents. Analysis of CD44 crystal structures reveal the disulfide bond to be solvent accessible and in the-LH hook configuration characteristic of labile disulfide bonds. Kinetic trapping and binding experiments on CD44-Fc chimeric proteins show the bond is preferentially reduced over the other disulfide bonds in CD44 and reduction inhibits the CD44-HA interaction. Furthermore cells transfected with CD44 no longer adhere to HA coated surfaces after pre-treatment with reducing agents. The implications of CD44 redox regulation are discussed in the context of immune function, disease and therapeutic strategies.

Ultrafast Hydrogen-Bonding Dynamics in Amyloid Fibrils.

Science.gov (United States)

Pazos, Ileana M; Ma, Jianqiang; Mukherjee, Debopreeti; Gai, Feng

2018-06-08

While there are many studies on the subject of hydrogen bonding dynamics in biological systems, few, if any, have investigated this fundamental process in amyloid fibrils. Herein, we seek to add insight into this topic by assessing the dynamics of a hydrogen bond buried in the dry interface of amyloid fibrils. To prepare a suitable model peptide system for this purpose, we introduce two mutations into the amyloid-forming Aβ(16-22) peptide. The first one is a lysine analog at position 19, which is used to help form structurally homogeneous fibrils, and the second one is an aspartic acid derivative (DM) at position 17, which is intended (1) to be used as a site-specific infrared probe and (2) to serve as a hydrogen-bond acceptor to lysine so that an inter-β-sheet hydrogen bond can be formed in the fibrils. Using both infrared spectroscopy and atomic force microscopy, we show that (1) this mutant peptide indeed forms well defined fibrils, (2) when bulk solvent is removed, there is no detectable water present in the fibrils, (3) infrared results obtained with the DM probe are consistent with a protofibril structure that is composed of two antiparallel β-sheets stacked in a parallel fashion, leading to formation of the expected hydrogen bond. Using two-dimensional infrared spectroscopy, we further show that the dynamics of this hydrogen bond occur on a timescale of ~2.3 ps, which is attributed to the rapid rotation of the -NH3+ group of lysine around its Cε-Nζ bond. Taken together, these results suggest that (1) DM is a useful infrared marker in facilitating structure determination of amyloid fibrils and (2) even in the tightly packed core of amyloid fibrils certain amino acid sidechains can undergo ultrafast motions, hence contributing to the thermodynamic stability of the system.

Cladding of aluminum on AISI 304L stainless steel by cold roll bonding: Mechanism, microstructure, and mechanical properties

Energy Technology Data Exchange (ETDEWEB)

Akramifard, H.R., E-mail: akrami.1367@ut.ac.ir [School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, P.O. Box 11155-4563, Tehran (Iran, Islamic Republic of); Mirzadeh, H., E-mail: hmirzadeh@ut.ac.ir [School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, P.O. Box 11155-4563, Tehran (Iran, Islamic Republic of); Advanced Metalforming and Thermomechanical Processing Laboratory, School of Metallurgy and Materials Engineering, University of Tehran, Tehran (Iran, Islamic Republic of); Parsa, M.H., E-mail: mhparsa@ut.ac.ir [School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, P.O. Box 11155-4563, Tehran (Iran, Islamic Republic of); Center of Excellence for High Performance Materials, School of Metallurgy and Materials Engineering, University of Tehran, Tehran (Iran, Islamic Republic of); Advanced Metalforming and Thermomechanical Processing Laboratory, School of Metallurgy and Materials Engineering, University of Tehran, Tehran (Iran, Islamic Republic of)

2014-09-08

The AA1050 aluminum alloy and AISI 304L stainless steel sheets were stacked together to fabricate Al/304L/Al clad sheet composites by the cold roll bonding process, which was performed at temperatures of ∼100 and 23 °C to produce austenitic and austenitic–martensitic microstructures in the AISI 304L counterpart, respectively. The peel test results showed that the threshold reduction required to make a suitable bond at room temperature is below 10%, which is significantly lower than the required reduction for cold roll bonding of Al sheets. The tearing of the Al sheet during the peel test signified that the bond strength of the roll bonded sheets by only 38% reduction has reached the strength of Al, which is a key advantage of the developed sheets. The extrusion of Al through the surface cracks and settling inside the 304L surface valleys due to strong affinity between Al and Fe was found to be the bonding mechanism. Subsequently, the interface and tensile behaviors of three-layered clad sheets after soaking at 200–600 °C for 1 h were investigated to characterize the effect of annealing treatment on the formation and thickening of intermetallic compound layer and the resultant mechanical properties. Field emission scanning electron microscopy, X-ray diffraction, and optical microscopy techniques revealed that an intermediate layer composed mainly of Al{sub 13}Fe{sub 4}, FeC and Al{sub 8}SiC{sub 7} forms during annealing at 500–600 °C. A significant drop in tensile stress–strain curves after the maximum point (UTS) was correlated to the interface debonding. It was found that the formation of intermediate layer by post heat treatment deteriorates the bond quality and encourages the debonding process. Moreover, the existence of strain-induced martensite in clad sheets was found to play a key role in the enhancement of tensile strength.

A pin-assisted retention technique for resin-bonded restorations.

Science.gov (United States)

Miara, P; Touati, B

1992-09-01

The value of pins for auxiliary retention has been demonstrated many times. The use of pins with resin-bonded restorations allows for improved aesthetics and less tooth reduction while increasing resistance to dislodging forces. Clinical and technical procedures for resin-bonded bridges with pin-assisted retention are presented.

Elimination of Plasmodium falciparum malaria in Tajikistan.

Science.gov (United States)

Kondrashin, Anatoly V; Sharipov, Azizullo S; Kadamov, Dilshod S; Karimov, Saifuddin S; Gasimov, Elkhan; Baranova, Alla M; Morozova, Lola F; Stepanova, Ekaterina V; Turbabina, Natalia A; Maksimova, Maria S; Morozov, Evgeny N

2017-05-30

Malaria was eliminated in Tajikistan by the beginning of the 1960s. However, sporadic introduced cases of malaria occurred subsequently probably as a result of transmission from infected mosquito Anopheles flying over river the Punj from the border areas of Afghanistan. During the 1970s and 1980s local outbreaks of malaria were reported in the southern districts bordering Afghanistan. The malaria situation dramatically changed during the 1990s following armed conflict and civil unrest in the newly independent Tajikistan, which paralyzed health services including the malaria control activities and a large-scale malaria epidemic occurred with more than 400,000 malaria cases. The malaria epidemic was contained by 1999 as a result of considerable financial input from the Government and the international community. Although Plasmodium falciparum constituted only about 5% of total malaria cases, reduction of its incidence was slower than that of Plasmodium vivax. To prevent increase in P. falciparum malaria both in terms of incidence and territory, a P. falciparum elimination programme in the Republic was launched in 200, jointly supported by the Government and the Global Fund for control of AIDS, tuberculosis and malaria. The main activities included the use of pyrethroids for the IRS with determined periodicity, deployment of mosquito nets, impregnated with insecticides, use of larvivorous fishes as a biological larvicide, implementation of small-scale environmental management, and use of personal protection methods by population under malaria risk. The malaria surveillance system was strengthened by the use of ACD, PCD, RCD and selective use of mass blood surveys. All detected cases were timely epidemiologically investigated and treated based on the results of laboratory diagnosis. As a result, by 2009, P. falciparum malaria was eliminated from all of Tajikistan, one year ahead of the originally targeted date. Elimination of P. falciparum also contributed towards

Energetics and chemical bonding of the 1,3,5-tridehydrobenzene triradical and its protonated form

International Nuclear Information System (INIS)

Hue Minh Thi Nguyen; Hoeltzl, Tibor; Gopakumar, G.; Veszpremi, Tamas; Peeters, Jozef; Minh Tho Nguyen

2005-01-01

Quantum chemical calculations were applied to investigate the electronic structure of the parent 1,3,5-tridehydrobenzene triradical (C 6 H 3 , TDB) and its anion (C 6 H 3 - ), cation (C 6 H 3 + ) and protonated form (C 6 H 4 + ). Our results obtained using the state-averaged complete active space self-consistent-field (CASSCF) followed by second-order multi-state multi-configuration perturbation theory, MS-CASPT2, and MRMP2 in conjunction with the large ANO-L and 6-311++G(3df,2p) basis set, confirm and reveal the followings: (i) TDB has a doublet 2 A 1 ground state with a 4 B 2 - 2 A 1 energy gap of 29kcal/mol, (ii) the ground state of the C 6 H 3 - anion in the triplet 3 B 2 being 4kcal/mol below the 1 A 1 state. (iii) the electron affinity (EA), ionization energy (IE) and proton affinity (PA) are computed to be: EA=1.6eV, IE=7.2eV, PA=227kcal/mol using UB3LYP/6-311++G(3df,2p)+ZPE; standard heat of formation ΔH f(298K,1atm) (TDB)=179+/-2kcal/mol was calculated with CBS-QB3 method. An atoms-in-molecules (AIM) analysis of the structure reveals that the topology of the electron density is similar in all compounds: hydrogens connect to a six-membered ring, except for the case of the 2 A 2 state of C 6 H 4 + (MBZ + ) which is bicyclic with fused five- and three-membered rings. Properties of the chemical bonds were characterized with Electron Localization Function (ELF) analysis, as well as Wiberg indices, Laplacian and spin density maps. We found that the radicals form separate monosynaptic basins on the ELF space, however its pair character remains high. In the 2 A 1 state of TDB, the radical center is mainly localized on the C1 atom, while in the 2 B 2 state it is equally distributed between the C3 and C5 atoms and, due to the symmetry, in the 4 B 2 state the C1, C2 and C3 atoms have the same radical character. There is no C3-C5 bond in the 2 A 1 state of TDB, but the interaction between these atoms is strong. The ground state of cation C 6 H 3 + (DHP), 1 A 1 , is

Indirect Versus Direct Heating of Sheet Materials: Superplastic Forming and Diffusion Bonding Using Lasers

Science.gov (United States)

Jocelyn, Alan; Kar, Aravinda; Fanourakis, Alexander; Flower, Terence; Ackerman, Mike; Keevil, Allen; Way, Jerome

2010-06-01

Many from within manufacturing industry consider superplastic forming (SPF) to be ‘high tech’, but it is often criticized as too complicated, expensive, slow and, in general, an unstable process when compared to other methods of manipulating sheet materials. Perhaps, the fundamental cause of this negative perception of SPF, and also of diffusion bonding (DB), is the fact that the current process of SPF/DB relies on indirect sources of heating to produce the conditions necessary for the material to be formed. Thus, heat is usually derived from the electrically heated platens of hydraulic presses, to a lesser extent from within furnaces and, sometimes, from heaters imbedded in ceramic moulds. Recent evaluations of these isothermal methods suggest they are slow, thermally inefficient and inappropriate for the process. In contrast, direct heating of only the material to be formed by modern, electrically efficient, lasers could transform SPF/DB into the first choice of designers in aerospace, automotive, marine, medical, architecture and leisure industries. Furthermore, ‘variable temperature’ direct heating which, in theory, is possible with a laser beam(s) may provide a means to control material thickness distribution, a goal of enormous importance as fuel efficient, lightweight structures for transportation systems are universally sought. This paper compares, and contrasts, the two systems and suggests how a change to laser heating might be achieved.

Methyl group dynamics in paracetamol and acetanilide: probing the static properties of intermolecular hydrogen bonds formed by peptide groups

Science.gov (United States)

Johnson, M. R.; Prager, M.; Grimm, H.; Neumann, M. A.; Kearley, G. J.; Wilson, C. C.

1999-06-01

Measurements of tunnelling and librational excitations for the methyl group in paracetamol and tunnelling excitations for the methyl group in acetanilide are reported. In both cases, results are compared with molecular mechanics calculations, based on the measured low temperature crystal structures, which follow an established recipe. Agreement between calculated and measured methyl group observables is not as good as expected and this is attributed to the presence of comprehensive hydrogen bond networks formed by the peptide groups. Good agreement is obtained with a periodic quantum chemistry calculation which uses density functional methods, these calculations confirming the validity of the one-dimensional rotational model used and the crystal structures. A correction to the Coulomb contribution to the rotational potential in the established recipe using semi-emipircal quantum chemistry methods, which accommodates the modified charge distribution due to the hydrogen bonds, is investigated.

Rh-Catalyzed (5+2) Cycloadditions of 3-Acyloxy-1,4-enynes and Alkynes: Computational Study of Mechanism, Reactivity, and Regioselectivity

Science.gov (United States)

Xu, Xiufang; Liu, Peng; Shu, Xing-zhong; Tang, Weiping; Houk, K. N.

2013-01-01

The mechanism of Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enyne (ACE) and alkynes is investigated using density functional theory calculations. The catalytic cycle involves 1,2-acyloxy migration, alkyne insertion, and reductive elimination to form the cycloheptatriene product. In contrast to the (5+2) cycloadditions with vinylcyclopropanes (VCP), in which alkyne inserts into a rhodium-allyl bond, alkyne insertion into a Rh–C(sp2) bond is preferred. The 1,2-acyloxy migration is found to be the rate-determining step of the catalytic cycle. The electron-rich p-dimethylaminobenzoate substrate promotes 1,2-acyloxy migration and significantly increases the reactivity. In the regioselectivity-determining alkyne insertion step, the alkyne substituent prefers to be distal to the forming C–C bond and thus distal to the OAc group in the product. PMID:23725341

Effect of interlayer bonding quality of asphalt layers on pavement performance

Science.gov (United States)

Jaskula, Piotr; Rys, Dawid

2017-09-01

The quality of interlayer bonding at the interfaces between the asphalt layers in flexible pavements affects the overall pavement performance. Lack or partial lack of interlayer bonding between asphalt layers can cause pavement’s premature failures such as rutting, slippage of the wearing course, cracking or simply a reduction in the calculated fatigue life of the pavement structure. This paper shows the case studies of investigation of actual or potential premature failure of newly reconstructed and constructed pavements where low quality of interlayer bonding has a dominant meaning. In situ and laboratory tests were performed and followed by analytical calculation of pavement structure where thicknesses of layers and maximum shear strengths obtained from the tests were used. During the investigation it was found out that a low quality of tack coat as well as the same aggregate gradation in the bonded asphalt mixtures were the main reasons behind the weak quality of interlayer bonding. Partial interlayer bonding has a strong influence on reduction of calculated fatigue life of pavement. The summary of the paper includes recommendations on how to avoid the low quality of interlayer bonding of asphalt layers.

Comparison of the corrosion behaviors of the glass-bonded sodalite ceramic waste form and reference HLW glasses

International Nuclear Information System (INIS)

Ebert, W. L.; Lewis, M. A.

1999-01-01

A glass-bonded sodalite ceramic waste form is being developed for the long-term immobilization of salt wastes that are generated during spent nuclear fuel conditioning activities. A durable waste form is prepared by hot isostatic pressing (HIP) a mixture of salt-loaded zeolite powders and glass frit. A mechanistic description of the corrosion processes is being developed to support qualification of the CWF for disposal. The initial set of characterization tests included two standard tests that have been used extensively to study the corrosion behavior of high level waste (HLW) glasses: the Material Characterization Center-1 (MCC-1) Test and the Product Consistency Test (PCT). Direct comparison of the results of tests with the reference CWF and HLW glasses indicate that the corrosion behaviors of the CWF and HLW glasses are very similar

Co-Au core-shell nanocrystals formed by sequential ion implantation into SiO2

International Nuclear Information System (INIS)

Kluth, P.; Hoy, B.; Johannessen, B.; Dunn, S. G.; Foran, G. J.; Ridgway, M. C.

2006-01-01

Co-Au core-shell nanocrystals (NCs) were formed by sequential ion implantation of Au and Co into thin SiO 2 . The NCs were investigated by means of transmission electron microscopy and extended x-ray absorption fine structure spectroscopy. The latter reveals a bond length expansion in the Co core compared to monatomic Co NCs. Concomitantly, a significant contraction of the bond length and a significant reduction of the effective Au-Au coordination number were observed in the Au shells. Increased Debye-Waller factors indicate significant strain in the NCs. These experimental results verify recent theoretical predictions

Synthesis of calcium arsenoalginate form elimination the arseniate ions in contaminated water

International Nuclear Information System (INIS)

Prieto Garcia, Francisco; Otazo Sanchez, Elena M; Gordillo Martinez, Alberto J and others

2007-01-01

Synthesis of calcium arsenoalginate was optimized using common sodium alginate, CaCl 2 and NaH 2 AsO 4 which brought the arsenic. In order to evaluate the co-precipitation efficiency and elimination of arsenic, several concentrations of as, ranging from 20 to 1000 μg.L 1 was tested including real contaminated water containing 480 μgL 1 of arsenic. optimized results, by means of factorial design matrix, pointed out the best synthesis conditions; sodium alginate concentration of 1.0 gL 1 pH 6, CaCl 2 concentration between 400-500 mgL 1 and room temperature. Re-dissolution of the precipitates is promoted than sedimentation when temperature is greater than room temperature. The precipitates are crystalline solids that in future studies will be characterized more extensively in order to elucidate potential applications. In contaminated water the arsenic was eliminated with an efficiency of 96% these result allows to consider that is possible to reduce arsenic concentration until levels according to Mexican standard

Water and saliva contamination effect on shear bond strength of brackets bonded with a moisture-tolerant light cure system.

Science.gov (United States)

Vicente, Ascensión; Mena, Ana; Ortiz, Antonio José; Bravo, Luis Alberto

2009-01-01

To evaluate the effects of water and saliva contamination on shear bond strength of brackets bonded with a moisture-tolerant light cure system. Brackets were bonded to 240 bovine lower incisors divided into 12 groups. Four bonding procedures were evaluated, including (1) TSEP/Transbond XT, (2) TMIP/ Transbond XT, (3) TSEP/Transbond PLUS, and (4) TMIP/Transbond PLUS, each under three different bonding conditions: without contamination, with water contamination, and with saliva contamination. Shear bond strength was measured with a universal testing machine. The adhesive remnant on the teeth was quantified with the use of image analyzing equipment. Without contamination, bond strengths for the four procedures were similar (P > .05). TSEP/Tranbond PLUS and TMIP/Transbond PLUS left significantly less adhesive on the teeth after debonding than TSEP/Transbond XT and TMIP/Transbond XT (P .017), although for TMIP/ Transbond XT, both variables showed significant reductions after contamination (P < .017). TSEP/Transbond PLUS, TMIP/Transbond PLUS, and TSEP/Transbond XT showed greater tolerance to wet conditions than was shown by TMIP/Transbond XT.

Properties of glass-bonded zeolite monoliths

International Nuclear Information System (INIS)

Lewis, M.A.; Fischer, D.F.; Murphy, C.D.

1994-01-01

It has been shown that mineral waste forms can be used to immobilize waste salt generated during the pyrochemical processing of spent fuel from the Integral Fast Reactor (IFR). Solid, leach resistant monoliths were formed by hot-pressing mixtures of salt-occluded zeolite A powders and glass frit at 990 K and 28 MPa. Additional samples have now been fabricated and tested. Normalized release rates for all elements, including iodide and chloride, were less than 1 g/m 2 d in 28-day tests in deionized water and in brine at 363 K (90 degrees C). Preliminary results indicate that these rates fall with time with both leachants and that the zeolite phase in the glass-bonded zeolite does not function as an ion exchanger. Some material properties were measured. The Poisson ratio and Young's modulus were slightly smaller in glass-bonded zeolite than in borosilicate glass. Density depended on zeolite fraction. The glass-bonded zeolite represents a promising mineral waste form for IFR salt

Fullerene-catalyzed reduction of azo derivatives in water under UV irradiation

KAUST Repository

Guo, Yong; Li, Wengang; Yan, Jingjing; Moosa, Basem; Amad, Maan H.; Werth, Charles; Khashab, Niveen M.

2012-01-01

Metal-free fullerene (C60) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH4. Use of NaBH4 by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C 60 catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C60 to interact with electron-donor moieties in azo dyes. Filling a vacancy: Experimental and theoretical methods have been combined to show that C60-catalyzed reductions of azo compounds form aromatic amines under UV irradiation (see scheme). The obtained results show that C60 acts as an electron acceptor to catalyze the reduction of azo compounds, and the role of UV irradiation is to increase the ability of C60 to interact with electron-donor moieties in azo compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fullerene-catalyzed reduction of azo derivatives in water under UV irradiation

KAUST Repository

Guo, Yong

2012-09-27

Metal-free fullerene (C60) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH4. Use of NaBH4 by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C 60 catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C60 to interact with electron-donor moieties in azo dyes. Filling a vacancy: Experimental and theoretical methods have been combined to show that C60-catalyzed reductions of azo compounds form aromatic amines under UV irradiation (see scheme). The obtained results show that C60 acts as an electron acceptor to catalyze the reduction of azo compounds, and the role of UV irradiation is to increase the ability of C60 to interact with electron-donor moieties in azo compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shear bond strength of composite bonded with three adhesives to Er,Cr:YSGG laser-prepared enamel.

Science.gov (United States)

Türkmen, Cafer; Sazak-Oveçoğlu, Hesna; Günday, Mahir; Güngör, Gülşad; Durkan, Meral; Oksüz, Mustafa

2010-06-01

To assess in vitro the shear bond strength of a nanohybrid composite resin bonded with three adhesive systems to enamel surfaces prepared with acid and Er,Cr:YSGG laser etching. Sixty extracted caries- and restoration-free human maxillary central incisors were used. The teeth were sectioned 2 mm below the cementoenamel junction. The crowns were embedded in autopolymerizing acrylic resin with the labial surfaces facing up. The labial surfaces were prepared with 0.5-mm reduction to receive composite veneers. Thirty specimens were etched with Er,Cr:YSGG laser. This group was also divided into three subgroups, and the following three bonding systems were then applied on the laser groups and the other three unlased groups: (1) 37% phosphoric acid etch + Bond 1 primer/adhesive (Pentron); (2) Nano-bond self-etch primer (Pentron) + Nano-bond adhesive (Pentron); and (3) all-in-one adhesive-single dose (Futurabond NR, Voco). All of the groups were restored with a nanohybrid composite resin (Smile, Pentron). Shear bond strength was measured with a Zwick universal test device with a knife-edge loading head. The data were analyzed with two-factor ANOVA. There were no significant differences in shear bond strength between self-etch primer + adhesive and all-in-one adhesive systems for nonetched and laser-etched enamel groups (P > .05). However, bond strength values for the laser-etched + Bond 1 primer/adhesive group (48.00 +/- 13.86 MPa) were significantly higher than the 37% phosphoric acid + Bond 1 primer/adhesive group (38.95 +/- 20.07 MPa) (P enamel surface more effectively than 37% phosphoric acid for subsequent attachment of composite material.

Ten years left to eliminate blinding trachoma

Directory of Open Access Journals (Sweden)

Haddad D.

2010-09-01

Full Text Available n 1997, the World Health Organization formed the Global Alliance to Eliminate Blinding Trachoma by 2020 (GET 2020, a coalition of governmental, non-governmental, research, and pharmaceutical partners. In 1998, the World Health Assembly urged member states to map blinding trachoma in endemic areas, implement the SAFE strategy (which stands for surgery for trichiasis, antibiotics, facial-cleanliness and environmental change, such as clean water and latrines and collaborate with the global alliance in its work to eliminate blinding trachoma.

Novel method for concentrating and drying polymeric nanoparticles: hydrogen bonding coacervate precipitation.

Science.gov (United States)

D'Addio, Suzanne M; Kafka, Concepcion; Akbulut, Mustafa; Beattie, Patrick; Saad, Walid; Herrera, Margarita; Kennedy, Michael T; Prud'homme, Robert K

2010-04-05

Nanoparticles have significant potential in therapeutic applications to improve the bioavailability and efficacy of active drug compounds. However, the retention of nanometer sizes during concentrating or drying steps presents a significant problem. We report on a new concentrating and drying process for poly(ethylene glycol) (PEG) stabilized nanoparticles, which relies upon the unique pH sensitive hydrogen bonding interaction between PEG and polyacid species. In the hydrogen bonding coacervate precipitation (HBCP) process, PEG protected nanoparticles rapidly aggregate into an easily filterable precipitate upon the addition various polyacids. When the resulting solid is neutralized, the ionization of the acid groups eliminates the hydrogen bonded structure and the approximately 100 nm particles redisperse back to within 10% of their original size when poly(acrylic acid) and citric acid are used and 45% when poly(aspartic acid) is used. While polyacid concentrations of 1-5 wt % were used to form the precipitates, the incorporation of the acid into the PEG layer is approximately 1:1 (acid residue):(ethylene oxide unit) in the final dried precipitate. The redispersion of dried beta-carotene nanoparticles protected with PEG-b-poly(lactide-co-glycolide) polymers dried by HBCP was compared with the redispersion of particles dried by freeze-drying with sucrose as a cryprotectant, spray freeze-drying, and normal drying. Freeze-drying with 0, 2, and 12 wt % sucrose solutions resulted in size increases of 350%, 50%, and 6%, respectively. Spray freeze-drying resulted in particles with increased sizes of 50%, but no cryoprotectant and only moderate redispersion energy was required. Conventional drying resulted in solids that could not be redispersed back to nanometer size. The new HBCP process offers a promising and efficient way to concentrate or convert nanoparticle dispersions into a stable dry powder form.

Challenges beyond elimination in leprosy.

Science.gov (United States)

Naaz, Farah; Mohanty, Partha Sarathi; Bansal, Avi Kumar; Kumar, Dilip; Gupta, Umesh Datta

2017-01-01

Every year >200,000 new leprosy cases are registered globally. This number has been fairly stable over the past 8 years. The World Health Organization has set a target to interrupt the transmission of leprosy globally by 2020. It is important, in terms of global action and research activities, to consider the eventuality of multidrug therapy (MDT) resistance developing. It is necessary to measure disease burden comprehensively, and contact-centered preventive interventions should be part of a global elimination strategy. Drug resistance is the reduction in effectiveness of a drug such as an antimicrobial or an antineoplastic in curing a disease or condition. MDT has proven to be a powerful tool in the control of leprosy, especially when patients report early and start prompt treatment. Adherence to and its successful completion is equally important. This paper has reviewed the current state of leprosy worldwide and discussed the challenges and also emphasizes the challenge beyond the elimination in leprosy.

Electrochemical reduction of disulfide-containing proteins for hydrogen/deuterium exchange monitored by mass spectrometry

DEFF Research Database (Denmark)

Mysling, Simon; Salbo, Rune; Ploug, Michael

2014-01-01

Characterization of disulfide bond-containing proteins by hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) requires reduction of the disulfide bonds under acidic and cold conditions, where the amide hydrogen exchange reaction is quenched (pH 2.5, 0 °C). The reduction typically...... of TCEP. In the present study, we explore the feasibility of using electrochemical reduction as a substitute for TCEP in HDX-MS analyses. Our results demonstrate that efficient disulfide bond reduction is readily achieved by implementing an electrochemical cell into the HDX-MS workflow. We also identify...... some challenges in using electrochemical reduction in HDX-MS analyses and provide possible conditions to attenuate these limitations. For example, high salt concentrations hamper disulfide bond reduction, necessitating additional dilution of the sample with aqueous acidic solution at quench conditions....

A retrieval-based approach to eliminating hindsight bias.

Science.gov (United States)

Van Boekel, Martin; Varma, Keisha; Varma, Sashank

2017-03-01

Individuals exhibit hindsight bias when they are unable to recall their original responses to novel questions after correct answers are provided to them. Prior studies have eliminated hindsight bias by modifying the conditions under which original judgments or correct answers are encoded. Here, we explored whether hindsight bias can be eliminated by manipulating the conditions that hold at retrieval. Our retrieval-based approach predicts that if the conditions at retrieval enable sufficient discrimination of memory representations of original judgments from memory representations of correct answers, then hindsight bias will be reduced or eliminated. Experiment 1 used the standard memory design to replicate the hindsight bias effect in middle-school students. Experiments 2 and 3 modified the retrieval phase of this design, instructing participants beforehand that they would be recalling both their original judgments and the correct answers. As predicted, this enabled participants to form compound retrieval cues that discriminated original judgment traces from correct answer traces, and eliminated hindsight bias. Experiment 4 found that when participants were not instructed beforehand that they would be making both recalls, they did not form discriminating retrieval cues, and hindsight bias returned. These experiments delineate the retrieval conditions that produce-and fail to produce-hindsight bias.

"Vibrational bonding": a new type of chemical bond is discovered.

Science.gov (United States)

Rhodes, Christopher J; Macrae, Roderick M

2015-01-01

A long-sought but elusive new type of chemical bond, occurring on a minimum-free, purely repulsive potential energy surface, has recently been convincingly shown to be possible on the basis of high-level quantum-chemical calculations. This type of bond, termed a vibrational bond, forms because the total energy, including the dynamical energy of the nuclei, is lower than the total energy of the dissociated products, including their vibrational zero-point energy. For this to be the case, the ZPE of the product molecule must be very high, which is ensured by replacing a conventional hydrogen atom with its light isotope muonium (Mu, mass = 1/9 u) in the system Br-H-Br, a natural transition state in the reaction between Br and HBr. A paramagnetic species observed in the reaction Mu +Br2 has been proposed as a first experimental sighting of this species, but definitive identification remains challenging.

Supra-molecular hydrogen-bonding patterns in the N(9)-H protonated and N(7)-H tautomeric form of an N(6) -benzoyl-adenine salt: N (6)-benzoyl-adeninium nitrate.

Science.gov (United States)

Karthikeyan, Ammasai; Jeeva Jasmine, Nithianantham; Thomas Muthiah, Packianathan; Perdih, Franc

2016-02-01

In the title molecular salt, C12H10N5O(+)·NO3 (-), the adenine unit has an N (9)-protonated N(7)-H tautomeric form with non-protonated N(1) and N(3) atoms. The dihedral angle between the adenine ring system and the phenyl ring is 51.10 (10)°. The typical intra-molecular N(7)-H⋯O hydrogen bond with an S(7) graph-set motif is also present. The benzoyl-adeninium cations also form base pairs through N-H⋯O and C-H⋯N hydrogen bonds involving the Watson-Crick face of the adenine ring and the C and O atoms of the benzoyl ring of an adjacent cation, forming a supra-molecular ribbon with R 2 (2)(9) rings. Benzoyl-adeninum cations are also bridged by one of the oxygen atoms of the nitrate anion, which acts as a double acceptor, forming a pair of N-H⋯O hydrogen bonds to generate a second ribbon motif. These ribbons together with π-π stacking inter-actions between the phenyl ring and the five- and six-membered adenine rings of adjacent mol-ecules generate a three-dimensional supra-molecular architecture.

An in vitro study to evaluate the effect of two ethanol-based and two acetone-based dental bonding agents on the bond strength of composite to enamel treated with 10% carbamide peroxide

Directory of Open Access Journals (Sweden)

Deepa Basavaraj Benni

2014-01-01

Full Text Available Background and Objective: Carbamide peroxide bleaching has been implicated in adversely affecting the bond strength of composite to enamel. The objective of this in vitro study was to evaluate the effect of ethanol-based (Clearfil S 3 bond, Kuraray, Adper Single bond 2, 3M ESPE dental products and acetone-based (Prime and Bond NT, Dentsply, One Step, Bisco bonding agents on the shear bond strength of composite to enamel treated with 10% carbamide peroxide bleaching agent. Materials and Methods: A total of 120 extracted human noncarious permanent incisors were randomly divided into two groups (control and experimental. Experimental group specimens were subjected to a bleaching regimen with a 10% carbamide peroxide bleaching system (Opalescence; Ultradent Products Inc, South Jordan, USA. Composite resin cylinders were bonded to the specimens using four bonding agents and shear bond strength was determined with universal testing machine. Results: There was no statistically significant difference in the shear bond strength between control and experimental groups with both ethanol-based (Clearfil S 3 Bond and Adper Single Bond 2 and acetone-based bonding agent (Prime and Bond NT and One Step. Interpretation and Conclusion: The adverse effect of bleaching on bonding composite to enamel can be reduced or eliminated by using either ethanol- or acetone-based bonding agent. Clinical Significances: Immediate bonding following bleaching procedure can be done using ethanol- or acetone-based bonding agent without compromising bond strength.

Dual passivation of intrinsic defects at the compound semiconductor/oxide interface using an oxidant and a reductant.

Science.gov (United States)

Kent, Tyler; Chagarov, Evgeniy; Edmonds, Mary; Droopad, Ravi; Kummel, Andrew C

2015-05-26

Studies have shown that metal oxide semiconductor field-effect transistors fabricated utilizing compound semiconductors as the channel are limited in their electrical performance. This is attributed to imperfections at the semiconductor/oxide interface which cause electronic trap states, resulting in inefficient modulation of the Fermi level. The physical origin of these states is still debated mainly because of the difficulty in assigning a particular electronic state to a specific physical defect. To gain insight into the exact source of the electronic trap states, density functional theory was employed to model the intrinsic physical defects on the InGaAs (2 × 4) surface and to model the effective passivation of these defects by utilizing both an oxidant and a reductant to eliminate metallic bonds and dangling-bond-induced strain at the interface. Scanning tunneling microscopy and spectroscopy were employed to experimentally determine the physical and electronic defects and to verify the effectiveness of dual passivation with an oxidant and a reductant. While subsurface chemisorption of oxidants on compound semiconductor substrates can be detrimental, it has been shown theoretically and experimentally that oxidants are critical to removing metallic defects at oxide/compound semiconductor interfaces present in nanoscale channels, oxides, and other nanostructures.

Forming of superplastic ceramics

Energy Technology Data Exchange (ETDEWEB)

Lesuer, D.R.; Wadsworth, J.; Nieh, T.G.

1994-05-01

Superplasticity in ceramics has now advanced to the stage that technologically viable superplastic deformation processing can be performed. In this paper, examples of superplastic forming and diffusion bonding of ceramic components are given. Recent work in biaxial gas-pressure forming of several ceramics is provided. These include yttria-stabilized, tetragonal zirconia (YTZP), a 20% alumina/YTZP composite, and silicon. In addition, the concurrent superplastic forming and diffusion bonding of a hybrid ceramic-metal structure are presented. These forming processes offer technological advantages of greater dimensional control and increased variety and complexity of shapes than is possible with conventional ceramic shaping technology.

Simulation of Bimetallic Bush Hot Rolling Bonding Process

Directory of Open Access Journals (Sweden)

Yaqin Tian

2015-01-01

Full Text Available Three-dimensional model of bimetallic bush was established including the drive roller and the core roller. The model adopted the appropriate interface assumptions. Based on the bonding properties of bimetallic bush the hot rolling process was analyzed. The optimum reduction ratio of 28% is obtained by using the finite element simulation software MARC on the assumption of the bonding conditions. The stress-strain distribution of three dimensions was research assumptions to interface deformation of rolling. At the same time, based on the numerical simulation, the minimum reduction ratio 20% is obtained by using a double metal composite bush rolling new technology from the experiment research. The simulation error is not more than 8%.

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

Science.gov (United States)

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

2011-04-12

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

Mitochondrial isocitrate dehydrogenase is inactivated upon oxidation and reactivated by thioredoxin-dependent reduction in Arabidopsis

Directory of Open Access Journals (Sweden)

Keisuke eYoshida

2014-09-01

Full Text Available Regulation of mitochondrial metabolism is essential for ensuring cellular growth and maintenance in plants. Based on redox-proteomics analysis, several proteins involved in diverse mitochondrial reactions have been identified as potential redox-regulated proteins. NAD+-dependent isocitrate dehydrogenase (IDH, a key enzyme in the tricarboxylic acid cycle, is one such candidate. In this study, we investigated the redox regulation mechanisms of IDH by biochemical procedures. In contrast to mammalian and yeast counterparts reported to date, recombinant IDH in Arabidopsis mitochondria did not show adenylate-dependent changes in enzymatic activity. Instead, IDH was inactivated by oxidation treatment and partially reactivated by subsequent reduction. Functional IDH forms a heterodimer comprising regulatory (IDH-r and catalytic (IDH-c subunits. IDH-r was determined to be the target of oxidative modifications forming an oligomer via intermolecular disulfide bonds. Mass spectrometric analysis combined with tryptic digestion of IDH-r indicated that Cys128 and Cys216 are involved in intermolecular disulfide bond formation. Furthermore, we showed that mitochondria-localized o-type thioredoxin (Trx-o promotes the reduction of oxidized IDH-r. These results suggest that IDH-r is susceptible to oxidative stress, and Trx-o serves to convert oxidized IDH-r to the reduced form that is necessary for active IDH complex.

Interfacial-Bonding-Regulated CO Oxidation over Pt Atoms Immobilized on Gas-Exfoliated Hexagonal Boron Nitride

KAUST Repository

Liu, Xin

2017-10-12

We compared the electronic structure and CO oxidation mechanisms over Pt atoms immobilized by both B-vacancies and N-vacancies on gas-exfoliated hexagonal boron nitride. We showed that chemical bonds are formed between the B atoms associated with dangling bonds around the vacancies and Pt atoms. These bonds not only alter the thermodynamics and kinetics for the aggregation and effectively immobilize Pt atoms, but also significantly change the composition and energetic distribution of the electronic states of the composites to circumvent CO poisoning and to favour coadsorption of CO and O2, which further regulates the reactions to proceed through a Langmuir-Hinshelwood mechanism. The CO oxidation over Pt atoms immobilized at N-vacancies involves formation of an intermediate with –C(O)-O−O- bonded to Pt, the generation of CO2 by peroxo O−O bond scission and the reduction of the remnant oxygen, and the calculated energy barriers are 0.49, 0.23 and 0.18 eV, respectively. Such small energy barriers are comparable to those over Pt atoms trapped at B-vacancies, showing the effectiveness of Pt/hexagonal boron nitride atomic composites as catalysts for CO oxidation. These findings also suggest the feasibility of regulating the reaction pathways over single atom catalysts via interfacial engineering.

Elimination of ketone vapors by adsorption on spherical MCM-41 and MCM-48 silicas decorated with thermally activated poly(furfuryl alcohol)

Energy Technology Data Exchange (ETDEWEB)

Machowski, Kamil [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland); Kuśtrowski, Piotr, E-mail: kustrows@chemia.uj.edu.pl [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland); Dudek, Barbara [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland); Michalik, Marek [Institute of Geological Sciences, Jagiellonian University, Oleandry 2a, 30-063 Kraków (Poland)

2015-09-01

Spherical MCM-41 and MCM-48 silicas with different arrangements of mesopores were synthesized in a water–alcohol solution of surfactant by the hard-templating method. The pore structure and morphology of the obtained materials were confirmed by powder X-ray diffraction (XRD), low-temperature adsorption of nitrogen and scanning electron microscopy (SEM). The surface of mesoporous silicas was decorated with small amounts of poly(furfuryl alcohol) (PFA), which was introduced by the precipitation polymerization and subsequently thermally activated at 523 K to form stable C=O surface species detected by FTIR spectroscopy. The adsorption capacity of the PFA/silica composites in the elimination of various ketone (acetone, methyl-ethyl ketone and methyl-isobutyl ketone) vapors was compared to the effectiveness of pristine silicas. It was found that the modification of silicas by thermally degraded PFA enhanced their adsorption capacity. This effect was attributed to the appearance of another type of surface centers (namely carbonyl groups), which beside silanols interact with ketone molecules via hydrogen bonds. DRIFT spectra showed that a ketone molecule is bonded on silanol species in its keto form, whereas on carbonyl functionalities in enol one. - Highlights: • Surface of spherical MCM-type silicas was decorated with poly(furfuryl alcohol). • Thermal degradation of deposited polymer resulted in formation of C=O species. • Carbonyl groups enhanced adsorption capacity of MCM-41 and MCM-48 silicas. • Adsorption of ketones in enol or keto forms was revealed by DRIFT measurements.

Elimination of ketone vapors by adsorption on spherical MCM-41 and MCM-48 silicas decorated with thermally activated poly(furfuryl alcohol)

International Nuclear Information System (INIS)

Machowski, Kamil; Kuśtrowski, Piotr; Dudek, Barbara; Michalik, Marek

2015-01-01

Spherical MCM-41 and MCM-48 silicas with different arrangements of mesopores were synthesized in a water–alcohol solution of surfactant by the hard-templating method. The pore structure and morphology of the obtained materials were confirmed by powder X-ray diffraction (XRD), low-temperature adsorption of nitrogen and scanning electron microscopy (SEM). The surface of mesoporous silicas was decorated with small amounts of poly(furfuryl alcohol) (PFA), which was introduced by the precipitation polymerization and subsequently thermally activated at 523 K to form stable C=O surface species detected by FTIR spectroscopy. The adsorption capacity of the PFA/silica composites in the elimination of various ketone (acetone, methyl-ethyl ketone and methyl-isobutyl ketone) vapors was compared to the effectiveness of pristine silicas. It was found that the modification of silicas by thermally degraded PFA enhanced their adsorption capacity. This effect was attributed to the appearance of another type of surface centers (namely carbonyl groups), which beside silanols interact with ketone molecules via hydrogen bonds. DRIFT spectra showed that a ketone molecule is bonded on silanol species in its keto form, whereas on carbonyl functionalities in enol one. - Highlights: • Surface of spherical MCM-type silicas was decorated with poly(furfuryl alcohol). • Thermal degradation of deposited polymer resulted in formation of C=O species. • Carbonyl groups enhanced adsorption capacity of MCM-41 and MCM-48 silicas. • Adsorption of ketones in enol or keto forms was revealed by DRIFT measurements.

Smart pH- and reduction-dual-responsive folate-PEG-coated polymeric lipid vesicles for tumor-triggered targeted drug delivery

Science.gov (United States)

Wang, Sheng; Wang, Hanjie; Liu, Zhongyun; Wang, Liangliang; Wang, Xiaomin; Su, Lin; Chang, Jin

2014-06-01

To improve their therapeutic index, designed nanocarriers should preferentially accumulate in tumor tissues and then rapidly enter tumor cells to release the encapsulated drugs in a triggered manner. In this article, a new kind of a smart pH- and reduction-dual-responsive drug delivery system based on folate-PEG-coated polymeric lipid vesicles (FPPLVs) formed from amphiphilic dextran derivatives was designed and prepared successfully. PEG chains with pH-sensitive hydrazone bonds, stearyl alcohol (SA) chains with reduction-sensitive disulfide bonds and folate were connected to a dextran main chain. The newly developed FPPLVs had a nano-sized structure (~50 nm) with a PEG coating. The in vitro DOX release profiles showed that the FPPLVs achieved a triggered drug release in response to acidic pH and reducing environments due to the cleavage of hydrazone bonds and disulfide bonds. It has also been demonstrated by an in vitro cellular uptake study that the FPPLVs lose their PEG coating as well as expose the folate in acidic conditions, which allows them to efficiently enter tumor cells through ligand-receptor interactions. In vitro cytotoxicity measurements also confirmed that FPPLVs exhibited pronounced antitumor activity against HeLa cells. These results suggest that FPPLVs are promising carriers for smart antitumor drug delivery applications.To improve their therapeutic index, designed nanocarriers should preferentially accumulate in tumor tissues and then rapidly enter tumor cells to release the encapsulated drugs in a triggered manner. In this article, a new kind of a smart pH- and reduction-dual-responsive drug delivery system based on folate-PEG-coated polymeric lipid vesicles (FPPLVs) formed from amphiphilic dextran derivatives was designed and prepared successfully. PEG chains with pH-sensitive hydrazone bonds, stearyl alcohol (SA) chains with reduction-sensitive disulfide bonds and folate were connected to a dextran main chain. The newly developed FPPLVs had a

Optimising strategies for Plasmodium falciparum malaria elimination in Cambodia: primaquine, mass drug administration and artemisinin resistance.

Directory of Open Access Journals (Sweden)

Richard J Maude

Full Text Available Malaria elimination requires a variety of approaches individually optimized for different transmission settings. A recent field study in an area of low seasonal transmission in South West Cambodia demonstrated dramatic reductions in malaria parasite prevalence following both mass drug administration (MDA and high treatment coverage of symptomatic patients with artemisinin-piperaquine plus primaquine. This study employed multiple combined strategies and it was unclear what contribution each made to the reductions in malaria.A mathematical model fitted to the trial results was used to assess the effects of the various components of these interventions, design optimal elimination strategies, and explore their interactions with artemisinin resistance, which has recently been discovered in Western Cambodia. The modelling indicated that most of the initial reduction of P. falciparum malaria resulted from MDA with artemisinin-piperaquine. The subsequent continued decline and near elimination resulted mainly from high coverage with artemisinin-piperaquine treatment. Both these strategies were more effective with the addition of primaquine. MDA with artemisinin combination therapy (ACT increased the proportion of artemisinin resistant infections, although much less than treatment of symptomatic cases with ACT, and this increase was slowed by adding primaquine. Artemisinin resistance reduced the effectiveness of interventions using ACT when the prevalence of resistance was very high. The main results were robust to assumptions about primaquine action, and immunity.The key messages of these modelling results for policy makers were: high coverage with ACT treatment can produce a long-term reduction in malaria whereas the impact of MDA is generally only short-term; primaquine enhances the effect of ACT in eliminating malaria and reduces the increase in proportion of artemisinin resistant infections; parasite prevalence is a better surveillance measure for

Solitons on H bonds in proteins

DEFF Research Database (Denmark)

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

2003-01-01

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

Connection between fragility, mean-squared displacement and shear modulus in two van der Waals bonded glass-forming liquids

DEFF Research Database (Denmark)

Hansen, Henriette Wase; Frick, Bernhard; Hecksher, Tina

2017-01-01

The temperature dependence of the high-frequency shear modulus measured in the kHz range is compared with the mean-squared displacement measured in the nanosecond range for the two van der Waals bonded glass-forming liquids cumene and 5-polyphenyl ether. This provides an experimental test for the...... for the assumption connecting two versions of the shoving model for the non-Arrhenius temperature dependence of the relaxation time in glass formers. The two versions of the model are also tested directly and both are shown to work well for these liquids....

Durability properties for adhesively bonded structural aerospace applications

International Nuclear Information System (INIS)

Shaffer, D.K.; Davis, G.D.; McNamara, D.K.; Shah, T.K.; Desai, A.

1992-01-01

This paper reports on the importance of good bond durability of adhesively joined aerospace components which has been recognized for many years. Military and civilian aircraft are exposed to harsh environments in addition to severe thermal and stress cycles during their service lives. Moisture is responsible for the majority of bond failures in the field. The presence of surface contaminants (e.g., fluoride, silicones) and the non-neutral pH of poor rinse water are common causes of adhesion problems in production environments. Honeycomb panels, stringer skins, doubler plates and core cowl assemblies are bonded joint structures that are subject to environmental- or contaminant-induced debonding. The identification and characterization of the causes of such bond failures leads to improved production quality, yield and cost reduction

46 CFR 540.6 - Surety bonds.

Science.gov (United States)

2010-10-01

... transportation. The requirements of Form FMC-132A, however, may be amended by the Commission in a particular case for good cause. (b) In the case of a surety bond which is to cover all passenger operations of the... shall be issued by a bonding company authorized to do business in the United States and acceptable to...

GeSn-on-insulator substrate formed by direct wafer bonding

Energy Technology Data Exchange (ETDEWEB)

Lei, Dian; Wang, Wei; Gong, Xiao, E-mail: elegong@nus.edu.sg, E-mail: yeo@ieee.org; Yeo, Yee-Chia, E-mail: elegong@nus.edu.sg, E-mail: yeo@ieee.org [Department of Electrical and Computer Engineering, National University of Singapore, Singapore 117576 (Singapore); Lee, Kwang Hong; Wang, Bing [Low Energy Electronic Systems (LEES), Singapore MIT Alliance for Research and Technology (SMART), 1 CREATE Way, #10-01 CREATE Tower, Singapore 138602 (Singapore); Bao, Shuyu [Low Energy Electronic Systems (LEES), Singapore MIT Alliance for Research and Technology (SMART), 1 CREATE Way, #10-01 CREATE Tower, Singapore 138602 (Singapore); School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Tan, Chuan Seng [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)

2016-07-11

GeSn-on-insulator (GeSnOI) on Silicon (Si) substrate was realized using direct wafer bonding technique. This process involves the growth of Ge{sub 1-x}Sn{sub x} layer on a first Si (001) substrate (donor wafer) followed by the deposition of SiO{sub 2} on Ge{sub 1-x}Sn{sub x}, the bonding of the donor wafer to a second Si (001) substrate (handle wafer), and removal of the Si donor wafer. The GeSnOI material quality is investigated using high-resolution transmission electron microscopy, high-resolution X-ray diffraction (HRXRD), atomic-force microscopy, Raman spectroscopy, and spectroscopic ellipsometry. The Ge{sub 1-x}Sn{sub x} layer on GeSnOI substrate has a surface roughness of 1.90 nm, which is higher than that of the original Ge{sub 1-x}Sn{sub x} epilayer before transfer (surface roughness is 0.528 nm). The compressive strain of the Ge{sub 1-x}Sn{sub x} film in the GeSnOI is as low as 0.10% as confirmed using HRXRD and Raman spectroscopy.

Proposal of new bonding technique 'Instantaneous Liquid Phase (ILP) Bonding'

International Nuclear Information System (INIS)

Zhang, Yue-Chang; Nakagawa, Hiroji; Matsuda, Fukuhisa.

1987-01-01

A new bonding technique named ''Instantaneous Liquid Phase (ILP) bonding'' suitable mainly for welding dissimilar materials was proposed by which instantaneous melting of one or two of the faying surfaces is utilized. The processes of ILP bonding are mainly consisted of three stages, namely the first stage forming thin liquid layer by rapid heating, the second stage joining both specimens by thin liquid layer, and the third stage cooling the specimens rapidly to avoid the formation of brittle layer. The welding temperatures of the specimens to be welded in ILP bonding are generally differentiated from each other. ILP bonding was applied for a variety of combinations of dissimilar materials of aluminum, aluminum alloys, titanium, titanium alloy, carbon steel, austenitic stainless steel, copper and tungsten, and for similar materials of stainless steel and nickel-base alloy. There were no microvoids in these welding joints, and the formation of brittle layer at the bonding interface was suppressed. The welded joints of Al + Ti, Cu + carbon steel and Cu + austenitic stainless steel showed the fracture in base metal having lower tensile strength. Further, the welded joints of Al + carbon steel, Al alloy + Ti, Al alloy + carbon steel or + austenitic stainless steel, Ti + carbon steel or + austenitic stainless steel showed better tensile properties in the comparison with diffusion welding. Furthermore, ILP bonding was available for welding same materials susceptible to hot cracking. Because of the existence of liquid layer, the welding pressure required was extremely low, and preparation of faying surface by simple tooling or polishing by no.80 emery paper was enough. The change in specimen length before and after welding was relatively little, only depending on the thickness of liquid layer. The welding time was very short, and thus high welding efficiency was obtained. (author)

Processing and Protection of Rare Earth Permanent Magnet Particulate for Bonded Magnet Applications

Energy Technology Data Exchange (ETDEWEB)

Sokolowski, Peter Kelly [Iowa State Univ., Ames, IA (United States)

2007-01-01

Rapid solidification of novel mixed rare earth-iron-boron, MRE₂Fe₁₄B (MRE = Nd, Y, Dy; currently), magnet alloys via high pressure gas atomization (HPGA) have produced similar properties and structures as closely related alloys produced by melt spinning (MS) at low wheel speeds. Recent additions of titanium carbide and zirconium to the permanent magnet (PM) alloy design in HPGA powder (using He atomization gas) have made it possible to achieve highly refined microstructures with magnetic properties approaching melt spun particulate at cooling rates of 10⁵-10⁶K/s. By producing HPGA powders with the desirable qualities of melt spun ribbon, the need for crushing ribbon was eliminated in bonded magnet fabrication. The spherical geometry of HPGA powders is more ideal for processing of bonded permanent magnets since higher loading fractions can be obtained during compression and injection molding. This increased volume loading of spherical PM powder can be predicted to yield a higher maximum energy product (BH)_max for bonded magnets in high performance applications. Passivation of RE-containing powder is warranted for the large-scale manufacturing of bonded magnets in applications with increased temperature and exposure to humidity. Irreversible magnetic losses due to oxidation and corrosion of particulates is a known drawback of RE-Fe-B based alloys during further processing, e.g. injection molding, as well as during use as a bonded magnet. To counteract these effects, a modified gas atomization chamber allowed for a novel approach to in situ passivation of solidified particle surfaces through injection of a reactive gas, nitrogen trifluoride (NF₃). The ability to control surface chemistry during atomization processing of fine spherical RE-Fe-B powders produced advantages over current processing methodologies. In particular, the capability to coat particles while 'in flight' may eliminate the

A Novel wave-form command shaper for overhead cranes

Directory of Open Access Journals (Sweden)

KHALED ALHAZZA

2013-12-01

Full Text Available In this work, a novel command shaping control strategy for oscillation reduction of simple harmonic oscillators is proposed, and validated experimentally. A wave-form acceleration command shaper is derived analytically. The performance of the proposed shaper is simulated numerically, and validated experimentally on a scaled model of an overhead crane. Amplitude modulation is used to enhance the shaper performance, which results in a modulated wave-form command shaper. It is determined that the proposed wave-form and modulated wave-form command shaper profiles are capable of eliminating travel and residual oscillations. Furthermore, unlike traditional impulse and step command shapers, the proposed command shaper has piecewise smoother acceleration, velocity, and displacement profiles. Experimental results using continuous and discrete commands are presented. Experiments with discrete commands involved embedding a saturation model-based feedback in the algorithm of the command shaper.

Sibling bereavement and continuing bonds.

Science.gov (United States)

Packman, Wendy; Horsley, Heidi; Davies, Betty; Kramer, Robin

2006-11-01

Historically, from a Freudian and medical model perspective, emotional disengagement from the deceased was seen as essential to the successful adaptation of bereavement. A major shift in the bereavement literature has occurred and it is now generally accepted that despite the permanence of physical separation, the bereaved remains involved and connected to the deceased and can be emotionally sustained through continuing bonds. The majority of literature has focused on adults and on the nature of continuing bonds following the death of a spouse. In this article, the authors demonstrate how the continuing bonds concept applies to the sibling relationship. We describe the unique continued relationship formed by bereaved children and adolescents following a sibling loss, highlight the factors that influence the siblings continuing bonds expressions, and offer clinical interventions. In our view, mental health professionals can play an important role in helping parents encourage activities that may facilitate the creation and maintenance of continuing bonds in their children.

Deriving the bond pricing equation

Directory of Open Access Journals (Sweden)

Kožul Nataša

2014-01-01

Full Text Available Given the recent focus on Eurozone debt crisis and the credit rating downgrade not only of US debt, but that of other countries and many UK major banking institutions, this paper aims to explain the concept of bond yield, its different measures and bond pricing equation. Yields on capital market instruments are rarely quoted on the same basis, which makes direct comparison between different as investment choices impossible. Some debt instruments are quoted on discount basis, whilst coupon-bearing ones accrue interest differently, offer different compounding opportunities, have different coupon payment frequencies, and manage non-business day maturity dates differently. Moreover, rules governing debt vary across countries, markets and currencies, making yield calculation and comparison a rather complex issue. Thus, some fundamental concepts applicable to debt instrument yield measurement, with focus on bond equation, are presented here. In addition, bond equation expressed in annuity form and used to apply Newton-Raphson algorithm to derive true bond yield is also shown.

Transition Metal Free C-N Bond Forming Dearomatizations and Aryl C-H Aminations by in Situ Release of a Hydroxylamine-Based Aminating Agent.

Science.gov (United States)

Farndon, Joshua J; Ma, Xiaofeng; Bower, John F

2017-10-11

We outline a simple protocol that accesses directly unprotected secondary amines by intramolecular C-N bond forming dearomatization or aryl C-H amination. The method is dependent on the generation of a potent electrophilic aminating agent released by in situ deprotection of O-Ts activated N-Boc hydroxylamines.

The architecture and effect of participation: a systematic review of community participation for communicable disease control and elimination. Implications for malaria elimination

Directory of Open Access Journals (Sweden)

Whittaker Maxine

2011-08-01

Full Text Available Abstract Background Community engagement and participation has played a critical role in successful disease control and elimination campaigns in many countries. Despite this, its benefits for malaria control and elimination are yet to be fully realized. This may be due to a limited understanding of the influences on participation in developing countries as well as inadequate investment in infrastructure and resources to support sustainable community participation. This paper reports the findings of an atypical systematic review of 60 years of literature in order to arrive at a more comprehensive awareness of the constructs of participation for communicable disease control and elimination and provide guidance for the current malaria elimination campaign. Methods Evidence derived from quantitative research was considered both independently and collectively with qualitative research papers and case reports. All papers included in the review were systematically coded using a pre-determined qualitative coding matrix that identified influences on community participation at the individual, household, community and government/civil society levels. Colour coding was also carried out to reflect the key primary health care period in which community participation programmes originated. These processes allowed exhaustive content analysis and synthesis of data in an attempt to realize conceptual development beyond that able to be achieved by individual empirical studies or case reports. Results Of the 60 papers meeting the selection criteria, only four studies attempted to determine the effect of community participation on disease transmission. Due to inherent differences in their design, interventions and outcome measures, results could not be compared. However, these studies showed statistically significant reductions in disease incidence or prevalence using various forms of community participation. The use of locally selected volunteers provided with

Elimination of salmonella from animal glandular products.

Science.gov (United States)

De Fiebre, C W; Burck, K T; Feldman, D

1969-03-01

Methods for the elimination of salmonellae from selected powdered pharmaceuticals of animal glandular origin were studied. Terminal heat treatment under carefully controlled conditions was effective for pancreatin-a powder containing proteolytic, amylolytic, and lipolytic enzymes prepared from hog pancreas glands. Use of this method resulted in a significant reduction in the number of salmonella-positive batches and also reduced the testing procedures required to confirm the absence of viable salmonellae among the majority of samples tested. Powders such as stomach substance and thyroid, in which the biological activity is not enzyme in nature, were treated successfully with acidified organic solvents. Other methods were investigated but were not suitable because of a deleterious effect on the biological activity or physical properties of the product or an inability to effect salmonella elimination.

Elimination of Salmonellae from Animal Glandular Products

Science.gov (United States)

De Fiebre, Conrad W.; Burck, Kenneth T.; Feldman, David

1969-01-01

Methods for the elimination of salmonellae from selected powdered pharmaceuticals of animal glandular origin were studied. Terminal heat treatment under carefully controlled conditions was effective for pancreatin—a powder containing proteolytic, amylolytic, and lipolytic enzymes prepared from hog pancreas glands. Use of this method resulted in a significant reduction in the number of salmonella-positive batches and also reduced the testing procedures required to confirm the absence of viable salmonellae among the majority of samples tested. Powders such as stomach substance and thyroid, in which the biological activity is not enzyme in nature, were treated successfully with acidified organic solvents. Other methods were investigated but were not suitable because of a deleterious effect on the biological activity or physical properties of the product or an inability to effect salmonella elimination. PMID:5780395

Disulfide Linkage Characterization of Disulfide Bond-Containing Proteins and Peptides by Reducing Electrochemistry and Mass Spectrometry

DEFF Research Database (Denmark)

Cramer, Christian N; Haselmann, Kim F; Olsen, Jesper V

2016-01-01

in protein sequencing by tandem MS (MS/MS). Electrochemical (EC) reduction of disulfide bonds has recently been demonstrated to provide efficient reduction efficiencies, significantly enhancing sequence coverages in online coupling with MS characterization. In this study, the potential use of EC disulfide...... link between parent disulfide-linked fragments and free reduced peptides in an LC-EC-MS platform of nonreduced proteolytic protein digestions. Here we report the successful use of EC as a partial reduction approach in mapping of disulfide bonds of intact human insulin (HI) and lysozyme. In addition, we...... established a LC-EC-MS platform advantageous in disulfide characterization of complex and highly disulfide-bonded proteins such as human serum albumin (HSA) by online EC reduction of nonreduced proteolytic digestions....

Bonding mechanisms in spot welded three layer combinations

DEFF Research Database (Denmark)

Moghadam, Marcel; Tiedje, Niels Skat; Seyyedian Choobi, Mahsa

2016-01-01

this interface. It has been shown previously that such a joint can reach relatively high strength resulting in plug failure in tensileshear testing. Additional strength due to these bonding mechanisms is also obtained in common spot welds in the so-called corona band around the weld nugget.......The strength of a spot weld generally stems from fusion bonding of the metal layers, but other solid state bonding mechanisms also contribute to the overall strength. Metallographic analyses are presented to identify the phases formed near and across the weld interfaces and to identify...... the occurring bonding mechanisms. When welding a combination of three galvanized steel layers where one outer layer is a thin low-carbon steel it is a common challenge to obtain nugget penetration into the thin low-carbon steel. It therefore happens in real production that no nugget is formed across...

Bonding in [CuNRR′]4 type clusters

Institute of Scientific and Technical Information of China (English)

WANG Bingwu; XU Guangxian; CHEN Zhida

2004-01-01

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

Unusually short chalcogen bonds involving organoselenium: insights into the Se-N bond cleavage mechanism of the antioxidant ebselen and analogues.

Science.gov (United States)

Thomas, Sajesh P; Satheeshkumar, K; Mugesh, Govindasamy; Guru Row, T N

2015-04-27

Structural studies on the polymorphs of the organoselenium antioxidant ebselen and its derivative show the potential of organic selenium to form unusually short Se⋅⋅⋅O chalcogen bonds that lead to conserved supramolecular recognition units. Se⋅⋅⋅O interactions observed in these polymorphs are the shortest such chalcogen bonds known for organoselenium compounds. The FTIR spectral evolution characteristics of this interaction from solution state to solid crystalline state further validates the robustness of this class of supramolecular recognition units. The strength and electronic nature of the Se⋅⋅⋅O chalcogen bonds were explored using high-resolution X-ray charge density analysis and atons-in-molecules (AIM) theoretical analysis. A charge density study unravels the strong electrostatic nature of Se⋅⋅⋅O chalcogen bonding and soft-metal-like behavior of organoselenium. An analysis of the charge density around Se-N and Se-C covalent bonds in conjunction with the Se⋅⋅⋅O chalcogen bonding modes in ebselen and its analogues provides insights into the mechanism of drug action in this class of organoselenium antioxidants. The potential role of the intermolecular Se⋅⋅⋅O chalcogen bonding in forming the intermediate supramolecular assembly that leads to the bond cleavage mechanism has been proposed in terms of electron density topological parameters in a series of molecular complexes of ebselen with reactive oxygen species (ROS). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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

2008-10-30

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

Analytical energy gradient for the two-component normalized elimination of the small component method

Science.gov (United States)

Zou, Wenli; Filatov, Michael; Cremer, Dieter

2015-06-01

The analytical gradient for the two-component Normalized Elimination of the Small Component (2c-NESC) method is presented. The 2c-NESC is a Dirac-exact method that employs the exact two-component one-electron Hamiltonian and thus leads to exact Dirac spin-orbit (SO) splittings for one-electron atoms. For many-electron atoms and molecules, the effect of the two-electron SO interaction is modeled by a screened nucleus potential using effective nuclear charges as proposed by Boettger [Phys. Rev. B 62, 7809 (2000)]. The effect of spin-orbit coupling (SOC) on molecular geometries is analyzed utilizing the properties of the frontier orbitals and calculated SO couplings. It is shown that bond lengths can either be lengthened or shortened under the impact of SOC where in the first case the influence of low lying excited states with occupied antibonding orbitals plays a role and in the second case the jj-coupling between occupied antibonding and unoccupied bonding orbitals dominates. In general, the effect of SOC on bond lengths is relatively small (≤5% of the scalar relativistic changes in the bond length). However, large effects are found for van der Waals complexes Hg2 and Cn2, which are due to the admixture of more bonding character to the highest occupied spinors.

Loss of metal ions, disulfide reduction and mutations related to familial ALS promote formation of amyloid-like aggregates from superoxide dismutase.

Directory of Open Access Journals (Sweden)

Zeynep A Oztug Durer

Full Text Available Mutations in the gene encoding Cu-Zn superoxide dismutase (SOD1 are one of the causes of familial amyotrophic lateral sclerosis (FALS. Fibrillar inclusions containing SOD1 and SOD1 inclusions that bind the amyloid-specific dye thioflavin S have been found in neurons of transgenic mice expressing mutant SOD1. Therefore, the formation of amyloid fibrils from human SOD1 was investigated. When agitated at acidic pH in the presence of low concentrations of guanidine or acetonitrile, metalated SOD1 formed fibrillar material which bound both thioflavin T and Congo red and had circular dichroism and infrared spectra characteristic of amyloid. While metalated SOD1 did not form amyloid-like aggregates at neutral pH, either removing metals from SOD1 with its intramolecular disulfide bond intact or reducing the intramolecular disulfide bond of metalated SOD1 was sufficient to promote formation of these aggregates. SOD1 formed amyloid-like aggregates both with and without intermolecular disulfide bonds, depending on the incubation conditions, and a mutant SOD1 lacking free sulfhydryl groups (AS-SOD1 formed amyloid-like aggregates at neutral pH under reducing conditions. ALS mutations enhanced the ability of disulfide-reduced SOD1 to form amyloid-like aggregates, and apo-AS-SOD1 formed amyloid-like aggregates at pH 7 only when an ALS mutation was also present. These results indicate that some mutations related to ALS promote formation of amyloid-like aggregates by facilitating the loss of metals and/or by making the intramolecular disulfide bond more susceptible to reduction, thus allowing the conversion of SOD1 to a form that aggregates to form resembling amyloid. Furthermore, the occurrence of amyloid-like aggregates per se does not depend on forming intermolecular disulfide bonds, and multiple forms of such aggregates can be produced from SOD1.

Energetics and chemical bonding of the 1,3,5-tridehydrobenzene triradical and its protonated form

Energy Technology Data Exchange (ETDEWEB)

Hue Minh Thi Nguyen [Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001 Heverlee, Leuven (Belgium); Faculty of Chemistry, University of Education, Hanoi (Viet Nam); Hoeltzl, Tibor [Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001 Heverlee, Leuven (Belgium); Department of Inorganic Chemistry, University of Technology and Economics Gellert ter 4, H-1521-Budapest (Hungary); Gopakumar, G. [Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001 Heverlee, Leuven (Belgium); Veszpremi, Tamas [Department of Inorganic Chemistry, University of Technology and Economics Gellert ter 4, H-1521-Budapest (Hungary); Peeters, Jozef [Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001 Heverlee, Leuven (Belgium); Minh Tho Nguyen [Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001 Heverlee, Leuven (Belgium)], E-mail: minh.nguyen@chem.kuleuven.be

2005-09-19

Quantum chemical calculations were applied to investigate the electronic structure of the parent 1,3,5-tridehydrobenzene triradical (C{sub 6}H{sub 3}, TDB) and its anion (C{sub 6}H{sub 3}{sup -}), cation (C{sub 6}H{sub 3}{sup +}) and protonated form (C{sub 6}H{sub 4}{sup +}). Our results obtained using the state-averaged complete active space self-consistent-field (CASSCF) followed by second-order multi-state multi-configuration perturbation theory, MS-CASPT2, and MRMP2 in conjunction with the large ANO-L and 6-311++G(3df,2p) basis set, confirm and reveal the followings: (i) TDB has a doublet {sup 2}A{sub 1} ground state with a {sup 4}B{sub 2}-{sup 2}A{sub 1} energy gap of 29kcal/mol, (ii) the ground state of the C{sub 6}H{sub 3}{sup -} anion in the triplet {sup 3}B{sub 2} being 4kcal/mol below the {sup 1}A{sub 1} state. (iii) the electron affinity (EA), ionization energy (IE) and proton affinity (PA) are computed to be: EA=1.6eV, IE=7.2eV, PA=227kcal/mol using UB3LYP/6-311++G(3df,2p)+ZPE; standard heat of formation {delta}H{sub f(298K,1atm)}(TDB)=179+/-2kcal/mol was calculated with CBS-QB3 method. An atoms-in-molecules (AIM) analysis of the structure reveals that the topology of the electron density is similar in all compounds: hydrogens connect to a six-membered ring, except for the case of the {sup 2}A{sub 2} state of C{sub 6}H{sub 4}{sup +} (MBZ{sup +}) which is bicyclic with fused five- and three-membered rings. Properties of the chemical bonds were characterized with Electron Localization Function (ELF) analysis, as well as Wiberg indices, Laplacian and spin density maps. We found that the radicals form separate monosynaptic basins on the ELF space, however its pair character remains high. In the {sup 2}A{sub 1} state of TDB, the radical center is mainly localized on the C1 atom, while in the {sup 2}B{sub 2} state it is equally distributed between the C3 and C5 atoms and, due to the symmetry, in the {sup 4}B{sub 2} state the C1, C2 and C3 atoms have the same

76 FR 66855 - United States Savings Bonds, Series EE, HH and I

Science.gov (United States)

2011-10-28

... registration of definitive series EE savings bonds? * * * If the bond was purchased as a gift or award and the... registered form. * * * * * * * * (c) Registration of bonds purchased as gifts. If the bonds were purchased as... savings bonds? * * * If the bond was purchased as a gift or award and the owner's TIN is not known, the...

Effects of type I collagen degradation on the durability of three adhesive systems in the early phase of dentin bonding.

Directory of Open Access Journals (Sweden)

Lin Hu

Full Text Available This study was designed to evaluate the effects of type I collagen degradation on the durability of three adhesive systems in the early phase of dentin bonding.Bonded dentin specimens were prepared using three different types of adhesive systems. Micro-tensile bond strength and degradation of collagen were tested before, and after 1 month or 4 months of aging in artificial saliva. The relationship between micro-tensile bond strength and collagen degradation was analyzed by calculating their Pearson's correlation coefficient.Aging induced time-dependent reduction in micro-tensile bond strengths for all the tested adhesive systems, although such reduction for the single-step self-etching adhesive G-Bond (GB was not statistically significant. The bond strength of the two-step self-etching primer adhesive system Clearfil SE Bond (SEB was similar to that of the two-step etch-and-rinse self-priming adhesive system Single Bond 2 (SB, and they were both significantly reduced after one or four months of aging. A negative correlation was found between the degree of collagen degradation and magnitude of micro-tensile bond strength (r = -0.65, p = 0.003. The Pearson's correlation coefficient was 0.426, indicating that 42.6% of the aging-induced reduction in bond strength can be explained by the degradation of collagen.In the early phase of dentin bonding, there was a negative correlation between the degree of collagen degradation and the magnitude of micro-tensile bond strength. The reduction of bond strength was accompanied by the degradation of collagen. These results provide evidence for the causative relationship between the degradation of collagen and the deterioration of dentin-adhesive interface.

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

International Nuclear Information System (INIS)

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

2009-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Colby, Denise; Bergman, Robert; Ellman, Jonathan

2010-05-13

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

Composite Laser Ceramics by Advanced Bonding Technology

Science.gov (United States)

Kamimura, Tomosumi; Honda, Sawao

2018-01-01

Composites obtained by bonding materials with the same crystal structure and different chemical compositions can create new functions that do not exist in conventional concepts. We have succeeded in bonding polycrystalline YAG and Nd:YAG ceramics without any interstices at the bonding interface, and the bonding state of this composite was at the atomic level, similar to the grain boundary structure in ceramics. The mechanical strength of the bonded composite reached 278 MPa, which was not less than the strength of each host material (269 and 255 MPa). Thermal conductivity of the composite was 12.3 W/mK (theoretical value) which is intermediate between the thermal conductivities of YAG and Nd:YAG (14.1 and 10.2 W/mK, respectively). Light scattering cannot be detected at the bonding interface of the ceramic composite by laser tomography. Since the scattering coefficients of the monolithic material and the composite material formed by bonding up to 15 layers of the same materials were both 0.10%/cm, there was no occurrence of light scattering due to the bonding. In addition, it was not detected that the optical distortion and non-uniformity of the refractive index variation were caused by the bonding. An excitation light source (LD = 808 nm) was collimated to 200 μm and irradiated into a commercial 1% Nd:YAG single crystal, but fracture damage occurred at a low damage threshold of 80 kW/cm2. On the other hand, the same test was conducted on the bonded interface of 1% Nd:YAG-YAG composite ceramics fabricated in this study, but it was not damaged until the excitation density reached 127 kW/cm2. 0.6% Nd:YAG-YAG composite ceramics showed high damage resistance (up to 223 kW/cm2). It was concluded that composites formed by bonding polycrystalline ceramics are ideal in terms of thermo-mechanical and optical properties. PMID:29425152

Composite Laser Ceramics by Advanced Bonding Technology.

Science.gov (United States)

Ikesue, Akio; Aung, Yan Lin; Kamimura, Tomosumi; Honda, Sawao; Iwamoto, Yuji

2018-02-09

Composites obtained by bonding materials with the same crystal structure and different chemical compositions can create new functions that do not exist in conventional concepts. We have succeeded in bonding polycrystalline YAG and Nd:YAG ceramics without any interstices at the bonding interface, and the bonding state of this composite was at the atomic level, similar to the grain boundary structure in ceramics. The mechanical strength of the bonded composite reached 278 MPa, which was not less than the strength of each host material (269 and 255 MPa). Thermal conductivity of the composite was 12.3 W/mK (theoretical value) which is intermediate between the thermal conductivities of YAG and Nd:YAG (14.1 and 10.2 W/mK, respectively). Light scattering cannot be detected at the bonding interface of the ceramic composite by laser tomography. Since the scattering coefficients of the monolithic material and the composite material formed by bonding up to 15 layers of the same materials were both 0.10%/cm, there was no occurrence of light scattering due to the bonding. In addition, it was not detected that the optical distortion and non-uniformity of the refractive index variation were caused by the bonding. An excitation light source (LD = 808 nm) was collimated to 200 μm and irradiated into a commercial 1% Nd:YAG single crystal, but fracture damage occurred at a low damage threshold of 80 kW/cm². On the other hand, the same test was conducted on the bonded interface of 1% Nd:YAG-YAG composite ceramics fabricated in this study, but it was not damaged until the excitation density reached 127 kW/cm². 0.6% Nd:YAG-YAG composite ceramics showed high damage resistance (up to 223 kW/cm²). It was concluded that composites formed by bonding polycrystalline ceramics are ideal in terms of thermo-mechanical and optical properties.

Rhenium-Promoted C-C Bond-Cleavage Reactions of Internal Propargyl Alcohols.

Science.gov (United States)

Lee, Kui Fun; Bai, Wei; Sung, Herman H Y; Williams, Ian D; Lin, Zhenyang; Jia, Guochen

2018-06-07

The first examples of C-C bond cleavage reactions of internal propargyl alcohols to give vinylidene complexes are described. Treatment of [Re(dppm) 3 ]I with RC≡CC(OH)R'R'' (R=aryl, alkyl; C(OH)R'R''=C(OH)Ph 2, C(OH)Me 2 , C(OH)HPh, C(OH)H 2 ) produced the vinylidene complexes ReI(=C=CHR)(dppm) 2 with the elimination of C(O)R'R''. Computational studies support that the reactions proceed through a β-alkynyl elimination of alkoxide intermediates Re{OC(R')(R'')C≡CR}(dppm) 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Progress in cold roll bonding of metals

International Nuclear Information System (INIS)

Li Long; Nagai, Kotobu; Yin Fuxing

2008-01-01

Layered composite materials have become an increasingly interesting topic in industrial development. Cold roll bonding (CRB), as a solid phase method of bonding same or different metals by rolling at room temperature, has been widely used in manufacturing large layered composite sheets and foils. In this paper, we provide a brief overview of a technology using layered composite materials produced by CRB and discuss the suitability of this technology in the fabrication of layered composite materials. The effects of process parameters on bonding, mainly including process and surface preparation conditions, have been analyzed. Bonding between two sheets can be realized when deformation reduction reaches a threshold value. However, it is essential to remove surface contamination layers to produce a satisfactory bond in CRB. It has been suggested that the degreasing and then scratch brushing of surfaces create a strong bonding between the layers. Bonding mechanisms, in which the film theory is expressed as the major mechanism in CRB, as well as bonding theoretical models, have also been reviewed. It has also been showed that it is easy for fcc structure metals to bond compared with bcc and hcp structure metals. In addition, hardness on bonding same metals plays an important part in CRB. Applications of composites produced by CRB in industrial fields are briefly reviewed and possible developments of CRB in the future are also described. Corrections were made to the abstract and conclusion of this article on 18 June 2008. The corrected electronic version is identical to the print version. (topical review)

Role of the Disulfide Bond in Prion Protein Amyloid Formation: A Thermodynamic and Kinetic Analysis.

Science.gov (United States)

Honda, Ryo

2018-02-27

Prion diseases are associated with the structural conversion of prion protein (PrP) to a β-sheet-rich aggregate, PrP Sc . Previous studies have indicated that a reduction of the disulfide bond linking C179 and C214 of PrP yields an amyloidlike β-rich aggregate in vitro. To gain mechanistic insights into the reduction-induced aggregation, here I characterized how disulfide bond reduction modulates the protein folding/misfolding landscape of PrP, by examining 1) the equilibrium stabilities of the native (N) and aggregated states relative to the unfolded (U) state, 2) the transition barrier separating the U and aggregated states, and 3) the final structure of amyloidlike misfolded aggregates. Kinetic and thermodynamic experiments revealed that disulfide bond reduction decreases the equilibrium stabilities of both the N and aggregated states by ∼3 kcal/mol, without changing either the amyloidlike aggregate structure, at least at the secondary structural level, or the transition barrier of aggregation. Therefore, disulfide bond reduction modulates the protein folding/misfolding landscape by entropically stabilizing disordered states, including the U and transition state of aggregation. This also indicates that the equilibrium stability of the N state, but not the transition barrier of aggregation, is the dominant factor determining the reduction-induced aggregation of PrP. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Bonding in Sulfur-Oxygen Compounds-HSO/SOH and SOO/OSO: An Example of Recoupled Pair π Bonding.

Science.gov (United States)

Lindquist, Beth A; Takeshita, Tyler Y; Woon, David E; Dunning, Thom H

2013-10-08

The ground states (X(2)A″) of HSO and SOH are extremely close in energy, yet their molecular structures differ dramatically, e.g., re(SO) is 1.485 Å in HSO and 1.632 Å in SOH. The SO bond is also much stronger in HSO than in SOH: 100.3 kcal/mol versus 78.8 kcal/mol [RCCSD(T)-F12/AVTZ]. Similar differences are found in the SO2 isomers, SOO and OSO, depending on whether the second oxygen atom binds to oxygen or sulfur. We report generalized valence bond and RCCSD(T)-F12 calculations on HSO/SOH and OSO/SOO and analyze the bonding in all four species. We find that HSO has a shorter and stronger SO bond than SOH due to the presence of a recoupled pair bond in the π(a″) system of HSO. Similarly, the bonding in SOO and OSO differs greatly. SOO is like ozone and has substantial diradical character, while OSO has two recoupled pair π bonds and negligible diradical character. The ability of the sulfur atom to form recoupled pair bonds provides a natural explanation for the dramatic variation in the bonding in these and many other sulfur-oxygen compounds.

Mechanics of wafer bonding: Effect of clamping

Science.gov (United States)

Turner, K. T.; Thouless, M. D.; Spearing, S. M.

2004-01-01

A mechanics-based model is developed to examine the effects of clamping during wafer bonding processes. The model provides closed-form expressions that relate the initial geometry and elastic properties of the wafers to the final shape of the bonded pair and the strain energy release rate at the interface for two different clamping configurations. The results demonstrate that the curvature of bonded pairs may be controlled through the use of specific clamping arrangements during the bonding process. Furthermore, it is demonstrated that the strain energy release rate depends on the clamping configuration and that using applied loads usually leads to an undesirable increase in the strain energy release rate. The results are discussed in detail and implications for process development and bonding tool design are highlighted.

Cathodic reduction of the duplex oxide films formed on copper in air with high relative humidity at 60 deg C

International Nuclear Information System (INIS)

Seo, M.; Ishikawa, Y.; Kodaira, M.; Sugimoto, A.; Nakayama, S.; Watanabe, M.; Furuya, S.; Minamitani, R.; Miyata, Y.; Nishikata, A.; Notoya, T.

2005-01-01

The cathodic reduction of duplex air-formed oxide film on copper was performed at a constant current density of i c = -50 μA cm -2 in deaerated 0.1 M KCl solution to investigate the sequence of cathodic reduction of each oxide layer and its mechanism. The single-phase thick CuO film on copper was also cathodically reduced at i c = -50 μA cm -2 or -2.5 mA cm -2 . The surface characterizations of the air-formed oxide film and single-phase CuO film before cathodic reduction and after partial or complete cathodic reduction were performed by XPS and X-ray diffraction, respectively. The two plateau regions appeared in the potential vs. time curve during cathodic reduction of the duplex air-formed oxide film on copper, while one plateau region was observed in the potential-time curve during cathodic reduction of the single-phase CuO film on copper. The potential in the first plateau region for the air-formed film coincided with that in the plateau region for the CuO film. The results of XPS and X-ray diffraction suggested that in the first plateau region, the outer CuO layer is directly reduced to metallic Cu, while in the second plateau region, the inner Cu 2 O layer is reduced to metallic Cu

Halogen-bonded network of trinuclear copper(II 4-iodopyrazolate complexes formed by mutual breakdown of chloroform and nanojars

Directory of Open Access Journals (Sweden)

Stuart A. Surmann

2016-11-01

Full Text Available Crystals of bis(tetrabutylammonium di-μ3-chlorido-tris(μ2-4-iodopyrazolato-κ2N:N′tris[chloridocuprate(II] 1,4-dioxane hemisolvate, (C16H36N2[Cu3(C3H2IN23Cl5]·0.5C4H8O or (Bu4N2[CuII3(μ3-Cl2(μ-4-I-pz3Cl3]·0.5C4H8O, were obtained by evaporating a solution of (Bu4N2[{CuII(μ-OH(μ-4-I-pz}nCO3] (n = 27–31 nanojars in chloroform/1,4-dioxane. The decomposition of chloroform in the presence of oxygen and moisture provides HCl, which leads to the breakdown of nanojars to the title trinuclear copper(II pyrazolate complex, and possibly CuII ions and free 4-iodopyrazole. CuII ions, in turn, act as catalyst for the accelerated decomposition of chloroform, ultimately leading to the complete breakdown of nanojars. The crystal structure presented here provides the first structural description of a trinuclear copper(II pyrazolate complex with iodine-substituted pyrazoles. In contrast to related trinuclear complexes based on differently substituted 4-R-pyrazoles (R = H, Cl, Br, Me, the [Cu3(μ-4-I-pz3Cl3] core in the title complex is nearly planar. This difference is likely a result of the presence of the iodine substituent, which provides a unique, novel feature in copper pyrazolate chemistry. Thus, the iodine atoms form halogen bonds with the terminal chlorido ligands of the surrounding complexes [mean length of I...Cl contacts = 3.48 (1 Å], leading to an extended two-dimensional, halogen-bonded network along (-110. The cavities within this framework are filled by centrosymmetric 1,4-dioxane solvent molecules, which create further bridges via C—H...Cl hydrogen bonds with terminal chlorido ligands of the trinuclear complex not involved in halogen bonding.

27 CFR 28.286 - Receipt in customs bonded warehouse.

Science.gov (United States)

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Receipt in customs bonded... in Customs Bonded Warehouse § 28.286 Receipt in customs bonded warehouse. On receipt of the distilled spirits or wine and the related TTB Form 5100.11 or 5110.30 as the case may be, the customs officer in...

Apatite and sodalite based glass-bonded waste forms for immobilization of 129I and mixed halide radioactive wastes

Energy Technology Data Exchange (ETDEWEB)

Goel, Ashutosh [Rutgers Univ., New Brunswick, NJ (United States); McCloy, John S. [Washington State Univ., Pullman, WA (United States); Riley, Brian J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Matyas, Josef [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2017-12-30

The goal of the project was to utilize the knowledge accumulated by the team, in working with minerals for chloride wastes and biological apatites, toward the development of advanced waste forms for immobilizing 129I and mixed-halide wastes. Based on our knowledge, experience, and thorough literature review, we had selected two minerals with different crystal structures and potential for high chemical durability, sodalite and CaP/PbV-apatite, to form the basis of this project. The focus of the proposed effort was towards: (i) low temperature synthesis of proposed minerals (iodine containing sodalite and apatite) leading to the development of monolithic waste forms, (ii) development of a fundamental understanding of the atomic-scale to meso-scale mechanisms of radionuclide incorporation in them, and (iii) understanding of the mechanism of their chemical corrosion, alteration mechanism, and rates. The proposed work was divided into four broad sections. deliverables. 1. Synthesis of materials 2. Materials structural and thermal characterization 3. Design of glass compositions and synthesis glass-bonded minerals, and 4. Chemical durability testing of materials.

Nickel-Catalyzed C sp2 –C sp3 Cross-Coupling via C–O Bond Activation

KAUST Repository

Guo, Lin; Hsiao, Chien-Chi; Yue, Huifeng; Liu, Xiangqian; Rueping, Magnus

2016-01-01

through Csp2-O substitution, without the restriction of β-hydride elimination. Moreover, the advantage of the newly developed method was demonstrated in a selective and sequential C-O bond activation process. © 2016 American Chemical Society.

Dissecting the role of disulfide bonds on the amyloid formation of insulin

International Nuclear Information System (INIS)

Li, Yang; Gong, Hao; Sun, Yue; Yan, Juan; Cheng, Biao; Zhang, Xin; Huang, Jing; Yu, Mengying; Guo, Yu; Zheng, Ling; Huang, Kun

2012-01-01

Highlights: ► We dissect how individual disulfide bond affects the amyloidogenicity of insulin. ► A controlled reduction system for insulin is established in this study. ► Disulfide breakage is associated with unfolding and increased amyloidogenicity. ► Breakage of A6-A11 is associated with significantly increased cytotoxicity. ► Analogs without A6-A11 have a higher potency to form high order toxic oligomers. -- Abstract: Disulfide bonds play a critical role in the stability and folding of proteins. Here, we used insulin as a model system, to investigate the role of its individual disulfide bond during the amyloid formation of insulin. Tris(2-carboxyethyl)phosphine (TCEP) was applied to reduce two of the three disulfide bonds in porcine insulin and the reduced disulfide bonds were then alkylated by iodoacetamide. Three disulfide bond-modified insulin analogs, INS-2 (lack of A6-A11), INS-3 (lack of A7-B7) and INS-6 (lack of both A6-A11 and A7-B7), were obtained. Far-UV circular dichroism (CD) spectroscopy results indicated that the secondary structure of INS-2 was the closest to insulin under neutral conditions, followed by INS-3 and INS-6, whereas in an acidic solution all analogs were essentially unfolded. To test how these modifications affect the amyloidogenicity of insulin, thioflavin-T (ThT) fluorescence and transmission electronic microscopy (TEM) were performed. Our results showed that all analogs were more prone to aggregation than insulin, with the order of aggregation rates being INS-6 > INS-3 > INS-2. Cross-linking of unmodified proteins (PICUP) assay results showed that analogs without A6-A11 (INS-2 and INS-6) have a higher potential for oligomerization than insulin and INS-3, which is accompanied with a higher cytotoxicity as the hemolytic assays of human erythrocytes suggested. The results indicated that breakage of A7-B7 induced more unfolding of the insulin structure and a higher amyloidogenicity than breakage of A6-A11, but breakage of A6

On the photostability of the disulfide bond

DEFF Research Database (Denmark)

Stephansen, Anne Boutrup; Larsen, Martin Alex Bjørn; Klein, Liv Bærenholdt

2014-01-01

Photostability is an essential property of molecular building blocks of nature. Disulfides are central in the structure determination of proteins, which is in striking contradiction to the result that the S-S bond is a photochemically labile structural entity that cleaves to form free radicals upon...... on a sub 50 fs timescale without further ado. In a cyclic motif resembling the cysteine-disulfide bond in proteins, light can perturb the S-S bond to generate short-lived diradicaloid species, but the sulfur atoms are conformationally restricted by the ring that prevents the sulfur atoms from flying apart...... the photostability of disulfide-bonds must be ascribed a cyclic structural arrangement....

H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds

Directory of Open Access Journals (Sweden)

Ibon Alkorta

2016-02-01

Full Text Available A search of the Cambridge Structural Database (CSD was carried out for phosphine-water and arsine-water complexes in which water is either the proton donor in hydrogen-bonded complexes, or the electron-pair donor in pnicogen-bonded complexes. The range of experimental P-O distances in the phosphine complexes is consistent with the results of ab initio MP2/aug’-cc-pVTZ calculations carried out on complexes H2XP:OH2, for X = NC, F, Cl, CN, OH, CCH, H, and CH3. Only hydrogen-bonded complexes are found on the H2(CH3P:HOH and H3P:HOH potential surfaces, while only pnicogen-bonded complexes exist on H2(NCP:OH2, H2FP:OH2, H2(CNP:OH2, and H2(OHP:OH2 surfaces. Both hydrogen-bonded and pnicogen-bonded complexes are found on the H2ClP:OH2 and H2(CCHP:OH2 surfaces, with the pnicogen-bonded complexes more stable than the corresponding hydrogen-bonded complexes. The more electronegative substituents prefer to form pnicogen-bonded complexes, while the more electropositive substituents form hydrogen-bonded complexes. The H2XP:OH2 complexes are characterized in terms of their structures, binding energies, charge-transfer energies, and spin-spin coupling constants 2hJ(O-P, 1hJ(H-P, and 1J(O-H across hydrogen bonds, and 1pJ(P-O across pnicogen bonds.

Hydrogen bonding in tight environments

DEFF Research Database (Denmark)

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

2016-01-01

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

Relationship between surface area for adhesion and tensile bond strength--evaluation of a micro-tensile bond test.

Science.gov (United States)

Sano, H; Shono, T; Sonoda, H; Takatsu, T; Ciucchi, B; Carvalho, R; Pashley, D H

1994-07-01

The purpose of this study was to test the null hypothesis that there is no relationship between the bonded surface area of dentin and the tensile strength of adhesive materials. The enamel was removed from the occlusal surface of extracted human third molars, and the entire flat surface was covered with resin composite bonded to the dentin to form a flat resin composite crown. Twenty-four hours later, the bonded specimens were sectioned parallel to the long axis of the tooth into 10-20 thin sections whose upper part was composed of resin composite with the lower half being dentin. These small sections were trimmed using a high speed diamond bur into an hourglass shape with the narrowest portion at the bonded interface. Surface area was varied by altering the specimen thickness and width. Tensile bond strength was measured using custom-made grips in a universal testing machine. Tensile bond strength was inversely related to bonded surface area. At surface areas below 0.4 mm2, the tensile bond strengths were about 55 MPa for Clearfil Liner Bond 2 (Kuraray Co., Ltd.), 38 MPa for Scotchbond MP (3M Dental Products), and 20 MPa for Vitremer (3M Dental Products). At these small surface areas all of the bond failures were adhesive in nature. This new method permits measurement of high bond strengths without cohesive failure of dentin. It also permits multiple measurements to be made within a single tooth.

Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)(-) bonded system.

Science.gov (United States)

Pylaeva, Svetlana; Allolio, Christoph; Koeppe, Benjamin; Denisov, Gleb S; Limbach, Hans-Heinrich; Sebastiani, Daniel; Tolstoy, Peter M

2015-02-14

We present a joint experimental and quantum chemical study on the influence of solvent dynamics on the protonation equilibrium in a strongly hydrogen bonded phenol-acetate complex in CD2Cl2. Particular attention is given to the correlation of the proton position distribution with the internal conformation of the complex itself and with fluctuations of the aprotic solvent. Specifically, we have focused on a complex formed by 4-nitrophenol and tetraalkylammonium-acetate in CD2Cl2. Experimentally we have used combined low-temperature (1)H and (13)C NMR and UV-vis spectroscopy and showed that a very strong OHO hydrogen bond is formed with proton tautomerism (PhOH···(-)OAc and PhO(-)···HOAc forms, both strongly hydrogen bonded). Computationally, we have employed ab initio molecular dynamics (70 and 71 solvent molecules, with and without the presence of a counter-cation, respectively). We demonstrate that the relative motion of the counter-cation and the "free" carbonyl group of the acid plays the major role in the OHO bond geometry and causes proton "jumps", i.e. interconversion of PhOH···(-)OAc and PhO(-)···HOAc tautomers. Weak H-bonds between CH(CD) groups of the solvent and the oxygen atom of carbonyl stabilize the PhOH···(-)OAc type of structures. Breaking of CH···O bonds shifts the equilibrium towards PhO(-)···HOAc form.

Nickel-Catalyzed C sp2 –C sp3 Cross-Coupling via C–O Bond Activation

KAUST Repository

Guo, Lin

2016-06-13

A new and efficient nickel-catalyzed alkylation of CAr-O electrophiles with B-alkyl-9-BBNs is described. The transformation is characterized by its functional group tolerance and provides a practical and versatile access to various Csp2-Csp3 bonds through Csp2-O substitution, without the restriction of β-hydride elimination. Moreover, the advantage of the newly developed method was demonstrated in a selective and sequential C-O bond activation process. © 2016 American Chemical Society.

Analysis reveals potential rangeland impacts if Williamson Act eliminated

Directory of Open Access Journals (Sweden)

William C. Wetzel

2012-10-01

Full Text Available California budget cuts have resulted in dramatic reductions in state funding for the Williamson Act, a land protection program that reduces property taxes for the owners of 15 million acres of California farms and rangeland. With state reimbursements to counties eliminated, the decision to continue Williamson Act contracts lies with individual counties. We investigated the consequences of eliminating the Williamson Act, using a geospatial analysis and a mail questionnaire asking ranchers for plans under a hypothetical elimination scenario. The geospatial analysis revealed that 72% of rangeland parcels enrolled in Williamson Act contracts contained habitat important for statewide conservation goals. Presented with the elimination scenario, survey respondents reported an intention to sell 20% of their total 496,889 acres. The tendency of survey participants to respond that they would sell land was highest among full-time ranchers with low household incomes and without off-ranch employment. A majority (76% of the ranchers who reported that they would sell land predicted that the buyers would develop it for nonagricultural uses, suggesting substantial changes to California's landscape in a future without the Williamson Act.

Stereoelectronic control in peptide bond formation. Ab initio calculations and speculations on the mechanism of action of serine proteases.

Science.gov (United States)

Gorenstein, D G; Taira, K

1984-01-01

Ab initio molecular orbital calculations have been performed on the reaction profile for the addition/elimination reaction between ammonia and formic acid, proceeding via a tetrahedral intermediate: NH3 + HCO2H----H2NCH(OH)2----NH2CHO + H2O. Calculated transition state energies for the first addition step of the reaction revealed that a lone pair on the oxygen of the OH group, which is antiperiplanar to the attacking nitrogen, stabilized the transition state by 3.9 kcal/mol, thus supporting the hypothesis of stereoelectronic control for this reaction. In addition, a secondary, counterbalancing stereoelectronic effect stabilizes the second step, water elimination, transition state by 3.1 kcal/mol if the lone pair on the leaving water oxygen is not antiperiplanar to the C-N bond. The best conformation for the transition states was thus one with a lone pair antiperiplanar to the adjacent scissile bond and also one without a lone-pair orbital on the scissile bond oxygen or nitrogen antiperiplanar to the adjacent polar bond. The significance of these stereoelectronic effects for the mechanism of action of serine proteases is discussed. PMID:6394065

Reversible conversion of valence-tautomeric copper metal-organic frameworks dependent single-crystal-to-single-crystal oxidation/reduction: a redox-switchable catalyst for C-H bonds activation reaction.

Science.gov (United States)

Huang, Chao; Wu, Jie; Song, Chuanjun; Ding, Ran; Qiao, Yan; Hou, Hongwei; Chang, Junbiao; Fan, Yaoting

2015-06-28

Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like Cu(I) framework and a topologically equivalent neutral Cu(I)Cu(II) mixed-valent framework. The unique conversion behavior of the Cu(I) framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C-H bonds.

Hanford Site annual waste reduction report

International Nuclear Information System (INIS)

Nichols, D.H.

1992-03-01

The US Department of Energy (DOE), Richland Field Office (RL) has developed and implemented a Hanford Site Waste Minimization and Pollution Prevention Awareness Plan that provides overall guidance and direction on waste minimization and pollution prevention awareness to the four contractors who manage and operate the Hanford Site for the RL. Waste reduction at the RL will be accomplished by following a hierarchy of environmental protection practices. First, waste generation will be eliminated or minimized through source reduction. Second, potential waste materials that cannot be eliminated or minimized will be recycled (i.e., used, reused, or reclaimed). Third, all waste that is nevertheless generated will be treated to reduce volume, toxicity, or mobility before storage or disposal. The scope of this waste reduction program will include nonhazardous, hazardous, radioactive mixed, and radioactive wastes

One period coupon bond valuation with revised first passage time approach and the application in Indonesian corporate bond

Science.gov (United States)

Maruddani, Di Asih I.; Rosadi, Dedi; Gunardic, Abdurakhman

2015-02-01

The value of a corporate bond is conventionally expressed in terms of zero coupon bond. In practice, the most common form of debt instrument is coupon bond and allows early default before maturity as safety covenant for the bondholder. This paper study valuation for one period coupon bond, a coupon bond that only give one time coupon at the bond period. It assumes that the model give bondholder the right to reorganize a firm if its value falls below a given barrier. Revised first passage time approach is applied for default time rule. As a result, formulas of equity, liability, and probability of default is derived for this specified model. Straightforward integration under risk neutral pricing is used for deriving those formulas. For the application, bond of Bank Rakyat Indonesia (BRI) as one of the largest bank in Indonesia is analyzed. R computing show that value of the equity is IDR 453.724.549.000.000, the liability is IDR 2.657.394.000.000, and the probability if default is 5.645305E-47 %.

Green synthesis of gold nanoparticles using aspartame and their catalytic activity for p-nitrophenol reduction

Science.gov (United States)

Wu, Shufen; Yan, Songjing; Qi, Wei; Huang, Renliang; Cui, Jing; Su, Rongxin; He, Zhimin

2015-05-01

We demonstrated a facile and environmental-friendly approach to form gold nanoparticles through the reduction of HAuCl4 by aspartame. The single-crystalline structure was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared (FTIR) results indicated that aspartame played a pivotal role in the reduction and stabilization of the gold crystals. The crystals were stabilized through the successive hydrogen-bonding network constructed between the water and aspartame molecules. Additionally, gold nanoparticles synthesized through aspartame were shown to have good catalytic activity for the reduction of p-nitrophenol to p-aminophenol in the presence of NaBH4.

Nondestructive testing of thermocompression bonds. Final report

International Nuclear Information System (INIS)

Hale, G.M.

1981-02-01

A Scanning Laser Acoustic Microscope (SLAM) was used to characterize hybrid microcircuit beam lead bonds formed on thin film networks by a thermocompression process. Results from subsequent pull testing show that the SLAM offered no significant advantage over visual inspection for detecting bad bonds. Infrared microscopy and resistance measurements were also reviewed and rejected as being ineffective inspection methods

Ab initio studies on the solvation, electronic structures and intracluster reactions in M(+)L(n), with M(+)=magnesium and calcium singly-charged ions, L=water, methanol, ammonia, and n=1-6, and the elimination of a hydrogen atom in H atom in hydrated sodium clusters

Science.gov (United States)

Chan, Ka Wai

The solvation and electronic structures of M+Ln, with M+ = Mg+ and Cat, L = H2O, CH 3OH and NH3, n=1-6 were investigated by ab initio calculations using G03 package and density functional theory based ab initio molecular dynamics (AIMD) simulations with projector augmented-wave (PAW) method and a planewave basis set using Vienna Ab initio Simulation Package (VASP). Furthermore, ab initio studies on the intracluster reactions of Mg+ and Ca+ ions with different solvent molecules, H2O, CH3OH and NH3, were also done using G03 package. Finally, the elimination of a H atom in Na(H2O)n was studied. Such studies on the interactions and reactivity in gas clusters can provide insights into their analogies existing in condense phase. Interactions of Mg+ and Ca+ ions in different solvent molecules, H2O, CH3OH and NH3, were calculated with B3LYP and MP2 methods with basis sets 6-31+g** and 6-311+g**. A systematic comparison on the structures and reactivities of these clusters should provide a better understanding on the interplay of the ion-solvent, solvent-solvent, and electron-solvent interactions. It can provide a better understanding on the structures and bonding of complexes having analogies to those existing in condense phase. For Mg+(CH3OH)n and Ca+(CH 3OH)n, both H-elimination from OH/CH bond and CH3-elimination were investigated. H-elimination from O---H bond becomes more accessible for large cluster due to the diffusion of electron density to O---H bond. Studies on the H-elimination in Mg+(NH3)n and H-elimination from C---H bond in Mg+(CH3OH) n show that the reaction barriers flatten above 20 kcal/mol as n reaches 4 and above. These calculation results prove that the source of loss of H atom in ground state Mg+(CH3OH)n should be through the O---H bond rather than through the C---H bond. Compared to Mg+(CH3OH)n, the reaction barriers for H-elimination in Mg+(NH3)n is much larger, which is in consistent with the experimental observation of little H-elimination for Mg

Reversible insertion of carbon dioxide into Pt(II)-hydroxo bonds.

Science.gov (United States)

Lohr, Tracy L; Piers, Warren E; Parvez, Masood

2013-10-01

The reactivity of three monomeric diimine Pt(II) hydroxo complexes, (NN)Pt(OH)R (NN = bulky diimine ligand; R = OH, ; R = C6H5, ; R = CH3, ) towards carbon dioxide has been investigated. Insertion into the Pt-OH bonds was found to be facile and reversible at low temperature for all compounds; the reaction with bis-hydroxide gives an isolable κ(2)-carbonato compound , with elimination of water.

Physical mechanisms of copper-copper wafer bonding

International Nuclear Information System (INIS)

Rebhan, B.; Hingerl, K.

2015-01-01

The study of the physical mechanisms driving Cu-Cu wafer bonding allowed for reducing the bonding temperatures below 200 °C. Metal thermo-compression Cu-Cu wafer bonding results obtained at such low temperatures are very encouraging and suggest that the process is possible even at room temperature if some boundary conditions are fulfilled. Sputtered (PVD) and electroplated Cu thin layers were investigated, and the analysis of both metallization techniques demonstrated the importance of decreasing Cu surface roughness. For an equal surface roughness, the bonding temperature of PVD Cu wafers could be even further reduced due to the favorable microstructure. Their smaller grain size enhances the length of the grain boundaries (observed on the surface prior bonding), acting as efficient mass transfer channels across the interface, and hence the grains are able to grow over the initial bonding interface. Due to the higher concentration of random high-angle grain boundaries, this effect is intensified. The model presented is explaining the microstructural changes based on atomic migration, taking into account that the reduction of the grain boundary area is the major driving force to reduce the Gibbs free energy, and predicts the subsequent microstructure evolution (grain growth) during thermal annealing

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

KAUST Repository

Chikalov, Igor

2011-04-02

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

Effect of transient liquid phase (TLP) bonding on the ductility of a Ni-base single crystal superalloy in a stress rupture test

International Nuclear Information System (INIS)

Liu, J.D.; Jin, T.; Zhao, N.R.; Wang, Z.H.; Sun, X.F.; Guan, H.R.; Hu, Z.Q.

2008-01-01

A Ni-base single crystal superalloy was transient liquid phase (TLP) bonded using a Ni-Cr-B amorphous foil at 1230 deg. C for 8 h. Stress rupture tests of the TLP joint and a matrix sample were carried out at 982 deg. C/248 MPa and 1010 deg. C/248 MPa. The microstructures and fracture surfaces were studied using scanning electron microscopy (SEM). Transmission electron microscopy (TEM) investigations were performed after creep rupture testing to examine the deformation substructures. The results show that the stress rupture ductility of TLP joints is significantly decreased compared to the matrix sample. This reduction of the ductility of TLP joints can be attributed to solid solution strengthening by boron atoms, subgrain boundaries formed in the bonding zone and the concentration of creep cavities formed during the last stage of the stress rupture test

INVESTMENTS IN BONDS ON ROMANIA’S CAPITAL MARKET

Directory of Open Access Journals (Sweden)

ILIE RĂSCOLEAN

2010-01-01

Full Text Available Capital market, both the primary and secondary record financial transactions not only through property titles, but also issues debt securities, designed to attract monetary funds in the form of loans or medium term. Bonds are securities, consisting of a long-term debt on a company giving the holder of Bonds (Bondholders claim equal rights, corresponding nominal value of the bond. Bonds can be bought either in the public offering period, from banks or corporations Brokerage Financial Services Distributors, or from the stock through a brokerage firm by a procedure similar to that for action. Investing in bonds also entails risks, among which include the risk of default, interest rate risks and currency risks.

Analytical energy gradient for the two-component normalized elimination of the small component method

Energy Technology Data Exchange (ETDEWEB)

Zou, Wenli; Filatov, Michael; Cremer, Dieter, E-mail: dcremer@smu.edu [Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, 3215 Daniel Ave, Dallas, Texas 75275-0314 (United States)

2015-06-07

The analytical gradient for the two-component Normalized Elimination of the Small Component (2c-NESC) method is presented. The 2c-NESC is a Dirac-exact method that employs the exact two-component one-electron Hamiltonian and thus leads to exact Dirac spin-orbit (SO) splittings for one-electron atoms. For many-electron atoms and molecules, the effect of the two-electron SO interaction is modeled by a screened nucleus potential using effective nuclear charges as proposed by Boettger [Phys. Rev. B 62, 7809 (2000)]. The effect of spin-orbit coupling (SOC) on molecular geometries is analyzed utilizing the properties of the frontier orbitals and calculated SO couplings. It is shown that bond lengths can either be lengthened or shortened under the impact of SOC where in the first case the influence of low lying excited states with occupied antibonding orbitals plays a role and in the second case the jj-coupling between occupied antibonding and unoccupied bonding orbitals dominates. In general, the effect of SOC on bond lengths is relatively small (≤5% of the scalar relativistic changes in the bond length). However, large effects are found for van der Waals complexes Hg{sub 2} and Cn{sub 2}, which are due to the admixture of more bonding character to the highest occupied spinors.

Comparison of hydroxyapatite and dental enamel for testing shear bond strengths.

Science.gov (United States)

Imthiaz, Nishat; Georgiou, George; Moles, David R; Jones, Steven P

2008-05-01

To investigate the feasibility of using artificial hydroxyapatite as a future biomimetic laboratory substitute for human enamel in orthodontic bond strength testing by comparing the shear bond strengths and nature of failure of brackets bonded to samples of hydroxyapatite and enamel. One hundred and fifty hydroxyapatite discs were prepared by compression at 20 tons and fired in a furnace at 1300 degrees C. One hundred and five enamel samples were prepared from the buccal and palatal/lingual surfaces of healthy premolars extracted for orthodontic purposes. Orthodontic brackets were bonded to each sample and these were subjected to shear bond strength testing using a custom-made jig mounted in an Instron Universal Testing Machine. The force value at bond failure was obtained, together with the nature of failure which was assessed using the Adhesive Remnant Index. The mean shear bond strength for the enamel samples was 16.62 MPa (95 per cent CI: 15.26, 17.98) and for the hydroxyapatite samples 20.83 MPa (95 per cent CI: 19.68, 21.98). The difference between the two samples was statistically significant (p enamel samples scored 2 or 3, while 49 per cent of the hydroxyapatite samples scored 0 or 1. Hydroxyapatite was an effective biomimetic substrate for bond strength testing with a mean shear bond strength value (20.83 MPa) at the upper end of the normal range attributed to enamel (15-20 MPa). Although the difference between the shear bond strengths for hydroxyapatite and enamel was statistically significant, hydroxyapatite could be used as an alternative to enamel for comparative laboratory studies until a closer alternative is found. This would eliminate the need for extracted teeth to be collected. However, it should be used with caution for quantitative studies where true bond strengths are to be investigated.

Dentine bond strength and antimicrobial activity evaluation of adhesive systems.

Science.gov (United States)

André, Carolina Bosso; Gomes, Brenda Paula Figueiredo Almeida; Duque, Thais Mageste; Stipp, Rafael Nobrega; Chan, Daniel Chi Ngai; Ambrosano, Glaucia Maria Bovi; Giannini, Marcelo

2015-04-01

This study evaluated the dentine bond strength (BS) and the antibacterial activity (AA) of six adhesives against strict anaerobic and facultative bacteria. Three adhesives containing antibacterial components (Gluma 2Bond (glutaraldehyde)/G2B, Clearfil SE Protect (MDPB)/CSP and Peak Universal Bond (PUB)/chlorhexidine) and the same adhesive versions without antibacterial agents (Gluma Comfort Bond/GCB, Clearfil SE Bond/CSB and Peak LC Bond/PLB) were tested. The AA of adhesives and control groups was evaluated by direct contact method against four strict anaerobic and four facultative bacteria. After incubation, according to the appropriate periods of time for each microorganism, the time to kill microorganisms was measured. For BS, the adhesives were applied according to manufacturers' recommendations and teeth restored with composite. Teeth (n=10) were sectioned to obtain bonded beams specimens, which were tested after artificial saliva storage for one week and one year. BS data were analyzed using two-way ANOVA and Tukey test. Saliva storage for one year reduces the BS only for GCB. In general G2B and GCB required at least 24h for killing microorganisms. PUB and PLB killed only strict anaerobic microorganisms after 24h. For CSP the average time to eliminate the Streptococcus mutans and strict anaerobic oral pathogens was 30 min. CSB showed no AA against facultative bacteria, but had AA against some strict anaerobic microorganisms. Storage time had no effect on the BS for most of the adhesives. The time required to kill bacteria depended on the type of adhesive and never was less than 10 min. Most of the adhesives showed stable bond strength after one year and the Clearfil SE Protect may be a good alternative in restorative procedures performed on dentine, considering its adequate bond strength and better antibacterial activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Tensile and fatigue properties of weld-bonded and adhesive-bonded magnesium alloy joints

International Nuclear Information System (INIS)

Xu, W.; Liu, L.; Zhou, Y.; Mori, H.; Chen, D.L.

2013-01-01

The microstructures, tensile and fatigue properties of weld-bonded (WB) AZ31B-H24 Mg/Mg joints with different sizes of bonding area were evaluated and compared with the adhesive-bonded (AB) Mg/Mg joints. Typical equiaxed dendritic structures containing divorced eutectic Mg 17 Al 12 particles formed in the fusion zone of both WB-1 (with a bonding area of 35 mm×35 mm) and WB-0.5 (with a bonding area of 17.5 mm×35 mm) joints. Less solidification shrinkage cracking was observed in the WB-0.5 joints than WB-1 joints. While the WB-0.5 joints exhibited a slightly lower maximum tensile shear stress than the AB-0.5 joints (with a bonding area of 17.5 mm×35 mm), the energy absorption was equivalent. Although the AB-0.5 joints exhibited a higher fatigue resistance at higher cyclic stress levels, both the AB-0.5 and WB-0.5 joints showed an equivalent fatigue resistance at lower cyclic stress levels. A higher fatigue limit was observed in the WB-0.5 joints than in the WB-1 joints owing to the presence of fewer shrinkage pores. Cohesive failure mode along the adhesive layer in conjunction with partial nugget pull-out from the weld was observed at the higher cyclic loads, and fatigue failure occurred in the base metal at the lower cyclic loads

Mutation choice to eliminate buried free cysteines in protein therapeutics.

Science.gov (United States)

Xia, Xue; Longo, Liam M; Blaber, Michael

2015-02-01

Buried free-cysteine (Cys) residues can contribute to an irreversible unfolding pathway that promotes protein aggregation, increases immunogenic potential, and significantly reduces protein functional half-life. Consequently, mutation of buried free-Cys residues can result in significant improvement in the storage, reconstitution, and pharmacokinetic properties of protein-based therapeutics. Mutational design to eliminate buried free-Cys residues typically follows one of two common heuristics: either substitution by Ser (polar and isosteric), or substitution by Ala or Val (hydrophobic); however, a detailed structural and thermodynamic understanding of Cys mutations is lacking. We report a comprehensive structure and stability study of Ala, Ser, Thr, and Val mutations at each of the three buried free-Cys positions (Cys16, Cys83, and Cys117) in fibroblast growth factor-1. Mutation was almost universally destabilizing, indicating a general optimization for the wild-type Cys, including van der Waals and H-bond interactions. Structural response to Cys mutation characteristically involved changes to maintain, or effectively substitute, local H-bond interactions-by either structural collapse to accommodate the smaller oxygen radius of Ser/Thr, or conversely, expansion to enable inclusion of novel H-bonding solvent. Despite the diverse structural effects, the least destabilizing average substitution at each position was Ala, and not isosteric Ser. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

TOPICAL REVIEW Progress in cold roll bonding of metals

Directory of Open Access Journals (Sweden)

Long Li, Kotobu Nagai and Fuxing Yin

2008-01-01

Full Text Available Layered composite materials have become an increasingly interesting topic in industrial development. Cold roll bonding (CRB, as a solid phase method of bonding same or different metals by rolling at room temperature, has been widely used in manufacturing large layered composite sheets and foils. In this paper, we provide a brief overview of a technology using layered composite materials produced by CRB and discuss the suitability of this technology in the fabrication of layered composite materials. The effects of process parameters on bonding, mainly including process and surface preparation conditions, have been analyzed. Bonding between two sheets can be realized when deformation reduction reaches a threshold value. However, it is essential to remove surface contamination layers to produce a satisfactory bond in CRB. It has been suggested that the degreasing and then scratch brushing of surfaces create a strong bonding between the layers. Bonding mechanisms, in which the film theory is expressed as the major mechanism in CRB, as well as bonding theoretical models, have also been reviewed. It has also been showed that it is easy for fcc structure metals to bond compared with bcc and hcp structure metals. In addition, hardness on bonding same metals plays an important part in CRB. Applications of composites produced by CRB in industrial fields are briefly reviewed and possible developments of CRB in the future are also described.

Thai students' mental model of chemical bonding

Science.gov (United States)

Sarawan, Supawadee; Yuenyong, Chokchai

2018-01-01

This Research was finding the viewing about concept of chemical bonding is fundamental to subsequent learning of various other topics related to this concept in chemistry. Any conceptions about atomic structures that students have will be shown their further learning. The purpose of this study is to interviews conceptions held by high school chemistry students about metallic bonding and to reveal mental model of atomic structures show according to the educational level. With this aim, the questionnaire prepared making use of the literature and administered for analysis about mental model of chemical bonding. It was determined from the analysis of answers of questionnaire the 10th grade, 11th grade and 12th grade students. Finally, each was shown prompts in the form of focus cards derived from curriculum material that showed ways in which the bonding in specific metallic substances had been depicted. Students' responses revealed that learners across all three levels prefer simple, realistic mental models for metallic bonding and reveal to chemical bonding.

Development of a reduction-sensitive diselenide-conjugated oligoethylenimine nanoparticulate system as a gene carrier

Directory of Open Access Journals (Sweden)

Cheng G

2012-07-01

Full Text Available Gang Cheng,1,2 Yiyan He,1 Li Xie,1 Yu Nie,1 Bin He,1 Zhirong Zhang,2 Zhongwei Gu11National Engineering Research Center for Biomaterials, 2Key Laboratory of Drug Targeting and Drug Delivery Systems, West China School of Pharmacy, Sichuan University, Chengdu, Sichuan, People's Republic of ChinaBackground: The reduction-sensitive cationic polymer is a promising nonviral carrier for gene delivery. Until now, disulfide bonds have been the only golden standard for its design. The aim of this research was to develop a novel reduction-responsive cationic polymer as a gene carrier.Methods: Polycationic carriers were synthesized by addition of branched oligoethylenimine 800 Da (OEI800 via an active ester containing diselenide bonds. Disulfide bonds cross-linked with OEI800-SSx and monoselenide bonds linked with OEI800-Sex were synthesized and compared. Their molecular weights and degradation properties were determined using gel permeation chromatography. Changes in particle size, morphology, and DNA binding were investigated by dynamic light scattering, transmission electron microscopy, and electrophoresis assay in a reduction environment. Cytotoxicity and transfection in vitro were evaluated in a murine melanoma cell line (B16F10 and a human cervical epithelial carcinoma cell line (HeLa, while intracellular degradation and dissociation with DNA were studied by confocal laser scanning microscopy with FITC-labeled OEI800 derivatives and Cy5-labeled DNA.Results: Diselenide-conjugated OEI800 (OEI800-Se Sex polymer carriers of high molecular weight were successfully synthesized. After compacting with DNA, the OEI800-SeSex polymers formed nanoparticles with an average size of 140 nm at an adequate C/P ratio. OEI800-Se Sex showed reduction-responsive degradation properties similar to those of the OEI800-SSx via gel permeation chromatography, dynamic light scattering, and transmission electron microscopy. OEI800-SeSex showed much lower cytotoxicity than PEI25k

Elimination of heavy metals from leachates by membrane electrolysis

Energy Technology Data Exchange (ETDEWEB)

Fischer, R. [Technische Universitaet Dresden, Institut fuer Siedlungs- und Industriewasserwirtschaft, Mommsenstrasse 13, 01062 Dresden (Germany); Seidel, H. [UFZ-Umweltforschungszentrum Leipzig-Halle GmbH, Department Bioremediation, Permoserstrasse 15, D-04318 Leipzig (Germany); Rahner, D. [Technische Universitaet Dresden, Institut fuer Physikalische Chemie und Eektrochemie, Mommsenstrasse 13, D-01062 Dresden (Germany); Morgenstern, P. [UFZ-Umweltforschungszentrum Leipzig-Halle GmbH, Department Analytik, Permoserstrasse 15, D-04318 Leipzig (Germany); Loeser, C. [Technische Universitaet Dresden, Institut fuer Lebensmittel- und Bioverfahrenstechnik, Bergstrasse 120, D-01062 Dresden (Germany)

2004-10-01

The elimination of heavy metals from bioleaching process waters (leachates) by electrolysis was studied in the anode and cathode region of a membrane electrolysis cell at current densities of 5-20 mA/cm{sup 2} using various electrode materials. The leaching waters containing a wide range of dissolved heavy metals, were high in sulfate, and had pH values of approx. 3. In preliminary tests using a rotating disc electrode the current density-potential curve (CPK) was recorded at a rotation velocity of 0, 1000 and 2000 rpm and a scan rate of 10 mV/s in order to collect information on the influence of transport processes on the electrochemical processes taking place at the electrodes. The electrochemical deposition-dissolution processes at the cathode are strongly dependent on the hydrodynamics. Detailed examination of the anodic oxidation of dissolved Mn(II) indicated that the manganese dioxide which formed adhered well to the electrode surface but in the cathodic return run it was again reduced. Electrode pairs of high-grade steel, lead and coal as well as material combinations were used to investigate heavy metal elimination in a membrane electrolysis cell. Using high-grade steel, lead and carbon electrode pairs, the reduction and deposition of Cu, Zn, Cr, Ni and some Cd in metallic or hydroxide form were observed in an order of 10-40 % in the cathode chamber. The dominant process in the anode chamber was the precipitation of manganese dioxide owing to the oxidation of dissolved Mn(II). Large amounts of heavy metals were co-precipitated by adsorption onto the insoluble MnO{sub 2}. High-grade steel and to some extent lead anodes were dissolved and hence were proven unsuitable as an anode material. These findings were largely confirmed by experiments using combination electrodes of coal and platinized titanium as an anode material and steel as a cathode material.The results indicate that electrochemical metal separation in the membrane electrolysis cell can represent a

Eliminating armaments

International Nuclear Information System (INIS)

Adams, R.

1998-01-01

The end of Cold War induced optimistic projections concerning disarmament, elimination of nuclear weapons, elimination of massive inequities - poverty, hatred, racism. All these goals should be achieved simultaneously, but little has been achieved so far

Bonding and Bridging Forms of Social Capital in Wildlife Tourism Microentrepreneurship: An Application of Social Network Analysis

Directory of Open Access Journals (Sweden)

Birendra KC

2018-01-01

Full Text Available Tourism has been recognized as an important economic sector, requiring a high degree of involvement from the entrepreneurial sector to diversify tourism products and services to meet increasing demand. Tourism is often considered a tool for economic development and a strategy to improve the livelihoods of rural citizens. Specifically, nature-based tourism, such as wildlife tourism, is growing faster than tourism in general, providing a myriad of opportunities for small-scale entrepreneurial engagement. However, several obstacles exist for these small-scale tourism enterprises, such as a lack of social capital. This study examined a network of wildlife tourism microentrepreneurs for bonding and bridging forms of social capital using a social network analysis approach, where bonding and bridging social capital have their own interpretation. Thirty-seven in-person interviews were conducted with wildlife tourism microentrepreneurs from North Carolina’s Pamlico Sound Region. The study revealed that microentrepreneurs interacted with each other in a bridging network structure. The ability to reciprocate with other members of the network was essential for business success. The results identified four key bridging ties connecting potential sub-groups in the network, connected to each other in a redundant fashion. We concluded that the formation of a bridging network structure was a function of entrepreneurial phenomena that may not promote a highly trusted, well-connected network. The findings and implications are further discussed in the paper.

High-rate reduction of copper oxide using atmospheric-pressure inductively coupled plasma microjets

International Nuclear Information System (INIS)

Tajima, Satomi; Tsuchiya, Shouichi; Matsumori, Masashi; Nakatsuka, Shigeki; Ichiki, Takanori

2011-01-01

Reduction of copper oxide was performed using an atmospheric-pressure inductively coupled plasma (AP-ICP) microjet while varying the input power P between 15 and 50 W. Cuprous oxide (Cu 2 O) and cupric oxide (CuO) were formed on the sputtered Cu surface by thermal annealing. Dynamic behavior of the microplasma jet, optical emission from H atoms, the substrate temperature, chemical bonding states of the treated surface, and the thickness of the reduced Cu layer were measured to study the fundamental reduction process. Surface composition and the thickness of the reduced Cu layer changed significantly with P. Rapid reduction of CuO and Cu 2 O was achieved at a rate of 493 nm/min at P = 50 W since high-density H atoms were produced by the AP-ICP microjet.

High-rate reduction of copper oxide using atmospheric-pressure inductively coupled plasma microjets

Energy Technology Data Exchange (ETDEWEB)

Tajima, Satomi; Tsuchiya, Shouichi [Department of Bioengineering, Graduate School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, 113-8656 (Japan); Matsumori, Masashi; Nakatsuka, Shigeki [Panasonic Factory Solutions Co., Ltd., 2-7 Matsuba-cho, Kadoma-city, Osaka, 571-8502 (Japan); Ichiki, Takanori, E-mail: ichiki@sogo.t.u-tokyo.ac.jp [Department of Bioengineering, Graduate School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, 113-8656 (Japan); Institute of Engineering Innovation, Graduate School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo, 113-8656 (Japan)

2011-08-01

Reduction of copper oxide was performed using an atmospheric-pressure inductively coupled plasma (AP-ICP) microjet while varying the input power P between 15 and 50 W. Cuprous oxide (Cu{sub 2}O) and cupric oxide (CuO) were formed on the sputtered Cu surface by thermal annealing. Dynamic behavior of the microplasma jet, optical emission from H atoms, the substrate temperature, chemical bonding states of the treated surface, and the thickness of the reduced Cu layer were measured to study the fundamental reduction process. Surface composition and the thickness of the reduced Cu layer changed significantly with P. Rapid reduction of CuO and Cu{sub 2}O was achieved at a rate of 493 nm/min at P = 50 W since high-density H atoms were produced by the AP-ICP microjet.

Hydrogen bonds and heat diffusion in α-helices: a computational study.

Science.gov (United States)

Miño, German; Barriga, Raul; Gutierrez, Gonzalo

2014-08-28

Recent evidence has shown a correlation between the heat diffusion pathways and the known allosteric communication pathways in proteins. Allosteric communication in proteins is a central, yet unsolved, problem in biochemistry, and the study and characterization of the structural determinants that mediate energy transfer among different parts of proteins is of major importance. In this work, we characterized the role of hydrogen bonds in diffusivity of thermal energy for two sets of α-helices with different abilities to form hydrogen bonds. These hydrogen bonds can be a constitutive part of the α-helices or can arise from the lateral chains. In our in vacuo simulations, it was observed that α-helices with a higher possibility of forming hydrogen bonds also had higher rates of thermalization. Our simulations also revealed that heat readily flowed through atoms involved in hydrogen bonds. As a general conclusion, according to our simulations, hydrogen bonds fulfilled an important role in heat diffusion in structural patters of proteins.

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

International Nuclear Information System (INIS)

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

2012-01-01

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

Stereochemistry of 1,2-elimination and proton-transfer reactions: toward a unified understanding.

Science.gov (United States)

Mohrig, Jerry R

2013-07-16

Many mechanistic and stereochemical studies have focused on the breaking of the C-H bond through base-catalyzed elimination reactions. When we began our research, however, chemists knew almost nothing about the stereospecificity of addition-elimination reactions involving conjugated acyclic carbonyl compounds, even though the carbonyl group is a pivotal functional group in organic chemistry. Over the last 25 years, we have studied the addition-elimination reactions of β-substituted acyclic esters, thioesters, and ketones in order to reach a comprehensive understanding of how electronic effects influence their stereochemistry. This Account brings together our understanding of the stereochemistry of 1,2-elimination and proton-transfer reactions, describing how each study has built upon previous work and contributed to our understanding of this field. When we began, chemists thought that anti stereospecificity in base-catalyzed 1,2-elimination reactions occurred via concerted E2 mechanisms, which provide a smooth path for anti elimination. Unexpectedly, we discovered that some E1cBirrev reactions produce the same anti stereospecificity as E2 reactions even though they proceed through diffusionally equilibrated, "free" enolate-anion intermediates. This result calls into question the conventional wisdom that anti stereochemistry must result from a concerted mechanism. While carrying out our research, we developed insights ranging from the role of historical contingency in the evolution of hydratase-dehydratase enzymes to the influence of buffers on the stereochemistry of H/D exchange in D2O. Negative hyperconjugation is the most important concept for understanding our results. This idea provides a unifying view for the largely anti stereochemistry in E1cBirrev elimination reactions and a basis for understanding the stereoelectronic influence of electron-withdrawing β-substituents on proton-transfer reactions.

WATER BOND FORMS IN THE DOUGH AND SORBTION PROPERTIES OF GLUTEN-FREE MACARONI PRODUCTS MADE FROM CORN FLOUR

Directory of Open Access Journals (Sweden)

Olexandr ROZHNO

2017-09-01

Full Text Available Authors have developed macaroni products made from fine meal corn flour by structure forming additives of different nature and without them. The correlation between water of different bond forms in macaroni dough with different structural forming additives and without them has been investigated. Results show that water of macro and microcapillaries is prevalent in the corn dough – 39.40 - 54.69 % of overall amount of water. Osmotically bound water amounts 18.75 – 28.04 %, adsorbically bound water -18.49 – 23.13 % of overall amount of water. The absorbtion capability of the macaroni products and amount of adsorbed water has been determined. The micropore structure of these samples was characterized. The correlation between structures of macaroni products, both amount of adsorbed moisture and energy of sorption were proven. The amount of monomolecular layer’s moisture for gluten-free corn macaroni products is significantly higher – in 1.2 – 1.5 times – when compared to the wheat macaroni products. Due to this fact, corn samples obtained higher energy of moisture sorption. The correlation between structural characteristics of the macaroni samples and their quality was shown.

Solder bond requirement for large, built-up, high-performance conductors

International Nuclear Information System (INIS)

Willig, R.L.

1981-01-01

Some large built-up conductors fabricated for large superconducting magnets are designed to operate above the maximum recovery current. Because the stability of these conductors is sensitive to the quality of the solder bond joining the composite superconductor to the high-conductivity substrate, a minimum bond requirement is necessary. The present analysis finds that the superconductor is unstable and becomes abruptly resistive when there are temperature excursions into the current sharing region of a poorly bonded conductor. This abrupt transition, produces eddy current heating in the vicinity of the superconducting filaments and causes a sharp reduction in the minimum propagating zone (MPZ) energy. This sensitivity of the MPZ energy to the solder bond contact area is used to specify a minimum bond requirement. For the superconducting MHD magnet built for the Component Development Integration Facility (CDIF), the minimum bonded surface area is .68 cm/sup 2//cm which is 44% of the composite perimeter. 5 refs

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

Directory of Open Access Journals (Sweden)

Adam A. Campos-Acevedo

2014-12-01

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

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

Science.gov (United States)

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

2014-12-15

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

[Application of thermosetting plastics to eliminate undercuts].

Science.gov (United States)

Bielawski, T

1989-01-01

The author proposes to utilize the properties of thermosetting plastics used in other fields to use them in prosthetics in order to eliminate undercuts. Application of extra equipment in claspograph in the form of studs of three dimension makes formation of undercuts' blockade easier improving the result of work at the same time.

A simulation study on the multi-pass rolling bond of 316L/Q345R stainless clad plate

Directory of Open Access Journals (Sweden)

Qin Qin

2015-07-01

Full Text Available This article describes an investigation into interface bonding research of 316L/Q345R stainless clad plate. A three-dimensional thermal–elastic–plastic model has been established using finite element analysis to model the multi-pass hot rolling process. Results of the model have been compared with those obtained from a rolling experiment of stainless clad plate. The comparisons of temperature and profile of the rolled stainless clad plate have indicated a satisfactory accuracy of finite element analysis simulation. Effects on interface bonding by different parameters including pre-heating temperature, multi-pass thickness reduction rules, rolling speed, covering rate, and different assemble patterns were analyzed systematically. The results show that higher temperature and larger thickness reduction are beneficial to achieve the bonding in vacuum hot rolling process. The critical reduction in the bond at the temperature of 1200 °C is 28%, and the critical thickness reduction reduces by about 2% when the temperature increases by 50 °C during the range from 1000 °C to 1250 °C. And the relationship between the minimum pass number and thickness reduction has been suggested. The results also indicate that large covering rate in the assemble pattern of outer soft and inner hard is beneficial to achieve the bond of stainless clad plate.

Sequential C-Si Bond Formations from Diphenylsilane: Application to Silanediol Peptide Isostere Precursors

DEFF Research Database (Denmark)

Nielsen, Lone; Skrydstrup, Troels

2008-01-01

and the first new carbon-silicon bond. The next step is the reduction of this hydridosilane with lithium metal providing a silyl lithium reagent, which undergoes a highly diastereoselective addition to an optically active tert-butanesulfinimine, thus generating the second C-Si bond. This method allows...

Monte Carlo simulation of AB-copolymers with saturating bonds

DEFF Research Database (Denmark)

Chertovich, A.C.; Ivanov, V.A.; Khokhlov, A.R.

2003-01-01

Structural transitions in a single AB-copolymer chain where saturating bonds can be formed between A- and B-units are studied by means of Monte Carlo computer simulations using the bond fluctuation model. Three transitions are found, coil-globule, coil-hairpin and globule-hairpin, depending...

Elimination of frequency noise from groundwater measurements

International Nuclear Information System (INIS)

Chien, Y.M.; Bryce, R.W.; Strait, S.R.; Yeatman, R.A.

1986-04-01

Groundwater response to atmospheric fluctuation can be effectively removed from downhole-pressure records using the systematic approach. The technique is not as successful for removal of earth tides, due to a probable discrepancy between the actual earth tide and the theoretical earth tide. The advantage of the systematic technique is that a causative relationship is established for each component of the pressure response removed. This concept of data reduction is easily understood and well accepted. The disadvantage is that a record of the stress causing the pressure fluctuation must be obtained. This may be done by monitoring or synthesizing the stress. Frequency analysis offers a simpler way to eliminate the undesirable hydrologic fluctuations from the downhole pressure. Frequency analysis may prove to be impractical if the fluctuations being removed have broadband characteristics. A combination of the two techniques, such as eliminating the atmospheric effect with the systematic method and the earth-tide fluctuations with the frequency method, is the most effective and efficient approach

Bonded exciplex formation: electronic and stereoelectronic effects.

Science.gov (United States)

Wang, Yingsheng; Haze, Olesya; Dinnocenzo, Joseph P; Farid, Samir; Farid, Ramy S; Gould, Ian R

2008-12-18

As recently proposed, the singlet-excited states of several cyanoaromatics react with pyridine via bonded-exciplex formation, a novel concept in photochemical charge transfer reactions. Presented here are electronic and steric effects on the quenching rate constants, which provide valuable support for the model. Additionally, excited-state quenching in poly(vinylpyridine) is strongly inhibited both relative to that in neat pyridine and also to conventional exciplex formation in polymers, consistent with a restrictive orientational requirement for the formation of bonded exciplexes. Examples of competing reactions to form both conventional and bonded exciplexes are presented, which illustrate the delicate balance between these two processes when their reaction energetics are similar. Experimental and computational evidence is provided for the formation of a bonded exciplex in the reaction of the singlet excited state of 2,6,9,10-tetracyanoanthracene (TCA) with an oxygen-substituted donor, dioxane, thus expanding the scope of bonded exciplexes.

Complete Mapping of Complex Disulfide Patterns with Closely-Spaced Cysteines by In-Source Reduction and Data-Dependent Mass Spectrometry

DEFF Research Database (Denmark)

Cramer, Christian N; Kelstrup, Christian D; Olsen, Jesper V

2017-01-01

bonds are present in complicated patterns. This includes the presence of disulfide bonds in nested patterns and closely spaced cysteines. Unambiguous mapping of such disulfide bonds typically requires advanced MS approaches. In this study, we exploited in-source reduction (ISR) of disulfide bonds during...... the electrospray ionization process to facilitate disulfide bond assignments. We successfully developed a LC-ISR-MS/MS methodology to use as an online and fully automated partial reduction procedure. Postcolumn partial reduction by ISR provided fast and easy identification of peptides involved in disulfide bonding......Mapping of disulfide bonds is an essential part of protein characterization to ensure correct cysteine pairings. For this, mass spectrometry (MS) is the most widely used technique due to fast and accurate characterization. However, MS-based disulfide mapping is challenged when multiple disulfide...

Silicon-to-silicon wafer bonding using evaporated glass

DEFF Research Database (Denmark)

Weichel, Steen; Reus, Roger De; Lindahl, M.

1998-01-01

Anodic bending of silicon to silicon 4-in. wafers using an electron-beam evaporated glass (Schott 8329) was performed successfully in air at temperatures ranging from 200 degrees C to 450 degrees C. The composition of the deposited glass is enriched in sodium as compared to the target material....... The roughness of the as-deposited films was below 5 nm and was found to be unchanged by annealing at 500 degrees C for 1 h in air. No change in the macroscopic edge profiles of the glass film was found as a function of annealing; however, small extrusions appear when annealing above 450 degrees C. Annealing...... of silicon/glass structures in air around 340 degrees C for 15 min leads to stress-free structures. Bonded wafer pairs, however, show no reduction in stress and always exhibit compressive stress. The bond yield is larger than 95% for bonding temperatures around 350 degrees C and is above 80% for bonding...

Renal lactate elimination is maintained during moderate exercise in humans

DEFF Research Database (Denmark)

Volianitis, Stefanos; Dawson, Ellen A; Dalsgaard, Mads

2012-01-01

(2) (CaO(2)-CvO(2)) and lactate concentration differences were 0.8 ± 0.2 and 0.02 ± 0.02 mmol x L(-1), respectively. During exercise, arterial lactate and CaO(2)-CvO(2) increased to 7.1 ± 1.1 and 2.6 ± 0.8 mmol x L(-1), respectively (P renal blood flow...... with no significant change in the renal venous erythropoietin concentration (0.8 ± 1.4 U x L(-1)). The a-v lactate concentration difference increased to 0.5 ± 0.8 mmol x L(-1), indicating similar lactate elimination as at rest. In conclusion, a -70% reduction in renal blood flow does not provoke critical renal......Reduced hepatic lactate elimination initiates blood lactate accumulation during incremental exercise. In this study, we wished to determine whether renal lactate elimination contributes to the initiation of blood lactate accumulation. The renal arterial-to-venous (a-v) lactate difference...

Protein disulfide bond generation in Escherichia coli DsbB–DsbA

International Nuclear Information System (INIS)

Inaba, Kenji

2008-01-01

The crystal structure of the DsbB–DsbA–ubiquinone ternary complex has revealed a mechanism of protein disulfide bond generation in Escherichia coli. Protein disulfide bond formation is catalyzed by a series of Dsb enzymes present in the periplasm of Escherichia coli. The crystal structure of the DsbB–DsbA–ubiquinone ternary complex provided important insights into mechanisms of the de novo disulfide bond generation cooperated by DsbB and ubiquinone and of the disulfide bond shuttle from DsbB to DsbA. The structural basis for prevention of the crosstalk between the DsbA–DsbB oxidative and the DsbC–DsbD reductive pathways has also been proposed

Protection of MOS capacitors during anodic bonding

Science.gov (United States)

Schjølberg-Henriksen, K.; Plaza, J. A.; Rafí, J. M.; Esteve, J.; Campabadal, F.; Santander, J.; Jensen, G. U.; Hanneborg, A.

2002-07-01

We have investigated the electrical damage by anodic bonding on CMOS-quality gate oxide and methods to prevent this damage. n-type and p-type MOS capacitors were characterized by quasi-static and high-frequency CV-curves before and after anodic bonding. Capacitors that were bonded to a Pyrex wafer with 10 μm deep cavities enclosing the capacitors exhibited increased leakage current and interface trap density after bonding. Two different methods were successful in protecting the capacitors from such damage. Our first approach was to increase the cavity depth from 10 μm to 50 μm, thus reducing the electric field across the gate oxide during bonding from approximately 2 × 105 V cm-1 to 4 × 104 V cm-1. The second protection method was to coat the inside of a 10 μm deep Pyrex glass cavity with aluminium, forming a Faraday cage that removed the electric field across the cavity during anodic bonding. Both methods resulted in capacitors with decreased interface trap density and unchanged leakage current after bonding. No change in effective oxide charge or mobile ion contamination was observed on any of the capacitors in the study.

31 CFR 360.26 - Application for relief; after receipt of bond.

Science.gov (United States)

2010-07-01

... coowners, if living) authorized under the regulations in this part to request payment of the bond. In addition: (1) If the bond is in beneficiary form and the owner and beneficiary are both living, the... the application is approved, relief will be granted either by the issuance of a bond bearing the same...

Pilot-scale equipment development for lithium-based reduction of spent oxide fuel

International Nuclear Information System (INIS)

Herrmann, S. D.

1998-01-01

An integral function of the electrometallurgical conditioning of DOE spent nuclear fuel is the standardization of waste forms. Argonne National Laboratory (ANL) has developed and is presently demonstrating the electrometallurgical conditioning of sodium-bonded metal fuel from Experimental Breeder Reactor II, resulting in uranium, ceramic waste, and metal waste forms. Engineering studies are underway at ANL in support of pilot-scale equipment development, which would precondition irradiated oxide fuel and likewise demonstrate the application of electrometallurgical conditioning to such non-metallic fuels. This paper highlights the integration of proposed spent oxide fuel conditioning with existing electrometallurgical processes. Additionally, technical bases for engineering activities to support a scale up of an oxide reduction process are described

CO2·- radical induced cleavage of disulfide bonds in proteins. A gamma-ray and pulse radiolysis mechanistic investigation

International Nuclear Information System (INIS)

Favaudon, V.; Tourbez, H.; Lhoste, J-M.; Houee-Levin, C.

1990-01-01

Disulfide bond reduction by the CO 2 ·- radical was investigated in aponeocarzinostatin, aporiboflavin-binding protein, and bovine immunoglobulin. Protein-bound cysteine free thiols were formed under γ-ray irradiation in the course of a pH-dependent and protein concentration dependent chain reaction. The chain efficiency increased upon acidification of the medium, with an apparent pK a around 5, and decreased abruptly below pH 3.6. It decreased also at neutral pH as cysteine accumulated. From pulse radiolysis analysis, CO 2 ·- proved able to induce rapid one-electron oxidation of thiols and of tyrosine phenolic groups in addition to one-electron donation to exposed disulfide bonds. The bulk rate constant of CO 2 ·- uptake by the native proteins was 5- to 10-fold faster at pH 3 than at pH 8, and the protonated form of the disulfide radical anion, appeared to be the major protein radical species formed under acidic conditions. Formation of the disulfide radical cation, phenoxyl radical Tyr-O · disproportionation, and phenoxyl radical induced oxidation of preformed thiol groups should also be taken into consideration to explain the fate of the oxygen-centered phenoxyl radical

Bonds broken and formed during the mixed-linkage glucan : xyloglucan endotransglucosylase reaction catalysed by Equisetum hetero-trans-β-glucanase.

Science.gov (United States)

Simmons, Thomas J; Fry, Stephen C

2017-03-08

Mixed-linkage glucan∶xyloglucan endotransglucosylase (MXE) is one of the three activities of the recently characterised hetero-trans-β-glucanase (HTG), which among land plants is known only from Equisetum species. The biochemical details of the MXE reaction were incompletely understood - details that would promote understanding of MXE's role in vivo and enable its full technological exploitation. We investigated HTG's site of attack on one of its donor substrates, mixed-linkage (1→3),(1→4)-β-d-glucan (MLG), with radioactive oligosaccharides of xyloglucan as the acceptor substrate. Comparing three different MLG preparations, we showed that the enzyme favours those with a high content of cellotetraose blocks. The reaction products were analysed by enzymic digestion, thin-layer chromatography (TLC), high-pressure liquid chromatography (HPLC) and gel-permeation chromatography (GPC). Equisetum HTG consistently cleaved the MLG at the third consecutive β-(1→4)-bond following (towards the reducing terminus) a β-(1→3)-bond. It then formed a β-(1→4)-bond between the MLG and the non-reducing terminal glucose residue of the xyloglucan oligosaccharide, consistent with its xyloglucan endotransglucosylase/hydrolase subfamily membership. Using size-homogeneous barley MLG as the donor substrate, we showed that HTG does not favour any particular region of the MLG chain relative to the polysaccharide's reducing and non-reducing termini; rather, it selects its target cellotetraosyl unit stochastically along the MLG molecule. This work improves our understanding of how enzymes can exhibit promiscuous substrate specificities and provides the foundations to explore strategies for engineering novel substrate specificities into transglycanases. © 2017 The Author(s).

Unexpected Hydration of a Triple Bond During DNA Synthesis

DEFF Research Database (Denmark)

Fatthalla, Maha I.; Pedersen, Erik B.

2016-01-01

acidic conditions, polarizes the triple bond in the intercalator and this makes hydration of the triple bond possible during the DNA synthesis and an oligonucleotide with 1-(indol-3-yl)-2-(pyren-1-yl)ethanone as the intercalator is formed. Insertion of the unhydrated and hydrated linker systems gave...

Bacteriophage-Derived Peptidase CHAPK Eliminates and Prevents Staphylococcal Biofilms

Directory of Open Access Journals (Sweden)

Mark Fenton

2013-01-01

Full Text Available New antibacterial agents are urgently needed for the elimination of biofilm-forming bacteria that are highly resistant to traditional antimicrobial agents. Proliferation of such bacteria can lead to significant economic losses in the agri-food sector. This study demonstrates the potential of the bacteriophage-derived peptidase, CHAPK, as a biocidal agent for the rapid disruption of biofilm-forming staphylococci, commonly associated with bovine mastitis. Purified CHAPK applied to biofilms of Staphylococcus aureus DPC5246 completely eliminated the staphylococcal biofilms within 4 h. In addition, CHAPK was able to prevent biofilm formation by this strain. The CHAPK lysin also reduced S. aureus in a skin decolonization model. Our data demonstrates the potential of CHAPK as a biocidal agent for prevention and treatment of biofilm-associated staphylococcal infections or as a decontaminating agent in the food and healthcare sectors.

Preservation of atomically clean silicon surfaces in air by contact bonding

DEFF Research Database (Denmark)

Grey, Francois; Ljungberg, Karin

1997-01-01

When two hydrogen-passivated silicon surfaces are placed in contact under cleanroom conditions, a weak bond is formed. Cleaving this bond under ultrahigh vacuum (UHV) conditions, and observing the surfaces with low energy electron diffraction and scanning tunneling microscopy, we find that the or...... reconstruction from oxidation in air, Contact bonding opens the way to novel applications of reconstructed semiconductor surfaces, by preserving their atomic structure intact outside of a UHV chamber. (C) 1997 American Institute of Physics.......When two hydrogen-passivated silicon surfaces are placed in contact under cleanroom conditions, a weak bond is formed. Cleaving this bond under ultrahigh vacuum (UHV) conditions, and observing the surfaces with low energy electron diffraction and scanning tunneling microscopy, we find...... that the ordered atomic structure of the surfaces is protected from oxidation, even after the bonded samples have been in air for weeks. Further, we show that silicon surfaces that have been cleaned and hydrogen-passivated in UHV can be contacted in UHV in a similarly hermetic fashion, protecting the surface...

27 CFR 28.133 - Disposition of forms.

Science.gov (United States)

2010-04-01

..., or Transportation to a Manufacturing Bonded Warehouse Return of Wines to Bonded Wine Cellar § 28.133 Disposition of forms. On receipt of the wines at the bonded wine cellar, the proprietor shall endorse, on each..., DEPARTMENT OF THE TREASURY LIQUORS EXPORTATION OF ALCOHOL Withdrawal of Wine Without Payment of Tax for...

Secondary waste form testing: ceramicrete phosphate bonded ceramics

International Nuclear Information System (INIS)

Singh, D.; Ganga, R.; Gaviria, J.; Yusufoglu, Y.

2011-01-01

The cleanup activities of the Hanford tank wastes require stabilization and solidification of the secondary waste streams generated from the processing of the tank wastes. The treatment of these tank wastes to produce glass waste forms will generate secondary wastes, including routine solid wastes and liquid process effluents. Liquid wastes may include process condensates and scrubber/off-gas treatment liquids from the thermal waste treatment. The current baseline for solidification of the secondary wastes is a cement-based waste form. However, alternative secondary waste forms are being considered. In this regard, Ceramicrete technology, developed at Argonne National Laboratory, is being explored as an option to solidify and stabilize the secondary wastes. The Ceramicrete process has been demonstrated on four secondary waste formulations: baseline, cluster 1, cluster 2, and mixed waste streams. Based on the recipes provided by Pacific Northwest National Laboratory, the four waste simulants were prepared in-house. Waste forms were fabricated with three filler materials: Class C fly ash, CaSiO 3 , and Class C fly ash + slag. Optimum waste loadings were as high as 20 wt.% for the fly ash and CaSiO 3 , and 15 wt.% for fly ash + slag filler. Waste forms for physical characterizations were fabricated with no additives, hazardous contaminants, and radionuclide surrogates. Physical property characterizations (density, compressive strength, and 90-day water immersion test) showed that the waste forms were stable and durable. Compressive strengths were >2,500 psi, and the strengths remained high after the 90-day water immersion test. Fly ash and CaSiO 3 filler waste forms appeared to be superior to the waste forms with fly ash + slag as a filler. Waste form weight loss was ∼5-14 wt.% over the 90-day immersion test. The majority of the weight loss occurred during the initial phase of the immersion test, indicative of washing off of residual unreacted binder components from

Secondary waste form testing : ceramicrete phosphate bonded ceramics.

Energy Technology Data Exchange (ETDEWEB)

Singh, D.; Ganga, R.; Gaviria, J.; Yusufoglu, Y. (Nuclear Engineering Division); ( ES)

2011-06-21

The cleanup activities of the Hanford tank wastes require stabilization and solidification of the secondary waste streams generated from the processing of the tank wastes. The treatment of these tank wastes to produce glass waste forms will generate secondary wastes, including routine solid wastes and liquid process effluents. Liquid wastes may include process condensates and scrubber/off-gas treatment liquids from the thermal waste treatment. The current baseline for solidification of the secondary wastes is a cement-based waste form. However, alternative secondary waste forms are being considered. In this regard, Ceramicrete technology, developed at Argonne National Laboratory, is being explored as an option to solidify and stabilize the secondary wastes. The Ceramicrete process has been demonstrated on four secondary waste formulations: baseline, cluster 1, cluster 2, and mixed waste streams. Based on the recipes provided by Pacific Northwest National Laboratory, the four waste simulants were prepared in-house. Waste forms were fabricated with three filler materials: Class C fly ash, CaSiO{sub 3}, and Class C fly ash + slag. Optimum waste loadings were as high as 20 wt.% for the fly ash and CaSiO{sub 3}, and 15 wt.% for fly ash + slag filler. Waste forms for physical characterizations were fabricated with no additives, hazardous contaminants, and radionuclide surrogates. Physical property characterizations (density, compressive strength, and 90-day water immersion test) showed that the waste forms were stable and durable. Compressive strengths were >2,500 psi, and the strengths remained high after the 90-day water immersion test. Fly ash and CaSiO{sub 3} filler waste forms appeared to be superior to the waste forms with fly ash + slag as a filler. Waste form weight loss was {approx}5-14 wt.% over the 90-day immersion test. The majority of the weight loss occurred during the initial phase of the immersion test, indicative of washing off of residual unreacted

Influence of ageing on glass and resin bonding of dental glass-ceramic veneer adhesion to zirconia: A fracture mechanics analysis and interpretation.

Science.gov (United States)

Swain, M V; Gee, C; Li, K C

2018-04-26

Adhesion plays a major role in the bonding of dental materials. In this study the adhesion of two glass-ceramic systems (IPS e.max and VITABLOCS) to a zirconia sintered substrate using a glass (for IPS e.max) and resin (VITABLOCS) before and after exposure to ageing for 14 days in distilled water at 37 °C are compared using two interfacial fracture mechanics tests, the 3 point bend Schwickerath (Kosyfaki and Swain, 2014; Schneider and Swain, 2015) and 4 point bend (Charalambides et al., 1989) approaches. Both tests result in stable crack extension from which the strain energy release rate (G, N/m or J/m 2 ) can be determined. In the case of the 3 PB test the Work of Fracture was also determined. In addition, the Schwickerath test enables determination of the critical stress for the onset of cracking to occur, which forms the basis of the ISO (ISO9693-2:2016) adhesion test for porcelain ceramic adhesion to zirconia. For the aged samples there was a significant reduction in the resin-bonded strengths (Schwickerath) and strain energy release rate (both 3 and 4 PB tests), which was not evident for the glass bonded specimens. Critical examination of the force-displacement curves showed that ageing of the resin resulted in a major change in the form of the curves, which may be interpreted in terms of a reduction in the critical stress to initiate cracking and also in the development of an R-curve. The extent of the reduction in strain energy release rate following ageing was greater for the Schwickerath test than the Charalambides test. The results are discussed in terms of; the basic mechanics of these two tests, the deterioration of the resin bonding following moisture exposure and the different dimensions of the specimens. These in-vitro results raise concerns regarding resin bonding to zirconia. The present study uses a novel approach to investigate the role of ageing or environmental degradation on the adhesive bonding of two dental ceramics to zirconia

Peptide bond-forming reagents HOAt and HATU are not mutagenic in the bacterial reverse mutation test.

Science.gov (United States)

Nicolette, John; Neft, Robin E; Vanosdol, Jessica; Murray, Joel

2016-04-01

The peptide bond-forming reagents 1-hydroxy-7-azabenzotriazole (HOAt, CAS 39968-33-7) and O-(7-Azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU, CAS 148893-10-1) either have structural alerts, unclassified features or are considered out of domain when evaluated for potential mutagenicity with in silico programs DEREK and CaseUltra. Since they are commonly used reagents in pharmaceutical drug syntheses, they may become drug substance or drug product impurities and would need to be either controlled to appropriately safe levels or tested for mutagenicity. Both reagents were tested in the bacterial reverse mutation (Ames) test at Covance, under GLP conditions, following the OECD test guideline and ICH S2(R1) recommendations and found to be negative. Our data show that HOAt and HATU-common pharmaceutical synthesis reagents-are not mutagenic, and can be treated as ordinary drug impurities. © 2016 Wiley Periodicals, Inc.

77 FR 37098 - Proposed Collection; Comment Request for Form 8038-CP

Science.gov (United States)

2012-06-20

... 8038-CP AGENCY: Internal Revenue Service (IRS), Treasury. ACTION: Notice and request for comments... Form 8038-CP, Return for Credit Payments to Issuers of Qualified Bonds. DATES: Written comments should... Issuers of Qualified Bonds. OMB Number: 1545-2142. Form Number: Form 8038-CP. Abstract: Form 8038-CP...

Selective disulfide reduction for labeling and enhancement of Fab antibody fragments

International Nuclear Information System (INIS)

Kirley, Terence L.; Greis, Kenneth D.; Norman, Andrew B.

2016-01-01

Many methods have been developed for chemical labeling and enhancement of the properties of antibodies and their common fragments, including the Fab and F(ab’) 2 fragments. Somewhat selective reduction of some antibody disulfide bonds has been previously achieved, yielding antibodies and antibody fragments that can be labeled at defined sites, enhancing their utility and properties. Selective reduction of the two hinge disulfide bonds present in F(ab’) 2 fragments using mild reduction has been useful. However, such reduction is often not quantitative and results in the reduction of multiple disulfide bonds, and therefore subsequent multiple labeling or conjugation sites are neither homogenous nor stoichiometric. Here, a simple and efficient selective reduction of the single disulfide bond linking the partial heavy chain and the intact light chain which compose the Fab fragment is accomplished utilizing tris(2-carboxyethyl)phosphine (TCEP) immobilized on agarose beads. The resultant reduced cysteine residues were labeled with several cysteine-selective fluorescent reagents, as well as by cysteine-directed PEGylation. These two cysteine residues can also be re-ligated by means of a bifunctional cysteine cross-linking agent, dibromobimane, thereby both restoring a covalent linkage between the heavy and light chains at this site, far removed from the antigen binding site, and also introducing a fluorescent probe. There are many other research and clinical uses for these selectively partially reduced Fab fragments, including biotinylation, toxin and drug conjugation, and incorporation of radioisotopes, and this technique enables simple generation of very useful Fab fragment derivatives with many potential applications. - Highlights: • TCEP agarose is effective for selective reduction of a single Fab disulfide bond. • This disulfide is solvent accessible and distant from the antigen binding site. • A variety of buffers of varying pHs can be used, simplifying

Bonding silicon nitride using glass-ceramic

International Nuclear Information System (INIS)

Dobedoe, R.S.

1995-01-01

Silicon nitride has been successfully bonded to itself using magnesium-aluminosilicate glass and glass-ceramic. For some samples, bonding was achieved using a diffusion bonder, but in other instances, following an initial degassing hold, higher temperatures were used in a nitrogen atmosphere with no applied load. For diffusion bonding, a small applied pressure at a temperature below which crystallisation occurs resulted in intimate contact. At slightly higher temperatures, the extent of the reaction at the interface and the microstructure of the glass-ceramic joint was highly sensitive to the bonding temperature. Bonding in a nitrogen atmosphere resulted in a solution-reprecipitation reaction. A thin layer of glass produced a ''dry'', glass-free joint, whilst a thicker layer resulted in a continuous glassy join across the interface. The chromium silicide impurities within the silicon nitride react with the nucleating agent in the glass ceramic, which may lead to difficulty in producing a fine glass-ceramic microstructure. Slightly lower temperatures in nitrogen resulted in a polycrystalline join but the interfacial contact was poor. It is hoped that one of the bonds produced may be developed to eventually form part of a graded joint between silicon nitride and a high temperature nickel alloy. (orig.)

A novel biomimetic orthodontic bonding agent helps prevent white spot lesions adjacent to brackets.

Science.gov (United States)

Manfred, Lauren; Covell, David A; Crowe, Jennifer J; Tufekci, Eser; Mitchell, John C

2013-01-01

To compare changes in enamel microhardness adjacent to orthodontic brackets after using bonding agents containing various compositions of bioactive glass compared to a traditional resin adhesive following a simulated caries challenge. Extracted human third molars (n  =  10 per group) had orthodontic brackets bonded using one of four novel bioactive glass (BAG)-containing orthodontic bonding agents (BAG-Bonds) or commercially available Transbond-XT. The four new adhesives contained BAG in varying percentages incorporated into a traditional resin monomer mixture. Teeth were cycled through low-pH demineralizing and physiologic-pH remineralizing solutions once each day over 14 days. Microhardness was measured on longitudinal sections of the teeth 100, 200, and 300 µm from the bracket edge and beneath the brackets, at depths of 25 to 200 µm from the enamel surface. Normalized hardness values were compared using three-way analysis of variance. Significantly less reduction in enamel microhardness was found with the experimental adhesives at depths of 25 and 50 µm at all distances from the bracket edge. In all groups, there were no significant changes in enamel microhardness past 125-µm depth. Results varied with the different BAG-Bonds, with 81BAG-Bond showing the smallest decrease in enamel microhardness. The BAG-Bonds tested in this study showed a reduction in the amount of superficial enamel softening surrounding orthodontic brackets compared to a traditional bonding agent. The results indicate that clinically, BAG-Bonds may aid in maintaining enamel surface hardness, therefore helping prevent white spot lesions adjacent to orthodontic brackets.

Application of density functional theory to the nitric oxide heterogeneous reduction mechanism in the presence of hydroxyl and carbonyl groups

International Nuclear Information System (INIS)

Zhang, Hai; Jiang, Xiumin; Liu, Jiaxun; Shen, Jun

2014-01-01

Highlights: • The role of hydroxyl and carbonyl groups are studied on two modified zigzag models. • Energetics and kinetics for the proposed pathways are chiefly investigated. • New active sites are beneficial for NO adsorption and N-O bond dissociation. • The highly exothermicity of C(NCO) formation is helpful for CO 2 and N 2 elimination. - Abstract: Comprehensive theoretical calculations are carried out to investigate the nitric oxide (NO) heterogeneous reduction mechanism in the presence of hydroxyl (-OH) and carbonyl (>C=O) groups. Energetics (activation energy and thermochemistry data) and kinetics (thermal rate constant) for the proposed pathways are provided by density functional theory (DFT) and conventional transition state theory (TST), respectively. The role played by -OH and >C=O has been clarified. In the presence of -OH, four stepwise reactions with the highest energy barrier of 251.7 kJ/mol are found to produce new active sites. Subsequently, a number of elementary reactions with energy barrier below 116.1 kJ/mol take place to reduce NO. The role of > C=O is to yield NCO intermediate. The formation of NCO is highly exothermic with 709.4 kJ/mol, which contributes to the elimination of carbon dioxide (CO 2 ) and nitrogen (N 2 ). The discovered mechanism is consistent with previous experimental observation that NO heterogeneous reduction is enhanced due to the presence of oxygen

Current status and future outlook for bonded neodymium permanent magnets (invited)

International Nuclear Information System (INIS)

Croat, J.J.

1997-01-01

Bonded neodymium magnets can provide significant size and weight reduction and/or performance enhancement over sintered and, particularly, bonded ferrite permanent magnets and, moreover, provide these benefits at reasonable cost. Primarily for these reasons, these bonded magnets are now used in a wide and growing range of computer peripheral, office automation, and consumer electronic applications and now constitute the fastest growing segment of the permanent magnet market. The current status of these materials will be reviewed. Included is a brief overview of the manufacture of these magnetically isotropic magnets and a discussion of their unique properties and features from the perspective of both bonded magnet producer and user. Major applications are discussed as are some of the factors that will drive the market for these materials in the future. New technical developments, including the status and outlook for anisotropic bonded materials, high remanance isotropic materials and high temperature bonded magnets will also be discussed. copyright 1997 American Institute of Physics

Morphology and stress at silicon-glass interface in anodic bonding

Energy Technology Data Exchange (ETDEWEB)

Tang, Jiali [Key Laboratory of Pressure Systems and Safety (MOE), School of Mechanical Engineering, East China University of Science and Technology, Shanghai 200237 (China); Cai, Cheng [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai (China); Ming, Xiaoxiang [Key Laboratory of Pressure Systems and Safety (MOE), School of Mechanical Engineering, East China University of Science and Technology, Shanghai 200237 (China); State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai 200237 (China); State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai (China); Yu, Xinhai, E-mail: yxhh@ecust.edu.cn [Key Laboratory of Pressure Systems and Safety (MOE), School of Mechanical Engineering, East China University of Science and Technology, Shanghai 200237 (China); State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai 200237 (China); Zhao, Shuangliang, E-mail: szhao@ecust.edu.cn [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai (China); Tu, Shan-Tung [Key Laboratory of Pressure Systems and Safety (MOE), School of Mechanical Engineering, East China University of Science and Technology, Shanghai 200237 (China); Liu, Honglai [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai (China)

2016-11-30

Highlights: • Amorphous SiO{sub 2} is the most probable silica morphology generated in anodic bonding. • Amorphous SiO{sub 2} thickness at the interface is at least 2 nm for 90 min anodic bonding. • Silicon oxidation rate at the interface is 0.022 nm min{sup −1} from 30 to 90 min. - Abstract: The morphologies and structural details of formed silica at the interface of silicon-glass anodic bonding determine the stress at the interface but they have been rarely clarified. In this study, a miniaturized anodic bonding device was developed and coupled with a Raman spectrometer. The silicon-glass anodic bonding was carried out and the evolution of the stress at the bonding interface was measured in situ by a Raman spectrometer. In addition, large-scale atomistic simulations were conducted by considering the formed silica with different morphologies. The most conceivable silica morphology was identified as the corresponding silicon-glass interfacial stress presents qualitatively agreement with the experimental observation. It was found that amorphous SiO{sub 2} is the silica morphology generated in anodic bonding. The amorphous SiO{sub 2} thickness is at least 2 nm in the case of 90 min anodic bonding at 400 °C with the DC voltage of −1000 V. The combination of experimental and simulation results can ascertain the silicon oxidation reaction rate in anodic bonding process, and under the above-mentioned condition, the reaction rate was estimated as 0.022 nm min{sup −1} from 30 to 90 min.

Selective disulfide reduction for labeling and enhancement of Fab antibody fragments.

Science.gov (United States)

Kirley, Terence L; Greis, Kenneth D; Norman, Andrew B

2016-11-25

Many methods have been developed for chemical labeling and enhancement of the properties of antibodies and their common fragments, including the Fab and F(ab') 2 fragments. Somewhat selective reduction of some antibody disulfide bonds has been previously achieved, yielding antibodies and antibody fragments that can be labeled at defined sites, enhancing their utility and properties. Selective reduction of the two hinge disulfide bonds present in F(ab') 2 fragments using mild reduction has been useful. However, such reduction is often not quantitative and results in the reduction of multiple disulfide bonds, and therefore subsequent multiple labeling or conjugation sites are neither homogenous nor stoichiometric. Here, a simple and efficient selective reduction of the single disulfide bond linking the partial heavy chain and the intact light chain which compose the Fab fragment is accomplished utilizing tris(2-carboxyethyl)phosphine (TCEP) immobilized on agarose beads. The resultant reduced cysteine residues were labeled with several cysteine-selective fluorescent reagents, as well as by cysteine-directed PEGylation. These two cysteine residues can also be re-ligated by means of a bifunctional cysteine cross-linking agent, dibromobimane, thereby both restoring a covalent linkage between the heavy and light chains at this site, far removed from the antigen binding site, and also introducing a fluorescent probe. There are many other research and clinical uses for these selectively partially reduced Fab fragments, including biotinylation, toxin and drug conjugation, and incorporation of radioisotopes, and this technique enables simple generation of very useful Fab fragment derivatives with many potential applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Alkyl Radicals as Hydrogen Bond Acceptors: Computational Evidence

DEFF Research Database (Denmark)

Hammerum, Steen

2009-01-01

Spectroscopic, energetic and structural information obtained by DFT and G3-type computational studies demonstrates that charged proton donors can form moderately strong hydrogen bonds to simple alkyl radicals. The presence of these bonds stabilizes the adducts and modifies their structure......, and gives rise to pronounced shifts of IR stretching frequencies and to increased absorption intensities. The hydrogen bond acceptor properties of alkyl radicals equal those of many conventional acceptors, e.g., the bond length changes and IR red-shifts suggest that tert-butyl radicals are slightly better...... acceptors than formaldehyde molecules, while propyl radicals are as good as H2O. The hydrogen bond strength appears to depend on the proton affinity of the proton donor and on the ionization energy of the acceptor alkyl radical, not on the donor-acceptor proton affinity difference, reflecting...

Redshift or adduct stabilization -- a computational study of hydrogen bonding in adducts of protonated carboxylic acids

DEFF Research Database (Denmark)

Olesen, Solveig Gaarn; Hammerum, Steen

2009-01-01

It is generally expected that the hydrogen bond strength in a D-H-A adduct is predicted by the difference between the proton affinities of D and A, measured by the adduct stabilization, and demonstrated by the IR redshift of the D-H bond stretching vibrational frequency. These criteria do...... not always yield consistent predictions, as illustrated by the hydrogen bonds formed by the E and Z OH groups of protonated carboxylic acids. The delta-PA and the stabilization of a series of hydrogen bonded adducts indicate that the E OH group forms the stronger hydrogen bonds, whereas the bond length...... carboxylic acids are different. The OH bond length and IR redshift afford the better measure of hydrogen bond strength....

Electronic structure and interatomic bonding in Al10V

International Nuclear Information System (INIS)

Jahnatek, M; Krajci, M; Hafner, J

2003-01-01

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

The elimination of charging in the PIXE analysis of thick biological samples

International Nuclear Information System (INIS)

Papper, C.S.; Chaudhri, M.A.; Rouse, J.L.

1978-01-01

A simple technique is described for the elimination of charging of thick biological samples subjected to proton bombardment. This involves evaporating a thin layer of carbon onto the target face and results in the reduction of background and therefore enhances the sensitivity of the technique. (Auth.)

Intermittent hemodialysis is superior to continuous veno-venous hemodialysis/hemodiafiltration to eliminate methanol and formate during treatment for methanol poisoning

Science.gov (United States)

Zakharov, Sergey; Pelclova, Daniela; Navratil, Tomas; Belacek, Jaromir; Kurcova, Ivana; Komzak, Ondrej; Salek, Tomas; Latta, Jiri; Turek, Radovan; Bocek, Robert; Kucera, Cyril; Hubacek, Jaroslav A; Fenclova, Zdenka; Petrik, Vit; Cermak, Martin; Hovda, Knut Erik

2014-01-01

During an outbreak of methanol poisonings in the Czech Republic in 2012, we were able to study methanol and formate elimination half-lives during intermittent hemodialysis (IHD) and continuous veno-venous hemodialysis/hemodiafiltration (CVVHD/HDF) and the relative impact of dialysate and blood flow rates on elimination. Data were obtained from 11 IHD and 13 CVVHD/HDF patients. Serum methanol and formate concentrations were measured by gas chromatography and an enzymatic method. The groups were relatively comparable, but the CVVHD/HDF group was significantly more acidotic (mean pH 6.9 vs. 7.1 IHD). The mean elimination half-life of methanol was 3.7 and formate 1.6 h with IHD, versus 8.1 and 3.6 h, respectively, with CVVHD/HDF (both significant). The 54% greater reduction in methanol and 56% reduction in formate elimination half-life during IHD resulted from the higher blood and dialysate flow rates. Increased blood and dialysate flow on the CVVHD/HDF also increased elimination significantly. Thus, IHD is superior to CVVHD/HDF for more rapid methanol and formate elimination, and if CVVHD/HDF is the only treatment available then elimination is greater with greater blood and dialysate flow rates. PMID:24621917

Topology of charge density of flucytosine and related molecules and characteristics of their bond charge distributions.

Science.gov (United States)

Murgich, Juan; Franco, Héctor J; San-Blas, Gioconda

2006-08-24

The molecular charge distribution of flucytosine (4-amino-5-fluoro-2-pyrimidone), uracil, 5-fluorouracil, and thymine was studied by means of density functional theory calculations (DFT). The resulting distributions were analyzed by means of the atoms in molecules (AIM) theory. Bonds were characterized through vectors formed with the charge density value, its Laplacian, and the bond ellipticity calculated at the bond critical point (BCP). Within each set of C=O, C-H, and N-H bonds, these vectors showed little dispersion. C-C bonds formed three different subsets, one with a significant degree of double bonding, a second corresponding to single bonds with a finite ellipticity produced by hyperconjugation, and a third one formed by a pure single bond. In N-C bonds, a decrease in bond length (an increase in double bond character) was not reflected as an increase in their ellipticity, as in all C-C bonds studied. It was also found that substitution influenced the N-C, C-O, and C-C bond ellipticity much more than density and its Laplacian at the BCP. The Laplacian of charge density pointed to the existence of both bonding and nonbonding maxima in the valence shell charge concentration of N, O, and F, while only bonding ones were found for the C atoms. The nonbonding maxima related to the sites for electrophilic attack and H bonding in O and N, while sites of nucleophilic attack were suggested by the holes in the valence shell of the C atoms of the carbonyl groups.

Note: Anodic bonding with cooling of heat-sensitive areas

DEFF Research Database (Denmark)

Vesborg, Peter Christian Kjærgaard; Olsen, Jakob Lind; Henriksen, Toke Riishøj

2010-01-01

Anodic bonding of silicon to glass always involves heating the glass and device to high temperatures so that cations become mobile in the electric field. We present a simple way of bonding thin silicon samples to borosilicate glass by means of heating from the glass side while locally cooling hea......-sensitive areas from the silicon side. Despite the high thermal conductivity of silicon, this method allows a strong anodic bond to form just millimeters away from areas essentially at room temperature....

Carbon elimination from silicon kerf: Thermogravimetric analysis and mechanistic considerations.

Science.gov (United States)

Vazquez-Pufleau, Miguel; Chadha, Tandeep S; Yablonsky, Gregory; Biswas, Pratim

2017-01-18

40% of ultrapure silicon is lost as kerf during slicing to produce wafers. Kerf is currently not being recycled due to engineering challenges and costs associated with removing its abundant impurities. Carbon left behind from the lubricant remains as one of the most difficult contaminants to remove in kerf without significant silicon oxidation. The present work enables to better understand the mechanism of carbon elimination in kerf which can aid the design of better processes for kef recycling and low cost photovoltaics. In this paper, we studied the kinetics of carbon elimination from silicon kerf in two atmospheres: air and N 2, under a regime of no-diffusion-limitation. We report the apparent activation energy in both atmospheres using three methods: Kissinger, and two isoconversional approaches. In both atmospheres, a bimodal apparent activation energy is observed, suggesting a two stage process. A reaction mechanism is proposed in which (a) C-C and C-O bond cleavage reactions occur in parallel with polymer formation; (b) at higher temperatures, this polymer fully degrades in air but leaves a tarry residue in N 2 that accounts for about 12% of the initial total carbon.

Bismuth-boron multiple bonding in BiB_2O"- and Bi_2B"-

International Nuclear Information System (INIS)

Jian, Tian; Cheung, Ling Fung; Chen, Teng-Teng; Wang, Lai-Sheng

2017-01-01

Despite its electron deficiency, boron is versatile in forming multiple bonds. Transition-metal-boron double bonding is known, but boron-metal triple bonds have been elusive. Two bismuth boron cluster anions, BiB_2O"- and Bi_2B"-, containing triple and double B-Bi bonds are presented. The BiB_2O"- and Bi_2B"- clusters are produced by laser vaporization of a mixed B/Bi target and characterized by photoelectron spectroscopy and ab initio calculations. Well-resolved photoelectron spectra are obtained and interpreted with the help of ab initio calculations, which show that both species are linear. Chemical bonding analyses reveal that Bi forms triple and double bonds with boron in BiB_2O"- ([Bi≡B-B≡O]"-) and Bi_2B"- ([Bi=B=Bi]"-), respectively. The Bi-B double and triple bond strengths are calculated to be 3.21 and 4.70 eV, respectively. This is the first experimental observation of Bi-B double and triple bonds, opening the door to design main-group metal-boron complexes with multiple bonding. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Consequences of acid strength for isomerization and elimination catalysis on solid acids.

Science.gov (United States)

Macht, Josef; Carr, Robert T; Iglesia, Enrique

2009-05-13

We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic

Economical benzene emission reduction

International Nuclear Information System (INIS)

Schuetz, R.

1999-01-01

Benzene has been classified as a toxic compound under the Canadian Environmental Protection Act. This has prompted the Alberta Energy and Utilities Board (AEUB) to introduce specific reporting and monitoring guidelines for the oil and gas industry regarding excessive benzene emissions. Glycol dehydration units have been determined to be the major single source of benzene emissions causing air and soil pollution. DualTank Corp. has designed a condensation and storage tank unit to enhance emission reduction, odour elimination and liquid recovery from dehydration units. Their newly designed combined tank unit consists of a large, uninsulated surface area for cooling, and an excessive internal volume for increased retention time. The first prototype was installed in December 1998 at an Enerplus Resources Site. The system provides excellent benzene emission reduction and the elimination of odours and visual plumes. Effective January 1, 1999, the petroleum and natural gas industry must either clean up excessive emissions voluntarily or face government imposed regulations, facility shutdowns and/or fines. 1 fig

77 FR 71794 - Agency Forms Undergoing Paperwork Reduction Act Review

Science.gov (United States)

2012-12-04

... Development--(OMB 0920-0840, Exp. 1/31/2013)--Revision--National Center for HIV/AIDS, Viral Hepatitis, STD, TB... transmitted diseases/infections (STD/STI), viral hepatitis, and tuberculosis elimination. Formative research... identities, and health care that underlie the epidemiology of HIV/AIDS, viral hepatitis, STDs, and TB in the...

Leakage Current Elimination of Four-Leg Inverter for Transformerless Three-Phase PV Systems

DEFF Research Database (Denmark)

Guo, Xiaoqiang; He, Ran; Jian, Jiamin

2016-01-01

Eliminating the leakage current is one of the most important issues for transformerless three phase photovoltaic (PV) systems. In this paper, the leakage current elimination of a three-phase four-leg PV inverter is investigated. With the common mode loop model established, the generation mechanism...... of the leakage current is clearly identified. Different typical carrier-based modulation methods and their corresponding common mode voltages are discussed. A new modulation strategy with Boolean logic function is proposed to achieve the constant common mode voltage for the leakage current reduction. Finally...

Process for improving the separation efficiency in the isolation of radioactive isotopes in elementary or chemically bonded form from liquids and gases

International Nuclear Information System (INIS)

Schmidberger, R.; Kirch, R.; Kock, W.

1986-01-01

In the process for the improvement of the separation efficiency in the isolation of radioactive isotopes in elementary or chemically bonded form from liquids or gases by ion exchange and adsorption, non-radioactive isotopes of the element to be isolated are added to the fluid before the isolation, whereas at the same time a large surplus of the non-radioactive isotopes to the radioactive isotopes is achieved by addition of only small quantities of compounds of the non-radioactive isotopes. (orig./RB) [de

Altering intra- to inter-molecular hydrogen bonding by dimethylsulfoxide: A TDDFT study of charge transfer for coumarin 343

Science.gov (United States)

Liu, Xiaochun; Yin, Hang; Li, Hui; Shi, Ying

2017-04-01

DFT and TDDFT methods were carried out to investigate the influences of intramolecular and intermolecular hydrogen bonding on excited state charge transfer for coumarin 343 (C343). Intramolecular hydrogen bonding is formed between carboxylic acid group and carbonyl group in C343 monomer. However, in dimethylsulfoxide (DMSO) solution, DMSO 'opens up' the intramolecular hydrogen bonding and forms solute-solvent intermolecular hydrogen bonded C343-DMSO complex. Analysis of frontier molecular orbitals reveals that intramolecular charge transfer (ICT) occurs in the first excited state both for C343 monomer and complex. The results of optimized geometric structures indicate that the intramolecular hydrogen bonding interaction is strengthened while the intermolecular hydrogen bonding is weakened in excited state, which is confirmed again by monitoring the shifts of characteristic peaks of infrared spectra. We demonstrated that DMSO solvent can not only break the intramolecular hydrogen bonding to form intermolecular hydrogen bonding with C343 but also alter the mechanism of excited state hydrogen bonding strengthening.

Energy-Saving Melting and Revert Reduction Technology (E-SMARRT): Lost Foam Thin Wall - Feasibility of Producing Lost Foam Castings in Aluminum and Magnesium Based Alloys

Energy Technology Data Exchange (ETDEWEB)

Fasoyinu, Yemi [CanmetMATERIALS; Griffin, John A. [University of Alabama - Birmingham

2014-03-31

With the increased emphasis on vehicle weight reduction, production of near-net shape components by lost foam casting will make significant inroad into the next-generation of engineering component designs. The lost foam casting process is a cost effective method for producing complex castings using an expandable polystyrene pattern and un-bonded sand. The use of un-bonded molding media in the lost foam process will impose less constraint on the solidifying casting, making hot tearing less prevalent. This is especially true in Al-Mg and Al-Cu alloy systems that are prone to hot tearing when poured in rigid molds partially due to their long freezing range. Some of the unique advantages of using the lost foam casting process are closer dimensional tolerance, higher casting yield, and the elimination of sand cores and binders. Most of the aluminum alloys poured using the lost foam process are based on the Al-Si system. Very limited research work has been performed with Al-Mg and Al-Cu type alloys. With the increased emphasis on vehicle weight reduction, and given the high-strength-to-weight-ratio of magnesium, significant weight savings can be achieved by casting thin-wall (≤ 3 mm) engineering components from both aluminum- and magnesium-base alloys.

Bond yield curve construction

Directory of Open Access Journals (Sweden)

Kožul Nataša

2014-01-01

Full Text Available In the broadest sense, yield curve indicates the market's view of the evolution of interest rates over time. However, given that cost of borrowing it closely linked to creditworthiness (ability to repay, different yield curves will apply to different currencies, market sectors, or even individual issuers. As government borrowing is indicative of interest rate levels available to other market players in a particular country, and considering that bond issuance still remains the dominant form of sovereign debt, this paper describes yield curve construction using bonds. The relationship between zero-coupon yield, par yield and yield to maturity is given and their usage in determining curve discount factors is described. Their usage in deriving forward rates and pricing related derivative instruments is also discussed.

Stress reduction of Cu-doped diamond-like carbon films from ab initio calculations

Directory of Open Access Journals (Sweden)

Xiaowei Li

2015-01-01

Full Text Available Structure and properties of Cu-doped diamond-like carbon films (DLC were investigated using ab initio calculations. The effect of Cu concentrations (1.56∼7.81 at.% on atomic bond structure was mainly analyzed to clarify the residual stress reduction mechanism. Results showed that with introducing Cu into DLC films, the residual compressive stress decreased firstly and then increased for each case with the obvious deterioration of mechanical properties, which was in agreement with the experimental results. Structural analysis revealed that the weak Cu-C bond and the relaxation of both the distorted bond angles and bond lengths accounted for the significant reduction of residual compressive stress, while at the higher Cu concentration the increase of residual stress attributed to the existence of distorted Cu-C structures and the increased fraction of distorted C-C bond lengths.

Intramolecular Hydrogen Bonding in (2-Hydroxybenzoyl)benzoylmethane Enol

DEFF Research Database (Denmark)

Hansen, Bjarke Knud Vilster; Winther, Morten; Spanget-Larsen, Jens

2014-01-01

, and the dienol form of 1,3-dibenzoylacetone. But in these examples the two H-bonds are equivalent, while in the case of OHDBM they are chemically different, involving one enolic and one phenolic hydroxy group. OHDBM is thus an interesting model compound with two competing H-bonds to the same carbonyl group......In the stable enol tautomer of the title compound (OHDBM), one carbonyl group is flanked by two β-hydroxy groups, giving rise to bifold intramolecular H-bonding. A similar situation is found in other β,β'-dihydroxy carbonyl compounds like chrysazin, anthralin, 2,2'-dihydroxybenzophenone...

It guides for the storage of reagents and elimination of waste of the laboratories of the headquarters Rodrigo Facio of the Costa Rica University

International Nuclear Information System (INIS)

Mata Bonilla, E. R.

1996-01-01

The Project guides for the storage of chemical reagents and elimination of waste of the laboratories of the campus Rodrigo Facio of the Costa Rica University, the objective to settle down in written form a method of storage of chemical reagents, as well as the basic elements for the establishment of a system of handling of chemical residuals for the laboratories of the campus. The storage of reagents in a laboratory requires that the probability of an accident is minimized and it should include the following elements: a classification of reagents and their later segregation (in accordance with the reactivity of each group), ventilation, illumination, controls and alarms in the event of fires, control of spills and an uniform system for the identification of reagents and storage area. The elimination of residuals of chemical reagents requires a series of stages to carry out of this operation in sure form for people, the property and the environment. In the first place it is required of an outline of the whole process of elimination of the waste, later on a system of classification of the produced residuals should be included that it contemplates the final method of elimination of the residual. Other elements that should take into account are: reduction of the volume of the waste, gathering methods, labeled and transport. In this work intends the System of Classification of Substances of the United Nations as classification method, segregation, and storage of the reagents of the laboratories of the campus [es

Comparison of shear bond strength of the stainless steel metallic brackets bonded by three bonding systems

Directory of Open Access Journals (Sweden)

Mehdi Ravadgar

2013-09-01

Full Text Available Introduction: In orthodontic treatment, it is essential to establish a satisfactory bond between enamel and bracket. After the self-etch primers (SEPs were introduced for the facilitation of bracket bonding in comparison to the conventional etch-and-bond system, multiple studies have been carried out on their shear bond strengths which have yielded different results. This study was aimed at comparing shear bond strengths of the stainless steel metallic brackets bonded by three bonding systems. Methods: In this experimental in vitro study, 60 extracted human maxillary premolar teeth were randomly divided into three equal groups: in the first group, Transbond XT (TBXT light cured composite was bonded with Transbond plus self-etching primer (TPSEP in the second group, TBXT composite was bonded with the conventional method of acid etching and in the third group, the self cured composite Unite TM bonding adhesive was bonded with the conventional method of acid etching. In all the groups, Standard edgewise-022 metallic brackets (American Orthodontics, Sheboygan, USA were used. Twenty-four hours after the completion of thermocycling, shear bond strength of brackets was measured by Universal Testing Machine (Zwick. In order to compare the shear bond strengths of the groups, the variance analysis test (ANOVA was adopted and p≤0.05 was considered as a significant level. Results: Based on megapascal, the average shear bond strength for the first, second, and third groups was 8.27±1.9, 9.78±2, and 8.92±2.5, respectively. There was no significant difference in the shear bond strength of the groups. Conclusions: Since TPSEP shear bond strength is approximately at the level of the conventional method of acid etching and within the desirable range for orthodontic brackets shear bond strength, applying TPSEP can serve as a substitute for the conventional method of etch and bond, particularly in orthodontic operations.

Comparison of shear bond strength of the stainless steel metallic brackets bonded by three bonding systems

Directory of Open Access Journals (Sweden)

Mehdi Ravadgar

2013-09-01

Full Text Available Introduction: In orthodontic treatment, it is essential to establish a satisfactory bond between enamel and bracket. After the self-etch primers (SEPs were introduced for the facilitation of bracket bonding in comparison to the conventional etch-and-bond system, multiple studies have been carried out on their shear bond strengths which have yielded different results. This study was aimed at comparing shear bond strengths of the stainless steel metallic brackets bonded by three bonding systems. Methods: In this experimental in vitro study, 60 extracted human maxillary premolar teeth were randomly divided into three equal groups: in the first group, Transbond XT (TBXT light cured composite was bonded with Transbond plus self-etching primer (TPSEP; in the second group, TBXT composite was bonded with the conventional method of acid etching; and in the third group, the self cured composite Unite TM bonding adhesive was bonded with the conventional method of acid etching. In all the groups, Standard edgewise-022 metallic brackets (American Orthodontics, Sheboygan, USA were used. Twenty-four hours after the completion of thermocycling, shear bond strength of brackets was measured by Universal Testing Machine (Zwick. In order to compare the shear bond strengths of the groups, the variance analysis test (ANOVA was adopted and p≤0.05 was considered as a significant level. Results: Based on megapascal, the average shear bond strength for the first, second, and third groups was 8.27±1.9, 9.78±2, and 8.92±2.5, respectively. There was no significant difference in the shear bond strength of the groups. Conclusions: Since TPSEP shear bond strength is approximately at the level of the conventional method of acid etching and within the desirable range for orthodontic brackets shear bond strength, applying TPSEP can serve as a substitute for the conventional method of etch and bond, particularly in orthodontic operations.

From bifluorenylidene dianion to dibenzo[g,p]chrysene dianion: sensitivity of anisotropy changes to bonding structure

DEFF Research Database (Denmark)

Shenhar, R.; Beust, R.; Hagen, Stefan

2002-01-01

Five polycyclic aromatic hydrocarbons of the C-26 series having similar bonding structure yield dianions upon reduction with lithium metal. Anisotropy changes, revealed from an advanced charge distribution analysis performed on these dianions, show a correlation to the bonding structure...

Calculations of kinetic isotope effects in the Hofmann eliminations of substituted (2-phenylethyl)trimethylammonium ions

International Nuclear Information System (INIS)

Lewis, D.E.; Sims, L.B.; Yamataka, H.; McKenna, J.

1980-01-01

Theoretical calculations of kinetic isotope effects (KIE) for the Hofmann elimination of the (2-phenylethyl)trimethylammonium ion (I,Z = H) have been carried out for an extensive series of transition-state models encompassing the Elcb-like region of the E2 mechanistic spectrum. The reaction coordinate employed corresponded to the irreversible fragmentation of the base-H'-C/sub β/-C/sub α/-N system, with proton transfer being the dominant contributor. Structural parameters (bond distances and angles) were related to the independent bond orders n/sub α-N/ and n/sub β-H'/ by empirical and semiempirical relationships. The most probable transition-state structure for the reaction was determined by interpolation of the experimental values for the β-D 2 and 15 N KIE into plots of the trends of the calculated KIE. The nonsolvated models obtained in this manner gave only poor agreement between calculated and experimental secondary deuterium (α-D 2 ) and leaving group deuterium [N(CD 3 )/sub x/(CH 3 )/sub 3-x/, x = 1 to 3) KIE; explicit consideration of differential solvation of the reactant and transition state afforded the most chemically reasonable resolution of these discrepancies. Using solvated models, transition-state structures were also determined for the Hofmann elimination of parasubstituted derivatives of I (Z = OCH 3 , Cl, CF 3 ). These transition states are related by a shift parallel to the central E2 diagogonal of an O'Ferrall-Jencks reaction diagram, as predicted by Thorton, indicating that, in the absence of other factors (differing solvent or base, etc.), the extent to which negative charge is accumulated at Cβ in the transition state is solely a factor of the leaving group. Both independent bond orders (n/sub α-N/ and n/sub β-H'/) exhibit a linear dependence on the sigma value of the substituent, allowing for the first time prediction of transition states

Backbone conformation affects duplex initiation and duplex propagation in hybridisation of synthetic H-bonding oligomers.

Science.gov (United States)

Iadevaia, Giulia; Núñez-Villanueva, Diego; Stross, Alexander E; Hunter, Christopher A

2018-06-06

Synthetic oligomers equipped with complementary H-bond donor and acceptor side chains form multiply H-bonded duplexes in organic solvents. Comparison of the duplex forming properties of four families of oligomers with different backbones shows that formation of an extended duplex with three or four inter-strand H-bonds is more challenging than formation of complexes that make only two H-bonds. The stabilities of 1 : 1 complexes formed between length complementary homo-oligomers equipped with either phosphine oxide or phenol recognition modules were measured in toluene. When the backbone is very flexible (pentane-1,5-diyl thioether), the stability increases uniformly by an order of magnitude for each additional base-pair added to the duplex: the effective molarities for formation of the first intramolecular H-bond (duplex initiation) and subsequent intramolecular H-bonds (duplex propagation) are similar. This flexible system is compared with three more rigid backbones that are isomeric combinations of an aromatic ring and methylene groups. One of the rigid systems behaves in exactly the same way as the flexible backbone, but the other two do not. For these systems, the effective molarity for formation of the first intramolecular H-bond is the same as that found for the other two backbones, but additional H-bonds are not formed between the longer oligomers. The effective molarities are too low for duplex propagation in these systems, because the oligomer backbones cannot adopt conformations compatible with formation of an extended duplex.

Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.

Science.gov (United States)

Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier

2016-08-19

Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity.

Ligand-Controlled Chemoselective C(acyl)–O Bond vs C(aryl)–C Bond Activation of Aromatic Esters in Nickel Catalyzed C(sp2)–C(sp3) Cross-Couplings

KAUST Repository

Chatupheeraphat, Adisak

2018-02-20

A ligand-controlled and site-selective nickel catalyzed Suzuki-Miyaura cross-coupling reaction with aromatic esters and alkyl organoboron reagents as coupling partners was developed. This methodology provides a facile route for C(sp2)-C(sp3) bond formation in a straightforward fashion by successful suppression of the undesired β-hydride elimination process. By simply switching the phosphorus ligand, the ester substrates are converted into the alkylated arenes and ketone products, respectively. The utility of this newly developed protocol was demonstrated by its wide substrate scope, broad functional group tolerance and application in the synthesis of key intermediates for the synthesis of bioactive compounds. DFT studies on the oxidative addition step helped rationalizing this intriguing reaction chemoselectivity: whereas nickel complexes with bidentate ligands favor the C(aryl)-C bond cleavage in the oxidative addition step leading to the alkylated product via a decarbonylative process, nickel complexes with monodentate phosphorus ligands favor activation of the C(acyl)-O bond, which later generates the ketone product.

Flip-chip bonded optoelectronic integration based on ultrathin silicon (UTSi) CMOS

Science.gov (United States)

Hong, Sunkwang; Ho, Tawei; Zhang, Liping; Sawchuk, Alexander A.

2003-06-01

We describe the design and test of flip-chip bonded optoelectronic CMOS devices based on Peregrine Semiconductor's 0.5 micron Ultra-Thin Silicon on sapphire (UTSi) technology. The UTSi process eliminates the substrate leakage that typically results in crosstalk and reduces parasitic capacitance to the substrate, providing many benefits compared to bulk silicon CMOS. The low-loss synthetic sapphire substrate is optically transparent and has a coefficient of thermal expansion suitable for flip-chip bonding of vertical cavity surface emitting lasers (VCSELs) and detectors. We have designed two different UTSi CMOS chips. One contains a flip-chip bonded 1 x 4 photodiode array, a receiver array, a double edge triggered D-flip flop-based 2047-pattern pseudo random bit stream (PRBS) generator and a quadrature-phase LC-voltage controlled oscillator (VCO). The other chip contains a flip-chip bonded 1 x 4 VCSEL array, a driver array based on high-speed low-voltage differential signals (LVDS) and a full-balanced differential LC-VCO. Each VCSEL driver and receiver has individual input and bias voltage adjustments. Each UTSi chip is mounted on different printed circuit boards (PCBs) which have holes with about 1 mm radius for optical output and input paths through the sapphire substrate. We discuss preliminary testing of these chips.

In-Depth Characterization of Protein Disulfide Bonds by Online Liquid Chromatography-Electrochemistry-Mass Spectrometry

Science.gov (United States)

Switzar, Linda; Nicolardi, Simone; Rutten, Julie W.; Oberstein, Saskia A. J. Lesnik; Aartsma-Rus, Annemieke; van der Burgt, Yuri E. M.

2016-01-01

Disulfide bonds are an important class of protein post-translational modifications, yet this structurally crucial modification type is commonly overlooked in mass spectrometry (MS)-based proteomics approaches. Recently, the benefits of online electrochemistry-assisted reduction of protein S-S bonds prior to MS analysis were exemplified by successful characterization of disulfide bonds in peptides and small proteins. In the current study, we have combined liquid chromatography (LC) with electrochemistry (EC) and mass analysis by Fourier transform ion cyclotron resonance (FTICR) MS in an online LC-EC-MS platform to characterize protein disulfide bonds in a bottom-up proteomics workflow. A key advantage of a LC-based strategy is the use of the retention time in identifying both intra- and interpeptide disulfide bonds. This is demonstrated by performing two sequential analyses of a certain protein digest, once without and once with electrochemical reduction. In this way, the "parent" disulfide-linked peptide detected in the first run has a retention time-based correlation with the EC-reduced peptides detected in the second run, thus simplifying disulfide bond mapping. Using this platform, both inter- and intra-disulfide-linked peptides were characterized in two different proteins, ß-lactoglobulin and ribonuclease B. In order to prevent disulfide reshuffling during the digestion process, proteins were digested at a relatively low pH, using (a combination of) the high specificity proteases trypsin and Glu-C. With this approach, disulfide bonds in ß-lactoglobulin and ribonuclease B were comprehensively identified and localized, showing that online LC-EC-MS is a useful tool for the characterization of protein disulfide bonds.

Flexural behaviour of partially bonded carbon fibre reinforced polymers strengthened concrete beams: Application to fire protection systems design

International Nuclear Information System (INIS)

Firmo, J.P.; Arruda, M.R.T.; Correia, J.R.; Tiago, C.

2015-01-01

Highlights: • The mechanical behaviour of partially bonded CFRP strengthened beams was modelled. • Two dimensional non-linear finite element models were developed. • Partially bonded beams can present similar flexural strength to fully bonded ones. • Relations between the bonded length and the strength reduction were proposed. • The proposed relations were used for the design of fire protection systems. - Abstract: Recent fire resistance tests on reinforced concrete (RC) beams strengthened with carbon fibre reinforced polymers (CFRP) laminates showed that it is possible to attain considerable fire endurance provided that thermal insulation is applied at the anchorage zones of the strengthening system. With such protection, although the CFRP laminate prematurely debonds in the central part of the beam, it transforms into a cable fixed at the extremities until one of the anchorage zones loses its bond strength. The main objective of this paper is to propose a simplified methodology for the design of fire protection systems for CFRP strengthened-RC beams, which is based on applying thicker insulation at the anchorage zones (promoting the above mentioned “cable behaviour”) and a thinner one at the current zone (avoiding tensile rupture of the carbon fibres). As a first step towards the validation of this methodology, finite element (FE) models were developed to simulate the flexural behaviour at ambient temperature of full-scale RC beams strengthened with CFRP laminates according to the externally bonded reinforcement (EBR) and near surface mounted (NSM) techniques, in both cases fully or partially bonded (the latter simulating the cable). The FE models were calibrated with results of 4-point bending tests on small-scale beams and then extended for different beam geometries, with spans (L) varying from 2 m to 5 m, in which the influence of the CFRP bonded length (l b ) and the loading type (point or uniformly distributed) on the strength reduction was

77 FR 15378 - Agency Information Collection Activities: Application for Withdrawal of Bonded Stores for Fishing...

Science.gov (United States)

2012-03-15

... Activities: Application for Withdrawal of Bonded Stores for Fishing Vessels and Certificate of Use AGENCY: U... information collection request to the Office of Management and Budget (OMB) for review and approval in accordance with the Paperwork Reduction Act: Application for Withdrawal of Bonded Stores for Fishing Vessels...

Modifications of the alpha,beta-double bond in chalcones only marginally affect the antiprotozoal activities

DEFF Research Database (Denmark)

Nielsen, S F; Kharazmi, A; Christensen, S B

1998-01-01

Methods for selective alkylation of chalcones in the alpha- or beta-position and for selective reduction of the alpha,beta-double bond have been developed. The antiparasitic potencies of the alpha,beta-double bond modified chalcones only differ marginally from the potencies of the parent chalcones...

OZONE DEPLETING SUBSTANCES ELIMINATION MANAGEMENT: THE SUCCESS STORY OF MACEDONIA

Directory of Open Access Journals (Sweden)

Margarita Matlievska

2013-04-01

Full Text Available Man, with its activities, produces and uses substances that have negative impact on the environment and the human health, and can cause an economic damage. Consequently, they have a great impact on quality of life. Among the most harmful chemicals are Ozone Depleting Substances that are subject of regulation with international conventions. This Paper supports the fact that each country has to undertake national efforts for ozone depleting substances reduction and elimination. In that respect, the general objective of the Paper is to present the Macedonian unique experience regarding its efforts to reduce or eliminate these substances. The following two aspects were subject to the research: national legislation which regulates the Ozone Depleting Substances import and export as well as the implementation of the projects that resulted with the elimination of Ozone Depleting Substances quantities in the period 1995 – 2010. The research outcomes confirm the starting research hypothesis i.e. that with adequately created and implemented national action, the amount of Ozone Depleting Substances consumption can dramatically fall.

75 FR 5855 - Proposed Collection; Comment Request for Form 8038-TC

Science.gov (United States)

2010-02-04

... 8038-TC AGENCY: Internal Revenue Service (IRS), Treasury. ACTION: Notice and request for comments... comments concerning Form 8038-TC, Information Return for Tax Credit Bonds. DATES: Written comments should...: Form 8038-TC. Abstract: Form 8038-TC will be used by issuers of qualified tax- exempt credit bonds...

Study of diffusion bonding in 6061 aluminum and development of future high-density fuels fabrication

International Nuclear Information System (INIS)

Prokofiev, I.G.; Wiencek, T.C.; McGann, D.J.

1997-01-01

Powder metallurgy dispersions of uranium alloys and silicides in an aluminum matrix have been developed by the RERTR program as a new generation of proliferation-resistant fuels. Testing uses fuel miniplates to simulate standard fuel with cladding and matrix in plate-type configurations. In order to seal the dispersion fuel plates, a diffusion bond must be established between the aluminum cover plates that surround the fuel meat. Four different variations of the standard method for roll-bonding 6061 aluminum were studied: mechanical cleaning, addition of a getter material, modifications to the standard chemical etching, and modifications to welding. Aluminum test pieces were subjected to a bend test after each rolling pass. Results, based on 400 samples, indicate that a reduction in thickness of at least 70% is required to produce a diffusion bond with the standard roll-bonding method, versus a 60% reduction when using a method in which the assembly was 100% welded and contained empty 9 mm holes near the frame corners. (author)

Hepatitis B in sub-Saharan Africa: strategies to achieve the 2030 elimination targets.

Science.gov (United States)

Spearman, C Wendy; Afihene, Mary; Ally, Reidwaan; Apica, Betty; Awuku, Yaw; Cunha, Lina; Dusheiko, Geoffrey; Gogela, Neliswa; Kassianides, Chris; Kew, Michael; Lam, Philip; Lesi, Olufunmilayo; Lohouès-Kouacou, Marie-Jeanne; Mbaye, Papa Saliou; Musabeyezu, Emmanuel; Musau, Betty; Ojo, Olusegun; Rwegasha, John; Scholz, Barbara; Shewaye, Abate B; Tzeuton, Christian; Sonderup, Mark W

2017-12-01

The WHO global health sector strategy on viral hepatitis, created in May, 2016, aims to achieve a 90% reduction in new cases of chronic hepatitis B and C and a 65% reduction in mortality due to hepatitis B and C by 2030. Hepatitis B virus (HBV) is endemic in sub-Saharan Africa, and despite the introduction of universal hepatitis B vaccination and effective antiviral therapy, the estimated overall seroprevalence of hepatitis B surface antigen remains high at 6·1% (95% uncertainty interval 4·6-8·5). In this Series paper, we have reviewed the literature to examine the epidemiology, burden of liver disease, and elimination strategies of hepatitis B in sub-Saharan Africa. This paper reflects a supranational perspective of sub-Saharan Africa, and recommends several priority elimination strategies that address the need both to prevent new infections and to diagnose and treat chronic infections. The key to achieving these elimination goals in sub-Saharan Africa is the effective prevention of new infections via universal implementation of the HBV birth-dose vaccine, full vaccine coverage, access to affordable diagnostics to identify HBV-infected individuals, and to enable linkage to care and antiviral therapy. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

International Nuclear Information System (INIS)

Hanna, Gabriel; Geva, Eitan

2010-01-01

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

Use of vacuum-steam-vacuum and ionizing radiation to eliminate Listeria innocua from ham.

Science.gov (United States)

Sommers, Christopher; Kozempel, Michael; Fan, Xuetong; Radewonuk, E Richard

2002-12-01

Listeria spp. are a frequent postprocess contaminant of ready-to-eat (RTE) meat products, including ham. Vacuum-steam-vacuum (VSV) technology has been used successfully to eliminate Listeria innocua from hot dogs. Ionizing radiation can eliminate Listeria spp. from RTE meats. However, the excessive application of either technology can cause changes in product quality, including structural changes, changes in cure color (redness), and lipid oxidation. In this study, two cycles of VSV were combined with 2.0 kGy of ionizing radiation to obtain 4.40- and 4.85-log10 reductions of L. innocua on ham meat and skin, respectively. The use of both treatments resulted in an additive, as opposed to synergistic, reduction of L. innocua on ham. The combination treatment did not cause statistically significant changes in product structure, color (redness), or lipid oxidation.

Development of dissimilar metal transition joint by hot roll bonding technique

International Nuclear Information System (INIS)

Nagai, Takayuki; Takeda, Seiichiro; Tanaka, Yasumasa; Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Ikenaga, Yoshiaki.

1994-01-01

Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called 'rotary reduction mill'. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by the hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author)

Development of dissimilar metal transition joint by hot roll bonding technique

International Nuclear Information System (INIS)

Nagai, Takayuki; Takeuchi, Masayuki; Takeda, Seiichiro; Shikakura, Sakae; Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Kajimura, Haruhiko.

1995-01-01

Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called 'rotary reduction mill'. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author)

Universal leakage elimination

International Nuclear Information System (INIS)

Byrd, Mark S.; Lidar, Daniel A.; Wu, L.-A.; Zanardi, Paolo

2005-01-01

'Leakage' errors are particularly serious errors which couple states within a code subspace to states outside of that subspace, thus destroying the error protection benefit afforded by an encoded state. We generalize an earlier method for producing leakage elimination decoupling operations and examine the effects of the leakage eliminating operations on decoherence-free or noiseless subsystems which encode one logical, or protected qubit into three or four qubits. We find that by eliminating a large class of leakage errors, under some circumstances, we can create the conditions for a decoherence-free evolution. In other cases we identify a combined decoherence-free and quantum error correcting code which could eliminate errors in solid-state qubits with anisotropic exchange interaction Hamiltonians and enable universal quantum computing with only these interactions

Structure determination of the Si(001)-(2 x 1)-H reconstruction by surface X-ray diffraction: Weakening of the dimer bond by the addition of hydrogen

DEFF Research Database (Denmark)

Lauridsen, E.M.; Baker, J.; Nielsen, M.

2000-01-01

The atomic structure of the monohydride Si(001)-(2 x 1)-H reconstruction has been investigated by surface X-ray diffraction. Atomic relaxations down to the eighth layer have been determined. The bond length of the hydrogenated silicon dimers was found to be 2.47 +/- 0.02 Angstrom. which is longer...... than the dimer bond of the clean (2 x 1)-reconstructed Si(001) surface and also 5% longer than the bulk bond length of 2.35 Angstrom. The differences to the (2 x 1) structure of the clean surface are discussed in terms of the elimination of the weak pi-bond character of the dimer bond by the addition...

Bonding characteristics in NiAl intermetallics with O impurity: a first-principles computational tensile test

International Nuclear Information System (INIS)

Hu Xuelan; Zhang Ying; Lu Guanghong; Wang Tianmin

2009-01-01

We have performed a first-principles computational tensile test on NiAl intermetallics with O impurity along the [001] crystalline direction on the (110) plane to investigate the tensile strength and the bonding characteristics of the NiAl-O system. We show that the ideal tensile strength is largely reduced due to the presence of O impurity in comparison with pure NiAl. The investigations of the atomic configuration and bond-length evolution show that O prefers to bond with Al, forming an O-Al cluster finally with the break of O-Ni bonds. The O-Ni bonds are demonstrated to be weaker than the O-Al bonds, and the reduced tensile strength originates from such weaker O-Ni bonds. A void-like structure forms after the break of the O-Ni and some Ni-Al bonds. Such a void-like structure can act as the initial nucleation or the propagation path of the crack, and thus produce large effects on the mechanical properties of NiAl.

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

DEFF Research Database (Denmark)

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

2017-01-01

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

Cohesive zone model for direct silicon wafer bonding

Science.gov (United States)

Kubair, D. V.; Spearing, S. M.

2007-05-01

Direct silicon wafer bonding and decohesion are simulated using a spectral scheme in conjunction with a rate-dependent cohesive model. The cohesive model is derived assuming the presence of a thin continuum liquid layer at the interface. Cohesive tractions due to the presence of a liquid meniscus always tend to reduce the separation distance between the wafers, thereby opposing debonding, while assisting the bonding process. In the absence of the rate-dependence effects the energy needed to bond a pair of wafers is equal to that needed to separate them. When rate-dependence is considered in the cohesive law, the experimentally observed asymmetry in the energetics can be explained. The derived cohesive model has the potential to form a bridge between experiments and a multiscale-modelling approach to understand the mechanics of wafer bonding.

Biochemistry of Catabolic Reductive Dehalogenation.

Science.gov (United States)

Fincker, Maeva; Spormann, Alfred M

2017-06-20

A wide range of phylogenetically diverse microorganisms couple the reductive dehalogenation of organohalides to energy conservation. Key enzymes of such anaerobic catabolic pathways are corrinoid and Fe-S cluster-containing, membrane-associated reductive dehalogenases. These enzymes catalyze the reductive elimination of a halide and constitute the terminal reductases of a short electron transfer chain. Enzymatic and physiological studies revealed the existence of quinone-dependent and quinone-independent reductive dehalogenases that are distinguishable at the amino acid sequence level, implying different modes of energy conservation in the respective microorganisms. In this review, we summarize current knowledge about catabolic reductive dehalogenases and the electron transfer chain they are part of. We review reaction mechanisms and the role of the corrinoid and Fe-S cluster cofactors and discuss physiological implications.

Study on dioxygen reduction by mutational modifications of the hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase

International Nuclear Information System (INIS)

Morishita, Hirotoshi; Kurita, Daisuke; Kataoka, Kunishige; Sakurai, Takeshi

2014-01-01

Highlights: • Proton transport pathway in bilirubin oxidase was mutated. • Two intermediates in the dioxygen reduction steps were trapped and characterized. • A specific glutamate for dioxygen reduction by multicopper oxidases was identified. - Abstract: The hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase is constructed with Glu463 and water molecules to transport protons for the four-electron reduction of dioxygen. Substitutions of Glu463 with Gln or Ala were attributed to virtually complete loss or significant reduction in enzymatic activities due to an inhibition of the proton transfer steps to dioxygen. The single turnover reaction of the Glu463Gln mutant afforded the highly magnetically interacted intermediate II (native intermediate) with a broad g = 1.96 electron paramagnetic resonance signal detectable at cryogenic temperatures. Reactions of the double mutants, Cys457Ser/Glu463Gln and Cys457Ser/Glu463Ala afforded the intermediate I (peroxide intermediate) because the type I copper center to donate the fourth electron to dioxygen was vacant in addition to the interference of proton transport due to the mutation at Glu463. The intermediate I gave no electron paramagnetic resonance signal, but the type II copper signal became detectable with the decay of the intermediate I. Structural and functional similarities between multicopper oxidases are discussed based on the present mutation at Glu463 in bilirubin oxidase

Study on dioxygen reduction by mutational modifications of the hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase

Energy Technology Data Exchange (ETDEWEB)

Morishita, Hirotoshi; Kurita, Daisuke; Kataoka, Kunishige; Sakurai, Takeshi, E-mail: tsakurai@se.kanazawa-u.ac.jp

2014-07-18

Highlights: • Proton transport pathway in bilirubin oxidase was mutated. • Two intermediates in the dioxygen reduction steps were trapped and characterized. • A specific glutamate for dioxygen reduction by multicopper oxidases was identified. - Abstract: The hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase is constructed with Glu463 and water molecules to transport protons for the four-electron reduction of dioxygen. Substitutions of Glu463 with Gln or Ala were attributed to virtually complete loss or significant reduction in enzymatic activities due to an inhibition of the proton transfer steps to dioxygen. The single turnover reaction of the Glu463Gln mutant afforded the highly magnetically interacted intermediate II (native intermediate) with a broad g = 1.96 electron paramagnetic resonance signal detectable at cryogenic temperatures. Reactions of the double mutants, Cys457Ser/Glu463Gln and Cys457Ser/Glu463Ala afforded the intermediate I (peroxide intermediate) because the type I copper center to donate the fourth electron to dioxygen was vacant in addition to the interference of proton transport due to the mutation at Glu463. The intermediate I gave no electron paramagnetic resonance signal, but the type II copper signal became detectable with the decay of the intermediate I. Structural and functional similarities between multicopper oxidases are discussed based on the present mutation at Glu463 in bilirubin oxidase.

Adaptive elimination of optical fiber transmission noise in fiber ocean bottom seismic system

Science.gov (United States)

Zhong, Qiuwen; Hu, Zhengliang; Cao, Chunyan; Dong, Hongsheng

2017-10-01

In this paper, a pressure and acceleration insensitive reference Interferometer is used to obtain laser and public noise introduced by transmission fiber and laser. By using direct subtraction and adaptive filtering, this paper attempts to eliminate and estimation the transmission noise of sensing probe. This paper compares the noise suppression effect of four methods, including the direct subtraction (DS), the least mean square error adaptive elimination (LMS), the normalized least mean square error adaptive elimination (NLMS) and the least square (RLS) adaptive filtering. The experimental results show that the noise reduction effect of RLS and NLMS are almost the same, better than LMS and DS, which can reach 8dB (@100Hz). But considering the workload, RLS is not conducive to the real-time operating system. When it comes to the same treatment effect, the practicability of NLMS is higher than RLS. The noise reduction effect of LMS is slightly worse than that of RLS and NLMS, about 6dB (@100Hz), but its computational complexity is small, which is beneficial to the real time system implementation. It can also be seen that the DS method has the least amount of computational complexity, but the noise suppression effect is worse than that of the adaptive filter due to the difference of the noise amplitude between the RI and the SI, only 4dB (@100Hz) can be reached. The adaptive filter can basically eliminate the influence of the transmission noise, and the simulation signal of the sensor is kept intact.

Generating Nice Linear Systems for Matrix Gaussian Elimination

Science.gov (United States)

Homewood, L. James

2004-01-01

In this article an augmented matrix that represents a system of linear equations is called nice if a sequence of elementary row operations that reduces the matrix to row-echelon form, through matrix Gaussian elimination, does so by restricting all entries to integers in every step. Many instructors wish to use the example of matrix Gaussian…

Development of dissimilar metal transition joint by hot bond rolling

International Nuclear Information System (INIS)

Kurokawa, Hiroyuki; Nakasuji, Kazuyuki; Kajimura, Haruhiko; Nagai, Takayuki; Takeda, Seiichiro.

1997-01-01

Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) to stainless steel piping are required for nuclear fuel reprocessing plants. The authors have developed dissimilar transition joints made of stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot bond rolling process of clad bars and clad pipes, using a newly developed mill called 'rotary reduction mill'. This report presents the manufacturing process of dissimilar transition joints produced from the clad pipe with three layers by the hot bond rolling. First, the method of hot bond rolling of clad pipe is proposed. Then, the mechanical and corrosion properties of the dissimilar transition joints are evaluated in detail by carrying out various tests. Finally, the rolling properties in the clad pipe method are discussed. (author)

Theoretical estimation of pnicogen bonds and hydrogen bonds in small heterocyclic complexes: Red-shifts and blue-shifts ruled by polarization effects

International Nuclear Information System (INIS)

Oliveira, Boaz G.

2014-01-01

Graphical abstract: - Highlights: • This paper definitively discusses the interaction strength. • Analyses of the red-shifts and blue-shift. • Stretch frequencies of the hydrogen bonds and pnicogen bonds in heterocyclic compounds. • Theoretical calculations derived from topological parameters of the Quantum Theory of Atoms in Molecules (QTAIM). • The analysis of the Natural Bond Orbital (NBO) in line with the Bent’s rule of the chemical bonding. - Abstract: The occurrence of pnicogen bonds (N⋯P) and hydrogen bonds (F⋯H or Cl⋯H) in heterocyclic complexes formed by C 2 H 5 N⋯PH 3 , C 2 H 5 N⋯PH 2 F and C 2 H 5 N⋯PH 2 Cl was investigated at the B3LYP/6-311++G(d,p) level of theory. Analysis of the infrared spectra revealed the appearance of both red and blue shifts for the P–H bonds. However, in the case of the P–F and P–Cl bonds only red shifts were observed. The phenomenology of these vibration modes was interpreted on the basis of the QTAIM atomic radii as well as the contributions of the s and p orbitals determined via NBO calculations. The results of this latter investigation are consistent with the rehybridization theory and the Bent rule for chemical bonding. The charge transfer between N and P was determined in order to verify whether these atoms present an acid or base profile upon the formation of the pnicogen bonds

Book-entry bonds as a variety of the debt securities

Directory of Open Access Journals (Sweden)

М. М. Кулик

2015-10-01

Full Text Available Problem Setting. The article is devoted to the allocation of the features of the legal order and legal nature of the book-entry bonds as a variety of the debt securities. Analysis of the recent researches and publications. The book-entry securities and their place among other objects of the civil legal relations from the moment of their appearance on the securities market have been devoted many scientific works and publications both Ukrainian scientists and scientists of other countries, in particular, E. Dyomushkina, L. Dobrynina, V. A. Barulin, D. Stepanov, E. Reshetin, V. L. Yarotsky, G. N. Shevchenko, O. V. Vygovsky, S. Ya. Vavzhenchuk and others. Paper objective. With regard of definitions of the bond as the debt security of the documentary form of issue which has been proposed by the scientists specialized on civil law problems  at different times of the development of the teaching on securities and specific features of the book–entry securities as certain rights, it is necessary to allocate  peculiarities of   the legal order and legal nature of the book-entry bonds as a variety of the debt securities. Paper main body. In the article the different approaches to the definition of the bond have been given. It is specified that the documentary bond as the debt security mediates or establishes   relations of   the loan between the issuer of the bond and its owner and  obligates the issuer to return a certain cash equivalent within a specified period and to pay a certain percentage (profit. On the base of the comparative analysis of the documentary and book-entry securities the content of which includes the certain rights, the features of the book-entry bond as the debt security have been allocated: 1 the content of the right, embodied in the decision on the issue of the securities and in the securities emission prospectus, includes property ( obligation right of the requirement by its owner to return their nominal value and the

Halogen Bonding Involving CO and CS with Carbon as the Electron Donor

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Janet E. Del Bene

2017-11-01

Full Text Available MP2/aug’-cc-pVTZ calculations have been carried out to investigate the halogen-bonded complexes formed when CO and CS act as electron-pair donors through C to ClF, ClNC, ClCl, ClOH, ClCN, ClCCH, and ClNH2. CO forms only complexes stabilized by traditional halogen bonds, and all ClY molecules form traditional halogen-bonded complexes with SC, except ClF which forms only an ion-pair complex. Ion-pair complexes are also found on the SC:ClNC and SC:ClCl surfaces. SC:ClY complexes stabilized by traditional halogen bonds have greater binding energies than the corresponding OC:ClY complexes. The largest binding energies are found for the ion-pair SC–Cl+:−Y complexes. The transition structures which connect the complex and the ion pair on SC:ClNC and SC:ClCl potential surfaces provide the barriers for inter-converting these structures. Charge-transfer from the lone pair on C to the σ-hole on Cl is the primary charge-transfer interaction stabilizing OC:ClY and SC:ClY complexes with traditional halogen bonds. A secondary charge-transfer occurs from the lone pairs on Cl to the in-plane and out-of-plane π antibonding orbitals of ClY. This secondary interaction assumes increased importance in the SC:ClNH2 complex, and is a factor leading to its unusual structure. C–O and C–S stretching frequencies and 13C chemical shieldings increase upon complex formation with ClY molecules. These two spectroscopic properties clearly differentiate between SC:ClY complexes and SC–Cl+:−Y ion pairs. Spin–spin coupling constants 1xJ(C–Cl for OC:ClY complexes increase with decreasing distance. As a function of the C–Cl distance, 1xJ(C–Cl and 1J(C–Cl provide a fingerprint of the evolution of the halogen bond from a traditional halogen bond in the complexes, to a chlorine-shared halogen bond in the transition structures, to a covalent bond in the ion pairs.

Short hydrogen bonds in the catalytic mechanism of serine proteases

Directory of Open Access Journals (Sweden)

VLADIMIR LESKOVAC

2008-04-01

Full Text Available The survey of crystallographic data from the Protein Data Bank for 37 structures of trypsin and other serine proteases at a resolution of 0.78–1.28 Å revealed the presence of hydrogen bonds in the active site of the enzymes, which are formed between the catalytic histidine and aspartate residues and are on average 2.7 Å long. This is the typical bond length for normal hydrogen bonds. The geometric properties of the hydrogen bonds in the active site indicate that the H atom is not centered between the heteroatoms of the catalytic histidine and aspartate residues in the active site. Taken together, these findings exclude the possibility that short “low-barrier” hydrogen bonds are formed in the ground state structure of the active sites examined in this work. Some time ago, it was suggested by Cleland that the “low-barrier hydrogen bond” hypothesis is operative in the catalytic mechanism of serine proteases, and requires the presence of short hydrogen bonds around 2.4 Å long in the active site, with the H atom centered between the catalytic heteroatoms. The conclusions drawn from this work do not exclude the validity of the “low-barrier hydrogen bond” hypothesis at all, but they merely do not support it in this particular case, with this particular class of enzymes.

Dehydration of alcohols over oxide catalysts: γ-eliminations -- stereospecificity and selectivity

International Nuclear Information System (INIS)

Siddhan, S.; Narayanan, K.

1979-01-01

The effect of alkali impregnation on alumina catalysts has been investigated by a physicochemical study of pure and modified alumina catalyst samples. The stereospecificity and selectivity of dehyration reactions, as well as the incidence of γ-elimination, have been studied by passing suitable substrates over catalyst samples. There was a change in the acidity-basicity balance in the sodium-impregnated alumina samples vis a vis pure alumina, while the surface area virtually remained constant. A higher propensity for γ-elimination was noticed with increases in basicity of the catalyst. 1-Olefin formation was found to be larger in more basic alumina- and thoria-catalyzed dehydration reactions. Thoria was strikingly unique in its capacity to dehydrate only alcohols, which have at least one β-hydrogen atom. Neopentyl alcohol could not be dehydrated even under drastic conditions. The modes of elimination in the case of alumina and thoria have been shown to be anti and syn, respectively, from the results of the dehydration studies with threo-3-methyl-2-pentanol. Studies of alcohols with proper β-substituents revealed that the cis preference is not universal in all catalytic eliminations but, in fact, depends on the mode of elimination. While cis-preference was noticed in alumina-catalyzed anti eliminations, trans-olefin was formed to a major amount in thoria-catalyzed syn-elimination processes. 9 figures, 13 tables

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

Science.gov (United States)

Setiawan, Dani; Cremer, Dieter

2016-10-01

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

Engineered disulfide bonds increase active-site local stability and reduce catalytic activity of a cold-adapted alkaline phosphatase.

Science.gov (United States)

Asgeirsson, Bjarni; Adalbjörnsson, Björn Vidar; Gylfason, Gudjón Andri

2007-06-01

Alkaline phosphatase is an extracellular enzyme that is membrane-bound in eukaryotes but resides in the periplasmic space of bacteria. It normally carries four cysteine residues that form two disulfide bonds, for instance in the APs of Escherichia coli and vertebrates. An AP variant from a Vibrio sp. has only one cysteine residue. This cysteine is second next to the nucleophilic serine in the active site. We have individually modified seven residues to cysteine that are on two loops predicted to be within a 5 A radius. Four of them formed a disulfide bond to the endogenous cysteine. Thermal stability was monitored by circular dichroism and activity measurements. Global stability was similar to the wild-type enzyme. However, a significant increase in heat-stability was observed for the disulfide-containing variants using activity as a measure, together with a large reduction in catalytic rates (k(cat)) and a general decrease in Km values. The results suggest that a high degree of mobility near the active site and in the helix carrying the endogenous cysteine is essential for full catalytic efficiency in the cold-adapted AP.

Contingent convertible bonds as countercyclical capital measures

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Francois Liebenberg

2017-06-01

Aim: The effectiveness of the CCB during contractions is not obvious. Contingent convertible (CoCo bonds – which are bond-like until triggered by a deterioration of a prescribed capital metric, at which point they convert into a form of equity – are explored as a supplementary countercyclical capital measure for such periods to establish whether or not they function effectively. Setting: The analysis is undertaken using global bank CoCo data, and then applied to South African banks. Methods: The Hodrick Prescott filter was applied to empirical historical data. Results: The CCB functions as a good countercyclical capital measure in times of economic expansion by absorbing losses and stabilising the capital base through equity issuance. Conclusion: The issuance of CoCo bonds – if their trigger mechanisms are designed correctly – may prove helpful to banks and the broader financial sector in times of economic contraction through the countercyclical capital properties that manifest through CoCo bonds under these economic conditions.

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

Science.gov (United States)

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

2004-10-01

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

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

Science.gov (United States)

Li, An Yong

2007-04-21

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

Costs of eliminating malaria and the impact of the global fund in 34 countries.

Directory of Open Access Journals (Sweden)

Brittany Zelman

Full Text Available International financing for malaria increased more than 18-fold between 2000 and 2011; the largest source came from The Global Fund to Fight AIDS, Tuberculosis and Malaria (Global Fund. Countries have made substantial progress, but achieving elimination requires sustained finances to interrupt transmission and prevent reintroduction. Since 2011, global financing for malaria has declined, fueling concerns that further progress will be impeded, especially for current malaria-eliminating countries that may face resurgent malaria if programs are disrupted.This study aims to 1 assess past total and Global Fund funding to the 34 current malaria-eliminating countries, and 2 estimate their future funding needs to achieve malaria elimination and prevent reintroduction through 2030.Historical funding is assessed against trends in country-level malaria annual parasite incidences (APIs and income per capita. Following Kizewski et al. (2007, program costs to eliminate malaria and prevent reintroduction through 2030 are estimated using a deterministic model. The cost parameters are tailored to a package of interventions aimed at malaria elimination and prevention of reintroduction.The majority of Global Fund-supported countries experiencing increases in total funding from 2005 to 2010 coincided with reductions in malaria APIs and also overall GNI per capita average annual growth. The total amount of projected funding needed for the current malaria-eliminating countries to achieve elimination and prevent reintroduction through 2030 is approximately US$8.5 billion, or about $1.84 per person at risk per year (PPY (ranging from $2.51 PPY in 2014 to $1.43 PPY in 2030.Although external donor funding, particularly from the Global Fund, has been key for many malaria-eliminating countries, sustained and sufficient financing is critical for furthering global malaria elimination. Projected cost estimates for elimination provide policymakers with an indication of the