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1

Oxidation kinetics, microstructure evolution and texture development in the reaction-bonded aluminum oxide (RBAO) process  

NASA Astrophysics Data System (ADS)

The reaction-bonded aluminum oxide (RBAO) process involves the solid state (T < 660°C) and liquid state (1000° < T < 660°C) oxidation of compacts of attrition milled Al and alpha alumina. When heated in air, the oxidation per unit area decreases for the higher surface attrition milled Al powders (i.e., 14.4 and 20.2 m2/g) but the total oxidation of the milled powder is ˜70% versus ˜9% for the as-received powder (surface area = 1.2 m2/g) because of the higher surface area. The solid state oxidation of Al powder sequentially follows parabolic, linear and non-linear rate laws. The solid state oxidation of RBAO compacts, liquid Al formation, and alpha alumina phase transformation during the RBAO process and their effect on final microstructure were investigated. Compact oxidation is controlled by heat transfer and the rate-controlling heat transfer mechanism is convection. Low heat transfer from the surface results in too rapid oxidation and a core-shell oxidation of the compact. The alpha-Al2O3 particles in the RBAO precursor behave like seed particles for the gamma to alpha alumina transformation in the RBAO process. Highly textured, dense alumina ceramics were fabricated by a new processing route which utilizes a mixture of Al metal powder, alpha alumina powder, alpha alumina platelet (template) particles and a liquid phase former. Texture development in liquid-phase sintered RBAO ceramics was studied during templated grain growth (TGG); a technique for developing crystallographic texture in ceramic bodies via the grain growth of aligned anisometric particles in a dense and fine grain size matrix. The process of TGG occurs in 3 stages: densification, initial growth of individual template particles, and template impingement and thickening. Texture development is directly related to the initial number of template particles and the inter-template spacing. The growth of alpha alumina template particles is anisotropic. Template growth in radial direction is controlled by diffusion through the liquid phase during a solution-precipitation growth process. Template growth in the thickness direction occurs by 2-D nucleation and growth.

Suvaci, Ender

2

Oxidation behavior in reaction-bonded aluminum-silicon alloy/alumina powder compacts  

SciTech Connect

Goal of this research is to determine the feasibility of producing low-shrinkage mullite/alumina composites by applying the reaction-bonded alumina (RBAO) process to an aluminum-silicon alloy/alumina system. Mirostructural and compositional changes during heat treatment were studied by removing samples from the furnace at different steps in the heating schedule and then using optical and scanning electron microscopy, EDS and XRD to characterize the powder compacts. Results suggest that the oxidation behavior of the alloy compact is different from the model proposed for the pure Al/alumina system.

Yokota, S.H.

1992-12-01

3

Oxidative C-C bond formation (Scholl reaction) with DDQ as an efficient and easily recyclable oxidant.  

PubMed

DDQ in the presence of an acid is known to oxidize a variety of aromatic donors to the corresponding cation radicals. Herein, we now demonstrate that the DDQ/H(+) system can be effectively utilized for the oxidative C-C bond formations or biaryl synthesis. The efficient preparation of a variety of polyaromatic hydrocarbons including graphitic hexa-peri-hexabenzocoronenes, ease of isolation of the clean products, and ready regeneration of DDQ from easily recovered reduced DDQ-H(2) advances the use of DDQ/H(+) for Scholl reactions. PMID:19594139

Zhai, Linyi; Shukla, Ruchi; Rathore, Rajendra

2009-08-01

4

Sintered-reaction Bonded Silicon Nitride Densified by a Gas Pressure Sintering Process Effects of Rare Earth Oxide Sintering Additives  

Microsoft Academic Search

Reaction-bonded silicon nitrides containing rare-earth oxide sintering additives were densified by gas pressure sintering. The sintering behavior, microstructure and mechanical properties of the resultant specimens were analyzed. For that purpose, Lu2O3-SiO2 (US), La2O3-MgO (AM) and Y2O3-Al2O3 (YA) additive systems were selected. Among the tested compositions, densification of silicon nitride occurred at the lowest temperature when using the La2O3-MgO system. Since

S. H. Lee; J. W. Ko; Y. J. Park; H. D. Kim; Hua-Tay Lin; Paul F Becher

2012-01-01

5

Oxidation effects on the mechanical properties of SiC fiber-reinforced reaction-bonded silicon nitride matrix composites  

NASA Technical Reports Server (NTRS)

The room temperature mechanical properties of SiC fiber reinforced reaction bonded silicon nitride composites were measured after 100 hrs exposure at temperatures to 1400 C in nitrogen and oxygen environments. The composites consisted of approx. 30 vol percent uniaxially aligned 142 micron diameter SiC fibers in a reaction bonded Si3N4 matrix. The results indicate that composites heat treated in a nitrogen environment at temperatures to 1400 C showed deformation and fracture behavior equivalent to that of the as-fabricated composites. Also, the composites heat treated in an oxidizing environment beyond 400 C yielded significantly lower tensile strength values. Specifically in the temperature range from 600 to 1000 C, composites retained approx. 40 percent of their as-fabricated strength, and those heat treated in the temperatures from 1200 to 1400 C retained 70 percent. Nonetheless, for all oxygen heat treatment conditions, composite specimens displayed strain capability beyond the matrix fracture stress; a typical behavior of a tough composite.

Bhatt, Ramakrishna T.

1989-01-01

6

Aromatic Cations from Oxidative Carbon–Hydrogen Bond Cleavage in Bimolecular Carbon–Carbon Bond Forming Reactions  

PubMed Central

Chromenes and isochromenes react quickly with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to form persistent aromatic oxocarbenium ions through oxidative carbon–hydrogen cleavage. This process is tolerant of electron-donating and electron-withdrawing groups on the benzene ring and additional substitution on the pyran ring. A variety of nucleophiles can be added to these cations to generate a diverse set of structures. PMID:22780559

Clausen, Dane J.

2012-01-01

7

Sintered-reaction Bonded Silicon Nitride Densified by a Gas Pressure Sintering Process Effects of Rare Earth Oxide Sintering Additives  

SciTech Connect

Reaction-bonded silicon nitrides containing rare-earth oxide sintering additives were densified by gas pressure sintering. The sintering behavior, microstructure and mechanical properties of the resultant specimens were analyzed. For that purpose, Lu2O3-SiO2 (US), La2O3-MgO (AM) and Y2O3-Al2O3 (YA) additive systems were selected. Among the tested compositions, densification of silicon nitride occurred at the lowest temperature when using the La2O3-MgO system. Since the Lu2O3-SiO2 system has the highest melting temperature, full densification could not be achieved after sintering at 1950oC. However, the system had a reasonably high bending strength of 527 MPa at 1200oC in air and a high fracture toughness of 9.2 MPa m1/2. The Y2O3-Al2O3 system had the highest room temperature bending strength of 1.2 GPa

Lee, S. H. [Korea Institute of Materials Science; Ko, J. W. [Korea Institute of Materials Science; Park, Y. J. [Korea Institute of Materials Science; Kim, H. D. [Korea Institute of Materials Science; Lin, Hua-Tay [ORNL; Becher, Paul F [ORNL

2012-01-01

8

Light-mediated heterogeneous cross dehydrogenative coupling reactions: metal oxides as efficient, recyclable, photoredox catalysts in C-C bond-forming reactions.  

PubMed

Let there be light: A heterogeneous photocatalytic system based on easily recyclable TiO(2) or ZnO allows cross dehydrogenative coupling reactions of tertiary amines. The newly developed protocols have successfully been applied to various C-C and C-P bond-forming reactions to provide nitro amines as well as amino ketones, nitriles and phosphonates. PMID:22314870

Rueping, Magnus; Zoller, Jochen; Fabry, David C; Poscharny, Konstantin; Koenigs, René M; Weirich, Thomas E; Mayer, Joachim

2012-03-19

9

Stereoelectronic effects in C-H bond oxidation reactions of Ni(I) N-heterocyclic carbene complexes.  

PubMed

Activation of O2 by the three-coordinate Ni(I) ring-expanded N-heterocyclic carbene complexes Ni(RE-NHC)(PPh3)Br (RE-NHC = 6-Mes, 1; 7-Mes, 2) produced the structurally characterized dimeric Ni(II) complexes Ni(6-Mes)(Br)(?-OH)(?-O-6-Mes')NiBr (3) and Ni(7-Mes)(Br)(?-OH)(?-O-7-Mes')NiBr (4) containing oxidized ortho-mesityl groups from one of the carbene ligands. NMR and mass spectrometry provided evidence for further oxidation in solution to afford bis-?-aryloxy compounds; the 6-Mes derivative was isolated, and its structure was verified. Low-temperature UV-visible spectroscopy showed that the reaction between 1 and O2 was too fast even at ca. -80 °C to yield any observable intermediates and also supported the formation of more than one oxidation product. Addition of O2 to Ni(I) precursors containing a less electron-donating diamidocarbene (6-MesDAC, 7) or less bulky 6- or 7-membered ring diaminocarbene ligands (6- or 7-o-Tol; 8 and 9) proceeded quite differently, affording phosphine and carbene oxidation products (Ni(O?PPh3)2Br2 and (6-MesDAC)?O) and the mononuclear Ni(II) dibromide complexes (Ni(6-o-Tol)(PPh3)Br2 (10) and (Ni(7-o-Tol)(PPh3)Br2 (11)) respectively. Electrochemical measurements on the five Ni(I) precursors show significantly higher redox potentials for 1 and 2, the complexes that undergo oxygen atom transfer from O2. PMID:24972307

Poulten, Rebecca C; López, Isidoro; Llobet, Antoni; Mahon, Mary F; Whittlesey, Michael K

2014-07-21

10

Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols  

SciTech Connect

This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and conditions, it was found that the oxidative dehydrogenation of dibenzylamine to Nbenzylidenebenzylamine, with N-methylmorpholine N-oxide (NMMO), was nearly quantitative (96%) within 24 h. However, the reaction with oxygen was much slower, with only a 52% yield of imine product over the same time period. Moreover, the rate of reaction was found to be influenced by the nature of the amine N-oxide. For example, the use of the weakly basic pyridine N-oxide (PyNO) led to an imine yield of only 6% after 24 h. A comparison of amine N-oxide and O2 was also examined in the oxidation of PhCH{sub 2}OH to PhCHO catalyzed by bulk gold. In this reaction, a 52% yield of the aldehyde was achieved when NMMO was used, while only a 7% product yield was afforded when O{sub 2} was the oxidant after 48 h. The bulk gold-catalyzed oxidative dehydrogenation of cyclic amines generates amidines, which upon treatment with Aerosil and water were found to undergo hydrolysis to produce lactams. Moreover, 5-, 6-, and 7-membered lactams could be prepared through a one-pot reaction of cyclic amines by treatment with oxygen, water, bulk gold, and Aerosil. This method is much more atom economical than industrial processes, does not require corrosive acids, and does not generate undesired byproducts. Additionally, the gold and Aerosil catalysts can be readily separated from the reaction mixture. The second project involved studying iron(III) tetraphenylporphyrin chloride, Fe(TPP)Cl, as a homogeneous catalyst for the generation of carbenes from diazo reagents and their reaction with heteroatom compounds. Fe(TPP)Cl, efficiently catalyzed the insertion of carbenes derived from methyl 2-phenyldiazoacetates into O-H bonds of aliphatic and aromatic alcohols. Fe(TPP)Cl was also found to be an effective catalyst for tandem N-H and O-H insertion/cyclization reactions when 1,2-diamines and 1,2-alcoholamines were treated with diazo reagents. This approach provides a one-pot process for synthesizing piperazinones and morpholinones and related analogues such as quinoxalinones and benzoxazin-2-ones.

Klobukowski, Erik

2011-12-29

11

Sensor/ROIC Integration using Oxide Bonding  

E-print Network

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

Zhenyu Ye; for the Fermilab Pixel R&D Group

2009-02-16

12

Transition-metal-free oxidative carboazidation of acrylamides via cascade C-N and C-C bond-forming reactions.  

PubMed

A novel transition-metal-free oxidative carboazidation of acrylamides using inexpensive NaN3 and K2S2O8 was achieved, which not only provided an efficient method to prepare various N3-substituted oxindoles, but also represented a novel strategy for C-N and C-C bond formation via a free-radical cascade process. This transformation exhibits excellent functional group tolerance, affording the desired oxindoles in good to excellent yields. PMID:24854242

Qiu, Jun; Zhang, Ronghua

2014-07-01

13

Sensor/ROIC Integration using Oxide Bonding  

SciTech Connect

We explore the Ziptronix Direct Bond Interconnect (DBI) technology [2] for the integration of sensors and readout integrated circuits (ROICs) for high energy physics. The technology utilizes an oxide bond to form a robust mechanical connection between layers which serves to assist with the formation of metallic interlayer connections. We report on testing results of sample sensors bonded to ROICs and thinned to 100 {micro}m.

Ye, Zhenyu; /Fermilab

2009-02-01

14

Effect of processing parameters on reaction bonding of silicon nitride  

NASA Technical Reports Server (NTRS)

Reaction bonded silicon nitride was developed. The relationship between the various processing parameters and the resulting microstructures was to design and synthesize reaction bonded materials with improved room temperature mechanical properties.

Richman, M. H.; Gregory, O. J.; Magida, M. B.

1980-01-01

15

Oxidant-free dehydrogenative coupling reactions via hydrogen evolution.  

PubMed

Oxidant-free dehydrogenative coupling reactions: Recently, coupling reactions have followed a novel strategy for the construction of C==C, C==N, C==P, and S==S bonds by dehydrogenation without using any extra oxidant, via H2 evolution. These breakthroughs inspire a new direction in the construction of chemical bonds, towards more sustainable, highly atom-economical, and environmentally benign synthetic methods. PMID:25139249

He, Ke-Han; Li, Yang

2014-10-01

16

Structure-reactivity relationships in oxidative carbon-carbon bond forming reactions: a mild and efficient approach to stereoselective syntheses of 2,6-disubstituted tetrahydropyrones.  

PubMed

Homobenzylic ethers with pendent enol acetate nucleophiles undergo highly efficient cleavage reactions followed by 6-endo cyclizations to form 2,6-disubstituted tetrahydropyrones with excellent stereocontrol at room temperature in the presence of the mild oxidant ceric ammonium nitrate. Cyclizations proceed through either stabilized or nonstabilized oxocarbenium ions. Structure-reactivity relationships are presented to provide a predictive guide for the design of radical cation cleavage processes. Unique sequences for preparing cyclization substrates based on stereoselective Lewis acid mediated acetal openings have been developed for the synthesis of complex substrates that are suitable for applications to the synthesis of biologically active natural products. PMID:15453792

Wang, Lijun; Seiders, John R; Floreancig, Paul E

2004-10-01

17

Oxidant Sensing by Reversible Disulfide Bond Formation*  

PubMed Central

Maintenance of the cellular redox balance is crucial for cell survival. An increase in reactive oxygen, nitrogen, or chlorine species can lead to oxidative stress conditions, potentially damaging DNA, lipids, and proteins. Proteins are very sensitive to oxidative modifications, particularly methionine and cysteine residues. The reversibility of some of these oxidative protein modifications makes them ideally suited to take on regulatory roles in protein function. This is especially true for disulfide bond formation, which has the potential to mediate extensive yet fully reversible structural and functional changes, rapidly adjusting the protein's activity to the prevailing oxidant levels. PMID:23861395

Cremers, Claudia M.; Jakob, Ursula

2013-01-01

18

Palladium nanoparticles bonded to two-dimensional iron oxide graphene nanosheets: a synergistic and highly reusable catalyst for the Tsuji-Trost reaction in water and air.  

PubMed

Low cost, high activity and selectivity, convenient separation, and increased reusability are the main requirements for noble-metal-nanocatalyst-catalyzed reactions. Despite tremendous efforts, developing noble-metal nanocatalysts to meet the above requirements remains a significant challenge. Here we present a general strategy for the preparation of strongly coupled Fe(3)O(4) and palladium nanoparticles (PdNPs) to graphene sheets by employing polyethyleneimine as the coupling linker. Transmission electron microscopic images show that Pd and Fe(3)O(4) nanoparticles are highly dispersed on the graphene surface, and the mean particle size of Pd is around 3?nm. This nanocatalyst exhibits synergistic catalysis by Pd nanoparticles supported on reduced graphene oxide (rGO) and a tertiary amine of polyethyleneimine (Pd/Fe(3)O(4)/PEI/rGO) for the Tsuji-Trost reaction in water and air. For example, the reaction of ethyl acetoacetate with allyl ethyl carbonate afforded the allylated product in more than 99?% isolated yield, and the turnover frequency reached 2200?h(-1). The yield of allylated products was 66?% for Pd/rGO without polyethyleneimine. The catalyst could be readily recycled by a magnet and reused more than 30?times without appreciable loss of activity. In addition, only about 7.5?% of Pd species leached off after 20?cycles, thus rendering this catalyst safer for the environment. PMID:25048270

Liu, Jian; Huo, Xing; Li, Tianrong; Yang, Zhengyin; Xi, Pinxian; Wang, Zhiyi; Wang, Baodui

2014-09-01

19

ChemTeacher Resource: Oxidation Reduction Reactions  

NSDL National Science Digital Library

This computer resource goes over oxidation reduction reactions and how they are broken down into half reactions. It explains which half reaction is the oxidation reaction and which one is the reduction, then has some summary questions at the end.

2012-08-02

20

Oxide formation: reaction details studied,  

E-print Network

-nitrosohydroxylamines undergo an alternative decomposition under very similar reaction conditions to liberate nitrous oxide, N2O to human health. Investigation of the molecular basis of these alternative reactions of N recent work at Newcastle on the mechanisms of decomposition of N-nitrosohydroxylamines in which we

Johnson, Edward A.

21

Reaction-bonded silicon nitride: its formation and properties  

Microsoft Academic Search

The theme of the review is the construction of a model embracing the mechanism of formation of reaction-bonded silicon nitride, the development of microstructure and mechanical properties. Possible nitridation reactions are discussed, with emphasis on kinetics and on phase composition and microstructure of the reaction product. The influence of Fe, a common impurity in silicon powders, and of H2, as

A. J. Moulson

1979-01-01

22

Recent advances in cinchona alkaloid catalysis for enantioselective carbon-nitrogen bond formation reactions.  

PubMed

Organocatalysis and cooperative catalysis are fast growing research areas. In these fields, cinchona alkaloids and their derivatives play a major role. The ready availability of both pseudo-enantiomeric pairs from natural sources makes them outstanding catalysts for reactions including oxidation, alkylation, cycloaddition, and carbene insertion. This short review focuses on recent achievements in the field of asymmetric carbon-nitrogen atom bond formation reactions using cinchona alkaloids and their derivatives. PMID:24359199

Saito, Hiroaki; Miyairi, Shinichi

2014-01-01

23

sp2 C-H bond activation in water and catalytic cross-coupling reactions.  

PubMed

The metal-catalysed successive activation and functionalisation of sp(2) C-H bonds is the at heart of synthetic innovations for the development of C-C bond cross-coupling processes. Against expectation catalytic C-H bond transformations can be performed in water as an available, renewable, safe solvent but most importantly as a partner improving the catalyst activity. The objective of the review is to present the catalytic successes for C-H bond transformations in water, discovered mainly during the last six years and involving mostly palladium and ruthenium catalysts, often with the help of a carboxylate partner for the initial key C-H bond deprotonation. Water is beneficial for the direct catalytic arylation with (hetero)aryl halides of functional arene ortho C-H bonds with pyridine, pyrazole, oxazoline, imine, urea, amide… directing groups leading to functional biaryl derivatives, polyheterocycles and polydentate ligands. Metal-catalysed activation of the sp(2) C-H bond in water also allows the cross-coupling reaction of two different C-H bonds in the presence of an oxidant and regioselective alkenylations of arenes, heterocycles and functional alkenes are now controlled. Annulation reactions via insertion of alkynes into both activated C-H and heteroatom-hydrogen bonds in water constitute new routes to heterocycles. PMID:23525331

Li, Bin; Dixneuf, Pierre H

2013-07-01

24

Isotope Effects in C-H Bond Activation Reactions by  

E-print Network

Isotope Effects in C-H Bond Activation Reactions by Transition Metals WILLIAM D. JONES Department to occur via transient -alkane complexes. This Account summarizes how isotope effects can be used to probe, the subject of isotope effects in some of these reactions will be examined in detail, as these effects

Jones, William D.

25

Acetic acid promoted metal-free aerobic carbon-carbon bond forming reactions at ?-position of tertiary amines.  

PubMed

The oxidative functionalization of the benzylic C-H bonds in tetrahydroisoquinolines and tetrahydro-?-carboline derivatives was investigated. C-C bond forming reactions proceeded with a range of nucleophiles (nitroalkane, enol silyl ether, indole, allylstannane, and tetrabutylammonium cyanide) under metal-free conditions and an oxygen atmosphere. Acetic acid caused a significant acceleration effect. PMID:25062493

Ueda, Hirofumi; Yoshida, Kei; Tokuyama, Hidetoshi

2014-08-15

26

Oxidation and Reduction Reactions in Organic Chemistry  

ERIC Educational Resources Information Center

A variety of approaches to the concept of oxidation and reduction appear in organic textbooks. The method proposed here is different than most published approaches. The oxidation state is calculated by totaling the number of heterogeneous atoms, [pi]-bonds, and rings. A comparison of the oxidation states of reactant and product determine what type…

Shibley, Ivan A., Jr.; Amaral, Katie E.; Aurentz, David J.; McCaully, Ronald J.

2010-01-01

27

Reactions of parylenes with double bonds: An ab initio study  

NASA Astrophysics Data System (ADS)

The reactions of the hydrogen atom transfer from various compounds (containing the same ethylene fragment in their framework) to the neutral di-para-xylylene dimer were examined at the B3LYP/6-31G level to estimate the corresponding kinetic barriers. Also, an alternative path (involving the ?-bond cleavage) for such reactions were considered. It was found that the certain derivatives should easily react with the dimer at room temperature since the overall reactions are thermodynamically favorable and kinetically possible.

Smuczy?ska, Sylwia; Skurski, Piotr; Bobrowski, Maciej

2012-12-01

28

Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.  

PubMed

In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change. PMID:25010751

González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson

2014-08-01

29

SULFUR DIOXIDE OXIDATION REACTIONS IN AQUEOUS SOLUTIONS  

EPA Science Inventory

This is the final report on a three year project to study the kinetics and mechanisms of some 105 reactions involving the aqueous oxidation of sulfur dioxide and nitrogen oxides in mixed catalyst-oxidant systems at low pH (0-3). The 105 systems involve six redox reaction types: S...

30

Theoretical investigation of the reaction between carbonyl oxides and ammonia.  

PubMed

The gas-phase reaction between carbonyl oxides and ammonia is investigated by quantum mechanical calculations. The density functional method B3LYP with the basis set 6-311++G(2d,2p) was employed for the geometry and energy optimization of the stationary points along the reaction path. The energies have been refined by CCSD(T) with various basis sets and Gaussian-3 level of theory. The reaction mechanisms are studied for three different carbonyl oxides, H2COO (methyl carbonyl oxide), CH3HCOO (ethyl carbonyl oxide), and (CH3)2COO (acetone carbonyl oxide). First, a prereactive complex is formed, where a hydrogen bond is formed between ammonia and the terminal oxygen atom in the COO moiety. Next, a structural rearrangement occurs, leading to the formation of a chemical bond between the nitrogen atom and the carbon in the COO moiety as well as a transfer of the hydrogen atom from nitrogen atom to the terminal oxygen atom in the COO moiety. The newly formed molecule is a hydroperoxide amine. All the studied reactions are exothermic. The estimated reaction rates range from 1.8 x 10(-13) to 6.9 x 10(-14) and to 5.1 x 10(-18) cm3 molecule(-1) s(-1) for H2COO, CH3HCOO, and (CH3)2COO, respectively. This shows that the investigated process are important in locations with intensive farming. PMID:19711931

Jørgensen, Solvejg; Gross, Allan

2009-09-24

31

Microstructural evolution in reaction-bonded silicon carbide  

Microsoft Academic Search

A detailed microstructural investigation of reaction-bonded silicon carbide has been performed using both fully-bonded and quenched samples and other specially prepared specimens containing large original single crystals of known crystallographic habit. The development of the epitaxial SiC overgrowth on the original SiC particles has been followed and found to proceed by the progressive growth and coalescence of identically-oriented nuclei. This

J. N. Ness; T. F. Page

1986-01-01

32

Dynamic fracture toughnesses of reaction-bonded silicon nitride  

NASA Technical Reports Server (NTRS)

The room-temperature dynamic fracture response of reaction-bonded silicon nitride is investigated using a hybrid experimental-numerical procedure. In this procedure, experimentally determined crack velocities are utilized to drive a dynamic finite-element code or dynamic finite-difference code in its generation mode in order to extract numerically the dynamic stress intensity factor of the fracturing specimen. Results show that the dynamic fracture toughness vs crack velocity relations of the two reaction-bonded silicon nitrides do not follow the general trend in those relations of brittle polymers and steel. A definite slow crack velocity during the initial phase of dynamic crack propagation is observed in reaction-bonded silicon nitride, which results in a nonunique dynamic fracture toughness vs crack velocity relation. In addition, it is found that a propagating crack will continue to propagate under a static stress intensity factor substantially lower than K(IC).

Kobayashi, A. S.; Emery, A. F.; Liaw, B. M.

1983-01-01

33

Revised role of selectfluor in homogeneous Au-catalyzed oxidative C-O bond formations.  

PubMed

The pairing of transition metal catalysis with the reagent Selectfluor (F-TEDA-BF4) has attracted considerable attention due to its utility in myriad C-C and C-heteroatom bond-forming reactions. However, little mechanistic information is available for Selectfluor-mediated transition metal-catalyzed reactions and controversy surrounds the precise role of Selectfluor in these processes. We present herein a systematic investigation of homogeneous Au-catalyzed oxidative C-O bond-forming reactions using density functional theory calculations. Currently, Selectfluor is thought to serve as an external oxidant in Au(I)/Au(III) catalysis. However, our investigations suggest that these reactions follow a newly proposed mechanism in which Selectfluor functions as an electrophilic fluorinating reagent involved in a fluorination/defluorination cycle. We have also explored Selectfluor-mediated gold-catalyzed homocoupling reactions, which, when cyclopropyl propargylbenzoate is used as a substrate, lead to an unexpected byproduct. PMID:25293670

Geng, Cuihuan; Zhu, Rongxiu; Li, Mingxia; Lu, Tongxiang; Wheeler, Steven E; Liu, Chengbu

2014-11-24

34

Photochemistry of intermolecular C-H bond activation reactions  

SciTech Connect

Goals at the onset were to obtain photophysical and photochemical data on transition-metal organometallic complexes which undergo light-induced intermolecular C-H bond activation reactions with hydrocarbon substrates. The complexes included these of rhodium and rhenium with such as cyclopentadiene, CO, phosphine, pyridines, etc.

Lees, A.J.

1994-09-01

35

Author's personal copy Bond cleavage reactions in substituted thiophenes  

E-print Network

Author's personal copy Bond cleavage reactions in substituted thiophenes by a rhodium complex with transition metal fragments has been elucidated. The fragment [(C5Me5)Rh(PMe3)] reacts with furan to give C -S bound complexes, although no C­H or C­S cleavage was observed [6]. A few reported investiga- tions

Jones, William D.

36

Oxidation electronics: bond–band–barrier correlation and its applications  

Microsoft Academic Search

This report features the recent progress in understanding the behaviour of atoms and valence electrons involved in the process of oxidation, and some technological development driven by the new knowledge. It is initiated and verified that a chemical bond contracts spontaneously at a surface associated with magnitude rise of the bond energy due to the coordination imperfection and that an

Chang Q. Sun

2003-01-01

37

Recent aspects of the proton transfer reaction in H-bonded complexes  

NASA Astrophysics Data System (ADS)

Proton transfer processes cover a very wide range of situations and time scales and they are of great interest from the viewpoint of chemical reactions in solution. These processes can occur via thermally activated crossing or tunneling. This review considers various aspects of this many-faceted field. Spectroscopic, dielectric, colligative and energetic properties and structures of various species with H-bonds are examined. Proton transfer reactions in water and organic solvents, and the contribution of various H-bonded species and ions to these processes are discussed. Among other topics, this survey includes the effects of solvent, acid-base stoichiometry, concentration, temperature and impurity on proton transfer reactions in complexes of phenols and carboxylic acids with amines, pyridines and pyridine N-oxides. The contribution of the nonstoichiometric acid-base complexes and ionic species to the reversible proton transfer mechanism is discussed.

Szafran, Miros?aw

1996-07-01

38

Alkali metal mediated C-C bond coupling reaction.  

PubMed

Metal catalyzed carbon-carbon (C-C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz)2, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz)2, the structure of [Li(Bz)2](-) was drastically changed: Bz-Bz parallel form was rapidly fluctuated as a function of time, and a new C-C single bond was formed in the C1-C1' position of Bz-Bz interaction system. In the hole capture, the intermolecular vibration between Bz-Bz rings was only enhanced. The mechanism of C-C bond formation in the electron capture was discussed on the basis of theoretical results. PMID:25681900

Tachikawa, Hiroto

2015-02-14

39

Diffusion bonding of the oxide dispersion strengthened steel PM2000  

NASA Astrophysics Data System (ADS)

Ferritic oxide dispersion strengthened (ODS) steels are well suited as structural materials, e.g. for claddings in fission reactors and for plasma facing components in fusion power plants due to their high mechanical and oxidation stability at high temperatures and their high irradiation resistance. PM2000 is an iron based ODS ferritic steel with homogeneously distributed nanometric yttria particles. Melting joining techniques are not suitable for such ODS materials because of the precipitation and agglomeration of the oxide particles and hence the loss of their strengthening effect. Solid state diffusion bonding is thus chosen to join PM2000 and is investigated in this work with a focus on oxide particles. The diffusion bonding process is aided by the computational modeling, including the influence of the ODS particles. For modeling the microstructure stability and the creep behavior of PM2000 at various, diffusion bonding relevant temperatures (50-80% Tm) are investigated. Particle distribution (TEM), strength (tensile test) and toughness (Charpy impact test) obtained at temperatures relevant for bonding serve as input for the prediction of optimal diffusion bonding parameters. The optimally bonded specimens show comparable strength and toughness relative to the base material.

Sittel, Wiebke; Basuki, Widodo W.; Aktaa, Jarir

2013-11-01

40

Reaction bonded niobium carbide ceramics from polymer-filler mixtures  

Microsoft Academic Search

Manufacturing of novel reaction bonded Niobium Carbide (NbC) containing ceramic composites derived from polymer\\/filler mixtures was investigated. Poly(methylsiloxane) filled with 40 vol.% of a mixture of metallic Niobium (Nb) (reactive filler) and alumina powder (inert filler) was pyrolysed in inert atmosphere up to 1450°C. During pyrolysis metallic niobium reacted with carbon from the decomposition products of the preceramic polymer binder

O. Dernovsek; J. C. Bressiani; A. H. A. Bressiani; W. Acchar; P. Greil

2000-01-01

41

Regio-selectivity of the Oxidative C-S Bond Formation in Ergothioneine and Ovothiol Biosyntheses  

PubMed Central

Ergothioneine (5) and ovothiol (8) are two novel thiol-containing natural products. Their C-S bonds are formed by oxidative coupling reactions catalyzed by EgtB and OvoA enzymes, respectively. In this work, it was discovered that besides catalyzing the oxidative coupling between histidine and cysteine (1 ? 6 conversion), OvoA can also catalyze a direct oxidative coupling between hercynine (2) and cysteine (2 ? 4 conversion), which can shorten the ergothioneine biosynthetic pathway by two steps. PMID:24016264

Song, Heng; Leninger, Maureen; Lee, Norman

2014-01-01

42

Transient liquid phase bonding of ferritic oxide dispersion strengthened alloys  

NASA Astrophysics Data System (ADS)

Oxide dispersion strengthened (ODS) alloys possess excellent properties including resistance to oxidation, corrosion, creep and thermal fatigue. In addition, ferritic ODS alloys exhibit resistance to void swelling and are of particular interest to the nuclear industry. The present study involves the joining of fuel cans to end caps that will be utilized in the nuclear industry. Mechanically alloyed (MA) ODS alloys possess coarse columnar grain structure strengthened with nanosize yttria dispersoids. In that past, fusion welding techniques resulted in microstructural disruption leading to poor joints. This work investigated joining of two ferritic MA ODS alloys, MA956 and PM2000, using; (a) Transient liquid phase (TLP) bonding and (b) Solid-state diffusion bonding. TLP bonds were prepared with MA956 and PM2000 in the unrecrystallized and recrystallized conditions using electron beam physical vapor deposited (EBPVD) boron thin films as interlayers. The use of thin interlayers reduced the amount of substrate dissolution and minimized the bondline microstructural disruption. Different bond orientations were also investigated. Successful bonds with better microstructural continuity were obtained when substrates were joined in the unrecrystallized condition followed by post bond recrystallization heat treatment with the substrate faying surface aligned along the working (extrusion or rolling) direction than when substrates were aligned perpendicular to the working direction. This was attributed to the number of yttria stringers cut by the bondline, which is less when the substrate faying surface is lying parallel to the working direction than when the substrate faying surface is lying perpendicular to the working direction. Solid-state diffusion bonding was conducted using MA956 and PM2000 in the unrecrystallized and recrystallized conditions. Bonding occurred only when an unrecrystallized substrate was involved. Bonding occurred at unusually low stresses. This may be attributed to the grain boundary diffusion, owing to submicron grain size of the unrecrystallized substrates. Post bond heat treatment was conducted in order to induce recrystallization in the bonds. Room temperature mechanical testing was conducted on the bonds and the bulk. Bond shear strengths and tensile strengths of up to 80% and 110% of bulk, respectively, were obtained. Defects in the bulk material such as porosity and unwanted fine grain formation were observed. Pore formation at the bondline during post bond heat treatment seems to decrease the bond strength. These defects were attributed to prior thermomechanical history of the materials.

Krishnardula, Venu Gopal

2006-04-01

43

Enantioselective Diels–Alder reactions catalyzed by hydrogen bonding  

PubMed Central

Like molecules of life (e.g., proteins and DNA), many pharmaceutical drugs are also asymmetric (chiral); they are not superimposable on their mirror images. One mirror image form (enantiomer) of a drug can have desirable activity, the other not. Consequently, the development of methods for the selective synthesis of one enantiomer is of great scientific and economic importance. We report here that a simple, commercially available chiral alcohol, ?,?,??,??-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL), catalyzes the all-carbon Diels–Alder reactions of aminosiloxydienes and substituted acroleins to afford the products in good yields and high enantioselectivities (up to 92% enantiomeric excess). It is remarkable that the reactions are promoted by hydrogen bonding, the ubiquitous “glue” that helps to keep water molecules together and holds up the 3D structures of proteins. Hydrogen bond catalysis is little used in chemical synthesis, wherein most reactions are promoted by complexes of Lewis acidic metal salts coordinated to chiral ligands. As it does for enzymes, hydrogen bonding not only organizes TADDOL into a well defined conformation, but, functioning as a Brønsted acid catalyst, it also activates the dienophile toward reaction with the diene. The gross structure of the TADDOL has been found to have a profound influence on both the rate and the enantioselectivity of the cycloadditions. These structure–function effects are rationalized by evaluating the conformation adopted by the TADDOLs in the crystal state. It is suggested that ?,?-stacking plays an central role in the overall catalytic cycle, in particular, the enantioselective step. PMID:15069185

Thadani, Avinash N.; Stankovic, Ana R.; Rawal, Viresh H.

2004-01-01

44

Friedel-crafts reaction of benzyl fluorides: selective activation of c?f bonds as enabled by hydrogen bonding.  

PubMed

A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C?F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C?F bonds in the presence of other benzylic leaving groups. PMID:25303636

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

2014-12-01

45

Comparison of the Catalytic Oxidation Reaction on Graphene Oxide and Reduced Graphene Oxide  

E-print Network

Comparison of the Catalytic Oxidation Reaction on Graphene Oxide and Reduced Graphene Oxide Laboratory (PAL), Pohang 790-784, Republic of Korea ABSTRACT: The capacities of graphene oxide (GO) and reduced graphene oxide (rGO) films grown on silicon substrate to cause the aniline to azobenzene oxidation

Kim, Sehun

46

Effect of bond coat creep and oxidation on TBC integrity  

NASA Technical Reports Server (NTRS)

The potential of thermal barrier coatings (TBCs) on high-pressure turbine (HPT) nozzles and blades is limited at present by the inability to quantitatively predict TBC life for these components. The goal is to isolate the major TBC failure mechanisms, which is part of the larger program aimed at developing TBC life prediction models. Based on the results of experiments to isolate TBC failure mechanisms, the effects of bond coat oxidation and bond coat creep on TBC integrity is discussed. In bond coat oxidation experiments, Rene prime 80 specimens coated with a NiCrAlY/ZrO2-8 percent Y2O3 TBC received isothermal pre-exposures at 2000 F in static argon, static air, or received no pre-exposure. The effects of oxidation due to the pre-exposures were determined by thermal cycle tests in both static air and static argon at 2000 F. To study the effect of bond coat creep on TBS behavior, four bond coats with different creep properties were evaluated by thermal cycle tests in air at 2000 F. The test results, the relative importance of these two failure mechanisms, and how their effects may be quantified will also be discussed.

Duderstadt, E. C.; Pilsner, B. H.

1985-01-01

47

Oxidative Reactions with Nonaqueous Enzymes  

SciTech Connect

The objective of this work is to demonstrate a proof-of-concept of enzymatic oxidative processing in nonaqueous media using alkene epoxidation and phenolic polymerization as relevant targets. This project will provide both the fundamental and applied investigations necessary to initiate the implementation of oxidative biocatalysts as commercially relevant alternatives to chemical processing in general, and to phenolic polymerizations and alkene epoxidation specifically. Thus, this work will address the Bioprocessing Solicitation Area to: (1) makes major improvements to phenolic polymerization and alkene epoxidation technologies; (2) is expected to be cost competitive with competing conventional processes; and (3) produces higher yields with less waste.

Jonathan S. Dordick; Douglas Clark; Brian H Davison; Alexander Klibanov

2001-12-30

48

Mechanistic Insights into N-N Bond Cleavage in Catalytic Guanylation Reactions between 1,2-Diarylhydrazines and Carbodiimides.  

PubMed

Cleavage of the N-N bond in 1,2-diarylhydrazine was achieved through an alkyllithium-catalyzed guanylation reaction of 1,2-diarylhydrazine with carbodiimide, affording guanidine and azo compounds. This N-N bond cleavage via thermal rearrangement was driven by an intramolecular proton shift. No reductants, oxidants, bases, or external protons were needed. The proposed mechanism has been well elucidated by the isolation, characterization, and reaction studies of two important amido lithium intermediates and an ArHN-substituted guanidine. PMID:25311373

Xu, Ling; Wang, Yu-Chen; Ma, Wangyang; Zhang, Wen-Xiong; Xi, Zhenfeng

2014-12-19

49

40 CFR 721.10375 - Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer...  

Code of Federal Regulations, 2013 CFR

...Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (generic...Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer with N-vinyl...

2013-07-01

50

40 CFR 721.10375 - Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer...  

Code of Federal Regulations, 2014 CFR

...Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (generic...Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer with N-vinyl...

2014-07-01

51

40 CFR 721.10375 - Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer...  

Code of Federal Regulations, 2012 CFR

...Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (generic...Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer with N-vinyl...

2012-07-01

52

O-H bond oxidation by a monomeric Mn(III)-OMe complex.  

PubMed

Manganese-containing, mid-valent oxidants (Mn(III)-OR) that mediate proton-coupled electron-transfer (PCET) reactions are central to a variety of crucial enzymatic processes. The Mn-dependent enzyme lipoxygenase is such an example, where a Mn(III)-OH unit activates fatty acid substrates for peroxidation by an initial PCET. This present work describes the quantitative generation of the Mn(III)-OMe complex, [Mn(III)(OMe)(dpaq)](+) (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate) via dioxygen activation by [Mn(II)(dpaq)](+) in methanol at 25 °C. The X-ray diffraction structure of [Mn(III)(OMe)(dpaq)](+) exhibits a Mn-OMe group, with a Mn-O distance of 1.825(4) Å, that is trans to the amide functionality of the dpaq ligand. The [Mn(III)(OMe)(dpaq)](+) complex is quite stable in solution, with a half-life of 26 days in MeCN at 25 °C. [Mn(III)(OMe)(dpaq)](+) can activate phenolic O-H bonds with bond dissociation free energies (BDFEs) of less than 79 kcal mol(-1) and reacts with the weak O-H bond of TEMPOH (TEMPOH = 2,2'-6,6'-tetramethylpiperidine-1-ol) with a hydrogen/deuterium kinetic isotope effect (H/D KIE) of 1.8 in MeCN at 25 °C. This isotope effect, together with other experimental evidence, is suggestive of a concerted proton-electron transfer (CPET) mechanism for O-H bond oxidation by [Mn(III)(OMe)(dpaq)](+). A kinetic and thermodynamic comparison of the O-H bond oxidation reactivity of [Mn(III)(OMe)(dpaq)](+) to other M(III)-OR oxidants is presented as an aid to gain more insight into the PCET reactivity of mid-valent oxidants. In contrast to high-valent counterparts, the limited examples of M(III)-OR oxidants exhibit smaller H/D KIEs and show weaker dependence of their oxidation rates on the driving force of the PCET reaction with O-H bonds. PMID:25597362

Wijeratne, Gayan B; Day, Victor W; Jackson, Timothy A

2015-02-01

53

The Reaction of Carbon Dioxide with Palladium Allyl Bonds  

PubMed Central

A family of palladium allyl complexes of the type bis(2-methylallyl)Pd(L) (L = PMe3 (1), PEt3 (2), PPh3 (3) or NHC (4); NHC = 1,3-Bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene) have been prepared through the reaction of bis(2-methylallyl)Pd with the appropriate free ligand. Compounds 1–4 contain one ?1 and one ?3-2-methylallyl ligand and 3 was characterized by X-ray crystallography. These complexes react rapidly with CO2 at low temperature to form well defined unidentate palladium carboxylates of the type (?3-2-methylallyl)Pd(OC(O)C4H7)(L) (L = PMe3 (6), PEt3 (7), PPh3 (8) or NHC (9). The structure of 9 was elucidated using X-ray crystallography. The mechanism of the reaction of 1–4 with CO2 was probed using a combination of experimental and theoretical (density functional theory) studies. The coordination mode of the allyl ligand is crucial and whereas nucleophilic ?1-allyls react rapidly with CO2, ?3-allyls do not react. We propose that the reaction of ?1-palladium allyls with CO2 does not proceed via direct insertion of CO2 into the Pd-C bond but through nucleophilic attack of the terminal olefin on electrophilic CO2, followed by an associative substitution at palladium. PMID:21218132

Wu, Jianguo; Green, Jennifer C.; Hruszkewycz, Damian P.; Incarvito, Christopher D.; Schmeier, Timothy J.

2010-01-01

54

THE OXIDATION NUMBER -HALF REACTION METHOD FOR BALANCING REDOX EQUATIONS  

E-print Network

THE OXIDATION NUMBER - HALF REACTION METHOD FOR BALANCING REDOX EQUATIONS The redox, and it is strongly recommended. Steps 1. Assign oxidation states to each element in the reaction and identify the species being oxidized and reduced. 2. Write separate half reactions for the oxidation and reduction

Le Roy, Robert J.

55

SURFACE REACTIONS OF OXIDES OF SULFUR  

EPA Science Inventory

Surface reactions of several sulfur-containing molecules have been studied in order to understand the mechanism by which sulfate ions are formed on atmospheric aerosols. At 25C the heterogeneous oxidation of SO2 by NO2 to sulfuric acid and sulfate ions occurred on hydrated silica...

56

If C–H Bonds Could Talk – Selective C–H Bond Oxidation  

PubMed Central

C–H oxidation has a long history and an ongoing presence in research at the forefront of chemistry and interrelated fields. As such, numerous highly useful texts and reviews have been written on this subject. Logically, these are generally written from the perspective of the scope and limitations of the reagents employed. This minireview instead attempts to emphasize chemoselectivity imposed by the nature of the substrate. Consequently many landmark discoveries in the field of C–H oxidation are not discussed, but hopefully the perspective taken herein will allow for the more ready incorporation of C–H oxidation reactions into synthetic planning. PMID:21413105

Newhouse, Timothy; Baran, Phil S.

2014-01-01

57

Palladium-catalyzed oxidative insertion of carbon monoxide to N-sulfonyl-2-aminobiaryls through C-H bond activation: access to bioactive phenanthridinone derivatives in one pot.  

PubMed

Palladium-catalyzed oxidative carbonylation of N-sulfonyl-2-aminobiaryls through C-H bond activation and C-C, C-N bond formation under TFA-free and milder conditions has been developed. The reaction tolerates a variety of substrates and provides biologically important phenanthridinone derivatives in yields up to 94%. PMID:23477600

Rajeshkumar, Venkatachalam; Lee, Tai-Hua; Chuang, Shih-Ching

2013-04-01

58

Palladium-Catalyzed Regioselective Benzylation-Annulation of Pyridine N-Oxides with Toluene Derivatives via Multiple C-H Bond Activations: Benzylation versus Arylation.  

PubMed

A palladium-catalyzed cross-dehydrogenative coupling (CDC) reaction of pyridine N-oxides with toluenes has been developed that operates under mild conditions. 2-Benzylpyridines can be obtained directly by this method via a CDC reaction between unactivated toluenes and pyridine N-oxides. In addition, azafluorene N-oxides, of value for future medicinal chemistry applications, can be obtained successfully by this procedure via four tandem C-H bond activations. PMID:25607468

Kianmehr, Ebrahim; Faghih, Nasser; Khan, Khalid Mohammed

2015-02-01

59

C-H bond functionalization: An aminated reaction  

NASA Astrophysics Data System (ADS)

Selective conversion of C-H bonds into C-N bonds to form N-heterocycles would streamline the synthesis of these important structural motifs. Now, an iron(II) catalyst has been developed that can transform alkyl azides into cyclic secondary amines by controlling the iron imido intermediate to react only with the nearby aliphatic C-H bond.

Driver, Tom G.

2013-09-01

60

Covalent Bonding and Orbital Reconstruction at an Oxide Interface.  

NASA Astrophysics Data System (ADS)

Atomically controlled interfaces between two materials can give rise to novel physical phenomena and functionalities. Modern synthesis methods have yielded high-quality heterostructures of oxide materials with competing order parameters. Orbital reconstructions and covalent bonding must be considered as important factors in the rational design of oxide heterostructures. Here we examine the interface between high-temperature superconducting (Y,Ca)Ba2Cu3O7 and metallic La2/3Ca1/3MnO3 by resonant x-ray spectroscopy. The resulting data show that electrons are transferred from Mn to Cu ions across the interface. This phenomenon is accompanied by the major reconstruction of the orbital occupation and symmetry in the CuO2 plane. Specifically, we report the experimental finding that unlike bulk at the interface Cu d3z2-r2 orbital is partially occupied and electronically active. This observation opens a path to orbital engineering of interface-controlled materials. J. Chakhalian et al, ``Covalent Bonding and Orbital Reconstruction at an Oxide Interface'', Science, v. 318, 1155 (2007).

Chakhalian, Jak; Freeland, John; Habermeier, Hans-Ulrich; Cristiani, Georg; Khaliullin, G.; van Veenendaal, Michel; Keimer, Bernhard

2008-03-01

61

Reaction of lincosamide antibiotics with manganese oxide in aqueous solution.  

PubMed

Lincosamides are among the most frequently detected antibacterial agents in effluents from wastewater treatment plants and surface runoff at agricultural production systems. Little is known about their transformations in the environment. This study revealed that manganese oxide caused rapid and extensive decomposition of clindamycin and lincomycin in aqueous solution. The reactions occurred mainly at the pyranose ring of lincosamides, initially by formation of complexes with Mn and cleavage of the ether linkage, leading to the formation of a variety of degradation products via subsequent hydrolytic and oxidative reactions. The results of LC-MS/MS and FTIR analysis confirm cleavage of the C-O-C bond in the pyranose ring, formation of multiple carbonyl groups, and transformation of the methylthio moiety to sulfur oxide. The overall transformation was controlled by interactions of cationic species of lincosamides with MnO(2) surfaces. The presence of electrolytes (i.e., NaCl, CaCl(2), and MnCl(2)) and dissolved organic matter in aqueous solution, and increase of solution pH, diminished lincosamide binding to MnO(2) hence reducing the rate and magnitude of the transformations. Results from this study indicate that manganese dioxides in soils and sediments could contribute to the decomposition of lincosamide antibiotics released into the environment. PMID:20476766

Chen, Wan-Ru; Ding, Yunjie; Johnston, Cliff T; Teppen, Brian J; Boyd, Stephen A; Li, Hui

2010-06-15

62

Polyorganosilazane preceramic binder development for reaction bonded silicon nitride composites  

SciTech Connect

This study has examined the use of two commercially available polyorganosilazanes for application as preceramic binders in a composite composed of silicon carbide fibers in a reaction bonded silicon nitride (RBSN) matrix. Ceramic monolithic and composite samples were produced. Density of monolithic and whisker reinforced RBSN samples containing the polysilazane binder was increased. Mercury intrusion porosimetry revealed a significant decrease in the pore sizes of samples containing a polyorganosilazane binder. Electron micrographs of samples containing the preceramic binder looked similar to control samples containing no precursor. Overall, incorporation of the polysilazane into monolithic and whisker reinforced samples resulted in significantly increased density and decreased porosity. Nitriding of the RBSN was slightly retarded by addition of the polysilazane binder. Samples with the preceramic binders contained increased contents of [alpha] versus [beta]-silicon nitride which may be due to interaction of hydrogen evolved from polysilazane pyrolysis with the nitriding process. Initial efforts to produce continuous fiber reinforced composites via this method have not realized the same improvements in density and porosity which have been observed for monolithic and whisker reinforced samples. Further, the addition of perceramic binder resulted in a more brittle fracture morphology as compared to similar composites made without the binder.

Mohr, D.L.; Starr, T.L. (Georgia Tech Research Inst., Atlanta, GA (United States))

1992-11-01

63

Polyorganosilazane preceramic binder development for reaction bonded silicon nitride composites  

SciTech Connect

This study has examined the use of two commercially available polyorganosilazanes for application as preceramic binders in a composite composed of silicon carbide fibers in a reaction bonded silicon nitride (RBSN) matrix. Ceramic monolithic and composite samples were produced. Density of monolithic and whisker reinforced RBSN samples containing the polysilazane binder was increased. Mercury intrusion porosimetry revealed a significant decrease in the pore sizes of samples containing a polyorganosilazane binder. Electron micrographs of samples containing the preceramic binder looked similar to control samples containing no precursor. Overall, incorporation of the polysilazane into monolithic and whisker reinforced samples resulted in significantly increased density and decreased porosity. Nitriding of the RBSN was slightly retarded by addition of the polysilazane binder. Samples with the preceramic binders contained increased contents of {alpha} versus {beta}-silicon nitride which may be due to interaction of hydrogen evolved from polysilazane pyrolysis with the nitriding process. Initial efforts to produce continuous fiber reinforced composites via this method have not realized the same improvements in density and porosity which have been observed for monolithic and whisker reinforced samples. Further, the addition of perceramic binder resulted in a more brittle fracture morphology as compared to similar composites made without the binder.

Mohr, D.L.; Starr, T.L. [Georgia Tech Research Inst., Atlanta, GA (United States)

1992-11-01

64

Interfacial bonding stabilizes rhodium and rhodium oxide nanoparticles on layered Nb oxide and Ta oxide supports.  

PubMed

Metal nanoparticles are commonly supported on metal oxides, but their utility as catalysts is limited by coarsening at high temperatures. Rhodium oxide and rhodium metal nanoparticles on niobate and tantalate supports are anomalously stable. To understand this, the nanoparticle-support interaction was studied by isothermal titration calorimetry (ITC), environmental transmission electron microscopy (ETEM), and synchrotron X-ray absorption and scattering techniques. Nanosheets derived from the layered oxides KCa2Nb3O10, K4Nb6O17, and RbTaO3 were compared as supports to nanosheets of Na-TSM, a synthetic fluoromica (Na0.66Mg2.68(Si3.98Al0.02)O10.02F1.96), and ?-Zr(HPO4)2·H2O. High surface area SiO2 and ?-Al2O3 supports were also used for comparison in the ITC experiments. A Born-Haber cycle analysis of ITC data revealed an exothermic interaction between Rh(OH)3 nanoparticles and the layered niobate and tantalate supports, with ?H values in the range -32 kJ·mol(-1) Rh to -37 kJ·mol(-1) Rh. In contrast, the interaction enthalpy was positive with SiO2 and ?-Al2O3 supports. The strong interfacial bonding in the former case led to "reverse" ripening of micrometer-size Rh(OH)3, which dispersed as 0.5 to 2 nm particles on the niobate and tantalate supports. In contrast, particles grown on Na-TSM and ?-Zr(HPO4)2·H2O nanosheets were larger and had a broad size distribution. ETEM, X-ray absorption spectroscopy, and pair distribution function analyses were used to study the growth of supported nanoparticles under oxidizing and reducing conditions, as well as the transformation from Rh(OH)3 to Rh nanoparticles. Interfacial covalent bonding, possibly strengthened by d-electron acid/base interactions, appear to stabilize Rh(OH)3, Rh2O3, and Rh nanoparticles on niobate and tantalate supports. PMID:24654835

Strayer, Megan E; Binz, Jason M; Tanase, Mihaela; Shahri, Seyed Mehdi Kamali; Sharma, Renu; Rioux, Robert M; Mallouk, Thomas E

2014-04-16

65

Oxygen radical-mediated oxidation reactions of an alanine peptide motif - density functional theory and transition state theory study  

PubMed Central

Background Oxygen-base (O-base) oxidation in protein backbone is important in the protein backbone fragmentation due to the attack from reactive oxygen species (ROS). In this study, an alanine peptide was used model system to investigate this O-base oxidation by employing density functional theory (DFT) calculations combining with continuum solvent model. Detailed reaction steps were analyzed along with their reaction rate constants. Results Most of the O-base oxidation reactions for this alanine peptide are exothermic except for the bond-breakage of the C?-N bond to form hydroperoxy alanine radical. Among the reactions investigated in this study, the activated energy of OH ?-H abstraction is the lowest one, while the generation of alkylperoxy peptide radical must overcome the highest energy barrier. The aqueous situation facilitates the oxidation reactions to generate hydroxyl alanine peptide derivatives except for the fragmentations of alkoxyl alanine peptide radical. The C?-C? bond of the alkoxyl alanine peptide radical is more labile than the peptide bond. Conclusion the rate-determining step of oxidation in protein backbone is the generation of hydroperoxy peptide radical via the reaction of alkylperoxy peptide radical with HO2. The stabilities of alkylperoxy peptide radical and complex of alkylperoxy peptide radical with HO2 are crucial in this O-base oxidation reaction. PMID:22524792

2012-01-01

66

An unusual carbon?carbon bond cleavage reaction during phosphinothricin biosynthesis  

SciTech Connect

Natural products containing phosphorus-carbon bonds have found widespread use in medicine and agriculture. One such compound, phosphinothricin tripeptide, contains the unusual amino acid phosphinothricin attached to two alanine residues. Synthetic phosphinothricin (glufosinate) is a component of two top-selling herbicides (Basta and Liberty), and is widely used with resistant transgenic crops including corn, cotton and canola. Recent genetic and biochemical studies showed that during phosphinothricin tripeptide biosynthesis 2-hydroxyethylphosphonate (HEP) is converted to hydroxymethylphosphonate (HMP). Here we report the in vitro reconstitution of this unprecedented C(sp{sup 3})-C(sp{sup 3}) bond cleavage reaction and X-ray crystal structures of the enzyme. The protein is a mononuclear non-haem iron(II)-dependent dioxygenase that converts HEP to HMP and formate. In contrast to most other members of this family, the oxidative consumption of HEP does not require additional cofactors or the input of exogenous electrons. The current study expands the scope of reactions catalysed by the 2-His-1-carboxylate mononuclear non-haem iron family of enzymes.

Cicchillo, Robert M.; Zhang, Houjin; Blodgett, Joshua A.V.; Whitteck, John T.; Li, Gongyong; Nair, Satish K.; van derDonk, Wilfred A.; Metcalf, William W.; (UIUC)

2010-01-12

67

Palladium-catalyzed cyclization reactions of allenes in the presence of unsaturated carbon-carbon bonds.  

PubMed

Modern synthetic chemists have looked for rapid and efficient ways to construct complex molecules while minimizing synthetic manipulation and maximizing atom-economy. Over the last few decades, researchers have made considerable progress toward these goals by taking full advantage of transition metal catalysis and the diverse reactivities of allenes, functional groups which include two cumulative carbon-carbon double bonds. This Account describes our efforts toward the development of Pd-catalyzed cyclization reactions of allenes in the presence of compounds that contain unsaturated carbon-carbon bonds such as alkenyl halides, simple alkenes, allenes, electron-deficient alkynes, or propargylic carbonates. First, we discuss the coupling-cyclization reactions of allenes bearing a nucleophilic functionality in the presence of alkenyl halides, simple alkenes, functionalized and nonfunctionalized allenes, or electron-deficient alkynes. These processes generally involve a Pd(II)-catalyzed sequence: cyclic nucleopalladation, insertion or nucleopalladation, and ?-elimination, reductive elimination, cyclic allylation or protonation. We then focus on Pd(0)-catalyzed cyclization reactions of allenes in the presence of propargylic carbonates. In these transformations, oxidative addition of propargylic carbonates with Pd(0) affords allenylpalladium(II) species, which then react with allenes via insertion or nucleopalladation. These transformations provide easy access to a variety of synthetically versatile monocyclic, dumbbell-type bicyclic, and fused multicyclic compounds. We have also prepared a series of highly enantioenriched products using an axial-to-central chirality transfer strategy. A range of allenes are now readily available, including optically active ones with central and/or axial chirality. Expansion of these reactions to include other types of functionalized allenes, such as allenyl thiols, allenyl hydroxyl amines, and other structures with differing steric and electronic character, could allow access to cyclic skeletons that previously were difficult to prepare. We anticipate that other studies will continue to explore this promising area of synthetic organic chemistry. PMID:24479609

Ye, Juntao; Ma, Shengming

2014-04-15

68

Graphene-hemin hybrid material as effective catalyst for selective oxidation of primary C-H bond in toluene  

PubMed Central

An effective hemin catalyst on graphene support for selective oxidation of primary C-H bond in toluene is reported with an over 50% conversion rate achieved at mild conditions. Significantly this hybrid material shows catalytic efficiency in toluene oxidation with selectivity towards benzoic acid. The role of graphene support is discussed here as providing large contact area between the catalyst and the substrate, maintaining hemin in catalytically active monomer form, attracting electron to promote site isolation, as well as protecting hemin from oxidative degradation during the reaction. Moreover, graphene is suggested to largely alter the final product selectivity, due to the different ?-? interaction strength between the graphene support and the substrate/oxidized products. With longer reaction time, overall conversion rate tends to maintain relatively unchanged while toluene undergoes a series of oxidation to convert mostly to benzoic acid.

Li, Yongjia; Huang, Xiaoqing; Li, Yujing; Xu, Yuxi; Wang, Yang; Zhu, Enbo; Duan, Xiangfeng; Huang, Yu

2013-01-01

69

Formation of porous surface layers in reaction bonded silicon nitride during processing  

NASA Technical Reports Server (NTRS)

Microstructural examination of reaction bonded silicon nitride (RBSN) has shown that there is often a region adjacent to the as-nitrided surfaces that is even more porous than the interior of this already quite porous material. Because this layer of large porosity is considered detrimental to both the strength and oxidation resistance of RBSN, a study was undertaken to determine if its formation could be prevented during processing. All test bars studied were made from a single batch of Si powder which was milled for 4 hours in heptane in a vibratory mill using high density alumina cylinders as the grinding media. After air drying the powder, bars were compacted in a single acting die and hydropressed.

Shaw, N. J.; Glasgow, T. K.

1979-01-01

70

Thermochemistry and reaction paths in the oxidation reaction of benzoyl radical: C6H5C•(?O).  

PubMed

Alkyl substituted aromatics are present in fuels and in the environment because they are major intermediates in the oxidation or combustion of gasoline, jet, and other engine fuels. The major reaction pathways for oxidation of this class of molecules is through loss of a benzyl hydrogen atom on the alkyl group via abstraction reactions. One of the major intermediates in the combustion and atmospheric oxidation of the benzyl radicals is benzaldehyde, which rapidly loses the weakly bound aldehydic hydrogen to form a resonance stabilized benzoyl radical (C6H5C(•)?O). A detailed study of the thermochemistry of intermediates and the oxidation reaction paths of the benzoyl radical with dioxygen is presented in this study. Structures and enthalpies of formation for important stable species, intermediate radicals, and transition state structures resulting from the benzoyl radical +O2 association reaction are reported along with reaction paths and barriers. Enthalpies, ?fH298(0), are calculated using ab initio (G3MP2B3) and density functional (DFT at B3LYP/6-311G(d,p)) calculations, group additivity (GA), and literature data. Bond energies on the benzoyl and benzoyl-peroxy systems are also reported and compared to hydrocarbon systems. The reaction of benzoyl with O2 has a number of low energy reaction channels that are not currently considered in either atmospheric chemistry or combustion models. The reaction paths include exothermic, chain branching reactions to a number of unsaturated oxygenated hydrocarbon intermediates along with formation of CO2. The initial reaction of the C6H5C(•)?O radical with O2 forms a chemically activated benzoyl peroxy radical with 37 kcal mol(-1) internal energy; this is significantly more energy than the 21 kcal mol(-1) involved in the benzyl or allyl + O2 systems. This deeper well results in a number of chemical activation reaction paths, leading to highly exothermic reactions to phenoxy radical + CO2 products. PMID:21942384

Sebbar, Nadia; Bozzelli, Joseph W; Bockhorn, Henning

2011-10-27

71

Effect of gate metal on chemical bonding state in metal/Pr-oxide/Ge gate stack structure  

NASA Astrophysics Data System (ADS)

We have investigated the impacts of the gate metal on the chemical bonding state in the metal/Pr-oxide/Ge gate stack structure by the hard X-ray photoelectron spectroscopy method and have tried to explain about the obtained results focusing on the difference of oxygen chemical potential (?O) among metal-oxide, Pr-oxide and Ge-oxide. The reductive character of the metals induces the reductive reaction of the Pr-oxide films. The reductive character changes the Pr valence state not only at the surface but also in the Pr-oxide films. The reductive character increases the ratio of Pr3+ to Pr4+ in the Pr-oxide films, suggesting the formation of the crystalline phase with high permittivity of h-Pr2O3. The reductive character of the metals also affects on the Pr-oxide/Ge interfacial structure. Besides it leads to the decrease in the amount of Ge atoms bonding with oxygen. These reductive reactions can be explained by ?O of the metals with reductive character lower than those of PrO2 formation and GeO2 formation. From the comparison of the results for the Ge and Si systems, it was found that the drawing reaction of oxygen, which means the pullout of oxygen in the Pr-oxide film, is facile for the Ge system, relating to ?O of GeO2 higher than that in SiO2. These results suggest that the selection of gate metals in the metal/Pr-oxide/Ge gate stack structure taking into account ?O is quite important to achieve the thin EOT, resulting in both the formation of the h-Pr2O3 crystalline phase of the Pr-oxide and the decrease in the amount of Ge-oxides.

Kato, Kimihiko; Sakashita, Mitsuo; Takeuchi, Wakana; Taoka, Noriyuki; Nakatsuka, Osamu; Zaima, Shigeaki

2013-05-01

72

Pinpointing double bonds in lipids by Paternò-Büchi reactions and mass spectrometry.  

PubMed

The positions of double bonds in lipids play critical roles in their biochemical and biophysical properties. In this study, by coupling Paternò-Büchi (P-B) reaction with tandem mass spectrometry, we developed a novel method that can achieve confident, fast, and sensitive determination of double bond locations within various types of lipids. The P-B reaction is facilitated by UV irradiation of a nanoelectrospray plume entraining lipids and acetone. Tandem mass spectrometry of the on-line reaction products via collision activation leads to the rupture of oxetane rings and the formation of diagnostic ions specific to the double bond location. PMID:24500881

Ma, Xiaoxiao; Xia, Yu

2014-03-01

73

Chemical bonding and stability of multilayer graphene oxide layers  

NASA Astrophysics Data System (ADS)

The chemistry of graphene oxide (GO) and its response to external stimuli such as temperature and light are not well understood and only approximately controlled. This understanding is however crucial to enable future applications of the material that typically are subject to environmental conditions. The nature of the initial GO is also highly dependent on the preparation and the form of the initial carbon material. Here, we consider both standard GO made from oxidizing graphite and layered GO made from oxidizing epitaxial graphene on SiC, and examine their evolution under different stimuli. The effect of the solvent on the thermal evolution of standard GO in vacuum is first investigated. In situ infrared absorption measurements clearly show that the nature of the last solvent in contact with GO prior to deposition on a substrate for vacuum annealing studies substantially affect the chemical evolution of the material as GO is reduced. Second, the stability of GO derived from epitaxial graphene (on SiC) is examined as a function of time. We show that hydrogen, in the form of CH, is present after the Hummers process, and that hydrogen favors the reduction of epoxide groups and the formation of water molecules. Importantly, this transformation can take place at room temperature, albeit slowly (~ one month). Finally, the chemical interaction (e.g. bonding) between GO layers in multilayer samples is examined with diffraction (XRD) methods, spectroscopic (IR, XPS, Raman) techniques, imaging (APF) and first principles modeling.

Gong, Cheng; Kim, Suenne; Zhou, Si; Hu, Yike; Acik, Muge; de Heer, Walt; Berger, Claire; Bongiorno, Angelo; Riedo, Eliso; Chabal, Yves

2014-03-01

74

Oxide treatments of Al 2024 for adhesive bonding- surface characterization  

NASA Astrophysics Data System (ADS)

A study was made to characterize the surface of oxides formed on Al 2024 in comparison to those formed on Al 1100, using Auger, ESCA, SIMS, FTIR and SEM/EDAX techniques. The pretreatments studied were chromate conversion coating, chromic acid anodizing and sulfuric acid anodizing. The specimens were evaluated as treated and after exposure to laboratory conditions ( T=25?3°C and relative humidity of 60?10%) for 6 months. In addition, a new surface pretreatment was studied, which was based on McDonnell Douglas P.S. 13201 specification. Adhesive bond strength of silicone rubbers and epoxy adhesives to pretreated Al 2024 was determined, using single lap joint specimens. It was shown that the main difference between the anodic coatings on Al 1100 and Al 2024 was the presence of copper on the surface in the latter. The presence of copper led us to postulate the mechanism of polymerization inhibition of 2 parts polysiloxane adhesive. The most suitable treatments for adhesive joining were found to be chromic acid sealed or unsealed anodizing for both Al 2024 and Al 1100. Our standard chromic acid anodizing gave higher bond strength for aluminum-adhesive joints than the "Douglas" process. as determined with several epoxy adhesives. Correlation between microscopic and macroscopic phenomena was established.

Fin, N.; Dodiuk, H.; Yaniv, A. E.; Drori, L.

1987-03-01

75

Bimolecular Coupling Reactions through Oxidatively Generated Aromatic Cations: Scope and Stereocontrol  

PubMed Central

Chromenes, isochromenes, and benzoxathioles react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form stable aromatic cations that react with a range of nucleophiles. These oxidative fragment coupling reactions provide rapid access to structurally diverse heterocycles. Conducting the reactions in the presence of a chiral Brønsted acid results in the formation of an asymmetric ion pair that can provide enantiomerically enriched products in a rare example of a stereoselective process resulting from the generation of a chiral electrophile through oxidative carbon–hydrogen bond cleavage. PMID:23913987

Cui, Yubo; Villafane, Louis A.; Clausen, Dane J.

2013-01-01

76

2-Halogenoimidazolium Salt Catalyzed Aza-Diels-Alder Reaction through Halogen-Bond Formation.  

PubMed

2-Halogenoimidazolium salts are found to catalyze aza-Diels-Alder reaction of aldimines with Danishefsky diene in an efficient manner. Comparative studies and titration experiments support the formation of halogen bonding between imines and catalysts. PMID:25551775

Takeda, Youhei; Hisakuni, Daichi; Lin, Chun-Hsuan; Minakata, Satoshi

2015-01-16

77

Interfacial Reactions between Oxide Films and Refractory Metal Substrates  

E-print Network

Interfacial Reactions between Oxide Films and Refractory Metal Substrates X. Xu, W. S. Oh, and D. W,thelatterbeingencapsulatedbythemolybdenum oxides. Above 1200 K, both metallic nickel and molybdenum oxides are evolved from the surface-grown oxide thin films on various metal substrates [for example, NiO/Mo(100), MgO/Mo(100) and Al2O3/Ta(110

Goodman, Wayne

78

Proton transfer reactions and hydrogen-bond networks in protein environments  

PubMed Central

In protein environments, proton transfer reactions occur along polar or charged residues and isolated water molecules. These species consist of H-bond networks that serve as proton transfer pathways; therefore, thorough understanding of H-bond energetics is essential when investigating proton transfer reactions in protein environments. When the pKa values (or proton affinity) of the H-bond donor and acceptor moieties are equal, significantly short, symmetric H-bonds can be formed between the two, and proton transfer reactions can occur in an efficient manner. However, such short, symmetric H-bonds are not necessarily stable when they are situated near the protein bulk surface, because the condition of matching pKa values is opposite to that required for the formation of strong salt bridges, which play a key role in protein–protein interactions. To satisfy the pKa matching condition and allow for proton transfer reactions, proteins often adjust the pKa via electron transfer reactions or H-bond pattern changes. In particular, when a symmetric H-bond is formed near the protein bulk surface as a result of one of these phenomena, its instability often results in breakage, leading to large changes in protein conformation. PMID:24284891

Ishikita, Hiroshi; Saito, Keisuke

2014-01-01

79

Analytic bond-order potential for atomistic simulations of zinc oxide  

E-print Network

Analytic bond-order potential for atomistic simulations of zinc oxide Paul Erhart1 , Niklas Juslin2 for zinc oxide and its elemental constituents is derived based on an analytical bond-order formalism. The model potential provides a good description of the bulk properties of various solid structures of zinc

Nordlund, Kai

80

Competitive oxygen-18 kinetic isotope effects expose OO bond formation in water oxidation  

E-print Network

Competitive oxygen-18 kinetic isotope effects expose O­O bond formation in water oxidation. Roth*a Competitive oxygen kinetic isotope effects (18 O KIEs) on water oxidation initiated by ruthenium during oxygenic photo- synthesis.1 Formation of the O­O bond in molecular oxygen has been proposed

Roth, Justine P.

81

Copper-Catalyzed Oxidative Heck Reactions between Alkyltrifluoroborates and Vinylarenes  

PubMed Central

We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented. PMID:23734764

Liwosz, Timothy W.; Chemler, Sherry R.

2013-01-01

82

Effects of Thermal Cycling on Thermal Expansion and Mechanical Properties of Sic Fiber-reinforced Reaction-bonded Si3n4 Composites  

NASA Technical Reports Server (NTRS)

Thermal expansion curves for SiC fiber-reinforced reaction-bonded Si3N4 matrix composites (SiC/RBSN) and unreinforced RBSN were measured from 25 to 1400 C in nitrogen and in oxygen. The effects of fiber/matrix bonding and cycling on the thermal expansion curves and room-temperature tensile properties of unidirectional composites were determined. The measured thermal expansion curves were compared with those predicted from composite theory. Predicted thermal expansion curves parallel to the fiber direction for both bonding cases were similar to that of the weakly bonded composites, but those normal to the fiber direction for both bonding cases resulted in no net dimensional changes at room temperature, and no loss in tensile properties from the as-fabricated condition. In contrast, thermal cycling in oxygen for both composites caused volume expansion primarily due to internal oxidation of RBSN. Cyclic oxidation affected the mechanical properties of the weakly bonded SiC/RBSN composites the most, resulting in loss of strain capability beyond matrix fracture and catastrophic, brittle fracture. Increased bonding between the SiC fiber and RBSN matrix due to oxidation of the carbon-rich fiber surface coating and an altered residual stress pattern in the composite due to internal oxidation of the matrix are the main reasons for the poor mechanical performance of these composites.

Bhatt, R. T.; Palczer, A. R.

1994-01-01

83

Oxidation Reactions Performed by Soluble Methane Monooxygenase Hydroxylase Intermediates Hperoxo and Q Proceed by Distinct Mechanisms†  

PubMed Central

Soluble methane monooxygenase is a bacterial enzyme that converts methane to methanol at a carboxylate-bridged diiron center with exquisite control. Because the oxidizing power required for this transformation is demanding, it is not surprising that the enzyme is also capable of hydroxylating and epoxidizing a broad range of hydrocarbon substrates in addition to methane. In this work we took advantage of this promiscuity of the enzyme to gain insight into the mechanisms of action of Hperoxo and Q, two oxidants that are generated sequentially during the reaction of reduced protein with O2. Using double-mixing stopped flow spectroscopy, we investigated the reactions of the two intermediate species with a panel of substrates of varying C–H bond strength. Three classes of substrates were identified according to the rate-determining step in the reaction. We show for the first time that an inverse trend exists between the rate constant of reaction with Hperoxo and the C–H bond strength of the hydrocarbon examined for those substrates in which C–H bond activation is rate-determining. Deuterium kinetic isotope effects revealed that reactions performed by Q, but not Hperoxo, involve extensive quantum mechanical tunneling. This difference sheds light on the observation that Hperoxo is not a potent enough oxidant to hydroxylate methane, whereas Q can perform this reaction in a facile manner. In addition, the reaction of Hperoxo with acetonitrile appears to proceed by a distinct mechanism in which a cyanomethide anionic intermediate is generated, bolstering the argument that Hperoxo is an electrophilic oxidant and operates via two-electron transfer chemistry. PMID:20681546

Tinberg, Christine E.; Lippard, Stephen J.

2010-01-01

84

Coupling between oxidation state and hydrogen bond conformation in heme proteins.  

PubMed

In all heme proteins for which crystal structures are available, the N(epsilon) of a histidyl residue is bonded to the heme iron and N(delta) is hydrogen bonded to a carbonyl oxygen of the peptide backbone. We investigate here the possibility that a change in oxidation state of the iron or a change in the geometry of this hydrogen bond might change the hydrogen bond strength in a functionally significant way. Dimerization energies obtained from ab initio molecular orbital calculations on the hydrogen-bonded dimer of imidazole and planar formamide are used to represent the strength of this hydrogen bond in heme proteins. The effect of a change in iron oxidation state is modeled by varying the positive charge on imidazole. The effect of a change in hydrogen bond geometry is studied by employing x-ray coordinates for reduced and oxidized cytochrome c, deoxy- and metmyoglobin, and deoxy- and methemoglobin. Our conclusions are that the strength of this hydrogen bond in heme proteins is sensitive to both the oxidation state of the iron atom and to geometry changes on the order of those obtained from the x-ray coordinates. We speculate that the changes in oxidation state may be functionally coupled with changes in hydrogen bond geometry and that this hydrogen bond represents a feasible pathway to link protein conformation with redox potential or reactivity of the iron atom. PMID:220604

Valentine, J S; Sheridan, R P; Allen, L C; Kahn, P C

1979-03-01

85

Adsorption and abstraction reactions of HCl on a single Si(100) dangling bond  

NASA Astrophysics Data System (ADS)

On a Si(100)-(2×1) surface with abundant dangling bonds, reaction of HCl molecules at room temperature is dominated by exothermic dissociative adsorption of H and Cl on two adjacent dangling bonds. This coadsorption reaction is blocked for an isolated dangling bond, yet surprisingly endothermic H or Cl abstractive adsorption occurs, as observed by in situ scanning tunneling microscopy. On an isolated dimer dangling bond (DB) pair, coadsorption of H and Cl is common as expected, but adsorption of a pair of abstracted Cl or H from two HCl molecules also occurs. These results, complemented by theoretical calculations, indicate that dissociative adsorption and abstractive reaction of a multiatom gas molecule can be initiated at a single DB by forming an intermediate adsorption state.

Li, Hong-Dao; Chang, Chan-Yuen; Chien, Ling-Ying; Chang, Shih-Hsin; Chiang, T.-C.; Lin, Deng-Sung

2011-02-01

86

Constraint Theory and Roken Bond Bending Constraints in Oxide Glasses  

NASA Astrophysics Data System (ADS)

The molecular structure of sodium tellurate glasses was established using ^{125}Te absorption and ^{129}I emission Mossbauer spectroscopies, differential scanning calorimetry (DSC), molar volume measurements and powder x-ray diffraction (XRD). The local atomic arrangement in these glasses is found to be different from that in corresponding crystals. This picture does not follow the usual thinking (Ioffe-Regel rule) about glass structure. The experimental evidence for this conclusion derives not only from Mossbauer spectroscopy but also from time-temperature -transformation curve and powder XRD measurements used to examine the crystallization of the bulk glasses. The TTT -curve exhibits both nucleation and growth branches, while XRD scans reveal growth of metastable phases before forming the stable crystalline phases. These results are in harmony with ^{23}Na solid state NMR results that reveal that sodium local environment in a x = 0.20 glass differs qualitatively from that of the crystalline counterpart. Results from DCS and XRD measurements reveal that at x = 0.18 several observables such as, dT_{g}/dx, activation energy for enthalpy relaxation, molar volume and Lamb-Mossbauer f factor, each display a threshold behavior. We believe that the physical origin of this threshold behavior comes from the rigidity percolation threshold. The constraint theory has recently been extended to include one-fold coordinated species and broken bond bending (beta) constraints. The latter was developed and has been applied successfully to many glass systems including the oxides, as we did for the first time in our Science paper, but also to chalcogenides and chalcohalides, etc.. In the experiments, the observed threshold apparently shifts to the over-constrained regime, i.e. > 2.4 in many glass systems. This shift is largely due to broken beta -constraint at some two-fold coordinated atoms, e.g. Se/S in chain segments and oxygen atoms. An example is g-Ge _{x}Se_{1-x } where one can understand the rigidity percolation threshold shift from x = 0.20 to x = 0.23, if one assumes a fraction of 20% chalcogen atoms have their bond angle constraints broken. A simple interpretation is that these chalcogen atoms (with broken bond bending constraints) represent short floppy chain-segments connecting the more rigid tetrahedral Ge(Se_{1/2} )_4 units. Thus the concept of broken bond bending constraints plays an important role in promoting glass forming tendency of materials. The extended constraint theory has also found application in aspect of mechanical property of hydrogenated diamond like carbon, silicon carbide and silicon thin films. We have established for the first time a linear relationship between measured hardness and hardness index, a geometric parameter derived from constraint theory. The slopes of such linear functions for different type materials are determined by chemical effect that reflect bonding type and interaction strength among atoms.

Zhang, Min

87

Method and reaction pathway for selectively oxidizing organic compounds  

DOEpatents

A method of selectively oxidizing an organic compound in a single vessel comprises: a) combining an organic compound, an acid solution in which the organic compound is soluble, a compound containing two oxygen atoms bonded to one another, and a metal ion reducing agent capable of reducing one of such oxygen atoms, and thereby forming a mixture; b) reducing the compound containing the two oxygen atoms by reducing one of such oxygen atoms with the metal ion reducing agent to, 1) oxidize the metal ion reducing agent to a higher valence state, and 2) produce an oxygen containing intermediate capable of oxidizing the organic compound; c) reacting the oxygen containing intermediate with the organic compound to oxidize the organic compound into an oxidized organic intermediate, the oxidized organic intermediate having an oxidized carbon atom; d) reacting the oxidized organic intermediate with the acid counter ion and higher valence state metal ion to bond the acid counter ion to the oxidized carbon atom and thereby produce a quantity of an ester incorporating the organic intermediate and acid counter ion; and e) reacting the oxidized organic intermediate with the higher valence state metal ion and water to produce a quantity of alcohol which is less than the quantity of ester, the acid counter ion incorporated in the ester rendering the carbon atom bonded to the counter ion less reactive with the oxygen containing intermediate in the mixture than is the alcohol with the oxygen containing intermediate.

Camaioni, Donald M. (Richland, WA); Lilga, Michael A. (Richland, WA)

1998-01-01

88

Topological reaction sites--very strong chalcogen bonds.  

PubMed

The analysis of interactions in complexes of S(CN)2, Se(CN)2, SFCl and SeFCl with F(-) and Cl(-) anions is performed here. The sulphur and selenium atoms act in these complexes as Lewis acid centres interacting with fluorine and chlorine anions. The arrangement of sub-units in complexes is in agreement with the ?-hole concept; particularly it is a result of contacts between positive and negative electrostatic potential sites. The interactions in complexes analyzed may be classified as very strong charge assisted chalcogen bonds and they possess numerous characteristics typical for covalent bonds. Even in the case of complexes of SFCl and SeFCl, i.e. SFCl2(-) and SeFCl2(-), the trivalency of the chalcogen atom is observed. The calculations were carried out at the MP2(full)/aug-cc-pVTZ level of approximation, the analyses were performed with the use of the Natural Bond Orbital (NBO) method, the Quantum Theory of 'Atoms in Molecules' (QTAIM) and the Electron Localization Function (ELF) approach. The results obtained by these methods are in agreement giving the consistent picture of the complexes' configurations and their electron charge distribution. The QTAIM and ELF approaches allow us to predict for S(CN)2, Se(CN)2, SFCl and SeFCl molecules the directions of nucleophilic attack. They are in line with the prediction based on the ?-hole concept. The Symmetry Adapted Perturbation Theory (SAPT) approach was also applied. PMID:24358473

Alikhani, Esmail; Fuster, Franck; Madebene, Bruno; Grabowski, S?awomir J

2014-02-14

89

Oxidative radical 1,2-alkylarylation of alkenes with ?-C(sp(3))-H bonds of acetonitriles involving 1,2-aryl migration.  

PubMed

A novel metal-free oxidative 1,2-alkylarylation of unactivated alkenes with the ?-C(sp(3))-H bonds of acetonitriles for the synthesis of 5-oxo-pentanenitriles is presented. In the presence of TBPB (tert-butyl peroxybenzoate), a variety of ?-aryl allylic alcohols underwent the 1,2-alkylarylation reaction with acetonitriles, giving 5-oxo-pentanenitriles in good to excellent yields. This method proceeds via the C(sp(3))-H oxidative coupling with the C-C double bond and 1,2-aryl-migration, and represents a new access to acyclic molecules through metal-free oxidative alkene 1,2-alkylarylation. PMID:25446150

Li, Yang; Liu, Bang; Li, Hai-Bing; Wang, Qiuan; Li, Jin-Heng

2015-01-21

90

Metal-phosphido and -phosphinidene complexes in P-E bond-forming reactions.  

PubMed

Metal complexes bearing terminal phosphido or phosphinidene ligands have become versatile tools in the stoichiometric and catalytic preparation of phosphorus-element bonds. This Perspective describes a selection of recent advances in this field, and certain emphasis has been placed on reactions that vary from what has been previously observed. Some of the general reactivity trends and mechanistic understanding in these metal-mediated reactions that has emerged are also described. Much of what is chronicled herein comes from a flux of reports over the last decade describing unique metal-mediated phosphorus-element bond formation reactions that are likely to stimulate further discoveries. PMID:19081965

Waterman, Rory

2009-01-01

91

Correlation among electronegativity, cation polarizability, optical basicity and single bond strength of simple oxides  

SciTech Connect

A suitable relationship between free-cation polarizability and electronegativity of elements in different valence states and with the most common coordination numbers has been searched on the basis of the similarity in physical nature of both quantities. In general, the cation polarizability increases with decreasing element electronegativity. A systematic periodic change in the polarizability against the electronegativity has been observed in the isoelectronic series. It has been found that generally the optical basicity increases and the single bond strength of simple oxides decreases with decreasing the electronegativity. The observed trends have been discussed on the basis of electron donation ability of the oxide ions and type of chemical bonding in simple oxides. - Graphical abstract: This figure shows the single bond strength of simple oxides as a function of element electronegativity. A remarkable correlation exists between these independently obtained quantities. High values of electronegativity correspond to high values of single bond strength and vice versa. It is obvious that the observed trend in this figure is closely related to the type of chemical bonding in corresponding oxide. Highlights: Black-Right-Pointing-Pointer A suitable relationship between free-cation polarizability and electronegativity of elements was searched. Black-Right-Pointing-Pointer The cation polarizability increases with decreasing element electronegativity. Black-Right-Pointing-Pointer The single bond strength of simple oxides decreases with decreasing the electronegativity. Black-Right-Pointing-Pointer The observed trends were discussed on the basis of type of chemical bonding in simple oxides.

Dimitrov, Vesselin, E-mail: vesselin@uctm.edu [Department of Silicate Technology, University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd., Sofia 1756 (Bulgaria)] [Department of Silicate Technology, University of Chemical Technology and Metallurgy, 8, Kl. Ohridski Blvd., Sofia 1756 (Bulgaria); Komatsu, Takayuki, E-mail: komatsu@mst.nagaokaut.ac.jp [Department of Materials Science and Technology, Nagaoka University of Technology, 1603-1 Kamitomioka-cho, Nagaoka 940-2188 (Japan)] [Department of Materials Science and Technology, Nagaoka University of Technology, 1603-1 Kamitomioka-cho, Nagaoka 940-2188 (Japan)

2012-12-15

92

LETTER TO THE EDITOR Surface Precipitation Reactions on Oxide Surfaces  

E-print Network

LETTER TO THE EDITOR Surface Precipitation Reactions on Oxide Surfaces Retention of heavy metal such processes. However, various mechanisms have been proposed for the sorption of cationic heavy metals on oxide of hydrolyzable metal ions on oxide surfaces. ©1992 Academic Press, Inc. The mechanisms of metal ion retention

Sparks, Donald L.

93

Transition metal catalyzed carbon-silicon bond forming reactions using chlorosilanes promoted by Grignard reagents.  

PubMed

New catalytic C--Si bond-forming reactions using chlorosilanes are described. These reactions proceed efficiently under mild conditions by the combined use of Grignard reagents and transition metal catalysts, such as Ti, Zr, Ni, and Pd. It is proposed that ate complex intermediates formed by the reaction of transition metals with Grignard reagents play important roles as the active catalytic species. The present study demonstrates the practical use of chlorosilanes in transition metal catalyzed silylation reactions providing convenient methods for allyl- or vinylsilane synthesis. The reaction pathways of these transformations as well as the scope and limitations are discussed. PMID:17318829

Terao, Jun; Kambe, Nobuaki

2007-01-01

94

Low-oxidation state indium-catalyzed C-C bond formation.  

PubMed

The development of innovative metal catalysis for selective bond formation is an important task in organic chemistry. The group 13 metal indium is appealing for catalysis because indium-based reagents are minimally toxic, selective, and tolerant toward various functional groups. Among elements in this group, the most stable oxidation state is typically +3, but in molecules with larger group 13 atoms, the chemistry of the +1 oxidation state is also important. The use of indium(III) compounds in organic synthesis has been well-established as Lewis acid catalysts including asymmetric versions thereof. In contrast, only sporadic examples of the use of indium(I) as a stoichiometric reagent have been reported: to the best of our knowledge, our investigations represent the first synthetic method that uses a catalytic amount of indium(I). Depending on the nature of the ligand or the counteranion to which it is coordinated, indium(I) can act as both a Lewis acid and a Lewis base because it has both vacant p orbitals and a lone pair of electrons. This potential ambiphilicity may offer unique reactivity and unusual selectivity in synthesis and may have significant implications for catalysis, particularly for dual catalytic processes. We envisioned that indium(I) could be employed as a metallic Lewis base catalyst to activate Lewis acidic boron-based pronucleophiles for selective bond formation with suitable electrophiles. Alternatively, indium(I) could serve as an ambiphilic catalyst that activates both reagents at a single center. In this Account, we describe the development of low-oxidation state indium catalysts for carbon-carbon bond formation between boron-based pronucleophiles and various electrophiles. We discovered that indium(I) iodide was an excellent catalyst for ?-selective allylations of C(sp(2)) electrophiles such as ketones and hydrazones. Using a combination of this low-oxidation state indium compound and a chiral semicorrin ligand, we developed catalytic highly enantioselective allylation, crotylation, and ?-chloroallylation reactions of hydrazones. These transformations proceeded with rare constitutional selectivities and remarkable diastereoselectivities. Furthermore, indium(I) triflate served as the most effective catalyst for allylations and propargylations of C(sp(3)) electrophiles such as O,O-acetals, N,O-aminals, and ethers, and we applied this methodology to carbohydrate chemistry. In addition, a catalyst system composed of indium(I) chloride and a chiral silver BINOL-phosphate facilitated the highly enantioselective allylation and allenylation of N,O-aminals. Overall, these discoveries demonstrate the versatility, efficiency, and sensitivity of low-oxidation state indium catalysts in organic synthesis. PMID:22626010

Schneider, Uwe; Kobayashi, Shu

2012-08-21

95

Preparation and properties of UV curable acrylic PSA by vinyl bonded graphene oxide  

NASA Astrophysics Data System (ADS)

Acrylic pressure sensitive adhesives (PSAs) with higher thermal stability for thin wafer handling were successfully prepared by forming composite with the graphene oxide (GO) nanoparticles modified to have vinyl groups via subsequent reaction with isophorone diisocyanate and 2-hydroxyethyl methacrylate. The acrylic copolymer was synthesized as a base resin for PSAs by solution radical polymerization of ethyl acrylate, 2-ethylhexyl acrylate, and acrylic acid followed by further modification with GMA to have the vinyl groups available for UV curing. The peel strength of PSA decreased with the increase of gel content which was dependent on both modified GO content and UV dose. Thermal stability of UV-cured PSA was improved noticeably with increasing the modified GO content mainly due to the strong and extensive interfacial bonding formed between the acrylic copolymer matrix and GO fillers

Pang, Beili; Ryu, Chong-Min; Jin, Xin; Kim, Hyung-Il

2013-11-01

96

Bond cleavage, fragment modification and reassembly in enantioselective three-component reactions  

PubMed Central

Chemical bond cleavage and reconstruction are common processes in traditional rearrangement reactions. In contrast, the process that involves bond cleavage, fragment modification and then reconstruction of the modified fragment provides an efficient way to build structurally diversified molecules. Here, we report a palladium(II)/chiral phosphoric acid catalysed three-component reaction of aryldiazoacetates, enamines and imines to afford ?-amino-?-oxo pentanoic acid derivatives in good yields with excellent diastereoselectivities and high enantioselectivities. The stereoselective reaction went through a unique process that involves cleavage of a C–N bond, modification of the resulting amino fragment and selective reassembly of the modified fragment. This innovative multi-component process represents a highly efficient way to build structurally diversified polyfunctional molecules in an atom and step economic fashion. A keto-iminium is proposed as a key intermediate and a chiral palladium/phosphate complex is proposed as an active catalyst. PMID:25586817

Zhang, Dan; Zhou, Jun; Xia, Fei; Kang, Zhenghui; Hu, Wenhao

2015-01-01

97

Insights into the bond-selective reaction of Cl + HOD(nOH) ? HCl + OD.  

PubMed

Bond-selective reaction dynamics of the title reaction is investigated using full-dimensional quantum dynamical (QD) and quasi-classical trajectory (QCT) methods on a newly constructed ab initio global potential energy surface. Both QD and QCT results indicate that excitation of the local OH vibration in the HOD reactant renders the reaction strongly bond selective, with the OD/OH branching ratio in quantitative agreement with the experiment. In addition, the reactivity is found to be greatly enhanced with the reactant vibrational excitation, thanks to the change of a direct rebound mechanism to a capture mechanism. The QCT calculations also yield product state distributions, which show that the HCl product is vibrationally and rotationally hot while the OD co-product is internally cold. The bond selectivity, vibrational enhancement, and product energy disposal are rationalized by the Sudden Vector Projection model. PMID:25571941

Li, Jun; Song, Hongwei; Guo, Hua

2015-01-28

98

Bond cleavage, fragment modification and reassembly in enantioselective three-component reactions.  

PubMed

Chemical bond cleavage and reconstruction are common processes in traditional rearrangement reactions. In contrast, the process that involves bond cleavage, fragment modification and then reconstruction of the modified fragment provides an efficient way to build structurally diversified molecules. Here, we report a palladium(II)/chiral phosphoric acid catalysed three-component reaction of aryldiazoacetates, enamines and imines to afford ?-amino-?-oxo pentanoic acid derivatives in good yields with excellent diastereoselectivities and high enantioselectivities. The stereoselective reaction went through a unique process that involves cleavage of a C-N bond, modification of the resulting amino fragment and selective reassembly of the modified fragment. This innovative multi-component process represents a highly efficient way to build structurally diversified polyfunctional molecules in an atom and step economic fashion. A keto-iminium is proposed as a key intermediate and a chiral palladium/phosphate complex is proposed as an active catalyst. PMID:25586817

Zhang, Dan; Zhou, Jun; Xia, Fei; Kang, Zhenghui; Hu, Wenhao

2015-01-01

99

The role of hydrogen bonding in the enzymatic reaction catalyzed by HIV-1 protease  

PubMed Central

The hydrogen-bond network in various stages of the enzymatic reaction catalyzed by HIV-1 protease was studied through quantum-classical molecular dynamics simulations. The approximate valence bond method was applied to the active site atoms participating directly in the rearrangement of chemical bonds. The rest of the protein with explicit solvent was treated with a classical molecular mechanics model. Two possible mechanisms were studied, general-acid/general-base (GA/GB) with Asp 25 protonated at the inner oxygen, and a direct nucleophilic attack by Asp 25. Strong hydrogen bonds leading to spontaneous proton transfers were observed in both reaction paths. A single-well hydrogen bond was formed between the peptide nitrogen and outer oxygen of Asp 125. The proton was diffusely distributed with an average central position and transferred back and forth on a picosecond scale. In both mechanisms, this interaction helped change the peptide-bond hybridization, increased the partial charge on peptidyl carbon, and in the GA/GB mechanism, helped deprotonate the water molecule. The inner oxygens of the aspartic dyad formed a low-barrier, but asymmetric hydrogen bond; the proton was not positioned midway and made a slightly elongated covalent bond, transferring from one to the other aspartate. In the GA/GB mechanism both aspartates may help deprotonate the water molecule. We observed the breakage of the peptide bond and found that the protonation of the peptidyl amine group was essential for the peptide-bond cleavage. In studies of the direct nucleophilic mechanism, the peptide carbon of the substrate and oxygen of Asp 25 approached as close as 2.3 ?. PMID:14739332

Trylska, Joanna; Grochowski, Pawe?; McCammon, J. Andrew

2004-01-01

100

In situ UV-visible assessment of extent of reduction during oxidation reactions on oxide catalysts  

E-print Network

In situ UV-visible assessment of extent of reduction during oxidation reactions on oxide catalysts as an Advance Article on the web 15th July 2003 The extent of reduction of active centers during oxidative to increase with increasing VOx domain size and propane/O2 ratio. Oxidative dehydrogenation (ODH) of alkanes

Bell, Alexis T.

101

Water oxidation reaction in natural and artificial photosynthetic systems  

SciTech Connect

Understanding the structure and mechanism of water oxidation catalysts is an essential component for developing artificial photosynthetic devices. In the natural water oxidation catalyst, the geometric and electronic structure of its inorganic core, the Mn{sub 4}CaO{sub 5} cluster, has been studied by spectroscopic and diffraction measurements. In inorganic systems, metal oxides seem to be good candidates for water oxidation catalysts. Understanding the reaction mechanism in both natural and oxide-based catalysts will helpin further developing efficient and robust water oxidation catalysts.

Yano, Junko; Yachandra, Vittal [Physical Biosciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Rd., Berkeley, CA 94720 (United States)

2013-12-10

102

40 CFR 721.10574 - Alkylcarboxy polyester acrylate reaction products with mixed metal oxides (generic).  

Code of Federal Regulations, 2014 CFR

...acrylate reaction products with mixed metal oxides (generic). 721.10574 Section...acrylate reaction products with mixed metal oxides (generic). (a) Chemical substance...acrylate reaction products with mixed metal oxides (PMN P-09-48) is subject...

2014-07-01

103

40 CFR 721.10574 - Alkylcarboxy polyester acrylate reaction products with mixed metal oxides (generic).  

Code of Federal Regulations, 2013 CFR

...acrylate reaction products with mixed metal oxides (generic). 721.10574 Section...acrylate reaction products with mixed metal oxides (generic). (a) Chemical...acrylate reaction products with mixed metal oxides (PMN P-09-48) is...

2013-07-01

104

Observation of {beta}-kinetic and {beta}-equilibrium isotope effects in organometallic oxidative addition reactions  

SciTech Connect

Secondary {Beta}-deuterium isotope effects have long been an important tool in the study of organic reaction mechanisms. Normal effects (k{sub H}/k{sub D} > 1) have been used to obtain evidence for hyperconjugation, and inverse effects (k{sub H}/k{sub D} > 1) have provided evidence for the steric and inductive influence of deuterium on the rates of organic transformations. Both steric and inductive effects have been proposed to result from the shorter average length of a C-D bond (1.107 {angstrom}) relative to a C-H bond (1.112 {angstrom}). Reported is an application of the {beta}-deuterium isotope effects to investigate both the rate and equilibrium of an organometallic transformation. The result of this work shows the apparently general electron-donating effect of {beta}-deuterium on oxidative addition reactions. The work establishes the existence of secondary {beta}-isotope effects in an organometallic oxidative addition reaction and suggests that the observation may be general. The results indicate that the effects are due to the inductive rather than the steric properties of deuterium. Oxidative addition causes an increase in the formal oxidation state at the metal center, lowering its charge density, and the magnitude and direction of the effect caused by {Beta}-deuterium substitutions are consistent with this interpretation. 13 refs., 1 fig., 2 tabs.

Hostetler, M.J.; Bergman, R.G. [Univ. of California, Berkeley, CA (United States)

1992-01-15

105

Transition-Metal-Catalyzed Laboratory-Scale Carbon–Carbon Bond-Forming Reactions of Ethylene  

PubMed Central

Ethylene, the simplest alkene, is the most abundantly synthesized organic molecule by volume. It is readily incorporated into transitionmetal–catalyzed carbon-carbon bond-forming reactions through migratory insertions into alkylmetal intermediates. Because of its D2h symmetry, only one insertion outcome is possible. This limits byproduct formation and greatly simplifies analysis. As described within this Minireview, many carbon–carbon bond-forming reactions incorporate a molecule (or more) of ethylene at ambient pressure and temperature. In many cases, a useful substituted alkene is incorporated into the product. PMID:24105881

Saini, Vaneet; Stokes, Benjamin J.; Sigman, Matthew S.

2014-01-01

106

Transition-metal-catalyzed laboratory-scale carbon-carbon bond-forming reactions of ethylene.  

PubMed

Ethylene, the simplest alkene, is the most abundantly synthesized organic molecule by volume. It is readily incorporated into transition-metal-catalyzed carbon-carbon bond-forming reactions through migratory insertions into alkylmetal intermediates. Because of its D2h symmetry, only one insertion outcome is possible. This limits byproduct formation and greatly simplifies analysis. As described within this Minireview, many carbon-carbon bond-forming reactions incorporate a molecule (or more) of ethylene at ambient pressure and temperature. In many cases, a useful substituted alkene is incorporated into the product. PMID:24105881

Saini, Vaneet; Stokes, Benjamin J; Sigman, Matthew S

2013-10-18

107

SiC continuous fiber-reinforced Si3N4 by infiltration and reaction bonding  

NASA Astrophysics Data System (ADS)

Difficulties encountered in the production of long-fiber reinforced ceramic-matrix composites via hot pressing and CVI can be circumvented through the use of the infiltration/consolidation of the long-fiber preforms with submicron particle slurries and reaction-bonding the resulting matrix, as is presently demonstrated for the case of SiC fibers and Si/Si3N4 particle slurries. High temperature fiber degradation during reaction bonding is avoided through the use of additives that lower the nitridation temperature and shorten process time. Attention is given to the microstructure and mechanical properties thus obtained; nearly complete impregnation is achieved.

Brandt, Jesper; Rundgren, Kent; Pompe, Robert; Swan, Hakan; O'Meara, Colette; Lundberg, Robert; Pejryd, Lars

1992-10-01

108

ATR-FTIR Spectroscopy Reveals Bond Formation During Bacterial Adhesion to Iron Oxide  

E-print Network

ATR-FTIR Spectroscopy Reveals Bond Formation During Bacterial Adhesion to Iron Oxide Sanjai J contribute to bacterial adhesion at positively charged surfaces, direct bonding of cell surface The contribution of various bacterial surface functional groups to adhesion at hematite and ZnSe surfaces

Chorover, Jon

109

Effect of silicon oxide, silicon nitride and polysilicon layers on the electrostatic pressure during anodic bonding  

Microsoft Academic Search

The quality of the anodic bonding between glass and silicon wafers coated with silicon oxide, silicon nitride and polysilicon layers has been investigated. We have used an electrostatic test to study the effect of these layers on the quality of the bond. The electrostatic test shows how the electrostatic pressure decreases with the increase of the thickness of the silicon

J. A. Plaza; J. Esteve; E. Lora-Tamayo

1998-01-01

110

Reaction of HppE with substrate analogues: evidence for carbon-phosphorus bond cleavage by a carbocation rearrangement.  

PubMed

(S)-2-hydroxypropylphosphonic acid ((S)-2-HPP) epoxidase (HppE) is an unusual mononuclear non-heme iron enzyme that catalyzes the oxidative epoxidation of (S)-2-HPP in the biosynthesis of the antibiotic fosfomycin. Recently, HppE has been shown to accept (R)-1-hydroxypropylphosphonic acid as a substrate and convert it to an aldehyde product in a reaction involving a biologically unprecedented 1,2-phosphono migration. In this study, a series of substrate analogues were designed, synthesized, and used as mechanistic probes to study this novel enzymatic transformation. The resulting data, together with insights obtained from density functional theory calculations, are consistent with a mechanism of HppE-catalyzed phosphono group migration that involves the formation of a carbocation intermediate. As such, this reaction represents a new paradigm for biological C-P bond cleavage. PMID:23672451

Chang, Wei-chen; Mansoorabadi, Steven O; Liu, Hung-wen

2013-06-01

111

The Reaction of HppE with Substrate Analogues: Evidence for Carbon-Phosphorus Bond Cleavage by a Carbocation Rearrangement  

PubMed Central

(S)-2-Hydroxypropylphosphonic acid ((S)-2-HPP) epoxidase (HppE) is an unusual mononuclear non-heme iron enzyme that catalyzes the oxidative epoxidation of (S)-2-HPP in the biosynthesis of the antibiotic fosfomycin. Recently, HppE has been shown to accept (R)-1-hydroxypropylphosphonic acid ((R)-1-HPP) as a substrate and convert it to an aldehyde product in a reaction involving a biologically unprecedented 1,2-phosphono migration. In this study, a series of substrate analogues were designed, synthesized, and used as mechanistic probes to study this novel enzymatic transformation. The resulting data, together with insights obtained from density functional theory calculations, are consistent with a mechanism of HppE-catalyzed phosphono group migration that involves the formation of a carbocation intermediate. As such, this reaction represents a new paradigm for biological C-P bond cleavage. PMID:23672451

Chang, Wei-chen; Mansoorabadi, Steven O.; Liu, Hung-wen

2013-01-01

112

Bonding  

NSDL National Science Digital Library

Bonding Purpose: To review the 3 Types of Bonds and the 4 Intermolecular Forces. Assignment: Answer the following questions on a separate piece of paper: 1) List the 3 types of bonding, give descriptions and one example of each 2) List the 4 intermolecular forces and draw examples of each. Be ...

Cutting, Mrs.

2008-03-08

113

Reaction mechanism between carbonyl oxide and hydroxyl radical: a theoretical study.  

PubMed

The reaction mechanism of carbonyl oxide with hydroxyl radical was investigated by using CASSCF, B3LYP, QCISD, CASPT2, and CCSD(T) theoretical approaches with the 6-311+G(d,p), 6-311+G(2df, 2p), and aug-cc-pVTZ basis sets. This reaction involves the formation of H2CO + HO2 radical in a process that is computed to be exothermic by 57 kcal/mol. However, the reaction mechanism is very complex and begins with the formation of a pre-reactive hydrogen-bonded complex and follows by the addition of HO radical to the carbon atom of H2COO, forming the intermediate peroxy-radical H2C(OO)OH before producing formaldehyde and hydroperoxy radical. Our calculations predict that both the pre-reactive hydrogen-bonded complex and the transition state of the addition process lie energetically below the enthalpy of the separate reactants (DeltaH(298K) = -6.1 and -2.5 kcal/mol, respectively) and the formation of the H2C(OO)OH adduct is exothermic by about 74 kcal/mol. Beyond this addition process, further reaction mechanisms have also been investigated, which involve the abstraction of a hydrogen of carbonyl oxide by HO radical, but the computed activation barriers suggest that they will not contribute to the gas-phase reaction of H2COO + HO. PMID:16539423

Mansergas, Alex; Anglada, Josep M

2006-03-23

114

Neutron Scattering Studies of Poly(ethylene Terephthalate) and Molecular Relaxation Through the Bond Interchange Reaction.  

NASA Astrophysics Data System (ADS)

In this work, the neutron scattering technique was extended to investigate bond interchange using intermediate angle neutron scattering (IANS). Methodology was developed to use IANS data to explore this reaction in poly(ethylene terephthalate), or PET. To effectively use the IANS region, background scattering was measured from block copolymers formed from perdeutero (D) and normal or hydrogenous (H) PET. Models have been developed from neutron transport theory, which allow backgrounds from other materials to be calculated. Currently, these models represent the best extrapolation technique for estimating backgrounds from a single known reference background. Using IANS data, the bond interchange reaction in melt processed samples of PET-H/PET-D was investigated. From this study, a statistical segment length, b, of 16.3 +/- 2.2 A was determined for PET. Furthermore, the copolymer formed through interchange showed a block number average degree of polymerization, n, of 2.2 +/- 0.2. This n was consistent with the value expected for complete randomization of the original PET -H and PET-D chains. However, it was also shown that care must be exercised in determining b when n is small. Subsequently, the bond interchange reaction was explored in drawn PET films. Solutions of the drawn films were used to reduce difficulties associated with analyzing anisotropic samples. This study showed that bond interchange occurred in drawn films at 70 and 90^circ C. An apparent activation energy of 16.2 +/- 8.0 kcal/mole was determined for the effective bond scission reaction. To explore the connection between bond interchange and mechanical properties of PET, creep experiments were performed between 47 and 70^circC, to investigate relaxation processes below the glass transition temperature of PET (ca 70^circC). The results of these creep studies reflected established relaxation behavior associated with gauche-trans isomerization. The creep studies were connected to the isomerization results by a bond interchange kinetic model. This model was used to fit established PET secondary isomerization data, and showed that the time constants for secondary gauche-trans isomerization are consistent with the bond interchange reaction. Therefore, it was concluded that chemical changes associated with bond interchange may influence the physical properties of PET. An understanding of the controlling molecular processes that influence the physical behavior of polymers can lead to industrial processes which are better able to impact desirable polymer properties.

Dubner, Walter Sterling

1990-01-01

115

The pathophysiology of extracellular hemoglobin associated with enhanced oxidative reactions  

PubMed Central

Hemoglobin (Hb) continuously undergoes autoxidation producing superoxide which dismutates into hydrogen peroxide (H2O2) and is a potential source for subsequent oxidative reactions. Autoxidation is most pronounced under hypoxic conditions in the microcirculation and for unstable dimers formed at reduced Hb concentrations. In the red blood cell (RBC), oxidative reactions are inhibited by an extensive antioxidant system. For extracellular Hb, whether from hemolysis of RBCs and/or the infusion of Hb-based blood substitutes, the oxidative reactions are not completely neutralized by the available antioxidant system. Un-neutralized H2O2 oxidizes ferrous and ferric Hbs to Fe(IV)-ferrylHb and OxyferrylHb, respectively. FerrylHb further reacts with H2O2 producing heme degradation products and free iron. OxyferrylHb, in addition to Fe(IV) contains a free radical that can undergo additional oxidative reactions. Fe(III)Hb produced during Hb autoxidation also readily releases heme, an additional source for oxidative stress. These oxidation products are a potential source for oxidative reactions in the plasma, but to a greater extent when the lower molecular weight Hb dimers are taken up into cells and tissues. Heme and oxyferryl have been shown to have a proinflammatory effect further increasing their potential for oxidative stress. These oxidative reactions contribute to a number of pathological situations including atherosclerosis, kidney malfunction, sickle cell disease, and malaria. The toxic effects of extracellular Hb are of particular concern with hemolytic anemia where there is an increase in hemolysis. Hemolysis is further exacerbated in various diseases and their treatments. Blood transfusions are required whenever there is an appreciable decrease in RBCs due to hemolysis or blood loss. It is, therefore, essential that the transfused blood, whether stored RBCs or the blood obtained by an Autologous Blood Recovery System from the patient, do not further increase extracellular Hb. PMID:25642190

Rifkind, Joseph M.; Mohanty, Joy G.; Nagababu, Enika

2015-01-01

116

Oxidation reactions of cytosine DNA components by hydroxyl radical and one-electron oxidants in aerated aqueous solutions.  

PubMed

Indirect evidence strongly suggests that oxidation reactions of cytosine and its minor derivative 5-methylcytosine play a major role in mutagenesis and cancer. Therefore, there is an emerging necessity to identify the final oxidation products of these reactions, to search for their formation in cellular DNA, and to assess their mutagenic features. In this Account, we report and discuss the main *OH and one-electron-mediated oxidation reactions, two of the most potent sources of DNA damage, of cytosine and 5-methylcytosine nucleosides that have been recently characterized. The addition of *OH to the 5,6-unsaturated double bond of cytosine and 5-methylcytosine generates final degradation products that resemble those observed for uracil and thymine. The main product from the oxidation of cytosine, cytosine glycol, has been shown to undergo dehydration at a much faster rate as a free nucleoside than when inserted into double-stranded DNA. On the other hand, the predominant *OH addition at C5 of cytosine or 5-methylcytosine leads to the formation of 5-hydroxy-5,6-dihydro radicals that give rise to novel products with an imidazolidine structure. The mechanism of the formation of imidazolidine products is accounted for by rearrangement reactions that in the presence of molecular oxygen likely involve an intermediate pyrimidine endoperoxide. The reactions of the radical cations of cytosine and 5-methylcytosine are governed by competitive hydration, mainly at C6 of the pyrimidine ring, and deprotonation from the exocyclic amino and methyl group, leading in most cases to products similar to those generated by *OH. 5-Hydroxypyrimidines, the dehydration products of cytosine and uracil glycols, have a low oxidation potential, and their one-electron oxidation results in a cascade of decomposition reactions involving the formation of isodialuric acid, dialuric acid, 5-hydroxyhydantoin, and its hydroxyketone isomer. In biology, GC --> AT transitions are the most common mutations in the genome of aerobic organisms, including the lacI gene in bacteria, lacI transgenes in rodents, and the HPRT gene in rodents and humans, so a more complete understanding of cytosine oxidation is an essential research goal. The data and insights presented here shed new light on oxidation reactions of cytosine and 5-methylcytosine and should facilitate their validation in cellular DNA. PMID:20078112

Wagner, J Richard; Cadet, Jean

2010-04-20

117

Effect of composition on the processing and properties of sintered reaction-bonded silicon nitride  

Microsoft Academic Search

The type of silicon powder and sintering additive were found to influence the processing and final mechanical properties of sintered reaction bonded silicon nitride. High purity silicon powders produced low -SiN content during nitridation. The Si powder type had no apparent effect on densification. More complete nitridation and higher room temperature mechanical properties were observed for the Si powders with

T. N. Tiegs; J. O. Kiggans; F. C. Montgomery; H. T. Lin; D. L. Barker; J. D. Snodgrass; E. M. Sabolsky; D. W. Coffey

1996-01-01

118

Investigating the Molecular Level Details of Catalytic Oxidation Reactions  

NASA Astrophysics Data System (ADS)

Gas-phase cluster reactivity studies are providing significant insight into the molecular level mechanisms of oxidation reactions occurring on catalytic surfaces. Our experimental approach, employing tandem mass spectrometry, uses mass selected metal oxide clusters to model specific catalytic active sites. This technique enables investigation of the influence of factors such as size, stoichiometry, charge state, and elemental composition on the reactivity of catalytic materials. Particular emphasis is on identifying species with enhanced activity for the selective oxidation of simple hydrocarbons and atmospheric pollutants. Recent findings pertain to the kinetics of ethylene oxidation in the presence of vanadium oxides and the oxidation of carbon monoxide in the presence of gold and iron. Through a combination of experiments and theoretical calculations we establish structure-reactivity relationships and propose general reaction mechanisms for these catalytic processes.

Johnson, Grant

2008-03-01

119

Theoretical Bond Dissociation Energies of Halo-Heterocycles: Trends and Relationships to Regioselectivity in Palladium-Catalyzed Cross-Coupling Reactions  

PubMed Central

Selectivity of the palladium-catalyzed cross-coupling reactions of heterocycles bearing multiple identical halogens is mainly determined by the relative ease of oxidative addition. This is related to both the energy to distort the carbon halogen bond to the transition-state geometry (related to the CX bond-dissociation energy) and to the interaction between the heterocycle ?* (LUMO) and PdL2 HOMO (J. Am. Chem. Soc. 2007, 129, 12664). The computed bond dissociation energies of a larger series of halo-heterocycles have been explored with B3LYP and higher accuracy G3B3 calculations. Quantitative trends in bond dissociation energies have been identified for five- and six-membered chloro and bromo substituted heterocycles with N, O, and S heteroatoms. PMID:19368385

Garcia, Yeimy; Schoenebeck, Franziska; Legault, Claude Y.; Merlic, Craig A.; Houk, K. N.

2009-01-01

120

Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen or hydrogen peroxide and sodium cyanide: sp3 C-H bond activation and carbon-carbon bond formation.  

PubMed

Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen in the presence of sodium cyanide and acetic acid gives the corresponding alpha-aminonitriles, which are highly useful intermediates for organic synthesis. The reaction is the first demonstration of direct sp(3) C-H bond activation alpha to nitrogen followed by carbon-carbon bond formation under aerobic oxidation conditions. The catalytic oxidation seems to proceed by (i) alpha-C-H activation of tertiary amines by the ruthenium catalyst to give an iminium ion/ruthenium hydride intermediate, (ii) reaction with molecular oxygen to give an iminium ion/ruthenium hydroperoxide, (iii) reaction with HCN to give the alpha-aminonitrile product, H2O2, and Ru species, (iv) generation of oxoruthenium species from the reaction of Ru species with H2O2, and (v) reaction of oxoruthenium species with tertiary amines to give alpha-aminonitriles. On the basis of the last two pathways, a new type of ruthenium-catalyzed oxidative cyanation of tertiary amines with H2O2 to give alpha-aminonitriles was established. The alpha-aminonitriles thus obtained can be readily converted to alpha-amino acids, diamines, and various nitrogen-containing heterocyclic compounds. PMID:18646852

Murahashi, Shun-ichi; Nakae, Takahiro; Terai, Hiroyuki; Komiya, Naruyoshi

2008-08-20

121

CHEMICAL REACTIONS OF AQUATIC HUMIC MATERIALS WITH SELECTED OXIDANTS  

EPA Science Inventory

A study was conducted to identify the specific organic reaction products of natural aquatic humic materials with selected oxidants (KMnO4, HOCl, Cl02, O3 and monochloramine). Reaction products were identified by GC/MS after solvent extraction and derivatization. The two most reac...

122

Concerted O Atom-Proton Transfer in the O—O Bond Forming Step in Water Oxidation  

SciTech Connect

As the terminal step in photosystem II, and a potential half-reaction for artificial photosynthesis, water oxidation (2H{sub 2}O ? O{sub 2 + 4e{sup -} + 4H{sup +}) is key, but it imposes a significant mechanistic challenge with requirements for both 4e{sup -}/4H{sup +} loss and O—O bond formation. Significant progress in water oxidation catalysis has been achieved recently by use of single-site Ru metal complex catalysts such as [Ru(Mebimpy)(bpy)(OH{sub 2})]{sup 2+} [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2?-bipyridine]. When oxidized from Ru{sup II}-OH{sub 2}{sup 2+} to Ru{sup V} = O{sup 3+}, these complexes undergo O—O bond formation by O-atom attack on a H{sub 2}O molecule, which is often the rate-limiting step. Microscopic details of O—O bond formation have been explored by quantum mechanical/molecular mechanical (QM/MM) simulations the results of which provide detailed insight into mechanism and a strategy for enhancing catalytic rates. It utilizes added bases as proton acceptors and concerted atom–proton transfer (APT) with O-atom transfer to the O atom of a water molecule in concert with proton transfer to the base (B). Base catalyzed APT reactivity in water oxidation is observed both in solution and on the surfaces of oxide electrodes derivatized by attached phosphonated metal complex catalysts. These results have important implications for catalytic, electrocatalytic, and photoelectrocatalytic water oxidation.

Chen, Zuofeng; Concepcion, Javier C.; Hu, Xiangqian; Yang, Weitao; Hoertz, Paul G.; Meyer, Thomas J

2010-01-01

123

A new approach to carbon-carbon bond formation: Development of aerobic Pd-catalyzed reductive coupling reactions of organometallic reagents and styrenes  

PubMed Central

Alkenes are attractive starting materials for organic synthesis and the development of new selective functionalization reactions are desired. Previously, our laboratory discovered a unique Pd-catalyzed hydroalkoxylation reaction of styrenes containing a phenol. Based upon deuterium labeling experiments, a mechanism involving an aerobic alcohol oxidation coupled to alkene functionalization was proposed. These results inspired the development of a new Pd-catalyzed reductive coupling reaction of alkenes and organometallic reagents that generates a new carbon-carbon bond. Optimization of the conditions for the coupling of both organostannanes and organoboronic esters is described and the initial scope of the transformation is presented. Additionally, several mechanistic experiments are outlined and support the rationale for the development of the reaction based upon coupling alcohol oxidation to alkene functionalization. PMID:20161306

Gligorich, Keith M.; Iwai, Yasumasa; Cummings, Sarah A.; Sigman, Matthew S.

2009-01-01

124

Organosulfur compounds: electrophilic reagents in transition-metal-catalyzed carbon-carbon bond-forming reactions.  

PubMed

Transition-metal-catalyzed carbon-carbon bond-forming reactions are among the most powerful methods in organic synthesis and play a crucial role in modern materials science and medicinal chemistry. Recent developments in the area of ligands and additives permit the cross-coupling of a large variety of reactants, including inexpensive and readily available sulfonyl chlorides. Their desulfitative carbon-carbon cross-coupling reactions (Negishi, Stille, carbonylative Stille, Suzuki-Miyaura, and Sonogashira-Hagihara-type cross-couplings and Mizoroki-Heck-type arylations) are reviewed together with carbon-carbon cross-coupling reactions with other organosulfur compounds as electrophilic reagents. PMID:16287179

Dubbaka, Srinivas Reddy; Vogel, Pierre

2005-12-01

125

Studies on the Reactive Species in Fluoride-Mediated Carbon-Carbon Bond-Forming Reactions: Carbanion Formation  

E-print Network

Studies on the Reactive Species in Fluoride-Mediated Carbon-Carbon Bond-Forming ReactionsVed October 27, 2005 The reactive species in fluoride-mediated carbon-carbon bond-forming reactions- methylsilicate (TASF) or crypt[2.1.1]-solvated lithium enolates. The catalytic cycle runs smoothly with the crypt

Reich, Hans J.

126

Reactions of calcium orthosilicate and barium zirconate with oxides and sulfates of various elements  

NASA Technical Reports Server (NTRS)

Calcium orthosilicate and barium zirconate were evaluated as the insulation layer of thermal barrier coatings for air cooled gas turbine components. Their reactions with various oxides and sulfates were studied at 1100 C and 1300 C for times ranging up to 400 and 200 hours, respectively. These oxides and sulfates represent potential impurities or additives in gas turbine fuels and in turbine combustion air, as well as elements of potential bond coat alloys. The phase compositions of the reaction products were determined by X-ray diffraction analysis. BaZrO3 and 2CaO-SiO2 both reacted with P2O5, V2O5, Cr2O3, Al2O3, and SiO2. In addition, 2CaO-SiO2 reacted with Na2O, BaO, MgO, and CoO and BaZrO3 reacted with Fe2O3.

Zaplatynsky, I.

1979-01-01

127

Dynamics, transition states, and timing of bond formation in Diels–Alder reactions  

PubMed Central

The time-resolved mechanisms for eight Diels–Alder reactions have been studied by quasiclassical trajectories at 298 K, with energies and derivatives computed by UB3LYP/6-31G(d). Three of these reactions were also simulated at high temperature to compare with experimental results. The reaction trajectories require 50–150 fs on average to transverse the region near the saddle point where bonding changes occur. Even with symmetrical reactants, the trajectories invariably involve unequal bond formation in the transition state. Nevertheless, the time gap between formation of the two new bonds is shorter than a C?C vibrational period. At 298 K, most Diels–Alder reactions are concerted and stereospecific, but at high temperatures (approximately 1,000 K) a small fraction of trajectories lead to diradicals. The simulations illustrate and affirm the bottleneck property of the transition state and the close connection between dynamics and the conventional analysis based on saddle point structure. PMID:22753502

Black, Kersey; Liu, Peng; Xu, Lai; Doubleday, Charles; Houk, Kendall N.

2012-01-01

128

Dynamics, transition states, and timing of bond formation in Diels-Alder reactions.  

PubMed

The time-resolved mechanisms for eight Diels-Alder reactions have been studied by quasiclassical trajectories at 298 K, with energies and derivatives computed by UB3LYP/6-31G(d). Three of these reactions were also simulated at high temperature to compare with experimental results. The reaction trajectories require 50-150 fs on average to transverse the region near the saddle point where bonding changes occur. Even with symmetrical reactants, the trajectories invariably involve unequal bond formation in the transition state. Nevertheless, the time gap between formation of the two new bonds is shorter than a C ? C vibrational period. At 298 K, most Diels-Alder reactions are concerted and stereospecific, but at high temperatures (approximately 1,000 K) a small fraction of trajectories lead to diradicals. The simulations illustrate and affirm the bottleneck property of the transition state and the close connection between dynamics and the conventional analysis based on saddle point structure. PMID:22753502

Black, Kersey; Liu, Peng; Xu, Lai; Doubleday, Charles; Houk, Kendall N

2012-08-01

129

Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides.  

PubMed

Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions. PMID:25469760

Indra, Arindam; Menezes, Prashanth W; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Das, Chittaranjan; Tallarida, Massimo; Schmeißer, Dieter; Strasser, Peter; Driess, Matthias

2014-12-17

130

Density functional theory calculations on oxidative C-C bond cleavage and N-O bond formation of [Ru(II)(bpy)2(diamine)](2+) via reactive ruthenium imide intermediates.  

PubMed

DFT calculations are performed on [Ru(II)(bpy)2(tmen)](2+) (M1, tmen = 2,3-dimethyl-2,3-butanediamine) and [Ru(II)(bpy)2(heda)](2+) (M2, head = 2,5-dimethyl-2,5-hexanediamine), and on the oxidation reactions of M1 to give the C-C bond cleavage product [Ru(II)(bpy)2(NH=CMe2)2](2+) (M3) and the N-O bond formation product [Ru(II)(bpy)2(ONCMe2CMe2NO)](2+) (M4). The calculated geometrical parameters and oxidation potentials are in good agreement with the experimental data. As revealed by the DFT calculations, [Ru(II)(bpy)2(tmen)](2+) (M1) can undergo oxidative deprotonation to generate Ru-bis(imide) [Ru(bpy)2(tmen-4?H)](+) (A) or Ru-imide/amide [Ru(bpy)2(tmen-3?H)](2+) (A') intermediates. Both A and A' are prone to C-C bond cleavage, with low reaction barriers (?G(?)) of 6.8 and 2.9?kcal?mol(-1) for their doublet spin states (2)A and (2)A', respectively. The calculated reaction barrier for the nucleophilic attack of water molecules on (2)A' is relatively high (14.2?kcal?mol(-1)). These calculation results are in agreement with the formation of the Ru(II)-bis(imine) complex M3 from the electrochemical oxidation of M1 in aqueous solution. The oxidation of M1 with Ce(IV) in aqueous solution to afford the Ru(II)-dinitrosoalkane complex M4 is proposed to proceed by attack of the cerium oxidant on the ruthenium imide intermediate. The findings of ESI-MS experiments are consistent with the generation of a ruthenium imide intermediate in the course of the oxidation. PMID:25267445

Guan, Xiangguo; Law, Siu-Man; Tse, Chun-Wai; Huang, Jie-Sheng; Che, Chi-Ming

2014-11-10

131

Oxidation of a polycrystalline silver foil by reaction with ozone  

NASA Astrophysics Data System (ADS)

The surface oxidation of a polycrystalline silver foil by reaction with ozone (5 mol% O 3 in O 2) at 300 K and ambient pressure was investigated. The morphology, microstructure and chemical composition of the oxide scale which developed on the foil surface during exposure to ozone was characterised by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The surface of silver foil was rapidly oxidised upon contact with ozone, initially producing a thick Ag 2O protective film. After 10 min reaction, the oxide film thickness was around 8-10 ?m. SEM analysis revealed that Ag 2O film thickening occurred via a discontinuous film growth mechanism. Growth stresses, resulting from the large lattice volume mismatch between the oxide and the metal, caused the oxide film to crack and flake extensively during development. Spallation of the oxide film exposed fresh silver metal to ozone, which lead to further Ag 2O deposition. The continued recurrence of this process resulted in the formation a thick, discontinuous Ag 2O film on the silver foil. After foil exposure to ozone for 300 min, the oxide film thickness was 17-20 ?m. Furthermore, Ag 2O at the surface of the oxide film was slowly oxidised to AgO with prolonged exposure to ozone. The combined results of our experimental studies were used to develop a better understanding of the oxidation of silver surfaces by O 3.

Waterhouse, G. I. N.; Bowmaker, G. A.; Metson, J. B.

2001-11-01

132

Formal carbene insertion into C-C bond: Rh(I)-catalyzed reaction of benzocyclobutenols with diazoesters.  

PubMed

A Rh(I)-catalyzed formal carbene insertion into C-C bond of benzocyclobutenols has been realized by employing diazoesters as carbene precursors. The product indanol derivatives were obtained in good yields and in diastereoselective manner under mild reaction conditions. All-carbon quaternary center is constructed at the carbenic carbon. This catalytic reaction involves selective cleavage of C-C bond, Rh(I) carbene insertion, and intramolecular aldol reaction. PMID:24512084

Xia, Ying; Liu, Zhenxing; Liu, Zhen; Ge, Rui; Ye, Fei; Hossain, Mohammad; Zhang, Yan; Wang, Jianbo

2014-02-26

133

Reactions of Propylene Oxide on Supported Silver Catalysts: Insights into Pathways Limiting Epoxidation Selectivity  

SciTech Connect

The reactions of propylene oxide (PO) on silver catalysts were studied to understand the network of parallel and sequential reactions that may limit the selectivity of propylene epoxidation by these catalysts. The products of the anaerobic reaction of PO on Ag/a-Al2O3 were propanal, acetone and allyl alcohol for PO conversions below 2–3%. As the conversion of PO was increased either by increasing the temperature or the contact time, acrolein was formed at the expense of propanal, indicating that acrolein is a secondary reaction product in PO decomposition. With addition of oxygen to the feedstream the conversion of PO increased moderately. In contrast to the experiments in absence of oxygen, CO2 was a signi?cant product while the selectivity to propanal decreased as soon as oxygen was introduced in the system. Allyl alcohol disappeared completely from the product stream in the presence of oxygen, reacting to form acrolein and CO2. The product distribution may be explained by a network of reactions involving two types of oxametallacycles formed by ring opening of PO: one with the oxygen bonded to C1 (OMC1, linear) and the other with oxygen bonded to C2 (OMC2, branched). OMC1 reacts to form PO, propanal, and allyl alcohol.

Kulkarni, Apoorva; Bedolla-Pantoja, Marco; Singh, Suyash; Lobo, Raul F.; Mavrikakis, Manos; Barteau, Mark A.

2012-02-04

134

Intramolecular anodic olefin coupling reactions: using competition studies to probe the mechanism of oxidative cyclization reactions.  

PubMed

A competition experiment was designed so that the relative rates of anodic cyclization reactions under various electrolysis conditions can be determined. Reactions with ketene dithioacetal and enol ether-based substrates that use lithium methoxide as a base were shown to proceed through radical cation intermediates that were trapped by a sulfonamide anion. Results for the oxidative coupling of a vinyl sulfide with a sulfonamide anion using the same conditions were consistent with the reaction proceeding through a nitrogen-radical. PMID:20302359

Xu, Hai-Chao; Moeller, Kevin D

2010-04-16

135

Intramolecular Anodic Olefin Coupling Reactions: Using Competition Studies to Probe the Mechanism of Oxidative Cyclization Reactions  

PubMed Central

A competition experiment was designed so that the relative rates of anodic cyclization reactions under various electrolysis conditions can be determined. Reactions with ketene dithioacetal and enol ether-based substrates that use lithium methoxide as a base were shown to proceed through radical cation intermediates that were trapped by a sulfonamide anion. Results for the oxidative coupling of a vinyl sulfide with a sulfonamide anion using the same conditions were consistent with the reaction proceeding through a nitrogen-radical. PMID:20302359

Xu, Hai-Chao; Moeller, Kevin D.

2014-01-01

136

A critical study of the role of the surface oxide layer in titanium bonding  

NASA Technical Reports Server (NTRS)

The molecular understanding of the role which the surface oxide layer of the adherend plays in titanium bonding is studied. The effects of Ti6-4 adherends pretreatment, bonding conditions, and thermal aging of the lap shear specimens were studied. The use of the SEM/EDAX and ESCA techniques to study surface morphology and surface composition was emphasized. In addition, contact angles and both infrared and visible reflection spectroscopy were used in ancillary studies.

Dias, S.; Wightman, J. P.

1982-01-01

137

Improving the bond strength between steel rebar and concrete by oxidation treatments of the rebar  

SciTech Connect

Oxidation treatments of steel rebar by water immersion (2--5 days) and ozone exposure increased the bond strength between steel rebar and concrete by 14% and 22% respectively. The treatments slightly increased the electrical contact resistivity between rebar and concrete. Increase of the water immersion time to 7 or 10 days caused the bond strength to decrease to values still above that of the case without water treatment. The contact resistivity increased monotonically with the water immersion time.

Fu, X.; Chung, D.D.L. [State Univ. of New York, Buffalo, NY (United States). Composite Materials Research Lab.] [State Univ. of New York, Buffalo, NY (United States). Composite Materials Research Lab.

1996-10-01

138

Covalent organic frameworks formed with two types of covalent bonds based on orthogonal reactions.  

PubMed

Covalent organic frameworks (COFs) are excellent candidates for various applications. So far, successful methods for the constructions of COFs have been limited to a few condensation reactions based on only one type of covalent bond formation. Thus, the exploration of a new judicious synthetic strategy is a crucial and emergent task for the development of this promising class of porous materials. Here, we report a new orthogonal reaction strategy to construct COFs by reversible formations of two types of covalent bonds. The obtained COFs consisting of multiple components show high surface area and high H2 adsorption capacity. The strategy is a general protocol applicable to construct not only binary COFs but also more complicated systems in which employing regular synthetic methods did not work. PMID:25581488

Zeng, Yongfei; Zou, Ruyi; Luo, Zhong; Zhang, Huacheng; Yao, Xin; Ma, Xing; Zou, Ruqiang; Zhao, Yanli

2015-01-28

139

Reaction bonded silicon carbide material characteristics as related to its use in high power laser systems  

NASA Astrophysics Data System (ADS)

Reaction bonded silicon carbide (RB SiC) is a durable material that is well-suited for use as a high power laser mirror substrate. The reaction bonded material has a low mass density, a high Young's Modulus, good thermal conductivity, and a very low coefficient of thermal expansion. All of these properties are beneficial in mirror substrates used in multikilowatt lasers. In conjunction with the development of RB SiC, special polishing processes, fabrication processes, and coatings have also been developed. In this paper we will present a comparison of the material properties of RB SiC and other mirror materials currently used in high power lasers. A brief overview of the critical fabrication and coating processes will also be reviewed. Finally, we will present thermal heat load test data showing the surface deformation of various high power mirrors used under heat loads typically found in laser systems operating at average powers greater than 10 kilowatts.

Pitschman, Matthew; Miller, Travis; Hedges, Alan R.; Rummel, Steve

2014-09-01

140

Assessment of density functional theory for thermochemical approaches based on bond separation reactions.  

PubMed

The recently proposed ATOMIC protocol is a fully ab initio thermochemical protocol that rests upon the concept of bond separation reactions (BSRs) to correct for systematic errors of composite wave function approaches. It achieves high accuracy for atomization energies and derived heats of formation if basis set requirements for all contributing components are balanced carefully. The present work explores the potential of density functionals as possible replacements of composite wave function approaches in the ATOMIC protocol. Twenty density functionals are examined for their accuracy in thermochemical predictions based on calculated bond-separation energies and precomputed high-level data for the small parent molecules entering BSRs. The best density functionals outperform CCSD (coupled cluster with singles and doubles excitations), but none reaches the accuracy of well-balanced composite wave function approaches that consider quasiperturbational connected triples excitations at least with small basis sets. Some functionals show unexpected problems with bond separation reactions and are analyzed further with a model of empirically calibrated bond additivity corrections. Finally, the benefit of adding empirical dispersion terms to common density functionals is analyzed in the context of BSR-corrected thermochemistry. PMID:23214917

Bakowies, Dirk

2013-01-10

141

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces  

NASA Technical Reports Server (NTRS)

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

Napier, Mary E.; Stair, Peter C.

1992-01-01

142

Radiation response of reaction-bonded and sintered SiC: Effects of boron isotopes  

NASA Astrophysics Data System (ADS)

The response of mechanical, thermal and microstructural properties of reaction-bonded SiC and sintered SiC were studied after reactor irradiation. The effects of 10B(n,?) 7Li reaction products were studied by doping the material from which samples were produced with enriched isotopes of 10B, 11B and natural boron. Silicon carbide doped with 10B exhibits a pronounced effect on the fracture strength. The thermal diffusivity decrease can account for the lowering of the resistance against thermal shock of irradiated material.

Carey, A. M.; Pineau, F. J.; Lee, C. W.; Corelli, J. C.

143

Brazing of reaction-bonded silicon carbide and Inconel 600 with an iron-based alloy  

Microsoft Academic Search

The objective of the present work was to join reaction-bonded silicon carbide to Inconel 600 (IN600, a nickel-based superalloy) for use in high temperature applications by brazing with an Fe-20wt% alloy. This joining method resulted in the molten filler metal reacting with the IN600 to form a Ni-Fe-Si solution, which in turn formed a liquid with the free silicon phase

J. R. McDermid; R. A. L. Drew

1990-01-01

144

Recent advances in reaction bonded silicon carbide optics and optical systems  

Microsoft Academic Search

SSG Precision Optronics, Inc. (SSG) has recently developed a number of Reaction Bonded (RB) Silicon Carbide (SiC) optical systems for space-based remote sensing and astronomical observing applications. RB SiC's superior material properties make it uniquely well suited to meet the image quality and long term dimensional stability requirements associated with these applications. An overview of the RB SiC manufacturing process

Joseph Robichaud; Jay Schwartz; David Landry; William Glenn; Brian Rider; Michael Chung

2005-01-01

145

Reaction bonded silicon nitride prepared from wet attrition-milled silicon. [fractography  

NASA Technical Reports Server (NTRS)

Silicon powder wet milled in heptane was dried, compacted into test bar shape, helium-sintered, and then reaction bonded in nitrogen-4 volume percent hydrogen. As-nitrided bend strengths averaged approximately 290 MPa at both room temperature and 1400 C. Fracture initiation appeared to be associated with subsurface flaws in high strength specimens and both subsurface and surface flaws in low strength specimens.

Herball, T. P.; Glasgow, T. K.; Shaw, N. J.

1980-01-01

146

Low pressure injection moulding of SiC platelet reinforced reaction bonded silicon nitride  

Microsoft Academic Search

Reaction-bonded Si3N4 toughened by oriented SiC platelets was fabricated via low pressure injection moulding (LPIM). Initially, the rheology of ceramic suspensions was optimized with respect to solid content, SiC platelet loading, particle surface properties and binder composition. Surface active additives were used to modify the particle–polymeric binder interphase in order to prevent particle reagglomeration, to reduce the viscosity and\\/or to

T KOSMAC; R JANSSEN

1997-01-01

147

Effect of hot isostatic pressing on reaction-bonded silicon nitride  

NASA Technical Reports Server (NTRS)

Specimens of nearly theoretical density have been obtained through the isostatic hot pressing of reaction-bonded silicon nitride under 138 MPa of pressure for two hours at 1850, 1950, and 2050 C. An amorphous phase that is introduced by the hot isostatic pressing partly accounts for the fact that while room temperature flexural strength more than doubles, the 1200 C flexural strength increases significantly only after pressing at 2050 C.

Watson, G. K.; Moore, T. J.; Millard, M. L.

1984-01-01

148

Diborane(4)-metal bonding: between hydrogen bridges and frustrated oxidative addition.  

PubMed

The metal complexes [M{HB(hpp)}(2)(CO)(4)] (M = Cr, Mo or W) and [M(cod){HB(hpp)}(2)Cl] (M = Rh or Ir) of the doubly-base stabilized diborane(4) ligand [HB(hpp)](2) were fully characterized and their bonding nature was investigated in detail. While bonding in the group 6 complexes predominantly occurs through the hydrogen atoms, the metal-ligand interaction in the group 9 complexes can be regarded as an early stage oxidative addition of the boron-boron bond leading to diboryl compounds. PMID:22526934

Wagner, Arne; Kaifer, Elisabeth; Himmel, Hans-Jörg

2012-05-28

149

Spin-assisted covalent bond mechanism in ``charge-ordering'' perovskite oxides  

NASA Astrophysics Data System (ADS)

First-principles density functional calculations on the metal-insulator transition (MIT) in perovskite CaFeO3 point to local ferromagnetic coupling as the microscopic origin for the electronic “charge order” transition. Our atomic, electronic, and magnetic structure analyses reveal that the MIT results from a spin-assisted covalent bonding mechanism between the O 2p and Fe 3d states with anisotropic Fe-O bonds and negligible intersite Fe-Fe charge transfer. We suggest that control of the lattice distortions, which mediate the covalent bond formation, in oxides containing late transition-metal row cations in high valence states provides a platform to tailor electronic transitions.

Cammarata, Antonio; Rondinelli, James M.

2012-11-01

150

Reaction dynamics. Extremely short-lived reaction resonances in Cl + HD (v = 1) ? DCl + H due to chemical bond softening.  

PubMed

The Cl + H2 reaction is an important benchmark system in the study of chemical reaction dynamics that has always appeared to proceed via a direct abstraction mechanism, with no clear signature of reaction resonances. Here we report a high-resolution crossed-molecular beam study on the Cl + HD (v = 1, j = 0) ? DCl + H reaction (where v is the vibrational quantum number and j is the rotational quantum number). Very few forward scattered products were observed. However, two distinctive peaks at collision energies of 2.4 and 4.3 kilocalories per mole for the DCl (v' = 1) product were detected in the backward scattering direction. Detailed quantum dynamics calculations on a highly accurate potential energy surface suggested that these features originate from two very short-lived dynamical resonances trapped in the peculiar H-DCl (v' = 2) vibrational adiabatic potential wells that result from chemical bond softening. We anticipate that dynamical resonances trapped in such wells exist in many reactions involving vibrationally excited molecules. PMID:25554783

Yang, Tiangang; Chen, Jun; Huang, Long; Wang, Tao; Xiao, Chunlei; Sun, Zhigang; Dai, Dongxu; Yang, Xueming; Zhang, Dong H

2015-01-01

151

Free-radical production and oxidative reactions of hemoglobin.  

PubMed Central

Mechanisms of autoxidation of hemoglobin, and its reactions with H2O2, O2-, and oxidizing or reducing xenobiotics are discussed. Reactive intermediates of such reactions can include drug free radicals, H2O2, and O2-, as well as peroxidatively active ferrylhemoglobin and methemoglobin-H2O2. The contributions of these species to hemoglobin denaturation and drug-induced hemolysis, and the actions of various protective agents, are considered. PMID:3007097

Winterbourn, C C

1985-01-01

152

Final Report: Catalytic Hydrocarbon Reactions over Supported Metal Oxides, August 1, 1995 - July 31, 1999  

SciTech Connect

The research program focused on the catalysis of hydrodesulfurization (HDS) over molybdenum-based catalysts and how catalyst composition, redox ability, structure and neighboring sites control the catalytic properties of metal oxides. We sought to understand the catalytic features/sites that control hydrogenation, hydrogenolysis, and isomerization during HDS. Unprompted silica-supported molybdenum oxides and molybdenum sulfides were studied. Model catalyst systems were prepared from organometallic precursors or cluster compounds to generate supported structures that feature Mo(II) and Mo(IV) cations that are isolated or in ensembles and that have either Mo-O or Mo-S bonds. Conventional MOS{sub 2} catalysts, which contain both edge and rim sites, were be studied. Finally, single-layer MOS{sub 2} structures were also prepared from 2H-MoS{sub 2} powder so that the model systems could be compared against a disulfide catalyst that only involves rim sites. Catalytic reactions for thiophene and tetrahydrothione were studied over the various catalysts. Oxidation states were determined using X-ray photoelectron spectroscopy. X-ray crystallography was used to characterize and follow changes in the MOS{sub 2} structures. The program on metal oxides prepared supported oxides that have a specific structure and oxidation state to serve as model templates for the more complex commercial catalysts and then employed these structures in reaction studies. This focus area examined the relationships between structure and cation redox characteristics in oxidation catalysis. Infrared and Raman spectroscopy were used to characterize the cations and reaction intermediates.

Ekerdt, John G.

1999-07-31

153

Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product  

NASA Technical Reports Server (NTRS)

Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

1997-01-01

154

Favorite Demonstration: Demonstrating Indigo Carmine Oxidation-Reduction Reactions--A Choreography for Chemical Reactions  

NSDL National Science Digital Library

The indigo carmine demonstration (Ferguson et al. 1973), also referred to as a traffic-light demonstration (Flinn Scientific 2007a), is an example of a set of oxidation-reduction reactions that occurs within one solution. This type of demonstration can be used to introduce the concept of chemical reaction to undergraduate nonscience majors. Through their observations guided by the instructor, students begin to develop and construct the following concepts: color changes, reaction rates, reversible reactions, energy requirements (endothermic/exothermic), and equilibrium.

Majerich, David M.; Schmuckler, Joseph S.

2008-03-01

155

Modelling the reaction behavior in reactive multilayer systems on substrates used for wafer bonding  

NASA Astrophysics Data System (ADS)

Exothermic self-propagating high-temperature synthesis of intermetallic compounds attain increasing interest in the field of wafer bonding in microelectronics and microsystems technology due to local heat generation. Numerical models of self-sustaining reactions in thin multilayer films can be used to predict velocity and shape of the reaction front. This work deals with heat losses to various substrate materials and material compounds used for wafer bonding as well as the prediction of minimal numbers of bilayers required for a self-propagating reaction front. We introduced a cylindrically symmetric finite element approach. In addition to that, the effect of temperature-dependent specific heat capacities was investigated. Numerical computations were performed for Pd/Al multilayers and are compared to experimental data. It was found that the developed formalism is suitable to determine the mutual influence of heat losses and reaction properties. Furthermore, it was demonstrated that minimal numbers of bilayers can be determined more precisely by including temperature-dependent specific heat capacities.

Masser, Robin; Braeuer, Joerg; Gessner, Thomas

2014-06-01

156

Predicting gold-mediated catalytic oxidative-coupling reactions from single crystal studies.  

PubMed

Though metallic gold is chemically inert under ambient conditions, its surface is extremely reactive and selective for many key oxidative chemical transformations when activated by atomic oxygen. A molecular-level understanding of the mechanism of these processes could allow researchers to design "green" catalytic processes mediated by gold-based materials. This Account focuses on the mechanistic framework for oxidative-coupling reactions established by fundamental studies on oxygen-activated Au(111) and the application of these principles to steady-state catalytic conditions. We also discuss the importance of the paradigms discovered both for predicting new oxidative-coupling reactions and for understanding existing literature. The mechanistic framework for the oxidative coupling of alcohols on gold surfaces predicts that new oxidative-coupling reactions should occur between amines and aldehydes and amines and alcohols as well as through alcohol carbonylation. Adsorbed atomic oxygen on the gold surface facilitates the activation of the substrates, and nucleophilic attack and ?-H elimination are the two fundamental reactions that propagate the versatile chemistry that ensues. In the self-coupling of primary alcohols, adsorbed atomic oxygen first activates the O-H bond in the hydroxyl group at ?150 K, which forms the corresponding adsorbed alkoxy groups. The rate-limiting step of the self-coupling reaction is the ?-H elimination reaction of alkoxy groups to form the corresponding aldehydes and occurs with an activation barrier of approximately 12 kcal/mol. The remaining alkoxy groups nucleophilically attack the electron-deficient aldehyde carbonyl carbon to yield the adsorbed "hemiacetal". This intermediate undergoes facile ?-H elimination to produce the final coupling products, esters with twice the number of carbon atoms as the starting alcohols. This mechanistic insight suggests that cross-coupling occurs between alcohols and aldehydes, based on the logic that the nucleophilic reaction should be independent of the origin of the aldehydes, whether formed in situ or introduced externally. As a further example, adsorbed amides, formed from deprotonation of amines by atomic oxygen, can also attack aldehydes nucleophilically to yield the corresponding amides. Our mechanistic framework can also explain more elaborate gold-mediated chemistry, such as a unique carbonylation reaction via two subsequent nucleophilic attacks. These model studies on well-defined Au(111) at low pressure predict steady-state catalytic behavior on nanoporous gold under practical conditions. The fundamental principles of this research can also explain many other oxygen-assisted gold-mediated reactions observed under ambient conditions. PMID:24387694

Xu, Bingjun; Madix, Robert J; Friend, Cynthia M

2014-03-18

157

Some kinetic aspects of unsteady-state partial oxidation reactions. Dynamic processes on metal oxide surfaces  

Microsoft Academic Search

It is shown that steady-state kinetic data do not allow the discrimination between the redox and associated mechanisms of the partial oxidation reactions. A discrimination between these mechanisms was performed using transient experiments. The obtained rate expressions are in agreement with experimental kinetic data for catalytic partial oxidation of o-xylene.An influence of the conjugate oxidation of a catalyst surface on

Yuri I. Pyatnitsky; Nina I. Ilchenko

1996-01-01

158

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

DOEpatents

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.

Cortright, Randy D. (Madison, WI); Dumesic, James A. (Verona, WI)

2011-01-18

159

Regioselective gold-catalyzed oxidative C-N bond formation.  

PubMed

A novel protocol for the regioselective intermolecular amination of various arenes has been developed. By using an I(III) oxidant in the presence of a Au(I) catalyst, a direct and novel route for regioselectively accessing a variety of substituted aniline moieties has been achieved with yields as high as 90%. Mechanistic insight suggests that regioselectivity can be predicted based on electrophilic aromatic metalation patterns. PMID:25539392

Marchetti, Louis; Kantak, Abhishek; Davis, Riley; DeBoef, Brenton

2015-01-16

160

Reversibility of heme-nitric oxide reactions for use in an inhaled nitric oxide sensor  

NASA Astrophysics Data System (ADS)

Nitric Oxide is a simple gaseous compound which serves as a regulatory molecule in a number of physiological processes. Due to its biological role as a potent local vasodilator,there has been widespread interest in the therapeutic use of gaseous nitric oxide a selective pulmonary vasodilator. Our goal is the development of a sensor for the direct and continuous measurement of inhaled nitric oxide concentrations. This study evaluated the reversibility of potential sensing compounds upon reaction with nitric oxide. Previously, absorption spectroscopy was used to study the sensitivity of the Fe II, Fe III and oxygenated forms of three biologically active hemes known to rapidly react with NO: hemoglobin, myoglobin, and cytochrome-c. This study focused on the photo-reversibility of the hem's reaction with nitric oxide. Hemoglobin, myoglobin and cytochrome-c in the Fe III state reversibly reacted with nitric oxide. Hemoglobin and myoglobin in the Fe II state non-reversibly reacted with nitric oxide to form an unstable product. Cytochrome-c (FeII) does not react with nitric oxide. The oxy forms of hemoglobin and myoglobin react with nitric oxide to form their respective met forms, unreversible via photolysis. For all reversible reactions, photolysis was gradual and complete within five minutes.

Parikh, Bhairavi R.; Soller, Babs R.; Rencus, Tal

1997-06-01

161

Efficient and directed peptide bond formation in the gas phase via ion/ion reactions  

PubMed Central

Amide linkages are among the most important chemical bonds in living systems, constituting the connections between amino acids in peptides and proteins. We demonstrate the controlled formation of amide bonds between amino acids or peptides in the gas phase using ion/ion reactions in a mass spectrometer. Individual amino acids or peptides can be prepared as reagents by (i) incorporating gas phase–labile protecting groups to silence otherwise reactive functional groups, such as the N terminus; (ii) converting the carboxyl groups to the active ester of N-hydroxysuccinimide; and (iii) incorporating a charge site. Protonation renders basic sites (nucleophiles) unreactive toward the N-hydroxysuccinimide ester reagents, resulting in sites with the greatest gas phase basicities being, in large part, unreactive. The N-terminal amines of most naturally occurring amino acids have lower gas phase basicities than the side chains of the basic amino acids (i.e., those of histidine, lysine, or arginine). Therefore, reagents may be directed to the N terminus of an existing “anchor” peptide to form an amide bond by protonating the anchor peptide’s basic residues, while leaving the N-terminal amine unprotonated and therefore reactive. Reaction efficiencies of greater than 30% have been observed. We propose this method as a step toward the controlled synthesis of peptides in the gas phase. PMID:24474750

McGee, William M.; McLuckey, Scott A.

2014-01-01

162

High temperature thermoelectric characterization of III-V semiconductor thin films by oxide bonding  

E-print Network

Page 1 High temperature thermoelectric characterization of III-V semiconductor thin films by oxide bonding technique is developed for high temperature thermoelectric characterization of the thin film III-W-N diffusion barrier. A thermoelectric material, thin film ErAs:InGaAlAs metal/semiconductor nanocomposite

Bowers, John

163

Diffusion bonding of aluminium oxide to stainless steel using stress relief interlayers  

Microsoft Academic Search

Aluminium oxide was diffusion bonded to AISI 304 steel using Ti, Cu or Mo as interlayer materials. It was observed that Ti joins easily to both ceramic and steel parts, giving an average shear strength equal to 20 MPa. However, within the experimental conditions applied, the adhesion between Al2O3 and Cu or Mo was unsuccessful. A finite element modelling (FEM)

Dilermando Travessa; Maurizio Ferrante; Gert den Ouden

2002-01-01

164

Kraft lignin\\/poly(ethylene oxide) blends: Effect of lignin structure on miscibility and hydrogen bonding  

Microsoft Academic Search

Blends of poly(ethylene oxide) (PEO) with softwood kraft lignin (SKL) were prepared by thermal blending. The miscibility behavior and hydrogen bonding of the blends were investigated by differential scanning calo- rimetry (DSC) and Fourier transform infrared (FTIR) spec- troscopy. The experimental results indicate that PEO was miscible with SKL, as shown by the existence of a single glass-transition temperature over

Satoshi Kubo; John F. Kadla

2005-01-01

165

Surface rumpling of a (Ni, Pt)Al bond coat induced by cyclic oxidation  

Microsoft Academic Search

The surface of an initially flat, platinum-modified nickel aluminide bond coat formed on a single crystal superalloy is shown to progressively roughen (“rumple”) with thermal cycling in air. Far less surface roughening occurs after isothermal oxidation or after the same number of thermal cycles but with a shorter high-temperature exposure in each cycle. Mechanisms of the observed rumpling and the

V. K Tolpygo; D. R Clarke

2000-01-01

166

Development of New Hydrogen Bond Donor Catalytic Methods and Their Applications to the Diels-Alder Reaction of Nitroalkenes.  

E-print Network

??The development of LUMO lowering double hydrogen bond donor catalysts, 2-aminopyridinium, for the Diels-Alder reaction of nitroalkenes is described. In addition, helical chiral 2-aminopyridinium variants… (more)

Jimenez, Andreina A

2012-01-01

167

Metal-induced B-H bond activation: reactions between half-sandwich Ir and Rh complexes with carboranylthioamide.  

PubMed

Novel half-sandwich metal (Ir, Rh) complexes constructed from carboranylthioamide ligands containing an unexpected metal-boron bond were synthesized and characterized. The strong base n-butyllithium is demonstrated to be necessary in the reaction process. PMID:25492590

Xu, Bin; Wang, Yin-Ping; Yao, Zi-Jian; Jin, Guo-Xin

2014-12-23

168

Carbon dioxide as a carbon source in organic transformation: carbon-carbon bond forming reactions by transition-metal catalysts.  

PubMed

Recent carbon-carbon bond forming reactions of carbon dioxide with alkenes, alkynes, dienes, aryl zinc compounds, aryl boronic esters, aryl halides, and arenes having acidic C-H bonds are reviewed in which transition-metal catalysts play an important role. PMID:22859266

Tsuji, Yasushi; Fujihara, Tetsuaki

2012-10-14

169

Water O-H bond activation by gas-phase plutonium atoms: reaction mechanisms and ab initio molecular dynamics study.  

PubMed

A thorough description of the reaction mechanisms, taking into account different possible spin states, offers insights into the gas-phase reaction of plutonium atoms with water. Two possible reactions (isomerization and dehydrogenation) are presented. These reactions are found to be exothermic, with the best thermochemical conditions observed for the dehydrogenation reaction at around 23.5 kcal?mol(-1). The nature of the chemical-bonding evolution along the reaction pathways are investigated by employing various methods including electron localization function, atoms in molecules, and Mayer bond order. Total, partial, and overlap population density of state diagrams and analyses are also presented. Reaction rates at elevated temperatures (T=298-2?000 K) are calculated by using variational transition-state theory with one-dimensional tunneling effects. In dynamics simulations, only the dehydrogenation reaction is observed, and found to be in good agreement with experimental values. PMID:25044793

Li, Peng; Niu, Wenxia; Gao, Tao; Wang, Hongyan

2014-10-01

170

Theoretical study of the reaction formalhydrazone with singlet oxygen. Fragmentation of the C=N bond, ene reaction and other processes.  

PubMed

Photobiologic and synthetic versatility of hydrazones has not yet been established with (1)O2 as a route to commonly encountered nitrosamines. Thus, to determine whether the "parent" reaction of formalhydrazone and (1)O2 leads to facile C=N bond cleavage and resulting nitrosamine formation, we have carried out CCSD(T)//DFT calculations and analyzed the energetics of the oxidation pathways. A [2 + 2] pathway occurs via diradicals and formation of 3-amino-1,2,3-dioxazetidine in a 16 kcal/mol(-1) process. Reversible addition or physical quenching of (1)O2 occurs either on the formalhydrazone carbon for triplet diradicals at 2-3 kcal mol(-1), or on the nitrogen (N(3)) atom forming zwitterions at ~15 kcal/mol(-1), although the quenching channel by charge-transfer interaction was not computed. The computations also predict a facile conversion of formalhydrazone and (1)O2 to hydroperoxymethyl diazene in a low-barrier 'ene' process, but no 2-amino-oxaziridine-O-oxide (perepoxide-like) intermediate was found. A Benson-like analysis (group increment calculations) on the closed-shell species are in accord with the quantum chemical results. PMID:24354600

Rudshteyn, Benjamin; Castillo, Alvaro; Ghogare, Ashwini A; Liebman, Joel F; Greer, Alexander

2014-01-01

171

Variations in pore structure of reaction-bonded silicon nitride /RBSN/  

NASA Technical Reports Server (NTRS)

A discussion is presented relating the observed pore structures (sizes) to the reaction mechanisms in reaction-bonded silicon nitride (alpha- and beta-Si3N4) on the basis of information available from the literature. While the techniques for reducing the residual macroporosity are quite well-developed for reaction-bonded Si3N4 (RBSN), it is important to be aware of three other orders of magnitude for porosity present in RBSN as a result of the nitriding process itself, and how these types of nitridation-induced porosity can be controlled. For ease of description, these types of nitridation-induced porosity are called micropores, nanopores, and picopores in order of their decreasing size. A scanning electron micrograph is presented, showing nanopores isolated in the unreacted Si and picopores in the alpha-matte Si3N4. The assumption that an alpha-matte growth mechanism is active explains the occurrence of nanopores and their partial filling with alpha-Si3N4, leaving behind very fine-grained alpha-matte and picopores.

Danforth, S. C.; Richman, M. H.

1979-01-01

172

Rhodium-catalyzed C-h activation of phenacyl ammonium salts assisted by an oxidizing C-N bond: a combination of experimental and theoretical studies.  

PubMed

Rh(III)-catalyzed C-H activation assisted by an oxidizing directing group has evolved to a mild and redox-economic strategy for the construction of heterocycles. Despite the success, these coupling systems are currently limited to cleavage of an oxidizing N-O or N-N bond. Cleavage of an oxidizing C-N bond, which allows for complementary carbocycle synthesis, is unprecedented. In this article, ?-ammonium acetophenones with an oxidizing C-N bond have been designed as substrates for Rh(III)-catalyzed C-H activation under redox-neutral conditions. The coupling with ?-diazo esters afforded benzocyclopentanones, and the coupling with unactivated alkenes such as styrenes and aliphatic olefins gave ortho-olefinated acetophenoes. In both systems the reactions proceeded with a broad scope, high efficiency, and functional group tolerance. Moreover, efficient one-pot coupling of diazo esters has been realized starting from ?-bromoacetophenones and triethylamine. The reaction mechanism for the coupling with diazo esters has been studied by a combination of experimental and theoretical methods. In particular, three distinct mechanistic pathways have been scrutinized by DFT studies, which revealed that the C-H activation occurs via a C-bound enolate-assisted concerted metalation-deprotonation mechanism and is rate-limiting. In subsequent C-C formation steps, the lowest energy pathway involves two rhodium carbene species as key intermediates. PMID:25569022

Yu, Songjie; Liu, Song; Lan, Yu; Wan, Boshun; Li, Xingwei

2015-02-01

173

Method for facilitating catalyzed oxidation reactions, device for facilitating catalyzed oxidation reactions  

DOEpatents

A catalytic process for the oxidation of organic. Oxygen is loaded into a metal foil by heating the foil while in contact with an oxygen-containing fluid. After cooling the oxygen-activated foil to room temperature, oxygen diffuses through the foil and oxidizes reactants exposed to the other side of the foil.

Beuhler, Robert J. (East Moriches, NY); White, Michael G. (Blue Point, NY); Hrbek, Jan (Rocky Point, NY)

2006-08-15

174

C-C bond fragmentation by Grob/Eschenmoser reactions, applications in dendrimer synthesis.  

PubMed

C-C bond fragmentation of structurally diverse carbocycles has been applied to the divergent synthesis of dendrimers. The fragmentation has been paired to deprotection or thio-Michael reaction, allowing the preparation of a fourth generation dendrimer of narrow molecular weight distribution. Methodologies to increase water solubility have been examined using appended carboxylic acid or oligoether moieties. In addition, incorporation of chiral prolinol derivatives has resulted in the synthesis of dendrimers that have been shown to catalyse the ?-amination of aldehydes in good yield and modest enantioselectivity. PMID:23925375

Hierold, Judith; Lupton, David W

2013-09-28

175

Bend strengths of reaction bonded silicon nitride prepared from dry attrition milled silicon powder  

NASA Technical Reports Server (NTRS)

Dry attrition milled silicon powder was compacted, sintered in helium, and reaction bonded in nitrogen-4 volume percent hydrogen. Bend strengths of bars with as-nitrided surfaces averaged as high as 210 MPa at room temperature and 220 MPa at 1400 C. Bars prepared from the milled powder were stronger than those prepared from as-received powder at both room temperature and at 1400 C. Room temperature strength decreased with increased milling time and 1400 C strength increased with increased milling time.

Herbell, T. P.; Glasgow, T. K.

1979-01-01

176

Reactions of metal ions at surfaces of hydrous iron oxide  

USGS Publications Warehouse

Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10-8.00 or 10-9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn3O4 can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn4+ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10-9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems. ?? 1977.

Hem, J.D.

1977-01-01

177

Hypochlorous acid-mediated protein oxidation: how important are chloramine transfer reactions and protein tertiary structure?  

PubMed

Hypochlorous acid (HOCl) is a powerful oxidant generated from H2O2 and Cl- by the heme enzyme myeloperoxidase, which is released from activated leukocytes. HOCl possesses potent antibacterial properties, but excessive production can lead to host tissue damage that occurs in numerous human pathologies. As proteins and amino acids are highly abundant in vivo and react rapidly with HOCl, they are likely to be major targets for HOCl. In this study, two small globular proteins, lysozyme and insulin, have been oxidized with increasing excesses of HOCl to determine whether the pattern of HOCl-mediated amino acid consumption is consistent with reported kinetic data for isolated amino acids and model compounds. Identical experiments have been carried out with mixtures of N-acetyl amino acids (to prevent reaction at the alpha-amino groups) that mimic the protein composition to examine the role of protein structure on reactivity. The results indicate that tertiary structure facilitates secondary chlorine transfer reactions of chloramines formed on His and Lys side chains. In light of these data, second-order rate constants for reactions of Lys side chain and Gly chloramines with Trp side chains and disulfide bonds have been determined, together with those for further oxidation of Met sulfoxide by HOCl and His side chain chloramines. Computational kinetic models incorporating these additional rate constants closely predict the experimentally observed amino acid consumption. These studies provide insight into the roles of chloramine formation and three-dimensional structure on the reactions of HOCl with isolated proteins and demonstrate that kinetic models can predict the outcome of HOCl-mediated protein oxidation. PMID:17676767

Pattison, David I; Hawkins, Clare L; Davies, Michael J

2007-08-28

178

Photocatalytic reaction centers in two-dimensional titanium oxide crystals.  

PubMed

Co-catalysts play an important role in photocatalytic water splitting. The co-catalyst is generally deposited in the form of nanoparticles on the catalyst surface, and is believed to provide water oxidation and reduction sites. However, the minimum size of a co-catalyst that can function as a reaction site and the detailed local environment of the photocatalytic reaction centers are not yet fully understood. Here, we show that even isolated single-atom Rh dopants in two-dimensional titanium oxide crystals can effectively act as co-catalysts for the water-splitting reaction. At an optimal doping concentration, the hydrogen production rate is increased substantially in comparison to that found with the undoped crystals. We also present first-principles simulations based on density functional theory to provide insights into the atomic-scale mechanism by which the isolated Rh dopants induce changes to the dissociation reaction energy landscape. These results provide new insights for better understanding the role of the co-catalyst in the photocatalytic reaction. PMID:25479408

Ida, Shintaro; Kim, Namhoon; Ertekin, Elif; Takenaka, Sakae; Ishihara, Tatsumi

2015-01-14

179

Crystal Structure of Reduced and of Oxidized Peroxiredoxin IV Enzyme Reveals a Stable Oxidized Decamer and a Non-disulfide-bonded Intermediate in the Catalytic Cycle*  

PubMed Central

Peroxiredoxin IV (PrxIV) is an endoplasmic reticulum-localized enzyme that metabolizes the hydrogen peroxide produced by endoplasmic reticulum oxidase 1 (Ero1). It has been shown to play a role in de novo disulfide formation, oxidizing members of the protein disulfide isomerase family of enzymes, and is a member of the typical 2-Cys peroxiredoxin family. We have determined the crystal structure of both reduced and disulfide-bonded, as well as a resolving cysteine mutant of human PrxIV. We show that PrxIV has a similar structure to other typical 2-Cys peroxiredoxins and undergoes a conformational change from a fully folded to a locally unfolded form following the formation of a disulfide between the peroxidatic and resolving cysteine residues. Unlike other mammalian typical 2-Cys peroxiredoxins, we show that human PrxIV forms a stable decameric structure even in its disulfide-bonded state. In addition, the structure of a resolving cysteine mutant reveals an intermediate in the reaction cycle that adopts the locally unfolded conformation. Interestingly the peroxidatic cysteine in the crystal structure is sulfenylated rather than sulfinylated or sulfonylated. In addition, the peroxidatic cysteine in the resolving cysteine mutant is resistant to hyper-oxidation following incubation with high concentrations of hydrogen peroxide. These results highlight some unique properties of PrxIV and suggest that the equilibrium between the fully folded and locally unfolded forms favors the locally unfolded conformation upon sulfenylation of the peroxidatic cysteine residue. PMID:21994946

Cao, Zhenbo; Tavender, Timothy J.; Roszak, Aleksander W.; Cogdell, Richard J.; Bulleid, Neil J.

2011-01-01

180

Raman spectroscopic characterization of the core-rim structure in reaction bonded boron carbide ceramics  

NASA Astrophysics Data System (ADS)

Raman spectroscopy was used to characterize the microstructure of reaction bonded boron carbide ceramics. Compositional and structural gradation in the silicon-doped boron carbide phase (rim), which develops around the parent boron carbide region (core) due to the reaction between silicon and boron carbide, was evaluated using changes in Raman peak position and intensity. Peak shifting and intensity variation from the core to the rim region was attributed to changes in the boron carbide crystal structure based on experimental Raman observations and ab initio calculations reported in literature. The results were consistent with compositional analysis determined by energy dispersive spectroscopy. The Raman analysis revealed the substitution of silicon atoms first into the linear 3-atom chain, and then into icosahedral units of the boron carbide structure. Thus, micro-Raman spectroscopy provided a non-destructive means of identifying the preferential positions of Si atoms in the boron carbide lattice.

Jannotti, Phillip; Subhash, Ghatu; Zheng, James Q.; Halls, Virginia; Karandikar, Prashant G.; Salamone, S.; Aghajanian, Michael K.

2015-01-01

181

Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution.  

PubMed

Reactions involving minerals and glasses in water are slow and difficult to probe spectroscopically but are fundamental to the performance of oxide materials in green technologies such as automotive thermoelectric power generation, CO2 capture and storage and water-oxidation catalysis; these must be made from geochemically common elements and operate in hydrous environments. Polyoxometalate ions (POMs) have structures similar to condensed oxide phases and can be used as molecular models of the oxide/water interface. Oxygen atoms in POM exchange isotopes at different rates, but, at present, there is no basis for predicting how the coordination environment and metal substitution influences rates and mechanisms. Here we identify low-energy metastable configurations that form from the breaking of weak bonds between metals and underlying highly coordinated oxygen atoms, followed by facile hydroxide, hydronium or water addition. The mediation of oxygen exchange by these stuffed structures suggests a new view of the relationship between structure and reactivity at the oxide/solution interface. PMID:22231599

Rustad, James R; Casey, William H

2012-03-01

182

Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution  

NASA Astrophysics Data System (ADS)

Reactions involving minerals and glasses in water are slow and difficult to probe spectroscopically but are fundamental to the performance of oxide materials in green technologies such as automotive thermoelectric power generation, CO2 capture and storage and water-oxidation catalysis; these must be made from geochemically common elements and operate in hydrous environments. Polyoxometalate ions (POMs) have structures similar to condensed oxide phases and can be used as molecular models of the oxide/water interface. Oxygen atoms in POM exchange isotopes at different rates, but, at present, there is no basis for predicting how the coordination environment and metal substitution influences rates and mechanisms. Here we identify low-energy metastable configurations that form from the breaking of weak bonds between metals and underlying highly coordinated oxygen atoms, followed by facile hydroxide, hydronium or water addition. The mediation of oxygen exchange by these stuffed structures suggests a new view of the relationship between structure and reactivity at the oxide/solution interface.

Rustad, James R.; Casey, William H.

2012-03-01

183

Identification and cleavage of breakable single bonds by selective oxidation, reduction, and hydrolysis. Annual report, October 1, 1980-September 30, 1981  

SciTech Connect

The objective of this project is to determine the structure of bituminous coal by determining the proportions of the various kinds of connecting bonds and how they can best be broken. Results obtained during the past quarter are presented for the following tasks: (1) extractions and fractionations of coal products which covers pyridine extraction, fractionation of TIPS fractions, EDA extraction of Illinois No. 6 coal and swelling ratios of coal samples; (2) experiments on breakable single bonds which cover reactions of ethylenediamine and model ethers, reaction of pyridine-extracted coal with Me/sub 3/SiI, Baeyer-Villiger oxidations, reaction to diphenylmethane with 15% HNO/sub 3/, cleavage of TIPS with ZnI/sub 2/, and cleavage of black acids; and (3) oxygen oxidation No. 18. Some of the highlights of these studies are: (1) some model ethers are not cleaved by EDA under extraction conditions; (2) oxidation of diaryl ketones with m-chloroperbenzoic acid and saponification of the resulting esters in promising for identifying ketones, (3) treatment of a black acid with pyridine hydroiodide reduced the acid's molecular weight and increased its solubility in pyridine, but treatment with ZnI/sub 2/ was ineffective; (4) in comparison with 0.1 M K/sub 2/S/sub 2/O/sub 8/, 0.01 M persulfate is relatively ineffective in accelerating oxidation of BnNH/sub 2/-extracted coal in water suspension. 2 figures, 3 tables.

Hirschon, A.S.; Zevely, J.; Mayo, F.R.

1981-11-12

184

Hydrogen production from methane through catalytic partial oxidation reactions  

NASA Astrophysics Data System (ADS)

This paper reviews recent developments in syn-gas production processes used for partial methane oxidation with and/or without steam. In particular, we examined different process charts (fixed bed, fluidised bed, membrane, etc.), kinds of catalysts (powders, foams, monoliths, etc.) and catalytically active phases (Ni, Pt, Rh, etc.). The explanation of the various suggested technical solutions accounted for the reaction mechanism that may selectively lead to calibrated mixtures of CO and H 2 or to the unwanted formation of products of total oxidation (CO 2 and H 2O) and pyrolysis (coke). Moreover, the new classes of catalysts allow the use of small reactors to treat large amounts of methane (monoliths) or separate hydrogen in situ from the other reaction products (membrane). This leads to higher conversions and selectivity than could have been expected thermodynamically. Although catalysts based on Rh are extremely expensive, they can be used to minimise H 2O formation by maximising H 2 yield.

Freni, S.; Calogero, G.; Cavallaro, S.

185

Variation in the reaction zone and its effects on the strength of diffusion bonded titanium–stainless steel couple  

Microsoft Academic Search

Solid state bonding was carried out between commercially pure titanium and 304 stainless steel at 850°C temperature for 30–150min under uniaxial load in vacuum. The transition joints were characterized using optical and scanning electron microscopes and revealed the presence of reaction layers in the diffusion zone. The chemical composition of these reaction products was determined by energy dispersive spectroscopy and

M. Ghosh; Samar Das; P. S. Banarjee; S. Chatterjee

2005-01-01

186

Hydrolysis of Surfactants Containing Ester Bonds: Modulation of Reaction Kinetics and Important Aspects of Surfactant Self-Assembly  

ERIC Educational Resources Information Center

The effects of self-assembly on the hydrolysis kinetics of surfactants that contain ester bonds are discussed. A number of examples on how reaction rates and apparent reaction orders can be modulated by changes in the conditions, including an instance of apparent zero-order kinetics, are presented. Furthermore, it is shown that the examples on…

Lundberg, Dan; Stjerndahl, Maria

2011-01-01

187

COPPER-CATALYZED CROSS-COUPLING REACTIONS: THE FORMATION OF CARBON-CARBON AND CARBON-SULFUR BONDS  

E-print Network

COPPER-CATALYZED CROSS-COUPLING REACTIONS: THE FORMATION OF CARBON-CARBON AND CARBON-SULFUR BONDS Chemistry #12;© Copyright by Craig G. Bates 2005 All Rights Reserved #12;COPPER-CATALYZED CROSS without her. Thank You January 24, 2005 #12;vi ABSTRACT COPPER-CATALYZED CROSS-COUPLING REACTIONS

Venkataraman, Dhandapani "DV"

188

Growth of Zinc Oxide Single Crystals by Vapor Phase Reaction  

Microsoft Academic Search

ZnO single crystals are grown by vapor phase reaction with ZnI2 source. When the growth region is maintained between 1150°C and 1200°C, crystals grow by oxidation, and between 970°C and 1020°C, by hydrolysis. Crystals are mainly needles 15 mm in length or plates 8 mm2 in area. Patterns suggesting their growth mechanisms are observed in their microphotographs. The present experiments

Masami Hirose

1971-01-01

189

Evidence concerning oxidation as a surface reaction in Baltic amber.  

PubMed

The aim of this study was to provide evidence about oxidation as a surface reaction during degradation of Baltic amber. A clear understanding of the amber-oxygen interaction modalities is essential to develop conservation techniques for museum collections of amber objects. Pellet-shaped samples, obtained from pressed amber powder, were subjected to accelerated thermal ageing. Cross-sections of the pellets were analyzed by infrared micro-spectroscopy, in order to identify and quantify changes in chemical properties. The experimental results showed strong oxidation exclusively at the exterior part of cross-sections from samples subjected to long-term thermal ageing, confirming that oxidation of Baltic amber starts from the surface. PMID:22277623

Pastorelli, Gianluca; Richter, Jane; Shashoua, Yvonne

2012-04-01

190

Evidence concerning oxidation as a surface reaction in Baltic amber  

NASA Astrophysics Data System (ADS)

The aim of this study was to provide evidence about oxidation as a surface reaction during degradation of Baltic amber. A clear understanding of the amber-oxygen interaction modalities is essential to develop conservation techniques for museum collections of amber objects. Pellet-shaped samples, obtained from pressed amber powder, were subjected to accelerated thermal ageing. Cross-sections of the pellets were analyzed by infrared micro-spectroscopy, in order to identify and quantify changes in chemical properties. The experimental results showed strong oxidation exclusively at the exterior part of cross-sections from samples subjected to long-term thermal ageing, confirming that oxidation of Baltic amber starts from the surface.

Pastorelli, Gianluca; Richter, Jane; Shashoua, Yvonne

2012-04-01

191

Role of the interfacial thermal barrier in the effective thermal diffusivity/conductivity of SiC-fiber-reinforced reaction-bonded silicon nitride  

NASA Technical Reports Server (NTRS)

Experimental thermal diffusivity data transverse to the fiber direction for composites composed of a reaction bonded silicon nitride matrix reinforced with uniaxially aligned carbon-coated silicon carbide fibers indicate the existence of a significant thermal barrier at the matrix-fiber interface. Calculations of the interfacial thermal conductances indicate that at 300 C and 1-atm N2, more than 90 percent of the heat conduction across the interface occurs by gaseous conduction. Good agreement is obtained between thermal conductance values for the oxidized composite at 1 atm calculated from the thermal conductivity of the N2 gas and those inferred from the data for the effective composite thermal conductivity.

Bhatt, Hemanshu; Donaldson, Kimberly Y.; Hasselman, D. P. H.; Bhatt, R. T.

1990-01-01

192

Elementary reaction modeling of solid oxide electrolysis cells: Main zones for heterogeneous chemical/electrochemical reactions  

NASA Astrophysics Data System (ADS)

A theoretical model of solid oxide electrolysis cells considering the heterogeneous elementary reactions, electrochemical reactions and the transport process of mass and charge is applied to study the relative performance of H2O electrolysis, CO2 electrolysis and CO2/H2O co-electrolysis and the competitive behavior of heterogeneous chemical and electrochemical reactions. In cathode, heterogeneous chemical reactions exist near the outside surface and the electrochemical reactions occur near the electrolyte. According to the mathematical analysis, the mass transfer flux D ?c determines the main zone size of heterogeneous chemical reactions, while the charge transfer flux ? ?V determines the other one. When the zone size of heterogeneous chemistry is enlarged, more CO2 could react through heterogeneous chemical pathway, and polarization curves of CO2/H2O co-electrolysis could be prone to H2O electrolysis. Meanwhile, when the zone size of electrochemistry is enlarged, more CO2 could react through electrochemical pathway, and polarization curves of CO2/H2O co-electrolysis could be prone to CO2 electrolysis. The relative polarization curves, the ratio of CO2 participating in electrolysis and heterogeneous chemical reactions, the mass and charge transfer flux and heterogeneous chemical/electrochemical reaction main zones are simulated to study the effects of cathode material characteristics (porosity, particle diameter and ionic conductivity) and operating conditions (gas composition and temperature).

Li, Wenying; Shi, Yixiang; Luo, Yu; Cai, Ningsheng

2015-01-01

193

Kinetics of the reaction of nitric oxide with hydrogen  

NASA Technical Reports Server (NTRS)

Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The reaction kinetics were studied in the temperature range 2400-4500 K using a shock-tube technique. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principle result of the study was the determination of the rate constant for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k sub 1 were obtained for each test through comparisons of measured and numerically predicted NO profiles.

Flower, W. L.; Hanson, R. K.; Kruger, C. H.

1974-01-01

194

Reaction rate oscillations during catalytic CO oxidation: A brief overview  

NASA Technical Reports Server (NTRS)

It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

Tsotsis, T. T.; Sane, R. C.

1987-01-01

195

Wetting and interfacial bonding in ionocovalent oxide-liquid metal D. Chatain, L. Coudurier and N. Eustathopoulos  

E-print Network

1055 Wetting and interfacial bonding in ionocovalent oxide-liquid metal systems D. Chatain, L compared to experimental results as regards the wettability of monocrystalline oxides by pure metals lead and of metallic additions to the metal on the wettability of the oxide is then discussed. Oxygen has two effects

Paris-Sud XI, Université de

196

Mechanistic investigation of oxidative Mannich reaction with tert-butyl hydroperoxide. The role of transition metal salt.  

PubMed

A general mechanism is proposed for transition metal-catalyzed oxidative Mannich reactions of N,N-dialkylanilines with tert-butyl hydroperoxide (TBHP) as the oxidant. The mechanism consists of a rate-determining single electron transfer (SET) that is uniform from 4-methoxy- to 4-cyano-N,N-dimethylanilines. The tert-butylperoxy radical is the major oxidant in the rate-determining SET step that is followed by competing backward SET and irreversible heterolytic cleavage of the carbon-hydrogen bond at the ?-position to nitrogen. A second SET completes the conversion of N,N-dimethylaniline to an iminium ion that is subsequently trapped by the nucleophilic solvent or the oxidant prior to formation of the Mannich adduct. The general role of Rh(2)(cap)(4), RuCl(2)(PPh(3))(3), CuBr, FeCl(3), and Co(OAc)(2) in N,N-dialkylaniline oxidations by T-HYDRO is to initiate the conversion of TBHP to tert-butylperoxy radicals. A second pathway, involving O(2) as the oxidant, exists for copper, iron, and cobalt salts. Results from linear free-energy relationship (LFER) analyses, kinetic and product isotope effects (KIE and PIE), and radical trap experiments of N,N-dimethylaniline oxidation by T-HYDRO in the presence of transition metal catalysts are discussed. Kinetic studies of the oxidative Mannich reaction in methanol and toluene are also reported. PMID:23298175

Ratnikov, Maxim O; Doyle, Michael P

2013-01-30

197

Probing the arenium-ion (protontransfer) versus the cation-radical (electron transfer) mechanism of Scholl reaction using DDQ as oxidant.  

PubMed

DDQ/H(+) system readily oxidizes a variety of electron donors with oxidation potential as high as approximately 1.7 V to the corresponding cation radicals. A re-examination of the controversial arenium-ion versus cation-radical mechanisms for Scholl reaction using DDQ/H(+) together with commonly utilized FeCl(3) as oxidants led us to demonstrate that the reaction proceeds largely via a cation-radical mechanism. The critical experimental evidence in support of a cation-radical pathway for the Scholl reaction includes the following: (i) There is no reaction in Scholl precursors in a mixture of dichloromethane and various acids (10% v/v). (ii) The necessity to use powerful oxidants such as ferric chloride (FeCl(3)) or DDQ/H(+) for Scholl reactions is inconsistent with the arenium-ion mechanism in light of the fact that aromatization of the dihydro intermediates (formed via arenium-ion mechanism) can be easily accomplished with rather weak oxidants such as iodine or air. (iii) Various Scholl precursors with oxidation potentials oxidative C-C bond formation with DDQ/H(+) as oxidant, whereas Scholl precursors with oxidation potentials greater than >1.7 V vs SCE do not react. (iv) Finally, the feasibility of the dicationic intermediate, formed by loss of two electrons, has been demonstrated by its generation from a tetraphenylene derivative using DDQ/H(+) as an oxidant. PMID:20575516

Zhai, Linyi; Shukla, Ruchi; Wadumethrige, Shriya H; Rathore, Rajendra

2010-07-16

198

Manufacture of ?1.2m reaction bonded silicon carbide mirror blank CFID  

NASA Astrophysics Data System (ADS)

Silicon carbide (SiC) is a new type candidate material for large-scale lightweight space mirror. Its low thermal distortion, high stiffness, fine optical quality and dimensional stability, make SiC an ideal material for large space born telescope. Since ten years Changchun institute optics, fine mechanics and physics (CIOMP) has developed reaction bonded SiC (RB-SiC) technology for space application, and can fabricate RB-SiC mirror with scale less than 1.0 meter for telescope. The green body is prepared with gel-casting method which is an attractive new ceramic forming process for making high-quality, complex-shaped ceramic parts. And then unmolding, drying, binder burning out, reacting bonded, the RB-SiC can be obtained. But with the development of space-born or ground telescope, the scale of primary mirror has exceeded 1.0 meter. So CIOMP has developed an assembly technique which called novel reaction-formed joint technology for larger RB-SiC mirror blank. The steps include joining of green bodies with mixture comprised of SiC particles and phenolic resin etc, firing, machining and sintering. Joining the ?1.2 meter RB-SiC mirror blank by the novel reaction-formed joint technology. And testing the welding layer's performance, the results show that the thickness of 54-77?m, the microstructure and thermal property can be comparable to the substrate and the mechanical property are excellent in bending strength of 307MPa.

Zhang, Ge; Zhao, Rucheng; Zhao, Wenxing; Bao, Jianxun

2010-05-01

199

Regioselective Oxidative Trifluoromethylation of Imidazoheterocycles via C(sp(2))-H Bond Functionalization.  

PubMed

Catalytic oxidative trifluoromethylation of imidazopyridines has been carried out at room temperature through the functionalization of the sp(2) C-H bond employing Langlois reagent under ambient air. A library of 3-(trifluoromethyl)imidazo[1,2-a]pyridines with broad functionalities have been synthesized regioselectively. This methodology is also applicable to imidazo[2,1-b]thiazole and benzo[d]imidazo[2,1-b]thiazole. PMID:25615451

Monir, Kamarul; Bagdi, Avik Kumar; Ghosh, Monoranjan; Hajra, Alakananda

2015-02-01

200

Behavior of aluminum oxide, intermetallics and voids in Cu–Al wire bonds  

Microsoft Academic Search

Nanoscale interfacial evolution in Cu–Al wire bonds during isothermal annealing from 175°C to 250°C was investigated by high resolution transmission electron microscopy (HRTEM). The native aluminum oxide film (?5nm thick) of the Al pad migrates towards the Cu ball during annealing. The formation of intermetallic compounds (IMC) is controlled by Cu diffusion, where the kinetics obey a parabolic growth law

H. Xu; C. Liu; V. V. Silberschmidt; S. S. Pramana; T. J. White; Z. Chen; V. L. Acoff

2011-01-01

201

Electronic structure and chemical bonding of a highly stable and aromatic auro-aluminum oxide cluster.  

PubMed

We have produced an auro-aluminum oxide cluster, Au2(AlO)2(-), as a possible model for an Au-alumina interface and investigated its electronic and structural properties using photoelectron spectroscopy and density functional theory. An extremely large energy gap (3.44 eV) is observed between the lowest unoccupied and the highest occupied molecular orbitals of Au2(AlO)2, suggesting its high electronic stability. The global minima of both Au2(AlO)2(-) and Au2(AlO)2 are found to have D2h symmetry with the two Au atoms bonded to the Al atoms of a nearly square-planar (AlO)2 unit. Chemical bonding analyses reveal a strong ? bond between Au and Al, as well as a completely delocalized ? bond over the (AlO)2 unit, rendering aromatic character to the Au2(AlO)2 cluster. The high electronic stability and novel chemical bonding uncovered for Au2(AlO)2 suggest that it may be susceptible to chemical syntheses as a stable compound if appropriate ligands can be found. PMID:24964367

Lopez, Gary V; Jian, Tian; Li, Wei-Li; Wang, Lai-Sheng

2014-07-17

202

Mechanism and regioselectivity for the reactions of propylene oxide with X(100)-2x1 surfaces (X = C, Si, Ge): a density functional cluster model investigation.  

PubMed

We have performed density functional cluster model calculations to explore the mechanism and regioselectivity for the reactions of propylene oxide with X(100)-2x1 surfaces (X = C, Si, and Ge). The computations reveal the following: (i) the reactions on Si(100) and Ge(100) are barrierless and highly exothermic; (ii) the reactions on X(100) (X = Si and Ge) are initiated by the formation of a dative-bonded precursor state followed by regioselective cleavage of the C2-O bond (C2 directly connected to the methyl-substituent) in propylene oxide, giving rise to a five-membered ring surface species; and (iii) the reaction on C(100), although highly exothermic, requires a large activation energy and would be kinetically forbidden at room temperature. PMID:16722754

Guo, Zheng; Lu, Xin

2006-06-01

203

Palladium-catalyzed oxidative arylalkylation of activated alkenes: dual C-H bond cleavage of an arene and acetonitrile.  

PubMed

Not one but two: The title reaction proceeds through the dual C-H bond cleavage of both aniline and acetonitrile. The reaction affords a variety of cyano-bearing indolinones in excellent yield. Mechanistic studies demonstrate that this reaction involves a fast arylation of the olefin and a rate-determining C-H activation of the acetonitrile. PMID:22076660

Wu, Tao; Mu, Xin; Liu, Guosheng

2011-12-23

204

Transition-metal-free C-C bond forming reactions of aryl, alkenyl and alkynylboronic acids and their derivatives.  

PubMed

Investigation of new methods for the synthesis of C-C bonds is fundamental for the development of new organic drugs and materials. Aryl-, alkenyl- and alkynylboronic acids and their derivatives constitute attractive reagents towards this end, due to their stability, low toxicity and ease of handling. However, these compounds are only moderately nucleophilic. Consequently, the most popular C-C bond forming reactions of these boronic acids, such as the Suzuki-Miyaura, Heck, and Hayashi-Miyaura reactions, or additions to C=O and C=N bonds, require catalysis by transition metals. However, due to the toxicity and cost of transition metals, some new methods for C-C bond formation using aryl-, alkenyl- and alkynylboronic acids under transition-metal-free conditions are beginning to emerge. In this tutorial review, the recent synthetic advances in this field are highlighted and discussed. PMID:25181967

Roscales, S; Csákÿ, A G

2014-12-21

205

Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions  

PubMed Central

Summary The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon–carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2. PMID:25383109

Jouffroy, Matthieu; Gramage-Doria, Rafael; Sémeril, David; Oberhauser, Werner; Toupet, Loïc

2014-01-01

206

Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon-carbon bond forming reactions.  

PubMed

The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki-Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon-carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki-Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2. PMID:25383109

Jouffroy, Matthieu; Gramage-Doria, Rafael; Sémeril, David; Armspach, Dominique; Matt, Dominique; Oberhauser, Werner; Toupet, Loïc

2014-01-01

207

The Influence of Interfaces on Reactions in Oxide Ceramics  

NASA Astrophysics Data System (ADS)

Many technologically important properties of crystalline solids are either determined by or strongly influenced by the presence and behavior of defects. Interfaces between two crystals (grain or phase boundaries) or between a crystal and a gas (surfaces) are perhaps the most technologically important class of defects because of the influence they exert on other defects (point defects, dislocations, pores and second-phase particles). Obtaining a thorough and fundamental description of interfaces including their influence on macroscale properties of solids is a daunting scientific challenge; in many important polycrystalline solids there will be a large number of interfaces with diverse, non-periodic atomic structures. In oxide ceramics, the situation is further complicated by, for example, segregated impurity atoms and amorphous interfacial films. This dissertation will describe a number of experiments involving reactions at interfaces in quite different oxide ceramic systems. By comparing observations in these different systems and with the observations of previous researchers, some general principles applicable to different types of interfaces in oxides will be described. However it will also be seen that in many cases reaction behavior will depend in a complicated way on the details of the interface and the external variables such as temperature. For this research, "reactions" refers primarily to charged point-defect reactions including segregation phenomena and phase transformations in which point-defect movement is a necessary feature. Dislocations will also make several brief appearances. These reactions are of particular practical interest because of their importance in the performance of solid oxide fuel cells and catalysts, both of which are important for alternative-energy technology. The primary experimental tool has been the transmission electron microscope (TEM) which combines high spatial resolution (0.1 nm or better) with the capability to detect many different signals resulting from electron scattering phenomena in solids, most importantly for this research, ionization events and constructive interference of electron waves. Analysis of these scattering phenomena enables local crystallographic, microstructural and compositional information to be obtained. These capabilities (particularly at high spatial resolution) are unique to the TEM and essential for understanding defects in solids; the technique also has several limitations that will be discussed.

Winterstein, Jonathan Paul

208

The partitioning of phosphoramide mustard and its aziridinium ions among alkylation and P-N bond hydrolysis reactions.  

PubMed

NMR (1H and 31P) and HPLC techniques were used to study the partitioning of phosphoramide mustard (PM) and its aziridinium ions among alkylation and P-N bond hydrolysis reactions as a function of the concentration and strength of added nucleophiles at 37 degrees C and pH 7.4. With water as the nucleophile, bisalkylation accounted for only 10-13% of the product distribution given by PM. The remainder of the products resulted from P-N bond hydrolysis reactions. With 50 mM thiosulfate or 55-110 mM glutathione (GSH), bisalkylation by a strong nucleophile increased to 55-76%. The rest of the PM was lost to either HOH alkylation or P-N bond hydrolysis reactions. Strong experimental and theoretical evidence was obtained to support the hypothesis that the P-N bond scission observed at neutral pH does not occur in the parent PM to produce nornitrogen mustard; rather it is an aziridinium ion derived from PM which undergoes P-N bond hydrolysis to give chloroethylaziridine. In every buffer studied (bis-Tris, lutidine, triethanolamine, and Tris), the decomposition of PM (with and without GSH) gave rise to 31P NMR signals which could not be attributed to products of HOH or GSH alkylation or P-N bond hydrolysis. The intensities of these unidentified signals were dependent on the concentration of buffer. PMID:9484502

Shulman-Roskes, E M; Noe, D A; Gamcsik, M P; Marlow, A L; Hilton, J; Hausheer, F H; Colvin, O M; Ludeman, S M

1998-02-12

209

Experimental investigation on material migration phenomena in micro-EDM of reaction-bonded silicon carbide  

NASA Astrophysics Data System (ADS)

Material migration between tool electrode and workpiece material in micro electrical discharge machining of reaction-bonded silicon carbide was experimentally investigated. The microstructural changes of workpiece and tungsten tool electrode were examined using scanning electron microscopy, cross sectional transmission electron microscopy and energy dispersive X-ray under various voltage, capacitance and carbon nanofibre concentration in the dielectric fluid. Results show that tungsten is deposited intensively inside the discharge-induced craters on the RB-SiC surface as amorphous structure forming micro particles, and on flat surface region as a thin interdiffusion layer of poly-crystalline structure. Deposition of carbon element on tool electrode was detected, indicating possible material migration to the tool electrode from workpiece material, carbon nanofibres and dielectric oil. Material deposition rate was found to be strongly affected by workpiece surface roughness, voltage and capacitance of the electrical discharge circuit. Carbon nanofibre addition in the dielectric at a suitable concentration significantly reduced the material deposition rate.

Liew, Pay Jun; Yan, Jiwang; Kuriyagawa, Tsunemoto

2013-07-01

210

Microstructure/property relationships for SiC filament-reinforced RBSN. [Reaction-bonded silicon nitride  

SciTech Connect

Reaction-bonded silicon nitride has been reinforced by SiC filaments. The strength and toughness of this composite is dependent on the microstructure and microchemistry of the fiber/matrix interface. Room temperature flexural strengths of 900 MPa have been observed. Weak interfacial bonding results in shear failure, whereas stronger bonding results in filament fracture and pullout. Auger analysis of the interface reveals that a pure carbon layer is responsible for shear failure. This material shows the highest strength because crack deflection in the carbon layer protects the SiC filament. 18 references.

Corbin, N.D.; Rossetti, G.A.,JR.; Hartline, S.D.

1986-08-01

211

How valence bond theory can help you understand your (bio)chemical reaction.  

PubMed

Almost a century has passed since valence bond (VB) theory was originally introduced to explain covalent bonding in the H2 molecule within a quantum mechanical framework. The past century has seen constant improvements in this theory, with no less than two distinct Nobel prizes based on work that is essentially developments in VB theory. Additionally, ongoing advances in both methodology and computational power have greatly expanded the scope of problems that VB theory can address. In this Tutorial Review, we aim to give the reader a solid understanding of the foundations of modern VB theory, using a didactic example of a model SN2 reaction to illustrate its immediate applications. This will be complemented by examples of challenging problems that at present can only be efficiently addressed by VB-based approaches. Finally, the ongoing importance of VB theory is demonstrated. It is concluded that VB will continue to be a major driving force for chemistry in the century to come. PMID:25352378

Shurki, Avital; Derat, Etienne; Barrozo, Alexandre; Kamerlin, Shina Caroline Lynn

2014-10-29

212

Bond strength of selected composite resin-cements to zirconium-oxide ceramic  

PubMed Central

Objectives: The aim of this study was to evaluate bond strengths of zirconium-oxide (zirconia) ceramic and a selection of different composite resin cements. Study Design: 130 Lava TM cylinders were fabricated. The cylinders were sandblasted with 80 µm aluminium oxide or silica coated with CoJet Sand. Silane, and bonding agent and/or Clearfil Ceramic Primer were applied. One hundred thirty composite cement cylinders, comprising two dual-polymerizing (Variolink II and Panavia F) and two autopolymerizing (Rely X and Multilink) resins were bonded to the ceramic samples. A shear test was conducted, followed by an optical microscopy study to identify the location and type of failure, an electron microscopy study (SEM and TEM) and statistical analysis using the Kruskal-Wallis test for more than two independent samples and Mann-Whitney for two independent samples. Given the large number of combinations, Bonferroni correction was applied (?=0.001). Results: Dual-polymerizing cements provided better adhesion values (11.7 MPa) than the autopolymerizing (7.47 MPa) (p-value M-W<0.001). The worst techniques were Lava TM + sandblasting + Silane + Rely X; Lava TM + sandblasting + Silane + Multilink and Lava TM + CoJet + silane + Multilink. Adhesive failure (separation of cement and ceramic) was produced at a lesser force than cohesive failure (fracture of cement) (p-value M-W<0.001). Electron microscopy confirmed that the surface treatments modified the zirconium-oxide ceramic, creating a more rough and retentive surface, thus providing an improved micromechanical interlocking between the cement and the ceramic. Key words:Shear bond strength, silica coating, surface treatment, zirconia ceramics, phosphate monomer. PMID:22926485

Fons-Font, Antonio; Amigó-Borrás, Vicente; Granell-Ruiz, María; Busquets-Mataix, David; Panadero, Rubén A.; Solá-Ruiz, Maria F.

2013-01-01

213

Thermal activation of N-H bonds by transition-metal oxide cations: does a hierarchy exist in the first row?  

PubMed

The thermal reactions of first-row transition-metal oxide cations [MO](+) (M=Sc-Ni, Zn) with ammonia have been studied by gas-phase experiments and computational methods. The activation of N-H bonds is brought about by the monoxides of the middle and late 3d metals Mn-Ni and Zn. The two primary reaction channels correspond to dehydration, which leads to [M(NH)](+), and hydrogen-atom abstraction to form [M(OH)](+). Oxygen-atom transfer from [MO](+) to NH(3) to produce neutral or ionized hydroxylamine was observed as a minor channel for some of the late transition-metal oxides. The computational analysis of these reactions, which was aimed at elucidating the reaction mechanisms and to uncover possible periodic trends across the first row, have been performed for the couples [MO](+) /NH(3) (M=Sc-Zn). Dehydration is found to be endothermic for the oxides of scandium to vanadium and exothermic for the other systems. Hydrogen-atom abstraction becomes exothermic starting with [MnO](+) and, finally, oxygen-atom transfer is feasible for the cationic oxides of nickel to zinc. PMID:21370291

Kretschmer, Robert; Zhang, Xinhao; Schlangen, Maria; Schwarz, Helmut

2011-03-28

214

Fly Ash and Mercury Oxidation/Chlorination Reactions  

SciTech Connect

Mercury is a known pollutant that has detrimental effect on human health and environment. The anthropogenic emissions of mercury account for 10 to 30% of worldwide mercury emissions. There is a need to control/reduce anthropogenic mercury emissions. Many mercury control technologies are available but their effectiveness is dependent on the chemical form of mercury, because different chemical forms of mercury have different physical and chemical properties. Mercury leaves the boiler in its elemental form but goes through various transformations in the post-combustion zone. There is a need to understand how fly ash and flue gas composition affect speciation, partitioning, and reactions of mercury under the full range of post-combustion zone conditions. This knowledge can then be used to predict the chemical transformation of mercury (elemental, oxidized or particulate) in the post combustion zone and thus help with the control of mercury emissions from coal-burning power plants. To accomplish this goal present study was conducted using five coal fly ashes. These ashes were characterized and their catalytic activity was compared under selected reaction conditions in a fixed bed reactor. Based on the results from these fly ash experiments, three key components (carbon, iron oxide and calcium oxide) were chosen. These three components were then used to prepare model fly ashes. Silica/alumina was used as a base for these model fly ashes. One, two or three component model fly ashes were then prepared to investigate mercury transformation reactions. The third set of experiments was performed with CuO and CuCl2 catalysts to further understand the mercury oxidation process. Based on the results of these three studies the key components were predicted for different fly ash compositions under variety of flue gas conditions. A fixed bed reactor system was used to conduct this study. In all the experiments, the inlet concentration of Hg0(g) was maintained at 35 {micro}g/m3 using a diffusion tube as the source of Hg0(g). All experiments were conducted using 4% O2 in nitrogen mix as a reaction gas, and other reactants (HCl, H2O and SO2, NO2, Br2) were added as required. The fixed bed reactor was operated over a temperature range of 200 to 400 C. In each experiment, the reactor effluent was analyzed using the modified Ontario-Hydro method. After each experiment, fly ash particles were also analyzed for mercury. The results show that the ability of fly ash to adsorb and/or oxidize mercury is primarily dependent on its carbon, iron and calcium content. There can be either one or more than one key component at a particular temperature and flue gas condition. Surface area played a secondary role in effecting the mercury transformations when compared to the concentration of the key component in the fly ash. Amount of carbon and surface area played a key important role in the adsorption of mercury. Increased concentration of gases in the flue gas other than oxygen and nitrogen caused decreased the amount of mercury adsorbed on carbon surface. Mercury adsorption by iron oxide primarily depended on the crystalline structure of iron oxide. {alpha}-Iron oxide had no effect on mercury adsorption or oxidation under most of the flue gas conditions, but ?-iron oxide adsorbed mercury under most of the flue gas conditions. Bromine is a very good oxidizing agent for mercury. But in the presence of calcium oxide containing fly ashes, all the oxidized mercury would be reduced to elemental form. Among the catalysts, it was observed that presence of free lattice chlorine in the catalyst was very important for the oxidation of mercury. But instead of using the catalyst alone, using it along with carbon may better serve the purpose by providing the adsorption surface for mercury and also some extra surface area for the reaction to occur (especially for fly ashes with low surface area).

Sukh Sidhu; Patanjali Varanasi

2008-12-31

215

Initial reaction of hafnium oxide deposited by remote plasma atomic layer deposition method  

SciTech Connect

A remote plasma atomic layer deposition (RPALD) method has been applied to grow a hafnium oxide thin film on the Si substrate. The deposition process was monitored by in situ XPS and the as-deposited structure and chemical bonding were examined by TEM and XPS. The in situ XPS measurement showed the presence of a hafnium silicate phase at the initial stage of the RPALD process up to the 20th cycle and indicated that no hafnium silicide was formed. The initial hafnium silicate was amorphous and grew to a thickness of approximately 2 nm. Based on these results and model reactions for silicate formation, we proposed an initial growth mechanism that includes adatom migration at nascent step edges. Density functional theory calculations on model compounds indicate that the hafnium silicate is thermodynamically favored over the hafnium silicide by as much as 250 kJ/mol.

Won, Youngdo; Park, Sangwook; Koo, Jaehyoung; Kim, Seokhoon; Kim, Jinwoo; Jeon, Hyeongtag [Department of Chemistry, Hanyang University, Seoul 133-791 (Korea, Republic of); Division of Materials Science and Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of)

2005-12-26

216

Application of chemical structure and bonding of actinide oxide materials for forensic science  

SciTech Connect

We are interested in applying our understanding of actinide chemical structure and bonding to broaden the suite of analytical tools available for nuclear forensic analyses. Uranium- and plutonium-oxide systems form under a variety of conditions, and these chemical species exhibit some of the most complex behavior of metal oxide systems known. No less intriguing is the ability of AnO{sub 2} (An: U, Pu) to form non-stoichiometric species described as AnO{sub 2+x}. Environmental studies have shown the value of utilizing the chemical signatures of these actinide oxide materials to understand transport following release into the environment. Chemical speciation of actinide-oxide samples may also provide clues as to the age, source, or process history of the material. The scientific challenge is to identify, measure and understand those aspects of speciation of actinide analytes that carry information about material origin and history most relevant to forensics. Here, we will describe our efforts in material synthesis and analytical methods development that we will use to provide the fundamental science to characterize actinide oxide molecular structures for forensic science. Structural properties and initial results to measure structural variability of uranium oxide samples using synchrotron-based X-ray Absorption Fine Structure will be discussed.

Wilkerson, Marianne Perry [Los Alamos National Laboratory

2010-01-01

217

Thermo-oxidative and hydrothermal ageing of epoxy-dicyandiamide adhesive in bonded stainless steel joints  

NASA Astrophysics Data System (ADS)

The ageing behaviour of stainless steel joints bonded with hot-curing adhesives is crucial for their reliability and durability in engineering applications. In industry, accelerated artificial ageing regimes are combined with short-term mechanical tests to simulate the in-service long-term behaviour and to predict the life time of the adhesive joints. With such a focus on mechanical bond strength, chemical changes in the adhesive are widely disregarded. Hence, neither the very causes for the decreasing performance of the joint nor their relevance for application can be revealed. Reasoning this study, lap shear samples of the stainless steel alloy 1.4376 are bonded with an epoxy-dicyandiamide adhesive and aged artificially under moderate thermo-oxidative (60 °C, dried air) or hydrothermal (60 °C, distilled water) condition. After testing (shear stress-strain analysis), chemical modifications of this adhesive due to ageing are detected on the fracture faces by ?-ATR-FTIR-spectroscopy as function of ageing time and position in the adhesive joint. The results attest high thermo-oxidative stability to these adhesive joints. For hydrothermal ageing, permeating water deteriorates the EP network from the edges towards the centre of the joint via hydrolysis of imine groups to ammonia, amine species and carbonyls.

Gaukler, J. Ch; Fehling, P.; Possart, W.

2009-09-01

218

Bis(trifluoromethyl)methylene Addition to Vinyl-Terminated SAMs: A Gas-Phase C–C Bond-Forming Reaction on a Surface  

PubMed Central

Vinyl-terminated self-assembled monolayers (SAMs) on silicon oxide substrates were chemically modified by the addition of a bis(trifluoromethyl)methylene group in a rare gas-phase C–C bond-forming reaction to directly generate films carrying terminal CF3 groups. The vinyl-terminated films were treated with hexafluoroacetone azine (HFAA) for modification. The films were characterized with ellipsometry, contact angle measurements, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). In this study, we find that for optimized conditions clean reactions occur on a surface between SAMs with terminal olefins and HFAA, and the product is consistent with bis(trifluoromethyl)cyclopropanation formation after nitrogen extrusion. PMID:24806554

2014-01-01

219

Bis(trifluoromethyl)methylene addition to vinyl-terminated SAMs: a gas-phase C-C bond-forming reaction on a surface.  

PubMed

Vinyl-terminated self-assembled monolayers (SAMs) on silicon oxide substrates were chemically modified by the addition of a bis(trifluoromethyl)methylene group in a rare gas-phase C-C bond-forming reaction to directly generate films carrying terminal CF3 groups. The vinyl-terminated films were treated with hexafluoroacetone azine (HFAA) for modification. The films were characterized with ellipsometry, contact angle measurements, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). In this study, we find that for optimized conditions clean reactions occur on a surface between SAMs with terminal olefins and HFAA, and the product is consistent with bis(trifluoromethyl)cyclopropanation formation after nitrogen extrusion. PMID:24806554

Adamkiewicz, Malgorzata; O'Hagan, David; Hähner, Georg

2014-05-20

220

Tailored synthesis of various nanomaterials by using a graphene-oxide-based gel as a nanoreactor and nanohybrid-catalyzed c?c bond formation.  

PubMed

New graphene oxide (GO)-based hydrogels that contain vitamin?B2 /B12 and vitamin?C (ascorbic acid) have been synthesized in water (at neutral pH value). These gel-based soft materials have been used to synthesize various metal nanoparticles, including Au, Ag, and Pd nanoparticles, as well as nanoparticle-containing reduced graphene oxide (RGO)-based nanohybrid systems. This result indicates that GO-based gels can be used as versatile reactors for the synthesis of different nanomaterials and hybrid systems on the nanoscale. Moreover, the RGO-based nanohybrid hydrogel with Pd nanoparticles was used as an efficient catalyst for C?C bond-formation reactions with good yields and showed high recyclability in Suzuki-Miyaura coupling reactions. PMID:25224859

Biswas, Abhijit; Banerjee, Arindam

2014-12-01

221

Calmodulin Methionine Residues are Targets For One-Electron Oxidation by Hydroxyl Radicals: Formation of S therefore N three-electron bonded Radical Complexes  

SciTech Connect

The one-electron (1e) oxidation of organic sulfides and methionine (Met) constitutes an important reaction mechanism in vivo.1,2 Evidence for a Cu(II)-catalyzed oxidation of Met35 in the Alzheimer's disease -amyloid peptide was obtained,3 and, based on theoretical studies, Met radical cations were proposed as intermediates.4 In the structure of -amyloid peptide, the formation of Met radical cations appears to be facilitated by a preexisting close sulfur-oxygen (S-O) interaction between the Met35 sulfur and the carbonyl oxygen of the peptide bond C-terminal to Ile31.5 Substitution of Ile31 with Pro31 abolishes this S-O interaction,5 significantly reducing the ability of -amyloid to reduce Cu(II), and converts the neurotoxic wild-type -amyloid into a non-toxic peptide.6 The preexisting S-O bond characterized for wild-type -amyloid suggests that electron transfer from Met35 to Cu(II) is supported through stabilization of the Met radical cation by the electron-rich carbonyl oxygen, generating an SO-bonded7 sulfide radical cation (Scheme 1, reaction 1).5

Nauser, Thomas; Jacoby, Michael E.; Koppenol, Willem H.; Squier, Thomas C.; Schoneich, Christian

2005-02-01

222

Gas-phase reaction of CeVO5(+) cluster ions with C2H4: the reactivity of cluster bonded peroxides.  

PubMed

Cerium-vanadium oxide cluster cations CeVO5(+) were generated by laser ablation, mass-selected using a quadrupole mass filter, thermalized through collisions with helium atoms, and then reacted with ethene molecules in a linear ion trap reactor. The cluster reactions have been characterized by time-of-flight mass spectrometry and density functional theory calculations. The CeVO5(+) cluster has a closed-shell electronic structure and contains a peroxide (O2(2-)) unit. The cluster bonded O2(2-) species is reactive enough to oxidize a C2H4 molecule to generate C2H4O2 that can be an acetic acid molecule. Atomic oxygen radicals (O(-)?), superoxide radicals (O2(-)?), and peroxides are the three common reactive oxygen species. The reactivity of cluster bonded O(-)? and O2(-)? radicals has been widely studied while the O2(2-) species were generally thought to be much less reactive or inert toward small molecules under thermal collision conditions. This work is among the first to report the reactivity of the peroxide unit on transition metal oxide clusters with hydrocarbon molecules, to the best of our knowledge. PMID:25573178

Ma, Jia-Bi; Meng, Jing-Heng; He, Sheng-Gui

2015-02-01

223

A radical process towards the development of transition-metal-free aromatic carbon-carbon bond-forming reactions.  

PubMed

Transition-metal-free cross-coupling reactions have been a hot topic in recent years. With the aid of a radical initiator, a number of unactivated arene C-H bonds can be directly arylated/functionalized by using aryl halides through homolytic aromatic substitution. Commercially available or specially designed promoters (e.g. diamines, diols, and amino alcohols) have been used to make this synthetically attractive method viable. This protocol offers an inexpensive, yet efficient route to aromatic C-C bond formations since transition metal catalysts and impurities can be avoided by using this reaction system. In this article, we focus on the significance of the reaction conditions (e.g. bases and promoters), which allow this type of reaction to proceed smoothly. Substrate scope limitations and challenges, as well as mechanistic discussion are also included. PMID:24166759

Chan, Tek Long; Wu, Yinuo; Choy, Pui Ying; Kwong, Fuk Yee

2013-11-18

224

Kinetics and Thermodynamics of Atmospherically Relevant Aqueous Phase Reactions of Pinene Oxide  

E-print Network

Kinetics and Thermodynamics of Atmospherically Relevant Aqueous Phase Reactions of Pinene Oxide products, kinetics, and equilibria of the aqueous phase reactions of that epoxide, -pinene oxide. The present results indicate that -pinene oxide will react very quickly with aqueous atmospheric particles

Elrod, Matthew J.

225

Overall Rate Constant Measurements of the Reaction of Chloroalkylperoxy Radicals with Nitric Oxide  

E-print Network

Overall Rate Constant Measurements of the Reaction of Chloroalkylperoxy Radicals with Nitric Oxide of the NO reaction with chloroalkylperoxy radicals derived from the Cl-initiated oxidation of several atmospherically the OH-initiated oxidation of alkenes) with NO yielded identical rate constants for all of the alkenes

Elrod, Matthew J.

226

Specific Bonds between an Iron Oxide Surface and Outer Membrane Cytochromes MtrC and OmcA from Shewanella oneidensis MR-1  

SciTech Connect

Shewanella oneidensis MR-1 is purported to express outer membrane cytochromes (e.g., MtrC and OmcA) that transfer electrons directly to Fe(III) in a mineral during anaerobic respiration.  A prerequisite for this type of reaction would be the formation of a stable bond between a cytochrome and an iron oxide surface.  Atomic force microscopy (AFM) was used to detect whether a specific bond forms between a hematite (Fe2O3) thin film, created with oxygen plasma assisted molecular beam epitaxy (MBE), and recombinant MtrC or OmcA molecules coupled to gold substrates.  Force spectra displayed a unique force signature indicative of a specific bond between each cytochrome and the hematite surface.  The strength of the OmcA-hematite bond was approximately twice as strong as the MtrC-hematite bond, but direct binding to hematite was twice as favorable for MtrC.  Reversible folding/unfolding reactions were observed for mechanically denatured MtrC molecules bound to hematite.  The force measurements for the hematite-cytochrome pairs were compared to spectra collected between an iron oxide and S. oneidensis under anaerobic conditions.  There is a strong correlation between the whole cell and pure protein force spectra suggesting that the unique binding attributes of each cytochrome complement one another and allow both MtrC and OmcA to play a prominent role in the transfer of electrons to Fe(III) in minerals.  Finally, by comparing the magnitude of binding force for the whole cell vs. pure protein data, we were able to estimate that a single bacterium of S. oneidensis (2 x 0.5 ?m) expresses ~104 cytochromes on its outer surface. 

Lower, Brian H.; Shi, Liang; Yongsunthon, Ruchirej; Droubay, Timothy C.; Mccready, David E.; Lower, Steven

2007-07-31

227

Designing a Cu(II)-ArCu(II)-ArCu(III)-Cu(I) catalytic cycle: Cu(II)-catalyzed oxidative arene C-H bond azidation with air as an oxidant under ambient conditions.  

PubMed

On the basis of our recent discovery of high valent organocopper compounds, we have designed and achieved efficient copper(II)-catalyzed oxidative arene C-H bond azidation under very mild aerobic conditions by using NaN3 as an azide source. In the presence of a Cu(II) catalyst, a number of azacalix[1]arene[3]pyridines underwent direct arene C-H bond cupration through an electrophilic aromatic metalation pathway to form an arylcopper(II) intermediate. Oxidized by a free copper(II) ion, the arylcopper(II) intermediate was transformed into an arylcopper(III) species that subsequently cross-coupled with azide to furnish the formation of aryl azide products with the release of a copper(I) ion. Under ambient catalytic reaction conditions, the copper(I) species generated was oxidized by air into copper(II), which entered into the next catalytic cycle. Application of the method was demonstrated by the synthesis of functional azacalix[1]arene[3]pyridines by means of simple and practical functional group transformations of azide. The showcase of the Cu(II)-ArCu(II)-ArCu(III)-Cu(I) catalytic cycle would provide a new strategy for the design of copper(II)-catalyzed aerobic oxidative arene C-H bond activation and transformations. PMID:25350606

Yao, Bo; Liu, Yang; Zhao, Liang; Wang, De-Xian; Wang, Mei-Xiang

2014-11-21

228

Oxidation Numbers, Oxidants, and Redox Reactions: Variants of the Electrophilic Bromination of Alkenes and Variants of the Application of Oxone  

ERIC Educational Resources Information Center

Oxidation-state and donor-acceptor concepts are important areas in the chemical education. Student worksheets containing problems that emphasize oxidation numbers, redox reactions of organic compounds, and stoichiometric reaction equations are presented. All of the examples are incorporated under one unifying topic: the production of vicinal…

Eissen, Marco; Strudthoff, Merle; Backhaus, Solveig; Eismann, Carolin; Oetken, Gesa; Kaling, Soren; Lenoir, Dieter

2011-01-01

229

New reduced ternary molybdenum oxide with infinite Mo-Mo bonded chains. [Mn/sub 1. 5/Mo/sub 8/O/sub 11/  

SciTech Connect

A novel reduced ternary oxide of molybdenum is reported. The phase contains infinite octahedral chains of bonded molybdenum atoms with an average oxidation state of 2.375. The pure material can be obtained using stoichiometric quantities of manganese molybdate, molybdenum trioxide, and molybdenum powder. The structure of the crystal was solved and consists of molybdenum oxide chains extending parallel to the c-axis with interconnection by various geometries of oxygen: including square planar, trigonal planar, and sawhorse. The molybdenum oxygen framework forms trigonal prismatic tunnels in which the ternary cations reside. Studies of the electrical and magnetic properties show that the title compound is a metallic conductor and a paramagnet with weak antiferromagnetic coupling. Ion exchange reactions on Mn/sub 1.5/Mo/sub 8/O/sub 11/ with various molten metal chloride salts are also presented. 26 refs., 8 figs., 10 tabs.

Carlson, C.D.

1986-01-01

230

Porous platinum mesoflowers with enhanced activity for methanol oxidation reaction  

SciTech Connect

Porous Pt and Pt-Ag alloy mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesized using Ag mesoflowers as sacrificial template by galvanic reaction. The silver content in Pt-Ag alloys can be facilely controlled by nitric acid treatment. And the pure Pt MFs can be obtained by selective removal of silver element from Pt{sub 72}Ag{sub 28} MFs electrochemically. Both Pt{sub 45}Ag{sub 55}, Pt{sub 72}Ag{sub 28} and pure Pt show a high catalytic performance in methanol oxidation reaction (MOR). Especially, pure Pt MFs exhibited a 2 to 3 times current density enhancement in MOR compared with the commercial used Pt black, which can be attributed to their porous nanostructure with 3-dimentional nature and small crystal sizes. - Graphical Abstract: The CVs of MOR on Pt (red) and Pt black (green) catalysts in 0.1 M HClO{sub 4} and 0.5 M CH{sub 3}OH for specific mass current. The insert shows the SEM images of two porous Pt MFs. Platinum mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesised with Ag mesoflowers as sacrificial template by galvanic replacement. The porous Pt MFs exhibited a more than 3 times enhancement in electrocatalytic performance for methanol oxidation reaction compared the commercial used Pt black. Highlights: Black-Right-Pointing-Pointer Porous Pt and Pt-Ag mesoflowers (MFs) were synthesized using Ag MFs sacrifical template. Black-Right-Pointing-Pointer Pt MFs presents an improved catalytic activity in MOR compared with Pt black. Black-Right-Pointing-Pointer We provided a facile approach for the development of high performance Pt electrocatalysts for fuel cells.

Zhuang Lina; Wang Wenjin; Hong Feng [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi'an Jiaotong University, Xi'an 710049 (China); Yang Shengchun, E-mail: ysch1209@mail.xjtu.edu.cn [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi'an Jiaotong University, Xi'an 710049 (China); You Hongjun, E-mail: hjyou@mail.xjtu.edu.cn [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi'an Jiaotong University, Xi'an 710049 (China); Fang Jixiang; Ding Bingjun [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi'an Jiaotong University, Xi'an 710049 (China)

2012-07-15

231

Oxidative Addition of Carbon–Carbon Bonds with a Redox-Active Bis(imino)pyridine Iron Complex  

PubMed Central

Addition of biphenylene to the bis(imino)pyridine iron dinitrogen complexes, (iPrPDI)Fe(N2)2 and [(MePDI)Fe(N2)]2(?2-N2) (RPDI = 2,6-(2,6-R2—C6H3— N=CMe)2C5H3N; R = Me, iPr), resulted in oxidative addition of a C—C bond at ambient temperature to yield the corresponding iron biphenyl compounds, (RPDI)Fe-(biphenyl). The molecular structures of the resulting bis-(imino)pyridine iron metallacycles were established by X-ray diffraction and revealed idealized square pyramidal geometries. The electronic structures of the compounds were studied by Mössbauer spectroscopy, NMR spectroscopy, magnetochemistry, and X-ray absorption and X-ray emission spectroscopies. The experimental data, in combination with broken-symmetry density functional theory calculations, established spin crossover (low to intermediate spin) ferric compounds antiferromagnetically coupled to bis(imino)pyridine radical anions. Thus, the overall oxidation reaction involves cooperative electron loss from both the iron center and the redox-active bis(imino)pyridine ligand. PMID:23043331

Darmon, Jonathan M.; Stieber, S. Chantal E.; Sylvester, Kevin T.; Fernández, Ignacio; Lobkovsky, Emil; Semproni, Scott P.; Bill, Eckhard; Wieghardt, Karl; DeBeer, Serena; Chirik, Paul J.

2013-01-01

232

Synthesis of Polysubstituted Pyrroles via Pd-Catalyzed Oxidative Alkene C-H Bond Arylation and Amination.  

PubMed

A novel Pd(II)-catalyzed oxidative approach to construct polysubstituted pyrroles from N-homoallylicamines and arylboronic acids was developed. This transformation is supposed to proceed through cascade formation of C-C and C-N bonds via oxidative arylation of unactive alkenes, followed by intramolecular aza-Wacker cyclization. PMID:25536027

Zheng, Jia; Huang, Liangbin; Huang, Chuyu; Wu, Wanqing; Jiang, Huanfeng

2015-01-16

233

Transition-metal/Lewis acid free synthesis of acyl benzothiophenes via C-C bond forming reaction.  

PubMed

A simple and single-step synthesis of 2- and 3-acyl substituted benzothiophenes has been described via environmentally benign acylation of benzothiophene with in situ generated acyl trifluoroacetates. Both aliphatic and aromatic carboxylic acids participated in trifluoroacetic anhydride/phosphoric acid mediated C-C bond forming reactions under solvent-free conditions affording acyl benzothiophenes in good overall yields. PMID:17961232

Pal, Sarbani; Khan, Mohammad Ashrafuddin; Bindu, P; Dubey, P K

2007-01-01

234

Metal amides as the simplest acid/base catalysts for stereoselective carbon-carbon bond-forming reactions.  

PubMed

In this paper, new possibilities for metal amides are described. Although typical metal amides are recognized as strong stoichiometric bases for deprotonation of inert or less acidic hydrogen atoms, transition-metal amides, namely silver and copper amides, show interesting abilities as one of the simplest acid/base catalysts in stereoselective carbon-carbon bond-forming reactions. PMID:23775980

Yamashita, Yasuhiro; Kobayashi, Sh?

2013-07-15

235

Transition-metal/Lewis acid free synthesis of acyl benzothiophenes via C-C bond forming reaction  

PubMed Central

A simple and single-step synthesis of 2- and 3-acyl substituted benzothiophenes has been described via environmentally benign acylation of benzothiophene with in situ generated acyl trifluoroacetates. Both aliphatic and aromatic carboxylic acids participated in trifluoroacetic anhydride/phosphoric acid mediated C-C bond forming reactions under solvent-free conditions affording acyl benzothiophenes in good overall yields. PMID:17961232

Pal, Sarbani; Khan, Mohammad Ashrafuddin; Bindu, P; Dubey, PK

2007-01-01

236

Aerobic oxidation reactions catalyzed by vanadium complexes of bis(phenolate) ligands.  

PubMed

Vanadium(V) complexes of the tridentate bis(phenolate)pyridine ligand H(2)BPP (H(2)BPP = 2,6-(HOC(6)H(2)-2,4-(t)Bu(2))(2)NC(5)H(3)) and the bis(phenolate)amine ligand H(2)BPA (H(2)BPA = N,N-bis(2-hydroxy-4,5-dimethylbenzyl)propylamine) have been synthesized and characterized. The ability of the complexes to mediate the oxidative C-C bond cleavage of pinacol was tested. Reaction of the complex (BPP)V(V)(O)(O(i)Pr) (4) with pinacol afforded the monomeric vanadium(IV) product (BPP)V(IV)(O)(HO(i)Pr) (6) and acetone. Vanadium(IV) complex 6 was oxidized rapidly by air at room temperature in the presence of NEt(3), yielding the vanadium(V) cis-dioxo complex [(BPP)V(V)(O)(2)]HNEt(3). Complex (BPA)V(V)(O)(O(i)Pr) (5) reacted with pinacol at room temperature, to afford acetone and the vanadium(IV) dimer [(BPA)V(IV)(O)(HO(i)Pr)](2). Complexes 4 and 5 were evaluated as catalysts for the aerobic oxidation of 4-methoxybenzyl alcohol and arylglycerol ?-aryl ether lignin model compounds. Although both 4 and 5 catalyzed the aerobic oxidation of 4-methoxybenzyl alcohol, complex 4 was found to be a more active and robust catalyst for oxidation of the lignin model compounds. The catalytic activities and selectivities of the bis(phenolate) complexes are compared to previously reported catalysts. PMID:22708725

Zhang, Guoqi; Scott, Brian L; Wu, Ruilian; Silks, L A Pete; Hanson, Susan K

2012-07-01

237

Laminate behavior for SiC fiber-reinforced reaction-bonded silicon nitride matrix composites  

NASA Technical Reports Server (NTRS)

The room temperature mechanical properties of SiC fiber reinforced reaction-bonded silicon nitride matrix composite laminates (SiC/RBSN) have been measured. The laminates contained approx 30 volume fraction of aligned 142-micron diameter SiC fiber in a porous RBSN matrix. Three types of laminate studied were unidirectional: (1) (0) sub 8, (2) (10) sub 8, and (3) (45) sub 8, and (90) sub 8; cross plied laminates (0 sub 2/90 sub 2); and angle plied laminates: (+45 sub 2/-45 sub 2). Each laminate contained eight fiber plies. Results of the unidirectionally reinforced composites tested at various angles to the reinforcement direction indicate large anisotropy in in-plane properties. In addition, strength properties of these composites along the fiber direction were independent of specimen gage length and were unaffected by notches normal to the fiber direction. Splitting parallel to the fiber at the notch tip appears to be the dominant crack blunting mechanism responsible for notch insensitive behavior of these composites. In-plane properties of the composites can be improved by 2-D laminate construction. Mechanical property results for (0 sub 2/90 sub 2)sub s and (+45/-45 sub 2) sub s laminates showed that their matrix failure strains were similar to that for (0) sub 8 laminates, but their primary elastic moduli, matrix cracking strengths, and ultimate composite strengths were lower. The elastic properties of unidirectional, cross-ply, and angle-ply composites can be predicted from modified constitutive equations and laminate theory. Further improvements in laminate properties may be achieved by reducing the matrix porosity and by optimizing the bond strength between the SiC fiber and RBSN matrix.

Rhatt, R. T.; Phillips, R. E.

1988-01-01

238

Role of bond strength on the lattice thermal expansion and oxide ion conductivity in quaternary pyrochlore solid solutions.  

PubMed

Quaternary pyrochlore-type solid solutions, CaGdZrNb(1-x)Ta(x)O(7) (x = 0, 0.2, 0.4, 0.6, 0.8, 1), were prepared by a high-temperature ceramic route. The pyrochlore phases of the compounds were confirmed by powder X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy. The crystallographic parameters of the pyrochlore compounds were accurately determined by Rietveld analysis of the powder XRD data. The isovalent substitution of Ta in place of Nb at the B site can reveal the effect of chemical bonding on lattice thermal expansion and oxide ion conductivity because both Nb and Ta have the same ionic radius (0.64 Å). Lattice thermal expansion coefficients of the samples were calculated from high-temperature XRD measurements, and it was found that the thermal expansion coefficient decreases with substitution of Ta. Oxide ion conductivity measured by a two-probe method also shows the same trend with substitution of Ta, and this can be attributed to the high bond strength of the Ta-O bond compared to that of the Nb-O bond. Microstructural characterization using scanning electron microscopy proves that the size of the grains has a small effect on the oxide ion conductivity. Our studies established the role of chemical bonding in deciding the conductivity of pyrochlore oxides and confirmed that the 48f-48f mechanism of oxide ion conduction is dominant in pyrochlore oxides. PMID:22280449

Radhakrishnan, A N; Prabhakar Rao, P; Mahesh, S K; Thampi, D S Vaisakhan; Koshy, Peter

2012-02-20

239

Reactions in 1,1,1-trifluoroacetone triggered by low energy electrons (0-10 eV): from simple bond cleavages to complex unimolecular reactions.  

PubMed

The impact of low energy electrons (0-10 eV) to 1,1,1-trifluoroacetone yields a variety of fragment anions which are formed via dissociative electron attachment (DEA) through three pronounced resonances located at 0.8 eV, near 4 eV, and in the energy range 8-9 eV. The fragment ions arise from different reactions ranging from the direct cleavage of one single or double bond (formation of F(-), CF3(-), O(-), (M-H)(-), and M-F)(-)) to remarkably complex unimolecular reactions associated with substantial geometric and electronic rearrangement in the transitory intermediate (formation of OH(-), FHF(-), (M-HF)(-), CCH(-), and HCCO(-). The ion CCH(-), for example, is formed by an excision of unit from the target molecule through the concerted cleavage of four bonds and recombination to H2O within the neutral component of the reaction. PMID:24828451

Illenberger, Eugen; Meinke, Martina C

2014-08-21

240

Extended Reaction Scope of Thiamine Diphosphate Dependent Cyclohexane-1,2-dione Hydrolase: From C?C Bond Cleavage to C?C Bond Ligation.  

PubMed

ThDP-dependent cyclohexane-1,2-dione hydrolase (CDH) catalyzes the C?C bond cleavage of cyclohexane-1,2-dione to 6-oxohexanoate, and the asymmetric benzoin condensation between benzaldehyde and pyruvate. One of the two reactivities of CDH was selectively knocked down by mutation experiments. CDH-H28A is much less able to catalyze the C?C bond formation, while the ability for C?C bond cleavage is still intact. The double variant CDH-H28A/N484A shows the opposite behavior and catalyzes the addition of pyruvate to cyclohexane-1,2-dione, resulting in the formation of a tertiary alcohol. Several acyloins of tertiary alcohols are formed with 54-94?% enantiomeric excess. In addition to pyruvate, methyl pyruvate and butane-2,3-dione are alternative donor substrates for C?C bond formation. Thus, the very rare aldehyde-ketone cross-benzoin reaction has been solved by design of an enzyme variant. PMID:25382418

Loschonsky, Sabrina; Wacker, Tobias; Waltzer, Simon; Giovannini, Pier Paolo; McLeish, Michael J; Andrade, Susana L A; Müller, Michael

2014-12-22

241

Rubber-to-metal bonding: An investigation of chemical reactions and adhesion at the interface  

NASA Astrophysics Data System (ADS)

Adhesion of rubber to steel plays an important role in many areas of technology. However, adhesion of natural rubber (NR) to most metals is poor due to the polarity of the rubber surface. In order to obtain adhesion, the substrates are often plated with brass, which is one of the few metals that NR will adhere to. The goal of this research was to elucidate the chemistry between rubber and brass at the interface and to develop primers that could replace the brass plating. Rubber fracture and model rubber experiments were used to determine the mechanisms responsible for adhesion between rubber and brass. Plasma polymerization was used to develop acetylene primers to replace brass plating. In the rubber fracture experiments, failure surfaces from rubber/brass lap joints and single wire adhesion tests were analyzed using X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR). It was concluded that a rubber boundary layer existed, which consisted of high levels of oxidation and silicon that were related to adhesion failure. The composition of this layer depended on cure cycle. Model rubber experiments were used to determine the effects of two vulcanization accelerators, N,N-dicyclohexyl-2-benzothiazole sulfenamide and N-tert-butyl-2-benzothiazole sulfenamide, on the reactions between rubber and brass. Squalene, a low molecular weight hydrocarbon was used in place of NR. The chemical reactions between rubber and brass were characterized by IR, Raman, and XPS analysis. Analysis of the brass substrates after reaction with the model rubber systems showed that stearates, copper oxide, and sulfides formed initially on the surface. This was followed by squalene deposition and polyene formation (crosslinking). The rates at which these reactions occurred depended on the accelerator. Plasma-polymerized acetylene primers were developed using a microwave reactor. It was determined that low levels of fragmentation of acetylene molecules led to good adhesion in the rubber/plasma film/steel system. Fragmentation was controlled by the processing parameters, such as pressure, power and flow ratio used in the deposition process. Rubber/steel lap joints prepared from steel adherends coated with plasma-polymerized acetylene films outperformed joints prepared from brass-plated steel adherends in tests of initial adhesion and durability of adhesion.

Bertelsen, Craig Michael

242

Multiple-Site Concerted Proton-Electron Transfer Reactions of Hydrogen-Bonded Phenols are Non-adiabatic and Well Described by Semi-Classical Marcus Theory  

PubMed Central

Photo-oxidations of hydrogen-bonded phenols using excited state polyarenes are described, to derive fundamental understanding of multiple-site concerted proton-electron transfer reactions (MS-CPET). Experiments have examined phenol-bases having ?CPh2NH2, ?Py, and ?CH2Py groups ortho to the phenol hydroxyl group and tert-butyl groups in the 4,6-positions for stability (HOAr-NH2, HOAr-Py, and HOAr-CH2Py, respectively; Py = pyridyl; Ph = phenyl). The photo-oxidations proceed by intramolecular proton transfer from the phenol to the pendent base concerted with electron transfer to the excited polyarene. For comparison, 2,4,6-tBu3C6H2OH, a phenol without a pendent base and tert-butyl groups in the 2,4,6-positions, has also been examined. Many of these bimolecular reactions are fast, with rate constants near the diffusion limit. Combining the photochemical kCPET values with those from prior thermal stopped-flow kinetic studies gives datasets for the oxidations of HOAr-NH2 and of HOAr-CH2Py that span over 107 in kCPET and nearly 0.9 eV in driving force (?Go?). Plots of log(kCPET) vs. ?Go? define a single Marcus parabola in each case, each including both excited state anthracenes and ground state aminium radical cations. These two datasets are thus well described by semi-classical Marcus theory, providing a strong validation of the use of this theory for MS-CPET. The parabolas give ?CPET ? 1.15–1.2 eV and Hab ? 20–30 cm?1. These experiments represent the most direct measurements of Hab for MS-CPET reactions to date. Although rate constants are available only up to the diffusion limit, the parabolas clearly peak well below the adiabatic limit of ca. 6 × 1012 s?1. Thus, this is a very clear demonstration that the reactions are non-adiabatic. The non-adiabatic character slows the reactions by a factor of ~45. Results for the oxidation of HOAr-Py, in which the phenol and base are conjugated, and for oxidation of 2,4,6-tBu3C6H2OH, which lacks a base, show that both have substantially lower ? and larger pre-exponential terms. The implications of these results for MS-CPET reactions are discussed. PMID:22974135

Schrauben, Joel N.; Cattaneo, Mauricio; Day, Thomas C.; Tenderholt, Adam L.; Mayer, James M.

2012-01-01

243

The GC/AED studies on the reactions of sulfur mustard with oxidants.  

PubMed

A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive. PMID:15876488

Popiel, Stanis?aw; Witkiewicz, Zygfryd; Szewczuk, Aleksander

2005-08-31

244

Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes  

E-print Network

The kinetics of the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) on polycrystalline platinum [Pt(pc)] and high surface area carbon-supported platinum nanoparticles (Pt/C) were studied in 0.1 M ...

Sheng, Wenchao

245

Ligand-based carbon-nitrogen bond forming reactions of metal dinitrosyl complexes with alkenes and their application to C-H bond functionalization.  

PubMed

Over the past few decades, researchers have made substantial progress in the development of transition metal complexes that activate and functionalize C-H bonds. For the most part, chemists have focused on aliphatic and aromatic C-H bonds and have put less effort into complexes that activate and functionalize vinylic C-H bonds. Our groups have recently developed a novel method to functionalize vinylic C-H bonds that takes advantage of the unique ligand-based reactivity of a rare class of metal dinitrosyl complexes. In this Account, we compare and discuss the chemistry of cobalt and ruthenium dinitrosyl complexes, emphasizing alkene binding, C-H functionalization, and catalysis. Initially discovered in the early 1970s by Brunner and studied more extensively in the 1980s by the Bergman group, the cyclopentadienylcobalt dinitrosyl complex CpCo(NO)2 reacts reversibly with alkenes to give, in many cases, stable and isolable cobalt dinitrosoalkane complexes. More recently, we found that treatment with strong bases, such as lithium hexamethyldisilazide, Verkade's base, and phosphazene bases, deprotonates these complexes and renders them nucleophilic at the carbon ? to the nitroso group. This conjugate anion of metal dinitrosoalkanes can participate in conjugate addition to Michael acceptors to form new carbon-carbon bonds. These functionalized cobalt complexes can further react through alkene exchange to furnish the overall vinylic C-H functionalized organic product. This stepwise sequence of alkene binding, functionalization, and retrocycloaddition represents an overall vinylic C-H functionalization reaction of simple alkenes and does not require directing groups. We have also developed an asymmetric variant of this reaction sequence and have used this method to synthesize C1- and C2-symmetric diene ligands with high enantioinduction. Building upon these stepwise reactions, we eventually developed a simple one-pot procedure that uses stoichiometric amounts of a cobalt dinitrosoalkane complex for both inter- and intramolecular C-H functionalization. We can achieve catalysis in one-pot intramolecular reactions with a limited range of substrates. Our groups have also reported an analogous ruthenium dinitrosyl complex. In analogy to the cobalt complex, this ruthenium complex reacts with alkenes in the presence of neutral bidentate ligands, such as TMEDA, to give octahedral dinitrosoalkane complexes. Intramolecular functionalization or cyclization of numerous ruthenium dinitrosoalkane complexes proceeds under mild reaction conditions to give the functionalized organic products in excellent yields. However, despite extensive efforts, so far we have not been able to carry out intermolecular reactions of these complexes with a variety of electrophiles or C-H functionalization reactions. Although additional work is necessary to further boost the catalytic capabilities of both cobalt and ruthenium dinitrosyl complexes for vinylic C-H functionalization of simple alkenes, we believe this ligand-based vinylic C-H functionalization reaction has provided chemists with a useful set of tools for organic synthesis. PMID:24359109

Zhao, Chen; Crimmin, Mark R; Toste, F Dean; Bergman, Robert G

2014-02-18

246

A study on thermal barrier coatings including thermal expansion mismatch and bond coat oxidation  

NASA Technical Reports Server (NTRS)

The present investigation deals with a plasma-sprayed thermal barrier coating (TBC) intended for high temperature applications to advanced gas turbine blades. Typically, this type of coating system consists of a zirconia-yttria ceramic layer with a nickel-chromium-aluminum bond coat on a superalloy substrate. The problem on hand is a complex one due to the fact that bond coat oxidation and thermal mismatch occur in the TBC. Cracking in the TBC has also been experimentally illustrated. A clearer understanding of the mechanical behavior of the TBC is investigated. The stress states in a model thermal barrier coating as it cools down in air is studied. The powerful finite element method was utilized to model a coating cylindrical specimen. Four successively refined finite element models were developed. Some results obtained using the first two models have been reported previously. The major accomplishment is the successful development of an elastic TBC finite element model known as TBCG with interface geometry between the ceramic layer and the bond coat. An equally important milestone is the near-completion of the new elastic-plastic TBC finite element model called TBCGEP which yielded initial results. Representative results are presented.

Chang, George C.; Phucharoen, Woraphat; Miller, Robert A.

1986-01-01

247

An oxidative carbon-carbon bond formation system in cycloalkane-based thermomorphic multiphase solution.  

PubMed

A selective anodic oxidation system in which a carbocation intermediate is generated exclusively by use of a temperature-controlled multiphase solution to separate the different stages of the reaction from each other and from the products is described. The formation of a thermomorphic middle layer in an electrolytic solution composed of c-Hex and LPC/MeNO2 results in enhanced interaction between aliphatic alkenes and polar unstable cation. PMID:18376846

Kim, Shokaku; Noda, Satoko; Hayashi, Kanako; Chiba, Kazuhiro

2008-05-01

248

Low-index nanopatterned barrier for hybrid oxide-free III-V silicon conductive bonding.  

PubMed

Oxide-free bonding of a III-V active stack emitting at 1300-1600 nm to a silicon-on-insulator wafer offers the capability to electrically inject lasers from the silicon side. However, a typical 500-nm-thick silicon layer notably attracts the fundamental guided mode of the silicon + III-V stack, a detrimental feature compared to established III-V Separate-Confinement Heterostructure (SCH) stacks. We experimentally probe with photoluminescence as an internal light source the guiding behavior for oxide-free bonding to a nanopatterned silicon wafer that acts as a low-index barrier. We use a sub-wavelength square array of small holes as an effective "low-index silicon" medium. It is weakly modulated along one dimension (superperiodic array) to outcouple the resulting guided modes to free space, where we use an angle-resolved spectroscopy study. Analysis of experimental branches confirms the capability to operate with a fundamental mode well localized in the III-V heterostructures. PMID:25321802

Bougot-Robin, Kristelle; Talneau, Anne; Benisty, Henri

2014-09-22

249

Creep analysis of solid oxide fuel cell with bonded compliant seal design  

NASA Astrophysics Data System (ADS)

Solid oxide fuel cell (SOFC) requires good sealant because it works in harsh conditions (high temperature, thermal cycle, oxidative and reducing gas environments). Bonded compliant seal (BCS) is a new sealing method for planar SOFC. It uses a thin foil metal to bond the window frame and cell, achieving the seal between window frame and cell. At high temperature, a comprehensive evaluation of its creep strength is essential for the adoption of BCS design. In order to characterize the creep behavior, the creep induced by thermal stresses in SOFC with BCS design is simulated by finite element method. The results show that the foil is compressed and large thermal stresses are generated. The initial peak thermal stress is located in the thin foil because the foil acts as a spring stores the thermal stresses by elastic and plastic deformation in itself. Serving at high temperature, initial thermal displacement is partially recovered because of the creep relaxation, which becomes a new discovered advantage for BCS design. It predicts that the failures are likely to happen in the middle of the cell edge and BNi-2 filler metal, because the maximum residual displacement and creep strain are located.

Jiang, Wenchun; Zhang, Yucai; Luo, Yun; Gong, J. M.; Tu, S. T.

2013-12-01

250

Destruction of hydrogen bonds of poly(N-isopropylacrylamide) aqueous solution by trimethylamine N-oxide.  

PubMed

Trimethylamine N-oxide (TMAO) is a compatible or protective osmolyte that stabilizes the protein native structure through non-bonding mechanism between TMAO and hydration surface of protein. However, we have shown here first time the direct binding mechanism for naturally occurring osmolyte TMAO with hydration structure of poly(N-isopropylacrylamide) (PNIPAM), an isomer of polyleucine, and subsequent aggregation of PNIPAM. The influence of TMAO on lower critical solution temperature (LCST) of PNIPAM was investigated as a function of TMAO concentration at different temperatures by fluorescence spectroscopy, viscosity (?), multi angle dynamic light scattering, zeta potential, and Fourier transform infrared (FTIR) spectroscopy measurements. To address some of the basis for further analysis of FTIR spectra of PNIPAM, we have also measured FTIR spectra for the monomer of N-isopropylacrylamide (NIPAM) in deuterium oxide (D(2)O) as a function of TMAO concentration. Our experimental results purportedly elucidate that the LCST values decrease with increasing TMAO concentration, which is mainly contributing to the direct hydrogen bonding of TMAO with the water molecules that are bound to the amide (-CONH) functional groups of the PNIPAM. We believed that the present work may act as a ladder to reach the heights of understanding of molecular mechanism between TMAO and macromolecule. PMID:22779616

Reddy, P Madhusudhana; Taha, Mohamed; Venkatesu, Pannuru; Kumar, Awanish; Lee, Ming-Jer

2012-06-21

251

Destruction of hydrogen bonds of poly(N-isopropylacrylamide) aqueous solution by trimethylamine N-oxide  

NASA Astrophysics Data System (ADS)

Trimethylamine N-oxide (TMAO) is a compatible or protective osmolyte that stabilizes the protein native structure through non-bonding mechanism between TMAO and hydration surface of protein. However, we have shown here first time the direct binding mechanism for naturally occurring osmolyte TMAO with hydration structure of poly(N-isopropylacrylamide) (PNIPAM), an isomer of polyleucine, and subsequent aggregation of PNIPAM. The influence of TMAO on lower critical solution temperature (LCST) of PNIPAM was investigated as a function of TMAO concentration at different temperatures by fluorescence spectroscopy, viscosity (?), multi angle dynamic light scattering, zeta potential, and Fourier transform infrared (FTIR) spectroscopy measurements. To address some of the basis for further analysis of FTIR spectra of PNIPAM, we have also measured FTIR spectra for the monomer of N-isopropylacrylamide (NIPAM) in deuterium oxide (D2O) as a function of TMAO concentration. Our experimental results purportedly elucidate that the LCST values decrease with increasing TMAO concentration, which is mainly contributing to the direct hydrogen bonding of TMAO with the water molecules that are bound to the amide (-CONH) functional groups of the PNIPAM. We believed that the present work may act as a ladder to reach the heights of understanding of molecular mechanism between TMAO and macromolecule.

Reddy, P. Madhusudhana; Taha, Mohamed; Venkatesu, Pannuru; Kumar, Awanish; Lee, Ming-Jer

2012-06-01

252

Effect of composition on the processing and properties of sintered reaction-bonded silicon nitride  

SciTech Connect

The type of silicon powder and sintering additive were found to influence the processing and final mechanical properties of sintered reaction bonded silicon nitride. High purity silicon powders produced low {alpha}-Si{sub 3}N{sub 4} content during nitridation. The Si powder type had no apparent effect on densification. More complete nitridation and higher room temperature mechanical properties were observed for the Si powders with higher Fe contents. However, the higher Fe contents resulted in greater high temperature strength degradation and so there was better high temperature strength retention with the higher purity Si. High {alpha}-Si{sub 3}N{sub 4} contents were found after nitridation with {alpha}-Si{sub 3}N{sub 4} seeded materials and with MgO-Y{sub 2}O{sub 3} as the sintering additive. Densification was inhibited by refractory additives, such as Y{sub 2}O{sub 3}-SiO{sub 2}. The highest room temperature strength and fracture toughness values correlated to high nitrided {alpha}-Si{sub 3}N{sub 4} contents. The high temperature strength behavior was similar for all additive types.

Tiegs, T.N.; Kiggans, J.O.; Montgomery, F.C.; Lin, H.T.; Barker, D.L.; Snodgrass, J.D.; Sabolsky, E.M.; Coffey, D.W.

1996-04-01

253

Formation of porous surface layers in reaction bonded silicon nitride during processing  

NASA Technical Reports Server (NTRS)

An effort was undertaken to determine if the formation of the generally observed layer of large porosity adjacent to the as-nitride surfaces of reaction bonded silicon nitrides could be prevented during processing. Isostatically pressed test bars were prepared from wet vibratory milled Si powder. Sintering and nitriding were each done under three different conditions:(1) bars directly exposed to the furnance atmosphere; (2) bars packed in Si powder; (3) bars packed in Si3N4 powder. Packing the bars in either Si of Si3N4 powder during sintering retarded formation of the layer of large porosity. Only packing the bars in Si prevented formation of the layer during nitridation. The strongest bars (316 MPa) were those sintered in Si and nitrided in Si3N4 despite their having a layer of large surface porosity; failure initiated at very large pores and inclusions. The alpha/beta ratio was found to be directly proportional to the oxygen content; a possible explanation for this relationship is discussed.

Shaw, N. J.; Glasgow, T. K.

1979-01-01

254

Recent advances in reaction bonded silicon carbide optics and optical systems  

NASA Astrophysics Data System (ADS)

SSG Precision Optronics, Inc. (SSG) has recently developed a number of Reaction Bonded (RB) Silicon Carbide (SiC) optical systems for space-based remote sensing and astronomical observing applications. RB SiC's superior material properties make it uniquely well suited to meet the image quality and long term dimensional stability requirements associated with these applications. An overview of the RB SiC manufacturing process is presented, along with a summary description of recently delivered RB SiC flight hardware. This hardware includes an RB SiC telescope and Pointing Mirror Assembly (PMA) for the Geostationary Imaging Fourier Transform Spectrometer (GIFTS) mission and an imaging telescope for the Long-Range Reconnaissance Imager (LORRI) mission. SSG continues to advance the state-of-the-technology with SiC materials and systems. A summary of development activities related to a low-cost, fracture tough, fiber reinforced RB SiC material formulation, novel tooling to produce monolithic, partially closed back mirror geometries, and extension of the technology to large aspheric mirrors is also provided.

Robichaud, Joseph; Schwartz, Jay; Landry, David; Glenn, William; Rider, Brian; Chung, Michael

2005-08-01

255

Kinetics and Mechanism of Iodide Oxidation by Iron(III): A Clock Reaction Approach  

ERIC Educational Resources Information Center

A simple method for studying the kinetics of a chemical reaction is described and the significance of reaction orders in deducing reaction mechanisms is demonstrated. In this student laboratory experiment, oxidation of iodide by iron(III) ions in an acidic medium is transformed into a clock reaction. By means of the initial rates method, it is…

Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

2008-01-01

256

A comprehensive theoretical study on the coupling reaction mechanism of propylene oxide with carbon dioxide catalyzed by copper(I) cyanomethyl.  

PubMed

The mechanistic details of the coupling reaction of propylene oxide with carbon dioxide catalyzed by copper(I) cyanomethyl to yield cyclic carbonate were elucidated by density functional theory (DFT) calculations at the B3LYP/6-311G** level. Our results reveal that the overall reaction is stepwise and considered to include two processes. In process 1, CO(2) insertion into the Cu(I)-C bond of copper(I) cyanomethyl affords activated carbon dioxide carriers. In process 2, O-coordination of propylene oxide molecule to the electrophilic copper center of carriers occurs. Herein, three possible pathways were investigated, and the calculated reaction free energy profiles were compared. It was found that carrier 8 reacting with propylene oxide is more favored than the other two carriers (6 and 7) both kinetically and thermodynamically. Several factors, such as the composition of catalyst, the coordinate environment of copper, and the symmetry of frontier molecular orbitals, affected the reaction mechanisms, and the outcomes were identified. The overall reaction is exothermic. In addition, natural bond orbital (NBO) analysis has been performed to study the effects of charge transfer and understand the nature of different interactions between atoms and groups. The present theoretical study explains satisfactorily the early reported experimental observations well and provides a clear profile for the cycloaddition of carbon dioxide with propylene oxide promoted by NCCH(2)Cu. PMID:19469523

Guo, Cai-Hong; Wu, Hai-Shun; Zhang, Xian-Ming; Song, Jiang-Yu; Zhang, Xiang

2009-06-18

257

Demonstration of the heterolytic O-O bond cleavage of putative nonheme iron(II)-OOH(R) complexes for Fenton and enzymatic reactions.  

PubMed

One-electron reduction of mononuclear nonheme iron(III) hydroperoxo (Fe(III)-OOH) and iron(III) alkylperoxo (Fe(III)-OOR) complexes by ferrocene (Fc) derivatives resulted in the formation of the corresponding iron(IV) oxo complexes. The conversion rates were dependent on the concentration and oxidation potentials of the electron donors, thus indicating that the reduction of the iron(III) (hydro/alkyl)peroxo complexes to their one-electron reduced iron(II) (hydro/alkyl)peroxo species is the rate-determining step, followed by the heterolytic O-O bond cleavage of the putative iron(II) (hydro/alkyl)peroxo species to give the iron(IV) oxo complexes. Product analysis supported the heterolytic O-O bond-cleavage mechanism. The present results provide the first example showing the one-electron reduction of iron(III) (hydro/alkyl)peroxo complexes and the heterolytic O-O bond cleavage of iron(II) (hydro/alkyl)peroxo species to form iron(IV) oxo intermediates which occur in nonheme iron enzymatic and Fenton reactions. PMID:24916304

Bang, Suhee; Park, Sora; Lee, Yong-Min; Hong, Seungwoo; Cho, Kyung-Bin; Nam, Wonwoo

2014-07-21

258

Residues in Human Arsenic (+3 Oxidation State) Methyltransferase Forming Potential Hydrogen Bond Network around S-adenosylmethionine  

PubMed Central

Residues Tyr59, Gly78, Ser79, Met103, Gln107, Ile136 and Glu137 in human arsenic (+3 oxidation state) methyltransferase (hAS3MT) were deduced to form a potential hydrogen bond network around S-adenosylmethionine (SAM) from the sequence alignment between Cyanidioschyzon merolae arsenite S-adenosylmethyltransferase (CmArsM) and hAS3MT. Herein, seven mutants Y59A, G78A, S79A, M103A, Q107A, I136A and E137A were obtained. Their catalytic activities and conformations were characterized and models were built. Y59A and G78A were completely inactive. Only 7.0%, 10.6% and 13.8% inorganic arsenic (iAs) was transformed to monomethylated arsenicals (MMA) when M103A, Q107A and I136A were used as the enzyme. The Vmax (the maximal velocity of the reaction) values of M103A, Q107A, I136A and E137A were decreased to 8%, 22%, 15% and 50% of that of WT-hAS3MT, respectively. The KM(SAM) (the Michaelis constant for SAM) values of mutants M103A, I136A and E137A were 15.7, 8.9 and 5.1 fold higher than that of WT-hAS3MT, respectively, indicating that their affinities for SAM were weakened. The altered microenvironment of SAM and the reduced capacity of binding arsenic deduced from KM(As) (the Michaelis constant for iAs) value probably synergetically reduced the catalytic activity of Q107A. The catalytic activity of S79A was higher than that of WT despite of the higher KM(SAM), suggesting that Ser79 did not impact the catalytic activity of hAS3MT. In short, residues Tyr59 and Gly78 significantly influenced the catalytic activity of hAS3MT as well as Met103, Ile136 and Glu137 because they were closely associated with SAM-binding, while residue Gln107 did not affect SAM-binding regardless of affecting the catalytic activity of hAS3MT. Modeling and our experimental results suggest that the adenine ring of SAM is sandwiched between Ile136 and Met103, the amide group of SAM is hydrogen bonded to Gly78 in hAS3MT and SAM is bonded to Tyr59 with van der Waals, cation-? and hydrogen bonding contacts. PMID:24124590

Li, Xiangli; Cao, Jing; Wang, Shuping; Geng, Zhirong; Song, Xiaoli; Hu, Xin; Wang, Zhilin

2013-01-01

259

Uraninite oxidation and dissolution induced by manganese oxide: A redox reaction between two insoluble minerals  

NASA Astrophysics Data System (ADS)

The longevity of subsurface U(IV) produced by reduction of U(VI) during in situ bioremediation can be limited by reoxidation to more mobile U(VI) species. Coupling of the biogeochemical cycles of U and Mn may affect the fate and transport of uranium. Manganese oxides can act as a powerful oxidant that accelerates the oxidative dissolution of UO2. This study investigated the physical and chemical factors controlling the interaction between UO2 and MnO2, which are both poorly soluble minerals. A multi-chamber reactor with a permeable membrane was used to eliminate direct contact of the two minerals while still allowing transport of aqueous species. The oxidation of UO2 was not significantly enhanced by MnO2 if the two solids were physically separated. Complete mixing of MnO2 with UO2 led to a much greater extent and rate of U oxidation. When direct contact is not possible, the reaction slowly progresses through release of soluble U(IV) with its adsorption and oxidation on MnO2. Continuously-stirred tank reactors (CSTRs) were used to quantify the steady-state rates of UO2 dissolution induced by MnO2. MnO2 dramatically promoted UO2 dissolution, but the degree of promotion leveled off once the MnO2:UO2 ratio exceeded a critical value. Substantial amounts of U(VI) and Mn(II) were retained on MnO2 surfaces. The total production of Mn(II) was less than that of U(VI), indicating that the fate of Mn products and their impact on UO2-MnO2 reaction kinetics were complicated and may involve formation of Mn(III) phases. At higher dissolved inorganic carbon concentrations, UO2 oxidation by MnO2 was faster and less U(VI) was adsorbed to MnO2. Such an inverse relationship suggested that U(VI) may passivate MnO2 surfaces. A conceptual model was developed to describe the oxidation rate of UO2 by MnO2. This model is potentially applicable to a broad range of water chemistry conditions and is relevant to other environmental redox processes involving two poorly soluble minerals.

Wang, Zimeng; Lee, Sung-Woo; Kapoor, Pratyul; Tebo, Bradley M.; Giammar, Daniel E.

2013-01-01

260

Effect of oxidation conditions on chlorination reaction of Zircaloy-4 hulls  

NASA Astrophysics Data System (ADS)

The effect of oxidation conditions on the chlorination reaction behavior was investigated by using Zircaloy-4 (Zry-4) hulls oxidized at various conditions. When the hulls were oxidized at 500, 600, and 700 °C for 5 h, decrease of reactant mass after the chlorination reaction at 380 °C for 3 h was 41.6, 26.0, and 0.0 wt.%, respectively, while that of fresh Zry-4 hulls was 54.1 wt.%. Surface analysis results revealed that the oxidation state of Zr is significantly dependent on the oxidation temperature. The effect of oxidation time was also investigated for the Zry-4 hulls oxidized at 500 and 700 °C up to 24 h. Based on the experimental results, it was concluded that the chlorination method is applicable to the Zry-4 hulls oxidized at 500 °C without removal of the surface oxide layers, while a pretreatment is required to recover Zr from the hulls oxidized at 700 °C.

Jeon, Min Ku; Kang, Kweon Ho; Heo, Chul Min; Yang, Jae Hwan; Lee, Chang Hwa; Park, Geun Il

2012-05-01

261

Enzymatic reactions involved in the repair of oxidized proteins  

Microsoft Academic Search

Proteins are the targets of reactive oxygen species, and cell aging is characterized by a build-up of oxidized proteins. Oxidized proteins tend to accumulate with age, due to either an increase in the rate of protein oxidation, a decrease in the rate of oxidized protein repair and degradation, or a combination of both mechanisms. Oxidized protein degradation is mainly carried

Jean Mary; Stephanie Vougier; Cedric R. Picot; Martine Perichon; Isabelle Petropoulos; Bertrand Friguet

2004-01-01

262

Efficient C-C bond splitting on Pt monolayer and sub-monolayer catalysts during ethanol electro-oxidation: Pt layer strain and morphology effects.  

PubMed

Efficient catalytic C-C bond splitting coupled with complete 12-electron oxidation of the ethanol molecule to CO2 is reported on nanoscale electrocatalysts comprised of a Pt monolayer (ML) and sub-monolayer (sML) deposited on Au nanoparticles (Au@Pt ML/sML). The Au@Pt electrocatalysts were synthesized using surface limited redox replacement (SLRR) of an underpotentially deposited (UPD) Cu monolayer in an electrochemical cell reactor. Au@Pt ML showed improved catalytic activity for ethanol oxidation reaction (EOR) and, unlike their Pt bulk and Pt sML counterparts, was able to generate CO2 at very low electrode potentials owing to efficient C-C bond splitting. To explain this, we explore the hypothesis that competing strain effects due to the Pt layer coverage/morphology (compressive) and the Pt-Au lattice mismatch (tensile) control surface chemisorption and overall activity. Control experiments on well-defined model Pt monolayer systems are carried out involving a wide array of methods such as high-energy X-ray diffraction, pair-distribution function (PDF) analysis, in situ electrochemical FTIR spectroscopy, and in situ scanning tunneling microscopy. The vibrational fingerprints of adsorbed CO provide compelling evidence on the relation between surface bond strength, layer strain and morphology, and catalytic activity. PMID:25081353

Loukrakpam, Rameshwori; Yuan, Qiuyi; Petkov, Valeri; Gan, Lin; Rudi, Stefan; Yang, Ruizhi; Huang, Yunhui; Brankovic, Stanko R; Strasser, Peter

2014-09-21

263

Experimental and theoretical study of the reactions between neutral vanadium oxide clusters and ethane, ethylene, and acetylene.  

PubMed

Reactions of neutral vanadium oxide clusters with small hydrocarbons, namely C2H6, C2H4, and C2H2, are investigated by experiment and density functional theory (DFT) calculations. Single photon ionization through extreme ultraviolet (EUV, 46.9 nm, 26.5 eV) and vacuum ultraviolet (VUV, 118 nm, 10.5 eV) lasers is used to detect neutral cluster distributions and reaction products. The most stable vanadium oxide clusters VO2, V2O5, V3O7, V4O10, etc. tend to associate with C2H4 generating products V(m)O(n)C2H4. Oxygen-rich clusters VO3(V2O5)(n=0,1,2...), (e.g., VO3, V3O8, and V5O13) react with C2H4 molecules to cause a cleavage of the C=C bond of C2H4 to produce (V2O5)(n)VO2CH2 clusters. For the reactions of vanadium oxide clusters (V(m)O(n)) with C2H2 molecules, V(m)O(n)C2H2 are assigned as the major products of the association reactions. Additionally, a dehydration reaction for VO3 + C2H2 to produce VO2C2 is also identified. C2H6 molecules are quite stable toward reaction with neutral vanadium oxide clusters. Density functional theory calculations are employed to investigate association reactions for V2O5 + C2H(x). The observed relative reactivity of C2 hydrocarbons toward neutral vanadium oxide clusters is well interpreted by using the DFT calculated binding energies. DFT calculations of the pathways for VO3+C2H4 and VO3+C2H2 reaction systems indicate that the reactions VO3+C2H4 --> VO2CH2 + H2CO and VO3+C2H2 --> VO2C2 + H2O are thermodynamically favorable and overall barrierless at room temperature, in good agreement with the experimental observations. PMID:18198869

Dong, Feng; Heinbuch, Scott; Xie, Yan; Rocca, Jorge J; Bernstein, Elliot R; Wang, Zhe-Chen; Deng, Ke; He, Sheng-Gui

2008-02-13

264

Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 C-H bond and Lewis acid catalysis.  

PubMed

Ruthenium porphyrins (particularly [Ru(2,6-Cl(2)tpp)CO]; tpp=tetraphenylporphinato) and RuCl(3) can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3-{[(N-aryl-N-alkyl)amino]methyl}indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp(3) C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl(2)tpp)CO]-catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants sigma (R(2)=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (k(H)/k(D)) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl/N-H indoles, paraformaldehyde, and anilines gave 3-[p-(dialkylamino)benzyl]indoles in up to 82% yield (conversion: up to 95%). PMID:20391566

Wang, Ming-Zhong; Zhou, Cong-Ying; Wong, Man-Kin; Che, Chi-Ming

2010-05-17

265

Oxidation Behavior of Thermal Barrier Coatings with a TiAl3 Bond Coat on ?-TiAl Alloy  

NASA Astrophysics Data System (ADS)

The thermal barrier coatings investigated in this paper included a TiAl3 bond coat and a yttria partially stabilized zirconia (YSZ) layer. The TiAl3 bond coat was prepared by deposition of aluminum by cold spray, followed by a heat-treatment. The YSZ layer was prepared by air plasma spray. The isothermal and cyclic oxidation tests were conducted at 900 °C for 1000 h and 500 cycles to test the oxidation resistance of the thermal barrier coatings. The microstructure and composition of the ?-TiAl alloy with and without the thermal barrier coatings after oxidation were investigated. The results showed that a dense TGO layer about 5 ?m had grown between the YSZ layer and the TiAl3 bond coat. The TGO had good adhesion to both the YSZ layer and the bond coat even after the TiAl3 bond coat entirely degraded into the TiAl2 phase, which decreased the inward oxygen diffusion. Thus, the thermal barrier coatings improved the oxidation resistance of ?-TiAl alloy effectively.

Wang, Jiqiang; Kong, Lingyan; Li, Tiefan; Xiong, Tianying

2015-02-01

266

Recent advances in the synthetic and mechanistic aspects of the ruthenium-catalyzed carbon–heteroatom bond forming reactions of alkenes and alkynes  

Microsoft Academic Search

The group’s recent advances in catalytic carbon-to-heteroatom bond forming reactions of alkenes and alkynes are described. For the C–O bond formation reaction, a well-defined bifunctional ruthenium-amido catalyst has been successfully employed for the conjugate addition of alcohols to acrylic compounds. The ruthenium-hydride complex (PCy3)2(CO)RuHCl was found to be a highly effective catalyst for the regioselective alkyne-to-carboxylic acid coupling reaction in

Chae S. Yi

2011-01-01

267

Ubiquinol oxidation in the cytochrome bc1 complex: Reaction mechanism and prevention of short-circuiting  

E-print Network

Review Ubiquinol oxidation in the cytochrome bc1 complex: Reaction mechanism and prevention oxidizes a ubiquinol molecule to ubiquinone by a unique ``bifurcated'' reaction where the two released electrons go to different acceptors: one is accepted by the mobile redox active domain of the [2Fe­2S] iron

Steinhoff, Heinz-Jürgen

268

Recent advances in transition-metal-free carbon-carbon and carbon-heteroatom bond-forming reactions using arynes.  

PubMed

This tutorial review is aimed at highlighting recent developments in transition-metal-free carbon-carbon and carbon-heteroatom bond-forming reactions utilizing a versatile class of reactive intermediates, viz., arynes, which hold the potential for numerous applications in organic synthesis. Key to the success of the resurgence of interest in the rich chemistry of arynes is primarily the mild condition for their generation by the fluoride-induced 1,2-elimination of 2-(trimethylsilyl)aryl triflates. Consequently, arynes have been employed for the construction of multisubstituted arenes with structural diversity and complexity. The versatile transition-metal-free applications of arynes include cycloaddition reactions, insertion reactions and multicomponent reactions. In addition, arynes have found applications in natural product synthesis. Herein, we present a concise account of the major developments that occurred in this field during the past eight years. PMID:22278415

Bhunia, Anup; Yetra, Santhivardhana Reddy; Biju, Akkattu T

2012-04-21

269

The interaction of reaction-bonded silicon carbide and inconel 600 with a nickel-based brazing alloy  

Microsoft Academic Search

The objective of the present research was to join reaction-bonded silicon carbide (RBSC) to INCONEL 600 (a nickel-based superalloy)\\u000a for use in advanced heat engine applications using either direct brazing or composite interlayer joining. Direct brazing experiments\\u000a employed American Welding Society (AWS) BNi-5, a commercial nickel-based brazing alloy, as a filler material; composite interlayers\\u000a consisted of intimate mixtures of ?-SiC

J. R. McDermid; M. D. Pugh; R. A. L. Drew

1989-01-01

270

The interaction of reaction-bonded silicon carbide and inconel 600 with a nickel-based brazing alloy  

Microsoft Academic Search

The objective of the present research was to join reaction-bonded silicon carbide (RBSC) to INCONEL 600 (a nickel-based superalloy) for use in advanced heat engine applications using either direct brazing or composite interlayer joining. Direct brazing experiments employed American Welding Society (AWS) BNi-5, a commercial nickel-based brazing alloy, as a filler material; composite interlayers consisted of intimate mixtures of alpha-SiC

J. R. McDermid; M. D. Pugh; R. A. L. Drew

1989-01-01

271

Magnesium-Mediated Cleavage of Phosphorus-Oxygen Bond: A Ribozyme Reaction  

Microsoft Academic Search

The hammerhead ribozyme belongs to the class of molecules known as antisense RNAs. However, because of short extra sequences that form the so-called catalytic loop, it can act as an enzyme. Since the catalytic domain captures Mg ions and Mg ions can cleave phosphodiester bonds, hammerhead ribozymes are recognized as metalloenzymes. In general, the cleavage of phosphodiester bonds involves acid\\/base

De-Min Zhou; Li-He Zhang; Masaya Orita; Sinya Sawata; Koichi Yoshinari; Kazunari Taira

1996-01-01

272

Competition between covalent bonding and charge transfer at complex-oxide interfaces.  

PubMed

Here we study the electronic properties of cuprate-manganite interfaces. By means of atomic resolution electron microscopy and spectroscopy, we produce a subnanometer scale map of the transition metal oxidation state profile across the interface between the high Tc superconductor YBa2Cu3O7-? and the colossal magnetoresistance compound (La,Ca)MnO3. A net transfer of electrons from manganite to cuprate with a peculiar nonmonotonic charge profile is observed. Model calculations rationalize the profile in terms of the competition between standard charge transfer tendencies (due to band mismatch), strong chemical bonding effects across the interface, and Cu substitution into the Mn lattice, with different characteristic length scales. PMID:24877959

Salafranca, Juan; Rincón, Julián; Tornos, Javier; León, Carlos; Santamaria, Jacobo; Dagotto, Elbio; Pennycook, Stephen J; Varela, Maria

2014-05-16

273

The mechanism of hydrocarbon oxygenate reforming: C-C bond scission, carbon formation, and noble-metal-free oxide catalysts.  

PubMed

Towards a molecular understanding of the mechanism behind catalytic reforming of bioderived hydrocarbon oxygenates, we explore the C-C bond scission of C2 model compounds (acetic acid, ethanol, ethylene glycol) on ceria model catalysts of different complexity, with and without platinum. Synchrotron photoelectron spectroscopy reveals that the reaction pathway depends very specifically on both the reactant molecule and the catalyst surface. Whereas C-C bond scission on Pt sites and on oxygen vacancies involves intermittent surface carbon species, the reaction occurs without any carbon formation and deposition for ethylene glycol on CeO2(111). PMID:24203922

Lykhach, Yaroslava; Neitzel, Armin; Šev?íková, Klára; Johánek, Viktor; Tsud, Nataliya; Skála, Tomáš; Prince, Kevin C; Matolín, Vladimír; Libuda, Jörg

2014-01-01

274

Examining the structure and bonding in complex oxides using aberration-corrected imaging and spectroscopy  

SciTech Connect

Our ability to directly characterize the atomic and electronic structures is crucial to developing a fundamental understanding of structure-property relationships in complex-oxide materials. Here, we examine one specific example, the misfit-layered thermoelectric material Ca3Co4O9, which exhibits a high Seebeck coefficient governed by spin-entropy transport as well as hopping-mediated electron transport. However, the role of oxygen and its bonding with cobalt in thermoelectric transport remains unclear. We use atomic-resolution annular bright-field imaging to directly image the oxygen sublattice and to combine our experimental data with multislice image calculations to find that the oxygen atoms in the CoO2 subsystem are highly ordered, while the oxygen-atomic columns are displaced in the Ca2CoO3 subsystem. Atomic-column-resolved electron energy-loss spectroscopy and spectrum image calculations are used to quantify the bonding in the different subsystems of incommensurate Ca3Co4O9. We find that the holes in the CoO2 subsystem are delocalized, which could be responsible for the p-type conductivity found in the CoO2 subsystem.

Klie, Robert F [University of Illinois, Chicago; Qiao, Q [University of Illinois at Chicago, Chicago, Illinois 60607, USA; Paulauskas, T [University of Illinois at Chicago, Chicago, Illinois 60607, USA; Ramassee, Q [SuperSTEM, Daresbury, United Kingdom; Oxley, Mark P [ORNL; Idrobo Tapia, Juan C [ORNL

2012-01-01

275

Chemical Bonding, Interfaces and Defects in Hafnium Oxide/Germanium Oxynitride Gate Stacks on Ge (100)  

SciTech Connect

Correlations among interface properties and chemical bonding characteristics in HfO{sub 2}/GeO{sub x}N{sub y}/Ge MIS stacks were investigated using in-situ remote nitridation of the Ge (100) surface prior to HfO{sub 2} atomic layer deposition (ALD). Ultra thin ({approx}1.1 nm), thermally stable and aqueous etch-resistant GeO{sub x}N{sub y} interfaces layers that exhibited Ge core level photoelectron spectra (PES) similar to stoichiometric Ge{sub 3}N{sub 4} were synthesized. To evaluate GeO{sub x}N{sub y}/Ge interface defects, the density of interface states (D{sub it}) was extracted by the conductance method across the band gap. Forming gas annealed (FGA) samples exhibited substantially lower D{sub it} ({approx} 1 x 10{sup 12} cm{sup -2} eV{sup -1}) than did high vacuum annealed (HVA) and inert gas anneal (IGA) samples ({approx} 1x 10{sup 13} cm{sup -2} eV{sup -1}). Germanium core level photoelectron spectra from similar FGA-treated samples detected out-diffusion of germanium oxide to the HfO{sub 2} film surface and apparent modification of chemical bonding at the GeO{sub x}N{sub y}/Ge interface, which is related to the reduced D{sub it}.

Oshima, Yasuhiro; /Stanford U., Materials Sci. Dept.; Sun, Yun; /SLAC, SSRL; Kuzum, Duygu; /Stanford U.; Sugawara, Takuya; Saraswat, Krishna C.; Pianetta, Piero; /SLAC, SSRL; McIntyre, Paul C.; /Stanford U., Materials Sci. Dept.

2008-10-31

276

Hydrogen bonds in 1:2 complexes of substituted pyridine N-oxides with pentachlorophenol  

NASA Astrophysics Data System (ADS)

Pyridine N-oxides form two types of crystalline complexes with phentachlorophenol, with 1:1 and 1:2 base-to-acid ratios. The 1:2 complex of 2,6-dimethylpyridine N-oxide with pentachlorophenol crystallizes in space group P1¯ with a = 7.335(1) Å, b = 11.324(2) Å, c = 15.824(2) Å, ? = 100.38(1)°, ? = 94.63(1)°, ? = 106.60(1)°, V = 1226.7(6) Å3 and Z = 2. The structure has been refined to R = 0.046 for 3408 observed Mo K? reflections. The oxygen atom of the N-oxide group accepts hydrogen bonds from two molecules of pentachlorophenol, with Otctdot;O distances of 2.639(5) and 2.642(5) Å and OHO angles of 141.2° and 157.6°, respectively. Both N?Otctdot;H?O bridges are formed in, or near, the directions of the electron lone-pairs of the N-oxygen atom. The two pentachlorophenol rings (A and B) are nearly parallel to each other and they are almost perpendicular to the pyridine ring. FTIR spectra of eleven 1:2 complexes in the solid state are similar and independent of the proton acceptor properties of the N-oxides. Five lines in the 35Cl NQR spectra of the 1:2 complexes provide evidence that both molecules of pentachlorophenol are equivalent. In CHCl 3 solution, all the 1:2 complexes exist as a mixture of the 1:1 complex and pentachlorophenol.

Dega-Szafran, Zofia; Kosturkiewicz, Zofia; Tykarska, Ewa; Szafran, Miroslaw; Lema?ski, Dariusz; Nogaj, Boles?aw

1997-02-01

277

Aerobic oxidative Mannich reaction promoted by catalytic amounts of stable radical cation salt.  

PubMed

A catalytic amount of triarylaminium salt is demonstrated to be an efficient initiator for oxidative Mannich reaction of tertiary amines and nonactivated ketones under mild neutral conditions. Air is essential for this reaction and acts as a terminal oxidant. Metal catalysts, acid or base additives, and stoichiometric amounts of chemical oxidants are all avoided in this methodology. Six examples of intramolecular cyclized products are also delivered. PMID:25244546

Huo, Congde; Wu, Mingxia; Jia, Xiaodong; Xie, Haisheng; Yuan, Yong; Tang, Jing

2014-10-17

278

Infrared Reflection Absorption Spectroscopy Study of CO Adsorption and Reaction on Oxidized Pd(100)  

E-print Network

to the adsorption energies of oxygen, the heats of formation of the bulk oxides, and the metal particle sizesInfrared Reflection Absorption Spectroscopy Study of CO Adsorption and Reaction on Oxidized Pd(100 oxidation on Pt group metals at temperatures between 450 and 600 K and pressures between 1 and 300 Torr

Goodman, Wayne

279

Biochemical Reaction Products of Nitric Oxide as Quantitative Markers of Primary Pulmonary Hypertension  

Microsoft Academic Search

Primary pulmonary hypertension (PPH) is a rare and fatal disease of unknown etiology. Inflammatory oxidant mechanisms and deficiency in nitric oxide (NO) have been implicated in the pathogenesis of pulmonary hypertension. In order to investigate abnormalities in oxidants and antioxidants in PPH, we studied intrapulmonary NO levels, biochemical reaction products of NO, and antioxidants (glu- tathione (GSH), glutathione peroxidase (GPx),

F. TAKAO KANEKO; ALEJANDRO C. ARROLIGA; RAED A. DWEIK; SUZY A. COMHAIR; DANIEL LASKOWSKI; RITA OPPEDISANO; MARY JANE THOMASSEN; SERPIL C. ERZURUM

1998-01-01

280

Structural and functional investigation of graphene oxide-Fe3O4 nanocomposites for the heterogeneous Fenton-like reaction  

NASA Astrophysics Data System (ADS)

Graphene oxide-iron oxide (GO-Fe3O4) nanocomposites were synthesised by co-precipitating iron salts onto GO sheets in basic solution. The results showed that formation of two distinct structures was dependent upon the GO loading. The first structure corresponds to a low GO loading up to 10 wt%, associated with the beneficial intercalation of GO within Fe3O4 nanoparticles and resulting in higher surface area up to 409 m2 g-1. High GO loading beyond 10 wt% led to the aggregation of Fe3O4 nanoparticles and the undesirable stacking of GO sheets. The presence of strong interfacial interactions (Fe-O-C bonds) between both components at low GO loading lead to 20% higher degradation of Acid Orange 7 than the Fe3O4 nanoparticles in heterogeneous Fenton-like reaction. This behaviour was attributed to synergistic structural and functional effect of the combined GO and Fe3O4 nanoparticles.

Zubir, Nor Aida; Yacou, Christelle; Motuzas, Julius; Zhang, Xiwang; Diniz da Costa, João C.

2014-04-01

281

Activation Energy of Tantalum-Tungsten Oxide Thermite Reaction  

SciTech Connect

The activation energy of a high melting temperature sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the High Pressure Spark Plasma Sintering (HPSPS) technique to 300 and 400 C to produce pellets with dimensions of 5 mm diameter by 1.5 mm height. A custom built ignition setup was developed to measure ignition temperatures at high heating rates (500-2000 C {center_dot} min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Unlike the 400 C samples, results show that the samples consolidated to 300 C undergo an abrupt change in temperature response prior to ignition. This change in temperature response has been attributed to the crystallization of the amorphous WO{sub 3} in the SG derived Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465-670 C. The activation energy of the SG derived Ta-WO{sup 3} thermite composite consolidated to 300 and 400 C were determined to be 37.787 {+-} 1.58 kJ {center_dot} mol{sup -1} and 57.381 {+-} 2.26 kJ {center_dot} mol{sup -1}, respectively.

Cervantes, O; Kuntz, J; Gash, A; Munir, Z

2010-02-25

282

Novel carbon–carbon bond formations for biocatalysis  

PubMed Central

Carbon–carbon bond formation is the key transformation in organic synthesis to set up the carbon backbone of organic molecules. However, only a limited number of enzymatic C–C bond forming reactions have been applied in biocatalytic organic synthesis. Recently, further name reactions have been accomplished for the first time employing enzymes on a preparative scale, for instance the Stetter and Pictet–Spengler reaction or oxidative C–C bond formation. Furthermore, novel enzymatic C–C bond forming reactions have been identified like benzylation of aromatics, intermolecular Diels-Alder or reductive coupling of carbon monoxide. PMID:21354781

Resch, Verena; Schrittwieser, Joerg H; Siirola, Elina; Kroutil, Wolfgang

2011-01-01

283

Adsorption and reaction of acrolein on titanium oxide single crystal surfaces: coupling versus condensation  

Microsoft Academic Search

The reactions of acrolein have been investigated on TiO2(001) single crystal surfaces by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS). Two carbon–carbon bond-forming reactions were observed. The first, on defect-containing surfaces, is reductive coupling to form olefins. The high reaction yield of ca. 80% shows the high activity of such surfaces

A. B. Sherrill; H. Idriss; M. A. Barteau; J. G. Chen

2003-01-01

284

Development of Nitric Oxide Oxidation Catalysts for the Fast SCR Reaction  

SciTech Connect

This study was undertaken in order to assess the potential for oxidizing NO to NO{sub 2} in flue gas environments, with the aim of promoting the so-called fast SCR reaction. In principle this can result in improved SCR kinetics and reduced SCR catalyst volumes. Prior to commencing experimental work, a literature study was undertaken to identify candidate catalysts for screening. Selection criteria comprised (1) proven (or likely) activity for NO oxidation, (2) low activity for SO2 oxidation (where data were available), and (3) inexpensive component materials. Catalysts identified included supported base metal oxides, supported and unsupported mixed metal oxides, and metal ion exchanged ZSM-5 (Fe, Co, Cu). For comparison purposes, several low loaded Pt catalysts (0.5 wt% Pt) were also included in the study. Screening experiments were conducted using a synthetic feed gas representative of flue gas from coal-fired utility boilers: [NO] = 250 ppm, [SO{sub 2}] = 0 or 2800 ppm, [H{sub 2}O] = 7%, [CO{sub 2}] = 12%, [O{sub 2}] = 3.5%, balance = N{sub 2}; T = 275-375 C. Studies conducted in the absence of SO{sub 2} revealed a number of supported and unsupported metal oxides to be extremely active for NO oxidation to NO{sub 2}. These included known catalysts (Co{sub 3}O{sub 4}/SiO{sub 2}, FeMnO{sub 3}, Cr{sub 2}O{sub 3}/TiO{sub 2}), as well as a new one identified in this work, CrFeO{sub x}/SiO{sub 2}. However, in the presence of SO{sub 2}, all the catalysts tested were found to be severely deactivated with respect to NO oxidation. Of these, Co{sub 3}O{sub 4}/SiO{sub 2}, Pt/ZSM-5 and Pt/CeO{sub 2} showed the highest activity for NO oxidation in the presence of SO{sub 2} (based on peak NO conversions to NO{sub 2}), although in no cases did the NO conversion exceed 7%. Reactor studies indicate there are two components to SO{sub 2}-induced deactivation of Co{sub 3}O{sub 4}/SiO{sub 2}, corresponding to an irreversible deactivation due to sulfation of the surface of the Co{sub 3}O{sub 4} phase, together with a reversible inhibition due to competitive adsorption of SO{sub 2} with NO on the catalyst. In an effort to minimize the deactivating effect of SO{sub 2} on Co{sub 3}O{sub 4}/SiO{sub 2}, two synthetic approaches were briefly examined. These consisted of (1) the incorporation of highly dispersed Co(II) ions in silica, as a non-sulfating matrix, via the sol-gel preparation of CoO-SiO{sub 2}; and (2) the sol-gel preparation of a mixed metal oxide, CoO-Nb{sub 2}O{sub 5}-SiO{sub 2}, with the aim of exploiting the acidity of the niobium oxide to minimize SO2 adsorption. While both catalysts showed almost no activity for NO oxidation in the absence of SO{sub 2}, when SO{sub 2} was present low activity was observed, indicating that SO{sub 2} acts as a promoter for NO oxidation over these materials. The kinetics of NO oxidation over Co{sub 3}O{sub 4}/SiO{sub 2}, Pt/SiO{sub 2} and Pt/CeO{sub 2} were also examined. Co{sub 3}O{sub 4}/SiO{sub 2} was found to exhibit a higher apparent activation energy for NO oxidation than the Pt catalysts, while the combined reaction order in NO and O{sub 2} for the three catalysts was very close to one. CO{sub 2} was found to have no effect on the kinetics of NO oxidation over these catalysts. The presence of H{sub 2}O caused a decrease in NO conversion for both Co{sub 3}O{sub 4}/SiO{sub 2} and Pt/CeO{sub 2} catalysts, while no effect was observed for Pt/SiO{sub 2}. The inhibiting effect of water was reversible and is attributed to competitive adsorption with the reactants. In sum, this study has shown that a variety of base metal catalysts are very active for NO oxidation. However, all of the catalysts studied are strongly deactivated in the presence of 2800 ppm SO{sub 2} at typical flue gas temperatures; consequently improving catalyst resistance to SO{sub x} will be a pre-requisite if the fast SCR concept is to be applied to coal-fired flue gas conditions.

Mark Crocker

2005-09-30

285

Simplified Reaction Mechanisms for the Oxidation of Hydrocarbon Fuels in Flames  

Microsoft Academic Search

Simplified reaction mechanisms for the oxidation of hydrocarbon fuels have been examined using a numerical laminar flame model. The types of mechanisms studied include one and two global reaction steps as well as quasi-global mechanisms. Reaction rate parameters were varied in order to provide the best agreement between computed and experimentally observed flame speeds in selected mixtures of fuel and

CHARLES K. WESTBROOK; FREDERICK L DRYER

1981-01-01

286

Coordinate Contribution of Lipid Oxidation and Maillard Reaction to the Nonenzymatic Food Browning  

Microsoft Academic Search

Lipid oxidation and the Maillard reaction are probably the two most important reactions in Food Science. Both include a whole network of different reactions in which an extraordinary complex mixture of compounds are obtained in very different amounts and produce important changes in food flavor, color, texture, and nutritional value, with positive and negative consequences. This article analyzes the interactions

ROSARIO ZAMORA; FRANCISCO J. HIDALGO

2005-01-01

287

Pyroprocessing of oxidized sodium-bonded fast reactor fuel - An experimental study of treatment options for degraded EBR-II fuel  

SciTech Connect

An experimental study was conducted to assess pyrochemical treatment options for degraded EBR-II fuel. As oxidized material, the degraded fuel would need to be converted back to metal to enable electrorefining within an existing electro-metallurgical treatment process. A lithium-based electrolytic reduction process was studied to assess the efficacy of converting oxide materials to metal with a particular focus on the impact of zirconium oxide and sodium oxide on this process. Bench-scale electrolytic reduction experiments were performed in LiCl-Li{sub 2}O at 650 C. degrees with combinations of manganese oxide (used as a surrogate for uranium oxide), zirconium oxide, and sodium oxide. In the absence of zirconium or sodium oxide, the electrolytic reduction of MnO showed nearly complete conversion to metal. The electrolytic reduction of a blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O showed substantial reduction of manganese, but only 8.5% of the zirconium was found in the metal phase. The electrolytic reduction of the same blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O - 6.2 wt% Na{sub 2}O showed substantial reduction of manganese, but zirconium reduction was even less at 2.4%. This study concluded that ZrO{sub 2} cannot be substantially reduced to metal in an electrolytic reduction system with LiCl - 1 wt% Li{sub 2}O at 650 C. degrees due to the perceived preferential formation of lithium zirconate. This study also identified a possible interference that sodium oxide may have on the same system by introducing a parasitic and cyclic reaction of dissolved sodium metal between oxidation at the anode and reduction at the cathode. When applied to oxidized sodium-bonded EBR-II fuel (e.g., U-10Zr), the prescribed electrolytic reduction system would not be expected to substantially reduce zirconium oxide, and the accumulation of sodium in the electrolyte could interfere with the reduction of uranium oxide, or at least render it less efficient.

Hermann, S.D.; Gese, N.J. [Separations Department, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415 (United States); Wurth, L.A. [Zinc Air Inc., 5314-A US Hwy 2 West, Columbia Falls, MT 59912 (United States)

2013-07-01

288

Competition between covalent bonding and charge transfer tendencies at complex-oxides interfaces  

NASA Astrophysics Data System (ADS)

Interfaces alter the subtle balance among different degrees of freedom responsible for exotic phenomena in complex oxides, such as cuprate-manganite interfaces. We study these interfaces by means of scanning transmission electron microscopy and theoretical calculations. Microscopy and EEL spectroscopy indicate that the interfaces are sharp, and the chemical profile is symmetric with two equivalent interfaces. Spectroscopy also allows us to establish an oxidation state profile with sub-nanometer resolution. We find an anomalous charge redistribution: a non-monotonic behavior of the occupancy of d orbitals in the manganite layers as a function of distance to the interface. Relying on model calculations, we establish that this profile is a result of the competition between standard charge transfer tendencies involving materials with different chemical potentials and strong bonding effects across the interface. The competition can be tuned by different factors (temperature, doping, magnetic fields...). As examples, we report different charge distributions as a function of doping of the manganite layers. ACKNOWLEDGEMENTS ORNL:U.S. DOE-BES, Material Sciences and Engineering Division & ORNL's ShaRE. UCM:Juan de la Cierva, Ramon y Cajal, & ERC Starting Investigator Award programs.

Salafranca, J.; Tornos, J.; García-Barriocanal, J.; León, C.; Santamaria, J.; Rincón, J.; Álvarez, G.; Pennycook, S. J.; Dagotto, E.; Varela, M.

2013-03-01

289

Theoretical study of bond distances and dissociation energies of actinide oxides AnO and AnO2.  

PubMed

In the present study we evaluated trends in the bond distances and dissociation enthalpies of actinide oxides AnO and AnO(2) (An = Th-Lr) on the basis of consistent computed data obtained by using density functional theory in conjunction with relativistic small-core pseudopotentials. Computations were carried out on AnO (An = Th-Lr) and AnO(2) (An = Np, Pu, Bk-Lr) species, while for the remaining AnO(2) species recent literature data (Theor. Chem. Acc. 2011, 129, 657) were utilized. The most important computed properties include the geometries, vibrational frequencies, dissociation enthalpies, and several excited electronic states. These molecular properties of the late actinide oxides (An = Bk-No) are reported here for the first time. We present detailed analyses of the bond distances, covalent bonding properties, and dissociation enthalpies. PMID:22471700

Kovács, Attila; Pogány, Peter; Konings, Rudy J M

2012-04-16

290

NITROGEN OXIDES REACTIONS WITHIN URBAN PLUMES TRANSPORTED OVER THE OCEAN  

EPA Science Inventory

The report describes an airborne measurements program in the downwind urban plume of Boston. The variables measured included ozone, nitric oxide, oxides of nitrogen, nitric acid, peroxyacetylnitrate, carbon monoxide, nonmethane hydrocarbon, freon-11, C1-C5 hydrocarbons, condensat...

291

High-temperature oxidation behavior of reaction-formed silicon carbide ceramics  

NASA Technical Reports Server (NTRS)

The oxidation behavior of reaction-formed silicon carbide (RFSC) ceramics was investigated in the temperature range of 1100 to 1400 C. The oxidation weight change was recorded by TGA; the oxidized materials were examined by light and electron microscopy, and the oxidation product by x-ray diffraction analysis (XRD). The materials exhibited initial weight loss, followed by passive weight gain (with enhanced parabolic rates, k(sub p)), and ending with a negative (logarithmic) deviation from the parabolic law. The weight loss arose from the oxidation of residual carbon, and the enhanced k(sub p) values from internal oxidation and the oxidation of residual silicon, while the logarithmic kinetics is thought to have resulted from crystallization of the oxide. The presence of a small amount of MoSi, in the RFSC material caused a further increase in the oxidation rate. The only solid oxidation product for all temperatures studied was silica.

Ogbuji, Linus U. J. T.; Singh, M.

1995-01-01

292

Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.  

PubMed

This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the ?-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. PMID:22023723

Sad, María E; Neurock, Matthew; Iglesia, Enrique

2011-12-21

293

Photo- and thermal-oxidation studies on methyl and phenyl linoleate: anti-oxidant behaviour and rates of reaction.  

PubMed

Photo-peroxidation of methyl and phenyl linoleate in methanol solutions at 25 degrees C, in the presence of methylene blue or 5,10,15,20-tetra(4-pyridyl)-porphyrin (TPP) as sensitisers of singlet oxygen, was found to proceed at more than 30 times the rate of the same polyunsaturated fatty acid (PUFA) ester species undergoing thermal-peroxidation in the bulk phase at 50 degrees C. The addition of anti-oxidants such as butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) quench the thermal-oxidation effectively but appear to only partially inhibit the photosensitized peroxidation reactions. The kinetics of the overall peroxidation reactions were followed by ultraviolet spectroscopy, measurements of hydroperoxide concentration and by high performance liquid chromatography (HPLC). The photo-peroxidation reaction proceeds more rapidly in chloroform solution as the lifetime of singlet oxygen is shown to be over ten times longer in chloroform than methanol. The initial fast reaction kinetics of the photo-peroxidation reactions were evaluated using a pulsed laser technique to show that singlet oxygen reacts competitively with both the anti-oxidants and the polyunsaturated fatty acid ester. Second order kinetic rate constants (in the range 10(5)-10(7) dm(3) mol(-1) s(-1)) were evaluated for the reactivity of singlet oxygen with a range of anti-oxidants and a singlet oxygen quencher, and the results used to explain the effect of anti-oxidants at different concentrations on the rate of the linoleate photo-peroxidation reaction. PMID:10974235

Chacón, J N; Gaggini, P; Sinclair, R S; Smith, F J

2000-09-01

294

Direct bonding of Cu to oxidized silicon nitride by wetting of molten Cu and Cu(O)  

Microsoft Academic Search

When pressureless sintered silicon nitride with the main additives Y2O3 and Al2O3, having a thermal conductivity K = 20 W\\/m K, was oxidized at 1240–1360 °C in still air, the resulting surface oxide layer easily bonded to a copper plate\\u000a in the temperature region between 1065 and 1083 °C, and in the oxygen concentration range of 0.008–0.39 wt%, as shown in a\\u000a Cu–O phase diagram. The oxide

Shun-Ichiro Tanaka

2010-01-01

295

Rhenium-catalyzed synthesis of 2H-1,2-oxaphosphorin 2-oxides via the regio- and stereoselective addition reaction of ?-keto phosphonates with alkynes.  

PubMed

Treatment of ?-keto phosphonates (Horner-Wadsworth-Emmons reagents) with terminal alkynes in the presence of a rhenium catalyst gave 2H-1,2-oxaphosphorin 2-oxides with various substitution patterns. The reaction proceeds via two consecutive processes: cleavage of a carbon-carbon ?-bond of the ?-keto phosphonate with insertion of the alkyne in a regio- and stereoselective manner, followed by cyclization of the resulting ?-phosphonyl ?,?-unsaturated ketone yielding the 2H-1,2-oxaphosphorin 2-oxide. Horner-Wadsworth-Emmons reagents were found to add to nonpolar unsaturated compounds under neutral conditions. PMID:25341380

Murai, Masahito; Nakamura, Masahiro; Takai, Kazuhiko

2014-11-01

296

Tuning the mechanical properties of graphene oxide paper and its associated polymer nanocomposites by controlling cooperative intersheet hydrogen bonding.  

PubMed

The mechanical properties of pristine graphene oxide paper and paper-like films of polyvinyl alcohol (PVA)-graphene oxide nanocomposite are investigated in a joint experimental-theoretical and computational study. In combination, these studies reveal a delicate relationship between the stiffness of these papers and the water content in their lamellar structures. ReaxFF-based molecular dynamics (MD) simulations elucidate the role of water molecules in modifying the mechanical properties of both pristine and nanocomposite graphene oxide papers, as bridge-forming water molecules between adjacent layers in the paper structure enhance stress transfer by means of a cooperative hydrogen-bonding network. For graphene oxide paper at an optimal concentration of ~5 wt % water, the degree of cooperative hydrogen bonding within the network comprising adjacent nanosheets and water molecules was found to optimally enhance the modulus of the paper without saturating the gallery space. Introducing PVA chains into the gallery space further enhances the cooperativity of this hydrogen-bonding network, in a manner similar to that found in natural biomaterials, resulting in increased stiffness of the composite. No optimal water concentration could be found for the PVA-graphene oxide nanocomposite papers, as dehydration of these structures continually enhances stiffness until a final water content of ~7 wt % (additional water cannot be removed from the system even after 12 h of annealing). PMID:22188595

Compton, Owen C; Cranford, Steven W; Putz, Karl W; An, Zhi; Brinson, L Catherine; Buehler, Markus J; Nguyen, SonBinh T

2012-03-27

297

An Intrinsically Disordered Photosystem II Subunit, PsbO, Provides a Structural Template and a Sensor of the Hydrogen-bonding Network in Photosynthetic Water Oxidation*  

PubMed Central

Photosystem II (PSII) is a membrane-bound enzyme that utilizes solar energy to catalyze the photooxidation of water. Molecular oxygen is evolved after four sequential light-driven oxidation reactions at the Mn4CaO5 oxygen-evolving complex, producing five sequentially oxidized states, Sn. PSII is composed of 17 membrane-spanning subunits and three extrinsic subunits, PsbP, PsbQ, and PsbO. PsbO is intrinsically disordered and plays a role in facilitation of the water oxidizing cycle. Native PsbO can be removed and substituted with recombinant PsbO, thereby restoring steady-state activity. In this report, we used reaction-induced Fourier transform infrared spectroscopy to obtain information concerning the role of PsbP, PsbQ, and PsbO during the S state cycle. Light-minus-dark difference spectra were acquired, monitoring structural changes associated with each accessible flash-induced S state transition in a highly purified plant PSII preparation (Triton X-100, octylthioglucoside). A comparison of S2 minus S1 spectra revealed that removal of PsbP and PsbQ had no significant effect on the data, whereas amide frequency and intensity changes were associated with PsbO removal. These data suggest that PsbO acts as an organizational template for the PSII reaction center. To identify any coupled conformational changes arising directly from PsbO, global 13C-PsbO isotope editing was employed. The reaction-induced Fourier transform infrared spectra of accessible S states provide evidence that PsbO spectral contributions are temperature (263 and 277 K) and S state dependent. These experiments show that PsbO undergoes catalytically relevant structural dynamics, which are coupled over long distance to hydrogen-bonding changes at the Mn4CaO5 cluster. PMID:23940038

Offenbacher, Adam R.; Polander, Brandon C.; Barry, Bridgette A.

2013-01-01

298

An intrinsically disordered photosystem II subunit, PsbO, provides a structural template and a sensor of the hydrogen-bonding network in photosynthetic water oxidation.  

PubMed

Photosystem II (PSII) is a membrane-bound enzyme that utilizes solar energy to catalyze the photooxidation of water. Molecular oxygen is evolved after four sequential light-driven oxidation reactions at the Mn4CaO5 oxygen-evolving complex, producing five sequentially oxidized states, Sn. PSII is composed of 17 membrane-spanning subunits and three extrinsic subunits, PsbP, PsbQ, and PsbO. PsbO is intrinsically disordered and plays a role in facilitation of the water oxidizing cycle. Native PsbO can be removed and substituted with recombinant PsbO, thereby restoring steady-state activity. In this report, we used reaction-induced Fourier transform infrared spectroscopy to obtain information concerning the role of PsbP, PsbQ, and PsbO during the S state cycle. Light-minus-dark difference spectra were acquired, monitoring structural changes associated with each accessible flash-induced S state transition in a highly purified plant PSII preparation (Triton X-100, octylthioglucoside). A comparison of S2 minus S1 spectra revealed that removal of PsbP and PsbQ had no significant effect on the data, whereas amide frequency and intensity changes were associated with PsbO removal. These data suggest that PsbO acts as an organizational template for the PSII reaction center. To identify any coupled conformational changes arising directly from PsbO, global (13)C-PsbO isotope editing was employed. The reaction-induced Fourier transform infrared spectra of accessible S states provide evidence that PsbO spectral contributions are temperature (263 and 277 K) and S state dependent. These experiments show that PsbO undergoes catalytically relevant structural dynamics, which are coupled over long distance to hydrogen-bonding changes at the Mn4CaO5 cluster. PMID:23940038

Offenbacher, Adam R; Polander, Brandon C; Barry, Bridgette A

2013-10-01

299

Rate of reaction with nitric oxide determines the hypertensive effect of cell-free hemoglobin.  

PubMed

Administration of extracellular hemoglobin-based oxygen carriers often induces mild increases in blood pressure. In order to test whether nitric oxide (NO) scavenging is responsible for the hypertensive effect, we constructed and tested a set of recombinant hemoglobins that vary in rates of reaction with NO. The results suggest that the rapid reactions of oxy- and deoxyhemoglobin with nitric oxide are the fundamental cause of the hypertension. The magnitude of the blood-pressure effect correlates directly with the in vitro rate of NO oxidation. Hemoglobins with decreased NO-scavenging activity may be more suitable for certain therapeutic applications than those that cause depletion of nitric oxide. PMID:9661203

Doherty, D H; Doyle, M P; Curry, S R; Vali, R J; Fattor, T J; Olson, J S; Lemon, D D

1998-07-01

300

Influence of Alumina Reaction Tube Impurities on the Oxidation of Chemically-Vapor-Deposited Silicon Carbide  

NASA Technical Reports Server (NTRS)

Pure coupons of chemically vapor deposited (CVD) SiC were oxidized for 100 h in dry flowing oxygen at 1300 C. The oxidation kinetics were monitored using thermogravimetry (TGA). The experiments were first performed using high-purity alumina reaction tubes. The experiments were then repeated using fused quartz reaction tubes. Differences in oxidation kinetics, scale composition, and scale morphology were observed. These differences were attributed to impurities in the alumina tubes. Investigators interested in high-temperature oxidation of silica formers should be aware that high-purity alumina can have significant effects on experiment results.

Opila, Elizabeth

1995-01-01

301

Aerosol synthesis and electrochemical analysis of niobium mixed-metal oxides for the ethanol oxidation reaction in acid and alkaline electrolyte  

NASA Astrophysics Data System (ADS)

Direct ethanol fuel cells are especially important among emerging electrochemical power systems with the potential to offset a great deal of the energy demand currently met through the use of fossil fuels. Ethanol can be refined from petroleum sources or attained from renewable biomass, and is more easily and safely stored and transported than hydrogen, methanol or gasoline. The full energy potential of ethanol in fuel cells can only be realized if the reaction follows a total oxidation pathway to produce CO2. This must be achieved by the development of advanced catalysts that are electrically conductive, stable in corrosive environments, contain a high surface area on which the reaction can occur, and exhibit a bi-functional effect for the ethanol oxidation reaction (EOR). The latter criterion is achievable in mixed-metal systems. Platinum is an effective metal for catalyzing surface reactions of many adsorbates and is usually implemented in the form of Pt nanoparticles supported on inexpensive carbon. This carbon is believed to be neutral in the catalysis of Pt. Instead, carbon can be replaced with carefully designed metals and metal oxides as co-catalysis or support structures that favorably alter the electronic structure of Pt slightly through a strong metal support interaction, while also acting as an oxygen source near adsorbates to facilitate the total oxidation pathway. Niobium mixed-metal-oxides were explored in this study as bi-functional catalyst supports to Pt nanoparticles. We developed a thermal aerosol synthesis process by which mesoporous powders of mixed-metal-oxides decorated with Pt nanoparticles could be obtained from liquid precursors within ˜5 seconds or less, followed by carefully refined chemical and thermal post-treatments. Exceptionally high surface areas of 170--180m2/g were achieved via a surfactant-templated 3D wormhole-type porosity, comparable on a per volume basis to commercial carbon blacks and high surface area silica supports. For the first time, in situ FTIR measurements in acid electrolyte showed that highly dispersed Pt nanoparticles (2--5nm) on NbRuyO z (at% 8Nb:1Ru) catalyze the formation of CO2 from ethanol in greater yield, and 0.35--0.4V lower, than Pt(111). Compared to conventional Pt/carbon, this indicates that, (1) Pt supported on NbRuyO z can be more effective at splitting the C---C bond in ethanol and, (2) the scission occurs at potentials more ideal for a higher efficiency fuel cell anode. Ex situ-microscopy revealed the polarization-induced two- and three-dimensional formation of Pt-NbOx interfacial adsorption sites responsible for the facilitation of the total oxidation pathway of ethanol. The results show that synthesis and post-treatment of niobia supports can bias the utility of Pt/niobia systems towards the ethanol oxidation reaction at the anode or the oxygen reduction reaction at the cathode. Experimental and computational-theoretical analyses indicate that the mechanism of interfacial site formation is dependent upon the local oxygen concentration, as well as the availability of multiple, energetically accessible oxidation states like those inherent to niobia. Future directions for the development of highly active, niobium-based materials tailored for efficient catalysis of the total oxidation pathway of ethanol are discussed.

Konopka, Daniel A.

302

Nickel-Catalyzed Carbon–Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations  

PubMed Central

The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described, employing a readily accessible catalyst (NiBr2·-diglyme/4,4?-di-t-butyl-2,2?-bipyridine, both commercially available); this also represents the initial example of the use of a Group 10 catalyst to cross-couple unactivated tertiary electrophiles to form carbon–carbon bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway. PMID:23281960

Zultanski, Susan L.; Fu, Gregory C.

2013-01-01

303

Radical O-O coupling reaction in diferrate-mediated water oxidation studied using multireference wave function theory.  

PubMed

The O-O (oxygen-oxygen) bond formation is widely recognized as a key step of the catalytic reaction of dioxygen evolution from water. Recently, the water oxidation catalyzed by potassium ferrate (K2FeO4) was investigated on the basis of experimental kinetic isotope effect analysis assisted by density functional calculations, revealing the intramolecular oxo-coupling mechanism within a di-iron(vi) intermediate, or diferrate [Sarma et al., J. Am. Chem. Soc., 2012, 134, 15371]. Here, we report a detailed examination of this diferrate-mediated O-O bond formation using scalable multireference electronic structure theory. High-dimensional correlated many-electron wave functions beyond the one-electron picture were computed using the ab initio density matrix renormalization group (DMRG) method along the O-O bond formation pathway. The necessity of using large active space arises from the description of complex electronic interactions and varying redox states both associated with two-center antiferromagnetic multivalent iron-oxo coupling. Dynamic correlation effects on top of the active space DMRG wave functions were additively accounted for by complete active space second-order perturbation (CASPT2) and multireference configuration interaction (MRCI) based methods, which were recently introduced by our group. These multireference methods were capable of handling the double shell effects in the extended active space treatment. The calculations with an active space of 36 electrons in 32 orbitals, which is far over conventional limitation, provide a quantitatively reliable prediction of potential energy profiles and confirmed the viability of the direct oxo coupling. The bonding nature of Fe-O and dual bonding character of O-O are discussed using natural orbitals. PMID:24686771

Kurashige, Yuki; Saitow, Masaaki; Chalupský, Jakub; Yanai, Takeshi

2014-06-28

304

Controlling hydrolysis reaction rates with binary ionic liquid mixtures by tuning hydrogen-bonding interactions.  

PubMed

The ability of a binary ionic liquid (IL) system consisting of a phosphonium transition state analogue (TSA) and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([BMIM][NTf(2)]) to accelerate the rate of the well-studied hydrolysis of a tert-alkyl picolinium salt by influencing the solvent structure was investigated. A significant rate enhancement was observed in the presence of the TSA; however, comparison with other cations illustrated that this enhancement was not unique to the chosen TSA. Instead, the rate enhancements were correlated with the dilution of hydrogen bonding by the added cations. This phenomenon was further examined by the use of 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ([BMMIM][NTf(2)]) as a cosolvent and the use of Reichardt's dye to measure the extent of hydrogen bonding on solutes in these systems. The rate increases are rationalized in terms of weaker hydrogen bonding from the solvent system to water. PMID:22263886

Weber, Cameron C; Masters, Anthony F; Maschmeyer, Thomas

2012-02-16

305

Chemical bonding, optical constants, and electrical resistivity of sputter-deposited gallium oxide thin films  

SciTech Connect

Gallium oxide (Ga{sub 2}O{sub 3}) thin films were made by sputter deposition employing a Ga{sub 2}O{sub 3} ceramic target for sputtering. The depositions were made over a wide range of substrate temperatures (T{sub s}), from 25 to 600?°C. The effect of T{sub s} on the chemical bonding, surface morphological characteristics, optical constants, and electrical properties of the grown films was evaluated using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and four-point probe measurements. XPS analyses indicate the binding energies (BE) of the Ga 2p doublet, i.e., the Ga 2p{sub 3/2} and Ga 2p{sub 1/2} peaks, are located at 1118.0 and 1145.0?eV, respectively, characterizing gallium in its highest chemical oxidation state (Ga{sup 3+}) in the grown films. The core level XPS spectra of O 1s indicate that the peak is centered at a BE???531?eV, which is also characteristic of Ga-O bonds in the Ga{sub 2}O{sub 3} phase. The granular morphology of the nanocrystalline Ga{sub 2}O{sub 3} films was evident from AFM measurements, which also indicate that the surface roughness of the films increases from 0.5?nm to 3.0?nm with increasing T{sub s}. The SE analyses indicate that the index of refraction (n) of Ga{sub 2}O{sub 3} films increases with increasing T{sub s} due to improved structural quality and packing density of the films. The n(?) of all the Ga{sub 2}O{sub 3} films follows the Cauchy's dispersion relation. The room temperature electrical resistivity was high (?200 ?-cm) for amorphous Ga{sub 2}O{sub 3} films grown at T{sub s}?=?RT-300?°C and decreased to ?1 ?-cm for nanocrystalline Ga{sub 2}O{sub 3} films grown at T{sub s}???500–600?°C. A correlation between growth conditions, microstructure, optical constants, and electrical properties of Ga{sub 2}O{sub 3} films is derived.

Ramana, C. V., E-mail: rvchintalapalle@utep.edu; Rubio, E. J.; Barraza, C. D.; Miranda Gallardo, A. [Department of Mechanical Engineering, University of Texas at El Paso, El Paso, Texas 79968 (United States); McPeak, Samantha [Department of Electrical and Computer Engineering, The University of Alabama, Tuscaloosa, Alabama 35487 (United States); Kotru, Sushma [Department of Electrical and Computer Engineering, The University of Alabama, Tuscaloosa, Alabama 35487 (United States); Materials for Information and Technology, The University of Alabama, Tuscaloosa, Alabama 35487 (United States); Grant, J. T. [Research Institute, University of Dayton, Dayton, Ohio 45469 (United States)

2014-01-28

306

Study of Zircaloy4: steam oxidation reaction kinetics. Final report  

Microsoft Academic Search

Experimental studies utilizing a ''Gleeble'' have been performed to evaluate the oxidation of reactor grade Zircaloy-4 tubing in steam throughout the 1200°F (649°C) to 1800°F (982°C) temperature range. Oxidation behavior in this temperature range was found to be substantially different from that predicted by either the Baker-Just equation or extrapolation of oxidation data from temperatures above 1800°F (982°C). Preoxidation of

R. R. Biederman; R. D. Jr. Sisson; J. K. Jones; W. G. Dobson

1978-01-01

307

Palladacycles with Palladium-Bonded Stereogenic Carbons: Tools for Exploring Reaction Pathways in Organometallic Chemistry  

E-print Network

of Organopalladium(IV) Complexes??????????25 2.3.1 Reactions Involving Generation of Pd(IV) Complexes via Reaction With Alkyl or Acyl Halides??????????..26 2.3.2 Reactions Involving Generation of Pd(IV) Complexes via Hypervalent Iodine..., palladium complexes or intermediates with a ?-bound alkyl group remain fairly rare due to the greater probability for ?-bound alkyl groups to have ?- hydrogens that are readily accessible for ?-hydride elimination. As a result, much less is known about...

Hershberger, John Charles

2009-01-01

308

Oxidized cellulose (Surgicel) based reaction post thyroidectomy mimicking an abscess: A case report  

PubMed Central

Introduction Surgicel (oxidized cellulose) is used for intra-operative haemostasis and adhesion prevention. Previously local tissue reactions to oxidized cellulose have been reported at many surgical sites, but not in the head and neck. Presentation of case A 56 year old lady presented 30 days following total thyroidectomy with wound swelling and erythema. Multiple sinuses were noted within the wound, through which oxidized cellulose partially extruded. Following removal of the un-absorbed material the symptoms resolved over 3 days. Discussion The absence of any systemic symptoms confirm that this was most likely a type four hypersensitivity reaction. The removal of the unabsorbed material was a further unique part of this case. Conclusion We present the first head and neck reaction to oxidized cellulose. This report serves to remind head and neck surgeons of the potential for local tissue reactions to this material. PMID:22572542

Royds, J.; Kieran, S.; Timon, C.

2012-01-01

309

Carbon-coated magnetic palladium: applications in partial oxidation of alcohols and coupling reactions.  

EPA Science Inventory

Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; catalyst can be used for oxidation of alcohols, amination reaction and arylation of aryl halides (cross coupli...

310

Bulk Gold-Catalyzed Reactions of Isocyanides, Amines, and Amine N-Oxides  

SciTech Connect

Bulk gold powder (5–50 ?m particles) catalyzes the reactions of isocyanides with amines and amine N-oxides to produce ureas. The reaction of n-butyl isocyanide (nBu–N?C) with di-n-propylamine and N-methylmorpholine N-oxide in acetonitrile, which was studied in the greatest detail, produced 3-butyl-1,1-dipropylurea (O?C(NHnBu)(NnPr2)) in 99% yield at 60 °C within 2 h. Sterically and electronically different isocyanides, amines, and amine N-oxides react successfully under these conditions. Detailed studies support a two-step mechanism that involves a gold-catalyzed reaction of adsorbed isocyanide with the amine N-oxide to form an isocyanate (RN?C?O), which rapidly reacts with the amine to give the urea product. These investigations show that bulk gold, despite its reputation for poor catalytic activity, is capable of catalyzing these reactions.

Klobukowski, Erik; Angelici, Robert; Woo, Keith L.

2012-01-26

311

PALLADIUM-CATALYZED OXIDATION OF STYRENE AND ALKENES IN PRESENCE OF IONIC LIQUIDS (WACKER REACTION)  

EPA Science Inventory

The use of ionic liquids in various synthetic transformations is gaining significance due to the enhanced reaction rates, potential for recycling and compatibility with various organic compounds and organometallic catalysts. Palladium-catalyzed oxidation of styrene and other alk...

312

Production of Acetic Acid from Carbohydrate Biomass by Two-Step Reaction with Alkaline Hydrothermal Reaction and Wet Oxidation  

Microsoft Academic Search

An investigation was carried out to improve the production of acetic acid by an alkaline two-step process, in which the first step is to accelerate the formation of lactic acid in a hydrothermal reaction with the addition of alkali, and the second step is further convert the lactic acid produced in the first step to acetic acid by oxidation with

X. Yan; F. Jin; K. Tohji; H. Enomoto

2007-01-01

313

Characterization of intermetallic compounds in Cu-Al ball bonds: Layer growth, mechanical properties and oxidation  

Microsoft Academic Search

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 electrical, thermal and mechanical properties. The layer growth and properties of these intermetallic compounds are crucial in

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

2011-01-01

314

Oxidative reactions and their impact on the properties of asphalt as a pavement binder  

E-print Network

OXIDATIVE REACTIONS AND THEIR IMPACT ON THE PROPERTIES OF ASPHALT AS A PAVE~ BINDER A Thesis by CHEE KEUNG LAU Submitted to the Office of Graduate Studies of Texas A & M University in partial fulfillment of the requirements for the degree... of MASTER OF SCIENCE December 1991 Major Subject: Chemical Engineering OXIDATIVE REACTIONS AND THEIR IMPACT ON THE PROPERTIES OF ASPHALT AS A PAVEMENT BINDER A Thesis by CHEE KEUNG LAU Approved as to style and content by: Charles J. over (Chair...

Lau, Chee Keung

2012-06-07

315

Role of van der Waals bonding in layered oxide: Bulk vanadium pentoxide  

E-print Network

Sparse matter is characterized by regions with low electron density and its understanding calls for methods to accurately calculate both the van der Waals (vdW) interactions and other bonding. Here we present a first-principles density functional theory (DFT) study of a layered oxide (V2O5) bulk structure which shows charge voids in between the layers and we highlight the role of the vdW forces in building up material cohesion. The result of previous first-principles studies involving semilocal approximations to the exchange-correlation functional in DFT gave results in good agreement with experiments for the two in-plane lattice parameters of the unit cell but overestimated the parameter for the stacking direction. To recover the third parameter we include the nonlocal (dispersive) vdW interactions through the vdW-DF method [Dion et al., Phys. Rev. Lett. 92, 246401 (2004)] testing also various choices of exchange flavors. We find that the transferable first-principle vdW-DF calculations stabilizes the bulk s...

Londero, Elisa

2010-01-01

316

Role of van der Waals bonding in layered oxide: Bulk vanadium pentoxide  

E-print Network

Sparse matter is characterized by regions with low electron density and its understanding calls for methods to accurately calculate both the van der Waals (vdW) interactions and other bonding. Here we present a first-principles density functional theory (DFT) study of a layered oxide (V2O5) bulk structure which shows charge voids in between the layers and we highlight the role of the vdW forces in building up material cohesion. The result of previous first-principles studies involving semilocal approximations to the exchange-correlation functional in DFT gave results in good agreement with experiments for the two in-plane lattice parameters of the unit cell but overestimated the parameter for the stacking direction. To recover the third parameter we include the nonlocal (dispersive) vdW interactions through the vdW-DF method [Dion et al., Phys. Rev. Lett. 92, 246401 (2004)] testing also various choices of exchange flavors. We find that the transferable first-principle vdW-DF calculations stabilizes the bulk structure. The vdW-DF method gives results in fairly good agreement with experiments for all three lattice parameters.

Elisa Londero; Elsebeth Schroder

2010-06-12

317

Basic character of rare earth metal alkoxides. Utilization in catalytic CC bond-forming reactions and catalytic asymmetric nitroaldol reactions  

Microsoft Academic Search

In a recent paper, the authors reported that Zr(O-t-Bu)â was an efficient and convenient basic reagent in organic synthesis. However, all reactions examined were performed with stoichiometric quantities of the reagent. The authors envisioned that rare earth metal alkoxides would be stronger bases than group 4 metal alkoxides due to the lower ionization potential (ca. 5.4-6.4 eV) and the lower

Hiroaki Sasai; Takeyuki Suzuki; Shigeru Arai; Takayoshi Arai; Masakatsu Shibasaki

1992-01-01

318

Catalytic asymmetric carbon-carbon bond-forming reaction utilizing rare earth metal complexes  

Microsoft Academic Search

Novel optically active rare earth complexes have made possible a catalytic asymmetric nitroaldol reaction for the first time. Structural elucidation reveals that the complexes consist of one rare earth metal, three lithium atoms, and three BINOL units. Applications of the catalytic asymmetric nitroaldol reaction to syntheses of several p-blockers and erythro-AYA have been also achieved. Although the lithium containing rare

Masakatsu Shibasaki; Hiroaki Sasai

1996-01-01

319

Stable gold(III) catalysts by oxidative addition of a carbon-carbon bond.  

PubMed

Low-valent late transition-metal catalysis has become indispensable to chemical synthesis, but homogeneous high-valent transition-metal catalysis is underdeveloped, mainly owing to the reactivity of high-valent transition-metal complexes and the challenges associated with synthesizing them. Here we report a carbon-carbon bond cleavage at ambient conditions by a Au(i) complex that generates a stable Au(iii) cationic complex. In contrast to the well-established soft and carbophilic Au(i) catalyst, this Au(iii) complex exhibits hard, oxophilic Lewis acidity. For example, we observed catalytic activation of ?,?-unsaturated aldehydes towards selective conjugate additions as well as activation of an unsaturated aldehyde-allene for a [2 + 2] cycloaddition reaction. The origin of the regioselectivity and catalytic activity was elucidated by X-ray crystallographic analysis of an isolated Au(iii)-activated cinnamaldehyde intermediate. The concepts revealed suggest a strategy for accessing high-valent transition-metal catalysis from readily available precursors. PMID:25612049

Wu, Chung-Yeh; Horibe, Takahiro; Jacobsen, Christian Borch; Toste, F Dean

2015-01-21

320

Stable gold(III) catalysts by oxidative addition of a carbon-carbon bond  

NASA Astrophysics Data System (ADS)

Low-valent late transition-metal catalysis has become indispensable to chemical synthesis, but homogeneous high-valent transition-metal catalysis is underdeveloped, mainly owing to the reactivity of high-valent transition-metal complexes and the challenges associated with synthesizing them. Here we report a carbon-carbon bond cleavage at ambient conditions by a Au(I) complex that generates a stable Au(III) cationic complex. In contrast to the well-established soft and carbophilic Au(I) catalyst, this Au(III) complex exhibits hard, oxophilic Lewis acidity. For example, we observed catalytic activation of ?,?-unsaturated aldehydes towards selective conjugate additions as well as activation of an unsaturated aldehyde-allene for a [2 + 2] cycloaddition reaction. The origin of the regioselectivity and catalytic activity was elucidated by X-ray crystallographic analysis of an isolated Au(III)-activated cinnamaldehyde intermediate. The concepts revealed suggest a strategy for accessing high-valent transition-metal catalysis from readily available precursors.

Wu, Chung-Yeh; Horibe, Takahiro; Jacobsen, Christian Borch; Toste, F. Dean

2015-01-01

321

Turning regioselectivity into stereoselectivity: efficient dual resolution of P-stereogenic phosphine oxides through bifurcation of the reaction pathway of a common intermediate.  

PubMed

Synthetic routes that provide facile access to either enantiomeric form of a target compound are particularly valuable. The crystallization-free dual resolution of phosphine oxides that gives highly enantioenriched materials (up to 94?% ee) in excellent yields is reported. Both enantiomeric oxides have been prepared from a single intermediate, (RP )-alkoxyphosphonium chloride, which is formed in the course of a selective dynamic kinetic resolution using a single enantiomer of menthol as the chiral auxiliary. The origin of the dual stereoselectivity lies in bifurcation of the reaction pathway of this intermediate, which works as a stereochemical railroad switch. Under controlled conditions, Arbuzov-type collapse of this intermediate proceeds through C?O bond fission with retention of the configuration at the phosphorus center. Conversely, alkaline hydrolysis of the P?O bond leads to the opposite SP ?enantiomer. PMID:24474623

Nikitin, Kirill; Rajendran, Kamalraj V; Müller-Bunz, Helge; Gilheany, Declan G

2014-02-10

322

Slag Metal Reactions in Binary CaF2-Metal Oxide Welding Fluxes  

E-print Network

) Slag Metal Reactions in Binary CaF2-Metal Oxide Welding Fluxes Some otherwise chemically stable fluxes may decompose into suboxides in the presence of welding arcs, thereby providing higher levels of 0 2 in weld metal than those oxides which do not form suboxides ABSTRACT. The stability of metal

Eagar, Thomas W.

323

Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals  

Microsoft Academic Search

Several Mn oxide minerals commonly occurring in soils were synthesized by modified or optimized methods. The morphologies, structures, compositions and surface properties of the synthesized Mn oxide minerals were characterized. Adsorption and redox reactions of heavy metals on these minerals in relation to the mineral structures and surface properties were also investigated. The synthesized birnessite, todorokite, cryptomelane, and hausmannite were

Xiong Han Feng; Li Mei Zhai; Wen Feng Tan; Fan Liu; Ji Zheng He

2007-01-01

324

Ceramic oxide reactions with V2O5 and SO3  

NASA Technical Reports Server (NTRS)

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Jones, R. L.; Williams, C. E.

1985-01-01

325

AQUEOUS-PHASE OXIDATION OF SLUDGE USING THE VERTICAL REACTION VESSEL SYSTEM  

EPA Science Inventory

The overall objective of the study was to provide plant-scale operating data on the wet-oxidation of municipal wastewater sludge utilizing the Vertical Reaction Vessel System and the effect of the return flow from the wet-oxidation process on the operation of the wastewater treat...

326

Rheological kinetics of thermo-sensitive supramolecular assemblies from poly( N-isopropyl acrylamide) and adenine-functionalized poly(ethylene oxide) stabilized by complementary multiple hydrogen bonds  

NASA Astrophysics Data System (ADS)

In this study, we synthesized a poly( N-isopropylacrylamide) (PNIPAm) through the polymerization of N-isopropylacrylamide in distilled water with azodiisobutyronitrile as the initiator and a bisadenine-functionalized poly(ethylene oxide) (A-PEO-A) from the reaction of adenine with a difunctionalized toluenesulfonyl-PEO. When blended together in distilled water, PNIPAm and A-PEO-A formed supramolecular aggregates stabilized through complementary multiple hydrogen bonds between the amide groups of PNIPAm and the adenine units of A-PEO-A. Agrawal integral equation and rheometry revealed the rheological kinetics of supramolecular assemblies, which were influenced significantly by the spherical micelles, large associated aggregates of spherical micelles, network structures, and toroid structures formed in aqueous solutions.

Cui, Hui-Wang; Kuo, Shiao-Wei

2014-05-01

327

Process of forming catalytic surfaces for wet oxidation reactions  

NASA Technical Reports Server (NTRS)

A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

Jagow, R. B. (inventor)

1977-01-01

328

The relationship between the amount of oxidation and activation energy on the steam oxidation reaction of Zircaloy-4 cladding  

NASA Astrophysics Data System (ADS)

Zirconium-based alloys are widely used as cladding material for light-water reactors, and in the case of a loss-of-coolant accident (LOCA), oxidation of the cladding by high temperature steam plays important roles in fuel rod failure and hydrogen generation during the accident. In this study, considering that the oxidation rate is related to the activation energy of the oxidation reaction, the relationship between the amount of oxidation and the activation energy of cladding oxidation by steam was investigated by thermogravimetry. The oxidation rate of the specimen decreased with increasing heating rate. The activation energy of oxidation was evaluated based on a non-isothermal kinetics theory. It was found that the activation energy of oxidation depends on the specimen weight gain. The activation energies showed constant values of ˜300 and ˜180 kJ/mol in the oxidation range between 30 and 120 g/m2 and above 120 g/m2, respectively. A master curve which expresses the amount of steam oxidation of Zircaloy-4 cladding was formulated based on the activation energies obtained.

Amaya, Masaki; Nagase, Fumihisa

2013-09-01

329

Mutagenicity screening of reaction products from the enzyme-catalyzed oxidation of phenolic pollutants  

SciTech Connect

Phenol-oxidizing enzymes such as peroxidases, laccases, and mushroom polyphenol oxidase are capable of catalyzing the oxidation of a wide range of phenolic pollutants. Although the use of these enzymes in waste-treatment applications has been proposed by a number of investigators, little information exists on the toxicological characteristics of the oxidation products. The enzymes chloroperoxidase, horseradish peroxidase, lignin peroxidase, and mushroom polyphenol oxidase were used in this study to catalyze the oxidation of phenol, several mono-substituted phenols, and pentachlorophenol. Seventeen reaction mixtures representing selected combinations of enzyme and parent phenol were subjected to mutagenicity screening using the Ames Salmonella typhimurium plate incorporation assay; five selected mixtures were also incubated with the S9 microsomal preparation to detect the possible presence of promutagens. The majority of reaction mixtures tested were not directly mutagenic, and none of those tested with S9 gave a positive response. Such lack of mutagenicity of enzymatic oxidation products provides encouragement for establishing the feasibility of enzyme-catalyzed oxidation as a waste-treatment process. The only positive responses were obtained with reaction products from the lignin peroxidase-catalyzed oxidation of 2-nitrophenol and 4-nitrophenol. Clear positive responses were observed when strain TA100 was incubated with 2-nitrophenol reaction-product mixtures, and when strain TA98 was incubated with the 4-nitrophenol reaction mixture. Additionally, 2,4-dinitrophenol was identified as a reaction product from 4-nitrophenol, and preliminary evidence indicates that both 2,4- and 2,6-dinitrophenol are produced from the oxidation of 2-nitrophenol. Possible mechanism by which these nitration reactions occur are discussed.

Massey, I.J.; Aitken, M.D.; Ball, L.M.; Heck, P.E. (Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Environmental Sciences and Engineering)

1994-11-01

330

Method to Improve Indium Bump Bonding via Indium Oxide Removal Using a Multi-Step Plasma Process  

NASA Technical Reports Server (NTRS)

A process for removing indium oxide from indium bumps in a flip-chip structure to reduce contact resistance, by a multi-step plasma treatment. A first plasma treatment of the indium bumps with an argon, methane and hydrogen plasma reduces indium oxide, and a second plasma treatment with an argon and hydrogen plasma removes residual organics. The multi-step plasma process for removing indium oxide from the indium bumps is more effective in reducing the oxide, and yet does not require the use of halogens, does not change the bump morphology, does not attack the bond pad material or under-bump metallization layers, and creates no new mechanisms for open circuits.

Greer, H. Frank (Inventor); Jones, Todd J. (Inventor); Vasquez, Richard P. (Inventor); Hoenk, Michael E. (Inventor); Dickie, Matthew R. (Inventor); Nikzad, Shouleh (Inventor)

2012-01-01

331

Rapid and effective oxidative pretreatment of woody biomass at mild reaction conditions and low oxidant loadings  

PubMed Central

Background One route for producing cellulosic biofuels is by the fermentation of lignocellulose-derived sugars generated from a pretreatment that can be effectively coupled with an enzymatic hydrolysis of the plant cell wall. While woody biomass exhibits a number of positive agronomic and logistical attributes, these feedstocks are significantly more recalcitrant to chemical pretreatments than herbaceous feedstocks, requiring higher chemical and energy inputs to achieve high sugar yields from enzymatic hydrolysis. We previously discovered that alkaline hydrogen peroxide (AHP) pretreatment catalyzed by copper(II) 2,2?-bipyridine complexes significantly improves subsequent enzymatic glucose and xylose release from hybrid poplar heartwood and sapwood relative to uncatalyzed AHP pretreatment at modest reaction conditions (room temperature and atmospheric pressure). In the present work, the reaction conditions for this catalyzed AHP pretreatment were investigated in more detail with the aim of better characterizing the relationship between pretreatment conditions and subsequent enzymatic sugar release. Results We found that for a wide range of pretreatment conditions, the catalyzed pretreatment resulted in significantly higher glucose and xylose enzymatic hydrolysis yields (as high as 80% for both glucose and xylose) relative to uncatalyzed pretreatment (up to 40% for glucose and 50% for xylose). We identified that the extent of improvement in glucan and xylan yield using this catalyzed pretreatment approach was a function of pretreatment conditions that included H2O2 loading on biomass, catalyst concentration, solids concentration, and pretreatment duration. Based on these results, several important improvements in pretreatment and hydrolysis conditions were identified that may have a positive economic impact for a process employing a catalyzed oxidative pretreatment. These improvements include identifying that: (1) substantially lower H2O2 loadings can be used that may result in up to a 50-65% decrease in H2O2 application (from 100 mg H2O2/g biomass to 35–50 mg/g) with only minor losses in glucose and xylose yield, (2) a 60% decrease in the catalyst concentration from 5.0 mM to 2.0 mM (corresponding to a catalyst loading of 25 ?mol/g biomass to 10 ?mol/g biomass) can be achieved without a subsequent loss in glucose yield, (3) an order of magnitude improvement in the time required for pretreatment (minutes versus hours or days) can be realized using the catalyzed pretreatment approach, and (4) enzyme dosage can be reduced to less than 30 mg protein/g glucan and potentially further with only minor losses in glucose and xylose yields. In addition, we established that the reaction rate is improved in both catalyzed and uncatalyzed AHP pretreatment by increased solids concentrations. Conclusions This work explored the relationship between reaction conditions impacting a catalyzed oxidative pretreatment of woody biomass and identified that significant decreases in the H2O2, catalyst, and enzyme loading on the biomass as well as decreases in the pretreatment time could be realized with only minor losses in the subsequent sugar released enzymatically. Together these changes would have positive implications for the economics of a process based on this pretreatment approach. PMID:23971902

2013-01-01

332

Multilayered thermal insulation formed of zirconia bonded layers of zirconia fibers and metal oxide fibers and method for making same  

DOEpatents

A multilayered thermal insulating composite is formed of a first layer of zirconia-bonded zirconia fibers for utilization near the hot phase or surface of a furnace or the like. A second layer of zirconia-bonded metal oxide fibers is attached to the zirconia fiber layer by a transition layer formed of intermingled zirconia fibers and metal oxide fibers. The thermal insulation is fabricated by vacuum molding with the layers being sequentially applied from aqueous solutions containing the fibers to a configured mandrel. A portion of the solution containing the fibers forming the first layer is intermixed with the solution containing the fibers of the second layer for forming the layer of mixed fibers. The two layers of fibers joined together by the transition layer are saturated with a solution of zirconium oxynitrate which provides a zirconia matrix for the composite when the fibers are sintered together at their nexi.

Wrenn, G.E. Jr.; Holcombe, C.E. Jr.

1988-09-13

333

Multilayered thermal insulation formed of zirconia bonded layers of zirconia fibers and metal oxide fibers and method for making same  

DOEpatents

A multilayered thermal insulating composite is formed of a first layer of zirconia-bonded zirconia fibers for utilization near the hot phase or surface of a furnace or the like. A second layer of zirconia-bonded metal oxide fibers is attached to the zirconia fiber layer by a transition layer formed of intermingled zirconia fibers and metal oxide fibers. The thermal insulation is fabricated by vacuum molding with the layers being sequentially applied from aqueous solutions containing the fibers to a configured mandrel. A portion of the solution containing the fibers forming the first layer is intermixed with the solution containing the fibers of the second layer for forming the layer of mixed fibers. The two layers of fibers joined together by the transition layer are saturated with a solution of zirconium oxynitrate which provides a zirconia matrix for the composite when the fibers are sintered together at their nexi.

Wrenn, Jr., George E. (Clinton, TN); Holcombe, Jr., Cressie E. (Farragut, TN)

1988-01-01

334

Recent advances in the synthetic and mechanistic aspects of the ruthenium-catalyzed carbon-heteroatom bond forming reactions of alkenes and alkynes*  

PubMed Central

The group’s recent advances in catalytic carbon-to-heteroatom bond forming reactions of alkenes and alkynes are described. For the C–O bond formation reaction, a well-defined bifunctional ruthenium-amido catalyst has been successfully employed for the conjugate addition of alcohols to acrylic compounds. The ruthenium-hydride complex (PCy3)2(CO)RuHCl was found to be a highly effective catalyst for the regioselective alkyne-to-carboxylic acid coupling reaction in yielding synthetically useful enol ester products. Cationic ruthenium-hydride catalyst generated in-situ from (PCy3)2(CO)RuHCl/HBF4·OEt2 was successfully utilized for both the hydroamination and related C–N bond forming reactions of alkenes. For the C–Si bond formation reaction, regio- and stereoselective dehydrosilylation of alkenes and hydrosilylation of alkynes have been developed by using a well-defined ruthenium-hydride catalyst. Scope and mechanistic aspects of these carbon-to-heteroatom bond-forming reactions are discussed. PMID:21278832

Yi, Chae S.

2010-01-01

335

Recent advances in the synthetic and mechanistic aspects of the ruthenium-catalyzed carbon-heteroatom bond forming reactions of alkenes and alkynes.  

PubMed

The group's recent advances in catalytic carbon-to-heteroatom bond forming reactions of alkenes and alkynes are described. For the C-O bond formation reaction, a well-defined bifunctional ruthenium-amido catalyst has been successfully employed for the conjugate addition of alcohols to acrylic compounds. The ruthenium-hydride complex (PCy(3))(2)(CO)RuHCl was found to be a highly effective catalyst for the regioselective alkyne-to-carboxylic acid coupling reaction in yielding synthetically useful enol ester products. Cationic ruthenium-hydride catalyst generated in-situ from (PCy(3))(2)(CO)RuHCl/HBF(4)·OEt(2) was successfully utilized for both the hydroamination and related C-N bond forming reactions of alkenes. For the C-Si bond formation reaction, regio- and stereoselective dehydrosilylation of alkenes and hydrosilylation of alkynes have been developed by using a well-defined ruthenium-hydride catalyst. Scope and mechanistic aspects of these carbon-to-heteroatom bond-forming reactions are discussed. PMID:21278832

Yi, Chae S

2011-01-01

336

Visible Light Mediated Oxidative C-N Bond Formation/Aromatization Cascade: A New Photocatalytic Entry to N-Arylindoles  

PubMed Central

Indoles: A joint effort of light and air We have developed a mild aerobic oxidation protocol using visible light photocatalysis to synthesize structurally diverse N-arylindoles. The procedure employs 4 mol% [Ru(bpz)3](PF6)2, 18W LED light, and is performed open to the atmosphere. Readily prepared o-stryryl anilines are converted to a variety of indoles via a cascade sequence composed of oxidation of anilines, C-N bond formation, and aromatization. A 1,2-carbon shift can be also incorporated into this cascade event to further extend the substrate scope of the method. bpz = 2, 2?-Bipyrazine PMID:22915489

Maity, Soumitra

2012-01-01

337

Metrical oxidation states of 2-amidophenoxide and catecholate ligands: structural signatures of metal-ligand ? bonding in potentially noninnocent ligands.  

PubMed

Catecholates and 2-amidophenoxides are prototypical "noninnocent" ligands which can form metal complexes where the ligands are best described as being in the monoanionic (imino)semiquinone or neutral (imino)quinone oxidation state instead of their closed-shell dianionic form. Through a comprehensive analysis of structural data available for compounds with these ligands in unambiguous oxidation states (109 amidophenolates, 259 catecholates), the well-known structural changes in the ligands with oxidation state can be quantified. Using these correlations, an empirical "metrical oxidation state" (MOS) which gives a continuous measure of the apparent oxidation state of the ligand can be determined based on least-squares fitting of its C-C, C-O, and C-N bond lengths to this single parameter (a simple procedure for doing so is provided via a spreadsheet in the Supporting Information). High-valent d(0) metal complexes, particularly those of vanadium(V) and molybdenum(VI), have ligands with unexpectedly positive, and generally nonintegral, MOS values. The structural effects in these complexes are attributed not to electron transfer, but rather to amidophenoxide- or catecholate-to-metal ? bonding, an interpretation supported by the systematic variation of the MOS values as a function of the degree of competition with the other ?-donating groups in the structures. PMID:22260321

Brown, Seth N

2012-02-01

338

Design and synthesis of chiral Zn2+ complexes mimicking natural aldolases for catalytic C-C bond forming reactions in aqueous solution.  

PubMed

Extending carbon frameworks via a series of C-C bond forming reactions is essential for the synthesis of natural products, pharmaceutically active compounds, active agrochemical ingredients, and a variety of functional materials. The application of stereoselective C-C bond forming reactions to the one-pot synthesis of biorelevant compounds is now emerging as a challenging and powerful strategy for improving the efficiency of a chemical reaction, in which some of the reactants are subjected to successive chemical reactions in just one reactor. However, organic reactions are generally conducted in organic solvents, as many organic molecules, reagents, and intermediates are not stable or soluble in water. In contrast, enzymatic reactions in living systems proceed in aqueous solvents, as most of enzymes generally function only within a narrow range of temperature and pH and are not so stable in less polar organic environments, which makes it difficult to conduct chemoenzymatic reactions in organic solvents. In this review, we describe the design and synthesis of chiral metal complexes with Zn2+ ions as a catalytic factor that mimic aldolases in stereoselective C-C bond forming reactions, especially for enantioselective aldol reactions. Their application to chemoenzymatic reactions in aqueous solution is also presented. PMID:24481060

Itoh, Susumu; Sonoike, Shotaro; Kitamura, Masanori; Aoki, Shin

2014-01-01

339

Design and Synthesis of Chiral Zn2+ Complexes Mimicking Natural Aldolases for Catalytic C–C Bond Forming Reactions in Aqueous Solution  

PubMed Central

Extending carbon frameworks via a series of C–C bond forming reactions is essential for the synthesis of natural products, pharmaceutically active compounds, active agrochemical ingredients, and a variety of functional materials. The application of stereoselective C–C bond forming reactions to the one-pot synthesis of biorelevant compounds is now emerging as a challenging and powerful strategy for improving the efficiency of a chemical reaction, in which some of the reactants are subjected to successive chemical reactions in just one reactor. However, organic reactions are generally conducted in organic solvents, as many organic molecules, reagents, and intermediates are not stable or soluble in water. In contrast, enzymatic reactions in living systems proceed in aqueous solvents, as most of enzymes generally function only within a narrow range of temperature and pH and are not so stable in less polar organic environments, which makes it difficult to conduct chemoenzymatic reactions in organic solvents. In this review, we describe the design and synthesis of chiral metal complexes with Zn2+ ions as a catalytic factor that mimic aldolases in stereoselective C–C bond forming reactions, especially for enantioselective aldol reactions. Their application to chemoenzymatic reactions in aqueous solution is also presented. PMID:24481060

Itoh, Susumu; Sonoike, Shotaro; Kitamura, Masanori; Aoki, Shin

2014-01-01

340

Evolution of chemical bonding and electron density rearrangements during D(3h) ? D(3d) reaction in monolayered TiS2: a QTAIM and ELF study.  

PubMed

Monolayered titanium disulfide TiS2, a prospective nanoelectronic material, was previously shown to be subject to an exothermic solid-state D3h -D3d reaction that proceeds via a newly discovered transition state. Here, we study the reaction in detail using topological methods of quantum chemistry (quantum theory of atoms in molecules and electron localization function analysis) and show how electron density and chemical bonding between the atoms change in the course of the reaction. The reaction is shown to undergo a series of topological catastrophes, associated with elementary chemical events such as break and formation of bonds (including the unexpected formation of S-S bonding between sulfur layers), and rearrangement of electron density of outer valence and core shells. PMID:24943852

Ryzhikov, Maxim R; Slepkov, Vladimir A; Kozlova, Svetlana G; Gabuda, Svyatoslav P

2014-08-15

341

SPECTROSCOPIC STUDY OF SURFACE REDOX REACTIONS WITH MANGANESE OXIDES  

EPA Science Inventory

Redox reactions involving soil minerals and materials are important processes in environmental chemistry, but unfortunately they only have been characterized in the solution phase. he lack of a suitable method has prevented investigations of the mineral surface component of redox...

342

Mass transfer model for two-layer TBP oxidation reactions  

Microsoft Academic Search

To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in

Laurinat

1994-01-01

343

Electron shuttling effect of the intermediate quinones in phenol oxidation by Fenton reaction  

SciTech Connect

Fenton-type reactions have been developed for destruction of organic contaminants in water. This advanced oxidation process (AOP) shows promise for onsite destruction of hazardous organic compounds in water without generating secondary pollutants commonly associated with conventional treatment processes. Fenton-type reactions generate hydroxyl radical by iron(II) decomposition of hydrogen peroxide. Hydroxyl radical reacts rapidly and non-selectively with most organic compounds, so deep, even complete degradation may be achieved. The overall oxidation of organic compounds by Fenton-type reactions is, however, complex and may involve a series of steps. Understanding the oxidation mechanism, therefore, is prerequisite to proper engineering of Fenton based remediation technologies. We present here the results of a kinetic investigation on iron catalyzed oxidation of phenol by hydrogen peroxide in water in the dark.

Chen, Ruzhong; Pignatello, J.J. [Connecticut Agricultural Experimental Station, New Haven, CT (United States)

1996-12-31

344

Asymmetric C-C bond-formation reaction with Pd: how to favor heterogeneous or homogeneous catalysis?  

PubMed

The enantioselective allylic alkylation of (E)-1,3-diphenylallyl acetate was studied to clarify the heterogeneous or homogeneous character of the Pd/Al(2)O(3)-(R)-BINAP catalyst system. A combined approach was applied: the catalytic tests were completed with in situ XANES measurements to follow the oxidation state of Pd as a function of the reaction conditions. The study revealed that the oxidized Pd (after exposure to ambient air) is efficiently reduced by the solvents THF and dioxane, and by the nucleophile sodium dimethyl malonate, and thus these conditions prevent Pd leaching. The chiral modifier BINAP plays a dual role: a considerable coverage of the Pd surface by the bulky compound slows down the initial reduction of the surface oxides but BINAP itself may consume surface oxygen (through its conversion to BINAPO and BINAPO(2)) and contribute to the maintenance of the active metal surface during the reaction. Carrying out the reaction under pressure in an inert gas atmosphere is important to minimize the oxygen diffusion into the reaction mixture and to avoid leaching. The (known) effect of temperature is critical as well: our catalyst system is inactive at room temperature, which is a clear deviation from the behavior of the corresponding homogeneous system. In contrast, halogenated solvents are easily dehalogenated on Pd/Al(2)O(3) and thus they favor leaching of the metal and formation of soluble compounds, analogous to classical metal corrosion in the presence of halide ions. The frequently observed dissolution of Pd in the presence of halogenated substrates may be explained similarly. PMID:20665580

Reimann, Sven; Grunwaldt, Jan-Dierk; Mallat, Tamas; Baiker, Alfons

2010-08-16

345

Kinetics and Mechanism of Oxidation Reactions of Porphyrin-Iron(IV)-Oxo Intermediates  

PubMed Central

The kinetics of reactions of three porphyrin-iron(IV)-oxo derivatives with alkenes and benzylic alcohols were measured. The iron-oxo systems studied were 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin-iron(IV)-oxo (2a), 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin-iron(IV)-oxo (2b), and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin-iron(IV)-oxo (2c). Species 2 were stable for hours at room temperature as dilute solutions in acetonitrile and reacted hundreds to thousands of times faster in the presence of high concentrations of substrates. Typical second-order rate constants determined from pseudo-first-order kinetic studies are 1–2 × 10?2 M?1 s?1 for reactions with styrene and 3 × 10?2 M?1 s?1 for reactions with benzyl alcohol. The reactivity order for the iron-oxo species was 2a > 2b > 2c, which is inverted from that expected on the basis of the electron demand of the porphyrin macrocycles, and the oxidation reaction was suppressed when excess porphyrin-iron(III) complex was added to reaction mixtures. These observations indicate that the reactions involve disproportionation of the iron(IV)-oxo species 2 to give an iron(III) species and a more highly oxidized iron species, presumed to be iron(IV)-oxo porphyrin radical cation, that is the true oxidant in the reactions. Analyses of the kinetics of oxidations of a series of para-substituted benzylic alcohols with Hammett ?+ substituent constants and with a dual parameter method developed by Jiang (Jiang, X. K. Acc. Chem. Res. 1997, 30, 283) indicated that considerable positive charge developed on the benzylic carbons in the oxidation reactions, as expected for electrophilic oxidants, and also that substantial radical character developed on the benzyl carbon in the transition states. PMID:17630728

Pan, Zhengzheng; Newcomb, Martin

2010-01-01

346

Significance of destruction reactions in determining net emission of nitrogen oxides  

SciTech Connect

A system model has been developed by coupling the hydrodynamics with the heterogeneous and homogeneous chemistries for a bubbling fluidized bed combustor in order to explain the observed emission trends of nitric and nitrous oxides as a function of bed temperature, excess air and operating pressure. Reduction of the nitrogen oxides in the bed results in only a small fraction of the nitrogen oxides formed by char oxidation being emitted from the bed. At low temperatures, the concentration of CO in the bed is higher than that at high temperatures. This enhances the NO reduction via the catalytic NO/CO destruction reaction. Increases in N{sub 2}O destruction rates at high temperatures lead to reduction in its emissions. As the excess air is increased, the char loading decreases with a consequent decrease in the reduction of nitrogen oxides over bed char and higher emissions. The destruction of nitric oxide within a single char particle immediately after its formation, however, is enhanced as the oxygen levels increase. At elevated operating pressures both the char loading and the residence time of gases in the bed is high. For these reasons, nitric oxide emissions decrease whereas nitrous oxide emissions pass through a maximum with increases in pressure. This behavior can be explained in terms of a competition between the formation and destruction reactions. Dominance of the destruction reactions in determining the net emissions suggest that the optimal operating conditions should be evaluated in order to maximize destruction within the bed.

Goal, S.K.; Beer, J.M.; Sarofim, A.F. [Massachusetts Inst. of Tech., Cambridge, MA (United States). Dept. of Chemical Engineering

1995-12-31

347

Determination of carbon by the oxidation reduction reaction with chromium  

NASA Technical Reports Server (NTRS)

Free carbon was determined in silicon and boron carbides in ash, oxides, and other materials by oxidation to carbon dioxide with a mixture of K2Cr2O7 + H2SO4. The determination was made from the amount of CR(6) consumed, by adding excess Mohr's salt and titrating with a standard solution of KMnO4. The amount of Cr(6) self reduced was determined in a blank test. Optimum oxidation and conditions were achieved when the volumes of 5% k2Cr2Oz and H2SO4 were equal. The mixture was boiled for 1-2 hours using a reflex condenser. The volume should not be reduced, in order to avoid an increase in the sulfuric acid concentration. The relative error was 4-7% for 0.005-0.04 g C and less than or equal to 3.5% for 0.1 g C.

Mashkovich, L.; Kuteynikov, A. F.

1978-01-01

348

Oxidative catalysis using the stoichiometric oxidant as a reagent: an efficient strategy for single-electron-transfer-induced tandem anion-radical reactions.  

PubMed

Oxidative single-electron transfer-catalyzed tandem reactions consisting of a conjugate addition and a radical cyclization are reported, which incorporate the mandatory terminal oxidant as a functionality into the product. PMID:25070407

Kafka, František; Holan, Martin; Hidasová, Denisa; Pohl, Radek; Císa?ová, Ivana; Klepetá?ová, Blanka; Jahn, Ullrich

2014-09-01

349

The high-temperature oxidation, reduction, and volatilization reactions of silicon and silicon carbide  

Microsoft Academic Search

A thermochemical analysis was made of the oxidation, reduction, and volatilization reactions which occur in the Si-O-C system. One characteristic feature is the high SiO(g) and SiO(g) + CO(g) pressures at the Si(s)-SiO2 and SiC(s)-SiO2(s) interfaces. Active oxidation with weight losses and passive oxidation with weight gains were found on oxidizing Si(s) and SiC(s) in low oxygen pressures above 1000°C.

Earl A. Gulbransen; Sven A. Jansson

1972-01-01

350

Transient liquid-phase bonding of ferritic oxide dispersion strengthened superalloy MA957 using a conventional nickel braze and a novel iron-base foil  

Microsoft Academic Search

It has been shown that an iron foil based on the Fe-B-Si system is a suitable material for use as a high-temperature interlayer for transient liquid-phase (TLP) bonding of ferritic oxide dispersion strengthened alloys. TLP bonding produced ferritic joints, free from intermetallic precipitates and identical in composition to that of the parent metal. In contrast, however, TLP bonding using the

T. I. Khan; E. R. Wallach

1995-01-01

351

Low interface defect density of atomic layer deposition BeO with self-cleaning reaction for InGaAs metal oxide semiconductor field effect transistors  

SciTech Connect

In this paper, we discuss atomic configuration of atomic layer deposition (ALD) beryllium oxide (BeO) using the quantum chemistry to understand the theoretical origin. BeO has shorter bond length, higher reaction enthalpy, and larger bandgap energy compared with those of ALD aluminum oxide. It is shown that the excellent material properties of ALD BeO can reduce interface defect density due to the self-cleaning reaction and this contributes to the improvement of device performance of InGaAs MOSFETs. The low interface defect density and low leakage current of InGaAs MOSFET were demonstrated using X-ray photoelectron spectroscopy and the corresponding electrical results.

Shin, H. S. [Department of Electronics Engineering, Chungnam National University, Daejeon (Korea, Republic of) [Department of Electronics Engineering, Chungnam National University, Daejeon (Korea, Republic of); SEMATECH, 2706 Montopolis Dr., Austin, Texas 78741 (United States); The University of Texas, Austin, Texas 78758 (United States); Yum, J. H. [SEMATECH, 2706 Montopolis Dr., Austin, Texas 78741 (United States) [SEMATECH, 2706 Montopolis Dr., Austin, Texas 78741 (United States); The University of Texas, Austin, Texas 78758 (United States); Johnson, D. W. [SEMATECH, 2706 Montopolis Dr., Austin, Texas 78741 (United States) [SEMATECH, 2706 Montopolis Dr., Austin, Texas 78741 (United States); Texas A and M University College Station, Texas 77843 (United States); Harris, H. R. [Texas A and M University College Station, Texas 77843 (United States)] [Texas A and M University College Station, Texas 77843 (United States); Hudnall, Todd W. [Texas State University, 601 University Drive, San Marcos, Texas 78666 (United States)] [Texas State University, 601 University Drive, San Marcos, Texas 78666 (United States); Oh, J. [Yonsei University, Incheon, 406-840 (Korea, Republic of)] [Yonsei University, Incheon, 406-840 (Korea, Republic of); Kirsch, P.; Wang, W.-E. [SEMATECH, 2706 Montopolis Dr., Austin, Texas 78741 (United States)] [SEMATECH, 2706 Montopolis Dr., Austin, Texas 78741 (United States); Bielawski, C. W.; Banerjee, S. K.; Lee, J. C. [The University of Texas, Austin, Texas 78758 (United States)] [The University of Texas, Austin, Texas 78758 (United States); Lee, H. D. [Department of Electronics Engineering, Chungnam National University, Daejeon (Korea, Republic of)] [Department of Electronics Engineering, Chungnam National University, Daejeon (Korea, Republic of)

2013-11-25

352

In Pursuit of an Ideal C-C Bond-Forming Reaction  

PubMed Central

Attempts to introduce the highly versatile vinyl group into other organic molecules in a chemo-, regio- and stereoselective fashion via catalytic activation of ethylene provided challenging opportunities to explore new ligand and salt effects in homogeneous catalysis. This review provides a personal account of the development of enantioselective reactions involving ethylene. PMID:19606231

RajanBabu, T. V.

2009-01-01

353

Catalytic isomerization of ethylenic hydroccarbons. XVIII. Effect of drying and reaction temperature on the isomerization of deuterated butenes over magnesium oxide  

SciTech Connect

The isomerization of selectively deuterated cis-2-butenes was investigated at 60 and 250/sup 0/C on magnesium oxide predried between 300 and 550/sup 0/C. A rise in the drying temperature increases the number of active sites, but modifies neither their nature, nor their strength. The working temperature has a marked influence on the reactions observed. At 60/sup 0/C, magnesium oxide catalyzes only double-bond migration without exchange of hydrogen between the olefin and the catalyst; at 250/sup 0/C, a multiple exchange of hydrogen occurs during double-bond migration. In both cases the active sites are basic O/sup 2 -/ ions associated with weak acid Mg/sup 2 +/ ions, but adjacent OH groups participate in the reaction at 250/sup 0/C. Some strong basic O/sup 2 -/ ions are also active at 250/sup 0/C, but they deactivate very rapidly: on these sites, double-bond migration and cis-trans isomerization, both without exchange, are observed. 29 references, 9 figures, 4 tables.

Lemberton, J.L.; Perot, G.; Guisnet, M.

1984-09-01

354

Enantioselective chemisorption of propylene oxide on a 2-butanol modified Pd(111) surface: the role of hydrogen-bonding interactions.  

PubMed

The enantioselective chemisorption of R- and S-propylene oxide has been measured either on clean Pd(111) that has been exposed to S-2-butanol at various temperatures to vary the proportion of 2-butanol and 2-butoxide species or by adsorbing S-2-butanol on oxygen-covered Pd(111) to form exclusively 2-butoxide. The results reveal that enantioselective chemisorption is only found when 2-butanol is present on the surface. This is ascribed to enantiospecific hydrogen-bonding interactions between 2-butanol and propylene oxide. Measurements of the variation in enantiospecificity with 2-butanol exposure suggest that propylene oxide can interact either with a single adsorbed 2-butanol molecule or, at higher coverages, with two adsorbed 2-butanol species to form enantioselective sites. PMID:18001023

Gao, Feng; Wang, Yilin; Burkholder, Luke; Tysoe, Wilfred T

2007-12-12

355

The Shono-type electroorganic oxidation of unfunctionalised amides. Carbon–carbon bond formation via electrogenerated N-acyliminium ions  

PubMed Central

Summary N-acyliminium ions are useful reactive synthetic intermediates in a variety of important carbon–carbon bond forming and cyclisation strategies in organic chemistry. The advent of an electrochemical anodic oxidation of unfunctionalised amides, more commonly known as the Shono oxidation, has provided a complementary route to the C–H activation of low reactivity intermediates. In this article, containing over 100 references, we highlight the development of the Shono-type oxidations from the original direct electrolysis methods, to the use of electroauxiliaries before arriving at indirect electrolysis methodologies. We also highlight new technologies and techniques applied to this area of electrosynthesis. We conclude with the use of this electrosynthetic approach to challenging syntheses of natural products and other complex structures for biological evaluation discussing recent technological developments in electroorganic techniques and future directions. PMID:25670975

2014-01-01

356

Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis  

E-print Network

cleavage of B-H and B-B bonds across the N-Pd bond in a cationic (PNP)Pd fragment, the C-H oxidative addition to a (PNP)Ir center and the recent results on the C-H and C-O oxidative addition in reactions of aryl carboxylates with the (PNP)Rh fragment...

Zhu, Yanjun

2012-07-16

357

Effect of presintering on the dielectric and mechanical properties of porous reaction-bonded silicon nitride  

Microsoft Academic Search

This paper presents the influence of presintering on the dielectric and mechanical properties of porous silicon nitride ceramics which were prepared by reaction sintering in flowing nitrogen atmosphere. Si3N4 ceramics containing 0.8mm spherical pores in diameter and with porosity of about 53% were made by adding 30% in mass pore-forming agent grains prepared by spray prilling. Green bodies were subjected

Jie Xu; Fa Luo; Dongmei Zhu; Xiaolei Su; Wancheng Zhou

2008-01-01

358

Preparation of leady oxide for lead-acid battery by cementation reaction  

NASA Astrophysics Data System (ADS)

The aim of this research is to prepare leady oxide with high specific area for lead-acid batteries by a new production process. Leady oxide is produced by a cementation reaction in 1.0 wt% HCl solution using a pure aluminum or a magnesium rod as the reductant. Leady oxide prepared in this process is much superior to Barton-pot or ball-mill oxide in terms of physical characteristics. The particle-size distribution of the leady oxide produced by this new process is similar to that of ball-mill oxide. Its acid absorption, however, is much higher because of the different particle shape with respect to ball-mill oxide. Ball-mill oxide is composed of particles of non-uniform plate shape, whereas the new leady oxide is composed of particles of perfect flat (flake) shape. The former oxide has higher specific surface area and greater acid absorption than ball-mill or Barton-pot oxide.

Shin, Joon-Ho; Kim, Ki-Won; Ahn, Hyo-Jun

359

Thermal effects on the mechanical properties of SiC fibre reinforced reaction-bonded silicon nitride matrix composites  

NASA Technical Reports Server (NTRS)

The elevated temperature four-point flexural strength and the room temperature tensile and flexural strength properties after thermal shock were measured for ceramic composites consisting of 30 vol pct uniaxially aligned 142 micron diameter SiC fibers in a reaction bonded Si3N4 matrix. The elevated temperature strengths were measured after 15 min of exposure in air at temperatures to 1400 C. Thermal shock treatment was accomplished by heating the composite in air for 15 min at temperatures to 1200 C and then quenching in water at 25 C. The results indicate no significant loss in strength properties either at temperature or after thermal shock when compared with the strength data for composites in the as-fabricated condition.

Bhatt, R. T.; Phillips, R. E.

1990-01-01

360

Mechanical properties of SiC fiber-reinforced reaction-bonded Si3N4 composites  

NASA Technical Reports Server (NTRS)

The room temperature mechanical and physical properties of silicon carbide fiber reinforced reaction-bonded silicon nitride composites (SiC/RBSN) have been evaluated. The composites contained 23 and 40 volume fraction of aligned 140 micro m diameter chemically vapor deposited SiC fibers. Preliminary results for composite tensile and bend strengths and fracture strain indicate that the composites displayed excellent properties when compared with unreinforced RBSN of comparable porosity. Fiber volume fraction showed little influence on matrix first cracking strain but did influence the stressed required for matrix first cracking and for ultimate composite fracture strength. It is suggested that by reducing matrix porosity and by increasing the volume fraction of the large diameter SiC fiber, it should be possible to further improve the composite stress at which the matrix first cracks.

Bhatt, R. T.

1985-01-01

361

Activation of methane by size-selected iron cluster cations, Fen+ (n=2-15): Cluster-CHx (x=0-3) bond energies and reaction mechanisms  

NASA Astrophysics Data System (ADS)

The kinetic energy dependences of the reactions of Fen+ (n=2-15) with CD4 are studied in a guided ion beam tandem mass spectrometer over the energy range of 0-10 eV. All reactions exhibit thresholds and two main products, FenD+ and FenCD2+, are formed. These primary products decompose at higher energies to form secondary and higher order products, FenCD+, FenC+, Fen-1D+, Fen-1CD2+, Fen-1CD+, and Fen-1C+. The cross-section magnitudes for the dehydrogenation products, FenCD2+, are observed to vary considerably as a function of cluster size; subsequent dehydrogenation to form FenC+ becomes more facile for larger clusters. Thresholds for the various primary and secondary reactions are analyzed and bond energies for iron cluster cation bonds to C, CD, CD2, and CD3 are determined. As a function of cluster size, these bond energies rapidly reach relatively constant values, which are argued to lie close to bulk phase values. The relative magnitudes in these bond energies are consistent with simple bond order considerations. On the basis of this thermochemistry, we find that there are barriers to the primary dehydrogenation reactions for all the clusters, except n=3 and 4. Evidence that this barrier for n?5 corresponds to the chemisorption step is discussed.

Liyanage, Rohana; Zhang, Xiao-Guang; Armentrout, P. B.

2001-12-01

362

Catalytic activity of anion-exchange resins modified with metal-porphine in oxidative reactions of phenols.  

PubMed

Anion-exchange resins modified with metal-porphine (M-Pr) have been investigated to develop a solid catalyst in the oxidative reaction of phenols by O2 in air. Co-Pr, which is easily prepared and separable from the reaction mixture, has been proved to accelerate the oxidative reaction of phenols such as 3,5-di-tertbutyl-4-hydroxyanisole. The resulting main oxidative products were identified to be quinones by using the GC-MS method. PMID:11086930

Iwado, A; Mifune, M; Kato, J; Oda, J; Chikuma, M; Motohashi, N; Saito, Y

2000-11-01

363

Process for the oxidation of materials in water at supercritical temperatures utilizing reaction rate enhancers  

SciTech Connect

A method is described for substantially completely oxidizing combustible materials in which an aqueous stream bearing the combustible materials is reacted in the presence of an oxidant comprising diatomic oxygen and at a temperature greater than the critical temperature of water and at a pressure greater than about 25 bar, within a reactor for a period of less than about 5 minutes to produce a reaction product stream, wherein the reaction is initiated in the presence of a rate enhancer comprising at least one oxidizing agent in addition to said oxidant selected from the group consisting of ozone, hydrogen peroxide, salts containing persulfate, salts containing permanganate, nitric acid, salts containing nitrate, oxyacids of chlorine and their corresponding salts, hypochlorous acid, salts containing hypochlorite, chlorous acid, salts containing chlorite, chloric acid, salts containing chlorate, perchloric acid, and salts containing perchlorate.

Swallow, K.C.; Killilea, W.R.; Hong, G.T.; Bourhis, A.L.

1993-08-03

364

Surface-catalyzed air oxidation reactions of hydrazines: Tubular reactor studies  

NASA Technical Reports Server (NTRS)

The surface-catalyzed air oxidation reactions of hydrazine, monomethylhydrazine, unsymmetrical dimethylhydrazine, symmetrical dimethylhydrazine, trimethylhydrazine and tetramethylhydrazine were investigated in a metal-powder packed turbular flow reactor at 55 plus or minus 3 C. Hydrazine was completely reacted on all surfaces studied. The major products of monomethylhydrazine (MMH) oxidation were methanol, methane and methyldiazene. The di-, tri- and tetra-methyl hydrazines were essentially unreactive under these conditions. The relative catalytic reactivities toward MMH are: Fe greater than Al2O3 greater than Ti greater than Zn greater than 316 SS greater than Cr greater than Ni greater than Al greater than 304L SS. A kinetic scheme and mechanism involving adsorption, oxidative dehydrogenation and reductive elimination reactions on a metal oxide surface are proposed.

Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

1988-01-01

365

Influence of aluminum oxide film on thermocompression bonding of gold wire to evaporated aluminum film  

NASA Technical Reports Server (NTRS)

The influence of Al surface condition on the thermocompression bonding of Au wires to Al electrodes for integrated electric circuits was studied. Au wires were connected to Al electrodes by nail-head bonding after various Al surface treatments. Bonding was evaluated by measuring the wire pull strength and fraction of the number of failures at Au-Al bonds to the total number of failures. Dependence of the fraction on applied load was derived theoretically with a parameter named critical load to take into consideration the differences in Al surface condition. The relation also held explicately for various surface treatments. Characterization of the Al surface was carried out by electron microscopy for chemical analysis.

Iwata, S.; Ishizaka, A.; Yamamoto, H.

1984-01-01

366

Asymmetric Intermolecular Boron Heck-Type Reactions via Oxidative Palladium(II) Catalysis Using Chiral Tridentate NHC-Amidate-Alkoxide Ligands  

PubMed Central

Chiral dimeric tridentate NHC-amidate-alkoxide palladium(II) complexes, 3a and 3b, effected oxidative boron Heck-type reactions of aryl boronic acids with both acyclic and cyclic alkenes at room temperature to afford the corresponding coupling products with high enantioselectivities. The high degree of enantioselection, far superior to existing methods, stems from differences in the non-bonding interactions in the proposed transition states, due to the influence from bulky substituents of the alkene substrates and the “counter axial groups” of the palladium (II) catalysts. PMID:19954185

Yoo, Kyung Soo; O’Neill, Justin; Sakaguchi, Satoshi; Giles, Richard; Lee, Joo Ho; Jung, Kyung Woon

2009-01-01

367

Gold-Catalyzed Oxidation of Propargylic Ethers with Internal C-C Triple Bonds: Impressive Regioselectivity Enabled by Inductive Effect.  

PubMed

Inductive perturbations of C-C triple bonds are shown to dictate the regiochemistry of gold-catalyzed oxidation of internal C-C triple bonds in the cases of propargylic ethers, resulting in highly regioselective formation of ?-alkoxy-?,?-unsaturated ketones (up to >50/1 selectivity) via ?-oxo gold carbene intermediates. Ethers derived from primary propargylic alcohols can be reliably transformed in good yields, and various functional groups are tolerated. With substrates derived from secondary propargylic alcohols, the development of a new P,N-bidentate ligand enables the minimization of competing alkyl group migration to the gold carbene center over the desired hydride migration; the preferred migration of a phenyl group, however, results in efficient formation of a ?-phenyl-?-alkoxy-?,?-unsaturated ketone. These results further advance the surrogacy of a propargyl moiety to synthetically versatile enone function with reliable and readily predictable regioselectivity. PMID:25284890

Ji, Kegong; D'Souza, Brendan; Nelson, Jon; Zhang, Liming

2014-11-01

368

Kinetics of the Reactions of Active Nitrogen with Oxygen and with Nitric Oxide  

Microsoft Academic Search

The rate of decay of nitrogen atoms in a fast-flow system in the presence of oxygen has been studied between 412 and 755 ^circK. Nitrogen atom concentrations were estimated by titration with nitric oxide. The slow primary step can be represented by begin{equation*}tag{1}N+O_2=NO+O.end{equation*} while the much more rapid secondary reaction (2) removes the nitric oxide formed in reaction (1) begin{equation*}tag{2}N+NO=N_a+O.end{equation*}

M. A. A. Clyne; B. A. Thrush

1961-01-01

369

Heterogeneous reactions of carbonyl sulfide on mineral oxides: mechanism and kinetics study  

NASA Astrophysics Data System (ADS)

The heterogeneous reactions of carbonyl sulfide (OCS) on the typical mineral oxides in the mineral dust particles were investigated using a Knudsen cell flow reactor and a diffuse reflectance UV-vis spectroscopy. The reaction pathway for OCS on mineral dust was identified based on the gaseous products and surface species. The hydrolysis of OCS and succeeding oxidation of intermediate products readily took place on ?-Al2O3, MgO, and CaO. Reversible and irreversible adsorption of OCS were observed on ?-Fe2O3 and ZnO, respectively, whereas no apparent uptake of OCS by SiO2 and TiO2 was observed. The reactivity of OCS on these oxides depends on both the basicity of oxides and the decomposition reactivity of oxides for H2S. Based on the individual uptake coefficients and chemical composition of authentic mineral dust, the uptake coefficient (?BET) of mineral dust was estimated to be in the range of 3.84×10-7-2.86×10-8. The global flux of OCS due to heterogeneous reactions and adsorption on mineral dust was estimated at 0.13-0.29 Tg yr-1, which is comparable to the annual flux of OCS for its reaction with ·OH.

Liu, Y.; Ma, J.; He, H.

2010-11-01

370

Activation of Noble Metals on Metal-Carbide Surfaces: Novel Catalysts for CO Oxidation, Desulfurization and Hydrogenation Reactions  

SciTech Connect

This perspective article focuses on the physical and chemical properties of highly active catalysts for CO oxidation, desulfurization and hydrogenation reactions generated by depositing noble metals on metal-carbide surfaces. To rationalize structure-reactivity relationships for these novel catalysts, well-defined systems are required. High-resolution photoemission, scanning tunneling microscopy (STM) and first-principles periodic density-functional (DF) calculations have been used to study the interaction of metals of Groups 9, 10 and 11 with MC(001) (M = Ti, Zr, V, Mo) surfaces. DF calculations give adsorption energies that range from 2 eV (Cu, Ag, Au) to 6 eV (Co, Rh, Ir). STM images show that Au, Cu, Ni and Pt grow on the carbide substrates forming two-dimensional islands at very low coverage, and three-dimensional islands at medium and large coverages. In many systems, the results of DF calculations point to the preferential formation of admetal-C bonds with significant electronic perturbations in the admetal. TiC(001) and ZrC(001) transfer some electron density to the admetals facilitating bonding of the adatom with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). For example, the Cu/TiC(001) and Au/TiC(001) systems are able to cleave both S-O bonds of SO{sub 2} at a temperature as low as 150 K, displaying a reactivity much larger than that of TiC(001) or extended surfaces of bulk copper and gold. At temperatures below 200 K, Au/TiC is able to dissociate O{sub 2} and perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(001) or Au(111), a Au/TiC(001) surface displays an activity for the hydrodesulfurization of thiophene higher than that of conventional Ni/MoS{sub x} catalysts. In general, the Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces. Thus, metal carbides are excellent supports for enhancing the chemical reactivity of noble metals.

Rodriguez J. A.; Illas, F.

2012-01-01

371

Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.  

PubMed

The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable. PMID:25108731

Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng

2014-08-01

372

Oxygen-functionalized few-layer graphene sheets as active catalysts for oxidative dehydrogenation reactions.  

PubMed

Nanostructured graphitic forms of carbons have shown intersting potential for catalysis research and are ideal candidates to substitute the conventional metal-oxide catalysts because they can be easily disposed, which enables a greener, more sustainable catalytic process. Few-layer graphene and its functionalized form offer the opportunity to investigate the nature of graphitic active sites for oxidation reactions in well-defined carbon-based catalysts. In this paper, we report the utilization of oxygen-functionalized few-layer graphene sheets containing variable amounts of oxygen in the heterogeneous catalytic oxidative dehydrogenation (ODH) reaction of isobutane at 400ºC. Interestingly, there is poor correlation between oxygen content and catalytic performance. Carbonyl groups were found to be highly stable, and graphene that had higher sp(2) character, the lowest oxygen content, and fewer edge sites presented the lowest specific rate of isobutane reaction, although the isobutene selectivity remained high. The reoxidation of the graphene surface occurred at the same rate as the ODH reaction suggesting a Mars-van Krevelen type of mechanism, similar to that which takes place on oxide surfaces. These results appear to suggest that a higher fraction of exposed edges where oxygen active sites can be formed and exchanged should lead to more active catalysts for ODH reactions. PMID:23471876

Schwartz, Viviane; Fu, Wujun; Tsai, Yu-Tung; Meyer, Harry M; Rondinone, Adam J; Chen, Jihua; Wu, Zili; Overbury, Steven H; Liang, Chengdu

2013-05-01

373

A combinatorial chemistry approach to the investigation of cerium oxide and plutonium oxide reactions with small molecules  

NASA Astrophysics Data System (ADS)

We are currently investigating the potential chemistry of the 3013 Standard waste storage containers. These containers are filled with waste that is a mixture of inorganic salts and plutonium oxide that has been calcined to remove water and other volatiles. There has been concern about possible pressure buildup due to the formation of hydrogen or other gases. We are utilizing a combinatorial chemistry approach to investigate a range of possible reactions that may occur in the containers with various concentrations of metal oxides and inorganic salts.

Brady, John T.; Warner, Benjamin P.; Bridgewater, Jon S.; Havrilla, George J.; Morris, David E.; Buscher, C. Thomas

2000-07-01

374

Key mechanistic features of enantioselective C-H bond activation reactions catalyzed by [(chiral mono-N-protected amino acid)-Pd(II)] complexes.  

PubMed

Monoprotected chiral amino acids have recently been established as a class of ligand scaffolds for effecting Pd-catalyzed enantioselective C-H bond activation reactions. However, to elucidate the mechanistic details and controlling factors of these reactions, more comprehensive studies are needed. In this work we report computational investigations into the key mechanistic features of enantioselective C-H bond activation reactions catalyzed by a [chiral (mono-N-protected amino acid)-Pd(II)] complex. Structural analysis points to a C-H insertion intermediate in which the nitrogen atom of the ligand is bound as a neutral ?-donor. The formation of this C-H insertion intermediate could, in principle, proceed via a "direct C-H cleavage" or via "initial N-H bond cleavage followed by C-H cleavage". The computational studies presented herein show that the pathway initiated by N-H bond cleavage is more kinetically favorable. It is shown that the first step of the reaction is the N-H bond cleavage by the coordinated acetate group (OAc). In the next stage, the weakly coordinated OAc(-) (the second acetate group) activates the ortho-C-H bond of the substrate and transfers the H-atom from the C-atom to the bound N-atom of the ligand. As a result, a new Pd-C bond is formed and the carbamate is converted from X-type to L-type ligand. The absolute configuration of the products that are predicted on the basis of the calculated energies of the transition states matches the experimental data. The calculated enantioselectivity is also comparable with the experimental result. On the basis of these data, the origin of the enantioselectivity can be largely attributed to steric repulsions in the transition states. PMID:22148424

Musaev, Djamaladdin G; Kaledin, Alexey; Shi, Bing-Feng; Yu, Jin-Quan

2012-01-25

375

Compounds producing the kreis color reaction with particular reference to oxidized milk fat  

Microsoft Academic Search

Summary  Evidence is presented which suggests that epihydrin aldehyde and its derivatives are not necessarily solely responsible for\\u000a the Kreis color reaction of oxidized fats. Malonic dialdehyde has been shown to give a positive reaction in the Kreis test\\u000a and the resulting color demonstrated to be spectrally similar to the Kreis colors obtained with epihydrin aldehyde diethyl\\u000a acetal, acrolein treated with

Stuart Patton; Mark Keeney; George W. Kurtz

1951-01-01

376

Kinetic and photochemical data for atmospheric chemistry reactions of the nitrogen oxides  

NASA Technical Reports Server (NTRS)

Data sheets for thermal and photochemical reactions of importance in the atmospheric chemistry of the nitrogen oxides are presented. For each reaction the available experimental data are summarized and critically evaluated, and a preferred value of the rate coefficient is given. The selection of the preferred value is discussed and an estimate of its accuracy is given. For the photochemical process, the data are summarized, and preferred for the photoabsorption cross section and primary quantum yields are given.

Hampson, R. F., Jr.

1980-01-01

377

Enzymatic oxidation of gallocatechin and epigallocatechin: effects of C-ring configuration on the reaction products.  

PubMed

Tea leaf is rich in pyrogallol-type catechins, and their oxidation is important in the generation of black tea polyphenols. In the present study, the enzymatic oxidation of three pyrogallol-type catechins, (+)- and (-)-gallocatechins and (-)-epigallocatechin, was compared. The reactions yielded unstable quinone products, which were trapped as condensation products with o-phenylenediamine. The oxidation of (+)-gallocatechin proceeded very slowly compared to the reaction of (-)-epigallocatechin, and yielded a proepitheaflagallin-type dimer as the major product, though oxidation of (-)-epigallocatechin gave predominantly dehydrotheasinensin C. The cis-configuration of the C-3 hydroxyl group and the B-ring of (-)-epigallocatechin was apparently crucial for rapid and selective production of dehydrotheasinensin C. Oxidation of (-)-gallocatechin proceeded in a manner similar to that of (+)-gallocatechin, and produced an enantiomer of the (+)-gallocatechin product. The results suggest that enzymes catalyze oxidation of the pyrogallol B-ring to the o-quinone, with subsequent non-enzymatic coupling reactions proceed under highly steric control. PMID:17888464

Matsuo, Yosuke; Yamada, Yuko; Tanaka, Takashi; Kouno, Isao

2008-12-01

378

Revealing different bonding modes of self-assembled octadecylphosphonic acid monolayers on oxides by time-of-flight secondary ion mass spectrometry: silicon vs aluminum.  

PubMed

Condensed octadecylphosphonic acid (OPA) dimers, i.e., two OPA molecules combined with the loss of a water molecule, were detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS) on OPA self-assembled monolayers (SAMs) that are only weakly bonded on the native oxide layer of a silicon wafer. In contrast, these condensed dimers were absent on OPA SAMs formed on the oxide layer of an aluminum film, where the OPA molecules are chemically bonded on the substrate through a P-O-Al linkage. These observations lead us to conclude that the OPA molecules in their SAMs have to be free from chemical bonding with the substrate in order for the primary ion beam to generate ion fragments of the condensed dimer. We demonstrate that the detection of condensed OPA dimers serves as an analytical criterion for TOF-SIMS to reveal the bonding mode of OPA molecules in their SAMs on different oxides. PMID:20349935

Nie, Heng-Yong

2010-04-15

379

Yttrium oxide/gadolinium oxide-modified platinum nanoparticles as cathodes for the oxygen reduction reaction.  

PubMed

Rare-earth-element (Y, Gd) modified Pt nanoparticles (NPs) supported on a carbon substrate (Vulcan XC-72) are synthesized via a water-in-oil chemical route. In both cases, X-ray diffraction (XRD) measurements show the non-formation of an alloyed material. Photoemission spectroscopy (XPS) results reveal that Y and Gd are oxidized. Additionally, no evidence of an electronic modification of Pt can be brought to light. Transmission electron microscopy (TEM) studies indicate that Pt-Y(2)O(3) and Pt-Gd(2)O(3) particles are well dispersed on the substrate-and that their average particle sizes are smaller than the Pt-NP sizes. The catalytic activity of the Pt-Y(2)O(3)/C and Pt-Gd(2)O(3)/C catalysts towards the oxygen reduction reaction (ORR) is studied in a 0.5?M H(2)SO(4) electrolyte. The surface and mass specific activities of the Pt-Y(2)O(3)/C catalyst towards the ORR at 0.9 V (vs. the reversible hydrogen electrode, RHE) are (54.3±1.2) ?A?cm(-2)(Pt) and MA=(23.1±0.5) mA?mg(-1)(Pt), respectively. These values are 1.3-, and 1.6-fold higher than the values obtained with a Pt/C catalyst. Although the as-prepared Pt-Gd(2)O(3)/C catalyst has a lower catalytic activity for the ORR compared to Pt/C, the heat-treated sample shows a surface specific activity of about (53.0±0.7) ?A?cm(-2) Pt , and a mass specific activity (MA) of about (18.2±0.5) mA?mg(-1) Pt at 0.9 V (vs. RHE). The enhancement of the ORR kinetics on the Pt-Y(2)O(3)/C and heat-treated Pt-Gd(2)O(3)/C catalysts could be associated with the formation of platinum NPs presenting modified surface properties. PMID:24819164

Luo, Yun; Habrioux, Aurélien; Calvillo, Laura; Granozzi, Gaetano; Alonso-Vante, Nicolas

2014-07-21

380

Iridium complexes containing mesoionic C donors: selective C(sp3)-H versus C(sp2)-H bond activation, reactivity towards acids and bases, and catalytic oxidation of silanes and water.  

PubMed

Metalation of a C2-methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp(3))-H bond activation of the C2-bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp(2))-H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp(2))-H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D(+) and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir-C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6,000?h(-1) with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol-4-ylidene ligands and is more than three times faster than with the triazolylidene analogue. PMID:25302630

Petronilho, Ana; Woods, James A; Mueller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

2014-11-24

381

Metal-free oxidative C(sp(3))-H bond functionalization of alkanes and alkylation-initiated radical 1,2-aryl migration in ?,?-diaryl allylic alcohols.  

PubMed

An oxidative C(sp(3))-H bond functionalization of alkanes and alkylation-initiated radical 1,2-aryl migration in ?,?-diaryl allylic alcohols using di-tert-butyl peroxide (DTBP) as the oxidant was established, which tolerates a wide range of simple alkane substrates and ?,?-diaryl allylic alcohols for direct preparation of ?-aryl-?-alkylated carbonyl ketones. PMID:25415337

Zhao, Jincan; Fang, Hong; Song, Ruichun; Zhou, Jie; Han, Jianlin; Pan, Yi

2015-01-11

382

Rhenium 2-oxoalkyl (enolate) complexes: Synthesis and carbon-carbon bond-forming reactions with nitriles  

SciTech Connect

The (2-oxoalkyl)rhenium complexes (rhenium enolates) (CO){sub 5}ReCH{sub 2}COR{sup 1} (R{sup 1} = OEt, Me, Ph, 1-3) can be prepared on a multigram scale by alkylation of (CO){sub 5}ReNa with ClCH{sub 2}COR{sup 1}. The secondary enolate (CO){sub 5}ReCH(Me)CO{sub 2}Et (4) can also be prepared in a similar fashion with use of MsOCH(Me)CO{sub 2}Et (Ms = CH{sub 3}SO{sub 2}{sup {minus}}). The mono(phosphine) enolates cis-(Ph{sub 3}P)(CO){sub 4}ReCH{sub 2}R{sup 2}(R{sup 2} = CO{sub 2}Et, CO{sub 2}Bu{sup t}, CONEt{sub 2}, COMe, COPh, CN, 8-13) are prepared in high yield via alkylation of (Ph{sub 3}P)(CO){sub 4}ReNa with ClCH{sub 2}R{sup 2}. Synthesis of the secondary enolate cis-(Ph{sub 3}P)(CO){sub 4}ReCH(Me)CO{sub 2}Et (14) is accomplished in 75% yield by alkylation with TfOCH(Me)CO{sub 2}Et (Tf = CF{sub 3}SO{sub 2}{sup {minus}}). The chelating phosphine complex is substitutionally inert under forcing thermal and photochemical conditions. Kinetic studies of the nitrile insertion reaction revealed a weak linear dependence of the rate constant of the reaction on the concentration of added CH{sub 3}CN in benzene; we believe this to be a medium effect.

Stack, J.G.; Doney, J.J.; Bergman, R.G.; Heathcock, C.H. (Univ. of California, Berkeley (USA))

1990-02-01

383

Antioxidant stoichiometry and the oxidative fate of vitamin E in peroxyl radical scavenging reactions  

Microsoft Academic Search

Oxidation ofR,R,R-?-tocopherol (vitamin E; TH) by peroxyl radicals generated from the azo initiator azobis(2,4-dimethylvaleronitrile) in acetonitrile, hexane, or in phospholipid liposomes yields 8a-(alkyldioxy)tocopherone adducts,\\u000a 8a-(hydroxy)tocopherone, and their hydrolysis product ?-tocopherolquinone TH oxidation also yields 4a,5-epoxy- and 7,8-epoxy-8a-(hydroperoxy)tocopherones\\u000a and their respective hydrolysis products 2,3-epoxy-?-tocopherolquinone and 5,6-epoxy-?-tocopherolquinone. Previous work indicates\\u000a that the distribution of TH oxidation products varies with reaction environment. We

Daniel C. Liebler; Jeanne A. Burr

1995-01-01

384

Chemical bonding in copper-based transparent conducting oxides: CuMO2 (M = In, Ga, Sc)  

NASA Astrophysics Data System (ADS)

The geometry and electronic structure of copper-based p-type delafossite transparent conducting oxides, CuMO2 (M = In, Ga, Sc), are studied using the generalized gradient approximation (GGA) corrected for on-site Coulomb interactions (GGA + U). The bonding and valence band compositions of these materials are investigated, and the origins of changes in the valence band features between group 3 and group 13 cations are discussed. Analysis of the effective masses at the valence and conduction band edge explains the experimentally reported conductivity trends.

Godinho, K. G.; Morgan, B. J.; Allen, J. P.; Scanlon, D. O.; Watson, G. W.

2011-08-01

385

Chemical bonding in copper-based transparent conducting oxides: CuMO2 (M = In, Ga, Sc).  

PubMed

The geometry and electronic structure of copper-based p-type delafossite transparent conducting oxides, CuMO(2) (M = In, Ga, Sc), are studied using the generalized gradient approximation (GGA) corrected for on-site Coulomb interactions (GGA + U). The bonding and valence band compositions of these materials are investigated, and the origins of changes in the valence band features between group 3 and group 13 cations are discussed. Analysis of the effective masses at the valence and conduction band edge explains the experimentally reported conductivity trends. PMID:21813950

Godinho, K G; Morgan, B J; Allen, J P; Scanlon, D O; Watson, G W

2011-08-24

386

Heterobifunctional PEG Ligands for Bioconjugation Reactions on Iron Oxide Nanoparticles  

PubMed Central

Ever since iron oxide nanoparticles have been recognized as promising scaffolds for biomedical applications, their surface functionalization has become even more important. We report the synthesis of a novel polyethylene glycol-based ligand that combines multiple advantageous properties for these applications. The ligand is covalently bound to the surface via a siloxane group, while its polyethylene glycol backbone significantly improves the colloidal stability of the particle in complex environments. End-capping the molecule with a carboxylic acid introduces a variety of coupling chemistry possibilities. In this study an antibody targeting plasminogen activator inhibitor-1 was coupled to the surface and its presence and binding activity was assessed by enzyme-linked immunosorbent assay and surface plasmon resonance experiments. The results indicate that the ligand has high potential towards biomedical applications where colloidal stability and advanced functionality is crucial. PMID:25275378

Bloemen, Maarten; Van Stappen, Thomas; Willot, Pieter; Lammertyn, Jeroen; Koeckelberghs, Guy; Geukens, Nick; Gils, Ann; Verbiest, Thierry

2014-01-01

387

Effect of dipolar fields, surface termination, and surface orientation on photochemical reactions on transition metal oxides  

NASA Astrophysics Data System (ADS)

Experiments have been conducted to determine the effects of dipolar fields, surface termination, and surface orientation on the photochemical reactivity of several transition metal oxides. These compounds include BaTiO3, SrTiO3, BaTi4O9, Sr2Nb2O 7, and Sr2Ta2O7 which were studied as polycrystalline ceramics, single crystals, micron-sized faceted particles, or some combination of these forms. The reduction of Ag+ from an aqueous AgNO3 solution (Ag0 product) and the oxidation of Pb2+ from an aqueous lead acetate solution (PbO 2 product) were selected as probe reactions because they leave insoluble products on the oxide surfaces. The reactivity of ferroelectric BaTiO3 was dominated by the effect of dipolar fields on the transport of photogenerated charge carriers. Silver was reduced on domains with a positive surface charge while lead was oxidized on domains with a negative surface charge. This reactivity implies that the dipolar field in individual domains drives photogenerated charge carriers to oppositely charged surfaces. This reaction mechanism results in a physical separation of the photogenerated charge carriers and the locations of the oxidation and reduction half reactions on the catalyst surface. Experiments performed on polycrystalline ceramics, single crystals, and micron-sized particles all showed this domain specific reactivity. SrTiO3 has the ideal cubic perovskite structure from which the tetragonally distorted ferroelectric BaTiO3 phase is derived. Polished and annealed surfaces of randomly oriented grain surfaces were bound by some combination of the following three planes: {110}, {111}, and a complex facet inclined approximately 24° from {100}. Surfaces with the complex {100} facet were found to be the most active for Ag reduction. Single crystal studies also showed that the nonpolar (100) surface is the most reactive and that the composition of the termination layer does not influence this reaction. However, the polar (111) and (110) surfaces had a non-uniform distribution of reaction products. For these orientations, the location of the reduction and oxidation reactions is determined by the chemical and charge terminations of the different terraces or facets. The reactivity for silver reduction on the faceted particles is ranked as (100) > (111) > (110) while the (100) surface was least reactive for lead oxidation. Overall, these results show that the photochemical reactivity of SrTiO3 is anisotropic and that on polar surfaces, dipolar fields arising from charged surface domains influence the transport of photogenerated charge carriers and promote spatially selective oxidation and reduction reactions. (Abstract shortened by UMI.)

Giocondi, Jennifer Lynn

388

Structural and functional investigation of graphene oxide-Fe3O4 nanocomposites for the heterogeneous Fenton-like reaction.  

PubMed

Graphene oxide-iron oxide (GO-Fe3O4) nanocomposites were synthesised by co-precipitating iron salts onto GO sheets in basic solution. The results showed that formation of two distinct structures was dependent upon the GO loading. The first structure corresponds to a low GO loading up to 10 wt%, associated with the beneficial intercalation of GO within Fe3O4 nanoparticles and resulting in higher surface area up to 409 m(2) g(-1). High GO loading beyond 10 wt% led to the aggregation of Fe3O4 nanoparticles and the undesirable stacking of GO sheets. The presence of strong interfacial interactions (Fe-O-C bonds) between both components at low GO loading lead to 20% higher degradation of Acid Orange 7 than the Fe3O4 nanoparticles in heterogeneous Fenton-like reaction. This behaviour was attributed to synergistic structural and functional effect of the combined GO and Fe3O4 nanoparticles. PMID:24699690

Zubir, Nor Aida; Yacou, Christelle; Motuzas, Julius; Zhang, Xiwang; Diniz da Costa, João C

2014-01-01

389

Structural and functional investigation of graphene oxide–Fe3O4 nanocomposites for the heterogeneous Fenton-like reaction  

PubMed Central

Graphene oxide–iron oxide (GO–Fe3O4) nanocomposites were synthesised by co-precipitating iron salts onto GO sheets in basic solution. The results showed that formation of two distinct structures was dependent upon the GO loading. The first structure corresponds to a low GO loading up to 10?wt%, associated with the beneficial intercalation of GO within Fe3O4 nanoparticles and resulting in higher surface area up to 409?m2 g?1. High GO loading beyond 10?wt% led to the aggregation of Fe3O4 nanoparticles and the undesirable stacking of GO sheets. The presence of strong interfacial interactions (Fe-O-C bonds) between both components at low GO loading lead to 20% higher degradation of Acid Orange 7 than the Fe3O4 nanoparticles in heterogeneous Fenton-like reaction. This behaviour was attributed to synergistic structural and functional effect of the combined GO and Fe3O4 nanoparticles. PMID:24699690

Zubir, Nor Aida; Yacou, Christelle; Motuzas, Julius; Zhang, Xiwang; Diniz da Costa, João C.

2014-01-01

390

Atomic-Scale Studies Of Structure And Bonding At Perovskite Oxide Heterointerfaces .  

E-print Network

??Perovskite oxides exhibit an almost universal range of ground states including insulator, semiconductor, metal, superconductor, ferromagnet, antiferromagnet, spin glass, ferroelectric, and piezoelectric. Many of these… (more)

Kourkoutis, Lena

2009-01-01

391

Oxidative Coupling of Dichalcogenides with Sodium Sulfinates via Copper-Catalyzed Cleavage of S-S and Se-Se Bonds.  

PubMed

A copper-catalyzed sulfonylation of disulfides was achieved using sodium sulfinates in air. The reaction formed various sulfur-sulfone bonds efficiently and afforded thiosulfonates in good yields. Selenosulfonates could also be prepared with this procedure. Furthermore, both chalcogenide groups on the dichalcogenides were available in these reactions. PMID:25562106

Taniguchi, Nobukazu

2015-02-01

392

Effect of electrochemical redox reaction on biochemical ammonium oxidation and chemical nitrite oxidation.  

PubMed

A modified graphite felt electrode with neutral red (NRelectrode) was shown to catalyze the chemical oxidation of nitrite to nitrate under aerobic conditions. The electrochemically oxidized NR-electrode (EO-NR-electrode) and reduced NR-electrode (ER-NR-electrode) catalyzed the oxidation of 1,094+/-39 mg/l and 382+/-45 mg/l of nitrite, respectively, for 24 h. The electrically uncharged NRelectrode (EU-NR-electrode) catalyzed the oxidation of 345+/-47 mg/l of nitrite for 24 h. The aerobic bacterial community immobilized in the EO-NR-electrode did not oxidize ammonium to nitrite; however, the aerobic bacterial community immobilized in the ER-NR-electrode bioelectrochemically oxidized 1,412+/-39 mg/l of ammonium for 48 h. Meanwhile, the aerobic bacterial community immobilized on the EU-NR-electrode biochemically oxidized 449+/-22 mg/l of ammonium for 48 h. In the continuous culture system, the aerobic bacterial community immobilized on the ER-NR-electrode bioelectrochemically oxidized a minimal 1,337+/-38 mg/l to a maximal 1,480+/-38 mg/l of ammonium to nitrate, and the community immobilized on the EU-NR-electrode biochemically oxidized a minimal 327+/-23 mg/l to a maximal 412+/-26 mg/l of ammonium to nitrate every two days. The bacterial communities cultivated in the ER-NR-electrode and EU-NR-electrode in the continuous culture system were analyzed by TGGE on the 20th and 50th days of incubation. Some ammoniumoxidizing bacteria were enriched on the ER-NR-electrode, but not on the EU-NR-electrode. PMID:20372016

Jeon, Bo Young; Seo, Ha Na; Kang, Seung Won; Park, Doo Hyun

2010-03-01

393

Comparative study of the reactions of metal oxides with H2S and SO2  

Microsoft Academic Search

The primary objective of this project is the investigation of the effects of pore structure on the capacity of porous metal oxides for removal of gaseous pollutants from flue gases of power plants (SO2) and hot coal gas (primarily H2S). Specifically, we intend to appropriately exploit the differences of the sulfidation and sulfation reactions (for instance, different molar volumes of

S. V. Sotirchos

1991-01-01

394

The reactions of O(ID) and OH with CH3OH, oxidation of the HCO radial, and the photochemical oxidation of formaldehyde. [photochemical reactions in stratosphere  

NASA Technical Reports Server (NTRS)

An experimental, laboratory study of the various photochemical reactions that can occur in the mesosphere and stratosphere is presented. N2O was photolyzed at 2139 A in the presence of CH3OH and CO. The O(id) produced in the photolysis reacted with CH3OH to produce OH radicals, and thus the reactions of both O(id) and OH were able to be studied. Also considered was the oxidation of the HCO radical. Mixtures of Cl2, O2, H2CO, and sometimes N2 or He were irradiated at 3660 A at several temperatures to photodecompose the Cl2. The photochemical oxidation of formaldehyde was studied as follows: formaldehyde in the presence of N2 and/or O2 (usually dry air) was photolyzed with a medium pressure Hg lamp used in conjunction with various filters which transmit different relative amounts of Hg lines from 2894 A to 3660 A. Results are presented and discussed, along with a description of experimental procedures and apparatus, and chemical reaction kinetics.

Osif, T. L.

1976-01-01

395

Ferrate(VI) oxidation of ?-lactam antibiotics: reaction kinetics, antibacterial activity changes, and transformation products.  

PubMed

Oxidation of ?-lactam antibiotics by aqueous ferrate(VI) was investigated to determine reaction kinetics, reaction sites, antibacterial activity changes, and transformation products. Apparent second-order rate constants (kapp) were determined in the pH range 6.0-9.5 for the reaction of ferrate(VI) with penicillins (amoxicillin, ampicillin, cloxacillin, and penicillin G), a cephalosporin (cephalexin), and several model compounds. Ferrate(VI) shows an appreciable reactivity toward the selected ?-lactams (kapp for pH 7 = 110-770 M(-1) s(-1)). The pH-dependent kapp could be well explained by considering species-specific reactions between ferrate(VI) and the ?-lactams (with reactions occurring at thioether, amine, and/or phenol groups). On the basis of the kinetic results, the thioether is the main reaction site for cloxacillin and penicillin G. In addition to the thioether, the amine is a reaction site for ampicillin and cephalexin, and amine and phenol are reaction sites for amoxicillin. HPLC/MS analysis showed that the thioether of ?-lactams was transformed to stereoisomeric (R)- and (S)-sulfoxides and then to a sulfone. Quantitative microbiological assay of ferrate(VI)-treated ?-lactam solutions indicated that transformation products resulting from the oxidation of cephalexin exhibited diminished, but non-negligible residual activity (i.e., ?24% as potent as the parent compound). For the other ?-lactams, the transformation products showed much lower (<5%) antibacterial potencies compared to the parent compounds. Overall, ferrate(VI) oxidation appears to be effective as a means of lowering the antibacterial activities of ?-lactams, although alternative approaches may be necessary to achieve complete elimination of cephalosporin activities. PMID:25073066

Karlesa, Anggita; De Vera, Glen Andrew D; Dodd, Michael C; Park, Jihye; Espino, Maria Pythias B; Lee, Yunho

2014-09-01

396

Kinetic Solvent Effects on the Reactions of the Cumyloxyl Radical with Tertiary Amides. Control over the Hydrogen Atom Transfer Reactivity and Selectivity through Solvent Polarity and Hydrogen Bonding.  

PubMed

A laser flash photolysis study on the role of solvent effects on hydrogen atom transfer (HAT) from the C-H bonds of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-formylpyrrolidine (FPRD), and N-acetylpyrrolidine (APRD) to the cumyloxyl radical (CumO(•)) was carried out. From large to very large increases in the HAT rate constant (kH) were measured on going from MeOH and TFE to isooctane (kH(isooctane)/kH(MeOH) = 5-12; kH(isooctane)/kH(TFE) > 80). This behavior was explained in terms of the increase in the extent of charge separation in the amides determined by polar solvents through solvent-amide dipole-dipole interactions and hydrogen bonding, where the latter interactions appear to play a major role with strong HBD solvents such as TFE. These interactions increase the electron deficiency of the amide C-H bonds, deactivating these bonds toward HAT to an electrophilic radical such as CumO(•), indicating that changes in solvent polarity and hydrogen bonding can provide a convenient method for deactivation of the C-H bond of amides toward HAT. With DMF, a solvent-induced change in HAT selectivity was observed, suggesting that solvent effects can be successfully employed to control the reaction selectivity in HAT-based procedures for the functionalization of C-H bonds. PMID:25545198

Salamone, Michela; Mangiacapra, Livia; Bietti, Massimo

2015-01-16

397

Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates  

SciTech Connect

Transition metal oxides exhibit a rich collection of electronic properties and have many practical applications in areas such as catalysis and ultra-high-density magnetic data storage. Therefore the development of switchable molecular transition metal oxides has potential for the engineering of single-molecule devices and nanoscale electronics. At present, the electronic properties of transition metal oxides can only be tailored through the irreversible introduction of dopant ions, modifying the electronic structure by either injecting electrons or core holes. Here we show that a molybdenum(VI) oxide 'polyoxometalate' molecular nanocluster containing two embedded redox agents is activated by a metallic surface and can reversibly interconvert between two electronic states. Upon thermal activation two electrons are ejected from the active sulphite anions and delocalized over the metal oxide cluster cage, switching it from a fully oxidized state to a two-electron reduced state along with the concomitant formation of an S-S bonding interaction between the two sulphur centres inside the cluster shell.

Fleming, C.; Long, D. L.; McMillian, N.; Johnston, J.; Bovet N.; Dhanak, V.; Gadegaard, N.; Kogerler, P.; Cronin, L.; Kadodwala, M.

2008-03-30

398

Influence of "Island-Like" Oxides in the Bond-Coat on the Stress and Failure Patterns of the Thermal-Barrier Coatings Fabricated by Atmospheric Plasma Spraying During Long-Term High Temperature Oxidation  

NASA Astrophysics Data System (ADS)

Thermal-barrier coatings (TBCs) are very important ceramic-coating materials due to their excellent performance at high temperature. The inner zone of the bond-coat is often easily endured oxidized (internal oxidation) in the process of thermal spraying and the long-time exposure to the high temperature, and the "island-like" oxides can be formed. Especially, when the bond-coat was fabricated by atmospheric plasma spraying (APS), this trend is more evident. In this paper, the stress distribution around the thermally grown oxide (TGO) has been calculated by the finite element method when the "island-like" oxides have been considered. The simulation results indicate that the maximum tensile stress and compressive stress existed in the TGO, and the existence of the "island-like" oxides will further decrease the maximum tensile stress level in the TGO. While the "island-like" oxides in the bond-coat will decrease the effective thickness of the TGO at the metallic layer/ceramic layer interface due to the oxidation of the metallic elements in the bond-coat. The crack propagation equation has been established and the failure mechanism of the TBC due to the formation and growth of the TGO has also been discussed in detail. The lifetime of the TBCs which have experienced high temperature oxidation has been predicted and the theoretical results agreed well with the experimental data.

Wang, L.; Zhao, Y. X.; Zhong, X. H.; Tao, S. Y.; Zhang, W.; Wang, Y.

2014-02-01

399

Experimental and theoretical studies of reactions of neutral vanadium and tantalum oxide clusters with NO and NH3  

E-print Network

Experimental and theoretical studies of reactions of neutral vanadium and tantalum oxide clusters; accepted 16 September 2010; published online 3 November 2010 Reactions of neutral vanadium and tantalum, a vanadium oxide catalyst is loaded on an anatase support as a monolayer, and the active VOx species

Rocca, Jorge J.

400

Aryl Ketone Synthesis via Tandem Orthoplatinated Triarylphosphite-Catalyzed Addition Reactions of Arylboronic Acids with Aldehydes Followed by Oxidation  

PubMed Central

Tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%. PMID:20849092

Liao, Yuan-Xi; Hu, Qiao-Sheng

2010-01-01

401

Aryl ketone synthesis via tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation.  

PubMed

Tandem orthoplatinated triaryl phosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%. PMID:20849092

Liao, Yuan-Xi; Hu, Qiao-Sheng

2010-10-15

402

Water-gas shift reaction on oxide/Cu(111): Rational catalyst screening from density functional theory  

NASA Astrophysics Data System (ADS)

Developing improved catalysts based on a fundamental understanding of reaction mechanism has become one of the grand challenges in catalysis. A theoretical understanding and screening the metal-oxide composite catalysts for the water-gas shift (WGS) reaction is presented here. Density functional theory was employed to identify the key step for the WGS reaction on the Au, Cu-oxide catalysts, where the calculated reaction energy for water dissociation correlates well with the experimental measured WGS activity. Accordingly, the calculated reaction energy for water dissociation was used as the scaling descriptor to screen the inverse model catalysts, oxide/Cu(111), for the better WGS activity. Our calculations predict that the WGS activity increases in a sequence: Cu(111), ZnO/Cu(111) < TiO2/Cu(111), ZrO2/Cu(111) < MoO3/Cu(111). Our results imply that the high performances of Au, Cu-oxide nanocatalysts in the WGS reaction rely heavily on the direct participation of both oxide and metal sites. The degree that the oxide is reduced by Cu plays an important role in determining the WGS activity of oxide/Cu catalysts. The reducible oxide can be transformed from the fully oxidized form to the reduced form due to the interaction with Cu and, therefore, the transfer of electron density from Cu, which helps in releasing the bottleneck water dissociation and, therefore, facilitating the WGS reaction on copper.

Liu, Ping

2010-11-01

403

Oxidation-induced intramolecular disulfide bond inactivates mitogen-activated protein kinase kinase 6 by inhibiting ATP binding  

PubMed Central

Mitogen-activated protein kinase kinase 6 (MKK6) is a member of the mitogen-activated protein kinase (MAPK) kinase (MAP2K) subfamily that specifically phosphorylates and activates the p38 MAPKs. Based on both biochemical and cellular assays, we found that MKK6 was extremely sensitive to oxidation: It was inactivated by oxidation and its kinase activity was fully restored upon treatment with a reducing agent. Detailed mechanistic studies showed that cysteines 109 and 196, two of the six cysteines in MKK6, formed an intramolecular disulfide bond upon oxidation that inactivated MKK6 by inhibiting its ATP binding. This mechanism is distinct from that seen in other redox-sensitive kinases. The two cysteines involved in intramolecular disulfide formation are conserved in all seven members of the MAP2K family. Consistently, we confirmed that other MAP2Ks were also sensitive to oxidation. Our work reveals that MKK6 and other MAP2Ks are a distinct class of cellular redox sensors. PMID:21078955

Diao, Yarui; Liu, Wei; Wong, Catherine C. L.; Wang, Xi; Lee, Kaman; Cheung, Po-yan; Pan, Lifeng; Xu, Tao; Han, Jiahuai; Yates, John R.; Zhang, Mingjie; Wu, Zhenguo

2010-01-01

404

The influence of porosity and morphology of hydrated oxide films on epoxy-aluminium bond durability  

Microsoft Academic Search

Clad aluminium alloy was pretreated by immersion in boiling water for times ranging between 30 s and 4 h. The chemical and physical properties of the films produced in the 100°C water were characterized by techniques including X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectroscopy (RBS), scanning electron microscopy (SEM), and secondary ion mass spectrometry (SIMS). The durability of the bonds

Andrew N. Rider

2001-01-01

405

Failure of gold and copper ball bonds due to intermetallic oxidation and corrosion  

Microsoft Academic Search

Strong interest in the replacement of gold bonding wire by copper in microelectronics packaging has highlighted poor performance of copper wire under moist conditions. Attempts have been made to address this problem by coating copper wire with palladium, which may be a solution for some applications but ignores the fundamental reasons for the poor performance of copper wire. Gold and

C. D. Breach; Ng Hun Shen; Teck Kheng Lee; R. Holliday

2011-01-01

406

Elucidation of the reaction mechanism during the removal of copper oxide by halogen surfactant at the surface of copper plate  

NASA Astrophysics Data System (ADS)

Although copper nanoparticles have various attractive properties, electrical applications of these was not achieved because of its surface oxide layer which prohibited electrical conduction. Thus, it can be considered that a new elimination method of the oxide on Cu surface, which simultaneously provide the resistance to re-oxidized, should be developed. In this study, the reaction between the metal oxide on Cu plate surface and halogen surfactant was introduced into development as a new elimination method of surface oxide layer. Since electrochemical and surface analysis are effective for analyzing the reaction mechanism which expected to be the reduction reaction of the oxide on metal surface, Cu electrode, which represented material of Cu nanoparticles surface, was used for the reaction mechanism analysis. The oxide is removed by controlling the temperature and selecting the optimal combination of solvents and the halogen surfactant (TIC). Results of electrochemical measurements strongly suggest that the chemical reaction between the oxides on the surface with the halogen surfactant is a substitution reaction which converts Cu oxide to Cu bromide, and continuously formed Cu bromide was dissolved into solvent. Totally, the oxide on the Cu surface was successfully eliminated.

Yokoyama, Shun; Takahashi, Hideyuki; Itoh, Takashi; Motomiya, Kenichi; Tohji, Kazuyuki

2013-01-01

407

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride  

PubMed Central

Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NOy) are also globally distributed, because NO formed in combustion processes is oxidized to NO2, HNO3, N2O5 and a variety of other nitrogen oxides during transport. Deposition of HCl and NOy onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO2 or N2O5 on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO2), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO2 in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist. PMID:19620710

Raff, Jonathan D.; Njegic, Bosiljka; Chang, Wayne L.; Gordon, Mark S.; Dabdub, Donald; Gerber, R. Benny; Finlayson-Pitts, Barbara J.

2009-01-01

408

Chemical oxidation of anthracite with hydrogen peroxide via the Fenton reaction  

USGS Publications Warehouse

Solutions of 30% H2O2 ranging from pH = 0 to pH = 11.5 have been used to oxidize anthracite at room temperature. The inorganic impurities, primarily pyrite, catalysed the oxidation and reduction of H2O2 (the Fenton reaction) to form the hydroxyl radical; the oxidation of the organic matter was minimal and was observed only in strong acidic solutions (pH < 1.5). After acid demineralization, samples of the same anthracite underwent a significant enhancement of oxidation in both acid and alkaline solutions (pH = 0.4-11.5). As all the iron had been removed from the surface and the reactions were completed in a much shorter time, the oxidation mechanism must have been of a different nature than that for the untreated anthracite. A qualitative model based on the catalytic decomposition of H2O2 by activated carbon sites in the coal surface is used to explain the oxidation of the demineralized anthracite. ?? 1984.

Heard, I.; Senftle, F.E.

1984-01-01

409

A new mechanism for DMS oxidation - reaction with stabilized Criegee radicals  

NASA Astrophysics Data System (ADS)

Oxidation is a key atmospheric process and impacts such issues as climate change, air quality, and acid rain. Current belief is that reactions involving OH and NO3 are the predominate mechanism in initiating removal processes. This outlook could change with the recent discovery that stabilized Criegee radicals (sCI) also have a significant capacity to oxidize compounds such as NO2 and SO2. Formed from the ozonolysis of alkenes, sCIs represent a new link between the biosphere and atmospheric oxidation chemistry. To determine the importance this newly discovered oxidant to the overall oxidizing capacity of the atmosphere, more information is required as to its reactivity with other compounds. Here we present results that show that sCIs also react with dimethyl sulfide, DMS. sCIs produced from tetra-methyl ethene, TME, were reacted with DMS. Unlike oxidation via OH, methane sulfonic acid, MSA, was found to be the dominate oxidation product. The formation of dimethyl sulfoxide, DMSO was also observed. These results represent an additional route of DMS atmospheric oxidation and can possibly explain anomalous observations made in the Pacific boundary layer.

Mauldin, L.; Berndt, T.; Sipilä, M.; Jokinen, T.; Stratmann, F.; Petäjä, T.; Kulmala, M. T.

2012-12-01

410

The carbon-bond mechanism: a condensed kinetic mechanism for photochemical smog  

SciTech Connect

Efforts to develop a model that can simulate photochemical smog with kinetic mechanisms are discussed. The carbon-bond mechanism is a set of generalized reactions that can be used to model photochemical oxidant formation. The theoretical framework of carbon-bond mechanism is outlined. Chemical variables that are incorporated into the carbon-bond mechanism model are described. Further work that is needed on the carbon-bond mechanism model is considered. (1 diagram, 13 graphs, 30 references, 2 tables)

Whitten, G.Z.; Hog, H.; Killus, J.P.

1980-06-01

411

Aqueous Phase Photo-Oxidation of Succinic Acid: Changes in Hygroscopic Properties and Reaction Products  

NASA Astrophysics Data System (ADS)

Atmospheric aerosol particles have been identified as important factors in understanding climate change. The extent to which aerosols affect climate is determined, in part, by hygroscopic properties which can change as a result of atmospheric processing. Dicarboxylic acids, components of atmospheric aerosol, have a wide range of hygroscopic properties and can undergo oxidation and photolysis reactions in the atmosphere. In this study, the hygroscopic properties of succinic acid aerosol, a non-hygroscopic four carbon dicarboxylic acid, were measured with a humidified tandem differential mobility analyzer (HTDMA) and compared to reaction products resulting from the aqueous phase photo-oxidation reaction of hydrogen peroxide and succinic acid. Reaction products were determined and quantified using gas chromatography-flame ionization detection (GC-FID) and GC-mass spectrometry (GC-MS) as a function of hydrogen peroxide:succinic acid concentration ratio and photolysis time. Although reaction products include larger non-hygroscopic dicarboxylic acids (e.g. adipic acid) and smaller hygroscopic dicarboxylic acids (e.g. malonic and oxalic acids), comparison of hygroscopic growth curves to Zdanovskii-Stokes-Robinson (ZSR) predictions suggests that the hygroscopic properties of many of the product mixtures are largely independent of the hygroscopicity of the individual components. This study provides a framework for future investigations to fully understand and predict the role of chemical reactions in altering atmospheric conditions that affect climate.

Hudson, P. K.; Ninokawa, A.; Hofstra, J.; de Lijser, P.

2013-12-01

412

Easy oxidative addition of the carbon-halogen bond by dimethylplatinum(II) complexes containing a related series of diimine ligands: Synthesis, spectral characterization and crystal structure  

NASA Astrophysics Data System (ADS)

Dimethylplatinum(II) complexes [PtMe2(NN)] {NN = 4,4?-Me2bpy (4,4?-dimethyl-2,2?-bipyridine); 5,5?-Me2bpy (5,5?-dimethyl-2,2?-bipyridine)} were reacted with alkyl halides (RX = EtI, EtBr) to yield the organoplatinum(IV) complexes [PtMe2RX(NN)]. On the basis of NMR data, the platinum(IV) product of each reaction contains almost exclusively the trans isomer but small traces of the cis isomers are also observed. On the other hand, the reaction of [PtMe2(NN)] {NN = bu2bpy (4,4?-di-tert-butyl-2,2?-bipyridine); 4,4?-Me2bpy; 5,5?-Me2bpy} with CH2Br2 gave a mixture of cis and trans-[PtMe2(CH2Br)Br(NN)] formed by the oxidative addition of one of the C-Br bonds. The formation of the cis isomer increases in the order of 5,5?-Me2bpy > bu2bpy > 4,4?-Me2bpy. The reaction of [PtMe2(NN)] {NN = bpy (2,2?-bipyridine), phen (1,10-phenanthroline)} with 1,8-dibromooctane or 1,9-dibromononane afforded the mononuclear complexes [PtMe2{(CH2)nBr}Br(NN)] (n = 8-9). The products were fully characterized by elemental analysis, 1H, 13C, HH COSY, HMQC, DEPT and DEPTQ-135 NMR spectroscopy. The crystal structure of [PtMe2EtI(4,4?-Me2bpy)] reveals that Pt(IV) atom is six-coordinated in a slightly distorted octahedral geometry with the ethyl group trans to iodide.

Momeni, Badri Z.; Fathi, Nastaran; Mohagheghi, Arezoo

2015-01-01

413

Oxidation-promoted activation of a ferrocene C-H bond by a rhodium complex.  

PubMed

The oxidation of a rhodium(I) complex containing a ferrocene-based heterodifunctional phosphine N-heterocyclic carbene (NHC) ligand produces a stable, planar chiral rhodium(III) complex with an unexpected C-H activation on ferrocene. The oxidation of rhodium(I) to rhodium(III) may be accomplished by initial oxidation of ferrocene to ferrocenium and subsequent electron transfer from rhodium to ferrocenium. Preliminary catalytic tests showed that the rhodium(III) complex is active for the Grignard-type arylation of 4-nitrobenzaldehyde via C-H activation of 2-phenylpyridine. PMID:23467475

Labande, Agnès; Debono, Nathalie; Sournia-Saquet, Alix; Daran, Jean-Claude; Poli, Rinaldo

2013-05-14

414

Catalytic migratory oxidative coupling of nitrones.  

PubMed

A Cu(I)-catalyzed migratory oxidative coupling between nitrones and heterocycles or a methylamine is described. Selective C-C bond-formation proceeds through cleavage of two C(sp(3))-H bonds concomitant with C?N double bond-migration. The reaction provides an alternating nitrone moiety, allowing for further synthetically useful transformations. Radical clock studies suggest that the nucleophilic addition of nitrones to an oxidatively generated carbocation is a key step. PMID:21766802

Hashizume, Shogo; Oisaki, Kounosuke; Kanai, Motomu

2011-08-19

415

Polymer- and silica-supported iron BPMEN-inspired catalysts for C-H bond functionalization reactions.  

PubMed

Direct catalytic C-H bond functionalization is a key challenge in synthetic chemistry, with many popular C-H activation methodologies involving precious-metal catalysts. In recent years, iron catalysts have emerged as a possible alternative to the more common precious-metal catalysts, owing to its high abundance, low cost, and low toxicity. However, iron catalysts are plagued by two key factors: the ligand cost and the low turnover numbers (TONs) typically achieved. In this work, two approaches are presented to functionalize the popular N(1),N(2)-dimethyl-N(1),N(2)-bis(pyridin-2-ylmethyl)ethane-1,2-diamine (BPMEN) ligand, so that it can be supported on porous silica or polymer resin supports. Four new catalysts are prepared and evaluated in an array of catalytic C-H functionalization reactions by using cyclohexane, cyclohexene, cyclooctane, adamantane, benzyl alcohol, and cumene with aqueous hydrogen peroxide. Catalyst recovery and recycling is demonstrated by using supported catalysts, which allows for a modest increase in the TON achieved with these catalysts. PMID:25272313

Feng, Yan; Moschetta, Eric G; Jones, Christopher W

2014-11-01

416

Gas-Phase Reactions of Cationic Vanadium-Phosphorus Oxide Clusters with C2Hx (x=4, 6): A DFT-Based Analysis of Reactivity Patterns  

PubMed Central

The reactivities of the adamantane-like heteronuclear vanadium-phosphorus oxygen cluster ions [VxP4?xO10].+ (x=0, 2–4) towards hydrocarbons strongly depend on the V/P ratio of the clusters. Possible mechanisms for the gas-phase reactions of these heteronuclear cations with ethene and ethane have been elucidated by means of DFT-based calculations; homolytic C–H bond activation constitutes the initial step, and for all systems the P–O. unit of the clusters serves as the reactive site. More complex oxidation processes, such as oxygen-atom transfer to, or oxidative dehydrogenation of the hydrocarbons require the presence of a vanadium atom to provide the electronic prerequisites which are necessary to bring about the 2e? reduction of the cationic clusters. PMID:23322620

Dietl, Nicolas; Zhang, Xinhao; van der Linde, Christian; Beyer, Martin K; Schlangen, Maria; Schwarz, Helmut

2013-01-01

417

Water-sensitive low-frequency vibrations of reaction intermediates during S-state cycling in photosynthetic water oxidation.  

PubMed

In photosynthetic water oxidation, two water molecules are converted to an oxygen molecule through five reaction intermediates, designated S(n) (n = 0-4), at the catalytic Mn cluster of photosystem II. To understand the mechanism of water oxidation, changes in the chemical nature of the substrate water as well as the Mn cluster need to be defined during S-state cycling. Here, we report for the first time a complete set of Fourier transform infrared difference spectra during S-state cycling in the low-frequency (670-350 cm(-1)) region, in which interactions between the Mn cluster and its ligands can be detected directly, in PS II core particles from Thermosynechococcus elongatus. Furthermore, vibrations from oxygen and/or hydrogen derived from the substrate water and changes in them during S-state cycling were identified using multiplex isotope-labeled water, including H2(18)O, D2(16)O, and D2(18)O. Each water isotope affected the low-frequency S-state cycling spectra, characteristically. The bands sensitive only to (16)O/(18)O exchange were assigned to the modes from structures involving Mn and oxygen having no interactions with hydrogen, while the bands sensitive only to H/D exchange were assigned to modes from amino acid side chains and/or polypeptide backbones that associate with water hydrogen. The bands sensitive to both (16)O/(18)O and H/D exchanges were attributed to the structure involving Mn and oxygen structurally coupled with hydrogen in a direct or an indirect manner through hydrogen bonds. These bands include the changes of intermediate species derived from substrate water during the process of photosynthetic water oxidation. PMID:15909976

Kimura, Yukihiro; Ishii, Asako; Yamanari, Toshihiro; Ono, Taka-aki

2005-05-31

418

Bonding principles of passivation mechanism at III-V-oxide interfaces  

NASA Astrophysics Data System (ADS)

We analyze the conditions necessary to passivate interfacial defects at III-V-oxide interfaces, in terms of an electron-counting rule. We propose that this rule, previously used to describe reconstructions at GaAs or ZnSe surfaces, acts during oxide growth or deposition, atomic layer by atomic layer. The need to satisfy this rule continuously drives the creation of interface defects, whose states can lie in the bulk band gap of the semiconductor.

Robertson, J.; Lin, L.

2011-11-01

419

Understanding the role of gold nanoparticles in enhancing the catalytic activity of manganese oxides in water oxidation reactions.  

PubMed

The Earth-abundant and inexpensive manganese oxides (MnOx ) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnOx catalysts are still much lower than that of nanostructured IrO2 and RuO2 catalysts. Herein, we demonstrate that doping MnOx polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnOx /AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn(3+) species, a small amount of AuNPs (<5?%) in ?-MnO2 /AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure ?-MnO2 . PMID:25284796

Kuo, Chung-Hao; Li, Weikun; Pahalagedara, Lakshitha; El-Sawy, Abdelhamid M; Kriz, David; Genz, Nina; Guild, Curtis; Ressler, Thorsten; Suib, Steven L; He, Jie

2015-02-16

420

Self-assembled platinum nanoflowers on polydopamine-coated reduced graphene oxide for methanol oxidation and oxygen reduction reactions.  

PubMed

The morphology- and size-controlled synthesis of branched Pt nanostructures on graphene is highly favorable for enhancing the electrocatalytic activity and stability of Pt. Herein, a facile approach is developed for the efficient synthesis of well-dispersed Pt nanoflowers (PtNFs) on the surface of polydopamine (PDA)-modified reduced graphene oxide (PDRGO), denoted as PtNFs/PDRGO, in high yield. The synthesis was performed by a simple heating treatment of an aqueous solution that contained K2PtCl4 and PDA-modified graphene oxide (GO) without the need for any additional reducing agent, seed, surfactant, or organic solvent. The coated PDA serves not only as a reducing agent, but also as cross-linker to anchor and stabilize PtNFs on the PDRGO support. The as-prepared PtNFs/PDRGO hybrid, with spatially and locally separated PtNFs on PDRGO, exhibits superior electrocatalytic activity and stability toward both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in alkaline solutions. PMID:25236885

Yu, Xueqing; Wang, Huan; Guo, Liping; Wang, Liang

2014-11-01

421

Calcium antagonists modulate oxidative stress and acrosomal reaction in rat spermatozoa  

PubMed Central

Introduction Calcium ions are vital in many biological processes and qualify as an almost ubiquitous intracellular second messenger. This indicates the multiplicity of the effects associated with drug actions aimed at interfering with calcium ions. To examine the cellular process involved in the induction of infertility in males by calcium antagonist (CA) even in the presence of normal semen parameters, we studied the effects of different CA namely; nifedipine, verapamil and diltiazem on oxidative balance and acrosome reaction in the sperm. Material and methods For this purpose, lipid peroxidation, antioxidants such as superoxide dismutase, catalase and reduced glutathione, and acrosomal reaction were determined in sperm samples of rats. Results Calcium antagonist causes significant oxidative stress in the epididymal sperm with increased malondialdehyde level and a concomitant decrease in antioxidant activities of catalase and superoxide dismutase. The percentage value of acrosomal-reacted sperm in the nifedipine, verapamil and diltiazem-treated rats were 41 ±2.45, 39 ±2.92 and 42 ±1.22 respectively, compared with the control group value of 86 ±2.92. Conclusions It appears CA oxidatively modify the sperm resulting in functional inhibition of acrosomal reaction. Suppression of the sperm acrosomal reaction is known to have serious adverse implications for fertilization. PMID:22291796

Morakinyo, Ayodele; Iranloye, Bolanle; Adegoke, Olufeyisipe

2011-01-01

422

Water Oxidation by a Cytochrome P450: Mechanism and Function of the Reaction  

PubMed Central

P450cam (CYP101A1) is a bacterial monooxygenase that is known to catalyze the oxidation of camphor, the first committed step in camphor degradation, with simultaneous reduction of oxygen (O2). We report that P450cam catalysis is controlled by oxygen levels: at high O2 concentration, P450cam catalyzes the known oxidation reaction, whereas at low O2 concentration the enzyme catalyzes the reduction of camphor to borneol. We confirmed, using 17O and 2H NMR, that the hydrogen atom added to camphor comes from water, which is oxidized to hydrogen peroxide (H2O2). This is the first time a cytochrome P450 has been observed to catalyze oxidation of water to H2O2, a difficult reaction to catalyze due to its high barrier. The reduction of camphor and simultaneous oxidation of water are likely catalyzed by the iron-oxo intermediate of P450cam, and we present a plausible mechanism that accounts for the 1?1 borneol:H2O2 stoichiometry we observed. This reaction has an adaptive value to bacteria that express this camphor catabolism pathway, which requires O2, for two reasons: 1) the borneol and H2O2 mixture generated is toxic to other bacteria and 2) borneol down-regulates the expression of P450cam and its electron transfer partners. Since the reaction described here only occurs under low O2 conditions, the down-regulation only occurs when O2 is scarce. PMID:23634216

Prasad, Brinda; Mah, Derrick J.; Lewis, Andrew R.; Plettner, Erika

2013-01-01

423

The McClure and Weiss models of Fe-O2 bonding for oxyhemes, and the HbO2 + NO reaction.  

PubMed

For the Fe-O2(S = 0) linkages of oxyhemes, valence bond (VB) structures are re-presented for the McClure [Fe(II)(S = 1) + O2(S = 1)], Pauling-Coryell [Fe(II)(S = 0) + O2*(S = 0)], and Weiss [Fe(III)(S = ½) + O2 (-)(S = ½)] models of bonding. The VB structures for the McClure and Weiss models are of the increased-valence type, with more electrons participating in bonding than occur in their component Lewis structures. The Fe-O bond number and O-O bond order for the McClure structure are correlated with measured Fe-O and O-O bond lengths for oxymyoglobin. Back-bonding from O2(-) to Fe(III) of the Weiss structure gives a restricted form of the McClure structure. The McClure and Weiss increased-valence structures are used to provide VB formulations of mechanisms for the oxyhemoglobin + NO reaction. The products of these two formulations are Hb(+) and NO3(-) (where Hb is hemoglobin) and Hb(+) and OONO(-), respectively. Because Hb(+) and NO3(-) are the observed products, they provide an experimental procedure for distinguishing the McClure and Weiss models. It is also shown that the same type of agreement between McClure-type theory and experiment occurs for oxycoboglobin + NO, cytochrome P450 monooxygenases, and related hydrogen atom transfer reactions. In the appendices, the results of density functional theory and multireference molecular orbital calculations for oxyhemes are related to one formulation of the increased-valence wavefunction for the McClure model, and theory is presented for the calculation of approximate weights for the Lewis structures that are components of the McClure increased-valence structure. PMID:24317540

Harcourt, Richard D

2014-01-01

424

Development of new palladium(0)-catalyzed reactions based on novel oxidative addition mode.  

PubMed

We have developed palladium(0)/monophosphine-catalyzed trans-selective arylative, alkenylative, alkylative, and alkynylative cyclization reactions of alkyne-aldehydes and -ketones with organoboron reagents. These reactions afford six-membered allylic alcohols with endo tri- or tetra-substituted olefin groups and/or five-membered counterparts with exo olefin groups. The ratios of these products are dramatically affected by alkyne substituents as well as the phosphine ligand. The remarkable trans selectivity of the process results from the novel reaction mechanism involving 'anti-Wacker'-type oxidative addition. Although the cyclization reactions are influenced by the length of the tether between the alkyne and carbonyl group, they can be applied to a multi-component synthesis of biologically important indenes bearing three substituent groups at 1, 2, 3-positions from available o-ethynylbenzaldehyde derivatives. A two-component coupling reaction in methanol provides 1H-indenols, while a three-component reaction involving secondary aliphatic amines as the third component in DMF affords 1H-indenamines. This method allows combinatorial preparation of unsymmetrically substituted 1H-indenes that cannot be prepared via previous synthetic routes. The same catalytic system can also transform allene-carbonyl compounds into 3-cyclohexenols and -cyclopentenols with alkyl, aryl, alkenyl, alkynyl, and boryl groups at C-3. Microwave irradiation efficiently increases not only the reaction rate but also the product yield by suppressing formation of hydroarylation byproducts. Cyclization of optically active 1,3-disubstituted allene-aldehyde reveals that the reaction proceeds through not carbopalladation but 'anti-Wacker'-type oxidative addition. PMID:18758139

Tsukamoto, Hirokazu

2008-09-01

425

Oxidative Degradation of Nadic-End-Capped Polyimides. 2; Evidence for Reactions Occurring at High Temperatures  

NASA Technical Reports Server (NTRS)

The oxidative degradation of PMR (for polymerization of monomeric reactants) polyimides at elevated temperatures was followed by cross-polarized magic angle spinning (Cp-MAS) NMR. C-13 labeling of selected sites in the polymers allowed for direct observation of the transformations arising from oxidation processes. As opposed to model compound studies, the reactions were followed directly in the polymer. The labeling experiments confirm the previously reported oxidation of the methylene carbon to ketone in the methylenedianiline portion of the polymer chain. They also show the formation of two other oxidized species, acid and ester, from this same carbon. In addition, the technique provides the first evidence of the kind of degradation reactions that are occurring in the nadic end caps. Several PMR formulations containing moieties determined to be present after oxidation, as suggested by the labeling study, were synthesized. Weight loss, FTIR, and natural abundance NMR of these derivatives were followed during aging. In this way, weight loss could be related to the observed transformations.

Meador, Mary Ann B.; Johnston, J. Christopher; Cavano, Paul J.; Frimer, Aryeh A.

1997-01-01

426

Rate Equations and Kinetic Parameters of the Reactions Involved in Pyrite Oxidation by Thiobacillus ferrooxidans  

PubMed Central

Rate equations and kinetic parameters were obtained for various reactions involved in the bacterial oxidation of pyrite. The rate constants were 3.5 ?M Fe2+ per min per FeS2 percent pulp density for the spontaneous pyrite dissolution, 10 ?M Fe2+ per min per mM Fe3+ for the indirect leaching with Fe3+, 90 ?M O2 per min per mg of wet cells per ml for the Thiobacillus ferrooxidans oxidation of washed pyrite, and 250 ?M O2 per min per mg of wet cells per ml for the T. ferrooxidans oxidation of unwashed pyrite. The Km values for pyrite concentration were similar and were 1.9, 2.5, and 2.75% pulp density for indirect leaching, washed pyrite