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Cerium-catalyzed oxidative C–C bond forming reactions  

Microsoft Academic Search

With respect to economical and ecological considerations, molecular oxygen is the oxidant of choice for functionalization of organic substrates. On the basis of our cerium-catalyzed ?-hydroxylation of ?-dicarbonyl compounds, we have developed an oxidative process for C–C bond formation in the presence of simple olefins like styrene. Products of these reactions, which are isolated as endoperoxidic 1,2-dioxane derivatives with potential

Jens Christoffers; Thomas Werner; Michael Rössle



Mechanisms and kinetics of reaction-bonded aluminium oxide ceramics  

Microsoft Academic Search

Reaction-bonded Al[sub 2]O[sub 3] (RBAO) ceramics were fabricated starting from mechanically alloyed Al[sub 2]O[sub 3]\\/Al, Al[sub 2]O[sub 3]\\/Al\\/ZrO[sub 2], and Al[sub 2]O[sub 3]\\/Al\\/ZrO[sub 2]\\/Zr mixtures. Isopressed compacts were heat-treated in air up to 1,550 C. Reaction-bonding mechanisms, kinetics, and the influence of ZrO[sub 2] and Zr additions are investigated. Independent of additive, oxidation of Al proceeds both as solid\\/gas and

Suxing Wu; Dietmar Holz; Nils Claussen



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.



Cleavage of S-S bond by nitric oxide (NO) in the presence of oxygen: a disproportionation reaction of two disulfides.  


Disulfide bond was cleaved by a catalytic amount of nitric oxide in the presence of oxygen, which was confirmed by experiments employing two symmetrical disulfides. The reaction resulted in the formation of unsymmetrical disulfides in nearly 50% yields. The steric hindrance of alkyl disulfide slowed the reaction rate, and an electron-donating group on the aryl disulfide promoted the reaction. The substituent and S-nitrosothiol effects suggested that the reaction was initialized with an oxidative process by NO+. PMID:11045462

Tsutsumi, N; Itoh, T; Ohsawa, A



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.



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.



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



A hydrogen-bonding network is important for oxidation and isomerization in the reaction catalyzed by cholesterol oxidase  

PubMed Central

Cholesterol oxidase is a flavoenzyme that catalyzes the oxidation and isomerization of 3?-hydroxysteroids. Structural and mutagenesis studies have shown that Asn485 plays a key role in substrate oxidation. The side chain makes an NH?? interaction with the reduced form of the flavin cofactor. A N485D mutant was constructed to further test the role of the amide group in catalysis. The mutation resulted in a 1800-fold drop in the overall k cat. Atomic resolution structures were determined for both the N485L and N485D mutants. The structure of the N485D mutant enzyme (at 1.0?Å resolution) reveals significant perturbations in the active site. As pre­dicted, Asp485 is oriented away from the flavin moiety, such that any stabilizing interaction with the reduced flavin is abolished. Met122 and Glu361 form unusual hydrogen bonds to the functional group of Asp485 and are displaced from the positions they occupy in the wild-type active site. The overall effect is to disrupt the stabilization of the reduced FAD cofactor during catalysis. Furthermore, a narrow transient channel that is shown to form when the wild-type Asn485 forms the NH?? interaction with FAD and that has been proposed to function as an access route of molecular oxygen, is not observed in either of the mutant structures, suggesting that the dynamics of the active site are altered. PMID:19923719

Lyubimov, Artem Y.; Chen, Lin; Sampson, Nicole S.; Vrielink, Alice



Geminal bond participation in Alder ene reaction  

Microsoft Academic Search

We applied the geminal bond participation theory to Alder ene reactions. The interaction between the ?-orbital at the Z-position of the double bond of propene and the ??-orbital of ethylene was predicted to be bonding, while that at the E-position should be antibonding. This prediction was confirmed by the bond model analysis of the model compound. These results suggest that

Yuji Naruse; Tomoharu Suzuki; Satoshi Inagaki



Linear metal-metal-bonded tetranuclear M-Mo-Mo-M complexes (M = Ir and Rh): oxidative metal-metal bond formation in a tetrametallic system and 1,4-addition reaction of alkyl halides.  


Reaction of Mo2(pyphos)4 (1) with [MCl(CO)2]2 (M = Ir and Rh) afforded linear tetranuclear complexes of a formula Mo2M2(CO)2(Cl)2(pyphos)4 (2, M = Ir; 3, M = Rh). X-ray diffraction studies confirmed that two "MCl(CO)" fragments are introduced into both axial sites of the Mo2 core in 1 and coordinated by two PPh2 groups in a trans fashion, thereby forming a square-planar geometry around each M(I) metal. Treatment of 2 and 3 with an excess amount of tBuNC and XylNC induced dissociation of the carbonyl and chloride ligands to yield the corresponding dicationic complexes [Mo2M2(pyphos)4(tBuNC)4](Cl)2 (5a, M = Ir; 6a, M = Rh) and [Mo2M2(pyphos)4(XylNC)4](Cl)2 (7, M = Ir; 8, M = Rh). Their molecular structures were characterized by spectroscopic data as well as X-ray diffraction studies of BPh4 derivatives [Mo2M2(pyphos)4(tBuNC)4](BPh4)2 (5b, M = Ir; 6c, M = Rh), which confirmed that there is no direct sigma-bonding interaction between the M(I) atom and the Mo2 core. The M(I) atom in 5 and 6 can be oxidized by either 2 equiv of [Cp2Fe][PF6] or an equimolar amount of I2 to afford Mo(II)2M(II)2 complexes, [Mo2M2(X)2(tBuNC)4(pyphos)4]2+ in which two Mo-M(II) single bonds are formed and the bond order of the Mo-Mo moiety has been decreased to three. The Ir(I) complex 5a reacted not only with methyl iodide but also with dichloromethane to afford the 1,4-oxidative addition products [Mo2Ir2(CH3)(I)(tBuNC)4(pyphos)4](Cl)2 (13) and [Mo2Ir2(CH2Cl)(Cl)(tBuNC)4(pyphos)4](Cl)2 (15), respectively, although the corresponding reactions using the Rh(I) analogue 6 did not proceed. Kinetic analysis of the reaction with CH3I suggested that the 1,4-oxidative addition to the Ir(I) complex occurs in an SN2 reaction mechanism. PMID:17608413

Ohashi, Masato; Shima, Asuka; Rüffer, Tobias; Mizomoto, Hitoshi; Kaneda, Yutaka; Mashima, Kazushi



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



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



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



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.



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



Oxidant-Free Dehydrogenative Coupling Reactions via Hydrogen Evolution.  


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



Boron oxides: Ab initio studies with natural bond orbital analysis  

Microsoft Academic Search

We employ abinitio theory and natural bond orbital (NBO) analysis to describe the structure, energetics, vibrational properties, and bonding in small boron oxides, BmOn, supplementing recent studies on isovalent aluminum oxide clusters, Al2On, in order to extend the overview of bonding tendencies in group IIIA metal oxides. The comparison of analogous boron and aluminum species reveals many surprising differences, such

A. V. Nemukhin; F. Weinhold



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.

Dr. Martin McClinton, Debbie McClinton, Dr. Miriam Douglass



Disulfide bond cleavage: a redox reaction without electron transfer.  


By using Car-Parrinello molecular dynamics (CPMD) simulations we have simulated a mechanically induced redox reaction. Previous single-molecule atomic force microscopy (AFM) experiments demonstrated that the reduction of disulfide bonds in proteins with the weak reducing agent dithiothreitol depends on a mechanical destabilization of the breaking bond. With reactive molecular dynamics simulations the single steps of the reaction mechanism can be elucidated and the motion of the electrons can be monitored. The simulations show that the redox reaction consists of the heterolytic cleavage of the S--S bond followed by a sequence of proton transfers. PMID:20349464

Hofbauer, Florian; Frank, Irmgard



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.


Pd-catalyzed oxidative coupling of arene C-H bonds with benzylic ethers as acyl equivalents.  


A palladium-catalyzed oxidative coupling of arene C-H bonds with benzylic ethers via C-H bond activation is described. The reaction proceeds efficiently with a broad range of substrates bearing conventional directing groups with excellent functional group compatibility. This protocol potentially provides opportunities to use dibenzyl ethers as new acyl equivalents for catalytic acylation reactions. PMID:24320114

Han, Sangil; Sharma, Satyasheel; Park, Jihye; Kim, Mirim; Shin, Youngmi; Mishra, Neeraj Kumar; Bae, Jong Jin; Kwak, Jong Hwan; Jung, Young Hoon; Kim, In Su



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


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



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.



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.



Synthesis of Sulfur-Containing Heterocycles through Oxidative Carbon-Hydrogen Bond Functionalization  

PubMed Central

Vinyl sulfides react rapidly and efficiently with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to form ?,?-unsaturated thiocarbenium ions through oxidative carbon–hydrogen bond cleavage. These electrophiles couple with appended ?-nucleophiles to yield sulfur-containing heterocycles through carbon–carbon bond formation. Several nucleophiles are compatible with the procedure and the reactions generally proceed through readily-predictable transition states. PMID:22420412

Cui, Yubo; Floreancig, Paul E.



Theoretical investigation of the reaction between carbonyl oxides and ammonia.  


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



A Nanoleakage Perspective on Bonding to Oxidized Dentin  

Microsoft Academic Search

The mechanism responsible for sodium-hypochlorite-induced reduction in dentin bond strength and its reversal with reducing agents is unknown. This study examined the relationship between nanoleakage and reversal of compromised bonding to oxidized dentin. Acid-etched dentin was completely depleted of demineralized collagen matrix when sodium hypochlorite was used. Specimens were bonded with two single-bottle dentin adhesives. They were immersed in ammoniacal

C. K. Y. Yiu; F. García-Godoy; F. R. Tay; D. H. Pashley; S. Imazato; N. M. King; S. C. N. Lai



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


We report direct activation of allylic alcohols using a hydrogen-bond-assisted palladium catalyst and use this for alkylation and amination reactions. The novel catalyst comprises a palladium complex based on a functionalized monodentate phosphoramidite ligand in combination with urea additives and affords linear alkylated and aminated allylic products selectively. Detailed kinetic analysis show that oxidative addition of the allyl alcohol is the rate-determining step, which is facilitated by hydrogen bonds between the alcohol, the ligand functional group, and the additional urea additive. PMID:24436302

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



Phase Evolution in Boride-Based Cermets and Reaction Bonding onto Plain Low Carbon Steel Substrate  

NASA Astrophysics Data System (ADS)

Reaction sinter bonding is a process that aims to bond two materials for improvement in properties through reactive sintering technique. The process has been effectively used to sinter hard materials like borides in situ which not only possess excellent oxidation resistance, good corrosion resistance but also resistant to abrasive wear. Sinter bonding is a unique surface modification process achieved through powder metallurgy and is competent with other techniques like boronizing sintering and sinter-brazing since it eliminates the additional operations of heat treatment and assembly and removes the inherent setbacks with these processes. This study focuses on identifying the phase evolution mechanism using characterization tools like x-ray diffractometry and energy dispersive spectroscopy and study of sinter bonding of the boron containing precursors (Mo-Cr-Fe-Ni-FeB-MoB) onto plain carbon steel. A microstructure containing Fe-based matrix dispersed with complex borides develops with temperature in the tape cast sheets. A fivefold increase in hardness between plain carbon steel in wrought condition and sinter bonded steel was observed. The multilayer consisted of a reaction zone adjacent to the interface and was investigated with the composition profile and hardness measurements. A model of sinter bonding between the cermet and the steel has also been proposed.

Palanisamy, B.; Upadhyaya, A.



Theoretical Study on the Dark Oxidation Reaction Mechanism of Ethers  

Microsoft Academic Search

The dark oxidation reactions of ethers including aether, isopropyl ether, phenyl isopropyl ether, and benzyl isopropyl ether have been studied by using density functional theory calculations. The structures of initial contact charge transfer complexes (CCTCs), transition states and caged radical intermediates have been located at the B3LYP\\/6-31G (d) level. The bonding nature of ethers with triplet O2 in CCTCs has

WANG Gui-Xiu; ZHU Rong-Xiu; LIU Cheng-Bu


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



Uranium oxidation: characterization of oxides formed by reaction with water  

SciTech Connect

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures.

Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.



Enantioselective Diels-Alder reactions catalyzed by hydrogen bonding.  


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, alpha,alpha,alpha',alpha'-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 pi,pi-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



Isolation, Characterization of an Intermediate in an Oxygen Atom-Transfer Reaction, and the Determination of the Bond Dissociation Energy  

SciTech Connect

Redox reactions coupled with the formal loss or gain of an oxygen atom are ubiquitous in chemical processes. Such reactions proceed through the reduction of the donor center (XO) and the oxidation of the acceptor (Y) molecule. Among many examples of the metal centered oxygen atom transfer (OAT) reactivity, those involving molybdenum complexes have been widely investigated due to their involvement in mononuclear molybdenum enzymes. The heat of reaction of the overall atom transfer process can be expressed as a difference between the bond dissociation energies (BDEs) of the oxygen-donor(X) and oxygen-acceptor(Y) bond, i.e., H=DX=o-DY=O.

Nemykin, Victor N.; Laskin, Julia; Basu, Partha



Palladium-catalyzed oxidative carbonylation reactions.  


Palladium-catalyzed coupling reactions have become a powerful tool for advanced organic synthesis. This type of reaction is of significant value for the preparation of pharmaceuticals, agrochemicals, as well as advanced materials. Both, academic as well as industrial laboratories continuously investigate new applications of the different methodologies. Clearly, this area constitutes one of the major topics in homogeneous catalysis and organic synthesis. Among the different palladium-catalyzed coupling reactions, several carbonylations have been developed and widely used in organic syntheses and are even applied in the pharmaceutical industry on ton-scale. Furthermore, methodologies such as the carbonylative Suzuki and Sonogashira reactions allow for the preparation of interesting building blocks, which can be easily refined further on. Although carbonylative coupling reactions of aryl halides have been well established, palladium-catalyzed oxidative carbonylation reactions are also interesting. Compared with the reactions of aryl halides, oxidative carbonylation reactions offer an interesting pathway. The oxidative addition step could be potentially avoided in oxidative reactions, but only few reviews exist in this area. In this Minireview, we summarize the recent development in the oxidative carbonylation reactions. PMID:23307763

Wu, Xiao-Feng; Neumann, Helfried; Beller, Matthias



Tailoring oxidation degrees of graphene oxide by simple chemical reactions  

SciTech Connect

High quality graphene oxide (GO) with controllable degrees of oxidation was synthesized by simple chemical reactions inspired by approaches to unzip single wall carbon nanotubes using strong oxidizing agents. As compared to the conventional Hummers method, these reactions are less exo-therm involved without emission of toxic gases. The structural characteristics of the synthesized GO with various oxidation degrees were evaluated by x-ray diffraction, x-ray photoelectron spectroscopy, Raman spectroscopy, thermal gravimetric analysis, and UV-vis-IR spectroscopy. GO with tailored degrees of oxidation displays tunable optoelectronic properties and may have a significant impact on developing graphene- or GO-based platforms for various technological applications.

Wang Gongkai [Key Laboratory for Anisotropy and Texture of Materials of Ministry of Education, Northeastern University, Shenyang, Liaoning 110004 (China); Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180 (United States); Sun Xiang; Lian Jie [Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180 (United States); Liu Changsheng [Key Laboratory for Anisotropy and Texture of Materials of Ministry of Education, Northeastern University, Shenyang, Liaoning 110004 (China)



Palladium-catalyzed oxidative C-N bond coupling involving a solvent-controlled regioselective bromination process.  


Stereoselective palladium-catalyzed oxidative C-N bond coupling reactions between aromatic amines and alkenes involving a solvent-controlled regioselective bromination process under 1 atm of oxygen atmosphere are disclosed, providing easy access to two different brominated enamines. The addition of hydrogen peroxide (30% aq) as a co-oxidant in the system is crucial for the dehydrogenative aminohalogenation under molecular oxygen (1 atm), and in such a case, the C-N bond coupling/electrophilic bromination reaction cascade is proposed. Furthermore, the different reaction media leads to a switched regioselectivity of the process. PMID:25010511

Ji, Xiaochen; Huang, Huawen; Xiong, Wenfang; Huang, Kunbo; Wu, Wanqing; Jiang, Huanfeng



Metal-Free Oxidative C(sp(3))-H Bond Functionalization of Alkanes and Conjugate Addition to Chromones.  


A metal-free oxidative C(sp(3))-H bond functionalization and subsequent conjugate addition reaction using di-tert-butyl peroxide (DTBP) as the oxidant was established, which tolerates a wide range of simple alkane substrates to react with different substituted chromones for direct preparation of 2-alkylchromanones. PMID:25255426

Zhao, Jincan; Fang, Hong; Qian, Ping; Han, Jianlin; Pan, Yi



Allenes and computational chemistry: from bonding situations to reaction mechanisms.  


The present review is focused on the application of computational/theoretical methods to the wide and rich chemistry of allenes. Special emphasis is made on the interplay and synergy between experimental and computational methodologies, rather than on recent developments in methods and algorithms. Therefore, this review covers the state-of-the-art applications of computational chemistry to understand and rationalize the bonding situation and vast reactivity of allenes. Thus, the contents of this review span from the most fundamental studies on the equilibrium structure and chirality of allenes to recent advances in the study of complex reaction mechanisms involving allene derivatives in organic and organometallic chemistry. PMID:24553788

Soriano, Elena; Fernández, Israel



Transition-metal-catalyzed C-S bond coupling reaction.  


Sulfur-containing molecules such as thioethers are commonly found in chemical biology, organic synthesis, and materials chemistry. While many reliable methods have been developed for preparing these compounds, harsh reaction conditions are usually required in the traditional methods. The transition metals have been applied in this field, and the palladium-catalyzed coupling of thiols with aryl halides and pseudo halides is one of the most important methods in the synthesis of thioethers. Other metals have also been used for the same purpose. Here, we summarize recent efforts in metal-catalyzed C-S bond cross-coupling reactions, focusing especially on the coupling of thiols with aryl- and vinyl halides based on different metals. PMID:24443103

Lee, Chin-Fa; Liu, Yi-Chen; Badsara, Satpal Singh



Chemical bonding in electron-deficient boron oxide clusters: core boronyl groups, dual 3c-4e hypervalent bonds, and rhombic 4c-4e bonds.  


We explore the structural and bonding properties of the electron-deficient boron oxide clusters, using a series of B3On(-/0/+) (n = 2-4) clusters as examples. Global-minimum structures of these boron oxide clusters are identified via unbiased Coalescence Kick and Basin Hopping searches, which show a remarkable size and charge-state dependence. An array of new bonding elements are revealed: core boronyl groups, dual 3c-4e hypervalent bonds (?-bonds), and rhombic 4c-4e bonds (o-bonds). In favorable cases, oxygen can exhaust all its 2s/2p electrons to facilitate the formation of B-O bonds. The current findings should help understand the bonding nature of low-dimensional boron oxide nanomaterials and bulk boron oxides. PMID:24619010

Chen, Qiang; Lu, Haigang; Zhai, Hua-Jin; Li, Si-Dian



Identification of products containing {single_bond}COOH, {single_bond}OH, and {single_bond}C{double_bond}O in atmospheric oxidation of hydrocarbons  

SciTech Connect

Atmospheric oxidation of hydrocarbons by hydroxyl radicals and ozone leads to products containing {single_bond}COOH, {single_bond}OH, and {single_bond}C{double_bond}O functional groups. The high polarity of such compounds precludes direct GC-MS analysis. In addition, many such compounds often exist in a single sample at trace levels. An analytical method has been developed to identify compounds containing one or more functional groups of carbonyl, carboxy, and hydroxy in atmospheric samples. In the method, {single_bond}C{double_bond}O groups are derivatized using O-(2,3,4,5,6-pentafluorobenzyl) hydroxy amine(PFBHA), and {single_bond}COOH and {single_bond}OH groups are derivatized using a silylation reagent N,O-bis(trimethylsilyl)-trifluoroacetamide (BSTFA). The derivatives are easily resolved by a GC column. The chemical ionization mass spectra of these derivatives exhibit several pseudomolecular ions, allowing unambiguous determination of molecular weights. Functional group identification is accomplished by monitoring the ions in the electron ionization mass spectra that are characteristic of each functional group derivative: m/z 181 for carbonyl and m/z 73 and 75 for carboxyl and hydroxy groups. The method is used to identify products in laboratory studies of ozone oxidation of {alpha}-pinene and {Delta}{sup 3}-carene.

Yu, J.; Flagan, R.C.; Seinfeld, J.H. [California Inst. of Tech., Pasadena, CA (United States)] [California Inst. of Tech., Pasadena, CA (United States)



Copper-catalyzed oxaziridine-mediated oxidation of C-H bonds.  


The highly regio- and chemoselective oxidation of activated C-H bonds has been observed via copper-catalyzed reactions of oxaziridines. The oxidation proceeded with a variety of substrates, primarily comprising allylic and benzylic examples, as well as one example of an otherwise unactivated tertiary C-H bond. The mechanism of the reaction is proposed to involve single-electron transfer to the oxaziridines to generate a copper-bound radical anion, followed by hydrogen atom abstraction and collapse to products, with regeneration of the catalyst by a final single-electron transfer event. The involvement of allylic radical intermediates was supported by a radical-trapping experiment with TEMPO. PMID:22830300

Motiwala, Hashim F; Gülgeze, Belgin; Aubé, Jeffrey



Hydrogen multicenter bond in oxide and nitride semiconductors  

NASA Astrophysics Data System (ADS)

Hydrogen is a very reactive atom, occurring in virtually all organic and in many inorganic compounds. It can form a purely covalent bond, in which two hydrogen atoms share a pair of electrons in a two-electron two-center bond, as well as polar covalent bonds, such as in an H2O molecule. In solids, hydrogen is usually considered as an interstitial impurity. In elemental semiconductors, such as silicon, hydrogen forms a three-center bond when located at the bond center. In compound semiconductors, hydrogen bonds to the anionic species in p-type material, and to the cationic species in n-type. Thus far, hydrogen in solids has been found to form chemical bonds with one, two, or at most three other atoms. Higher coordination numbers are exceedingly rare and have been reported only for clusters. In this talk we will show that hydrogen is capable of forming multicenter bonds in solids, occupying substitutional sites. As examples, we discuss substitutional hydrogen impurities in oxides (ZnO, MgO, SnO2, TiO2) [1,2] and nitrides (InN, AlN, GaN) [3]. Based on first-principles calculations we show that hydrogen replaces oxygen (nitrogen) and forms genuine chemical bonds with multiple metal atoms, in truly multicoordinated configurations. These multicenter bonds are surprisingly strong despite the large hydrogen-metal distances when compared to typical values in hydrogen two-center bonds. Hydrogen in the multicenter bond configuration is a shallow donor in a number of materials. In conducting oxides, it provides a consistent explanation for the observed dependence of electrical conductivity on oxygen partial pressure, thus resolving a long-standing controversy on the role of point defects in unintentional n-type conductivity [1,2]. [4pt] [1] A. Janotti and C. G Van de Walle, Nature Materials 6, 44 (2007). [0pt] [2] A. K. Singh, A. Janotti, M. Scheffler, and C. G. Van de Walle, Phys. Rev. Lett. 101, 055502 (2008). [0pt] [3] A. Janotti and C. G. Van de Walle, Appl. Phys. Lett. 92, 032104 (2008).

Janotti, Anderson



Graphite Oxidation Thermodynamics/Reactions  

SciTech Connect

The vulnerability of graphite-matrix spent nuclear fuel to oxidation by the ambient atmosphere if the fuel canister is breached was evaluated. Thermochemical and kinetic data over the anticipated range of storage temperatures (200 to 400 C) were used to calculate the times required for a total carbon mass loss of 1 mgcm-2 from a fuel specimen. At 200 C, the time required to produce even this small loss is large, 900,000 yr. However, at 400 C the time required is only 1.9 yr. The rate of oxidation at 200 C is negligible, and the rate even at 400 C is so small as to be of no practical consequence. Therefore, oxidation of the spent nuclear fuel upon a loss of canister integrity is not anticipated to be a concern based upon the results of this study.

Propp, W.A.



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



Photchemistry of intermolecular C-H bond activation reactions  

SciTech Connect

We have focused mainly on the solution photochemistry of the CpRh(CO){sub 2} and Cp*Rh(CO){sub 2} (Cp = {eta}{sup 5}-C{sub 5}H{sub 5}; Cp* = {eta}{sup 5}-C{sub 5}Me{sub 5}) systems. Previously, we had found that the photosubstitutional chemistry of CpRh(CO){sub 2} apparently proceeds via an associative process; this was an unexpected finding and it brought into question the assignment of a 16-electron CpRh(CO) intermediate (formed by initial CO dissociation) in these photochemical substitution and C-H bond activation reactions. In other related studies, we have been exploring the photochemical transformations taking place in a series of high nuclearity osmium cluster complexes. 7 refs., 1 fig., 1 tab.

Lees, A.J.



Nonaqueous processing of silicon for reaction-bonded silicon nitride  

SciTech Connect

Ethanolic silicon suspensions, with and without a polyethoxylated amine of low molecular weight, were studied by rheological, adsorption, electrophoretic, and sedimentation methods. Pellets were pressure-cast and nitrided to form reaction-bonded silicon nitride. Density and binding strength in the green state relate well to rheological behavior and other colloidal aspects of the suspensions used, particularly the additive's role and distribution. Density and degree of nitridation in the final state are not importantly affected by the additive's use. Its greatest benefit is to modify the binding strength in the green state. The mode by which this small molecule affects the processing of silicon consists of adsorption, combined with an increased electrostatic interparticle repulsion which increases the suspension viscosity and that of undried pellets. Although the improved binding strength is accompanied by decreased green and nitrided densities, high degrees of conversion to silicon nitride are still achieved.

DeLiso, E.M. (Rutgers Univ., Piscataway, NJ (United States). Center for Ceramic Research); Bleier, A. (Oak Ridge National Lab., TN (United States))



Relationship between the oxidation potential of the bacteriochlorophyll dimer and electron transfer in photosynthetic reaction centers.  


The primary electron donor in the photosynthetic reaction center from purple bacteria is a bacteriochlorophyll dimer containing four conjugated carbonyl groups that may form hydrogen bonds with amino acid residues. Spectroscopic analyses of a set of mutant reaction centers confirm that hydrogen bonds can be formed between each of these carbonyl groups and histidine residues in the reaction center subunits. The addition of each hydrogen bond is correlated with an increase in the oxidation potential of the dimer, resulting in a 355-mV range in the midpoint potential. The resulting changes in the free-energy differences for several reactions involving the dimer are related to the electron transfer rates using the Marcus theory. These reactions include electron transfer from cytochrome c2 to the oxidized dimer, charge recombination from the primary electron acceptor quinone, and the initial forward electron transfer. PMID:8847341

Allen, J P; Williams, J C



Single-Molecule Force Spectroscopy Measurements of Bond Elongation during a Bimolecular Reaction  

E-print Network

to probe the TS of disulfide bond reduction, a bimolecular nucleophilic substitution (SN2) reaction. We use calculations of the role of solvent molecules in the reduction TS of an SN2 reaction. These results demonstrateSingle-Molecule Force Spectroscopy Measurements of Bond Elongation during a Bimolecular Reaction

Koti, Ainavarapu Sri Rama


Low temperature direct bonding mechanisms of tetraethyl orthosilicate based silicon oxide films deposited by plasma enhanced chemical vapor deposition  

NASA Astrophysics Data System (ADS)

Bonding behaviour and surface adhesion mechanisms of tetraethyl orthosilicate silicon oxide films are investigated. Prior to the bonding, infrared absorption spectroscopy was used to assess chemical composition of the bonding layers. The incorporation of -OH groups during the deposition process and the moisture absorption is shown and a specific effect of the applied RF power is highlighted. A strong correlation is found between trapped species and the evolution of the bonded layers during subsequent thermal annealing. The first observed phenomenon is an overall hardness reduction of the film deposited at low RF power which results in an increase of local adhesion area, hence an enhancement of the bonding energy. In the meantime, in this configuration water production is promoted in the volume of the film through silanol condensation and silicon oxidation occurs at the interface between the bonding layer and the silicon bulk. As a by-product of this reaction, hydrogen is released and it migrates towards the bonding interface. As a consequence, defects appear at the bonding interface. Thanks to the use of a stop barrier at the bulk interface, silicon oxidation is prevented, defect free bonding is obtained and the described scenario is confirmed.

Sabbione, C.; Di Cioccio, L.; Vandroux, L.; Nieto, J.-P.; Rieutord, F.



Creep and fracture of a vitreous-bonded aluminium oxide  

Microsoft Academic Search

Creep and creep-rupture behaviour of a commercial grade of glass-bonded, 96% aluminum oxide was characterized as a function of temperature and applied stress. The creep data were fitted to the classical empirical relation usually used to describe this phenomenon. The apparent activation enthalpy, ?H = 926 kJ mol-1, and the stress exponent,n = 4.8, lie at the high end of

S. M. Wiederhorn; B. J. Hockey; R. F. Krause; K. Jakus



Direct-Coupling O? Bond Forming Pathway in Cobalt Oxide Water Oxidation Catalysts  

E-print Network

We report a catalytic mechanism for water oxidation in a cobalt oxide cubane model compound, in which the crucial O–O bond formation step takes place by direct coupling between two CoIV(O) metal oxo groups. Our results are ...

Wang, Lee-Ping


Dynamic diselenide bonds: exchange reaction induced by visible light without catalysis.  


Dynamic covalent bonds are extensively employed in dynamic combinatorial chemistry. The metathesis reaction of disulfide bonds is widely used, but requires catalysis or irradiation with ultraviolet (UV) light. It was found that diselenide bonds are dynamic covalent bonds and undergo dynamic exchange reactions under mild conditions for diselenide metathesis. This reaction is induced by irradiation with visible light and stops in the dark. The exchange is assumed to proceed through a radical mechanism, and experiments with 2,2,6,6-tetramethylpiperidin-1-yloxyl (TEMPO) support this assumption. Furthermore, the reaction can be conducted in different solvents, including protic solvents. Diselenide metathesis can also be used to synthesize diselenide-containing asymmetric block copolymers. This work thus entails the use of diselenide bonds as dynamic covalent bonds, the development of a dynamic exchange reaction under mild conditions, and an extension of selenium-related dynamic chemistry. PMID:24842614

Ji, Shaobo; Cao, Wei; Yu, Ying; Xu, Huaping




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...


Valence-bond description of chemical reactions on Born-Oppenheimer molecular dynamics trajectories  

Microsoft Academic Search

The nature of chemical bonds on dynamic paths was investigated using the complete active space valence-bond (CASVB) method and the Born-Oppenheimer dynamics. To extract the chemical bond picture during reactions, a scheme to collect contributions from several VB (resonance) structures into a small numbers of indices was introduced. In this scheme, a tree diagram for the VB structures is constructed

Nao Noguchi; Haruyuki Nakano




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.


Mullite fiber reinforced reaction bonded Si3N4 composites  

NASA Technical Reports Server (NTRS)

Fracture toughnesses of brittle ceramic materials have been improved by introducing reinforcements and carefully tailored interface layers. Silicon carbide and Si3N4 have been emphasized as matrices of structural composites intended for high temperature service because they combine excellent mechanical, chemical, thermal and physical properties. Both matrices have been successfully toughened with SiC fibers, whiskers and particles for ceramic matrix composite (CMC) parts made by sintering, hot pressing or reaction forming processes. These SiC reinforced CMCs have exhibited significantly improved toughnesses at low and intermediate temperature levels, as well as retention of properties at high temperatures for selected exposures; however, they are vulnerable to attack from elevated temperature dry and wet oxidizing atmospheres after the matrix has cracked. Property degradation results from oxidation of interface layers and/or reinforcements. The problem is particularly acute for small diameter (-20 tim) polymer derived SiC fibers used for weavable toes. This research explored opportunities for reinforcing Si3N4 matrices with fibers having improved environmental stability; the findings should also be applicable to SiC matrix CMCs.

Saleh, T.; Sayir, A.; Lightfoot, A.; Haggerty, J.



Metal-Free Intermolecular Oxidative C-N Bond Formation via Tandem C-H and N-H Bond Functionalization  

PubMed Central

The development of a novel intermolecular oxidative amination reaction, a synthetic transformation that involves the simultaneous functionalization of both an N-H and C-H bond, is described. The process, which is mediated by an I(III) oxidant and contains no metal catalysts, provides a rapid and green method for synthesizing protected anilines from simple arenes and phthalimide. Mechanistic investigations indicate that the reaction proceeds via nucleophilic attack of the phthalimide on an aromatic radical cation, as opposed to the electrophilic aromatic amination that has been reported for other I(III) amination reactions. The application of this new reaction to the synthesis of a variety of substituted aniline derivatives is demonstrated. PMID:22010982

Kantak, Abhishek A.; Potavathri, Shathaverdhan; Barham, Rose A.; Romano, Kaitlyn M.



Metal-free intermolecular oxidative C-N bond formation via tandem C-H and N-H bond functionalization.  


The development of a novel intermolecular oxidative amination reaction, a synthetic transformation that involves the simultaneous functionalization of both a N-H and C-H bond, is described. The process, which is mediated by an I(III) oxidant and contains no metal catalysts, provides a rapid and green method for synthesizing protected anilines from simple arenes and phthalimide. Mechanistic investigations indicate that the reaction proceeds via nucleophilic attack of the phthalimide on an aromatic radical cation, as opposed to the electrophilic aromatic amination that has been reported for other I(III) amination reactions. The application of this new reaction to the synthesis of a variety of substituted aniline derivatives is demonstrated. PMID:22010982

Kantak, Abhishek A; Potavathri, Shathaverdhan; Barham, Rose A; Romano, Kaitlyn M; DeBoef, Brenton



Metal-Free Tandem Oxidative Aryl Migration and C-C Bond Cleavage: Synthesis of ?-Ketoamides and Esters from Acrylic Derivatives.  


A novel tandem metal-free oxidative aryl migration/C-C bond-cleavage reaction, mediated by hypervalent iodine reagent, has been discovered. The presented transformation provided straightforward access to important ?-ketoamide and ?-ketoester derivatives from readily available acrylic derivatives via a concerted process of 1,2-aryl shift concomitant with C-C bond cleavage. PMID:25343425

Liu, Le; Du, Liang; Zhang-Negrerie, Daisy; Du, Yunfei; Zhao, Kang



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)



Iron Oxide/Aluminum Fast Thermite Reaction  

NASA Astrophysics Data System (ADS)

The self-sustained thermite reaction between iron oxide (Fe2O3) and aluminum (Al) is commonly slow. This paper presents an experimental study to evaluate the reaction regression rates of these thermite mixtures with or without continuous electrical discharge. Two thermite compositions are tested: stoichiometric (Al2O3 and Fe as the only products) and over aluminized. To generate a fast and stable front propagation in thermite material, a long channel configuration is used and the reaction is assisted with a continuous electrical discharge between two copper plates (external confinement). The reaction velocity is evaluated by the regression rate, which is measured by optical methods. The assisted reaction is compared to the original self-sustained reaction, as a function of the composition. The electrical discharge level is also measured with a current monitor and oscilloscope. The thermodynamic properties of reaction products are predicted by a thermochemical code, named THOR, assuming an isobar adiabatic combustion and using HL equation of state.

Morgado, J.; Durães, L.; Campos, J.; Portugal, A.



A Macroscopic Reaction: Direct Covalent Bond Formation between Materials Using a Suzuki-Miyaura Cross-Coupling Reaction  

NASA Astrophysics Data System (ADS)

Cross-coupling reactions are important to form C-C covalent bonds using metal catalysts. Although many different cross-coupling reactions have been developed and applied to synthesize complex molecules or polymers (macromolecules), if cross-coupling reactions are realized in the macroscopic real world, the scope of materials should be dramatically broadened. Here, Suzuki-Miyaura coupling reactions are realized between macroscopic objects. When acrylamide gel modified with an iodophenyl group (I-gel) reacts with a gel possessing a phenylboronic group (PB-gel) using a palladium catalyst, the gels bond to form a single object. This concept can also be adapted for bonding between soft and hard materials. I-gel or PB-gel selectively bonds to the glass substrates whose surfaces are modified with an electrophile or nucleophile, respectively.

Sekine, Tomoko; Kakuta, Takahiro; Nakamura, Takashi; Kobayashi, Yuichiro; Takashima, Yoshinori; Harada, Akira



Oxidation reactions on neutral cobalt oxide clusters: experimental and theoretical studies  

E-print Network

Oxidation reactions on neutral cobalt oxide clusters: experimental and theoretical studies Yan Xie.1039/b915590b Reactions of neutral cobalt oxide clusters (ComOn, m = 3�9, n = 3�13) with CO, NO, C2H2 the oxidation reactions; the Co3O4 cluster has the highest reactivity for reactions with CO and NO. Cluster

Rocca, Jorge J.


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


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



Valence-bond description of chemical reactions on Born-Oppenheimer molecular dynamics trajectories  

NASA Astrophysics Data System (ADS)

The nature of chemical bonds on dynamic paths was investigated using the complete active space valence-bond (CASVB) method and the Born-Oppenheimer dynamics. To extract the chemical bond picture during reactions, a scheme to collect contributions from several VB (resonance) structures into a small numbers of indices was introduced. In this scheme, a tree diagram for the VB structures is constructed with the numbers of the ionic bonds treated as generation. A pair of VB structures is related to each other if one VB structure is transferred into the other by changing a covalent bond to an ionic bond. The former and latter VB structures are named parent and child structures, respectively. The weights of the bond pictures are computed as the sum of the CASVB occupation numbers running from the top generation to the bottom along the descent of the VB structures. Thus, a number of CASVB occupation numbers are collected into a small number of indices, and a clear bond picture may be obtained from the CASVB wave function. The scheme was applied to the hydrogen exchange reaction H2+F-->H+HF and the Diels-Alder reaction C5H6(cyclopentadiene)+CH2=CH2(ethylene)-->C7H10(norbornene). In both the reactions, the scheme gave a clear picture for the Born-Oppenheimer dynamics trajectories. The reconstruction of the bonds during reactions was well described by following the temporal changes in weight.

Noguchi, Nao; Nakano, Haruyuki



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.



Concerted proton-electron transfer in the oxidation of hydrogen-bonded phenols.  


Three phenols with pendant, hydrogen-bonded bases (HOAr-B) have been oxidized in MeCN with various one-electron oxidants. The bases are a primary amine (-CPh(2)NH(2)), an imidazole, and a pyridine. The product of chemical and quasi-reversible electrochemical oxidations in each case is the phenoxyl radical in which the phenolic proton has transferred to the base, (*)OAr-BH(+), a proton-coupled electron transfer (PCET) process. The redox potentials for these oxidations are lower than for other phenols, predominately from the driving force for proton movement. One-electron oxidation of the phenols occurs by a concerted proton-electron transfer (CPET) mechanism, based on thermochemical arguments, isotope effects, and DeltaDeltaG(++)/DeltaDeltaG degrees . The data rule out stepwise paths involving initial electron transfer to form the phenol radical cations [(*)(+)HOAr-B] or initial proton transfer to give the zwitterions [(-)OAr-BH(+)]. The rate constant for heterogeneous electron transfer from HOAr-NH(2) to a platinum electrode has been derived from electrochemical measurements. For oxidations of HOAr-NH(2), the dependence of the solution rate constants on driving force, on temperature, and on the nature of the oxidant, and the correspondence between the homogeneous and heterogeneous rate constants, are all consistent with the application of adiabatic Marcus theory. The CPET reorganization energies, lambda = 23-56 kcal mol(-)(1), are large in comparison with those for electron transfer reactions of aromatic compounds. The reactions are not highly non-adiabatic, based on minimum values of H(rp) derived from the temperature dependence of the rate constants. These are among the first detailed analyses of CPET reactions where the proton and electron move to different sites. PMID:16669677

Rhile, Ian J; Markle, Todd F; Nagao, Hirotaka; DiPasquale, Antonio G; Lam, Oanh P; Lockwood, Mark A; Rotter, Katrina; Mayer, James M



Influences of interface oxidation on transmission laser bonding of wafers for microsystem packaging  

Microsoft Academic Search

In the fabrication of micro-devices and systems, wafer bonding offers a unique opportunity for constructing complicated three-dimensional structures. In this paper, a wafer bonding technique, called transmission laser bonding (TLB), is studied with focus on the effects of interface oxidation and contact pressure on the bonding strength. The TLB is implemented for bonding Pyrex glass-to-silicon wafers, with and without interface

Ampere A. Tseng; Jong-Seung Park; George P. Vakanas; Hongtao Wu; Miroslav Raudensky; T. P. Chen



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



Reactions of the cumyloxyl and benzyloxyl radicals with strong hydrogen bond acceptors. Large enhancements in hydrogen abstraction reactivity determined by substrate/radical hydrogen bonding.  


A kinetic study on hydrogen abstraction from strong hydrogen bond acceptors such as DMSO, HMPA, and tributylphosphine oxide (TBPO) by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals was carried out in acetonitrile. The reactions with CumO(•) were described in terms of a direct hydrogen abstraction mechanism, in line with the kinetic deuterium isotope effects, k(H)/k(D), of 2.0 and 3.1 measured for reaction of this radical with DMSO/DMSO-d(6) and HMPA/HMPA-d(18). Very large increases in reactivity were observed on going from CumO(•) to BnO(•), as evidenced by k(H)(BnO(•))/k(H)(CumO(•)) ratios of 86, 4.8 × 10(3), and 1.6 × 10(4) for the reactions with HMPA, TBPO, and DMSO, respectively. The k(H)/k(D) of 0.91 and 1.0 measured for the reactions of BnO(•) with DMSO/DMSO-d(6) and HMPA/HMPA-d(18), together with the k(H)(BnO(•))/k(H)(CumO(•)) ratios, were explained on the basis of the formation of a hydrogen-bonded prereaction complex between the benzyloxyl ?-C-H and the oxygen atom of the substrates followed by hydrogen abstraction. This is supported by theoretical calculations that show the formation of relatively strong prereaction complexes. These observations confirm that in alkoxyl radical reactions specific hydrogen bond interactions can dramatically influence the hydrogen abstraction reactivity, pointing toward the important role played by structural and electronic effects. PMID:23153316

Salamone, Michela; DiLabio, Gino A; Bietti, Massimo



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



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



Glass wafers bonding via Diels–Alder reaction at mild temperature  

Microsoft Academic Search

In this paper, we introduced a novel bonding method of glass wafers by Diels–Alder reaction at mild temperature. After standard hydroxylization and aminosilylation, two wafers were modified by 2-furaldehyde and maleic anhydride, respectively. Then they were brought into close contact and tightly held with a clamping fixture. A strong bonding could be achieved by annealing for 5h at 200°C. Bonding

Minjie Zhang; Jianying Zhao; Lianxun Gao



Topological description of the bond-breaking and bond-forming processes of the alkene protonation reaction in zeolite chemistry: an AIM study  

Microsoft Academic Search

Density functional theory and atoms in molecules theory were used to study bond breakage and bond formation in the trans-2-butene\\u000a protonation reaction in an acidic zeolitic cluster. The progress of this reaction along the intrinsic reaction coordinate,\\u000a in terms of several topological properties of relevant bond critical points and atomic properties of the key atoms involved\\u000a in these concerted mechanisms,

María Fernanda Zalazar; Nélida Maria Peruchena


Strength of hot isostatically pressed and sintered reaction bonded silicon nitrides containing Y2O3  

NASA Technical Reports Server (NTRS)

The hot isostatic pressing of reaction bonded Si3N4 containing Y2O3 produced specimens with greater room temperature strengths than those by high pressure nitrogen sintering of the same material. Average room temperature bend strengths for hot isostatically pressed reaction bonded silicon nitride and high pressure nitrogen sintered reaction bonded silicon nitride were 767 and 670 MPa, respectively. Values of 472 and 495 MPa were observed at 1370 C. For specimens of similar but lower Y2O3 content produced from Si3N4 powder using the same high pressure nitrogen sintering conditions, the room temperature strength was 664 MPa and the 1370 C strength was 402 MPa. The greater strengths of the reaction bonded silicon nitride materials in comparison to the sintered silicon nitride powder material are attributed to the combined effect of processing method and higher Y2O3 content.

Sanders, William A.; Mieskowski, Diane M.



Mechanistic studies on metal-catalyzed carbon-nitrogen bond forming reactions  

E-print Network

Mechanistic studies on copper and palladium-catalyzed C-N bond forming reactions are described. To understand the mechanistic details of these processes, several principles of physical organic chemistry have been employed. ...

Strieter, Eric R



Topological reaction sites--very strong chalcogen bonds.  


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



Reactions involving shifting of the double bond in cyclic ethers  

SciTech Connect

4-Methylenetetrahydropyran undergoes isomerization to 4-methyl-5,6-dihydropyran in the presence of sodium on aluminum oxide. Both pyrans are converted to a vinyl ether, viz., 4-methyl-2,3-dihydropyran, under the influence of iron pentacarbonyl.

Ibatullin, U.G.; Petrushina, T.F.; Akhmadeeva, A.A.; Safarov, M.G.



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.



Nickel-Catalyzed Coupling Reactions of Alkyl Electrophiles, Including Unactivated Tertiary Halides, to Generate Carbon–Boron Bonds  

PubMed Central

Through the use of a catalyst formed in situ from NiBr2•diglyme and a pybox ligand (both of which are commercially available), we have achieved our first examples of coupling reactions of unactivated tertiary alkyl electrophiles, as well as our first success with nickel-catalyzed couplings that generate bonds other than C–C bonds. Specifically, we have determined that this catalyst accomplishes Miyaura-type borylations of unactivated tertiary, secondary, and primary alkyl halides with diboron reagents to furnish alkylboronates, a family of compounds with substantial (and expanding) utility, under mild conditions; indeed, the umpolung borylation of a tertiary alkyl bromide can be achieved at a temperature as low as ?10 °C. The method exhibits good functional-group compatibility and is regiospecific, both of which can be issues with traditional approaches to the synthesis of alkylboronates. In contrast to seemingly related nickel-catalyzed C–C bond-forming processes, tertiary halides are more reactive than secondary or primary halides in this nickel-catalyzed C–B bond-forming reaction; this divergence is particularly noteworthy in view of the likelihood that both transformations follow an inner-sphere electron-transfer pathway for oxidative addition. PMID:22668072

Dudnik, Alexander S.



Nickel-catalyzed coupling reactions of alkyl electrophiles, including unactivated tertiary halides, to generate carbon-boron bonds.  


Through the use of a catalyst formed in situ from NiBr(2)·diglyme and a pybox ligand (both of which are commercially available), we have achieved our first examples of coupling reactions of unactivated tertiary alkyl electrophiles, as well as our first success with nickel-catalyzed couplings that generate bonds other than C-C bonds. Specifically, we have determined that this catalyst accomplishes Miyaura-type borylations of unactivated tertiary, secondary, and primary alkyl halides with diboron reagents to furnish alkylboronates, a family of compounds with substantial (and expanding) utility, under mild conditions; indeed, the umpolung borylation of a tertiary alkyl bromide can be achieved at a temperature as low as -10 °C. The method exhibits good functional-group compatibility and is regiospecific, both of which can be issues with traditional approaches to the synthesis of alkylboronates. In contrast to seemingly related nickel-catalyzed C-C bond-forming processes, tertiary halides are more reactive than secondary or primary halides in this nickel-catalyzed C-B bond-forming reaction; this divergence is particularly noteworthy in view of the likelihood that both transformations follow an inner-sphere electron-transfer pathway for oxidative addition. PMID:22668072

Dudnik, Alexander S; Fu, Gregory C



Benzyl radical addition reaction through the homolytic cleavage of a benzylic C-H bond.  


Direct generation of a benzyl radical by C-H bond activation of toluenes and the addition reaction of the resulting radical to an electron deficient olefin were developed. The reaction of dimethyl fumarate with toluene in the presence of Et(3)B as a radical initiator at reflux afforded 2-benzylsuccinic acid dimethyl ester in good yield. PMID:21331427

Ueda, Masafumi; Kondoh, Eiko; Ito, Yuta; Shono, Hiroko; Kakiuchi, Maiko; Ichii, Yuki; Kimura, Takahiro; Miyoshi, Tetsuya; Naito, Takeaki; Miyata, Okiko



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.



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.



Nitric oxide in star-forming regions: further evidence for interstellar N-O bonds.  


Nitric oxide has been newly detected towards several star-forming clouds, including Orion-KL, Sgr B2(N), W33A, W51M, and DR21(OH) via its J = 3/2 --> 1/2 transitions near 150 GHz, using the FCRAO 14 m telescope. Both lambda-doubling components of NO were observed towards all sources. Column densities derived for nitric oxide in these clouds are N approximately 10(15)-10(16) cm-2, corresponding to fractional abundances of f approximately 0.5-1.0 x 10(-8), relative to H2. Towards Orion-KL, the NO line profile suggests that the species arises primarily from hot, dense gas. Nitric oxide may arise from warm material toward the other clouds as well. Nitric oxide in star-forming regions could be synthesized by high-temperature reactions, although the observed abundances do not disagree with values predicted from low-temperature, ion-molecule chemistry by more than one order of magnitude. The abundance of NO, unlike other simple interstellar nitrogen compounds, does appear to be reproduced by chemical models, at least to a good approximation. Regardless of the nature of formation of NO, it appears to be a common constituent of warm, dense molecular clouds. N-O bonds may therefore be more prevalent than previously thought. PMID:11538086

Ziurys, L M; McGonagle, D; Minh, Y; Irvine, W M



Oxidative addition of ? bonds to an Al(I) center.  


The Al(I) compound NacNacAl (1, NacNac = [ArNC(Me)CHC(Me)NAr](-) and Ar = 2,6-Pr(i)2C6H3) reacts with H-X (X = H, Si, B, Al, C, N, P, O) ? bonds of H2, silanes, borane (HBpin, pin = pinacolate), allane (NacNacAlH2), phosphine (HPPh2), amines, alcohol (Pr(i)OH), and Cp*H (Cp* = pentamethylcyclopentadiene) to give a series of hydride derivatives of the four-coordinate aluminum NacNacAlH(X), which are characterized herein by spectroscopic methods (NMR and IR) and X-ray diffraction. This method allows for the syntheses of the first boryl hydride of aluminum and novel silyl hydride and phosphido hydride derivatives. In the case of the addition of NacNacAlH2, the reaction is reversible, proving the possibility of reductive elimination from the species NacNacAlH(X). PMID:24893309

Chu, Terry; Korobkov, Ilia; Nikonov, Georgii I



Effect of bonding variables on TLP bonding of oxide dispersion strengthened superalloy  

Microsoft Academic Search

Transient liquid phase (TLP) bonding has evolved as a successful alternative joining technique for high service temperature\\u000a components (e.g., vanes and blades for aircraft gas turbine engines) made from superalloys when neither fusion welding nor\\u000a solid-state bonding techniques are successful. However, study shows that the optimization of bonding variables is critical\\u000a to achieve a metallurgically sound joint free from deleterious

Ratan Kumar Saha; Tahir I. Khan



Method and reaction pathway for selectively oxidizing organic compounds  


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)



Enantioselective aldol reactions catalyzed by chiral phosphine oxides.  


The development of enantioselective aldol reactions catalyzed by chiral phosphine oxides is described. The aldol reactions presented herein do not require the prior preparation of the masked enol ethers from carbonyl compounds as aldol donors. The reactions proceed through a trichlorosilyl enol ether intermediate, formed in situ from carbonyl compounds, which then acts as the aldol donor. Phosphine oxides activate the trichlorosilyl enol ethers to afford the aldol adducts with high stereoselectivities. This procedure was used to realize a directed cross-aldol reaction between ketones and two types of double aldol reactions (a reaction at one/two ? position(s) of a carbonyl group) with high diastereo- and enantioselectivities. PMID:23828817

Kotani, Shunsuke; Sugiura, Masaharu; Nakajima, Makoto



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


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



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



LOBA: A Localized Orbital Bonding Analysis with Application to a Model Dimanganese Catalyst for Water Oxidation  

E-print Network

for Water Oxidation Alex J. W. Thom and Eric J. Sundstrom Department of Chemistry, University of California that this analysis produces both the oxidation state of the metal and chemically intuitive views of bonding. This is in contrast to simple population analyses where the oxidation states are not reproduced and more complex

Alavi, Ali


Bonding Interactions Generated by Halogen Oxidation of Zirconium(IV) Redox-Active Ligand Complexes  

E-print Network

-based redox activity.1 Three basic oxidation states domi- nate the coordination chemistry of catecholate· -· Bonding Interactions Generated by Halogen Oxidation of Zirconium(IV) Redox-Active Ligand of pdaLi2 with ZrCl4, reacts rapidly with halogen oxidants to afford the new product ZrX2(disq)2 (3, X

Baik, Mu-Hyun


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.



Interfacial Reactions between Oxide Films and Refractory Metal Substrates  

E-print Network

upon quenching the interfacial reaction. Upon reaction of alumina with Ta(110), aluminum desorbs of bulk oxide materials, yet remain conductive; thus their properties can be investigated with an array difficulties related to poor thermal and electrical conduc- tivity typically experienced with bulk oxides.4

Goodman, Wayne


Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?  


The origin of the experimentally known preference for [6,6] over [5,6] bonds in cycloaddition reactions involving C60 has been computationally explored. To this end, the Diels-Alder reaction between cyclopentadiene and C60 has been analysed by means of the recently introduced activation strain model of reactivity in combination with the energy decomposition analysis method. Other issues, such as the aromaticity of the corresponding transition states, have also been considered. These results indicate that the major factor controlling the observed regioselectivity is the more stabilising interaction between the deformed reactants in the [6,6] reaction pathway along the entire reaction coordinate. PMID:23576307

Fernández, Israel; Solà, Miquel; Bickelhaupt, F Matthias



Empirical valence bond model of an SN2 reaction in polar and nonpolar solvents  

NASA Astrophysics Data System (ADS)

A new model for the substitution nucleophilic reaction (SN2) in solution is described using the empirical valence bond (EVB) method. The model includes a generalization to three dimensions of a collinear gas phase EVB model developed by Mathis et al. [J. Mol. Liq. 61, 81 (1994)] and a parametrization of solute-solvent interactions of four different solvents (water, ethanol, chloroform, and carbon tetrachloride). The model is used to compute (in these four solvents) reaction free energy profiles, reaction and solvent dynamics, a two-dimensional reaction/solvent free energy map, as well as a number of other properties that in the past have mostly been estimated.

Benjamin, Ilan



E1 reaction-induced synthesis of hydrophilic oxide nanoparticles in a non-hydrophilic solvent  

NASA Astrophysics Data System (ADS)

In this paper, tert-amyl alcohol was employed to directly react with metal chlorides for the preparation of oxide nanoparticles. Some typical metal oxide or hydroxides with different morphologies, such as TiO2 nanoparticles, TiO2 nanorods, FeOOH nanowires, Fe2O3 nanoparticles, and SnO2 nanoparticles, can be easily fabricated through such simple chemical reactions. E1 reaction was found to play the leading role in the synthesis of metal oxides attributed to better stability of tertiary carbocations in tert-amyl alcohol and the strong interaction of metal chlorides with hydroxyl groups that results in the easy dissociation of carbon-oxygen bonds in tert-amyl alcohol. SN1 reaction can also occur in certain reactions due to nucleophilic substitution of chloride ions for hydroxyl groups. As-prepared metal oxides show good compatibility with an aqueous system while they were synthesized in a non-hydrophilic solvent probably attributed to the specific E1 reaction mechanism involving the generation of water, and can be directly incorporated into an aqueous soluble polymer, such as PVA, to exhibit many promising applications.In this paper, tert-amyl alcohol was employed to directly react with metal chlorides for the preparation of oxide nanoparticles. Some typical metal oxide or hydroxides with different morphologies, such as TiO2 nanoparticles, TiO2 nanorods, FeOOH nanowires, Fe2O3 nanoparticles, and SnO2 nanoparticles, can be easily fabricated through such simple chemical reactions. E1 reaction was found to play the leading role in the synthesis of metal oxides attributed to better stability of tertiary carbocations in tert-amyl alcohol and the strong interaction of metal chlorides with hydroxyl groups that results in the easy dissociation of carbon-oxygen bonds in tert-amyl alcohol. SN1 reaction can also occur in certain reactions due to nucleophilic substitution of chloride ions for hydroxyl groups. As-prepared metal oxides show good compatibility with an aqueous system while they were synthesized in a non-hydrophilic solvent probably attributed to the specific E1 reaction mechanism involving the generation of water, and can be directly incorporated into an aqueous soluble polymer, such as PVA, to exhibit many promising applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr32255b

Hu, Ming-Jun; Gao, Jiefeng; Yang, Shiliu; Dong, Yucheng; Ping Wong, Julia Shuk; Xu, Jiaju; Shan, Guangcun; Li, Robert K. Y.



Effects of nucleophile, oxidative damage, and nucleobase orientation on the glycosidic bond cleavage in deoxyguanosine.  


Deglycosylation of nucleotides occurs during many essential biological processes, including DNA repair, and is initiated by a variety of nucleophiles. In the present work, density functional theory (B3LYP) was used to investigate the thermodynamics and kinetics of the glycosidic bond cleavage reaction in the model nucleoside forms of guanine and its major oxidation product, 8-oxoguanine. Base excision facilitated by four different nucleophiles (hydroxyl anion (fully activated water), formate-water complex (partially activated water), lysine, and proline) was considered, which spans nucleophiles involved in a collection of spontaneous and enzyme-catalyzed processes. Because some enzymes that catalyze deglycosylation can accommodate more than one orientation of the base with respect to the sugar moiety, the effects of the (anti/syn) base orientation on the barrier height were also considered. We find that the nucleophile has a very large effect on the overall (gas-phase) reaction energetics. Although this effect decreases in different (polar) environments, the nucleophile has the greatest influence on the overall reaction as compared to whether the base is damaged or to the base orientation. Furthermore, the effects are significant in environments that most closely resemble (nonpolar) enzymatic active sites. Our results provide a greater understanding of the relative effects of the nucleophile, damage to the nucleobase, and the nucleobase orientation with respect to the sugar moiety on the deglycosylation pathway, which provide qualitative explanations for relative base excision rates observed in some biological systems. PMID:20095611

Shim, Eun Jung; Przybylski, Jennifer L; Wetmore, Stacey D



The oxide anion accelerated retro-diels-alder reaction.  


The widespread application of the retro-Diels-Alder reaction in synthesis has been hampered by the high temperatures usually required to effect cycloreversion. The discovery of the anionic oxy-Cope reaction was followed by predictions that the accelerating effect of the oxide anion should also be observed with other pericyclic reactions. Recently, such predictions have been confirmed for the retro-Diels-Alder reaction, which often proceeds rapidly at room temperature by oxide anion rate acceleration. Such mild retro-Diels-Alder reactions have now been employed in the synthesis of a range of molecular targets, including temperature-sensitive enediynes. PMID:24022946

Bunnage, M E; Nicolaou, K C



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


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



Conversion of levulinate into succinate through catalytic oxidative carbon-carbon bond cleavage with dioxygen.  


Grand Cleft Oxo: Levulinate, available from biomass, is oxidized into succinate through manganese(III)-catalyzed selective cleavage of C?C bonds with molecular oxygen. In addition to levulinate, a wide range of aliphatic methyl ketones also undergo oxidative C?C bond cleavage at the carbonyl group. This procedure offers a route to valuable dicarboxylic acids from biomass resources by nonfermentive approaches. PMID:23922234

Liu, Junxia; Du, Zhongtian; Lu, Tianliang; Xu, Jie



Natural bond orbital analysis of the intrinsic reaction barriers in nucleophilic displacements  

Microsoft Academic Search

Applications of natural bond orbital (NBO) analysis to the intrinsic reaction barriers involved in identity nucleophilic substitutions of halides (X = F, Cl or Br) at various carbon centres such as methyl, acyl, vinyl, imidoyl, cyclopropenyl and cyclopentadienyl halides are surveyed. The most important transition state stabilization in the piattack (SN~) path is the proximate sigma --> sigma* charge-transfer interactions,

Ikchoon Lee



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)



Dark reaction of oxidation of iodine by hydrogen peroxide  

Microsoft Academic Search

The oxidation of iodine in darkness was studied in the system HâOâ-Iâ-HNOâ by a potentiometric method using an ion-selective electrode and a spectrophotometric method. The concentration limits of the reaction was established. The reaction rate is satisfactorily described by the equation of a first-order reaction. It was established experimentally that the maximum of the reaction rate constant lies in the

P. N. Moskalev; V. P. Sedov; V. K. Isupov



Hydrogen bonding constrains free radical reaction dynamics at serine and threonine residues in peptides.  


Free radical-initiated peptide sequencing (FRIPS) mass spectrometry derives advantage from the introduction of highly selective low-energy dissociation pathways in target peptides. An acetyl radical, formed at the peptide N-terminus via collisional activation and subsequent dissociation of a covalently attached radical precursor, abstracts a hydrogen atom from diverse sites on the peptide, yielding sequence information through backbone cleavage as well as side-chain loss. Unique free-radical-initiated dissociation pathways observed at serine and threonine residues lead to cleavage of the neighboring N-terminal C?-C or N-C? bond rather than the typical C?-C bond cleavage observed with other amino acids. These reactions were investigated by FRIPS of model peptides of the form AARAAAXAA, where X is the amino acid of interest. In combination with density functional theory (DFT) calculations, the experiments indicate the strong influence of hydrogen bonding at serine or threonine on the observed free radical chemistry. Hydrogen bonding of the side-chain hydroxyl group with a backbone carbonyl oxygen aligns the singly occupied ? orbital on the ?-carbon and the N-C? bond, leading to low-barrier ?-cleavage of the N-C? bond. Interaction with the N-terminal carbonyl favors a hydrogen-atom transfer process to yield stable c and z(•) ions, whereas C-terminal interaction leads to effective cleavage of the C?-C bond through rapid loss of isocyanic acid. Dissociation of the C?-C bond may also occur via water loss followed by ?-cleavage from a nitrogen-centered radical. These competitive dissociation pathways from a single residue illustrate the sensitivity of gas-phase free radical chemistry to subtle factors such as hydrogen bonding that affect the potential energy surface for these low-barrier processes. PMID:24605822

Thomas, Daniel A; Sohn, Chang Ho; Gao, Jinshan; Beauchamp, J L



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.



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

NASA Astrophysics Data System (ADS)

The mechanisms by which mechanical forces regulate the kinetics of a chemical reaction are unknown. In my lecture I will demonstrate how we use single molecule force-clamp spectroscopy and protein engineering to study the effect of force on the kinetics of thiol/disulfide exchange. Reduction of disulfide bond via the thiol/disulfide exchange chemical reaction is crucial in regulating protein function and is of common occurrence in mechanically stressed proteins. While reduction is thought to proceed through a substitution nucleophilic bimolecular (SN2) reaction, the role of a mechanical force in modulating this chemical reaction is unknown. We apply a constant stretching force to single engineered disulfide bonds and measure their rate of reduction by dithiothreitol (DTT). We find that while the reduction rate is linearly dependent on the concentration of DTT, it is exponentially dependent on the applied force, increasing 10-fold over a 300 pN range. This result predicts that the disulfide bond lengthens by 0.34 å at the transition state of the thiol/disulfide exchange reaction. In addition to DTT, we also study the reduction of the engineered disulfide bond by the E. coli enzyme thioredoxin (Trx). Thioredoxins are enzymes that catalyze disulfide bond reduction in all organisms. As before, we apply a mechanical force in the range of 25-450 pN to the engineered disulfide bond substrate and monitor the reduction of these bonds by individual enzymes. In sharp contrast with the data obtained with DTT, we now observe two alternative forms of the catalytic reaction, the first requiring a reorientation of the substrate disulfide bond, causing a shortening of the substrate polypeptide by 0.76±0.07 å, and the second elongating the substrate disulfide bond by 0.21±0.01 å. These results support the view that the Trx active site regulates the geometry of the participating sulfur atoms, with sub-ångström precision, in order to achieve efficient catalysis. Single molecule atomic force microscopy (AFM) techniques, as shown here, can probe dynamic rearrangements within an enzyme's active site which cannot be resolved with any other current structural biological technique. Furthermore, our work at the single bond level directly demonstrates that thiol/disulfide exchange in proteins is a force-dependent chemical reaction. Our findings suggest that mechanical force plays a role in disulfide reduction in vivo, a property which has never been explored by traditional biochemistry. 1.-Wiita, A.P., Ainavarapu, S.R.K., Huang, H.H. and Julio M. Fernandez (2006) Force-dependent chemical kinetics of disulfide bond reduction observed with single molecule techniques. Proc Natl Acad Sci U S A. 103(19):7222-7 2.-Wiita, A.P., Perez-Jimenez, R., Walther, K.A., Gräter, F. Berne, B.J., Holmgren, A., Sanchez-Ruiz, J.M., and Fernandez, J.M. (2007) Probing the chemistry of thioredoxin catalysis with force. Nature, 450:124-7.

Fernandez, Julio M.



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 Reactions: Carbanion Formation by Desilylation with Fluoride and Enolates Margaret M. Biddle and Hans J. ReichVed October 27, 2005 The reactive species in fluoride-mediated carbon-carbon bond-forming reactions

Reich, Hans J.


Reactions of a uranium (IV) tertiary alkyl bond. Facile ligand-assisted reduction and insertion of ethylene and carbon monoxide  

SciTech Connect

Reaction of (MeC{sub 5}H{sub 4}){sub 3}UX (X = Cl, MeC{sub 5}H{sub 4}) with t-BuLi affords the tertiary alkyl complex (MeC{sub 5}H{sub 4}){sub 3}U(t-Bu). Despite uranium(IV) generally being the preferred oxidation state in organometallic systems, (MeC{sub 5}H{sub 4}){sub 3}U(t-Bu) reacts with Lewis bases (L = PMe{sub 3}, THF, RCN, RNC) to yield the reduced uranium(III) base adducts (MeC{sub 5}H{sub 4}){sub 3}U(L). Carbon monoxide undergoes migratory insertion into the metal tertiary alkyl bond. The resulting acyl derivative decomposes at 90{degree}C to yield insoluble uranium-containing products and a mixture of tert-butyltoluenes by ring expansion of a methylcyclopentadienyl ligand. Ethylene also undergoes migratory insertion into the metal tertiary alkyl bond. No subsequent insertion of ethylene into the metal carbon bond takes place after the first equivalent has inserted. In marked contrast, reaction of various (MeC{sub 5}H{sub 4}){sub 3}ThX (X = Cl, I, MeC{sub 5}H{sub 4}, O-2,6-Me{sub 2}C{sub 6}H{sub 3}, OTs) compounds with t-BuLi gave intractable materials. However, reaction of the cationic species [(RC{sub 5}H{sub 4}){sub 3}Th](BPh{sub 4}) (R = Me{sub 3}Si, t-Bu) with t-BuLi yields the new thorium hydrides (RC{sub 5}H{sub 4}){sub 3}ThH. 40 refs., 2 figs.

Weydert, M.; Brennan, J.G.; Andersen, R.A.; Bergman, R.G. [Lawrence Berkeley Lab., CA (United States)



Iodine Oxide Thermite Reactions: Physical and Biological Effects  

NASA Astrophysics Data System (ADS)

We investigated the potential for some thermite-like material reactions to kill bacteria spores. Iodine oxides and silver oxides react vigorously with metals like aluminum, tantalum, and neodymium. These reactions theoretically produce temperatures as high as 8000K, leading to vaporization of the reactants, producing very hot iodine and/or silver gases. We performed a series of computations and experiments to characterize these reactions under both quasi-static and ballistic impact conditions. Criteria for impact reaction were established. Measurements of temperature and pressure changes and chemical evolution will be reported. Basic combustion characterizations of these reactions, such as thermal equilibrium analysis and reaction propagation rates as well as ignition sensitivity, will be discussed. Additionally, testing protocols were developed to characterize the biocidal effects of these reactive materials on B. subtilis spores. The evidence from these tests indicates that these reactions produce heat, pressure, and highly biocidal gases.

Russell, Rod; Pantoya, Michelle; Bless, Stephan; Clark, William



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

NASA Astrophysics Data System (ADS)

Amino-functionalized gold nanoparticles with a diameter of around 5 nm were immobilized onto the surface of graphene oxide sheets (GOS) by covalent bonding through a simple amidation reaction. Pristine graphite was firstly oxidized and exfoliated to obtain GOS, which further were acylated with thionyl chloride to give acyl chloride bound GOS. Gold nanoparticles (AuNPs) were functionalized using 4-aminothiophenol in a single-phase system to introduce amino groups on their surface through the well-developed Au-S chemistry. Subsequently, amino groups of AuNPs were reacted with acyl chloride groups of GOS to form a novel hybrid material containing GOS and AuNPs. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), energy dispersive X-ray (EDX) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy were used to study the changes in surface functionalities and demonstrate the successful immobilization of AuNPs on GOS surface. High resolution transmission electron microscopy (HR-TEM), field emission scanning electronic microscopy (FE-SEM), and atomic force microscopy (AFM) were employed to investigate the morphologies of prepared AuNPs and their distribution onto the GOS surface. Thermogravimetric analysis (TGA) was used to characterize the thermal stability of the samples on heating.

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



E1 reaction-induced synthesis of hydrophilic oxide nanoparticles in a non-hydrophilic solvent.  


In this paper, tert-amyl alcohol was employed to directly react with metal chlorides for the preparation of oxide nanoparticles. Some typical metal oxide or hydroxides with different morphologies, such as TiO(2) nanoparticles, TiO(2) nanorods, FeOOH nanowires, Fe(2)O(3) nanoparticles, and SnO(2) nanoparticles, can be easily fabricated through such simple chemical reactions. E1 reaction was found to play the leading role in the synthesis of metal oxides attributed to better stability of tertiary carbocations in tert-amyl alcohol and the strong interaction of metal chlorides with hydroxyl groups that results in the easy dissociation of carbon-oxygen bonds in tert-amyl alcohol. S(N)1 reaction can also occur in certain reactions due to nucleophilic substitution of chloride ions for hydroxyl groups. As-prepared metal oxides show good compatibility with an aqueous system while they were synthesized in a non-hydrophilic solvent probably attributed to the specific E1 reaction mechanism involving the generation of water, and can be directly incorporated into an aqueous soluble polymer, such as PVA, to exhibit many promising applications. PMID:22990362

Hu, Ming-Jun; Gao, Jiefeng; Yang, Shiliu; Dong, Yucheng; Wong, Julia Shuk Ping; Xu, Jiaju; Shan, Guangcun; Li, Robert K Y



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


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



Complementarity of reaction force and electron localization function analyses of asynchronicity in bond formation in Diels-Alder reactions.  


We have computationally compared three Diels-Alder cycloadditions involving cyclopentadiene and substituted ethylenes; one of the reactions is synchronous, while the others are slightly or highly asynchronous. Synchronicity and weak asynchronicity are characterized by the reaction force constant ?(?) having just a single minimum in the transition region along the intrinsic reaction coordinate ?, while for high asynchronicity ?(?) has a negative maximum with minima on both sides. The electron localization function (ELF) shows that the features of ?(?) can be directly related to the formation of the new C-C bonds between the diene and the dienophile. There is thus a striking complementarity between ?(?) and ELF; ?(?) identifies the key points along ? and ELF describes what is happening at those points. PMID:24589878

Yepes, Diana; Murray, Jane S; Pérez, Patricia; Domingo, Luis R; Politzer, Peter; Jaque, Pablo



Formation of Aromatics in Thermally Induced Reactions of Chemically Bonded RP-C18 Stationary Phase.  


In continuation of the research on the thermally induced chemical transformation of the silica-based chemically bonded stationary phases (C18), the oxidative cleavage of the silicon-carbon bonds with hydrogen peroxide and potassium fluoride was utilized, followed by the gas chromatography coupled with mass spectrometry (GC-MS) study of the resulting products. These investigations allowed determination of the probable structures of certain thermal modification products as the various different alkyl derivatives of the phenylsilane ligands. Apart from aromatic compounds, the products with unsaturated bonds and carbonyl functionalities were found in the analyzed extracts. The analysis of the GC-MS chromatograms reveals that under the applied working conditions, the investigated process runs with relatively low yields. PMID:24105920

Prus, Wojciech



High temperature heterogeneous reaction kinetics and mechanisms of tungsten oxidation  

NASA Astrophysics Data System (ADS)

Tungsten, which is a material used in many high temperature applications, is limited by its susceptibility to oxidation at elevated temperatures. Although tungsten has the highest melting temperature of any metal, at much lower temperatures volatile oxides are formed during oxidation with oxygen containing species. This differs from many heterogeneous oxidation reactions involving metals since most reactions form very stable oxides that have higher melting or boiling points than the pure metal (e.g., aluminum, iron). Understanding heterogeneous oxidation and vaporization processes may allow for the expansion and improvement of high temperature tungsten applications. In order to increase understanding of the oxidation processes of tungsten, there is a need to develop reaction mechanisms and kinetics for oxidation processes involving oxidizers and environmental conditions of interest. Tungsten oxidation was thoroughly studied in the past, and today there is a good phenomenological understanding of these processes. However, as the design of large scale systems increasingly relies on computer modeling there becomes a need for improved descriptions of chemical reactions. With the increase in computing power over the last several decades, and the development of quantum chemistry and physics theories, heterogeneous systems can be modeled in detail at the molecular level. Thermochemical parameters that may not be measured experimentally may now be determined theoretically, a tool that was previously unavailable to scientists and engineers. Additionally, chemical kinetic modeling software is now available for both homogeneous and heterogeneous reactions. This study takes advantage of these new theoretical tools, as well as a thermogravimetric (TG) flow reactor developed as part of this study to learn about mechanisms and kinetics of tungsten oxidation. Oxidizers of interest are oxygen (O2), carbon dioxide (CO 2), water (H2O), and other oxidizers present in combustion and energy systems. The primary application for this research topic is the migration of erosion processes in solid rocket motor nozzles. Since oxidation is the primary erosion mechanism of tungsten based nozzles, mitigation of this process through improved comprehension of the chemical mechanisms will increase performance of future rocket systems. In this dissertation, results of the high temperature reaction rates of bulk tungsten are studied using TG analysis in oxidizing atmospheres of O2, CO2, and H2O using helium (He) as an inert carrier gas. Isothermal reaction rates were determined at temperatures up to 1970 K, and oxidizing species partial pressures up to 64.6 torr. Kinetic parameters such as activation energies, frequency factors, and pressure exponents were determined for each reactive system. An important contribution of this work was quantifying the effects of carbon monoxide (CO) on the CO2 reaction, and hydrogen (H2) on the H2O reaction. In both cases the non-oxidizing species significantly reduced oxidation rates. Results have led to new interpretations and thought processes for limiting nozzle erosion in rocket motors. Combined with the TG analysis, as well as recent theoretical interpretations of reaction thermodynamics and kinetics, a new mechanism for tungsten and O2 oxidation has been developed using a one-dimensional numerical model of the TG flow reactor. Important chemical processes and species are also identified for reaction systems involving H2O and CO2. In the future, additional studies are needed to improve our understanding of these chemical species and processes so that more advanced kinetic mechanisms may be developed. In addition to a detailed analysis of high temperature tungsten corrosion processes, synthetic graphite corrosion processes are studied in detail as well. Details of these studies are presented in an attached appendix of this dissertation. These studies considered not only oxidation processes, but decomposition of synthetic graphite in the presence of reducing and inert gas environments.

Sabourin, Justin L.


Catalytic asymmetric stetter reaction onto vinylphosphine oxides and vinylphosphonates.  


An intramolecular Stetter reaction of vinylphosphine oxides and vinylphosphonates has been developed. Treatment of an aldehyde with a nucleophilic N-heterocyclic carbene catalyst allows for addition of an acyl anion equivalent into a vinylphosphine oxide or vinylphosphonate Michael acceptor in yields up to 99% and ee values up to 96%. PMID:18549233

Cullen, Steven C; Rovis, Tomislav



The Effect of Metal Oxide on Nanoparticles from Thermite Reactions  

ERIC Educational Resources Information Center

The purpose of this research was to determine how metal oxide used in a thermite reaction can impact the production of nanoparticles. The results showed the presence of nanoparticles (less than 1 micron in diameter) of at least one type produced by each metal oxide. The typical particles were metallic spheres, which ranged from 300 nanometers in…

Moore, Lewis Ryan



Real-time monitoring of intermediates reveals the reaction pathway in the thiol-disulfide exchange between disulfide bond formation protein A (DsbA) and B (DsbB) on a membrane-immobilized quartz crystal microbalance (QCM) system.  


Disulfide bond formation protein B (DsbBS-S,S-S) is an inner membrane protein in Escherichia coli that has two disulfide bonds (S-S, S-S) that play a role in oxidization of a pair of cysteine residues (SH, SH) in disulfide bond formation protein A (DsbASH,SH). The oxidized DsbAS-S, with one disulfide bond (S-S), can oxidize proteins with SH groups for maturation of a folding preprotein. Here, we have described the transient kinetics of the oxidation reaction between DsbASH,SH and DsbBS-S,S-S. We immobilized DsbBS-S,S-S embedded in lipid bilayers on the surface of a 27-MHz quartz crystal microbalance (QCM) device to detect both formation and degradation of the reaction intermediate (DsbA-DsbB), formed via intermolecular disulfide bonds, as a mass change in real time. The obtained kinetic parameters (intermediate formation, reverse, and oxidation rate constants (kf, kr, and kcat, respectively) indicated that the two pairs of cysteine residues in DsbBS-S,S-S were more important for the stability of the DsbA-DsbB intermediate than ubiquinone, an electron acceptor for DsbBS-S,S-S. Our data suggested that the reaction pathway of almost all DsbASH,SH oxidation processes would proceed through this stable intermediate, avoiding the requirement for ubiquinone. PMID:24145032

Yazawa, Kenjiro; Furusawa, Hiroyuki; Okahata, Yoshio




EPA Science Inventory

A laboratory study has been conducted on heterogeneous reactions of nitrogen dioxide and nitric oxide to evaluate their potential role in reaction in polluted urban atmosphere. The results of this study suggest that nitrogen dioxide decomposes on a wide variety of solids likely t...


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



The role of intramolecular hydrogen bonds in nucleophilic addition reactions of ketenaminals  

NASA Astrophysics Data System (ADS)

Quantum-chemical calculations of the geometries and electronic structures of molecules of ketenaminals 3-(diaminomethylene)-2,4-pentanedione and dimethyl-2-(diaminomethylene)-malonate and calculations of the structures of intermediates in the reaction of the nucleophilic addition of the ketenaminals to the acetonitrile molecule are performed by B3LYP/6-31+G** method. Two possible scenarios of the process are shown, depending on the mutual orientation of reacting molecules. The nucleophilic addition proceeds in two stages. It is found that the rate-limiting stage of the process is the transfer of the proton of the intramolecular hydrogen bond in a ketenaminal molecule. The experimentally observed faster reaction of pyrimidine formation for the 3-(diaminomethylene)-2,4-pentanedione molecule relative to that for dimethyl-2-(diaminomethylene)-malonate is explained by the hydrogen bond being stronger and the barrier of proton transfer from the aminogroup to the ketogroup oxygen falling upon nucleophilic attack in the former molecule.

Isaev, A. N.



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


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



Reaction Pathways and Energetics of Etheric C?O Bond Cleavage Catalyzed by Lanthanide Triflates  

SciTech Connect

Efficient and selective cleavage of etheric C?O bonds is crucial for converting biomass into platform chemicals and liquid transportation fuels. In this contribution, computational methods at the DFT B3LYP level of theory are employed to understand the efficacy of lanthanide triflate catalysts (Ln(OTf)3, Ln = La, Ce, Sm, Gd, Yb, and Lu) in cleaving etheric C?O bonds. In agreement with experiment, the calculations indicate that the reaction pathway for C?O cleavage occurs via a C?H ? O?H proton transfer in concert with weakening of the C?O bond of the coordinated ether substrate to ultimately yield a coordinated alkenol. The activation energy for this process falls as the lanthanide ionic radius decreases, reflecting enhanced metal ion electrophilicity. Details of the reaction mechanism for Yb(OTf)3-catalyzed ring opening are explored in depth, and for 1-methyl-d3-butyl phenyl ether, the computed primary kinetic isotope effect of 2.4 is in excellent agreement with experiment (2.7), confirming that etheric ring-opening pathway involves proton transfer from the methyl group alpha to the etheric oxygen atom, which is activated by the electrophilic lanthanide ion. Calculations of the catalytic pathway using eight different ether substrates indicate that the more rapid cleavage of acyclic versus cyclic ethers is largely due to entropic effects, with the former C?O bond scission processes increasing the degrees of freedom/particles as the transition state is approached.

Assary, Rajeev S.; Atesin, Abdurrahman C.; Li, Zhi; Curtiss, Larry A.; Marks, Tobin J.



Isotopic Tracer Studies of Reaction Pathways for Propane Oxidative Dehydrogenation on Molybdenum Oxide Catalysts  

E-print Network

Isotopic Tracer Studies of Reaction Pathways for Propane Oxidative Dehydrogenation on Molybdenum of propane over ZrO2-supported MoOx catalysts. Competitive reactions of C3H6 and CH3 13 CH2CH3 showed combustion of propene, or by direct combustion of propane. A mixture of C3H8 and C3D8 undergoes oxidative

Iglesia, Enrique


Molecular dynamics simulation of oxides with ionic–covalent bonds  

Microsoft Academic Search

A “semi-classical” method was developed for molecular dynamics simulation of a system with ionic–covalent bonds like silica. The ionic charges were calculated by minimization of the potential energy on each step of molecular dynamics simulation. Ionic–covalent potential was used in modeling of SiO2 molecule, non-crystalline silica, and calcium metasilicate. The internal energy of a system includes energies of silicon ionization,

D. K Belashchenko; O. I Ostrovski



Asymmetric vinylogous aldol reaction via H-bond-directing dienamine catalysis.  


The enantioselective direct vinylogous aldol reaction of 3-methyl 2-cyclohexen-1-one with ?-keto esters has been developed. The key to success was the design of a bifunctional primary amine-thiourea catalyst that can combine H-bond-directing activation and dienamine catalysis. The simultaneous dual activation of the two reacting partners results in high reactivity while securing high levels of stereocontrol. PMID:23259650

Bastida, David; Liu, Yankai; Tian, Xu; Escudero-Adán, Eduardo; Melchiorre, Paolo



Optical surfacing of one-meter-class reaction bonded silicon carbide  

Microsoft Academic Search

Optical fabrication methods for a one meter reaction bonded optical grade silicon carbide (RBO SiC) substrate have been successfully developed and demonstrated by Itek Optical Systems in Lexington, Massachusetts. A 1.125 m multiplied by .825 m RBO SiC panel, the largest SiC ever fabricated, has been ground and polished to a surface figure of lambda\\/20 rms at lambda equals .6328

Robert S. Breidenthal; Regina Galat-Skey; John J. Geany



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.


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.  


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, heda=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 (ONCMe2 CMe2 NO)](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



The basics of oxidants in water treatment. Part B: ozone reactions.  


The oxidation of organic and inorganic compounds during ozonation can occur via ozone or OH radicals or a combination thereof. Ozone is an electrophile with a high selectivity. The reactions of ozone with inorganic compounds are typically fast and occur by an oxygen atom transfer reaction. Organic micropollutants are oxidised with ozone selectively. Ozone reacts mainly with double bonds, activated aromatic systems and non-protonated amines. The kinetics of direct ozone reactions depend strongly on the speciation (acid-base, metal complexation). The reaction of OH radicals with the majority of inorganic and organic compounds is nearly diffusion-controlled. The degree of oxidation by ozone and OH radicals is given by the corresponding kinetics and the ratio of the concentration of the two oxidants. Product formation from the ozonation of organic micropollutants has only been established for a few compounds. Numerous organic and inorganic ozonation disinfection/oxidation byproducts have been identified. The byproduct of main concern is bromate, which is formed in bromide-containing waters. A low drinking water standard of 10 microgL(-1) has been set for bromate. In certain cases (bromide > approximately 50 microgL(-1)), it may be necessary to use control measures to lower bromate formation (lowering of pH, ammonia addition, chlorination-ammonia process). PMID:17674823

von Gunten, U



Influence of Protein Conformation on Disulfide Bond Formation in the Oxidative Folding of Ribonuclease T 1  

Microsoft Academic Search

In oxidative protein folding the interdependence between the acquisition of an ordered native-like conformation and disulfide bond formation was investigated by using the C2S\\/C10N variant of ribonuclease T1as a model. This protein of 104 residues has a single disulfide bond between Cys6 and Cys103. In the reduced form it is unfolded in the presence of urea, but native-like folded when

Christian Frech; Franz X. Schmid



Structures of the aluminum oxides studied by ab initio methods with natural bond orbital analysis  

Microsoft Academic Search

We present a comprehensive theoretical analysis for the low-lying isomeric structures, energetics, and vibrational properties of dinuclear aluminum oxides Al2On (n=1–4) to aid interpretation of experimental spectroscopic data for these species. We also carried out natural population and natural bond orbital (NBO) analysis of the correlated and uncorrelated abinitio wave functions in order to elucidate the general bonding principles governing

A. V. Nemukhin; F. Weinhold



Palladium-mediated C-C bond forming reactions: Cross-coupling reactions of organozinc and organotin reagents with purinones and triazines  

SciTech Connect

Palladium-mediated cross coupling reactions of organozinc and organotin reagents were used to form C-C bonds on heterocyclic substrates (8-bromopurin-6-ones and monochloro-1,3,5-triazines). These reactions represent the first examples of such coupling reactions on the above heterocyclic systems and they offer new ways to introduce a variety of carbon substituents into purinones and triazines.

Xia, Y.; Mirzai, B.; Chackalamannil, S. [Schering-Plough Research Institute, Kenilworth, NJ (United States)



Thermal oxidative degradation reactions of perfluoroalkylethers  

NASA Technical Reports Server (NTRS)

The mechanisms operative in thermal oxidative degradation of Fomblin Z and hexafluoropropene oxide derived fluids and the effect of alloys and additives upon these processes are investigated. The nature of arrangements responsible for the inherent thermal oxidative instability of the Fomblin Z fluids is not established. It was determined that this behavior is not associated with hydrogen end groups or peroxy linkages. The degradation rate of these fluids at elevated temperatures in oxidizing atmospheres is dependent on the surface/volume ratio. Once a limiting ratio is reached, a steady rate appears to be attained. Based on elemental analysis and oxygen consumption data, CF2OCF2CF2O2, no. CF2CF2O, is one of the major arrangements present. The action of the M-50 and Ti(4 Al, 4 Mn) alloys is much more drastic in the case of Fomblin Z fluids than that observed for the hexafluoropropene derived materials. The effectiveness of antioxidation anticorrosion additives, P-3 and phospha-s-triazine, in the presence of metal alloys is very limited at 316 C; at 288 C the additives arrested almost completely the fluid degradation. The phospha-s-triazine appears to be at least twice as effective as the P-3 compound; it also protected the coupon better. The Ti(4 Al, 4 Mn) alloy degraded the fluid mainly by chain scission processes this takes place to a much lesser degree with M-50.

Paciorek, K. L.; Ito, T. I.; Kratzer, R. H.



Iron-promoted C-C bond cleavage of 1,3-diketones: a route to 1,2-diketones under mild reaction conditions.  


A conceptual method for the preparation of 1,2-diketones is reported. The selective C-C bond cleavage of 1,3-diketones affords the 1,2-diketones in high yields under mild reaction conditions in air by the use of FeCl(3) as the catalyst and tert-butyl nitrite (TBN) as the oxidant without the use of solvent. The possible reaction mechanism is discussed. This protocol provides an expeditious route to the useful 1,2-diketones. PMID:21627329

Huang, Lehao; Cheng, Kai; Yao, Bangben; Xie, Yongju; Zhang, Yuhong



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

NASA Technical Reports Server (NTRS)

Scanning electron microscope/X-ray photoelectron spectroscopy (SEM/XPS) analysis of fractured adhesively bonded Ti 6-4 samples is discussed. The text adhesives incuded NR 056X polyimide, polypheylquinoxaline (PPQ), and LARC-13 polyimide. Differentiation between cohesive and interfacial failure was based on the absence of presence of a Ti 2p XPS photopeak. In addition, the surface oxide layer on Ti-(6A1-4V) adherends is characterized and bond strength and durability are addressed. Bond durability in various environmental conditions is discussed.

Dias, S.; Wightman, J. P.



Bonding between oxide ceramics and adhesive cement systems: a systematic review.  


The following aims were set for this systematic literature review: (a) to make an inventory of existing methods to achieve bondable surfaces on oxide ceramics and (b) to evaluate which methods might provide sufficient bond strength. Current literature of in vitro studies regarding bond strength achieved using different surface treatments on oxide ceramics in combination with adhesive cement systems was selected from PubMed and systematically analyzed and completed with reference tracking. The total number of publications included for aim a was 127 studies, 23 of which were used for aim b. The surface treatments are divided into seven main groups: as-produced, grinding/polishing, airborne particle abrasion, surface coating, laser treatment, acid treatment, and primer treatment. There are large variations, making comparison of the studies difficult. An as-produced surface of oxide ceramic needs to be surface treated to achieve durable bond strength. Abrasive surface treatment and/or silica-coating treatment with the use of primer treatment can provide sufficient bond strength for bonding oxide ceramics. This conclusion, however, needs to be confirmed by clinical studies. There is no universal surface treatment. Consideration should be given to the specific materials to be cemented and to the adhesive cement system to be used. PMID:24123837

Papia, Evaggelia; Larsson, Christel; du Toit, Madeleine; Vult von Steyern, Per



Acid-catalyzed oxidative addition of a C-H bond to a square planar d? iridium complex.  


While the addition of C-H bonds to three-coordinate Ir(I) fragments is a central theme in the field of C-H bond activation, addition to square planar four-coordinate complexes is far less precedented. The dearth of such reactions may be attributed, at least in part, to kinetic factors elucidated in seminal work by Hoffmann. C-H additions to square planar carbonyl complexes in particular are unprecedented, in contrast to the extensive chemistry of oxidative addition of other substrates (e.g., H2, HX) to Vaska's Complex and related species. We report that Bronsted acids will catalyze the addition of the alkynyl C-H bond of phenylacetylene to the pincer complex (PCP)Ir(CO). The reaction occurs to give exclusively the trans-C-H addition product. Our proposed mechanism, based on kinetics and DFT calculations, involves initial protonation of (PCP)Ir(CO) to generate a highly active five-coordinate cationic intermediate, which forms a phenylacetylene adduct that is then deprotonated to give product. PMID:24896665

Hackenberg, Jason D; Kundu, Sabuj; Emge, Thomas J; Krogh-Jespersen, Karsten; Goldman, Alan S



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.



Cluster reactivity experiments: employing mass spectrometry to investigate the molecular level details of catalytic oxidation reactions.  


Mass spectrometry is the most widely used tool in the study of the properties and reactivity of clusters in the gas phase. In this article, we demonstrate its use in investigating the molecular-level details of oxidation reactions occurring on the surfaces of heterogeneous catalysts via cluster reactivity experiments. Guided ion beam mass spectrometry (GIB-MS) employing a quadrupole-octopole-quadrupole (Q-O-Q) configuration enables mass-selected cluster ions to be reacted with various chemicals, providing insight into the effect of size, stoichiometry, and ionic charge state on the reactivity of catalyst materials. For positively charged tungsten oxide clusters, it is shown that species having the same stoichiometry as the bulk, WO(3)(+), W(2)O(6)(+), and W(3)O(9)(+), exhibit enhanced activity and selectivity for the transfer of a single oxygen atom to propylene (C(3)H(6)), suggesting the formation of propylene oxide (C(3)H(6)O), an important monomer used, for example, in the industrial production of plastics. Furthermore, the same stoichiometric clusters are demonstrated to be active for the oxidation of CO to CO(2), a reaction of significance to environmental pollution abatement. The findings reported herein suggest that the enhanced oxidation reactivity of these stoichiometric clusters may be due to the presence of radical oxygen centers (W-O) with elongated metal-oxygen bonds. The unique insights gained into bulk-phase oxidation catalysis through the application of mass spectrometry to cluster reactivity experiments are discussed. PMID:18687883

Johnson, Grant E; Tyo, Eric C; Castleman, A W



Aqueous oxidative Heck reaction as a protein-labeling strategy.  


An increasing number of chemical reactions are being employed for bio-orthogonal ligation of detection labels to protein-bound functional groups. Several of these strategies, however, are limited in their application to pure proteins and are ineffective in complex biological samples such as cell lysates. Here we present the palladium-catalyzed oxidative Heck reaction as a new and robust bio-orthogonal strategy for linking functionalized arylboronic acids to protein-bound alkenes in high yields and with excellent chemoselectivity even in the presence of complex protein mixtures from living cells. Advantageously, this reaction proceeds under aerobic conditions, whereas most other metal-catalyzed reactions require inert atmosphere. PMID:24376051

Ourailidou, Maria Eleni; van der Meer, Jan-Ytzen; Baas, Bert-Jan; Jeronimus-Stratingh, Margot; Gottumukkala, Aditya L; Poelarends, Gerrit J; Minnaard, Adriaan J; Dekker, Frank J



Cofactor-apoprotein hydrogen bonding in oxidized and fully reduced flavodoxin monitored by trans-hydrogen-bond scalar couplings.  


Hydrogen bonding plays a key role in the tight binding of the FMN cofactor and the regulation of its redox properties in flavodoxins. Hydrogen bonding interactions can be directly observed in solution by multidimensional heteronuclear NMR spectroscopy through the scalar couplings between donor and acceptor nuclei. Here we report on the detection of intermolecular trans-hydrogen-bond couplings ((h)J) between the flavin ring system and the backbone of Desulfovibrio vulgaris flavodoxin in the oxidized and the two-electron reduced states. For this purpose, experiments are adapted from pulse sequences previously applied to determining (h)J coupling constants in nucleic acid-base pairs and proteins. The resulting (h2)J(N,N), (h4)J(N,N), (h3)J(C,N), and (h1)J(H,N) couplings involve the (15)N(1), (13)C(2), and (15)N(3) nuclei of the pyrimidine moiety of FMN, whereas no such interactions are detectable for (13)C(4) and (15)N(5). Several long-range (15)N-(15)N, (13)C-(15)N, and (1)H-(15)N J-coupling constants within the flavin are obtained as "by-products". The magnitudes of both (h)J and regular J couplings are found to be dependent on the redox state. In general, good correlations between (h)J coupling constants and donor-group (1)H chemical shifts and also crystallographic donor-acceptor distances are observed. PMID:15515086

Löhr, Frank; Yalloway, Gary N; Mayhew, Stephen G; Rüterjans, Heinz



Carbon-nitrogen bond-forming reactions in supercritical and expanded-liquid carbon dioxide media : green synthetic chemistry with multiscale reaction and phase behavior modeling  

E-print Network

The goal of this work was to develop a detailed understanding of carbon-nitrogen (C-N) bond-forming reactions of amines carried out in supercritical and expanded-liquid carbon dioxide (CO2) media. Key motivations behind ...

Ciccolini, Rocco P



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


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[double bond, length as m-dash]O and C[double bond, length as m-dash]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



Pathways to soot oxidation: reaction of OH with phenanthrene radicals.  


Energetics and kinetics of the oxidation of possible soot surface sites by hydroxyl radicals were investigated theoretically. Energetics were calculated by employing density functional theory. Three candidate reactions were selected as suitable prototypes of soot oxidation by OH. The first two, OH + benzene and OH + benzene-phenol complex, did not produce pathways that lead to substantial CO expulsion. The third reaction, OH attack on the phenanthrene radical, had multiple pathways leading to CO elimination. The kinetics of the latter reaction system were determined by solving the master equations with the MultiWell suite of codes. The barrierless reaction rates of this system were computed using the VariFlex program. The computations were carried out over the ranges 1500-2500 K and 0.01-10 atm. At higher temperatures, above 2000 K, the oxidation of phenanthrene radicals by OH followed a chemically activated path. At temperatures lower than 2000 K, chemical activation was not sufficient to drive the reaction to products; reaction progress was impeded by intermediate adducts rapidly de-energizing before reaching products. In such cases, the reaction system was modeled by treating the accumulating adducts as distinct chemical species and computing their kinetics via thermal decomposition. The overall rate coefficient of phenanthrene radical oxidation by OH forming CO was found to be insensitive to pressure and temperature and is approximately 1 × 10(14) cm(3) mol(-1) s(-1). The oxidation of phenanthrene radicals by OH is shown to be controlled by two main processes: H atom migration/elimination and oxyradical decomposition. H atom migration and elimination made possible relatively rapid rearrangement of the aromatic edge to form oxyradicals with favorable decomposition rates. The reaction then continues down the fastest oxyradical pathways, eliminating CO. PMID:24761798

Edwards, David E; Zubarev, Dmitry Yu; Lester, William A; Frenklach, Michael



Physical autocatalysis driven by a bond-forming thiol-ene reaction.  


Autocatalysis has been extensively studied because it is central to the propagation of living systems. Chemical systems which self-reproduce like living cells would offer insight into principles underlying biology and its emergence from inanimate matter. Protocellular models feature a surfactant boundary, providing compartmentalization in the form of a micelle or vesicle and any model of the emergence of cellular life must account for the appearance, and evolution of, such boundaries. Here, we describe an autocatalytic system where two relatively simple components combine to form a more complex product. The reaction products aggregate into micelles that catalyse molecular self-reproduction. Study of the reaction kinetics and aggregation behaviour suggests a mechanism involving micelle-mediated physical autocatalysis and led to the rational design of a second-generation system. These reactions are driven by irreversible bond formation and provide a working model for the autocatalytic formation of protocells from the coupling of two simple molecular components. PMID:25178358

Bissette, Andrew J; Odell, Barbara; Fletcher, Stephen P



Bond length and radii variations in fluoride and oxide molecules and crystals  

NASA Astrophysics Data System (ADS)

Molecular orbital calculations completed on fluoride molecules containing first and second row cations have generated bond lengths, R, that match those observed for coordinated polyhedra in crystals to within ˜0.04 Å, on average. The calculated bond lengths and those observed for fluoride crystals can be ranked with the expression R=Kp -0.22, where p=s/r, s is the Pauling strength of the bond, r is the row number of the cation and K=1.34. The exponent -0.22 (? -2/9) is the same as that observed for oxide, nitride and sulfide molecules and crystals. Bonded radii for the fluoride anion, obtained from theoretical electron density maps, increase linearly with bond length. Those calculated for the cations as well as for the fluoride anion match calculated promolecule radii to within ˜0.03 Å, on average, suggesting that the electron density distributions in the vicinity of the minima along the bond paths possess a significant atomic component despite bond type. Bonded radii for Si and O ions provided by experimental electron density maps measured for the oxides coesite, danburite and stishovite match those calculated for a series of monosilicic acid molecules. The resulting radii increase with bond length and coordination number with the radius of the oxide ion increasing at a faster rate than that of the Si cation. The oxide ion within danburite exhibits several distinct radii, ranging between 0.9 and 1.2 Å, rather than a single radius with each exhibiting a different radius along each of the nonequivalent bonds with B, Si and Ca. Promolecule radii calculated for the coordinated polyhedra in danburite match procrystal radii obtained in a structure analysis to within 0.002 Å. The close agreement between these two sets of radii and experimentally determined bonded radii lends credence to Slater's statement that the difference between the electron density distribution observed for a crystal and that calculated for a procrystal (IAM) model of the crystal “would be small and subtle, and very hard to determine by examination of the total charge density.”

Nicoll, J. S.; Gibbs, G. V.; Boisen, M. B.; Downs, R. T.; Bartelmehs, K. L.



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.



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


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



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.



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.



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


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.; Dumesic, James A.



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


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)



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


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)



Oligomerization reactions of deoxyribonucleotides on montmorillonite clay: the effect of mononucleotide structure on phosphodiester bond formation.  


Adenine deoxynucleotides bind more strongly to Na(+)-montmorillonite than do the corresponding ribonucleotides. Thymidine nucleotides binds less strongly to Na(+)-montmorillonite than do the corresponding adenine deoxynucleotides. Oligomers of 2'-dpA up to the tetramer were detected in the reaction 2'-d-5'-AMP with EDAC (a water-soluble carbodiimide) in the presence of Na(+)-montmorillonite. Reaction of 3'-d-5'-AMP with EDAC on Na(+)-montmorillonite yields 3'-d-2',5'-pApA while the reaction of 2'-d-3'-AMP yields almost exclusively 3',5'-cdAMP. The reaction of 5'-TMP under the same reaction conditions give 3',5'-cpTpT and 3',5'-pTpT while 3'-TMP gives mainly 3',5'-cpT. The yield of dinucleotide products (dpNpN) containing the phosphodiester bond is 1% or less when Na(+)-montmorillonite is omitted from the reaction mixture. PMID:11538680

Ferris, J P; Kamaluddin



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



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


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



The reaction of nitroso oxides with olefins: Concerted or nonconcerted addition?  

NASA Astrophysics Data System (ADS)

The mechanism of the interaction of nitroso oxides (RNOO) with olefins was studied at MCQDPT2/6-311+G(3 df, 2 p)//CASSCF(10; 9)/6-311G( d) level of theory. The following reaction channels were considered: ( 1) (3 + 2)-cycloaddition and nonconcerted biradical addition of nitroso oxide ( 2) through the terminal oxygen atom and ( 3) through the nitrogen atom to the C=C multiple bond. It was shown for the cases of ( A) cis/trans-HNOO + C2H4, ( B) cis/trans-HNOO + C2F4, ( C) cis/trans-PhNOO + C2H4, and ( D) cis/trans-PhNOO + C2H3CH3 model systems that the typical reaction of nitroso oxides with alkenes was cycloaddition. For olefins with a decreased electron density at the multiple bond, as in system B, a substantial contribution of the one-center mechanism with the formation of biradical intermediates is possible.

Talipov, M. R.; Khursan, S. L.; Safiullin, R. L.



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.



Analysis of the oxidation reactions of CaS  

Microsoft Academic Search

The chemical reactions of dense pellets of solid CaS in oxidizing atmospheres were studied by using continuous thermogravimetric analysis and iodimetric titration of SO2 in the off-gas. The experiments covered a temperature range of 1223 to 1853 K, and Ar-O2 mixtures varying from 1 to 100 pct O2. The oxidation of CaS was found to be a complex process involving

D. C. Lynch; J. F. Elliott



Analysis of the oxidation reactions of CaS  

Microsoft Academic Search

The chemical reactions of dense pellets of solid CaS in oxidizing atmospheres were studied by using continuous thermogravimetric\\u000a analysis and iodimetric titration of SO2 in the off-gas. The experiments covered a temperature range of 1223 to 1853 K, and Ar-O2 mixtures varying from 1 to 100 pct O2. The oxidation of CaS was found to be a complex process involving

D. C. Lynch; J. F. Elliott



Plasma-activated direct bonding of diamond-on-insulator wafers to thermal oxide grown silicon wafers  

E-print Network

Plasma-activated direct bonding of diamond-on-insulator wafers to thermal oxide grown silicon microscopy, profilometer and wafer bow measurements. Plasma-activated direct bonding of DOI wafers to thermal September 2010 Keywords: Diamond-on-insulator Plasma activation Ultrananocrystalline diamond Direct bonding

Akin, Tayfun


Water o?h bond activation by gas-phase plutonium atoms: reaction mechanisms and ab initio molecular dynamics study.  


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



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



Study of reaction between uranium oxides and liquid nitrogen tetroxide  

Microsoft Academic Search

The kinetics of the reaction between the oxide forms of uranium (UOâ, UâOâ, UO\\/sub 3am\\/, ..beta..-, epsilon-, and ..gamma..-UOâ) and liquid nitrogen tetroxide at 20°C were studied. It was shown that the most reactive is amorphous UOâ. It was found that in the series of polymorphous modifications of uranium trioxide, the reaction of UOâ and UâOâ with nitrogen tetroxide is

L. V. Kobets; G. N. Klavsut; V. M. Dolgov; D. S. Umreiko



Oxidative addition of C--H bonds in organic molecules to transition metal centers  

SciTech Connect

Alkanes are among the most chemically inert organic molecules. They are reactive toward a limited range of reagents, such as highly energetic free radicals and strongly electrophilic and oxidizing species. This low reactivity is a consequence of the C--H bond energies in most saturated hydrocarbons. These values range from 90 to 98 kcal/mole for primary and secondary C--H bonds; in methane, the main constituent of natural gas, the C--H bond energy is 104 kcal/mole. This makes methane one of the most common but least reactive organic molecules in nature. This report briefly discusses the search for metal complexes capable of undergoing the C--H oxidative addition process allowing alkane chemistry to be more selective than that available using free radical reagents. 14 refs.

Bergman, R.G.



The Oxidation Behavior of TBC with Cold Spray CoNiCrAlY Bond Coat  

NASA Astrophysics Data System (ADS)

Cold gas dynamic spray (CGDS) has been considered a potential technique to produce the metallic bond coat for TBC applications, because of its fast deposition rate and low deposition temperature. This article presents the influence of spray processes for bond coat, including air plasma spray, high velocity oxy-fuel, and in particular CGDS, on the oxidation performance of TBCs with a Co-32Ni-21Cr-8Al-0.5Y (wt.%) bond coat and an air plasma sprayed topcoat. Oxidation behavior of the TBCs was evaluated by examining the coating microstructural evolution, TGO growth behavior, and crack propagation during thermal exposure at 1050 °C. The relationship between the TGO growth and crack propagation will be discussed.

Chen, W. R.; Irissou, E.; Wu, X.; Legoux, J.-G.; Marple, B. R.



Nucleation and growth of cracks in vitreous-bonded aluminum oxide at elevated temperatures  

Microsoft Academic Search

The nucleation and growth of cracks was studied at elevated temperatures on a grade of vitreous-bonded aluminium oxide that contained approx. =8 vol% glass at the grain boundaries. Cracks were observed to nucleate within the vitreous phase, close to the tensile surface of the flexural test specimens used in these experiments. Crack nucleation occurred at a strain of approx. =0.08%

K. Jakus; S. M. Wiederhorn; B. J. Hockey



Silver-mediated oxidative vinylic C-H bond sulfenylation of enamides with disulfides.  


A silver-mediated oxidative vinylic C-H bond sulfenylation of enamides was developed. This method is compatible with diaryl and dialkyl disulfides to deliver biologically precious chalcogenated olefins efficiently. A plausible non-chain radical mechanism was proposed for understanding this novel sulfenylation based on the mechanistic studies. PMID:25354883

Yang, Luo; Wen, Qing; Xiao, Fuhong; Deng, Guo-Jun



High-Temperature Thermoelectric Characterization of IIIV Semiconductor Thin Films by Oxide Bonding  

E-print Network

High-Temperature Thermoelectric Characterization of III­V Semiconductor Thin Films by Oxide Bonding-temperature thermoelectric charac- terization of thin-film III­V semiconductor materials that suffer from the side- effect-temperature surface passivation, and metallization with a Ti-W-N diffusion barrier. A thermoelectric material, thin


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


Intramolecular Hydrogen Bonding: A Potential Strategy for More Bioavailable Inhibitors of Neuronal Nitric Oxide Synthase  

PubMed Central

Selective neuronal nitric oxide synthase (nNOS) inhibitors have therapeutic applications in the treatment of numerous neurodegenerative diseases. Here we report the synthesis and evaluation of a series of inhibitors designed to have increased cell membrane permeability via intramolecular hydrogen bonding. Their potencies were examined in both purified enzyme and cell-based assays; a comparison of these results demonstrates that two of the new inhibitors display significantly increased membrane permeability over previous analogs. NMR spectroscopy provides evidence of intramolecular hydrogen bonding under physiological conditions in two of the inhibitors. Crystal structures of the inhibitors in the nNOS active site confirm the predicted non-intramolecular hydrogen bonded binding mode. Intramolecular hydrogen bonding may be an effective approach for increasing cell membrane permeability without affecting target protein binding. PMID:22370337

Labby, Kristin Jansen; Xue, Fengtian; Kraus, James M.; Ji, Haitao; Mataka, Jan; Li, Huiying; Martasek, Pavel; Roman, Linda J.; Poulos, Thomas L.; Silverman, Richard B.



Thermochemical properties and bond dissociation enthalpies of 3- to 5-member ring cyclic ether hydroperoxides, alcohols, and peroxy radicals: cyclic ether radical + (3)O(2) reaction thermochemistry.  


The formation of cyclic ethers is a major product in the oxidation of hydrocarbons, and the oxidation of biomass derived alcohols. Cyclic ethers are formed in the initial reactions of alkyl radicals with dioxygen in combustion and precombustion processes that occur at moderate temperatures. They represent a significant part of the oxygenated pollutants found in the exhaust gases of engines. Cyclic ethers can also be formed from atmospheric reactions of olefins. Additionally, cyclic ethers have been linked to the formation of the secondary organic aerosol (SOA) in the atmosphere. In combustion and thermal oxidation processes these cyclic ethers will form radicals that react with (3)O2 to form peroxy radicals. Density functional theory and higher level ab initio calculations are used to calculate thermochemical properties and bond dissociation enthalpies of 3 to 5 member ring cyclic ethers (oxirane, yC2O, oxetane, yC3O, and oxolane, yC4O), corresponding hydroperoxides, alcohols, hydroperoxy alkyl, and alkyl radicals which are formed in these oxidation reaction systems. Trends in carbon-hydrogen bond dissociation energies for the ring and hydroperoxide group relative to ring size and to distance from the ether group are determined. Bond dissociation energies are calculated for use in understanding effects of the ether oxygen in the cyclic ethers, their stability, and kinetic properties. Geometries, vibration frequencies, and enthalpies of formation, ?H°f,298, are calculated at the B3LYP/6-31G(d,p), B3LYP/6-31G(2d,2p), the composite CBS-QB3, and G3MP2B3 methods. Entropy and heat capacities, S°(T) and Cp°(T) (5 K ? T ? 5000), are determined using geometric parameters and frequencies from the B3LYP/6-31G(d,p) calculations. The strong effects of ring strain on the bond dissociation energies in these peroxy systems are also of fundamental interest. Oxetane and oxolane exhibit a significant stabilization, 10 kcal mol(-1), lower ?fH°298 when an oxygen group is on the ether carbon relative to the isomer with the oxygen group on a secondary carbon. Relative to alkane systems the ether oxygen decreases bond dissociation energies (BDEs) on carbon sites adjacent to the ether by ?5 kcal mol(-1), and increases BDEs on nonether carbons ?1 kcal mol(-1). The cyclic structures have significant effects on the C-H, CO-OH, COO-H, and CO-H bond dissociation enthalpies. These values can be used to help calibrate calculations of larger more complex bicyclic and tricyclic hydrocarbon and ether species. PMID:24660891

Auzmendi-Murua, Itsaso; Bozzelli, Joseph W



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.



Oligomerization reactions of deoxyribonucleotides on montmorillonite clay - The effect of mononucleotide structure on phosphodiester bond formation  

NASA Technical Reports Server (NTRS)

The formation of oligomers from deoxynucleotides, catalyzed by Na(+)-montmorillonite, was investigated with special attention given to the effect of the monomer structure on the phosphodiester bond formation. It was found that adenine deoxynucleotides bind more strongly to montmorillonite than do the corresponding ribonucleotides and thymidine nucleotides. Tetramers of 2-prime-dpA were detected in the reaction of 2-prime-d-5-prime-AMP with a water-soluble carbodiimide EDAC in the presence of Na(+)-montmorillonite, illustrating the possible role of minerals in the formation of biopolymers on the primitive earth.

Ferris, James P.; KAMALUDDIN



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

SciTech Connect

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

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



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.



Lanthanide Triflate-Catalyzed Carbon-Carbon Bond-Forming Reactions in Organic Synthesis  

Microsoft Academic Search

Versatile carbon-carbon bond-forming reactions using lanthanide triflates (Ln(OTf)3) as catalysts are discussed. Lanthanide triflates are new types of Lewis acids different from typical Lewis acids such as\\u000a AlCl3, BF3, SnCl4, etc. While most Lewis acids are decomposed or deactivated in the presence of water, lanthanide triflates are stable and\\u000a works as Lewis acids in water solutions. Many nitrogen-containing compounds such

Sh? Kobayashi


High-temperature tensile properties of fiber reinforced reaction bonded silicon nitride  

NASA Technical Reports Server (NTRS)

Measurements of tensile properties of unidirectional silicon carbide fiber-reinforced reaction-bonded silicon nitride (SiC/RBSN) composite specimens were carried out in air at 25, 1300, and 1500 C, using a new testing technique and a specially designed gripping system that minimizes bending moment and assures that failure always occurred in the gage section. The material was found to display metallike stress-strain behavior at all temperatures tested, and a noncatastrophic failure beyond the matrix fracture. The tensile properties were found to be temperature dependent, with the values of the ultimate tensile strength decreasing with temperature, from 543 MPa at 25 C to 169 at 1500 C.

Jablonski, David A.; Bhatt, Ramakrishna T.



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.



Cyclic Oxidation Behavior of HVOF Bond Coatings Deposited on La- and Y-doped Superalloys  

SciTech Connect

One suggested strategy for improving the performance of thermal barrier coating (TBC) systems used to protect hot section components in gas turbines is the addition of low levels of dopants to the Ni-base superalloy substrate. To quantify the benefit of these dopants, the oxidation behavior of three commercial superalloys with different Y and La contents was evaluated with and without a NiCoCrAlYHfSi bond coating deposited by high velocity oxygen fuel (HVOF) spraying. Cyclic oxidation experiments were conducted in dry O{sub 2} at 1050, 1100 and 1150 C. At the highest temperature, the bare superalloy without La showed more attack due to its lower Al content but no difference in oxidation rate or scale adhesion was noted at lower temperatures. With a bond coating, the alumina scale was non-uniform in thickness and spalled at each temperature. Among the three coated superalloys, no clear difference in oxide growth rate or scale adhesion was observed. Evaluations with a YSZ top coat and a bond coating without Hf are needed to better determine the effect of superalloy dopants on high temperature oxidation performance.

Pint, Bruce A [ORNL; Bestor, Michael A [ORNL; Haynes, James A [ORNL



Oxidation of triclosan by ferrate: reaction kinetics, products identification and toxicity evaluation.  


The oxidation of triclosan by commercial grade aqueous ferrate (Fe(VI)) was investigated and the reaction kinetics as a function of pH (7.0-10.0) were experimentally determined. Intermediate products of the oxidation process were characterized using both GC-MS and RRLC-MS/MS techniques. Changes in toxicity during the oxidation process of triclosan using Fe(VI) were investigated using Pseudokirchneriella subcapitata growth inhibition tests. The results show that triclosan reacted rapidly with Fe(VI), with the apparent second-order rate constant, k(app), being 754.7 M(-1) s(-1) at pH 7. At a stoichiometric ratio of 10:1 (Fe(VI):triclosan), complete removal of triclosan was achieved. Species-specific rate constants, k, were determined for reaction of Fe(VI) with both the protonated and deprotonated triclosan species. The value of k determined for neutral triclosan was 6.7(±1.9)×10(2) M(-1) s(-1), while that measured for anionic triclosan was 7.6(±0.6)×10(3) M(-1) s(-1). The proposed mechanism for the oxidation of triclosan by the Fe(VI) involves the scission of ether bond and phenoxy radical addition reaction. Coupling reaction may also occur during Fe(VI) degradation of triclosan. Overall, the degradation processes of triclosan resulted in a significant decrease in algal toxicity. The toxicity tests showed that Fe(VI) itself dosed in the reaction did not inhibit green algae growth. PMID:21093982

Yang, Bin; Ying, Guang-Guo; Zhao, Jian-Liang; Zhang, Li-Juan; Fang, Yi-Xiang; Nghiem, Long Duc



Variational RRKM theory calculation of thermal rate constant for carbon—hydrogen bond fission reaction of nitro benzene  

NASA Astrophysics Data System (ADS)

The present work provides quantitative results for the rate of unimolecular carbon-hydrogen bond fission reaction of benzene and nitro benzene at elevated temperatures up to 2000 K. The potential energy surface for each C-H (in the ortho, meta, and para sites) bond fission reaction of nitro benzene was investigated by ab initio calculations. The geometry and vibrational frequencies of the species involved in this process were optimized at the MP2 level of theory, using the cc-pvdz basis set. Since C-H bond fission channel is barrier less reaction, we have used variational RRKM theory to predict rate constants. By means of calculated rate constant at the different temperatures, the activation energy and exponential factor were determined. The Arrhenius expression for C-H bond fission reaction of nitro benzene on the ortho, meta and para sites are k( T) = 2.1 × 1017exp(-56575.98/ T), k( T) = 2.1 × 1017exp(-57587.45/ T), and k( T) = 3.3 × 1016exp(-57594.79/ T) respectively. The Arrhenius expression for C-H bond fission reaction of benzene is k( T) = 2 × 1018exp(-59343.48.18/ T). The effect of NO2 group, location of hydrogen atoms on the substituted benzene ring, reaction degeneracy, benzene ring resonance and tunneling effect on the rate expression have been discussed.

Manesh, Afshin Taghva; Heidarnezhad, Zabi alah; Masnabadi, Nasrin



Biotransformations Utilizing ?-Oxidation Cycle Reactions in the Synthesis of Natural Compounds and Medicines.  


?-Oxidation cycle reactions, which are key stages in the metabolism of fatty acids in eucaryotic cells and in processes with a significant role in the degradation of acids used by microbes as a carbon source, have also found application in biotransformations. One of the major advantages of biotransformations based on the ?-oxidation cycle is the possibility to transform a substrate in a series of reactions catalyzed by a number of enzymes. It allows the use of sterols as a substrate base in the production of natural steroid compounds and their analogues. This route also leads to biologically active compounds of therapeutic significance. Transformations of natural substrates via ?-oxidation are the core part of the synthetic routes of natural flavors used as food additives. Stereoselectivity of the enzymes catalyzing the stages of dehydrogenation and addition of a water molecule to the double bond also finds application in the synthesis of chiral biologically active compounds, including medicines. Recent advances in genetic, metabolic engineering, methods for the enhancement of bioprocess productivity and the selectivity of target reactions are also described. PMID:23443116

Swizdor, Alina; Panek, Anna; Milecka-Tronina, Natalia; Ko?ek, Teresa



Biotransformations Utilizing ?-Oxidation Cycle Reactions in the Synthesis of Natural Compounds and Medicines  

PubMed Central

?-Oxidation cycle reactions, which are key stages in the metabolism of fatty acids in eucaryotic cells and in processes with a significant role in the degradation of acids used by microbes as a carbon source, have also found application in biotransformations. One of the major advantages of biotransformations based on the ?-oxidation cycle is the possibility to transform a substrate in a series of reactions catalyzed by a number of enzymes. It allows the use of sterols as a substrate base in the production of natural steroid compounds and their analogues. This route also leads to biologically active compounds of therapeutic significance. Transformations of natural substrates via ?-oxidation are the core part of the synthetic routes of natural flavors used as food additives. Stereoselectivity of the enzymes catalyzing the stages of dehydrogenation and addition of a water molecule to the double bond also finds application in the synthesis of chiral biologically active compounds, including medicines. Recent advances in genetic, metabolic engineering, methods for the enhancement of bioprocess productivity and the selectivity of target reactions are also described. PMID:23443116

OEwizdor, Alina; Panek, Anna; Milecka-Tronina, Natalia; Kolek, Teresa



General aspect of catalytic hydrogenation and isomerization reactions on oxide catalyst. Characteristics of the reactions via ionic and nonionic intermediates  

SciTech Connect

An analysis of new and available data, mostly published by Tanaka and Okuhara, on the hydrogenation of alkenes and conjugated dienes and the hydrogen-deuterium exchange on the oxides of cadmium, magnesium, zinc, cobalt, chromium, thorium, zirconium, and lanthanum, and on molybdenum disulfide suggested that the partial hydrogenation of conjugated dienes catalyzed by cadmium and magnesium oxide proceeds by a mechanism which is similar to that of diene hydrogenation on supported alkali metals or on alkali metal hydride and involves allyl carbanion intermediates. The same ionic mechanism apparently also occurs in the double-bond migration of n-alkenes on cadmium oxide, and the isomerization catalyzed by molybdenum disulfide. The nonionic reaction mechanism via o-alkyl and o- or m-allyl intermediates apparently proceeds on active sites of a definite structure, i.e., a specific degree of coordination, but the ionic mechanism seems to depend only on the acidity or basicity of the sites. The nonspecific nature of the site for the ionic mechanism may result in high resistance to poisoning.

Tanaka, K.; Okuhara, T.



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


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)



Methyl viologen radical reactions with several oxidizing agents. [Gamma Radiation  

SciTech Connect

The rates of oxidation of the methyl viologen radical by peroxodisulfate and hydrogen peroxide has been investigated. The methyl viologen free radical was produced by pulse radiolysis. The reaction of the peroxodisulfate radical with the methyl viologen radical was first order in both species, and the reaction rate constant is reported. A el-radiation study revealed a chain decomposition of the peroxodisulfate radical involving the methyl viologen radical when methanol, ethanol, or 2-propanol was present. Loss of the methyl viologen radical was then no longer observed to be a simple first-order reaction. The reaction of hydrogen peroxide with the methyl viologen radical was very slow in the presence of 1 M methanol. A much faster reaction in the absence of methanol was interpreted to be a reaction of the methyl viologen radical with the peroxy radicals. Hydrogen peroxide, in contrast to the chain decomposition of peroxodisulfate radicals, does not participate in a chain reaction involving the methyl viologen radical and methanol. Rate constants for the reaction of methyl viologen radical with dichromate radical, iodate radical, and ferricyanide radical are reported.

Levey, G.; Ebbesen, T.W.



Gold supported on well-ordered ceria films: nucleation, growth and morphology in CO oxidation reaction  

E-print Network

are found to be stable in O2 ambient up to 10 mbar, meanwhile gold sintering emerges at CO pressures above oxidation reaction. KEY WORDS: gold; ceria; CO oxidation; thin films; scanning tunneling microscopy. 1 oxidation, selective oxidation of propene to propene oxide, water gas shift reaction, NO reduction

Gao, Hongjun


Surface reactions of (sub)monolayers of small organic species on oxidized silicon  

NASA Astrophysics Data System (ADS)

The preparation of (sub)monolayers of small and short-chain organic molecules on oxide-covered silicon is described. The molecular end groups and their chemical reactions were characterized by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, spectroscopic ellipsometry (IR-UV), laserinduced desorption of monolayers (LIDOM), X-ray photoelectron spectroscopy (XPS), and contact-angle experiments. Surface species were identified and their reactions were monitored by FTIR analysis of characteristic vibrational modes. This includes bottom-up synthesis of siloxane chains, diverse reactions of double bonds, and specific molecular transformations such as the Diels-Alder reaction. Layer thicknesses could be estimated with a sensitivity of ~0.02 nm and accuracy of ~0.05 nm by oxidation of the hydrocarbons. This was achieved by in situ real-time detection of the corresponding thickness changes by spectroscopic ellipsometry. From time-of-flight (TOF) experiments, which provided the desorption temperature and mass of the emitted species, the thermal stability, chemical transformation, and fragmentation pattern of chemisorbed species could be extracted. To analyze the hydrophilic or hydrophobic nature of functionalized surfaces the surface energy and wettability were determined.

Salingue, N.; Lingenfelser, D.; Prunici, P.; Hess, P.



Reaction Energies of Oxides using Random Phase Approximation  

NASA Astrophysics Data System (ADS)

Oxides are widely used in industrial heterogeneous catalysis, photo catalysis, electrochemistry and in making batteries and fuel cells. To facilitate the computational engineer and design of novel materials in these fields, it is vital important to quantitatively predict the formation and reactions energies of the oxides. LDA/GGA, the success of which has largely relied on the mysterious error cancellation in the exchange-correlation term, generally failed for these oxides, showing systematic and non-canceling errors. Recently, the use of exact exchange (EXX), plus correlation energy from Random Phase Approximation (RPA) emerges as a promising approach to obtain non-empirical exchange-correlation terms. Exact exchange energy is free of self-interaction error, while RPA correlation energy takes into account dynamic electronic screening and is fully non-local. EXX+RPA has shown to systematically improve lattice constants, atomization energies, adsorption energies, reaction barriers for a wide range of systems that have ironic, covalent and van der Waals interactions. In this talk I will present our results comparing RPA and GGA functional for the formation and reaction energies of oxides.

Yan, Jun; Hummelshoej, Jens; Nørskov, Jens



Electrophilic, Ambiphilic, and Nucleophilic C-H bond Activation: Understanding the electronic continuum of C-H bond activation through transition-state and reaction pathway interaction energy decompositions  

SciTech Connect

The potential energy and interaction energy profiles for metal- and metal?ligand-mediated alkane C?H bond activation were explored using B3LYP density functional theory (DFT) and the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA). The set of complexes explored range from late transition metal group 10 (Pt and Pd) and group 11 (Au) metal centers to group 7?9 (Ir, Rh, Ru, and W) metal centers as well as a group 3 Sc complex. The coordination geometries, electron metal count (d{sup 8}, d{sup 6}, d{sup 4}, and d{sup 0}), and ligands (N-heterocycles, O-donor, phosphine, and Cp*) are also diverse. Quantitative analysis using ALMO-EDA of both directions of charge-transfer stabilization (occupied to unoccupied orbital stabilization) energies between the metal?ligand fragment and the coordinated C?H bond in the transition state for cleavage of the C?H bond allows classification of C?H activation reactions as electrophilic, ambiphilic, or nucleophilic on the basis of the net direction of charge-transfer energy stabilization. This bonding pattern transcends any specific mechanistic or bonding paradigm, such as oxidative addition, ?-bond metathesis, or substitution. Late transition metals such as Au(III), Pt(II), Pd(II), and Rh(III) metal centers with N-heterocycle, halide, or O-donor ligands show electrophilically dominated reaction profiles with forward charge-transfer from the C?H bond to the metal, leading to more stabilization than reverse charge transfer from the metal to the C?H bond. Transition states and reaction profiles for d{sup 6} Ru(II) and Ir(III) metals with Tp and acac ligands were found to have nearly equal forward and reverse charge-transfer energy stabilization. This ambiphilic region also includes the classically labeled electrophilic cationic species Cp*(PMe{sub 3})Ir(Me). Nucleophilic character, where the metal to C?H bond charge-transfer interaction is most stabilizing, was found in metathesis reactions with W(II) and Sc(III) metal center complexes in reactions as well as late transition metal Ir(I) and Rh(I) pincer complexes that undergo C?H bond insertion. Comparison of pincer ligands shows that the PCP ligand imparts more nucleophilic character to an Ir metal center than a deprotonated PNP ligand. The PCP and POCOP ligands do not show a substantial difference in the electronics of C?H activation. It was also found that Rh(I) is substantially more nucleophilic than Ir(I). Lastly, as a qualitative approximation, investigation of transition-state fragment orbital energies showed that relative frontier orbital energy gaps correctly reflect electrophilic, ambiphilic, or nucleophilic charge-transfer stabilization patterns.

Ess, Daniel H; Goddard, William A; Periana, Roy A



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



Ternary Electrocatalysts for Oxidizing Ethanol to Carbon Dioxide: Making Ir Capable of Splitting C-C bond  

SciTech Connect

Splitting the C-C bond is the main obstacle to electroxidation of ethanol (EOR) to CO2. We recently demonstrated that the ternary PtRhSnO2 electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We synthesized, characterized and compared the properties of several ternary electrocatalysts. Carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO2 NP core decorated with multi-metallic nanoislands (MM = PtIr, PtRh, IrRh, PtIrRh) were prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM /SnO2 NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity towards CO2 formation of several of these MM /SnO2/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO2/C catalysts. We demonstrate that the PtIr/SnO2/C catalyst with high Ir content shows outstanding catalytic property with the most negative EOR onset potential and reasonably good selectivity towards ethanol complete oxidation to CO2. PtRh/SnO2/C catalysts with a moderate Rh content exhibit the highest EOR selectivity, as deduced from infrared studies.

Li, Meng [Brookhaven National Laboratory (BNL); Cullen, David A [ORNL; Sasaki, Kotaro [Brookhaven National Laboratory (BNL); Marinkovic, N. [University of Delaware; More, Karren Leslie [ORNL; Adzic, Radoslav R. [Brookhaven National Laboratory (BNL)



Effect of loading rate on dynamic fracture of reaction bonded silicon nitride  

NASA Technical Reports Server (NTRS)

Wedge-loaded, modified tapered double cantilever beam (WL-MTDCB) specimens under impact loading were used to determine the room temperature dynamic fracture response of reaction bonded silicon nitride (RBSN). The crack extension history, with the exception of the terminal phase, was similar to that obtained under static loading. Like its static counterpart, a distinct crack acceleration phase, which was not observed in dynamic fracture of steel and brittle polymers, was noted. Unlike its static counterpart, the crack continued to propagate at nearly its terminal velocity under a low dynamic stress intensity factor during the terminal phase of crack propagation. These and previously obtained results for glass and RBSN show that dynamic crack arrest under a positive dynamic stress intensity factor is unlikely in static and impact loaded structural ceramics.

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



Gelcasting of silicon preforms for the production of sintered reaction-bonded silicon nitride  

SciTech Connect

Gelcasting of silicon metal for the production of sintered reaction-bonded silicon nitride (SRBSN) was investigated in order to identify associated advantages over conventional forming techniques, i.e., die and isostatic pressing. Compacts were formed from identical powder mixtures by both gelcasting and pressing, and were nitrided and sintered to produce SRBSN ceramics using both conventional and microwave heating. Characterization of the samples included measurement of green density, green and nitrided pore structure, weight gain during nitridation, final density, microstructure, toughness, and flexural strength. It was found that a more uniform pore structure existed in the green gelcast samples. It is believed that this pore configuration aided in nitridation, and manifested itself in a more uniform final microstructure. In addition, improved mechanical properties were achieved in the gelcast samples. This improvement can be attributed to green microstructure homogeneity. An additional finding of this study was that microwave hearing combined with gelcast forming resulted in SRBSN materials with improved mechanical properties.

Kiggans, J.O. Jr.; Nunn, S.D.; Tiegs, T.N.; Davisson, C.C.; Coffey, D.W. [Oak Ridge National Lab., TN (United States); Maria, J.P. [Pennsylvania State Univ., University Park, PA (United States)



An in vitro study to evaluate the effects of addition of zinc oxide to an orthodontic bonding agent  

PubMed Central

Objective: The objective of this study is to test the antimicrobial effect of zinc oxide when incorporated into an orthodontic bonding material and to check the effect of addition of zinc oxide on the shear bond strength of the bonding material. Materials and Methods: Zinc oxide was added to a resin modified light cure glass ionomer cement (GIC) (Fuji Ortho LC GC America, Alsip, Ill) to make modified bonding agent containing 13% and 23.1% ZnO and the antimicrobial assay was done using agar disc diffusion method. Discs of the modified bonding agent were prepared and a culture of Streptococcus mutans mixed with soft agar was poured over it and incubated at 38°C for 48 h and zones of inhibition were measured. The test was repeated after a month to check the antimicrobial effect. In addition shear bond strength of the brackets bonded with the modified bonding agent was tested. Results: The agar disc showed zones of inhibition around the modified bonding agent and the antimicrobial activity was more when the concentration of ZnO was increased. The antimicrobial effect was present even after a month. The shear bond strength decreased as the concentration of ZnO increased. Conclusion: The incorporation of ZnO into a resin modified light cure GIC (Fuji Ortho LC GC America, Alsip, Ill) added antimicrobial property to the original compound. PMID:24966757

Jatania, Archana; Shivalinga, B. M.



Reaction Mechanism and Kinetics of Enargite Oxidation at Roasting Temperatures  

NASA Astrophysics Data System (ADS)

Roasting of enargite (Cu3AsS4) in the temperature range of 648 K to 898 K (375 °C to 625 °C) in atmospheres containing variable amounts of oxygen has been studied by thermogravimetric methods. From the experimental results of weight loss/gain data and X-ray diffraction (XRD) analysis of partially reacted samples, the reaction mechanism of the enargite oxidation was determined, which occurred in three sequential stages:

Padilla, Rafael; Aracena, Alvaro; Ruiz, Maria C.



Cation insertion reactions of electrochromic tungsten and iridium oxide films  

NASA Astrophysics Data System (ADS)

Electrochemical coloration mechanisms of electrochromic (EC), amorphous tungsten and iridium oxide films have been investigated by direct elemental analysis of their compositions in oxidized and reduced states. Combined Rutherford backscattering and nuclear-reaction-analysis techniques were employed to determine the identities and concentrations of ions injected as charge compensators from the contacting electrolyte during EC redox reactions. In aqueous electrolytes, the cathodic coloration of an anodically formed, hydrous tungsten oxide film (composition ~WO3.H2O), is accompanied by injection of protons, in accordance with mechanisms determined for anhydrous WO3. The anodic coloration and coloration bleaching of an anodically formed, hydrous iridium oxide (IROX) film, which has a varying degree of hydration throughout its thickness, is accompanied by ejection and injection of H+ and H3O+ ions. In nonaqueous aprotic electrolytes, the slow but reversible insertion of Li+ (r=0.60 Å) and Na+ (r=0.95 Å) ions into IROX films has been successfully demonstrated for the first time. Li+ ions were found to exchange with H+ ions in these hydrous films. No evidence could be found for insertion of K+ (r=1.33 Å), F- (r=1.36 Å), or OH- (r=1.55 Å) ions as charge compensators. These results provide a measure of the size and concentration of vacancies and defects in amorphous IROX films.

McIntyre, J. D. E.; Basu, S.; Peck, W. F., Jr.; Brown, W. L.; Augustyniak, W. M.



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


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



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.



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.



Characterization of catalytic lanthanum oxide for double bond isomerization of n-butenes  

E-print Network

Material and Prepared La(OH)3, 2 Temperature Dependence of Surface Area and Phase Composi- tion of Lanthanum Oxide Catalyst. 20 24 3 Initial 1-Butene Reaction Rates at O'C for Successive Experiments Involving No Catalyst Pretreatment between Runs..., 37 LIST OF FIGURES Figure Page Schematic Representation of the Apparatus. . 16 Dependence of initial 1-butene reaction rate on final calcination temperature of La203. Solid points, normal pretreatment; open points, normal pretreatment; open...

Fox, Janan Sherlene



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; Amigo-Borras, Vicente; Granell-Ruiz, Maria; Busquets-Mataix, David; Panadero, Ruben A.; Sola-Ruiz, Maria F.



Effect of phosphate-bonded investments on titanium reaction layer and crown fit.  


This study analyzed the reaction layer and measured the marginal crown fit of cast titanium applied to different phosphate-bonded investments, prepared under the following conditions (liquid concentration/casting temperature): Rema Exakt (RE) - 100%/237 degrees C, 75%/287 degrees C, Castorit Super C (CS)-100%/70 degrees C, 75%/141 degrees C and Rematitan Plus (RP)- 100%/430 degrees C (special to titanium cast, as the control group). The reaction layer was studied using the Vickers hardness test, and analyzed by two way ANOVA and Tukey's HSD tests (alpha = 0.05). Digital photographs were taken of the crowns seated on the die, the misfit was measured using an image analysis system and One-way ANOVA, and Tukey's test was applied (alpha = 0.05). The hardness decreased from the surface (601.17 VHN) to 150 microm (204.03 VHN). The group CS 75%/141 degrees C presented higher hardness than the other groups, revealing higher surface contamination, but there were no differences among the groups at measurements deeper than 150 mum. The castings made with CS - 100%/70 degrees C presented the lowest levels of marginal misfit, followed by RE -100%/237 degrees C. The conventional investments CS (100%) and RE (100%) showed better marginal fit than RP, but the CS (75%) had higher surface contamination. PMID:20658031

Rocha, Sicknan Soares da; Nogueira, Fabiane; Pieralini, Anelise Rodolfo Ferreira; Ribeiro, Ricardo Faria; Adabo, Gelson Luis



Bond forming reactions of carbyne and nitrene complexes. Final technical report for DE-FG02-96ER14608  

SciTech Connect

An isolobal relationship among terminal carbyne, nitrene and oxo ligands provided the basis for our efforts to explore new synthetic routes to such complexes and to probe bond forming reactions of these ligands. The specific goals of this project were to explore reactions of carbyne and nitrene ligands, and a summary of our results follows. Manipulation of metal-ligand pi bonds to control reactivity patterns provided the conceptual basis for this work. New transformations and coupling reactions of the CR and NR moieties bound to metal centers have been explored and transformations of carbyne or nitrene ligands have been achieved. Perhaps the most exciting results have come in the area of the simplest ligand: the CH carbyne unit. Treatment of [Tp'(CO){sub 2}W{triple_bond}C-PPh{sub 3}] [PF{sub 6}] Tp' = hydridotris(3,5-dimethylpyrazolylborate) with Na[HBEt{sub 3}] forms the methylidyne complex Tp' (CO){sub 2}W{triple_bond}C-H via formyl and carbene intermediates. Protonation of the Tp'(CO){sub 2}W{triple_bond}C-H methylidyne complex yields the cationic agostic methylidene complex, [Tp'(CO){sub 2}W=CH{sub 2}][BF{sub 4}]. The methylidyne complex with a pK{sub a} of 28.7 can be deprotonated to provide the anionic terminal carbide Tp' (CO){sub 2}W{triple_bond}C-Li; a resonance at 556 ppm in the {sup 13}C NMR spectrum has been assigned to the carbide carbon. Addition of excess Na[HBEt{sub 3}] to Tp'(CO){sub 2}W{triple_bond}C-H generates the anionic methylidene complex [Na] [Tp'(CO){sub 2}W{triple_bond}CH{sub 2}].

Templeton, J.L.



Oxidation versus carboxamidomethylation of S-S bond in ranid frog peptides: pro and contra for de novo MALDI-MS sequencing.  


Five natural peptides isolated from ranid skin secretions of European frog species of Rana ridibunda and Rana arvalis (molecular masses 3516, 2674, 2636, 1874, and 1810 Da) were studied by MALDI-TOF/TOF to compare two procedures of disulfide bond cleavage: (1) performic oxidation and (2) reduction/carboxamidomethylation. The processes are relevant for the elucidation of the amino acid sequence inside the seven-member cystine ring at the C-terminus. The results clearly demonstrated that oxidation of the disulfide bond led to notably higher abundances of b- and y-ions, corresponding to the C-terminal peptide bonds, than reduction/carboxamidomethylation. This conclusion is true for all five peptides studied. Besides that, the oxidation procedure is simpler than carboxamidomethylation, as it is a one-step process with no purification required. The oxidation is more reproducible. The results were similar each time the peptide was subjected to the process. It was successfully applied to all five peptides while reduction/carboxamidomethylation failed in the case of brevinin-1Ra, despite all variations of reaction conditions. PMID:18280749

Samgina, Tatiana Y; Artemenko, Konstantin A; Gorshkov, Vladimir A; Poljakov, Nikita B; Lebedev, Albert T



Analysis of diatomic bond dissociation and formation in terms of the reaction force and the position-dependent reaction force constant  

Microsoft Academic Search

Bond dissociation and formation in diatomic molecules are analyzed in terms of the reaction force F(R) and the reaction force constant ?(R). These were determined for a group of 13 molecules from their extended-Rydberg potential energy functions V(R), which are of near-experimental quality. From F(R) and ?(R) comes a two-stage description of dissociation\\/formation. In dissociation, the first stage involves stretching

Jane S. Murray; Alejandro Toro-Labbé; Tim Clark; Peter Politzer



Chiral BINOL-derived phosphoric acids: privileged Brønsted acid organocatalysts for C-C bond formation reactions.  


BINOL-derived phosphoric acids have emerged during the last five years as powerful chiral Brønsted acid catalysts in many enantioselective processes. The most successful transformations carried out with chiral BINOL phosphates include C-C bond formation reactions. The recent advances have been reviewed in this article with a focus being placed on hydrocyanations, aldol-type, Mannich, Friedel-Crafts, aza-ene-type, Diels-Alder, as well as cascade and multi-component reactions. PMID:20820680

Zamfir, Alexandru; Schenker, Sebastian; Freund, Matthias; Tsogoeva, Svetlana B



Oxidation Reactions of Dithiocarbamate Complexes of Ruthenium(II).  


The reaction of Ru(Et(2)dtc)(2)(DMSO)(2) (Et(2)dtc = N,N-diethyldithiocarbamate; DMSO = dimethyl sulfoxide) with t-BuNC gave trans-Ru(Et(2)dtc)(2)(CN-t-Bu)(2), 1. Complex 1 crystallizes in the monoclinic space group P2(1)/n with a = 9.753(2) Å, b = 11.583(2) Å, c = 12.974(2) Å, and beta = 91.8(2) degrees for Z = 2. The crystal structure of 1 shows the trans disposition of the two isocyanides; the mean Ru-S and Ru-C distances are 2.409 and 1.977(2) Å, respectively. Treatment of [Ru(diene)Cl(2)](n)() with Na(Et(2)dtc) afforded Ru(Et(2)dtc)(2)(diene) (diene = bicyclo[2.2.1]hepta-2,5-diene (NBD), 2, 1,5-cyclooctadiene (COD), 3). Complex 2 crystallizes in the triclinic space group P&onemacr; with a = 7.316(1) Å, b = 10.346(1) Å, c = 15.123(2) Å, alpha = 103.69(2) degrees, beta = 93.54(2) degrees, and gamma = 100.61(2) degrees for Z = 2. The mean Ru-S and Ru-C distances in 2 are 2.416 and 2.137 Å, respectively. The reaction of cis-Ru(Et(2)dtc)(2)(CO)(2) with iodine gave the 2:1 molecular iodine complex cis-Ru(Et(2)dtc)(2)(CO)(2).(1)/(2)I(2) 4, which crystallizes in the monoclinic space group P2(1)/c with a = 7.347(2), b = 22.227(2) Å, c = 12.891(2) Å, and beta =95.98 (2) degrees for Z = 4. The mean Ru-S and Ru-C and the I-I distances in complex 4 are 2.427, 1.903, and 2.745(1) Å, respectively. Treatment of Ru(Et(2)dtc)(2)(DMSO)(2) with I(2) gave the linear Ru(II)-Ru(III)-Ru(III) trimer [Ru(3)(Et(2)dtc)(6)(DMSO)(2)](I(3))(2), 5, which crystallizes in the triclinic space group P&onemacr; with a = 14.125(3) Å, b = 20.829(6) Å, c = 13.658(3) Å, alpha = 97.57(2) degrees, beta = 110.01(2) degrees, and gamma = 71.25(2) degrees for Z = 2. The structure of complex 6 can be viewed as consisting of a {Ru(2)(III)(Et(2)dtc)(4)}(2+) core and a {Ru(II)(Et(2)dtc)(2)(DMSO)(2)} moiety, which are linked together via the two dithiocarbamate sulfurs of the latter. While the two Ru(III) centers are connected by a Ru-Ru single bond (Ru-Ru = 2.826(2) Å), there is no direct interaction between the Ru(III) and Ru(II) centers. Oxidation of Ru(Et(2)dtc)(2)L(2) (L = PPh(3), t-BuNC) by I(2) gave the respective [Ru(Et(2)dtc)(2)L(2)](+) cations. The reaction of cis-Ru(Et(2)dtc)(2)(PPh(3))(2) with excess tosyl azide gave the diamagnetic Ru(IV) tetrazene complex Ru(Et(2)dtc)(2)(Ts(2)N(4)), 7. Complex 7 crystallizes in the triclinic space group P&onemacr; with a = 10.380(1) Å, b = 11.322(1) Å, c = 15.310(1) Å, alpha = 106.84(2) degrees, beta = 106.87(2) degrees, and gamma = 92.63(2) degrees for Z = 2. The Ru-S and Ru-N(alpha) distances in 7 are 2.385 and 1.98 Å, respectively. The formal potentials of the Ru dithiocarbamate complexes were determined by cyclic voltammetry. PMID:11670104

Leung, Wa-Hung; Chim, Joyce L. C.; Hou, Hongwei; Hun, Tom S. M.; Williams, Ian D.; Wong, Wing-Tak



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


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



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



RH and H2 production in reactions between ROH and small molybdenum oxide cluster anions.  


To test recent computational studies on the mechanism of metal oxide cluster anion reactions with water [Ramabhadran, R. O.; et al. J. Phys. Chem. Lett. 2010, 1, 3066; Ramabhadran, R. O.; et al. J. Am. Chem. Soc. 2013, 135, 17039], the reactivity of molybdenum oxo–cluster anions, Mo(x)O(y)(–) (x = 1 – 4; y ? 3x) toward both methanol (MeOH) and ethanol (EtOH) has been studied using mass spectrometric analysis of products formed in a high-pressure, fast-flow reactor. The size-dependent product distributions are compared to previous Mo(x)O(y)(–) + H2O/D2O reactivity studies, with particular emphasis on the Mo2O(y)(–) and Mo3O(y)(–) series. In general, sequential oxidation, Mo(x)O(y)(–) + ROH ? Mo(x)O(y+1)(–) + RH, and addition reactions, Mo(x)O(y)(–) + ROH ? Mo(x)O(y+1)RH(–), largely corresponded with previously studied Mo(x)O(y)(–) + H2O/D2O reactions [Rothgeb, D. W., Mann, J. E., and Jarrold, C. C. J. Chem. Phys. 2010, 133, 054305], though with much lower rate constants than those determined for Mo(x)O(y)(–) + H2O/D2O reactions. This finding is consistent with the computational studies that suggested that ?H mobility on the cluster–water complex was an important feature in the overall reactivity. There were several notable differences between cluster–ROH and cluster–water reactions associated with lower R–OH bond dissociation energies relative to the HO–H dissociation energy. PMID:24661103

Waller, Sarah E; Jarrold, Caroline C



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.



Effect of bonding temperature on transient liquid phase bonding behavior of a Ni-based oxide dispersion-strengthened superalloy  

Microsoft Academic Search

The effect of joining temperature on the transient liquid phase (TLP) bonding of MA758 superalloy was investigated. The TLP\\u000a bonds were made at temperatures of 1100 and 1200 °C. Analysis was undertaken to determine the changes within the joint microstructure.\\u000a The bonding temperature affected the extent of parent metal dissolution, the time for isothermal solidification, and the attainment\\u000a of microstructural

R. K. Saha; T. I. Khan



Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe{sub 2}O{sub 4} complex oxide catalyst  

SciTech Connect

The CaFe{sub 2}O{sub 4} spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 {sup o}C which was lower than that of ferrite prepared by other methods. CaFe{sub 2}O{sub 4} catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H{sub 2}O{sub 2} (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 {+-} 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 {+-} 2 mol% and minor product phenyl acetaldehyde up to 9 {+-} 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H{sub 2}O{sub 2} molar ratio and solvents on the conversion and product distribution were studied.

Pardeshi, Satish K., E-mail: [Department of Chemistry, University of Pune, Ganeshkhind, Pune 411007 (India); Pawar, Ravindra Y. [Department of Chemistry, University of Pune, Ganeshkhind, Pune 411007 (India)] [Department of Chemistry, University of Pune, Ganeshkhind, Pune 411007 (India)



Reactions of 4-nitro-1,2,3-triazole with alkylating agents and compounds with activated multiple bonds  

SciTech Connect

When 4-nitro-1,2,3-triazole is alkylated, a mixture of N1- and N2-isomers is formed, with the latter usually predominating. The same behavior is also observed in addition reactions of 4-nitrotriazole to activated multiple bonds.

Vereshchagin, L.I.; Kuznetsova, N.I.; Kirillova, L.P.; Shcherbakov, V.V.; Sukhanov, G.T.; Gareev, G.A.



Using Reduced Catalysts for Oxidation Reactions: Mechanistic Studies of the "Periana-Catalytica" System for CH4 Oxidation  

E-print Network

Using Reduced Catalysts for Oxidation Reactions: Mechanistic Studies of the "Periana-Catalytica" System for CH4 Oxidation Oleg A. Mironov, Steven M. Bischof, Michael M. Konnick, Brian G. Hashiguchi: Designing oxidation catalysts based on CH activation with reduced, low oxidation state species is a seeming

Goddard III, William A.


Recent advances in catalytic C-N bond formation: a comparison of cascade hydroaminomethylation and reductive amination reactions with the corresponding hydroamidomethylation and reductive amidation reactions.  


The design and catalytic implementation of tandem reactions to selectively create nitrogen-containing products under mild conditions has encountered numerous challenges in synthetic chemistry. Several known classes of homogeneously catalyzed carbon-nitrogen bond formation including hydroamination, hydroamidation, hydroaminoalkylation, hydroaminomethylation and reductive amination were reported in the literature. More recently, a new class of C-N bond formation consisting of hydroamidomethylation and reductive amidation extended the applicability of these synthetic methodologies. The tandem reactions do considerably impact on the selectivity and efficiency of synthetic strategies. This review highlights and compares selected examples of the hydroaminomethylation, reductive amination, hydroamidomethylation and reductive amidation reactions, and thus consequently reveals their potential applications in synthetic chemistry as well as chemical industries. PMID:25098332

Raoufmoghaddam, Saeed



Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds.  


N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald-Hartwig-type reactions, copper-mediated Ullmann-type and Chan-Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan-Lam reactions. Chan-Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald-Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C-N bond formation in the course of a total synthesis or drug synthesis. PMID:21286396

Fischer, Carolin; Koenig, Burkhard



Reactions of oxidatively activated arylamines with thiols: reaction mechanisms and biologic implications. An overview.  

PubMed Central

Aromatic amines belong to a group of compounds that exert their toxic effects usually after oxidative biotransformation, primarily in the liver. In addition, aromatic amines also undergo extrahepatic activation to yield free arylaminyl radicals. The reactive intermediates are potential promutagens and procarcinogens, and responsible for target tissue toxicity. Since thiols react with these intermediates at high rates, it is of interest to know the underlying reaction mechanisms and the toxicologic implications. Phenoxyl radicals from aminophenols and aminyl radicals from phenylenediamines quickly disproportionate to quinone imines and quinone diimines. Depending on the structure, Michael addition or reduction reactions with thiols may prevail. Products of sequential oxidation/addition reactions (e.g., S-conjugates of aminophenols) are occasionally more toxic than the parent compounds because of their higher autoxidizability and their accumulation in the kidney. Even after covalent binding of quinone imines to protein SH groups, the resulting thioethers are able to autoxidize. The quinoid thioethers can then cross-link the protein by addition to neighboring nucleophiles. The reactions of nitrosoarenes with thiols yield a so-called "semimercaptal" from which various branching reactions detach, depending on substituents. Compounds with strong pi-donors, like 4-nitrosophenetol, give a resonance-stabilized N-(thiol-S-yl)-arylamine cation that may lead to bicyclic products, thioethers, and DNA adducts. Examples of toxicologic implications of the interactions of nitroso compounds with thiols are given for nitrosoimidazoles, heterocyclic nitroso compounds from protein pyrolysates, and nitrosoarenes. These data indicate that interactions of activated arylamines with thiols may not be regarded exclusively as detoxication reactions. PMID:7889834

Eyer, P



CO oxidation as a prototypical reaction for heterogeneous processes.  


CO oxidation, although seemingly a simple chemical reaction, provides us with a panacea that reveals the richness and beauty of heterogeneous catalysis. The Fritz Haber Institute is a place where a multidisciplinary approach to study the course of such a heterogeneous reaction can be generated in house. Research at the institute is primarily curiosity driven, which is reflected in the five sections comprising this Review. We use an approach based on microscopic concepts to study the interaction of simple molecules with well-defined materials, such as clusters in the gas phase or solid surfaces. This approach often asks for the development of new methods, tools, and materials to prove them, and it is exactly this aspect, both, with respect to experiment and theory, that is a trade mark of our institute. PMID:21960461

Freund, Hans-Joachim; Meijer, Gerard; Scheffler, Matthias; Schlögl, Robert; Wolf, Martin



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



Analysis of the oxidation reactions of CaS  

NASA Astrophysics Data System (ADS)

The chemical reactions of dense pellets of solid CaS in oxidizing atmospheres were studied by using continuous thermogravimetric analysis and iodimetric titration of SO2 in the off-gas. The experiments covered a temperature range of 1223 to 1853 K, and Ar-O2 mixtures varying from 1 to 100 pct O2. The oxidation of CaS was found to be a complex process involving the formation of CaO and CaSO4. Within the experimental conditions stated, three different processes were observed: 1) Weight loss with the formation of CaO and SO2 which occurred at high temperatures and low partial pressures of O2. 2) Weight gain which occurred at low temperatures and high partial pressures of O2. 3) Combination of a) weight gain with the overall formation of CaSO4 and b) weight loss with the overall oxidation of CaS to CaO and the decomposition of CaSO4 leading to an oscillatory behavior which occurred at intermediate temperatures and intermediate to high partial pressures of O2. The boundaries between these three processes are distinct. The rate of oxidation of the sulfide is limited first by the transport of O2 across the gas boundary layer and later by the diffusion of O2 through the porous reaction product. From these results and the Ca-S-0 stability diagram, it is possible to predict the experimental conditions which will produce processes of weight gain, weight loss and oscillatory behavior.

Lynch, D. C.; Elliott, J. F.



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


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



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


Reduction of a phosphorus oxide and acid reaction set  

SciTech Connect

It has been predicted for some time that hypersonic aircraft will suffer from diminished fuel efficiency due to the slow speed of radical recombination in the nozzle of the aircraft and the consequent expulsion of high-energy fragments during high Mach number flight. The addition of small amounts of phosphine combustion products (phosphorus oxides and acids) to water vapor has been found to result in a faster relaxation rate of OH to its equilibrium density following H{sub 2}O photolysis. This article describes the systematic construction of a reaction model of 162 phosphorus reactions among 17 phosphorus-containing species. Those reactions that contribute to the reestablishment of equilibrium following the perturbation of the system by H{sub 2}O photolysis or by an increase in temperature are identified. A thermodynamic free energy function is used to quantify the rate of system relaxation back to equilibrium for a series of 36 reaction conditions covering a temperature range of 1,500 to 3,000 K, a gas density range of 5 {times} 10{sup {minus}7} to 5 {times} 10{sup {minus}5} mol/cm{sup 3} and a fuel equivalence ratio of 0.8 to 1.2.

Twarowski, A. [Rockwell International Science Center, Thousand Oaks, CA (United States)] [Rockwell International Science Center, Thousand Oaks, CA (United States)



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



Phase transformation and bond coat oxidation behavior of plasma-sprayed zirconia thermal barrier coating  

Microsoft Academic Search

ZrO2–CeO2–Y2O3 and ZrO2–Y2O3 thermal barrier coatings were prepared using the air plasma spray process. Phase transformation in the ceramic top coating, bond coat oxidation and thermal barrier properties were investigated to compare ZrO2–CeO2–Y2O3 with ZrO2–Y2O3 at 1300°C under high temperature thermal cycles. In the as-sprayed condition, both coatings showed a 7?11% porosity fraction and typical lamellar structures formed by continuous

C. H. Lee; H. K. Kim; H. S. Choi; H. S. Ahn



Temperature-dependent size exclusion chromatography for the in situ investigation of dynamic bonding/debonding reactions.  


Polymers capable of dynamic bonding/debonding reactions are of great interest in modern day research. Potential applications can be found in the fields of self-healing materials or printable networks. Since temperature is often used as a stimulus for triggering reversible bonding reactions, an analysis operating at elevated temperatures is very useful for the in situ investigation of the reaction mechanism, as unwanted side effects can be minimized when performing the analyses at the same temperature at which the reactions occur. A temperature-dependent size exclusion chromatographic system (TD SEC) has been optimized for investigating the kinetics of retro Diels-Alder-based depolymerization of Diels-Alder polymers. The changing molecular weight distribution of the analyzed polymers during depolymerization gives valuable quantitative information on the kinetics of the reactions. Adequate data interpretation methods were developed for the correct evaluation of the chromatograms. The results are confirmed by high-temperature dynamic light scattering, thermogravimetric analysis, and time-resolved nuclear magnetic resonance spectroscopy at high temperatures. In addition, the SEC system and column material stability under application conditions were assessed using thermoanalysis methods, infrared spectroscopy, nitrogen physisorption, and scanning electron microscopy. The findings demonstrate that the system is stable and, thus, we can reliably characterize such dynamically bonding/debonding systems with TD SEC. PMID:23877179

Brandt, Josef; Guimard, Nathalie K; Barner-Kowollik, Christopher; Schmidt, Friedrich G; Lederer, Albena



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.; Fernandez, Ignacio; Lobkovsky, Emil; Semproni, Scott P.; Bill, Eckhard; Wieghardt, Karl; DeBeer, Serena; Chirik, Paul J.



Oxidative addition of carbon-carbon bonds with a redox-active bis(imino)pyridine iron complex.  


Addition of biphenylene to the bis(imino)pyridine iron dinitrogen complexes, ((iPr)PDI)Fe(N(2))(2) and [((Me)PDI)Fe(N(2))](2)(?(2)-N(2)) ((R)PDI = 2,6-(2,6-R(2)-C(6)H(3)-N?CMe)(2)C(5)H(3)N; R = Me, (i)Pr), resulted in oxidative addition of a C-C bond at ambient temperature to yield the corresponding iron biphenyl compounds, ((R)PDI)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



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



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.



Optical surfacing of one-meter-class reaction bonded silicon carbide  

NASA Astrophysics Data System (ADS)

Optical fabrication methods for a one meter reaction bonded optical grade silicon carbide (RBO SiC) substrate have been successfully developed and demonstrated by Itek Optical Systems in Lexington, Massachusetts. A 1.125 m multiplied by .825 m RBO SiC panel, the largest SiC ever fabricated, has been ground and polished to a surface figure of lambda/20 rms at lambda equals .6328 nm. The single most critical technology area for RBO SiC optics has been attaining a high quality optical surface finish; this bimodal material requires particular processing techniques due to the hardness differences between the silicon and silicon carbide components. The measured surface finish quality for this one meter mirror is 15.5 angstrom rms, nearly twice as good as the specified 25 angstrom rms. Furthermore, the variation of surface finish over the mirror area is very low, sigma equals 2 angstrom. The mirror represents the state-of-the-art for lightweight, high quality SiC optical mirrors.

Breidenthal, Robert S.; Galat-Skey, Regina; Geany, John J.



Dimensional stability of bare and coated reaction-bonded silicon carbide  

NASA Astrophysics Data System (ADS)

Reaction bonded silicon carbide (RB SiC) is a two phase mirror material which is readily formable to near-net-shape but can be difficult to polish to a high quality optical surface. The usual solution is the addition of a thick layer of silicon (Si) which may be polished to very high optical quality but which may have a thermal distortion problem due to the mismatch in thermal expansion of the two materials. The second solution is the application of a thick layer of chemically vapor deposited (CVD) SiC which can be polished to high quality but not as readily as the Si. The CVD SiC can also have a mismatch since it is deposited at high temperature and is beta SiC compared to the alpha in the substrate. We have chosen to develop a low temperature method for depositing amorphous SiC which should provide both a polishable surface and a better match of properties. To determine the levels of thermally induced distortion in SiC mirrors we have cryogenically tested 6-inch diameter spherical RB SiC mirrors bare and with polished coatings of amorphous SiC Si and CVD SiC. Results from this program are presented which show that all but the CVD SiC coated mirror are thermally stable. 1.

Magida, Matthew B.; Paquin, Roger A.; Richmond, James J.



Poly(ethylene oxide)-bonded stationary phase for separation of inorganic anions in capillary ion chromatography.  


A tosylated-poly(ethylene oxide) (PEO) reagent was reacted with primary amino groups of an aminopropylsilica packing material (TSKgel NH2-60) in acetonitrile to form PEO-bonded stationary phase. The reaction was a single and simple step reaction. The prepared stationary phase was able to separate inorganic anions. The retention behavior of six common inorganic anions on the prepared stationary phase was examined under various eluent conditions in order to clarify its separation/retention mechanism. The elution order of the tested anions was iodate, bromate, bromide, nitrate, iodide, and thiocyanate, which was similar as observed in common ion chromatography. The retention of inorganic anions could be manipulated by ion exchange interaction which is expected that the eluent cation is coordinated among the PEO chains and it works as the anion-exchange site. Cations and anions of the eluent therefore affected the retention of sample anions. We demonstrated that the retention of the analyte anions decreased with increasing eluent concentration. The repeatability of retention time for the six anions was satisfactory on this column with relative standard deviation values from 1.1 to 4.3% when 10mM sodium chloride was used as the eluent. Compared with the unmodified TSKgel NH2-60, the prepared stationary phase retained inorganic anions more strongly and the selectivity was also improved. The present stationary phase was applied for the determination of inorganic anions contained in various water samples. PMID:23659983

Linda, Roza; Lim, Lee Wah; Takeuchi, Toyohide



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


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



Kinetics and dynamics of oxidation reactions involving an adsorbed CO species on bulk and supported platinum and copper-oxide  

SciTech Connect

The proposed research is an integrated experimental and modeling study of oxidation reactions involving CO as a key player -- be it a reactant, adsorbed intermediate, and/or partial oxidation product -- in the catalytic sequence and chemistry. The reaction systems of interest in the project include CO, formaldehyde, and methanol oxidation by O{sub 2} and CO oxidation by NO, on both Pt and copper oxide catalysts. These reactions are of importance in automobile exhaust catalysis. There is a paucity of rate data in the literature for these important environmental control reactions. The goal of this research is to better understand the catalytic chemistry and kinetics of oxidations reactions involving CO as an adsorbed intermediate. Successfully meeting this goal requires an integration of basic kinetic measurements, in situ catalyst surface monitoring, kinetic modeling, and nonlinear mathematical tools.

Harold, M.P.



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.  


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



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.



From Ketones to Esters by a Cu-Catalyzed Highly Selective C(CO)-C(alkyl) Bond Cleavage: Aerobic Oxidation and Oxygenation with Air.  


The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process. PMID:25251943

Huang, Xiaoqiang; Li, Xinyao; Zou, Miancheng; Song, Song; Tang, Conghui; Yuan, Yizhi; Jiao, Ning



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


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



Spectroscopic Characterization of Mixed Fe-Ni Oxide Electrocatalysts for the Oxygen Evolution Reaction in Alkaline  

E-print Network

with hydrogen evolution. The hydrogen evolution reaction is a relatively simple reaction that readily occursSpectroscopic Characterization of Mixed Fe-Ni Oxide Electrocatalysts for the Oxygen Evolution Information ABSTRACT: Mixed Fe-Ni oxide electrocatalysts for the oxygen evolution reaction in alkaline

Frenkel, Anatoly


Lubricating Properties of Some Bonded Fluoride and Oxide Coatings for Temperature to 1500 F  

NASA Technical Reports Server (NTRS)

The lubricating properties of some experimental ceramic coatings, diffusion-bonded fluoride coatings, and ceramic-bonded fluoride coatings were determined. The experiments were conducted in an air atmosphere at a sliding velocity of 430 feet per minute and at temperatures from 75 to 1500 F. Several ceramic coatings provided substantial reductions in friction coefficient and rider wear (compared with the unlubricated metals). For example, a cobaltous oxide (CoO) base coating gave friction coefficients of 0.24 to 0.36 within the temperature range of 75 to 1400 F; serious galling and welding of the metal surfaces were prevented. The friction coefficients were higher than the arbitrary maximum (0.2) usually considered for effective boundary lubrication. However, when a moderately high friction coefficient can be tolerated, this type of coating may be a useful antiwear composition. Diffusion-bonded calcium fluoride (CaF2) on Haynes Stellite 21 and on Inconel X gave friction coefficients of 0.1 to 0.2 at 1500 F. Endurance life was dependent on the thermal history of the coating; life improved with increased exposure time at elevated temperatures prior to running. Promising results were obtained with ceramic-bonded CaF2 on Inconel X. Effective lubrication and good adherence were obtained with a 3 to 1 ratio of CaF2 to ceramic. A very thin sintered and burnished film of CaF2 applied to the surface of this coating further improved lubrication, particularly above 1350 F. The friction coefficient was 0.2 at 500 F and decreased with increasing temperature to 0.06-at 1500 F. It was 0.25 at 75 F and 0.22 at 250 F.

Sliney, Harold E.



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



Reactions of Charged Substrates. 5. The Solvolysis and Sodium Azide Substitution Reactions of Benzylpyridinium Ions in Deuterium Oxide.  


Second-order rate constants and activation values were measured for the reactions with NaN(3) of a series of 4-Y-substituted (Y = MeO, Me, H, Cl, and NO(2)) benzyl 3'-Z-substituted (Z = CN, CONH(2), H, F, Ac) pyridinium chlorides in deuterium oxide. 3'-Cyanopyridine substrates reacted much faster than nicotinamide and pyridine substrates; in the pyridine series the 4-Me, 4-H, and 4-Cl benzyl analogs did not react for up to 6 months at 96()() degrees C in 1.7 M NaN(3). The 3'-cyanopyridine substrates do not exhibit borderline kinetic behavior, but the nicotinamide substrates do. The Hammett plot is flat for the NaN(3) reaction of 3'-cyanopyridine substrates and increasingly V-shaped for the nicotinamide and pyridine substrates. The values of beta(LG) (four-point plot) for the NaN(3) reaction of the 4-MeO benzyl substrates is -1.45, which is usually interpreted as being a very "late" activated complex. Two-point Brønsted "plots" for the other benzyl derivatives and for two N-methylpyridinium ions give values of beta(LG) in the same range. The second-order rate constant and activation values for N-methyl-3'-cyanopyridinium iodide are within the same range as those for the benzyl substrates. For the hydrolysis reaction, the Hammett plot is linear for 3'-cyanopyridine substrates (rho(+) = -1.24) and flat for the nicotinamide substrates. The extent of hydrolysis of 0.005-0.05 M solutions of the 3'-cyanopyridinie substrates depended on the initial concentration of substrate, and hydrolysis was slowed significantly or stopped completely in the presence of exogenous 3-cyanopyridine. These results show that an equilibrium is established among the products for the 4-MeO, 4-Me, 4-H, and 4-Cl substrates; the 4-NO(2) substrate reacted too slowly to discern any difference. Data for the extent of hydrolysis were fitted by an equation derived assuming the equilibrium. Despite this limitation on a classic test of mechanism, the rates and rho values are consistent with direct displacement by solvent and not with a unimolecular process. These results, which are rationalized in terms of the Pross-Shaik model, suggest that there are no ion-dipole complex intermediates in the benzyl series and show that borderline kinetic behavior is a function of leaving group ability and is not necessarily related to a change in mechanism. A computational approach was used to evaluate anomalous beta(LG) values for the hydrolysis and nucleophilic substitution reactions of the methypyridinium ion substrates. It was found that neither the Nu-substrate bond lengths nor the difference in charge matched the beta(LG) values. The value of DeltaDeltaS() of -15 gibbs/mol between (4-methoxybenzyl)-3'-cyanopyridinium chloride and the corresponding dimethylsulfonium chloride in the NaN(3) reaction, which is the result of the solvation of the pyridine at the transition state and the lack of solvation of SMe(2), is used to argue that the source of NAD(+) glycohydrolase "catalysis" of NAD(+) bond cleavage is the result of desolvation of the leaving group upon binding. PMID:11667662

Buckley, Neil; Oppenheimer, Norman J.



Selectivity of Chemisorbed Oxygen in C–H Bond Activation and CO Oxidation and Kinetic Consequences for CH?–O? Catalysis on Pt and Rh Clusters  

SciTech Connect

Rate measurements, density functional theory (DFT) within the framework of transition state theory, and ensemble-averaging methods are used to probe oxygen selectivities, defined as the reaction probability ratios for O* reactions with CO and CH?, during CH?–O? catalysis on Pt and Rh clusters. CO? and H?O are the predominant products, but small amounts of CO form as chemisorbed oxygen atoms (O*) are depleted from cluster surfaces. Oxygen selectivities, measured using ¹²CO–¹³CH?–O? reactants, increase with O?/ CO ratio and O* coverage and are much larger than unity at all conditions on Pt clusters. These results suggest that O* reacts much faster with CO than with CH?, causing any CO that forms and desorbs from metal cluster surfaces to react along the reactor bed with other O* to produce CO? at any residence time required for detectable extents of CH? conversion. O* selectivities were also calculated by averaging DFTderived activation barriers for CO and CH? oxidation reactions over all distinct surface sites on cubo-octahedral Pt clusters (1.8 nm diameter, 201 Pt atoms) at low O* coverages, which are prevalent at low O? pressures during catalysis. CO oxidation involves non-activated molecular CO adsorption as the kinetically relevant step on exposed Pt atoms vicinal of chemisorbed O* atoms (on *–O* site pairs). CH? oxidation occurs via kinetically relevant C–H bond activation on *–* site pairs involving oxidative insertion of a Pt atom into one of the C–H bonds in CH?, forming a three-centered HC?–Pt–H transition state. C–H bond activation barriers reflect the strength of Pt–CH? and Pt–H interactions at the transition state, which correlates, in turn, with the Pt coordination and with CH? * binding energies. Ensemble-averaged O* selectivities increase linearly with O?/CO ratios, which define the O* coverages, via a proportionality constant. The proportionality constant is given by the ratio of rate constants for O? dissociation and C–H bond activation elementary steps; the values for this constant are much larger than unity and are higher on larger Pt clusters (1.8–33 nm) at all temperatures (573–1273 K) relevant for CH?–O? reactions. The barriers for the kinetically relevant C–H bond dissociation step increase, while those for CO oxidation remain unchanged as the Pt coordination number and cluster size increase, and lead, in turn, to higher O* selectivities on larger Pt clusters. Oxygen selectivities were much larger on Rh than Pt, because the limiting reactants for CO oxidation were completely consumed in ¹²CO–¹³CH?–O? mixtures, consistent with lower CO/O? ratios measured by varying the residence time and O?/CH? ratio independently in CH?–O? reactions. These mechanistic assessments and theoretical treatments for O* selectivity provide rigorous evidence of low intrinsic limits of the maximum CO yields, thus confirming that direct catalytic partial oxidation of CH? to CO (and H?) does not occur at the molecular scale on Pt and Rh clusters. CO (and H?) are predominantly formed upon complete O? depletion from the sequential reforming steps.

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



Hydrogen bonding to the cysteine ligand of superoxide reductase: acid-base control of the reaction intermediates.  


Superoxide reductase (SOR) is a non-heme iron metalloenzyme that detoxifies superoxide radical in microorganisms. Its active site consists of an unusual non-heme Fe(2+) center in a [His4Cys1] square pyramidal pentacoordination, with the axial cysteine ligand proposed to be an essential feature in catalysis. Two NH peptide groups from isoleucine 118 and histidine 119 establish hydrogen bonds involving the sulfur ligand (Desulfoarculus baarsii SOR numbering). To investigate the catalytic role of these hydrogen bonds, the isoleucine 118 residue of the SOR from Desulfoarculus baarsii was mutated into alanine, aspartate, or serine residues. Resonance Raman spectroscopy showed that the mutations specifically induced an increase of the strength of the Fe(3+)-S(Cys) and S-C?(Cys) bonds as well as a change in conformation of the cysteinyl side chain, which was associated with the alteration of the NH hydrogen bonding involving the sulfur ligand. The effects of the isoleucine mutations on the reactivity of SOR with O2 (•-) were investigated by pulse radiolysis. These studies showed that the mutations induced a specific increase of the pK a of the first reaction intermediate, recently proposed to be an Fe(2+)-O2 (•-) species. These data were supported by density functional theory calculations conducted on three models of the Fe(2+)-O2 (•-) intermediate, with one, two, or no hydrogen bonds involving the sulfur ligand. Our results demonstrated that the hydrogen bonds between the NH (peptide) and the cysteine ligand tightly control the rate of protonation of the Fe(2+)-O2 (•-) reaction intermediate to form an Fe(3+)-OOH species. PMID:23917995

Tremey, Emilie; Bonnot, Florence; Moreau, Yohann; Berthomieu, Catherine; Desbois, Alain; Favaudon, Vincent; Blondin, Geneviève; Houée-Levin, Chantal; Nivière, Vincent



Methandiide as a non-innocent ligand in carbene complexes: from the electronic structure to bond activation reactions and cooperative catalysis.  


The synthesis of a ruthenium carbene complex based on a sulfonyl-substituted methandiide and its application in bond activation reactions and cooperative catalysis is reported. In the complex, the metal-carbon interaction can be tuned between a Ru-C single bond with additional electrostatic interactions and a Ru=C double bond, thus allowing the control of the stability and reactivity of the complex. Hence, activation of polar and non-polar bonds (O-H, H-H) as well as dehydrogenation reactions become possible. In these reactions the carbene acts as a non-innocent ligand supporting the bond activation as nucleophilic center in the 1,2-addition across the metal-carbon double bond. This metal-ligand cooperativity can be applied in the catalytic transfer hydrogenation for the reduction of ketones. This concept opens new ways for the application of carbene complexes in catalysis. PMID:25047390

Becker, Julia; Modl, Tanja; Gessner, Viktoria H



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

PubMed Central

Escherichia coli DsbB has four essential cysteine residues, among which Cys41 and Cys44 form a CXXC redox active site motif and the Cys104-Cys130 disulfide bond oxidizes the active site cysteines of DsbA, the disulfide bond formation factor in the periplasm. Functional respiratory chain is required for the cell to keep DsbA oxidized. In this study, we characterized the roles of essential cysteines of DsbB in the coupling with the respiratory chain. Cys104 was found to form the inactive complex with DsbA under respiration-defective conditions. While DsbB, under normal aerobic conditions, is in the oxidized state, having two intramolecular disulfide bonds, oxidation of Cys104 and Cys130 requires the presence of Cys41-Cys44. Remarkably, the Cys41-Cys44 disulfide bond is refractory to reduction by a high concentration of dithiothreitol, unless the membrane is solubilized with a detergent. This reductant resistance requires both the respiratory function and oxygen, since Cys41-Cys44 became sensitive to the reducing agent when membrane was prepared from quinone- or heme-depleted cells or when a membrane sample was deaerated. Thus, the Cys41-Val-Leu-Cys44 motif of DsbB is kept both strongly oxidized and strongly oxidizing when DsbB is integrated into the membrane with the normal set of respiratory components. PMID:10064586

Kobayashi, T; Ito, K



The basics of oxidants in water treatment. Part A: OH radical reactions.  


The Advanced Oxidation Processes (AOPs) are based on the reactions of the highly reactive *OH radicals. The formation of *OH by the various AOPs and their ensuing reactions are reviewed. PMID:17674822

von Sonntag, C



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


Kinetics modeling and reaction mechanism of ferrate(VI) oxidation of benzotriazoles.  


Benzotriazoles (BTs) are high production volume chemicals with broad application in various industrial processes and in households, and have been found to be omnipresent in aquatic environments. We investigated oxidation of five benzotriazoles (BT: 1H-benzotriazole; 5MBT: 5-methyl-1H-benzotriazole; DMBT: 5,6-dimethyl-1H-benzotriazole hydrate; 5CBT: 5-chloro-1H-benzotriazole; HBT: 1-hydroxybenzotriazole) by aqueous ferrate (Fe(VI)) to determine reaction kinetics as a function of pH (6.0-10.0), and interpreted the reaction mechanism of Fe(VI) with BTs by using a linear free-energy relationship. The pK(a) values of BT and DMBT were also determined using UV-Visible spectroscopic method in order to calculate the species-specific rate constants, and they were 8.37 ± 0.0 and 8.98 ± 0.08 respectively. Each of BTs reacted moderately with Fe(VI) with the k(app) ranged from 7.2 to 103.8 M(-1)s(-1) at pH 7.0 and 24 ± 1 °C. When the molar ratio of Fe(VI) and BTs increased up to 30:1, the removal rate of BTs reached about >95% in buffered milli-Q water or secondary wastewater effluent. The electrophilic oxidation mechanism of the above reaction was illustrated by using a linear free-energy relationship between pH-dependence of species-specific rate constants and substituent effects (?(p)). Fe(VI) reacts initially with BTs by electrophilic attack at the 1,2,3-triazole moiety of BT, 5MBT, DMBT and 5CBT, and at the N-OH bond of HBT. Moreover, for BT, 5MBT, DMBT and 5CBT, the reactions with the species HFeO(4)(-) predominantly controled the reaction rates. For HBT, the species H(2)FeO(4) with dissociated HBT played a major role in the reaction. The results showed that Fe(VI) has the ability to degrade benzotriazoles in water. PMID:21334710

Yang, Bin; Ying, Guang-Guo; Zhang, Li-Juan; Zhou, Li-Jun; Liu, Shan; Fang, Yi-Xiang



Radiolytic oxidation of propane: Computer modeling of the reaction scheme  

NASA Astrophysics Data System (ADS)

The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25°C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. Minor products include i-butyl alcohol, t-amyl alcohol, n-butyl alcohol, n-amyl alcohol, and i-amyl alcohol. Small yields of i-hexyl alcohol and n-hexyl alcohol were also observed. There was no apparent difference in the G-values at pressures of 50, 100 and 150 torr. When the oxygen concentration was decreased below 5%, the yields of acetone, i-propyl alcohol, and n-propyl alcohol increased, the propionaldehyde yield decreased, and the yields of other products remained constant. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases.

Gupta, Avinash K.; Hanrahan, Robert J.


Oxidative addition of the C?-C? bond in ?-O-4 linkage of lignin to transition metals using a relativistic pseudopotential-based ccCA-ONIOM method.  


A multi-level multi-layer QM/QM method, the relativistic pseudopotential correlation-consistent composite approach within an ONIOM framework (rp-ccCA-ONIOM), was applied to study the oxidative addition of the C(?)-C(?) bond in an archetypal arylglycerol ?-aryl ether (?-O-4 linkage) substructure of lignin to Ni, Cu, Pd and Pt transition metal atoms. The chemically active high-level layer is treated using the relativistic pseudopotential correlation-consistent composite approach (rp-ccCA), an efficient methodology designed to reproduce an accuracy that would be obtained using the more computationally demanding CCSD(T)/aug-cc-pCV?Z-PP, albeit at a significantly reduced computational cost, while the low-level layer is computed using B3LYP/cc-pVTZ. The thermodynamic and kinetic feasibilities of the model reactions are reported in terms of enthalpies of reactions at 298 K (?H°(298)) and activation energies (?H-act). The results obtained from the rp-ccCA:B3LYP hybrid method are compared to the corresponding values using CCSD(T) and several density functionals including B3LYP, M06, M06 L, B2PLYP, mPWPLYP and B2GP-PLYP. The energetics of the oxidative addition of C?C bond in ethane to Ni, Cu, Pd and Pt atoms are also reported to demonstrate that the rp-ccCA method effectively reproduces the accuracy of the CCSD(T)/aug-cc-pCV?Z method. Our results show that in the catalytic activation of the C(?)-C(?) bond of ?-O-4, the use of platinum metal catalysts will lead to the most thermodynamically favored reaction with the lowest activation barrier. PMID:22144374

Oyedepo, Gbenga A; Wilson, Angela K



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


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



Reaction of Coadsorbed Nitric Oxide and Nitrogen Atoms on Rh(111)  

Microsoft Academic Search

We have studied the reaction of nitrogen atoms (N) with nitric oxide molecules (NO) coadsorbed on a Rh(lll) catalyst in order to isolate the reaction of these two species as an elementary step (e.g., in the NO + CO reaction mechanism) and determine the products of that reaction. Electron beam dissociation of adsorbed NO was used to cleanly prepare N

D. N. Belton; C. L. Dimaggio; S. J. Schmieg; K. Y. S. Ng



Factors limiting selectivity in C3 and C4 amm(oxidation) reactions  

Microsoft Academic Search

An extensive data-mining study of C3 and C4 selective oxidation and ammoxidation reactions occurring in the gas phase over solid catalysts has been conducted. The reactions include the amm(oxidation) of propane, propene, isobutane and isobutene to produce ?,?-unsaturated mononitriles and unsaturated carboxylic acids. Selectivity–conversion plots were generated for each reaction from the patent and scientific literature. For each reaction there

A. Costine; B. K. Hodnett



(Selective carbon oxygen bond scission during reactions of oxygenates on single crystal catalysts)  

SciTech Connect

We have discovered that the carbon-oxygen bond in methanol can be selectively broken if the surface structure of the platinum catalyst is appropriately tailored. The objective of this project is to determine if variations in surface structure allow one to selectively break C-O and C-H bonds. The decomposition of a wide range of oxygenates on several carefully chosen faces of group VIII metals will be examined to see when C-O bond scission occurs and what new chemistry we can find on stepped surfaces.

Not Available



[Selective carbon oxygen bond scission during reactions of oxygenates on single crystal catalysts]. Progress report  

SciTech Connect

We have discovered that the carbon-oxygen bond in methanol can be selectively broken if the surface structure of the platinum catalyst is appropriately tailored. The objective of this project is to determine if variations in surface structure allow one to selectively break C-O and C-H bonds. The decomposition of a wide range of oxygenates on several carefully chosen faces of group VIII metals will be examined to see when C-O bond scission occurs and what new chemistry we can find on stepped surfaces.

Not Available



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.



Bond valence sums in coordination chemistry. The calculation of the oxidation state of samarium in complexes containing samarium bonded only to oxygen.  


A simple method is presented for calculating the oxidation state of Sm in complexes where Sm is bonded only to O ligands. A total of 88 SmO(n)() fragments with n = 4-12 were retrieved from the Cambridge Structural Database and were analyzed using the bond valence sum (BVS) method. New R(0) values for Sm(II)-O of 2.116(21) A and for Sm(III)-O of 2.055(13) A were derived. The average R(0) value of 2.086 A gives a good approximation of the oxidation state of the Sm ion, either +2 or +3, from the observed distances without any assumptions. The Sm-O distances for +2 and +3 complexes with coordination numbers of 4-11 are tabulated and reflect the requirement that the BVS must equal the oxidation state. The distances for CN = 12 were not included because of problems with the reported crystal structures. Several X-ray structure determinations where the BVS and the oxidation state did not agree are discussed. PMID:12691581

Palenik, Gus J



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


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



Nucleation and growth of cracks in vitreous-bonded aluminum oxide at elevated temperatures  

SciTech Connect

The nucleation and growth of cracks was studied at elevated temperatures on a grade of vitreous-bonded aluminium oxide that contained approx. =8 vol% glass at the grain boundaries. Cracks were observed to nucleate within the vitreous phase, close to the tensile surface of the flexural test specimens used in these experiments. Crack nucleation occurred at a strain of approx. =0.08% to 0.12% which corresponded to a crack nucleation time of approx. =35% of the time to failure by creep rupture. Once nucleated, cracks propagated along grain boundaries, as long as the stress for crack propagation was maintained. The crack velocity for cracks that were nucleated by the creep process was found to be linearly proportional to the apparent stress intensity factor, whereas for cracks that were nucleated by indentation, the crack velocity was proportional to the fourth power of the apparent stress intensity factor.

Jakus, K.; Wiederhorn, S.M.; Hockey, B.J.



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



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.



Pentavalent Uranium Oxide via Reduction of [UO2]2+ Under Hydrothermal Reaction Conditions  

SciTech Connect

The synthesis, crystal structure and spectroscopic characterization of [UV(H2O)2(UVIO2)2O4(OH)](H2O)4 (1), a mixed-valent UV/UVI oxide material, are reported. The hydrothermal reaction of UO22+ with Zn and hydrazine at 120 °C for three days yields 1 in the form of a dark red crystalline solid. Compound 1 has been characterized by a combination of single-crystal and powder X-ray diffraction (XRD), elemental analysis, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The structure consists of an extended sheet of edge and point shared UVI pentagonal bipyramids that are further connected by edge sharing to square bipyramidal UV units. The overall topology is similar to the mineral ianthinite. The uranium L|||-edge XAS revealed features consistent with those observed by single-crystal X-ray diffraction. High resolution XPS data analysis of the U4f region confirmed the oxidation states of U as originally assigned from XRD analysis and bond valence summations.

Belai, Nebebech; Frisch, Mark; Ilton, Eugene S.; Ravel, Bruce; Cahill, Christopher L.



Pentavalent Uranium Oxide via Reduction of [UO2]2+ Under Hydrothermal Reaction Conditions  

SciTech Connect

The synthesis, crystal structure, and spectroscopic characterization of [UV(H2O)2(UVIO2)2O4(OH)](H2O)4 (1), a mixed-valent UV/UVI oxide material, are reported. The hydrothermal reaction of UO22+ with Zn and hydrazine at 120 degrees C for three days yields 1 in the form of a dark red crystalline solid. Compound 1 has been characterized by a combination of single-crystal and powder X-ray diffraction (XRD), elemental analysis, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The structure consists of an extended sheet of edge and corner shared UVI pentagonal bipyramids that are further connected by edge sharing to square bipyramidal UV units. The overall topology is similar to the mineral ianthinite. The uranium L|||-edge XAS revealed features consistent with those observed by single-crystal X-ray diffraction. High resolution XPS data analysis of the U4f region confirmed the oxidation states of U as originally assigned from XRD analysis and bond valence summations.

Balai, N.; Frisch, M; Ilton, E; Ravel, B; Cahill, C



Preparation of dicarboxylic acid-type gemini surfactant via Diels-Alder reaction & ozone oxidation.  


We wish to report a novel preparation method for Gemsurf analogs as well as dicarboxylic acid-type Gemini surfactant from Diels-Alder adducts of 2-trimethylsilyloxy-1,3-butadiene, in which ozone oxidation is adopted to convert C=C double bond to dicarboxylic acid without any additional oxidant. PMID:23728332

Chau, Huynh N; Kawase, Tokuzo; Oida, Tatsuo



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


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



Nitric oxide in star-forming regions - Further evidence for interstellar N-O bonds  

NASA Technical Reports Server (NTRS)

Nitric oxide has been newly detected toward several star-forming clouds, including Orion-KL, Sgr B2(N), W33A, W51M, and DR21(OH) via its J = 3/2-1/2 transitions near 150 GHz, using the FCRAO 14 m telescope. Both lambda-doubling components of NO were observed toward all sources. Column densities derived for nitric oxide in these clouds are 10 to the 15th-10 to the 16th/sq cm, corresponding to fractional abundances of 0.5-1.0 x 10 to the -8th, relative to H2. Toward Orion-KL, the NO line profile suggests that the species arises primarily from hot, dense gas. Nitric oxide may arise from warm material toward the other clouds as well. Nitric oxide in star-forming regions could be synthesized by high-temperature reactions, although the observed abundances do not disagree with values predicted from low-temperature, ion-molecule chemistry by more than one order of magnitude.

Ziurys, L. M.; Mcgonagle, D.; Minh, Y.; Irvine, W. M.



Cleavage of NH bonds by active oxygen on Ag(110). II. Selective oxidation of ethylamine to acetonitrile  

NASA Astrophysics Data System (ADS)

The adsorption of ethylamine on Ag(110) and its reaction with adsorbed oxygen was studied with temperature programmed reaction spectroscopy (TPRS), X-ray photoelectron spectroscopy (XPS), and electron energy loss vibrational spectroscopy (EELS). Adsorption of ethylamine on the clean Ag(110) surface proceeds at 110 K without dissociation. Desorption from the multilayer occurs at 160 K, and a series of broader desorption peaks from monolayer states are observed from 150 to 400 K. The chemical shift of the N(1s) X-ray photoelectron spectrum indicates that ethylamine bonds through the nitrogen lone pair in the monolayer. The reaction of ethylamine with adsorbed oxygen starts with the formation of adsorbed CH 3CH 2NH and adsorbed hydroxyl groups upon adsorption at 110 K. These species undergo further reaction to yield water from 280 to 370 K, and hydrogen, acetonitrile, and regenerated ethylamine at 370 K. Acetonitrile is the only carbon-containing product observed (other than ethylamine), indicative of highly selective bond breaking processes. Deuterium labeling experiments showed that preadsorbed oxygen activates the N?H bonds, leading to water formation, while the hydrogen product evolved at higher temperatures originates from the carbon skeleton via C?H bond metallation by the silver surface. Disproportionation of CH 3CH 2NH groups was identified. Ethylamine is formed by rate-limiting C?H bond cleavage of adsorbed CH 3CH 2N. No evidence was found for the activation of either C?C or C?N bonds, and the surface metallation of N?H bonds does not occur.

Thornburg, D. M.; Madix, R. J.



Advances in the Stille reaction and new methods for continuous flow Pd-catalyzed C-N bond forming reactions  

E-print Network

Chapter 1: A highly active catalyst system based upon a biaryl monophosphine ligand, XPhos, for the palladium-catalyzed Stille reaction has been developed. This method allows for the coupling of aryl chlorides with a range ...

Naber, John R. (John Robert)



Oxidative purification of carbon nanotubes and its impact on catalytic performance in oxidative dehydrogenation reactions.  


Oxidative purification with mild diluted HNO3 followed by NaOH washing lowers the amount of amorphous carbon attached to multiwalled carbon nanotubes (CNTs). The graphitic structure improves remarkably by further annealing in argon at elevated temperatures, that is, 1173, 1573, and 1973 K. The influence of the purification treatment on the catalytic activity of the CNTs is investigated for the oxidative dehydrogenation (ODH) of ethylbenzene and propane as probe reactions. All samples tend to approach an appropriately ordered structure and Raman analysis of the used samples displays a D/G band ratio of 0.95-1.42. Oxygen functionalities are partly removed by the annealing treatment and can be rebuilt to some extent by oxygen molecules in the ODH reactant flow. The presence of amorphous carbon is detrimental to the catalytic performance as it allows for unwanted functional groups occurring in parallel with the formation of the selective (di)ketonic active sites. PMID:20112335

Rinaldi, Ali; Zhang, Jian; Frank, Benjamin; Su, Dang Sheng; Abd Hamid, Sharifah Bee; Schlögl, Robert



Haptoglobin alters oxygenation and oxidation of hemoglobin and decreases propagation of peroxide-induced oxidative reactions.  


We compared oxygenation and anaerobic oxidation reactions of a purified complex of human hemoglobin (Hb) and haptoglobin (Hb-Hp) to those of uncomplexed Hb. Under equilibrium conditions, Hb-Hp exhibited active-site heterogeneity and noncooperative, high-affinity O(2) binding (n(1/2)=0.88, P(1/2)=0.33 mm Hg in inorganic phosphate buffer at pH 7 and 25 °C). Rapid-reaction kinetics also exhibited active-site heterogeneity, with a slower process of O(2) dissociation and a faster process of CO binding relative to uncomplexed Hb. Deoxygenated Hb-Hp had significantly reduced absorption at the ?(max) of 430 nm relative to uncomplexed Hb, as occurs for isolated Hb subunits that lack T-state stabilization. Under comparable experimental conditions, the redox potential (E(1/2)) of Hb-Hp was found to be +54 mV, showing that it is much more easily oxidized than uncomplexed Hb (E(1/2)=+125 mV). The Nernst plots for Hb-Hp oxidation showed no cooperativity and slopes less than unity indicated active-site heterogeneity. The redox potential of Hb-Hp was unchanged by pH over the range of 6.4-8.3. Exposure of Hb-Hp to excess hydrogen peroxide (H(2)O(2)) produced ferryl heme, which was found to be more kinetically inert in the Hb-Hp complex than in uncomplexed Hb. The negative shift in the redox potential of Hb-Hp and its stabilized ferryl state may be central elements in the protection against Hb-induced oxidative damage afforded by formation of the Hb-Hp complex. PMID:22841869

Banerjee, Sambuddha; Jia, Yiping; Siburt, Claire J Parker; Abraham, Bindu; Wood, Francine; Bonaventura, Celia; Henkens, Robert; Crumbliss, Alvin L; Alayash, Abdu I



Reactions of rhenium and manganese carbonyl complexes with 1,8-bis(diphenylphosphino)naphthalene: Ligand chelation, C–H and C–P bond-cleavage reactions  

Microsoft Academic Search

Reaction of [Re2(CO)8(MeCN)2] with 1,8-bis(diphenylphosphino)naphthalene (dppn) afforded three mono-rhenium complexes fac-[Re(CO)3(?1:?1-PPh2C10H6)(PPh2H)] (1), fac-[Re(CO)3{?1:?1:?1-(O)PPh2C10H6(O)PPh(C6H4)}] (2) and fac-[ReCl(CO)3(?2-PPh2C10H6PPh2)] (3). Compounds 1–3 are formed by Re–Re bond cleavage and P–C and C–H bond activation of the dppn ligand. Each of these three complexes have three CO groups arranged in facial fashion. Compound 1 contains a chelating cyclometalated diphenylnaphthylphosphine ligand and a terminally coordinated

Shariff E. Kabir; Faruque Ahmed; Shishir Ghosh; Mohammad R. Hassan; Muhammad S. Islam; Ayesha Sharmin; Derek A. Tocher; Daniel T. Haworth; Sergey V. Lindeman; Tasneem A. Siddiquee; Dennis W. Bennett; Kenneth I. Hardcastle



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.



A quantum chemical topological analysis of the C-C bond formation in organic reactions involving cationic species.  


ELF topological analysis of the ionic Diels-Alder (I-DA) reaction between the N,N-dimethyliminium cation and cyclopentadiene (Cp) has been performed in order to characterise the C-C single bond formation. The C-C bond formation begins in the short range of 2.00-1.96 Åvia a C-to-C pseudoradical coupling between the most electrophilic center of the iminium cation and one of the two most nucleophilic centers of Cp. The electron density of the pseudoradical center generated at the most electrophilic carbon of the iminium cation comes mainly from the global charge transfer which takes place along the reaction. Analysis of the global reactivity indices indicates that the very high electrophilic character of the iminium cation is responsible for the negative activation energy found in the gas phase. On the other hand, the analysis of the radical P(k)(o) Parr functions of the iminium cation, and the nucleophilic P(k)(-) Parr functions of Cp makes the characterisation of the most favourable two-center interaction along the formation of the C-C single bond possible. PMID:24901220

Domingo, Luis R; Pérez, Patricia



Caries and periodontal reactions associated with long-term use of different types of bonded lingual retainers.  


An investigation was carried out (1) to test the tendency of different types of bonded retainers to accumulate plaque and calculus and (2) to find out whether long-term use of bonded retainers caused any damage to the teeth involved. Two test groups of patients--one with 3-3 retainers made of 0.032-inch spiral wire, and the other with 3-3 retainers made of 0.032-inch plain wire--and a reference group of persons without 3-3 retainers were compared. Also, a test group of patients with retainers made of flexible spiral wire (0.0195 inch) bonded lingually to each anterior tooth in the maxilla was compared to a reference group of patients with retention plates in the maxilla. All the persons selected had received routine orthodontic treatment with a multibonded edgewise light wire technique and had been out of active treatment for 1 to 8 years. Different indices were used to score accumulation of plaque and calculus, prevalence of caries, and periodontal reactions. The findings indicated that there was no basis on which to claim that retainers made of spiral wire accumulated more plaque and calculus than retainers made of plain wire. The presence of a bonded lingual retainer and the occasional accumulation of plaque and calculus gingival to the retainer wire after long-term use caused no apparent damage to the hard and soft tissues adjacent to the wire. PMID:6380296

Artun, J



Clays and oxide minerals as catalysts and nanocatalysts in Fenton-like reactions — A review  

Microsoft Academic Search

Advanced oxidation processes (AOP), involving the generation of highly oxidizing radical species, have attracted much attention because of their potential in eliminating recalcitrant organic pollutants from different environmental matrices. Among the most investigated AOP is the Fenton reaction in which hydroxyl radicals (HO) are generated through the catalytic reaction of Fe(II)\\/Fe(III) in the presence of hydrogen peroxide. The use of

E. G. Garrido-Ramírez; B. K. G Theng; M. L. Mora




Microsoft Academic Search

Intermediates from the oxidation of phosphorothioates, (RO)3PS, were studied previously at low temperature using, P NMR, UV and Raman spectra. Now reported is further information about the structure of intermediates and about their reactions, both of which afford significant clues as to how phosphorothioates may produce adverse biological reactions after they have been oxidized biologically. Mass spectra identified intermediates corresponding

Joel Swinson; Lamar Field; Norman E. Heimer; Michael P. Stone; John R. Van Wazer



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



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


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



The deep oxidation of chemical warfare agent models: facile catalytic oxidative cleavage of phosphorus-carbon and sulfur-carbon bonds using dioxygen  

Microsoft Academic Search

In water, metallic palladium on carbon was found to catalyze the deep oxidation of organophosphorus and organosulfur compounds\\u000a by dioxygen at 90C in the presence of carbon monoxide. This system presents the first examples of catalytic cleavage of phosphorus-carbon\\u000a bonds. Starting with trimethylphosphine oxide, the phosphorus-containing products formed by sequential P-C cleavage were dimethylphosphinic\\u000a acid, methylphosphonic acid, and phosphoric acid.

T. Hogan; R. Simpson; M. Lin; A. Sen



A general synthesis of ynones from aldehydes via oxidative C-C bond cleavage under aerobic conditions.  


We describe a direct synthesis of various ynones from readily available aldehydes and hypervalent alkynyl iodides. In this method, a gold catalyst and a secondary amine work synergistically to produce the trisubstituted allenyl aldehyde, which can be converted to the desired ynone through an in situ C-C bond oxidative cleavage using molecular oxygen. PMID:25133731

Wang, Zhaofeng; Li, Li; Huang, Yong



Highly diastereoselective and regioselective copper-catalyzed nitrosoformate dearomatization reaction under aerobic-oxidation conditions.  


An unprecedented copper-catalyzed acylnitroso dearomatization reaction, which expands the traditional acylnitroso ene reaction and acylnitroso Diels-Alder reaction to a new type of transformation, has been developed under aerobic oxidation. Intermolecular and intra-/intermolecular reaction modes demonstrate an entirely different N- or O-acylnitroso selectivity. Hence, we can utilize this reaction as a highly diastereoselective access to a series of new pyrroloindoline derivatives, which are important structural motifs for natural-product synthesis. PMID:24590772

Yang, Weibo; Huang, Long; Yu, Yang; Pflästerer, Daniel; Rominger, Frank; Hashmi, A Stephen K



A Novel Reaction of Peroxiredoxin 4 towards Substrates in Oxidative Protein Folding  

PubMed Central

Peroxiredoxin 4 (Prx4) is the only endoplasmic reticulum localized peroxiredoxin. It functions not only to eliminate peroxide but also to promote oxidative protein folding via oxidizing protein disulfide isomerase (PDI). In Prx4-mediated oxidative protein folding we discovered a new reaction that the sulfenic acid form of Prx4 can directly react with thiols in folding substrates, resulting in non-native disulfide cross-linking and aggregation. We also found that PDI can inhibit this reaction by exerting its reductase and chaperone activities. This discovery discloses an off-pathway reaction in the Prx4-mediated oxidative protein folding and the quality control role of PDI. PMID:25137134

Wang, Xi'e; Wang, Xi; Wang, Chih-chen



Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air  

NASA Astrophysics Data System (ADS)

High molecular weight (300-650 Da) naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night during spring and summer in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of ?-pinene (C10H16) oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC). The ions were identified as clusters of the nitrate ion (NO3-) and ?-pinene oxidation products reaching oxygen to carbon ratios of 0.7-1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4- (Hyytiälä) and C3F5O2- (JPAC). The most abundant products in the ion spectra were identified as C105H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. ?-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where ?-pinene on average is 4-5 times less abundant than ?-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1-1 ppt (~106-107 molec cm-3). This is in a similar range as the amount of gaseous H2SO4 in Hyytiälä during day-time. As these highly oxidized organics are roughly 3 times heavier, likely with extremely low vapor pressures, their role in the initial steps of new aerosol particle formation and growth may be important and needs to be explored in more detail in the future.

Ehn, M.; Kleist, E.; Junninen, H.; Petäjä, T.; Lönn, G.; Schobesberger, S.; Dal Maso, M.; Trimborn, A.; Kulmala, M.; Worsnop, D. R.; Wahner, A.; Wildt, J.; Mentel, Th. F.



Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air  

NASA Astrophysics Data System (ADS)

High molecular weight (300-650 Da) naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of ?-pinene (C10H16) oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC). The ions were identified as clusters of the nitrate ion (NO3-) and ?-pinene oxidation products reaching oxygen to carbon ratios of 0.7-1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4- (Hyytiälä) and C3F5O2- (JPAC). The most abundant products in the ion spectra were identified as C10H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. ?-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where ?-pinene on average is 4-5 times less abundant than ?-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1-1 ppt (~106-107 molec cm-3). This is in a similar range as the amount of gaseous H2SO4 in Hyytiälä during day-time. As these highly oxidized organics are roughly 3 times heavier, likely with extremely low vapor pressures, their role in the initial steps of new aerosol particle formation and growth may be important and needs to be explored in more detail in the future.

Ehn, M.; Kleist, E.; Junninen, H.; Petäjä, T.; Lönn, G.; Schobesberger, S.; Dal Maso, M.; Trimborn, A.; Kulmala, M.; Worsnop, D. R.; Wahner, A.; Wildt, J.; Mentel, Th. F.



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.



Surface Reactions of Uranium Oxide Powder, Thin Films and Single Crystals  

SciTech Connect

The review deals with surface reactions of the complex uranium oxide systems with relevance to catalysis and the environment. After a brief introduction on the properties of uranium oxides, the focus of the review is on surface science studies of defined structures of uranium oxides which are entirely on UO{sub 2} because of the lack of available model on other uranium oxide systems. Powder work is also included as it has given considerable information related to the dynamics between the many phases of uranium oxides. Many chemical reactions are mapped and these include water dissociative adsorption and reaction, CO oxidation and reductive coupling, as well as the reaction of oxygen containing organic compounds such as alcohols, aldehydes, ketones and carboxylic acids in addition to a few examples of sulfur and nitrogen containing compounds.

Idriss, H.



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.



Comparative analysis of oxidation methods of reaction-sintered silicon carbide for optimization of oxidation-assisted polishing.  


Combination of the oxidation of reaction-sintered silicon carbide (RS-SiC) and the polishing of the oxide is an effective way of machining RS-SiC. In this study, anodic oxidation, thermal oxidation, and plasma oxidation were respectively conducted to obtain oxides on RS-SiC surfaces. By performing scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM-EDX) analysis and scanning white light interferometry (SWLI) measurement, the oxidation behavior of these oxidation methods was compared. Through ceria slurry polishing, the polishing properties of the oxides were evaluated. Analysis of the oxygen element on polished surfaces by SEM-EDX was conducted to evaluate the remaining oxide. By analyzing the three oxidation methods with corresponding polishing process on the basis of schematic diagrams, suitable application conditions for these methods were clarified. Anodic oxidation with simultaneous polishing is suitable for the rapid figuring of RS-SiC with a high material removal rate; polishing of a thermally oxidized surface is suitable for machining RS-SiC mirrors with complex shapes; combination of plasma oxidation and polishing is suitable for the fine finishing of RS-SiC with excellent surface roughness. These oxidation methods are expected to improve the machining of RS-SiC substrates and promote the application of RS-SiC products in the fields of optics, molds, and ceramics. PMID:24216836

Shen, Xinmin; Dai, Yifan; Deng, Hui; Guan, Chaoliang; Yamamura, Kazuya



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... 2.4.2 Solid-Phase Organic Synthesis Utilizing Polymer-bound Transition Metal Complexes as Catalysts????????....34 2.4.3 Solid-Phase Organic Synthesis utilizing Polymer-bound Transition Metal Complexes as Reagents...

Hershberger, John Charles



The reaction between nitric oxide and alpha-tocopherol: a reappraisal.  


Recently Gorbunov et al. reported that nitric oxide (.NO) can directly oxidize alpha-tocopherol to alpha-tocopheroxyl radical (Gorbunov et al., Biochem. Biophys. Res. Commun., 219, 835-841, 1996). We have reinvestigated this reaction and report that a direct reaction between .NO and alpha-tocopherol does not occur. However, the reaction between .NO and oxygen generates an oxidant which oxidizes alpha-tocopherol to alpha-tocopheryl quinone. Exposure of alpha-tocopherol to a low flux of .NO generated from spermine NONOate (100 microM) results in no consumption of alpha-tocopherol under either aerobic or anaerobic conditions. A higher flux of .NO, generated from 1 mM spermine NONOate, oxidizes alpha-tocopherol only under aerobic conditions. Artifactual oxidation of alpha-tocopherol can be observed when using commercial .NO that is contaminated with higher oxides of nitrogen, such as dinitrogen trioxide and dinitrogen tetraoxide. PMID:8713109

Hogg, N; Singh, R J; Goss, S P; Kalyanaraman, B



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 This review is focused on the mechanism of ubiquinol oxidation by the cytochrome bc1 complex (bc1 oxidized, the reduced FeS domain remains docked to cytochrome b until electron(s) pass through cytochrome b

Steinhoff, Heinz-Jürgen


Phosphine oxide-catalyzed enantioselective intramolecular aldol reaction via regioselective enolization of unsymmetrical diketones with tetrachlorosilane.  


The phosphine oxide-catalyzed asymmetric intramolecular aldol reactions of diketones were investigated. The combination of tetrachlorosilane and a chiral phosphine oxide catalyst promoted the acetyl-selective enolization of diketones, and the subsequent intramolecular aldol reaction occurred in an enantioselective manner. The introduction of two trimethylsilyl groups at the 4- and 4'-positions in BINAP dioxide catalyst improved the enantioselectivity. This reaction provides an effective synthetic method to access ?-tertiary-hydroxy cyclohexanones in high yields and with high enantioselectivity. PMID:25192225

Kotani, Shunsuke; Aoki, Shohei; Sugiura, Masaharu; Ogasawara, Masamichi; Nakajima, Makoto



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


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



Influence of reaction conditions on sol-precipitation process producing silicon oxide particles  

Microsoft Academic Search

The influence of TEOS, water, and ammonia concentrations on the sol-precipitation process for producing silicon oxide particles was investigated. When the hydrolysis and condensation were assumed as simple first-order reactions, the hydrolysis and condensation reaction coefficients were enhanced with an increase in the ammonia concentration due to its catalytic role in the reactions. Likewise, the increased hydrolysis coefficient with increased

Kyung-Soo Kim; Jun-Kyung Kim; Woo-Sik Kim



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




A Comprehensive Chemical Kinetic Reaction Mechanism for Oxidation and Pyrolysis of Propane and Propene  

Microsoft Academic Search

Abstract—A detailed chemical kinetic reaction mechanism is developed to describe the oxidation and pyrolysis of propane and propene. The mechanism consists of 163 elementary reactions among 4l chemical species. New rate expressions are developed for a number of reactions of propane, propene, and intermediate hydrocarbon species with radicals including H, 0, and OH. The mechanism is tested by comparisons between




Bonding principles of the Passivation Mechanism at III-V -- oxide Interfaces  

NASA Astrophysics Data System (ADS)

It has always been much more difficult to make FETs from GaAs than Si, because of `Fermi level pinning' and the difficulty of passivating its surfaces and interfaces. These issues have been discussed from the early days of PCSI by Spicer et al [1] with their ``unified defect model.'' Hasegawa [2] introduced the idea of ``Disorder Induced Gap states'' (DIGS). Since 1997 it has been possible to make inverted MOSFETs on GaAs using the epitaxial Gadolinium gallium oxide [3], but the main impetuous has been since 2003 to use atomic layer dpeosition to make scalable FETs, as recently acheived by Intel [4]. The obvious question is why GaAs is so much more difficult to passivate than Si. The early answer was that the native oxide was poor. But since the advent of good deposited ALD oxides on Si such as HfO2 or Al2O3, this answer is no good, as they should also work on GaAs. They do to an extent, but the interfacial density of states is still too large and the CV p lots are distorted. The cause of the defects is cannot be due to stress. The reason must be some underlying chemical reason. I show that the reason is the polar nature of bonding in GaAa and other III-Vs, and the driving force to keep the Fermi level in a gap. The electron counting rule of Pashley [5] that describes surface reconstruction is shown to be a variant of auto-compensation, and it is proposed to work more generally, at each layer deposition or growth on GaAs [6]. This leads to a continuous generation of defects if it is not satisfied. So the answer is to deposit oxide layers that meet this rule, and also break up any surface reconstructions that would lead to As-As dimers [6]. [4pt] [1] W E Spicer, Phys Rev Lett 44 420 (1980)[0pt] [2] H Hasegawa, J Vac Sci Technol B 5 1097 (1987)[0pt] [3] M Hong et al, Science 283 1897 (1997)[0pt] [4] M Radosavljevic, et al, IEDM (2009) p13.1[0pt] [5] M D Pashley, Phys Rev B 40 10481 (1989)[0pt] [6] J Robertson, L Lin, App Phys Letts (submitted), App Phys Lett 98 082903 (2011)

Robertson, John



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



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



Rh-Catalyzed Intermolecular Reactions of Cyclic ?-Diazocarbonyl Compounds with Selectivity Over Tertiary C-H Bond Migration  

PubMed Central

Intermolecular Rh-catalyzed reactions of cyclic ?-diazocarbonyl compounds with chemoselectivity over ?-hydride elimination are described. These methods represent the first general intermolecular reactions of Rh-carbenoids that are selective over tertiary ?-C?H bond migration. Successful transformations include cyclopropanation, cyclopropenation, and various X–H insertion reactions with a broad scope of substrates. We propose that the intermolecular approach of substrates to carbenes from acyclic diazo precursors may be relatively slow due to a steric interaction with the ester function, which is perpendicular to the ?-system of the carbene. For carbenes derived from 5- and 6-membered cyclic ?-diazocarbonyls, it is proposed that the carbene is constrained to be more conjugated with the carbonyl, thereby relieving the steric interaction for intermolecular reactions, and accelerating the rate of intermolecular reactivity relative to intramolecular ?-hydride migration. However, attempts to use ?-diazo-?-ethylcaprolactone in intermolecular cyclopropanation with styrene were unsuccessful. It is proposed that the conformational flexibility of the 7-membered ring allows the carbonyl to be oriented perpendicular to Rh-carbene. The significant intermolecular interaction between the carbonyl and approaching substrate is in agreement with the poor ability of ?-diazo-?-ethylcaprolactone to participate in intermolecular cyclopropanation reactions. DFT calculations provide support for the mechanistic proposals that are described. PMID:22676258

DeAngelis, Andrew; Dmitrenko, Olga; Fox, Joseph M.




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...


Ultrasonic and micromechanical study of damage and elastic properties of SiC/RBSN ceramic composites. [Reaction Bonded Silicon Nitride  

NASA Technical Reports Server (NTRS)

Ultrasonic techniques are employed to develop methods for nondestructive evaluation of elastic properties and damage in SiC/RBSN composites. To incorporate imperfect boundary conditions between fibers and matrix into a micromechanical model, a model of fibers having effective anisotropic properties is introduced. By inverting Hashin's (1979) microstructural model for a composite material with microscopic constituents the effective fiber properties were found from ultrasonic measurements. Ultrasonic measurements indicate that damage due to thermal shock is located near the surface, so the surface wave is most appropriate for estimation of the ultimate strength reduction and critical temperature of thermal shock. It is concluded that bonding between laminates of SiC/RBSN composites is severely weakened by thermal oxidation. Generally, nondestructive evaluation of thermal oxidation effects and thermal shock shows good correlation with measurements previously performed by destructive methods.

Chu, Y. C.; Hefetz, M.; Rokhlin, S. I.; Baaklini, G. Y.



Analysis of fuel oxidation reaction steps in Ni\\/GDC anode electrode of solid oxide fuel cells by using palladium nanoparticles  

Microsoft Academic Search

Fuel oxidation reaction in anode electrode of solid oxide fuel cells (SOFC) is a multi-step reaction. The oxidation reaction begins with dissociative adsorption of fuel molecule on the surface of the electrode and subsequently diffusion of hydrogen atoms to the triple phase boundary sites, where the hydrogen atom combines with the oxygen ion and forms water; the final product of

Alireza Babaei; San Ping Jiang



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.



Imbalance of heterologous protein folding and disulfide bond formation rates yields runaway oxidative stress  

PubMed Central

Background The protein secretory pathway must process a wide assortment of native proteins for eukaryotic cells to function. As well, recombinant protein secretion is used extensively to produce many biologics and industrial enzymes. Therefore, secretory pathway dysfunction can be highly detrimental to the cell and can drastically inhibit product titers in biochemical production. Because the secretory pathway is a highly-integrated, multi-organelle system, dysfunction can happen at many levels and dissecting the root cause can be challenging. In this study, we apply a systems biology approach to analyze secretory pathway dysfunctions resulting from heterologous production of a small protein (insulin precursor) or a larger protein (?-amylase). Results HAC1-dependent and independent dysfunctions and cellular responses were apparent across multiple datasets. In particular, processes involving (a) degradation of protein/recycling amino acids, (b) overall transcription/translation repression, and (c) oxidative stress were broadly associated with secretory stress. Conclusions Apparent runaway oxidative stress due to radical production observed here and elsewhere can be explained by a futile cycle of disulfide formation and breaking that consumes reduced glutathione and produces reactive oxygen species. The futile cycle is dominating when protein folding rates are low relative to disulfide bond formation rates. While not strictly conclusive with the present data, this insight does provide a molecular interpretation to an, until now, largely empirical understanding of optimizing heterologous protein secretion. This molecular insight has direct implications on engineering a broad range of recombinant proteins for secretion and provides potential hypotheses for the root causes of several secretory-associated diseases. PMID:22380681



Influence of interfacial shear strength on the mechanical properties of SiC fiber reinforced reaction-bonded silicon nitride matrix composites  

NASA Technical Reports Server (NTRS)

The influence of fiber/matrix interface microstructure and interfacial shear strength on the mechanical properties of a fiber-reinforced ceramic composite was evaluated. The composite consisted of approximately 30 vol percent uniaxially aligned 142 microns diameter SiC fibers (Textron SCS-6) in a reaction-bonded Si3N4 matrix (SiC/RBSN). The interface microstructure was varied by controlling the composite fabrication conditions and by heat treating the composite in an oxidizing environment. Interfacial shear strength was determined by the matrix crack spacing method. The results of microstructural examination indicate that the carbon-rich coating provided with the as-produced SiC fibers was stable in composites fabricated at 1200 C in a nitrogen or in a nitrogen plus 4 percent hydrogen mixture for 40 hr. However this coating degraded in composites fabricated at 1350 C in N2 + 4 percent H2 for 40 and 72 hr and also in composites heat treated in an oxidizing environment at 600 C for 100 hr after fabrication at 1200 C in a nitrogen. It was determined that degradation occurred by carbon removal which in turn had a strong influence on interfacial shear strength and other mechanical properties. Specifically, as the carbon coating was removed, the composite interfacial shear strength, primary elastic modulus, first matrix cracking stress, and ultimate tensile strength decreased, but the first matrix cracking strain remained nearly the same.

Bhatt, Ramakrishna T.



Putative hydrogen bond to tyrosine M208 in photosynthetic reaction centers from Rhodobacter capsulatus significantly slows primary charge separation.  


Slow, ?50 ps, P* ? P(+)HA(-) electron transfer is observed in Rhodobacter capsulatus reaction centers (RCs) bearing the native Tyr residue at M208 and the single amino acid change of isoleucine at M204 to glutamic acid. The P* decay kinetics are unusually homogeneous (single exponential) at room temperature. Comparative solid-state NMR of [4'-(13)C]Tyr labeled wild-type and M204E RCs show that the chemical shift of Tyr M208 is significantly altered in the M204E mutant and in a manner consistent with formation of a hydrogen bond to the Tyr M208 hydroxyl group. Models based on RC crystal structure coordinates indicate that if such a hydrogen bond is formed between the Glu at M204 and the M208 Tyr hydroxyl group, the -OH would be oriented in a fashion expected (based on the calculations by Alden et al., J. Phys. Chem. 1996, 100, 16761-16770) to destabilize P(+)BA(-) in free energy. Alteration of the environment of Tyr M208 and BA by Glu M204 via this putative hydrogen bond has a powerful influence on primary charge separation. PMID:24902471

Saggu, Miguel; Carter, Brett; Zhou, Xiaoxue; Faries, Kaitlyn; Cegelski, Lynette; Holten, Dewey; Boxer, Steven G; Kirmaier, Christine



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.



Selective, nickel-catalyzed carbon-carbon bond-forming reactions of alkynes  

E-print Network

Catalytic addition reactions to alkynes are among the most useful and efficient methods for preparing diverse types of substituted olefins. Controlling both regioselectivity and (EIZ)- selectivity in such transformations ...

Miller, Karen M. (Karen Marie)



Effect of Oxidation and SiO2 Coating on the Bonding Strength of Ti-Porcelain  

NASA Astrophysics Data System (ADS)

Investigations on the effect of oxidation on titanium-ceramic adhesion were performed. Cast pure titanium was subjected to surface modification by preoxidation and introduction of an intermediate layer of SiO2 by sol-gel process. Specimens were characterized by TG-DSC, XRD, and SEM/EDS. The adhesion between the titanium and porcelain was evaluated by three-point flexure bond test. Failure of the titanium-porcelain with preoxidation treatment predominantly occurred at the titanium-oxide interface. Preoxidation treatment did not affect the fracture mode of the titanium-ceramic system and did not increase the bonding strength of Ti-porcelain. The SEM results revealed the existence of microcracks on the SiO2 coating surface oxidized at 800 °C in an air furnace. During the porcelain fusion, minute amounts of oxygen were able to penetrate the cracks and caused localized oxidation of the Ti-substrate. Failure of the titanium-porcelain with SiO2 coating predominantly occurred at the SiO2 layer. The SiO2 coating served as an effective oxygen diffusion barrier and improved the mechanical and chemical bonding between porcelain and titanium.

Guo, Litong; Liu, Xiaochen; Zhu, Yabo; Xu, Cheng; Gao, Jiqiang; Guo, Tianwen



Palladium and gold nanotubes as oxygen reduction reaction and alcohol oxidation reaction catalysts in base.  


Palladium (PdNTs) and gold nanotubes (AuNTs) were synthesized by the galvanic displacement of silver nanowires. PdNTs and AuNTs have wall thicknesses of 6?nm, outer diameters of 60?nm, and lengths of 5-10 and 5-20??m, respectively. Rotating disk electrode experiments showed that the PdNTs and AuNTs have higher area normalized activities for the oxygen reduction reaction (ORR) than conventional nanoparticle catalysts. The PdNTs produced an ORR area activity that was 3.4, 2.2, and 3.7?times greater than that on carbon-supported palladium nanoparticles (Pd/C), bulk polycrystalline palladium, and carbon-supported platinum nanoparticles (Pt/C), respectively. The AuNTs produced an ORR area activity that was 2.3, 9.0, and 2.0?times greater than that on carbon-supported gold nanoparticles (Au/C), bulk polycrystalline gold, and Pt/C, respectively. The PdNTs also had lower onset potentials than Pd/C and Pt/C for the oxidation of methanol (0.236?V), ethanol (0.215?V), and ethylene glycol (0.251?V). In comparison to Pt/C, the PdNTs and AuNTs further demonstrated improved alcohol tolerance during the ORR. PMID:24757078

Alia, Shaun M; Duong, Kathlynne; Liu, Toby; Jensen, Kurt; Yan, Yushan



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


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



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



Fundamental kinetics and mechanistic pathways for oxidation reactions in supercritical water  

NASA Technical Reports Server (NTRS)

Oxidation of the products of human metabolism in supercritical water has been shown to be an efficient way to accomplish the on-board water/waste recycling in future long-term space flights. Studies of the oxidation kinetics of methane to carbon dioxide in supercritical water are presented in this paper in order to enhance the fundamental understanding of the oxidation of human waste compounds in supercritical water. It is concluded that, although the elementary reaction models remain the best hope for simulating oxidation in supercritical water, several modifications to existing mechanisms need to be made to account for the role of water in the reaction mechanism.

Webley, Paul A.; Tester, Jefferson W.



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.


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



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


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



Reactivity of biomimetic iron(II)-2-aminophenolate complexes toward dioxygen: mechanistic investigations on the oxidative C-C bond cleavage of substituted 2-aminophenols.  


The isolation and characterization of a series of iron(II)-2-aminophenolate complexes [(6-Me3-TPA)Fe(II)(X)](+) (X = 2-amino-4-nitrophenolate (4-NO2-HAP), 1; X = 2-aminophenolate (2-HAP), 2; X = 2-amino-3-methylphenolate (3-Me-HAP), 3; X = 2-amino-4-methylphenolate (4-Me-HAP), 4; X = 2-amino-5-methylphenolate (5-Me-HAP), 5; X = 2-amino-4-tert-butylphenolate (4-(t)Bu-HAP), 6 and X = 2-amino-4,6-di-tert-butylphenolate (4,6-di-(t)Bu-HAP), 7) and an iron(III)-2-amidophenolate complex [(6-Me3-TPA)Fe(III)(4,6-di-(t)Bu-AP)](+) (7(Ox)) supported by a tripodal nitrogen ligand (6-Me3-TPA = tris(6-methyl-2-pyridylmethyl)amine) are reported. Substituted 2-aminophenols were used to prepare the biomimetic iron(II) complexes to understand the effect of electronic and structural properties of aminophenolate rings on the dioxygen reactivity and on the selectivity of C-C bond cleavage reactions. Crystal structures of the cationic parts of 5·ClO4 and 7·BPh4 show six-coordinate iron(II) centers ligated by a neutral tetradentate ligand and a monoanionic 2-aminophenolate in a bidentate fashion. While 1·BPh4 does not react with oxygen, other complexes undergo oxidative transformation in the presence of dioxygen. The reaction of 2·ClO4 with dioxygen affords 2-amino-3H-phenoxazin-3-one, an auto-oxidation product of 2-aminophenol, whereas complexes 3·BPh4, 4·BPh4, 5·ClO4 and 6·ClO4 react with O2 to exhibit C-C bond cleavage of the bound aminophenolates. Complexes 7·ClO4 and 7(Ox)·BPh4 produce a mixture of 4,6-di-tert-butyl-2H-pyran-2-imine and 4,6-di-tert-butyl-2-picolinic acid. Labeling experiments with (18)O2 show the incorporation of one oxygen atom from dioxygen into the cleavage products. The reactivity (and stability) of the intermediate, which directs the course of aromatic ring cleavage reaction, is found to be dependent on the nature of ring substituent. The presence of two tert-butyl groups on the aminophenolate ring in 7·ClO4 makes the complex slow to cleave the C-C bond of 4,6-di-(t)Bu-HAP, whereas 4·BPh4 containing 4-Me-HAP displays fastest reactivity. Density functional theory calculations were conducted on [(6-Me3-TPA)Fe(III)(4-(t)Bu-AP)](+) (6(Ox)) to gain a mechanistic insight into the regioselective C-C bond cleavage reaction. On the basis of the experimental and computational studies, an iron(II)-2-iminobenzosemiquinonate intermediate is proposed to react with dioxygen resulting in the oxidative C-C bond cleavage of the coordinated 2-aminophenolates. PMID:24787025

Chakraborty, Biswarup; Bhunya, Sourav; Paul, Ankan; Paine, Tapan Kanti



Evolution of chemical bonding and electron density rearrangements during D(3h) ? D(3d) reaction in monolayered TiS2: a QTAIM and ELF study.  


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



Cleavage of aromatic carbon-carbon bonds. [Cleavage reactions with o-terphenyl  

SciTech Connect

The search for a model substrate to use in evaluating relative reactivity of H-donors, under coal liquefaction conditions has led to this study of o-terphenyl. Results of cleavage reaction studies with o-terphenyl show that o-terphenyl couples in the presence of model H-donors and many coal derived solvents to form triphenylene, and forms biphenyl by cleavage. The latter reaction is of more interest as the yields are substantial, and the yields have application to the study of properties of solvents. Attempts to elucidate the mechanism involved kinetic studies, and reaction with a deuterated H-donor. The best mechanism appears to be that in which the low steady-state concentration of reactive H-donor attacks either ipso position in o-terphenyl followed by cleavage. This mechanism is known to occur at high temperatures. 7 references, 3 tables.

Kline, E.A.; Teichert, W.P.; Farnum, B.W.



Redox-Neutral ?-C-H Bond Functionalization of Secondary Amines with Concurrent C-P Bond Formation/N-Alkylation  

PubMed Central

Redox-neutral formation of C–P bonds in the ?-position of amines was achieved via a process that features a combination of an oxidative ?-C–H bond functionalization and a reductive N-alkylation. Benzoic acid functions as an efficient catalyst in this three-component reaction of cyclic secondary amines, aldehydes and phosphine oxides to provide rapid access to ?-amino phosphine oxides not easily accessible by classic Kabachnik-Fields reactions. PMID:23957378

Das, Deepankar; Seidel, Daniel



Redox-neutral ?-C-H bond functionalization of secondary amines with concurrent C-P bond formation/N-alkylation.  


Redox-neutral formation of C-P bonds in the ?-position of amines was achieved via a process that features a combination of an oxidative ?-C-H bond functionalization and a reductive N-alkylation. Benzoic acid functions as an efficient catalyst in this three-component reaction of cyclic secondary amines, aldehydes and phosphine oxides to provide rapid access to ?-amino phosphine oxides not easily accessible by classic Kabachnik-Fields reactions. PMID:23957378

Das, Deepankar; Seidel, Daniel



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


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)



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


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.



Solvent-free oxidation of primary carbon-hydrogen bonds in toluene using Au-Pd alloy nanoparticles.  


Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO(2) are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO(2) supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites. PMID:21233383

Kesavan, Lokesh; Tiruvalam, Ramchandra; Ab Rahim, Mohd Hasbi; bin Saiman, Mohd Izham; Enache, Dan I; Jenkins, Robert L; Dimitratos, Nikolaos; Lopez-Sanchez, Jose A; Taylor, Stuart H; Knight, David W; Kiely, Christopher J; Hutchings, Graham J



Sporicidal effects of iodine-oxide thermite reaction products  

NASA Astrophysics Data System (ADS)

Iodine pentoxide-aluminum thermite reactions have been driven by impacts at 1000 m/s on steel plates 3 mm or thicker. This reaction releases iodine gas that is known to be a sporicide. To test the impact reactions for sporicidal effects, reactions took place in closed chambers containing dried Bacillus subtilis spores. The reduction in colony-forming units was dependent on the exposure time; long exposure times resulted in a 105 decrease in germination rate. This was shown to be due to the gas exposure rather than the heat or turbulence. Sporicidal effectiveness was increased by adding neodymium and saran resin.

Russell, Rod; Bless, Stephan; Blinkova, Alexandra; Chen, Tiffany



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)



Thermal oxidative degradation reactions of linear perfluoroalkyl ethers  

NASA Technical Reports Server (NTRS)

Thermal and thermal oxidative stability studies were performed on linear perfluoroalkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors is reported. The linear perfluoroalkyl ethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoroalkyl ether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating. Previously announced in STAR as N82-26468

Jones, W. R., Jr.; Paclorek, K. J. L.; Ito, T. I.; Kratzer, R. H.



Identification of the carbon dangling bond center at the 4H-SiC/SiO(2) interface by an EPR study in oxidized porous SiC.  


We report the observation of a paramagnetic interface defect in thermally oxidized porous n-type doped 4H-SiC/SiO(2). Based on its axial symmetry and resolved hyperfine interactions it is attributed to an sp(3) carbon dangling bond center situated at the SiC side of the interface. This center is electrically active and pins the Fermi level in the oxidized samples. No silicon related paramagnetic dangling bond centers are observed. The formation of dangling bond centers seems to be related to interstitial oxygen diffusion at the interface during the oxidation process. PMID:14753997

Cantin, J L; von Bardeleben, H J; Shishkin, Y; Ke, Y; Devaty, R P; Choyke, W J



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.



Reactions of sulfur dioxide with ammonia: Dependence on oxygen and nitric oxide  

SciTech Connect

The influence of oxygen and nitric oxide on the reactions of sulfur dioxide with ammonia were studied in a simulated flue gas in the range of 0--20% oxygen and 0--300 ppm nitric oxide at temperatures in the range of 40--60 C. A Fourier transform infrared spectrometer (FT-IR) analyzed the reaction products deposited on the reactor surface and revealed that ammonium sulfate was the main product of the reactions, with sulfamic acid and ammonium sulfamate as the minor products. The results showed that oxygen and nitric oxide enhanced the oxidation reactions of sulfur dioxide to form ammonium sulfate. The yield of the minor products markedly increased in the presence of nitrogen dioxide. The size and number concentration of product aerosols increased at lower temperature. The fraction of sulfur dioxide which formed aerosols increased with sulfur dioxide removal.

Hirota, Koichi; Maekelae, J.; Tokunaga, Okihiro [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan)] [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan)




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...


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.



Liquid-phase reaction-bonding of silicon carbide using alloyed silicon-molybdenum melts  

Microsoft Academic Search

The authors have investigated reaction-forming of silicon carbide by the infiltration of carbonaceous preforms using alloyed silicon melts, in order to synthesize composite materials free of the residual silicon phase that has previously limited mechanical properties and upper use temperatures. In this approach, rejection of the alloying component(s) from the primary silicon carbide phase into the remaining melt results in

Robert P. Messner; Yet-Ming Chiang



Influence of zinc-oxide eugenol, formocresol, and ferric sulfate on bond strength of dentin adhesives to primary teeth.  


This study evaluated in vitro the influence of a temporary filling {zinc oxide-eugenol (ZOE)} and two pulpotomy agents {formocresol (FC) and ferric sulfate (FS)} on shear bond strength (SBS) of two dentin adhesives to the dentin of primary molars. A total of 80 dentin surfaces were prepared and randomly allocated into 10 groups of 8 specimens each. Groups were subjected to different treatments, which included covering with a paste of ZOE mixed at different powder:liquid (P:L) ratios, placement on a gauze soaked in FC or FS, or they received no pretreatment and served as a control. XRV Herculite composite cylinders were bonded to dentin surfaces using Prime and Bond NT adhesive resin or Opti Bond Solo Plus adhesive resin. SBSs were determined using the lnstron testing machine running at a crosshead speed of 0.5 mm/min. The use of ZOE mixed at the lower P:L ratio of 10g:2g significantly decreased the values of SBS of the two adhesives. The use of two pulpotomy agents (FC and FS) significantly decreased the SBS of the two adhesives. The bond strength to dentin of primary teeth was influenced by the pulpotomy agents used and the ZOE P:L ratio but not by the adhesive system used. PMID:16127468

Salama, Fouad Saad



Identification and cleavage of breakable single bonds by selective oxidation, reduction, and hydrolysis. Quarterly report No. 9, October 1-December 31, 1980  

SciTech Connect

Objective is to determine the structure of bituminous coal with emphasis on the crosslinks and breakable single bonds. Some of the highlights of this quarter are: (1) large-scale extraction of benzylamine-extracted coal with ethylene diamine-dimethyl sulfoxide (EDA-DMSO) led to 50.4% recovery of soluble material and 40.5% recovery of undissolved coal; (2) EDA-DMSO extraction appears to have removed essentially all of the ether and ester links in both fractions, leaving only hydrocarbon links; (3) extraction of whole coal by a mixture of N-methylpyrrolidinone (NMP) and EDA is no better than EDA-DMSO, even though NMP alone is a better solvent than DMSO alone; (4) investigators have no evidence that NaOCl will oxidize sulfide links to sulfuric acid and NaOCl appears to be unsuitable for determining sulfide links in coal; (5) black acid fraction from several NaOCl oxidations precipitated between pH 4.98 and 4.66 was characterized; (6) measurements of hydroxyl and carboxyl contents on pyridine and benzylamine extracts and extracted coal show increases in carboxyl content on reactions of these fractions with alcoholic KOH, and an increase in hydroxyl content on reactions of the pyridine-extracted coal with benzylamine, consistent with ester cleavage. 6 tables.

Pavelka, L.A.; Mayo, F.R.; Zevely, J.



Sporicidal Effects of Iodine-oxide Thermite Reaction Products  

NASA Astrophysics Data System (ADS)

Iodine pentoxide-aluminum thermite reactions have been driven by impacts at 1000 m/s on steel plates 3 mm or thicker. The activation energy of this material reaction is 197 J/g. The reactivity is increased by reducing grain size. This reaction releases iodine gas that is known to be a sporicide. In order to test the impact reactions for sporicidal effects, reactions took place in closed chambers containing dried Bacillus subtilis spores. The reduction in colony-forming units was dependent on the exposure time; long exposure times resulted in a 10^5 decrease in germination rate. This was shown to be due to the gas exposure and not the heat or turbulence. Sporicidal effectiveness was increased by adding neodymium and saran resin. The sporicidal effect is very dependent on exposure time, ranging from about 90% kill for times on the order of a second to 99.99% for one-hour times.

Russell, Rod; Bless, Stephan; Blinkova, Alexandra; Chen, Tiffany



Observation of exothermic reaction during laser-assisted iron oxide coating on aluminum alloy  

Microsoft Academic Search

Aluminum and Fe3O4 reacts readily in what is known as thermite reaction to produce large amount of heat. Attempts were made to coat Fe-oxide on A319 cast aluminum alloy employing a high power laser to exploit this reaction. High-speed, high-resolution infrared thermography was employed to study the thermal conditions during the laser treatment. Parallel experiment using a less exothermic oxide

S. Nayak; Hsin Wang; Edward A. Kenik; Ian M. Anderson; Narendra B. Dahotre



Mechanism of the quenching of the tris(bipyridine)ruthenium(II) emission by persulfate: implications for photoinduced oxidation reactions.  


A revised mechanism for the oxidation of the excited state of Ru(bpy)3(2+) with the persulfate anion is described in this work. The formation of the precursor complex in the electron transfer reaction involves ion pairing between the metal complex in ground and excited states and S2O8(2-). The equilibrium constant for the ion-pair formation (K(IP) = 2.7 M(-1)) was determined from electrochemical measurements and analysis of thermal reaction between Ru(bpy)3(2+) and persulfate. It was found to be consistent with the calculated value estimated from the Debye-Hückel model. The analysis of rate constants for reactions between persulfate and various metal complexes indicates that thermal and photochemical reactions most likely proceed through a common pathway. Extremely high reorganization energy (ca. 3.54 eV) for the electron transfer obtained from fitting experimental data with the Marcus equation is indicative of significant nuclear reorganization during the electron transfer step. In view of these results the electron transfer can be described as dissociative probably involving substantial elongation or complete scission of the O-O bond. The proposed model accurately describes experimental results for the quenching of *Ru(bpy)3(2+) over a wide range of persulfate concentrations and resolves some discrepancies between the values of K(IP) and k(et) previously reported. The implications of various factors such as the ionic strength and dielectric constant of the medium are discussed in relation to measurements of the quantum yields in photodriven oxidation reactions employing the Ru(bpy)3(2+)/persulfate couple. PMID:24040757

Lewandowska-Andralojc, A; Polyansky, D E



Oxidation kinetics of reaction products formed in uranium metal corrosion.  

SciTech Connect

The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O{sub 2} and Ar-20%O{sub 2} were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates.

Totemeier, T. C.



Dynamic kinetic resolution of N-benzoyl-DL-amino acids via peptide bond forming reactions.  


Dynamic kinetic resolution (DKR) was demonstrated in the carbodiimide-mediated couplings of N-benzoyl-DL-amino acids with L-amino acid esters: the yields of the D-L-peptides significantly exceeded 50% in some cases. N-Benzoyl-DL-t-leucine afforded the D-L-peptide almost exclusively (up to 96% yield) in the reaction with methyl L-prolinate, which is the most efficient DKR obtained in the field of amino acids and derivatives. PMID:19508192

Miyazawa, T; Hamada, T



Hydroxyl Radical Recycling in Isoprene Oxidation Driven by Hydrogen Bonding and Hydrogen Tunneling: The Upgraded LIM1 Mechanism.  


The Leuven isoprene mechanism, proposed earlier to aid in rationalizing the unexpectedly high hydroxyl radical (OH) concentrations in isoprene-rich, low-nitric-oxide (NO) regions ( Peeters ; et al. Phys. Chem. Chem. Phys . 2009 , 11 , 5935 ), is presented in an upgraded and extended version, LIM1. The kinetics of the crucial reactions in the proposed isoprene-peroxy radical interconversion and isomerization pathways are re-evaluated theoretically, on the basis of energy barriers computed at the much higher CCSD(T)/aug-cc-pVTZ//QCISD/6-311G(d,p) level of theory, and using multiconformer partition functions obtained at the M06-2X/6-311++G(3df,2p) level that, different from the B3LYP level used in our earlier work, accounts for the crucial London dispersion effects in the H-bonded systems involved. The steady-state fraction of the specific Z-?-OH-peroxy radical isomers/conformers that can isomerize by a 1,6-H shift is shown to be largely governed by hydrogen-bond strengths, whereas their isomerization itself is found to occur quasi-exclusively by hydrogen atom tunneling. The isomer-specific Z-?-OH-peroxy 1,6-H-shift rate coefficients are predicted to be of the order of 1 s(-1) at 298 K, but the experimentally accessible bulk rate coefficients, which have to be clearly distinguished from the former, are 2 orders of magnitude lower due to the very low Z-?-OH-peroxy steady-state fractions that are only around or below 0.01 at low to moderate NO and depend on the peroxy lifetime. Two pathways subsequent to the peroxy radical 1,6-H shift are identified, the earlier predicted route yielding the photolabile hydroperoxy-methylbutenals (HPALDs), and a second, about equally important path, to dihydroperoxy-carbonyl peroxy radicals (di-HPCARP). Taking this into account, our predicted bulk peroxy isomerization rate coefficients are about a factor 1.8 higher than the available experimental results for HPALD production ( Crounse ; et al. Phys. Chem. Chem. Phys. 2011 , 13 , 13607 ), which is within the respective uncertainty margins. We also show that the experimental temperature dependence of the HPALD production rates as well as the observed kinetic isotope effect for per-deuterated isoprene support quantitatively our theoretical peroxy interconversion rates. Global modeling implementing LIM1 indicates that on average about 28% of the isoprene peroxys react via the 1,6-H-shift isomerization route, representing 100-150 Tg carbon per year. The fast photolysis of HPALDs we proposed earlier as primary OH regeneration mechanism ( Peeters and Muller . Phys. Chem. Chem. Phys . 2010 , 12 , 14227 ) found already experimental confirmation ( Wolfe ; et al. Phys. Chem. Chem. Phys. 2012 , 14 , 7276 ); based on further theoretical work in progress, reaction schemes are presented of the oxy coproduct radicals from HPALD photolysis and of the di-HPCARP radicals from the second pathway following peroxy isomerization that are both expected to initiate considerable additional OH recycling. PMID:25010574

Peeters, Jozef; Müller, Jean-François; Stavrakou, Trissevgeni; Nguyen, Vinh Son



Measurement of reaction enthalpy during pressure oxidation of sulphide minerals  

Microsoft Academic Search

A calorimetric method for determining the enthalpy of the aqueous oxidation of sulfide minerals at high temperatures and oxygen\\u000a pressures has been developed and evaluated under conditions relevant to industrial pressure oxidation operations. This information\\u000a is important for heat balance calculation and optimization of the pressure reactor design. Experiments were carried out on\\u000a a differential scanning calorimeter (DSC) with a

I. Bylina; L. Trevani; S. C. Mojumdar; P. Tremaine; V. G. Papangelakis



Molecular Orbital Studies of Zinc Oxide Chemical Vapor Deposition: Gas-Phase Radical Reactions  

E-print Network

, intermediate complexes, and products have been optimized with B3LYP/6-31G(d), and energetics have been computed were combined to give a G2(MP2)-like estimate of the enthalpy and free energy. Initiation reactions oxide nanostructures which have unique optical and electrical properties. Zinc oxide nanowires

Schlegel, H. Bernhard


Non-heme iron hydroperoxo species in superoxide reductase as a catalyst for oxidation reactions.  


The non-heme high-spin ferric iron hydroperoxo species formed in superoxide reductase catalyzes oxidative aldehyde deformylation through its nucleophilic character. This species also acts as an electrophile to catalyze oxygen atom transfer in sulfoxidation reactions, highlighting the oxidation potential of non-heme iron hydroperoxo species. PMID:25283601

Rat, S; Ménage, S; Thomas, F; Nivière, V




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...


Mechanism of the Heck reaction: nature of oxidative addition and alkene insertion  

E-print Network

stages of the Heck reaction suggest it should be. This study seeks to elucidate the nature of the oxidative addition of aryl halide to a palladium catalyst using a ligand that has been shown to have high activity in facilitating oxidative addition...

Evans, Anthony Steven



Structure Sensitivity of Photochemical Oxidation and Reduction Reactions on SrTiO3 Surfaces  

E-print Network

and water purifiers,4 ­ 6 self-cleaning surface treatments,7 and water photolysis catalysts8,9 are examples species. When these reactions occur on the surface of an oxide pigment particle embedded in a composite of photochemical reactions on BaTiO3 sur- faces indicate that internal dipolar fields can drive photogenerated

Rohrer, Gregory S.


Reaction of catalytic oxidation by liquid water and its application to waste water purification  

SciTech Connect

In this paper the results of experiments and some considerations of theoretical and practical problems devoted to a new type of chemical reaction--oxidation of organic substances by liquid water with the aid of noble metal catalyst--are given. Some problems of application such as reaction to self-purification of industrial waste waters are also considered.

Ioffe, I.I. [All-Union Inst. of Pulp and Paper Industry, Leningrad (Russian Federation)] [All-Union Inst. of Pulp and Paper Industry, Leningrad (Russian Federation); Rubinskaya, E.V. [All-Union Inst. of Petrochemical Processes, Leningrad (Russian Federation)] [All-Union Inst. of Petrochemical Processes, Leningrad (Russian Federation)



Development of a redox-free Mitsunobu reaction exploiting phosphine oxides as precursors to dioxyphosphoranes.  


The development of the first redox-free protocol for the Mitsunobu reaction is described. This has been achieved by exploiting triphenylphosphine oxide--the unwanted by-product in the conventional Mitsunobu reaction--as the precursor to the active P(V) coupling reagent. Multinuclear NMR studies are consistent with hydroxyl activation via an alkoxyphosphonium salt. PMID:24871529

Tang, Xiaoping; Chapman, Charlotte; Whiting, Matthew; Denton, Ross




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...


Studies on the thermal reactions of aluminium oxides and hydroxides  

Microsoft Academic Search

The gibbsite ??-alumina decomposition (in air) and the?-alumina ? boehmite transformation (under hydrothermal conditions) were investigated isothermally. Reaction products were characterized by TG and X-ray diffraction.

C. Novák; G. Pokol; K. Tomor; J. K?míves; S. Gál



Mechanical behavior of fiber reinforced SiC/RBSN ceramic matrix composites - Theory and experiment. [Reaction Bonded Silicon Nitride  

NASA Technical Reports Server (NTRS)

The mechanical behavior of continuous fiber reinforced SiC/RBSN (Reaction Bonded Silicon Nitride) composites with various fiber contents is evaluated. Both catastrophic and noncatastrophic failures are observed in tensile specimens. Damage and failure mechanisms are identified via in-situ monitoring using NDE (nondestructive evaluation) techniques throughout the loading history. Effects of fiber/matrix interface debonding (splitting) parallel to fibers are discussed. Statistical failure behavior of fibers is also observed, especially when the interface is weak. Micromechanical models incorproating residual stresses to calculate the critical matrix cracking strength, ultimate strength, and work of pull-out are reviewed and used to predict composite response. For selected test problems, experimental measurements are compared to analytical predictions.

Chulya, Abhisak; Gyekenyesi, John P.; Bhatt, Ramakrishna T.



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, Ramakrishna T.



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)




SciTech Connect

Our present understanding of the mechanisms of organometallic reactions stems almost completely from investigation of complexes containing only one metal. Recently interest has been increasing in the synthesis, structure elucidation and reaction mechanisms of polynuclear clusters, complexes containing more than one metal. This attention derives partially from the possibility that polynuclear catalysts and reagents might be designed in such a way that the metals could interact, generating cooperative systems which might be much more selective than their mononuclear analogs. Another stimulant to this work has been the relationship of cluster complexes to larger multi-metal systems, such as heterogeneous catalysts. Many polynuclear clusters have been prepared and characterized, and some of these have been found to function as unique catalysts or catalyst precursors. However, very little is yet known about how chemical transformations take place at multinuclear reaction centers. Given this paucity of information, they decided a few years ago to initiate mechanistic study of simple cluster systems containing two metal centers, in which each of the metals has a {sigma}-bound organic ligand attached to it. They also choose to focus on reactions of these complexes in which new carbon-carbon or carbon-hydrogen bonds are formed. This Account describes the work on such a system: a binuclear alkyl cobalt complex capable of transferring both alkyl groups to a molecule of carbon monoxide. In this work they have adopted as one of our highest priorities the determination of whether the cluster 'holds together' during its reactions, a question that is in our opinion too often ignored in such studies. They have found that isotope crossover experiments provide a powerful tool for investigating this structural integrity questions, and in this Account they outline a number of examples in which such crossover experiments have provided important, and occasionally surprising, informationa bout the mechanisms involved in the reactions of binuclear cluster complexes. Also summarized are studies of the reactions of related mononuclear complexes which have provided information critical to understanding the chemistry of these binuclear system.

Bergman, Robert G.



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



The aniline-to-azobenzene oxidation reaction on monolayer graphene or graphene oxide surfaces fabricated by benzoic acid.  


The oxidation of aniline to azobenzene was conducted in the presence of either monolayer graphene (EG) or graphene-oxide-like surface, such as GOx, under ultra-high vacuum conditions maintaining a 365-nm UV light exposure to enhance the oxidation reaction. The surface-bound products were investigated using micro Raman spectroscopy, high-resolution photoemission spectroscopy, and work function measurements. The oxygen carriers present on the GOx surfaces, but not on the EG surfaces, acted as reaction reagents to facilitate the oxidation reaction from aniline to azobenzene. Increasing the aniline concentration at 300 K confirmed that the exchange ratio from the aniline to the azobenzene was enhanced, as determined by the intensity ratio between the aniline- and azobenzene-induced N 1 s core-level spectra. The work function changed dramatically as the aniline concentration increased, indicating that the aniline on the GOx surface conveyed n-type doping characteristics at a low coverage level. A higher aniline concentration increased the p-type doping character by increasing the azobenzene concentration on the GOx surface. A comparison of the oxidation reactivity of aniline molecules on the EG or GOx surfaces revealed the role of the oxygen carriers on the GOx surfaces in the context of catalytic oxidation. PMID:24229051

Lee, Myungjin; Kim, Kijeong; Lee, Hangil



The aniline-to-azobenzene oxidation reaction on monolayer graphene or graphene oxide surfaces fabricated by benzoic acid  

PubMed Central

The oxidation of aniline to azobenzene was conducted in the presence of either monolayer graphene (EG) or graphene-oxide-like surface, such as GOx, under ultra-high vacuum conditions maintaining a 365-nm UV light exposure to enhance the oxidation reaction. The surface-bound products were investigated using micro Raman spectroscopy, high-resolution photoemission spectroscopy, and work function measurements. The oxygen carriers present on the GOx surfaces, but not on the EG surfaces, acted as reaction reagents to facilitate the oxidation reaction from aniline to azobenzene. Increasing the aniline concentration at 300 K confirmed that the exchange ratio from the aniline to the azobenzene was enhanced, as determined by the intensity ratio between the aniline- and azobenzene-induced N 1 s core-level spectra. The work function changed dramatically as the aniline concentration increased, indicating that the aniline on the GOx surface conveyed n-type doping characteristics at a low coverage level. A higher aniline concentration increased the p-type doping character by increasing the azobenzene concentration on the GOx surface. A comparison of the oxidation reactivity of aniline molecules on the EG or GOx surfaces revealed the role of the oxygen carriers on the GOx surfaces in the context of catalytic oxidation. PMID:24229051



Theoretical elucidation of a classic reaction: protonation of the quadruple bond of the octachlorodimolybdate(II,II) [Mo2Cl8]4- anion.  


The protonation reaction of the unbridged quadruple metal-metal bond of [Mo(2)Cl(8)](4-) anion producing the triply bonded hydride [Mo(2)(?-H)(?-Cl)(2)Cl(6)](3-) is studied by accurate Density Functional Theory computations. The reactant, product, stable intermediates, and transition states are located on the potential energy surface. The water solvent is explicitly included in the calculations. Full reaction profiles are calculated and compared to experimental data. The mechanism of the reaction is fully elucidated. This involves two steps. The first is a proton transfer from an oxonium ion to the quadruple bond, being rate determining. The second, involves the internal rearrangement of chlorine atoms and is much faster. Activation energies with a mean value of 19 kcal/mol are calculated, in excellent agreement with experimental values. PMID:22122199

Simandiras, Emmanuel D; Tsakiroglou, Metaxia; Psaroudakis, Nikolaos; Liakos, Dimitrios G; Mertis, Konstantinos



A Deeper Look into Thiophene Coordination Prior to Oxidative Addition of the C-S Bond to Platinum(0): A Computational Study  

E-print Network

A Deeper Look into Thiophene Coordination Prior to Oxidative Addition of the C-S Bond to Platinum(0 predict that the initial 2 -coordination of thiophene through the CdC double bond is energetically more favorable than coordination through the sulfur atom (G ) 9.3 kcal/mol). There are three well

Jones, William D.


Dopant local bonding and electrical activity near Si,,001...-oxide interfaces Zhiyong Zhou, Michael L. Steigerwald, Richard A. Friesner, and Louis Brus  

E-print Network

the forming gas interface passivation. In contrast, B and Al show tetrahedral bonding for all charge states P is more stable bonded to four Si atoms adjacent to the interface. © 2005 American Institute of dopants within a few silicon layers of the Si 001 -oxide interface. The control of the distribution


Rasta resin-triphenylphosphine oxides and their use as recyclable heterogeneous reagent precursors in halogenation reactions  

PubMed Central

Summary Heterogeneous polymer-supported triphenylphosphine oxides based on the rasta resin architecture have been synthesized, and applied as reagent precursors in a wide range of halogenation reactions. The rasta resin–triphenylphosphine oxides were reacted with either oxalyl chloride or oxalyl bromide to form the corresponding halophosphonium salts, and these in turn were reacted with alcohols, aldehydes, aziridines and epoxides to form halogenated products in high yields after simple purification. The polymer-supported triphenylphosphine oxides formed as a byproduct during these reactions could be recovered and reused numerous times with no appreciable decrease in reactivity. PMID:24991294

Xia, Xuanshu



Elementary Steps of Syngas Reactions on Mo2C(001): Adsorption Thermochemistry and Bond Dissociation  

SciTech Connect

Density functional theory (DFT) and ab initio thermodynamics are applied in order to investigate the most stable surface and subsurface terminations of Mo{sub 2}C(001) as a function of chemical potential and in the presence of syngas. The Mo-terminated (001) surface is then used as a model surface to evaluate the thermochemistry and energetic barriers for key elementary steps in syngas reactions. Adsorption energy scaling relations and Broensted-Evans-Polanyi relationships are established and used to place Mo{sub 2}C into the context of transition metal surfaces. The results indicate that the surface termination is a complex function of reaction conditions and kinetics. It is predicted that the surface will be covered by either C{sub 2}H{sub 2} or O depending on conditions. Comparisons to transition metals indicate that the Mo-terminated Mo{sub 2}C(001) surface exhibits carbon reactivity similar to transition metals such as Ru and Ir, but is significantly more reactive towards oxygen.

Medford, Andrew



Nano-Bonding of Silicon Oxides-based surfaces at Low Temperature: Bonding Interphase Modeling via Molecular Dynamics and Characterization of Bonding Surfaces Topography, Hydro-affinity and Free Energy  

NASA Astrophysics Data System (ADS)

In this work, a new method, "Nanobonding(TM)" [1,2] is conceived and researched to bond Si-based surfaces, via nucleation and growth of a 2 D silicon oxide SiOxHx interphase connecting the surfaces at the nanoscale across macroscopic domains. Nanobonding cross-bridges two smooth surfaces put into mechanical contact in an O2/H 2O mixed ambient below T ?200 °C via arrays of SiOxH x molecules connecting into a continuous macroscopic bonding interphase. Nano-scale surface planarization via wet chemical processing and new spin technology are compared via Tapping Mode Atomic Force Microscopy (TMAFM) , before and after nano-bonding. Nanobonding uses precursor phases, 2D nano-films of beta-cristobalite (beta-c) SiO2, nucleated on Si(100) via the Herbots-Atluri (H-A) method [1]. beta-c SiO2 on Si(100) is ordered and flat with atomic terraces over 20 nm wide, well above 2 nm found in native oxides. When contacted with SiO2 this ultra-smooth nanophase can nucleate and grow domains with cross-bridging molecular strands of hydroxylated SiOx, instead of point contacts. The high density of molecular bonds across extended terraces forms a strong bond between Si-based substrates, nano- bonding [2] the Si and silica. A new model of beta-cristobalite SiO2 with its <110> axis aligned along Si[100] direction is simulated via ab-initio methods in a nano-bonded stack with beta-c SiO2 in contact with amorphous SiO2 (a-SiO2), modelling cross-bridging molecular bonds between beta-c SiO2 on Si(100) and a-SiO2 as during nanobonding. Computed total energies are compared with those found for Si(100) and a-SiO2 and show that the presence of two lattice cells of !-c SiO2 on Si(100) and a-SiO2 lowers energy when compared to Si(100)/ a-SiO 2 Shadow cone calculations on three models of beta-c SiO2 on Si(100) are compared with Ion Beam Analysis of H-A processed Si(100). Total surface energy measurements via 3 liquid contact angle analysis of Si(100) after H-A method processing are also compared. By combining nanobonding experiments, TMAFM results, surface energy data, and ab-initio calculations, an atomistic model is derived and nanobonding is optimized. [1] US Patent 6,613,677 (9/2/03), 7,851,365 (12/14/10), [2] Patent Filed: 4/30/09, 10/1/2011

Whaley, Shawn D.


Advances in the electrochemical simulation of oxidation reactions mediated by cytochrome p450.  


Combining electrochemistry with mass spectrometry constitutes an increasingly useful approach for simulating reactions catalyzed by cytochrome P450 (CYP450). In this review, we discuss the ability of the electrochemical cell to act as a reliable tool to mimic CYP450. The electrochemical oxidation process and CYP450-catalyzed reactions are compared in terms of mechanistic pathways, chemical structures of reactive intermediate metabolites, and final chemical structures of oxidation products. The oxidation reactions mediated by CYP450 are known to occur by either a single electron transfer (SET) or a hydrogen atom transfer (HAT) mechanism. The similarities between the reactions mediated electrochemically or by CYP450 are discussed in terms of SET and HAT mechanisms. PMID:25285807

Bussy, Ugo; Boujtita, Mohammed



Reaction kinetics for the high temperature oxidation of Pu--1wt%Ga in water vapor  

SciTech Connect

Oxidation of plutonium metal is greatly accelerated by the presence of water vapor. The magnitude of the effect of water vapor on oxidation kinetics is determined by temperature, water concentration, and oxygen concentration. Most of the previous work has been directed toward evaluating the effect of moisture on the atmospheric oxidation of plutonium. Work on the isolation and characterization of the water reaction with plutonium has been very limited. The present work was undertaken to determine the kinetics of the plutonium--water reaction over a wide range of temperature and pressure. Reaction kinetics were measured using a vacuum microbalance system. The temperature range investigated was 100--500/degree/C. The effect of water vapor pressure on reaction kinetics was determined at 300/degree/C by varying the water pressure from 0.1 to 15 Torr. 2 figs.

Stakebake, J L; Saba, M A



Multiple reaction fronts in the oxidation-reduction of iron-rich uranium ores  

SciTech Connect

When a container of radioactive waste is buried underground, it eventually corrodes, and leakage of radioactive material to the surrounding rock occurs. Depending on the chemistry of the rock, many different reactions may occur. A particular case concerns the oxidation and reduction of uranium ores by infiltrating groundwater, since UO[sub 3] is relatively soluble (and hence potentially transportable to the water supply), whereas UO[sub 2] is essentially insoluble. It is therefore of concern to those involved with radioactive waste disposal to understand the mechanics of uranium transport through reduction and oxidation reactions. This paper describes the oxidation of iron-rich uranium-bearing rocks by infiltration of groundwater. A reaction-diffusion model is set up to describe the sequence of reactions involving iron oxidation, uranium oxidation and reduction, sulfuric acid production, and dissolution of the host rock that occur. On a geological timescale of millions of years, the reactions occur very fast in very thin reaction fronts. It is shown that the redox front that separates oxidized (orange) rock from reduced (black) rock must actually consist of two separate fronts that move together, at which the two separate processes of uranium oxidation and iron reduction occur, respectively. Between these fronts, a high concentration of uranium is predicted. The mechanics of this process are not specific to uranium-mediated redox reactions, but apply generally and may be used to explain the formation of concentrated ore deposits in extended veins. On the long timescales of relevance, a quasi-static response results, and the problem can be solved explicitly in one dimension. This provides a framework for studying more realistic two-dimensional problems in fissured rocks and also for the future study of uraninite nodule formation.

Dewynne, J.N. (Univ. of Southampton (United Kingdom). Faculty of Mathematical Studies); Fowler, A.C. (Oxford Univ. (United Kingdom). Mathematical Inst.); Hagan, P.S. (Los Alamos National Lab., NM (United States))



Catalytic C-CN bond activation.  


Synthetic organic reactions through C-CN activation by transition metal catalysis are reviewed. C-CN bond activation by metal complexes proceeds mainly via two pathways; oxidative addition and C-CN cleavage accompanied by silylisonitrile formation. Both the elemental reactions have been successfully applied to the catalytic reactions, including hydrodecyanation of nitriles, cross-coupling using nitriles as electrophiles, cyanation of aryl halides and arenes using organic nitriles as cyanating agents, and carbocyanation of unsaturated compounds. PMID:24549840

Nakao, Yoshiaki



Reactions of (Cp(CO) sub 2 Fe double bond CHAr) sup + (Ar = p-C sub 6 H sub 4 OMe) with O double bond N-Ar prime (Ar prime = C sub 6 H sub 5 , p-C sub 6 H sub 4 NMe sub 2 ) and PhN double bond NPh  

SciTech Connect

Organometallic products formed from the reaction of an electrophilic iron carbene complex with nitrosoarenes or azobenzene reflect net insertion of the ArN{double bond}X moiety into the Fe{double bond}CHAr bond. Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} and Cp(CO){sub 2}FeN(Ph)-N(Ph){double bond}CHAr{sup +} (Ar = p-C{sub 6}H{sub 4}OMe, Ar{prime} = p-C{sub 6}H{sub 4}NMe{sub 2}) have been isolated and spectroscopically characterized; the crystal structure of Cp(CO){sub 2}Fe-O-N(Ph){double bond}CHAr{sup +} is reported. Exposure of acetone solutions of Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} or Cp(CO){sub 2}FeN(Ph)-N(Ph){double bond}char{sup +} to light yields imine products Ar{prime}N{double bond}CHAr or PhN{double bond}CHAr, respectively. There is no evidence to support the formation of the simple stoichiometric iron-containing products of these reactions, the oxo and nitrene complexes Cp(CO){sub 2}Fe{double bond}O{sup +} and Cp(CO){sub 2}Fe{double bond}NPh{sup +}. Hydrolysis of the nitrone complexes Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} in aqueous acetone yields aldehyde products Ar{prime}CHO. 30 refs., 1 fig., 4 tabs.

Peng, Wei-Jun; Gamble, A.S.; Templeton, J.L.; Brookhart, M. (Univ. of North Carolina, Chapel Hill (USA))



Assessment of theoretical procedures for a diverse set of isomerization reactions involving double-bond migration in conjugated dienes  

NASA Astrophysics Data System (ADS)

We introduce a representative database of 60 accurate diene isomerization energies obtained by means of the high-level, ab initio Wn-F12 thermochemical protocols. The isomerization reactions involve a migration of one double bond that breaks the ?-conjugated system. The considered dienes involve a range of hydrocarbon functional groups, including linear, branched, and cyclic moieties. This set of benchmark isomerization energies allows an assessment of the performance of more approximate theoretical procedures for the calculation of ?-conjugation stabilization energies in dienes. We evaluate the performance of a large number of density functional theory (DFT) and double-hybrid DFT (DHDFT) procedures. We find that, with few exceptions (most notably BMK-D3 and M05-2X), conventional DFT procedures have difficulty describing reactions of the type: conjugated diene ? non-conjugated diene, with root mean square deviations (RMSDs) between 4.5 and 11.7 kJ mol-1. However, DHDFT procedures show excellent performance with RMSDs well below the ‘chemical accuracy’ threshold.

Yu, Li-Juan; Karton, Amir



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

NASA Astrophysics Data System (ADS)

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 ?-SiC and BNi-5 powders. Both methods resulted in the liquid filler metal forming a Ni-Si liquid with the free Si in the RBSC, which, in turn, reacted vigorously with the SiC component of the RBSC to form low melting point constituents in both starting materials and Cr carbides at the metal-ceramic interface. Using solution thermodynamics, it was shown that a Ni-Si liquid of greater than 60 at. pct Ni will decompose a-SiC at the experimental brazing temperature of 1200 ‡C; these calculations are consistent with the experimentally observed composition profiles and reaction morphology within the ceramic. It was concluded that the joining of RBSC to INCONEL 600 using a nickel-based brazing alloy is not feasible due to the inevitability of the filler metal reacting with the ceramic, degrading the high-temperature properties of the base materials.

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



The oxidative dechlorination reaction of 2,4,6-trichlorophenol in dilute aqueous suspensions of manganese oxides  

SciTech Connect

Oxidation of 2,4,6-trichlorophenol (TCP) by layered manganese oxides (Na and Co-buserite) in dilute acidified aqueous suspension gives 2,6-dichloro-p-benzoquinone as a major product. This compound is likely to further polymerize and become incorporated into humus like materials. The oxidation rate was higher at lower pH and higher on Na-buserite compared to Co-buserite. TCP reacted at a faster rate than unsubstituted phenol at pH3 and 5.5, which is explained by (a) the lower half-wave potential of TCP compared to phenol; (b) a stronger bond dipole associated with the electronegative halogen, favoring an addition step in nucleophilic substitution; and (c) easier depronation of TCP at the manganese oxide-water interface due to its lower pK[sub a]. IR spectroscopy shows that TCP adsorbs in deprotonated form on the surface of manganese oxide, and it cannot be washed from the surface by water. Nucleophilic attack by addition-elimination is suggested as a mechanism of TCP dechlorination and oxidation.

Ukrainczyk, L.; McBride, M.B. (Cornell Univ., Ithaca, NY (United States). Dept. of Soil, Crop and Atmospheric Sciences)



Theoretical study of reactions of HO{sub 2} in low-temperature oxidation of benzene  

SciTech Connect

We have generated a set of thermodynamic and kinetic parameters for the reactions involving HO{sub 2} in the very early stages of benzene oxidation at low temperatures using density functional theory (DFT). In particular, we report the rate constants for the reactions of HO{sub 2} with benzene and phenyl. The calculated reaction rate constant for the abstraction of H-C{sub 6}H{sub 5} by HO{sub 2} is found to be in good agreement with the limited experimental values. HO{sub 2} addition to benzene is found to be more important than direct abstraction. We show that the reactions of HO{sub 2} with the phenyl radical generate the propagating radical OH in a highly exoergic reaction. The results presented herein should be useful in modeling the oxidation of aromatic compounds at low temperatures. (author)

Altarawneh, Mohammednoor [Chemical Engineering Department, Al-Hussein Bin Talal University, Ma'an (Jordan); Dlugogorski, Bogdan Z.; Kennedy, Eric M.; Mackie, John C. [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia)



Microstructures of brazed and solid-state diffusion bonded joints of tungsten with oxide dispersion strengthened steel  

NASA Astrophysics Data System (ADS)

The brazed and solid-state diffusion bonded (SSDB) joints of tungsten with oxide dispersion strengthened (ODS) steel were fabricated to use ODS steels as a structure component of first wall with tungsten as a plasma facing material in fusion blankets. Particular attention was paid to changes in the microstructure and chemical compositions in the bonding region. W was found to diffuse significantly into ODS steel, whereas there was only a limited diffusion of Fe and Cr from the ODS steel into W; these results are consistent with the diffusivity of each element. Interdiffusion multi-layer containing a layer with high concentration of B and of C was produced in the brazed joint and the SSDB joint, respectively.

Oono, Naoko; Noh, Sanghoon; Iwata, Noriyuki; Nagasaka, Takuya; Kasada, Ryuta; Kimura, Akihiko



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.



Oxidative cyclodehydrogenation reaction for the design of extended 2D and 3D carbon nanostructures: A theoretical study  

NASA Astrophysics Data System (ADS)

We present a theoretical study on the main mechanistic features of the oxidative cyclodehydrogenation reaction of oligophenylene precursors affording the planar corresponding fully benzenoid, planar polycyclic aromatic hydrocarbons (BPAHs), molecular nanostructures of emerging interest in the field of nanotechnology. We firstly consider the transformation of o-terphenyl molecules, C 18H 14, into triphenylene, C 18H 12. Then, our calculations are extended to the primary ring-closure processes promoted in hexaphenylbenzene molecules, C 42H 30, via the same reactive approach which is experimentally known to yield hexa- peri-hexabenzocoronene, C 42H 18, as final product. To predict reliable reaction mechanisms, the critical points on the potential energy surfaces of interest are studied by using density functional theory with the hybrid functional B3LYP and the 3-21G basis set. Particular attention is paid to the role that radical cation intermediates may play in this reaction. The study suggests a step by step mechanism in which the new C-C bonds are formed and dehydrogenated one at a time until the final fully benzenoid product is obtained. The conclusions drawn from these preliminary investigations form the basis for a more thorough understanding of the synthetic strategy leading to much larger and complex conjugated carbon nanostructures.

Di Stefano, Marco; Negri, Fabrizia; Carbone, Paola; Müllen, Klaus



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)



Synthesis of Morphology Controlled Aluminum Oxide by Hydrothermal Reaction  

NASA Astrophysics Data System (ADS)

Plate-like and wire-like aluminum oxides were successfully synthesized by hydrothermal method without any template additives. Al(NO3)3·9H2O aqueous solution and precipitator were mixed and introduced to a Teflon lined autoclave, followed by heat treatment at 200°C for 24 h. By controlling the concentration of starting material and precipitator, the products with different morphologies were selectively obtained, i.e., the 2-dimensional platelike particles with a diameter of about 8?m were synthesized at low aluminum concentration (0.1 mol/L), while 1-dimensional wire-like products of about 10?m in length were synthesized at high aluminum concentration (0.2 mol/L). The plate-like particles and wire-like particles consisted of single phase of aluminum oxide hydroxide (boehmite, AlOOH) and the sodium aluminate, respectively.

Yang, L.; Yin, S.; Sato, T.



Synthesis of Morphology Controlled Aluminum Oxide by Hydrothermal Reaction  

Microsoft Academic Search

Plate-like and wire-like aluminum oxides were successfully synthesized by hydrothermal method without any template additives. Al(NO3)3·9H2O aqueous solution and precipitator were mixed and introduced to a Teflon lined autoclave, followed by heat treatment at 200°C for 24 h. By controlling the concentration of starting material and precipitator, the products with different morphologies were selectively obtained, i.e., the 2-dimensional platelike particles

L. Yang; S. Yin; T. Sato



Extraordinary hydrogen evolution and oxidation reaction activity from carbon nanotubes and graphitic carbons.  


The hydrogen evolution reaction, 2H(+) + 2e(–) ? H2, and its converse, the hydrogen oxidation reaction, H2 ? 2H(+) + 2e(–), are central to any realization of a hydrogen economy. Various forms of carbon have been used for decades as the precious metal catalyst support in these reactions. Here we report the unexpected result that single-wall carbon nanotubes and some graphitic carbons, activated by brief exposure to electrochemical potentials that induce hydrogen evolution in intercalating acids combined with extended soak times in such acids, acquire an activity for these reactions that exceeds that of known nonprecious metal catalysts. PMID:25017805

Das, Rajib Kumar; Wang, Yan; Vasilyeva, Svetlana V; Donoghue, Evan; Pucher, Ilaria; Kamenov, George; Cheng, Hai-Ping; Rinzler, Andrew G



Catalytic constructive deoxygenation of lignin-derived phenols: new C-C bond formation processes from imidazole-sulfonates and ether cleavage reactions.  


As part of a programme aimed at exploiting lignin as a chemical feedstock for less oxygenated fine chemicals, several catalytic C-C bond forming reactions utilising guaiacol imidazole sulfonate are demonstrated. These include the cross-coupling of a Grignard, a non-toxic cyanide source, a benzoxazole, and nitromethane. A modified Meyers reaction is used to accomplish a second constructive deoxygenation on a benzoxazole functionalised anisole. PMID:25130565

Leckie, Stuart M; Harkness, Gavin J; Clarke, Matthew L



Unusual carbon-sulfur bond cleavage in the reaction of a new type of bulky hexathioether with a zerovalent palladium complex.  


The reaction of a bulky hexathioether, TbtS(o-Phen)S(o-Phen)SS(o-Phen)S(o-Phen)STbt (o-Phen = o-phenylene, Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl) (1), with 3 molar amounts of Pd(PPh3)4 afforded trinuclear palladium complex bridged by two benzenedithiolato ligands via a three-step palladium insertion reaction into one sulfur-sulfur and two carbon-sulfur bonds of 1. PMID:16372097

Shimizu, Daisuke; Takeda, Nobuhiro; Tokitoh, Norihiro



The oxidative inactivation of cytochrome P450 in monooxygenase reactions.  


Possible mechanisms of cytochrome P450 self-inactivation during catalytic turnover have been considered. Two ways of hemoprotein inactivation are so far known. The first, studied extensively by many authors, is the formation of active substrate intermediates, capable of modifying heme and apoenzyme. The second way, revealed quite recently and resulting from uncoupled cytochrome P450-catalyzed monooxygenase reactions, is yet to be clarified. Briefly, it involves formation of hydrogen peroxide in the hemoprotein active center, which interacts with the enzyme associated Fe2+, thereby generating hydroxyl radicals that bleach the heme and modify the apoenzyme. This mechanism operates with substrates and cytochrome P450 forms with partially coupled monooxygenase reactions, thus causing the formation of hydrogen peroxide as a byproduct. PMID:8299999

Karuzina, I I; Archakov, A I



Revealing different bonding modes of self-assembled octadecylphosphonic acid monolayers on oxides by time-of-flight secondary ion mass spectrometry: silicon vs aluminum.  


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



Probing ligand effects on O-O bond formation of Ru-catalyzed water oxidation: a computational survey.  


Ligand effects of some representative monomeric Ru-based water oxidation catalysts on the key O-O formation step are revealed in this work. Three effects, namely, cis-effect, net charge effect, and steric hindrance effect, are identified, which can exert sizable modulation on the O-O formation barriers for the two widely accepted O-O formation mechanisms of WNA (water nucleophilic attack) and I2M (direct coupling of two high-valent metal oxo units). The study demonstrates that, through the way of ligand design, there remains a large space for improving O-O bond formation reactivity. PMID:24968205

Kang, Runhua; Chen, Kejuan; Yao, Jiannian; Shaik, Sason; Chen, Hui



Palladium(II)-catalyzed dehydrogenative cross-coupling between two C(sp3)-H bonds: unexpected C=C bond formation.  


C=C bond construction: A palladium-catalyzed oxidative C(sp3)-H/C(sp3)-H cross-coupling is shown to forge C=C bonds rather than C(sp3)-C(sp3) bonds through reactions of indolin-2-ones or benzofuran-2-ones with O-benzoyl hydroxylamines in the absence of an added oxidant. PMID:23780778

Li, Gaocan; Qian, Shengyou; Wang, Chunxia; You, Jingsong



Short-step synthesis of tamoxifen and its derivatives via the three-component coupling reaction and migration of the double bond  

Microsoft Academic Search

The anti-tumor agent, tamoxifen, is easily synthesized by the successive allylation of benzaldehyde and the Friedel–Crafts alkylation reaction of anisole with the intermediary homoallyl silyl ethers, followed by the migration of the double bond to form the desired tetra-substituted ethylenes. Several derivatives of tamoxifen are also produced according to a similar synthetic strategy.

Isamu Shiina; Masahiko Suzuki; Kazutoshi Yokoyama



Metal-free aerobic oxidative C-N bond cleavage of tertiary amines for the synthesis of N-heterocycles with high atom efficiency.  


An efficient metal-free aerobic oxidative C-N bond cleavage of tertiary amines has been developed to construct N-heterocycles using molecular oxygen as the sole oxidant with high atom efficiency, in which all of the three alkyl groups in tertiary amines can be utilized and transformed into N-heterocycles. PMID:24788750

Chen, Xiuling; Chen, Tieqiao; Zhou, Yongbo; Han, Daoqing; Han, Li-Biao; Yin, Shuang-Feng



Oxidation of glycine by Phaseolus leghaemoglobin with associated catabolic reactions at the haem.  

PubMed Central

Leghaemoglobin from the root nodules of kidney bean (Phaseolus vulgaris) reacts in alkaline glycine solutions as a glycine oxidase in a reaction that may also be regarded as a coupled oxidation. Leghaemoglobin is reduced to the ferrous form by glycinate, the oxygen complex is formed, and finally the haem is attacked to yield a green reaction product. Glycine is simultaneously oxidized to glyoxylate, and hydrogen peroxide is generated. The initial velocity of the formation of the green product is proportional to the concentrations of leghaemoglobin and glycine, and the optimum pH for the reaction is 10.2. The green product is not formed if carbon monoxide, azide of imidazole is bound to the haem, whereas oxidation of glycine to glyoxylate is not inhibited by azide and not essentially by carbon monoxide. Haem breakdown is activated by digestion of leghaemoglobin by carboxypeptidase, and partly inhibited by catalase and superoxide dismutase. PMID:743243

Lehtovaara, P



Iridium Complexes Containing Mesoionic C Donors: Selective C(sp(3) )?H versus C(sp(2) )?H Bond Activation, Reactivity Towards Acids and Bases, and Catalytic Oxidation of Silanes and Water.  


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 Na2 CO3 , 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



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.



Classification of metal-oxide bonded interactions based on local potential-and kinetic-energy densities  

E-print Network

as shared covalent bonds. C­O and S­O bonded interactions classify as both intermediate and covalent bonded with a substantial component of covalent character and the C­O single-bonded interaction classifies as a covalent bond whereas their local electronic energy density values indicate that they are each covalent bonded

Crawford, T. Daniel


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



Scope and mechanistic study of the ruthenium-catalyzed ortho-C-H bond activation and cyclization reactions of arylamines with terminal alkynes.  


The cationic ruthenium hydride complex [(PCy(3))(2)(CO)(CH(3)CN)(2)RuH](+)BF(4)(-) was found to be a highly effective catalyst for the C-H bond activation reaction of arylamines and terminal alkynes. The regioselective catalytic synthesis of substituted quinoline and quinoxaline derivatives was achieved from the ortho-C-H bond activation reaction of arylamines and terminal alkynes by using the catalyst Ru(3)(CO)(12)/HBF(4).OEt(2). The normal isotope effect (k(CH)/k(CD) = 2.5) was observed for the reaction of C(6)H(5)NH(2) and C(6)D(5)NH(2) with propyne. A highly negative Hammett value (rho = -4.4) was obtained from the correlation of the relative rates from a series of meta-substituted anilines, m-XC(6)H(4)NH(2), with sigma(p) in the presence of Ru(3)(CO)(12)/HBF(4).OEt(2) (3 mol % Ru, 1:3 molar ratio). The deuterium labeling studies from the reactions of both indoline and acyclic arylamines with DCCPh showed that the alkyne C-H bond activation step is reversible. The crossover experiment from the reaction of 1-(2-amino-1-phenyl)pyrrole with DCCPh and HCCC(6)H(4)-p-OMe led to preferential deuterium incorporation to the phenyl-substituted quinoline product. A mechanism involving rate-determining ortho-C-H bond activation and intramolecular C-N bond formation steps via an unsaturated cationic ruthenium acetylide complex has been proposed. PMID:16316246

Yi, Chae S; Yun, Sang Young



Protein-Cofactor Interactions in Bacterial Reaction Centers from Rhodobacter sphaeroides R-26: I. Identification of the ENDOR Lines Associated with the Hydrogen Bonds to the Primary Quinone Q A ? ?  

Microsoft Academic Search

Hydrogen bonds are important in determining the structure and function of biomolecules. Of particular interest are hydrogen bonds to quinones, which play an important role in the bioenergetics of respiration and photosynthesis. In this work we investigated the hydrogen bonds to the two carbonyl oxygens of the semiquinone QA?? in the well-characterized reaction center from the photosynthetic bacterium Rhodobacter sphaeroides

M. Flores; R. Isaacson; E. Abresch; R. Calvo; W. Lubitz; G. Feher



Computerized infrared spectroscopic study of surface reactions on selected lanthanide oxides  

Microsoft Academic Search

The natures of adsorption sites on LaâOâ, NdâOâ, and selected praseodymium oxides were investigated by examining surface reactions of probe molecules using computerized transmission ir spectroscopy on unsupported samples. Additionally, the rehydration\\/dehydration behavior and crystallographic phase transitions of these oxides were examined in pretreatment temperature experiments involving rehydration of the sesquioxides to hydroxides by water exposure. Following rehydration of LaâOâ




Kinetics of the reactions of carbon containing zinc oxide composites under microwave irradiation  

Microsoft Academic Search

As a fundamental study for the recycling of EAF dust using microwave heating, the reduction rate of a zinc oxide composite\\u000a by solid carbon under microwave irradiation was investigated. It was found that the reduction of zinc oxide by solid carbon\\u000a under microwave irradiation was much faster than the conventional method, and the activation energy for the reaction under\\u000a microwave

Eunju Kim; Seungyoun Cho; Joonho Lee



Permanganate oxidation of arsenic(III): Reaction stoichiometry and the characterization of solid product  

Microsoft Academic Search

Permanganate (MnO4?) has widely been used as an effective oxidant for drinking water treatment systems, as well as for in situ treatment of groundwater impacted by various organic contaminants. The reaction stoichiometry of As(III) oxidation by permanganate has been assumed to be 1.5, based on the formation of solid product, which is putatively considered to be MnO2(s). This study determined

Giehyeon Lee; Kyungsun Song; Jongseong Bae



Kinetics of the electrochemical oxidation of organic compounds at BDD anodes: modelling of surface reactions  

Microsoft Academic Search

This paper presents the results of a numerical study of the kinetics of electrochemical oxidation of different organic substances\\u000a at boron doped diamond (BDD).\\u000a \\u000a It is well established that oxidation of organics at BDD anodes takes place in the potential region of oxygen evolution, through\\u000a reaction steps in which OH radicals are involved: these radicals can react with organic compounds

Michele Mascia; Annalisa Vacca; Simonetta Palmas; Anna Maria Polcaro



Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.  


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



The water dissociation reaction on clean and oxidized iron (110)  

NASA Astrophysics Data System (ADS)

The interaction of H2O with the clean Fe(110) surface, Fe(110) surfaces with absorbed oxygen, and Fe(110) surfaces after bulk oxygen penetration were investigated using UPS. At 225 K, surface absorbed hydroxyl groups are present on all surfaces studied. On initially clean Fe(110) and surfaces with up to half monolayer of absorbed oxygen, heating the hydroxyl layer produced at 225 to 360 K causes hydrogen and water desorption and additional oxygen deposition relative to the starting surface. Beyond one-half monolayer of initial oxygen coverage, dehydroxylation proceeded exclusively via water desorption with the quantitative restoration of the initial surface composition. These results demonstrate that the (110) surface of iron is passive toward oxidation by water alone below 360 K, after the first monolayer.

Dwyer, D. J.; Kelemen, S. R.; Kaldor, A.



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



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.



¹?F magnetic resonance probes for live-cell detection of peroxynitrite using an oxidative decarbonylation reaction.  


We report a newly discovered oxidative decarbonylation reaction of isatins that is selectively mediated by peroxynitrite (ONOO(-)) to provide anthranilic acid derivatives. We have harnessed this rapid and selective transformation to develop two reaction-based probes, 5-fluoroisatin and 6-fluoroisatin, for the low-background readout of ONOO(-) using (19)F magnetic resonance spectroscopy. 5-fluoroisatin was used to non-invasively detect ONOO(-) formation in living lung epithelial cells stimulated with interferon-? (IFN-?). PMID:25180249

Bruemmer, Kevin J; Merrikhihaghi, Sara; Lollar, Christina T; Morris, Siti Nur Sarah; Bauer, Johannes H; Lippert, Alexander R



Yttrium oxide/gadolinium oxide-modified platinum nanoparticles as cathodes for the oxygen reduction reaction.  


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



Journal of Photochemistry and Photobiology A: Chemistry 185 (2007) 301311 Photodriven reduction and oxidation reactions on colloidal semiconductor  

E-print Network

and oxidation reactions on colloidal semiconductor particles: Implications for prebiotic synthesis Xiang V. 1). Zinc sulfide, a semiconductor which occurs in nature as the minerals sphalerite and wurtzite