Elucidating the oxide growth mechanism on platinum at the cathode in PEM fuel cells.

PubMed

Redmond, Erin L; Setzler, Brian P; Alamgir, Faisal M; Fuller, Thomas F

2014-03-21

Simulations of platinum oxidation in literature have yet to fully replicate an experimental cyclic voltammogram. In this manuscript a mechanism for platinum oxidation is proposed based upon the results of in operando X-ray absorption spectroscopy, where it was found that PtO2 is present at longer hold times. A new method to quantify extended X-ray absorption fine structure data is presented, and the extent of oxidation is directly compared to electrochemical data. This comparison indicated that PtO2 was formed at the expense of an initial oxide species. From previous literature studies it can be concluded that the rate of platinum oxidation is not a function of only potential and coverage. To that end, the concept of a heterogeneous oxide layer was introduced into the model, whereby place-exchanged PtO2 structures of varying energy states are formed through a single transition state. This treatment allowed, for the first time, the simulation of the correct current-potential behavior at varying scan rates and upper potential limits.

A proton-NMR investigation of the fully reduced cytochrome c7 from Desulfuromonas acetoxidans. Comparison between the reduced and the oxidized forms.

PubMed

Assfalg, M; Banci, L; Bertini, I; Bruschi, M; Giudici-Orticoni, M T; Turano, P

1999-12-01

The solution structure via 1H NMR of the fully reduced form of cytochrome c7 has been obtained. The protein sample was kept reduced by addition of catalytic amounts of Desulfovibrio gigas iron hydrogenase in H2 atmosphere after it had been checked that the presence of the hydrogenase did not affect the NMR spectrum. A final family of 35 conformers with rmsd values with respect to the mean structure of 8.7 +/- 1.5 nm and 12.4 +/- 1.3 nm for the backbone and heavy atoms, respectively, was obtained. A highly disordered loop involving residues 54-61 is present. If this loop is ignored, the rmsd values are 6.2 +/- 1.1 nm and 10.2 +/- 1.0 nm for the backbone and heavy atoms, respectively, which represent a reasonable resolution. The structure was analyzed and compared with the already available structure of the fully oxidized protein. Within the indetermination of the two solution structures, the result for the two redox forms is quite similar, confirming the special structural features of the three-heme cluster. A useful comparison can be made with the available crystal structures of cytochromes c3, which appear to be highly homologous except for the presence of a further heme. Finally, an analysis of the factors affecting the reduction potentials of the heme irons was performed, revealing the importance of net charges in differentiating the reduction potential when the other parameters are kept constant.

Biological iron oxidation by Gallionella spp. in drinking water production under fully aerated conditions.

PubMed

de Vet, W W J M; Dinkla, I J T; Rietveld, L C; van Loosdrecht, M C M

2011-11-01

Iron oxidation under neutral conditions (pH 6.5-8) may be a homo- or heterogeneous chemically- or a biologically-mediated process. The chemical oxidation is supposed to outpace the biological process under slightly alkaline conditions (pH 7-8). The iron oxidation kinetics and growth of Gallionella spp. - obligatory chemolithotrophic iron oxidizers - were assessed in natural, organic carbon-containing water, in continuous lab-scale reactors and full-scale groundwater trickling filters in the Netherlands. From Gallionella cell numbers determined by qPCR, balances were made for all systems. The homogeneous chemical iron oxidation occurred in accordance with the literature, but was retarded by a low water temperature (13 °C). The contribution of the heterogeneous chemical oxidation was, despite the presence of freshly formed iron oxyhydroxides, much lower than in previous studies in ultrapure water. This could be caused by the adsorption of natural organic matter (NOM) on the iron oxide surfaces. In the oxygen-saturated natural water with a pH ranging from 6.5 to 7.7, Gallionella spp. grew uninhibited and biological iron oxidation was an important, and probably the dominant, process. Gallionella growth was not even inhibited in a full-scale filter after plate aeration. From this we conclude that Gallionella spp. can grow under neutral pH and fully aerated conditions when the chemical iron oxidation is retarded by low water temperature and inhibition of the autocatalytic iron oxidation. Copyright © 2011 Elsevier Ltd. All rights reserved.

Electron-transfer and acid-base properties of a two-electron oxidized form of quaterpyrrole that acts as both an electron donor and an acceptor.

PubMed

Zhang, Min; E, Wenbo; Ohkubo, Kei; Sanchez-Garcia, David; Yoon, Dae-Wi; Sessler, Jonathan L; Fukuzumi, Shunichi; Kadish, Karl M

2008-02-21

Electron-transfer interconversion between the four-electron oxidized form of a quaterpyrrole (abbreviated as P4 for four pyrroles) and the two-electron oxidized form (P4H2) as well as between P4H2 and its fully reduced form (P4H4) bearing analogous substituents in the alpha- and beta-pyrrolic positions was studied by means of cyclic voltammetry and UV-visible spectroelectrochemistry combined with ESR and laser flash photolysis measurements. The two-electron oxidized form, P4H2, acts as both an electron donor and an electron acceptor. The radical cation (P4H2*+) and radical anion (P4H2*-) are both produced by photoinduced electron transfer from dimeric 1-benzyl-1,4-dihydronicotinamide to P4H2, whereas the cation radical form of the compound is also produced by electron-transfer oxidation of P4H2 with [Ru(bpy)3]3+. The ESR spectra of P4H2*+ and P4H2*- were recorded at low temperature and exhibit spin delocalization over all four pyrrole units. Thus, the two-electron oxidized form of the quaterpyrrole (P4H2) displays redox and electronic features analogous to those seen in the case of porphyrins and may be considered as a simple, open-chain model of this well-studied tetrapyrrolic macrocycle. The dynamics of deprotonation from P4H2*+ and disproportionation of P4H2 were examined by laser flash photolysis measurements of photoinduced electron-transfer oxidation and reduction of P4H2, respectively.

In situ observation of the formation of hollow zinc oxide shells

DOE PAGES

Tringe, J. W.; Levie, H. W.; El-Dasher, B. S.; ...

2011-06-14

Single crystal zinc particles, 1–2 μm1–2 μm in diameter, were observed in situ with transmission electron microscopy during sublimation. The rate of sublimation is strongly dependent on the presence of a surface oxide layer. Near 375°, minimally oxidized Zn surfaces sublime in tens of seconds, consistent with a model in which the particle behaves similarly to an isolated microscale effusion cell. By contrast, zinc particles fully enclosed by oxide sublime less than one-tenth as quickly. Here these results provide new insight into the synthesis mechanisms of hollow ZnO microspheres and related structures formed from metallic zinc at elevated temperatures.

Iminium salts and their derivatives as models for catalytic water oxidation

NASA Astrophysics Data System (ADS)

Khatmullin, Renat R.

The solar energy utilization is one of the most promising strategies for catering the ever-increasing energy demand in a renewable manner. For this reason, several approaches are pursued for solar energy storage, one of which involves the photocatalytic splitting of water. Over recent years, much research has been directed towards the design of transition-metal based water oxidation catalysts to obtain oxygen based on transition metal complexes. The major drawback of most of these catalysts is the cost of transition- metal complexes. For these reasons, the main focus of our research is based on the design of a fully organic catalyst suitable for water oxidation. Our group recently discovered that a flavinium ion performs electrode-mediated electrocatalytic water oxidation at large overpotentials. It was found that catalysis occurs only in the presence of the electrodes that produce active oxides on their surfaces. The mechanism of the catalysis by the flavinium ions was proposed to involve the coupling reaction two oxygen-centered radicals, one of which is derived from to the flavin moiety and the other one is formed at the electrode surface. The electrochemical oxidation of the formed peroxide species then proposed to release the oxygen molecule and recover the catalyst. However, it is important to note, that the detailed study of the mechanism is limited due the fact that electrode participates in the catalytic cycle. For these reasons, it is crucial to develop a fully homogeneous system to study the mechanism of the catalysis. One approach towards a fully molecular catalysis involves a system composed of two- iminium ion moieties joined covalently by a suitable linker. The mechanism of a catalysis is proposed to involve four individual steps: (i) pseudobase formation via a reaction of flavinium ions with water; (ii) proton-coupled oxidation of pseudobases to generate alkoxyl radicals; (iii) coupling of alkoxyl radicals to generate the peroxide intermediate; (iv) two-electron oxidation of the peroxide to release molecular oxygen and regenerate the catalyst. Therefore, we decided to study each individual step of the proposed mechanism above in great detail. A series of iminium salts and their pseudobases were synthesized. It was found that the efficiency of a pseudobase formation depends on the nature of heterocyclic ion and the nature of substituents bound to it. The proton-coupled electrocatalytic oxidation of pseudobases was studied using cyclic voltammetry. We found that the deprotonation of the amine radical cation formed after one-electron oxidation of pseudobase derivative occurs via two competing pathways: OH vs. C-H deprotonation. To elucidate the side responsible for C-H deprotonation event we synthesized the methoxy derivatives of iminium ions since these compounds do not contain an O-H proton. Additionally, to investigate the general chemistry of the alkoxyl radicals, we prepared 2- ethyl-4-nitroisoquinolinium hydroperoxide. Since hydroperoxides also tend to form alkoxyl radicals upon the decomposition, we decided to investigate the thermal behavior of 2-ethyl-4-nitroisoquinolinium hydroperoxide. The thermal decomposition was investigated using steady-state UV/Vis and NMR spectroscopy. Finally in order to study the two electron-oxidation processes of peroxide leading to the formation of oxygen we report the modified procedures for the synthesis of symmetric peroxide xanthrene based moiety.

Preliminary crystallographic analysis of the oxidized form of a two mono-nuclear iron centres protein from Desulfovibrio desulfuricans ATCC 27774.

PubMed Central

Coelho, A. V.; Matias, P. M.; Carrondo, M. A.; Tavares, P.; Moura, J. J.; Moura, I.; Fülop, V.; Hajdu, J.; Le Gall, J.

1996-01-01

Crystals of the fully oxidized form of desulfoferrodoxin were obtained by vapor diffusion from a solution containing 20% PEG 4000, 0.1 M HEPES buffer, pH 7.5, and 0.2 M CaCl2. Trigonal and/or rectangular prisms could be obtained, depending on the temperature used for the crystal growth. Trigonal prisms belong to the rhombohedral space group R32, with a = 112.5 A and c = 63.2 A; rectangular prisms belong to the monoclinic space group C2, with a = 77.7 A, b = 80.9 A, c = 53.9 A, and beta = 98.1 degrees. The crystallographic asymmetric unit of the rhombohedral crystal form contains one molecule. There are two molecules in the asymmetric unit of the monoclinic form, in agreement with the self-rotation function. PMID:8762151

Photon-induced oxidation of graphene/Ir(111) by SO2 adsorption

NASA Astrophysics Data System (ADS)

Böttcher, Stefan; Vita, Hendrik; Horn, Karsten

2015-11-01

We prepare a single layer of graphene oxide by adsorption and subsequent photo-dissociation of SO2 on graphene/Ir(111). Epoxidic oxygen is formed as the main result of this process on graphene, as judged from the appearance of characteristic spectroscopic features in the C 1s and O 1s core level lines. The different stages of decomposition of SO2 into its photo-fragments are examined during the oxidation process. NEXAFS at the carbon K edge reveals a strong disturbance of the graphene backbone after oxidation and upon SO adsorption. The oxide phase is stable up to room temperature, and is fully reversible upon annealing at elevated temperatures. A band gap opening of 330 ± 60 meV between the valence and conduction bands is observed in the graphene oxide phase.

Biochemical characterization of the purple form of Marinobacter hydrocarbonoclasticus nitrous oxide reductase

PubMed Central

Dell'Acqua, Simone; Pauleta, Sofia R.; Moura, José J. G.; Moura, Isabel

2012-01-01

Nitrous oxide reductase (N2OR) catalyses the final step of the denitrification pathway—the reduction of nitrous oxide to nitrogen. The catalytic centre (CuZ) is a unique tetranuclear copper centre bridged by inorganic sulphur in a tetrahedron arrangement that can have different oxidation states. Previously, Marinobacter hydrocarbonoclasticus N2OR was isolated with the CuZ centre as CuZ*, in the [1Cu2+ : 3Cu+] redox state, which is redox inert and requires prolonged incubation under reductive conditions to be activated. In this work, we report, for the first time, the isolation of N2OR from M. hydrocarbonoclasticus in the ‘purple’ form, in which the CuZ centre is in the oxidized [2Cu2+ : 2Cu+] redox state and is redox active. This form of the enzyme was isolated in the presence of oxygen from a microaerobic culture in the presence of nitrate and also from a strictly anaerobic culture. The purple form of the enzyme was biochemically characterized and was shown to be a redox active species, although it is still catalytically non-competent, as its specific activity is lower than that of the activated fully reduced enzyme and comparable with that of the enzyme with the CuZ centre in either the [1Cu2+ : 3Cu+] redox state or in the redox inactive CuZ* state. PMID:22451106

A study of the switching mechanism and electrode material of fully CMOS compatible tungsten oxide ReRAM

NASA Astrophysics Data System (ADS)

Chien, W. C.; Chen, Y. C.; Lai, E. K.; Lee, F. M.; Lin, Y. Y.; Chuang, Alfred T. H.; Chang, K. P.; Yao, Y. D.; Chou, T. H.; Lin, H. M.; Lee, M. H.; Shih, Y. H.; Hsieh, K. Y.; Lu, Chih-Yuan

2011-03-01

Tungsten oxide (WO X ) resistive memory (ReRAM), a two-terminal CMOS compatible nonvolatile memory, has shown promise to surpass the existing flash memory in terms of scalability, switching speed, and potential for 3D stacking. The memory layer, WO X , can be easily fabricated by down-stream plasma oxidation (DSPO) or rapid thermal oxidation (RTO) of W plugs universally used in CMOS circuits. Results of conductive AFM (C-AFM) experiment suggest the switching mechanism is dominated by the REDOX (Reduction-oxidation) reaction—the creation of conducting filaments leads to a low resistance state and the rupturing of the filaments results in a high resistance state. Our experimental results show that the reactions happen at the TE/WO X interface. With this understanding in mind, we proposed two approaches to boost the memory performance: (i) using DSPO to treat the RTO WO X surface and (ii) using Pt TE, which forms a Schottky barrier with WO X . Both approaches, especially the latter, significantly reduce the forming current and enlarge the memory window.

Easy on-demand single-pass self-assembly and modification to fabricate gold@graphene-based anti-inflammatory nanoplatforms

NASA Astrophysics Data System (ADS)

Byeon, Jeong Hoon; Park, Jae Hong

2016-10-01

Zwitterionic chitosan (ZC) was modified by fully (both for lateral dimension and thickness) nanodimensional gold-graphene oxide (Au@GO) flakes under visible light and the potential of the resulting materials as biomedical nanoplatforms was investigated. Fully nanodimensional GO flakes floating in nitrogen gas were incorporated with Au nanoparticles to form Au@GO nanoflakes, and the Au@GO was then incorporated with ZC droplets to form the Au@GO-ZC hybrid nanoparticles. The collected particles were exposed to visible light to induce the photocatalytic activity of the Au@GO nanoflakes towards the ZC derivatives. The visible-light-exposed particles show different chemical and surface properties from the unexposed particles, while there were no significant differences in cytotoxicity and macrophage inflammatory protein production. This work suggests that incorporating fully nanodimensional Au@GO flakes with ZC is a suitable technique for ambient photo-modification of the chitosans’ surface property without significant changes in size and shape and increases in cytotoxicity and inflammatory response.

Improved toughness of silicon carbide

NASA Technical Reports Server (NTRS)

Palm, J. A.

1976-01-01

Impact energy absorbing layers (EALs) comprised of partially densified silicon carbide were formed in situ on fully sinterable silicon carbide substrates. After final sintering, duplex silicon carbide structures resulted which were comprised of a fully sintered, high density silicon carbide substrate or core, overlayed with an EAL of partially sintered silicon carbide integrally bonded to its core member. Thermal cycling tests proved such structures to be moderately resistant to oxidation and highly resistant to thermal shock stresses. The strength of the developed structures in some cases exceeded but essentially it remained the same as the fully sintered silicon carbide without the EAL. Ballistic impact tests indicated that substantial improvements in the toughness of sintered silicon carbide were achieved by the use of the partially densified silicon carbide EALs.

Arsenic in hydrothermal apatite: Oxidation state, mechanism of uptake, and comparison between experiments and nature

NASA Astrophysics Data System (ADS)

Liu, Weihua; Mei, Yuan; Etschmann, Barbara; Brugger, Joël; Pearce, Mark; Ryan, Chris G.; Borg, Stacey; Wykes, Jeremey; Kappen, Peter; Paterson, David; Boesenberg, Ulrike; Garrevoet, Jan; Moorhead, Gareth; Falkenberg, Gerald

2017-01-01

Element substitution that occurs during fluid-rock interaction permits assessment of fluid composition and interaction conditions in ancient geological systems, and provides a way to fix contaminants from aqueous solutions. We conducted a series of hydrothermal mineral replacement experiments to determine whether a relationship can be established between arsenic (As) distribution in apatite and fluid chemistry. Calcite crystals were reacted with phosphate solutions spiked with As(V), As(III), and mixed As(III)/As(V) species at 250 °C and water-saturated pressure. Arsenic-bearing apatite rims formed in several hours, and within 48 h the calcite grains were fully replaced. X-ray Absorption Near-edge Spectroscopy (XANES) data show that As retained the trivalent oxidation state in the fully-reacted apatite grown from solutions containing only As(III). Extended X-ray Fine Spectroscopy (EXAFS) data reveal that these As(III) ions are surrounded by about three oxygen atoms at an Assbnd O bond length close to that of an arsenate group (AsO43-), indicating that they occupy tetrahedral phosphate sites. The three-coordinated As(III)-O3 structure, with three oxygen atoms and one lone electron pair around As(III), was confirmed by geometry optimization using ab initio molecular simulations. The micro-XANES imaging data show that apatite formed from solutions spiked with mixed As(III) and As(V) retained only As(V) after completion of the replacement reaction; in contrast, partially reacted samples revealed a complex distribution of As(V)/As(III) ratios, with As(V) concentrated in the center of the grain and As(III) towards the rim. Most natural apatites from the Ernest Henry iron oxide copper gold deposit, Australia, show predominantly As(V), but two grains retained some As(III) in their core. The As-anomalous amphibolite-facies gneiss from Binntal, Switzerland, only revealed As(V), despite the fact that these apatites in both cases formed under conditions where As(III) is expected to be the dominant As form in hydrothermal fluids. These results show that incorporation of As in apatite is a complicated process, and sensitive to the local fluid composition during crystallization, and that some of the complexity in As zoning in partially reacted apatite may be due to local fluctuations of As(V)/As(III) ratios in the fluid and to kinetic effects during the mineral replacement reaction. Our study shows for the first time that As(III) can be incorporated into the apatite structure, although not as efficiently as As(V). Uptake of As(III) is probably highly dependent on the reaction mechanism. As(III)O33- moieties replace phosphate groups, but cause a high strain on the lattice; as a result, As(III) is easily exchanged (or oxidized) for As(V) during hydrothermal recrystallization, and the fully reacted grains only record the preferred oxidation state (i.e., As(V)) from mixed-oxidation state solutions. Overall this study shows that the observed oxidation state of As in apatite may not reflect the original As(III)/As(V) ratio of the parent fluid, due to the complex nature of As(III) uptake and possible in situ oxidation during recrystallization.

The kinetics of the oxidation of cytochrome c by Paracoccus cytochrome c peroxidase.

PubMed

Gilmour, R; Goodhew, C F; Pettigrew, G W; Prazeres, S; Moura, J J; Moura, I

1994-06-15

In work that is complementary to our investigation of the spectroscopic features of the cytochrome c peroxidase from Paracoccus denitrificans [Gilmour, Goodhew, Pettigrew, Prazeres, Moura and Moura (1993) Biochem. J. 294, 745-752], we have studied the kinetics of oxidation of cytochrome c by this enzyme. The enzyme, as isolated, is in the fully oxidized form and is relatively inactive. Reduction of the high-potential haem at pH 6 with ascorbate results in partial activation of the enzyme. Full activation is achieved by addition of 1 mM CaCl2. Enzyme activation is associated with formation of a high-spin state at the oxidized low-potential haem. EGTA treatment of the oxidized enzyme prevents activation after reduction with ascorbate, while treatment with EGTA of the reduced, partially activated, form abolishes the activity. We conclude that the active enzyme is a mixed-valence form with the low-potential haem in a high-spin state that is stabilized by Ca2+. Dilution of the enzyme results in a progressive loss of activity, the extent of which depends on the degree of dilution. Most of the activity lost upon dilution can be recovered after reconcentration. The M(r) of the enzyme on molecular-exclusion chromatography is concentration-dependent, with a shift to lower values at lower concentrations. Values of M(r) obtained are intermediate between those of a monomer (39,565) and a dimer. We propose that the active form of the enzyme is a dimer which dissociates at high dilution to give inactive monomers. From the activity of the enzyme at different dilutions, a KD of 0.8 microM can be calculated for the monomerdimer equilibrium. The cytochrome c peroxidase oxidizes horse ferrocytochrome c with first-order kinetics, even at high ferrocytochrome c concentrations. The maximal catalytic-centre activity ('turnover number') under the assay conditions used is 62,000 min-1, with a half-saturating ferrocytochrome c concentration of 3.3 microM. The corresponding values for the Paracoccus cytochrome c-550 (presumed to be the physiological substrate) are 85,000 min-1 and 13 microM. However, in this case, the kinetics deviate from first-order progress curves at all ferrocytochrome c concentrations. Consideration of the periplasmic environment in Paracoccus denitrificans leads us to propose that the enzyme will be present as the fully active dimer supplied with saturating ferrocytochrome c-550.

Method of joining ITM materials using a partially or fully-transient liquid phase

DOEpatents

Butt, Darryl Paul; Cutler, Raymond Ashton; Rynders, Steven Walton; Carolan, Michael Francis

2006-03-14

A method of forming a composite structure includes: (1) providing first and second sintered bodies containing first and second multicomponent metallic oxides having first and second identical crystal structures that are perovskitic or fluoritic; (2) providing a joint material containing at least one metal oxide: (a) containing (i) at least one metal of an identical IUPAC Group as at least one sintered body metal in one of the multicomponent metallic oxides, (ii) a first row D-Block transition metal not contained in the multicomponent metallic oxides, and/or (iii) a lanthanide not contained in the multicomponent metallic oxides; (b) free of metals contained in the multicomponent metallic oxides; (c) free of cations of boron, silicon, germanium, tin, lead, arsenic, antimony, phosphorus and tellurium; and (d) having a melting point below the sintering temperatures of the sintered bodies; and (3) heating to a joining temperature above the melting point and below the sintering temperatures.

Hydrazines and carbohydrazides produced from oxidized carbon in earth's primitive environment

NASA Technical Reports Server (NTRS)

Folsome, C. E.; Brittain, A.; Smith, A.; Chang, S.

1981-01-01

Whether abiological organic compounds can be formed from the interactions of energy sources with nitrogen, oxidized carbon and water is held to be of importance in geochemical models of the primordial earth atmosphere. It is reported that experiments using quenched spark discharges through molecular nitrogen on aqueous suspensions of CaCO3 and other reactants to simulate the hydrosphere/atmosphere interface yield hydrazine and carbohydrazine in significant but low yields. Such reactions in primitive aquatic environments may have supplied a pathway for chemical evolution and the origin of life, on a primitive earth in which fully oxidized states of carbon were available for the primary synthesis of organic matter.

Electron transfer and reaction mechanism of laccases.

PubMed

Jones, Stephen M; Solomon, Edward I

2015-03-01

Laccases are part of the family of multicopper oxidases (MCOs), which couple the oxidation of substrates to the four electron reduction of O2 to H2O. MCOs contain a minimum of four Cu's divided into Type 1 (T1), Type 2 (T2), and binuclear Type 3 (T3) Cu sites that are distinguished based on unique spectroscopic features. Substrate oxidation occurs near the T1, and electrons are transferred approximately 13 Å through the protein via the Cys-His pathway to the T2/T3 trinuclear copper cluster (TNC), where dioxygen reduction occurs. This review outlines the electron transfer (ET) process in laccases, and the mechanism of O2 reduction as elucidated through spectroscopic, kinetic, and computational data. Marcus theory is used to describe the relevant factors which impact ET rates including the driving force, reorganization energy, and electronic coupling matrix element. Then, the mechanism of O2 reaction is detailed with particular focus on the intermediates formed during the two 2e(-) reduction steps. The first 2e(-) step forms the peroxide intermediate, followed by the second 2e(-) step to form the native intermediate, which has been shown to be the catalytically relevant fully oxidized form of the enzyme.

Structural evidence for the partially oxidized dipyrromethene and dipyrromethanone forms of the cofactor of porphobilinogen deaminase: structures of the Bacillus megaterium enzyme at near-atomic resolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Azim, N.; Deery, E.; Warren, M. J.

The enzyme porphobilinogen deaminase (PBGD; hydroxymethylbilane synthase; EC 2.5.1.61) catalyses a key early step in the biosynthesis of tetrapyrroles in which four molecules of the monopyrrole porphobilinogen are condensed to form a linear tetrapyrrole. Two near-atomic resolution structures of PBGD from B. megaterium are reported that demonstrate the time-dependent accumulation of partially oxidized forms of the cofactor, including one that possesses a tetrahedral C atom in the terminal pyrrole ring. The enzyme porphobilinogen deaminase (PBGD; hydroxymethylbilane synthase; EC 2.5.1.61) catalyses an early step of the tetrapyrrole-biosynthesis pathway in which four molecules of the monopyrrole porphobilinogen are condensed to form amore » linear tetrapyrrole. The enzyme possesses a dipyrromethane cofactor, which is covalently linked by a thioether bridge to an invariant cysteine residue (Cys241 in the Bacillus megaterium enzyme). The cofactor is extended during the reaction by the sequential addition of the four substrate molecules, which are released as a linear tetrapyrrole product. Expression in Escherichia coli of a His-tagged form of B. megaterium PBGD has permitted the X-ray analysis of the enzyme from this species at high resolution, showing that the cofactor becomes progressively oxidized to the dipyrromethene and dipyrromethanone forms. In previously solved PBGD structures, the oxidized cofactor is in the dipyromethenone form, in which both pyrrole rings are approximately coplanar. In contrast, the oxidized cofactor in the B. megaterium enzyme appears to be in the dipyrromethanone form, in which the C atom at the bridging α-position of the outer pyrrole ring is very clearly in a tetrahedral configuration. It is suggested that the pink colour of the freshly purified protein is owing to the presence of the dipyrromethene form of the cofactor which, in the structure reported here, adopts the same conformation as the fully reduced dipyrromethane form.« less

Formation of multiple levels of porous silicon for buried insulators and conductors in silicon device technologies

DOEpatents

Blewer, Robert S.; Gullinger, Terry R.; Kelly, Michael J.; Tsao, Sylvia S.

1991-01-01

A method of forming a multiple level porous silicon substrate for semiconductor integrated circuits including anodizing non-porous silicon layers of a multi-layer silicon substrate to form multiple levels of porous silicon. At least one porous silicon layer is then oxidized to form an insulating layer and at least one other layer of porous silicon beneath the insulating layer is metallized to form a buried conductive layer. Preferably the insulating layer and conductive layer are separated by an anodization barrier formed of non-porous silicon. By etching through the anodization barrier and subsequently forming a metallized conductive layer, a fully or partially insulated buried conductor may be fabricated under single crystal silicon.

Characterization of strain relaxation behavior in Si1- x Ge x epitaxial layers by dry oxidation

NASA Astrophysics Data System (ADS)

Jang, Hyunchul; Kim, Byongju; Koo, Sangmo; Park, Seran; Ko, Dae-Hong

2017-11-01

We fabricated fully strained Si0.77Ge0.23 epitaxial layers on Si substrates and investigated their strain relaxation behaviors under dry oxidation and the effect of oxidation temperatures and times. After the oxidation process, a Ge-rich layer was formed between the oxide and the remaining Si0.77Ge0.23 layer. Using reciprocal space mapping measurements, we confirmed that the strain of the Si0.77Ge0.23 layers was efficiently relaxed after oxidation, with a maximum relaxation value of 70% after oxidation at 850 °C for 120 min. The surface of Si0.77Ge0.23 layer after strain relaxation by dry oxidation was smoother than a thick Si0.77Ge0.23 layer, which achieved a similar strain relaxation value by increasing the film thickness. Additionally, N2 annealing was performed in order to compare its effect on the relaxation compared to dry oxidation and to identify relaxation mechanisms, other than the thermally driven ones, occurring during dry oxidation.

A density functional theory study on the active center of Fe-only hydrogenase: characterization and electronic structure of the redox states.

PubMed

Liu, Zhi-Pan; Hu, P

2002-05-08

We have carried out extensive density functional theory (DFT) calculations for possible redox states of the active center in Fe-only hydrogenases. The active center is modeled by [(H(CH(3))S)(CO)(CN(-))Fe(p)(mu-DTN)(mu-CO)Fe(d)(CO)(CN(-))(L)](z)() (z is the net charge in the complex; Fe(p)= the proximal Fe, Fe(d) = the distal Fe, DTN = (-SCH(2)NHCH(2)S-), L is the ligand that bonds with the Fe(d) at the trans position to the bridging CO). Structures of possible redox states are optimized, and CO stretching frequencies are calculated. By a detailed comparison of all the calculated structures and the vibrational frequencies with the available experimental data, we find that (i) the fully oxidized, inactive state is an Fe(II)-Fe(II) state with a hydroxyl (OH(-)) group bonded at the Fe(d), (ii) the oxidized, active state is an Fe(II)-Fe(I) complex which is consistent with the assignment of Cao and Hall (J. Am. Chem. Soc. 2001, 123, 3734), and (iii) the fully reduced state is a mixture with the major component being a protonated Fe(I)-Fe(I) complex and the other component being its self-arranged form, Fe(II)-Fe(II) hydride. Our calculations also show that the exogenous CO can strongly bond with the Fe(II)-Fe(I) species, but cannot bond with the Fe(I)-Fe(I) complex. This result is consistent with experiments that CO tends to inhibit the oxidized, active state, but not the fully reduced state. The electronic structures of all the redox states have been analyzed. It is found that a frontier orbital which is a mixing state between the e(g) of Fe and the 2 pi of the bridging CO plays a key role concerning the reactivity of Fe-only hydrogenases: (i) it is unoccupied in the fully oxidized, inactive state, half-occupied in the oxidized, active state, and fully occupied in the fully reduced state; (ii) the e(g)-2 pi orbital is a bonding state, and this is the key reason for stability of the low oxidation states, such as Fe(I)-Fe(I) complexes; and (iii) in the e(g)-2 pi orbital more charge accumulates between the bridging CO and the Fe(d) than between the bridging CO and the Fe(p), and the occupation increase in this orbital will enhance the bonding between the bridging CO and the Fe(d), leading to the bridging-CO shift toward the Fe(d).

Active site CP-loop dynamics modulate substrate binding, catalysis, oligomerization, stability, over-oxidation and recycling of 2-Cys Peroxiredoxins.

PubMed

Kamariah, Neelagandan; Eisenhaber, Birgit; Eisenhaber, Frank; Grüber, Gerhard

2018-04-01

Peroxiredoxins (Prxs) catalyse the rapid reduction of hydrogen peroxide, organic hydroperoxide and peroxynitrite, using a fully conserved peroxidatic cysteine (C P ) located in a conserved sequence Pxxx(T/S)xxC P motif known as C P -loop. In addition, Prxs are involved in cellular signaling pathways and regulate several redox-dependent process related disease. The effective catalysis of Prxs is associated with alterations in the C P -loop between reduced, Fully Folded (FF), and oxidized, Locally Unfolded (LU) conformations, which are linked to dramatic changes in the oligomeric structure. Despite many studies, little is known about the precise structural and dynamic roles of the C P -loop on Prxs functions. Herein, the comprehensive biochemical and biophysical studies on Escherichia coli alkyl hydroperoxide reductase subunit C (EcAhpC) and the C P -loop mutants, EcAhpC-F45A and EcAhpC-F45P reveal that the reduced form of the C P -loop adopts conformational dynamics, which is essential for effective peroxide reduction. Furthermore, the point mutants alter the structure and dynamics of the reduced form of the C P -loop and, thereby, affect substrate binding, catalysis, oligomerization, stability and overoxidiation. In the oxidized form, due to restricted C P -loop dynamics, the EcAhpC-F45P mutant favours a decamer formation, which enhances the effective recycling by physiological reductases compared to wild-type EcAhpC. In addition, the study reveals that residue F45 increases the specificity of Prxs-reductase interactions. Based on these studies, we propose an evolution of the C P -loop with confined sequence conservation within Prxs subfamilies that might optimize the functional adaptation of Prxs into various physiological roles. Copyright © 2018 Elsevier Inc. All rights reserved.

Fully Enzymatic Membraneless Glucose|Oxygen Fuel Cell That Provides 0.275 mA cm(-2) in 5 mM Glucose, Operates in Human Physiological Solutions, and Powers Transmission of Sensing Data.

PubMed

Ó Conghaile, Peter; Falk, Magnus; MacAodha, Domhnall; Yakovleva, Maria E; Gonaus, Christoph; Peterbauer, Clemens K; Gorton, Lo; Shleev, Sergey; Leech, Dónal

2016-02-16

Coimmobilization of pyranose dehydrogenase as an enzyme catalyst, osmium redox polymers [Os(4,4'-dimethoxy-2,2'-bipyridine)2(poly(vinylimidazole))10Cl](+) or [Os(4,4'-dimethyl-2,2'-bipyridine)2(poly(vinylimidazole))10Cl](+) as mediators, and carbon nanotube conductive scaffolds in films on graphite electrodes provides enzyme electrodes for glucose oxidation. The recombinant enzyme and a deglycosylated form, both expressed in Pichia pastoris, are investigated and compared as biocatalysts for glucose oxidation using flow injection amperometry and voltammetry. In the presence of 5 mM glucose in phosphate-buffered saline (PBS) (50 mM phosphate buffer solution, pH 7.4, with 150 mM NaCl), higher glucose oxidation current densities, 0.41 mA cm(-2), are obtained from enzyme electrodes containing the deglycosylated form of the enzyme. The optimized glucose-oxidizing anode, prepared using deglycosylated enzyme coimmobilized with [Os(4,4'-dimethyl-2,2'-bipyridine)2(poly(vinylimidazole))10Cl](+) and carbon nanotubes, was coupled with an oxygen-reducing bilirubin oxidase on gold nanoparticle dispersed on gold electrode as a biocathode to provide a membraneless fully enzymatic fuel cell. A maximum power density of 275 μW cm(-2) is obtained in 5 mM glucose in PBS, the highest to date under these conditions, providing sufficient power to enable wireless transmission of a signal to a data logger. When tested in whole human blood and unstimulated human saliva maximum power densities of 73 and 6 μW cm(-2) are obtained for the same fuel cell configuration, respectively.

Synthesis and disulfide bond connectivity-activity studies of a kalata B1-inspired cyclopeptide against dengue NS2B-NS3 protease.

PubMed

Gao, Yaojun; Cui, Taian; Lam, Yulin

2010-02-01

Kalata B1 is a plant protein with remarkable thermal, chemical and enzymatic stability. Its potential applications could be centered on the possibility of using its cyclic structure and cystine knot motif as a scaffold for the design of stable pharmaceuticals. To discover potent dengue NS2B-NS3 protease inhibitors, we have prepared various kalata B1 analogues by varying the amino acid sequence. Mass spectrometric and biochemical investigations of these analogues revealed a cyclopeptide whose two fully oxidized forms are substrate-competitive inhibitors of the dengue viral NS2B-NS3 protease. Both oxidized forms showed potent inhibition with K(i) of 1.39+/-0.35 and 3.03+/-0.75 microM, respectively. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Spectroscopic Definition of the CuZ° Intermediate in Turnover of Nitrous Oxide Reductase and Molecular Insight into the Catalytic Mechanism.

PubMed

Johnston, Esther M; Carreira, Cíntia; Dell'Acqua, Simone; Dey, Somdatta Ghosh; Pauleta, Sofia R; Moura, Isabel; Solomon, Edward I

2017-03-29

Spectroscopic methods and density functional theory (DFT) calculations are used to determine the geometric and electronic structure of Cu Z °, an intermediate form of the Cu 4 S active site of nitrous oxide reductase (N 2 OR) that is observed in single turnover of fully reduced N 2 OR with N 2 O. Electron paramagnetic resonance (EPR), absorption, and magnetic circular dichroism (MCD) spectroscopies show that Cu Z ° is a 1-hole (i.e., 3Cu I Cu II ) state with spin density delocalized evenly over Cu I and Cu IV . Resonance Raman spectroscopy shows two Cu-S vibrations at 425 and 413 cm -1 , the latter with a -3 cm -1 O 18 solvent isotope shift. DFT calculations correlated to these spectral features show that Cu Z ° has a terminal hydroxide ligand coordinated to Cu IV , stabilized by a hydrogen bond to a nearby lysine residue. Cu Z ° can be reduced via electron transfer from Cu A using a physiologically relevant reductant. We obtain a lower limit on the rate of this intramolecular electron transfer (IET) that is >10 4 faster than the unobserved IET in the resting state, showing that Cu Z ° is the catalytically relevant oxidized form of N 2 OR. Terminal hydroxide coordination to Cu IV in the Cu Z ° intermediate yields insight into the nature of N 2 O binding and reduction, specifying a molecular mechanism in which N 2 O coordinates in a μ-1,3 fashion to the fully reduced state, with hydrogen bonding from Lys397, and two electrons are transferred from the fully reduced μ 4 S 2- bridged tetranuclear copper cluster to N 2 O via a single Cu atom to accomplish N-O bond cleavage.

Smoldering and Flame Resistant Textiles via Conformal Barrier Formation.

PubMed

Zammarano, Mauro; Cazzetta, Valeria; Nazaré, Shonali; Shields, J Randy; Kim, Yeon Seok; Hoffman, Kathleen M; Maffezzoli, Alfonso; Davis, Rick

2016-12-07

A durable and flexible silicone-based backcoating (halogen free) is applied to the backside of an otherwise smoldering-prone and flammable fabric. When exposed to fire, cyclic siloxanes (produced by thermal decomposition of the backcoating) diffuse through the fabric in the gas phase. The following oxidation of the cyclic siloxanes forms a highly conformal and thermally stable coating that fully embeds all individual fibers and shields them from heat and oxidation. As a result, the combustion of the fabric is prevented. This is a novel fire retardant mechanism that discloses a powerful approach towards textiles and multifunctional flexible materials with combined smoldering/flaming ignition resistance and fire-barrier properties.

A Review of Aspects of Oxidative Hair Dye Chemistry with Special Reference to N-Nitrosamine Formation

PubMed Central

Lewis, David; Mama, John; Hawkes, Jamie

2013-01-01

This review discusses a new aspect to the safety profile of oxidative hair dyes using data already in the public domain. These dyes contain secondary amines that are capable of forming potentially carcinogenic nitrosamine derivatives when exposed to atmospheric pollution. Numerous scientific articles confirm the existence of secondary amines in hair dyes (and their intermediates), the possibility of nitrosation by atmospheric NOx of secondary amines to give the N-nitrosamines, and the significant safety risks on N-nitrosamines. It is believed that such nitrosamine derivatives should be investigated more fully in the interests of consumer safety. PMID:28809322

Controllable growth of aluminum nanorods using physical vapor deposition

PubMed Central

2014-01-01

This letter proposes and experimentally demonstrates that oxygen, through action as a surfactant, enables the growth of aluminum nanorods using physical vapor deposition. Based on the mechanism through which oxygen acts, the authors show that the diameter of aluminum nanorods can be controlled from 50 to 500 nm by varying the amount of oxygen present, through modulating the vacuum level, and by varying the substrate temperature. When grown under medium vacuum, the nanorods are in the form of an aluminum metal - aluminum oxide core-shell. The thickness of the oxide shell is ~2 nm as grown and is stable when maintained in ambient for 30 days or annealed in air at 475 K for 1 day. As annealing temperature is increased, the nanorod morphology remains stable while the ratio of oxide shell to metallic core increases, resulting in a fully aluminum oxide nanorod at 1,475 K. PMID:25170334

A Hexanuclear Iron(II) Layer with Two Square-Planar FeO4 Units Spanned by Tetrasiloxide Ligands: Mimicking of Minerals and Catalysts.

PubMed

Manicke, N; Hoof, S; Keck, M; Braun-Cula, B; Feist, M; Limberg, C

2017-07-17

A hexanuclear iron(II) siloxide complex has been prepared by reacting an incompletely condensed silsesquioxane first with NaOMe and then with Fe(OTf) 2 . In the process of product formation, the siloxane framework undergoes a transformation and it was shown that this happens already upon addition of base: Treatment of the ligand precursor with NaOMe leads to a completely condensed silsesquioxane cage with 12 Si atoms that is composed of 2 equiv of the tetrasiloxide ligands found in the product complex. Its iron centers form a two-dimensional array reminiscent of the situations found in minerals and two-dimensional oxide films caused by segregation of FeO x and silica. As the hexairon(II) assembly contains two high-spin square-planar FeO 4 units-suggested to represent the active sites in Fe-zeolites, which react with N 2 O to generate strongly oxidizing sites-it was treated with Me 3 NO. This led to the oxidation of two of the iron centers to the oxidation state +III and elimination of one iron ion, so that a pentanuclear, mixed valent iron siloxide was formed. All complexes were fully characterized.

Surface characteristics of anodized and hydrothermally treated titatnium with an increasing concentration of calcium ion

NASA Astrophysics Data System (ADS)

Park, Il Song; Bae, Tae Sung; Seol, Kyeong Won

2006-10-01

Titanium is widely used as an implant material due to its good mechanical properties and the excellent biocompatibility of the oxide film on the surface. To modify the unstable oxide surface of pure titanium, plasma electrolytic oxidation was applied in this study. The electrolyte used for anodizing was a mixture of GP (glycerophosphate disodium salt) and CA (calcium acetate). In addition, a hydrothermal treatment was performed to precipitate a calcium phosphate crystal on the titanium oxide layer for bioactivity. The effect of the CA concentration of the electrolyte on the surface of titanium was investigated, with CA concentrations at 0.1 M, 0.2 M, and 0.3 M. A high concentration of CA results in a low breakdown voltage; hence many large micropores were formed on the anodized surface. Moreover, the size of the HA crystals was more minute in proportion to the increasing concentration of CA. The crystal phase of titanium dioxide was mainly anatase, and a rutile phase was also observed. As the size and/or amount of HA crystals increased, the surface roughness increased. However, the surface roughness could be decreased by fully and uniformly covering the surface with HA crystals. The corrosion resistance in the saline solution was increased by anodic spark oxidation. In addition, it was slightly increased by a hydrothermal treatment. It is considered that a more stable and thicker titanium oxide layer is formed by anodic oxidation and a hydrothermal treatment.

Fuel cells with doped lanthanum gallate electrolyte

NASA Astrophysics Data System (ADS)

Feng, Man; Goodenough, John B.; Huang, Keqin; Milliken, Christopher

Single cells with doped lanthanum gallate electrolyte material were constructed and tested from 600 to 800°C. Both ceria and the electrolyte material were mixed with NiO powder respectively to form composite anodes. Doped lanthanum cobaltite was used exclusively as the cathode material. While high power density from the solid oxide fuel cells at 800°C was achieved. our results clearly indicate that anode overpotential is the dominant factor in the power loss of the cells. Better anode materials and anode processing methods need to be found to fully utilize the high ionic conductivity of the doped lanthanum galiate and achieve higher power density at 800°C from solid oxide fuel cells.

Ethylene Glycol Adsorption and Reaction over CeOX(111) Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mullins, David R; Chen, Tsung-Liang

2011-01-01

This study reports the interaction of ethylene glycol with well-ordered CeO{sub x}(111) thin film surfaces. Ethylene glycol initially adsorbs on fully oxidized CeO{sub 2}(111) and reduced CeO{sub 2-x}(111) through the formation of one C-O-Ce bond and then forms a second alkoxy bond after annealing. On fully oxidized CeO{sub 2}(111) both recombination of ethylene glycol and water desorption occur at low temperature leaving stable -OCH{sub 2}CH{sub 2}O- (ethylenedioxy) intermediates and oxygen vacancies on the surface. This ethylenedioxy intermediate goes through C-C bond scission to produce formate species which then react to produce CO and CO{sub 2}. The formation of water resultsmore » in the reduction of the ceria. On a reduced CeO{sub 2-x}(111) surface the reaction selectivity shifts toward a dehydration process. The ethylenedioxy intermediate decomposes by breaking a C-O bond and converts into an enolate species. Similar to the reaction of acetaldehyde on reduced CeO{sub 2-x}(111), the enolate reacts to produce acetaldehyde, acetylene, and ethylene. The loss of O from ethylene glycol leads to a small amount of oxidation of the reduced ceria.« less

Ethylene Glycol Adsorption and Reaction over CeOX(111) Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

T Chen; D Mullins

2011-12-31

This study reports the interaction of ethylene glycol with well-ordered CeO{sub x}(111) thin film surfaces. Ethylene glycol initially adsorbs on fully oxidized CeO{sub 2}(111) and reduced CeO{sub 2-x}(111) through the formation of one C-O-Ce bond and then forms a second alkoxy bond after annealing. On fully oxidized CeO{sub 2}(111) both recombination of ethylene glycol and water desorption occur at low temperature leaving stable -OCH{sub 2}CH{sub 2}O- (ethylenedioxy) intermediates and oxygen vacancies on the surface. This ethylenedioxy intermediate goes through C-C bond scission to produce formate species which then react to produce CO and CO{sub 2}. The formation of water resultsmore » in the reduction of the ceria. On a reduced CeO{sub 2-x}(111) surface the reaction selectivity shifts toward a dehydration process. The ethylenedioxy intermediate decomposes by breaking a C-O bond and converts into an enolate species. Similar to the reaction of acetaldehyde on reduced CeO{sub 2-x}(111), the enolate reacts to produce acetaldehyde, acetylene, and ethylene. The loss of O from ethylene glycol leads to a small amount of oxidation of the reduced ceria.« less

Self-assembly of a tetrahedral 58-nuclear barium vanadium oxide cluster.

PubMed

Kastner, Katharina; Puscher, Bianka; Streb, Carsten

2013-01-07

We report the synthesis and characterization of a molecular barium vanadium oxide cluster featuring high nuclearity and high symmetry. The tetrameric, 2.3 nm cluster H(5)[Ba(10)(NMP)(14)(H(2)O)(8)[V(12)O(33)](4)Br] is based on a bromide-centred, octahedral barium scaffold which is capped by four previously unknown [V(12)O(33)](6-) clusters in a tetrahedral fashion. The compound represents the largest polyoxovanadate-based heterometallic cluster known to date. The cluster is formed in organic solution and it is suggested that the bulky N-methyl-2-pyrrolidone (NMP) solvent ligands allow the isolation of this giant molecule and prevent further condensation to a solid-state metal oxide. The cluster is fully characterized using single-crystal XRD, elemental analysis, ESI mass spectrometry and other spectroscopic techniques.

Lactate: link between glycolytic and oxidative metabolism.

PubMed

Brooks, George A

2007-01-01

Once thought to be the consequence of oxygen lack in contracting skeletal muscle, the glycolytic product lactate is formed and utilised continuously under fully aerobic conditions. 'Cell-cell' and 'intracellular lactate shuttle' concepts describe the roles of lactate in delivery of oxidative and gluconeogenic substrates as well as in cell signalling. Examples of cell-cell shuttles include lactate exchanges (i) between white-glycolytic and red-oxidative fibres within a working muscle bed; (ii) between working skeletal muscle and heart; and (iii) between tissues of net lactate release and gluconeogenesis. Lactate shuttles exist in diverse tissues including in the brain, where a shuttle between astrocytes and neurons is linked to glutamatergic signalling. Because lactate, the product of glycogenolysis and glycolysis, is disposed of by oxidative metabolism, lactate shuttling unites the two major processes of cellular energy transduction. Lactate disposal is mainly through oxidation, especially during exercise when oxidation accounts for 70-75% of removal and gluconeogenesis the remainder. Lactate flux occurs down proton and concentration gradients that are established by the mitochondrial lactate oxidation complex. Marathon running is a power activity requiring high glycolytic and oxidative fluxes; such activities require lactate shuttling. Knowledge of the lactate shuttle is yet to be imparted to the sport.

Fully solar-driven thermo- and electrochemistry for advanced oxidation processes (STEP-AOPs) of 2-nitrophenol wastewater.

PubMed

Nie, Chunhong; Shao, Nan; Wang, Baohui; Yuan, Dandan; Sui, Xin; Wu, Hongjun

2016-07-01

The STEP (Solar Thermal Electrochemical Process) for Advanced Oxidation Processes (AOPs, combined to STEP-AOPs), fully driven by solar energy without the input of any other forms of energy and chemicals, is introduced and demonstrated from the theory to experiments. Exemplified by the persistent organic pollutant 2-nitrophenol in water, the fundamental model and practical system are exhibited for the STEP-AOPs to efficiently transform 2-nitrophenol into carbon dioxide, water, and the other substances. The results show that the STEP-AOPs system performs more effectively than classical AOPs in terms of the thermodynamics and kinetics of pollutant oxidation. Due to the combination of solar thermochemical reactions with electrochemistry, the STEP-AOPs system allows the requisite electrolysis voltage of 2-nitrophenol to be experimentally decreased from 1.00 V to 0.84 V, and the response current increases from 18 mA to 40 mA. STEP-AOPs also greatly improve the kinetics of the oxidation at 30 °C and 80 °C. As a result, the removal rate of 2-nitrophenol after 1 h increased from 19.50% at 30 °C to 32.70% at 80 °C at constant 1.90 V. Mechanistic analysis reveals that the oxidation pathway is favorably changed because of thermal effects. The tracking of the reaction displayed that benzenediol and hydroquinone are initial products, with maleic acid and formic acid as sequential carboxylic acid products, and carbon dioxide as the final product. The theory and experiments on STEP-AOPs system exemplified by the oxidation of 2-nitrophenol provide a broad basis for extension of the STEP and AOPs for rapid and efficient treatment of organic wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetic and spectroscopic characterization of tungsten-substituted DMSO reductase from Rhodobacter sphaeroides.

PubMed

Pacheco, Josué; Niks, Dimitri; Hille, Russ

2018-03-01

We have examined the kinetic and spectroscopic properties of a tungsten-substituted form of DMSO reductase from Rhodobacter sphaeroides, an enzyme that normally possesses molybdenum. Partial reduction with sodium dithionite yields a well-resolved W(V) EPR signal of the so-called "high-g split" type that exhibits markedly greater g-anisotropy than the corresponding Mo(V) signal of the native form of the enzyme, with the g values shifted to higher magnetic field by as much as Δg ave  = 0.056. Deuteration of the enzyme confirms that the coupled proton is solvent-exchangeable, allowing us to accurately simulate the tungsten hyperfine coupling. Global curve-fitting analysis of UV/vis absorption spectra observed in the course of the reaction of the tungsten-substituted enzyme with sodium dithionite affords a well-defined absorption spectrum for the W(V) species. Surprisingly, the absorption spectrum for this species exhibits significantly larger molar extinction coefficients than either the reduced or the oxidized spectrum. This spectrum, in conjunction with those for fully oxidized W(VI) and fully reduced W(IV) enzyme, has been used to deconvolute the absorption spectra seen in the course of turnover, in the which enzyme is reacted with sodium dithionite and DMSO, demonstrating that the W(V) is an authentic catalytic intermediate that accumulates to approximately 50% of the total enzyme in the steady state.

Structural and electronic snapshots during the transition from a Cu(II) to Cu(I) metal center of a lytic polysaccharide monooxygenase by X-ray photoreduction.

PubMed

Gudmundsson, Mikael; Kim, Seonah; Wu, Miao; Ishida, Takuya; Momeni, Majid Hadadd; Vaaje-Kolstad, Gustav; Lundberg, Daniel; Royant, Antoine; Ståhlberg, Jerry; Eijsink, Vincent G H; Beckham, Gregg T; Sandgren, Mats

2014-07-04

Lytic polysaccharide monooxygenases (LPMOs) are a recently discovered class of enzymes that employ a copper-mediated, oxidative mechanism to cleave glycosidic bonds. The LPMO catalytic mechanism likely requires that molecular oxygen first binds to Cu(I), but the oxidation state in many reported LPMO structures is ambiguous, and the changes in the LPMO active site required to accommodate both oxidation states of copper have not been fully elucidated. Here, a diffraction data collection strategy minimizing the deposited x-ray dose was used to solve the crystal structure of a chitin-specific LPMO from Enterococcus faecalis (EfaCBM33A) in the Cu(II)-bound form. Subsequently, the crystalline protein was photoreduced in the x-ray beam, which revealed structural changes associated with the conversion from the initial Cu(II)-oxidized form with two coordinated water molecules, which adopts a trigonal bipyramidal geometry, to a reduced Cu(I) form in a T-shaped geometry with no coordinated water molecules. A comprehensive survey of Cu(II) and Cu(I) structures in the Cambridge Structural Database unambiguously shows that the geometries observed in the least and most reduced structures reflect binding of Cu(II) and Cu(I), respectively. Quantum mechanical calculations of the oxidized and reduced active sites reveal little change in the electronic structure of the active site measured by the active site partial charges. Together with a previous theoretical investigation of a fungal LPMO, this suggests significant functional plasticity in LPMO active sites. Overall, this study provides molecular snapshots along the reduction process to activate the LPMO catalytic machinery and provides a general method for solving LPMO structures in both copper oxidation states. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Diabetes and renal tubular cell apoptosis

PubMed Central

Habib, Samy L

2013-01-01

Apoptosis contributes to the development of diabetic nephropathy, but the mechanism by which high glucose induces apoptosis is not fully understood. Apoptosis of tubular epithelial cells is a major feature of diabetic kidney disease, and hyperglycemia triggers the generation of free radicals and oxidant stress in tubular cells. Hyperglycemia and high glucose in vitro also lead to apoptosis, a form of programmed cell death. High glucose similar to those seen with hyperglycemia in people with diabetes mellitus, lead to accelerated apoptosis, a form of programmed cell death characterized by cell shrinkage, chromatin condensation and DNA fragmentation, in variety of cell types, including renal proximal tubular epithelial cells. PMID:23593533

Diabetes and renal tubular cell apoptosis.

PubMed

Habib, Samy L

2013-04-15

Apoptosis contributes to the development of diabetic nephropathy, but the mechanism by which high glucose induces apoptosis is not fully understood. Apoptosis of tubular epithelial cells is a major feature of diabetic kidney disease, and hyperglycemia triggers the generation of free radicals and oxidant stress in tubular cells. Hyperglycemia and high glucose in vitro also lead to apoptosis, a form of programmed cell death. High glucose similar to those seen with hyperglycemia in people with diabetes mellitus, lead to accelerated apoptosis, a form of programmed cell death characterized by cell shrinkage, chromatin condensation and DNA fragmentation, in variety of cell types, including renal proximal tubular epithelial cells.

Noncovalent magnetic control and reversible recovery of graphene oxide using iron oxide and magnetic surfactants.

PubMed

McCoy, Thomas M; Brown, Paul; Eastoe, Julian; Tabor, Rico F

2015-01-28

The unique charging properties of graphene oxide (GO) are exploited in the preparation of a range of noncovalent magnetic GO materials, using microparticles, nanoparticles, and magnetic surfactants. Adsorption and desorption are controlled by modification of pH within a narrow window of <2 pH units. The benefit conferred by using charge-based adsorption is that the process is reversible, and the GO can be captured and separated from the magnetic nanomaterial, such that both components can be recycled. Iron oxide (Fe2O3) microparticles form a loosely flocculated gel network with GO, which is demonstrated to undergo magnetic compressional dewatering in the presence of an external magnetic field. For composites formed from GO and Fe2O3 nanoparticles, it is found that low Fe2O3:GO mass ratios (<5:1) favor flocculation of GO, whereas higher ratios (>5:1) cause overcharging of the surfaces resulting in restabilization. The effectiveness of the GO adsorption and magnetic capture process is demonstrated by separating traditionally difficult-to-recover gold nanoparticles (d ≈ 10 nm) from water. The fully recyclable nature of the assembly and capture process, combined with the vast adsorption capacity of GO, presents obvious and appealing advantages for applications in decontamination and water treatment.

Fabrication of Cu2 O-based Materials for Lithium-Ion Batteries.

PubMed

Zhang, Li; Li, Qinyuan; Xue, Huaiguo; Pang, Huan

2018-05-25

The improvement of the performance of advanced batteries has played a key role in the energy research community since its inception. Therefore, it is necessary to explore high-performance materials for applications in advanced batteries. Among the variety of materials applied in batteries, much research has been dedicated to examine cuprous oxide materials as working electrodes in lithium cells to check their suitability as anodes for Li-ion cells and this has revealed great working capacities because of their specific characteristics (polymorphic forms, controllable structure, high cycling capacity, etc.). Thus, cuprous oxide and its composites will be fully introduced in this Review for their applications in advanced batteries. It is believed that, in the future, both the study and the impact of cuprous oxide and its composites will be much more profound and lasting. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical aspects of studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.

2010-10-01

The study of adsorption of oxygen on transition metal surface is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. The structures formed on transition metal surfaces vary from simple adlayers of chemisorbed oxygen to oxygen diffusion into the sub-surface region and the formation of oxides. In this work we present the results of an ab-initio investigation of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. Calculations are also performed for the on-surface adsorption of oxygen on the unreconstructed Cu(001) surface for coverages up to one monolayer to use for comparison. The geometry of the surfaces with adsorbed oxygen is fully optimized. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy.

Neelaredoxin, an iron-binding protein from the syphilis spirochete, Treponema pallidum, is a superoxide reductase.

PubMed

Jovanović, T; Ascenso, C; Hazlett, K R; Sikkink, R; Krebs, C; Litwiller, R; Benson, L M; Moura, I; Moura, J J; Radolf, J D; Huynh, B H; Naylor, S; Rusnak, F

2000-09-15

Treponema pallidum, the causative agent of venereal syphilis, is a microaerophilic obligate pathogen of humans. As it disseminates hematogenously and invades a wide range of tissues, T. pallidum presumably must tolerate substantial oxidative stress. Analysis of the T. pallidum genome indicates that the syphilis spirochete lacks most of the iron-binding proteins present in many other bacterial pathogens, including the oxidative defense enzymes superoxide dismutase, catalase, and peroxidase, but does possess an orthologue (TP0823) for neelaredoxin, an enzyme of hyperthermophilic and sulfate-reducing anaerobes shown to possess superoxide reductase activity. To analyze the potential role of neelaredoxin in treponemal oxidative defense, we examined the biochemical, spectroscopic, and antioxidant properties of recombinant T. pallidum neelaredoxin. Neelaredoxin was shown to be expressed in T. pallidum by reverse transcriptase-polymerase chain reaction and Western blot analysis. Recombinant neelaredoxin is a 26-kDa alpha(2) homodimer containing, on average, 0.7 iron atoms/subunit. Mössbauer and EPR analysis of the purified protein indicates that the iron atom exists as a mononuclear center in a mixture of high spin ferrous and ferric oxidation states. The fully oxidized form, obtained by the addition of K(3)(Fe(CN)(6)), exhibits an optical spectrum with absorbances at 280, 320, and 656 nm; the last feature is responsible for the protein's blue color, which disappears upon ascorbate reduction. The fully oxidized protein has a A(280)/A(656) ratio of 10.3. Enzymatic studies revealed that T. pallidum neelaredoxin is able to catalyze a redox equilibrium between superoxide and hydrogen peroxide, a result consistent with it being a superoxide reductase. This finding, the first description of a T. pallidum iron-binding protein, indicates that the syphilis spirochete copes with oxidative stress via a primitive mechanism, which, thus far, has not been described in pathogenic bacteria.

Improved adhesion of ultra-hard carbon films on cobalt–chromium orthopaedic implant alloy

PubMed Central

Vaid, Rishi; Diggins, Patrick; Weimer, Jeffrey J.; Koopman, M.; Vohra, Yogesh K.

2010-01-01

While interfacial graphite formation and subsequent poor film adhesion is commonly reported for chemical vapor deposited hard carbon films on cobalt-based materials, we find the presence of O2 in the feedgas mixture to be useful in achieving adhesion on a CoCrMo alloy. Nucleation studies of surface structure before formation of fully coalesced hard carbon films reveal that O2 feedgas helps mask the catalytic effect of cobalt with carbon through early formation of chromium oxides and carbides. The chromium oxides, in particular, act as a diffusion barrier to cobalt, minimizing its migration to the surface where it would otherwise interact deleteriously with carbon to form graphite. When O2 is not used, graphitic soot forms and films delaminate readily upon cooling to room temperature. Continuous 1 μm-thick nanostructured carbon films grown with O2 remain adhered with measured hardness of 60 GPa and show stable, non-catastrophic circumferential micro-cracks near the edges of indent craters made using Rockwell indentation. PMID:21221739

TiOx thin films grown on Pd(100) and Pd(111) by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Farstad, M. H.; Ragazzon, D.; Grönbeck, H.; Strømsheim, M. D.; Stavrakas, C.; Gustafson, J.; Sandell, A.; Borg, A.

2016-07-01

The growth of ultrathin TiOx (0≤x≤2) films on Pd(100) and Pd(111) surfaces by chemical vapor deposition (CVD), using Titanium(IV)isopropoxide (TTIP) as precursor, has been investigated by high resolution photoelectron spectroscopy, low energy electron diffraction and scanning tunneling microscopy. Three different TiOx phases and one Pd-Ti alloy phase have been identified for both surfaces. The Pd-Ti alloy phase is observed at the initial stages of film growth. Density functional theory (DFT) calculations for Pd(100) and Pd(111) suggest that Ti is alloyed into the second layer of the substrate. Increasing the TTIP dose yields a wetting layer comprising Ti2 + species (TiOx, x ∼0.75). On Pd(100), this phase exhibits a mixture of structures with (3 × 5) and (4 × 5) periodicity with respect to the Pd(100) substrate, while an incommensurate structure is formed on Pd(111). Most importantly, on both surfaces this phase consists of a zigzag pattern similar to observations on other reactive metal surfaces. Further increase in coverage results in growth of a fully oxidized (TiO2) phase on top of the partially oxidized layer. Preliminary investigations indicate that the fully oxidized phase on both Pd(100) and Pd(111) may be the TiO2(B) phase.

12Cao-7Al2o3 Electride Hollow Cathode

NASA Technical Reports Server (NTRS)

Martinez, Rafael A. (Inventor); Williams, John D. (Inventor); Rand, Lauren P. (Inventor)

2016-01-01

The use of the electride form of 12CaO-7Al.sub.2O.sub.3, or C12A7, as a low work function electron emitter in a hollow cathode discharge apparatus is described. No heater is required to initiate operation of the present cathode, as is necessary for traditional hollow cathode devices. Because C12A7 has a fully oxidized lattice structure, exposure to oxygen does not degrade the electride. The electride was surrounded by a graphite liner since it was found that the C12A7 electride converts to it's eutectic (CA+C3A) form when heated (through natural hollow cathode operation) in a metal tube.

12CaO-7Al2O3 Electride Hollow Cathode

NASA Technical Reports Server (NTRS)

Williams, John D. (Inventor); Rand, Lauren P. (Inventor); Martinez, Rafael A. (Inventor)

2017-01-01

The use of the electride form of 12CaO-7Al2O3, or C12A7, as a low work function electron emitter in a hollow cathode discharge apparatus is described. No heater is required to initiate operation of the present cathode, as is necessary for traditional hollow cathode devices. Because C12A7 has a fully oxidized lattice structure, exposure to oxygen does not degrade the electride. The electride was surrounded by a graphite liner since it was found that the C12A7 electride converts to it's eutectic (CA+C3A) form when heated (through natural hollow cathode operation) in a metal tube.

Corrosion behavior and oxide properties of Zr 1.1 wt%Nb 0.05 wt%Cu alloy

NASA Astrophysics Data System (ADS)

Park, Jeong-Yong; Choi, Byung-Kwon; Yoo, Seung Jo; Jeong, Yong Hwan

2006-12-01

The corrosion behavior and oxide properties of Zr-1.1 wt%Nb-0.05 wt%Cu (ZrNbCu) and Zircaloy-4 have been investigated. The corrosion rate of the ZrNbCu alloy was much lower than that of the Zirclaoy-4 in the 360 °C water and 360 °C PWR-simulating loop condition without a neutron flux and it was increased with an increase of the final annealing temperature from 470 °C to 570 °C. TEM observations revealed that the precipitates in the ZrNbCu were β-Nb and ZrNbFe-precipitate with β-Nb being more frequently observed and that the precipitates were more finely distributed in the ZrNbCu alloy. It was also observed that the oxides of the ZrNbCu and Zircaloy-4 consisted of two and seven layers, respectively, after 1000 days in the PWR-simulating loop condition and that the thickness of a fully-developed layer was higher in the ZrNbCu than in the Zircaloy-4. It was also found that the β-Nb in ZrNbCu was oxidized more slowly when compared to the Zr(Fe, Cr) 2 in Zirclaoy-4 when the precipitates in the oxide were observed by TEM. Cracks were observed in the vicinity of the oxidized Zr(Fe, Cr) 2, while no cracks were formed near β-Nb which had retained a metallic state. From the results obtained, it is suggested that the oxide formed on the ZrNbCu has a more protective nature against a corrosion when compared to that of the Zircaloy-4.

Vacancies and holes in bulk and at 180° domain walls in lead titanate

NASA Astrophysics Data System (ADS)

Paillard, Charles; Geneste, Grégory; Bellaiche, Laurent; Dkhil, Brahim

2017-12-01

Domain walls (DWs) in ferroic materials exhibit a plethora of unexpected properties that are different from the adjacent ferroic domains. Still, the intrinsic/extrinsic origin of these properties remains an open question. Here, density functional theory calculations are used to investigate the interaction between vacancies and 180° DWs in the prototypical ferroelectric PbTiO3, with a special emphasis on cationic vacancies and released holes. All vacancies are more easily formed within the DW than in the domains. This is interpreted, using a phenomenological model, as the partial compensation of an extra-tensile stress when the defect is created inside the DW. Oxygen vacancies are found to be always fully ionized, independently of the thermodynamic conditions, while cationic vacancies can be either neutral or partially ionized (oxygen-rich conditions), or fully ionized (oxygen-poor conditions). Therefore, in oxidizing conditions, holes are induced by neutral and partially ionized Pb vacancies. In the bulk PbTiO3, these holes are more stable as delocalized rather than small polarons, but at DWs, the two forms are found to be possible.

Zirconium-based conversion film formation on zinc, aluminium and magnesium oxides and their interactions with functionalized molecules

NASA Astrophysics Data System (ADS)

Fockaert, L. I.; Taheri, P.; Abrahami, S. T.; Boelen, B.; Terryn, H.; Mol, J. M. C.

2017-11-01

Zirconium-based conversion treatment of zinc, aluminium and magnesium oxides have been studied in-situ using ATR-FTIR in a Kretschmann geometry. This set-up was coupled to an electrochemical cell, which allowed to obtain chemical and electrochemical information simultaneously as a function of conversion time. This elucidated the strong relation between physico-chemical surface properties and zirconium-based conversion kinetics. Whereas the surface hydroxyl density of zinc and aluminium increased during conversion, magnesium (hydr)oxide was shown to dissolve in the acid solution. Due to this dissolution, strong surface alkalization can be expected, explaining the rapid conversion kinetics. AES depth profiling was used to determine the final oxide thickness and elemental composition. This confirmed that magnesium is most active and forms a zirconium oxide layer approximately 10 times thicker than zinc. On the other hand, the presence of zirconium oxide on aluminium is very low and can be considered as not fully covering the metal oxide. Additionally, the converted oxide chemistry was related to the bonding mechanisms of amide functionalized molecules using ATR-FTIR and XPS. It was shown that inclusion of zirconium altered the acid-base properties, increasing the substrate proton donating capabilities in case of magnesium oxide and increasing hydrogen bonding and Bronsted interactions due to increased surface hydroxide fractions on zinc and aluminium substrates.

Friction, wear, and transfer of carbon and graphite to copper, chromium, and aluminum metal surfaces in vacuum

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

Sliding friction experiments were conducted with amorphous and fully graphitized carbons sliding on copper and on films of chromium and aluminum on copper. Auger emission spectroscopy analysis was used to monitor carbon transfer to the metal surfaces. Friction and wear were also measured. Metal surfaces were examined both in the clean state and with normal oxides present. Results indicate that different metals have an important effect on friction, wear, and transfer characteristics. With amorphous carbon, the least chemically active metal gave the highest wear and amount of carbon transfer. Both forms of carbon gave lower friction and wear and lower transfer rates when in contact with clean, as opposed to oxide-covered, chromium surfaces. With copper, the reverse was true; cleaning was detrimental.

Core/shell structured Zn/ZnO nanoparticles synthesized by gaseous laser ablation with enhanced photocatalysis efficiency

NASA Astrophysics Data System (ADS)

Song, Lu; Wang, Yafei; Ma, Jing; Zhang, Qinghua; Shen, Zhijian

2018-06-01

Zinc oxide (ZnO) is a competitive candidate in semiconductor photocatalysts, only if the efficiency could be fully optimized especially by tailored nanostructures. Here we report a kind of core/shell structured Zn/ZnO nanoparticles with enhanced photocatalysis efficiency, which were synthesized by a highly-productive gaseous laser ablation method. The nanodroplets generated by laser ablation would be reduced to zinc in the protective atmosphere, and further be oxidized at surface to form a specific core/shell structured Zn/ZnO nanoparticles within seconds. Thanks to the formation of this Zn-ZnO Schottky junction, the photocatalysis degradation efficiency of such core/shell Zn/ZnO nanostructure is significantly improved owing to the enhanced visible light absorption and inhibited carrier recombination by introducing the metallic zinc.

Structural Characterization of Biogenic Manganese Oxides Produced in Sea Water

NASA Astrophysics Data System (ADS)

Webb, S. M.; Bargar, J. R.; Tebo, B. M.

2003-12-01

Manganese oxides have been coined as the "scavengers of the sea" and play important roles in both marine and freshwater systems. Natural manganese oxide nanoparticles and grain coatings are ubiquitous in the environment and profoundly impact the quality of sediments via their ability to degrade and sequester contaminants. These oxides are believed to form dominantly via oxidation of Mn(II) by marine and freshwater bacteria and have extremely high sorptive capacities for heavy metals. We have used XANES, EXAFS, and synchrotron (SR)-XRD techniques to study biogenic manganese oxides produced by spores of the marine Bacillus sp., strain SG-1 in seawater as a function of reaction time under fully in-situ conditions. The primary biogenic solid-phase Mn oxide product is a hexagonal layered phyollomanganate with an oxidation state similar to that in delta-MnO2. XRD data show the biooxides to have a phyllomanganate 10 basal plane spacing, suggesting the interlayer is hydrated and contains calcium. As the experiment continues, the initial biooxide changes to show triclinic symmetry. Fits to these EXAFS spectra suggest the octahedral layers have low Mn octahedral site vacancies in the lattice and the latyers bend to accommodate Jahn-Teller distortions creating the change in symmetry. The oxides observed in this study as models of Mn(II) bio-oxidation may be representative of the most abundant manganese oxide phase suspended in the oxic and sub-oxic zones of the oceanic water column.

Nitric oxide and superoxide dismutase modulate endothelial progenitor cell function in type 2 diabetes mellitus.

PubMed

Hamed, Saher; Brenner, Benjamin; Aharon, Anat; Daoud, Deeb; Roguin, Ariel

2009-10-30

The function of endothelial progenitor cells (EPCs), which are key cells in vascular repair, is impaired in diabetes mellitus. Nitric oxide (NO) and reactive oxygen species can regulate EPC functions. EPCs tolerate oxidative stress by upregulating superoxide dismutase (SOD), the enzyme that neutralizes superoxide anion (O2-). Therefore, we investigated the roles of NO and SOD in glucose-stressed EPCs. The functions of circulating EPCs from patients with type 2 diabetes were compared to those from healthy individuals. Healthy EPCs were glucose-stressed, and then treated with insulin and/or SOD. We assessed O2- generation, NO production, SOD activity, and their ability to form colonies. EPCs from diabetic patients generated more O2-, had higher NAD(P)H oxidase and SOD activity, but lower NO bioavailability, and expressed higher mRNA and protein levels of p22-phox, and manganese SOD and copper/zinc SOD than those from the healthy individuals. Plasma glucose and HbA1c levels in the diabetic patients were correlated negatively with the NO production from their EPCs. SOD treatment of glucose-stressed EPCs attenuated O2- generation, restored NO production, and partially restored their ability to form colonies. Insulin treatment of glucose-stressed EPCs increased NO production, but did not change O2- generation and their ability to form colonies. However, their ability to produce NO and to form colonies was fully restored after combined SOD and insulin treatment. Our data provide evidence that SOD may play an essential role in EPCs, and emphasize the important role of antioxidant therapy in type 2 diabetic patients.

Fast and fully-scalable synthesis of reduced graphene oxide

NASA Astrophysics Data System (ADS)

Abdolhosseinzadeh, Sina; Asgharzadeh, Hamed; Seop Kim, Hyoung

2015-05-01

Exfoliation of graphite is a promising approach for large-scale production of graphene. Oxidation of graphite effectively facilitates the exfoliation process, yet necessitates several lengthy washing and reduction processes to convert the exfoliated graphite oxide (graphene oxide, GO) to reduced graphene oxide (RGO). Although filtration, centrifugation and dialysis have been frequently used in the washing stage, none of them is favorable for large-scale production. Here, we report the synthesis of RGO by sonication-assisted oxidation of graphite in a solution of potassium permanganate and concentrated sulfuric acid followed by reduction with ascorbic acid prior to any washing processes. GO loses its hydrophilicity during the reduction stage which facilitates the washing step and reduces the time required for production of RGO. Furthermore, simultaneous oxidation and exfoliation significantly enhance the yield of few-layer GO. We hope this one-pot and fully-scalable protocol paves the road toward out of lab applications of graphene.

Burning Graphene Layer-by-Layer

PubMed Central

Ermakov, Victor A.; Alaferdov, Andrei V.; Vaz, Alfredo R.; Perim, Eric; Autreto, Pedro A. S.; Paupitz, Ricardo; Galvao, Douglas S.; Moshkalev, Stanislav A.

2015-01-01

Graphene, in single layer or multi-layer forms, holds great promise for future electronics and high-temperature applications. Resistance to oxidation, an important property for high-temperature applications, has not yet been extensively investigated. Controlled thinning of multi-layer graphene (MLG), e.g., by plasma or laser processing is another challenge, since the existing methods produce non-uniform thinning or introduce undesirable defects in the basal plane. We report here that heating to extremely high temperatures (exceeding 2000 K) and controllable layer-by-layer burning (thinning) can be achieved by low-power laser processing of suspended high-quality MLG in air in “cold-wall” reactor configuration. In contrast, localized laser heating of supported samples results in non-uniform graphene burning at much higher rates. Fully atomistic molecular dynamics simulations were also performed to reveal details of oxidation mechanisms leading to uniform layer-by-layer graphene gasification. The extraordinary resistance of MLG to oxidation paves the way to novel high-temperature applications as continuum light source or scaffolding material. PMID:26100466

Tuning the band gap in silicene by oxidation.

PubMed

Du, Yi; Zhuang, Jincheng; Liu, Hongsheng; Xu, Xun; Eilers, Stefan; Wu, Kehui; Cheng, Peng; Zhao, Jijun; Pi, Xiaodong; See, Khay Wai; Peleckis, Germanas; Wang, Xiaolin; Dou, Shi Xue

2014-10-28

Silicene monolayers grown on Ag(111) surfaces demonstrate a band gap that is tunable by oxygen adatoms from semimetallic to semiconducting type. With the use of low-temperature scanning tunneling microscopy, we find that the adsorption configurations and amounts of oxygen adatoms on the silicene surface are critical for band gap engineering, which is dominated by different buckled structures in √13 × √13, 4 × 4, and 2√3 × 2√3 silicene layers. The Si-O-Si bonds are the most energy-favored species formed on √13 × √13, 4 × 4, and 2√3 × 2√3 structures under oxidation, which is verified by in situ Raman spectroscopy as well as first-principles calculations. The silicene monolayers retain their structures when fully covered by oxygen adatoms. Our work demonstrates the feasibility of tuning the band gap of silicene with oxygen adatoms, which, in turn, expands the base of available two-dimensional electronic materials for devices with properties that is hardly achieved with graphene oxide.

Universal Responses of Cyclic-Oxidation Models Studied

NASA Technical Reports Server (NTRS)

Smialek, James L.

2003-01-01

Oxidation is an important degradation process for materials operating in the high-temperature air or oxygen environments typical of jet turbine or rocket engines. Reaction of the combustion gases with the component material forms surface layer scales during these oxidative exposures. Typically, the instantaneous rate of reaction is inversely proportional to the existing scale thickness, giving rise to parabolic kinetics. However, more realistic applications entail periodic startup and shutdown. Some scale spallation may occur upon cooling, resulting in loss of the protective diffusion barrier provided by a fully intact scale. Upon reheating, the component will experience accelerated oxidation due to this spallation. Cyclic-oxidation testing has, therefore, been a mainstay of characterization and performance ranking for high-temperature materials. Models simulate this process by calculating how a scale spalls upon cooling and regrows upon heating (refs. 1 to 3). Recently released NASA software (COSP for Windows) allows researchers to specify a uniform layer or discrete segments of spallation (ref. 4). Families of model curves exhibit consistent regularity and trends with input parameters, and characteristic features have been empirically described in terms of these parameters. Although much insight has been gained from experimental and model curves, no equation has been derived that can describe this behavior explicitly as functions of the key oxidation parameters.

Reactions of electron-transfer flavoprotein and electron-transfer flavoprotein: ubiquinone oxidoreductase.

PubMed Central

Ramsay, R R; Steenkamp, D J; Husain, M

1987-01-01

Electron-transfer flavoprotein:ubiquinone oxidoreductase (ETF-Q oxidoreductase) catalyses the re-oxidation of reduced electron-transfer flavoprotein (ETF) with ubiquinone-1 (Q-1) as the electron acceptor. A kinetic assay for the enzyme was devised in which glutaryl-CoA in the presence of glutaryl-CoA dehydrogenase was used to reduce ETFox. and the reduction of Q-1 was monitored at 275 nm. The partial reactions involved in the overall assay system were examined. Glutaryl-CoA dehydrogenase catalyses the rapid reduction of ETFox. to the anionic semiquinone (ETF.-), but reduces ETF.- to the fully reduced form (ETFhq) at a rate that is about 6-fold lower. ETF.-, but not ETFhq, is directly re-oxidized by Q-1 at a rate that, depending on the steady-state concentration of ETF.-, may contribute significantly to the overall reaction. ETF-Q oxidoreductase catalyses rapid disproportionation of ETF.- with an equilibrium constant of about 1.0 at pH 7.8. In the presence of Q-1 it also catalyses the re-oxidation of ETFhq at a rate that is faster than that of the overall reaction. Rapid-scan experiments indicated the formation of ETF.-, but its fractional concentration in the early stages of the re-oxidation of ETFhq is low. The data indicate that the re-oxidation of ETFhq proceeds at a rate that is adequate to account for the overall rate of electron transfer from glutaryl-CoA to Q-1. An unusual property of ETF-Q oxidoreductase seems to be that it not only catalyses the re-oxidation of the reduced forms of ETF but also facilitates the complete reduction of ETFox. to ETFhq by disproportionation of the radical. PMID:3593226

Linking Mn(II)-oxidizing bacteria to natural attenuation at a former U mining site

NASA Astrophysics Data System (ADS)

Akob, D.; Bohu, T.; Beyer, A.; Schäffner, F.; Händel, M.; Johnson, C.; Merten, D.; Büchel, G.; Totsche, K.; Küsel, K.

2012-04-01

Uranium mining near Ronneburg, Germany resulted in widespread environmental contamination with acid mine drainage (AMD) and high concentrations of heavy metals and radionuclides. Despite physical remediation of the area, groundwater is still a source of heavy metal contaminants, e.g., Cd, Ni, Co, Cu and Zn, to nearby ecosystems. However, natural attenuation of heavy metals is occurring in Mn oxide rich soils and sediments ranging in pH from 5 to 7. While microorganisms readily oxidize Mn(II) and precipitate Mn oxides at pH ~7 under oxic conditions, few studies describe Mn(II)-oxidizing bacteria (MOB) at pH ~5 and/or in the presence of heavy metals. In this study we (1) isolated MOB from the contaminated Ronneburg area at pH 5.5 and 7 and (2) evaluated the biological formation of Mn oxides. We isolated nine MOB strains at pH 7 (members of the Proteobacteria, Actinobacteria, Bacteroidetes, and Firmicutes phyla) and a single isolate at pH 5.5 (Oxalobacteraceae isolate AB_14, within the β-Proteobacteria). LA-ICP-MS showed that all isolates accumulated Mn and Fe in their biomass. However, the Oxalobacteraceae isolate AB_14 oxidizes more Mn without additional Fe in the medium. Preliminary FTIR analysis indicated that all isolates formed precipitates, which showed absorption bands that were characteristic for birnessite. High resolution TEM showed variable morphology of precipitates and EDS confirmed the presence of Mn oxides. Isolate AB_14 was not surrounded with precipitates whereas our Actinobacteria isolate AB_18 was encrusted with Mn oxides. Electron diffraction is currently being used to confirm the presence of birnessite and other Mn oxide phases. This, the first known report of any organism capable of Mn oxidation at low pH, demonstrated that MOB can be involved in the natural attenuation of both moderately acidic and neutral pH soils and sediments via the formation of biogenic Mn oxides. Future work will fully evaluate the minerals formed in this process as well as their interactions with contaminating heavy metals and radionuclides.

Constraining the timing of the Great Oxidation Event within the Rubisco phylogenetic tree.

PubMed

Kacar, B; Hanson-Smith, V; Adam, Z R; Boekelheide, N

2017-09-01

Ribulose 1,5-bisphosphate (RuBP) carboxylase/oxygenase (RuBisCO, or Rubisco) catalyzes a key reaction by which inorganic carbon is converted into organic carbon in the metabolism of many aerobic and anaerobic organisms. Across the broader Rubisco protein family, homologs exhibit diverse biochemical characteristics and metabolic functions, but the evolutionary origins of this diversity are unclear. Evidence of the timing of Rubisco family emergence and diversification of its different forms has been obscured by a meager paleontological record of early Earth biota, their subcellular physiology and metabolic components. Here, we use computational models to reconstruct a Rubisco family phylogenetic tree, ancestral amino acid sequences at branching points on the tree, and protein structures for several key ancestors. Analysis of historic substitutions with respect to their structural locations shows that there were distinct periods of amino acid substitution enrichment above background levels near and within its oxygen-sensitive active site and subunit interfaces over the divergence between Form III (associated with anoxia) and Form I (associated with oxia) groups in its evolutionary history. One possible interpretation is that these periods of substitutional enrichment are coincident with oxidative stress exerted by the rise of oxygenic photosynthesis in the Precambrian era. Our interpretation implies that the periods of Rubisco substitutional enrichment inferred near the transition from anaerobic Form III to aerobic Form I ancestral sequences predate the acquisition of Rubisco by fully derived cyanobacterial (i.e., dual photosystem-bearing, oxygen-evolving) clades. The partitioning of extant lineages at high clade levels within our Rubisco phylogeny indicates that horizontal transfer of Rubisco is a relatively infrequent event. Therefore, it is possible that the mutational enrichment periods between the Form III and Form I common ancestral sequences correspond to the adaptation of key oxygen-sensitive components of Rubisco prior to, or coincident with, the Great Oxidation Event. © 2017 The Authors. Geobiology Published by John Wiley & Sons Ltd.

Oxyhydroxide of metallic nanowires in a molecular H2O and H2O2 environment and their effects on mechanical properties.

PubMed

Aral, Gurcan; Islam, Md Mahbubul; Wang, Yun-Jiang; Ogata, Shigenobu; Duin, Adri C T van

2018-06-14

To avoid unexpected environmental mechanical failure, there is a strong need to fully understand the details of the oxidation process and intrinsic mechanical properties of reactive metallic iron (Fe) nanowires (NWs) under various aqueous reactive environmental conditions. Herein, we employed ReaxFF reactive molecular dynamics (MD) simulations to elucidate the oxidation of Fe NWs exposed to molecular water (H2O) and hydrogen peroxide (H2O2) environment, and the influence of the oxide shell layer on the tensile mechanical deformation properties of Fe NWs. Our structural analysis shows that oxidation of Fe NWs occurs with the formation of different iron oxide and hydroxide phases in the aqueous molecular H2O and H2O2 oxidizing environments. We observe that the resulting microstructure due to pre-oxide shell layer formation reduces the mechanical stress via increasing the initial defect sites in the vicinity of the oxide region to facilitate the onset of plastic deformation during tensile loading. Specifically, the oxide layer of Fe NWs formed in the H2O2 environment has a relatively significant effect on the deterioration of the mechanical properties of Fe NWs. The weakening of the yield stress and Young modulus of H2O2 oxidized Fe NWs indicates the important role of local oxide microstructures on mechanical deformation properties of individual Fe NWs. Notably, deformation twinning is found as the primary mechanical plastic deformation mechanism of all Fe NWs, but it is initially observed at low strain and stress level for the oxidized Fe NWs.

Relationship of microstructure properties to oxygen impurities in nanocrystalline silicon photovoltaic materials

NASA Astrophysics Data System (ADS)

Xu, H.; Wen, C.; Liu, H.; Li, Z. P.; Shen, W. Z.

2013-03-01

We have fully investigated the correlation of microstructure properties and oxygen impurities in hydrogenated nanocrystalline silicon photovoltaic films. The achievement has been realized through a series of different hydrogen dilution ratio treatment by plasma enhanced chemical vapor deposition system. Raman scattering, x-ray diffraction, and ultraviolet-visible transmission techniques have been employed to characterize the physical structural characterization and to elucidate the structure evolution. The bonding configuration of the oxygen impurities was investigated by x-ray photoelectron spectroscopy and the Si-O stretching mode of infrared-transmission, indicating that the films were well oxidized in SiO2 form. Based on the consistence between the proposed structure factor and the oxygen content, we have demonstrated that there are two dominant disordered structure regions closely related to the post-oxidation contamination: plate-like configuration and clustered microvoids.

Acrolein oxidizes the cytosolic and mitochondrial thioredoxins in human endothelial cells.

PubMed

Szadkowski, Adam; Myers, Charles R

2008-01-14

Acrolein is a reactive aldehyde that is a widespread environmental pollutant and can be generated endogenously from lipid peroxidation. The thioredoxin (Trx) system in endothelial cells plays a major role in the maintenance of cellular thiol redox balance, and is critical for cell survival. Normally, cells maintain the cytosolic (Trx1) and mitochondrial (Trx2) thioredoxins largely in the reduced state. In human microvascular endothelial cells, Trx1 was more sensitive than Trx2 to oxidation by acrolein. A 30-min exposure to 2.5 microM acrolein caused partial oxidation of Trx1 but not Trx2. The active site dithiol of Trx1 was essentially completely oxidized by 5 microM acrolein whereas 12.5 microM was required for complete oxidation of Trx2. Partial recovery of the Trx1 redox status was observed over a 4h acrolein-free recovery period, with increases in the reduced form and decreases in the fully oxidized form. For cells treated with 2.5 or 5 microM acrolein the recovery did not require protein synthesis, whereas protein synthesis was required for the return of reduced Trx1 in cells treated with 12.5 microM acrolein. Pretreatment of cells with N-acetylcysteine (NAC) resulted in partial protection of Trx1 from oxidation by acrolein. In cells treated with acrolein for 30 min, followed by a 14- to 16-h acrolein-free period, small but significant cytotoxic effects were observed with 2.5 microM acrolein whereas all cells were adversely affected by >or= 12.5 microM. NAC pretreatment significantly decreased the percentage of stressed cells subsequently exposed to 5 or 12.5 microM acrolein. Given the critical role of the thioredoxins in cell survival, the ability of acrolein to oxidize both thioredoxins should be taken into account for a thorough understanding of its cytotoxic effects.

Composition-controlled active-passive transition and corrosion behavior of Fe-Cr(Mo)-Zr-B bulk amorphous steels

NASA Astrophysics Data System (ADS)

Si, Jiajia; Wu, Yidong; Wang, Tan; Liu, Yanhui; Hui, Xidong

2018-07-01

Various corrosive environments in daily life and industry have put forward high requirement on corrosion resistance of metals, especially steels. Unlike the strict demand in Cr content of crystalline stainless steels, amorphous steels (ASs) with lower Cr content can be endowed with outstanding corrosion resistance, while the intrinsic mechanism is not fully understood. Herein, we present a novel Fe92-x-y-zCrxMoyZr8Bz (6 ≤ x ≤ 40, 0 ≤ y ≤ 22, and 12 ≤ z ≤ 18) bulk amorphous steel (BAS) forming system and reveal the synergistic effect of Cr and Mo in determining the chemical stability of oxide films. It has been found the Fe92-x-zCrxZr8Bz BASs with 1 mm in diameter display a Cr-controlling active-passive transition at the Cr threshold of ∼25% in 1 M hydrochloric acid. When adding minor Mo into the BASs, the Cr threshold can be remarkably reduced by forming favorable hexavalent Mo oxides. The generation of Mo6+ is facilitated by atomic selective dissolution at the interface and can promote the passivation. In contrast, when the Cr content of the Mo-doped glasses exceeds 25%, few Mo6+ oxides would produce as the prior formation of protective passive films inhibits the further oxidation of Mo. Therefore, manipulating the active-passive transition properly is crucial to designing ASs with high stainlessness.

Role of Oxidative Damage in Radiation-Induced Bone Loss

NASA Technical Reports Server (NTRS)

Schreurs, Ann-Sofie; Alwood, Joshua S.; Limoli, Charles L.; Globus, Ruth K.

2014-01-01

During prolonged spaceflight, astronauts are exposed to both microgravity and space radiation, and are at risk for increased skeletal fragility due to bone loss. Evidence from rodent experiments demonstrates that both microgravity and ionizing radiation can cause bone loss due to increased bone-resorbing osteoclasts and decreased bone-forming osteoblasts, although the underlying molecular mechanisms for these changes are not fully understood. We hypothesized that excess reactive oxidative species (ROS), produced by conditions that simulate spaceflight, alter the tight balance between osteoclast and osteoblast activities, leading to accelerated skeletal remodeling and culminating in bone loss. To test this, we used the MCAT mouse model; these transgenic mice over-express the human catalase gene targeted to mitochondria, the major organelle contributing free radicals. Catalase is an anti-oxidant that converts reactive species, hydrogen peroxide into water and oxygen. This animal model was selected as it displays extended lifespan, reduced cardiovascular disease and reduced central nervous system radio-sensitivity, consistent with elevated anti-oxidant activity conferred by the transgene. We reasoned that mice overexpressing catalase in mitochondria of osteoblast and osteoclast lineage cells would be protected from the bone loss caused by simulated spaceflight. Over-expression of human catalase localized to mitochondria caused various skeletal phenotypic changes compared to WT mice; this includes greater bone length, decreased cortical bone area and moment of inertia, and indications of altered microarchitecture. These findings indicate mitochondrial ROS are important for normal bone-remodeling and skeletal integrity. Catalase over-expression did not fully protect skeletal tissue from structural decrements caused by simulated spaceflight; however there was significant protection in terms of cellular oxidative damage (MDA levels) to the skeletal tissue. Furthermore, we used an array of countermeasures (Antioxidant diets and injections) to prevent the radiation-induced bone loss, although these did not prevent bone loss, analysis is ongoing to determine if these countermeasure protected radiation-induced damage to other tissues.

Comprehensive Analysis of the Gas- and Particle-Phase Products of VOC Oxidation

NASA Astrophysics Data System (ADS)

Bakker-Arkema, J.; Ziemann, P. J.

2017-12-01

Controlled environmental chamber studies are important for determining atmospheric reaction mechanisms and gas and aerosol products formed in the oxidation of volatile organic compounds (VOCs). Such information is necessary for developing detailed chemical models for use in predicting the atmospheric fate of VOCs and also secondary organic aerosol (SOA) formation. However, complete characterization of atmospheric oxidation reactions, including gas- and particle-phase product yields, and reaction branching ratios, are difficult to achieve. In this work, we investigated the reactions of terminal and internal alkenes with OH radicals in the presence of NOx in an attempt to fully characterize the chemistry of these systems while minimizing and accounting for the inherent uncertainties associated with environmental chamber experiments. Gas-phase products (aldehydes formed by alkoxy radical decomposition) and particle-phase products (alkyl nitrates, β-hydroxynitrates, dihydroxynitrates, 1,4-hydroxynitrates, 1,4-hydroxycarbonyls, and dihydroxycarbonyls) formed through pathways involving addition of OH to the C=C double bond as well as H-atom abstraction were identified and quantified using a suite of analytical techniques. Particle-phase products were analyzed in real time with a thermal desorption particle beam mass spectrometer; and off-line by collection onto filters, extraction, and subsequent analysis of functional groups by derivatization-spectrophotometric methods developed in our lab. Derivatized products were also separated by liquid chromatography for molecular quantitation by UV absorbance and identification using chemical ionization-ion trap mass spectrometry. Gas phase aldehydes were analyzed off-line by collection onto Tenax and a 5-channel denuder with subsequent analysis by gas chromatography, or by collection onto DNPH-coated cartridges and subsequent analysis by liquid chromatography. The full product identification and quantitation, with careful minimization of uncertainties for the various components of the experiment and analyses, demonstrates our capability to comprehensively and accurately analyze the complex chemical composition of products formed in the oxidation of organic compounds in laboratory chamber studies.

Electrical compensation by Ga vacancies in Ga2O3 thin films

NASA Astrophysics Data System (ADS)

Korhonen, E.; Tuomisto, F.; Gogova, D.; Wagner, G.; Baldini, M.; Galazka, Z.; Schewski, R.; Albrecht, M.

2015-06-01

The authors have applied positron annihilation spectroscopy to study the vacancy defects in undoped and Si-doped Ga2O3 thin films. The results show that Ga vacancies are formed efficiently during metal-organic vapor phase epitaxy growth of Ga2O3 thin films. Their concentrations are high enough to fully account for the electrical compensation of Si doping. This is in clear contrast to another n-type transparent semiconducting oxide In2O3, where recent results show that n-type conductivity is not limited by cation vacancies but by other intrinsic defects such as Oi.

Bioavailable flavonoids: cytochrome P450-mediated metabolism of methoxyflavones.

PubMed

Walle, U Kristina; Walle, Thomas

2007-11-01

Methoxylated flavones were recently shown to be promising cancer chemopreventive agents. Their high metabolic stability compared with the hydroxylated analogs was shown in our laboratory using the human hepatic S9 fraction with cofactors for glucuronidation, sulfation, and oxidation. In the present study, the resistance of methoxylated flavones toward oxidative metabolism was investigated with human liver microsomes and recombinant cytochrome P450 (P450) isoforms. Among 15 methoxylated flavones investigated, the two partially methylated compounds, tectochrysin and kaempferide, were among the most susceptible to microsomal oxidation (Cl(int) 283 and 82 ml/min/kg). Of the fully methylated compounds, 5,7-dimethoxyflavone and 5-methoxyflavone were the most stable (Cl(int) 13 and 18 ml/min/kg, respectively), whereas 4'-methoxyflavone, 3'-methoxyflavone, 5,4'-dimethoxyflavone, and 7,3'-dimethoxyflavone were the least stable (Cl(int) 161, 140, 119, and 92 ml/min/kg, respectively), emphasizing the importance of the positions of the methoxy substituents in the flavone ring system. Among the five P450 isoforms tested, CYP1A1 showed the highest rate of metabolism of fully methylated compounds, followed by CYP1A2 and CYP3A4. CYP2C9 and CYP2D6 gave minimal disappearance of the parent compound. Finally, in incubations with hepatic S9 fraction with cofactors for oxidation and both conjugation reactions, partially methylated flavones, as expected, were much less metabolically stable than fully methylated flavones, confirming that oxidative demethylation is the rate-limiting metabolic reaction for fully methylated flavones only. In summary, the rate of oxidative metabolism of methoxylated flavones, mainly involving CYP1A1 and CYP1A2, varied widely, even between compounds with very similar structures.

3-Axis Fully-Integrated Capacitive Tactile Sensor with Flip-Bonded CMOS on LTCC Interposer.

PubMed

Asano, Sho; Muroyama, Masanori; Nakayama, Takahiro; Hata, Yoshiyuki; Nonomura, Yutaka; Tanaka, Shuji

2017-10-25

This paper reports a 3-axis fully integrated differential capacitive tactile sensor surface-mountable on a bus line. The sensor integrates a flip-bonded complementary metal-oxide semiconductor (CMOS) with capacitive sensing circuits on a low temperature cofired ceramic (LTCC) interposer with Au through vias by Au-Au thermo-compression bonding. The CMOS circuit and bonding pads on the sensor backside were electrically connected through Au bumps and the LTCC interposer, and the differential capacitive gap was formed by an Au sealing frame. A diaphragm for sensing 3-axis force was formed in the CMOS substrate. The dimensions of the completed sensor are 2.5 mm in width, 2.5 mm in length, and 0.66 mm in thickness. The fabricated sensor output coded 3-axis capacitive sensing data according to applied 3-axis force by three-dimensional (3D)-printed pins. The measured sensitivity was as high as over 34 Count/mN for normal force and 14 to 15 Count/mN for shear force with small noise, which corresponds to less than 1 mN. The hysteresis and the average cross-sensitivity were also found to be less than 2% full scale and 11%, respectively.

3-Axis Fully-Integrated Capacitive Tactile Sensor with Flip-Bonded CMOS on LTCC Interposer †

PubMed Central

Asano, Sho; Nakayama, Takahiro; Hata, Yoshiyuki; Tanaka, Shuji

2017-01-01

This paper reports a 3-axis fully integrated differential capacitive tactile sensor surface-mountable on a bus line. The sensor integrates a flip-bonded complementary metal-oxide semiconductor (CMOS) with capacitive sensing circuits on a low temperature cofired ceramic (LTCC) interposer with Au through vias by Au-Au thermo-compression bonding. The CMOS circuit and bonding pads on the sensor backside were electrically connected through Au bumps and the LTCC interposer, and the differential capacitive gap was formed by an Au sealing frame. A diaphragm for sensing 3-axis force was formed in the CMOS substrate. The dimensions of the completed sensor are 2.5 mm in width, 2.5 mm in length, and 0.66 mm in thickness. The fabricated sensor output coded 3-axis capacitive sensing data according to applied 3-axis force by three-dimensional (3D)-printed pins. The measured sensitivity was as high as over 34 Count/mN for normal force and 14 to 15 Count/mN for shear force with small noise, which corresponds to less than 1 mN. The hysteresis and the average cross-sensitivity were also found to be less than 2% full scale and 11%, respectively. PMID:29068429

Electrochromic properties of poly (1-(phenyl)-2,5-di(2-thienyl)-1H-pyrrole-co-3,4-ethylenedioxy thiophene) and its application in electrochromic devices

NASA Astrophysics Data System (ADS)

Tarkuc, S.; Sahmetlioglu, E.; Tanyeli, C.; Akhmedov, I. M.; Toppare, L.

2008-06-01

Electrochemical copolymerization of 1-(phenyl)-2,5-di(2-thienyl)-1H-pyrrole (PTP) with 3,4-ethylenedioxy thiophene (EDOT) was carried out in acetonitrile (AN)/NaClO4/LiClO4 (0.1 M) solvent-electrolyte couple via potentiodynamic electrolysis. Characterizations of the resulting copolymer were performed via cyclic voltammetry (CV), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and spectroelectrochemical analysis. Spectroelectrochemical analyses show that the copolymer of PTP with EDOT has an electronic band gap (due to π to π∗ transition) of 1.9 eV at 480 nm, with a claret red in the fully reduced form and a blue color in the fully oxidized form. Via kinetic studies, the optical contrast (ΔT %) was found to be 8% for P(PTP-co-EDOT). Results showed that the time required to reach 95% of the ultimate transmittance was 1.7 s for the copolymer. The P(PTP-co-EDOT) film was used to construct a dual type polymer electrochromic device (ECDs) with poly(3,4-ethylenedioxy thiophene) (PEDOT). Spectroelectrochemistry, electrochromic switching and open circuit memory of the device were investigated.

Nitric oxide and superoxide dismutase modulate endothelial progenitor cell function in type 2 diabetes mellitus

PubMed Central

Hamed, Saher; Brenner, Benjamin; Aharon, Anat; Daoud, Deeb; Roguin, Ariel

2009-01-01

Background The function of endothelial progenitor cells (EPCs), which are key cells in vascular repair, is impaired in diabetes mellitus. Nitric oxide (NO) and reactive oxygen species can regulate EPC functions. EPCs tolerate oxidative stress by upregulating superoxide dismutase (SOD), the enzyme that neutralizes superoxide anion (O2-). Therefore, we investigated the roles of NO and SOD in glucose-stressed EPCs. Methods The functions of circulating EPCs from patients with type 2 diabetes were compared to those from healthy individuals. Healthy EPCs were glucose-stressed, and then treated with insulin and/or SOD. We assessed O2- generation, NO production, SOD activity, and their ability to form colonies. Results EPCs from diabetic patients generated more O2-, had higher NAD(P)H oxidase and SOD activity, but lower NO bioavailability, and expressed higher mRNA and protein levels of p22-phox, and manganese SOD and copper/zinc SOD than those from the healthy individuals. Plasma glucose and HbA1c levels in the diabetic patients were correlated negatively with the NO production from their EPCs. SOD treatment of glucose-stressed EPCs attenuated O2- generation, restored NO production, and partially restored their ability to form colonies. Insulin treatment of glucose-stressed EPCs increased NO production, but did not change O2- generation and their ability to form colonies. However, their ability to produce NO and to form colonies was fully restored after combined SOD and insulin treatment. Conclusion Our data provide evidence that SOD may play an essential role in EPCs, and emphasize the important role of antioxidant therapy in type 2 diabetic patients. PMID:19878539

Functions and Unique Diversity of Genes and Microorganisms Involved in Arsenite Oxidation from the Tailings of a Realgar Mine

PubMed Central

E, Guoji; Wang, Jianing; Wang, Nian; Chen, Xiaoming; Mu, Yao; Li, Hao; Yang, Ye; Liu, Yichen; Wang, Yanxin

2016-01-01

ABSTRACT The tailings of the Shimen realgar mine have unique geochemical features. Arsenite oxidation is one of the major biogeochemical processes that occurs in the tailings. However, little is known about the functional and molecular aspects of the microbial community involved in arsenite oxidation. Here, we fully explored the functional and molecular features of the microbial communities from the tailings of the Shimen realgar mine. We collected six samples of tailings from sites A, B, C, D, E, and F. Microcosm assays indicated that all of the six sites contain both chemoautotrophic and heterotrophic arsenite-oxidizing microorganisms; their activities differed considerably from each other. The microbial arsenite-oxidizing activities show a positive correlation with soluble arsenic concentrations. The microbial communities of the six sites contain 40 phyla of bacteria and 2 phyla of archaea that show extremely high diversity. Soluble arsenic, sulfate, pH, and total organic carbon (TOC) are the key environmental factors that shape the microbial communities. We further identified 114 unique arsenite oxidase genes from the samples; all of them code for new or new-type arsenite oxidases. We also isolated 10 novel arsenite oxidizers from the samples, of which 4 are chemoautotrophic and 6 are heterotrophic. These data highlight the unique diversities of the arsenite-oxidizing microorganisms and their oxidase genes from the tailings of the Shimen realgar mine. To the best of our knowledge, this is the first report describing the functional and molecular features of microbial communities from the tailings of a realgar mine. IMPORTANCE This study focused on the functional and molecular characterizations of microbial communities from the tailings of the Shimen realgar mine. We fully explored, for the first time, the arsenite-oxidizing activities and the functional gene diversities of microorganisms from the tailings, as well as the correlation of the microbial activities/diversities with environmental factors. The findings of this study help us to better understand the diversities of the arsenite-oxidizing bacteria and the geochemical cycle of arsenic in the tailings of the Shimen realgar mine and gain insights into the microbial mechanisms by which the secondary minerals of the tailings were formed. This work also offers a set of unique arsenite-oxidizing bacteria for basic research of the molecular regulation of arsenite oxidation in bacterial cells and for the environmentally friendly bioremediation of arsenic-contaminated groundwater. PMID:27663031

Functions and Unique Diversity of Genes and Microorganisms Involved in Arsenite Oxidation from the Tailings of a Realgar Mine.

PubMed

Zeng, Xian-Chun; E, Guoji; Wang, Jianing; Wang, Nian; Chen, Xiaoming; Mu, Yao; Li, Hao; Yang, Ye; Liu, Yichen; Wang, Yanxin

2016-12-15

The tailings of the Shimen realgar mine have unique geochemical features. Arsenite oxidation is one of the major biogeochemical processes that occurs in the tailings. However, little is known about the functional and molecular aspects of the microbial community involved in arsenite oxidation. Here, we fully explored the functional and molecular features of the microbial communities from the tailings of the Shimen realgar mine. We collected six samples of tailings from sites A, B, C, D, E, and F. Microcosm assays indicated that all of the six sites contain both chemoautotrophic and heterotrophic arsenite-oxidizing microorganisms; their activities differed considerably from each other. The microbial arsenite-oxidizing activities show a positive correlation with soluble arsenic concentrations. The microbial communities of the six sites contain 40 phyla of bacteria and 2 phyla of archaea that show extremely high diversity. Soluble arsenic, sulfate, pH, and total organic carbon (TOC) are the key environmental factors that shape the microbial communities. We further identified 114 unique arsenite oxidase genes from the samples; all of them code for new or new-type arsenite oxidases. We also isolated 10 novel arsenite oxidizers from the samples, of which 4 are chemoautotrophic and 6 are heterotrophic. These data highlight the unique diversities of the arsenite-oxidizing microorganisms and their oxidase genes from the tailings of the Shimen realgar mine. To the best of our knowledge, this is the first report describing the functional and molecular features of microbial communities from the tailings of a realgar mine. This study focused on the functional and molecular characterizations of microbial communities from the tailings of the Shimen realgar mine. We fully explored, for the first time, the arsenite-oxidizing activities and the functional gene diversities of microorganisms from the tailings, as well as the correlation of the microbial activities/diversities with environmental factors. The findings of this study help us to better understand the diversities of the arsenite-oxidizing bacteria and the geochemical cycle of arsenic in the tailings of the Shimen realgar mine and gain insights into the microbial mechanisms by which the secondary minerals of the tailings were formed. This work also offers a set of unique arsenite-oxidizing bacteria for basic research of the molecular regulation of arsenite oxidation in bacterial cells and for the environmentally friendly bioremediation of arsenic-contaminated groundwater. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Macrophage Depletion Impairs Skeletal Muscle Regeneration: the Roles of Pro-fibrotic Factors, Inflammation, and Oxidative Stress.

PubMed

Xiao, Weihua; Liu, Yu; Chen, Peijie

2016-12-01

Muscle contusion is one of the most common muscle injuries in sports medicine. Macrophages play complex roles in the regeneration of skeletal muscle. However, the roles of macrophages, especially the mechanisms involved, in the regeneration of muscle contusion are still not fully understood. We hypothesize that the depletion of macrophages impairs skeletal muscle regeneration and that pro-fibrotic factors, inflammation, and oxidative stress may be involved in the process. To test these hypotheses, we constructed a muscle contusion injury and a macrophage depletion model and followed it up with morphological and gene expression analyses. The data showed that fibrotic scars were formed in the muscle of contusion injury, and they deteriorated in the mice of macrophage depletion. Furthermore, the sizes of regenerating myofibers were significantly reduced by macrophage depletion. Pro-fibrotic factors, inflammatory cytokines, chemokines, and oxidative stress-related enzymes increased significantly after muscle injury. Moreover, the expression of these factors was delayed by macrophage depletion. Most of them were still significantly higher in the later stage of regeneration. These results suggest that macrophage depletion impairs skeletal muscle regeneration and that pro-fibrotic factors, inflammation, and oxidative stress may play important roles in the process.

Numerical modelling of soot formation and oxidation in laminar coflow non-smoking and smoking ethylene diffusion flames

NASA Astrophysics Data System (ADS)

Liu, Fengshan; Guo, Hongsheng; Smallwood, Gregory J.; Gülder, Ömer L.

2003-06-01

A numerical study of soot formation and oxidation in axisymmetric laminar coflow non-smoking and smoking ethylene diffusion flames was conducted using detailed gas-phase chemistry and complex thermal and transport properties. A modified two-equation soot model was employed to describe soot nucleation, growth and oxidation. Interaction between the gas-phase chemistry and soot chemistry was taken into account. Radiation heat transfer by both soot and radiating gases was calculated using the discrete-ordinates method coupled with a statistical narrow-band correlated-k based band model, and was used to evaluate the simple optically thin approximation. The governing equations in fully elliptic form were solved. The current models in the literature describing soot oxidation by O2 and OH have to be modified in order to predict the smoking flame. The modified soot oxidation model has only moderate effects on the calculation of the non-smoking flame, but dramatically affects the soot oxidation near the flame tip in the smoking flame. Numerical results of temperature, soot volume fraction and primary soot particle size and number density were compared with experimental data in the literature. Relatively good agreement was found between the prediction and the experimental data. The optically thin approximation radiation model significantly underpredicts temperatures in the upper portion of both flames, seriously affecting the soot prediction.

Formation and Repair of Mismatches Containing Ribonucleotides and Oxidized Bases at Repeated DNA Sequences*

PubMed Central

Cilli, Piera; Minoprio, Anna; Bossa, Cecilia; Bignami, Margherita; Mazzei, Filomena

2015-01-01

The cellular pool of ribonucleotide triphosphates (rNTPs) is higher than that of deoxyribonucleotide triphosphates. To ensure genome stability, DNA polymerases must discriminate against rNTPs and incorporated ribonucleotides must be removed by ribonucleotide excision repair (RER). We investigated DNA polymerase β (POL β) capacity to incorporate ribonucleotides into trinucleotide repeated DNA sequences and the efficiency of base excision repair (BER) and RER enzymes (OGG1, MUTYH, and RNase H2) when presented with an incorrect sugar and an oxidized base. POL β incorporated rAMP and rCMP opposite 7,8-dihydro-8-oxoguanine (8-oxodG) and extended both mispairs. In addition, POL β was able to insert and elongate an oxidized rGMP when paired with dA. We show that RNase H2 always preserves the capacity to remove a single ribonucleotide when paired to an oxidized base or to incise an oxidized ribonucleotide in a DNA duplex. In contrast, BER activity is affected by the presence of a ribonucleotide opposite an 8-oxodG. In particular, MUTYH activity on 8-oxodG:rA mispairs is fully inhibited, although its binding capacity is retained. This results in the reduction of RNase H2 incision capability of this substrate. Thus complex mispairs formed by an oxidized base and a ribonucleotide can compromise BER and RER in repeated sequences. PMID:26338705

Transport across the cell-membrane dictates nanoparticle fate and toxicity: a new paradigm in nanotoxicology

NASA Astrophysics Data System (ADS)

Guarnieri, Daniela; Sabella, Stefania; Muscetti, Ornella; Belli, Valentina; Malvindi, Maria Ada; Fusco, Sabato; de Luca, Elisa; Pompa, Pier Paolo; Netti, Paolo A.

2014-08-01

The toxicity of metallic nanoparticles (MNPs) has been fully ascertained, but the mechanisms underlying their cytotoxicity remain still largely unclear. Here we demonstrate that the cytotoxicity of MNPs is strictly reliant on the pathway of cellular internalization. In particular, if otherwise toxic gold, silver, and iron oxide NPs are forced through the cell membrane bypassing any form of active mechanism (e.g., endocytosis), no significant cytotoxic effect is registered. Pneumatically driven NPs across the cell membrane show a different distribution within the cytosol compared to NPs entering the cell by active endocytosis. Specifically, they exhibit free random Brownian motions within the cytosol and do not accumulate in lysosomes. Results suggest that intracellular accumulation of metallic nanoparticles into endo-lysosomal compartments is the leading cause of nanotoxicity, due to consequent nanoparticle degradation and in situ release of metal ions.The toxicity of metallic nanoparticles (MNPs) has been fully ascertained, but the mechanisms underlying their cytotoxicity remain still largely unclear. Here we demonstrate that the cytotoxicity of MNPs is strictly reliant on the pathway of cellular internalization. In particular, if otherwise toxic gold, silver, and iron oxide NPs are forced through the cell membrane bypassing any form of active mechanism (e.g., endocytosis), no significant cytotoxic effect is registered. Pneumatically driven NPs across the cell membrane show a different distribution within the cytosol compared to NPs entering the cell by active endocytosis. Specifically, they exhibit free random Brownian motions within the cytosol and do not accumulate in lysosomes. Results suggest that intracellular accumulation of metallic nanoparticles into endo-lysosomal compartments is the leading cause of nanotoxicity, due to consequent nanoparticle degradation and in situ release of metal ions. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr02008a

Lactate shuttles in nature.

PubMed

Brooks, G A

2002-04-01

Once thought to be the consequence of oxygen lack in contracting skeletal muscle, the glycolytic product lactate is formed and utilized continuously under fully aerobic conditions. "Cell-cell" and "intracellular lactate shuttle" concepts describe the roles of lactate in the delivery of oxidative and gluconeogenic substrates, as well as in cell signalling. Examples of cell-cell shuttles include lactate exchanges between white-glycolytic and red-oxidative fibres within a working muscle bed, between working skeletal muscle and heart, and between tissues of net lactate release and gluconeogenesis. Lactate exchange between astrocytes and neurons that is linked to glutamatergic signalling in the brain is an example of a lactate shuttle supporting cell-cell signalling. Lactate uptake by mitochondria and pyruvate-lactate exchange in peroxisomes are examples of intracellular lactate shuttles. Lactate exchange between sites of production and removal is facilitated by monocarboxylate transport proteins, of which there are several isoforms, and, probably, also by scaffolding proteins. The mitochondrial lactate-pyruvate transporter appears to work in conjunction with mitochondrial lactate dehydrogenase, which permits lactate to be oxidized within actively respiring cells. Hence mitochondria function to establish the concentration and proton gradients necessary for cells with high mitochondrial densities (e.g. cardiocytes) to take up and oxidize lactate. Arteriovenous difference measurements on working cardiac and skeletal muscle beds as well as NMR spectral analyses of these tissues show that lactate is formed and oxidized within the cells of formation in vivo. Glycolysis and lactate oxidation within cells permits high flux rates and the maintenance of redox balance in the cytosol and mitochondria. Other examples of intracellular lactate shuttles include lactate uptake and oxidation in sperm mitochondria and the facilitation of beta-oxidation in peroxisomes by pyruvate-lactate exchange. An ancient origin to the utility of lactate shuttling is implied by the observation that mitochondria of Saccharomyces cerevisiae contain flavocytochrome b(2), a lactate-cytochrome c oxidoreductase that couples lactate dehydrogenation to the reduction of cytochrome c. The presence of cell-cell and intracellular lactate shuttles gives rise to the notion that glycolytic and oxidative pathways can be viewed as linked, as opposed to alternative, processes, because lactate, the product of one pathway, is the substrate for the other.

Hollow PdCo alloy nanospheres with mesoporous shells as high-performance catalysts for methanol oxidation.

PubMed

Sheng, Guoqing; Chen, Jiahui; Ye, Huangqing; Hu, Zhixiong; Fu, Xian-Zhu; Sun, Rong; Huang, Weixin; Wong, Ching-Ping

2018-07-15

Monodisperse hollow mesoporous PdCo alloy nanospheres are prepared via a simple galvanic replacement reaction. The as-prepared PdCo hollow nanospheres have small diameter, such as Pd 78 Co 22 nanospheres of diameter about 25 nm and mesoporous shells about 4-5 nm. The Pd 78 Co 22 hollow mesoporous nanospheres possess the largest electrochemical active surface areas (ECSA, 53.91 m 2  g -1 ), mass activity (1488 mA mg -1 ) and specific activity (2.76 mA cm -2 ) towards to methanol oxidation relative to the Pd 68 Co 32 , Pd 92 Co 8 hollow mesoporous nanospheres and commercial Pd/C catalysts. Moreover, the activity of Pd 78 Co 22 after long-term stability tests is still the best and even better than those of fresh Pd 68 Co 32 and commercial Pd/C catalysts. The PdCo catalysts not only effectively reduce the Pd usage by forming hollow structure, but also fully realize the Pd-Co alloying effects for enhancing the methanol oxidation catalytic performance. Copyright © 2018 Elsevier Inc. All rights reserved.

Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides

DOE PAGES

Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin; ...

2015-10-29

Although Li- and Mn-rich transition metal oxides have been extensively studied as high-capacity cathode materials for Li-ion batteries, the crystal structure of these materials in their pristine state is not yet fully understood. Here we apply complementary electron microscopy and spectroscopy techniques at multi-length scale on well-formed Li1.2(Ni0.13Mn0.54Co0.13)O2 crystals with two different morphologies as well as two commercially available materials with similar compositions, and unambiguously describe the structural make-up of these samples. Systematically observing the entire primary particles along multiple zone axes reveals that they are consistently made up of a single phase, save for rare localized defects and amore » thin surface layer on certain crystallographic facets. Finally and more specifically, we show the bulk of the oxides can be described as an aperiodic crystal consisting of randomly stacked domains that correspond to three variants of monoclinic structure, while the surface is composed of a Co- and/or Ni-rich spinel with antisite defects.« less

Sulfur Mustard Toxicity Following Dermal Exposure

PubMed Central

Paromov, Victor; Suntres, Zacharias; Smith, Milton; Stone, William L.

2007-01-01

Objective: Sulfur mustard (bis-2-(chloroethyl) sulfide) is a chemical warfare agent (military code: HD) causing extensive skin injury. The mechanisms underlying HD-induced skin damage are not fully elucidated. This review will critically evaluate the evidence showing that oxidative stress is an important factor in HD skin toxicity. Oxidative stress results when the production of reactive oxygen (ROS) and/or reactive nitrogen oxide species (RNOS) exceeds the capacity of antioxidant defense mechanisms. Methods: This review will discuss the role of oxidative stress in the pathophysiology of HD skin toxicity in both in vivo and in vitro model systems with emphasis on the limitations of the various model systems. Evidence supporting the therapeutic potential of antioxidants and antioxidant liposomes will be evaluated. Antioxidant liposomes are effective vehicles for delivering both lipophilic (incorporated into the lipid bilayers) and water-soluble (encapsulated in the aqueous inner-spaces) antioxidants to skin. The molecular mechanisms interconnecting oxidative stress to HD skin toxicity are also detailed. Results: DNA repair and inflammation, in association with oxidative stress, induce intracellular events leading to apoptosis or to a programmable form of necrosis. The free radical, nitric oxide (NO), is of considerable interest with respect to the mechanisms of HD toxicity. NO signaling pathways are important in modulating inflammation, cell death, and wound healing in skin cells. Conclusions: Potential future directions are summarized with emphasis on a systems biology approach to studying sulfur mustard toxicity to skin as well as the newly emerging area of redox proteomics. PMID:18091984

New Screening Test Developed for the Blanching Resistance of Copper Alloys

NASA Technical Reports Server (NTRS)

Thomas-Ogbuji, Linus U.

2004-01-01

NASA's extensive efforts towards more efficient, safer, and more affordable space transportation include the development of new thrust-cell liner materials with improved capabilities and longer lives. For rocket engines fueled with liquid hydrogen, an important metric of liner performance is resistance to blanching, a phenomenon of localized wastage by cycles of oxidation-reduction due to local imbalance in the oxygen-fuel ratio. The current liner of the Space Shuttle Main Engine combustion chamber, a Cu-3Ag-0.5Zr alloy (NARloy-Z) is degraded in service by blanching. Heretofore, evaluating a liner material for blanching resistance involved elaborate and expensive hot-fire tests performed on rocket test stands. To simplify that evaluation, researchers at the NASA Glenn Research Center developed a screening test that uses simple, in situ oxidation-reduction cycling in a thermogravimetric analyzer (TGA). The principle behind this test is that resistance to oxidation or to the reduction of oxide, or both, implies resistance to blanching. Using this test as a preliminary tool to screen alloys for blanching resistance can improve reliability and save time and money. In this test a small polished coupon is hung in a TGA furnace at the desired (service) temperature. Oxidizing and reducing gases are introduced cyclically, in programmed amounts. Cycle durations are chosen by calibration, such that all copper oxides formed by oxidation are fully reduced in the next reduction interval. The sample weight is continuously acquired by the TGA as usual.

Solution processable broadband transparent mixed metal oxide nanofilm optical coatings via substrate diffusion doping.

PubMed

Glynn, Colm; Aureau, Damien; Collins, Gillian; O'Hanlon, Sally; Etcheberry, Arnaud; O'Dwyer, Colm

2015-12-21

Devices composed of transparent materials, particularly those utilizing metal oxides, are of significant interest due to increased demand from industry for higher fidelity transparent thin film transistors, photovoltaics and a myriad of other optoelectronic devices and optics that require more cost-effective and simplified processing techniques for functional oxides and coatings. Here, we report a facile solution processed technique for the formation of a transparent thin film through an inter-diffusion process involving substrate dopant species at a range of low annealing temperatures compatible with processing conditions required by many state-of-the-art devices. The inter-diffusion process facilitates the movement of Si, Na and O species from the substrate into the as-deposited vanadium oxide thin film forming a composite fully transparent V0.0352O0.547Si0.4078Na0.01. Thin film X-ray diffraction and Raman scattering spectroscopy show the crystalline component of the structure to be α-NaVO3 within a glassy matrix. This optical coating exhibits high broadband transparency, exceeding 90-97% absolute transmission across the UV-to-NIR spectral range, while having low roughness and free of surface defects and pinholes. The production of transparent films for advanced optoelectronic devices, optical coatings, and low- or high-k oxides is important for planar or complex shaped optics or surfaces. It provides opportunities for doping metal oxides to ternary, quaternary or other mixed metal oxides on glass, encapsulants or other substrates that facilitate diffusional movement of dopant species.

Arsenic contamination of the environment: a new perspective from central-east India.

PubMed

Pandey, Piyush Kant; Yadav, Sushma; Nair, Sumita; Bhui, Ashish

2002-09-01

This paper reports a regional contamination of the environment in central-east India that does not share geology or boundary with the Bengal Delta Plain. About 30,000 people residing in 30 villages and towns are directly exposed to arsenic and more than 200,000 people are "at risk." Complete geographical extent of this contamination is being established, and this newly reported contaminated area could be quite large. This paper further reports that the mechanisms involved in arsenic mobilisation are complex and the two theories of arsenic mobilisation, i.e., pyrite oxidation and oxyhydroxides reduction, do not fully explain the high levels of arsenic contamination. This paper also proposes the "oxidation-reduction theory" for arsenic mobilisation where the arsenic originates from the arsenopyrite oxidation and the arsenic thus mobilised forms the minerals and gets reduced underground in favourable Eh conditions. The stoppage of water withdrawal from the contaminated sources did not result in lowering of arsenic levels as expected according to the heavy groundwater extraction theory (pyrite oxidation theory). Cases of arsenicosis in the region are on the rise and the switchover to less contaminated water has not reversed the arsenicosis progression in the affected persons even after 2 years. Surface water of the rivers is also being contaminated because of the probable dislocation of contaminated groundwater due to the heavy rains in monsoon season, which indicates that the river water could be a major carrier of arsenic in dissolved or adsorbed forms that may be a cause of contamination of the delta plains.

Uremic Toxicity of Advanced Glycation End Products in CKD

PubMed Central

Stinghen, Andréa E.M.; Massy, Ziad A.; Vlassara, Helen; Striker, Gary E.

2016-01-01

Advanced glycation end products (AGEs), a heterogeneous group of compounds formed by nonenzymatic glycation reactions between reducing sugars and amino acids, lipids, or DNA, are formed not only in the presence of hyperglycemia, but also in diseases associated with high levels of oxidative stress, such as CKD. In chronic renal failure, higher circulating AGE levels result from increased formation and decreased renal clearance. Interactions between AGEs and their receptors, including advanced glycation end product–specific receptor (RAGE), trigger various intracellular events, such as oxidative stress and inflammation, leading to cardiovascular complications. Although patients with CKD have a higher burden of cardiovascular disease, the relationship between AGEs and cardiovascular disease in patients with CKD is not fully characterized. In this paper, we review the various deleterious effects of AGEs in CKD that lead to cardiovascular complications and the role of these AGEs in diabetic nephropathy. We also discuss potential pharmacologic approaches to circumvent these deleterious effects by reducing exogenous and endogenous sources of AGEs, increasing the breakdown of existing AGEs, or inhibiting AGE-induced inflammation. Finally, we speculate on preventive and therapeutic strategies that focus on the AGE-RAGE axis to prevent vascular complications in patients with CKD. PMID:26311460

No effect of H2O degassing on the oxidation state of magmatic liquids

NASA Astrophysics Data System (ADS)

Waters, Laura E.; Lange, Rebecca A.

2016-08-01

The underlying cause for why subduction-zone magmas are systematically more oxidized than those formed at mid-ocean spreading ridges is a topic of vigorous debate. It is either a primary feature inherited from the subduction of oxidized oceanic crust into the mantle or a secondary feature that develops because of H2O degassing and/or magma differentiation. Low total iron contents and high melt H2O contents render rhyolites sensitive to any effect of H2O degassing on ferric-ferrous ratios. Here, pre-eruptive magmatic Fe2+ concentrations, measured using Fe-Ti oxides that co-crystallized with silicate phenocrysts under hydrous conditions, are compared with Fe2+ post-eruptive concentrations in ten crystal-poor, fully-degassed obsidian samples; five are microlite free. No effect of H2O degassing on the ferric-ferrous ratio is found. In addition, Fe-Ti oxide data from this study and the literature show that arc magmas are systematically more oxidized than both basalts and hydrous silicic melts from Iceland and Yellowstone prior to extensive degassing. Nor is there any evidence that differentiation (i.e., crystal fractionation, crustal assimilation) is the cause of the higher redox state of arc magmas relative to those of Iceland/Yellowstone rhyolites. Instead, the evidence points to subduction of oxidized crust and the release of an H2O-rich fluid and/or melt with a high oxygen fugacity (fO2), which plays a role during H2O-flux melting of the mantle in creating basalts that are relatively oxidized.

Direct determination of resonance energy transfer in photolyase: structural alignment for the functional state.

PubMed

Tan, Chuang; Guo, Lijun; Ai, Yuejie; Li, Jiang; Wang, Lijuan; Sancar, Aziz; Luo, Yi; Zhong, Dongping

2014-11-13

Photoantenna is essential to energy transduction in photoinduced biological machinery. A photoenzyme, photolyase, has a light-harvesting pigment of methenyltetrahydrofolate (MTHF) that transfers its excitation energy to the catalytic flavin cofactor FADH¯ to enhance DNA-repair efficiency. Here we report our systematic characterization and direct determination of the ultrafast dynamics of resonance energy transfer from excited MTHF to three flavin redox states in E. coli photolyase by capturing the intermediates formed through the energy transfer and thus excluding the electron-transfer quenching pathway. We observed 170 ps for excitation energy transferring to the fully reduced hydroquinone FADH¯, 20 ps to the fully oxidized FAD, and 18 ps to the neutral semiquinone FADH(•), and the corresponding orientation factors (κ(2)) were determined to be 2.84, 1.53 and 1.26, respectively, perfectly matching with our calculated theoretical values. Thus, under physiological conditions and over the course of evolution, photolyase has adopted the optimized orientation of its photopigment to efficiently convert solar energy for repair of damaged DNA.

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

PubMed

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

2011-01-07

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

Mass spectrometric characterization of human serum albumin dimer: A new potential biomarker in chronic liver diseases.

PubMed

Naldi, Marina; Baldassarre, Maurizio; Nati, Marina; Laggetta, Maristella; Giannone, Ferdinando Antonino; Domenicali, Marco; Bernardi, Mauro; Caraceni, Paolo; Bertucci, Carlo

2015-08-10

Human serum albumin (HSA) undergoes several structural alterations affecting its properties in pro-oxidant and pro-inflammatory environments, as it occurs during liver cirrhosis. These modifications include the formation of albumin dimers. Although HSA dimers were reported to be an oxidative stress biomarker, to date nothing is known about their role in liver cirrhosis and related complications. Additionally, no high sensitive analytical method was available for HSA dimers assessment in clinical settings. Thus the HSA dimeric form in human plasma was characterized by mass spectrometry using liquid chromatography tandem mass spectrometry (LC-ESI-Q-TOF) and matrix assisted laser desorption time of flight (MALDI-TOF) techniques. N-terminal and C-terminal truncated HSA, as well as the native HSA, undergo dimerization by binding another HSA molecule. This study demonstrated the presence of both homo- and hetero-dimeric forms of HSA. The dimerization site was proved to be at Cys-34, forming a disulphide bridge between two albumin molecules, as determined by LC-MS analysis after tryptic digestion. Interestingly, when plasma samples from cirrhotic subjects were analysed, the dimer/monomer ratio resulted significantly increased when compared to that of healthy subjects. These isoforms could represent promising biomarkers for liver disease. Additionally, this analytical approach leads to the relative quantification of the residual native HSA, with fully preserved structural integrity. Copyright © 2014 Elsevier B.V. All rights reserved.

Porous Ni-Fe alloys as anode support for intermediate temperature solid oxide fuel cells: I. Fabrication, redox and thermal behaviors

NASA Astrophysics Data System (ADS)

Wang, Xin; Li, Kai; Jia, Lichao; Zhang, Qian; Jiang, San Ping; Chi, Bo; Pu, Jian; Jian, Li; Yan, Dong

2015-03-01

Porous Ni-Fe anode supports for intermediate solid oxide fuel cells are prepared by reducing the sintered NiO-(0-50 wt. %) Fe2O3 composites in H2, their microstructure, redox and thermal expansion/cycling characteristics are systematically investigated. The sintered NiO-Fe2O3 composites are consisted of NiO and NiFe2O4, and are fully reducible to porous metallic Ni-Fe alloys in H2 at temperatures between 600 and 750 °C. The porous structure contains pores in bimodal distribution with larger pores between the sintered particles and smaller ones inside the particles. The oxidation resistance of the Ni-Fe alloy anode supports at 600 and 750 °C is increased by the addition of Fe, their oxidation kinetics obeys a multistage parabolic law in the form of (Percentageweightgain /Specificsurfacearea) 2 =kp · t , where kp is the rate constant and t the oxidation time. The dimension of the Ni-Fe anode supports is slightly changed without disintegrating their structure, and Fe addition is beneficial to the redox stability. The TEC of the Ni-Fe alloy anode supports decreases with the increase of Fe content. The anode supports containing Fe is less stable in dimension during thermal cycles due to the continuous sintering, but the dimension change after thermal cycles is within 1%.

Characterization of a Flavoprotein Oxidase from Opium Poppy Catalyzing the Final Steps in Sanguinarine and Papaverine Biosynthesis*

PubMed Central

Hagel, Jillian M.; Beaudoin, Guillaume A. W.; Fossati, Elena; Ekins, Andrew; Martin, Vincent J. J.; Facchini, Peter J.

2012-01-01

Benzylisoquinoline alkaloids are a diverse class of plant specialized metabolites that includes the analgesic morphine, the antimicrobials sanguinarine and berberine, and the vasodilator papaverine. The two-electron oxidation of dihydrosanguinarine catalyzed by dihydrobenzophenanthridine oxidase (DBOX) is the final step in sanguinarine biosynthesis. The formation of the fully conjugated ring system in sanguinarine is similar to the four-electron oxidations of (S)-canadine to berberine and (S)-tetrahydropapaverine to papaverine. We report the isolation and functional characterization of an opium poppy (Papaver somniferum) cDNA encoding DBOX, a flavoprotein oxidase with homology to (S)-tetrahydroprotoberberine oxidase and the berberine bridge enzyme. A query of translated opium poppy stem transcriptome databases using berberine bridge enzyme yielded several candidate genes, including an (S)-tetrahydroprotoberberine oxidase-like sequence selected for heterologous expression in Pichia pastoris. The recombinant enzyme preferentially catalyzed the oxidation of dihydrosanguinarine to sanguinarine but also converted (RS)-tetrahydropapaverine to papaverine and several protoberberine alkaloids to oxidized forms, including (RS)-canadine to berberine. The Km values of 201 and 146 μm for dihydrosanguinarine and the protoberberine alkaloid (S)-scoulerine, respectively, suggested high concentrations of these substrates in the plant. Virus-induced gene silencing to reduce DBOX transcript levels resulted in a corresponding reduction in sanguinarine, dihydrosanguinarine, and papaverine accumulation in opium poppy roots in support of DBOX as a multifunctional oxidative enzyme in BIA metabolism. PMID:23118227

Reduction of protein radicals by GSH and ascorbate: potential biological significance.

PubMed

Gebicki, Janusz M; Nauser, Thomas; Domazou, Anastasia; Steinmann, Daniel; Bounds, Patricia L; Koppenol, Willem H

2010-11-01

The oxidation of proteins and other macromolecules by radical species under conditions of oxidative stress can be modulated by antioxidant compounds. Decreased levels of the antioxidants glutathione and ascorbate have been documented in oxidative stress-related diseases. A radical generated on the surface of a protein can: (1) be immediately and fully repaired by direct reaction with an antioxidant; (2) react with dioxygen to form the corresponding peroxyl radical; or (3) undergo intramolecular long range electron transfer to relocate the free electron to another amino acid residue. In pulse radiolysis studies, in vitro production of the initial radical on a protein is conveniently made at a tryptophan residue, and electron transfer often leads ultimately to residence of the unpaired electron on a tyrosine residue. We review here the kinetics data for reactions of the antioxidants glutathione, selenocysteine, and ascorbate with tryptophanyl and tyrosyl radicals as free amino acids in model compounds and proteins. Glutathione repairs a tryptophanyl radical in lysozyme with a rate constant of (1.05±0.05)×10(5) M(-1) s(-1), while ascorbate repairs tryptophanyl and tyrosyl radicals ca. 3 orders of magnitude faster. The in vitro reaction of glutathione with these radicals is too slow to prevent formation of peroxyl radicals, which become reduced by glutathione to hydroperoxides; the resulting glutathione thiyl radical is capable of further radical generation by hydrogen abstraction. Although physiologically not significant, selenoglutathione reduces tyrosyl radicals as fast as ascorbate. The reaction of protein radicals formed on insulin, β-lactoglobulin, pepsin, chymotrypsin and bovine serum albumin with ascorbate is relatively rapid, competes with the reaction with dioxygen, and the relatively innocuous ascorbyl radical is formed. On the basis of these kinetics data, we suggest that reductive repair of protein radicals may contribute to the well-documented depletion of ascorbate in living organisms subjected to oxidative stress.

Functional characterization of Mia40p, the central component of the disulfide relay system of the mitochondrial intermembrane space.

PubMed

Grumbt, Barbara; Stroobant, Vincent; Terziyska, Nadia; Israel, Lars; Hell, Kai

2007-12-28

Mia40p and Erv1p are components of a translocation pathway for the import of cysteine-rich proteins into the intermembrane space of mitochondria. We have characterized the redox behavior of Mia40p and reconstituted the disulfide transfer system of Mia40p by using recombinant functional C-terminal fragment of Mia40p, Mia40C, and Erv1p. Oxidized Mia40p contains three intramolecular disulfide bonds. One disulfide bond connects the first two cysteine residues in the CPC motif. The second and the third bonds belong to the twin CX(9)C motif and bridge the cysteine residues of two CX(9)C segments. In contrast to the stabilizing disulfide bonds of the twin CX(9)C motif, the first disulfide bond was easily accessible to reducing agents. Partially reduced Mia40C generated by opening of this bond as well as fully reduced Mia40C were oxidized by Erv1p in vitro. In the course of this reaction, mixed disulfides of Mia40C and Erv1p were formed. Reoxidation of fully reduced Mia40C required the presence of the first two cysteine residues in Mia40C. However, efficient reoxidation of a Mia40C variant containing only the cysteine residues of the twin CX(9)C motif was observed when in addition to Erv1p low amounts of wild type Mia40C were present. In the reconstituted system the thiol oxidase Erv1p was sufficient to transfer disulfide bonds to Mia40C, which then could oxidize the variant of Mia40C. In summary, we reconstituted a disulfide relay system consisting of Mia40C and Erv1p.

Prompt and easy activation by specific thioredoxins of calvin cycle enzymes of Arabidopsis thaliana associated in the GAPDH/CP12/PRK supramolecular complex.

PubMed

Marri, Lucia; Zaffagnini, Mirko; Collin, Valérie; Issakidis-Bourguet, Emmanuelle; Lemaire, Stéphane D; Pupillo, Paolo; Sparla, Francesca; Miginiac-Maslow, Myroslawa; Trost, Paolo

2009-03-01

The Calvin cycle enzymes glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and phosphoribulokinase (PRK) can form under oxidizing conditions a supramolecular complex with the regulatory protein CP12. Both GAPDH and PRK activities are inhibited within the complex, but they can be fully restored by reduced thioredoxins (TRXs). We have investigated the interactions of eight different chloroplast thioredoxin isoforms (TRX f1, m1, m2, m3, m4, y1, y2, x) with GAPDH (A(4), B(4), and B(8) isoforms), PRK and CP12 (isoform 2), all from Arabidopsis thaliana. In the complex, both A(4)-GAPDH and PRK were promptly activated by TRX f1, or more slowly by TRXs m1 and m2, but all other TRXs were ineffective. Free PRK was regulated by TRX f1, m1, or m2, while B(4)- and B(8)-GAPDH were absolutely specific for TRX f1. Interestingly, reductive activation of PRK caged in the complex was much faster than reductive activation of free oxidized PRK, and activation of A(4)-GAPDH in the complex was much faster (and less demanding in terms of reducing potential) than activation of free oxidized B(4)- or B(8)-GAPDH. It is proposed that CP12-assembled supramolecular complex may represent a reservoir of inhibited enzymes ready to be released in fully active conformation following reduction and dissociation of the complex by TRXs upon the shift from dark to low light. On the contrary, autonomous redox-modulation of GAPDH (B-containing isoforms) would be more suited to conditions of very active photosynthesis.

Chemicl-looping combustion of coal with metal oxide oxygen carriers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siriwardane, R.; Tian, H.; Richards, G.

2009-01-01

The combustion and reoxidation properties of direct coal chemical-looping combustion (CLC) over CuO, Fe2O3, Co3O4, NiO, and Mn2O3 were investigated using thermogravimetric analysis (TGA) and bench-scale fixed-bed flow reactor studies. When coal is heated in either nitrogen or carbon dioxide (CO2), 50% of weight loss was observed because of partial pyrolysis, consistent with the proximate analysis. Among various metal oxides evaluated, CuO showed the best reaction properties: CuO can initiate the reduction reaction as low as 500 °C and complete the full combustion at 700 °C. In addition, the reduced copper can be fully reoxidized by air at 700 °C.more » The combustion products formed during the CLC reaction of the coal/metal oxide mixture are CO2 and water, while no carbon monoxide was observed. Multicycle TGA tests and bench-scale fixed-bed flow reactor tests strongly supported the feasibility of CLC of coal by using CuO as an oxygen carrier. Scanning electron microscopy (SEM) images of solid reaction products indicated some changes in the surface morphology of a CuO-coal sample after reduction/oxidation reactions at 800 °C. However, significant surface sintering was not observed. The interactions of fly ash with metal oxides were investigated by X-ray diffraction and thermodynamic analysis. Overall, the results indicated that it is feasible to develop CLC with coal by metal oxides as oxygen carriers.« less

Experimental and theoretical screening of nanoscale oxide reactivity with LiBH4

NASA Astrophysics Data System (ADS)

Opalka, S. M.; Tang, X.; Laube, B. L.; Vanderspurt, T. H.

2009-05-01

Experimentation, thermodynamic modeling, and atomic modeling were combined to screen the reactivity of SiO2, Al2O3, and ZrO2 nanoscale oxides with LiBH4. Equilibrium thermodynamic modeling showed that the reactions of oxides with LiBH4 could lead to formation of stable Li-bearing oxide and metal boride phases. Experimentation was conducted to evaluate the discharge/recharge reaction products of nanoscale oxide-LiBH4 mixtures. Thermal gravimetric analyses-mass spectroscopy and x-ray diffraction revealed significant SiO2 destabilization of LiBH4 dehydrogenation, resulting in the formation of lithium silicate and boric acid. A smaller amount of lithium metaborate and boric acid was formed with Al2O3. No destabilization products were observed with ZrO2. Density functional theory atomic modeling predicted much stronger LiBH4 interfacial adsorption on the SiO2 and Al2O3 surfaces than on the ZrO2 surface, which was consistent with the experimental findings. Following dehydrogenation, interfacial Li atoms were predicted to strongly adsorb on the oxide surfaces effectively competing with LiH formation. The interfacial Li interactions with Al2O3 and ZrO2 were equal in strength in the fully hydrided and dehydrided states, so that their predicted net effect on LiBH4 dehydrogenation was insignificant. Zirconia was selected for nanoframework development based on the combined observations of compatibility and weaker associative interactions with LiBH4.

Formation and Repair of Mismatches Containing Ribonucleotides and Oxidized Bases at Repeated DNA Sequences.

PubMed

Cilli, Piera; Minoprio, Anna; Bossa, Cecilia; Bignami, Margherita; Mazzei, Filomena

2015-10-23

The cellular pool of ribonucleotide triphosphates (rNTPs) is higher than that of deoxyribonucleotide triphosphates. To ensure genome stability, DNA polymerases must discriminate against rNTPs and incorporated ribonucleotides must be removed by ribonucleotide excision repair (RER). We investigated DNA polymerase β (POL β) capacity to incorporate ribonucleotides into trinucleotide repeated DNA sequences and the efficiency of base excision repair (BER) and RER enzymes (OGG1, MUTYH, and RNase H2) when presented with an incorrect sugar and an oxidized base. POL β incorporated rAMP and rCMP opposite 7,8-dihydro-8-oxoguanine (8-oxodG) and extended both mispairs. In addition, POL β was able to insert and elongate an oxidized rGMP when paired with dA. We show that RNase H2 always preserves the capacity to remove a single ribonucleotide when paired to an oxidized base or to incise an oxidized ribonucleotide in a DNA duplex. In contrast, BER activity is affected by the presence of a ribonucleotide opposite an 8-oxodG. In particular, MUTYH activity on 8-oxodG:rA mispairs is fully inhibited, although its binding capacity is retained. This results in the reduction of RNase H2 incision capability of this substrate. Thus complex mispairs formed by an oxidized base and a ribonucleotide can compromise BER and RER in repeated sequences. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

[Scanning electron microscopy observation of the growth of osteoblasts on Ti-24Nb-4Zr-8Sn modified by micro-arc oxidation and alkali-heat treatment and implant-bone interface].

PubMed

Han, Xue; Liu, Hong-Chen; Wang, Dong-Sheng; Li, Shu-Jun; Yang, Rui

2011-01-01

To observe the efficacy of micro-arc oxidation and alkali-heat treatment (MAH) on Ti-24Nb-4Zr-8Sn (Ti2448). Disks (diameter of 14.5 mm, thickness of 1 mm) and cylinders (diameter of 3 mm, height of 10 mm) were fabricated from Ti2448 alloy. Samples were divided into three groups: polished (Ti2448), micro-arc oxidation(MAO-Ti2448), micro-arc oxidation and alkali-heat treatment (MAH-Ti2448). MC3T3-E1 osteoblastic cells were cultured on the disks and cell morphology was observed with scanning electron microscopy (SEM) aftre 3 days. The cylinder samples were implanted in the tibia of dogs and implant-bone interface was observed with SEM after 3 months. A rough and porous structure was shown in both MAO and MAH group. The MC3T3-E1 cells on the MAH-Ti2448 discs spread fully in intimate contact with the underlying coarse surface through active cytoskeletal extentions. Osseointegration was formed in the implant-bone interface in MAH samples. MAH treatment can provide a more advantageous Ti2448 surface to osteoblastic cells than MAO treatment does, and the former can improve the implant-bone integration.

Time-resolved in situ XAS study of the preparation of supported gold clusters.

PubMed

Bus, Eveline; Prins, Roel; van Bokhoven, Jeroen A

2007-07-07

Incipient-wetness impregnation of gamma-Al(2)O(3) with HAuCl(4) and subsequent removal of chlorine with NaOH, and deposition-precipitation of HAuCl(4) on TiO(2) at pH 7 resulted in supported Au(3+) species. Time-resolved in situ XAS at the Au L(3) edge showed that the Al(2)O(3)-supported oxidic or hydroxidic species were reduced in hydrogen at 440 K to yield small metallic gold clusters. The Au(3+) precursor decomposed to metallic gold in inert atmosphere at 573 K and in oxidizing atmosphere above 623 K. In all atmospheres, initially small clusters were formed that gradually grew with increasing temperature. The TiO(2)-supported species were considerably less stable. In hydrogen and carbon monoxide, Au(0) clusters of 1 to 1.5 nm were formed at room temperature, which was the lowest temperature studied. In inert and oxidizing atmosphere, the Au(3+) precursor decomposed fully to metallic gold at 530 K, as shown by XAS and temperature-programmed experiments. Large clusters were obtained already in the initial stage of reduction. Residual chlorine inhibited the reduction and led to sintering of the gold clusters. Exposure of the TiO(2)-supported catalyst precursor to light or the X-ray beam led to partial reduction, and STEM showed that storage of the reduced gold clusters under ambient conditions led to agglomeration and bimodal cluster-size distributions.

Effect of native oxide layers on copper thin-film tensile properties: A reactive molecular dynamics study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skarlinski, Michael D., E-mail: michael.skarlinski@rochester.edu; Quesnel, David J.; Department of Mechanical Engineering, University of Rochester, Rochester, New York 14627

2015-12-21

Metal-oxide layers are likely to be present on metallic nano-structures due to either environmental exposure during use, or high temperature processing techniques such as annealing. It is well known that nano-structured metals have vastly different mechanical properties from bulk metals; however, difficulties in modeling the transition between metallic and ionic bonding have prevented the computational investigation of the effects of oxide surface layers. Newly developed charge-optimized many body [Liang et al., Mater. Sci. Eng., R 74, 255 (2013)] potentials are used to perform fully reactive molecular dynamics simulations which elucidate the effects that metal-oxide layers have on the mechanical propertiesmore » of a copper thin-film. Simulated tensile tests are performed on thin-films while using different strain-rates, temperatures, and oxide thicknesses to evaluate changes in yield stress, modulus, and failure mechanisms. Findings indicate that copper-thin film mechanical properties are strongly affected by native oxide layers. The formed oxide layers have an amorphous structure with lower Cu-O bond-densities than bulk CuO, and a mixture of Cu{sub 2}O and CuO charge character. It is found that oxidation will cause modifications to the strain response of the elastic modulii, producing a stiffened modulii at low temperatures (<75 K) and low strain values (<5%), and a softened modulii at higher temperatures. While under strain, structural reorganization within the oxide layers facilitates brittle yielding through nucleation of defects across the oxide/metal interface. The oxide-free copper thin-film yielding mechanism is found to be a tensile-axis reorientation and grain creation. The oxide layers change the observed yielding mechanism, allowing for the inner copper thin-film to sustain an FCC-to-BCC transition during yielding. The mechanical properties are fit to a thermodynamic model based on classical nucleation theory. The fit implies that the oxidation of the films reduces the activation volume for yielding.« less

Manganese Complexes: Diverse Metabolic Routes to Oxidative Stress Resistance in Prokaryotes and Yeast

PubMed Central

2013-01-01

Abstract Significance: Antioxidant enzymes are thought to provide critical protection to cells against reactive oxygen species (ROS). However, many organisms can fully compensate for the loss of such enzymatic defenses by accumulating metabolites and Mn2+, which can form catalytic Mn-antioxidants. Accumulated metabolites can direct reactivity of Mn2+ with superoxide and specifically shield proteins from oxidative damage. Recent Advances: There is mounting evidence that Mn-Pi (orthophosphate) complexes act as potent scavengers of superoxide in all three branches of life. Moreover, it is evident that Mn2+ in complexes with carbonates, peptides, nucleosides, and organic acids can also form catalytic Mn-antioxidants, pointing to diverse metabolic routes to oxidative stress resistance. Critical Issues: What conditions favor utility of Mn-metabolites versus enzymatic means for removing ROS? Mn2+-metabolite defenses are critical for preserving the activity of repair enzymes in Deinococcus radiodurans exposed to intense radiation stress, and in Lactobacillus plantarum, which lacks antioxidant enzymes. In other microorganisms, Mn-antioxidants can serve as an auxiliary protection when enzymatic antioxidants are insufficient or fail. These findings of a critical role of Mn-antioxidants in the survival of prokaryotes under oxidative stress parallel the trends developing for the simple eukaryote Saccharomyces cerevisiae. Future Directions: Phosphates, peptides and organic acids are just a snapshot of the types of anionic metabolites that promote such reactivity of Mn2+. Their probable roles in pathogen defense against the host immune response and in ROS-mediated signaling pathways are also areas that are worthy of serious investigation. Moreover, it is clear that these protective chemical processes can be harnessed for practical purposes. Antioxid. Redox Signal. 19, 933–944. PMID:23249283

Redox properties of vanadium ions in SBA-15-supported vanadium oxide: an FTIR spectroscopic study.

PubMed

Venkov, Tzvetomir V; Hess, Christian; Jentoft, Friederike C

2007-02-13

The state of vanadium ions in VxOy/SBA-15 (2.7 wt % V) was studied with FTIR spectroscopy using CO and NO as probe molecules. Neither CO (at 85 K) nor NO (at RT) adsorb on the oxidized sample because of the coordinative saturation of V5+ ions and the covalent character of the V5+=O bond. After treatment of the sample in 50 kPa H2 at 673 K, the V5+ ions are reduced to two different types of V3+ sites, as manifested by carbonyl bands at 2189 and 2177 cm-1. In the presence of O2 at 85 K, thus formed V3+ ions are partly oxidized to V4+ sites showing carbonylic bands at 2202 and 2190 cm-1. When the reduced sample is exposed to O2 at room temperature, the V3+ ions are fully oxidized to V5+. The adsorption of NO on the reduced VxOy/SBA-15 shows that the V3+ and V4+ ions possess two effective coordinative vacancies and as a result can adsorb two NO molecules forming the respective V3+(NO)2 and V4+(NO)2 dinitrosyls. The introduction of O2 to the VxOy/SBA-15-NO system leads to reoxidation of the V3+ and V4+ ions to V5+ and formation of bridged (1639 cm-1) and bidentate (1573 cm-1) surface nitrates. After coadsorption of CO and NO on the reduced sample the formation of surface mixed carbonyl-nitrosyls (2108 and 1723 cm-1) was observed for the first time.

Fullerol ionic fluids.

PubMed

Fernandes, Nikhil; Dallas, Panagiotis; Rodriguez, Robert; Bourlinos, Athanasios B; Georgakilas, Vasilios; Giannelis, Emmanuel P

2010-09-01

We report for the first time an ionic fluid based on hydroxylated fullerenes (fullerols). The ionic fluid was synthesized by neutralizing the fully protonated fullerol with an amine terminated polyethylene/polypropylene oxide oligomer (Jeffamine). The ionic fluid was compared to a control synthesized by mixing the partially protonated form (sodium form) of the fullerols with the same oligomeric amine in the same ratio as in the ionic fluids (20 wt% fullerol). In the fullerol fluid the ionic bonding significantly perturbs the thermal transitions and melting/crystallization behavior of the amine. In contrast, both the normalized heat of fusion and crystallization of the amine in the control are similar to those of the neat amine consistent with a physical mixture of the fullerols/amine with minimal interactions. In addition to differences in thermal behavior, the fullerol ionic fluid exhibits a complex viscoelastic behavior intermediate between the neat Jeffamine (liquid-like) and the control (solid-like).

Fullerol ionic fluids

NASA Astrophysics Data System (ADS)

Fernandes, Nikhil; Dallas, Panagiotis; Rodriguez, Robert; Bourlinos, Athanasios B.; Georgakilas, Vasilios; Giannelis, Emmanuel P.

2010-09-01

We report for the first time an ionic fluid based on hydroxylated fullerenes (fullerols). The ionic fluid was synthesized by neutralizing the fully protonated fullerol with an amine terminated polyethylene/polypropylene oxide oligomer (Jeffamine®). The ionic fluid was compared to a control synthesized by mixing the partially protonated form (sodium form) of the fullerols with the same oligomeric amine in the same ratio as in the ionic fluids (20 wt% fullerol). In the fullerol fluid the ionic bonding significantly perturbs the thermal transitions and melting/crystallization behavior of the amine. In contrast, both the normalized heat of fusion and crystallization of the amine in the control are similar to those of the neat amine consistent with a physical mixture of the fullerols/amine with minimal interactions. In addition to differences in thermal behavior, the fullerol ionic fluid exhibits a complex viscoelastic behavior intermediate between the neat Jeffamine® (liquid-like) and the control (solid-like).

Method for preparing hydrous titanium oxide spherules and other gel forms thereof

DOEpatents

Collins, J.L.

1998-10-13

The present invention are methods for preparing hydrous titanium oxide spherules, hydrous titanium oxide gels such as gel slabs, films, capillary and electrophoresis gels, titanium monohydrogen phosphate spherules, hydrous titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite sorbent, titanium monohydrogen phosphate spherules having suspendible particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, titanium oxide spherules in the form of anatase, brookite or rutile, titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite, hydrous titanium oxide fiber materials, titanium oxide fiber materials, hydrous titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite, titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite and spherules of barium titanate. These variations of hydrous titanium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters and ceramics. 6 figs.

Method for preparing hydrous titanium oxide spherules and other gel forms thereof

DOEpatents

Collins, Jack L.

1998-01-01

The present invention are methods for preparing hydrous titanium oxide spherules, hydrous titanium oxide gels such as gel slabs, films, capillary and electrophoresis gels, titanium monohydrogen phosphate spherules, hydrous titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite sorbent, titanium monohydrogen phosphate spherules having suspendible particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, titanium oxide spherules in the form of anatase, brookite or rutile, titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite, hydrous titanium oxide fiber materials, titanium oxide fiber materials, hydrous titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite, titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite and spherules of barium titanate. These variations of hydrous titanium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters and ceramics.

Picking a Fight with Water, and Water Lost ... an Electron

NASA Astrophysics Data System (ADS)

Herr, Jonathan D.

The global need for energy is increasing, as is the importance of producing energy by green and renewable methodologies. This document outlines a research program dedicated to investigating a possible source for this form of energy generation and storage: solar fuels. The photon-induced splitting of water into molecular hydrogen and oxygen is currently hindered by large overpotentials from the oxidation half-reaction of water-splitting. This study concentrated on fundamental models of water-spitting chemistry, using a physical and computational chemistry analysis. The oxidation was first explored via ab initio electronic structure calculations of bare cationic water clusters, comprised of 2 to 21 molecules, in order to determine key electronic interactions that facilitate oxidation. Deeper understanding of these interactions could serve as guides for the development of viable water oxidation catalysts (WOC) designed to reduce overpotentials. The cationic water cluster study was followed by an investigation into hydrated copper (I) clusters, which acted as precursor models for real WOCs. Analyzing how the copper ion perturbed the properties of water clusters led to important electronic considerations for the development of WOCs, such as copper-water interactions that go beyond simple electrostatics. The importance of diagnostic thermodynamic properties, as well as anharmonic characteristics being persistent throughout oxidized water clusters, necessitated the use of quantum and classical molecular dynamics (MD) routines. Therefore, two new methods for accelerating computationally demanding classical and quantum MD methods were developed to increase their accessibility. The first method utilized a new form of electronic extrapolation - a linear prediction routine incorporating a Burg minimization - to decrease the iterations required for solving the electronic equations throughout the dynamics. The second method utilized a multiple-timestepping description of the potential energy term in the path integral molecular dynamics (PIMD) formalism. This method led to reductions of computational time by allowing the use of less computationally laborious methods for portions of the simulation and resulted in negligible increase of error. The determination of the fundamental driving forces within water oxidation and the development of acceleration techniques for important electronic structure methods will help drive progress into fully solar-initiated water oxidation.

High Activity of Au/K/TiO 2(110) for CO Oxidation: Alkali-Metal-Enhanced Dispersion of Au and Bonding of CO

DOE PAGES

Rodriguez, Jose A.; Grinter, David C.; Ramirez, Pedro J.; ...

2018-02-14

In this paper, images from scanning tunneling microscopy show high mobility for potassium (K) on an oxidized TiO 2(110) surface. At low coverages, the alkali metal occupies mainly terrace sites of the o-TiO 2(110) system. The results of X-ray photoelectron spectroscopy indicate that K is fully ionized. The electron transferred from K to the titania affects the reactivity of this oxide, favoring the dispersion of Au particles on the terraces of the o-TiO 2(110) surface. When small coverages of K and Au are present on the o-TiO 2(110) system, only a few K–Au pairs are formed and the alkali metalmore » affects Au chemisorption mainly through the oxide interactions. Addition of K to Au/o-TiO 2(110) enhances the reactivity of the system, opening new reaction paths for the adsorption and oxidation of carbon monoxide. CO can undergo disproportionation (2CO → C ads + CO 2,ads) on K/o-TiO 2(110) and Au/K/o-TiO 2(110) surfaces. The Au–KO x interface binds CO much better than plain Au–TiO 2, increasing the surface coverage of CO and facilitating its oxidation. Kinetic tests show that K promotes CO oxidation on Au/TiO 2. Finally, turnover frequencies of 2.1 and 10.8 molecules (Au site) -1 s –1 were calculated for oxidation of CO on Au/o-TiO 2(110) and Au/K/o-TiO 2(110) catalysts, respectively.« less

High Activity of Au/K/TiO 2(110) for CO Oxidation: Alkali-Metal-Enhanced Dispersion of Au and Bonding of CO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez, Jose A.; Grinter, David C.; Ramirez, Pedro J.

In this paper, images from scanning tunneling microscopy show high mobility for potassium (K) on an oxidized TiO 2(110) surface. At low coverages, the alkali metal occupies mainly terrace sites of the o-TiO 2(110) system. The results of X-ray photoelectron spectroscopy indicate that K is fully ionized. The electron transferred from K to the titania affects the reactivity of this oxide, favoring the dispersion of Au particles on the terraces of the o-TiO 2(110) surface. When small coverages of K and Au are present on the o-TiO 2(110) system, only a few K–Au pairs are formed and the alkali metalmore » affects Au chemisorption mainly through the oxide interactions. Addition of K to Au/o-TiO 2(110) enhances the reactivity of the system, opening new reaction paths for the adsorption and oxidation of carbon monoxide. CO can undergo disproportionation (2CO → C ads + CO 2,ads) on K/o-TiO 2(110) and Au/K/o-TiO 2(110) surfaces. The Au–KO x interface binds CO much better than plain Au–TiO 2, increasing the surface coverage of CO and facilitating its oxidation. Kinetic tests show that K promotes CO oxidation on Au/TiO 2. Finally, turnover frequencies of 2.1 and 10.8 molecules (Au site) -1 s –1 were calculated for oxidation of CO on Au/o-TiO 2(110) and Au/K/o-TiO 2(110) catalysts, respectively.« less

Notum is required for neural and head induction via Wnt deacylation, oxidation, and inactivation.

PubMed

Zhang, Xinjun; Cheong, Seong-Moon; Amado, Nathalia G; Reis, Alice H; MacDonald, Bryan T; Zebisch, Matthias; Jones, E Yvonne; Abreu, Jose Garcia; He, Xi

2015-03-23

Secreted Wnt morphogens are essential for embryogenesis and homeostasis and require a lipid/palmitoleoylate modification for receptor binding and activity. Notum is a secreted Wnt antagonist that belongs to the α/β hydrolase superfamily, but its mechanism of action and roles in vertebrate embryogenesis are not fully understood. Here, we report that Notum hydrolyzes the Wnt palmitoleoylate adduct extracellularly, resulting in inactivated Wnt proteins that form oxidized oligomers incapable of receptor binding. Thus, Notum is a Wnt deacylase, and palmitoleoylation is obligatory for the Wnt structure that maintains its active monomeric conformation. Notum is expressed in naive ectoderm and neural plate in Xenopus and is required for neural and head induction. These findings suggest that Notum is a prerequisite for the "default" neural fate and that distinct mechanisms of Wnt inactivation by the Tiki protease in the Organizer and the Notum deacylase in presumptive neuroectoderm orchestrate vertebrate brain development. Copyright © 2015 Elsevier Inc. All rights reserved.

Ergot Alkaloid Biosynthesis in the Maize (Zea mays) Ergot Fungus Claviceps gigantea.

PubMed

Bragg, Paige E; Maust, Matthew D; Panaccione, Daniel G

2017-12-13

Biosynthesis of the dihydrogenated forms of ergot alkaloids is of interest because many of the ergot alkaloids used as pharmaceuticals may be derived from dihydrolysergic acid (DHLA) or its precursor dihydrolysergol. The maize (Zea mays) ergot pathogen Claviceps gigantea has been reported to produce dihydrolysergol, a hydroxylated derivative of the common ergot alkaloid festuclavine. We hypothesized expression of C. gigantea cloA in a festuclavine-accumulating mutant of the fungus Neosartorya fumigata would yield dihydrolysergol because the P450 monooxygenase CloA from other fungi performs similar oxidation reactions. We engineered such a strain, and high performance liquid chromatography and liquid chromatography-mass spectrometry analyses demonstrated the modified strain produced DHLA, the fully oxidized product of dihydrolysergol. Accumulation of high concentrations of DHLA in field-collected C. gigantea sclerotia and discovery of a mutation in the gene lpsA, downstream from DHLA formation, supported our finding that DHLA rather than dihydrolysergol is the end product of the C. gigantea pathway.

CO2 sensing properties of electro-spun Ca-doped ZnO fibres.

PubMed

Pantò, Fabiola; Leonardi, Salvatore Gianluca; Fazio, Enza; Frontera, Patrizia; Bonavita, Anna; Neri, Giovanni; Antonucci, Pierluigi; Neri, Fortunato; Santangelo, Saveria

2018-07-27

The availability of low-cost, high-performing sensors for carbon dioxide detection in the environment may play a crucial role for reducing CO 2 emissions and limiting global warming. In this study, calcium-doped zinc oxide nanofibres with different Ca to Zn loading ratios (1:40 or 1:20) are synthesised via electro-spinning, thoroughly characterised and, for the first time, tested as an active material for the detection of carbon dioxide. The results of their characterisation show that the highly porous fibres consist of interconnected grains of oxide with the hexagonal wurtzite structure of zincite. Depending on the Ca:Zn loading ratio, calcium fully or partly segregates to form calcite on the fibre surface. The high response of the sensor based on the fibres with the highest Ca-doping level can be attributed to the synergy between the fibre morphology and the basicity of Ca-ion sites, which favour the diffusion of the gas molecules within the sensing layer and the CO 2 adsorption, respectively.

Ischemia-reperfusion injury of the cochlea: pharmacological strategies for cochlear protection and implications of glutamate and reactive oxygen species.

PubMed

Tabuchi, Keiji; Nishimura, Bungo; Tanaka, Shuho; Hayashi, Kentaro; Hirose, Yuki; Hara, Akira

2010-06-01

A large amount of energy produced by active aerobic metabolism is necessary for the cochlea to maintain its function. This makes the cochlea vulnerable to blockade of cochlear blood flow and interruption of the oxygen supply. Although certain forms of human idiopathic sudden sensorineural hearing loss reportedly arise from ischemic injury, the pathological mechanism of cochlear ischemia-reperfusion injury has not been fully elucidated. Recent animal studies have shed light on the mechanisms of cochlear ischemia-reperfusion injury. It will help in the understanding of the pathology of cochlear ischemia-reperfusion injury to classify this injury into ischemic injury and reperfusion injury. Excitotoxicity, mainly observed during the ischemic period, aggravates the injury of primary auditory neurons. On the other hand, oxidative damage induced by hydroxyl radicals and nitric oxide enhances cochlear reperfusion injury. This article briefly summarizes the generation mechanisms of cochlear ischemia-reperfusion injury and potential therapeutic targets that could be developed for the effective management of this injury type.

Single-electron-occupation metal-oxide-semiconductor quantum dots formed from efficient poly-silicon gate layout

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carroll, Malcolm S.; rochette, sophie; Rudolph, Martin

We introduce a silicon metal-oxide-semiconductor quantum dot structure that achieves dot-reservoir tunnel coupling control without a dedicated barrier gate. The elementary structure consists of two accumulation gates separated spatially by a gap, one gate accumulating a reservoir and the other a quantum dot. Control of the tunnel rate between the dot and the reservoir across the gap is demonstrated in the single electron regime by varying the reservoir accumulation gate voltage while compensating with the dot accumulation gate voltage. The method is then applied to a quantum dot connected in series to source and drain reservoirs, enabling transport down tomore » the single electron regime. Finally, tuning of the valley splitting with the dot accumulation gate voltage is observed. This split accumulation gate structure creates silicon quantum dots of similar characteristics to other realizations but with less electrodes, in a single gate stack subtractive fabrication process that is fully compatible with silicon foundry manufacturing.« less

Friction, Wear, and Surface Damage of Metals as Affected by Solid Surface Films

NASA Technical Reports Server (NTRS)

Bisson, Edmond E; Johnson, Robert L; Swikert, Max A; Godfrey, Douglas

1956-01-01

As predicted by friction theory, experiments showed that friction and surface damage of metals can be reduced by solid surface films. The ability of materials to form surface films that prevent welding was a very important factor in wear of dry and boundary lubricated surfaces. Films of graphitic carbon on cast irons, nio on nickel alloys, and feo and fe sub 3 o sub 4 on ferrous materials were found to be beneficial. Abrasive films such as fe sub 2 o sub 3 or moo sub 3 were definitely detrimental. It appears that the importance of oxide films to friction and wear processes has not been fully appreciated.

RETINOIC ACID SYNTHESIS AND DEGRADATION

PubMed Central

Kedishvili, Natalia Y.

2017-01-01

Retinoic acid was identified as the biologically active form of vitamin A almost 70 years ago, but the exact enzymes and control mechanisms that regulate its biosynthesis and degradation are yet to be fully defined. The currently accepted model postulates that RA is produced in two sequential oxidative steps: first, retinol is oxidized reversibly to retinaldehyde, and then retinaldehyde is oxidized irreversibly to RA, which is inactivated by conversion to hydroxylated derivatives. This chapter describes the history, development and recent advances in our understanding of the enzymatic pathways and mechanisms that control the rate of RA production and degradation. Gene knockout studies provided strong evidence that the members of the short chain dehydrogenase reductase superfamily of proteins play indispensable roles in retinoic acid biosynthesis during development. Furthermore, recent finding that two of these proteins regulate the rate of retinoic acid biosynthesis by mutually activating each other provided a novel insight into the mechanism of this regulation. Despite significant progress made since the middle of the 20th century many unanswered questions still remain, and there is much to be learned, especially about trafficking of the hydrophobic retinoid substrates between membrane bound and cytosolic enzymes and the roles of the retinoid binding proteins. PMID:27830503

Creep Forming of Carbon-Reinforced Ceramic-Matrix Composites

NASA Technical Reports Server (NTRS)

Vaughn, Wallace L.; Scotti, Stephan J.; Ashe, Melissa P.; Connolly, Liz

2007-01-01

A set of lecture slides describes an investigation of creep forming as a means of imparting desired curvatures to initially flat stock plates of carbon-reinforced ceramic-matrix composite (C-CMC) materials. The investigation is apparently part of a continuing effort to develop improved means of applying small CCMC repair patches to reinforced carbon-carbon leading edges of aerospace vehicles (e.g., space shuttles) prior to re-entry into the atmosphere of the Earth. According to one of the slides, creep forming would be an intermediate step in a process that would yield a fully densified, finished C-CMC part having a desired size and shape (the other steps would include preliminary machining, finish machining, densification by chemical vapor infiltration, and final coating). The investigation included experiments in which C-CMC disks were creep-formed by heating them to unspecified high temperatures for time intervals of the order of 1 hour while they were clamped into single- and double-curvature graphite molds. The creep-formed disks were coated with an oxidation- protection material, then subjected to arc-jet tests, in which the disks exhibited no deterioration after exposure to high-temperature test conditions lasting 490 seconds.

Formation of aggregated nanoparticle spheres through femtosecond laser surface processing

NASA Astrophysics Data System (ADS)

Tsubaki, Alfred T.; Koten, Mark A.; Lucis, Michael J.; Zuhlke, Craig; Ianno, Natale; Shield, Jeffrey E.; Alexander, Dennis R.

2017-10-01

A detailed structural and chemical analysis of a class of self-organized surface structures, termed aggregated nanoparticle spheres (AN-spheres), created using femtosecond laser surface processing (FLSP) on silicon, silicon carbide, and aluminum is reported in this paper. AN-spheres are spherical microstructures that are 20-100 μm in diameter and are composed entirely of nanoparticles produced during femtosecond laser ablation of material. AN-spheres have an onion-like layered morphology resulting from the build-up of nanoparticle layers over multiple passes of the laser beam. The material properties and chemical composition of the AN-spheres are presented in this paper based on scanning electron microscopy (SEM), focused ion beam (FIB) milling, transmission electron microscopy (TEM), and energy dispersive x-ray spectroscopy (EDX) analysis. There is a distinct difference in the density of nanoparticles between concentric rings of the onion-like morphology of the AN-sphere. Layers of high-density form when the laser sinters nanoparticles together and low-density layers form when nanoparticles redeposit while the laser ablates areas surrounding the AN-sphere. The dynamic nature of femtosecond laser ablation creates a variety of nanoparticles that make-up the AN-spheres including Si/C core-shell, nanoparticles that directly fragmented from the base material, nanoparticles with carbon shells that retarded oxidation, and amorphous, fully oxidized nanoparticles.

Structural studies on Desulfovibrio gigas cytochrome c3 by two-dimensional 1H-nuclear-magnetic-resonance spectroscopy.

PubMed Central

Piçarra-Pereira, M A; Turner, D L; LeGall, J; Xavier, A V

1993-01-01

Several aromatic amino acid residues and haem resonances in the fully reduced form of Desulfovibrio gigas cytochrome c3 are assigned, using two-dimensional 1H n.m.r., on the basis of the interactions between the protons of the aromatic amino acids and the haem protons as well as the intrahaem distances known from the X-ray structure [Kissinger (1989) Ph.D. Thesis, Washington State University]. The interhaem interactions observed in the n.m.r. spectra are in full agreement with the D. gigas X-ray structure and also with the n.m.r. data from Desulfovibrio vulgaris (Hildenborough) [Turner, Salgueiro, LeGall and Xavier (1992) Eur. J. Biochem. 210, 931-936]. The good correlation between the calculated ring-current shifts and the observed chemical shifts strongly supports the present assignments. Observation of the two-dimensional nuclear-Overhauser-enhancement spectra of the protein in the reduced, intermediate and fully oxidized stages led to the ordering of the haems in terms of their midpoint redox potentials and their identification in the X-ray structure. The first haem to oxidize is haem I, followed by haems II, III and IV, numbered according to the Cys ligand positions in the amino acid sequences [Mathews (1985) Prog. Biophys. Mol. Biol. 54, 1-56]. Although the haem core architecture is the same for the different Desulfovibrio cytochromes c3, the order of redox potentials is different. PMID:8397514

Peroxiredoxin VI Oxidation in Cerebrospinal Fluid Correlates with TBI Outcome

PubMed Central

Manevich, Y.; Hutchens, S.; Halushka, P.V.; Tew, K.D.; Townsend, D. M.; Jauch, E.C.; Borg, K.

2014-01-01

Traumatic brain injury (TBI) patients would benefit from the identification of reliable biomarkers to predict outcomes and treatment strategies. In our study, cerebrospinal fluid (CSF) from patients with severe TBI was evaluated for oxidant stress-mediated damage progression after hospital admission and subsequent ventriculostomy placement. Interestingly, substantial levels of peroxiredoxin VI (Prdx6), a major antioxidant enzyme normally found in astrocytes, were detected in CSF from control and TBI patients, and were not associated with blood contamination. Functionally, Prdx6 and its associated binding partner glutathione S-transferase pi (GSTP1-1, also detected in CSF) act in tandem to detoxify lipid peroxidation damage to membranes. We found Prdx6 was fully active in CSF of control patients but becomes significantly inactivated (oxidized) under TBI. Furthermore, significant and progressive oxidation of “buried” protein thiol in CSF of TBI patients (as compared to that of non-trauma control) were detected over a 24h period following hospital admission, with increased oxidation correlating with severity of trauma. Conversely, recovery of Prdx6 activity after 24h indicated more favorable patient outcome. Not only is this the first report of an extracellular form of Prdx6 but also the first report of its detection at a substantial level in CSF. Taken together, our data suggest a meaningful correlation between TBI-initiated oxidation of Prdx6, its specific phospholipid hydroperoxide peroxidase activity, and severity of trauma outcome. Consequently, we propose that Prdx6 redox status detection has the potential to be a biomarker for TBI outcome and a future indicator of therapeutic efficacy. PMID:24726861

Electrochemical oxidation coupled with liquid chromatography and mass spectrometry to study the oxidative stability of active pharmaceutical ingredients in solution: A comparison of off-line and on-line approaches.

PubMed

Torres, Susana; Brown, Roland; Zelesky, Todd; Scrivens, Garry; Szucs, Roman; Hawkins, Joel M; Taylor, Mark R

2016-11-30

Stability studies of pharmaceutical drug products and pharmaceutical active substances are important to research and development in order to fully understand and maintain product quality and safety throughout its shelf-life. Oxidative forced degradation studies are among the different types of stability studies performed by the pharmaceutical industry in order to understand the intrinsic stability of drug molecules. We have been comparing the use of electrochemistry as an alternative oxidative forced degradation method to traditional forced degradation and accelerated stability studies. Using the electrochemical degradation approach the substrate oxidation takes place in a commercially available electrochemical cell and the effluent of the cell can be either a) directly infused into the mass spectrometer or b) injected in a chromatographic column for separation of the different products formed prior to the mass spectrometry analysis. To enable the study of large numbers of different experimental conditions and molecules we developed a new dual pump automated electrochemical screening platform. This system used a HPLC pump and autosampler to load and wash the electrochemical cell and deliver the oxidized sample plug to a second injection loop. This system enabled the automatic sequential analyses of large numbers of different solutions under varied experimental conditions without need for operator intervention during the run sequence. Here we describe the system and evaluate its performance using a test molecule with well characterized stability and compare results to those obtained using an off-line electrochemistry approach. Copyright © 2016 Elsevier B.V. All rights reserved.

Method of making maximally dispersed heterogeneous catalysts

DOEpatents

Jennison, Dwight R [Albuquerque, NM

2005-11-15

A method of making a catalyst with monolayer or sub-monolayer metal by controlling the wetting characteristics on the support surface and increasing the adhesion between the catalytic metal and an oxide layer. There are two methods that have been demonstrated by experiment and supported by theory. In the first method, which is useful for noble metals as well as others, a negatively-charged species is introduced to the surface of a support in sub-ML coverage. The layer-by-layer growth of metal deposited onto the oxide surface is promoted because the adhesion strength of the metal-oxide interface is increased. This method can also be used to achieve nanoislands of metal upon sub-ML deposition. The negatively-charged species can either be deposited onto the oxide surface or a compound can be deposited that dissociates on, or reacts with, the surface to form the negatively-charged species. The deposited metal adatoms can thereby bond laterally to the negatively-charged species as well as vertically to the oxide surface. Thus the negatively-charged species serve as anchors for the metal. In the second method, a chemical reaction that occurs when most metals are deposited on a fully hydroxylated oxide surface is used to create cationic metal species that bind strongly both to the substrate and to metallic metal atoms. These are incorporated into the top layer of the substrate and bind strongly both to the substrate and to metallic metal atoms. In this case, these oxidized metal atoms serve as the anchors. Here, as in the previous method, nanoislands of catalytic metal can be achieved to increase catalytic activity, or monolayers or bilayers of reactive metal can also be made.

Arsenic (+3 Oxidation State) Methyltransferase and the Methylation of Arsenicals

PubMed Central

Thomas, David J.; Li, Jiaxin; Waters, Stephen B.; Xing, Weibing; Adair, Blakely M.; Drobna, Zuzana; Devesa, Vicenta; Styblo, Miroslav

2008-01-01

Metabolic conversion of inorganic arsenic into methylated products is a multistep process that yields mono-, di-, and trimethylated arsenicals. In recent years, it has become apparent that formation of methylated metabolites of inorganic arsenic is not necessarily a detoxification process. Intermediates and products formed in this pathway may be more reactive and toxic than inorganic arsenic. Like all metabolic pathways, understanding the pathway for arsenic methylation involves identification of each individual step in the process and the characterization of the molecules which participate in each step. Among several arsenic methyltransferases that have been identified, arsenic (+3 oxidation state) methyltransferase is the one best characterized at the genetic and functional levels. This review focuses on phylogenetic relationships in the deuterostomal lineage for this enzyme and on the relation between genotype for arsenic (+3 oxidation state) methyltransferase and phenotype for conversion of inorganic arsenic to methylated metabolites. Two conceptual models for function of arsenic (+3 oxidation state) methyltransferase which posit different roles for cellular reductants in the conversion of inorganic arsenic to methylated metabolites are compared. Although each model accurately represents some aspects of enzyme’s role in the pathway for arsenic methylation, neither model is a fully satisfactory representation of all the steps in this metabolic pathway. Additional information on the structure and function of the enzyme will be needed to develop a more comprehensive model for this pathway. PMID:17202581

Formation of a cytochrome c-nitrous oxide reductase complex is obligatory for N2O reduction by Paracoccus pantotrophus.

PubMed

Rasmussen, Tim; Brittain, Thomas; Berks, Ben C; Watmough, Nicholas J; Thomson, Andrew J

2005-11-07

Nitrous oxide reductase (N2OR) catalyses the final step of bacterial denitrification, the two-electron reduction of nitrous oxide (N2O) to dinitrogen (N2). N2OR contains two metal centers; a binuclear copper center, CuA, that serves to receive electrons from soluble donors, and a tetranuclear copper-sulfide center, CuZ, at the active site. Stopped flow experiments at low ionic strengths reveal rapid electron transfer (kobs=150 s-1) between reduced horse heart (HH) cytochrome c and the CuA center in fully oxidized N2OR. When fully reduced N2OR was mixed with oxidized cytochrome c, a similar rate of electron transfer was recorded for the reverse reaction, followed by a much slower internal electron transfer from CuZ to CuA(kobs=0.1-0.4 s-1). The internal electron transfer process is likely to represent the rate-determining step in the catalytic cycle. Remarkably, in the absence of cytochrome c, fully reduced N2OR is inert towards its substrate, even though sufficient electrons are stored to initiate a single turnover. However, in the presence of reduced cytochrome c and N2O, a single turnover occurs after a lag-phase. We propose that a conformational change in N2OR is induced by its specific interaction with cytochrome c that in turn either permits electron transfer between CuA and CuZ or controls the rate of N2O decomposition at the active site.

Nitrous oxide emissions affected by biochar and nitrogen stabilizers

USDA-ARS?s Scientific Manuscript database

Both biochar and N fertilizer stabilizers (N transformation inhibitors) are potential strategies to reduce nitrous oxide (N2O) emissions from fertilization, but the mechanisms and/or N transformation processes affecting the N dynamics are not fully understood. This research investigated N2O emission...

One-pot synthesis of star-shaped macromolecules containing polyglycidol and poly(ethylene oxide) arms.

PubMed

Lapienis, Grzegorz; Penczek, Stanislaw

2005-01-01

Synthesis of fully hydrophilic star-shaped macromolecules with different kinds of arms (A(x)B(y)C(z)) based on polyglycidol (PGL, A(x)) and poly(ethylene oxide) (PEO, C(z)) arms and diepoxy compounds (diglycidyl ethers of ethylene glycol (DGEG) or neopentyl glycol (DGNG) in the core, B(y)) forming the core is described. Precursors of arms were prepared by polymerization of glycidol with protected -OH groups. The first-generation stars were formed in the series of consecutive-parallel reactions of arms A(x) with diepoxy compounds (B). These first-generation stars (A(x)B(y)), having approximately O-, Mt+ groups on the cores, were used as multianionic initiators for the second generation of arms (C(z)) built by polymerization of ethylene oxide. The products with M(n) up to 10(5) and having up to approximately 40 arms were obtained. The number of arms (f) was determined by direct measurements of M(n) of the first-generation stars (M(n) of arms A(x) is known), compared with f calculated from the branching index g, determined from R(g) measured with size-exclusion chromatography (SEC) triple detection with TriSEC software. The progress of the star formation was monitored by 1H NMR and SEC. These novel water-soluble stars, having a large number of hydroxyl groups, both at the ends of PEO arms as well as within the PGL arms, can be functionalized and further used for attaching compounds of interest. This approach opens, therefore, a new way of "multiPEGylation".

Method for preparing hydrous zirconium oxide gels and spherules

DOEpatents

Collins, Jack L.

2003-08-05

Methods for preparing hydrous zirconium oxide spherules, hydrous zirconium oxide gels such as gel slabs, films, capillary and electrophoresis gels, zirconium monohydrogen phosphate spherules, hydrous zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite sorbent, zirconium monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite, hydrous zirconium oxide fiber materials, zirconium oxide fiber materials, hydrous zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite and spherules of barium zirconate. The hydrous zirconium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process are useful as inorganic ion exchangers, catalysts, getters and ceramics.

Method for preparing hydrous iron oxide gels and spherules

DOEpatents

Collins, Jack L.; Lauf, Robert J.; Anderson, Kimberly K.

2003-07-29

The present invention is directed to methods for preparing hydrous iron oxide spherules, hydrous iron oxide gels such as gel slabs, films, capillary and electrophoresis gels, iron monohydrogen phosphate spherules, hydrous iron oxide spherules having suspendable particles homogeneously embedded within to form composite sorbents and catalysts, iron monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent, iron oxide spherules having suspendable particles homogeneously embedded within to form a composite of hydrous iron oxide fiber materials, iron oxide fiber materials, hydrous iron oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, iron oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, dielectric spherules of barium, strontium, and lead ferrites and mixtures thereof, and composite catalytic spherules of barium or strontium ferrite embedded with oxides of Mg, Zn, Pb, Ce and mixtures thereof. These variations of hydrous iron oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters, dielectrics, and ceramics.

Redox-controlled dinitrosyl formation at the diiron-oxo center of NorA.

PubMed

Cramm, Rainer; Strube, Katja

2008-01-01

In the denitrifying bacterium Ralstonia eutropha H16, the NorA protein is coproduced with the respiratory nitric oxide (NO) reductase. NorA contains a diiron-oxo center, which can form stable adducts with dioxygen and NO. In contrast to other diiron proteins, the formation of NorA-NO requires both fully reduced protein and additional electrons. A minor fraction of in vitro NorA-NO represents a paramagnetic dinitrosyl iron complex (DNIC), while the major fraction is attributed to a DNIC of the structure {Fe(NO)(2)}, which shows no electron paramagnetic resonance. The NorA-DNIC may be formed either upon direct reaction of the protein with NO or upon incubation with nitrite due to an intrinsic nitrite reduction activity of NorA that liberates NO. NorA can be purified rapidly as a six histidine-tagged derivative from overproducing cells of Escherichia coli. This chapter describes procedures for the preparation of different redox forms of NorA for the formation of NorA adducts with NO, dioxygen, and azide, as well as for the quantification of NorA-bound NO.

N-acetylcysteine inhibits the up-regulation of mitochondrial biogenesis genes in livers from rats fed ethanol chronically

USDA-ARS?s Scientific Manuscript database

Background: Chronic ethanol (EtOH) administration to experimental animals induces hepatic oxidative stress and up-regulates mitochondrial biogenesis. The mechanisms by which chronic EtOH up-regulates mitochondrial biogenesis have not been fully explored. In this work, we hypothesized that oxidative ...

Electrochromic nickel oxide simultaneously doped with lithium and a metal dopant

DOEpatents

Gillaspie, Dane T; Weir, Douglas G

2014-04-01

An electrochromic device comprising a counter electrode layer comprised of lithium metal oxide which provides a high transmission in the fully intercalated state and which is capable of long-term stability, is disclosed. Methods of making an electrochromic device comprising such a counter electrode are also disclosed.

Electrochromic nickel oxide simultaneously doped with lithium and a metal dopant

DOEpatents

Gillaspie, Dane T.; Weir, Douglas Glenn John

2017-05-16

An electrochromic device comprising a counter electrode layer comprised of lithium metal oxide which provides a high transmission in the fully intercalated state and which is capable of long-term stability, is disclosed. Methods of making an electrochromic device comprising such a counter electrode are also disclosed.

Products of BVOC oxidation: ozone and organic aerosols

NASA Astrophysics Data System (ADS)

Wildt, Jürgen; Andres, Stefanie; Carriero, Giulia; Ehn, Mikael; Fares, Silvano; Hoffmann, Thorsten; Hacker, Lina; Kiendler-Scharr, Astrid; Kleist, Einhard; Paoletti, Elena; Pullinen, Iida; Rohrer, Franz; Rudich, Yinon; Springer, Monika; Tillmann, Ralf; Wahner, Andreas; Wu, Cheng; Mentel, Thomas

2015-04-01

Biogenic Volatile Organic Compounds (BVOC) are important precursors in photochemical O3 and secondary organic aerosol (SOA) formation. We conducted a series of laboratory experiments with OH-induced oxidation of monoterpenes to elucidate pathways and efficiencies of O3 and SOA formation. At high NOx conditions ([BVOC] / [NOx] < 7 ppbC / ppb) photochemical ozone formation was observed. For -pinene as individual BVOC as well as for the monoterpene mixes emitted from different plant species we observed increasing ozone formation with increasing [NOX]. Between 2 and 3 O3-molecules were formed from 1 monoterpene when ozone formation was BVOC limited. Under such high NOX conditions, new particle formation was suppressed. Increasing [BVOC] / [NOX] ratios caused increasing efficiency of new particle formation indicating that peroxy radicals are the key intermediates in both, photochemical ozone- and new particle formation. The classical chemistry of peroxy radicals is well established (e.g. Master Chemical Mechanism). Peroxy radicals are produced by addition of molecular oxygen to the alkyl radical formed after OH attack at the BVOC. They either react with NO which leads to ozone formation or they react with other peroxy radicals and form chemically stable products (hydroperoxides, alkoholes and ketones). Much less knowledge exists on such reactions for Highly Oxidized Peroxy Radicals, (HOPR). Such HOPR were observed during ozonolysis of several volatiles and, in case of monoterpenes as precursors, they can contain more than 12 Oxygen atoms (Mentel et al., 2015). Although the OH-initiated formation of HOPR is yet not fully understood, their basic gas phase reactions seem to follow classical photochemical rules. In reactions with NO they can act as precursor for O3 and in reactions with other HOPR or with classical less oxidized peroxy radicals they can form highly oxidized stable products and alkoxy radicals. In addition, HOPR-HOPR reactions lead to the formation of dimers that, in case of monoterpenes as reactants, consist of a skeleton with 20 carbon atoms. These dimers seem to play a major role in new particle formation and their existence may explain the observations of Wildt et al. (2014) who found power law dependence with an exponent approaching -2 between new particle formation and ozone formation. The monomer products of HOPR-HOPR reactions play a dominant role in SOA mass formation because their vapour pressures are low enough to allow condensation on pre-existing particulate matter (Ehn et al., 2014). Furthermore, the minor impacts of NOX on particle mass formation (Wildt et al., 2014) are explainable by similar yields of alkoxy radicals in HOPR-HOPR and HOPR-NO reactions, respectively.

Fused silicon-rich coatings for superalloys

NASA Technical Reports Server (NTRS)

Smialek, J. L.

1974-01-01

Various compositions of nickel-silicon and aluminum-silicon slurries were sprayed on IN 100 specimens and fusion-sintered to form fully dense coatings. Cyclic furnace oxidation tests in 1 atm air at 1100 C showed all the coatings to be protective for at least 600 hours, and one slurry, Al-60Si, was protective for 1000 hours. This coating also protected NASA TAZ 8A and NASA-TRW VIA for 1000 hours in the same furnace test. Alloys B 1900, TD-NiCr, and Mar-M200 were protected for lesser times, while NX 188 and NASA WAZ 20 were scarcely protected at all. Limited stress-rupture testing on 0.64-cm-diam IN 100 specimens detected no degradation of mechanical properties due to silicon diffusion.

Selective epitaxial growth properties and strain characterization of Si1- x Ge x in SiO2 trench arrays

NASA Astrophysics Data System (ADS)

Koo, Sangmo; Jang, Hyunchul; Ko, Dae-Hong

2017-04-01

In this study, we investigated the formation of a Si1- x Ge x fin structure in SiO2 trench arrays via an ultra-high-vacuum chemical-vapor deposition (UHV-CVD) selective epitaxial growth (SEG) process. Defect generation and microstructures of Si1- x Ge x fin structures with different Ge concentrations ( x = 0.2, 0.3 and 0.45) were examined. In addition, the strain evolution of a Si1- x Ge x fin structure was analyzed by using reciprocal space mapping (RSM). An (111) facet was formed from the Si1- x Ge x epi-layer and SiO2 trench wall interface to minimize the interface and the surface energy. The Si1- x Ge x fin structures were fully relaxed along the direction perpendicular to the trenches regardless of the Ge concentration. On the other hand, the fin structures were fully or partially strained along the direction parallel to the trenches depending on the Ge concentration: fully strained Si0.8Ge0.2 and Si0.7Ge0.3, and a Si0.55Ge0.45 strain-relaxed buffer. We further confirmed that the strain on the Si1- x Ge x fin structures remained stable after oxide removal and H2/N2 post-annealing.

Effect of pretreatment on pd/Al2O3 catalyst for catalytic oxidation of o-xylene at low temperature.

PubMed

Huang, Shaoyong; Zhang, Changbin; He, Hong

2013-06-01

The effect of pretreatment on Pd/Al2O3 catalysts for the catalytic oxidation of o-xylene at low temperature was studied by changing the pretreatment and testing conditions. The fresh and pretreated Pd/Al2O3 catalysts were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results showed that the pretreatment dramatically changed the Pd/PdO ratio and then significantly affected the Pd/Al2O3 activity; while the pretreatment had not much influence on Pd particle size. The Pd/Al2O3 pre-reduced at 300 degrees C/400 degrees C, which has fully reduced Pd species, showed the highest activity; while the fresh Pd/Al2O3, which has fully oxidized Pd species, presented the worst performance, indicating the Pd chemical state plays an important role in the catalytic activity for the o-xylene oxidation. It is concluded that metallic Pd is the active species on the Pd/Al2O3 catalyst for the catalytic oxidation of o-xylene at low temperature.

Synergistic Computational and Microstructural Design of Next- Generation High-Temperature Austenitic Stainless Steels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karaman, Ibrahim; Arroyave, Raymundo

The purpose of this project was to: 1) study deformation twinning, its evolution, thermal stability, and the contribution on mechanical response of the new advanced stainless steels, especially at elevated temperatures; 2) study alumina-scale formation on the surface, as an alternative for conventional chromium oxide, that shows better oxidation resistance, through alloy design; and 3) design new generation of high temperature stainless steels that form alumina scale and have thermally stable nano-twins. The work involved few baseline alloys for investigating the twin formation under tensile loading, thermal stability of these twins, and the role of deformation twins on the mechanicalmore » response of the alloys. These baseline alloys included Hadfield Steel (Fe-13Mn-1C), 316, 316L and 316N stainless steels. Another baseline alloy was studied for alumina-scale formation investigations. Hadfield steel showed twinning but undesired second phases formed at higher temperatures. 316N stainless steel did not show signs of deformation twinning. Conventional 316 stainless steel demonstrated extensive deformation twinning at room temperature. Investigations on this alloy, both in single crystalline and polycrystalline forms, showed that deformation twins evolve in a hierarchical manner, consisting of micron–sized bundles of nano-twins. The width of nano-twins stays almost constant as the extent of strain increases, but the width and number of the bundles increase with increasing strain. A systematic thermomechanical cycling study showed that the twins were stable at temperatures as high as 900°C, after the dislocations are annealed out. Using such cycles, volume fraction of the thermally stable deformation twins were increased up to 40% in 316 stainless steel. Using computational thermodynamics and kinetics calculations, we designed two generations of advanced austenitic stainless steels. In the first generation, Alloy 1, which had been proposed as an alumina-forming austenitic stainless steel, is fully austenitic, but possesses carbides that were not dissolvable and could not be controlled. This alloy also did not show deformation twinning. Alloy 2 was designed based on alloy 1, but was not fully austenitic and had significant traces of uncontrollable precipitates as well. Alloy 3, also designed based on alloy 1, was mainly austenitic with evolution of a second phase along the grain boundaries, but also had precipitates that were not controllable. Based on the knowledge gained from the first generation of the designed steels, two more steels, called PGAA1 and PGAA2, were proposed using genetic algorithms that, based on the modelling, were supposed to exhibit alumina-scale formation. PGAA1, however, did not demonstrate a fully austenitic structure. PGAA2 could achieve a mostly austenitic structure through thermo-mechanical processing, and was then used for oxidation tests. The oxidation tests of PGAA2, with and without nitrogen impurities, along with alloy 1, suggested that PGAA2 can form alumina-scale similar to alloy 1, but N impurity will prevent formation of such a scale, probably through formation of aluminum nitrides. For the above mentioned genetic algorithm framework of alloy design, separate models were developed for specific design criteria. For prediction of alumina formation in stainless steels, a model was constructed based off of two criteria – effective valence and third element effect. These criteria capture the thermodynamics and kinetics of alumina formation in steels. To test the efficacy and robustness of this model, they were tested against alloys in the literature which had been experimentally verified to exhibit alumina formation and the predictions were in excellent agreement with the experiments. Another meta-model for prediction of twinning in unknown steel compositions was developed by an informatics based machine learning/data mining approach. Stacking Fault Energy data was captured from the literature for a large number of steel compositions and then this data was used to build a classifier to predict deformation mechanisms. Here a training set-test set based analysis was performed to test performance. The above genetic algorithm based optimization framework for alloy design was exhibited to be a successful methodology for accelerated materials discovery in the context of alloy design.« less

Method for forming a potential hydrocarbon sensor with low sensitivity to methane and CO

DOEpatents

Mukundan, Rangachary; Brosha, Eric L.; Garzon, Fernando

2003-12-02

A hydrocarbon sensor is formed with an electrolyte body having a first electrolyte surface with a reference electrode depending therefrom and a metal oxide electrode body contained within the electrolyte body and having a first electrode surface coplanar with the first electrolyte surface. The sensor was formed by forming a sintered metal-oxide electrode body and placing the metal-oxide electrode body within an electrolyte powder. The electrolyte powder with the metal-oxide electrode body was pressed to form a pressed electrolyte body containing the metal-oxide electrode body. The electrolyte was removed from an electrolyte surface above the metal-oxide electrode body to expose a metal-oxide electrode surface that is coplanar with the electrolyte surface. The electrolyte body and the metal-oxide electrode body were then sintered to form the hydrocarbon sensor.

Green and scalable production of colloidal perovskite nanocrystals and transparent sols by a controlled self-collection process

NASA Astrophysics Data System (ADS)

Liu, Shuangyi; Huang, Limin; Li, Wanlu; Liu, Xiaohua; Jing, Shui; Li, Jackie; O'Brien, Stephen

2015-07-01

Colloidal perovskite oxide nanocrystals have attracted a great deal of interest owing to the ability to tune physical properties by virtue of the nanoscale, and generate thin film structures under mild chemical conditions, relying on self-assembly or heterogeneous mixing. This is particularly true for ferroelectric/dielectric perovskite oxide materials, for which device applications cover piezoelectrics, MEMs, memory, gate dielectrics and energy storage. The synthesis of complex oxide nanocrystals, however, continues to present issues pertaining to quality, yield, % crystallinity, purity and may also suffer from tedious separation and purification processes, which are disadvantageous to scaling production. We report a simple, green and scalable ``self-collection'' growth method that produces uniform and aggregate-free colloidal perovskite oxide nanocrystals including BaTiO3 (BT), BaxSr1-xTiO3 (BST) and quaternary oxide BaSrTiHfO3 (BSTH) in high crystallinity and high purity. The synthesis approach is solution processed, based on the sol-gel transformation of metal alkoxides in alcohol solvents with controlled or stoichiometric amounts of water and in the stark absence of surfactants and stabilizers, providing pure colloidal nanocrystals in a remarkably low temperature range (15 °C-55 °C). Under a static condition, the nanoscale hydrolysis of the metal alkoxides accomplishes a complete transformation to fully crystallized single domain perovskite nanocrystals with a passivated surface layer of hydroxyl/alkyl groups, such that the as-synthesized nanocrystals can exist in the form of super-stable and transparent sol, or self-accumulate to form a highly crystalline solid gel monolith of nearly 100% yield for easy separation/purification. The process produces high purity ligand-free nanocrystals excellent dispersibility in polar solvents, with no impurity remaining in the mother solution other than trace alcohol byproducts (such as isopropanol). The afforded stable and transparent suspension/solution can be treated as inks, suitable for printing or spin/spray coating, demonstrating great capabilities of this process for fabrication of high performance dielectric thin films. The simple ``self-collection'' strategy can be described as green and scalable due to the simplified procedure from synthesis to separation/purification, minimum waste generation, and near room temperature crystallization of nanocrystal products with tunable sizes in extremely high yield and high purity.Colloidal perovskite oxide nanocrystals have attracted a great deal of interest owing to the ability to tune physical properties by virtue of the nanoscale, and generate thin film structures under mild chemical conditions, relying on self-assembly or heterogeneous mixing. This is particularly true for ferroelectric/dielectric perovskite oxide materials, for which device applications cover piezoelectrics, MEMs, memory, gate dielectrics and energy storage. The synthesis of complex oxide nanocrystals, however, continues to present issues pertaining to quality, yield, % crystallinity, purity and may also suffer from tedious separation and purification processes, which are disadvantageous to scaling production. We report a simple, green and scalable ``self-collection'' growth method that produces uniform and aggregate-free colloidal perovskite oxide nanocrystals including BaTiO3 (BT), BaxSr1-xTiO3 (BST) and quaternary oxide BaSrTiHfO3 (BSTH) in high crystallinity and high purity. The synthesis approach is solution processed, based on the sol-gel transformation of metal alkoxides in alcohol solvents with controlled or stoichiometric amounts of water and in the stark absence of surfactants and stabilizers, providing pure colloidal nanocrystals in a remarkably low temperature range (15 °C-55 °C). Under a static condition, the nanoscale hydrolysis of the metal alkoxides accomplishes a complete transformation to fully crystallized single domain perovskite nanocrystals with a passivated surface layer of hydroxyl/alkyl groups, such that the as-synthesized nanocrystals can exist in the form of super-stable and transparent sol, or self-accumulate to form a highly crystalline solid gel monolith of nearly 100% yield for easy separation/purification. The process produces high purity ligand-free nanocrystals excellent dispersibility in polar solvents, with no impurity remaining in the mother solution other than trace alcohol byproducts (such as isopropanol). The afforded stable and transparent suspension/solution can be treated as inks, suitable for printing or spin/spray coating, demonstrating great capabilities of this process for fabrication of high performance dielectric thin films. The simple ``self-collection'' strategy can be described as green and scalable due to the simplified procedure from synthesis to separation/purification, minimum waste generation, and near room temperature crystallization of nanocrystal products with tunable sizes in extremely high yield and high purity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02351c

The effect of copper and silver on the properties of Au-ZnO catalyst and its activity in glycerol oxidation

NASA Astrophysics Data System (ADS)

Kaskow, Iveta; Decyk, Piotr; Sobczak, Izabela

2018-06-01

The goal of this work was to use ZnO as a support for gold and copper (Au-Cu system) or gold and silver (Au-Ag system) and comparison of the effect of copper and silver on the properties of gold and its activity in glycerol oxidation with oxygen in the liquid phase. The samples prepared were fully characterized by XRD, TEM techniques and UV-vis, XPS, ESR spectroscopic methods. It was found that the introduction of copper and silver changed the electronic state of gold loaded on ZnO by the electron transfer between metals. Three different metallic gold species were identified in calcined catalysts: (Au°)δ- (Au-ZnO), (Au°)η- (AuCu-ZnO) and (Au°)γ- (AuAg-ZnO), where δ-,η-,γ- indicate a different partial negative charge on metallic gold and γ > δ > η. The results showed that (Au°)η- centers (metallic gold with the lowest negative charge) formed on AuCu-ZnO were the most active in glycerol oxidation. The increase in the negative charge on metallic gold loaded on AuAg-ZnO reduced the gold activity in silver containing sample. The glyceric acid adsorption and desorption rate influenced the selectivity of the catalysts.

The role of the CeO 2 /BiVO 4 interface in optimized Fe–Ce oxide coatings for solar fuels photoanodes

DOE PAGES

Shinde, A.; Li, G.; Zhou, L.; ...

2016-09-09

Solar fuel generators entail a high degree of materials integration, and efficient photoelectrocatalysis of the constituent reactions hinges upon the establishment of highly functional interfaces. Our recent application of high throughput experimentation to interface discovery for solar fuels photoanodes has revealed several surprising and promising mixed-metal oxide coatings for BiVO 4. Furthermore, when using sputter deposition of composition and thickness gradients on a uniform BiVO 4 film, we systematically explore photoanodic performance as a function of the composition and loading of Fe–Ce oxide coatings. This combinatorial materials integration study not only enhances the performance of this new class of materialsmore » but also identifies CeO 2 as a critical ingredient that merits detailed study. A heteroepitaxial CeO 2(001)/BiVO4(010) interface is identified in which Bi and V remain fully coordinated to O such that no surface states are formed. Ab initio calculations of the integrated materials and inspection of the electronic structure reveals mechanisms by which CeO 2 facilitates charge transport while mitigating deleterious recombination. Our results support the observations that addition of Ce to BiVO 4 coatings greatly enhances photoelectrocatalytic activity, providing an important strategy for developing a scalable solar fuels technology.« less

Formation of W(3)A(1) electron-transferring flavoprotein (ETF) hydroquinone in the trimethylamine dehydrogenase x ETF protein complex.

PubMed

Jang, M H; Scrutton, N S; Hille, R

2000-04-28

The electron-transferring flavoprotein (ETF) from Methylophilus methylotrophus (sp. W(3)A(1)) exhibits unusual oxidation-reduction properties and can only be reduced to the level of the semiquinone under most circumstances (including turnover with its physiological reductant, trimethylamine dehydrogenase (TMADH), or reaction with strong reducing reagents such as sodium dithionite). In the present study, we demonstrate that ETF can be reduced fully to its hydroquinone form both enzymatically and chemically when it is in complex with TMADH. Quantitative titration of the TMADH x ETF protein complex with sodium dithionite shows that a total of five electrons are taken up by the system, indicating that full reduction of ETF occurs within the complex. The results indicate that the oxidation-reduction properties of ETF are perturbed upon binding to TMADH, a conclusion further supported by the observation of a spectral change upon formation of the TMADH x ETF complex that is due to a change in the environment of the FAD of ETF. The results are discussed in the context of ETF undergoing a conformational change during formation of the TMADH x ETF electron transfer complex, which modulates the spectral and oxidation-reduction properties of ETF such that full reduction of the protein can take place.

Glutathione and Glutaredoxin Act as a Backup of Human Thioredoxin Reductase 1 to Reduce Thioredoxin 1 Preventing Cell Death by Aurothioglucose*

PubMed Central

Du, Yatao; Zhang, Huihui; Lu, Jun; Holmgren, Arne

2012-01-01

Thioredoxin reductase 1 (TrxR1) in cytosol is the only known reductant of oxidized thioredoxin 1 (Trx1) in vivo so far. We and others found that aurothioglucose (ATG), a well known active-site inhibitor of TrxR1, inhibited TrxR1 activity in HeLa cell cytosol but had no effect on the viability of the cells. Using a redox Western blot analysis, no change was observed in redox state of Trx1, which was mainly fully reduced with five sulfhydryl groups. In contrast, auranofin killed cells and oxidized Trx1, also targeting mitochondrial TrxR2 and Trx2. Combining ATG with ebselen gave a strong synergistic effect, leading to Trx1 oxidation, reactive oxygen species accumulation, and cell death. We hypothesized that there should exist a backup system to reduce Trx1 when only TrxR1 activity was lost. Our results showed that physiological concentrations of glutathione, NADPH, and glutathione reductase reduced Trx1 in vitro and that the reaction was strongly stimulated by glutaredoxin1. Simultaneous depletion of TrxR activity by ATG and glutathione by buthionine sulfoximine led to overoxidation of Trx1 and loss of HeLa cell viability. In conclusion, the glutaredoxin system and glutathione have a backup role to keep Trx1 reduced in cells with loss of TrxR1 activity. Monitoring the redox state of Trx1 shows that cell death occurs when Trx1 is oxidized, followed by general protein oxidation catalyzed by the disulfide form of thioredoxin. PMID:22977247

A Positron Annihilation Study of Corrosion of Aluminum and Aluminum Alloy by NaOH

NASA Astrophysics Data System (ADS)

Wu, Y. C.; Zhai, T.; Coleman, P. G.

2012-08-01

Corrosion of fully-annealed pure aluminum and a continuous-cast AA2037 aluminum alloy (solutionized and water quenched) in a 1M NaOH solution for various periods of time were analyzed with positron beam-based Doppler broadening spectroscopy. By varying the energy of the incident positron beam, corrosion-induced defects at different depths from the surface were detected. It was found that the Doppler-broadened annihilation line-width parameter was significantly increased near the surface of pure aluminum after corrosion, probably due to the interaction between positrons and nanometer-sized voids formed near the aluminum surface during corrosion. Examination by atomic force microscopy indicated that many pits were formed on the aluminum surface after corrosion. In contrast, a significant decrease in the line-width parameter was observed in AA2037 alloy after corrosion and interpreted as being caused by copper enrichment at the metal-oxide interface during corrosion; such enrichment at large cavity sites was confirmed by energy dispersion spectrometry.

Mechanism of acetaminophen inhibition of cyclooxygenase isoforms.

PubMed

Ouellet, M; Percival, M D

2001-03-15

Acetaminophen has similar analgesic and antipyretic properties to nonsteroidal antiinflammatory drugs (NSAIDs), which act via inhibition of cyclooxygenase enzymes. However, unlike NSAIDs, acetaminophen is at best weakly antiinflammatory. The mechanism by which acetaminophen exerts its therapeutic action has yet to be fully determined, as under most circumstances, acetaminophen is a very weak cyclooxygenase inhibitor. The potency of acetaminophen against both purified ovine cyclooxygenase-1 (oCOX-1) and human cyclooxygenase-2 (hCOX-2) was increased approximately 30-fold by the presence of glutathione peroxidase and glutathione to give IC50 values of 33 microM and 980 microM, respectively. Acetaminophen was found to be a good reducing agent of both oCOX-1 and hCOX-2. The results are consistent with a mechanism of inhibition of acetaminophen in which it acts to reduce the active oxidized form of COX to the resting form. Inhibition would therefore be more effective under conditions of low peroxide concentration, consistent with the known tissue selectivity of acetaminophen.

Anodic voltammetric behavior and determination of rosiglitazone in pharmaceutical dosage forms and biological fluids on solid electrode.

PubMed

Dogan-Topal, Burcu; Tuncel, Secil; Ozkan, Sibel A

2010-09-01

The anodic voltammetric behavior and electroanalytical determination of rosiglitazone was studied using cyclic, linear sweep, differential pulse and square wave voltammetric techniques on glassy carbon electrode. The oxidation of rosiglitazone was irreversible and exhibited diffusion controlled process depending on pH. Different parameters were tested to optimize the conditions for the determination of the oxidation mechanism of rosiglitazone. The dependence of current intensities and potentials on pH, concentration, scan rate, nature of the buffer was also investigated. According to the linear relationship between the peak current and the concentration, differential pulse and square wave voltammetric methods for rosiglitazone assay in pharmaceutical dosage forms and biological fluids were developed. A linear response was obtained within the range of 1x10-6M - 6x10-5M in 0.1 M H2SO4 and acetate buffer at pH 5.70 for both voltammetric methods in human serum samples. The practical analytical value of the method is demonstrated by quantitative determination of rosiglitazon in pharmaceutical formulation and human serum, without the need for separation or complex sample preparation, since there was no interference from the excipients and endogenous substances. The methods were fully validated and successfully applied to the high throughput determination of the drug in tablets and human serum with good recoveries.

Omeprazole, a specific inhibitor of gastric (H/sup +/-K/sup +/)-ATPase, is a H/sup +/-activated oxidizing agent of sulfhydryl groups

DOE Office of Scientific and Technical Information (OSTI.GOV)

Im, W.B.; Sih, J.C.; Blakeman, D.P.

1985-04-25

Omeprazole (5-methoxy-2-(((4-methoxy-3,5- dimethylpyridinyl)methyl)sulfinyl)-1H-benzimidazole) appeared to inhibit gastric (H/sup +/-K/sup +/)-ATPase by oxidizing its essential sulfhydryl groups, since the gastric ATPase inactivated by the drug in vivo or in vitro recovered its K+-dependent ATP hydrolyzing activity upon incubation with mercaptoethanol. Biological reducing agents like cysteine or glutathione, however, were unable to reverse the inhibitory effect of omeprazole. Moreover, acidic environments enhanced the potency of omeprazole. The chemical reactivity of omeprazole with mercaptans is also consistent with the biological action of omeprazole. The N-sulfenylated compound reacted at neutral pH with another stoichiometric amount of ethyl mercaptan to produce omeprazole sulfide quantitatively. Themore » gastric polypeptides of 100 kilodaltons representing (H/sup +/-K/sup +/)-ATPase in the rat gastric mucosa or isolated hog gastric membranes were covalently labeled with (/sup 14/C)omeprazole. The radioactive label bound to the ATPase, however, could not be displaced by mercaptoethanol under the identical conditions where the ATPase activity was fully restored. These observations suggest that the essential sulfhydryl groups which reacted with omeprazole did not form a stable covalent bond with the drug, but rather that they further reacted with adjacent sulfhydryl groups to form disulfides which could be reduced by mercaptoethanol.« less

Mechanical and thermal characterization of a ceramic/glass composite seal for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Dev, Bodhayan; Walter, Mark E.; Arkenberg, Gene B.; Swartz, Scott L.

2014-01-01

Solid oxide fuel cells (SOFCs) require seals that can function in harsh, elevated temperature environments. Comprehensive characterization and understanding of seals is needed for commercially viable SOFCs. The present research focuses on a novel ceramic/glass composite seal that is produced by roller compaction or tape casting of glass and ceramic powders and an organic binder. Upon heat treatment, micro-voids and surface anomalies are formed. Increased heating and cooling rates during the heat treatment resulted in more and larger voids. The first goal of the current research is to suggest an appropriate heating and cooling rate to minimize the formation of microstructural defects. After identifying an appropriate cure cycle, seals were thermally cycled and then characterized with laser dilatometry, X-ray diffraction, and sonic resonance. From these experiments the crystalline phases, thermal expansion, and elastic properties were determined. Subsequently compression testing with an acoustic emission (AE) sensor and post-test microstructural analysis were used to identify the formation of damage. By fully understanding the characteristics of this ceramic/glass composite seal, next generation seals can be fabricated for improved performance.

Composite oxygen transport membrane

DOEpatents

Lu, Zigui; Plonczak, Pawel J.; Lane, Jonathan A.

2016-11-08

A method is described of producing a composite oxygen ion membrane and a composite oxygen ion membrane in which a porous fuel oxidation layer and a dense separation layer and optionally, a porous surface exchange layer are formed on a porous support from mixtures of (Ln.sub.1-xA.sub.x).sub.wCr.sub.1-yB.sub.yO.sub.3-.delta. and a doped zirconia. Preferred materials are (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.7Fe.sub.0.3O.sub.3-.delta. for the porous fuel oxidation layer, (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.5Fe.sub.0.5O.sub.3-.delta. for the dense separation layer, and (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.3Fe.sub.0.7O.sub.3-.delta. for the porous surface exchange layer. Firing the said fuel activation and separation layers in nitrogen atmosphere unexpectedly allows the separation layer to sinter into a fully densified mass.

Crystallization Kinetics of a Solid Oxide Fuel Cell Seal Glass by Differential Thermal Analysis

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Gamble, Eleanor A.

2005-01-01

Crystallization kinetics of a barium calcium aluminosilicate glass (BCAS), a sealant material for planar solid oxide fuel cells, have been investigated by differential thermal analysis (DTA). From variation of DTA peak maximum temperature with heating rate, the activation energy for glass crystallization was calculated to be 259 kJ/mol. Development of crystalline phases on thermal treatments of the glass at various temperatures has been followed by powder x-ray diffraction. Microstructure and chemical composition of the crystalline phases were investigated by scanning electron microscopy and energy dispersive spectroscopic (EDS) analysis. BaSiO3 and hexacelsian (BaAl2Si2O8) were the primary crystalline phases whereas monoclinic celsian (BaAl2Si2O8) and (Ba(x), Ca(y))SiO4 were also detected as minor phases. Needle-shaped BaSiO3 crystals are formed first, followed by the formation of other phases at longer times of heat treatments. The glass does not fully crystallize even after long term heat treatments at 750 to 900 C.

Block copolymer lithography of rhodium nanoparticles for high temperature electrocatalysis.

PubMed

Boyd, David A; Hao, Yong; Li, Changyi; Goodwin, David G; Haile, Sossina M

2013-06-25

We present a method for forming ordered rhodium nanostructures on a solid support. The approach makes use of a block copolymer to create and assemble rhodium chloride nanoparticles from solution onto a surface; subsequent plasma and thermal processing are employed to remove the polymer and fully convert the nanostructures to metallic rhodium. Films cast from a solution of the triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) dissolved in toluene with rhodium(III) chloride hydrate were capable of producing a monolayer of rhodium nanoparticles of uniform size and interparticle spacing. The nanostructures were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The electrocatalytic performance of the nanoparticles was investigated with AC impedance spectroscopy. We observed that the addition of the particles to a model solid oxide fuel cell anode provided up to a 14-fold improvement in the anode activity as evidenced by a decrease in the AC impedance resistance. Examination of the anode after electrochemical measurement revealed that the basic morphology and distribution of the particles were preserved.

Effects of various additives on sintering of aluminum nitride

NASA Technical Reports Server (NTRS)

Komeya, K.; Inoue, H.; Tsuge, A.

1982-01-01

Effects of thirty additives on sintering A/N were investigated. The addition of alkali earth oxides and rare earth oxides gave fully densified aluminum nitride. This is due to the formation of nitrogen-containing aluminate liquid in the system aluminum nitride-alkali earth oxides or rare earth oxides. Microstructural studies of the sintered specimens with the above two types of additives suggested that the densification was due to the liquid phase sintering. Additions of silicon compounds resulted in poor densification by the formation of highly refractory compounds such as A/N polytypes.

Fully transparent thin film transistors based on zinc oxide channel layer and molybdenum doped indium oxide electrodes

NASA Astrophysics Data System (ADS)

MÄ dzik, Mateusz; Elamurugu, Elangovan; Viegas, Jaime

2016-03-01

In this work we report the fabrication of thin film transistors (TFT) with zinc oxide channel and molybdenum doped indium oxide (IMO) electrodes, achieved by room temperature sputtering. A set of devices was fabricated, with varying channel width and length from 5μm to 300μm. Output and transfer characteristics were then extracted to study the performance of thin film transistors, namely threshold voltage and saturation current, enabling to determine optimal fabrication process parameters. Optical transmission in the UV-VIS-IR are also reported.

Oxide film on metal substrate reduced to form metal-oxide-metal layer structure

NASA Technical Reports Server (NTRS)

Youngdahl, C. A.

1967-01-01

Electrically conductive layer of zirconium on a zirconium-oxide film residing on a zirconium substrate is formed by reducing the oxide in a sodium-calcium solution. The reduced metal remains on the oxide surface as an adherent layer and seems to form a barrier that inhibits further reaction.

Scaling behavior of fully spin-coated TFT

NASA Astrophysics Data System (ADS)

Mondal, Sandip; Kumar, Arvind; Rao, K. S. R. Koteswara; Venkataraman, V.

2017-05-01

We studied channel scaling behavior of fully spin coated, low temperature solution processed thin film transistor (TFT) fabricated on p++ - Si (˜1021 cm-3) as bottom gate. The solution processed, spin coated 40 nm thick amorphous Indium Gallium Zinc Oxide (a-IGZO) and 50 nm thick amorphous zirconium di-oxide (a-ZrO2) has been used as channel and low leakage dielectric at 350°C respectively. The channel scaling effect of the TFT with different width/length ratio (W/L= 2.5, 5 and 15) for same channel length (L = 10 μm) has been demonstrated. The lowest threshold voltage (Vth) is 6.25 V for the W/L=50/10. The maximum field effect mobility (μFE) has been found to be 0.123 cm2/Vs from W/L of 50/10 with the drain to source voltage (VD) of 10V and 20V gate to source voltage (VG). We also demonstrated that there is no contact resistance effect on the mobility of the fully sol-gel spin coated TFT.

Role of copper oxides in contact killing of bacteria.

PubMed

Hans, Michael; Erbe, Andreas; Mathews, Salima; Chen, Ying; Solioz, Marc; Mücklich, Frank

2013-12-31

The potential of metallic copper as an intrinsically antibacterial material is gaining increasing attention in the face of growing antibiotics resistance of bacteria. However, the mechanism of the so-called "contact killing" of bacteria by copper surfaces is poorly understood and requires further investigation. In particular, the influences of bacteria-metal interaction, media composition, and copper surface chemistry on contact killing are not fully understood. In this study, copper oxide formation on copper during standard antimicrobial testing was measured in situ by spectroscopic ellipsometry. In parallel, contact killing under these conditions was assessed with bacteria in phosphate buffered saline (PBS) or Tris-Cl. For comparison, defined Cu2O and CuO layers were thermally generated and characterized by grazing incidence X-ray diffraction. The antibacterial properties of these copper oxides were tested under the conditions used above. Finally, copper ion release was recorded for both buffer systems by inductively coupled plasma atomic absorption spectroscopy, and exposed copper samples were analyzed for topographical surface alterations. It was found that there was a fairly even growth of CuO under wet plating conditions, reaching 4-10 nm in 300 min, but no measurable Cu2O was formed during this time. CuO was found to significantly inhibit contact killing, compared to pure copper. In contrast, thermally generated Cu2O was essentially as effective in contact killing as pure copper. Copper ion release from the different surfaces roughly correlated with their antibacterial efficacy and was highest for pure copper, followed by Cu2O and CuO. Tris-Cl induced a 10-50-fold faster copper ion release compared to PBS. Since the Cu2O that primarily forms on copper under ambient conditions is as active in contact killing as pure copper, antimicrobial objects will retain their antimicrobial properties even after oxide formation.

Varying the Lewis base coordination of the Y2N2 core in the reduced dinitrogen complexes {[(Me3Si)2N]2(L)Y}2(μ-η2:η2-N2) (L = benzonitrile, pyridines, triphenylphosphine oxide, and trimethylamine N-oxide).

PubMed

Corbey, Jordan F; Farnaby, Joy H; Bates, Jefferson E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2012-07-16

The effect of the neutral donor ligand, L, on the Ln(2)N(2) core in the (N═N)(2-) complexes, [A(2)(L)Ln](2)(μ-η(2):η(2)-N(2)) (Ln = Sc, Y, lanthanide; A = monoanion; L = neutral ligand), is unknown since all of the crystallographically characterized examples were obtained with L = tetrahydrofuran (THF). To explore variation in L, displacement reactions between {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2)), 1, and benzonitrile, pyridine (py), 4-dimethylaminopyridine (DMAP), triphenylphosphine oxide, and trimethylamine N-oxide were investigated. THF is displaced by all of these ligands to form {[(Me(3)Si)(2)N](2)(L)Y}(2)(μ-η(2):η(2)-N(2)) complexes (L = PhCN, 2; py, 3; DMAP, 4; Ph(3)PO, 5; Me(3)NO, 6) that were fully characterized by analytical, spectroscopic, density functional theory, and X-ray crystallographic methods. The crystal structures of the Y(2)N(2) cores in 2-5 are similar to that in 1 with N-N bond distances between 1.255(3) Å and 1.274(3) Å, but X-ray analysis of the N-N distance in 6 shows it to be shorter: 1.198(3) Å.

The nanosphere iron mineral(s) in Mars soil

NASA Technical Reports Server (NTRS)

Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

1993-01-01

A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.

The oxygenase-peroxidase theory of Bach and Chodat and its modern equivalents: change and permanence in scientific thinking as shown by our understanding of the roles of water, peroxide, and oxygen in the functioning of redox enzymes.

PubMed

Nicholls, P

2007-10-01

Alexander Bach was both revolutionary politician and biochemist. His earliest significant publication, "Tsar-golod" ("The Tsar of Hunger"), introduced Marxist thought to Russian workers. In exile for 30 years, he moved to study the dialectic of the oxidases. When his theory of oxidases as combinations of oxygenases and peroxidases was developed (circa 1900) the enzyme concept was not fully formulated, and the enzyme/substrate distinction not yet made. Peroxides however were then and remain now significant intermediates, when either free or bound, in oxidase catalyses. The aerobic dehydrogenase/peroxidase/catalase coupled systems which were studied slightly later clarified the Bach model and briefly became an oxidase paradigm. Identification of peroxidase as a metalloprotein, a key step in understanding oxidase and peroxidase mechanisms, postdated Bach's major work. Currently we recognize catalytic organic peroxides in flavoprotein oxygenases; such organic peroxides are also involved in lipid oxidation and tryptophan radical decay. But most physiologically important peroxides are now known to be bound to transition metals (either Fe or Cu) and formed both directly and indirectly (from oxygen). The typical stable metalloprotein peroxide product is the ferryl state. When both peroxide oxidizing equivalents are retained the second equivalent is held as a protein or porphyrin radical. True metal peroxide complexes are unstable. But often water molecules mark the spot where the original peroxide decayed. The cytochrome c oxidase Fe-Cu center can react with either peroxide or oxygen to form the intermediate higher oxidation states P and F. In its resting state water molecules and hydroxyl ions can be seen marking the original location of the oxygen or peroxide molecule.

Structural characterization of ferric hemoglobins from three antarctic fish species of the suborder notothenioidei.

PubMed

Vergara, Alessandro; Franzese, Marisa; Merlino, Antonello; Vitagliano, Luigi; Verde, Cinzia; di Prisco, Guido; Lee, H Caroline; Peisach, Jack; Mazzarella, Lelio

2007-10-15

Spontaneous autoxidation of tetrameric Hbs leads to the formation of Fe (III) forms, whose physiological role is not fully understood. Here we report structural characterization by EPR of the oxidized states of tetrameric Hbs isolated from the Antarctic fish species Trematomus bernacchii, Trematomus newnesi, and Gymnodraco acuticeps, as well as the x-ray crystal structure of oxidized Trematomus bernacchii Hb, redetermined at high resolution. The oxidation of these Hbs leads to formation of states that were not usually detected in previous analyses of tetrameric Hbs. In addition to the commonly found aquo-met and hydroxy-met species, EPR analyses show that two distinct hemichromes coexist at physiological pH, referred to as hemichromes I and II, respectively. Together with the high-resolution crystal structure (1.5 A) of T. bernacchii and a survey of data available for other heme proteins, hemichrome I was assigned by x-ray crystallography and by EPR as a bis-His complex with a distorted geometry, whereas hemichrome II is a less constrained (cytochrome b5-like) bis-His complex. In four of the five Antartic fish Hbs examined, hemichrome I is the major form. EPR shows that for HbCTn, the amount of hemichrome I is substantially reduced. In addition, the concomitant presence of a penta-coordinated high-spin Fe (III) species, to our knowledge never reported before for a wild-type tetrameric Hb, was detected. A molecular modeling investigation demonstrates that the presence of the bulkier Ile in position 67beta in HbCTn in place of Val as in the other four Hbs impairs the formation of hemichrome I, thus favoring the formation of the ferric penta-coordinated species. Altogether the data show that ferric states commonly associated with monomeric and dimeric Hbs are also found in tetrameric Hbs.

Nitroxides protect horseradish peroxidase from H2O2-induced inactivation and modulate its catalase-like activity.

PubMed

Samuni, Amram; Maimon, Eric; Goldstein, Sara

2017-08-01

Horseradish peroxidase (HRP) catalyzes H 2 O 2 dismutation while undergoing heme inactivation. The mechanism underlying this process has not been fully elucidated. The effects of nitroxides, which protect metmyoglobin and methemoglobin against H 2 O 2 -induced inactivation, have been investigated. HRP reaction with H 2 O 2 was studied by following H 2 O 2 depletion, O 2 evolution and heme spectral changes. Nitroxide concentration was followed by EPR spectroscopy, and its reactions with the oxidized heme species were studied using stopped-flow. Nitroxide protects HRP against H 2 O 2 -induced inactivation. The rate of H 2 O 2 dismutation in the presence of nitroxide obeys zero-order kinetics and increases as [nitroxide] increases. Nitroxide acts catalytically since its oxidized form is readily reduced to the nitroxide mainly by H 2 O 2 . The nitroxide efficacy follows the order 2,2,6,6-tetramethyl-piperidine-N-oxyl (TPO)>4-OH-TPO>3-carbamoyl proxyl>4-oxo-TPO, which correlates with the order of the rate constants of nitroxide reactions with compounds I, II, and III. Nitroxide catalytically protects HRP against inactivation induced by H 2 O 2 while modulating its catalase-like activity. The protective role of nitroxide at μM concentrations is attributed to its efficient oxidation by P940, which is the precursor of the inactivated form P670. Modeling the dismutation kinetics in the presence of nitroxide adequately fits the experimental data. In the absence of nitroxide the simulation fits the observed kinetics only if it does not include the formation of a Michaelis-Menten complex. Nitroxides catalytically protect heme proteins against inactivation induced by H 2 O 2 revealing an additional role played by nitroxide antioxidants in vivo. Copyright © 2017 Elsevier B.V. All rights reserved.

The Influence of Al2O3 Powder Morphology on the Properties of Cu-Al2O3 Composites Designed for Functionally Graded Materials (FGM)

NASA Astrophysics Data System (ADS)

Strojny-Nędza, Agata; Pietrzak, Katarzyna; Węglewski, Witold

2016-08-01

In order to meet the requirements of an increased efficiency applying to modern devices and in more general terms science and technology, it is necessary to develop new materials. Combining various types of materials (such as metals and ceramics) and developing composite materials seem to be suitable solutions. One of the most interesting materials includes Cu-Al2O3 composite and gradient materials (FGMs). Due to their potential properties, copper-alumina composites could be used in aerospace industry as rocket thrusters and components in aircraft engines. The main challenge posed by copper matrix composites reinforced by aluminum oxide particles is obtaining the uniform structure with no residual porosity (existing within the area of the ceramic phase). In the present paper, Cu-Al2O3 composites (also in a gradient form) with 1, 3, and 5 vol.% of aluminum oxide were fabricated by the hot pressing and spark plasma sintering methods. Two forms of aluminum oxide (αAl2O3 powder and electrocorundum) were used as a reinforcement. Microstructural investigations revealed that near fully dense materials with low porosity and a clear interface between the metal matrix and ceramics were obtained in the case of the SPS method. In this paper, the properties (mechanical, thermal, and tribological) of composite materials were also collected and compared. Technological tests were preceded by finite element method analyses of thermal stresses generated in the gradient structure, and additionally, the role of porosity in the formation process of composite properties was modeled. Based on the said modeling, technological conditions for obtaining FGMs were proposed.

One-Dimensional Metal-Oxide Nanostructures for Solar Photocatalytic Water-Splitting

NASA Astrophysics Data System (ADS)

Wang, Fengyun; Song, Longfei; Zhang, Hongchao; Luo, Linqu; Wang, Dong; Tang, Jie

2017-08-01

Because of their unique physical and chemical properties, one-dimensional (1-D) metal-oxide nanostructures have been extensively applied in the areas of gas sensors, electrochromic devices, nanogenerators, and so on. Solar water-splitting has attracted extensive research interest because hydrogen generated from solar-driven water splitting is a clean, sustainable, and abundant energy source that not only solves the energy crisis, but also protects the environment. In this comprehensive review, the main synthesis methods, properties, and especially prominent applications in solar water splitting of 1-D metal-oxides, including titanium dioxide (TiO2), zinc oxide (ZnO), tungsten trioxide (WO3), iron oxide (Fe2O3), and copper oxide (CuO) are fully discussed.

Intense photoluminescence from amorphous tantalum oxide films

NASA Astrophysics Data System (ADS)

Zhu, Minmin; Zhang, Zhengjun; Miao, Wei

2006-07-01

Tantalum oxide films were deposited on silicon substrates at a temperature of ˜450°C by heating a pure tantalum foil in a rough vacuum. The films were amorphous in structure and consisted of fully oxidized Ta2O5 and (TaOx, x <2.5) suboxides. This feature resulted in strong visible light emission from the films further oxidized in the air at temperatures of 200-300°C. The mechanism for this photoluminescence behavior of the amorphous tantalum oxide films was also investigated and discussed. This study suggests that wide-band-gap materials could act as effective visible light emitters and provides a simple route to synthesize such materials.

Oxidative Stress as Estimated by Gamma-Glutamyl Transferase Levels Amplifies the Alkaline Phosphatase-Dependent Risk for Mortality in ESKD Patients on Dialysis

PubMed Central

Mattace-Raso, Francesco; van Saase, Jan L. C. M.; Postorino, Maurizio; Tripepi, Giovanni Luigi; Mallamaci, Francesca; PROGREDIRE Study Group

2016-01-01

Alkaline phosphatase (Alk-Phos) is a powerful predictor of death in patients with end-stage kidney disease (ESKD) and oxidative stress is a strong inducer of Alk-Phos in various tissues. We tested the hypothesis that oxidative stress, as estimated by a robust marker of systemic oxidative stress like γ-Glutamyl-Transpeptidase (GGT) levels, may interact with Alk-Phos in the high risk of death in a cohort of 993 ESKD patients maintained on chronic dialysis. In fully adjusted analyses the HR for mortality associated with Alk-Phos (50 IU/L increase) was progressively higher across GGT quintiles, being minimal in patients in the first quintile (HR: 0.89, 95% CI: 0.77–1.03) and highest in the GGT fifth quintile (HR: 1.13, 95% CI: 1.03–1.2) (P for the effect modification = 0.02). These findings were fully confirmed in sensitivity analyses excluding patients with preexisting liver disease, excessive alcohol intake, or altered liver disease biomarkers. GGT amplifies the risk of death associated with high Alk-Phos levels in ESKD patients. This observation is compatible with the hypothesis that oxidative stress is a strong modifier of the adverse biological effects of high Alk-Phos in this population. PMID:27525053

Integration of strained and relaxed silicon thin films on silicon wafers via engineered oxide heterostructures: Experiment and theory

NASA Astrophysics Data System (ADS)

Seifarth, O.; Dietrich, B.; Zaumseil, P.; Giussani, A.; Storck, P.; Schroeder, T.

2010-10-01

Strained and relaxed single crystalline Si on insulator systems is an important materials science approach for future Si-based nanoelectronics. Layer transfer techniques are the dominating global integration approach over the whole wafer system but are difficult to scale down for local integration purposes limited to the area of the future device. In this respect, the heteroepitaxy approach by two simple subsequent epitaxial deposition steps of the oxide and the Si thin film is a promising way. We introduce tailored (Pr2O3)1-x(Y2O3)x oxide heterostructures on Si(111) as flexible heteroepitaxy concept for the integration of either strained or fully relaxed single crystalline Si thin films. Two different buffer concepts are explored by a combined experimental and theoretical study. First, the growth of fully relaxed single crystalline Si films is achieved by the growth of mixed PrYO3 insulators on Si(111) whose lattice constant is matched to Si. Second, isomorphic oxide-on-oxide epitaxy is exploited to grow strained Si films on lattice mismatched Y2O3/Pr2O3/Si(111) support systems. A thickness dependent multilayer model, based on Matthew's approach for strain relaxation by misfit dislocations, is presented to describe the experimental data.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jingjing; Yang, Zheng; Shkrob, Ilya A.

1,4-Dimethoxybenzene derivatives are materials of choice for use as catholytes in nonaqueous redox flow batteries, as they exhibit high open-circuit potentials and excellent electrochemical reversibility. However, chemical stability of these materials in their oxidized form needs to be improved. Disubstitution in the arene ring is used to suppress parasitic reactions of their radical cations, but this does not fully prevent ring-addition reactions. By incorporating bicyclic substitutions and ether chains into the dialkoxybenzenes, a novel catholyte molecule, 9,10-bis(2-methoxyethoxy)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanenoanthracene (BODMA), is obtained and exhibits greater solubility and superior chemical stability in the charged state. As a result, a hybrid flow cell containingmore » BODMA is operated for 150 charge–discharge cycles with minimal loss of capacity.« less

Nanoscale self-templating for oxide epitaxy with large symmetry mismatch

DOE PAGES

Gao, Xiang; Lee, Shinbuhm; Nichols, John A.; ...

2016-12-02

Direct observations using scanning transmission electron microscopy unveil an intriguing interfacial bi-layer that enables epitaxial growth of a strain-free, monoclinic, bronze-phase VO 2(B) thin film on a perovskite SrTiO 3 (STO) substrate. For this study, we observe an ultrathin (2–3 unit cells) interlayer best described as highly strained VO 2(B) nanodomains combined with an extra (Ti,V)O 2 layer on the TiO 2 terminated STO (001) surface. By forming a fully coherent interface with the STO substrate and a semi-coherent interface with the strain-free epitaxial VO 2(B) film above, the interfacial bi-layer enables the epitaxial connection of the two materials despitemore » their large symmetry and lattice mismatch.« less

Synthesis of continuous boron nitride nanofibers by solution coating electrospun template fibers

NASA Astrophysics Data System (ADS)

Qiu, Yejun; Yu, Jie; Yin, Jing; Tan, Cuili; Zhou, Xiaosong; Bai, Xuedong; Wang, Enge

2009-08-01

Continuous boron nitride nanofibers (BNNFs) have been synthesized from boric oxide (B2O3) coatings deposited on stabilized electrospun polyacrylonitrile fibers (S-PANFs). The B2O3 overcoatings were prepared by impregnating the S-PANFs with B2O3 ethanol solutions. By successive heat treatments at 800 °C in NH3/O2 mixture, 1100 °C in pure NH3, and 1500 °C in N2, the S-PANFs were fully removed and the B2O3 coatings deflate to form solid fibers and transform into the BNNFs. The S-PANF template was fully removed by introducing O2 during nitridation, and thus resulted in the formation of the BNNFs. The diameter of the BNNFs can be effectively controlled by changing the mass concentration of the B2O3 solution, and diameters from 43 to 230 nm were obtained by changing the B2O3 mass concentration from 0.25% to 4.8%. The obtained BNNFs are crystallized with the (002) planes oriented in parallel to the fiber axis. This method provides a powerful tool for obtaining BNNFs with controllable diameters, especially extremely thin BNNFs.

Synthesis of continuous boron nitride nanofibers by solution coating electrospun template fibers.

PubMed

Qiu, Yejun; Yu, Jie; Yin, Jing; Tan, Cuili; Zhou, Xiaosong; Bai, Xuedong; Wang, Enge

2009-08-26

Continuous boron nitride nanofibers (BNNFs) have been synthesized from boric oxide (B(2)O(3)) coatings deposited on stabilized electrospun polyacrylonitrile fibers (S-PANFs). The B(2)O(3) overcoatings were prepared by impregnating the S-PANFs with B(2)O(3) ethanol solutions. By successive heat treatments at 800 degrees C in NH(3)/O(2) mixture, 1100 degrees C in pure NH(3), and 1500 degrees C in N(2), the S-PANFs were fully removed and the B(2)O(3) coatings deflate to form solid fibers and transform into the BNNFs. The S-PANF template was fully removed by introducing O(2) during nitridation, and thus resulted in the formation of the BNNFs. The diameter of the BNNFs can be effectively controlled by changing the mass concentration of the B(2)O(3) solution, and diameters from 43 to 230 nm were obtained by changing the B(2)O(3) mass concentration from 0.25% to 4.8%. The obtained BNNFs are crystallized with the (002) planes oriented in parallel to the fiber axis. This method provides a powerful tool for obtaining BNNFs with controllable diameters, especially extremely thin BNNFs.

Assessment of the reduction methods used to develop chemical schemes: building of a new chemical scheme for VOC oxidation suited to three-dimensional multiscale HOx-NOx-VOC chemistry simulations

NASA Astrophysics Data System (ADS)

Szopa, S.; Aumont, B.; Madronich, S.

2005-09-01

The objective of this work was to develop and assess an automatic procedure to generate reduced chemical schemes for the atmospheric photooxidation of volatile organic carbon (VOC) compounds. The procedure is based on (i) the development of a tool for writing the fully explicit schemes for VOC oxidation (see companion paper Aumont et al., 2005), (ii) the application of several commonly used reduction methods to the fully explicit scheme, and (iii) the assessment of resulting errors based on direct comparison between the reduced and full schemes.

The reference scheme included seventy emitted VOCs chosen to be representative of both anthropogenic and biogenic emissions, and their atmospheric degradation chemistry required more than two million reactions among 350000 species. Three methods were applied to reduce the size of the reference chemical scheme: (i) use of operators, based on the redundancy of the reaction sequences involved in the VOC oxidation, (ii) grouping of primary species having similar reactivities into surrogate species and (iii) grouping of some secondary products into surrogate species. The number of species in the final reduced scheme is 147, this being small enough for practical inclusion in current three-dimensional models. Comparisons between the fully explicit and reduced schemes, carried out with a box model for several typical tropospheric conditions, showed that the reduced chemical scheme accurately predicts ozone concentrations and some other aspects of oxidant chemistry for both polluted and clean tropospheric conditions.

Synthesis, structure, and electronic properties of a dimer of Ru(bpy)2 doubly bridged by methoxide and pyrazolate.

PubMed

Jude, Hershel; Rein, Francisca N; White, Peter S; Dattelbaum, Dana M; Rocha, Reginaldo C

2008-09-01

The heterobridged dinuclear complex cis,cis-[(bpy) 2Ru(mu-OCH 3)(mu-pyz)Ru(bpy) 2] (2+) ( 1; bpy = 2,2'-bipyridine; pyz = pyrazolate) was synthesized and isolated as a hexafluorophosphate salt. Its molecular structure was fully characterized by X-ray crystallography, (1)H NMR spectroscopy, and ESI mass spectrometry. The compound 1.(PF 6) 2 (C 44H 38F 12N 10OP 2Ru 2) crystallizes in the monoclinic space group P2 1/ c with a = 13.3312(4) A, b = 22.5379(6) A, c = 17.2818(4) A, beta = 99.497(2) degrees , V = 5121.3(2) A (3), and Z = 4. The meso diastereoisomeric form was exclusively found in the crystal structure, although the NMR spectra clearly demonstrated the presence of two stereoisomers in solution (rac and meso forms at approximately 1:1 ratio). The electronic properties of the complex in acetonitrile were investigated by cyclic voltammetry and UV-vis and NIR-IR spectroelectrochemistries. The stepwise oxidation of the Ru (II)-Ru (II) complex into the mixed-valent Ru (II)-Ru (III) and fully oxidized Ru (III)-Ru (III) states is fully reversible on the time scale of the in situ (spectro)electrochemical measurements. The mixed-valent species displays strong electronic coupling, as evidenced by the large splitting between the redox potentials for the Ru(III)/Ru(II) couples (Delta E 1/2 = 0.62 V; K c = 3 x 10 (10)) and the appearance of an intervalence transfer (IT) band at 1490 nm that is intense, narrow, and independent of solvent. Whereas this salient band in the NIR region originates primarily from highest-energy of the three IT transitions predicted for Ru(II)-Ru(III) systems, a weaker absorption band corresponding to the lowest-energy IT transition was clearly evidenced in the IR region ( approximately 3200 cm (-1)). The observation of totally coalesced vibrational peaks in the 1400-1650 cm (-1) range for a set of five bpy spectator vibrations in Ru (II)-Ru (III) relative to Ru (II)-Ru (II) and Ru (III)-Ru (III) provided evidence for rapid electron transfer and valence averaging on the picosecond time scale. Other than a relatively short Ru...Ru distance (3.72 A for the crystalline Ru (II)-Ru (II) complex), the extensive communication between metal centers is attributed mostly to the pi-donor ability of the bridging ligands (pyz, OMe) combined with the pi-acceptor ability of the peripheral (bpy) ligands.

76 FR 35086 - Proposed Information Collection (Fully Developed Claim (Fully Developed Claims-Applications for...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-06-15

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Method of forming buried oxide layers in silicon

DOEpatents

Sadana, Devendra Kumar; Holland, Orin Wayne

2000-01-01

A process for forming Silicon-On-Insulator is described incorporating the steps of ion implantation of oxygen into a silicon substrate at elevated temperature, ion implanting oxygen at a temperature below 200.degree. C. at a lower dose to form an amorphous silicon layer, and annealing steps to form a mixture of defective single crystal silicon and polycrystalline silicon or polycrystalline silicon alone and then silicon oxide from the amorphous silicon layer to form a continuous silicon oxide layer below the surface of the silicon substrate to provide an isolated superficial layer of silicon. The invention overcomes the problem of buried isolated islands of silicon oxide forming a discontinuous buried oxide layer.

Structure for HTS composite conductors and the manufacture of same

DOEpatents

Cotton, J.D.; Riley, G.N. Jr.

1999-06-01

A superconducting oxide composite structure including a superconducting oxide member, a metal layer surrounding the superconducting oxide member, and an insulating layer of a complex oxide formed in situ adjacent to the superconducting oxide member and the metal layer is provided together with a method of forming such a superconducting oxide composite structure including encapsulating a superconducting oxide member or precursor within a metal matrix layer from the group of: (1) a reactive metal sheath adjacent to the superconducting oxide member or precursor, the reactive metal sheath surrounded by a second metal layer or (2) an alloy containing a reactive metal; to form an intermediate product, and, heating the intermediate product at temperatures and for time sufficient to form an insulating layer of a complex oxide in situ, the insulating layer to the superconducting oxide member or precursor and the metal matrix layer. 10 figs.

Structure for hts composite conductors and the manufacture of same

DOEpatents

Cotton, James D.; Riley, Jr., Gilbert Neal

1999-01-01

A superconducting oxide composite structure including a superconducting oxide member, a metal layer surrounding the superconducting oxide member, and an insulating layer of a complex oxide formed in situ adjacent to the superconducting oxide member and the metal layer is provided together with a method of forming such a superconducting oxide composite structure including encapsulating a superconducting oxide member or precursor within a metal matrix layer from the group of: (i) a reactive metal sheath adjacent to the superconducting oxide member or precursor, the reactive metal sheath surrounded by a second metal layer or (ii) an alloy containing a reactive metal; to form an intermediate product, and, heating the intermediate product at temperatures and for time sufficient to form an insulating layer of a complex oxide in situ, the insulating layer to the superconducting oxide member or precursor and the metal matrix layer.

Mesoporous metal oxide graphene nanocomposite materials

DOEpatents

Liu, Jun; Aksay, Ilhan A.; Kou, Rong; Wang, Donghai

2016-05-24

A nanocomposite material formed of graphene and a mesoporous metal oxide having a demonstrated specific capacity of more than 200 F/g with particular utility when employed in supercapacitor applications. A method for making these nanocomposite materials by first forming a mixture of graphene, a surfactant, and a metal oxide precursor, precipitating the metal oxide precursor with the surfactant from the mixture to form a mesoporous metal oxide. The mesoporous metal oxide is then deposited onto a surface of the graphene.

Materials and processing approaches for foundry-compatible transient electronics.

PubMed

Chang, Jan-Kai; Fang, Hui; Bower, Christopher A; Song, Enming; Yu, Xinge; Rogers, John A

2017-07-11

Foundry-based routes to transient silicon electronic devices have the potential to serve as the manufacturing basis for "green" electronic devices, biodegradable implants, hardware secure data storage systems, and unrecoverable remote devices. This article introduces materials and processing approaches that enable state-of-the-art silicon complementary metal-oxide-semiconductor (CMOS) foundries to be leveraged for high-performance, water-soluble forms of electronics. The key elements are ( i ) collections of biodegradable electronic materials (e.g., silicon, tungsten, silicon nitride, silicon dioxide) and device architectures that are compatible with manufacturing procedures currently used in the integrated circuit industry, ( ii ) release schemes and transfer printing methods for integration of multiple ultrathin components formed in this way onto biodegradable polymer substrates, and ( iii ) planarization and metallization techniques to yield interconnected and fully functional systems. Various CMOS devices and circuit elements created in this fashion and detailed measurements of their electrical characteristics highlight the capabilities. Accelerated dissolution studies in aqueous environments reveal the chemical kinetics associated with the underlying transient behaviors. The results demonstrate the technical feasibility for using foundry-based routes to sophisticated forms of transient electronic devices, with functional capabilities and cost structures that could support diverse applications in the biomedical, military, industrial, and consumer industries.

Materials and processing approaches for foundry-compatible transient electronics

NASA Astrophysics Data System (ADS)

Chang, Jan-Kai; Fang, Hui; Bower, Christopher A.; Song, Enming; Yu, Xinge; Rogers, John A.

2017-07-01

Foundry-based routes to transient silicon electronic devices have the potential to serve as the manufacturing basis for “green” electronic devices, biodegradable implants, hardware secure data storage systems, and unrecoverable remote devices. This article introduces materials and processing approaches that enable state-of-the-art silicon complementary metal-oxide-semiconductor (CMOS) foundries to be leveraged for high-performance, water-soluble forms of electronics. The key elements are (i) collections of biodegradable electronic materials (e.g., silicon, tungsten, silicon nitride, silicon dioxide) and device architectures that are compatible with manufacturing procedures currently used in the integrated circuit industry, (ii) release schemes and transfer printing methods for integration of multiple ultrathin components formed in this way onto biodegradable polymer substrates, and (iii) planarization and metallization techniques to yield interconnected and fully functional systems. Various CMOS devices and circuit elements created in this fashion and detailed measurements of their electrical characteristics highlight the capabilities. Accelerated dissolution studies in aqueous environments reveal the chemical kinetics associated with the underlying transient behaviors. The results demonstrate the technical feasibility for using foundry-based routes to sophisticated forms of transient electronic devices, with functional capabilities and cost structures that could support diverse applications in the biomedical, military, industrial, and consumer industries.

Precursor composites for oxygen dispersion hardened silver sheathed superconductor composites

DOEpatents

Podtburg, E.R.

1999-06-22

An oxide superconductor composite having improved texture and durability is disclosed. The oxide superconductor composite includes an oxide superconductor phase substantially surrounded with/by a noble metal matrix, the noble metal matrix comprising a metal oxide in an amount effective to form metal oxide domains that increase hardness of the composite. The composite is characterized by a degree of texture at least 10% greater than a comparable oxide superconductor composite lacking metal oxide domains. An oxide superconducting composite may be prepared by oxidizing the precursor composite under conditions effective to form solute metal oxide domains within the silver matrix and to form a precursor oxide in the precursor alloy phase; subjecting the oxidized composite to a softening anneal under conditions effective to relieve stress within the noble metal phase; and converting the oxide precursor into an oxide superconductor. 1 fig.

Precursor composites for oxygen dispersion hardened silver sheathed superconductor composites

DOEpatents

Podtburg, Eric R.

1999-01-01

An oxide superconductor composite having improved texture and durability. The oxide superconductor composite includes an oxide superconductor phase substantially surrounded with/by a noble metal matrix, the noble metal matrix comprising a metal oxide in an amount effective to form metal oxide domains that increase hardness of the composite. The composite is characterized by a degree of texture at least 10% greater than a comparable oxide superconductor composite lacking metal oxide domains. An oxide superconducting composite may be prepared by oxidizing the precursor composite under conditions effective to form solute metal oxide domains within the silver matrix and to form a precursor oxide in the precursor alloy phase; subjecting the oxidized composite to a softening anneal under conditions effective to relieve stress within the noble metal phase; and converting the oxide precursor into an oxide superconductor.

Oxidation of Alloy 600 and Alloy 690: Experimentally Accelerated Study in Hydrogenated Supercritical Water

NASA Astrophysics Data System (ADS)

Moss, Tyler; Cao, Guoping; Was, Gary S.

2017-04-01

The objective of this study is to determine whether the oxidation of Alloys 600 and 690 in supercritical water occurs by the same mechanism in subcritical water. Coupons of Alloys 690 and 600 were exposed to hydrogenated subcritical and supercritical water from 633 K to 673 K (360 °C to 400 °C) and the oxidation behavior was observed. By all measures of oxide character and behavior, the oxidation process is the same above and below the supercritical line. Similar oxide morphologies, structures, and chemistries were observed for each alloy across the critical point, indicating that the oxidation mechanism is the same in both subcritical and supercritical water. Oxidation results in a multi-layer oxide structure composed of particles of NiO and NiFe2O4 formed by precipitation on the outer surface and a chromium-rich inner oxide layer formed by diffusion of oxygen to the metal-oxide interface. The inner oxide on Alloy 600 is less chromium rich than that observed on Alloy 690 and is accompanied by preferential oxidation of grain boundaries. The inner oxide on Alloy 690 initially forms by internal oxidation before a protective layer of chromium-rich MO is formed with Cr2O3 at the metal-oxide interface. Grain boundaries in Alloy 690 act as fast diffusion paths for chromium that forms a protective Cr2O3 layer at the surface, preventing grain boundary oxidation from occurring.

Buried oxide layer in silicon

DOEpatents

Sadana, Devendra Kumar; Holland, Orin Wayne

2001-01-01

A process for forming Silicon-On-Insulator is described incorporating the steps of ion implantation of oxygen into a silicon substrate at elevated temperature, ion implanting oxygen at a temperature below 200.degree. C. at a lower dose to form an amorphous silicon layer, and annealing steps to form a mixture of defective single crystal silicon and polycrystalline silicon or polycrystalline silicon alone and then silicon oxide from the amorphous silicon layer to form a continuous silicon oxide layer below the surface of the silicon substrate to provide an isolated superficial layer of silicon. The invention overcomes the problem of buried isolated islands of silicon oxide forming a discontinuous buried oxide layer.

Manufacture of ceramic tiles from fly ash

DOEpatents

Hnat, James G.; Mathur, Akshay; Simpson, James C.

1999-01-01

The present invention relates to a process for forming glass-ceramic tiles. Fly ash containing organic material, metal contaminants, and glass forming materials is oxidized under conditions effective to combust the organic material and partially oxidize the metallic contaminants and the glass forming materials. The oxidized glass forming materials are vitrified to form a glass melt. This glass melt is then formed into tiles containing metallic contaminants.

Aggregation and Stability of Reduced Graphene Oxide: Complex Roles of Divalent Cations, pH, and Natural Organic Matter

EPA Science Inventory

The aggregation and stability of graphene oxide (GO) and three successively reduced GO (rGO) nanomaterials were investigated. Reduced GO species were partially reduced GO (rGO-1h), intermediately reduced GO (rGO-2h), and fully reduced GO (rGO-5h). Specifically, influence of pH, i...

Investigation of Thin Layered Cobalt Oxide Nano-Islands on Gold

NASA Astrophysics Data System (ADS)

Bajdich, Michal; Walton, Alex S.; Fester, Jakob; Arman, Mohammad A.; Osiecki, Jacek; Knudsen, Jan; Vojvodic, Aleksandra; Lauritsen, Jeppe V.

2015-03-01

Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER), but the synergistic effect of contact with gold is yet to be fully understood. The synthesis of three distinct types of thin-layered cobalt oxide nano-islands supported on a single crystal gold (111) substrate is confirmed by combination of STM and XAS methods. In this work, we present DFT+U theoretical investigation of above nano-islands using several previously known structural models. Our calculations confirm stability of two low-oxygen pressure phases: (a) rock-salt Co-O bilayer and (b) wurtzite Co-O quadlayer and single high-oxygen pressure phase: (c) O-Co-O trilayer. The optimized geometries agree with STM structures and calculated oxidation states confirm the conversion from Co2+ to Co3+ found experimentally in XAS. The O-Co-O trilayer islands have the structure of a single layer of CoOOH proposed to be the true active phase for OER catalyst. For that reason, the effect of water on the Pourbaix stabilities of basal planes and edge sites is fully investigated. Lastly, we also present the corresponding OER theoretical overpotentials.

Heterojunction fully depleted SOI-TFET with oxide/source overlap

NASA Astrophysics Data System (ADS)

Chander, Sweta; Bhowmick, B.; Baishya, S.

2015-10-01

In this work, a hetero-junction fully depleted (FD) Silicon-on-Insulator (SOI) Tunnel Field Effect Transistor (TFET) nanostructure with oxide overlap on the Germanium-source region is proposed. Investigations using Synopsys Technology Computer Aided Design (TCAD) simulation tools reveal that the simple oxide overlap on the Germanium-source region increases the tunneling area as well as the tunneling current without degrading the band-to-band tunneling (BTBT) and improves the device performance. More importantly, the improvement is independent of gate overlap. Simulation study shows improvement in ON current, subthreshold swing (SS), OFF current, ION/IOFF ration, threshold voltage and transconductance. The proposed device with hafnium oxide (HfO2)/Aluminium Nitride (AlN) stack dielectric material offers an average subthreshold swing of 22 mV/decade and high ION/IOFF ratio (∼1010) at VDS = 0.4 V. Compared to conventional TFET, the Miller capacitance of the device shows the enhanced performance. The impact of the drain voltage variation on different parameters such as threshold voltage, subthreshold swing, transconductance, and ION/IOFF ration are also found to be satisfactory. From fabrication point of view also it is easy to utilize the existing CMOS process flows to fabricate the proposed device.

Bacillus subtilis vegetative isolate surviving chlorine dioxide exposure: an elusive mechanism of resistance.

PubMed

Martin, D J H; Wesgate, R L; Denyer, S P; McDonnell, G; Maillard, J-Y

2015-12-01

Oxidizing agents such as chlorine dioxide are widely used microbicides, including for disinfection of medical equipment. We isolated a Bacillus subtilis isolate from a washer-disinfector whose vegetative form demonstrated unique resistance to chlorine dioxide (0·03%) and hydrogen peroxide (7·5%). The aim of this study was to understand the mechanisms of resistance expressed by this isolate. A range of resistance mechanisms were investigated in the B. subtilis isolate and a reference B. subtilis strain (ATCC 6051) to include bacterial cell aggregation, the presence of profuse exopolysaccharide (EPS), and the expression of detoxification enzymes. The basis of resistance of the isolate to high concentrations of oxidizing agents was not linked to the presence of endospores. Although, the presence of EPS, aggregation and expression of detoxification enzymes may play a role in bacterial survival to low concentrations of chlorine dioxide, it is unlikely that the mechanisms helped tested to survive the bactericidal effect of higher oxidizer concentrations. Overall, the mechanisms conferring resistance to chlorine dioxide and hydrogen peroxide remains elusive. Based on recent advances in the mode of action of oxidizing agents and notably hydrogen peroxide, we postulate that additional efficient intracellular mechanisms may be involved to explain significant resistance to in-use concentrations of commonly used high-level disinfectants. The isolation of a highly resistant vegetative Gram-positive bacterium to a highly reactive oxidizing agent is worrying. Understanding the mechanisms conferring such resistance is essential to effectively control such bacterial isolates. Here, we postulate that there are still mechanisms of bacterial resistance that have not been fully characterized. © 2015 The Authors published by John Wiley & Sons Ltd on behalf of Society for Applied Microbiology.

2013 Early Career Achievement Award--Proteomics of muscle- and species-specificity in meat color stability.

PubMed

Suman, S P; Rentfrow, G; Nair, M N; Joseph, P

2014-03-01

Meat color is the most important quality trait influencing consumer purchase decisions. The interinfluential interactions between myoglobin and biomolecules govern color stability in meat. The advances in proteomics, such as high throughput analytical tools in mass spectrometry, 2-dimensional electrophoresis, and bioinformatics, offer themselves as robust techniques to characterize the proteome basis of muscle- and species-specific meat color phenomena. Differential abundance of chaperones and antioxidant proteins contributes to muscle-specific color stability in beef; the greater abundance of chaperones and antioxidant proteins in color-stable Longissimus lumborum than in color-labile Psoas major protects myoglobin and contributes to superior color stability of beef Longissimus steaks. Lipid oxidation-induced myoglobin oxidation is more critical to beef color than pork color due to the inherent differences in myoglobin chemistry; the number of nucleophilic histidine residues adducted by reactive aldehydes is greater in beef myoglobin than in pork myoglobin. Preferential adduction of secondary products of lipid oxidation to beef myoglobin accelerates metmyoglobin formation at a greater degree than in its pork counterpart. Mass spectrometric investigations revealed that although cherry-red carboxymyoglobin is more stable than oxymyoglobin, both redox forms undergo lipid oxidation-induced oxidation in model systems. The accuracy of mass spectrometry to detect the molecular mass of proteins has been applied to differentiate myoglobins from closely related meat animals, such as goats and sheep or emu and ostrich. In addition, this approach indicated that turkey myoglobin is 350 Da greater in molecular mass than beef myoglobin, and the unique biochemistry of turkey myoglobin could be responsible for its greater thermostability in model systems as well as the pink color defect observed in fully cooked uncured turkey products.

Low-temperature reduction of Ge oxide by Si and SiH4 in low-pressure H2 and Ar environment

NASA Astrophysics Data System (ADS)

Minami, Kaichiro; Moriya, Atsushi; Yuasa, Kazuhiro; Maeda, Kiyohiko; Yamada, Masayuki; Kunii, Yasuo; Niwano, Michio; Murota, Junichi

2015-08-01

Introduction of Ge into ULSIs has become increasingly attractive because of the higher carrier mobility of Ge. Since Ge native oxide is formed easily in cleanroom air, the control of formation and reduction of the Ge oxide is requested for the introduction of Ge layers into Si process. Here, the reactions between gas phase Ge oxide and Si substrate and between the Ge oxide on Ge epitaxial layer and SiH4 are investigated. The native-oxidized Ge amount is obtained by calculating from chemically shifted peak intensity of Ge 3d measured by X-ray photoelectron spectroscopy. By the adsorption of the Ge oxide on Si(1 0 0) surface, pure Ge and Si oxide are formed on the Si surface even at 350 °C and the formed Ge amount tends to correspond to the oxidized Si amount, independently of the heat-treatment environment of H2 and Ar under the condition that Si oxide is not reduced by H2. By SiH4 treatment, the amount of the oxidized Ge on the Ge layer decreases drastically even at 350 °C and Si oxide is formed on the Ge layer. From these results, it is suggested that the Ge oxide is reduced even at 350 °C by Si or SiH4, and the Si oxide and the pure Ge are formed.

Trinuclear ruthenium dioxolene complexes based on the bridging ligand hexahydroxytriphenylene: electrochemistry, spectroscopy, and near-infrared electrochromic behaviour associated with a reversible seven-membered redox chain.

PubMed

Grange, Christopher S; Meijer, Anthony J H M; Ward, Michael D

2010-01-07

The trinuclear complexes [{(R2bipy)2Ru}3(mu3-HHTP)](PF6)3 [1(PF6)3, R = H; 2(PF6)3, R = 4-tBu] contain three {Ru(R2bipy)2}2+ fragments connected to the triangular tris-chelating ligand hexahydroxytriphenylene (H6HHTP). This bridging ligand contains three dioxolene-type binding sites, each of which can reversibly convert between dianionic catecholate (cat), monoanionic semiquinone (sq) or neutral quinone (q) redox states. The bridging ligand as a whole can therefore exist in seven different redox states from fully reduced [cat,cat,cat]6- through to fully oxidised, neutral [q,q,q]. Cyclic voltammetry of 1(PF6)3 in MeCN reveals six redox processes of which the three at more positive potentials (the sq/q couples) are reversible but the three at more negative potentials (the sq/cat couples) are irreversible with distorted wave shapes due to the insolubility of the reduced forms of the complex. In contrast, the more soluble complex 2(PF6)3 displays six reversible one-electron redox processes making all components of a seven-membered redox chain accessible. UV/Vis/NIR spectro-electrochemical studies reveal rich spectroscopic behaviour, with--in particular--very intense transitions in the near-IR region in many of the oxidation states associated with Ru(II)-->(dioxolene) MLCT and bridging ligand centred pi-pi* transitions. TDDFT calculations were used to analyse the electronic spectra in all seven oxidation states; the calculated spectra generally show very good agreement with experiment, which has allowed a fairly complete assignment of the low-energy transitions. The strong electrochromism of the complexes in the near-IR region has formed the basis of an optical window in which a thin film of 1(PF6)3 or 2(PF6)3 on a conductive glass surface can be reversibly and rapidly switched between redox states that alternate between strongly absorbing or near-transparent at 1100 nm, with--for 2(PF6)3--the switching being stable and reversible in water over thousands of cycles.

Thermal oxidation of single crystal aluminum antimonide and materials having the same

DOEpatents

Sherohman, John William; Yee, Jick Hong; Coombs, III, Arthur William; Wu, Kuang Jen J.

2012-12-25

In one embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a partial vacuum atmosphere at a temperature conducive for air adsorbed molecules to desorb, surface molecule groups to decompose, and elemental Sb to evaporate from a surface of the AlSb crystal and exposing the AlSb crystal to an atmosphere comprising oxygen to form a crystalline oxide layer on the surface of the AlSb crystal. In another embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a non-oxidizing atmosphere at a temperature conducive for decomposition of an amorphous oxidized surface layer and evaporation of elemental Sb from the AlSb crystal surface and forming stable oxides of Al and Sb from residual surface oxygen to form a crystalline oxide layer on the surface of the AlSb crystal.

Development and assessement of the GECKO-A multiphase modelling tool for the atmospheric oxidation of biogenic organic compounds

NASA Astrophysics Data System (ADS)

Valorso, Richard; Raventos-Duran, Teresa; Aumont, Bernard; Camredon, Marie; Ng, Nga L.; Seinfeld, John H.

2010-05-01

The evaluation of the impacts of secondary organics on pollution episodes, climate and the tropospheric oxidizing capacity requires modelling tools that track the identity and reactivity of organic carbon in the various stages down to the ultimate oxidation products. The fully explicit representation of hydrocarbon oxidation, from the initial compounds to the final product CO2, requires a very large number of chemical reactions and intermediate species, far in excess of the number that can be reasonably written manually. We developed a "self generating approach" to explicitly describe (i) the gas phase oxidation schemes of organic compounds under general tropospheric conditions and (ii) the partitioning of secondary organics between gas and condensed phases. This approach was codified in a computer program, GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere). This method allows prediction of multiphase mass budget using first principles. However, due to computational limitations, fully explicit chemical schemes can only be generated for species up to C8. We recently implemented a reduction protocol in GECKO-A to allow the generation of oxidation schemes for long chain organics. This protocol was applied to develop highly detailed oxidation schemes for biogenic compounds. The relevance of the generated schemes was assessed using experiments performed in the Caltech smog chamber for various NOx conditions. The first results show a systematic overestimation of the simulated SOA concentrations by GECKO-A. Several hypotheses were tested to find the origin of the discrepancies beetwen model and measurements.

A prototype hybrid 7π quinone-fused 1,3,2-dithiazolyl radical.

PubMed

Decken, A; Mailman, A; Passmore, J; Rautiainen, J M; Scherer, W; Scheidt, E-W

2011-01-28

Reaction of 1,4-naphthoquinone and SNSMF(6) (M = As, Sb) in SO(2) solution in a 1 : 2 molar ratio led to the naphthoquinone fused 1,3,2-dithiazolylium salts, 3MF(6) quantitatively by multinuclear NMR (87% isolated yield of 3SbF(6)) via the cycloaddition and oxidative dehydrogenation chemistry of SNS(+) with formation of NH(4)SbF(6) and S(8). The product 3SbF(6) was fully characterized by IR, Raman, multinuclear {(1)H, (13)C, (14)N} NMR, elemental analysis, cyclic voltammetry and single crystal X-ray crystallography. The reduction of 3SbF(6) with ferrocene (Cp(2)Fe) in refluxing acetonitrile (CH(3)CN) led to the first isolation of a fused quinone-thiazyl radical, 3˙ in 73% yield. The prototype hybrid quinone-thiazyl radical 3˙ was fully characterized by IR, Raman microscopy, EI-MS, elemental analysis, solution and solid state EPR, magnetic susceptibility (2-370 K) and was found to form π*-π* dimers in the solid state as determined by single crystal X-ray crystallography. Furthermore, the thermal decomposition of 3˙ led to a novel quinone-fused 1,2,3,4-tetrathiine, 10 (x = 2) and the known 1,2,5-thiadiazole, 11. The energetics of the cycloadditon and oxidative dehydrogenation chemistry of SNS(+) and 1,4-naphthoquinone leading to 3SbF(6) were estimated in the gas phase and SO(2) solution by DFT calculations (PBE0/6-311G(d)) and lattice enthalpies obtained by the volume based thermodynamic (VBT) approach in the solid state. The gas phase ion energetics (ionization potential (IP) and electron affinity (EA)) of 3˙ are compared to related 1,3,2- and 1,2,3-dithiazolyl radicals.

Manufacture of ceramic tiles from fly ash

DOEpatents

Hnat, J.G.; Mathur, A.; Simpson, J.C.

1999-08-10

The present invention relates to a process for forming glass-ceramic tiles. Fly ash containing organic material, metal contaminants, and glass forming materials is oxidized under conditions effective to combust the organic material and partially oxidize the metallic contaminants and the glass forming materials. The oxidized glass forming materials are vitrified to form a glass melt. This glass melt is then formed into tiles containing metallic contaminants. 6 figs.

Unveiling the Formation Pathway of Single Crystalline Porous Silicon Nanowires

PubMed Central

Zhong, Xing; Qu, Yongquan; Lin, Yung-Chen; Liao, Lei; Duan, Xiangfeng

2011-01-01

Porous silicon nanowire is emerging as an interesting material system due to its unique combination of structural, chemical, electronic, and optical properties. To fully understand their formation mechanism is of great importance for controlling the fundamental physical properties and enabling potential applications. Here we present a systematic study to elucidate the mechanism responsible for the formation of porous silicon nanowires in a two-step silver-assisted electroless chemical etching method. It is shown that silicon nanowire arrays with various porosities can be prepared by varying multiple experimental parameters such as the resistivity of the starting silicon wafer, the concentration of oxidant (H2O2) and the amount of silver catalyst. Our study shows a consistent trend that the porosity increases with the increasing wafer conductivity (dopant concentration) and oxidant (H2O2) concentration. We further demonstrate that silver ions, formed by the oxidation of silver, can diffuse upwards and re-nucleate on the sidewalls of nanowires to initiate new etching pathways to produce porous structure. The elucidation of this fundamental formation mechanism opens a rational pathway to the production of wafer-scale single crystalline porous silicon nanowires with tunable surface areas ranging from 370 m2·g−1 to 30 m2·g−1, and can enable exciting opportunities in catalysis, energy harvesting, conversion, storage, as well as biomedical imaging and therapy. PMID:21244020

Expression, refolding and bio-structural analysis of a tetravalent recombinant dengue envelope domain III protein for serological diagnosis.

PubMed

Combe, Maxime; Lacoux, Xavier; Martinez, Jérôme; Méjan, Odile; Luciani, Françoise; Daniel, Soizic

2017-05-01

Dengue is a mosquito-borne disease caused by four genetically and serologically related viruses that affect several millions of people. Envelope domain III (EDIII) of the viral envelope protein contains dengue virus (DENV) type-specific and DENV complex-reactive antigenic sites. Here, we describe the expression in Escherichia coli, the refolding and bio-structural analysis of envelope domain III of the four dengue serotypes as a tetravalent dengue protein (EDIIIT2), generating an attractive diagnostic candidate. In vitro refolding of denatured EDIIIT2 was performed by successive dialysis with decreasing concentrations of chaotropic reagent and in the presence of oxidized glutathione. The efficiency of refolding was demonstrated by protein mobility shifting and fluorescent visualization of labeled cysteine in non-reducing SDS-PAGE. The identity and the fully oxidized state of the protein were verified by mass spectrometry. Analysis of the structure by fluorescence, differential scanning calorimetry and circular dichroism showed a well-formed structural conformation mainly composed of β-strands. A label-free immunoassay based on biolayer interferometry technology was subsequently used to evaluate antigenic properties of folded EDIIIT2 protein using a panel of dengue IgM positive and negative human sera. Our data collectively support the use of an oxidatively refolded EDIIIT2 recombinant chimeric protein as a promising antigen in the serological diagnosis of dengue virus infections. Copyright © 2017 Elsevier Inc. All rights reserved.

Erythrocyte Sialic Acid Content during Aging in Humans: Correlation with Markers of Oxidative Stress

PubMed Central

Mehdi, Mohammad Murtaza; Singh, Prabhakar; Rizvi, Syed Ibrahim

2012-01-01

Sialic acids are substituted neuraminic acid derivatives which are typically found at the outermost end of glycan chains on the membrane in all cell types. The role of erythrocyte membrane sialic acids during aging has been established however the relationship between sialic acid and oxidative stress is not fully understood. The present work was undertaken to analyze the relationship between erythrocyte membrane sialic acid with its plasma level, membrane and plasma lipid hydroperoxide levels and plasma total antioxidant capacity. Results show that sialic acid content decreases significantly (P < 0.001) in RBC membrane (r = −0.901) and increases in plasma (r = 0.860) as a function of age in humans. Lipid peroxidation measured in the form of hydroperoxides increases significantly (P < 0.001) in plasma (r = 0.830) and RBC membranes (r = 0.875) with age in humans. The Trolox Equivalent Total Antioxidant Capacity (TETAC) of plasma was found to be significantly decreased (P < 0.001, r = −0.844). We observe significant correlations between decrease of erythrocyte membrane sialic acid and plasma lipid hydroperoxide and TETAC. Based on the observed correlations, we hypothesize that increase in oxidative stress during aging may influence the sialic acid decomposition from membrane thereby altering the membrane configuration affecting many enzymatic and transporter activities. Considering the importance of plasma sialic acid as a diagnostic parameter, it is important to establish age-dependent reference. PMID:22377734

Erythrocyte sialic acid content during aging in humans: correlation with markers of oxidative stress.

PubMed

Mehdi, Mohammad Murtaza; Singh, Prabhakar; Rizvi, Syed Ibrahim

2012-01-01

Sialic acids are substituted neuraminic acid derivatives which are typically found at the outermost end of glycan chains on the membrane in all cell types. The role of erythrocyte membrane sialic acids during aging has been established however the relationship between sialic acid and oxidative stress is not fully understood. The present work was undertaken to analyze the relationship between erythrocyte membrane sialic acid with its plasma level, membrane and plasma lipid hydroperoxide levels and plasma total antioxidant capacity. Results show that sialic acid content decreases significantly (P< 0.001) in RBC membrane (r= -0.901) and increases in plasma (r=0.860) as a function of age in humans. Lipid peroxidation measured in the form of hydroperoxides increases significantly (P<0.001) in plasma (r=0.830) and RBC membranes (r=0.875) with age in humans. The Trolox Equivalent Total Antioxidant Capacity (TETAC) of plasma was found to be significantly decreased (P< 0.001, r=-0.844). We observe significant correlations between decrease of erythrocyte membrane sialic acid and plasma lipid hydroperoxide and TETAC. Based on the observed correlations, we hypothesize that increase in oxidative stress during aging may influence the sialic acid decomposition from membrane thereby altering the membrane configuration affecting many enzymatic and transporter activities. Considering the importance of plasma sialic acid as a diagnostic parameter, it is important to establish age-dependent reference.

Role of hydration and water coordination in micellization of Pluronic block copolymers.

PubMed

Šturcová, Adriana; Schmidt, Pavel; Dybal, Jiří

2010-12-15

Raman, attenuated total reflectance FTIR, near-infrared spectroscopy, and DFT calculations have been used in a study of aqueous solutions of three tri-block copolymers poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) or PEO-PPO-PEO with commercial names Pluronic PE6200, PE6400 and F68. It is shown that the process of micellization as a response to increased temperature is reflected in the hydroxyl stretching region of infrared and Raman spectra, which contains information both about restructuring of water and changes of polymer chains in polymer/water aggregates. Raman spectra exhibit differences between individual Pluronics even at temperatures below the critical micellization temperature (CMT). According to the attenuated total reflection (ATR) FTIR spectra, the same five water coordination types defined by the number of donated/accepted hydrogen bonds are present in interacting water as in bulk water. It indicates that models considering mixed states of water with different hydrogen bonding environments provide appropriate descriptions of bound water both below and above the CMT. Above the CMT, aggregate hydration increases in the order PE6400 < PE6200 < F68, although that does not fully correspond to the EO/PO ratio, and points to the differences in microstructure of aggregates formed by each copolymer. This study relates nanoscale phenomena (hydrophobic and hydrophilic hydration) with the mesoscale phenomenon of micellization. Copyright © 2010 Elsevier Inc. All rights reserved.

Corrosion of pre-oxidized nickel alloy X-750 in simulated BWR environment

NASA Astrophysics Data System (ADS)

Tuzi, Silvia; Lai, Haiping; Göransson, Kenneth; Thuvander, Mattias; Stiller, Krystyna

2017-04-01

Samples of pre-oxidized Alloy X-750 were exposed to a simulated boiling water reactor environment in an autoclave at a temperature of 286 °C and a pressure of 80 bar for four weeks. The effect of alloy iron content on corrosion was investigated by comparing samples with 5 and 8 wt% Fe, respectively. In addition, the effect of two different surface pre-treatments was investigated. The microstructure of the formed oxide scales was studied using mainly electron microscopy. The results showed positive effects of an increased Fe content and of removing the deformed surface layer by pickling. After four weeks of exposure the oxide scale consists of oxides formed in three different ways. The oxide formed during pre-oxidization at 700 °C, mainly consisting of chromia, is partly still present. There is also an outer oxide consisting of NiFe2O4 crystals, reaching a maximum size of 3 μm, which has formed by precipitation of dissolved metal ions. Finally, there is an inner nanocrystalline and porous oxide, with a metallic content reflecting the alloy composition, which has formed by corrosion.

Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; May, A. A.; Nguyen, N. T.; Lipsky, E. M.; Donahue, N. M.; Gutierrez, A.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2013-09-01

The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter after three hours of oxidation inside the chamber at typical atmospheric oxidant levels. Therefore, the contribution of light duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3-7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photo-oxidizing exhaust from newer (LEV1 and LEV2) vehicles was only modestly lower (38%) than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions in non-methane organic gas emissions. These data suggest that a complex and non-linear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the time scale of these experiments, the mixture of organic vapors emitted by newer vehicles appear to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the non-methane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. These results for light-duty gasoline vehicles contrast with the results from a companion study of on-road heavy-duty diesel trucks; in that study late model (2007 and later) diesel trucks equipped with catalyzed diesel particulate filters emitted very little primary PM, and the photo-oxidized emissions produced negligible amounts of SOA.

How is a metabolic intermediate formed in the mechanism-based inactivation of cytochrome P450 by using 1,1-dimethylhydrazine: hydrogen abstraction or nitrogen oxidation?

PubMed

Hirao, Hajime; Chuanprasit, Pratanphorn; Cheong, Ying Yi; Wang, Xiaoqing

2013-06-03

A precise understanding of the mechanism-based inactivation of cytochrome P450 enzymes (P450s) at the quantum mechanical level should allow more reliable predictions of drug-drug interactions than those currently available. Hydrazines are among the molecules that act as mechanism-based inactivators to terminate the function of P450s, which are essential heme enzymes responsible for drug metabolism in the human body. Despite its importance, the mechanism explaining how a metabolic intermediate (MI) is formed from hydrazine is not fully understood. We used density functional theory (DFT) calculations to compare four possible mechanisms underlying the reaction between 1,1-dimethylhydrazine (or unsymmetrical dimethylhydrazine, UDMH) and the reactive compound I (Cpd I) intermediate of P450. Our DFT calculations provided a clear view on how an aminonitrene-type MI is formed from UDMH. In the most favorable pathway, hydrogen is spontaneously abstracted from the N2 atom of UDMH by Cpd I, followed by a second hydrogen abstraction from the N2 atom by Cpd II. Nitrogen oxidation of nitrogen atoms and hydrogen abstraction from the C-H bond of the methyl group were found to be less favorable than the hydrogen abstraction from the N-H bond. We also found that the reaction of protonated UDMH with Cpd I is rather sluggish. The aminonitrene-type MI binds to the ferric heme more strongly than a water molecule. This is consistent with the notion that the catalytic cycle of P450 is impeded when such an MI is produced through the P450-catalyzed reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of sol-gel based magnetic 45S5 bioglass and bioglass-ceramics containing iron oxide.

PubMed

Shankhwar, Nisha; Srinivasan, A

2016-05-01

Multicomponent oxide powders with nominal compositions of (45-x)·SiO2·24.5CaO·24.5Na2O·6P2O5xFe2O3 (in wt.%) were prepared by a modified sol-gel procedure. X-ray diffraction (XRD) patterns and high resolution transmission electron microscope images of the sol-gel products show fully amorphous structure for Fe2O3 substitutions up to 2 wt.%. Sol-gel derived 43SiO2·24.5CaO·24.5Na2O·6P2O5·2Fe2O3 glass (or bioglass 45S5 with SiO2 substituted with 2 wt.% Fe2O3), exhibited magnetic behavior with a coercive field of 21 Oe, hysteresis loop area of 33.25 erg/g and saturation magnetization of 0.66 emu/g at an applied field of 15 kOe at room temperature. XRD pattern of this glass annealed at 850 °C for 1h revealed the formation of a glass-ceramic containing sodium calcium silicate and magnetite phases in nanocrystalline form. Temperature dependent magnetization and room temperature electron spin resonance data have been used to obtain information on the magnetic phase and distribution of iron ions in the sol-gel glass and glass-ceramic samples. Sol-gel derived glass and glass-ceramic exhibit in-vitro bioactivity by forming a hydroxyapatite surface layer under simulated physiological conditions and their bio-response is superior to their melt quenched bulk counterparts. This new form of magnetic bioglass and bioglass ceramics opens up new and more effective biomedical applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Surface chemistry and corrosion behavior of Inconel 625 and 718 in subcritical, supercritical, and ultrasupercritical water

NASA Astrophysics Data System (ADS)

Rodriguez, David; Merwin, Augustus; Karmiol, Zachary; Chidambaram, Dev

2017-05-01

Corrosion behavior of Inconel 625 and 718 in subcritical, supercritical and ultrasupercritical water was studied as a function of temperature and time. The change in the chemistry of the as-received surface film on Inconel 625 and 718 after exposure to subcritical water at 325 °C and supercritical water at 425 °C and 527.5 °C for 2 h was studied. After exposure to 325 °C subcritical water, the CrO42- based film formed; however minor quantities of NiFexCr2-xO4 spinel compounds were observed. The oxide film formed on both alloys when exposed to supercritical water at 425 °C consisted of NiFexCr2-xO4 spinel. The surface films on both alloys were identified as NiFe2O4 when exposed to supercritical water at 527.5 °C. To characterize the fully developed oxide layer, studies were conducted at test solution temperatures of 527.5 and 600 °C. Samples were exposed to these temperatures for 24, 96, and 200 h. Surface chemistry was analyzed using X-ray diffraction, as well as Raman and X-ray photoelectron spectroscopies. Inconel 718 exhibited greater mass gain than Inconel 625 for all temperatures and exposure times. The differences in corrosion behavior of the two alloys are attributed to the lower content of chromium and increased iron content of Inconel 718 as compared to Inconel 625.

The tetrahydrobiopterin radical with high- and low-spin heme in neuronal nitric oxide synthase -- a new indicator of the extent of NOS coupling

PubMed Central

Krzyaniak, Matthew D.; Cruce, Alex A.; Vennam, Preethi; Lockart, Molly; Berka, Vladimir; Tsai, Ah-Lim; Bowman, Michael K.

2016-01-01

Reaction intermediates trapped during the single-turnover reaction of the neuronal ferrous nitric oxide synthase oxygenase domain (Fe(II)nNOSOX) show four EPR spectra of free radicals. Fully-coupled nNOSOX with cofactor (tetrahydrobiopterin, BH4) and substrate (l-arginine) forms the typical BH4 cation radical with an EPR spectrum ~4.0 mT wide and hyperfine tensors similar to reports for a biopterin cation radical in inducible NOSOX (iNOSOX). With excess thiol, nNOSox lacking BH4 and l-arg is known to produce superoxide. In contrast, we find that nNOSOX with BH4 but no l-arg forms two radicals with rather different, fast (~ 250 µs at 5 K) and slower (~ 500 µs at 20 K), electron spin relaxation rates and a combined ~7.0 mT wide EPR spectrum. Rapid freeze-quench CW- and pulsed-EPR measurements are used to identify these radicals and their origin. These two species are the same radical with identical nuclear hyperfine couplings, but with spin-spin couplings to high-spin (4.0 mT component) or low-spin (7.0 mT component) Fe(III) heme. Uncoupled reactions of nNOS leave the enzyme in states that can be chemically reduced to sustain unregulated production of NO and reactive oxygen species in ischemia-reperfusion injury. The broad EPR signal is a convenient indicator of uncoupled nNOS reactions producing low-spin Fe(III) heme. PMID:27989753

The nature of the exchange coupling between high-spin Fe(III) heme o3 and CuBII in Escherichia coli quinol oxidase, cytochrome bo3: MCD and EPR studies.

PubMed

Cheesman, Myles R; Oganesyan, Vasily S; Watmough, Nicholas J; Butler, Clive S; Thomson, Andrew J

2004-04-07

Fully oxidized cytochrome bo3 from Escherichia coli has been studied in its oxidized and several ligand-bound forms using electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectroscopies. In each form, the spin-coupled high-spin Fe(III) heme o3 and CuB(II) ion at the active site give rise to similar fast-relaxing broad features in the dual-mode X-band EPR spectra. Simulations of dual-mode spectra are presented which show that this EPR can arise only from a dinuclear site in which the metal ions are weakly coupled by an anisotropic exchange interaction of J 1 cm-1. A variable-temperature and magnetic field (VTVF) MCD study is also presented for the cytochrome bo3 fluoride and azide derivatives. New methods are used to extract the contribution to the MCD of the spin-coupled active site in the presence of strong transitions from low-spin Fe(III) heme b. Analysis of the MCD data, independent of the EPR study, also shows that the spin-coupling within the active site is weak with J approximately 1 cm-1. These conclusions overturn a long-held view that such EPR signals in bovine cytochrome c oxidase arise from an S' = 2 ground state resulting from strong exchange coupling (J > 10(2) cm-1) within the active site.

Computational Study of the Aza-Michael Addition of the Flavonoid (+)-Taxifolin in the Inhibition of β-Amyloid Fibril Aggregation.

PubMed

Ginex, Tiziana; Trius, Marta; Luque, F Javier

2018-04-17

Inhibition of abnormal protein self-aggregation is an attractive strategy against amyloidogenic diseases, but has found limited success due to the complexity of protein self-assembly, the absence of fully reproducible aggregation assays, and the scarce knowledge of the inhibition mechanisms by small molecules. In this context, catechol-containing compounds may lead to covalent adducts with amyloid fibrils that interfere with the aggregation process. In particular, the covalent adduct formed between the oxidized form of (+)-taxifolin and an β-amyloid (Aβ42) suggests the involvement of a specific recognition motif that enables the chemical reaction with Aβ42. In this study, we have examined the mechanisms implicated in the aza-Michael addition of the o-quinone species of (+)-taxifolin with Aβ42 fibrils. The results support the binding of (+)-taxifolin to the hydrophobic groove delimited by the edges defined by Lys16 and Glu22 residues in the fibril. The chemical reaction proceeds through the nucleophilic attack of the deprotonated amino group of a Lys16 residue in a process activated by the interaction between the o-quinone ring with a vicinal Lys16 residue, as well as by a water-assisted proton transfer, which is the rate-limiting step of the reaction. This specific inhibition mechanism, which may explain the enhanced anti-aggregating activity of oxidized flavonoids compared to fresh compounds, holds promise for developing disease-modifying therapies. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physiological plasticity of the thermophilic ammonia oxidizing archaeon Nitrosocaldus yellowstonii in response to a changing environment

NASA Astrophysics Data System (ADS)

Jewell, T.; Johnson, A.; Gelsinger, D.; de la Torre, J. R.

2012-12-01

Our understanding of nitrogen biogeochemical cycling in high temperature environments underwent a dramatic revision with the discovery of ammonia oxidizing archaea (AOA). The importance of AOA to the global nitrogen cycle came to light when recent studies of marine AOA demonstrated the dominance of these organisms in the ocean microbiome and their role as producers of the greenhouse gas nitrous oxide (N2O). Understanding how AOA respond to fluctuating environments is crucial to fully comprehending their contribution to global biogeochemical cycling and climate change. In this study we use the thermophilic AOA Nitrosocaldus yellowstonii strain HL72 to explore the physiological plasticity of energy metabolism in these organisms. Previous studies have shown that HL72 grows autotrophically by aerobically oxidizing ammonia (NH3) to nitrite (NO2-). Unlike studies of marine AOA, we find that HL72 can grow over a wide ammonia concentration range (0.25 - 10 mM NH4Cl) with comparable generation times when in the presence of 0.25 to 4 mM NH4Cl. However, preliminary data indicate that amoA, the alpha subunit of ammonia monooxygenase (AMO), is upregulated at low ammonia concentrations (<50 μM) compared to growth at 1 mM. Although the ammonia oxidation pathway has not been fully elucidated, we have shown that nitric oxide (NO) appears to be a key intermediate: exponentially growing HL72 produces significant NO and the removal of NO using a scavenger reversibly inhibits growth. In addition to AMO, the HL72 genome also contains sequences for a urease encoded by subunits ureABC and an active urea transporter. Urea ((NH2)2CO) is an organic compound ubiquitous to aquatic and soil habitats that, when hydrolyzed, forms NH3 and CO2. We examined urea as an alternate source of ammonia for the ammonia oxidation pathway. HL72 grows over a wide range of urea concentrations (0.25 - 10 mM) at rates comparable to growth on ammonia. In a substrate competition experiment HL72 preferentially consumed NH3 from NH4Cl when both substrates were provided in equal molar concentrations. However, the urease alpha subunit ureC was expressed in both the presence and absence of urea. One consequence of urea hydrolysis is consumption of intracellular protons during the reaction. As ammonia oxidation produces H+, leading to a decrease in pH, the hydrolysis of urea prior to ammonia oxidation may help alleviate metabolism-driven pH change in HL72. A survey of archaeal ureC sequences from metagenomic data covering a range of hydrothermal features revealed that ureolytic potential is common to many Nitrosocaldus-like organisms and is geographically widespread. Measurements of urea from siliceous circumneutral springs indicate that the concentrations are generally low, below 10 μM. One possible explanation for low steady state urea concentrations is high consumption rates by ureolytic organisms. This, combined with abiotic thermal degradation, may mask high fluxes of urea in microbial hot spring communities.

Process for forming a homogeneous oxide solid phase of catalytically active material

DOEpatents

Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

1995-01-01

A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

Effect of Si Content on Oxide Formation on Surface of Molten Fe-Cr-C Alloy Bath During Oxygen Top Blowing

NASA Astrophysics Data System (ADS)

Mihara, Ryosuke; Gao, Xu; Kim, Sun-joong; Ueda, Shigeru; Shibata, Hiroyuki; Seok, Min Oh; Kitamura, Shin-ya

2018-02-01

Using a direct observation experimental method, the oxide formation behavior on the surface of Fe-Cr-5 mass pct C-Si alloy baths during decarburization by a top-blown Ar-O2 mixture was studied. The effects of the initial Si and Cr content of the alloy, temperature, and oxygen feed ratio on oxide formation were investigated. The results showed that, for alloys without Si, oxide particles, unstable oxide films, and stable oxide films formed sequentially. The presence of Si in the alloy changed the formation behavior of stable oxide film, and increased the crucial C content when stable oxide film started to form. Increasing the temperature, decreasing the initial Cr content, and increasing the ratio of the diluting gas decreased the critical C content at which a stable oxide film started to form. In addition, the P CO and a_{{{Cr}2 {O}3 }} values at which oxides started to form were estimated using Hilty's equation and the equilibrium relation to understand the formation conditions and the role of each parameter in oxide formation.

Understanding the interface of six-shell cuboctahedral and icosahedral palladium clusters on reduced graphene oxide: experimental and theoretical study.

PubMed

Gracia-Espino, Eduardo; Hu, Guangzhi; Shchukarev, Andrey; Wågberg, Thomas

2014-05-07

Studies on noble-metal-decorated carbon nanostructures are reported almost on a daily basis, but detailed studies on the nanoscale interactions for well-defined systems are very rare. Here we report a study of reduced graphene oxide (rGOx) homogeneously decorated with palladium (Pd) nanoclusters with well-defined shape and size (2.3 ± 0.3 nm). The rGOx was modified with benzyl mercaptan (BnSH) to improve the interaction with Pd clusters, and N,N-dimethylformamide was used as solvent and capping agent during the decoration process. The resulting Pd nanoparticles anchored to the rGOx-surface exhibit high crystallinity and are fully consistent with six-shell cuboctahedral and icosahedral clusters containing ~600 Pd atoms, where 45% of these are located at the surface. According to X-ray photoelectron spectroscopy analysis, the Pd clusters exhibit an oxidized surface forming a PdO(x) shell. Given the well-defined experimental system, as verified by electron microscopy data and theoretical simulations, we performed ab initio simulations using 10 functionalized graphenes (with vacancies or pyridine, amine, hydroxyl, carboxyl, or epoxy groups) to understand the adsorption process of BnSH, their further role in the Pd cluster formation, and the electronic properties of the graphene-nanoparticle hybrid system. Both the experimental and theoretical results suggest that Pd clusters interact with functionalized graphene by a sulfur bridge while the remaining Pd surface is oxidized. Our study is of significant importance for all work related to anchoring of nanoparticles on nanocarbon-based supports, which are used in a variety of applications.

Persistence of tungsten oxide particle/fiber mixtures in artificial human lung fluids

PubMed Central

2010-01-01

Background During the manufacture of tungsten metal for non-sag wire, tungsten oxide powders are produced as intermediates and can be in the form of tungsten trioxide (WO3) or tungsten blue oxides (TBOs). TBOs contain fiber-shaped tungsten sub-oxide particles of respirable or thoracic size. The aim of this research was to investigate whether fiber-containing TBOs had prolonged biodurability in artificial lung fluids compared to tungsten metal or WO3 and therefore potentially could pose a greater inhalation hazard. Methods Dissolution of tungsten metal, WO3, one fiber-free TBO (WO2.98), and three fiber-containing TBO (WO2.81, WO2.66, and WO2.51) powders were measured for the material as-received, dispersed, and mixed with metallic cobalt. Solubility was evaluated using artificial airway epithelial lining fluid (SUF) and macrophage phagolysosomal simulant fluid (PSF). Results Dissolution rates of tungsten compounds were one to four orders of magnitude slower in PSF compared to SUF. The state of the fiber-containing TBOs did not influence their dissolution in either SUF or PSF. In SUF, fiber-containing WO2.66 and WO2.51 dissolved more slowly than tungsten metal or WO3. In PSF, all three fiber-containing TBOs dissolved more slowly than tungsten metal. Conclusions Fiber-containing TBO powders dissolved more slowly than tungsten metal and WO3 powders in SUF and more slowly than tungsten metal in PSF. Existing pulmonary toxicological information on tungsten compounds indicates potential for pulmonary irritation and possibly fibrosis. Additional research is needed to fully understand the hazard potential of TBOs. PMID:21126345

Multidimensional Fuel Performance Code: BISON

DOE Office of Scientific and Technical Information (OSTI.GOV)

BISON is a finite element based nuclear fuel performance code applicable to a variety of fuel forms including light water reactor fuel rods, TRISO fuel particles, and metallic rod and plate fuel (Refs. [a, b, c]). It solves the fully-coupled equations of thermomechanics and species diffusion and includes important fuel physics such as fission gas release and material property degradation with burnup. BISON is based on the MOOSE framework (Ref. [d]) and can therefore efficiently solve problems on 1-, 2- or 3-D meshes using standard workstations or large high performance computers. BISON is also coupled to a MOOSE-based mesoscale phasemore » field material property simulation capability (Refs. [e, f]). As described here, BISON includes the code library named FOX, which was developed concurrent with BISON. FOX contains material and behavioral models that are specific to oxide fuels.« less

Unusual Internal Electron Transfer in Conjugated Radical Polymers.

PubMed

Li, Fei; Gore, Danielle N; Wang, Shaoyang; Lutkenhaus, Jodie L

2017-08-07

Nitroxide-containing organic radical polymers (ORPs) have captured attention for their high power and fast redox kinetics. Yet a major challenge is the polymer's aliphatic backbone, resulting in a low electronic conductivity. Recent attempts that replace the aliphatic backbone with a conjugated one have not met with success. The reason for this is not understood until now. We examine a family of polythiophenes bearing nitroxide radical groups, showing that while both species are electrochemically active, there exists an internal electron transfer mechanism that interferes with stabilization of the polymer's fully oxidized form. This finding directs the future design of conjugated radical polymers in energy storage and electronics, where careful attention to the redox potential of the backbone relative to the organic radical species is needed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conductive buffer layers and overlayers for the thermal stability of coated conductors

NASA Astrophysics Data System (ADS)

Cantoni, C.; Aytug, T.; Verebelyi, D. T.; Paranthaman, M.; Specht, E. D.; Norton, D. P.; Christen, D. K.

2001-03-01

We analyze fundamental issues related to the thermal and electrical stability of a coated conductor during its operation. We address the role of conductive buffer layers in the stability of Ni-based coated conductors, and the effect of a metallic cap layer on the electrical properties of Ni alloy-based superconducting tapes. For the first case we report on the fabrication of a fully conductive RABiTS architecture formed of bilayers of conductive oxides SrRuO3 and LaNiO3 on textured Ni tapes. For the second case we discuss measurements of current-voltage relations on Ag/YBa2Cu3O7-d and Cu/Ag/ YBa2Cu3O7-d prototype multilayers on insulating substrates. Limitations on the overall tape structure and properties that are posed by the stability requirement are presented.

Oxide nanomaterials: synthetic developments, mechanistic studies, and technological innovations.

PubMed

Patzke, Greta R; Zhou, Ying; Kontic, Roman; Conrad, Franziska

2011-01-24

Oxide nanomaterials are indispensable for nanotechnological innovations, because they combine an infinite variety of structural motifs and properties with manifold morphological features. Given that new oxide materials are almost reported on a daily basis, considerable synthetic and technological work remains to be done to fully exploit this ever increasing family of compounds for innovative nano-applications. This calls for reliable and scalable preparative approaches to oxide nanomaterials and their development remains a challenge for many complex nanostructured oxides. Oxide nanomaterials with special physicochemical features and unusual morphologies are still difficult to access by classic synthetic pathways. The limitless options for creating nano-oxide building blocks open up new technological perspectives with the potential to revolutionize areas ranging from data processing to biocatalysis. Oxide nanotechnology of the 21st century thus needs a strong interplay of preparative creativity, analytical skills, and new ideas for synergistic implementations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidation state of marine manganese nodules

USGS Publications Warehouse

Piper, D.Z.; Basler, J.R.; Bischoff, J.L.

1984-01-01

Analyses of the bulk oxidation state of marine manganese nodules indicates that more than 98% of the Mn in deep ocean nodules is present as Mn(IV). The samples were collected from three quite different areas: the hemipelagic environment of the Guatemala Basin, the pelagic area of the North Pacific, and seamounts in the central Pacific. Results of the study suggest that todorokite in marine nodules is fully oxidized and has the following stoichiometry: (K, Na, Ca, Ba).33(Mg, Cu, Ni).76Mn5O22(H2O)3.2. ?? 1984.

Comment on "Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts".

PubMed

Nakamura, Junji; Fujitani, Tadahiro; Kuld, Sebastian; Helveg, Stig; Chorkendorff, Ib; Sehested, Jens

2017-09-01

Kattel et al (Reports, 24 March 2017, p. 1296) report that a zinc on copper (Zn/Cu) surface undergoes oxidation to zinc oxide/copper (ZnO/Cu) during carbon dioxide (CO 2 ) hydrogenation to methanol and conclude that the Cu-ZnO interface is the active site for methanol synthesis. Similar experiments conducted two decades ago by Fujitani and Nakamura et al demonstrated that Zn is attached to formate rather than being fully oxidized. Copyright © 2017, American Association for the Advancement of Science.

Method of manufacturing tin-doped indium oxide nanofibers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ozcan, Soydan; Naskar, Amit K

2017-06-06

A method of making indium tin oxide nanofibers includes the step of mixing indium and tin precursor compounds with a binder polymer to form a nanofiber precursor composition. The nanofiber precursor composition is co-formed with a supporting polymer to form a composite nanofiber having a precursor composition nanofiber completely surrounded by the supporting polymer composition. The supporting polymer composition is removed from the composite nanofiber to expose the precursor composition nanofiber. The precursor composition nanofiber is then heated in the presence of oxygen such as O.sub.2 to form indium tin oxide and to remove the binder polymer to form anmore » indium tin oxide nanofiber. A method of making metal oxide nanofibers is also disclosed.« less

Possible Dynamically Gated Conductance along Heme Wires in Bacterial Multiheme Cytochromes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Dayle MA; Rosso, Kevin M.

2014-07-24

The staggered cross decaheme configuration of electron transfer co-factors in the outer-membrane cytochrome MtrF may serve as a prototype for conformationally-gated multi-heme electron transport. Derived from the bacterium Shewanella oneidensis, the staggered cross configuration reveals intersecting c-type octaheme and tetraheme “wires” containing thermodynamic “hills” and “valleys”, suggesting that the protein structure may include a dynamical mechanism for conductance and pathway switching depending on enzymatic functional need. Recent molecular simulations have established the pair-wise electronic couplings, redox potentials, and reorganization energies to predict the maximum conductance along the various heme wire pathways by sequential hopping of a single electron (PNAS (2014)more » 11,611-616). Here, we expand this information with classical molecular and statistical mechanics calculations of large-amplitude protein dynamics in MtrF, to address its potential to modulate pathway conductance, including assessment of the effect of the total charge state. Explicit solvent molecular dynamics simulations of fully oxidized and fully reduced MtrF employing ten independent 50-ns simulations at 300 K and 1 atm showed that reduced MtrF is more expanded and explores more conformational space than oxidized MtrF, and that heme reduction leads to increased heme solvent exposure. The slowest mode of collective decaheme motion is 90% similar between the oxidized and reduced states, and consists primarily of inter-heme separation with minor rotational contributions. The frequency of this motion is 1.7×107 s 1 for fully-oxidized and fully-reduced MtrF, respectively, slower than the downhill electron transfer rates between stacked heme pairs at the octaheme termini and faster than the electron transfer rates between parallel hemes in the tetraheme chain. This implies that MtrF uses slow conformational fluctuations to modulate electron flow along the octaheme pathway, apparently for the purpose of increasing the residence time of electrons on lowest potential hemes 4 and 9. This apparent gating mechanism should increase the success rate of electron transfer from MtrF to low potential environmental acceptors via these two solvent-exposed hemes.« less

Electrochemically deposited cobalt/platinum (Co/Pt) film into porous silicon: Structural investigation and magnetic properties

NASA Astrophysics Data System (ADS)

Harraz, F. A.; Salem, A. M.; Mohamed, B. A.; Kandil, A.; Ibrahim, I. A.

2013-01-01

A nanostructured CoPt magnetic film was deposited from a single electrolyte into porous silicon layer by an electrochemical technique, followed by annealing at 600 °C in Ar atmosphere during which the CoPt alloy was converted to L10 ordered phase. Porous silicon with pore diameter between 5 and 100 nm was firstly fabricated by galvanostatic anodization of n-type silicon wafer in the presence of CrO3 as oxidizing agent and ethanol or sodium lauryl sulfate as surfactants. The role of the surfactant on the produced pore size and morphology was investigated by means of UV-vis spectra. As-formed porous silicon was consequently used as a template for the electrodeposition of magnetic CoPt film. The phase formation, microstructure and the magnetic properties were fully analyzed by XRD, FE-SEM, EDS and VSM measurements. It was found that, upon annealing the coercivity was significantly increased due to the transformation to the L10 ordered structure. The saturation magnetization and remanence ratio were also found to increase, indicating no loss of Co content or oxidation reaction after the annealing. Results of synthesis and characterization of CoPt/porous silicon nanocomposite are addressed and thoroughly discussed.

Suppressing spontaneous polarization of p-GaN by graphene oxide passivation: Augmented light output of GaN UV-LED

PubMed Central

Jeong, Hyun; Jeong, Seung Yol; Park, Doo Jae; Jeong, Hyeon Jun; Jeong, Sooyeon; Han, Joong Tark; Jeong, Hee Jin; Yang, Sunhye; Kim, Ho Young; Baeg, Kang-Jun; Park, Sae June; Ahn, Yeong Hwan; Suh, Eun-Kyung; Lee, Geon-Woong; Lee, Young Hee; Jeong, Mun Seok

2015-01-01

GaN-based ultraviolet (UV) LEDs are widely used in numerous applications, including white light pump sources and high-density optical data storage. However, one notorious issue is low hole injection rate in p-type transport layer due to poorly activated holes and spontaneous polarization, giving rise to insufficient light emission efficiency. Therefore, improving hole injection rate is a key step towards high performance UV-LEDs. Here, we report a new method of suppressing spontaneous polarization in p-type region to augment light output of UV-LEDs. This was achieved by simply passivating graphene oxide (GO) on top of the fully fabricated LED. The dipole layer formed by the passivated GO enhanced hole injection rate by suppressing spontaneous polarization in p-type region. The homogeneity of electroluminescence intensity in active layers was improved due to band filling effect. As a consequence, the light output was enhanced by 60% in linear current region. Our simple approach of suppressing spontaneous polarization of p-GaN using GO passivation disrupts the current state of the art technology and will be useful for high-efficiency UV-LED technology. PMID:25586148

Interplay between O2 and SnO2: oxygen ionosorption and spectroscopic evidence for adsorbed oxygen.

PubMed

Gurlo, Alexander

2006-10-13

Tin dioxide is the most commonly used material in commercial gas sensors based on semiconducting metal oxides. Despite intensive efforts, the mechanism responsible for gas-sensing effects on SnO(2) is not fully understood. The key step is the understanding of the electronic response of SnO(2) in the presence of background oxygen. For a long time, oxygen interaction with SnO(2) has been treated within the framework of the "ionosorption theory". The adsorbed oxygen species have been regarded as free oxygen ions electrostatically stabilized on the surface (with no local chemical bond formation). A contradiction, however, arises when connecting this scenario to spectroscopic findings. Despite trying for a long time, there has not been any convincing spectroscopic evidence for "ionosorbed" oxygen species. Neither superoxide ions O(2)(-), nor charged atomic oxygen O,(-) nor peroxide ions O(2)(2-) have been observed on SnO(2) under the real working conditions of sensors. Moreover, several findings show that the superoxide ion does not undergo transformations into charged atomic oxygen at the surface, and represents a dead-end form of low-temperature oxygen adsorption on reduced metal oxide.

Defining a Materials Database for the Design of Copper Binary Alloy Catalysts for Electrochemical CO2 Conversion.

PubMed

Lee, Chan Woo; Yang, Ki Dong; Nam, Dae-Hyun; Jang, Jun Ho; Cho, Nam Heon; Im, Sang Won; Nam, Ki Tae

2018-01-24

While Cu electrodes are a versatile material in the electrochemical production of desired hydrocarbon fuels, Cu binary alloy electrodes are recently proposed to further tune reaction directionality and, more importantly, overcome the intrinsic limitation of scaling relations. Despite encouraging empirical demonstrations of various Cu-based metal alloy systems, the underlying principles of their outstanding performance are not fully addressed. In particular, possible phase segregation with concurrent composition changes, which is widely observed in the field of metallurgy, is not at all considered. Moreover, surface-exposed metals can easily form oxide species, which is another pivotal factor that determines overall catalytic properties. Here, the understanding of Cu binary alloy catalysts for CO 2 reduction and recent progress in this field are discussed. From the viewpoint of the thermodynamic stability of the alloy system and elemental mixing, possible microstructures and naturally generated surface oxide species are proposed. These basic principles of material science can help to predict and understand metal alloy structure and, moreover, act as an inspiration for the development of new binary alloy catalysts to further improve CO 2 conversion and, ultimately, achieve a carbon-neutral cycle. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growth, stability and decomposition of Mg2Si ultra-thin films on Si (100)

NASA Astrophysics Data System (ADS)

Sarpi, B.; Zirmi, R.; Putero, M.; Bouslama, M.; Hemeryck, A.; Vizzini, S.

2018-01-01

Using Auger Electron Spectroscopy (AES), Scanning Tunneling Microscopy/Spectroscopy (STM/STS) and Low Energy Electron Diffraction (LEED), we report an in-situ study of amorphous magnesium silicide (Mg2Si) ultra-thin films grown by thermally enhanced solid-phase reaction of few Mg monolayers deposited at room temperature (RT) on a Si(100) surface. Silicidation of magnesium films can be achieved in the nanometric thickness range with high chemical purity and a high thermal stability after annealing at 150 °C, before reaching a regime of magnesium desorption for temperatures higher than 350 °C. The thermally enhanced reaction of one Mg monolayer (ML) results in the appearance of Mg2Si nanometric crystallites leaving the silicon surface partially uncovered. For thicker Mg deposition nevertheless, continuous 2D silicide films are formed with a volcano shape surface topography characteristic up to 4 Mg MLs. Due to high reactivity between magnesium and oxygen species, the thermal oxidation process in which a thin Mg2Si film is fully decomposed (0.75 eV band gap) into a magnesium oxide layer (6-8 eV band gap) is also reported.

Suppressing spontaneous polarization of p-GaN by graphene oxide passivation: augmented light output of GaN UV-LED.

PubMed

Jeong, Hyun; Jeong, Seung Yol; Park, Doo Jae; Jeong, Hyeon Jun; Jeong, Sooyeon; Han, Joong Tark; Jeong, Hee Jin; Yang, Sunhye; Kim, Ho Young; Baeg, Kang-Jun; Park, Sae June; Ahn, Yeong Hwan; Suh, Eun-Kyung; Lee, Geon-Woong; Lee, Young Hee; Jeong, Mun Seok

2015-01-14

GaN-based ultraviolet (UV) LEDs are widely used in numerous applications, including white light pump sources and high-density optical data storage. However, one notorious issue is low hole injection rate in p-type transport layer due to poorly activated holes and spontaneous polarization, giving rise to insufficient light emission efficiency. Therefore, improving hole injection rate is a key step towards high performance UV-LEDs. Here, we report a new method of suppressing spontaneous polarization in p-type region to augment light output of UV-LEDs. This was achieved by simply passivating graphene oxide (GO) on top of the fully fabricated LED. The dipole layer formed by the passivated GO enhanced hole injection rate by suppressing spontaneous polarization in p-type region. The homogeneity of electroluminescence intensity in active layers was improved due to band filling effect. As a consequence, the light output was enhanced by 60% in linear current region. Our simple approach of suppressing spontaneous polarization of p-GaN using GO passivation disrupts the current state of the art technology and will be useful for high-efficiency UV-LED technology.

570 mV photovoltage, stabilized n-Si/CoO x heterojunction photoanodes fabricated using atomic layer deposition

DOE PAGES

Zhou, Xinghao; Liu, Rui; Sun, Ke; ...

2016-01-08

Heterojunction photoanodes, consisting of n-type crystalline Si(100) substrates coated with a thin ~50 nm film of cobalt oxide fabricated using atomic-layer deposition (ALD), exhibited photocurrent-onset potentials of -205 ± 20 mV relative to the formal potential for the oxygen-evolution reaction (OER), ideal regenerative solar-to-O 2(g) conversion efficiencies of 1.42 ± 0.20%, and operated continuously for over 100 days (~2500 h) in 1.0 M KOH(aq) under simulated solar illumination. The ALD CoO x thin film: (i) formed a heterojunction with the n-Si(100) that provided a photovoltage of 575 mV under 1 Sun of simulated solar illumination; (ii) stabilized Si photoanodes thatmore » are otherwise unstable when operated in aqueous alkaline electrolytes; and, (iii) catalyzed the oxidation of water, thereby reducing the kinetic overpotential required for the reaction and increasing the overall efficiency relative to electrodes that do not have an inherently electrocatalytic coating. The process provides a simple, effective method for enabling the use of planar n-Si(100) substrates as efficient and durable photoanodes in fully integrated, photovoltaic-biased solar fuels generators.« less

Thermodynamic and electron paramagnetic resonance characterization of flavin in succinate dehydrogenase.

PubMed

Ohnishi, T; King, T E; Salerno, J C; Blum, H; Bowyer, J R; Maida, T

1981-06-10

Thermodynamic parameters of succinate dehydrogenase flavin were determined potentiometrically from the analysis of free radical signal levels as a function of the oxidation-reduction potential. Midpoint redox potentials of consecutive 1-electron transfer steps are -127 and -31 mV at pH 7.0. This corresponds to a stability constant of intermediate stability, 2.5 x 10(-2), which suggests flavin itself may be a converter from n = 2 to n = 1 electron transfer steps. The pK values of the free radical (FlH . in equilibrium Fl . -) and the fully reduced form (FlH2 in equilibrium FlH-) were estimated as 8.0 +/- 0.2 and 7.7 +/- 0.2, respectively. Succinate dehydrogenase flavosemiquinone elicits an EPR spectrum at g = 2.00 with a peak to peak width of 1.2 mT even in the protonated form, suggesting the delocalization in the unpaired electron density. A close proximity of succinate dehydrogenase flavin and iron-sulfur cluster S-1 was demonstrated based on the enhancement of flavin spin relaxation by Center S-1.

Method for destroying hazardous organics and other combustible materials in a subcritical/supercritical reactor

DOEpatents

Janikowski, Stuart K.

2000-01-01

A waste destruction method using a reactor vessel to combust and destroy organic and combustible waste, including the steps of introducing a supply of waste into the reactor vessel, introducing a supply of an oxidant into the reactor vessel to mix with the waste forming a waste and oxidant mixture, introducing a supply of water into the reactor vessel to mix with the waste and oxidant mixture forming a waste, water and oxidant mixture, reciprocatingly compressing the waste, water and oxidant mixture forming a compressed mixture, igniting the compressed mixture forming a exhaust gas, and venting the exhaust gas into the surrounding atmosphere.

Self-assembled SnO2 micro- and nanosphere-based gas sensor thick films from an alkoxide-derived high purity aqueous colloid precursor

NASA Astrophysics Data System (ADS)

Kelp, G.; Tätte, T.; Pikker, S.; Mändar, H.; Rozhin, A. G.; Rauwel, P.; Vanetsev, A. S.; Gerst, A.; Merisalu, M.; Mäeorg, U.; Natali, M.; Persson, I.; Kessler, V. G.

2016-03-01

Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300 °C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400 °C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped.Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300 °C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400 °C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped. Electronic supplementary information (ESI) available: IR spectrum of additives found in the residual butanol layer formed during precursor preparation. See DOI: 10.1039/c5nr07942j

Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

NASA Astrophysics Data System (ADS)

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

1984-04-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The 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. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

Role of surface oxidation on the size dependent mechanical properties of nickel nanowires: a ReaxFF molecular dynamics study.

PubMed

Aral, Gurcan; Islam, Md Mahbubul; van Duin, Adri C T

2017-12-20

Highly reactive metallic nickel (Ni) is readily oxidized by oxygen (O 2 ) molecules even at low temperatures. The presence of the naturally resulting pre-oxide shell layer on metallic Ni nano materials such as Ni nanowires (NW) is responsible for degrading the deformation mechanisms and related mechanical properties. However, the role of the pre-oxide shell layer on the metallic Ni NW coupled with the complicated mechanical deformation mechanism and related properties have not yet been fully and independently understood. For this reason, the ReaxFF reactive force field for Ni/O interactions was used to investigate the effect of surface oxide layers and the size-dependent mechanical properties of Ni NWs under precisely controlled tensile loading conditions. To directly quantify the size dependent surface oxidation effect on the tensile mechanical deformation behaviour and related properties for Ni NWs, first, ReaxFF-molecular dynamics (MD) simulations were carried out to study the oxidation kinetics on the free surface of Ni NWs in a molecular O 2 environment as a function of various diameters (D = 5.0, 6.5, and 8.0 nm) of the NWs, but at the same length. Single crystalline, pure metallic Ni NWs were also studied as a reference. The results of the oxidation simulations indicate that a surface oxide shell layer with limiting thickness of ∼1.0 nm was formed on the free surface of the bare Ni NW, typically via dissociation of the O-O bonds and the subsequent formation of Ni-O bonds. Furthermore, we investigated the evolution of the size-dependent intrinsic mechanical elastic properties of the core-oxide shell (Ni/Ni x O y ) NWs by comparing them with their un-oxidized counterparts under constant uniaxial tensile loading. We found that the oxide shell layer significantly decreases the mechanical properties of metallic Ni NW as well as facilitates the initiation of plastic deformation as a function of decreasing diameter. The disordered oxide shell layer on the Ni NW's surface remarkably reduces the yield stress and Young's modulus, due to the increased softening effects with the decreasing NW diameter, compared to un-oxidized counterparts. Moreover, the onset of plastic deformation occurs at a relatively low yielding strain and stress level for the smaller diameter of oxide-coated Ni NWs in comparison to their pure counterparts. Furthermore, for pure Ni NWs, Young's modulus, the yielding stress and strain slightly decrease with the decrease in the diameter size of Ni NWs.

Homogeneous-oxide stack in IGZO thin-film transistors for multi-level-cell NAND memory application

NASA Astrophysics Data System (ADS)

Ji, Hao; Wei, Yehui; Zhang, Xinlei; Jiang, Ran

2017-11-01

A nonvolatile charge-trap-flash memory that is based on amorphous indium-gallium-zinc-oxide thin film transistors was fabricated with a homogeneous-oxide structure for a multi-level-cell application. All oxide layers, i.e., tunneling layer, charge trapping layer, and blocking layer, were fabricated with Al2O3 films. The fabrication condition (including temperature and deposition method) of the charge trapping layer was different from those of the other oxide layers. This device demonstrated a considerable large memory window of 4 V between the states fully erased and programmed with the operation voltage less than 14 V. This kind of device shows a good prospect for multi-level-cell memory applications.

Stability of Pseudobrookite-Type Titanium Oxides

NASA Technical Reports Server (NTRS)

Xirouchakis, Dimistrios

2002-01-01

Orthorhombic, (Bbmm), (Al, Fe, Cr, Ti)(sub 2) TiO5-(Mg, Fe)Ti2O5 solid solutions (pseudobrookites, s.l.) are found either as an oxidation product of ilmenite and/or spinel or a primary crystallizing phase in igneous and metamorphic rocks on Earth (e.g., basalt flows, crustal and mantle xenoliths, hornfels), and basaltic rocks on the Moon. Moreover, orthorhombic oxides are often part of the crystalline matrix in glass/ceramics with useful applications, and play a major role in the industrial production of TiO2. To fully exploit the potential of these compounds as petrogenetic indicators and/or useful materials we need to quantitatively understand the factors controlling their properties and stability, and thus, to extrapolate beyond the calibrating experiments. For that purpose, we need to combine thermochemistry, phase equilibrium, and in situ P-V-T-cation disorder experimental data that presently either are incomplete or lacking. Perhaps, the most complete data set is that for MgTi2O5 (karrooite) which allows the calibration of models for the Gibbs free energy of the MgTi2O5 as a function of pressure, temperature, and the Mg2+-Ti4+ distribution between the two nonequivalent octahedral sites. Consequently, the effect of cation disorder on MgTi2O5 stability, and the phase relations among MgTi2O5, other titanium oxides, and silicate minerals can be examined. Calculated phase relations in the Mg-Ti-Si-O system and phase equilibrium experiments in Fe-bearing compositions suggest that pseudobrookite-type oxides may be a more common in rocks than previously realized. However, homogeneous and heterogeneous equilibria, and crystallization paths likely affect their stability. For example, isobaric increases in temperature favor disordering and thus entropy-stabilization, in contrast, isothermal increases in pressure have the opposite effect. Although, currently, the potential effect of composition to cation disorder cannot be fully explored, it appears that enrichment in trivalent cations probably enhances entropy-stabilization and thus may increase the stability of (Al, Fe, Cr, Ti)-rich pseudobrookites relative to that of (Mg, Fe)-rich ones. In addition, high-temperature, nearly isothermal, decompression paths of olivine+orthopyroxene+oxide assemblages may favor pseudobrookites (s.l.) over rutile and/or ilmenite, in contrast, cooling at low pressures seems to favor ilmenite and/or rutile. In the case of crustal and mantle xenoliths, the presence or absence of orthorhombic oxides is probably controlled by reactions with olivine, orthopyroxene, ilmenite, and rutile. In oceanic mantle xenoliths such reactions may also involve a TiO2-enriched but not SiO2-enriched melt/fluid, because pseudobrookites (s.l.) would react with the SiO2-enriched melt/fluid to form orthopyroxene and rutile. Parenthetically, experiments and model calculations in the Mg-Ti-Si-O system suggest that low degree partial melting of low-TiO2 bulk compositions may produce Ti-enriched liquids in equilibrium with olivine, orthopyroxen ad=nd MgTi2O5, rutile or ilmenite.

Simulation and optimization of ammonia removal at low temperature for a double channel oxidation ditch based on fully coupled activated sludge model (FCASM): a full-scale study.

PubMed

Yang, Min; Sun, Peide; Wang, Ruyi; Han, Jingyi; Wang, Jianqiao; Song, Yingqi; Cai, Jing; Tang, Xiudi

2013-09-01

An optimal operating condition for ammonia removal at low temperature, based on fully coupled activated sludge model (FCASM), was determined in a full-scale oxidation ditch process wastewater treatment plant (WWTP). The FCASM-based mechanisms model was calibrated and validated with the data measured on site. Several important kinetic parameters of the modified model were tested through respirometry experiment. Validated model was used to evaluate the relationship between ammonia removal and operating parameters, such as temperature (T), dissolved oxygen (DO), solid retention time (SRT) and hydraulic retention time of oxidation ditch (HRT). The simulated results showed that low temperature have a negative effect on the ammonia removal. Through orthogonal simulation tests of the last three factors and combination with the analysis of variance, the optimal operating mode acquired of DO, SRT, HRT for the WWTP at low temperature were 3.5 mg L(-1), 15 d and 14 h, respectively. Copyright © 2013 Elsevier Ltd. All rights reserved.

XPS and EELS characterization of Mn2SiO4, MnSiO3 and MnAl2O4

NASA Astrophysics Data System (ADS)

Grosvenor, A. P.; Bellhouse, E. M.; Korinek, A.; Bugnet, M.; McDermid, J. R.

2016-08-01

X-ray Photoelectron Spectroscopy (XPS) and Electron Energy Loss Spectroscopy (EELS) are strong candidate techniques for characterizing steel surfaces and substrate-coating interfaces when investigating the selective oxidation and reactive wetting of advanced high strength steels (AHSS) during the continuous galvanizing process. However, unambiguous identification of ternary oxides such as Mn2SiO4, MnSiO3, and MnAl2O4 by XPS or EELS, which can play a significant role in substrate reactive wetting, is difficult due to the lack of fully characterized standards in the literature. To resolve this issue, samples of Mn2SiO4, MnSiO3 and MnAl2O4 were synthesized and characterized by XPS and EELS. The unique features of the XPS and EELS spectra for the Mn2SiO4, MnSiO3 and MnAl2O4 standards were successfully derived, thereby allowing investigators to fully differentiate and identify these oxides at the surface and subsurface of Mn, Si and Al alloyed AHSS using these techniques.

Relation between film character and wafer alignment: critical alignment issues on HV device for VLSI manufacturing

NASA Astrophysics Data System (ADS)

Lo, Yi-Chuan; Lee, Chih-Hsiung; Lin, Hsun-Peng; Peng, Chiou-Shian

1998-06-01

Several continuous splits for wafer alignment target topography conditions to improve epitaxy film alignment were applied. The alignment evaluation among former layer pad oxide thickness (250 angstrom - 500 angstrom), drive oxide thickness (6000 angstrom - 10000 angstrom), nitride film thickness (600 angstrom - 1500 angstrom), initial oxide etch (fully wet etch, fully dry etch and dry plus wet etch) will be split to this experiment. Also various epitaxy deposition recipe such as: epitaxy source (SiHCl2 or SiCHCl3) and growth rate (1.3 micrometer/min approximately 2.0 micrometer/min) will be used to optimize the process window for alignment issue. All the reflectance signal and cross section photography of alignment target during NIKON stepper alignment process will be examined. Experimental results show epitaxy recipe plays an important role to wafer alignment. Low growth rate with good performance conformity epitaxy lead to alignment target avoid washout, pattern shift and distortion. All the results (signal monitor and film character) combined with NIKON's stepper standard laser scanning alignment system will be discussed in this paper.

[The relationship between oxidized form glutathione, coenzyme II and carotid artery atherosclerosis].

PubMed

Huang, Yan-sheng; Wang, Shu-ren; Zhi, Yan-fang; Xu, Bo-shi; Sun, Lin; Wu, Yu; Lu, Jian-min; Dai, Fu-min

2006-06-01

To explore the relationship between plasma redox status and atherosclerosis. IVUS was performed in common carotid in the neck of 167 patients with heart diseases. Patients were divided into three groups: plaque-forming group (A, n = 79), intima-thickening group (B, n = 52) and control group (C, n = 36). Plasma glutathione (reduced form GSH and oxidized form GSSG), nicotinamide adenine dinucleotide phosphate (reduced form NADPH and oxidized form NADP(+)), oxidized low density lipoprotein (ox-LDL) and malondialdehyde (MDA) were measured in all patients. The GSH/GSSG and NADPH/NADP(+) redox potential were calculated according to Nernst equation, and correlation analysis performed. GSH and GSH/GSSG gradually reduced and GSH/GSSG redox potential gradually increased in proportion to the thickening of artery intima (from Group C to Group A, P < 0.05). Similar but milder results were shown for NADPH and NADPH/NADP(+) redox status. The products of oxidative stress ox-LDL and MDA also increased significantly (P < 0.05) in proportion to the thickening of artery intima. GSH/GSSG redox potential is positively correlated to ox-LDL (P < 0.05). The redox status shifted to oxidizing direction in proportion to the intima thickness. The imbalance of plasma redox status deviating to oxidation might be implicated in oxidized injury of lipid, intima thickening and atherosclerosis progress.

Effects of alloy heat treatment on oxidation kinetics and scale morphology for Crofer 22 APU

NASA Astrophysics Data System (ADS)

Magdefrau, Neal J.; Chen, Lei; Sun, Ellen Y.; Aindow, Mark

2013-11-01

The effect of alloy heat treatment on the oxidation kinetics and oxide scale microstructure of Crofer 22 APU has been studied. Parabolic oxidation rate constants were measured for the as-received alloy and after pre-oxidation heat treatment in argon at 1050 °C for 1 and 4 h. The oxide scale microstructure was investigated using scanning electron microscopy, focused ion beam milling and transmission electron microscopy. It was found that the alloy forms a two-layer scale with a continuous chromia layer and a discontinuous MnCr2O4 overlayer. Two forms of internal oxides were also formed: subscale pockets of spinel and isolated TiOx precipitates in the underlying alloy. The pre-oxidation heat treatment had a profound effect on the grain size and morphology of the Cr2O3 and MnCr2O4 layers in the scale. The heat-treated samples exhibit a 3.5× lower parabolic oxidation rate constant than the as-received Crofer 22 APU. This improvement in oxidation resistance is attributed to the dramatic differences in the morphology of the oxide scale that forms during the earliest stages of oxidation (<5 h). The implications of these findings for oxidation mechanisms and long-term SOFC performance are discussed.

Detecting Hydrogen Chloride (HCl) in the Polluted Marine Boundary Layer Using Cavity Ring-Down Spectroscopy (CRDS)

NASA Astrophysics Data System (ADS)

Furlani, T.; Dawe, K.; VandenBoer, T. C.; Young, C.

2017-12-01

Oxidation initiated with chlorine atoms yields more ozone than oxidation initiated with hydroxyl radicals. Reasons for this are not fully understood, but the implications for mechanisms of oxidation chemistry are significant.1,2 Chlorine atoms have not been directly measured to date in the atmosphere and its abundance is usually inferred through steady-state approximations from all known formation and loss processes. A major reservoir for chlorine in the troposphere is by proton abstraction of organic compounds to form HCl.3 HCl can also be formed heterogeneously via acid displacement reactions with ubiquitously-found sodium chloride (NaCl) on solid surfaces with nitric acid (HNO3). The majority of the available chloride in the marine boundary layer comes from the sea salt in and around marine derived sea-spray aerosols. HCl is not a perfect sink and can react with hydroxyl radicals or be photolyzed to form chlorine atoms. The balance between loss and formation processes of chlorine atoms from HCl is highly dependent on many external factors, such as the wet and dry deposition rate of HCl. Measuring HCl in the gas and aerosol phase is important to the understanding of chlorine chemistry in the polluted marine boundary layer. HCl levels in the polluted marine boundary layer are typically between 100pptv-1ppbv,3 requiring the sensitive and selective detection capabilities of cavity ring-down spectroscopy (CRDS).4 We measured HCl using a Picarro CRDS in the polluted marine boundary layer for the first time. Measurements were conducted during April and May of 2017 in St. John's, Newfoundland and Labrador. The performance of the instrument will be discussed, as well as observations of HCl in the context of local conditions. References1Osthoff, H. D. et al. Nat. Geosci 1, 324-328 (2008). 2Young, C. J. et al. Atmos. Chem. Phys. 14, 3427-3440 (2014). 3Crisp, T. a et al. J. Geophys. Res. Atmos. 6897-6915 (2014). 4Hagen, C. L. et al. Atmos. Meas. Tech. 7, 345-357 (2014).

Densification of oxide superconductors by hot isostatic pressing

NASA Astrophysics Data System (ADS)

Tien, J. K.; Borofka, J. C.; Hendrix, B. C.; Caulfield, T.; Reichman, S. H.

1988-07-01

Currently, consolidation of high Tc superconductor powders is done by sintering, which is not effective in the reduction of porosity. This work assesses the feasibility of hot isostatic pressing (HIP) to obtain fully dense bulk superconductor using HIP modeling and experimental verification. It is concluded that fully dense YBa2Cu3O7 can be obtained in reasonable times at temperatures down to around 650 °C. The trade-offs between temperature, time, and pressure are examined as well as the effects of powder particle size, powder grain size, and trapped gas pressure. The model has. been verified by experiment under three conditions: 100 MPa HIP at 900 °C for 2 hours, 100 MPa HIP at 750 °C for 2 hours, and sintering at 950 °C for 16 hours. The additional advantages of HIPing oxide superconductors are also discussed.

Mesoporous metal oxide microsphere electrode compositions and their methods of making

DOEpatents

Paranthaman, Mariappan Parans; Liu, Hansan; Brown, Gilbert M.; Sun, Xiao-Guang; Bi, Zhonghe

2016-12-06

Compositions and methods of making are provided for mesoporous metal oxide microspheres electrodes. The mesoporous metal oxide microsphere compositions comprise (a) microspheres with an average diameter between 200 nanometers (nm) and 10 micrometers (.mu.m); (b) mesopores on the surface and interior of the microspheres, wherein the mesopores have an average diameter between 1 nm and 50 nm and the microspheres have a surface area between 50 m.sup.2/g and 500 m.sup.2/g. The methods of making comprise forming composite powders. The methods may also comprise refluxing the composite powders in a basic solution to form an etched powder, washing the etched powder with an acid to form a hydrated metal oxide, and heat-treating the hydrated metal oxide to form mesoporous metal oxide microspheres.

Electro-deposition of superconductor oxide films

DOEpatents

Bhattacharya, Raghu N.

2001-01-01

Methods for preparing high quality superconducting oxide precursors which are well suited for further oxidation and annealing to form superconducting oxide films. The method comprises forming a multilayered superconducting precursor on a substrate by providing an electrodeposition bath comprising an electrolyte medium and a substrate electrode, and providing to the bath a plurality of precursor metal salts which are capable of exhibiting superconducting properties upon subsequent treatment. The superconducting precursor is then formed by electrodepositing a first electrodeposited (ED) layer onto the substrate electrode, followed by depositing a layer of silver onto the first electrodeposited (ED) layer, and then electrodepositing a second electrodeposited (ED) layer onto the Ag layer. The multilayered superconducting precursor is suitable for oxidation at a sufficient annealing temperature in air or an oxygen-containing atmosphere to form a crystalline superconducting oxide film.

Initial stage corrosion of nanocrystalline copper particles and thin films

NASA Astrophysics Data System (ADS)

Tao, Weimin

1997-12-01

Corrosion behavior is an important issue in nanocrystalline materials research and development. A very fine grain size is expected to have significant effects on the corrosion resistance of these novel materials. However, both the macroscopic corrosion properties and the corresponding structure evolution during corrosion have not been fully studied. Under such circumstances, conducting fundamental research in this area is important and necessary. In this study, high purity nanocrystalline and coarse-grained copper were selected as our sample material, sodium nitrite aqueous solution at room temperature and air at a high temperature were employed as corrosive environments. The weight loss testing and electrochemical methods were used to obtain the macroscopic corrosion properties, whereas the high resolution transmission electron microscope was employed for the structure analysis. The weight loss tests indicate that the corrosion rate of nanocrystalline copper is about 5 times higher than that of coarse-grained copper at the initial stage of corrosion. The electrochemical measurements show that the corrosion potential of the nanocrystalline copper has a 230 mV negative shift in comparison with that of the coarse-grained copper. The nanocrystalline copper also exhibits a significantly higher exchange current density than the coarse-grained copper. High resolution TEM revealed that the surface structure changes at the initial stage of corrosion. It was found that the first copper oxide layer formed on the surface of nanocrystalline copper thin film contains a large density of high angle grain boundaries, whereas that formed on the surface of coarse-grained copper shows highly oriented oxide nuclei and appears to show a strong tendency for forming low angle grain boundaries. A correlation between the macroscopic corrosion properties and the structure characteristics is proposed for the nanocrystalline copper based on the concept of the "apparent" exchange current density associated with mass transport of ions in the oxide layer. A hypothesis is developed that the high corrosion rate of the nanocrystalline copper is closely associated with the structure of the copper oxide layer. Therefore, a high "apparent" exchange current density for the nanocrystalline copper is associated with the high angle grain boundary structure in the initial oxide layer. Additional structure analysis was also carried out: (a) High resolution TEM imaging has provided a cross sectional view of the epitaxial interface between nanocrystalline copper and copper (I) oxide and explicitly discloses the presence of interface defects such as misfit dislocations. Based on this observation, a mechanism was proposed to explain the Cu/Cusb2O interface misfit accommodation. This appears to be the first time this interface has been directly examined. (b) A nanocrystalline analogue to a cross-section of Gwathmey's copper single crystal sphere was revealed by high resolution TEM imaging. A partially oxidized nanocrystalline copper particle is used to examine the variation of the Cu/Cusb2O orientation relationship with respect to changes in surface orientation. A new orientation relationship, Cu (011) //Cusb2O (11), ˜ Cu(011)//Cusb2O(111), was found for the oxidation of nanocrystalline copper.

[Ultrasound induced the formation of nitric oxide and nitrosonium ions in water and aqueous solutions].

PubMed

Stepuro, I I; Adamchuk, R I; Stepuro, V I

2004-01-01

Nitric oxide, nitrosonium ions, nitrites, and nitrates are formed in water saturated with air under the action of ultrasound. Nitrosonium ions react with water and hydrogen peroxide to form nitrites and nitrates in sonicated solution, correspondingly. Nitric oxide is practically completely released from sonicated water into the atmosphere and reacts with air oxygen, forming NOx compounds. The oxidation of nitric oxide in aqueous medium by hydroxyl radicals and dissolved oxygen is a minor route of the formation of nitrites and nitrates in ultrasonic field.

Performance of Transuranic-Loaded Fully Ceramic Micro-Encapsulated Fuel in LWRs Final Report, Including Void Reactivity Evaluation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michael A. Pope; R. Sonat Sen; Brian Boer

2011-09-01

The current focus of the Deep Burn Project is on once-through burning of transuranics (TRU) in light-water reactors (LWRs). The fuel form is called Fully-Ceramic Micro-encapsulated (FCM) fuel, a concept that borrows the tri-isotropic (TRISO) fuel particle design from high-temperature reactor technology. In the Deep Burn LWR (DB-LWR) concept, these fuel particles are pressed into compacts using SiC matrix material and loaded into fuel pins for use in conventional LWRs. The TRU loading comes from the spent fuel of a conventional LWR after 5 years of cooling. Unit cell and assembly calculations have been performed using the DRAGON-4 code tomore » assess the physics attributes of TRU-only FCM fuel in an LWR lattice. Depletion calculations assuming an infinite lattice condition were performed with calculations of various reactivity coefficients performed at each step. Unit cells and assemblies containing typical UO2 and mixed oxide (MOX) fuel were analyzed in the same way to provide a baseline against which to compare the TRU-only FCM fuel. Then, assembly calculations were performed evaluating the performance of heterogeneous arrangements of TRU-only FCM fuel pins along with UO2 pins.« less

Substrate independent approach for synthesis of graphene platelet networks.

PubMed

Shashurin, A; Fang, X; Zemlyanov, D; Keidar, M

2017-06-23

Graphene platelet networks (GPNs) comprised of randomly oriented graphene flakes two to three atomic layers thick are synthesized using a novel plasma-based approach. The approach uses a substrate capable of withstanding synthesis temperatures around 800 °C, but is fully independent of the substrate material. The synthesis occurs directly on the substrate surface without the necessity of any additional steps. GPNs were synthesized on various substrate materials including silicon (Si), thermally oxidized Si (SiO 2 ), molybdenum (Mo), nickel (Ni) and copper (Cu), nickel-chromium (NiCr) alloy and alumina ceramics (Al 2 O 3 ). The mismatch between the atomic structures of sp 2 honeycomb carbon networks and the substrate material is fully eliminated shortly after the synthesis initiation, namely when about 100 nm thick deposits are formed on the substrate. GPN structures synthesized on a substrate at a temperature of about 800 °C are significantly more porous in comparison to the much denser packed amorphous carbon deposits synthesized at lower temperatures. The method proposed here can potentially revolutionize the area of electrochemical energy storage by offering a single-step direct approach for the manufacture of graphene-based electrodes for non-Faradaic supercapacitors. Mass production can be achieved using this method if a roll-to-roll system is utilized.

Substrate independent approach for synthesis of graphene platelet networks

NASA Astrophysics Data System (ADS)

Shashurin, A.; Fang, X.; Zemlyanov, D.; Keidar, M.

2017-06-01

Graphene platelet networks (GPNs) comprised of randomly oriented graphene flakes two to three atomic layers thick are synthesized using a novel plasma-based approach. The approach uses a substrate capable of withstanding synthesis temperatures around 800 °C, but is fully independent of the substrate material. The synthesis occurs directly on the substrate surface without the necessity of any additional steps. GPNs were synthesized on various substrate materials including silicon (Si), thermally oxidized Si (SiO2), molybdenum (Mo), nickel (Ni) and copper (Cu), nickel-chromium (NiCr) alloy and alumina ceramics (Al2O3). The mismatch between the atomic structures of sp2 honeycomb carbon networks and the substrate material is fully eliminated shortly after the synthesis initiation, namely when about 100 nm thick deposits are formed on the substrate. GPN structures synthesized on a substrate at a temperature of about 800 °C are significantly more porous in comparison to the much denser packed amorphous carbon deposits synthesized at lower temperatures. The method proposed here can potentially revolutionize the area of electrochemical energy storage by offering a single-step direct approach for the manufacture of graphene-based electrodes for non-Faradaic supercapacitors. Mass production can be achieved using this method if a roll-to-roll system is utilized.

Characterization of thin MoO3 films formed by RF and DC-magnetron reactive sputtering for gas sensor applications

NASA Astrophysics Data System (ADS)

Yordanov, R.; Boyadjiev, S.; Georgieva, V.; Vergov, L.

2014-05-01

The present work discusses a technology for deposition and characterization of thin molybdenum oxide (MoOx, MoO3) films studied for gas sensor applications. The samples were produced by reactive radio-frequency (RF) and direct current (DC) magnetron sputtering. The composition and microstructure of the films were studied by XPS, XRD and Raman spectroscopy, the morphology, using high resolution SEM. The research was focused on the sensing properties of the sputtered thin MoO3 films. Highly sensitive gas sensors were implemented by depositing films of various thicknesses on quartz resonators. Making use of the quartz crystal microbalance (QCM) method, these sensors were capable of detecting changes in the molecular range. Prototype QCM structures with thin MoO3 films were tested for sensitivity to NH3 and NO2. Even in as-deposited state and without heating the substrates, these films showed good sensitivity. Moreover, no additional thermal treatment is necessary, which makes the production of such QCM gas sensors simple and cost-effective, as it is fully compatible with the technology for producing the initial resonator. The films are sensitive at room temperature and can register concentrations as low as 50 ppm. The sorption is fully reversible, the films are stable and capable of long-term measurements.

Methods for making lithium vanadium oxide electrode materials

DOEpatents

Schutts, Scott M.; Kinney, Robert J.

2000-01-01

A method of making vanadium oxide formulations is presented. In one method of preparing lithium vanadium oxide for use as an electrode material, the method involves: admixing a particulate form of a lithium compound and a particulate form of a vanadium compound; jet milling the particulate admixture of the lithium and vanadium compounds; and heating the jet milled particulate admixture at a temperature below the melting temperature of the admixture to form lithium vanadium oxide.

Efficient assessment of modified nucleoside stability under conditions of automated oligonucleotide synthesis: characterization of the oxidation and oxidative desulfurization of 2-thiouridine.

PubMed

Sochacka, E

2001-01-01

In order to efficiently assess the chemical stability of modified nucleosides to the reagents and conditions of automated oligonucleotide synthesis, we designed, developed and tested a scheme in which the modified nucleoside, directly attached to a solid support, is exposed to the cyclic chemistry of the instrument. Stability of 2-thiouridine against different oxidizers was investigated. Tertbutyl hydroperoxide (1 M) in anhydrous acetonitrile was a more effective oxidizer for the incorporation of 2-thiouridine into oligonucleotide chains than the same oxidizer in methylene chloride. Carbon tetrachloride/water in the presence of a basic catalyst was superior in maintaining the thiocarbonyl function, but its utility for RNA synthesis has yet to be fully tested, whereas 2-phenylsulfonyloxaziridine was a very efficient reagent for oxidative desulfurization of 2-thiouridine.

NASA interdisciplinary collaboration in tribology. A review of oxidational wear

NASA Technical Reports Server (NTRS)

Quinn, T. F. J.

1983-01-01

An in-depth review of oxidational wear of metals is presented. Special emphasis is given to a description of the concept of oxidational wear and the formulation of an Oxidational Wear Theory. The parallelism between the formation of an oxide film for dry contact conditions and the formation of other surface films for a lubricated contact is discussed. The description of oxidational wear is prefaced with a unification of wear modes into two major classes of mild and severe wear including both lubricated and dry contacts. Oxidational wear of metals is a class of mild wear where protective oxide films are formed at real areas of contact and during the time of contact at temperataure T sub c. When the oxide reaches a critical thickness, frequently in the range of 1 to 3 microns, the oxide breaks up and eventually appears as a wear particle. These oxides are preferentially formed on plateaux which alternately carry the load as they reach their critical thickness and are removed. If the system is operated at elevated temperatures, thick oxides can form both out of contact and between the plateaux. Temperature is important in determining the structure of the oxide film present. Spinel oxide (Fe3O4) which forms above 300 C is more protective than the lower temperature rhomobohedral (alpha-Fe2O3) oxide which is abrasive. An Oxidational Wear Theory is derived using a modified Archard wear law expressed in terms of activation energy (Qp) and Arrhenius constant (Ap).

Physical characterization of a new composition of oxidized zirconium-2.5 wt% niobium produced using a two step process for biomedical applications

NASA Astrophysics Data System (ADS)

Pawar, V.; Weaver, C.; Jani, S.

2011-05-01

Zirconium and particularly Zr-2.5 wt%Nb (Zr2.5Nb) alloy are useful for engineering bearing applications because they can be oxidized in air to form a hard surface ceramic. Oxidized zirconium (OxZr) due to its abrasion resistant ceramic surface and biocompatible substrate alloy has been used as a bearing surface in total joint arthroplasty for several years. OxZr is characterized by hard zirconium oxide (oxide) formed on Zr2.5Nb using one step thermal oxidation carried out in air. Because the oxide is only at the surface, the bulk material behaves like a metal, with high toughness. The oxide, furthermore, exhibits high adhesion to the substrate because of an oxygen-rich diffusion hardened zone (DHZ) interposing between the oxide and the substrate. In this study, we demonstrate a two step process that forms a thicker DHZ and thus increased depth of hardening than that can be obtained using a one step oxidation process. The first step is thermal oxidation in air and the second step is a heat treatment in vacuum. The second step drives oxygen from the oxide formed in the first step deeper into the substrate to form a thicker DHZ. During the process only a portion of the oxide is dissolved. This new composition (DHOxZr) has approximately 4-6 μm oxide similar to that of OxZr. The nano-hardness of the oxide is similar but the DHZ is approximately 10 times thicker. The stoichiometry of the oxide is similar and a secondary phase rich in oxygen is present through the entire thickness. Due to the increased depth of hardening, the critical load required for the onset of oxide cracking is approximately 1.6 times more than that of the oxide of OxZr. This new composition has a potential to be used as a bearing surface in applications where greater depth of hardening is required.

Simultaneous determination of blonanserin and its four metabolites in human plasma using ultra-performance liquid chromatography-tandem mass spectrometry.

PubMed

Zhou, Ying; Liu, Ming; Jiang, Ji; Wang, Hongyun; Hu, Pei

2013-11-15

A sensitive and rapid method based on ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) was developed and validated for the simultaneous determination of blonanserin, its major active metabolite (N-deethyl form) and other three metabolites (N-oxide form, Ethylenediamine form and Carboxylate form) in human plasma. Plasma samples were pre-purified by solid-phase extraction (SPE) and analyzed using a gradient chromatographic separation over an Acquity UPLC CSH C18 column. The mobile phase consisted of acetonitrile-water containing 5mM ammonium formate and 0.1% formic acid at a flow rate of 0.5mL/min. Positive electrospray ionization was employed as the ionization source in the multiple reaction monitoring (MRM) mode. The analysis time was about 3.5min. The method was fully validated over the concentration range of 0.01-1ng/mL for all analytes. The lower limit of quantification (LLOQ) was 0.01ng/mL. Inter- and intra-batch precision was less than 15% and the accuracy was within 85-115%. The mean extraction recoveries of all analytes at two concentration levels were consistent. Selectivity, matrix effect and stability were also validated. The method was applied to the pharmacokinetic study of blonanserin in Chinese healthy subjects. Copyright © 2013 Elsevier B.V. All rights reserved.

Transparent nanocrystalline ZnO and ZnO:Al coatings obtained through ZnS sols

NASA Astrophysics Data System (ADS)

Kolobkova, E. V.; Evstropiev, S. K.; Nikonorov, N. V.; Vasilyev, V. N.; Evstropyev, K. S.

2017-11-01

Thin and uniform ZnO and ZnO:Al coatings were prepared on glass surfaces by using film-forming colloidal solutions containing small ZnS nanoparticles and polyvinylpyrrolidone as a polymer stabilizer. Film-forming ZnS sols were synthesized in the mixed water-propanol-2 solutions by chemical reaction between zinc nitrate and sodium sulfide. The addition of modifying component such as Al(NO3)3 into the film-forming solutions allows one to obtain thin and uniform ZnO:Al coatings. An increase in the sodium sulfide content in film-forming solutions leads to the growth of light absorption in the UV. The evolution of a coating material at all technological stages from the ZnS sols up to the transparent ZnO and ZnO:Al2O3 coatings (the latter kind being denoted further, in accord with a common practice, by ZnO:Al) was studied using the optical spectroscopy, XRD analysis, DSC-TGA, and SEM methods. The chemical processes of decomposing salts and the polymer occur by heating the intermediate composite ZnS/polyvinylpyrrolidone coatings in the 280-500 °C temperature range. Experimental data show that the ZnO and ZnO:Al coatings prepared consist of the slightly elongated oxide nanoparticles. These coatings fully cover the glass surface and demonstrate a high transparency in the UV and visible.

Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media.

PubMed

Zhang, Biaobiao; Li, Fei; Zhang, Rong; Ma, Chengbing; Chen, Lin; Sun, Licheng

2016-06-30

A Ru(III)-O-Ru(IV)-O-Ru(III) type trinuclear species was crystallographically characterized in water oxidation by Ru(bda)(pic)2 (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) under neutral conditions. The formation of a ruthenium trimer due to the reaction of Ru(IV)[double bond, length as m-dash]O with Ru(II)-OH2 was fully confirmed by chemical, electrochemical and photochemical methods. Since the oxidation of the trimer was proposed to lead to catalyst decomposition, the photocatalytic water oxidation activity was rationally improved by the suppression of the formation of the trimer.

Materials and processing approaches for foundry-compatible transient electronics

PubMed Central

Chang, Jan-Kai; Fang, Hui; Bower, Christopher A.; Song, Enming; Yu, Xinge; Rogers, John A.

2017-01-01

Foundry-based routes to transient silicon electronic devices have the potential to serve as the manufacturing basis for “green” electronic devices, biodegradable implants, hardware secure data storage systems, and unrecoverable remote devices. This article introduces materials and processing approaches that enable state-of-the-art silicon complementary metal-oxide-semiconductor (CMOS) foundries to be leveraged for high-performance, water-soluble forms of electronics. The key elements are (i) collections of biodegradable electronic materials (e.g., silicon, tungsten, silicon nitride, silicon dioxide) and device architectures that are compatible with manufacturing procedures currently used in the integrated circuit industry, (ii) release schemes and transfer printing methods for integration of multiple ultrathin components formed in this way onto biodegradable polymer substrates, and (iii) planarization and metallization techniques to yield interconnected and fully functional systems. Various CMOS devices and circuit elements created in this fashion and detailed measurements of their electrical characteristics highlight the capabilities. Accelerated dissolution studies in aqueous environments reveal the chemical kinetics associated with the underlying transient behaviors. The results demonstrate the technical feasibility for using foundry-based routes to sophisticated forms of transient electronic devices, with functional capabilities and cost structures that could support diverse applications in the biomedical, military, industrial, and consumer industries. PMID:28652373

A multi-scaled hybrid orthopedic implant: bone ECM-shaped Sr-HA nanofibers on the microporous walls of a macroporous titanium scaffold.

PubMed

Han, Yong; Zhou, Jianhong; Zhang, Lan; Xu, Kewei

2011-07-08

We report here, for the first time, a novel multi-scaled hybrid orthopedic implant material consisting of a macroporous Ti scaffold, whose macropores' walls have a microporous titania layer which is fully covered with nanofibers of Sr-doped hydroxyapatite (Sr-HA). The microporous titania layer is formed on and within the Ti scaffold by micro-arc oxidation, which firmly binds to the Ti substrate and contains Ca2+, Sr2+ and PO4(3-) ions. It is then hydrothermally treated to form Sr-HA nanofibers. During the hydrothermal treatment, Sr-HA nanoprisms nucleate from Ca0.5Sr0.5TiO3 pre-formed on the TiO2 and grow in length to nanofibers at the expense of Ca2+, Sr2+ and PO4(3-) ions that migrate from the TiO2. These Sr-HA nanofibers construct a network structure similar to the hierarchical organization of bone extracellular matrix (ECM), and the resulting nanofibrous surface displays a firm adhesion to substrate, superhydrophilicity and apatite-inducing ability. The induced apatite prefers to nucleate on the basal-faceted surfaces of Sr-HA nanofibers. The nanofiber-walled scaffold has a great potential for load-bearing orthotopic use.

Ocean manganese nodules as stromatolite with a fractal like-signature

NASA Astrophysics Data System (ADS)

Akai, Junji; Akiyama, Shigeki; Tsuchiyama, Akira; Akai, Kurumi

Deep-sea manganese (Mn) nodules are problematic in terms of factors such as their characteristic form and genesis. There are many reports of bacterial species from manganese nodules. However, the genesis of these nodules has not been fully confirmed. Samples, mainly from the Clarion Clipperton Fracture zone in the Pacific Ocean, were examined by mineralogical methods and X-ray CT. Thin sections of these samples showed columnar stromatolite structures with rhythmic bands. Mineralized bacteria were observed by SEM and TEM. Surface morphology could be described as having a fractal-like nature. The fractal characteristics of spherical to dome-like forms were fundamentally composed of at least four ranks. The 4th order form corresponds to the stromatolite dome top shapes. Similar granular domain units and porous characteristics in manganese nodules were clearly observed by X-ray CT sections. Mathematical simulation based on fractal models reproduced similar morphological characteristics to the natural samples. So, we arrived at the concluding hypothesis that manganese nodules are aggregated stromatolite with fractal-like characteristics. Furthermore, we discussed the possibility that the nature of the layer manganese oxide minerals as the major component of the nodule and associated Fe-oxyhydroxide minerals may become an absorber/scavenger of strategic heavy metals and also toxic metals in the environments.

A multi-scaled hybrid orthopedic implant: bone ECM-shaped Sr-HA nanofibers on the microporous walls of a macroporous titanium scaffold

NASA Astrophysics Data System (ADS)

Han, Yong; Zhou, Jianhong; Zhang, Lan; Xu, Kewei

2011-07-01

We report here, for the first time, a novel multi-scaled hybrid orthopedic implant material consisting of a macroporous Ti scaffold, whose macropores' walls have a microporous titania layer which is fully covered with nanofibers of Sr-doped hydroxyapatite (Sr-HA). The microporous titania layer is formed on and within the Ti scaffold by micro-arc oxidation, which firmly binds to the Ti substrate and contains Ca2 + , Sr2 + and PO43 - ions. It is then hydrothermally treated to form Sr-HA nanofibers. During the hydrothermal treatment, Sr-HA nanoprisms nucleate from Ca0.5Sr0.5TiO3 pre-formed on the TiO2 and grow in length to nanofibers at the expense of Ca2 + , Sr2 + and PO43 - ions that migrate from the TiO2. These Sr-HA nanofibers construct a network structure similar to the hierarchical organization of bone extracellular matrix (ECM), and the resulting nanofibrous surface displays a firm adhesion to substrate, superhydrophilicity and apatite-inducing ability. The induced apatite prefers to nucleate on the basal-faceted surfaces of Sr-HA nanofibers. The nanofiber-walled scaffold has a great potential for load-bearing orthotopic use.

Ultrasonic Al₂O₃ Ceramic Thermometry in High-Temperature Oxidation Environment.

PubMed

Wei, Yanlong; Gao, Yubin; Xiao, Zhaoqian; Wang, Gao; Tian, Miao; Liang, Haijian

2016-11-11

In this study, an ultrasonic temperature measurement system was designed with Al₂O₃ high-temperature ceramic as an acoustic waveguide sensor and preliminarily tested in a high-temperature oxidation environment. The test results indicated that the system can indeed work stably in high-temperature environments. The relationship between the temperature and delay time of 26 °C-1600 °C ceramic materials was also determined in order to fully elucidate the high-temperature oxidation of the proposed waveguide sensor and to lay a foundation for the further application of this system in temperatures as high as 2000 °C.

The Effect of Experimental Hyperthyroidism on Characteristics of Actin-Myosin Interaction in Fast and Slow Skeletal Muscles.

PubMed

Kopylova, G V; Shchepkin, D V; Bershitsky, S Y

2018-05-01

The molecular mechanism of the failure of contractile function of skeletal muscles caused by oxidative damage to myosin in hyperthyroidism is not fully understood. Using an in vitro motility assay, we studied the effect of myosin damage caused by oxidative stress in experimental hyperthyroidism on the actin-myosin interaction and its regulation by calcium. We found that hyperthyroidism-induced oxidation of myosin is accompanied by a decrease in the sliding velocity of the regulated thin filaments in the in vitro motility assay, and this effect is increased with the duration of the pathological process.

Method for heat treating and sintering metal oxides with microwave radiation

DOEpatents

Holcombe, Cressie E.; Dykes, Norman L.; Meek, Thomas T.

1989-01-01

A method for microwave sintering materials, primarily metal oxides, is described. Metal oxides do not normally absorb microwave radiation at temperatures ranging from about room temperature to several hundred degrees centrigrade are sintered with microwave radiation without the use of the heretofore required sintering aids. This sintering is achieved by enclosing a compact of the oxide material in a housing or capsule formed of a oxide which has microwave coupling properties at room temprature up to at least the microwave coupling temperature of the oxide material forming the compact. The heating of the housing effects the initial heating of the oxide material forming the compact by heat transference and then functions as a thermal insulator for the encased oxide material after the oxide material reaches a sufficient temperature to adequately absorb or couple with microwave radiation for heating thereof to sintering temperature.

Precision Assembly of Systems on Surfaces (PASS)

DTIC Science & Technology

2015-02-06

As a result, under other funding we are pursuing applications of this method for the detection of biogenic amines that are indicators of meat ...conductive materials are made from indium tin oxide or fluorinated tin oxide. The latter involves the substitution of a F- for an O-2 and leads to n...generated by spoiling meat . Our fully drawn sensors and ability to fabricate materials on many substrates has assisted us in ongoing experiments directed

Treatment of Anemia in Heart Failure: Potential Risks and Benefits of Intravenous Iron Therapy in Cardiovascular Disease

PubMed Central

Jelani, Qurat-ul-ain; Katz, Stuart D.

2010-01-01

Iron-deficiency anemia is common is patients with heart failure (HF), but the optimum diagnostic tests to detect iron deficiency and the treatment options to replete iron have not been fully characterized. Recent studies in patients with HF indicate that intravenous iron can rapidly replenish iron stores in patients having iron-deficiency anemia, with resultant increased hemoglobin levels and improved functional capacity. Preliminary data from a sub-group analysis also suggests that supplemental intravenous iron therapy can improve functional capacity even in those subjects without anemia. The mechanisms responsible for this observation are not fully characterized, but may be related to beneficial effects of iron supplementation on mitochondrial respiration in skeletal muscle. The long-term safety of using intravenous iron supplementation in HF populations is not known. Iron is a known pro-oxidant factor that can inhibit nitric oxide signaling and irreversibly injury cells. Increased iron stores are associated with vascular endothelial dysfunction and increased risk of coronary heart disease events. Additional clinical trials are needed to more fully characterize the therapeutic potential and safety of intravenous iron in HF patients. PMID:20699672

Wet-cupping removes oxidants and decreases oxidative stress.

PubMed

Tagil, Suleyman Murat; Celik, Huseyin Tugrul; Ciftci, Sefa; Kazanci, Fatmanur Hacievliyagil; Arslan, Muzeyyen; Erdamar, Nazan; Kesik, Yunus; Erdamar, Husamettin; Dane, Senol

2014-12-01

Wet-cupping therapy is one of the oldest known medical techniques. Although it is widely used in various conditions such as acute\\chronic inflammation, infectious diseases, and immune system disorders, its mechanism of action is not fully known. In this study, we investigated the oxidative status as the first step to elucidate possible mechanisms of action of wet cupping. Wet cupping therapy is implemented to 31 healthy volunteers. Venous blood samples and Wet cupping blood samples were taken concurrently. Serum nitricoxide, malondialdehyde levels and activity of superoxide dismutase and myeloperoxidase were measured spectrophotometrically. Wet cupping blood had higher activity of myeloperoxidase, lower activity of superoxide dismutase, higher levels of malondialdehyde and nitricoxide compared to the venous blood. Wet cupping removes oxidants and decreases oxidative stress. Copyright © 2014 Elsevier Ltd. All rights reserved.

A Novel Drug Delivery Vesicle Development to Reverse Neurodegeneration: Analysis of the Interactions among Protein, Graphene Oxide and Liposome

NASA Astrophysics Data System (ADS)

Miraz, Md Alamin

In this study, Liposome was decorated with graphene oxide (GO) to synthesize fully-biocompatible theranostic vesicle that can carry bovine serum albumin (BSA) as a model protein. Graphene oxide has been studied as one of the most promising platforms for promoting the growth and repair of neurons. Our graphene oxide based structure could account for the high efficiency of protein loading and deliver to the damaged neuron cell which can reverse the neurodegeneration associated with Alzheimer's disease. The resultant vesicle exhibited high stability in aqueous solution. We investigated the protein adsorption capacity and protein interaction to carbon-based nanomaterials. The Liposome, graphene oxide and bovine serum albumin (BSA) are all biocompatible and hence will not trigger an immune response in vivo.

Selective Tuning of Elastin-like Polypeptide Properties via Methionine Oxidation.

PubMed

Petitdemange, Rosine; Garanger, Elisabeth; Bataille, Laure; Dieryck, Wilfrid; Bathany, Katell; Garbay, Bertrand; Deming, Timothy J; Lecommandoux, Sébastien

2017-02-13

We have designed and prepared a recombinant elastin-like polypeptide (ELP) containing precisely positioned methionine residues, and performed the selective and complete oxidation of its methionine thioether groups to both sulfoxide and sulfone derivatives. Since these oxidation reactions substantially increase methionine residue polarity, they were found to be a useful means to precisely adjust the temperature responsive behavior of ELPs in aqueous solutions. In particular, lower critical solution temperatures were found to be elevated in oxidized sample solutions, but were not eliminated. These transition temperatures were found to be further tunable by the use of solvents containing different Hofmeister salts. Overall, the ability to selectively and fully oxidize methionine residues in ELPs proved to be a convenient postmodification strategy for tuning their transition temperatures in aqueous media.

Oxidation Resistance, Electrical and Thermal Conductivity, and Spectral Emittance of Fully Dense HfB2 and ZrB2 with SiC, TaSi2, and LaB6 Additives

DTIC Science & Technology

2012-01-26

Resistance , Electrical and Thermal Conductivity, and Spectral Emittance of Fully Dense HfB2 and ZrB2 "With SiC, TaSi2, and LaB6 Additives Sb. GRANT NUMBER... RESISTANCE , ELECTRICAL AND THERMAL CONDUCTIVITY, AND SPECTRAL EMITTANCE OF FULLY DENSE HfB2 AND ZrB2 WITH SiC, TaSi2, AND LaB6 ADDITIVES Air Force Office...thickened regions with dry 220 grit SiC sandpaper so that a low- resistance electrical connection could be achieved. A handheld multimeter was used to measure

Carbothermic reduction and prereduced charge for producing aluminum-silicon alloys

DOEpatents

Stevenson, David T.; Troup, Robert L.

1985-01-01

Disclosed is a method for the carbothermic reduction of aluminum oxide to form an aluminum alloy including producing silicon carbide by heating a first mix of carbon and silicon oxide in a combustion reactor to an elevated temperature sufficient to produce silicon carbide at an accelerated rate, the heating being provided by an in situ combustion with oxygen gas, and then admixing the silicon carbide with carbon and aluminum oxide to form a second mix and heating the second mix in a second reactor to an elevated metal-forming temperature sufficient to produce aluminum-silicon alloy. The prereduction step includes holding aluminum oxide substantially absent from the combustion reactor. The metal-forming step includes feeding silicon oxide in a preferred ratio with silicon carbide.

Spark Plasma Sintering As a Solid-State Recycling Technique: The Case of Aluminum Alloy Scrap Consolidation

PubMed Central

Paraskevas, Dimos; Vanmeensel, Kim; Vleugels, Jef; Dewulf, Wim; Deng, Yelin; Duflou, Joost R.

2014-01-01

Recently, “meltless” recycling techniques have been presented for the light metals category, targeting both energy and material savings by bypassing the final recycling step of remelting. In this context, the use of spark plasma sintering (SPS) is proposed in this paper as a novel solid-state recycling technique. The objective is two-fold: (I) to prove the technical feasibility of this approach; and (II) to characterize the recycled samples. Aluminum (Al) alloy scrap was selected to demonstrate the SPS effectiveness in producing fully-dense samples. For this purpose, Al alloy scrap in the form of machining chips was cold pre-compacted and sintered bellow the solidus temperature at 490 °C, under elevated pressure of 200 MPa. The dynamic scrap compaction, combined with electric current-based joule heating, achieved partial fracture of the stable surface oxides, desorption of the entrapped gases and activated the metallic surfaces, resulting in efficient solid-state chip welding eliminating residual porosity. The microhardness, the texture, the mechanical properties, the microstructure and the density of the recycled specimens have been investigated. An X-ray computed tomography (CT) analysis confirmed the density measurements, revealing a void-less bulk material with homogeneously distributed intermetallic compounds and oxides. The oxide content of the chips incorporated within the recycled material slightly increases its elastic properties. Finally, a thermal distribution simulation of the process in different segments illustrates the improved energy efficiency of this approach. PMID:28788153

Spark Plasma Sintering As a Solid-State Recycling Technique: The Case of Aluminum Alloy Scrap Consolidation.

PubMed

Paraskevas, Dimos; Vanmeensel, Kim; Vleugels, Jef; Dewulf, Wim; Deng, Yelin; Duflou, Joost R

2014-08-06

Recently, "meltless" recycling techniques have been presented for the light metals category, targeting both energy and material savings by bypassing the final recycling step of remelting. In this context, the use of spark plasma sintering (SPS) is proposed in this paper as a novel solid-state recycling technique. The objective is two-fold: (I) to prove the technical feasibility of this approach; and (II) to characterize the recycled samples. Aluminum (Al) alloy scrap was selected to demonstrate the SPS effectiveness in producing fully-dense samples. For this purpose, Al alloy scrap in the form of machining chips was cold pre-compacted and sintered bellow the solidus temperature at 490 °C, under elevated pressure of 200 MPa. The dynamic scrap compaction, combined with electric current-based joule heating, achieved partial fracture of the stable surface oxides, desorption of the entrapped gases and activated the metallic surfaces, resulting in efficient solid-state chip welding eliminating residual porosity. The microhardness, the texture, the mechanical properties, the microstructure and the density of the recycled specimens have been investigated. An X-ray computed tomography (CT) analysis confirmed the density measurements, revealing a void-less bulk material with homogeneously distributed intermetallic compounds and oxides. The oxide content of the chips incorporated within the recycled material slightly increases its elastic properties. Finally, a thermal distribution simulation of the process in different segments illustrates the improved energy efficiency of this approach.

Photocatalytic Oxidation of Isoprene on Hydrated Atmospheric Mineral Dusts

NASA Astrophysics Data System (ADS)

Hoffmann, M. R.; Kameel, F. R.; Colussi, A. J.

2011-12-01

Mineral dust aerosols, an important fraction in the tropospheric aerosol budget, contain transition metal-based semiconductor particles that absorb light and may support diverse chemical transformations. Dust aerosol is primary, mostly originates from deserts, but includes fly ash emitted by power plants, and can be carried over long distances. We propose that such semiconductor particles may produce secondary organic aerosol (SOA) via surface-activated photochemical processes in aqueous media. Isoprene, the most abundant anthropogenic VOC is deemed to be incorporated into SOA by various mechanisms that remain to be fully characterized. We suggest that condensed-phase chemistry, in addition to gas-phase transformations, plays an important role in SOA formation. Isoprene is only slightly soluble in water, but it would react at diffusionally-controlled rates with photochemically generated OH-radicals in aqueous phase to produce more complex, polar compounds via oxidation and polymerization processes. We have found that the similar products are formed in the photolysis of aqueous hydrogen peroxide solutions or titanium dioxide suspensions in the presence of dissolved isoprene, as revealed by HPLC analysis with online high-resolution positive ion electrospray ionization mass spectrometric detection, and 1H and 13C nuclear magnetic resonance spectrometry. In contrast, hematite suspensions display negligible photocatalytic activity toward isoprene oxidation. These results suggest that atmospheric heterogeneous semiconductor photocatalysis of isoprene may play a significant role in global secondary organic aerosol formation under overly dusty conditions. Full product characterization is underway that aims at identifying species that may have adverse health/respiratory effects.

Effect of thin oxide layers incorporated in spin valve structures

NASA Astrophysics Data System (ADS)

Gillies, M. F.; Kuiper, A. E. T.; Leibbrandt, G. W. R.

2001-06-01

The enhancement of the magnetoresistance effect, induced by incorporating nano-oxide layers (NOLs) in a bottom-type spin valve, was studied for various preparation conditions. The effect of a NOL in the Co90Fe10 pinned layer was found to depend critically on the oxygen pressure applied to form the thin oxide film. Pressures over 10-3 Torr O2 yield oxides thicker than about 0.7 nm, which apparently deteriorate the biasing field which exists over the oxide. The magnetoresistance values can further be raised by forming a specular reflecting oxide on top of the sense layer. Promising results were obtained with an Al2O3 capping layer formed in a solid-state oxidation reaction that occurs spontaneously when a thin Al layer is deposited on the oxidized surface of the Co90Fe10 sense layer.

Cyclization Reactions through DDQ-Mediated Vinyl Oxazolidinone Oxidation

PubMed Central

Liu, Lei; Floreancig, Paul E.

2009-01-01

Vinyl oxazolidinones react with DDQ to form α,β-unsaturated acyliminium ions in a new method for forming electrophiles under oxidative conditions. Appended nucleophiles undergo 1,4-addition reactions with these intermediates to form cyclic vinyl oxazolidinones with good levels of diastereocontrol, highlighting a new approach to utilizing oxidative carbon–hydrogen bond functionalization to increase molecular complexity. PMID:19552390

The effects of water vapor on the oxidation behavior of alumina forming austenitic stainless steels

DOE PAGES

Yanar, N. M.; Lutz, B. S.; Garcia-Fresnillo, L.; ...

2015-08-19

The isothermal oxidation behavior of three alumina forming austenitic (AFA) stainless steels with varying composition was studied at 650 and 800 °C in dry air and gases which contained water vapor. The AFA alloys exhibited better oxidation resistance than a “good chromia former” at 650 °C, particularly in H 2O-containing atmospheres by virtue of alumina-scale formation. Although the AFA alloys were more resistant than chromia formers, their oxidation resistance was degraded at 650 °C in the presence of water vapor. In dry air the AFA alloys formed, thin continuous alumina scales, whereas in Ar–4%H 2–3%H 2O the areas of continuousmore » alumina were reduced and Fe oxide-rich nodules and regions of Cr, Mn-rich oxides formed. In some regions internal oxidation of the aluminum occurred in the H 2O-containing gas. The alloy OC8 had slightly better resistance than OC4 or OC5 in this atmosphere. The alumina-forming capability of the AFA alloys decreases with increasing temperature and, at 800 °C, they are borderline alumina formers, even in dry air. The oxidation resistance of all three alloys was degraded at 800 °C in atmospheres, which contained water vapor (Air–10%H 2O, Ar–3%H 2O and Ar–4%H 2–3%H 2O). The areas, which formed continuous alumina, were reduced in these atmospheres and areas of internal oxidation occurred. However, as a result of the borderline alumina-forming capability of the AFA alloys it was not possible to determine which of the H2O-containing atmospheres was more severe or to rank the alloys in terms of their performance. The experimental results indicate that the initial microstructure of the AFA alloys also plays a role in their oxidation performance. Less protective oxides formed at 800 °C when alloy OC8 was equilibrated before exposure rather than being exposed in the as-processed condition. As a result, the reason for this is the presence of different phases in the bulk of the two specimens.« less

The effects of water vapor on the oxidation behavior of alumina forming austenitic stainless steels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yanar, N. M.; Lutz, B. S.; Garcia-Fresnillo, L.

The isothermal oxidation behavior of three alumina forming austenitic (AFA) stainless steels with varying composition was studied at 650 and 800 °C in dry air and gases which contained water vapor. The AFA alloys exhibited better oxidation resistance than a “good chromia former” at 650 °C, particularly in H 2O-containing atmospheres by virtue of alumina-scale formation. Although the AFA alloys were more resistant than chromia formers, their oxidation resistance was degraded at 650 °C in the presence of water vapor. In dry air the AFA alloys formed, thin continuous alumina scales, whereas in Ar–4%H 2–3%H 2O the areas of continuousmore » alumina were reduced and Fe oxide-rich nodules and regions of Cr, Mn-rich oxides formed. In some regions internal oxidation of the aluminum occurred in the H 2O-containing gas. The alloy OC8 had slightly better resistance than OC4 or OC5 in this atmosphere. The alumina-forming capability of the AFA alloys decreases with increasing temperature and, at 800 °C, they are borderline alumina formers, even in dry air. The oxidation resistance of all three alloys was degraded at 800 °C in atmospheres, which contained water vapor (Air–10%H 2O, Ar–3%H 2O and Ar–4%H 2–3%H 2O). The areas, which formed continuous alumina, were reduced in these atmospheres and areas of internal oxidation occurred. However, as a result of the borderline alumina-forming capability of the AFA alloys it was not possible to determine which of the H2O-containing atmospheres was more severe or to rank the alloys in terms of their performance. The experimental results indicate that the initial microstructure of the AFA alloys also plays a role in their oxidation performance. Less protective oxides formed at 800 °C when alloy OC8 was equilibrated before exposure rather than being exposed in the as-processed condition. As a result, the reason for this is the presence of different phases in the bulk of the two specimens.« less

Frozen, Fully-Cooked Products and Botulism--Food Safety Advisory

MedlinePlus

... Administrative Forms Standard Forms Skip Navigation Z7_0Q0619C0JGR010IFST1G5B10H1 Web Content Viewer (JSR 286) Actions ${title} Loading... / Topics / ... Frozen Fully-cooked Products and Botulism Z7_0Q0619C0JGR010IFST1G5B10H3 Web Content Viewer (JSR 286) Actions ${title} Loading... Z7_ ...

Uncoordinated MAC for Adaptive Multi Beam Directional Networks: Analysis and Evaluation

DTIC Science & Technology

2016-08-01

control (MAC) policies for emerging systems that are equipped with fully digital antenna arrays which are capable of adaptive multi-beam directional...Adaptive Beam- forming, Multibeam, Directional Networking, Random Access, Smart Antennas I. INTRODUCTION Fully digital beamforming antenna arrays that...are capable of adaptive multi-beam communications are quickly becoming a reality. These antenna arrays allow users to form multiple simultaneous

Structural Characterization of Ferric Hemoglobins from Three Antarctic Fish Species of the Suborder Notothenioidei

PubMed Central

Vergara, Alessandro; Franzese, Marisa; Merlino, Antonello; Vitagliano, Luigi; Verde, Cinzia; di Prisco, Guido; Lee, H. Caroline; Peisach, Jack; Mazzarella, Lelio

2007-01-01

Spontaneous autoxidation of tetrameric Hbs leads to the formation of Fe (III) forms, whose physiological role is not fully understood. Here we report structural characterization by EPR of the oxidized states of tetrameric Hbs isolated from the Antarctic fish species Trematomus bernacchii, Trematomus newnesi, and Gymnodraco acuticeps, as well as the x-ray crystal structure of oxidized Trematomus bernacchii Hb, redetermined at high resolution. The oxidation of these Hbs leads to formation of states that were not usually detected in previous analyses of tetrameric Hbs. In addition to the commonly found aquo-met and hydroxy-met species, EPR analyses show that two distinct hemichromes coexist at physiological pH, referred to as hemichromes I and II, respectively. Together with the high-resolution crystal structure (1.5 Å) of T. bernacchii and a survey of data available for other heme proteins, hemichrome I was assigned by x-ray crystallography and by EPR as a bis-His complex with a distorted geometry, whereas hemichrome II is a less constrained (cytochrome b5-like) bis-His complex. In four of the five Antartic fish Hbs examined, hemichrome I is the major form. EPR shows that for HbCTn, the amount of hemichrome I is substantially reduced. In addition, the concomitant presence of a penta-coordinated high-spin Fe (III) species, to our knowledge never reported before for a wild-type tetrameric Hb, was detected. A molecular modeling investigation demonstrates that the presence of the bulkier Ile in position 67β in HbCTn in place of Val as in the other four Hbs impairs the formation of hemichrome I, thus favoring the formation of the ferric penta-coordinated species. Altogether the data show that ferric states commonly associated with monomeric and dimeric Hbs are also found in tetrameric Hbs. PMID:17545238

Vitamin C. Biosynthesis, recycling and degradation in mammals.

PubMed

Linster, Carole L; Van Schaftingen, Emile

2007-01-01

Vitamin C, a reducing agent and antioxidant, is a cofactor in reactions catalyzed by Cu(+)-dependent monooxygenases and Fe(2+)-dependent dioxygenases. It is synthesized, in vertebrates having this capacity, from d-glucuronate. The latter is formed through direct hydrolysis of uridine diphosphate (UDP)-glucuronate by enzyme(s) bound to the endoplasmic reticulum membrane, sharing many properties with, and most likely identical to, UDP-glucuronosyltransferases. Non-glucuronidable xenobiotics (aminopyrine, metyrapone, chloretone and others) stimulate the enzymatic hydrolysis of UDP-glucuronate, accounting for their effect to increase vitamin C formation in vivo. Glucuronate is converted to l-gulonate by aldehyde reductase, an enzyme of the aldo-keto reductase superfamily. l-Gulonate is converted to l-gulonolactone by a lactonase identified as SMP30 or regucalcin, whose absence in mice leads to vitamin C deficiency. The last step in the pathway of vitamin C synthesis is the oxidation of l-gulonolactone to l-ascorbic acid by l-gulonolactone oxidase, an enzyme associated with the endoplasmic reticulum membrane and deficient in man, guinea pig and other species due to mutations in its gene. Another fate of glucuronate is its conversion to d-xylulose in a five-step pathway, the pentose pathway, involving identified oxidoreductases and an unknown decarboxylase. Semidehydroascorbate, a major oxidation product of vitamin C, is reconverted to ascorbate in the cytosol by cytochrome b(5) reductase and thioredoxin reductase in reactions involving NADH and NADPH, respectively. Transmembrane electron transfer systems using ascorbate or NADH as electron donors serve to reduce semidehydroascorbate present in neuroendocrine secretory vesicles and in the extracellular medium. Dehydroascorbate, the fully oxidized form of vitamin C, is reduced spontaneously by glutathione, as well as enzymatically in reactions using glutathione or NADPH. The degradation of vitamin C in mammals is initiated by the hydrolysis of dehydroascorbate to 2,3-diketo-l-gulonate, which is spontaneously degraded to oxalate, CO(2) and l-erythrulose. This is at variance with bacteria such as Escherichia coli, which have enzymatic degradation pathways for ascorbate and probably also dehydroascorbate.

Performance characteristics of a nanoscale double-gate reconfigurable array

NASA Astrophysics Data System (ADS)

Beckett, Paul

2008-12-01

The double gate transistor is a promising device applicable to deep sub-micron design due to its inherent resistance to short-channel effects and superior subthreshold performance. Using both TCAD and SPICE circuit simulation, it is shown that the characteristics of fully depleted dual-gate thin-body Schottky barrier silicon transistors will not only uncouple the conflicting requirements of high performance and low standby power in digital logic, but will also allow the development of a locally-connected reconfigurable computing mesh. The magnitude of the threshold shift effect will scale with device dimensions and will remain compatible with oxide reliability constraints. A field-programmable architecture based on the double gate transistor is described in which the operating point of the circuit is biased via one gate while the other gate is used to form the logic array, such that complex heterogeneous computing functions may be developed from this homogeneous, mesh-connected organization.

Very early reaction intermediates detected by microsecond time scale kinetics of cytochrome cd1-catalyzed reduction of nitrite.

PubMed

Sam, Katharine A; Strampraad, Marc J F; de Vries, Simon; Ferguson, Stuart J

2008-10-10

Paracoccus pantotrophus cytochrome cd(1) is a nitrite reductase found in the periplasm of many denitrifying bacteria. It catalyzes the reduction of nitrite to nitric oxide during the denitrification part of the biological nitrogen cycle. Previous studies of early millisecond intermediates in the nitrite reduction reaction have shown, by comparison with pH 7.0, that at the optimum pH, approximately pH 6, the earliest intermediates were lost in the dead time of the instrument. Access to early time points (approximately 100 micros) through use of an ultra-rapid mixing device has identified a spectroscopically novel intermediate, assigned as the Michaelis complex, formed from reaction of fully reduced enzyme with nitrite. Spectroscopic observation of the subsequent transformation of this species has provided data that demand reappraisal of the general belief that the two subunits of the enzyme function independently.

Evaluation of selenium in dietary supplements using elemental speciation.

PubMed

Kubachka, Kevin M; Hanley, Traci; Mantha, Madhavi; Wilson, Robert A; Falconer, Travis M; Kassa, Zena; Oliveira, Aline; Landero, Julio; Caruso, Joseph

2017-03-01

Selenium-enriched dietary supplements containing various selenium compounds are readily available to consumers. To ensure proper selenium intake and consumer confidence, these dietary supplements must be safe and have accurate label claims. Varying properties among selenium species requires information beyond total selenium concentration to fully evaluate health risk/benefits A LC-ICP-MS method was developed and multiple extraction methods were implemented for targeted analysis of common "seleno-amino acids" and related oxidation products, selenate, selenite, and other species relatable to the quality and/or accuracy of the labeled selenium ingredients. Ultimately, a heated water extraction was applied to recover selenium species from non-selenized yeast supplements in capsule, tablet, and liquid forms. For selenized yeast supplements, inorganic selenium was monitored as a means of assessing selenium yeast quality. A variety of commercially available selenium supplements were evaluated and discrepancies between labeled ingredients and detected species were noted. Published by Elsevier Ltd.

Evaluation of selenium in dietary supplements using elemental speciation

PubMed Central

Kubachka, Kevin M.; Hanley, Traci; Mantha, Madhavi; Wilson, Robert A.; Falconer, Travis M.; Kassa, Zena; Oliveira, Aline; Landero, Julio; Caruso, Joseph

2016-01-01

Selenium-enriched dietary supplements containing various selenium compounds are readily available to consumers. To ensure proper selenium intake and consumer confidence, these dietary supplements must be safe and have accurate label claims. Varying properties among selenium species requires information beyond total selenium concentration to fully evaluate health risk/benefits A LC-ICP-MS method was developed and multiple extraction methods were implemented for targeted analysis of common “seleno-amino acids” and related oxidation products, selenate, selenite, and other species relatable to the quality and/or accuracy of the labeled selenium ingredients. Ultimately, a heated water extraction was applied to recover selenium species from non-selenized yeast supplements in capsule, tablet, and liquid forms. For selenized yeast supplements, inorganic selenium was monitored as a means of assessing selenium yeast quality. A variety of commercially available selenium supplements were evaluated and discrepancies between labeled ingredients and detected species were noted. PMID:27719915

‘Umpolung’ Reactivity in Semiaqueous Amide and Peptide Synthesis

PubMed Central

Shen, Bo; Makley, Dawn M.; Johnston, Jeffrey N.

2010-01-01

The amide functional group is one of Nature’s key functional and structural elements, most notably within peptides. Amides are also key intermediates in the preparation of a diverse range of therapeutic small molecules. Its construction using available methods focuses principally upon dehydrative approaches, although oxidative and radical-based methods are representative alternatives. During the carbon-nitrogen bond forming step in most every example, the carbon and nitrogen bear electrophilic and nucleophilic character, respectively. Here we show that activation of amines and nitroalkanes with an electrophilic iodine source in wet THF can lead directly to amide products. Preliminary observations support a mechanistic construct in which reactant polarity is reversed (umpolung) during C-N bond formation relative to traditional approaches. The use of nitroalkanes as acyl anion equivalents provides a conceptually innovative approach to amide and peptide synthesis, and one that might ultimately provide for efficient peptide synthesis that is fully reliant on enantioselective methods. PMID:20577205

Water-Vapor-Mediated Close-Spaced Vapor Transport Growth of Epitaxial Gallium Indium Phosphide Films on Gallium Arsenide Substrates

DOE PAGES

Greenaway, Ann L.; Bachman, Benjamin F.; Boucher, Jason W.; ...

2018-01-12

Ga 1–xIn xP is a technologically important III–V ternary semiconductor widely utilized in commercial and record-efficiency solar cells. We report the growth of Ga 1–xIn xP by water-vapor-mediated close-spaced vapor transport. Because growth of III–V semiconductors in this system is controlled by diffusion of metal oxide species, we find that congruent transport from the mixed powder source requires complete annealing to form a single alloy phase. Growth from a fully alloyed source at water vapor concentrations of ~7000 ppm in H 2 at 850 °C affords smooth films with electron mobility of 1070 cm 2 V –1 s –1 andmore » peak internal quantum efficiency of ~90% for carrier collection in a nonaqueous photoelectrochemical test cell.« less

Proteomic methods for analysis of S-nitrosation⋄

PubMed Central

Kettenhofen, Nicholas; Broniowska, Katarzyna; Keszler, Agnes; Zhang, Yanhong; Hogg, Neil

2007-01-01

This review discusses proteomic methods to detect and identify S-nitrosated proteins. Protein S-nitrosation, the post-translational modification of thiol residues to form S-nitrosothiols, has been suggested to be a mechanism of cellular redox signaling by which nitric oxide can alter cellular function through modification of protein thiol residues. It has become apparent that methods that will detect and identify low levels of S-nitrosated protein in complex protein mixtures are required in order to fully appreciate the range, extent and selectivity of this modification in both physiological and pathological conditions. While many advances have been made in the detection of either total cellular S-nitrosation or individual S-nitrosothiols, proteomic methods for the detection of S-nitrosation are in relative infancy. This review will discuss the major methods that have been used for the proteomic analysis of protein S-nitrosation and discuss the pros and cons of this methodology. PMID:17360249

A hybrid nanomemristor/transistor logic circuit capable of self-programming

PubMed Central

Borghetti, Julien; Li, Zhiyong; Straznicky, Joseph; Li, Xuema; Ohlberg, Douglas A. A.; Wu, Wei; Stewart, Duncan R.; Williams, R. Stanley

2009-01-01

Memristor crossbars were fabricated at 40 nm half-pitch, using nanoimprint lithography on the same substrate with Si metal-oxide-semiconductor field effect transistor (MOS FET) arrays to form fully integrated hybrid memory resistor (memristor)/transistor circuits. The digitally configured memristor crossbars were used to perform logic functions, to serve as a routing fabric for interconnecting the FETs and as the target for storing information. As an illustrative demonstration, the compound Boolean logic operation (A AND B) OR (C AND D) was performed with kilohertz frequency inputs, using resistor-based logic in a memristor crossbar with FET inverter/amplifier outputs. By routing the output signal of a logic operation back onto a target memristor inside the array, the crossbar was conditionally configured by setting the state of a nonvolatile switch. Such conditional programming illuminates the way for a variety of self-programmed logic arrays, and for electronic synaptic computing. PMID:19171903

A hybrid nanomemristor/transistor logic circuit capable of self-programming.

PubMed

Borghetti, Julien; Li, Zhiyong; Straznicky, Joseph; Li, Xuema; Ohlberg, Douglas A A; Wu, Wei; Stewart, Duncan R; Williams, R Stanley

2009-02-10

Memristor crossbars were fabricated at 40 nm half-pitch, using nanoimprint lithography on the same substrate with Si metal-oxide-semiconductor field effect transistor (MOS FET) arrays to form fully integrated hybrid memory resistor (memristor)/transistor circuits. The digitally configured memristor crossbars were used to perform logic functions, to serve as a routing fabric for interconnecting the FETs and as the target for storing information. As an illustrative demonstration, the compound Boolean logic operation (A AND B) OR (C AND D) was performed with kilohertz frequency inputs, using resistor-based logic in a memristor crossbar with FET inverter/amplifier outputs. By routing the output signal of a logic operation back onto a target memristor inside the array, the crossbar was conditionally configured by setting the state of a nonvolatile switch. Such conditional programming illuminates the way for a variety of self-programmed logic arrays, and for electronic synaptic computing.

Tubulin Dimer Reversible Dissociation

PubMed Central

Schuck, Peter; Sackett, Dan L.

2016-01-01

Tubulins are evolutionarily conserved proteins that reversibly polymerize and direct intracellular traffic. Of the tubulin family only αβ-tubulin forms stable dimers. We investigated the monomer-dimer equilibrium of rat brain αβ-tubulin using analytical ultracentrifugation and fluorescence anisotropy, observing tubulin in virtually fully monomeric and dimeric states. Monomeric tubulin was stable for a few hours and exchanged into preformed dimers, demonstrating reversibility of dimer dissociation. Global analysis combining sedimentation velocity and fluorescence anisotropy yielded Kd = 84 (54–123) nm. Dimer dissociation kinetics were measured by analyzing the shape of the sedimentation boundary and by the relaxation of fluorescence anisotropy following rapid dilution of labeled tubulin, yielding koff in the range 10−3–10−2 s−1. Thus, tubulin dimers reversibly dissociate with moderately fast kinetics. Monomer-monomer association is much less sensitive than dimer-dimer association to solution changes (GTP/GDP, urea, and trimethylamine oxide). PMID:26934918

Mitochondrial lipids in neurodegeneration.

PubMed

Aufschnaiter, Andreas; Kohler, Verena; Diessl, Jutta; Peselj, Carlotta; Carmona-Gutierrez, Didac; Keller, Walter; Büttner, Sabrina

2017-01-01

Mitochondrial dysfunction is a common feature of many neurodegenerative diseases, including proteinopathies such as Alzheimer's or Parkinson's disease, which are characterized by the deposition of aggregated proteins in the form of insoluble fibrils or plaques. The distinct molecular processes that eventually result in mitochondrial dysfunction during neurodegeneration are well studied but still not fully understood. However, defects in mitochondrial fission and fusion, mitophagy, oxidative phosphorylation and mitochondrial bioenergetics have been linked to cellular demise. These processes are influenced by the lipid environment within mitochondrial membranes as, besides membrane structure and curvature, recruitment and activity of different proteins also largely depend on the respective lipid composition. Hence, the interaction of neurotoxic proteins with certain lipids and the modification of lipid composition in different cell compartments, in particular mitochondria, decisively impact cell death associated with neurodegeneration. Here, we discuss the relevance of mitochondrial lipids in the pathological alterations that result in neuronal demise, focussing on proteinopathies.

Second generation PMR polyimide/fiber composites

NASA Technical Reports Server (NTRS)

Cavano, P. J.

1979-01-01

A second generation polymerization monomeric reactants (PMR) polyimdes matrix system (PMR 2) was characterized in both neat resin and composite form with two different graphite fiber reinforcements. Three different formulated molecular weight levels of laboratory prepared PMR 2 were examined, in addition to a purchased experimental fully formulated PMR 2 precurser solution. Isothermal aging of graphite fibers, neat resin samples and composite specimens in air at 316 C were investigated. Humidity exposures at 65 C and 97 percent relative humidity were conducted for both neat resin and composites for eight day periods. Anaerobic char of neat resin and fire testing of composites were conducted with PMR 15, PMR 2, and an epoxy system. Composites were fire tested on a burner rig developed for this program. Results indicate that neat PMR 2 resins exhibit excellent isothermal resistance and that PMR 2 composite properties appear to be influenced by the thermo-oxidative stability of the reinforcing fiber.

Annulated Dialkoxybenzenes as Catholyte Materials for Non-aqueous Redox Flow Batteries: Achieving High Chemical Stability through Bicyclic Substitution

DOE PAGES

Zhang, Jingjing; Yang, Zheng; Shkrob, Ilya A.; ...

2017-07-21

1,4-Dimethoxybenzene derivatives are materials of choice for use as catholytes in nonaqueous redox flow batteries, as they exhibit high open-circuit potentials and excellent electrochemical reversibility. However, chemical stability of these materials in their oxidized form needs to be improved. Disubstitution in the arene ring is used to suppress parasitic reactions of their radical cations, but this does not fully prevent ring-addition reactions. By incorporating bicyclic substitutions and ether chains into the dialkoxybenzenes, a novel catholyte molecule, 9,10-bis(2-methoxyethoxy)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanenoanthracene (BODMA), is obtained and exhibits greater solubility and superior chemical stability in the charged state. As a result, a hybrid flow cell containingmore » BODMA is operated for 150 charge–discharge cycles with minimal loss of capacity.« less

Water-Vapor-Mediated Close-Spaced Vapor Transport Growth of Epitaxial Gallium Indium Phosphide Films on Gallium Arsenide Substrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenaway, Ann L.; Bachman, Benjamin F.; Boucher, Jason W.

Ga 1–xIn xP is a technologically important III–V ternary semiconductor widely utilized in commercial and record-efficiency solar cells. We report the growth of Ga 1–xIn xP by water-vapor-mediated close-spaced vapor transport. Because growth of III–V semiconductors in this system is controlled by diffusion of metal oxide species, we find that congruent transport from the mixed powder source requires complete annealing to form a single alloy phase. Growth from a fully alloyed source at water vapor concentrations of ~7000 ppm in H 2 at 850 °C affords smooth films with electron mobility of 1070 cm 2 V –1 s –1 andmore » peak internal quantum efficiency of ~90% for carrier collection in a nonaqueous photoelectrochemical test cell.« less

[Synthesis and biological activity of substance P analogs].

PubMed

Liu, S Y; Zhong, M N; Dong, Y X; Li, Y L; Yuan, X M

1997-12-01

Substance P (SP) and its three analogs were synthesized through solid-phase procedure. The fully-protected peptide-resin was cleaved with anhydrous HF.--SH of Cys in [Cys5,9] SP(4-11) was protected with Acm, then deprotected through Iodine oxidation method, the disulfide bridge cyclization was formed subsequently. The crude product was purified on C18 RP-HPLC. The results of guinea-pig isolated ileum test (GPI) showed that the potency of the analogs was as follows: [AcGln5, Pro9] SP(5-11) > SP > SP(4-11) > [Cys5,9] SP(4-11). They induced GPI to contract very fast and showed the characteristics of tachykinin. On the writing test in mice, the results showed: [Cys5,9] SP(4-11) > SP > SP(4-11) > [AcGln5, Pro9] SP(5-11). The biological tests showed that the SP analogs have some extent of selectivity.

More rapid polar ozone depletion through the reaction of HOCl with HCl on polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Prather, Michael J.

1992-01-01

The direct reaction of HOCl with HCl is shown here to play a critical part in polar ozone loss. Observations of high levels of OClO and ClO in the springtime Antarctic stratosphere confirm that most of the available chlorine is in the form of ClO(x). But current photochemical models have difficulty converting HCl to ClO(x) rapidly enough in early spring to account fully for the observations. Here, a chemical model is used to show that the direct reaction of HOCl with HCl provides the missing mechanism. As alternative sources of nitrogen-containing oxidants have been converted in the late autumn to inactive HNO3 by known reactions on the sulfate layer aerosols, the reaction of HOCl with HCl on polar stratospheric clouds becomes the most important pathway for releasing that stratospheric chlorine which goes into polar night as HCl.

Properties of zinc tin oxide thin film by aerosol assisted chemical vapor deposition (AACVD)

NASA Astrophysics Data System (ADS)

Riza, Muhammad Arif; Rahman, Abu Bakar Abd; Sepeai, Suhaila; Ludin, Norasikin Ahmad; Teridi, Mohd Asri Mat; Ibrahim, Mohd Adib

2018-05-01

This study focuses on the properties of ZTO which have been deposited by a low-cost method namely aerosol assisted chemical vapor deposition (AACVD). The precursors used in this method were zinc acetate dihidrate and tin chloride dihydrate for ZTO thin film deposition. Both precursors were mixed and stirred until fully dissolved before deposition. The ZTO was deposited on borosilicate glass substrate for the investigation of optical properties. The films deposited have passed the scotch tape adherence test. XRD revealed that the crystal ZTO is slightly in the form of perovskite structure but several deteriorations were also seen in the spectrum. The UV-Vis analysis showed high transmittance of ˜85% and the band gap was calculated to be 3.85 eV. The average thickness of the film is around 284 nm. The results showed that the ZTO thin films have been successfully deposited by the utilization of AACVD method.

NADPH Oxidase Activation Contributes to Heavy Ion Irradiation–Induced Cell Death

PubMed Central

Wang, Yupei; Liu, Qing; Zhao, Weiping; Zhou, Xin; Miao, Guoying; Sun, Chao

2017-01-01

Increased oxidative stress plays an important role in heavy ion radiation–induced cell death. The mechanism involved in the generation of elevated reactive oxygen species (ROS) is not fully illustrated. Here we show that NADPH oxidase activation is closely related to heavy ion radiation–induced cell death via excessive ROS generation. Cell death and cellular ROS can be greatly reduced in irradiated cancer cells with the preincubation of diphenyleneiodium, an inhibitor of NADPH oxidase. Most of the NADPH oxidase (NOX) family proteins (NOX1, NOX2, NOX3, NOX4, and NOX5) showed increased expression after heavy ion irradiation. Meanwhile, the cytoplasmic subunit p47phox was translocated to the cell membrane and localized with NOX2 to form reactive NADPH oxidase. Our data suggest for the first time that ROS generation, as mediated by NADPH oxidase activation, could be an important contributor to heavy ion irradiation–induced cell death. PMID:28473742

Oxide strengthened molybdenum-rhenium alloy

DOEpatents

Bianco, Robert; Buckman, Jr., R. William

2000-01-01

Provided is a method of making an ODS molybdenum-rhenium alloy which includes the steps of: (a) forming a slurry containing molybdenum oxide and a metal salt dispersed in an aqueous medium, the metal salt being selected from nitrates or acetates of lanthanum, cerium or thorium; (b) heating the slurry in the presence of hydrogen to form a molybdenum powder comprising molybdenum and an oxide of the metal salt; (c) mixing rhenium powder with the molybdenum powder to form a molybdenum-rhenium powder; (d) pressing the molybdenum-rhenium powder to form a molybdenum-rhenium compact; (e) sintering the molybdenum-rhenium compact in hydrogen or under a vacuum to form a molybdenum-rhenium ingot; and (f) compacting the molybdenum-rhenium ingot to reduce the cross-sectional area of the molybdenum-rhenium ingot and form a molybdenum-rhenium alloy containing said metal oxide. The present invention also provides an ODS molybdenum-rhenium alloy made by the method. A preferred Mo--Re-ODS alloy contains 7-14 weight % rhenium and 2-4 volume % lanthanum oxide.

Method of separating short half-life radionuclides from a mixture of radionuclides

DOEpatents

Bray, Lane A.; Ryan, Jack L.

1999-01-01

The present invention is a method of removing an impurity of plutonium, lead or a combination thereof from a mixture of radionuclides that contains the impurity and at least one parent radionuclide. The method has the steps of (a) insuring that the mixture is a hydrochloric acid mixture; (b) oxidizing the acidic mixture and specifically oxidizing the impurity to its highest oxidation state; and (c) passing the oxidized mixture through a chloride form anion exchange column whereupon the oxidized impurity absorbs to the chloride form anion exchange column and the 22.sup.9 Th or 2.sup.27 Ac "cow" radionuclide passes through the chloride form anion exchange column. The plutonium is removed for the purpose of obtaining other alpha emitting radionuclides in a highly purified form suitable for medical therapy. In addition to plutonium; lead, iron, cobalt, copper, uranium, and other metallic cations that form chloride anionic complexes that may be present in the mixture; are removed from the mixture on the chloride form anion exchange column.

Method of separating short half-life radionuclides from a mixture of radionuclides

DOEpatents

Bray, L.A.; Ryan, J.L.

1999-03-23

The present invention is a method of removing an impurity of plutonium, lead or a combination thereof from a mixture of radionuclides that contains the impurity and at least one parent radionuclide. The method has the steps of (a) insuring that the mixture is a hydrochloric acid mixture; (b) oxidizing the acidic mixture and specifically oxidizing the impurity to its highest oxidation state; and (c) passing the oxidized mixture through a chloride form anion exchange column whereupon the oxidized impurity absorbs to the chloride form anion exchange column and the {sup 229}Th or {sup 227}Ac ``cow`` radionuclide passes through the chloride form anion exchange column. The plutonium is removed for the purpose of obtaining other alpha emitting radionuclides in a highly purified form suitable for medical therapy. In addition to plutonium, lead, iron, cobalt, copper, uranium, and other metallic cations that form chloride anionic complexes that may be present in the mixture are removed from the mixture on the chloride form anion exchange column. 8 figs.

Thermodynamic Analysis of Oxygen-Enriched Direct Smelting of Jamesonite Concentrate

NASA Astrophysics Data System (ADS)

Zhang, Zhong-Tang; Dai, Xi; Zhang, Wen-Hai

2017-12-01

Thermodynamic analysis of oxygen-enriched direct smelting of jamesonite concentrate is reported in this article. First, the occurrence state of lead, antimony and other metallic elements in the smelting process was investigated theoretically. Then, the verification test was carried out. The results indicate that lead and antimony mainly exist in the alloy in the form of metallic lead and metallic antimony. Simultaneously, lead and antimony were also oxidized into the slag in the form of lead-antimony oxide. Iron and copper could be oxidized into the slag in the form of oxides in addition to combining with antimony in the alloy, while zinc was mainly oxidized into the slag in the form of zinc oxide. The verification test indicates that the main phases in the alloy contain metallic lead, metallic antimony and a small amount of Cu2Sb, FeSb2 intermetallic compounds, and the slag is mainly composed of kirschsteinite, fayalite and zinc oxide, in agreement with the thermodynamic analysis.

The Cross-Sectional Investigation of Oxide Scale FeCr Alloys and Commercial Ferritic Steel Implanted with Lanthanum and Titanium Dopants after Oxidation Test at 900°C

NASA Astrophysics Data System (ADS)

Saryanto, Hendi; Sebayang, Darwin; Untoro, Pudji; Sujitno, Tjipto

2018-03-01

The cross-sectional examinations of oxide scales formed by oxidation on the surface of FeCr alloys and Ferritic Steel that implanted with lanthanum and titanium dopants were observed and investigated. Scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS) has been used to study the cross-sectional oxides produced by specimens after oxidation process. X-ray diffraction (XRD) analysis was used to strengthen the analysis of the oxide scale morphology, oxide phases and oxidation products. Cross-sectional observations show the effectiveness of La implantation for improving thinner and stronger scale/substrate interface during oxidation process. The result shows that the thickness of oxide scales formed on the surface of La implanted FeCr alloy and ferritic steel was found less than 3 μm and 300 μm, respectively. The oxide scale formed on the surface of La implanted specimens consisted roughly of Cr2O3 with a small amount of FeO mixture, which indicates that lanthanum implantation can improve the adherence, reduce the growth of the oxide scale as well as reduce the Cr evaporation. On the other side, the oxide scale formed on the surface of FeCr alloys and ferritic steel that implanted with titanium dopant was thicker, indicating that significant increase in oxidation mass gain. It can be noticed that titanium implantation ineffectively promotes Cr rich oxide. At the same time, the amount of Fe increased and diffused outwards, which caused the formation and rapid growth of FeO.

Effects of nitric oxide on neuromuscular properties of developing zebrafish embryos.

PubMed

Jay, Michael; Bradley, Sophie; McDearmid, Jonathan Robert

2014-01-01

Nitric oxide is a bioactive signalling molecule that is known to affect a wide range of neurodevelopmental processes. However, its functional relevance to neuromuscular development is not fully understood. Here we have examined developmental roles of nitric oxide during formation and maturation of neuromuscular contacts in zebrafish. Using histochemical approaches we show that elevating nitric oxide levels reduces the number of neuromuscular synapses within the axial swimming muscles whilst inhibition of nitric oxide biosynthesis has the opposite effect. We further show that nitric oxide signalling does not change synapse density, suggesting that the observed effects are a consequence of previously reported changes in motor axon branch formation. Moreover, we have used in vivo patch clamp electrophysiology to examine the effects of nitric oxide on physiological maturation of zebrafish neuromuscular junctions. We show that developmental exposure to nitric oxide affects the kinetics of spontaneous miniature end plate currents and impacts the neuromuscular drive for locomotion. Taken together, our findings implicate nitrergic signalling in the regulation of zebrafish neuromuscular development and locomotor maturation.

Method of forming supported doped palladium containing oxidation catalysts

DOEpatents

Mohajeri, Nahid

2014-04-22

A method of forming a supported oxidation catalyst includes providing a support comprising a metal oxide or a metal salt, and depositing first palladium compound particles and second precious metal group (PMG) metal particles on the support while in a liquid phase including at least one solvent to form mixed metal comprising particles on the support. The PMG metal is not palladium. The mixed metal particles on the support are separated from the liquid phase to provide the supported oxidation catalyst.

Alloy composition effects on oxidation products of VIA, B-1900, 713C, and 738X: A high temperature diffractometer study

NASA Technical Reports Server (NTRS)

Garlick, R. G.; Lowell, C.

1973-01-01

High temperature X-ray diffraction studies were performed to investigate isothermal and cyclic oxidation at 1000 and 1100 C of the nickel-base superalloys VIA, B-1900, 713C, and 738X. Oxidation was complex. The major oxides, Al2O3, Cr2O3, and the spinels, formed in amounts consistent with alloy chemistry. The alloys VIA and B-1900 (high Al, low Cr alloys) tended to form Al2O3 and NiAl2O4; 738X (high Cr, low Al) formed Cr2O3 and NiCr2O4. A NiTa2O6 type of oxide formed in amounts approximately proportional to the refractory metal content of the alloy. One of the effects of cycling was to increase the amount of spinels formed.

On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions.

PubMed

Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch; Ziegelbauer, Joseph M; Luski, Shalom; Aurbach, Doron; Halalay, Ion C

2017-02-08

We demonstrate herein that Mn 3+ and not Mn 2+ , as commonly accepted, is the dominant dissolved manganese cation in LiPF 6 -based electrolyte solutions of Li-ion batteries with lithium manganate spinel positive and graphite negative electrodes chemistry. The Mn 3+ fractions in solution, derived from a combined analysis of electron paramagnetic resonance and inductively coupled plasma spectroscopy data, are ∼80% for either fully discharged (3.0 V hold) or fully charged (4.2 V hold) cells, and ∼60% for galvanostatically cycled cells. These findings agree with the average oxidation state of dissolved Mn ions determined from X-ray absorption near-edge spectroscopy data, as verified through a speciation diagram analysis. We also show that the fractions of Mn 3+ in the aprotic nonaqueous electrolyte solution are constant over the duration of our experiments and that disproportionation of Mn 3+ occurs at a very slow rate.

Fully printable transparent monolithic solid-state dye-sensitized solar cell with mesoscopic indium tin oxide counter electrode.

PubMed

Yang, Ying; Ri, Kwangho; Rong, Yaoguang; Liu, Linfeng; Liu, Tongfa; Hu, Min; Li, Xiong; Han, Hongwei

2014-09-07

We present a new transparent monolithic mesoscopic solid-state dye-sensitized solar cell based on trilamellar films of mesoscopic TiO2 nanocrystalline photoanode, a ZrO2 insulating layer and an indium tin oxide counter electrode (ITO-CE), which were screen-printed layer by layer on a single substrate. When the thickness of the ITO-CE was optimized to 2.1 μm, this very simple and fully printable solid-state DSSC with D102 dye and spiro-OMeTAD hole transport materials presents efficiencies of 1.73% when irradiated from the front side and 1.06% when irradiated from the rear side under a standard simulated sunlight condition (AM 1.5 Global, 100 mW cm(-2)). Higher parameters could be expected with a better transparent mesoscopic counter electrode and hole conductor for the printable monolithic mesoscopic solid-state DSSC.

Materials for advanced turbine engines. Volume 1: Advanced blade tip seal system

NASA Technical Reports Server (NTRS)

Zelahy, J. W.; Fairbanks, N. P.

1982-01-01

Project 3, the subject of this technical report, was structured toward the successful engine demonstration of an improved-efficiency, long-life, tip-seal system for turbine blades. The advanced tip-seal system was designed to maintain close operating clearances between turbine blade tips and turbine shrouds and, at the same time, be resistant to environmental effects including high-temperature oxidation, hot corrosion, and thermal cycling. The turbine blade tip comprised an environmentally resistant, activated-diffussion-bonded, monocrystal superalloy combined with a thin layer of aluminium oxide abrasive particles entrapped in an electroplated NiCr matrix. The project established the tip design and joint location, characterized the single-crystal tip alloy and abrasive tip treatment, and established the manufacturing and quality-control plans required to fully process the blades. A total of 171 blades were fully manufactured, and 100 were endurance and performance engine-tested.

Charge localization and ordering in A 2 Mn 8 O 16 hollandite group oxides: Impact of density functional theory approaches

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaltak, Merzuk; Fernandez-Serra, Marivi; Hybertsen, Mark S.

The phases of A 2Mn 8O 16 hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in density functional theory. Three examples (A = Ag, Li, and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn 3d electrons are more explicitly considered with the DFT + Umore » approach. Finally, selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low-U and a high-U approach. In the low-U case, the materials are described as band metals with a high-symmetry, tetragonal crystal structure. In the high-U case, the electrons donated by A result in formation of local Mn 3+ centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low-temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. Lastly, while competing effects in the local magnetic coupling are subtle, the fully anisotropic implementation of DFT + U gives the best overall agreement with results from the hybrid functional.« less

A Novel Biomolecule-Mediated Reduction of Graphene Oxide: A Multifunctional Anti-Cancer Agent.

PubMed

Choi, Yun-Jung; Kim, Eunsu; Han, JaeWoong; Kim, Jin-Hoi; Gurunathan, Sangiliyandi

2016-03-18

Graphene oxide (GO) is a monolayer of carbon atoms that form a dense honeycomb structure, consisting of hydroxyl and epoxide functional groups on the two accessible sides and carboxylic groups at the edges. In contrast, graphene is a two-dimensional sheet of sp2-hybridized carbon atoms packed into a honeycomb lattice. Graphene has great potential for use in biomedical applications due to its excellent physical and chemical properties. In this study, we report a facile and environmentally friendly approach for the synthesis of reduced graphene oxide (rGO) using uric acid (UA). The synthesized uric acid-reduced graphene oxide (UA-rGO) was fully characterized by ultraviolet-visible (UV-Vis) absorption spectra, X-ray diffraction (XRD), dynamic light scattering (DLS), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and Raman spectroscopy. GO and UA-rGO induced a dose-dependent decrease in cell viability and induced cytotoxicity in human ovarian cancer cells. The results from this study suggest that UA-rGO could cause apoptosis in mammalian cells. The toxicity of UA-rGO is significantly higher than GO. Based on our findings, UA-rGO shows cytotoxic effects against human ovarian cancer cells, and its synthesis is environmentally friendly. UA-rGO significantly inhibits cell viability by increasing lactate dehydrogenase (LDH) release, reactive oxygen species (ROS) generation, activation of caspase-3, and DNA fragmentation. This is the first report to describe the comprehensive effects of UA-rGO in ovarian cancer cells. We believe that the functional aspects of newly synthesized UA-rGO will provide advances towards various biomedical applications in the near future.

Interactive Physics and Characteristics of Photons and Photoelectrons in Hyperbranched Zinc Oxide Nanostructures

NASA Astrophysics Data System (ADS)

Torix, Garrett

As is commonly known, the world is full of technological wonders, where a multitude of electronic devices and instruments continuously help push the boundaries of scientific knowledge and discovery. These new devices and instruments of science must be utilized at peak efficiency in order to benefit humanity with the most advanced scientific knowledge. In order to attain this level of efficiency, the materials which make up these electronics, or possibly more important, the fundamental characteristics of these materials, must be fully understood. The following research attempted to uncover the properties and characteristics of a selected family of materials. Herein, zinc oxide (ZnO) nanomaterials were investigated and subjected to various, systematical tests, with the aim of discovering new and useful properties. The various nanostructures were grown on a quartz substrate, between a pair of gold electrodes, and subjected to an electrical bias which produced a measurable photocurrent under sufficient lighting conditions. This design formed a novel photodetector device, which, when combined with a simple solar cell and a methodical set of experimental trials, allowed several unique phenomena to be studied. Under various conditions, the device photocurrent as a function of applied voltage, as well as transmitted light, were measured and compared between devices of different ZnO morphologies. Zinc oxide is an absorber of ultraviolet (UV) light. UV absorbing materials and devices have uses in solar cells, long range communications, and astronomical observational equipment, hence, a better understanding of zinc oxide nanostructures and their properties can lead to more efficient utilization of UV light, improved solar cell technology, and a better understanding of the basic science in photon-to-electricity conversion.

Charge localization and ordering in A 2 Mn 8 O 16 hollandite group oxides: Impact of density functional theory approaches

DOE PAGES

Kaltak, Merzuk; Fernandez-Serra, Marivi; Hybertsen, Mark S.

2017-12-01

The phases of A 2Mn 8O 16 hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in density functional theory. Three examples (A = Ag, Li, and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn 3d electrons are more explicitly considered with the DFT + Umore » approach. Finally, selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low-U and a high-U approach. In the low-U case, the materials are described as band metals with a high-symmetry, tetragonal crystal structure. In the high-U case, the electrons donated by A result in formation of local Mn 3+ centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low-temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. Lastly, while competing effects in the local magnetic coupling are subtle, the fully anisotropic implementation of DFT + U gives the best overall agreement with results from the hybrid functional.« less

Water-dispersible sugar-coated iron oxide nanoparticles. An evaluation of their relaxometric and magnetic hyperthermia properties.

PubMed

Lartigue, Lenaic; Innocenti, Claudia; Kalaivani, Thangavel; Awwad, Azzam; Sanchez Duque, Maria del Mar; Guari, Yannick; Larionova, Joulia; Guérin, Christian; Montero, Jean-Louis Georges; Barragan-Montero, Véronique; Arosio, Paolo; Lascialfari, Alessandro; Gatteschi, Dante; Sangregorio, Claudio

2011-07-13

Synthesis of functionalized magnetic nanoparticles (NPs) for biomedical applications represents a current challenge. In this paper we present the synthesis and characterization of water-dispersible sugar-coated iron oxide NPs specifically designed as magnetic fluid hyperthermia heat mediators and negative contrast agents for magnetic resonance imaging. In particular, the influence of the inorganic core size was investigated. To this end, iron oxide NPs with average size in the range of 4-35 nm were prepared by thermal decomposition of molecular precursors and then coated with organic ligands bearing a phosphonate group on one side and rhamnose, mannose, or ribose moieties on the other side. In this way a strong anchorage of the organic ligand on the inorganic surface was simply realized by ligand exchange, due to covalent bonding between the Fe(3+) atom and the phosphonate group. These synthesized nanoobjects can be fully dispersed in water forming colloids that are stable over very long periods. Mannose, ribose, and rhamnose were chosen to test the versatility of the method and also because these carbohydrates, in particular rhamnose, which is a substrate of skin lectin, confer targeting properties to the nanosystems. The magnetic, hyperthermal, and relaxometric properties of all the synthesized samples were investigated. Iron oxide NPs of ca. 16-18 nm were found to represent an efficient bifunctional targeting system for theranostic applications, as they have very good transverse relaxivity (three times larger than the best currently available commercial products) and large heat release upon application of radio frequency (RF) electromagnetic radiation with amplitude and frequency close to the human tolerance limit. The results have been rationalized on the basis of the magnetic properties of the investigated samples.

Charge localization and ordering in A2Mn8O16 hollandite group oxides: Impact of density functional theory approaches

NASA Astrophysics Data System (ADS)

Kaltak, Merzuk; Fernández-Serra, Marivi; Hybertsen, Mark S.

2017-12-01

The phases of A2Mn8O16 hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in density functional theory. Three examples (A = Ag, Li, and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn 3 d electrons are more explicitly considered with the DFT + U approach. Finally, selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low-U and a high-U approach. In the low-U case, the materials are described as band metals with a high-symmetry, tetragonal crystal structure. In the high-U case, the electrons donated by A result in formation of local Mn3 + centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low-temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. Finally, while competing effects in the local magnetic coupling are subtle, the fully anisotropic implementation of DFT + U gives the best overall agreement with results from the hybrid functional.

Nickel oxide nanoparticles film produced by dead biomass of filamentous fungus

PubMed Central

Salvadori, Marcia Regina; Nascimento, Cláudio Augusto Oller; Corrêa, Benedito

2014-01-01

The synthesis of nickel oxide nanoparticles in film form using dead biomass of the filamentous fungus Aspergillus aculeatus as reducing agent represents an environmentally friendly nanotechnological innovation. The optimal conditions and the capacity of dead biomass to uptake and produce nanoparticles were evaluated by analyzing the biosorption of nickel by the fungus. The structural characteristics of the film-forming nickel oxide nanoparticles were analyzed by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). These techniques showed that the nickel oxide nanoparticles had a size of about 5.89 nm and were involved in a protein matrix which probably permitted their organization in film form. The production and uptake of nickel oxide nanoparticles organized in film form by dead fungal biomass bring us closer to sustainable strategies for the biosynthesis of metal oxide nanoparticles. PMID:25228324

Role of Al in Zn bath on the formation of the inhibition layer during hot-dip galvanizing for a 1.2Si-1.5Mn transformation-induced plasticity steel

NASA Astrophysics Data System (ADS)

Wang, Kuang-Kuo; Hsu, Chiung-Wen; Chang, Liuwen; Gan, Dershin; Yang, Kuo-Cheng

2013-11-01

This study investigated the interaction between the Al in the Zn bath and the surface oxides formed by selective oxidation on a 1.2Si-1.5Mn TRIP steel during hot-dip galvanizing. XPS and TEM were employed for characterization. The results indicated that the amorphous xMnO·SiO2 oxide could react with Al to form a Si-Mn-Al-containing oxide. The crystalline MnSiO3 and Mn2SiO4 oxides could be largely reduced by Al to form holes in the oxide film. Consequently, the steel covered by a layer of mixed xMnO·SiO2 and MnSiO3 could form a continuous Fe2Al5 inhibition layer and showed the highest galvanizability among the three samples examined.

About structural phase state of coating based on zirconium oxide formed by microplasma oxidation method

NASA Astrophysics Data System (ADS)

Gubaidulina, Tatiana A.; Sergeev, Viktor P.; Kuzmin, Oleg S.; Fedorischeva, Marina V.; Kalashnikov, Mark P.

2017-12-01

The oxide-ceramic coating based of zirconium oxide is formed by the method of microplasma oxidation. The producing modes of the oxide layers on E110 zirconium alloy are under testing. It was found that using microplasma treatment of E110 zirconium in aluminosilicate electrolyte makes possible the formation of porous oxide-ceramic coatings based on zirconium alloyed by aluminum and niobium. The study is focused on the modes how to form heat-shielding coatings with controlled porosity and minimal amount of microcracks. The structural-phase state of the coating is studied by X-ray diffraction analysis and scanning electron microscopy (SEM). It was found that the ratio of the monoclinic and tetragonal phases changes with the change occurring in the coating formation modes.

Evaluation of Pterin, a Promising Drug Candidate from Cyanide Degrading Bacteria.

PubMed

Mahendran, Ramasamy; Thandeeswaran, Murugesan; Kiran, Gopikrishnan; Arulkumar, Mani; Ayub Nawaz, K A; Jabastin, Jayamanoharan; Janani, Balraj; Anto Thomas, Thomas; Angayarkanni, Jayaraman

2018-06-01

Pterin is a member of the compounds known as pteridines. They have the same nucleus of 2-amino-4-hydroxypteridine (pterin); however, the side-chain is different at the position 6, and the state of oxidation of the ring may exist in different form viz. tetrahydro, dihydro, or a fully oxidized form. In the present study, the microorganisms able to utilize cyanide, and heavy metals have been tested for the efficient production of pterin compound. The soil samples contaminated with cyanide and heavy metals were collected from Salem steel industries, Tamil Nadu, India. Out of 77 isolated strains, 40 isolates were found to utilize sodium cyanate as nitrogen source at different concentrations. However, only 13 isolates were able to tolerate maximum concentration (60 mM) of sodium cyanate and were screened for pterin production. Among the 13 isolates, only 1 organism showed maximum production of pterin, and the same was identified as Bacillus pumilus SVD06. The compound was extracted and purified by preparative high-performance liquid chromatography and analyzed by UV/visible, FTIR, and fluorescent spectrum. The antioxidant property of the purified pterin compound was determined by cyclic voltammetry. In addition, antimicrobial activity of pterin was also studied which was substantiated by antagonistic activity against Escherichia coli, and Pseudomonas aeruginosa. Besides that the pterin compound was proved to inhibit the formation of biofilm. The extracted pterin compounds could be proposed further not only for antioxidant and antimicrobial but also for its potency to aid as anticancer and psychotic drugs in future.

Structural Evolution of a Ni Alloy Surface During High-Temperature Oxidation

DOE PAGES

Oleksak, Richard P.; Carney, Casey S.; Holcomb, Gordon R.; ...

2017-11-20

We show that considerable structural transformations occur at a Ni alloy surface during the transient stages of high-temperature oxidation. This was demonstrated by exposing the alloy to high-temperature CO 2 for short times at both atmospheric and supercritical pressures. A protective Cr-rich oxide layer formed after only 5 min at 700 °C and persisted for longer exposures up to 500 h. Voids formed and grew over time by the condensation of metal vacancies generated during oxidation, while the alloy surface recrystallized after sufficient oxidation had occurred. The oxygen potential established at the oxide/alloy interface led to oxidation along the newlymore » formed grain boundaries as well as adjacent to and inside of the voids. Al, the most stable oxide-former and present at low concentration in the alloy, was preferentially oxidized in these regions. Furthermore, the results provide an improved understanding of the internal oxidation of Al and its role in enhancing scale adhesion for this class of Ni alloys.« less

Morphology and electronic structure of the oxide shell on the surface of iron nanoparticles.

PubMed

Wang, Chongmin; Baer, Donald R; Amonette, James E; Engelhard, Mark H; Antony, Jiji; Qiang, You

2009-07-01

An iron (Fe) nanoparticle exposed to air at room temperature will be instantly covered by an oxide shell that is typically approximately 3 nm thick. The nature of this native oxide shell, in combination with the underlying Fe(0) core, determines the physical and chemical behavior of the core-shell nanoparticle. One of the challenges of characterizing core-shell nanoparticles is determining the structure of the oxide shell, that is, whether it is FeO, Fe(3)O(4), gamma-Fe(2)O(3), alpha-Fe(2)O(3), or something else. The results of prior characterization efforts, which have mostly used X-ray diffraction and spectroscopy, electron diffraction, and transmission electron microscopic imaging, have been framed in terms of one of the known Fe-oxide structures, although it is not necessarily true that the thin layer of Fe oxide is a known Fe oxide. In this Article, we probe the structure of the oxide shell on Fe nanoparticles using electron energy loss spectroscopy (EELS) at the oxygen (O) K-edge with a spatial resolution of several nanometers (i.e., less than that of an individual particle). We studied two types of representative particles: small particles that are fully oxidized (no Fe(0) core) and larger core-shell particles that possess an Fe core. We found that O K-edge spectra collected for the oxide shell in nanoparticles show distinct differences from those of known Fe oxides. Typically, the prepeak of the spectra collected on both the core-shell and the fully oxidized particles is weaker than that collected on standard Fe(3)O(4). Given the fact that the origin of this prepeak corresponds to the transition of the O 1s electron to the unoccupied state of O 2p hybridized with Fe 3d, a weak pre-edge peak indicates a combination of the following four factors: a higher degree of occupancy of the Fe 3d orbital; a longer Fe-O bond length; a decreased covalency of the Fe-O bond; and a measure of cation vacancies. These results suggest that the coordination configuration in the oxide shell on Fe nanoparticles is defective as compared to that of their bulk counterparts. Implications of these defective structural characteristics on the properties of core-shell structured iron nanoparticles are discussed.

Characterization of interfacial reactions and oxide films on 316L stainless steel in various simulated PWR primary water environments

NASA Astrophysics Data System (ADS)

Chen, Junjie; Xiao, Qian; Lu, Zhanpeng; Ru, Xiangkun; Peng, Hao; Xiong, Qi; Li, Hongjuan

2017-06-01

The effect of water chemistry on the electrochemical and oxidizing behaviors of 316L SS was investigated in hydrogenated, deaerated and oxygenated PWR primary water at 310 °C. Water chemistry significantly influenced the electrochemical impedance spectroscopy parameters. The highest charge-transfer resistance and oxide-film resistance occurred in oxygenated water. The highest electric double-layer capacitance and constant phase element of the oxide film were in hydrogenated water. The oxide films formed in deaerated and hydrogenated environments were similar in composition but different in morphology. An oxide film with spinel outer particles and a compact and Cr-rich inner layer was formed in both hydrogenated and deaerated water. Larger and more loosely distributed outer oxide particles were formed in deaerated water. In oxygenated water, an oxide film with hematite outer particles and a porous and Ni-rich inner layer was formed. The reaction kinetics parameters obtained by electrochemical impedance spectroscopy measurements and oxidation film properties relating to the steady or quasi-steady state conditions in the time-period of measurements could provide fundamental information for understanding stress corrosion cracking processes and controlling parameters.

Ultra-low loss fully-etched grating couplers for perfectly vertical coupling compatible with DUV lithography tools

NASA Astrophysics Data System (ADS)

Dabos, G.; Pleros, N.; Tsiokos, D.

2016-03-01

Hybrid integration of VCSELs onto silicon-on-insulator (SOI) substrates has emerged as an attractive approach for bridging the gap between cost-effective and energy-efficient directly modulated laser sources and silicon-based PICs by leveraging flip-chip (FC) bonding techniques and silicon grating couplers (GCs). In this context, silicon GCs, should comply with the process requirements imposed by the complimentary-metal-oxide-semiconductor manufacturing tools addressing in parallel the challenges originating from the perfectly vertical incidence. Firstly, fully etched GCs compatible with deep-ultraviolet lithography tools offering high coupling efficiencies are imperatively needed to maintain low fabrication cost. Secondly, GC's tolerance to VCSEL bonding misalignment errors is a prerequisite for practical deployment. Finally, a major challenge originating from the perfectly vertical coupling scheme is the minimization of the direct back-reflection to the VCSEL's outgoing facet which may destabilize its operation. Motivated from the above challenges, we used numerical simulation tools to design an ultra-low loss, bidirectional VCSEL-to-SOI optical coupling scheme for either TE or TM polarization, based on low-cost fully etched GCs with a Si-layer of 340 nm without employing bottom reflectors or optimizing the buried-oxide layer. Comprehensive 2D Finite-Difference-Time- Domain simulations have been performed. The reported GC layout remains fully compatible with the back-end-of-line (BEOL) stack associated with the 3D integration technology exploiting all the inter-metal-dielectric (IMD) layers of the CMOS fab. Simulation results predicted for the first time in fully etched structures a coupling efficiency of as low as -0.87 dB at 1548 nm and -1.47 dB at 1560 nm with a minimum direct back-reflection of -27.4 dB and -14.2 dB for TE and TM polarization, respectively.

Colloidal inorganic nanocrystals: Nucleation, growth and biological applications

NASA Astrophysics Data System (ADS)

Lynch, Jared James

Colloidal inorganic nanocrystals are a class of material whose size ranges from a few nanometers to a hundred nanometers in dimension. These nanocrystals have size dependent properties that differ significantly from the bulk material counterparts. Due to their unique physical properties colloidal inorganic nanocrystals have several promising applications in a diverse range of areas, such as biomedical diagnosis, catalysis, plasmonics, high-density data storage and solar energy conversion. This dissertation presents the study of the formation of iron oxide nanocrystals under the influence of solvent and Ar gas bubbles, the phase transfer of metal oxide nanocrystals into water using inorganic ions, and the doping of semiconductor CdS/ZnS core/shell nanocrystals with copper and silver ions. First, the formation of iron oxide nanocrystals is investigated in the presence of boiling solvent or Ar bubbles. Using a non-injection based synthesis method, the thermal decomposition of iron oleate was studied under various reaction conditions, and the role of the bubbles on the nucleation and growth of iron oxide nanocrystals was determined. Kinetics studies were used to elucidate how latent heat transfer from the bubbles allows for "active monomers" to form preferentially from exothermic reactions taking place during nucleation. General insights into colloidal inorganic nanocrystal formation are discussed. Second, a non-injection based synthesis for CdS/ZnS core/shell nanocrystals is used to make high quality semiconductor particles which are intentionally doped with Cu or Ag ions. The Ag ions effect on the optical properties of the CdS/ZnS nanocrystals is investigated. The absorption and fluorescence of the samples is measured as a function of time and temperature. Proposed mechanisms for the observations are given and thoroughly discussed. Comparisons between previous results for Cu doped CdS/ZnS nanocrystals are also made to further understand how doping of semiconductor nanocrystals can be realized. Finally, a novel phase transfer process is demonstrated using inorganic salts, such as sodium arsenite, to make water soluble metal oxide nanocrystals. The water soluble iron oxide nanocrystals are fully characterized by several complementary techniques and then used in cellular studies. The arsenite-coated iron oxide composite nanocrystals (AICN) are shown to be effective cancer therapy agents.

Green and Mild Oxidation: An Efficient Strategy toward Water-Dispersible Graphene.

PubMed

You, Xiaofei; Yang, Siwei; Li, Jipeng; Deng, Yuan; Dai, Lianqi; Peng, Xiong; Huang, Haoguang; Sun, Jing; Wang, Gang; He, Peng; Ding, Guqiao; Xie, Xiaoming

2017-01-25

Scalable fabrication of water-dispersible graphene (W-Gr) is highly desirable yet technically challenging for most practical applications of graphene. Herein, a green and mild oxidation strategy to prepare bulk W-Gr (dispersion, slurry, and powder) with high yield was proposed by fully exploiting structure defects of thermally reduced graphene oxide (TRGO) and oxidizing radicals generated from hydrogen peroxide (H 2 O 2 ). Owing to the increased carboxyl group from the mild oxidation process, the obtained W-Gr can be redispersed in low-boiling solvents with a reasonable concentration. Benefiting from the modified surface chemistry, macroscopic samples processed from the W-Gr show good hydrophilicity (water contact angle of 55.7°) and excellent biocompatibility, which is expected to be an alternative biomaterial for bone, vessel, and skin regeneration. In addition, the green and mild oxidation strategy is also proven to be effective for dispersing other carbon nanomaterials in a water system.

Water exchange in manganese-based water-oxidizing catalysts in photosynthetic systems: from the water-oxidizing complex in photosystem II to nano-sized manganese oxides.

PubMed

Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Eaton-Rye, Julian J; Tomo, Tatsuya; Nishihara, Hiroshi; Satoh, Kimiyuki; Carpentier, Robert; Shen, Jian-Ren; Allakhverdiev, Suleyman I

2014-09-01

The water-oxidizing complex (WOC), also known as the oxygen-evolving complex (OEC), of photosystem II in oxygenic photosynthetic organisms efficiently catalyzes water oxidation. It is, therefore, responsible for the presence of oxygen in the Earth's atmosphere. The WOC is a manganese-calcium (Mn₄CaO₅(H₂O)₄) cluster housed in a protein complex. In this review, we focus on water exchange chemistry of metal hydrates and discuss the mechanisms and factors affecting this chemical process. Further, water exchange rates for both the biological cofactor and synthetic manganese water splitting are discussed. The importance of fully unveiling the water exchange mechanism to understand the chemistry of water oxidation is also emphasized here. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. Copyright © 2014 Elsevier B.V. All rights reserved.

Fundamentals of Passive Oxidation In SiC and Si3N4

NASA Technical Reports Server (NTRS)

Thomas-Ogbuji, Linus U.

1998-01-01

The very slow oxidation kinetics of silicon carbide and silicon nitride, which derive from their adherent and passivating oxide films, has been explored at length in a broad series of studies utilizing thermogravimetric analysis, electron and optical micrography, energy dispersive spectrometry, x-ray diffractometry, micro-analytical depth profiling, etc. Some interesting microstructural phenomena accompanying the process of oxidation in the two materials will be presented. In Si3N4 the oxide is stratified, with an SiO2 topscale (which is relatively impervious to O2)underlain by a coherent subscale of silicon oxynitride which is even less permeable to O2- Such "defence in depth" endows Si3N4 with what is perhaps the highest oxidation resistance of any material, and results in a unique set of oxidation processes. In SiC the oxidation reactions are much simpler, yet new issues still emerge; for instance, studies involving controlled devitrification of the amorphous silica scale confirmed that the oxidation rate of SiC drops by more than an order of magnitude when the oxide scale fully crystallizes.

Formation of alcohol conversion catalysts

DOEpatents

Wachs, Israel E.; Cai, Yeping

2001-01-01

The method of the present invention involves a composition containing an intimate mixture of (a) metal oxide support particles and (b) a catalytically active metal oxide from Groups VA, VIA, or VIIA, its method of manufacture, and its method of use for converting alcohols to aldehydes. During the conversion process, catalytically active metal oxide from the discrete catalytic metal oxide particles migrates to the oxide support particles and forms a monolayer of catalytically active metal oxide on the oxide support particle to form a catalyst composition having a higher specific activity than the admixed particle composition.

Carbothermic reduction and prereduced charge for producing aluminum-silicon alloys

DOEpatents

Stevenson, D.T.; Troup, R.L.

1985-01-01

Disclosed is a method for the carbothermic reduction of aluminum oxide to form an aluminum alloy including producing silicon carbide by heating a first mix of carbon and silicon oxide in a combustion reactor to an elevated temperature sufficient to produce silicon carbide at an accelerated rate, the heating being provided by an in situ combustion with oxygen gas, and then admixing the silicon carbide with carbon and aluminum oxide to form a second mix and heating the second mix in a second reactor to an elevated metal-forming temperature sufficient to produce aluminum-silicon alloy. The prereduction step includes holding aluminum oxide substantially absent from the combustion reactor. The metal-forming step includes feeding silicon oxide in a preferred ratio with silicon carbide. 1 fig.

Partial oxidation catalyst

DOEpatents

Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

2000-01-01

A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

Thermal oxidation behavior of an Al-Li-Cu-Mg-Zr alloy

NASA Astrophysics Data System (ADS)

Ahmad, Maqsood

1987-04-01

The chemical composition of oxide films formed during thermal treatments of an Al-Li-Cu-Mg-Zr alloy has been studied by means of Auger electron spectroscopy and X-ray photoelectron spectroscopy. The oxide layers formed after oxidation of 2.5 minutes to 30 minutes at 530 °C in lab air have been characterized. In the early stages of oxidation the surface is composed of both the lithium rich oxides and magnesium rich oxides. However, after longer oxidation times the oxidation of lithium becomes predominant and the air/oxide interface is completely covered by lithium compounds. Oxidation products formed on the alloy surface have been studied by X-ray diffraction analysis. The following three phases, namely, Li2CO3, α-Li5AlO4, and γ-LiAlO2, were identified. During heat treatment in lab air at 530 °C and at atmospheric pressure the dominating reaction product is Li2CO3. Due to the selective oxidation of lithium a soft surface layer is developed. The width of the soft layer formed during solution heat treatments carried out in lab air and in salt bath environments has been determined by microhardness measurements. The lithium concentration profiles were calculated from a diffusion equation. The depletion of alloying elements from the near surface region during heat treatments has been investigated using energy dispersive X-ray analysis. The oxide morphology was examined using scanning electron microscopy and optical microscopy.

Thermal oxidation behavior of an Al-Li-Cu-Mg-Zr alloy

NASA Astrophysics Data System (ADS)

Ahmad, Maqsood

1987-05-01

The chemical composition of oxide films formed during thermal treatments of an Al-Li-Cu-Mg-Zr alloy has been studied by means of Auger electron spectroscopy and X-ray photoelectron spectroscopy. The oxide layers formed after oxidation of 2.5 minutes to 30 minutes at 530 °C in lab air have been characterized. In the early stages of oxidation the surface is composed of both the lithium rich oxides and magnesium rich oxides. However, after longer oxidation times the oxidation of lithium becomes predominant and the air/oxide interface is completely covered by lithium compounds. Oxidation products formed on the alloy surface have been studied by X-ray diffraction analysis. The following three phases, namely, Li2CO3, α-Li5AlO4, and γ-LiAlO2, were identified. During heat treatment in lab air at 530 °C and at atmospheric pressure the dominating reaction product is Li2CO3. Due to the selective oxidation of lithium a soft surface layer is developed. The width of the soft layer formed during solution heat treatments carried out in lab air and in salt bath environments has been determined by microhardness measurements. The lithium concentration profiles were calculated from a diffusion equation. The depletion of alloying elements from the near surface region during heat treatments has been investigated using energy dispersive X-ray analysis. The oxide morphology was examined using scanning electron microscopy and optical microscopy.

Morphology, Microstructure and Transport Properties of ZnO Decorated SiO2 Nanoparticles (Preprint)

DTIC Science & Technology

2010-04-15

ZnO decorated SiO2 nanoparticles . While the growth conditions we employ for synthesis of ZnO nanocrys- tals are similar to... oxide nanocrystal synthesis on semiconductor oxide nanoparticles is an area yet to be fully explored. One advantage of this approach is that it enables... nanoparticles were resuspended. This washing process was repeated three times. In the hydrolytic ZnO synthesis method, a 1 ml suspension of SiO2 nanoshells

A fully spray-coated fuel cell membrane electrode assembly using Aquivion ionomer with a graphene oxide/cerium oxide interlayer

NASA Astrophysics Data System (ADS)

Breitwieser, Matthias; Bayer, Thomas; Büchler, Andreas; Zengerle, Roland; Lyth, Stephen M.; Thiele, Simon

2017-05-01

A novel multilayer membrane electrode assembly (MEA) for polymer electrolyte membrane fuel cells (PEMFCs) is fabricated in this work, within a single spray-coating device. For the first time, direct membrane deposition is used to fabricate a PEMFC by spraying the short-side-chain ionomer Aquivion directly onto the gas diffusion electrodes. The fully sprayed MEA, with an Aquivion membrane 10 μm in thickness, achieved a high power density of 1.6 W/cm2 for H2/air operation at 300 kPaabs. This is one of the highest reported values for thin composite membranes operated in H2/air atmosphere. By the means of confocal laser scanning microscopy, individual carbon fibers from the gas diffusion layer are identified to penetrate through the micro porous layer (MPL), likely causing a low electrical cell resistance in the range of 150 Ω cm2 through the thin sprayed membranes. By spraying a 200 nm graphene oxide/cerium oxide (GO/CeO2) interlayer between two layers of Aquivion ionomer, the impact of the electrical short is eliminated and the hydrogen crossover current density is reduced to about 1 mA/cm2. The peak power density of the interlayer-containing MEA drops only by 10% compared to a pure Aquivion membrane of similar thickness.

Oxidation-chlorination of binary Ni-Cr alloys in flowing Ar-O2-Cl2 gas mixtures at 1200 K

NASA Technical Reports Server (NTRS)

Mcnallan, M. J.; Lee, Y. Y.; Chang, Y. W.; Jacobson, N. S.; Doychak, J.

1991-01-01

Nickel-chromium alloys are resistant to oxidation because of the selective oxidation of chromium to form a protective Cr2O3 scale. In chlorine-containing environments, volatile corrosion products can also be formed. The mixed oxidation-chlorination of Ni-4.5Cr, Ni-13.8Cr, and Ni-26.5Cr (by weight) alloys in Ar-O2-Cl2 gas mixtures is investigated using thermogravimetric analysis and atmospheric-pressure-sampling mass spectrometry, followed by examination of the corrosion products using scanning electron microscopy and X-ray diffraction analysis. The overall kinetics of the corrosion are affected by the relative amounts of oxides and chlorides formed and the composition of the oxide corrosion products.

Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model - Part 1: Assessing the influence of constrained multi-generational ageing

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

2015-09-01

Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data; and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the Statistical Oxidation Model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional UCD/CIT air quality model and applied to air quality episodes in California and the eastern US. The mass, composition and properties of SOA predicted using SOM are compared to SOA predictions generated by a traditional "two-product" model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation. Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions tested. Consequently, the use of low and high NOx yields perturbs SOA concentrations by a factor of two and are probably a much stronger determinant in 3-D models than constrained multi-generational oxidation. While total predicted SOA mass is similar for the SOM and two-product models, the SOM model predicts increased SOA contributions from anthropogenic (alkane, aromatic) and sesquiterpenes and decreased SOA contributions from isoprene and monoterpene relative to the two-product model calculations. The SOA predicted by SOM has a much lower volatility than that predicted by the traditional model resulting in better qualitative agreement with volatility measurements of ambient OA. On account of its lower-volatility, the SOA mass produced by SOM does not appear to be as strongly influenced by the inclusion of oligomerization reactions, whereas the two-product model relies heavily on oligomerization to form low volatility SOA products. Finally, an unconstrained contemporary hybrid scheme to model multi-generational oxidation within the framework of a two-product model in which "ageing" reactions are added on top of the existing two-product parameterization is considered. This hybrid scheme formed at least three times more SOA than the SOM during regional simulations as a result of excessive transformation of semi-volatile vapors into lower volatility material that strongly partitions to the particle phase. This finding suggests that these "hybrid" multi-generational schemes should be used with great caution in regional models.

Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model - Part 1: Assessing the influence of constrained multi-generational ageing

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

2016-02-01

Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the statistical oxidation model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional University of California at Davis / California Institute of Technology (UCD/CIT) air quality model and applied to air quality episodes in California and the eastern USA. The mass, composition and properties of SOA predicted using SOM were compared to SOA predictions generated by a traditional two-product model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation.Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions tested. Consequently, the use of low and high NOx yields perturbs SOA concentrations by a factor of two and are probably a much stronger determinant in 3-D models than multi-generational oxidation. While total predicted SOA mass is similar for the SOM and two-product models, the SOM model predicts increased SOA contributions from anthropogenic (alkane, aromatic) and sesquiterpenes and decreased SOA contributions from isoprene and monoterpene relative to the two-product model calculations. The SOA predicted by SOM has a much lower volatility than that predicted by the traditional model, resulting in better qualitative agreement with volatility measurements of ambient OA. On account of its lower-volatility, the SOA mass produced by SOM does not appear to be as strongly influenced by the inclusion of oligomerization reactions, whereas the two-product model relies heavily on oligomerization to form low-volatility SOA products. Finally, an unconstrained contemporary hybrid scheme to model multi-generational oxidation within the framework of a two-product model in which ageing reactions are added on top of the existing two-product parameterization is considered. This hybrid scheme formed at least 3 times more SOA than the SOM during regional simulations as a result of excessive transformation of semi-volatile vapors into lower volatility material that strongly partitions to the particle phase. This finding suggests that these hybrid multi-generational schemes should be used with great caution in regional models.

Bonding of sapphire to sapphire by eutectic mixture of aluminum oxide and zirconium oxide

NASA Technical Reports Server (NTRS)

Deluca, J. J. (Inventor)

1975-01-01

Bonding of an element comprising sapphire, ruby or blue sapphire to another element of such material with a eutectic mixture of aluminum oxide and zirconium oxide is discussed. The bonding mixture may be applied in the form of a distilled water slurry or by electron beam vapor deposition. In one embodiment the eutectic is formed in situ by applying a layer of zirconium oxide and then heating the assembly to a temperature above the eutectic temperature and below the melting point of the material from which the elements are formed. The formation of a sapphire rubidium maser cell utilizing eutectic bonding is shown.

Thermal conversion of biomass to valuable fuels, chemical feedstocks and chemicals

DOEpatents

Peters, William A [Lexington, MA; Howard, Jack B [Winchester, MA; Modestino, Anthony J [Hanson, MA; Vogel, Fredreric [Villigen PSI, CH; Steffin, Carsten R [Herne, DE

2009-02-24

A continuous process for the conversion of biomass to form a chemical feedstock is described. The biomass and an exogenous metal oxide, preferably calcium oxide, or metal oxide precursor are continuously fed into a reaction chamber that is operated at a temperature of at least 1400.degree. C. to form reaction products including metal carbide. The metal oxide or metal oxide precursor is capable of forming a hydrolizable metal carbide. The reaction products are quenched to a temperature of 800.degree. C. or less. The resulting metal carbide is separated from the reaction products or, alternatively, when quenched with water, hydolyzed to provide a recoverable hydrocarbon gas feedstock.

Basic materials physics of transparent conducting oxides.

PubMed

Edwards, P P; Porch, A; Jones, M O; Morgan, D V; Perks, R M

2004-10-07

Materials displaying the remarkable combination of high electrical conductivity and optical transparency already from the basis of many important technological applications, including flat panel displays, solar energy capture and other opto-electronic devices. Here we present the basic materials physics of these important materials centred on the nature of the doping process to generate n-type conductivity in transparent conducting oxides, the associated transition to the metallic (conducting) state and the detailed properties of the degenerate itinerant electron gas. The aim is to fully understand the origins of the basic performance limits of known materials and to set the scene for new or improved materials which will breach those limits for new-generation transparent conducting materials, either oxides, or beyond oxides.

Methane and nitrous oxide emissions from municipal wastewater treatment - results from a long-term study.

PubMed

Daelman, M R J; van Voorthuizen, E M; van Dongen, L G J M; Volcke, E I P; van Loosdrecht, M C M

2013-01-01

Methane and nitrous oxide emissions from a fully covered municipal wastewater treatment plant were measured on-line during 16 months. At the plant under study, nitrous oxide contributed three-quarters to the plant's carbon footprint, while the methane emission was slightly larger than the indirect carbon dioxide emission related to the plant's electricity and natural gas consumption. This contrasted with two other wastewater treatment plants, where more than 80% of the carbon footprint came from the indirect carbon dioxide emission. The nitrous oxide emission exhibited a seasonal dynamic, of which the cause remains unclear. Three types of air filter were investigated with regard to their effectiveness to remove methane from the off-gas.

Dopant selection for control of charge carrier density and mobility in amorphous indium oxide thin-film transistors: Comparison between Si- and W-dopants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitoma, Nobuhiko, E-mail: MITOMA.Nobuhiko@nims.go.jp, E-mail: TSUKAGOSHI.Kazuhito@nims.go.jp; Kizu, Takio; Lin, Meng-Fang

The dependence of oxygen vacancy suppression on dopant species in amorphous indium oxide (a-InO{sub x}) thin film transistors (TFTs) is reported. In a-InO{sub x} TFTs incorporating equivalent atom densities of Si- and W-dopants, absorption of oxygen in the host a-InO{sub x} matrix was found to depend on difference of Gibbs free energy of the dopants for oxidation. For fully oxidized films, the extracted channel conductivity was higher in the a-InO{sub x} TFTs containing dopants of small ionic radius. This can be explained by a reduction in the ionic scattering cross sectional area caused by charge screening effects.

Pyrocarbons prepared by carbonisation of polymers adsorbed or synthesised on a surface of silica and mixed oxides

NASA Astrophysics Data System (ADS)

Gun'ko, V. M.; Skubiszewska-Zi ęba, J.; Leboda, R.; Voronin, E. F.; Zarko, V. I.; Levitskaya, S. I.; Brei, V. V.; Guzenko, N. V.; Kazakova, O. A.; Seledets, O.; Janusz, W.; Chibowski, S.

2004-04-01

Initial oxides fumed silica, alumina/silica and titania/silica and silica gel and hybrid adsorbents with pyrocarbon formed on these oxide substrates by carbonisation of immobilised (adsorbed or synthesised) polymers such as starch, methyl cellulose, polyvinylpyrrolidone, polystyrene, and polybutylvinyl ether were studied by adsorption, AFM, TEM, and FTIR methods. Polymer/oxide materials were investigated by nitrogen and Pb(II) adsorption, FTIR, and potentiometric titration methods. Analysis of nitrogen adsorption-desorption isotherms by different methods, FTIR spectra, AFM and TEM images of the initial and hybrid adsorbents reveals that the morphology of the substrates significantly changes on carbonisation of oxygen-containing polymers because of hydrothermal treatment of them by water eliminated as a product of pyrolysis. Contribution of own microporosity of pyrocarbon deposits formed on carbonisation of immobilised polymers is greater (dependent on reaction conditions) than that on pyrolysis of low-molecular compounds at the same oxide substrates. Pyrocarbon particles formed on silica gel are larger than those formed on fumed oxides and larger than those formed on silica gel on pyrolysis of low-molecular compounds.

Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

DOEpatents

Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

1996-01-01

An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

DOEpatents

Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

1996-09-24

An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M{sub x}Z{sub y}Mn{sub (1{minus}y)}O{sub 2}, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell. 11 figs.

Characteristics of oxide scale formed on Cu-bearing austenitic stainless steel during early stages of high temperature oxidation

NASA Astrophysics Data System (ADS)

Swaminathan, Srinivasan; Krishna, Nanda Gopala; Kim, Dong-Ik

2015-10-01

Oxide scale evolution on Cu-bearing austenitic stainless steel 304H at 650 °C, in ambient air, for exposure times 100, 300, 500 and 1000 h, has been investigated. Surface morphology and chemistry of the oxide scale grown were examined using SEM/EDX and XPS. The oxidation kinetics was determined by measuring the weight change using an electronic balance. At the initial stage, up to 500 h of exposure time, the oxidation rate was rapid due to surface reactions governed primarily by oxygen ingress, and then, dropped to a low rate after prolonged oxidation for 1000 h. The diffusion of reactants through the initially formed oxide scale limits the oxidation rate at longer times, thus, the progress of reaction followed the parabolic kinetics. The formed oxide scale was enriched significantly with segregation and subsequent oxidation of Nb, and finely dispersed metallic Cu particles. Within the time frame of oxidation, the oxide scale was mainly composed of mixed oxides such as FeCr2O4 and MnCr2O4 along with the binary oxides of Fe, Cr and Mn. Moreover, the precipitation fraction of Cu-rich particles on the oxide scale increased markedly with increase of exposure times. The chemical heterogeneity of oxide scale suggests that the oxidation occurred in a non-selective manner.

STUDY OF THE OXIDATION OF NON-ALLOYED ZIRCONIUM AND OF OXYGEN DIFFUSION IN THE OXIDE FILM AND IN THE METAL (in French)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Debuigne, J.; Lehr, P.

1963-12-01

The oxidation processes of zirconium at 600-850 deg C were studied. A micrographic and radiocrystallographic analysis of the oxide layers formed at the surface of the metal was carried out. The kinetic results, weight gains as function nf time, were completed by the study of oxygen diffusion through the oxide layer formed and in the underlying metal. (auth)

The mitochondrial outer membrane protein mitoNEET is a redox enzyme catalyzing electron transfer from FMNH2 to oxygen or ubiquinone.

PubMed

Wang, Yiming; Landry, Aaron P; Ding, Huangen

2017-06-16

Increasing evidence suggests that mitoNEET, a target of the type II diabetes drug pioglitazone, is a key regulator of energy metabolism in mitochondria. MitoNEET is anchored to the mitochondrial outer membrane via its N-terminal α helix domain and hosts a redox-active [2Fe-2S] cluster in its C-terminal cytosolic region. The mechanism by which mitoNEET regulates energy metabolism in mitochondria, however, is not fully understood. Previous studies have shown that mitoNEET specifically interacts with the reduced flavin mononucleotide (FMNH 2 ) and that FMNH 2 can quickly reduce the mitoNEET [2Fe-2S] clusters. Here we report that the reduced mitoNEET [2Fe-2S] clusters can be readily oxidized by oxygen. In the presence of FMN, NADH, and flavin reductase, which reduces FMN to FMNH 2 using NADH as the electron donor, mitoNEET mediates oxidation of NADH with a concomitant reduction of oxygen. Ubiquinone-2, an analog of ubiquinone-10, can also oxidize the reduced mitoNEET [2Fe-2S] clusters under anaerobic or aerobic conditions. Compared with oxygen, ubiquinone-2 is more efficient in oxidizing the mitoNEET [2Fe-2S] clusters, suggesting that ubiquinone could be an intrinsic electron acceptor of the reduced mitoNEET [2Fe-2S] clusters in mitochondria. Pioglitazone or its analog NL-1 appears to inhibit the electron transfer activity of mitoNEET by forming a unique complex with mitoNEET and FMNH 2 The results suggest that mitoNEET is a redox enzyme that may promote oxidation of NADH to facilitate enhanced glycolysis in the cytosol and that pioglitazone may regulate energy metabolism in mitochondria by inhibiting the electron transfer activity of mitoNEET. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

In Situ Integration of Anisotropic SnO₂ Heterostructures inside Three-Dimensional Graphene Aerogel for Enhanced Lithium Storage.

PubMed

Yao, Xin; Guo, Guilue; Ma, Xing; Zhao, Yang; Ang, Chung Yen; Luo, Zhong; Nguyen, Kim Truc; Li, Pei-Zhou; Yan, Qingyu; Zhao, Yanli

2015-12-02

Three-dimensional (3D) graphene aerogel (GA) has emerged as an outstanding support for metal oxides to enhance the overall energy-storage performance of the resulting hybrid materials. In the current stage of the studies, metals/metal oxides inside GA are in uncrafted geometries. Introducing structure-controlled metal oxides into GA may further push electrochemical properties of metal oxide-GA hybrids. Using rutile SnO2 as an example, we demonstrated here a facile hydrothermal strategy combined with a preconditioning technique named vacuum-assisted impregnation for in situ construction of controlled anisotropic SnO2 heterostructures inside GA. The obtained hybrid material was fully characterized in detail, and its formation mechanism was investigated by monitoring the phase-transformation process. Rational integration of the two advanced structures, anisotropic SnO2 and 3D GA, synergistically led to enhanced lithium-storage properties (1176 mAh/g for the first cycle and 872 mAh/g for the 50th cycle at 100 mA/g) as compared with its two counterparts, namely, rough nanoparticles@3D GA and anisotropic SnO2@2D graphene sheets (618 and 751 mAh/g for the 50th cycle at 100 mA/g, respectively). It was also well-demonstrated that this hybrid material was capable of delivering high specific capacity at rapid charge/discharge cycles (1044 mAh/g at 100 mA/g, 847 mAh/g at 200 mA/g, 698 mAh/g at 500 mA/g, and 584 mAh/g at 1000 mA/g). The in situ integration strategy along with vacuum-assisted impregnation technique presented here shows great potential as a versatile tool for accessing a variety of sophisticated smart structures in the form of anisotropic metals/metal oxides within 3D GA toward useful applications.

Anomalous radiation effects in fully depleted SOI MOSFETs fabricated on SIMOX

NASA Astrophysics Data System (ADS)

Li, Ying; Niu, Guofu; Cressler, J. D.; Patel, J.; Marshall, C. J.; Marshall, P. W.; Kim, H. S.; Reed, R. A.; Palmer, M. J.

2001-12-01

We investigate the proton tolerance of fully depleted silicon-on-insulator (SOI) MOSFETs with H-gate and regular-gate structural configurations. For the front-gate characteristics, the H-gate does not show the edge leakage observed in the regular-gate transistor. An anomalous kink in the back-gate linear I/sub D/-V/sub GS/ characteristics of the fully depleted SOI nFETs has been observed at high radiation doses. This kink is attributed to charged traps generated in the bandgap at the buried oxide/silicon film interface during irradiation. Extensive two-dimensional simulations with MEDICI were used to understand the physical origin of this kink. We also report unusual self-annealing effects in the devices when they are cooled to liquid nitrogen temperature.

Single Additive Enables 3D Printing of Highly Loaded Iron Oxide Suspensions.

PubMed

Hodaei, Amin; Akhlaghi, Omid; Khani, Navid; Aytas, Tunahan; Sezer, Dilek; Tatli, Buse; Menceloglu, Yusuf Z; Koc, Bahattin; Akbulut, Ozge

2018-03-21

A single additive, a grafted copolymer, is designed to ensure the stability of suspensions of highly loaded iron oxide nanoparticles (IOPs) and to facilitate three-dimensional (3D) printing of these suspensions in the filament form. This poly (ethylene glycol)-grafted copolymer of N-[3(dimethylamino)propyl]methacrylamide and acrylic acid harnesses both electrostatic and steric repulsion to realize an optimum formulation for 3D printing. When used at 1.15 wt % (by the weight of IOPs), the suspension attains ∼81 wt % solid loading-96% of the theoretical limit as calculated by the Krieger-Dougherty equation. Rectangular, thick-walled toroidal, and thin-walled toroidal magnetic cores and a porous lattice structure are fabricated to demonstrate the utilization of this suspension as an ink for 3D printing. The electrical and magnetic properties of the magnetic cores are characterized through impedance spectroscopy (IS) and vibrating sample magnetometry (VSM), respectively. The IS indicates the possibility of utilizing wire-wound 3D printed cores as the inductive coils. The VSM verifies that the magnetic properties of IOPs before and after the ink formulation are kept almost unchanged because of the low dosage of the additive. This particle-targeted approach for the formulation of 3D printing inks allows embodiment of a fully aqueous system with utmost target material content.

Isoprene derived secondary organic aerosol in a global aerosol chemistry climate model

NASA Astrophysics Data System (ADS)

Stadtler, Scarlet; Kühn, Thomas; Taraborrelli, Domenico; Kokkola, Harri; Schultz, Martin

2017-04-01

Secondary organic aerosol (SOA) impacts earth's climate and human health. Since its precursor chemistry and its formation are not fully understood, climate models cannot catch its direct and indirect effects. Global isoprene emissions are higher than any other non-methane hydrocarbons. Therefore, SOA from isoprene-derived, low volatile species (iSOA) is simulated using a global aerosol chemistry climate model ECHAM6-HAM-SALSA-MOZ. Isoprene oxidation in the chemistry model MOZ is following a novel semi-explicit scheme, embedded in a detailed atmospheric chemical mechanism. For iSOA formation four low volatile isoprene oxidation products were identified. The group method by Nanoonlal et al. 2008 was used to estimate their evaporation enthalpies ΔHvap. To calculate the saturation concentration C∗(T) the sectional aerosol model SALSA uses the gas phase concentrations simulated by MOZ and their corresponding ΔHvap to obtain the saturation vapor pressure p∗(T) from the Clausius Clapeyron equation. Subsequently, the saturation concentration is used to calculate the explicit kinetic partitioning of these compounds forming iSOA. Furthermore, the irreversible heterogeneous reactions of IEPOX and glyoxal from isoprene were included. The possibility of reversible heterogeneous uptake was ignored at this stage, leading to an upper estimate of the contribution of glyoxal to iSOA mass.

Local electrical properties of thermally grown oxide films formed on duplex stainless steel surfaces

NASA Astrophysics Data System (ADS)

Guo, L. Q.; Yang, B. J.; He, J. Y.; Qiao, L. J.

2018-06-01

The local electrical properties of thermally grown oxide films formed on ferrite and austenite surfaces of duplex stainless steel at different temperatures were investigated by Current sensing atomic force microscopy, X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES). The current maps and XPS/AES analyses show that the oxide films covering austenite and ferrite surfaces formed at different temperatures exhibit different local electrical characteristics, thickness and composition. The dependence of electrical conductivity of oxide films covering austenite and ferrite surface on the formation temperature is attributed to the film thickness and semiconducting structures, which is intrinsically related to thermodynamics and kinetics process of film grown at different temperature. This is well elucidated by corresponding semiconductor band structures of oxide films formed on austenite and ferrite phases at different temperature.

Mechanistic Insights into the Catalytic Oxidation of Carboxylic Acids on Au/TiO 2: Partial Oxidation of Propionic and Butyric Acid to Gold Ketenylidene through Unsaturated Acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

McEntee, Monica; Tang, Wenjie; Neurock, Matthew

Here, the partial oxidation of model C 2–C 4 (acetic, propionic, and butyric) carboxylic acids on Au/TiO 2 catalysts consisting of Au particles ~3 nm in size was investigated using transmission infrared spectroscopy and density functional theory. All three acids readily undergo oxidative dehydrogenation on Au/TiO 2. Propionic and butyric acid dehydrogenate at the C2–C3 positions, whereas acetic acid dehydrogenates at the C1–C2 position. The resulting acrylate and crotonate intermediates are subsequently oxidized to form β-keto acids that decarboxylate. All three acids form a gold ketenylidene intermediate, Au 2C=C=O, along the way to their full oxidation to form CO 2.more » Infrared measurements of Au 2C=C=O formation as a function of time provides a surface spectroscopic probe of the kinetics for the activation and oxidative dehydrogenation of the alkyl groups in the carboxylate intermediates that form.« less

Mechanistic Insights into the Catalytic Oxidation of Carboxylic Acids on Au/TiO 2: Partial Oxidation of Propionic and Butyric Acid to Gold Ketenylidene through Unsaturated Acids

DOE PAGES

McEntee, Monica; Tang, Wenjie; Neurock, Matthew; ...

2014-12-12

Here, the partial oxidation of model C 2–C 4 (acetic, propionic, and butyric) carboxylic acids on Au/TiO 2 catalysts consisting of Au particles ~3 nm in size was investigated using transmission infrared spectroscopy and density functional theory. All three acids readily undergo oxidative dehydrogenation on Au/TiO 2. Propionic and butyric acid dehydrogenate at the C2–C3 positions, whereas acetic acid dehydrogenates at the C1–C2 position. The resulting acrylate and crotonate intermediates are subsequently oxidized to form β-keto acids that decarboxylate. All three acids form a gold ketenylidene intermediate, Au 2C=C=O, along the way to their full oxidation to form CO 2.more » Infrared measurements of Au 2C=C=O formation as a function of time provides a surface spectroscopic probe of the kinetics for the activation and oxidative dehydrogenation of the alkyl groups in the carboxylate intermediates that form.« less

Reaction products and oxide thickness formed by Ti out-diffusion and oxidization in poly-Pt/Ti/SiO 2/Si with oxide films deposited

NASA Astrophysics Data System (ADS)

Chen, Changhong; Huang, Dexiu; Zhu, Weiguang; Feng, Yi; Wu, Xigang

2006-08-01

In the paper, we present experimental results to enhance the understanding of Ti out-diffusion and oxidization in commercial poly-Pt/Ti/SiO 2/Si wafers with perovskite oxide films deposited when heat-treated in flowing oxygen ambient. It indicates that when heat-treated at 550 and 600 °C, PtTi 3+PtTi and PtTi are the reaction products from interfacial interaction, respectively; while heat-treated at 650 °C and above, the products become three layers of titanium oxides instead of the alloys. Confirmed to be rutile TiO 2, the first two layers spaced by 65 nm encapsulate the Pt surface by the first layer with 60 nm thick forming at its surface and by the next layer with 35 nm thick inserting its original layer. In addition, the next layer is formed as a barrier to block up continuous diffusion paths of Ti, and thus results in the last layer of TiO 2- x formed by the residual Ti oxidizing.

Iron-phosphate ceramics for solidification of mixed low-level waste

DOEpatents

Aloy, Albert S.; Kovarskaya, Elena N.; Koltsova, Tatiana I.; Macheret, Yevgeny; Medvedev, Pavel G.; Todd, Terry

2000-01-01

A method of immobilizing mixed low-level waste is provided which uses low cost materials and has a relatively long hardening period. The method includes: forming a mixture of iron oxide powders having ratios, in mass %, of FeO:Fe.sub.2 O.sub.3 :Fe.sub.3 O.sub.4 equal to 25-40:40-10:35-50, or weighing a definite amount of magnetite powder. Metallurgical cinder can also be used as the source of iron oxides. A solution of the orthophosphoric acid, or a solution of the orthophosphoric acid and ferric oxide, is formed and a powder phase of low-level waste and the mixture of iron oxide powders or cinder (or magnetite powder) is also formed. The acid solution is mixed with the powder phase to form a slurry with the ratio of components (mass %) of waste:iron oxide powders or magnetite:acid solution=30-60:15-10:55-30. The slurry is blended to form a homogeneous mixture which is cured at room temperature to form the final product.

Structure, morphology, and photoluminescence of porous Si nanowires: effect of different chemical treatments

PubMed Central

2013-01-01

The structure and light-emitting properties of Si nanowires (SiNWs) fabricated by a single-step metal-assisted chemical etching (MACE) process on highly boron-doped Si were investigated after different chemical treatments. The Si nanowires that result from the etching of a highly doped p-type Si wafer by MACE are fully porous, and as a result, they show intense photoluminescence (PL) at room temperature, the characteristics of which depend on the surface passivation of the Si nanocrystals composing the nanowires. SiNWs with a hydrogen-terminated nanostructured surface resulting from a chemical treatment with a hydrofluoric acid (HF) solution show red PL, the maximum of which is blueshifted when the samples are further chemically oxidized in a piranha solution. This blueshift of PL is attributed to localized states at the Si/SiO2 interface at the shell of Si nanocrystals composing the porous SiNWs, which induce an important pinning of the electronic bandgap of the Si material and are involved in the recombination mechanism. After a sequence of HF/piranha/HF treatment, the SiNWs are almost fully dissolved in the chemical solution, which is indicative of their fully porous structure, verified also by transmission electron microscopy investigations. It was also found that a continuous porous Si layer is formed underneath the SiNWs during the MACE process, the thickness of which increases with the increase of etching time. This supports the idea that porous Si formation precedes nanowire formation. The origin of this effect is the increased etching rate at sites with high dopant concentration in the highly doped Si material. PMID:24025542

NOVEL CERAMIC MEMBRANE BIOREACTOR FOR LOW-FLOW SYSTEMS - PHASE I

EPA Science Inventory

Improved low-flow (50,000 gallons per day) sanitary wastewater treatment systems are needed. CeraMem Corporation's proposed approach includes a membrane bioreactor (MBR) using fully proven biological processes for biological oxygen demand oxidation and (optionally) fo...

Selective oxidation of cube textured Ni and Ni-Cr substrate for the formation of cube textured NiO as a component buffer layer for REBa 2Cu 3O 7+ x (REBCO) coated conductors

NASA Astrophysics Data System (ADS)

Lockman, Z.; Goldacker, W.; Nast, R.; deBoer, B.; MacManus-Driscoll, J. L.

2002-08-01

Thermal oxidation of cube textured, pure Ni and Ni-Cr tapes was undertaken under different oxidation conditions to form cube textured NiO for the use as a first component of buffer layer for the coated conductor. Cube textured NiO was formed on pure Ni after oxidising for more than 130 min in O 2 at 1250 °C. The oxide thickness was >30 μm. Much shorter oxidation times (20-40 min, NiO thickness of ∼5 μm) and lower temperature (1050 °C) were required to form a similar texture on Ni-Cr foils. In addition, NiO formed on Ni-13%Cr was more highly textured than Ni-10%Cr. A Cr 2O 3 inner layer and NiO outer layer was formed on the Ni-Cr alloys.

Niobium oxide nanocolumns formed via anodic alumina with modulated pore diameters

NASA Astrophysics Data System (ADS)

Pligovka, A.; Zakhlebayeva, A.; Lazavenka, A.

2018-03-01

Niobium oxide nanocolumns with modulated diameters were formed for the first time. An Al/Nb bilayer specimen was prepared by successive sputter-deposition of 300 nm niobium layer and 1200 nm aluminum layer onto silicon wafer. Regular anodic alumina matrix with modulated pore diameters was formed by sequential anodization of initial specimen in tartaric acid at 180 V, and in oxalic acid at 37 V. Further potentiodynamic reanodization of the specimen up to 400 V causes the simultaneous growth of 440 nm continuous niobium oxide layer beneath the alumina film and two types of an array of oxide nanocolumns (thick – with 100 nm width and 630 nm high and thin – with 25 nm width and 170 nm high), which are the filling of the alumina pores. The morphology of the formed anodic niobium oxide nanocolumns with modulated diameters was determined by field emission scanning electron microscopy. The formed nanostructures can be used for perspective devices of nano- and optoelectronics such as photonic crystals.

Increased Postprandial Nonesterified Fatty Acid Appearance and Oxidation in Type 2 Diabetes Is Not Fully Established in Offspring of Diabetic Subjects

PubMed Central

Normand-Lauzière, François; Frisch, Frédérique; Labbé, Sébastien M.; Bherer, Patrick; Gagnon, René; Cunnane, Stephen C.; Carpentier, André C.

2010-01-01

Background It has been proposed that abnormal postprandial plasma nonesterified fatty acid (NEFA) metabolism may participate in the development of tissue lipotoxicity and type 2 diabetes (T2D). We previously found that non-diabetic offspring of two parents with T2D display increased plasma NEFA appearance and oxidation rates during intravenous administration of a fat emulsion. However, it is currently unknown whether plasma NEFA appearance and oxidation are abnormal during the postprandial state in these subjects at high-risk of developing T2D. Methodology Palmitate appearance and oxidation rates and glycerol appearance rate were determined in eleven healthy offspring of two parents with T2D (positive family history, FH+), 13 healthy subjects without first-degree relatives with T2D (FH-) and 12 subjects with T2D at fasting, during normoglycemic hyperinsulinemic clamp and during continuous oral intake of a standard liquid meal to achieve steady postprandial NEFA and triacylglycerols (TG) without and with insulin infusion to maintain similar glycemia in all three groups. Principal Findings Plasma palmitate appearance and oxidation were higher at fasting and during the clamp conditions in the T2D group (all P<0.05). In the postprandial state, palmitate appearance, oxidative and non oxidative rates were all elevated in T2D (all P<0.05) but not in FH+. Both T2D and FH+ displayed elevated postprandial TG vs. FH- (P<0.001). Acute correction of hyperglycemia during the postprandial state did not affect these group differences. Increased waist circumference and BMI were positively associated with elevated postprandial plasma palmitate appearance and oxidation. Conclusions/Significance Postprandial plasma NEFA intolerance observed in subjects with T2D is not fully established in non-diabetic offspring of both parents with T2D, despite the presence of increased postprandial plasma TG in the later. Elevated postprandial plasma NEFA appearance and oxidation in T2D is observed despite acute correction of the exaggerated glycemic excursion in this group. PMID:20532041

How do light harvesting proteins support long lived quantum coherences

DTIC Science & Technology

2017-01-31

the structural basis for these two forms, our aim is to generate hybrid proteins via synthetic biology approaches. We have shown that we can fully...SUBJECT TERMS quantum biology , light harvesting, photosynthesis, AOARD 16.  SECURITY CLASSIFICATION OF: 17.  LIMITATION OF ABSTRACT SAR 18.  NUMBER OF...these two forms, our aim is to generate hybrid proteins via synthetic biology approaches. We have shown that we can fully unfold and separate the

Method for forming pyrrone molding powders and products of said method

NASA Technical Reports Server (NTRS)

Hughes, C. T.; Mchenry, R. J. (Inventor)

1972-01-01

The formation of pyrrone resins of the ladder or semiladder structure is described. The technique involves initial formation of fully cyclized prepolymers having an average degree of polymerization of about 1.5, one with acidic terminal groups, another with amine terminal groups. Thereafter the prepolymers are intimately admixed on a 1:1 stoichiometric basis. The resulting powder mixture is molded at elevated pressures and temperatures to form a fully cyclized resin.

Microstructure and Oxidation of (La,Sr)CrO3-Added Ti3SiC2 Composites.

PubMed

Lee, Dong Bok

2015-11-01

Composites of Ti3SiC2-(10, 20, 40)wt% La0.8Sr0.2CrO3 were synthesized by hot pressing powders of Ti3SiC2 and La0.8Sr0.2CrO3. These powders reacted to form stable TiC carbides and LaTiO3, Cr2Ti4O11, La2O3, and SrCrO4 oxides during hot pressing. The composites consisted primarily of a fine TiC-rich matrix phase and coarse Ti3SiC2 dispersoids. The addition of oxidation-immune La0.8Sr0.2CrO3 into Ti3SiC2 increased the oxidation rate because TiC formed during hot pressing. During oxidation of the composites at 800-1000 degrees C for 100 h in air, Ti diffused outward to form an outer rutile-TiO2 layer, and oxygen transported inward to form an inner oxide layer.

Defect and Ordered Tungsten Oxides Encapsulated Inside 2H-W X2( X=S and Se) Fullerene-Related Structures

NASA Astrophysics Data System (ADS)

Sloan, Jeremy; Hutchison, John L.; Tenne, Reshef; Feldman, Yishay; Tsirlina, Tatyana; Homyonfer, Moshe

1999-04-01

Complex tungsten oxides, consisting of nonstoichiometric oxides of the form WO3-xand stoichiometric lamellar oxides of the form {001}RWnO3n-1(n=3 to 6) have been observed incorporated within 2H-WX2(X=S or Se) inorganic fullerene-like (IF) structures by HRTEM. These encapsulates were formed from a gas-solid reaction between H2Xand disordered WO3-xprecursors exhibiting a range of particle sizes and morphologies. The microstructures of most of the encapsulated oxides could be described in terms of {hkl}Rcrystallographic shear (CS) structures formed relative to an ReO3-type (R) substructure. Smaller spheroidal WO3-xencapsulates were frequently found to exhibit random {103}RCS defects of the Wadsley type, while larger, needle encapsulates were found to form exclusively {001}RWnO3n-1type lamellar structures that were predominantely ordered. Spheriodal encapsulates with randomly spaced {001}RCS planes were also observed encapsulated inside 2H-WSe2IF structures. The growth and morphologies of the encapsulating 2H-WX2shells were profoundly influenced by those of the precursor oxides used in their formation. Ordering mechanisms were proposed with respect to the formation of the ordered encapsulated oxides from the disordered precursors.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zongyuan; Duchoň, Tomáš; Wang, Huanru

We have studied the reaction of ethanol and water over Ni–CeO 2-x(111) model surfaces to elucidate the mechanistic steps associated with the ethanol steam reforming (ESR) reaction. Our results provide insights about the importance of hydroxyl groups to the ESR reaction over Ni-based catalysts. Systematically, we have investigated the reaction of ethanol on Ni–CeO 2-x(111) at varying Ce³⁺ concentrations (CeO 1.8–2.0) with absence/presence of water using a combination of soft X-ray photoelectron spectroscopy (sXPS) and temperature-programmed desorption (TPD). Consistent with previous reports, upon annealing, metallic Ni formed on reduced ceria while NiO was the main component on fully oxidized ceria.more » Ni⁰ is the active phase leading to both the C–C and C–H cleavage of ethanol but is also responsible for carbon accumulation or coking. We have identified a Ni₃C phase that formed prior to the formation of coke. At temperatures above 600K, the lattice oxygen from ceria and the hydroxyl groups from water interact cooperatively in the removal of coke, likely through a strong metal–support interaction between nickel and ceria that facilitates oxygen transfer.« less

Controlling the degradation kinetics of porous iron by poly(lactic-co-glycolic acid) infiltration for use as temporary medical implants

PubMed Central

Yusop, Abdul Hakim Md; Daud, Nurizzati Mohd; Nur, Hadi; Kadir, Mohammed Rafiq Abdul; Hermawan, Hendra

2015-01-01

Iron and its alloy have been proposed as biodegradable metals for temporary medical implants. However, the formation of iron oxide and iron phosphate on their surface slows down their degradation kinetics in both in vitro and in vivo scenarios. This work presents new approach to tailor degradation behavior of iron by incorporating biodegradable polymers into the metal. Porous pure iron (PPI) was vacuum infiltrated by poly(lactic-co-glycolic acid) (PLGA) to form fully dense PLGA-infiltrated porous iron (PIPI) and dip coated into the PLGA to form partially dense PLGA-coated porous iron (PCPI). Results showed that compressive strength and toughness of the PIPI and PCPI were higher compared to PPI. A strong interfacial interaction was developed between the PLGA layer and the iron surface. Degradation rate of PIPI and PCPI was higher than that of PPI due to the effect of PLGA hydrolysis. The fast degradation of PIPI did not affect the viability of human fibroblast cells. Finally, this work discusses a degradation mechanism for PIPI and the effect of PLGA incorporation in accelerating the degradation of iron. PMID:26057073

Large-aperture Tunable Plasma Meta-material to Interact with Electromagnetic Waves

NASA Astrophysics Data System (ADS)

Corke, Thomas; Matlis, Eric

2016-11-01

The formation of spatially periodic arrangements of glow discharge plasma resulting from charge instabilities were investigated as a tuneable plasma meta-material. The plasma was formed between two 2-D parallel dielectric covered electrodes: one consisting of an Indium-Tin-Oxide coated glass sheet, and the other consisting of a glass-covered circular electrode. The dielectric covered electrodes were separated by a gap that formed a 2-D channel. The gap spacing was adjustable. The electrodes were powered by a variable amplitude AC generator. The parallel electrode arrangement was placed in a variable pressure vacuum chamber. Various combinations of gap spacing, pressure and voltage resulted in the formation of spatially periodic arrangements (lattice) of glow discharge plasma. The lattice spacing perfectly followed 2-D packing theory, and was fully adjustable through the three governing parameters. Lattice arrangements were designed to interact with electromagnetic (EM) waves in the frequency range between 10GHz-80GHz. Its feasibility was investigate through an EM wave simulation that we adapted to allow for plasma permittivity. The results showed a clear suppression of the EM wave amplitude through the plasma gratings. Supported by AFOSR.

Method of making a ceramic with preferential oxygen reactive layer

NASA Technical Reports Server (NTRS)

Wang, Hongyu (Inventor); Luthra, Krishan Lal (Inventor)

2003-01-01

A method of forming an article. The method comprises forming a silicon-based substrate that is oxidizable by reaction with an oxidant to form at least one gaseous product and applying an intermediate layer/coating onto the substrate, wherein the intermediate layer/coating is oxidizable to a nongaseous product by reaction with the oxidant in preference to reaction of the silicon-containing substrate with the oxidant.

Ceramic with preferential oxygen reactive layer

NASA Technical Reports Server (NTRS)

Wang, Hongyu (Inventor); Luthra, Krishan Lal (Inventor)

2001-01-01

An article comprises a silicon-containing substrate and an external environmental/thermal barrier coating. The external environmental/thermal barrier coating is permeable to diffusion of an environmental oxidant and the silicon-containing substrate is oxidizable by reaction with oxidant to form at least one gaseous product. The article comprises an intermediate layer/coating between the silicon-containing substrate and the environmental/thermal barrier coating that is oxidizable to a nongaseous product by reaction with the oxidant in preference to reaction of the silicon-containing substrate with the oxidant. A method of forming an article, comprises forming a silicon-based substrate that is oxidizable by reaction with oxidant to at least one gaseous product and applying an intermediate layer/coating onto the substrate, wherein the intermediate layer/coating is oxidizable to a nongaseous product by reaction with the oxidant in preference to reaction of the silicon-containing substrate with the oxidant.

Molecular water oxidation mechanisms followed by transition metals: state of the art.

PubMed

Sala, Xavier; Maji, Somnath; Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Llobet, Antoni

2014-02-18

One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood. Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed. In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen-oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M-O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for these catalysts.

Current status of Westinghouse tubular solid oxide fuel cell program

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parker, W.G.

1996-04-01

In the last ten years the solid oxide fuel cell (SOFC) development program at Westinghouse has evolved from a focus on basic material science to the engineering of fully integrated electric power systems. Our endurance for this cell is 5 to 10 years. To date we have successfully operated at power for over six years. For power plants it is our goal to have operated before the end of this decade a MW class power plant. Progress toward these goals is described.

Rational engineering of Geobacter sulfurreducens electron transfer components: A foundation for building improved Geobacter-based bioelectrochemical technologies

DOE PAGES

Dantas, Joana M.; Morgado, Leonor; Aklujkar, Muktak; ...

2015-07-30

Multiheme cytochromes have been implicated in Geobacter sulfurreducens extracellular electron transfer (EET). These proteins are potential targets to improve EET and enhance bioremediation and electrical current production by G. sulfurreducens. However, the functional characterization of multiheme cytochromes is particularly complex due to the co-existence of several microstates in solution, connecting the fully reduced and fully oxidized states. Throughout the last decade, new strategies have been developed to characterize multiheme redox proteins functionally and structurally. These strategies were used to reveal the functional mechanism of G. sulfurreducens multiheme cytochromes and also to identify key residues in these proteins for EET. Inmore » previous studies, we set the foundations for enhancement of the EET abilities of G. sulfurreducens by characterizing a family of five triheme cytochromes (PpcA-E). These periplasmic cytochromes are implicated in electron transfer between the oxidative reactions of metabolism in the cytoplasm and the reduction of extracellular terminal electron acceptors at the cell's outer surface. The results obtained suggested that PpcA can couple e -/H + transfer, a property that might contribute to the proton electrochemical gradient across the cytoplasmic membrane for metabolic energy production. The structural and functional properties of PpcA were characterized in detail and used for rational design of a family of 23 single site PpcA mutants. In this review, we summarize the functional characterization of the native and mutant proteins. Mutants that retain the mechanistic features of PpcA and adopt preferential e -/H + transfer pathways at lower reduction potential values compared to the wild-type protein were selected for in vivo studies as the best candidates to increase the electron transfer rate of G. sulfurreducens. For the first time G. sulfurreducens strains have been manipulated by the introduction of mutant forms of essential proteins with the aim to develop and improve bioelectrochemical technologies.« less

Near-infrared light controlled photocatalytic activity of carbon quantum dots for highly selective oxidation reaction

NASA Astrophysics Data System (ADS)

Li, Haitao; Liu, Ruihua; Lian, Suoyuan; Liu, Yang; Huang, Hui; Kang, Zhenhui

2013-03-01

Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize the transformation from benzyl alcohol to benzaldehyde with high selectivity (100%) and conversion (92%) under NIR light irradiation. HO&z.rad; is the main active oxygen specie in benzyl alcohol selective oxidative reaction confirmed by terephthalic acid photoluminescence probing assay (TA-PL), selecting toluene as the substrate. Such metal-free photocatalytic system also selectively converts other alcohol substrates to their corresponding aldehydes with high conversion, demonstrating a potential application of accessing traditional alcohol oxidation chemistry.Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize the transformation from benzyl alcohol to benzaldehyde with high selectivity (100%) and conversion (92%) under NIR light irradiation. HO&z.rad; is the main active oxygen specie in benzyl alcohol selective oxidative reaction confirmed by terephthalic acid photoluminescence probing assay (TA-PL), selecting toluene as the substrate. Such metal-free photocatalytic system also selectively converts other alcohol substrates to their corresponding aldehydes with high conversion, demonstrating a potential application of accessing traditional alcohol oxidation chemistry. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00092c

Oxidation and formation of deposit precursors in hydrocarbon fuels

NASA Technical Reports Server (NTRS)

Mayo, F. R.; Lan, B.; Cotts, D. B.; Buttrill, S. E., Jr.; St.john, G. A.

1983-01-01

The oxidation of two jet turbine fuels and some pure hydrocarbons was studied at 130 C with and without the presence of small amounts of N-methyl pyrrole (NMP) or indene. Tendency to form solid-deposit precursors was studied by measuring soluble gum formation as well as dimer and trimer formation using field ionization mass spectrometry. Pure n-dodecane oxidized fastest and gave the smallest amount of procursors. An unstable fuel oil oxidized much slower but formed large amounts of precursors. Stable Jet A fuel oxidized slowest and gave little precursors. Indene either retarded or accelerated the oxidation of n-dodecane, depending on its concentration, but always caused more gum formation. The NMP greatly retarded n-dodecane oxidation but accelerated Jet A oxidation and greatly increased the latter's gum formation. In general, the additive reacted faster and formed most of the gum. Results are interpreted in terms of classical cooxidation theory. The effect of oxygen pressure on gum formation is also reported.

Control of interfacial properties of Pr-oxide/Ge gate stack structure by introduction of nitrogen

NASA Astrophysics Data System (ADS)

Kato, Kimihiko; Kondo, Hiroki; Sakashita, Mitsuo; Nakatsuka, Osamu; Zaima, Shigeaki

2011-06-01

We have demonstrated the control of interfacial properties of Pr-oxide/Ge gate stack structure by the introduction of nitrogen. From C- V characteristics of Al/Pr-oxide/Ge 3N 4/Ge MOS capacitors, the interface state density decreases without the change of the accumulation capacitance after annealing. The TEM and TED measurements reveal that the crystallization of Pr-oxide is enhanced with annealing and the columnar structure of cubic-Pr 2O 3 is formed after annealing. From the depth profiles measured using XPS with Ar sputtering for the Pr-oxide/Ge 3N 4/Ge stack structure, the increase in the Ge component is not observed in a Pr-oxide film and near the interface between a Pr-oxide film and a Ge substrate. In addition, the N component segregates near the interface region, amorphous Pr-oxynitride (PrON) is formed at the interface. As a result, Pr-oxide/PrON/Ge stacked structure without the Ge-oxynitride interlayer is formed.

Syn-anti conformational switching in an ethane-bridged Co(II)bisporphyrin induced by external stimuli: effects of inter-macrocyclic interactions, axial ligation and chemical and electrochemical oxidations.

PubMed

Dey, Soumyajit; Rath, Sankar Prasad

2014-02-07

The syn-anti conformational switching has been demonstrated in the ethane-bridged dicobalt(II)bisporphyrin which is present in the syn-form only. The addition of either perylene or axial ligands to Co(II)(bisporphyrin) completely transforms the syn form into the anti because of strong π-π interaction and axial coordination, respectively. The complex undergoes four 1e-oxidations in CH2Cl2 which are indicative of strong through space interactions between the two cofacial Co-porphyrins at 295 K. The first oxidation is a metal centered one and occurs at a potential much lower than that of the monomeric analog. However, the second oxidation, which is again metal centered, was at a significantly higher potential. The large difference between the first two oxidations, as observed here, is due to much stronger inter-porphyrin interactions. The step-wise oxidations have been performed both chemically and electro-chemically while the progress of the reactions was monitored by UV-visible and (1)H NMR spectroscopy. After 1e-oxidation, a very broad (1)H NMR signal results with increased difference between two meso resonances, which indicates that the two macrocycles are in the syn-form with lesser interplanar separation as also observed by DFT. However, 2e-oxidation results in the stabilization of the anti form. The addition of axial ligands to Co(II)(bisporphyrin) also completely transforms the syn form into the anti form. While additions of THF and I2/I(-) both result in the formation of five-coordinate complexes, Co(II) is oxidized to Co(III) in the case of the latter. However, additions of 1-methylimidazole, pyridine and pyrazine as axial ligands result in the formation of a six-coordinate complex in which Co(II) is spontaneously oxidized to Co(III) in air.

A fully integrated oven controlled microelectromechanical oscillator -- Part I. Design and fabrication

DOE PAGES

Wojciechowski, Kenneth E.; Baker, Michael S.; Clews, Peggy J.; ...

2015-06-24

Our paper reports the design and fabrication of a fully integrated oven controlled microelectromechanical oscillator (OCMO). This paper begins by describing the limits on oscillator frequency stability imposed by the thermal drift and electronic properties (Q, resistance) of both the resonant tank circuit and feedback electronics required to form an electronic oscillator. An OCMO is presented that takes advantage of high thermal isolation and monolithic integration of both micromechanical resonators and electronic circuitry to thermally stabilize or ovenize all the components that comprise an oscillator. This was achieved by developing a processing technique where both silicon-on-insulator complementary metal-oxide-semiconductor (CMOS) circuitrymore » and piezoelectric aluminum nitride, AlN, micromechanical resonators are placed on a suspended platform within a standard CMOS integrated circuit. Operation at microscale sizes achieves high thermal resistances (~10 °C/mW), and hence thermal stabilization of the oscillators at very low-power levels when compared with the state-of-the-art ovenized crystal oscillators, OCXO. This constant resistance feedback circuit is presented that incorporates on platform resistive heaters and temperature sensors to both measure and stabilize the platform temperature. Moreover, the limits on temperature stability of the OCMO platform and oscillator frequency imposed by the gain of the constant resistance feedback loop, placement of the heater and temperature sensing resistors, as well as platform radiative and convective heat losses are investigated.« less

Tunable molten oxide pool assisted plasma-melter vitrification systems

DOEpatents

Titus, Charles H.; Cohn, Daniel R.; Surma, Jeffrey E.

1998-01-01

The present invention provides tunable waste conversion systems and apparatus which have the advantage of highly robust operation and which provide complete or substantially complete conversion of a wide range of waste streams into useful gas and a stable, nonleachable solid product at a single location with greatly reduced air pollution to meet air quality standards. The systems provide the capability for highly efficient conversion of waste into high quality combustible gas and for high efficiency conversion of the gas into electricity by utilizing a high efficiency gas turbine or an internal combustion engine. The solid product can be suitable for various commercial applications. Alternatively, the solid product stream, which is a safe, stable material, may be disposed of without special considerations as hazardous material. In the preferred embodiment, the arc plasma furnace and joule heated melter are formed as a fully integrated unit with a common melt pool having circuit arrangements for the simultaneous independently controllable operation of both the arc plasma and the joule heated portions of the unit without interference with one another. The preferred configuration of this embodiment of the invention utilizes two arc plasma electrodes with an elongated chamber for the molten pool such that the molten pool is capable of providing conducting paths between electrodes. The apparatus may additionally be employed with reduced use or without further use of the gases generated by the conversion process. The apparatus may be employed as a net energy or net electricity producing unit where use of an auxiliary fuel provides the required level of electricity production. Methods and apparatus for converting metals, non-glass forming waste streams and low-ash producing inorganics into a useful gas are also provided. The methods and apparatus for such conversion include the use of a molten oxide pool having predetermined electrical, thermal and physical characteristics capable of maintaining optimal joule heating and glass forming properties during the conversion process.

Interfacing epitaxial oxides to gallium nitride

NASA Astrophysics Data System (ADS)

Losego, Mark Daniel

Molecular beam epitaxy (MBE) is lauded for its ability to control thin film material structures at the atomic level. This precision of control can improve performance of microelectronic devices and cultivate the development of novel device structures. This thesis explores the utility of MBE for designing interfaces between oxide epilayers and the wide band gap semiconductor gallium nitride (GaN). The allure of wide gap semiconductor microelectronics (like GaN, 3.4 eV) is their ability to operate at higher frequencies, higher powers, and higher temperatures than current semiconductor platforms. Heterostructures between ferroelectric oxides and GaN are also of interest for studying the interaction between GaN's fixed polarization and the ferroelectric's switchable polarization. Two major obstacles to successful integration of oxides with GaN are: (1) interfacial trap states; and (2) small electronic band offsets across the oxide/nitride interface due to the semiconductor's large band gap. For this thesis, epitaxial rocksalt oxide interfacial layers (˜8 eV band gap) are investigated as possible solutions to overcoming the challenges facing oxide integration with GaN. The cubic close-packed structure of rocksalt oxides forms a suitable epitaxial interface with the hexagonal close-packed wurtzite lattice of GaN. Three rocksalt oxide compounds are investigated in this thesis: MgO, CaO, and YbO. All are found to have a (111) MO || (0001) GaN; <1 10> MO || <11 20> GaN epitaxial relationship. Development of the epilayer microstructure is dominated by the high-energy polar growth surface (drives 3D nucleation) and the interfacial symmetry, which permits the formation of twin boundaries. Using STEM, strain relief for these ionicly bonded epilayers is observed to occur through disorder within the initial monolayer of growth. All rocksalt oxides demonstrate chemical stability with GaN to >1000°C. Concurrent MBE deposition of MgO and CaO is known to form complete solid solutions. By controlling the composition of these alloys, the oxide's lattice parameter can be engineered to match GaN and reduce interfacial state density. Compositional control is a universal challenge to oxide MBE, and the MgO-CaO system (MCO) is further complicated by magnesium's high volatility and the lack of a thermodynamically stable phase. Through a detailed investigation of MgO's deposition rate and subsequent impact on MCO composition, the process space for achieving lattice-matched compositions to GaN are fully mapped. Lattice-matched compositions are demonstrated to have the narrowest off-axis rocking curve widths ever reported for an epitaxial oxide deposited directly on GaN (0.7° in φ-circle for 200 reflection). Epitaxial deposition of the ferroelectric (Ba,Sr)TiO3 by hot RF sputtering on GaN surfaces is also demonstrated. Simple MOS capacitors are fabricated from epitaxial rocksalt oxides and (Ba,Sr)TiO3 layers deposited on n-GaN substrates. Current-voltage measurements reveal that BST epilayers have 5 orders of magnitude higher current leakage than rocksalt epilayers. This higher leakage is attributed to the smaller band offset expected at this interface; modeling confirms that electronic transport occurs by Schottky emission. In contrast, current transport across the rocksalt oxide/GaN interface occurs by Frenkel-Poole emission and can be reduced with pre-deposition surface treatments. Finally, through this work, it is realized that the integration of oxides with III-nitrides requires an appreciation of many different fields of research including materials science, surface science, and electrical engineering. By recognizing the importance that each of these fields play in designing oxide/III-nitride interfaces, this thesis has the opportunity to explore other related phenomena including accessing metastable phases through MBE (ytterbium monoxide), spinodal decomposition in metastable alloys (MCO), how polar surfaces grown by MBE compensate their bound surface charge, room temperature epitaxy, and the use of surface modification to achieve selective epitaxial deposition (SeEDed growth).

Is hepatic oxidative stress a main driver of dietary selenium toxicity in white sturgeon (Acipenser transmontanus)?

PubMed

Zee, Jenna; Patterson, Sarah; Wiseman, Steve; Hecker, Markus

2016-11-01

Most species of sturgeon have experienced significant population declines and poor recruitment over the past decades, leading many, including white sturgeon (Acipenser transmontanus), to be listed as endangered. Reasons for these declines are not yet fully understood but benthic lifestyle, longevity, and delayed sexual maturation likely render sturgeon particularly susceptible to factors such as habitat alteration and contaminant exposures. One contaminant of particular concern to white sturgeon is selenium (Se), especially in its more bioavailable form selenomethionine (SeMet), as it is known to efficiently bioaccumulate in prey items of this species. Studies have shown white sturgeon to be among the most sensitive species of fish to dietary SeMet as well as other pollutants such as metals, dioxin-like chemicals and endocrine disrupters. One of the primary hypothesized mechanisms of toxicity of SeMet in fish is oxidative stress; however, little is know about the specific mode by which SeMet affects the health of white sturgeon. Therefore, the aim of this study was to characterize oxidative stress and associated antioxidant responses as a molecular event of toxicity, and to link it with the pathological effects observed previously. Specifically, three-year-old white sturgeon were exposed for 72 days via their diet to 1.4, 5.6, 22.4 or 104.4µg Se per g feed (dm). Doses were chosen to range over a necessary Se intake level, current environmentally relevant intakes and an intake representing predicted increases of Se release. Lipid hydroperoxides, which are end products of lipid oxidation, were quantified as a marker of oxidative stress. Changes in gene expression of glutathione peroxidase (GPx), superoxide dismutase, catalase, glutathione S-transferase, apoptosis inducing factor and caspase 3 were quantified as markers of the response to oxidative stress. Concentrations of lipid hydroperoxides were highly variable within dose groups and no dose response was observed. GPx expression was significantly increased in the low dose group indicating an induced antioxidant response. Expression of other genes were not significantly induced or suppressed. Overall, there was very little evidence of oxidative stress, and therefore, in contrast to previous reports on other species of teleost fishes, oxidative stress is not believed to be a main driver of toxicity in white sturgeon exposed to SeMet. Copyright © 2016 Elsevier Inc. All rights reserved.

Method of producing solution-derived metal oxide thin films

DOEpatents

Boyle, Timothy J.; Ingersoll, David

2000-01-01

A method of preparing metal oxide thin films by a solution method. A .beta.-metal .beta.-diketonate or carboxylate compound, where the metal is selected from groups 8, 9, 10, 11, and 12 of the Periodic Table, is solubilized in a strong Lewis base to form a homogeneous solution. This precursor solution forms within minutes and can be deposited on a substrate in a single layer or a multiple layers to form a metal oxide thin film. The substrate with the deposited thin film is heated to change the film from an amorphous phase to a ceramic metal oxide and cooled.

Engineering a Cysteine-Free Form of Human Fibroblast Growth Factor-1 for “Second Generation” Therapeutic Application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, Xue; Kumru, Ozan S.; Blaber, Sachiko I.

Human fibroblast growth factor-1 (FGF-1) has broad therapeutic potential in regenerative medicine but has undesirable biophysical properties of low thermostability and 3 buried cysteine (Cys) residues (at positions 16, 83, and 117) that interact to promote irreversible protein unfolding under oxidizing conditions. Mutational substitution of such Cys residues eliminates reactive buried thiols but cannot be accomplished simultaneously at all 3 positions without also introducing further substantial instability. The mutational introduction of a novel Cys residue (Ala66Cys) that forms a stabilizing disulfide bond (i.e., cystine) with one of the extant Cys residues (Cys83) effectively eliminates one Cys while increasing overall stability.more » This increase in stability offsets the associated instability of remaining Cys substitution mutations and permits production of a Cys-free form of FGF-1 (Cys16Ser/Ala66Cys/Cys117Ala) with only minor overall instability. The addition of a further stabilizing mutation (Pro134Ala) creates a Cys-free FGF-1 mutant with essentially wild-type biophysical properties. The elimination of buried free thiols in FGF-1 can substantially increase the protein half-life in cell culture. Here, we show that the effective cell survival/mitogenic functional activity of a fully Cys-free form is also substantially increased and is equivalent to wild-type FGF-1 formulated in the presence of heparin sulfate as a stabilizing agent. The results identify this Cys-free FGF-1 mutant as an advantageous “second generation” form of FGF-1 for therapeutic application.« less

Single-Phase Rare-Earth Oxide/Aluminum Oxide Glasses

NASA Technical Reports Server (NTRS)

Weber, J. K. Richard; Abadie, John G.; Hixson, April D.; Nordine, Paul C.

2006-01-01

Glasses that comprise rare-earth oxides and aluminum oxide plus, optionally, lesser amounts of other oxides, have been invented. The other oxide(s) can include SiO2, B2O3, GeO2, and/or any of a variety of glass-forming oxides that have been used heretofore in making a variety of common and specialty glasses. The glasses of the invention can be manufactured in bulk single-phase forms to ensure near uniformity in optical and mechanical characteristics, as needed for such devices as optical amplifiers, lasers, and optical waveguides (including optical fibers). These glasses can also be formulated to have high indices of refraction, as needed in some of such devices.

Inhibiting Corrosion Cracking: Crack Tip Chemistry and Physics.

DTIC Science & Technology

1986-03-14

suggests that a surface film is formed by adsorption of nitrite on the C- metal surface, followed by a reaction to form oxide and ammonia. The same A... adsorption -reaction mechanism was proposed for other oxidizing inhibitors, e.g., chrmnate and molybdate. Although nonoxidizing inhibitors, require the...properties are attributed either to a capacity to "repair" the oxide film formed on the metal in an electrolyte, or to adsorption of the oxyanicn

Organized energetic composites based on micro and nanostructures and methods thereof

DOEpatents

Gash, Alexander E.; Han, Thomas Yong-Jin; Sirbuly, Donald J.

2012-09-04

An ordered energetic composite structure according to one embodiment includes an ordered array of metal fuel portions; and an oxidizer in gaps located between the metal fuel portions. An ordered energetic composite structure according to another embodiment includes at least one metal fuel portion having an ordered array of nanopores; and an oxidizer in the nanopores. A method for forming an ordered energetic composite structure according to one embodiment includes forming an ordered array of metal fuel portions; and depositing an oxidizer in gaps located between the metal fuel portions. A method for forming an ordered energetic composite structure according to another embodiment includes forming an ordered array of nanopores in at least one metal fuel portion; and depositing an oxidizer in the nanopores.

Highly oxidized graphene oxide and methods for production thereof

DOEpatents

Tour, James M.; Kosynkin, Dmitry V.

2016-08-30

A highly oxidized form of graphene oxide and methods for production thereof are described in various embodiments of the present disclosure. In general, the methods include mixing a graphite source with a solution containing at least one oxidant and at least one protecting agent and then oxidizing the graphite source with the at least one oxidant in the presence of the at least one protecting agent to form the graphene oxide. Graphene oxide synthesized by the presently described methods is of a high structural quality that is more oxidized and maintains a higher proportion of aromatic rings and aromatic domains than does graphene oxide prepared in the absence of at least one protecting agent. Methods for reduction of graphene oxide into chemically converted graphene are also disclosed herein. The chemically converted graphene of the present disclosure is significantly more electrically conductive than is chemically converted graphene prepared from other sources of graphene oxide.

Influence of Yttrium Ion-Implantation on the Growth Kinetics and Micro-Structure of NiO Oxide Film

NASA Astrophysics Data System (ADS)

Jin, Huiming; Adriana, Felix; Majorri, Aroyave

2008-02-01

Isothermal and cyclic oxidation behaviours of pure and yttrium-implanted nickel were studied at 1000°C in air. Scanning electronic microscopy (SEM) and transmission electronic microscopy (TEM) were used to examine the micro-morphology and structure of oxide scales formed on the nickel substrate. It was found that Y-implantation significantly improved the anti-oxidation ability of nickel in both isothermal and cyclic oxidizing experiments. Laser Raman microscopy was also used to study the stress status of oxide scales formed on nickel with and without yttrium. The main reason for the improvement in anti-oxidation of nickel was that Y-implantation greatly reduced the growing speed and grain size of NiO. This fine-grained NiO oxide film might have better high temperature plasticity and could relieve parts of compressive stress by means of creeping, and maintained a ridge character and a relatively low internal stress level. Hence yttrium ion-implantation remarkably enhanced the adhesion of protective NiO oxide scale formed on the nickel substrate.

Fuel cell anode configuration for CO tolerance

DOEpatents

Uribe, Francisco A.; Zawodzinski, Thomas A.

2004-11-16

A polymer electrolyte fuel cell (PEFC) is designed to operate on a reformate fuel stream containing oxygen and diluted hydrogen fuel with CO impurities. A polymer electrolyte membrane has an electrocatalytic surface formed from an electrocatalyst mixed with the polymer and bonded on an anode side of the membrane. An anode backing is formed of a porous electrically conductive material and has a first surface abutting the electrocatalytic surface and a second surface facing away from the membrane. The second surface has an oxidation catalyst layer effective to catalyze the oxidation of CO by oxygen present in the fuel stream where at least the layer of oxidation catalyst is formed of a non-precious metal oxidation catalyst selected from the group consisting of Cu, Fe, Co, Tb, W, Mo, Sn, and oxides thereof, and other metals having at least two low oxidation states.

Effect of electrolyte temperature on the formation of self-organized anodic niobium oxide microcones in hot phosphate-glycerol electrolyte

NASA Astrophysics Data System (ADS)

Yang, S.; Aoki, Y.; Habazaki, H.

2011-07-01

Nanoporous niobium oxide films with microcone-type surface morphology were formed by anodizing at 10 V in glycerol electrolyte containing 0.6 mol dm -3 K 2HPO 4 and 0.2 mol dm -3 K 3PO 4 in a temperature range of 428-453 K. The microcones appeared after prolonged anodizing, but the required time was largely reduced by increasing electrolyte temperature. The anodic oxide was initially amorphous at all temperatures, but crystalline oxide nucleated during anodizing. The anodic oxide microcones, which were crystalline, appeared on surface as a consequence of preferential chemical dissolution of initially formed amorphous oxide. The chemical dissolution of an initially formed amorphous layer was accelerated by increasing the electrolyte temperature, with negligible influence of the temperature on the morphology of microcones up to 448 K.

Interface Physics in Complex Oxide Heterostructures

NASA Astrophysics Data System (ADS)

Zubko, Pavlo; Gariglio, Stefano; Gabay, Marc; Ghosez, Philippe; Triscone, Jean-Marc

2011-03-01

Complex transition metal oxides span a wide range of crystalline structures and play host to an incredible variety of physical phenomena. High dielectric permittivities, piezo-, pyro-, and ferroelectricity are just a few of the functionalities offered by this class of materials, while the potential for applications of the more exotic properties like high temperature superconductivity and colossal magnetoresistance is still waiting to be fully exploited. With recent advances in deposition techniques, the structural quality of oxide heterostructures now rivals that of the best conventional semiconductors, taking oxide electronics to a new level. Such heterostructures have enabled the fabrication of artificial multifunctional materials. At the same time they have exposed a wealth of phenomena at the boundaries where compounds with different structural instabilities and electronic properties meet, giving unprecedented access to new physics emerging at oxide interfaces. Here we highlight some of these exciting new interface phenomena.

Spatially resolved variations in reflectivity across iron oxide thin films

NASA Astrophysics Data System (ADS)

Kelley, Chris S.; Thompson, Sarah M.; Gilks, Daniel; Sizeland, James; Lari, Leonardo; Lazarov, Vlado K.; Matsuzaki, Kosuke; LeFrançois, Stéphane; Cinque, Gianfelice; Dumas, Paul

2017-11-01

The spin polarising properties of the iron oxide magnetite (Fe3O4) make it attractive for use in spintronic devices, but its sensitivity to compositional and structural variations make it challenging to prepare reliably. Infrared microspectroscopy and modelling are used to determine the spatial variation in the chemical composition of three thin films of iron oxide; one prepared by pulsed laser deposition (PLD), one by molecular beam epitaxy (MBE) deposition of iron whilst simultaneously flowing oxygen into the chamber and one by flowing oxygen only once deposition is complete. The technique is easily able to distinguish between films which contain metallic iron and different iron oxide phases as well as spatial variations in composition across the films. The film grown by post-oxidising iron is spatially uniform but not fully oxidised, the film grown by simultaneously oxidising iron showed spatial variation in oxide composition while the film grown by PLD was spatially uniform magnetite.

Biopolyester-based systems containing naturally occurring compounds with enhanced thermo-oxidative stability.

PubMed

Arrigo, Rossella; Morici, Elisabetta; Dintcheva, Nadka Tzankova

2016-11-02

This work presents a sustainable approach for the stabilization of polylactic acid (PLA) against thermo-oxidative aging. Naturally occurring phenolic and polyphenolic compounds, such as ferulic acid (FerAc), vanillic acid (VanAc), quercetin (Querc) and vitamin E (VitE), were introduced into PLA. The preliminary characterization of the systems formulated containing different amounts of natural stabilizers showed that all compounds used acted as plasticizers, leading to a decrease in rheological functions with respect to neat PLA, without significantly modifying the crystallinity of the raw material. The study of the thermo-oxidative behavior of neat PLA and PLA/natural compound systems, performed by spectrometric and thermal analyses, indicated that all stabilizers considered were able to exert a remarkable antioxidant action against thermo-oxidative phenomena. All natural compounds considered are thus proposed as ecofriendly stabilizers, to get fully bio-based polymer systems with enhanced thermo-oxidative stability, suitable for biomedical applications.

High temperature oxidation of alumina forming cast austenitic stainless steels within an environment of pure steam

NASA Astrophysics Data System (ADS)

Prenzlow, Elmer A.

Steam cracking of hydrocarbons in the petrochemical industry is a multibillion dollar industry. The processes performed in these plants create byproducts that negatively affect the integrity of stainless steel piping through high temperature corrosion. Alloys used presently in industry rely on the formation of chromium oxide (chromia) as a protective layer between the bulk metal pipe and chemical byproducts. However, chromia can become susceptible to attack from aggressive species such as carbon, water vapor, and sulfur compounds, thus creating a need for a better protection method. A new series of austenitic stainless steels have been developed in recent years that, rather than forming chromia, create a protective layer of aluminum oxide (alumina) under oxidative conditions. These alloys have high nickel content for the stabilization of the austenitic phase, and a more thermodynamically stable oxide layer relative to the traditional chromia formers. Consequently, alumina forming alloys have been proposed as replacements for chromia forming alloys in the petrochemical industry. General oxidation testing has been performed on alumina forming alloys under dry and 10% water vapor conditions. However, oxidation conditions in industry resemble a 100% steam environment. Therefore, test methods to mimic such conditions are needed so that alloys can be tested and developed further for these applications. Four alloys with aluminum contents ranging from 2.6 to 3.9 wt% were cut from centrifugally cast pipes and subjected to oxidation in an environment of pure steam for up to 30 hours, at temperatures of 800 °C and 950 °C. Samples were analyzed using Raman, SEM, and EDS and showed a continuous alumina layer free of cracks. The alumina layer thickness increased with time. Additionally, larger thicknesses were observed in samples oxidized at 950 °C from those of 800 °C. Thickness measurements were used to calculate parabolic and non-parabolic oxidation rate constants. Samples were compared using calculated parabolic and modified parabolic rates of oxidation. Plots for the prediction of oxide layer thickness were generated both for the Wagner model of parabolic oxidation, and an experimentally determined modification to said model. Oxide scale thickness as formed in pure steam was shown to be related to the aluminum content of the alloy and the temperature and time of exposure. Further testing of alumina forming stainless steels in other concentrations of steam would allow for the determination of steam's effect on alumina formation kinetics. In addition, tests at additional temperatures between 800 and 950 °C would allow for the calculation of activation energies and full understanding of the oxide layer. Finally, the analysis of alumina layer thickness effects on coking performance in a petrochemical application would allow for the potential transition of these alloys into the commercial market.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coker, Eric Nicholas; Miller, James E.

A thermal oxidation-reduction cycle is disclosed that uses iron titanium oxide as the reactive material. The cycle may be used for the thermal splitting of water and/or carbon dioxide to form hydrogen and/or carbon monoxide. The formed compounds may be used as syngas precursors to form fuels.

Influence of oxidation temperature on the oxide scale formation of NiCoCrAl coatings

NASA Astrophysics Data System (ADS)

Sugiarti, E.; Zaini, K. A.; Sundawa, R.; Wang, Y.; Ohnuki, S.; Hayashi, S.

2017-04-01

Intermetalic coatings of NiCoCrAl have been successfully developed on low carbon steel substrate to improve oxidation resistance in extreme environments. The influence of oxidation temperature on the oxide scale formation was studied in the temperature range of 600-1000 °C. The measurements were made in air under isothermal oxidation test for 100 h. The surface morphology showed that a cauliflower like structure developed entire the oxide scale of sample oxidized at 800 °C and 1000 °C, while partly distributed on the surface of sample oxidized at 600 °C. The XRD analysis identified Cr2O3 phase predominantly formed on the oxidized sample at 600 °C and meta-stable Al2O3 with several polymorphs crystalline structures: η, δ, θ, κ, and α-Al2O3 at relatively high temperatures, i.e. 800 °C and 1000 °C. A Cross-sectional microstructure showed that complex and porous structures formed on the top surface of 600 °C and 1000 °C samples. In contrast, a very thin oxide scale formed on 800 °C oxidized samples and it appeared to act as a diffusion barrier of oxygen to diffuse inward, hence could increase in the service life of carbon steel substrate.

Light transmissive electrically conductive oxide electrode formed in the presence of a stabilizing gas

DOEpatents

Tran, Nang T.; Gilbert, James R.

1992-08-04

A light transmissive, electrically conductive oxide is doped with a stabilizing gas such as H.sub.2 and H.sub.2 O. The oxide is formed by sputtering a light transmissive, electrically conductive oxide precursor onto a substrate at a temperature from 20.degree. C. to 300.degree. C. Sputtering occurs in a gaseous mixture including a sputtering gas and the stabilizing gas.

Cytochrome c-promoted cardiolipin oxidation generates singlet molecular oxygen.

PubMed

Miyamoto, Sayuri; Nantes, Iseli L; Faria, Priscila A; Cunha, Daniela; Ronsein, Graziella E; Medeiros, Marisa H G; Di Mascio, Paolo

2012-10-01

The interaction of cytochrome c (cyt c) with cardiolipin (CL) induces protein conformational changes that favor peroxidase activity. This process has been correlated with CL oxidation and the induction of cell death. Here we report evidence demonstrating the generation of singlet molecular oxygen [O(2)((1)Δ(g))] by a cyt c-CL complex in a model membrane containing CL. The formation of singlet oxygen was directly evidenced by luminescence measurements at 1270 nm and by chemical trapping experiments. Singlet oxygen generation required cyt c-CL binding and occurred at pH values higher than 6, consistent with lipid-protein interactions involving fully deprotonated CL species and positively charged residues in the protein. Moreover, singlet oxygen formation was specifically observed for tetralinoleoyl CL species and was not observed with monounsaturated and saturated CL species. Our results show that there are at least two mechanisms leading to singlet oxygen formation: one with fast kinetics involving the generation of singlet oxygen directly from CL hydroperoxide decomposition and the other involving CL oxidation. The contribution of the first mechanism was clearly evidenced by the detection of labeled singlet oxygen [(18)O(2)((1)Δ(g))] from liposomes supplemented with 18-oxygen-labeled CL hydroperoxides. However quantitative analysis showed that singlet oxygen yield from CL hydroperoxides was minor (<5%) and that most of the singlet oxygen is formed from the second mechanism. Based on these data and previous findings we propose a mechanism of singlet oxygen generation through reactions involving peroxyl radicals (Russell mechanism) and excited triplet carbonyl intermediates (energy transfer mechanism).

Did Mineral Surface Chemistry and Toxicity Contribute to Evolution of Microbial Extracellular Polymeric Substances?

PubMed Central

Campbell, Jay M.; Zhang, Nianli; Hickey, William J.

2012-01-01

Abstract Modern ecological niches are teeming with an astonishing diversity of microbial life in biofilms closely associated with mineral surfaces, which highlights the remarkable success of microorganisms in conquering the challenges and capitalizing on the benefits presented by the mineral–water interface. Biofilm formation capability likely evolved on early Earth because biofilms provide crucial cell survival functions. The potential toxicity of mineral surfaces toward cells and the complexities of the mineral–water–cell interface in determining the toxicity mechanisms, however, have not been fully appreciated. Here, we report a previously unrecognized role for extracellular polymeric substances (EPS), which form biofilms in shielding cells against the toxicity of mineral surfaces. Using colony plating and LIVE/DEAD staining methods in oxide suspensions versus oxide-free controls, we found greater viability of wild-type, EPS-producing strains of Pseudomonas aeruginosa PAO1 compared to their isogenic knockout mutant with defective biofilm-producing capacity. Oxide toxicity was specific to its surface charge and particle size. High resolution transmission electron microscopy (HRTEM) images and assays for highly reactive oxygen species (hROS) on mineral surfaces suggested that EPS shield via both physical and chemical mechanisms. Intriguingly, qualitative as well as quantitative measures of EPS production showed that toxic minerals induced EPS production in bacteria. By determining the specific toxicity mechanisms, we provide insight into the potential impact of mineral surfaces in promoting increased complexity of cell surfaces, including EPS and biofilm formation, on early Earth. Key Words: Mineral toxicity—Bacteria—EPS evolution—Biofilms—Cytotoxicity—Silica—Anatase—Alumina. Astrobiology 12, 785–798. PMID:22934560

Advanced degradation of brominated epoxy resin and simultaneous transformation of glass fiber from waste printed circuit boards by improved supercritical water oxidation processes.

PubMed

Liu, Kang; Zhang, Zhiyuan; Zhang, Fu-Shen

2016-10-01

This work investigated various supercritical water oxidation (SCWO) systems, i.e. SCWO1 (only water), SCWO2 (water+H2O2) and SCWO3 (water+H2O2/NaOH), for waste printed circuit boards (PCBs) detoxification and recycling. Response surface methodology (RSM) was applied to optimize the operating conditions of the optimal SCWO3 systems. The optimal reaction conditions for debromination were found to be the NaOH of 0.21g, the H2O2 volume of 9.04mL, the time of 39.7min, maximum debromination efficiency of 95.14%. Variance analysis indicated that the factors influencing debromination efficiency was in the sequence of NaOH>H2O2>time. Mechanism studies indicated that the dissociated ions from NaOH in supercritical water promoted the debromination of brominated epoxy resins (BERs) through an elimination reaction and nucleophilic substitution. HO2, produced by H2O2 could induce the oxidation of phenol ring to open (intermediates of BERs), which were thoroughly degraded to form hydrocarbons, CO2, H2O and NaBr. In addition, the alkali-silica reaction between OH(-) and SiO2 induced the phase transformation of glass fibers, which were simultaneously converted into anorthite and albite. Waste PCBs in H2O2/NaOH improved SCWO system were fully degraded into useful products and simultaneously transformed into functional materials. These findings are helpful for efficient recycling of waste PCBs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sphaerotilus natans encrusted with nanoball-shaped Fe(III) oxide minerals formed by nitrate-reducing mixotrophic Fe(II) oxidation

PubMed Central

Park, Sunhwa; Kim, Dong-Hun; Lee, Ji-Hoon; Hur, Hor-Gil

2014-01-01

Ferrous iron has been known to function as an electron source for iron-oxidizing microorganisms in both anoxic and oxic environments. A diversity of bacteria has been known to oxidize both soluble and solid-phase Fe(II) forms coupled to the reduction of nitrate. Here, we show for the first time Fe(II) oxidation by Sphaerotilus natans strain DSM 6575T under mixotrophic condition. Sphaerotilus natans has been known to form a sheath structure enclosing long chains of rod-shaped cells, resulting in a thick biofilm formation under oxic conditions. Here, we also demonstrate that strain DSM 6575T grows mixotrophically with pyruvate, Fe(II) as electron donors and nitrate as an electron acceptor and single cells of strain DSM 6575T are dominant under anoxic conditions. Furthermore, strain DSM 6575T forms nanoball-shaped amorphous Fe(III) oxide minerals encrusting on the cell surfaces through the mixotrophic iron oxidation reaction under anoxic conditions. We propose that cell encrustation results from the indirect Fe(II) oxidation by biogenic nitrite during nitrate reduction and that causes the bacterial morphological change to individual rod-shaped single cells from filamentous sheath structures. This study extends the group of existing microorganisms capable of mixotrophic Fe(II) oxidation by a new strain, S. natans strain DSM 6575T, and could contribute to biogeochemical cycles of Fe and N in the environment. PMID:24965827

Oxide compounds on Ni-Cr alloys.

PubMed

Baran, G R

1984-11-01

Five Ni-Cr alloys were studied in order to identify the compounds formed on the alloy surface during oxidation under conditions similar to those encountered during dental laboratory procedures prior to application of porcelain. After the alloys were oxidized, the films covering the surfaces were removed with the aid of a Br-methanol solution. X-ray diffraction was used to analyze the compounds formed. Oxides of nearly all elements contained by the alloys were found after low-temperature (650 degrees C) oxidation, while NiO and particularly Cr2O3 were predominant after oxidation at high temperatures (1000 degrees C).

Size-Dependent Neurotoxicity of Aluminum Oxide Particles: a Comparison Between Nano- and Micrometer Size on the Basis of Mitochondrial Oxidative Damage.

PubMed

Mirshafa, Atefeh; Nazari, Mehdi; Jahani, Daniel; Shaki, Fatemeh

2018-06-01

Aluminum nanoparticles (AlNPs) are among the most abundantly produced nanosized particles in the market. There is limited information about the potential harmful effects of aluminum oxide due to its particle size on human health. Considering the toxic effects of Al on brain as its target tissue, in this study, the toxicity of nanoparticles, microparticles, and ionic forms of Al on rat brain and isolated mitochondria was evaluated. Sixty male Wistar rats were divided into ten groups (six rats each), in which group I was the control, and the other groups were administered different doses of Al nanoparticles, Al microparticles (AlMP), and Al ionic forms (2, 4, and 8 mg/kg, i.p.) for 28 days. After 24 h, the animals were killed, brain tissue was separated, the mitochondrial fraction was isolated, and oxidative stress markers were measured. Also, mitochondrial function was assayed by MTT test. The results showed that all forms of Al particles induced ROS formation, lipid peroxidation, protein oxidation, glutathione depletion, mitochondrial dysfunction, and gait abnormalities in a dose-dependent manner. In addition, Al particles decreased mitochondrial membrane potential. These data indicated that oxidative stress might contribute to the toxicity effects of Al. Comparison of oxidative stress markers between all forms of Al revealed that the toxic effect of AlNP on brain tissue was substantially more than that caused by AlMP and bulk form. This study showed more neurotoxicity of AlNPs compared to other forms on brain oxidative damage that probably is due to more penetration into the brain.

Low-Temperature Sintering of AlN Ceramics by Sm2O3-Y2O3-CaO Sintering Additives Formed via Decomposition of Nitrate Solutions

NASA Astrophysics Data System (ADS)

Zhan, Jun; Cao, Ye; Zhang, Hao; Guo, Jun; Zhang, Jianhua; Geng, Chunlei; Shi, Changdong; Cui, Song; Tang, Wenming

2017-01-01

The Sm, Y and Ca anhydrous nitrates were mixed with the AlN powder in ethanol and then decomposed into the Sm2O3-Y2O3-CaO sintering additives via calcining. Low-temperature sintering of the AlN ceramics was carried out at temperature range from 1675 to 1750 °C. Effects of the composition and adding amount of the sintering additives on the phases, microstructures and properties of the AlN ceramics were investigated. During sintering the AlN ceramics, main secondary phases of CaYAl3O7 and CaSmAl3O7 form. The relative density, bending strength and thermal conductivity of the AlN ceramics increase with the increase in the rare-earth oxides in them. The thermal conductivity of the sintered AlN ceramics is also greatly affected by the distribution of the secondary phases. As sintered at 1750 °C, the AlN ceramics by adding the sintering additives of 2 wt.% Sm2O3, 2 wt.% Y2O3 and 1 wt.% CaO formed via decomposition of their nitrates is fully dense and have the optimal bending strength and thermal conductivity of 402.1 MPa and 153.7 W/(m K), respectively.

Oxidation of anthracene using waste Mn oxide minerals: the importance of wetting and drying sequences.

PubMed

Clarke, Catherine; Tourney, Janette; Johnson, Karen

2012-02-29

PAHs are a common problem in contaminated urban soils due to their recalcitrance. This study presents results on the oxidation of anthracene on synthetic and natural Mn oxide surfaces. Evaporation of anthracene spiked Mn oxide slurries in air results in the oxidation of 30% of the anthracene to anthraquinone. Control minerals, quartz and calcite, also oxidised a small but significant proportion of the anthracene (4.5% and 14% conversion, respectively) when spiked mineral slurries were evaporated in air. However, only Mn oxide minerals showed significant anthracene oxidation (5-10%) when evaporation took place in the absence of oxygen (N2 atmosphere). In the fully hydrated systems where no drying took place, natural Mn oxides showed an increase in anthracene oxidation with decreasing pH, with a conversion of 75% anthracene at pH 4. These results show both acidification and drying favor the oxidation of anthracene on Mn oxide mineral surfaces. It has also been demonstrated that non-redox active mineral surfaces, such as calcite, may play a role in contaminant breakdown during wetting and drying sequences. Given that climate changes suggest that wetting and drying sequences are likely to become more significant these results have important implications for contaminated land remediation technologies. Copyright © 2012 Elsevier B.V. All rights reserved.

Directed spatial organization of zinc oxide nanostructures

DOEpatents

Hsu, Julia [Albuquerque, NM; Liu, Jun [Richland, WA

2009-02-17

A method for controllably forming zinc oxide nanostructures on a surface via an organic template, which is formed using a stamp prepared from pre-defined relief structures, inking the stamp with a solution comprising self-assembled monolayer (SAM) molecules, contacting the stamp to the surface, such as Ag sputtered on Si, and immersing the surface with the patterned SAM molecules with a zinc-containing solution with pH control to form zinc oxide nanostructures on the bare Ag surface.

Formation and corrosion of a 410 SS/ceramic composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, X.; Ebert, W. L.; Indacochea, J. E.

This study evaluates the possible use of alloy/ceramic composite waste forms to immobilize metallic and oxide waste streams generated during the electrochemical reprocessing of spent reactor fuel in a single waste form. A representative composite material AOC410 was made to evaluate the microstructure and corrosion behavior at alloy/ceramic interfaces by reacting 410 stainless steel with Zr, Mo, and a mixture of lanthanide oxides. Essentially all of the Zr reacted with lanthanide oxides to form lanthanide zirconate, which combined with the remaining lanthanide oxides to form a porous ceramic network encapsulated by alloy as a composite puck. Excess alloy formed amore » metal bead on top of the composite. The alloys in the composite and bead were both mixture of martensite grains and ferrite grains with carbide precipitates. FeCrMo intermetallic phases also precipitated in the ferrite grains in the composite part. Ferrite surrounding carbides was sensitized and the least corrosion resistant in electrochemical corrosion tests conducted in an acidic brine electrolyte; ferrite neighboring martensite grains and intermetallics corroded galvanically. The lanthanide oxide domains dissolved chemically, but lanthanide zirconate domains did not dissolve. The presence of oxide phases did not affect corrosion of the neighboring alloy phases. These results suggest the longterm corrosion of a composite waste form can be evaluated by using separate material degradation models for the alloy and ceramic phases.« less

Tailoring the Oxygen Content of Graphite and Reduced Graphene Oxide for Specific Applications.

PubMed

Morimoto, Naoki; Kubo, Takuya; Nishina, Yuta

2016-02-25

Graphene oxide (GO) is widely recognized as a promising material in a variety of fields, but its structure and composition has yet to be fully controlled. We have developed general strategies to control the oxidation degree of graphene-like materials via two methods: oxidation of graphite by KMnO4 in H2SO4 (oGO), and reduction of highly oxidized GO by hydrazine (rGO). Even though the oxygen content may be the same, oGO and rGO have different properties, for example the adsorption ability, oxidation ability, and electron conductivity. These differences in property arise from the difference in the underlying graphitic structure and the type of defect present. Our results can be used as a guideline for the production of tailor-made graphitic carbons. As an example, we show that rGO with 23.1 wt% oxygen showed the best performance as an electrode of an electric double-layer capacitor.

Tailoring the Oxygen Content of Graphite and Reduced Graphene Oxide for Specific Applications

NASA Astrophysics Data System (ADS)

Morimoto, Naoki; Kubo, Takuya; Nishina, Yuta

2016-02-01

Graphene oxide (GO) is widely recognized as a promising material in a variety of fields, but its structure and composition has yet to be fully controlled. We have developed general strategies to control the oxidation degree of graphene-like materials via two methods: oxidation of graphite by KMnO4 in H2SO4 (oGO), and reduction of highly oxidized GO by hydrazine (rGO). Even though the oxygen content may be the same, oGO and rGO have different properties, for example the adsorption ability, oxidation ability, and electron conductivity. These differences in property arise from the difference in the underlying graphitic structure and the type of defect present. Our results can be used as a guideline for the production of tailor-made graphitic carbons. As an example, we show that rGO with 23.1 wt% oxygen showed the best performance as an electrode of an electric double-layer capacitor.

Moessbauer spectra of ferrite catalysts used in oxidative dehydrogenation

NASA Technical Reports Server (NTRS)

Cares, W. R.; Hightower, J. W.

1971-01-01

Room temperature Mossbauer spectroscopy was used to examine bulk changes which occur in low surface area CoFe2O4 and CuFe2O4 catalysts as a result of contact with various mixtures of trans-2-butene and O2 during oxidative dehydrogenation reactions at about 420 C. So long as there was at least some O2 in the gas phase, the CoFe2O4 spectrum was essentially unchanged. However, the spectrum changed from a random spinel in the oxidized state to an inverse spinel as it was reduced by oxide ion removal. The steady state catalyst lies very near the fully oxidized state. More dramatic solid state changes occurred as the CuFe2O4 underwent reduction. Under severe reduction, the ferrite was transformed into Cu and Fe3O4, but it could be reversibly recovered by oxidation. An intense doublet located near zero velocity persisted in all spectra of CuFe2O4 regardless of the state of reduction.

The anaerobic degradation of organic matter in Danish coastal sediments - Iron reduction, manganese reduction, and sulfate reduction

NASA Technical Reports Server (NTRS)

Canfield, Donald E.; Thamdrup, BO; Hansen, Jens W.

1993-01-01

A combination of porewater and solid phase analysis as well as a series of sediment incubations are used to quantify organic carbon oxidation by dissimilatory Fe reduction, Mn reduction, and sulfate reduction, in sediments from the Skagerrak (located off the northeast coast of Jutland, Denmark). Solid phase data are integrated with incubation results to define the zones of the various oxidation processes. At S(9), surface Mn enrichments of up to 3.5 wt pct were found, and with such a ready source of Mn, dissimilatory Mn reduction was the only significant anaerobic process of carbon oxidation in the surface 10 cm of the sediment. At S(4) and S(6), active Mn reduction occurred; however, most of the Mn reduction may have resulted from the oxidation of acid volatile sulfides and Fe(2+) rather than by a dissimilatory sulfate. Dissolved Mn(2+) was found to completely adsorb onto sediment containing fully oxidized Mn oxides.

Manganese oxide-based materials as electrochemical supercapacitor electrodes.

PubMed

Wei, Weifeng; Cui, Xinwei; Chen, Weixing; Ivey, Douglas G

2011-03-01

Electrochemical supercapacitors (ECs), characteristic of high power and reasonably high energy densities, have become a versatile solution to various emerging energy applications. This critical review describes some materials science aspects on manganese oxide-based materials for these applications, primarily including the strategic design and fabrication of these electrode materials. Nanostructurization, chemical modification and incorporation with high surface area, conductive nanoarchitectures are the three major strategies in the development of high-performance manganese oxide-based electrodes for EC applications. Numerous works reviewed herein have shown enhanced electrochemical performance in the manganese oxide-based electrode materials. However, many fundamental questions remain unanswered, particularly with respect to characterization and understanding of electron transfer and atomic transport of the electrochemical interface processes within the manganese oxide-based electrodes. In order to fully exploit the potential of manganese oxide-based electrode materials, an unambiguous appreciation of these basic questions and optimization of synthesis parameters and material properties are critical for the further development of EC devices (233 references).

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

PubMed Central

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-01-01

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-12-01

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g-1 based on solid-state redox reaction of oxide ions.

Nitric oxide mitigates arsenic-induced oxidative stress and genotoxicity in Vicia faba L.

PubMed

Shukla, Pratiksha; Singh, A K

2015-09-01

The protective effects of nitric oxide (NO) against arsenic (As)-induced structural disturbances in Vicia faba have been investigated. As treatment (0.25, 0.50, and 1 mM) resulted in a declined growth of V. faba seedlings. Arsenic treatment stimulates the activity of SOD and CAT while the activities of APX and GST content were decreased. The oxidative stress markers such as superoxide radical, hydrogen peroxide and malondialdehyde (lipid peroxidation) contents were enhanced by As. Overall results revealed that significant accumulation of As suppressed growth, photosynthesis, antioxidant enzymes (SOD, CAT, APX, and GST activity), mitotic index, and induction of different chromosomal abnormalities, hence led to oxidative stress. The concentration of SNP (0.02 mM) was very effective in counteracting the adverse effect of As toxicity. These abnormalities use partially or fully reversed by a simultaneous application of As and NO donor and sodium nitroprusside and has an ameliorating effect against As-induced oxidative stress and genotoxicity in V. faba roots.

Flavin binding to the deca-heme cytochrome MtrC: Insights from computational molecular simulation

DOE PAGES

Breuer, Marian; Rosso, Kevin  M.; Blumberger, Jochen

2015-12-15

Here, certain dissimilatory bacteria have the remarkable ability to use extracellular metal oxide minerals instead of oxygen as terminal electron sinks, using a process known as “extracellular respiration”. Specialized multiheme cytochromes located on the outer membrane of the microbe were shown to be crucial for electron transfer from the cell surface to the mineral. This process is facilitated by soluble, biogenic flavins secreted by the organism for the purpose of acting as an electron shuttle. However, their interactions with the outer-membrane cytochromes are not established on a molecular scale. Here, we study the interaction between the outer-membrane deca-heme cytochrome MtrCmore » from Shewanella oneidensis and flavin mononucleotide (FMN in fully oxidized quinone form) using computational docking. We find that interaction of FMN with MtrC is significantly weaker than with known FMN-binding proteins, but identify a mildly preferred interaction site close to heme 2 with a dissociation constant (K d) = 490 μM, in good agreement with recent experimental estimates, K d = 255 μM. The weak interaction with MtrC can be qualitatively explained by the smaller number of hydrogen bonds that the planar headgroup of FMN can form with this protein compared to FMN-binding proteins. Molecular dynamics simulation gives indications for a possible conformational switch upon cleavage of the disulphide bond of MtrC, but without concomitant increase in binding affinities according to this docking study. Overall, our results suggest that binding of FMN to MtrC is reversible and not highly specific, which may be consistent with a role as redox shuttle that facilitates extracellular respiration.« less

Experimentally Dissecting the Origins of Peroxiredoxin Catalysis.

PubMed

Nelson, Kimberly J; Perkins, Arden; Van Swearingen, Amanda E D; Hartman, Steven; Brereton, Andrew E; Parsonage, Derek; Salsbury, Freddie R; Karplus, P Andrew; Poole, Leslie B

2018-03-01

Peroxiredoxins (Prxs) are ubiquitous cysteine-based peroxidases involved in oxidant defense and signal transduction. Despite much study, the precise roles of conserved residues remain poorly defined. In this study, we carried out extensive functional and structural characterization of 10 variants of such residues in a model decameric bacterial Prx. Three active site proximal mutations of Salmonella typhimurium AhpC, T43V, R119A, and E49Q, lowered catalytic efficiency with hydrogen peroxide by 4-5 orders of magnitude, but did not affect reactivity toward their reductant, AhpF. pK a values of the peroxidatic cysteine were also shifted up by 1-1.3 pH units for these and a decamer disruption mutant, T77I. Except for the decamer-stabilizing T77V, all mutations destabilized decamers in the reduced form. In the oxidized form, three mutants-T77V, T43A, and T43S-exhibited stabilized decamers and were more efficiently reduced by AhpF than wild-type AhpC. Crystal structures of most mutants were solved and many showed alterations in stability of the fully folded active site loop. This is the first study of Prx mutants to comprehensively assess the effects of mutations on catalytic activities, the active site cysteine pK a , and the protein structure and oligomeric status. The Arg119 side chain must be properly situated for efficient catalysis, but for other debilitating variants, the functional defects could be explained by structural perturbations and/or associated decamer destabilization rather than direct effects. This underscores the importance of our comprehensive approach. A remarkable new finding was the preference of the reductant for decamers. Antioxid. Redox Signal. 28, 521-536.

The nature and origin of sesquiterpenoids in some tertiary fossil resins

NASA Astrophysics Data System (ADS)

Grantham, P. J.; Douglas, A. G.

1980-11-01

Analyses of two Tertiary fossil resins and a Tertiary montan wax have revealed the presence of a number of sesquiterpenoids. Using gas chromatographic retention data obtained on both polar and non-polar stationary phases and mass spectral comparisons with authentic compounds, the sesquiterpenoids α-cedrene, cedrane, cuparene, cedren-10-one, 8βH cedran-9-one and cuparenic acid have been identified in the fossil resin retinellite and a montain wax (both Oligocene) from lignite beds in the Bovey basin of Devon, England, and in the Pliocene fossil resin ionite from the lone valley of California. U.S.A. The sesquiterpenoids α-cedrene, cuparene and cuparenic acid are characteristic constituents of the essential oils of the Cupressaceae, a family of trees and shrubs of the order Coniferales, and it is argued that these fossil resins, and the montan wax, were derived from older forms of this family of plants. The ketones cedren-10-one and 8βH cedran-9-one, and the saturated hydrocarbon cedrane, are not reported to be constituents of modern genera of Cupressaceae and may have been formed during diagenesis. The cedrane occurring in these deposits appears to be a chemical hydrogenation product of α-cedrene. The ketones, on the other hand, may have resulted from the oxidation of α-cedrene although the mechanism of these reactions is not clear. If the ketones are not undetected constituents of these plants, then the presence in these deposits of both oxidised and fully-reduced α-cedrene products infers that separate phases of oxidation and reduction occurred during the diagenesis of the fossil resins and the montan wax.

[Apatite-forming ability of pure titanium implant after micro-arc oxidation treatment].

PubMed

Tian, Zhihui; Zhang, Yu; Wang, Lichao; Nan, Kaihui

2013-10-01

To investigate the apatite forming ability of pure titanium implant after micro-arc oxidation treatment in simulated body fluid (SBF) and obtain implants with calcium phosphate (Ca-P) layers. The implants were immersed in (SBF) after micro-arc oxidation treatment for different time lengths, and their apatite forming ability and the morphology and constituents of the Ca-P layers formed on the sample surface were analyzed using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive electron probe. After immersion in SBF, large quantities of Ca-P layers were induced on the surface of the samples. The Ca-P layers were composed of octacalcium phosphate and carbonated hydroxyapatite, and the crystals showed a plate-like morphology with an oriented growth. The implants with micro-arc oxidation treatment show good apatite forming ability on the surface with rich calcium and phosphorus elements. The formed layers are composed of bone-like apatite including octacalcium phosphate and carbonated hydroxyapatite.

Low melting high lithia glass compositions and methods

DOEpatents

Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.

2003-09-23

The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste uranium oxides The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

Holocene Concentrations of Methane in the Atmosphere are in Part Proportional to Concentrations of Sulfur Dioxide and Inversely Proportional to the Oxidizing Capacity of the Atmosphere

NASA Astrophysics Data System (ADS)

Ward, P. L.

2008-12-01

The atmosphere cleans itself by oxidizing pollutants. The primary oxidant is the hydroxyl radical (OH) formed by photodissociation of ozone in the near ultra-violet. Ozone and OH are in limited supply. Sulfur dioxide (SO2) absorbs near ultraviolet light limiting production of OH and reacts immediately with any available OH, forming sulfuric acid. Methane reacts more slowly with OH and will typically not be oxidized until there is little SO2. Thus a high concentration of methane indicates low oxidizing capacity. The rate at which SO2 is injected into the atmosphere controls oxidizing capacity and climate change in four ways: 1. Moderate rate: Large volcanic eruptions (VEI >=6) lower global temperatures for a few years when they are separated by years to decades so the oxidizing capacity of the atmosphere can fully recover. In 1991, Pinatubo volcano in the Philippines erupted 20 Mt SO2 and 491 Mt H2O, the largest volcanic eruption since 1912. The SO2 was oxidized primarily by OH to form a 99% pure aerosol of sulfuric acid and water at an elevation of 20-23 km. This aerosol reflected sunlight, lowering the world's temperature on average 0.4°C for three years. Ozone levels were reduced by 10%. Methane increased by 15 ppb for a year. The e-folding time for SO2 was 35 days. 2. High rate: When large eruptions occur once to several times per year, there is insufficient oxidizing capacity leading to increases in methane and other greenhouse gases and global warming. There were 15 times in the Holocene when large volcanoes erupted on average at least every year for 7 to 21 years. Man is now putting as much SO2 from burning fossil fuels into the atmosphere every year as one large volcano, causing current global warming. The two previous times were from 818-838 AD, the onset of the Medieval Warming Period, and from 180-143 BC, the onset of the Roman Warm Period. 3. Low rate: When there are no large eruptions for decades, the oxidizing capacity can catch up, cleaning the atmosphere, removing most of the methane and other pollutants. A clean atmosphere leads to cooling and drought. The 8.2 ka event is a classic example, but similar decadal droughts around 6.2, 5.8, 5.4, 4.2, and 2.9 ka caused the demise of major civilizations. 4. Extreme rate: Whereas large volcanic eruptions produce 10-1000 km3 of andesitic and silicic tephra, flood basalt eruptions produce as much as 3,000,000 km3 of basalt containing 10 to 100 times more SO2 per km3. The result is runaway global warming, widespread acid rain, and mass extinctions. The link between SO2 and global warming is good news because we have developed many efficient technologies that burn fossil fuels with less SO2 emission and scrub SO2 out of smoke stacks. Efforts to reduce acid rain have been successful in reducing manmade emissions of SO2 by >20% since 1980 and thereby reducing methane concentrations. Sudden increases in methane during the Pleistocene Dansgaard-Oeschger events follow sudden increases in volcanism. High rainfall especially in the Sahara and high methane concentrations in the early Holocene are clearly related to increased volcanism that brought about the end of the Ice Age. Increases in global warming at 3170 BC, 161 BC, and 828 AD are contemporaneous with short-term increases in methane. The rapid increase in SO2 from burning fossil fuels since 1850 can explain much of the corresponding rapid increase in methane. But during the last 5000 years, volcanism has been relatively constant and thus it can not explain the observed gradual increase in methane.

THERMODYNAMIC MODELING OF LIQUID AEROSOLS CONTAINING DISSOLVED ORGANICS AND ELECTROLYTES

EPA Science Inventory

Many tropospheric aerosols contain large fractions of soluble organic material, believed to derive from the oxidation of precursors such alpha-pinene. The chemical composition of aerosol organic matter is complex and not yet fully understood.

The key properties of solu...

Prospects for utilization of air liquefaction and enrichment system (ALES) propulsion in fully reusable launch vehicles

NASA Technical Reports Server (NTRS)

Bond, W. H.; Yi, A. C.

1993-01-01

A concept is shown for a fully reusable, earth to orbit launch vehicle with horizontal takeoff and landing, employing an air-turborocket for low speed and a rocket for high speed acceleration, both using LH2 fuel. The turborocket employs a modified liquid air cycle to supply the oxidizer. The rocket uses 90 percent pure LOX that is collected from the atmosphere, separated, and stored during operation of the turborocket from about Mach 2 to Mach 5 or 6. The takeoff weight and the thrust required at takeoff are markedly reduced by collecting the rocket oxidizer in-flight. The paper shows an approach and the corresponding technology needs for using ALES propulsion in a SSTO vehicle. Reducing the trajectory altitude at the end of collection reduces the wing area and increases payload. The use of state-of-the-art materials, such as graphite polyimide, is critical to meet the structure weight objective for SSTO. Configurations that utilize 'waverider' aerodynamics show great promise to reduce the vehicle weight.

Two-color vibrational, femtosecond, fully resonant electronically enhanced CARS (FREE-CARS) of gas-phase nitric oxide.

PubMed

Stauffer, Hans U; Roy, Sukesh; Schmidt, Jacob B; Wrzesinski, Paul J; Gord, James R

2016-09-28

A resonantly enhanced, two-color, femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) approach is demonstrated and used to explore the nature of the frequency- and time-dependent signals produced by gas-phase nitric oxide (NO). Through careful selection of the input pulse wavelengths, this fully resonant electronically enhanced CARS (FREE-CARS) scheme allows rovibronic-state-resolved observation of time-dependent rovibrational wavepackets propagating on the vibrationally excited ground-state potential energy surface of this diatomic species. Despite the use of broadband, ultrafast time-resolved input pulses, high spectral resolution of gas-phase rovibronic transitions is observed in the FREE-CARS signal, dictated by the electronic dephasing timescales of these states. Analysis and computational simulation of the time-dependent spectra observed as a function of pump-Stokes and Stokes-probe delays provide insight into the rotationally resolved wavepacket motion observed on the excited-state and vibrationally excited ground-state potential energy surfaces of NO, respectively.

Method for implementation of back-illuminated CMOS or CCD imagers

NASA Technical Reports Server (NTRS)

Pain, Bedabrata (Inventor)

2008-01-01

A method for implementation of back-illuminated CMOS or CCD imagers. An oxide layer buried between silicon wafer and device silicon is provided. The oxide layer forms a passivation layer in the imaging structure. A device layer and interlayer dielectric are formed, and the silicon wafer is removed to expose the oxide layer.

Biological Oxidation of As (III) in a Full-Scale Iron Removal Plant

EPA Science Inventory

The effectiveness of arsenic removal from water is largely dependent on the oxidation state of the arsenic. As (III) is much more difficult to remove relative to the oxidized As (V) form. Arsenic in ground waters across the Midwest is typically in the form of As (III), and ther...

Full thermomechanical coupling in modelling of micropolar thermoelasticity

NASA Astrophysics Data System (ADS)

Murashkin, E. V.; Radayev, Y. N.

2018-04-01

The present paper is devoted to plane harmonic waves of displacements and microrotations propagating in fully coupled thermoelastic continua. The analysis is carried out in the framework of linear conventional thermoelastic micropolar continuum model. The reduced energy balance equation and the special form of the Helmholtz free energy are discussed. The constitutive constants providing fully coupling of equations of motion and heat conduction are considered. The dispersion equation is derived and analysed in the form bi-cubic and bi-quadratic polynoms product. The equation are analyzed by the computer algebra system Mathematica. Algebraic forms expressed by complex multivalued square and cubic radicals are obtained for wavenumbers of transverse and longitudinal waves. The exact forms of wavenumbers of a plane harmonic coupled thermoelastic waves are computed.

Effects of monoamine oxidase inhibition by clorgyline, deprenil or tranylcypromine on 5-hydroxytryptamine concentrations in rat brain and hyperactivity following subsequent tryptophan administration.

PubMed Central

Green, A R; Youdim, M B

1975-01-01

1 The effect of various doses of tranylcypromine on the degree of inhibition of rat brain monoamine oxidase (MAO) using 5-hydroxytryptamine (5-HT), dopamine and phenylethylamine as substrates has been examined 120 min after injection of the inhibitor. The concentration of brain 5-HT was also examined both after tranylcypromine alone and also when L-tryptophan (100 mg/kg) had been given 30 min after the tranylcypromine. 2 All doses of tranylcypromine greater than 2.5 mg/kg totally inhibited MAO oxidation of 5-HT, phenylethylamine and dopamine as measured in vitro and produced a similar rise of brain 5-HT in vivo. When tryptophan was also given, there was a further rise of brain 5-HT, which was comparable after all doses of tranylcypromine above 2.5 mg/kg and the characteristic syndrome of hyperactivity made is appearance. 3 Clorgyline (a "Type A" MAO inhibitor), in doses up to 10 mg/kg, did not totally inhibit MAO activity towards phenylethylamine although it did inhibit 5-HT oxidation by 100%. Deprenil (a "Type B" MAO inhibitor) at doses up to 10 mg/kg did not fully inhibit 5-HT oxidation although phenylethylamine oxidation was inhibited almost completely. Administration of either compound alone did not produce as great an accumulation of brain 5-HT as that seen after tranylcypromine (2.5 mg/kg) and subsequent administration of tryptophan did not cause hyperactivity or the rise of brain 5-HT seen after tranylcypromine (2.5 mg/kg) plus tryptophan. 4 Administration of clorgyline plus deprenil (2.5 mg/kg of each) almost totally inhibited oxidation of both 5-HT and phenylethylamine; subsequent tryptophan administration resulted in a rise of brain 5-HT nearly as great as that seen following tranylcypromine (2.5 mg/kg) plus tryptophan and the animals became hyperactive. 5 No evidence was found pointing to the formation of any other 5-substituted indole in the brain following tranylcypromine plus L-tryptophan administration as suggested by others. 6 It is concluded that while 5-HT may normally be metabolized in the brain by "Tye A" MAO in vivo, when this form is inhibited, 5-HT can still be metabolized by "Type B" enzyme. It is only when both forms are almost totally inhibited that the largest rise of brain 5-HT is seen and subsequent tryptophan administration produces the hyperactivity syndrome. PMID:1203627

The formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia)

NASA Astrophysics Data System (ADS)

Majzlan, Juraj; Lalinská, Bronislava; Chovan, Martin; Jurkovič, L.'ubomír; Milovská, Stanislava; Göttlicher, Jörg

2007-09-01

The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold ˜380,000 m 3 of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 ± 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS 2; arsenopyrite, FeAsS; berthierite, FeSb 2S 4) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ μ-XANES experiments indicate that As in the weathering rims is fully oxidized (As 5+). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As 2O 5 and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As 5+. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 Å, that is, increasing polymerization of the iron octahedra to form larger units with fewer adsorption sites. Therefore, although ferrihydrite is an excellent material for capturing arsenic, its use as a medium for a long-term storage of As has to be considered with a great caution because it will tend to release arsenic as it ages.

Synthesis of soluble conducting polymers by acoustic mixing

DOEpatents

Kane, Marie C.

2016-09-13

A method including combining an aniline monomer, an oxidant, water and an organic solvent; subjecting the combination to acoustic mixing to form an emulsion; and recovering a polyaniliine from the combination. A method including combining a aniline monomer, an oxidant, water and an organic solvent; forming a polyaniline by acoustic mixing the combination; and recovering the polyaniliine from the combination. A method including forming a combination of an aniline monomer, an oxidant, water and an organic solvent in the absence of an emulsifier; acoustic mixing the combination for a time period to form a polyaniline; and recovering a polyaniliine from the combination.

Nitrous oxide-forming codenitrification catalyzed by cytochrome P450nor.

PubMed

Su, Fei; Takaya, Naoki; Shoun, Hirofumi

2004-02-01

Intact cells of the denitrifying fungus Fusarium oxysporum were previously shown to catalyze codenitrification to form a hybrid nitrous oxide (N2O) species from nitrite and other nitrogen compounds such as azide and ammonia. Here we show that cytochrome P450nor can catalyze the codenitrification reaction to form N2O from nitric oxide (NO) but not nitrite, and azide or ammonia. The results show that the direct substrate of the codenitrification by intact cells should not be nitrite but NO, which is formed from nitrite by the reaction of a dissimilatory nitrite reductase.

Reactive aldehyde metabolites from the anti-HIV drug abacavir: amino acid adducts as possible factors in abacavir toxicity.

PubMed

Charneira, Catarina; Godinho, Ana L A; Oliveira, M Conceição; Pereira, Sofia A; Monteiro, Emília C; Marques, M Matilde; Antunes, Alexandra M M

2011-12-19

Abacavir is a nucleoside reverse transcriptase inhibitor marketed since 1999 for the treatment of infection with the human immunodeficiency virus type 1 (HIV). Despite its clinical efficacy, abacavir administration has been associated with serious and sometimes fatal toxic events. Abacavir has been reported to undergo bioactivation in vitro, yielding reactive species that bind covalently to human serum albumin, but the haptenation mechanism and its significance to the toxic events induced by this anti-HIV drug have yet to be elucidated. Abacavir is extensively metabolized in the liver, resulting in inactive glucuronide and carboxylate metabolites. The metabolism of abacavir to the carboxylate involves a two-step oxidation via an unconjugated aldehyde, which under dehydrogenase activity isomerizes to a conjugated aldehyde. Concurrently with metabolic oxidation, the two putative aldehyde metabolites may be trapped by nucleophilic side groups in proteins yielding covalent adducts, which can be at the onset of the toxic events associated with abacavir. To gain insight into the role of aldehyde metabolites in abacavir-induced toxicity and with the ultimate goal of preparing reliable and fully characterized prospective biomarkers of exposure to the drug, we synthesized the two putative abacavir aldehyde metabolites and investigated their reaction with the α-amino group of valine. The resulting adducts were subsequently stabilized by reduction with sodium cyanoborohydride and derivatized with phenyl isothiocyanate, leading in both instances to the formation of the same phenylthiohydantoin, which was fully characterized by NMR and MS. These results suggest that the unconjugated aldehyde, initially formed in vivo, rapidly isomerizes to the thermodynamically more stable conjugated aldehyde, which is the electrophilic intermediate mainly involved in reaction with bionucleophiles. Moreover, we demonstrated that the reaction of the conjugated aldehyde with nitrogen bionucleophiles occurs exclusively via Schiff base formation, whereas soft sulfur nucleophiles react by Michael-type 1,4-addition to the α,β-unsaturated system. The synthetic phenylthiohydantoin adduct was subsequently used as standard for LC-ESI-MS monitoring of N-terminal valine adduct formation, upon modification of human hemoglobin in vitro with the conjugated abacavir aldehyde, followed by reduction and Edman degradation. The same postmodification strategy was applied to investigate the products formed by incubation of abacavir with rat liver cytosol, followed by trapping with ethyl valinate. In both instances, the major adduct detected corresponded to the synthetic phenylthiohydantoin standard. These results suggest that abacavir metabolism to the carboxylate(s) via aldehyde intermediate(s) could be a factor in the toxic events elicited by abacavir administration. Furthermore, the availability of a reliable and fully characterized synthetic standard of the abacavir adduct with the N-terminal valine of hemoglobin and its easy detection in the model hemoglobin modifications support the usefulness of this adduct as a prospective biomarker of abacavir toxicity in humans. © 2011 American Chemical Society

Method for making hydrogen rich gas from hydrocarbon fuel

DOEpatents

Krumpelt, M.; Ahmed, S.; Kumar, R.; Doshi, R.

1999-07-27

A method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400 C for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide. 4 figs.

Method for making hydrogen rich gas from hydrocarbon fuel

DOEpatents

Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

1999-01-01

A method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

Alkali resistant optical coatings for alkali lasers and methods of production thereof

DOEpatents

Soules, Thomas F; Beach, Raymond J; Mitchell, Scott C

2014-11-18

In one embodiment, a multilayer dielectric coating for use in an alkali laser includes two or more alternating layers of high and low refractive index materials, wherein an innermost layer includes a thicker, >500 nm, and dense, >97% of theoretical, layer of at least one of: alumina, zirconia, and hafnia for protecting subsequent layers of the two or more alternating layers of high and low index dielectric materials from alkali attack. In another embodiment, a method for forming an alkali resistant coating includes forming a first oxide material above a substrate and forming a second oxide material above the first oxide material to form a multilayer dielectric coating, wherein the second oxide material is on a side of the multilayer dielectric coating for contacting an alkali.

Preparation of energy storage materials

DOEpatents

Li, Lin Song; Jia, Quanxi

2003-01-01

A process is provided for the preparation of a metallic oxide composite including mixing an aqueous solution of a water-soluble metal compound and colloidal silica, depositing the mixture upon a substrate, heating the mixture-coated substrates at temperatures from about 150.degree. C. to about 300.degree. C. for time sufficient to form a metallic oxide film, and, removing the silica from the metallic oxide film whereby a porous metal oxide structure is formed.

Preparation Of Energy Storage Materials

DOEpatents

Li, Lin Song; Jia, Quanxi

2003-12-02

A process is provided for the preparation of a metallic oxide composite including mixing an aqueous solution of a water-soluble metal compound and colloidal silica, depositing the mixture upon a substrate, heating the mixture-coated substrates at temperatures from about 150.degree. C. to about 300.degree. C. for time sufficient to form a metallic oxide film, and, removing the silica from the metallic oxide film whereby a porous metal oxide structure is formed.

Method of forming a joint

DOEpatents

Butt, Darryl Paul; Cutler, Raymond Ashton; Rynders, Steven Walton; Carolan, Michael Francis

2006-08-22

A method of joining at least two sintered bodies to form a composite structure, including providing a first multicomponent metallic oxide having a perovskitic or fluorite crystal structure; providing a second sintered body including a second multicomponent metallic oxide having a crystal structure of the same type as the first; and providing at an interface a joint material containing at least one metal oxide containing at least one metal identically contained in at least one of the first and second multicomponent metallic oxides. The joint material is free of cations of Si, Ge, Sn, Pb, P and Te and has a melting point below the sintering temperatures of both sintered bodies. The joint material is heated to a temperature above the melting point of the metal oxide(s) and below the sintering temperatures of the sintered bodies to form the joint. Structures containing such joints are also disclosed.

Thermal Oxidation of a Carbon Condensate Formed in High-Frequency Carbon and Carbon-Nickel Plasma Flow

NASA Astrophysics Data System (ADS)

Churilov, G. N.; Nikolaev, N. S.; Cherepakhin, A. V.; Dudnik, A. I.; Tomashevich, E. V.; Trenikhin, M. V.; Bulina, N. G.

2018-02-01

We have reported on the comparative characteristics of thermal oxidation of a carbon condensate prepared by high-frequency arc evaporation of graphite rods and a rod with a hollow center filled with nickel powder. In the latter case, along with different forms of nanodisperse carbon, nickel particles with nickel core-carbon shell structures are formed. It has been found that the processes of the thermal oxidation of carbon condensates with and without nickel differ significantly. Nickel particles with the carbon shell exhibit catalytic properties with respect to the oxidation of nanosized carbon structures. A noticeable difference between the temperatures of the end of the oxidation process for various carbon nanoparticles and nickel particles with the carbon shell has been established. The study is aimed at investigations of the effect of nickel nanoparticles on the dynamics of carbon condensate oxidation upon heating in the argon-oxygen flow.

The classical equation of state of fully ionized plasmas

NASA Astrophysics Data System (ADS)

Eisa, Dalia Ahmed

2011-03-01

The aim of this paper is to calculate the analytical form of the equation of state until the third virial coefficient of a classical system interacting via an effective potential of fully Ionized Plasmas. The excess osmotic pressure is represented in the forms of a convergent series expansions in terms of the plasma Parameter μ _{ab} = {{{e_a e_b χ } over {DKT}}}, where χ2 is the square of the inverse Debye radius. We consider only the thermal equilibrium plasma.

Removal of sulfur and nitrogen containing pollutants from discharge gases

DOEpatents

Joubert, James I.

1986-01-01

Oxides of sulfur and of nitrogen are removed from waste gases by reaction with an unsupported copper oxide powder to form copper sulfate. The resulting copper sulfate is dissolved in water to effect separation from insoluble mineral ash and dried to form solid copper sulfate pentahydrate. This solid sulfate is thermally decomposed to finely divided copper oxide powder with high specific surface area. The copper oxide powder is recycled into contact with the waste gases requiring cleanup. A reducing gas can be introduced to convert the oxide of nitrogen pollutants to nitrogen.

Electrode structures and surfaces for Li batteries

DOEpatents

Thackeray, Michael M.; Kang, Sun-Ho; Balasubramanian, Mahalingam; Croy, Jason

2017-03-14

This invention relates to methods of preparing positive electrode materials for electrochemical cells and batteries. It relates, in particular, to a method for fabricating lithium-metal-oxide electrode materials for lithium cells and batteries. The method comprises contacting a hydrogen-lithium-manganese-oxide material with one or more metal ions, preferably in an acidic solution, to insert the one or more metal ions into the hydrogen-lithium-manganese-oxide material; heat-treating the resulting product to form a powdered metal oxide composition; and forming an electrode from the powdered metal oxide composition.

Interphase for ceramic matrix composites reinforced by non-oxide ceramic fibers

NASA Technical Reports Server (NTRS)

DiCarlo, James A. (Inventor); Bhatt, Ramakrishna (Inventor); Morscher, Gregory N. (Inventor); Yun, Hee-Mann (Inventor)

2008-01-01

A ceramic matrix composite material is disclosed having non-oxide ceramic fibers, which are formed in a complex fiber architecture by conventional textile processes; a thin mechanically weak interphase material, which is coated on the fibers; and a non-oxide or oxide ceramic matrix, which is formed within the interstices of the interphase-coated fiber architecture. During composite fabrication or post treatment, the interphase is allowed to debond from the matrix while still adhering to the fibers, thereby providing enhanced oxidative durability and damage tolerance to the fibers and the composite material.

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

NASA Technical Reports Server (NTRS)

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

1995-01-01

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.

Exhaustive oxidation of a nickel dithiolate complex: some mechanistic insights en route to sulfate formation.

PubMed

Hosler, Erik R; Herbst, Robert W; Maroney, Michael J; Chohan, Balwant S

2012-01-21

A study of the step-wise oxidation of a Ni(II) diaminodithiolate complex through the formation of sulfate, the ultimate sulfur oxygenate, is reported. Controlled oxygenations or peroxidations of a neutral, planar, tetracoordinate, low-spin Ni(II) complex of a N(2)S(2)-donor ligand, (N,N'-dimethyl-N-N'-bis(2-mecaptoethyl)-1,3-propanediaminato) nickel(ii) (1), led to a series of sulfur oxygenates that have been isolated and characterized by ESI-MS and single-crystal X-ray diffraction. A monosulfenate complex (2) was detected by ESI-MS as a product of oxidation with one equivalent of H(2)O(2). However, this complex proved too unstable to isolate. Reaction of the dithiolate (1) with two equivalents of H(2)O(2) or one O(2) molecule leads to the formation of a monosulfinate complex (3), which was isolated and fully characterized by crystallography. The oxidation product of the monosulfinate (3) produced with either O(2) or H(2)O(2) is an interesting dimeric complex containing both sulfonate and thiolate ligands (4), this complex was fully characterized by crystallography, details of which were reported earlier by us. A disulfonate complex (7) is produced by reaction of 1 in the presence of O(2) or by reaction with exactly six equivalents of H(2)O(2). This complex was isolated and also fully characterized by crystallography. Possible intermediates in the conversion of the monosulfinate complex (3) to the disulfonate complex (7) include complexes with mixed sulfonate/sulfenate (5) or sulfonate/sulfinate (6) ligands. Complex 5, a four-oxygen adduct of 1, was not detected, but the sulfonate/sulfinate complex (6) was isolated and characterized. The oxidation chemistry of 1 is very different from that reported for other planar cis-N(2)S(2) Ni(ii) complexes including N,N'-dimethyl-N-N'-bis(2-mecaptoethyl)-1,3-ethylenediaminato) nickel(II), (8), and N,N'-bis(mercaptoethyl)-1,5-diazacyclooctane nickel(II). To address the structural aspects of the reactivity differences, the crystal structure of 8 was also determined. A comparison of the structures of planar Ni(II) complexes containing cis-dithiolate ligands, strongly suggests that the differences in reactivity are determined in part by the degree of flexibility that is allowed by the NN' chelate ring.

Formation and aging of secondary organic aerosol from toluene: Changes in chemical composition, volatility, and hygroscopicity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

Formation and aging of secondary organic aerosol from toluene: Changes in chemical composition, volatility, and hygroscopicity

DOE PAGES

Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; ...

2015-07-24

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

Forcing Cesium into Higher Oxidation States Using Useful hard x-ray Induced Chemistry under High Pressure

NASA Astrophysics Data System (ADS)

Sneed, D.; Pravica, M.; Kim, E.; Chen, N.; Park, C.; White, M.

2017-10-01

This paper discusses our attempt to synthesize higher oxidation forms of cesium fluoride by pressurizing cesium fluoride in a fluorine-rich environment created via the x-ray decomposition of potassium tetrafluoroborate. This was done in order to confirm recent theoretical predictions of higher oxidation forms of CsFn. We discuss the development of a technique to produce molecular fluorine in situ via useful hard x-ray photochemistry, and the attempt to utilize this technique to form higher oxidation states of cesium fluoride. In order to verify the formation of the novel stoichiometric species of CsFn. X-ray Absorption Near Edge Spectroscopy (XANES) centered on the cesium K-edge was performed to probe the oxidation state of cesium as well as the local molecular coordination around Cs.

Ultra-Smooth, Fully Solution-Processed Large-Area Transparent Conducting Electrodes for Organic Devices

PubMed Central

Jin, Won-Yong; Ginting, Riski Titian; Ko, Keum-Jin; Kang, Jae-Wook

2016-01-01

A novel approach for the fabrication of ultra-smooth and highly bendable substrates consisting of metal grid-conducting polymers that are fully embedded into transparent substrates (ME-TCEs) was successfully demonstrated. The fully printed ME-TCEs exhibited ultra-smooth surfaces (surface roughness ~1.0 nm), were highly transparent (~90% transmittance at a wavelength of 550 nm), highly conductive (sheet resistance ~4 Ω ◻−1), and relatively stable under ambient air (retaining ~96% initial resistance up to 30 days). The ME-TCE substrates were used to fabricate flexible organic solar cells and organic light-emitting diodes exhibiting devices efficiencies comparable to devices fabricated on ITO/glass substrates. Additionally, the flexibility of the organic devices did not degrade their performance even after being bent to a bending radius of ~1 mm. Our findings suggest that ME-TCEs are a promising alternative to indium tin oxide and show potential for application toward large-area optoelectronic devices via fully printing processes. PMID:27808221

Ultra-Smooth, Fully Solution-Processed Large-Area Transparent Conducting Electrodes for Organic Devices

NASA Astrophysics Data System (ADS)

Jin, Won-Yong; Ginting, Riski Titian; Ko, Keum-Jin; Kang, Jae-Wook

2016-11-01

A novel approach for the fabrication of ultra-smooth and highly bendable substrates consisting of metal grid-conducting polymers that are fully embedded into transparent substrates (ME-TCEs) was successfully demonstrated. The fully printed ME-TCEs exhibited ultra-smooth surfaces (surface roughness ~1.0 nm), were highly transparent (~90% transmittance at a wavelength of 550 nm), highly conductive (sheet resistance ~4 Ω ◻-1), and relatively stable under ambient air (retaining ~96% initial resistance up to 30 days). The ME-TCE substrates were used to fabricate flexible organic solar cells and organic light-emitting diodes exhibiting devices efficiencies comparable to devices fabricated on ITO/glass substrates. Additionally, the flexibility of the organic devices did not degrade their performance even after being bent to a bending radius of ~1 mm. Our findings suggest that ME-TCEs are a promising alternative to indium tin oxide and show potential for application toward large-area optoelectronic devices via fully printing processes.

Ultra-Smooth, Fully Solution-Processed Large-Area Transparent Conducting Electrodes for Organic Devices.

PubMed

Jin, Won-Yong; Ginting, Riski Titian; Ko, Keum-Jin; Kang, Jae-Wook

2016-11-03

A novel approach for the fabrication of ultra-smooth and highly bendable substrates consisting of metal grid-conducting polymers that are fully embedded into transparent substrates (ME-TCEs) was successfully demonstrated. The fully printed ME-TCEs exhibited ultra-smooth surfaces (surface roughness ~1.0 nm), were highly transparent (~90% transmittance at a wavelength of 550 nm), highly conductive (sheet resistance ~4 Ω ◻ -1 ), and relatively stable under ambient air (retaining ~96% initial resistance up to 30 days). The ME-TCE substrates were used to fabricate flexible organic solar cells and organic light-emitting diodes exhibiting devices efficiencies comparable to devices fabricated on ITO/glass substrates. Additionally, the flexibility of the organic devices did not degrade their performance even after being bent to a bending radius of ~1 mm. Our findings suggest that ME-TCEs are a promising alternative to indium tin oxide and show potential for application toward large-area optoelectronic devices via fully printing processes.

Reduced Graphene Oxides: Influence of the Reduction Method on the Electrocatalytic Effect towards Nucleic Acid Oxidation

PubMed Central

Báez, Daniela F.; Pardo, Helena; Laborda, Ignacio; Marco, José F.; Yáñez, Claudia; Bollo, Soledad

2017-01-01

For the first time a critical analysis of the influence that four different graphene oxide reduction methods have on the electrochemical properties of the resulting reduced graphene oxides (RGOs) is reported. Starting from the same graphene oxide, chemical (CRGO), hydrothermal (hTRGO), electrochemical (ERGO), and thermal (TRGO) reduced graphene oxide were produced. The materials were fully characterized and the topography and electroactivity of the resulting glassy carbon modified electrodes were also evaluated. An oligonucleotide molecule was used as a model of DNA electrochemical biosensing. The results allow for the conclusion that TRGO produced the RGOs with the best electrochemical performance for oligonucleotide electroanalysis. A clear shift in the guanine oxidation peak potential to lower values (~0.100 V) and an almost two-fold increase in the current intensity were observed compared with the other RGOs. The electrocatalytic effect has a multifactorial explanation because the TRGO was the material that presented a higher polydispersity and lower sheet size, thus exposing a larger quantity of defects to the electrode surface, which produces larger physical and electrochemical areas. PMID:28677654

Oxidation kinetics of Haynes 230 alloy in air at temperatures between 650 and 850 °C

NASA Astrophysics Data System (ADS)

Jian, Li; Jian, Pu; Bing, Hua; Xie, Guangyuan

Haynes 230 alloy was oxidized in air at temperatures between 650 and 850 °C. Thermogravimetry was used to measure the kinetics of oxidation. The formed oxides were identified by the thin film (small angle) X-ray diffraction technique. Cr 2O 3 and MnCr 2O 4 were found in the oxide scale. Multi-stage oxidation kinetics was observed, and each stage follows Wagner's parabolic law. The first slow oxidation stage corresponded to the growth of an Cr 2O 3 layer, controlled by Cr ions diffusion through the dense Cr 2O 3 scale. The faster second stage was a result of rapid diffusion of Mn ions passing through the established Cr 2O 3 scale to form MnCr 2O 4 on top of the Cr 2O 3 layer. A duplex oxide scale is expected. The third stage, with a rate close to that of the first stage, only appeared for oxidation in the intermediate temperature range, i.e., 750-800 °C, which can be explained by the interruption of the Mn flux that forms MnCr 2O 4.

Water Photo-oxidation Initiated by Surface-Bound Organic Chromophores.

PubMed

Eberhart, Michael S; Wang, Degao; Sampaio, Renato N; Marquard, Seth L; Shan, Bing; Brennaman, M Kyle; Meyer, Gerald J; Dares, Christopher; Meyer, Thomas J

2017-11-15

Organic chromophores can be synthesized by established methods and offer an opportunity to expand overall solar spectrum utilization for dye-sensitized photoelectrosynthesis cells. However, there are complications in the use of organic chromophores arising from the instability of their oxidized forms, the inability of their oxidized forms to activate a water oxidation catalyst, or the absence of a sufficiently reducing excited state for electron injection into appropriate semiconductors. Three new triarylamine donor-acceptor organic dyes have been investigated here for visible-light-driven water oxidation. They offer highly oxidizing potentials (>1 V vs NHE in aqueous solution) that are sufficient to drive a water oxidation catalyst and excited-state potentials (∼-1.2 V vs NHE) sufficient to inject into TiO 2 . The oxidized form of one of the chromophores is sufficiently stable to exhibit reversible electrochemistry in aqueous solution. The chromophores also have favorable photophysics. Visible-light-driven oxygen production by an organic chromophore for up to 1 h of operation has been demonstrated with reasonable faradaic efficiencies for measured O 2 production. The properties of organic chromophores necessary for successfully driving water oxidation in a light-driven system are explored along with strategies for improving device performance.

Method of forming low cost, formable High T(subc) superconducting wire

NASA Technical Reports Server (NTRS)

Smialek, James L. (Inventor)

1989-01-01

A ceramic superconductivity part, such as a wire, is produced through the partial oxidation of a specially formulated copper alloy in a core. The alloys contains low level of quantities of rare earth and alkaline earth dopant elements. Upon oxidation at high temperatures, and superconducting oxide phases are formed as a thin film.

Unexpected Catalytic Reactions of Silyl-protected Enoldiazoacetates With Nitrile Oxides That Form 5- Arylaminofuran-2(3H)-one-4-carboxylates

PubMed Central

Xu, Xinfang; Shabashov, Dmitry; Zavalij, Peter Y.; Doyle, Michael P.

2012-01-01

Silyl-protected enoldiazoacetates undergo dirhodium(II) catalyzed reactions with nitrile oxides to form acid-labile ketenimines via dipolar cycloaddition of nitrile oxides to a donor/acceptor cyclopropene and Lossen rearrangement of the dipolar adduct; acid catalysis converts the ketenimine to the furan product. PMID:22272728

THE EFFECT OF OXIDANTS ON THE PROPERTIES OF FE (III) PARTICLES AND SUSPENSIONS FORMED FROM THE OXIDATION OF FE (II)

EPA Science Inventory

Oxidation of Fe(II) to Fe(III) is an important reaction in drinking water treatment and distribution systems, and the ferric particles that form are a major source of consumer complaints of colored water. Ferrous iron is found naturally in many ground waters and can be released ...

Short Range-Ordered Minerals: Insight into Aqueous Alteration Processes on Mars

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Morris, R. V.; Golden, D. C.

2011-01-01

Short range-ordered (SRO) aluminosilicates (e.g., allophane) and nanophase ferric oxides (npOx) are common SRO minerals derived during aqueous alteration of basaltic materials. NpOx refers to poorly crystalline or amorphous alteration products that can be any combination of superparamagnetic hematite and/or goethite, akaganeite, schwertmannite, ferrihydrite, iddingsite, and nanometer-sized ferric oxide particles that pigment palagonitic tephra. Nearly 30 years ago, SRO phases were suggested as alteration phases on Mars based on similar spectral properties for altered basaltic tephra on the slopes of Mauna Kea in Hawaii and Martian bright regions measured by Earth-based telescopes. Detailed characterization of altered basaltic tephra on Mauna Kea have identified a variety of alteration phases including allophane, npOx, hisingerite, jarosite, alunite, hematite, goethite, ferrihydrite, halloysite, kaolinite, smectite, and zeolites. The presence of npOx and other Fe-bearing minerals (jarosite, hematite, goethite) was confirmed by the M ssbauer Spectrometer onboard the Mars Exploration Rovers. Although the presence of allophane has not been definitely identified on Mars robotic missions, chemical analysis by the Spirit and Opportunity rovers and thermal infrared spectral orbital measurements suggest the presence of allophane or allophane-like phases on Mars. SRO phases form under a variety of environmental conditions on Earth ranging from cold and arid to warm and humid, including hydrothermal conditions. The formation of SRO aluminosilicates such as allophane (and crystalline halloysite) from basaltic material is controlled by several key factors including activity of water, extent of leaching, Si activity in solution, and available Al. Generally, a low leaching index (e.g., wet-dry cycles) and slightly acidic to alkaline conditions are necessary. NpOx generally form under aqueous oxidative weathering conditions, although thermal oxidative alteration may occasional be involved. The style of aqueous alteration (hydrolytic vs. acid sulfate) impacts which phases will form (e.g., oxides, oxysulfates, and oxyhydroxides). Knowledge on the formation processes of SRO phases in basaltic materials on Earth has allowed significant enhancement in our understanding of the aqueous processes at work on Mars. The 2011 Mars Science Laboratory (MSL) will provide an instrument suite that should improve our understanding of the mineralogical and chemical compositions of SRO phases. CheMin is an X-ray diffraction instrument that may provide broad X-ray diffraction peaks for SRO phases; e.g., broad peaks around 0.33 and 0.23 nm for allophane. Sample Analysis at Mars (SAM) heats samples and detects evolved gases of volatile-bearing phases including SRO phases (i.e., carbonates, sulfates, hydrated minerals). The Alpha Particle X-ray Spectrometer (APXS) and ChemCam element analyzers will provide chemical characterization of samples. The identification of SRO phases in surface materials on MSL will be challenging due to their nanocrystalline properties; their detection and identification will require utilizing the MSL instrument suite in concert. Ultimately, sample return missions will be required to definitively identify and fully characterize SRO minerals with state-of-the-art laboratory instrumentation back on Earth.

The effect of variations of cobalt content on the cyclic oxidation resistance of selected Ni-base superalloys

NASA Technical Reports Server (NTRS)

Barrett, Charles A.

1987-01-01

Cobalt levels were systematically varied in the Ni-base turbine alloys U-700 (cast), U-700m (PM/HIP), Waspaloy, Mar-M-247, In-738, Nimonic-115, U-720, and SX-R-150. the cobalt levels ranged from 0 wt pct to the nominal commercial content in each alloy. the alloys were tested in cyclic oxidation in static air at 1000, 1100 and 1150 C for 500, 200, and 100 hr, respectively. An oxidation attack parameter, Ka, derived from the specific weight change versus time data was used to evaluate the oxidation behavior of the alloys along with X-ray diffraction analysis of the surface oxides. The alloys tend to form either Cr2O3/chromite spinel or Al2O3/aluminate spinel depending on the Cr/Al ratio in the alloys. Alloys with a ratio of 3.5 or higher tend to favor the Cr oxides while those under 3.0 form mostly Al oxides. In general the Al2O3/aluminate spinel forming alloys have the better oxidation resistance. Increased cobalt content lowers the scaling resistance of the higher Cr allys while a 5.0 wt pct Co content is optimum for the Al controlling alloys. The refractory metals, particularly Ta, appear beneficial to both types of oxides, perhaps due to the formation of the omnipresent trirutile Ni(Ta, Cb, Mo, W)2O6. Both scales break down as increasing amounts of NiO are formed.

Recrystallization characteristics and interfacial oxides on the compression bonding interface

NASA Astrophysics Data System (ADS)

Xie, Bijun; Sun, Mingyue; Xu, Bin; Li, Dianzhong

2018-05-01

Up to now, the mechanism of interface bonding is still not fully understood. This work presents interfacial characteristics of 316LN stainless steel bonding joint after cold compression bonding with subsequent annealing. EBSD analysis shows that fine recrystallization grains preferentially appear near the bonding interface and grow towards both sides of the interface. Transmission electron microscopy reveals that initial cold compression bonding disintegrates the native oxide scales and brings pristine metal from both sides of the interface come into intimate contact, while the broken oxide particles are remained at the original interface. The results indicate that partial bonding can be achieved by cold compression bonding with post-annealing treatment and recrystallization firstly occurs along the bonding interface. However, the interfacial oxides impede the recrystallization grains step over the interface and hinder the complete healing of the bonding interface.

Ruthenium water oxidation catalysts containing the non-planar tetradentate ligand, biisoquinoline dicarboxylic acid (biqaH2).

PubMed

Scherrer, Dominik; Schilling, Mauro; Luber, Sandra; Fox, Thomas; Spingler, Bernhard; Alberto, Roger; Richmond, Craig J

2016-12-06

Two ruthenium complexes containing the tetradentate ligand [1,1'-biisoquinoline]-3,3'-dicarboxylic acid, and 4-picoline or 6-bromoisoquinoline as axial ligands have been prepared. The complexes have been fully characterised and initial studies on their potential to function as molecular water oxidation catalysts have been performed. Both complexes catalyse the oxidation of water in acidic media with Ce IV as a stoichiometric chemical oxidant, although turnover numbers and turnover frequencies are modest when compared with the closely related Ru-bda and Ru-pda analogues. Barriers for the water nucleophilic attack and intermolecular coupling pathways were obtained from density functional theory calculations and the crucial influence of the ligand framework in determining the most favourable reaction pathway was elucidated from a combined analysis of the theoretical and experimental results.

Superlubricating graphene and graphene oxide films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sumant, Anirudha V.; Erdemir, Ali; Choi, Junho

A system and method for forming at least one of graphene and graphene oxide on a substrate and an opposed wear member. The system includes graphene and graphene oxide formed by an exfoliation process or solution processing method to dispose graphene and/or graphene oxide onto a substrate. The system further includes an opposing wear member disposed on another substrate and a gas atmosphere of an inert gas like N2, ambient, a humid atmosphere and a water solution.

A review on photocatalytic CO2 reduction using perovskite oxide nanomaterials

NASA Astrophysics Data System (ADS)

Zeng, Sheng; Kar, Piyush; Thakur, Ujwal Kumar; Shankar, Karthik

2018-02-01

As the search for efficient catalysts for CO2 photoreduction continues, nanostructured perovskite oxides have emerged as a class of high-performance photocatalytic materials. The perovskite oxide candidates for CO2 photoreduction are primarily nanostructured forms of titanates, niobates, tantalates and cobaltates. These materials form the focus of this review article because they are much sought-after due to their nontoxic nature, adequate chemical stability, and tunable crystal structures, bandgaps and surface energies. As compared to conventional semiconductors and nanomaterial catalysts, nanostructured perovskite oxides also exhibit an extended optical-absorption edge, longer charge carrier lifetimes, and favorable band-alignment with respect to reduction potential of activated CO2 and reduction products of the same. While CO2 reduction product yields of several hundred μmol-1 h-1 are observed with many types of perovskite oxide nanomaterials in stand-alone forms, yield of such quantities are not common with semiconductor nanomaterials of other types. In this review, we present current state-of-the-art synthesis methods to form perovskite oxide nanomaterials, and procedures to engineer their bandgaps. This review also presents a comprehensive summary and discussion on crystal structures, defect distribution, morphologies and electronic properties of the perovskite oxides, and correlation of these properties to CO2 photoreduction performance. This review offers researchers key insights for developing advanced perovskite oxides in order to further improve the yields of CO2 reduction products.

Origin of high photoconductive gain in fully transparent heterojunction nanocrystalline oxide image sensors and interconnects.

PubMed

Jeon, Sanghun; Song, Ihun; Lee, Sungsik; Ryu, Byungki; Ahn, Seung-Eon; Lee, Eunha; Kim, Young; Nathan, Arokia; Robertson, John; Chung, U-In

2014-11-05

A technique for invisible image capture using a photosensor array based on transparent conducting oxide semiconductor thin-film transistors and transparent interconnection technologies is presented. A transparent conducting layer is employed for the sensor electrodes as well as interconnection in the array, providing about 80% transmittance at visible-light wavelengths. The phototransistor is a Hf-In-Zn-O/In-Zn-O heterostructure yielding a high quantum-efficiency in the visible range. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low temperature processed complementary metal oxide semiconductor (CMOS) device by oxidation effect from capping layer.

PubMed

Wang, Zhenwei; Al-Jawhari, Hala A; Nayak, Pradipta K; Caraveo-Frescas, J A; Wei, Nini; Hedhili, M N; Alshareef, H N

2015-04-20

In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190 °C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field.

Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

PubMed Central

Wang, Zhenwei; Al-Jawhari, Hala A.; Nayak, Pradipta K.; Caraveo-Frescas, J. A.; Wei, Nini; Hedhili, M. N.; Alshareef, H. N.

2015-01-01

In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190°C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field. PMID:25892711

Surface spectroscopy studies of the oxidation behavior of uranium

NASA Astrophysics Data System (ADS)

Bloch, J.; Atzmony, U.; Dariel, M. P.; Mintz, M. H.; Shamir, N.

1982-02-01

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) techniques were utilized to study the oxidation behavior of clean uranium surfaces, at very low pressures of various atmospheres (UHV, H 2, O 2, and CO 2), at room temperature. Both for O 2 and CO 2, a precursor chemisorbed oxygen species has been identified at the very initial stage of the oxidation reaction. This chemisorbed oxygen transforms to the oxide form at a rate which depends on the pressure of the oxidizing atmosphere. Residual gaseous carbon compounds which are present even under UHV conditions result in the simultaneous formation of surface carbide which accompanies the initial stage of oxidation. This carbide however decomposes later as oxidation proceeds. Adventitious hydrocarbon adsorption occurs on the formed oxide layer.

In Situ Formation Of Reactive Barriers For Pollution Control

DOEpatents

Gilmore, Tyler J.; Riley, Robert G.

2004-04-27

A method of treating soil contamination by forming one or more zones of oxidized material in the path of percolating groundwater is disclosed. The zone or barrier region is formed by delivering an oxidizing agent into the ground for reaction with an existing soil component. The oxidizing agent modifies the existing soil component creating the oxidized zone. Subsequently when soil contaminates migrate into the zone, the oxidized material is available to react with the contaminates and degrade them into benign products. The existing soil component can be an oxidizable mineral such as manganese, and the oxidizing agent can be ozone gas or hydrogen peroxide. Soil contaminates can be volatile organic compounds. Oxidized barriers can be used single or in combination with other barriers.

High-temperature oxidation of advanced FeCrNi alloy in steam environments

NASA Astrophysics Data System (ADS)

Elbakhshwan, Mohamed S.; Gill, Simerjeet K.; Rumaiz, Abdul K.; Bai, Jianming; Ghose, Sanjit; Rebak, Raul B.; Ecker, Lynne E.

2017-12-01

Alloys of iron-chromium-nickel are being explored as alternative cladding materials to improve safety margins under severe accident conditions. Our research focuses on non-destructively investigating the oxidation behavior of the FeCrNi alloy "Alloy 33" using synchrotron-based methods. The evolution and structure of oxide layer formed in steam environments were characterized using X-ray diffraction, hard X-ray photoelectron spectroscopy, X-ray fluorescence methods and scanning electron microscopy. Our results demonstrate that a compact and continuous oxide scale was formed consisting of two layers, chromium oxide and spinel phase (FeCr2O4) oxides, wherein the concentration of the FeCr2O4 phase decreased from the surface to the bulk-oxide interface.

Alcohol-Soluble Electron-Transport Materials for Fully Solution-Processed Green PhOLEDs.

PubMed

Chen, Fudong; Wang, Shirong; Xiao, Yin; Peng, Feng; Zhou, Nonglin; Ying, Lei; Li, Xianggao

2018-05-18

Two alcohol-soluble electron-transport materials (ETMs), diphenyl(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)phosphine oxide (pPBIPO) and (3,5-bis(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)diphenylphosphine oxide (mBPBIPO), have been synthesized. The physical properties of these ETMs were investigated and they both exhibited high electron-transport mobilities (1.67×10 -4 and 2.15×10 -4  cm 2  V -1  s -1 ), high glass-transition temperatures (81 and 110 °C), and low LUMO energy levels (-2.87 and -2.82 eV, respectively). The solubility of PBIPO in n-butyl alcohol was more than 20 mg mL -1 , which meets the requirement for fully solution-processed organic light-emitting diodes (OLEDs). Fully solution-processed green-phosphorescent OLEDs were fabricated by using alcohol-soluble PBIPO as electron-transport layers (ETLs), and they exhibited high current efficiencies, power efficiencies, and external quantum efficiencies of up to 38.43 cd A -1 , 26.64 lm W -1 , and 10.87 %, respectively. Compared with devices that did not contain PBIPO as an ETM, the performance of these devices was much improved, which indicated the excellent electron-transport properties of PBIPO. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Macro controlling of copper oxide deposition processes and spray mode by using home-made fully computerized spray pyrolysis system

NASA Astrophysics Data System (ADS)

Essa, Mohammed Sh.; Chiad, Bahaa T.; Shafeeq, Omer Sh.

2017-09-01

Thin Films of Copper Oxide (CuO) absorption layer have been deposited using home-made Fully Computerized Spray Pyrolysis Deposition system FCSPD on glass substrates, at the nozzle to substrate distance equal to 20,35 cm, and computerized spray mode (continues spray, macro-control spray). The substrate temperature has been kept at 450 °c with the optional user can enter temperature tolerance values ± 5 °C. Also that fixed molar concentration of 0.1 M, and 2D platform speed or deposition platform speed of 4mm/s. more than 1000 instruction program code, and specific design of graphical user interface GUI to fully control the deposition process and real-time monitoring and controlling the deposition temperature at every 200 ms. The changing in the temperature has been recorded during deposition processes, in addition to all deposition parameters. The films have been characterized to evaluate the thermal distribution over the X, Y movable hot plate, the structure and optical energy gap, thermal and temperature distribution exhibited a good and uniform distribution over 20 cm2 hot plate area, X-ray diffraction (XRD) measurement revealed that the films are polycrystalline in nature and can be assigned to monoclinic CuO structure. Optical band gap varies from 1.5-1.66 eV depending on deposition parameter.

Investigation of veritcal graded channel doping in nanoscale fully-depleted SOI-MOSFET

NASA Astrophysics Data System (ADS)

Ramezani, Zeinab; Orouji, Ali A.

2016-10-01

For achieving reliable transistor, we investigate an amended channel doping (ACD) engineering which improves the electrical and thermal performances of fully-depleted silicon-on-insulator (SOI) MOSFET. We have called the proposed structure with the amended channel doping engineering as ACD-SOI structure and compared it with a conventional fully-depleted SOI MOSFET (C-SOI) with uniform doping distribution using 2-D ATLAS simulator. The amended channel doping is a vertical graded doping that is distributed from the surface of structure with high doping density to the bottom of channel, near the buried oxide, with low doping density. Short channel effects (SCEs) and leakage current suppress due to high barrier height near the source region and electric field modification in the ACD-SOI in comparison with the C-SOI structure. Furthermore, by lower electric field and electron temperature near the drain region that is the place of hot carrier generation, we except the improvement of reliability and gate induced drain lowering (GIDL) in the proposed structure. Undesirable Self heating effect (SHE) that become a critical challenge for SOI MOSFETs is alleviated in the ACD-SOI structure because of utilizing low doping density near the buried oxide. Thus, refer to accessible results, the ACD-SOI structure with graded distribution in vertical direction is a reliable device especially in low power and high temperature applications.

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Mahne, Nika; Schafzahl, Bettina; Leypold, Christian; Leypold, Mario; Grumm, Sandra; Leitgeb, Anita; Strohmeier, Gernot A.; Wilkening, Martin; Fontaine, Olivier; Kramer, Denis; Slugovc, Christian; Borisov, Sergey M.; Freunberger, Stefan A.

2017-03-01

Non-aqueous metal-oxygen batteries depend critically on the reversible formation/decomposition of metal oxides on cycling. Irreversible parasitic reactions cause poor rechargeability, efficiency, and cycle life, and have predominantly been ascribed to the reactivity of reduced oxygen species with cell components. These species, however, cannot fully explain the side reactions. Here we show that singlet oxygen forms at the cathode of a lithium-oxygen cell during discharge and from the onset of charge, and accounts for the majority of parasitic reaction products. The amount increases during discharge, early stages of charge, and charging at higher voltages, and is enhanced by the presence of trace water. Superoxide and peroxide appear to be involved in singlet oxygen generation. Singlet oxygen traps and quenchers can reduce parasitic reactions effectively. Awareness of the highly reactive singlet oxygen in non-aqueous metal-oxygen batteries gives a rationale for future research towards achieving highly reversible cell operation.

Hexavalent Chrome Free Coatings for Electronics Electromagnetic Interference (EMI) Shielding Effectiveness (SE) Interim Test Report

NASA Technical Reports Server (NTRS)

Kessel, Kurt R.

2015-01-01

Test specimen configuration was provided by Parker Chomerics. The EMI gasket used in this project was Cho-Seal 6503E. Black oxide alloy steel socket head bolts were used to hold the plates together. Non-conductive spacers were used to control the amount of compression on the gaskets. The following test fixture specifications were provided by Parker Chomerics. The CHO-TP09 test plate sets selected for this project consist of two aluminum plates manufactured to the specifications detailed in CHO­-TP09. The first plate, referred to as the test frame, is illustrated in Figure 1. The test frame is designed with a cutout in the center and two alternating bolt patterns. One pattern is used to bolt the test frame to the corresponding test cover plate (Figure 2), forming a test plate set. The second pattern accepts the hardware used to mount the fully assembled test plate set to the main adapter plate (Figure 3).