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Sample records for 4n nanometric oxides

  1. Development of graphene-nanometre-sized cerium oxide-incorporated aluminium and its electrochemical evaluation

    NASA Astrophysics Data System (ADS)

    Ashraf, P. Muhamed; Thomas, Saly N.; Edwin, Leela

    2016-02-01

    Graphene-nanometre-sized cerium oxide-incorporated aluminium was prepared and its electrochemical and surface morphological characteristics were studied. The atomic force micrographs and scanning electron micrographs evaluation highlighted that the graphene and nanometre-sized cerium oxide in aluminium had decreased the surface roughness and improved the surface morphological characteristics. The graphene: nanometre-sized cerium oxide (ratios 1:2 or 2:1) with lesser amounts of particle in the matrix showed excellent corrosion resistance in the marine environment as evidenced by linear polarization, electrochemical impedance and weight loss studies. Introduction of graphene in the aluminium matrix showed a barrier separation between the outermost layer and inner layer, increased roughness and increased corrosion. The material is found to be a potential candidate for use in marine environment.

  2. Observation of Nanometric Silicon Oxide Bifilms in a Water-Atomized Hypereutectic Cast Iron Powder

    NASA Astrophysics Data System (ADS)

    Boisvert, Mathieu; Christopherson, Denis; L'Espérance, Gilles

    2016-06-01

    This study investigated the reasons for the irregular structure of primary graphite nodules that were formed in a hypereutectic cast iron powder during water atomization. The graphite nodules contain a significant amount of micron-sized pores and multiple nanometric voids that formed from silicon oxide bifilms. The bifilms theory is often used to explain the mechanisms responsible for the presence of pores in castings. However, even if many results presented in the literature tend to corroborate the existence of bifilms, to this date, only indirect evidences of their existence were presented. The observations presented in this paper are the first to show the double-sided nature of these defects. These observations support the bifilms theory and give an explanation for the presence of porosities in castings. The bifilms were used as substrate for graphite growth during solidification. The irregular structure of the graphite nodules is a consequence of the rather random structure of the bifilms that were introduced in the melt as a result of turbulences on the surface of the melt during pouring. The confirmation of the existence of bifilms can contribute to the understanding of the mechanical properties of various metallic parts.

  3. Oxygen stoichiometry control of nanometric oxide compounds: The case of titanium ferrites

    SciTech Connect

    Millot, N.

    2011-10-15

    Three techniques have been coupled with an original device, based on H{sub 2}/H{sub 2}O equilibrium, controlling oxygen partial pressure: XRD, TGA and DC conductivity in order to characterize very reactive compounds such as nanometric powders. From XRD, both the structure and the oxygen stoichiometry (thanks to their lattice parameter) were investigated in situ. From TGA, it was the oxygen stoichiometry (thanks to mass gain or loss) which was determined. From DC conductivity, it was both the structure and the oxygen stoichiometry (thanks to the activation energy) which were obtained. The advantages were to determine very rapidly and with a small amount of powder the equilibrium conditions (T, pO{sub 2}) necessary to obtain the desired phase and stoichiometry. These methods have been evaluated for nanometric titanium ferrites. Two phenomena have been observed during the reducing process: the precipitation of a rhombohedral phase and a significant grain growth linked together. - Graphical abstract: XRD patterns of Fe{sub 3(1-{delta})}O{sub 4} nanometric powders obtained in situ during a reducing treatment. The stoichiometric compound was obtained by a thermal annealing at 460 deg. C under pO{sub 2}=3x10{sup -26} Pa ({Phi}{sub DRX}=100 nm). In inset, data of the experimental lattice parameter compared to the theoretical one. {alpha} represents the rhomboedrical phase which precipitates during this thermal treatment, then disappeared. Highlights: > The control of the deviation from oxygen stoichiometry is rarely consider in literature. > At the nanometric scale, it is necessary to develop synthesis routes under appropriate atmosphere. > These synthesis must be coupled with in situ characterization tools. > It opens the door to fast and precise studies concerning the evolution of nanometric materials.

  4. Synthesis of nanometric iron and chromium oxide films by reactive pulsed laser deposition for photo-thermo sensors

    NASA Astrophysics Data System (ADS)

    Mulenko, S. A.

    2011-02-01

    Films based on oxides of transitional metals have semiconducting properties that make them up-to-date materials for functional electronics. The reactive pulsed laser deposition (RPLD) allows the control of thickness and stoichiometry of deposits in order to obtain semiconductor structures with accurately tailored thickness and band gap. It is very important to study electrical, structural and optical properties of these semiconducting nanometric films, as sensing characteristics strongly depend on these properties. We deposited iron oxide (Fe2O3-X; 0 <= x <= 1) and chromium oxide (Cr3-XO3-Y; 0 <= x <= 2; 0 <= y <= 2) films on <100> Si substrate by RPLD using a KrF laser. The deposited nanometric films (thickness 50-200 nm) of iron and chromium oxides have large thermo electromotive force (e.m.f.) coefficient (S). The S coefficient of iron oxide films varied in the range 0.8-1.65 mV/K in the temperature range 210-322 K. The maximum value of the S coefficient (1.65mV/K) was measured in the temperature range 270-290 K. The largest photosensitivity (F) of iron oxides films was about 44 Vc/W for white light at power density (I) of about 6×10-3 W/cm2. As regards chromium oxide films, the S coefficient varied in the range 0.30-4.5 mV/K in the temperature range 210-333 K, with the maximum of 3.5-4.5 mV/K in the temperature range 270-290 K. The largest photosensitivity of chromium oxide films was about 2.5 Vc/W at I≅6×10-3 W/cm2. Our results show that RPLD is a very simple procedure to synthesize of iron and chromium oxide nanometric films with variable stoichiometry and, consequently, with different values of their band gap result in variable the S coefficient and the photosensitivity (F). The deposited films present large thermo e.m.f. coefficient and high photosensitivity that make them up-to-date materials for photo-thermo sensors.

  5. Synthesis of nanometric iron and chromium oxide films by reactive pulsed laser deposition for photo-thermo sensors

    NASA Astrophysics Data System (ADS)

    Mulenko, S. A.

    2010-07-01

    Films based on oxides of transitional metals have semiconducting properties that make them up-to-date materials for functional electronics. The reactive pulsed laser deposition (RPLD) allows the control of thickness and stoichiometry of deposits in order to obtain semiconductor structures with accurately tailored thickness and band gap. It is very important to study electrical, structural and optical properties of these semiconducting nanometric films, as sensing characteristics strongly depend on these properties. We deposited iron oxide (Fe2O3-X; 0 <= x <= 1) and chromium oxide (Cr3-XO3-Y; 0 <= x <= 2; 0 <= y <= 2) films on <100> Si substrate by RPLD using a KrF laser. The deposited nanometric films (thickness 50-200 nm) of iron and chromium oxides have large thermo electromotive force (e.m.f.) coefficient (S). The S coefficient of iron oxide films varied in the range 0.8-1.65 mV/K in the temperature range 210-322 K. The maximum value of the S coefficient (1.65mV/K) was measured in the temperature range 270-290 K. The largest photosensitivity (F) of iron oxides films was about 44 Vc/W for white light at power density (I) of about 6×10-3 W/cm2. As regards chromium oxide films, the S coefficient varied in the range 0.30-4.5 mV/K in the temperature range 210-333 K, with the maximum of 3.5-4.5 mV/K in the temperature range 270-290 K. The largest photosensitivity of chromium oxide films was about 2.5 Vc/W at I≅6×10-3 W/cm2. Our results show that RPLD is a very simple procedure to synthesize of iron and chromium oxide nanometric films with variable stoichiometry and, consequently, with different values of their band gap result in variable the S coefficient and the photosensitivity (F). The deposited films present large thermo e.m.f. coefficient and high photosensitivity that make them up-to-date materials for photo-thermo sensors.

  6. Magnetotactic bacteria form magnetite from a phosphate-rich ferric hydroxide via nanometric ferric (oxyhydr)oxide intermediates.

    PubMed

    Baumgartner, Jens; Morin, Guillaume; Menguy, Nicolas; Perez Gonzalez, Teresa; Widdrat, Marc; Cosmidis, Julie; Faivre, Damien

    2013-09-10

    The iron oxide mineral magnetite (Fe3O4) is produced by various organisms to exploit magnetic and mechanical properties. Magnetotactic bacteria have become one of the best model organisms for studying magnetite biomineralization, as their genomes are sequenced and tools are available for their genetic manipulation. However, the chemical route by which magnetite is formed intracellularly within the so-called magnetosomes has remained a matter of debate. Here we used X-ray absorption spectroscopy at cryogenic temperatures and transmission electron microscopic imaging techniques to chemically characterize and spatially resolve the mechanism of biomineralization in those microorganisms. We show that magnetite forms through phase transformation from a highly disordered phosphate-rich ferric hydroxide phase, consistent with prokaryotic ferritins, via transient nanometric ferric (oxyhydr)oxide intermediates within the magnetosome organelle. This pathway remarkably resembles recent results on synthetic magnetite formation and bears a high similarity to suggested mineralization mechanisms in higher organisms. PMID:23980143

  7. Magnetotactic bacteria form magnetite from a phosphate-rich ferric hydroxide via nanometric ferric (oxyhydr)oxide intermediates

    PubMed Central

    Baumgartner, Jens; Morin, Guillaume; Menguy, Nicolas; Perez Gonzalez, Teresa; Widdrat, Marc; Cosmidis, Julie; Faivre, Damien

    2013-01-01

    The iron oxide mineral magnetite (Fe3O4) is produced by various organisms to exploit magnetic and mechanical properties. Magnetotactic bacteria have become one of the best model organisms for studying magnetite biomineralization, as their genomes are sequenced and tools are available for their genetic manipulation. However, the chemical route by which magnetite is formed intracellularly within the so-called magnetosomes has remained a matter of debate. Here we used X-ray absorption spectroscopy at cryogenic temperatures and transmission electron microscopic imaging techniques to chemically characterize and spatially resolve the mechanism of biomineralization in those microorganisms. We show that magnetite forms through phase transformation from a highly disordered phosphate-rich ferric hydroxide phase, consistent with prokaryotic ferritins, via transient nanometric ferric (oxyhydr)oxide intermediates within the magnetosome organelle. This pathway remarkably resembles recent results on synthetic magnetite formation and bears a high similarity to suggested mineralization mechanisms in higher organisms. PMID:23980143

  8. 4-N,N-Dimethylaminopyridine promoted selective oxidation of methyl aromatics with molecular oxygen.

    PubMed

    Zhang, Zhan; Gao, Jin; Wang, Feng; Xu, Jie

    2012-01-01

    4-N,N-Dimethylaminopyridine (DMAP) as catalyst in combination with benzyl bromide was developed for the selective oxidation of methyl aromatics. DMAP exhibited higher catalytic activity than other pyridine analogues, such as 4-carboxypyridine, 4-cyanopyridine and pyridine. The sp3 hybrid carbon-hydrogen (C-H) bonds of different methyl aromatics were successfully oxygenated with molecular oxygen. The real catalyst is due to the formation of a pyridine onium salt from the bromide and DMAP. The onium salt was well characterized by NMR and the reaction mechanism was discussed. PMID:22466855

  9. Bacterial nanometric amorphous Fe-based oxide: a potential lithium-ion battery anode material.

    PubMed

    Hashimoto, Hideki; Kobayashi, Genki; Sakuma, Ryo; Fujii, Tatsuo; Hayashi, Naoaki; Suzuki, Tomoko; Kanno, Ryoji; Takano, Mikio; Takada, Jun

    2014-04-23

    Amorphous Fe(3+)-based oxide nanoparticles produced by Leptothrix ochracea, aquatic bacteria living worldwide, show a potential as an Fe(3+)/Fe(0) conversion anode material for lithium-ion batteries. The presence of minor components, Si and P, in the original nanoparticles leads to a specific electrode architecture with Fe-based electrochemical centers embedded in a Si, P-based amorphous matrix. PMID:24689687

  10. Synthesis of nanometric iron oxide films by RPLD and LCVD for thermo-photo sensors

    NASA Astrophysics Data System (ADS)

    Mulenko, S. A.; Gorbachuk, N. T.

    2011-11-01

    Iron oxide films were deposited on <100> Si substrates by reactive pulsed laser deposition (RPLD) using a KrF laser (248 nm). These films were deposited too by laser (light) chemical vapor deposition (LCVD) using continuous ultraviolet photodiode radiation (360 nm). The deposited films demonstrated semiconducting properties. These films had large thermo-electromotive force (e.m.f.) coefficient ( S) and high photosensitivity ( F). For films deposited by RPLD the S coefficient varied in the range 0.8-1.65 mV/K at 205-322 K. This coefficient depended on the band gap ( E g ) of the semiconductor films, which varied in the range 0.43-0.93 eV. The largest F value found was 44 Vc/W for white light at power density I≅0.006 W/cm2. Using LCVD, iron oxide films were deposited from iron carbonyl vapor. For these films, the S coefficient varied in the range -0.5 to 1.5 mV/K at 110-330 K. The S coefficient depended on E g of the semiconductor films, which varied in the range 0.44-0.51 eV. The largest F value of these films was about 40 Vc/W at the same I≅0.006 W/cm2. Our results showed that RPLD and LCVD can be used to synthesize iron oxide thin films with variable stoichiometry and, consequently, with different values of E g . These films have large S coefficient and high photosensitivity F and therefore can be used as multi-parameter sensors: thermo-photo sensors.

  11. New photosensitive nanometric graphite oxide composites as antimicrobial material with prolonged action.

    PubMed

    Gerasymchuk, Y; Lukowiak, A; Wedzynska, A; Kedziora, A; Bugla-Ploskonska, G; Piatek, D; Bachanek, T; Chernii, V; Tomachynski, L; Strek, W

    2016-06-01

    A new conjugate material based on partially reduced graphite oxide (rGO), silver nanoparticles (Ag), and bis(lysinato)zirconium(IV) phthalocyanine complex (ZrPc) was obtained. Its optical properties (absorption and photoluminescence) after dispersion in solvents were examined. The antimicrobial properties were tested to determine the effect of the composite on the following bacterial strains: Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli, which are responsible for many infections and are one of the pathogens the most difficult to treatment. The results obtained for rGO-ZrPc-Ag composite were compared with the properties of GO, GO-ZrPc, and rGO-Ag structures. The influence of the near-infrared irradiation on the antimicrobial activity of ZrPc- and Ag-doped materials against bacteria was observed for very low concentration (0.32mg/mL) of GO-ZrPc to stop the growth of P. aeruginosa in comparison to the nonirradiated sample (41mg/mL). The usefulness of this material in therapy, such as wound infection treatment or endodontic treatment, as antibacterial agent with sustained action was discussed. PMID:26991210

  12. Chemical synthesis, characterisation, and biocompatibility of nanometre scale porous anodic aluminium oxide membranes for use as a cell culture substrate for the vero cell line: a preliminary study.

    PubMed

    Poinern, Gérrard Eddy Jai; Le, Xuan Thi; O'Dea, Mark; Becker, Thomas; Fawcett, Derek

    2014-01-01

    In this preliminary study we investigate for the first time the biomedical potential of using porous anodic aluminium oxide (AAO) membranes as a cell substrate for culturing the Cercopithecus aethiops (African green monkey) Kidney (Vero) epithelial cell line. One advantage of using the inorganic AAO membrane is the presence of nanometre scale pore channels that allow the exchange of molecules and nutrients across the membrane. The size of the pore channels can be preselected by adjusting the controlling parameters of a temperature controlled two-step anodization process. The cellular interaction and response of the Vero cell line with an in-house synthesised AAO membrane, a commercially available membrane, and a glass control were assessed by investigating cell adhesion, morphology, and proliferation over a 72 h period. The number of viable cells proliferating over the respective membrane surfaces revealed that the locally produced in-house AAO membrane had cells numbers similar to the glass control. The study revealed evidence of focal adhesion sites over the surface of the nanoporous membranes and the penetration of cellular extensions into the pore structure as well. The outcome of the study has revealed that nanometre scale porous AAO membranes have the potential to become practical cell culture scaffold substrates with the capability to enhance adhesion and proliferation of Vero cells. PMID:24579077

  13. Chemical Synthesis, Characterisation, and Biocompatibility of Nanometre Scale Porous Anodic Aluminium Oxide Membranes for Use as a Cell Culture Substrate for the Vero Cell Line: A Preliminary Study

    PubMed Central

    Poinern, Gérrard Eddy Jai; Le, Xuan Thi; Becker, Thomas; Fawcett, Derek

    2014-01-01

    In this preliminary study we investigate for the first time the biomedical potential of using porous anodic aluminium oxide (AAO) membranes as a cell substrate for culturing the Cercopithecus aethiops (African green monkey) Kidney (Vero) epithelial cell line. One advantage of using the inorganic AAO membrane is the presence of nanometre scale pore channels that allow the exchange of molecules and nutrients across the membrane. The size of the pore channels can be preselected by adjusting the controlling parameters of a temperature controlled two-step anodization process. The cellular interaction and response of the Vero cell line with an in-house synthesised AAO membrane, a commercially available membrane, and a glass control were assessed by investigating cell adhesion, morphology, and proliferation over a 72 h period. The number of viable cells proliferating over the respective membrane surfaces revealed that the locally produced in-house AAO membrane had cells numbers similar to the glass control. The study revealed evidence of focal adhesion sites over the surface of the nanoporous membranes and the penetration of cellular extensions into the pore structure as well. The outcome of the study has revealed that nanometre scale porous AAO membranes have the potential to become practical cell culture scaffold substrates with the capability to enhance adhesion and proliferation of Vero cells. PMID:24579077

  14. Metallic Co4N Porous Nanowire Arrays Activated by Surface Oxidation as Electrocatalysts for the Oxygen Evolution Reaction.

    PubMed

    Chen, Pengzuo; Xu, Kun; Fang, Zhiwei; Tong, Yun; Wu, Junchi; Lu, Xiuli; Peng, Xu; Ding, Hui; Wu, Changzheng; Xie, Yi

    2015-12-01

    Designing highly efficient electrocatalysts for oxygen evolution reaction (OER) plays a key role in the development of various renewable energy storage and conversion devices. In this work, we developed metallic Co4N porous nanowire arrays directly grown on flexible substrates as highly active OER electrocatalysts for the first time. Benefiting from the collaborative advantages of metallic character, 1D porous nanowire arrays, and unique 3D electrode configuration, surface oxidation activated Co4N porous nanowire arrays/carbon cloth achieved an extremely small overpotential of 257 mV at a current density of 10 mA cm(-2), and a low Tafel slope of 44 mV dec(-1) in an alkaline medium, which is the best OER performance among reported Co-based electrocatalysts to date. Moreover, in-depth mechanistic investigations demonstrate the active phases are the metallic Co4N core inside with a thin cobalt oxides/hydroxides shell during the OER process. Our finding introduces a new concept to explore the design of high-efficiency OER electrocatalysts. PMID:26437900

  15. Interfaces: nanometric dielectrics

    NASA Astrophysics Data System (ADS)

    Lewis, T. J.

    2005-01-01

    The incorporation of nanometric size particles in a matrix to form dielectric composites shows promise of materials (nanodielectrics) with new and improved properties. It is argued that the properties of the interfaces between the particles and the matrix, which will themselves be of nanometric dimensions, will have an increasingly dominant role in determining dielectric performance as the particle size decreases. The forces that determine the electrical and dielectric properties of interfaces are considered, with emphasis on the way in which they might influence composite behaviour. A number of examples are given in which interfaces at the nanometric level exercise both passive and active control over dielectric, optical and conductive properties. Electromechanical properties are also considered, and it is shown that interfaces have important electrostrictive and piezoelectric characteristics. It is demonstrated that the process of poling, namely subjecting macroscopic composite materials to electrical stress and raised temperatures to create piezoelectric materials, can be explained in terms of optimizing the collective response of the nanometric interfaces involved. If the electrical and electromechanical features are coupled to the long-established electrochemical properties, interfaces represent highly versatile active elements with considerable potential in nanotechnology.

  16. Adsorption of 4-n-Nonylphenol and Bisphenol-A on Magnetic Reduced Graphene Oxides: A Combined Experimental and Theoretical Studies.

    PubMed

    Jin, Zhongxiu; Wang, Xiangxue; Sun, Yubing; Ai, Yuejie; Wang, Xiangke

    2015-08-01

    Adsorption of 4-n-nonylphenol (4-n-NP) and bisphenol A (BPA) on magnetic reduced graphene oxides (rGOs) as a function of contact time, pH, ionic strength and humic acid were investigated by batch techniques. Adsorption of 4-n-NP and BPA were independent of pH at 3.0- 8.0, whereas the slightly decreased adsorption was observed at pH 8.0-11.0. Adsorption kinetics and isotherms of 4-n-NP and BPA on magnetic rGOs can be satisfactorily fitted by pseudo-second-order kinetic and Freundlich model, respectively. The maximum adsorption capacities of magnetic rGOs at pH 6.5 and 293 K were 63.96 and 48.74 mg/g for 4-n-NP and BPA, respectively, which were significantly higher than that of activated carbon. Based on theoretical calculations, the higher adsorption energy of rGOs + 4-n-NP was mainly due to π-π stacking and flexible long alkyl chain of 4-n-NP, whereas adsorption of BPA on rGOs was energetically favored by a lying-down configuration due to π-π stacking and dispersion forces, which was further demonstrated by FTIR analysis. These findings indicate that magnetic rGOs is a promising adsorbent for the efficient elimination of 4-n-NP/BPA from aqueous solutions due to its excellent adsorption performance and simple magnetic separation, which are of great significance for the remediation of endocrine-disrupting chemicals in environmental cleanup. PMID:26161689

  17. Nickel(II) complexes of tripodal 4N ligands as catalysts for alkane oxidation using m-CPBA as oxidant: ligand stereoelectronic effects on catalysis.

    PubMed

    Balamurugan, Mani; Mayilmurugan, Ramasamy; Suresh, Eringathodi; Palaniandavar, Mallayan

    2011-10-01

    Several mononuclear Ni(II) complexes of the type [Ni(L)(CH(3)CN)(2)](BPh(4))(2) 1-7, where L is a tetradentate tripodal 4N ligand such as N,N-dimethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L1), N,N-diethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L2), N,N-dimethyl-N'-(1-methyl-1H-imidazol-2-ylmethyl)-N'-(pyrid-2-ylmethyl)ethane-1,2-diamine (L3), N,N-dimethyl-N',N'-bis(1-methyl-1H-imidazol-2-ylmethyl)ethane-1,2-diamine (L4), N,N-dimethyl-N',N'-bis(quinolin-2-ylmethyl)ethane-1,2-diamine (L5), tris(benzimidazol-2-ylmethyl)amine (L6) and tris(pyrid-2-ylmethyl)amine (L7), have been isolated and characterized using CHN analysis, UV-Visible spectroscopy and mass spectrometry. The single-crystal X-ray structures of the complexes [Ni(L1)(CH(3)CN)(H(2)O)](ClO(4))(2) 1a, [Ni(L2)(CH(3)CN)(2)](BPh(4))(2) 2, [Ni(L3)(CH(3)CN)(2)](BPh(4))(2) 3 and [Ni(L4)(CH(3)CN)(2)](BPh(4))(2) 4 have been determined. All these complexes possess a distorted octahedral coordination geometry in which Ni(II) is coordinated to four nitrogen atoms of the tetradentate ligands and two CH(3)CN (2, 3, 4) or one H(2)O and one CH(3)CN (1a) are located in cis positions. The Ni-N(py) bond distances (2.054(2)-2.078(3) Å) in 1a, 2 and 3 are shorter than the Ni-N(amine) bonds (2.127(2)-2.196(3) Å) because of sp(2) and sp(3) hybridizations of the pyridyl and tertiary amine nitrogens respectively. In 3 the Ni-N(im) bond (2.040(5) Å) is shorter than the Ni-N(py) bond (2.074(4) Å) due to the stronger coordination of imidazole compared with the pyridine donor. In dichloromethane/acetonitrile solvent mixture, all the Ni(ii) complexes possess an octahedral coordination geometry, as revealed by the characteristic ligand field bands in the visible region. They efficiently catalyze the hydroxylation of alkanes when m-CPBA is used as oxidant with turnover number (TON) in the range of 340-620 and good alcohol selectivity for cyclohexane (A/K, 5-9). By replacing one of the pyridyl donors in TPA by a weakly

  18. Lower Saccharide Nanometric Materials and Methods

    SciTech Connect

    Schilling, Christopher H.; Tomasik, Piotr; Sikora, Marek

    2004-07-13

    A ceramic composition having at least one nanometric ceramic powder, at least one lower saccharide, and water. The composition is useful in many industrial applications, including preparation of stronger and substantially defect free green and sintered ceramic bodies.

  19. Ultrasonic cavitation for obtainment of nanometric sized particles

    NASA Astrophysics Data System (ADS)

    Santos, A.; Guzmán, R.; Espinosa, J.; Estrada, J.

    2016-02-01

    This project aims to determine the possibility of obtaining nanometric size particles of aluminium oxide (Al2O3) and titanium dioxide (TiO2) from commercial micron-sized powders, through the physical principle of ultrasonic cavitation, in order to be used as supply material in coatings made through a process of thermal spray by flame. The tests are performed on a Hielscher UIP 1000hd Ultrasonics equipment, in a 20 micron wave amplitude and in times of 6, 8, 12, 18 and 24 hours. The determination of the particle size is done through image processing using ImageJ software, obtained by the technique of scanning electron microscopy (SEM); while the elemental composition of the processed samples is analyzed through the technique of energy dispersing spectroscopy (EDS). The results show that Al2O3 and TiO2 have a reduction behaviour of the particles size after being subjected to ultrasonic cavitation, however is only reached the nanometric size in the TiO2 samples.

  20. Rheological Properties of Aqueous Nanometric Alumina Suspensions

    SciTech Connect

    Chuanping Li

    2004-12-19

    Colloidal processing is an effective and reliable approach in the fabrication of the advanced ceramic products. Successful colloidal processing of fine ceramic powders requires accurate control of the rheological properties. The accurate control relies on the understanding the influences of various colloidal parameters on the rheological properties. Almost all research done on the rheology paid less attention to the interactions of particle and solvent. However, the interactions of the particles are usually built up through the media in which the particles are suspended. Therefore, interactions of the particle with the media, the adsorbed layers on the particle surface, and chemical and physical properties of media themselves must influence the rheology of the suspension, especially for the dense suspensions containing nanosized particles. Relatively little research work has been reported in this area. This thesis addresses the rheological properties of nanometric alumina aqueous suspensions, and paying more attention to the interactions between particle and solvent, which in turn influence the particle-particle interactions. Dense nanometric alumina aqueous suspensions with low viscosity were achieved by environmentally-benign fructose additives. The rheology of nanometric alumina aqueous suspensions and its variation with the particle volume fraction and concentration of fructose were explored by rheometry. The adsorptions of solute (fructose) and solvent (water) on the nanometric alumina particle surfaces were measured and analyzed by TG/DSC, TOC, and NMR techniques. The mobility of water molecules in the suspensions and its variation with particle volume fractions and fructose additive were determined by the {sup 17}O NMR relaxation method. The interactions between the nanometric alumina particles in water and fructose solutions were investigated by AFM. The results indicated that a large number of water layers were physically bound on the particles' surfaces

  1. Synthesis and characterisation of cobalt, nickel and copper complexes with tripodal 4N ligands as novel catalysts for the homogeneous partial oxidation of alkanes

    PubMed Central

    Tordin, Elisa; List, Manuela; Monkowius, Uwe; Schindler, Siegfried; Knör, Günther

    2013-01-01

    Four new compounds of the general formula [M(L)(CH3COO)][PF6], where L is a tetradentate tripodal ligand such as tris[2-(dimethylamino)ethyl]amine (L1) or (2-aminoethyl)bis(2-pyridylmethyl)amine (L2) and M is Co(II), Ni(II) or Cu(II), have been prepared employing a simple two-step synthesis. The compounds have been characterised by elemental analysis, mass spectroscopy, IR spectroscopy and X-ray diffraction. The catalytic properties of the derivatives containing the aliphatic ligand L1 have been investigated in particular toward the oxidation of cyclohexane and adamantane in the presence of the sacrificial oxidant m-CPBA (meta-chloroperbenzoic acid). Good TONs and selectivity have been determined for the cobalt and nickel compounds. PMID:23805005

  2. Mapping functional groups on oxidised multi-walled carbon nanotubes at the nanometre scale.

    PubMed

    Goode, A E; Hine, N D M; Chen, S; Bergin, S D; Shaffer, M S P; Ryan, M P; Haynes, P D; Porter, A E; McComb, D W

    2014-06-28

    Despite voluminous research on the acid oxidation of carbon nanotubes (CNTs), there is a distinct lack of experimental results showing distributions of functional groups at the nanometre length scale. Here, functional peaks have been mapped across individual multi-walled CNTs with low-dose, monochromated electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM). Density functional theory simulations show that the EELS features are consistent with oxygenated functional groups, most likely carboxyl moieties. PMID:24827593

  3. Frequency dependent study of the correlation functions in EPR spectroscopy--The Cole-Davidson approach. II. 2,N-(4-n-Butyl benzilidene) 4-amino 2,2,6,6-tetramethyl piperidine 1-oxide in toluene.

    PubMed

    Hwang, Jimmy S; Al-Janabi, Yahya T; Oweimreen, Ghassan A

    2010-11-01

    EPR linewidth measurements of 2,N-(4-n-butyl benzilidene) 4-amino 2,2,6,6-tetramethyl piperidine 1-oxide (BBTMPO) in toluene at 1 GHz (L-Band), 4 GHz (S-Band), 9 GHz (X-Band) and 34 GHz (Q-Band) microwave frequencies indicate the presence of a distribution of relaxation times. The empirical response parameter introduced by Cole-Davidson for the analysis of dielectric relaxation in liquids has been used for the analysis of EPR relaxation data in the L-Band and S-Band frequency regions. The Cole-Davidson parameter can assume values in the range 0 < β ≤ 1. When β = 1, one obtains the Debye-type spectral density. The calculated linewidth data at 1 GHz and 4 GHz agree with a Cole-Davidson parameter of 0.7 for the spherocone shaped BBMTPO solute. β < 1 at the L- and S-bands suggests the presence of an asymmetrical distribution of relaxation times associated with different modes of relaxation mechanisms or internal molecular motions. This study shows EPR experiments at low microwave frequencies are more sensitive to the shape of the correlation function. Differences between this study and an earlier study [6] on perdeuterated 2,2,6,6-tetramethly-4-piperidone N oxide (PD-Tempone) in toluene are attributed to the size of and absence of deuteration in the BBTMPO probe. PMID:20843735

  4. The biological response to nanometre-sized polymer particles.

    PubMed

    Liu, Aiqin; Richards, Laura; Bladen, Catherine L; Ingham, Eileen; Fisher, John; Tipper, Joanne L

    2015-09-01

    Recently, nanometre-sized UHMWPE particles generated from hip and knee replacements have been identified in vitro and in vivo. UHMWPE particles in the 0.1-1.0μm size range have been shown to be more biologically active than larger particles, provoking an inflammatory response implicated in late aseptic loosening of total joint replacements. The biological activity of nanometre-sized particles has not previously been studied. The biological response to clinically-relevant UHMWPE wear particles including nanometre-sized and micrometre-sized, along with polystyrene particles (FluoSpheres 20nm, 60nm, 200nm and 1.0μm), and nanometre-sized model polyethylene particles (Ceridust 3615®), was determined in terms of osteolytic cytokine release from primary human peripheral blood mononuclear cells (PBMNCs). Nanometre-sized UHMWPE wear particles, nanometre-sized Ceridust 3615® and 20nm FluoSpheres had no significant effect on TNF-α, IL-1β, IL-6 and IL-8 release from PBMNCs at a concentration of 100μm(3) particles per cell after 12 and 24h. The micrometre-size UHMWPE wear particles (0.1-1.0μm) and 60nm, 200nm and 1.0μm FluoSpheres caused significantly elevated osteolytic cytokine release from PBMNCs. These results indicated that particles below circa 50nm fail to activate PBMNCs and that particle size, composition and morphology played a crucial role in cytokine release by particle stimulated macrophages. PMID:26004221

  5. Deep-subwavelength Nanometric Image Reconstruction using Fourier Domain Optical Normalization

    PubMed Central

    Qin, Jing; Silver, Richard M.; Barnes, Bryan M.; Zhou, Hui; Dixson, Ronald G.; Henn, Mark-Alexander

    2016-01-01

    Quantitative optical measurements of deep sub-wavelength, three-dimensional, nanometric structures with sensitivity to sub-nanometer details address an ubiquitous measurement challenge. A Fourier domain normalization approach is used in the Fourier optical imaging code to simulate the full three-dimensional scattered light field of nominally 15 nm sized structures, accurately replicating the light field as a function of the focus position. Using the full three-dimensional light field, nanometer scale details such as a 2 nm thin conformal oxide and nanometer topography are rigorously fitted for features less than 1/30th of the wavelength in size. The densely packed structures are positioned nearly an order of magnitude closer than the conventional Rayleigh resolution limit and can be measured with sub-nanometer parametric uncertainties. This approach enables a practical measurement sensitivity to size variations of only a few atoms in size using a high throughput optical configuration with broad application in measuring nanometric structures and nanoelectronic devices. PMID:26925297

  6. Design and fabrication of transmission quarter phase retarder at wavelength 1064 nm, using optical nanometric thin films

    NASA Astrophysics Data System (ADS)

    Moradi, Zahra; Jahanshah, Fariborz; Fallah, Hamid Reza; Haji Mahmoodzade, Morteza; Sahraee, Masoume; Zabolian, Hosein

    2016-08-01

    We designed and fabricated the transmission quarter-wave plate phase retarder at 1064 nm using optical nanometric thin films of silicon oxide and titanium oxide. Final design consists of 32 layers. Transmissions of polarizations are equal and ≥99 % and their phase difference is 90°. System consists of two 16 layers systems that coated with the same condition on BK7 glass substrates then attached together with optical glue. Electron beam evaporation method was used for depositing materials. Photo spectrometer was used for measuring transmission spectrum of system. Transmission of polarizations was ≥95 % and equal. A polarimeter was used for testing systems. Polarization of beam was circular.

  7. Molecular dynamics simulations of nanometric cutting mechanisms of amorphous alloy

    NASA Astrophysics Data System (ADS)

    Zhu, Peng-Zhe; Qiu, Chen; Fang, Feng-Zhou; Yuan, Dan-Dan; Shen, Xue-Cen

    2014-10-01

    Molecular dynamics simulations are employed to study the nanometric cutting process of Cu50Zr50 amorphous alloy. The effects of cutting depth, cutting speed and tool edge radius on the cutting force, workpiece pile-up and temperature of the cutting region are studied to investigate the mechanisms of the material removal and surface formation in the nanometric cutting process. It is found that the material removal of amorphous alloy workpiece is mainly based on extrusion at the nanoscale instead of shearing at the macroscale. The plastic deformation of amorphous alloy is mainly due to the formation of shear transformation zones during the nanometric cutting process. The results also suggest that bigger cutting depth and cutting speed will lead to larger tangential force and normal force. However, the tool edge radius has a negligible effect on the tangential force although the normal force increases with the increase of tool edge radius. The workpiece pile-up increases with an increase of the cutting depth, but decreases with an increase of the edge radius of the tool. The workpiece pile-up is not significantly affected by the cutting speed. It is also found that larger cutting depth and cutting speed will result in higher temperature in the cutting region of workpiece and the average Newtonian layer temperature of the tool. Tool edge radius has no significant effect on the temperature distribution of the workpiece and the average Newtonian layer temperature of the tool.

  8. Technical Note: Nanometric organic photovoltaic thin film detectors for dose monitoring in diagnostic x-ray imaging

    SciTech Connect

    Elshahat, Bassem; Gill, Hardeep Singh; Kumar, Jayant; Filipyev, Ilya; Zygmanski, Piotr; Shrestha, Suman; Karellas, Andrew; Hesser, Jürgen; Sajo, Erno

    2015-07-15

    Purpose: To fabricate organic photovoltaic (OPV) cells with nanometric active layers sensitive to ionizing radiation and measure their dosimetric characteristics in clinical x-ray beams in the diagnostic tube potential range of 60–150 kVp. Methods: Experiments were designed to optimize the detector’s x-ray response and find the best parameter combination by changing the active layer thickness and the area of the electrode. The OPV cell consisted of poly (3-hexylthiophene-2,5-diyl): [6,6]-phenyl C{sub 61} butyric acid methyl ester photoactive donor and acceptor semiconducting organic materials sandwiched between an aluminum electrode as an anode and an indium tin oxide electrode as a cathode. The authors measured the radiation-induced electric current at zero bias voltage in all fabricated OPV cells. Results: The net OPV current as a function of beam potential (kVp) was proportional to kVp{sup −0.5} when normalized to x-ray tube output, which varies with kVp. Of the tested configurations, the best combination of parameters was 270 nm active layer thicknesses with 0.7 cm{sup 2} electrode area, which provided the highest signal per electrode area. For this cell, the measured current ranged from approximately 0.7 to 2.4 nA/cm{sup 2} for 60–150 kVp, corresponding to about 0.09 nA–0.06 nA/mGy air kerma, respectively. When compared to commercial amorphous silicon thin film photovoltaic cells irradiated under the same conditions, this represents 2.5 times greater sensitivity. An additional 40% signal enhancement was observed when a 1 mm layer of plastic scintillator was attached to the cells’ beam-facing side. Conclusions: Since both OPVs can be produced as flexible devices and they do not require external bias voltage, they open the possibility for use as thin film in vivo detectors for dose monitoring in diagnostic x-ray imaging.

  9. Failure of semiclassical models to describe resistivity of nanometric, polycrystalline tungsten films

    SciTech Connect

    Choi, Dooho; Liu, Xuan; Schelling, Patrick K.; Coffey, Kevin R.; Barmak, Katayun

    2014-03-14

    The impact of electron scattering at surfaces and grain boundaries in nanometric polycrystalline tungsten (W) films was studied. A series of polycrystalline W films ranging in thickness from 10 to 310 nm and lateral grain size from 74 to 133 nm were prepared on thermally oxidized Si. The Fuchs-Sondheimer surface-scattering model and Mayadas-Shatzkes grain-boundary scattering model were employed for quantitative analyses. Predictions from the theoretical models were found to deviate systematically from the experimental data. Possible reasons for the failure of the theoretical models to describe the experimental data are explored. Finally, a discussion of the crucial features lacking from existing models is presented, along with possible avenues for improving the models to result in better agreement with experimental data.

  10. Achieving sub-nanometre particle mapping with energy-filtered TEM.

    PubMed

    Lozano-Perez, S; de Castro Bernal, V; Nicholls, R J

    2009-09-01

    A combination of state-of-the-art instrumentation and optimized data processing has enabled for the first time the chemical mapping of sub-nanometre particles using energy-filtered transmission electron microscopy (EFTEM). Multivariate statistical analysis (MSA) generated reconstructed datasets where the signal from particles smaller than 1 nm in diameter was successfully isolated from the original noisy background. The technique has been applied to the characterization of oxide dispersion strengthened (ODS) reduced activation FeCr alloys, due to their relevance as structural materials for future fusion reactors. Results revealed that most nanometer-sized particles had a core-shell structure, with an Yttrium-Chromium-Oxygen-rich core and a nano-scaled Chromium-Oxygen-rich shell. This segregation to the nanoparticles caused a decrease of the Chromium dissolved in the matrix, compromising the corrosion resistance of the alloy. PMID:19505762

  11. Dispersion of heavy ion deposited energy in nanometric electronic devices: Experimental measurements and simulation possibilities

    NASA Astrophysics Data System (ADS)

    Raine, M.; Gaillardin, M.; Paillet, P.; Duhamel, O.; Martinez, M.; Bernard, H.

    2015-12-01

    The dispersion of heavy ion deposited energy is explored in nanometric electronic devices. Experimental data are reported, in a large thin SOI diode and in a SOI FinFET device, showing larger distributions of collected charge in the nanometric volume device. Geant4 simulations are then presented, using two different modeling approaches. Both of them seem suitable to evaluate the dispersion of deposited energy induced by heavy ion beams in advanced electronic devices with nanometric dimensions.

  12. Universal Long-Range Nanometric Bending of Water by Light

    NASA Astrophysics Data System (ADS)

    Verma, Gopal; Singh, Kamal P.

    2015-10-01

    Resolving mechanical effects of light on fluids has fundamental importance with wide applications. Most experiments to date on optofluidic interface deformation exploited radiation forces exerted by normally incident lasers. However, the intriguing effects of photon momentum for any configuration, including the unique total internal reflection regime, where an evanescent wave leaks above the interface, remain largely unexplored. A major difficulty in resolving nanomechanical effects has been the lack of a sensitive detection technique. Here, we devise a simple setup whereby a probe laser produces high-contrast Newton-ring-like fringes from a sessile water drop. The mechanical action of the photon momentum of a pump beam modulates the fringes, thus allowing us to perform a direct noninvasive measurement of a nanometric bulge with sub-5-nm precision. Remarkably, a <10 nm difference in the height of the bulge due to different laser polarizations and nonlinear enhancement in the bulge near total internal reflection is isolated. In addition, the nanometric bulge is shown to extend far longer, 100 times beyond the pump spot. Our high precision data validate the century-old Minkowski theory for a general angle and offer potential for novel optofluidic devices and noncontact nanomanipulation strategies.

  13. Universal Long-Range Nanometric Bending of Water by Light.

    PubMed

    Verma, Gopal; Singh, Kamal P

    2015-10-01

    Resolving mechanical effects of light on fluids has fundamental importance with wide applications. Most experiments to date on optofluidic interface deformation exploited radiation forces exerted by normally incident lasers. However, the intriguing effects of photon momentum for any configuration, including the unique total internal reflection regime, where an evanescent wave leaks above the interface, remain largely unexplored. A major difficulty in resolving nanomechanical effects has been the lack of a sensitive detection technique. Here, we devise a simple setup whereby a probe laser produces high-contrast Newton-ring-like fringes from a sessile water drop. The mechanical action of the photon momentum of a pump beam modulates the fringes, thus allowing us to perform a direct noninvasive measurement of a nanometric bulge with sub-5-nm precision. Remarkably, a <10  nm difference in the height of the bulge due to different laser polarizations and nonlinear enhancement in the bulge near total internal reflection is isolated. In addition, the nanometric bulge is shown to extend far longer, 100 times beyond the pump spot. Our high precision data validate the century-old Minkowski theory for a general angle and offer potential for novel optofluidic devices and noncontact nanomanipulation strategies. PMID:26551814

  14. Femtosecond and nanometre visualization of structural dynamics in superheated nanoparticles

    NASA Astrophysics Data System (ADS)

    Gorkhover, Tais; Schorb, Sebastian; Coffee, Ryan; Adolph, Marcus; Foucar, Lutz; Rupp, Daniela; Aquila, Andrew; Bozek, John D.; Epp, Sascha W.; Erk, Benjamin; Gumprecht, Lars; Holmegaard, Lotte; Hartmann, Andreas; Hartmann, Robert; Hauser, Günter; Holl, Peter; Hömke, Andre; Johnsson, Per; Kimmel, Nils; Kühnel, Kai-Uwe; Messerschmidt, Marc; Reich, Christian; Rouzée, Arnaud; Rudek, Benedikt; Schmidt, Carlo; Schulz, Joachim; Soltau, Heike; Stern, Stephan; Weidenspointner, Georg; White, Bill; Küpper, Jochen; Strüder, Lothar; Schlichting, Ilme; Ullrich, Joachim; Rolles, Daniel; Rudenko, Artem; Möller, Thomas; Bostedt, Christoph

    2016-02-01

    The ability to observe ultrafast structural changes in nanoscopic samples is essential for understanding non-equilibrium phenomena such as chemical reactions, matter under extreme conditions, ultrafast phase transitions and intense light-matter interactions. Established imaging techniques are limited either in time or spatial resolution and typically require samples to be deposited on a substrate, which interferes with the dynamics. Here, we show that coherent X-ray diffraction images from isolated single samples can be used to visualize femtosecond electron density dynamics. We recorded X-ray snapshot images from a nanoplasma expansion, a prototypical non-equilibrium phenomenon. Single Xe clusters are superheated using an intense optical laser pulse and the structural evolution of the sample is imaged with a single X-ray pulse. We resolved ultrafast surface softening on the nanometre scale at the plasma/vacuum interface within 100 fs of the heating pulse. Our study is the first time-resolved visualization of irreversible femtosecond processes in free, individual nanometre-sized samples.

  15. Nanometre-scale thermometry in a living cell.

    PubMed

    Kucsko, G; Maurer, P C; Yao, N Y; Kubo, M; Noh, H J; Lo, P K; Park, H; Lukin, M D

    2013-08-01

    Sensitive probing of temperature variations on nanometre scales is an outstanding challenge in many areas of modern science and technology. In particular, a thermometer capable of subdegree temperature resolution over a large range of temperatures as well as integration within a living system could provide a powerful new tool in many areas of biological, physical and chemical research. Possibilities range from the temperature-induced control of gene expression and tumour metabolism to the cell-selective treatment of disease and the study of heat dissipation in integrated circuits. By combining local light-induced heat sources with sensitive nanoscale thermometry, it may also be possible to engineer biological processes at the subcellular level. Here we demonstrate a new approach to nanoscale thermometry that uses coherent manipulation of the electronic spin associated with nitrogen-vacancy colour centres in diamond. Our technique makes it possible to detect temperature variations as small as 1.8 mK (a sensitivity of 9 mK Hz(-1/2)) in an ultrapure bulk diamond sample. Using nitrogen-vacancy centres in diamond nanocrystals (nanodiamonds), we directly measure the local thermal environment on length scales as short as 200 nanometres. Finally, by introducing both nanodiamonds and gold nanoparticles into a single human embryonic fibroblast, we demonstrate temperature-gradient control and mapping at the subcellular level, enabling unique potential applications in life sciences. PMID:23903748

  16. Synthesis and Cytostatic Evaluation of 4-N-Alkanoyl and 4-N-Alkyl Gemcitabine Analogues

    PubMed Central

    Pulido, Jesse; Sobczak, Adam J.; Balzarini, Jan; Wnuk, Stanislaw F.

    2014-01-01

    Couplings of gemcitabine with the functionalized carboxylic acids (C9-C13) or reactions of 4-N-tosylgemcitabine with the corresponding alkyl amines afforded 4-N-alkanoyl and 4-N-alkyl gemcitabine derivatives. The analogues with a terminal hydroxyl group on the alkyl chain were efficiently fluorinated under conditions that are compatible with protocols for 18F labeling. The 4-N-alkanoylgemcitabines showed potent cytostatic activities in the low nM range against a panel of tumor cell lines while cytotoxicity of the 4-N-alkylgemcitabines were in the low μM range. The cytotoxicity for the 4-N-alkanoylgemcitabine analogues were reduced approximately by two orders of magnitude in the 2′-deoxycytidine kinase (dCK)-deficient CEM/dCK- cell line whereas cytotoxicity of the 4-N-alkylgemcitabines were only 2-5 times lower. None of the compounds acted as efficient substrates for cytosolic dCK, and therefore, the 4-N-alkanoyl analogues need to be converted first to gemcitabine to display a significant cytostatic potential, while 4-N-alkyl derivatives attain the modest activity without “measurable” conversion to gemcitabine. PMID:24341356

  17. Coherent Diffractive Imaging: From Nanometric Down to Picometric Resolution

    NASA Astrophysics Data System (ADS)

    De Caro, Liberato; Carlino, Elvio; Siliqi, Dritan; Giannini, Cinzia

    Coherent diffractive imaging (CDI) is a novel technique for inspecting (crystalline and non-crystalline) matter from nanometric down to picometric resolution. It was used originally with X-rays and, more recently, with electrons (so-called electron diffractive imaging, or EDI). This chapter introduces basic concepts concerning CDI and addresses the different types of X-ray CDI experiments that have been conducted, namely plane wave CDI from isolated objects in forward scattering, focused-beam Fresnel CDI from isolated objects in forward scattering, Bragg CDI from nanocrystals, and keyhole CDI and ptychography from extended objects. A CDI experiment with a transmission electron microscope, alternatively named an EDI experiment, is also introduced.

  18. Nanometric Finishing on Biomedical Implants by Abrasive Flow Finishing

    NASA Astrophysics Data System (ADS)

    Subramanian, Kavithaa Thirumalai; Balashanmugam, Natchimuthu; Shashi Kumar, Panaghra Veeraiah

    2016-01-01

    Abrasive flow finishing (AFF) is a non-conventional finishing technique that offers better accuracy, efficiency, consistency, economy in finishing of complex/difficult to machine materials/components and provides the possibility of effective automation as aspired by the manufacturing sector. The present study describes the finishing of a hip joint made of ASTM grade Co-Cr alloy by Abrasive Flow Machining (AFM) process. The major input parameters of the AFF process were optimized for achieving nanometric finishing of the component. The roughness average (Ra) values were recorded during experimentation using surface roughness tester and the results are discussed in detail. The surface finished hip joints were characterized using Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and residual stress analysis using X-Ray Diffraction (XRD). The discussion lays emphasis on the significance, efficacy and versatile nature of the AFF process in finishing of bio-medical implants.

  19. Linear nanometric tunnel junction sensors with exchange pinned sensing layer

    SciTech Connect

    Leitao, D. C. Silva, A. V.; Cardoso, S.; Ferreira, R.; Paz, E.; Deepack, F. L.; Freitas, P. P.

    2014-05-07

    Highly sensitive nanosensors with high spatial resolution provide the necessary features for high accuracy imaging of isolated magnetic nanoparticles. In this work, we report the fabrication and characterization of MgO-barrier magnetic tunnel junction nanosensors, with two exchange-pinned electrodes. The perpendicular magnetization configuration for field sensing is set using a two-step annealing process, where the second annealing temperature was optimized to yield patterned sensors responses with improved linearity. The optimized circular nanosensors show sensitivities up to 0.1%/Oe, larger than previously reported for nanometric sensors and comparable to micrometric spin-valves. Our strategy avoids the use of external permanent biasing or demagnetizing fields (large for smaller structures) to achieve a linear response, enabling the control of the linear operation range using only the stack and thus providing a small footprint device.

  20. Nanometric resolution magnetic resonance imaging methods for mapping functional activity in neuronal networks

    PubMed Central

    Boretti, Albert; Castelletto, Stefania

    2016-01-01

    This contribution highlights and compares some recent achievements in the use of k-space and real space imaging (scanning probe and wide-filed microscope techniques), when applied to a luminescent color center in diamond, known as nitrogen vacancy (NV) center. These techniques combined with the optically detected magnetic resonance of NV, provide a unique platform to achieve nanometric magnetic resonance imaging (MRI) resolution of nearby nuclear spins (known as nanoMRI), and nanometric NV real space localization. • Atomic size optically detectable spin probe. • High magnetic field sensitivity and nanometric resolution. • Non-invasive mapping of functional activity in neuronal networks. PMID:27144128

  1. Nanometric resolution magnetic resonance imaging methods for mapping functional activity in neuronal networks.

    PubMed

    Boretti, Albert; Castelletto, Stefania

    2016-01-01

    This contribution highlights and compares some recent achievements in the use of k-space and real space imaging (scanning probe and wide-filed microscope techniques), when applied to a luminescent color center in diamond, known as nitrogen vacancy (NV) center. These techniques combined with the optically detected magnetic resonance of NV, provide a unique platform to achieve nanometric magnetic resonance imaging (MRI) resolution of nearby nuclear spins (known as nanoMRI), and nanometric NV real space localization. •Atomic size optically detectable spin probe.•High magnetic field sensitivity and nanometric resolution.•Non-invasive mapping of functional activity in neuronal networks. PMID:27144128

  2. Nanometre-scale germanium photodetector enhanced by optical antennas

    NASA Astrophysics Data System (ADS)

    Tang, Liang

    2008-10-01

    The use of optics to make connections within and between electronic chips has been the subject of research for over 20 years because it could solve many of the problems experienced in electrical systems. A critical challenge for the convergence of optics and electronics is that the micrometre scale of optics is significantly larger than the nanometre scale of modern electronic devices. In the conversion from photons to electrons by photodetectors, this size incompatibility often leads to substantial penalties in power dissipation, area, latency and noise. A photodetector can be made smaller by using a subwavelength active region which, however, could result in very low responsivity because of the diffraction limit of the light. In our first approach to tackle this problem, we use a C-shaped nano-aperture antenna in a thin metal layer to enhance the photocurrent response of a subwavelength photodetector. The single C-shaped aperture, without any other supporting surface structures, can collect light from a large area and concentrate it into a tiny volume of semiconductor. We demonstrated the first antenna-enhanced photodetector at near-infrared wavelengths. In our second approach, we exploit the idea of a dipole antenna from radio waves, but at near infrared wavelengths (˜ 1.3 mum), to concentrate radiation into a nanometre-scale Ge photodetector. Despite the small antenna size (˜ 380 nm long) and the different properties of metals at such high frequencies (˜ 230 THz), the antenna has qualitatively similar behavior to the common radio-frequency half-wave (i.e., half wavelength long) Hertz dipole. It gives a relative enhancement of 20 times in the resulting photocurrent in the subwavelength Ge detector element, which has an active volume of 0.00072 mum 3, two orders of magnitude smaller than previously demonstrated detectors at such wavelengths. Photodetectors are one of the most critical components in optoelectronic integration, and decreasing their size may

  3. Novel designs of nanometric parity preserving reversible compressor

    NASA Astrophysics Data System (ADS)

    Shoaei, Soghra; Haghparast, Majid

    2014-08-01

    Reversible logic is a new field of study that has applications in optical information processing, low power CMOS design, DNA computing, bioinformatics, and nanotechnology. Low power consumption is a basic issue in VLSI circuits today. To prevent the distribution of errors in the quantum circuit, the reversible logic gates must be converted into fault-tolerant quantum operations. Parity preserving is used to realize fault tolerant in this circuits. This paper proposes a new parity preserving reversible gate. We named it NPPG gate. The most significant aspect of the NPPG gate is that it can be used to produce parity preserving reversible full adder circuit. The proposed parity preserving reversible full adder using NPPG gate is more efficient than the existing designs in term of quantum cost and it is optimized in terms of number of constant inputs and garbage outputs. Compressors are of importance in VLSI and digital signal processing applications. Effective VLSI compressors reduce the impact of carry propagation of arithmetic operations. They are built from the full adder blocks. We also proposed three new approaches of parity preservation reversible 4:2 compressor circuits. The third design is better than the previous two in terms of evaluation parameters. The important contributions have been made in the literature toward the design of reversible 4:2 compressor circuits; however, there are not efforts toward the design of parity preservation reversible 4:2 compressor circuits. All the scales are in the nanometric criteria.

  4. Nanometric depth resolution from multi-focal images in microscopy

    PubMed Central

    Dalgarno, Heather I. C.; Dalgarno, Paul A.; Dada, Adetunmise C.; Towers, Catherine E.; Gibson, Gavin J.; Parton, Richard M.; Davis, Ilan; Warburton, Richard J.; Greenaway, Alan H.

    2011-01-01

    We describe a method for tracking the position of small features in three dimensions from images recorded on a standard microscope with an inexpensive attachment between the microscope and the camera. The depth-measurement accuracy of this method is tested experimentally on a wide-field, inverted microscope and is shown to give approximately 8 nm depth resolution, over a specimen depth of approximately 6 µm, when using a 12-bit charge-coupled device (CCD) camera and very bright but unresolved particles. To assess low-flux limitations a theoretical model is used to derive an analytical expression for the minimum variance bound. The approximations used in the analytical treatment are tested using numerical simulations. It is concluded that approximately 14 nm depth resolution is achievable with flux levels available when tracking fluorescent sources in three dimensions in live-cell biology and that the method is suitable for three-dimensional photo-activated localization microscopy resolution. Sub-nanometre resolution could be achieved with photon-counting techniques at high flux levels. PMID:21247948

  5. Nanometric inclusions of carbonates in Kokchetav diamonds from Kazakhstan: A new constraint for the depth of metamorphic diamond crystallization

    NASA Astrophysics Data System (ADS)

    Dobrzhinetskaya, Larissa F.; Wirth, Richard; Green, Harry W.

    2006-03-01

    Previous studies have revealed that microdiamonds from the Kokchetav ultra-high pressure metamorphic terrane of Kazakhstan contain nanometric scale inclusions of Si-, Fe-, Ti-, and Cr-oxides. Because the structure of SiO 2 inclusions was not confirmed to be coesite or stishovite due to their very small size, such diamonds formerly served only as an indicator of a minimum pressure, ca. 4 GPa. Geothermobarometry applied to Kokchetav diamond-bearing rocks yielded a wide range of conditions: T = 700 °C-1250 °C, and P = 4-9 GPa. Our paper presents transmission electron microscopy studies with focused ion beam assistance that indicate that diamonds from marbles contain inclusions of aragonite (CaCO 3) and magnesite (MgCO 3), and that aragonite and nitrogen-bearing nanometric particles are associated with dislocations reflecting diamond growth at relatively high-temperature conditions. We determined the boundary of dolomite stability using the reaction CaMg(CO 3) 2 (dolomite) = CaCO 3 (aragonite) + MgCO 3. This allowed us to utilize available experimental data to evaluate the pressure at which diamond was crystallized. Taking into consideration uncertainties existing between experimental data produced in different laboratories, we propose the pressure for Kokchetav diamond crystallization to be ˜ 6 to 9 GPa. This evaluation is based on the assumption that temperature was determined correctly as 980 °C (minimum) and 1250 °C (maximum) for diamond-grade dolomitic marbles. Our data provide strong evidence that the metasedimentary rocks of the Kokchetav massif containing diamonds were subducted to the depth of ˜ 190-280 km.

  6. TOPICAL REVIEW Organic photovoltaics: principles and techniques for nanometre scale characterization

    NASA Astrophysics Data System (ADS)

    Nicholson, Patrick G.; Castro, Fernando A.

    2010-12-01

    The photoconversion efficiency of state-of-the-art organic solar cells has experienced a remarkable increase in the last few years, with reported certified efficiency values of up to 8.3%. This increase has been due to an improved understanding of the underlying physics, synthetic discovery and the realization of the pivotal role that morphological optimization plays. Advances in nanometre scale characterization have underpinned all three factors. Here we give an overview of the current understanding of the fundamental processes in organic photovoltaic devices, on optimization considerations and on recent developments in nanometre scale measuring techniques. Finally, recommendations for future developments from the perspective of characterization techniques are set forth.

  7. Molecular dynamic simulation for nanometric cutting of single-crystal face-centered cubic metals

    PubMed Central

    2014-01-01

    In this work, molecular dynamics simulations are performed to investigate the influence of material properties on the nanometric cutting of single crystal copper and aluminum with a diamond cutting tool. The atomic interactions in the two metallic materials are modeled by two sets of embedded atom method (EAM) potential parameters. Simulation results show that although the plastic deformation of the two materials is achieved by dislocation activities, the deformation behavior and related physical phenomena, such as the machining forces, machined surface quality, and chip morphology, are significantly different for different materials. Furthermore, the influence of material properties on the nanometric cutting has a strong dependence on the operating temperature. PMID:25426007

  8. On the mechanism of material removal in nanometric cutting of metallic glass

    NASA Astrophysics Data System (ADS)

    Zhu, Pengzhe; Fang, Fengzhou

    2014-08-01

    Metallic glasses find wide applications in nanotechnology and micro electro-mechanical systems because of their unique physical properties due to their amorphous structures. The material removal mechanism in nanometric cutting of Cu50Zr50, a typical metallic glass, is studied using molecular dynamics method. The chip formation, workpiece deformation and scratching forces under various scratching depths, scratching velocities and temperatures are investigated. The effect of void defect on the cutting behaviors of metallic glass is also explored. The results show that the material removal in nanometric cutting process is based on extrusion instead of shearing, achieving a good understanding of material removal at the nanoscale.

  9. Molecular dynamic simulation for nanometric cutting of single-crystal face-centered cubic metals.

    PubMed

    Huang, Yanhua; Zong, Wenjun

    2014-01-01

    In this work, molecular dynamics simulations are performed to investigate the influence of material properties on the nanometric cutting of single crystal copper and aluminum with a diamond cutting tool. The atomic interactions in the two metallic materials are modeled by two sets of embedded atom method (EAM) potential parameters. Simulation results show that although the plastic deformation of the two materials is achieved by dislocation activities, the deformation behavior and related physical phenomena, such as the machining forces, machined surface quality, and chip morphology, are significantly different for different materials. Furthermore, the influence of material properties on the nanometric cutting has a strong dependence on the operating temperature. PMID:25426007

  10. Surface Modification of Nanometre Silicon Carbide Powder with Polystyrene by Inductively Coupled Plasma

    NASA Astrophysics Data System (ADS)

    Wei, Gang; Meng, Yuedong; Zhong, Shaofeng; Liu, Feng; Jiang, Zhongqing; Shu, Xingsheng; Ren, Zhaoxing; Wang, Xiangke

    2008-02-01

    An investigation was made into polystyrene (PS) grafted onto nanometre silicon carbide (SiC) particles. In our experiment, the grafting polymerization reaction was induced by a radio frequency (RF) inductively coupled plasma (ICP) treatment of the nanometre powder. FTIR (Fourier transform infrared spectrum) and XPS (X-ray photoelectron spectroscopy) results reveal that PS is grafted onto the surface of silicon carbide powder. An analysis is presented on the effectiveness of this approach as a function of plasma operating variables including the plasma treating power, treating time, and grafting reaction temperature and time.

  11. Three-dimensional nanometre localization of nanoparticles to enhance super-resolution microscopy

    NASA Astrophysics Data System (ADS)

    Bon, Pierre; Bourg, Nicolas; Lécart, Sandrine; Monneret, Serge; Fort, Emmanuel; Wenger, Jérôme; Lévêque-Fort, Sandrine

    2015-07-01

    Meeting the nanometre resolution promised by super-resolution microscopy techniques (pointillist: PALM, STORM, scanning: STED) requires stabilizing the sample drifts in real time during the whole acquisition process. Metal nanoparticles are excellent probes to track the lateral drifts as they provide crisp and photostable information. However, achieving nanometre axial super-localization is still a major challenge, as diffraction imposes large depths-of-fields. Here we demonstrate fast full three-dimensional nanometre super-localization of gold nanoparticles through simultaneous intensity and phase imaging with a wavefront-sensing camera based on quadriwave lateral shearing interferometry. We show how to combine the intensity and phase information to provide the key to the third axial dimension. Presently, we demonstrate even in the occurrence of large three-dimensional fluctuations of several microns, unprecedented sub-nanometre localization accuracies down to 0.7 nm in lateral and 2.7 nm in axial directions at 50 frames per second. We demonstrate that nanoscale stabilization greatly enhances the image quality and resolution in direct stochastic optical reconstruction microscopy imaging.

  12. Theoretical study of the thermally induced structural fluctuations in sub-nanometre size gold clusters

    NASA Astrophysics Data System (ADS)

    Cabrera-Trujillo, José Manuel; Martín Montejano-Carrizales, Juan; Aguilera-Granja, Faustino; Posada-Amarillas, Álvaro

    2015-07-01

    A reactive potential model and the classical molecular dynamics method (RMD) have been used to study the structure and energetics of sub-nanometre size gold clusters through well-known structural models reported in the literature for AuN, with N = 19, 20 and 21 atoms. After several simulated-annealing simulations for temperatures up to 1500 K, the AuN clusters clearly evolve to well-defined structures at room temperature. For the studied gold clusters, the low-lying structures are single- and double-icosahedra with mobile atoms on the surface, in agreement with experimental results on sub-nanometre size gold clusters exhibiting shape oscillations at room temperature and also with those involved in the design of molecules based on gold superatoms [J.-I. Nishigaki, K. Koyasu, T. Tsukuda, Chem. Rec. 14, 897 (2014)]. The evolution of the structural stability of the AuN clusters under exceptional thermal conditions is analysed by comparing the size and temperature variations of the centrosymmetry parameter and the potential energy. A key understanding of the various possible structural changes undergone by these tiny particles is thus developed. The usefulness of the RMD to study nanometre or sub-nanometre size gold clusters is shown.

  13. Three-dimensional nanometre localization of nanoparticles to enhance super-resolution microscopy

    PubMed Central

    Bon, Pierre; Bourg, Nicolas; Lécart, Sandrine; Monneret, Serge; Fort, Emmanuel; Wenger, Jérôme; Lévêque-Fort, Sandrine

    2015-01-01

    Meeting the nanometre resolution promised by super-resolution microscopy techniques (pointillist: PALM, STORM, scanning: STED) requires stabilizing the sample drifts in real time during the whole acquisition process. Metal nanoparticles are excellent probes to track the lateral drifts as they provide crisp and photostable information. However, achieving nanometre axial super-localization is still a major challenge, as diffraction imposes large depths-of-fields. Here we demonstrate fast full three-dimensional nanometre super-localization of gold nanoparticles through simultaneous intensity and phase imaging with a wavefront-sensing camera based on quadriwave lateral shearing interferometry. We show how to combine the intensity and phase information to provide the key to the third axial dimension. Presently, we demonstrate even in the occurrence of large three-dimensional fluctuations of several microns, unprecedented sub-nanometre localization accuracies down to 0.7 nm in lateral and 2.7 nm in axial directions at 50 frames per second. We demonstrate that nanoscale stabilization greatly enhances the image quality and resolution in direct stochastic optical reconstruction microscopy imaging. PMID:26212705

  14. Properties of Diamond and Diamond-Like Clusters in Nanometric Dimensions

    NASA Technical Reports Server (NTRS)

    Halicioglu, Timur; Langhoff, Stephen R. (Technical Monitor)

    1996-01-01

    Variations in materials properties of small clusters of nanometric dimensions were investigated. Investigations were carried out for diamond and diamond-like particles in spherical shapes. Calculations were performed for clusters containing over 1000 carbon atoms. Results indicate that as the cluster size diminishes, (i) the average cohesive energy becomes weaker, (ii) the excess surface energy increases, and (iii) the value for stiffness decreases.

  15. Confined phase separation in SiOX nanometric thin layers

    NASA Astrophysics Data System (ADS)

    Roussel, M.; Talbot, E.; Pareige, C.; Pratibha Nalini, R.; Gourbilleau, F.; Pareige, P.

    2013-11-01

    Phase separation in silicon-rich silica/silica multilayers was investigated using Atom Probe Tomography and Atomistic Kinetic Monte Carlo simulation. It is shown that the thickness of silicon-rich silicon oxide sublayers plays an important role during phase transformation. It determines the morphology of Si-rich phase formed after subsequent annealing, which is of prime interest for microelectronic and optoelectronic applications. Monte Carlo simulation reveals that the formation of isolated Si clusters can be achieved even in the case of spinodal decomposition and is directly related to the ratio between the spinodal wavelength and the sublayer thickness.

  16. Interdiffusion in nanometric Fe/Ni multilayer films

    SciTech Connect

    Liu, JX; Barmak, K

    2015-03-01

    Fe (3.1 nm)/Ni (3.3 nm)](20) multilayer films were prepared by DC magnetron sputtering onto oxidized Si(100) substrates. The Fe and Ni layers were shown to both be face-centered cubic by x-ray diffraction. Interdiffusion of the Fe and Ni layers in the temperature range of 300-430 degrees C was studied by x-ray reflectivity. From the decay of the integral intensity of the superlattice peak, the activation energy and the pre-exponential term for the effective interdiffusion coefficient were determined as to 1.06 +/- 0.07 eV and 5 x 10(-10) cm(2)/s, respectively. The relevance of the measured interdiffusion coefficient to the laboratory timescale synthesis of L1(0) ordered FeNi as a rare-earth free permanent magnet is discussed. (C) 2015 American Vacuum Society.

  17. Genetic characterization of avian influenza subtype H4N6 and H4N9 from live bird market, Thailand

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A one year active surveillance program for influenza A viruses among avian species in a live-bird market (LBM) in Bangkok, Thailand was conducted in 2009. Out of 970 samples collected, influenza A virus subtypes H4N6 (n=2) and H4N9 (n=1), were isolated from healthy Muscovy ducks. All three viruses w...

  18. Interdiffusion in nanometric Fe/Ni multilayer films

    SciTech Connect

    Liu, Jiaxing Barmak, Katayun

    2015-03-15

    [Fe (3.1 nm)/Ni (3.3 nm)]{sub 20} multilayer films were prepared by DC magnetron sputtering onto oxidized Si(100) substrates. The Fe and Ni layers were shown to both be face-centered cubic by x-ray diffraction. Interdiffusion of the Fe and Ni layers in the temperature range of 300–430 °C was studied by x-ray reflectivity. From the decay of the integral intensity of the superlattice peak, the activation energy and the pre-exponential term for the effective interdiffusion coefficient were determined as to 1.06 ± 0.07 eV and 5 × 10{sup −10} cm{sup 2}/s, respectively. The relevance of the measured interdiffusion coefficient to the laboratory timescale synthesis of L1{sub 0} ordered FeNi as a rare-earth free permanent magnet is discussed.

  19. What holds paper together: Nanometre scale exploration of bonding between paper fibres

    PubMed Central

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

    2013-01-01

    Paper, a man-made material that has been used for hundreds of years, is a network of natural cellulosic fibres. To a large extent, it is the strength of bonding between these individual fibres that controls the strength of paper. Using atomic force microscopy, we explore here the mechanical properties of individual fibre-fibre bonds on the nanometre scale. A single fibre-fibre bond is loaded with a calibrated cantilever statically and dynamically until the bond breaks. Besides the calculation of the total energy input, time dependent processes such as creep and relaxation are studied. Through the nanometre scale investigation of the formerly bonded area, we show that fibrils or fibril bundles play a crucial role in fibre-fibre bonding because they act as bridging elements. With this knowledge, new fabrication routes can be deduced to increase the strength of an ancient product that is in fact an overlooked high-tech material. PMID:23969946

  20. Transition from near-field thermal radiation to phonon heat conduction at sub-nanometre gaps.

    PubMed

    Chiloyan, Vazrik; Garg, Jivtesh; Esfarjani, Keivan; Chen, Gang

    2015-01-01

    When the separation of two surfaces approaches sub-nanometre scale, the boundary between the two most fundamental heat transfer modes, heat conduction by phonons and radiation by photons, is blurred. Here we develop an atomistic framework based on microscopic Maxwell's equations and lattice dynamics to describe the convergence of these heat transfer modes and the transition from one to the other. For gaps >1 nm, the predicted conductance values are in excellent agreement with the continuum theory of fluctuating electrodynamics. However, for sub-nanometre gaps we find the conductance is enhanced up to four times compared with the continuum approach, while avoiding its prediction of divergent conductance at contact. Furthermore, low-frequency acoustic phonons tunnel through the vacuum gap by coupling to evanescent electric fields, providing additional channels for energy transfer and leading to the observed enhancement. When the two surfaces are in or near contact, acoustic phonons become dominant heat carriers. PMID:25849305

  1. Peculiar effective elastic anisotropy of nanometric multilayers studied by surface Brillouin scattering

    NASA Astrophysics Data System (ADS)

    Faurie, D.; Djemia, P.; Castelnau, O.; Brenner, R.; Belliard, L.; Le Bourhis, E.; Goudeau, Ph; Renault, P.-O.

    2015-12-01

    We show in this paper by using a two-scale transition model that the elastic anisotropy of a thin film specimen can be tuned by appropriate stacking design. The anisotropic behaviour is illustrated for two monophase thin films, namely W which is perfectly elastically isotropic and Au which is strongly elastically anisotropic, and for a nanometric W/Au multilayers. The experimental measurements show that the model capture the elastic anisotropy rather well even for a nanometric multilayer stacking (period of 12 nm) and that the elastic anisotropy of W/Au multilayer is more pronounced than the ones of the two components for a fraction of 50%. This enhanced anisotropy is discussed in view of the multilayer microstructure.

  2. Spin waves damping in nanometre-scale magnetic materials (Review Article)

    NASA Astrophysics Data System (ADS)

    Krivoruchko, V. N.

    2015-09-01

    Spin dynamics in magnetic nanostructured materials is a topic of great current interest. To describe spin motions in such magnetic systems, the phenomenological Landau-Lifshitz (LL), or the LL-Gilbert (LLG), equation is widely used. Damping term is one of the dominant features of magnetization dynamics and plays an essential role in these equations of motion. The form of this term is simple; however, an important question arises whether it provides a proper description of the magnetization coupling to the thermal bath and the related magnetic fluctuations in the real nanometre-scale magnetic materials. It is now generally accepted that for nanostructured systems the damping term in the LL (LLG) equation fails to account for the systematics of the magnetization relaxation, even at the linear response level. In ultrathin films and nanostructured magnets particular relaxation mechanisms arise, extrinsic and intrinsic, which are relevant at nanometre-length scales, yet are not so efficient in bulk materials. These mechanisms of relaxation are crucial for understanding the magnetization dynamics that results in a linewidth dependence on the nanomagnet's size. We give an overview of recent efforts regarding the description of spin waves damping in nanostructured magnetic materials. Three types of systems are reviewed: ultrathin and exchange-based films, magnetic nanometre-scale samples and patterned magnetic structures. The former is an example of a rare case where consideration can be done analytically on microscopic footing. The latter two are typical samples when analytical approaches hardly have to be developed and numerical calculations are more fruitful. Progress in simulations of magnetization dynamics in nanometre-scale magnets gives hopes that a phenomenological approach can provide us with a realistic description of spin motions in expanding diverse of magnetic nanostructures.

  3. Fabrication and characterization of nanometric SiOx/SiOy multilayer structures obtained by LPCVD

    SciTech Connect

    Román-López, S.; Aceves-Mijares, M.; Pedraza-Chávez, J.; Carrillo-López, J.

    2014-05-15

    This work presents the fabrication of nanometric multilayer structures and their characterization by Atomic Force Microscopy, Photoluminescence and Fourier Transform Infra Red spectroscopy. The structures were deposited by Low Pressure Chemical Vapor Deposition (LPCVD). Three types of multilayer structure were fabricated. After the deposition some samples were annealed in N{sub 2} ambient for three hours. It was found that the structures keep the characteristics of each layer.

  4. Fabrication and characterization of nanometric SiOx/SiOy multilayer structures obtained by LPCVD

    NASA Astrophysics Data System (ADS)

    Román-López, S.; Aceves-Mijares, M.; Carrillo-López, J.; Pedraza-Chávez, J.

    2014-05-01

    This work presents the fabrication of nanometric multilayer structures and their characterization by Atomic Force Microscopy, Photoluminescence and Fourier Transform Infra Red spectroscopy. The structures were deposited by Low Pressure Chemical Vapor Deposition (LPCVD). Three types of multilayer structure were fabricated. After the deposition some samples were annealed in N2 ambient for three hours. It was found that the structures keep the characteristics of each layer.

  5. Structural changes of polysulfone membrane use for hemodialysis in the consecutive regime: nanometric analysis by AFM

    NASA Astrophysics Data System (ADS)

    Batina, Nikola; Acosta García, Ma. Cristina; Avalos Pérez, Angélica; Alberto Ramírez, Mario; Franco, Martha; Pérez Gravas, Héctor; Cadena Méndez, Miguel

    2013-08-01

    Nowadays, the hemodialytic treatment of patients with either acute or chronic renal failure has been improved by promoting biocompatibility in the use of new materials and improve membrane surface characteristics. Low and high flux polysulfone membranes (PM) used in dialysis and ultra filtration have been studied in order to understand the geometry and surface chemistry of the pores at inner (nanometric) and outer (micrometric) membrane parts. The surface changes of polysulfone cartridge membrane (PM) during different number of consecutive reuse trials: after 1st, 10th and 23th times of use. The morphology of the hollow fibers surfaces was studied by means of the atomic force microscopy (AFM) imaging and the surface roughness analysis. The roughness of both inner and outer part of PM surface increases with numbers of reuse trails. Thus, small and medium size pores were wiped out when the number of uses changed from zero to 23 on the outer surface. The pore density decreases. The inner part of membrane shows some nanometric size deformation in forms of new openings and raptures. The AFM analysis show differences in the PM morphology at the nanometric level, not previously revealed, which could be important in the evaluation of the PM.

  6. Nanometre-scale evidence for interfacial dissolution-reprecipitation control of silicate glass corrosion.

    PubMed

    Hellmann, Roland; Cotte, Stéphane; Cadel, Emmanuel; Malladi, Sairam; Karlsson, Lisa S; Lozano-Perez, Sergio; Cabié, Martiane; Seyeux, Antoine

    2015-03-01

    Silicate glasses are durable solids, and yet they are chemically unstable in contact with aqueous fluids-this has important implications for numerous industrial applications related to the corrosion resistance of glasses, or the biogeochemical weathering of volcanic glasses in seawater. The aqueous dissolution of synthetic and natural glasses results in the formation of a hydrated, cation-depleted near-surface alteration zone and, depending on alteration conditions, secondary crystalline phases on the surface. The long-standing accepted model of glass corrosion is based on diffusion-coupled hydration and selective cation release, producing a surface-altered zone. However, using a combination of advanced atomic-resolution analytical techniques, our data for the first time reveal that the structural and chemical interface between the pristine glass and altered zone is always extremely sharp, with gradients in the nanometre to sub-nanometre range. These findings support a new corrosion mechanism, interfacial dissolution-reprecipitation. Moreover, they also highlight the importance of using analytical methods with very high spatial and mass resolution for deciphering the nanometre-scale processes controlling corrosion. Our findings provide evidence that interfacial dissolution-reprecipitation may be a universal reaction mechanism that controls both silicate glass corrosion and mineral weathering. PMID:25559424

  7. Osteogenic lineage restriction by osteoprogenitors cultured on nanometric grooved surfaces: the role of focal adhesion maturation.

    PubMed

    Cassidy, John W; Roberts, Jemma N; Smith, Carol-Anne; Robertson, Mary; White, Kate; Biggs, Manus J; Oreffo, Richard O C; Dalby, Matthew J

    2014-02-01

    The differentiation of progenitor cells is dependent on more than biochemical signalling. Topographical cues in natural bone extracellular matrix guide cellular differentiation through the formation of focal adhesions, contact guidance, cytoskeletal rearrangement and ultimately gene expression. Osteoarthritis and a number of bone disorders present as growing challenges for our society. Hence, there is a need for next generation implantable devices to substitute for, or guide, bone repair in vivo. Cellular responses to nanometric topographical cues need to be better understood in vitro in order to ensure the effective and efficient integration and performance of these orthopedic devices. In this study, the FDA-approved plastic polycaprolactone was embossed with nanometric grooves and the response of primary and immortalized osteoprogenitor cells observed. Nanometric groove dimensions were 240 nm or 540 nm deep and 12.5 μm wide. Cells cultured on test surfaces followed contact guidance along the length of groove edges, elongated along their major axis and showed nuclear distortion; they formed more focal complexes and lower proportions of mature adhesions relative to planar controls. Down-regulation of the osteoblast marker genes RUNX2 and BMPR2 in primary and immortalized cells was observed on grooved substrates. Down-regulation appeared to directly correlate with focal adhesion maturation, indicating the involvement of ERK 1/2 negative feedback pathways following integrin-mediated FAK activation. PMID:24252447

  8. Energy dependent track structure parametrisations for protons and carbon ions based on nanometric simulations

    NASA Astrophysics Data System (ADS)

    Alexander, Frauke; Villagrasa, Carmen; Rabus, Hans; Wilkens, Jan J.

    2015-09-01

    The BioQuaRT project within the European Metrology Research Programme aims at correlating ion track structure characteristics with the biological effects of radiation and develops measurement and simulation techniques for determining ion track structure on different length scales from about 2 nm to about 10 μm. Within this framework, we investigate methods to translate track-structure quantities derived on a nanometre scale to macroscopic dimensions. Input data sets were generated by simulations of ion tracks of protons and carbon ions in liquid water using the Geant 4 Monte Carlo toolkit with the Geant4-DNA processes. Based on the energy transfer points - recorded with nanometre resolution - we investigated parametrisations of overall properties of ion track structure. Three different track structure parametrisations have been developed using the distances to the 10 next neighbouring ionisations, the radial energy distribution and ionisation cluster size distributions. These parametrisations of nanometric track structure build a basis for deriving biologically relevant mean values which are essential in the clinical situation where each voxel is exposed to a mixed radiation field. Contribution to the Topical Issue "COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy", edited by Andrey Solov'yov, Nigel Mason, Gustavo García, Eugene Surdutovich.

  9. Nanometric Graphene Oxide Framework Membranes with Enhanced Heavy Metal Removal via Nanofiltration.

    PubMed

    Zhang, Yu; Zhang, Sui; Chung, Tai-Shung

    2015-08-18

    A novel dual-modification strategy, including (1) the cross-linking and construction of a GO framework by ethylenediamine (EDA) and (2) the amine-enrichment modification by hyperbranched polyethylenimine (HPEI), has been proposed to design stable and highly charged GO framework membranes with the GO selective layer thickness of 70 nm for effective heave metal removal via nanofiltration (NF). Results from sonication experiments and positron annihilation spectroscopy confirmed that EDA cross-linking not only enhanced structural stability but also enlarged the nanochannels among the laminated GO nanosheets for higher water permeability. HPEI 60K was found to be the most effective post-treatment agent that resulted in GO framework membranes with a higher surface charge and lower transport resistance. The newly developed membrane exhibited a high pure water permeability of 5.01 L m(-2) h(-1) bar(-1) and comparably high rejections toward Mg(2+), Pb(2+), Ni(2+), Cd(2+), and Zn(2+). These results have demonstrated the great potential of GO framework materials in wastewater treatment and may provide insights for the design and fabrication of the next generation two-dimensional (2D)-based NF membranes. PMID:26197200

  10. Sub-nanometrically resolved chemical mappings of quantum-cascade laser active regions

    NASA Astrophysics Data System (ADS)

    Pantzas, Konstantinos; Beaudoin, Grégoire; Patriarche, Gilles; Largeau, Ludovic; Mauguin, Olivia; Pegolotti, Giulia; Vasanelli, Angela; Calvar, Ariane; Amanti, Maria; Sirtori, Carlo; Sagnes, Isabelle

    2016-05-01

    A procedure that produces sub-nanometrically resolved chemical mappings of MOCVD-grown InGaAs/InAlAs/InP quantum cascade lasers is presented. The chemical mappings reveal that, although the structure is lattice-matched to InP, the InAlAs barriers do not attain the nominal aluminum content—48%—and are, in fact, InGaAlAs quaternaries. This information is used to adjust the aluminum precursor flow and fine-tune the composition of the barriers, resulting in a significant improvement of the fabricated lasers.

  11. Engineering a Biocompatible Scaffold with Either Micrometre or Nanometre Scale Surface Topography for Promoting Protein Adsorption and Cellular Response

    PubMed Central

    Le, Xuan; Poinern, Gérrard Eddy Jai; Ali, Nurshahidah; Berry, Cassandra M.; Fawcett, Derek

    2013-01-01

    Surface topographical features on biomaterials, both at the submicrometre and nanometre scales, are known to influence the physicochemical interactions between biological processes involving proteins and cells. The nanometre-structured surface features tend to resemble the extracellular matrix, the natural environment in which cells live, communicate, and work together. It is believed that by engineering a well-defined nanometre scale surface topography, it should be possible to induce appropriate surface signals that can be used to manipulate cell function in a similar manner to the extracellular matrix. Therefore, there is a need to investigate, understand, and ultimately have the ability to produce tailor-made nanometre scale surface topographies with suitable surface chemistry to promote favourable biological interactions similar to those of the extracellular matrix. Recent advances in nanoscience and nanotechnology have produced many new nanomaterials and numerous manufacturing techniques that have the potential to significantly improve several fields such as biological sensing, cell culture technology, surgical implants, and medical devices. For these fields to progress, there is a definite need to develop a detailed understanding of the interaction between biological systems and fabricated surface structures at both the micrometre and nanometre scales. PMID:23533416

  12. Laser pyrolysis fabrication of ferromagnetic gamma'-Fe4N and FeC nanoparticles

    NASA Technical Reports Server (NTRS)

    Grimes, C. A.; Qian, D.; Dickey, E. C.; Allen, J. L.; Eklund, P. C.

    2000-01-01

    Using the laser pyrolysis method, single phase gamma'-Fe4N nanoparticles were prepared by a two step method involving preparation of nanoscale iron oxide and a subsequent gas-solid nitridation reaction. Single phase Fe3C and Fe7C3 could be prepared by laser pyrolysis from Fe(CO)5 and 3C2H4 directly. Characterization techniques such as XRD, TEM and vibrating sample magnetometer were used to measure phase structure, particle size and magnetic properties of these nanoscale nitride and carbide particles. c2000 American Journal of Physics.

  13. Potential for 4-n-nonylphenol biodegradation in stream sediments

    USGS Publications Warehouse

    Bradley, P.M.; Barber, L.B.; Kolpin, D.W.; McMahon, P.B.; Chapelle, F.H.

    2008-01-01

    The potential for in situ biodegradation of 4-nonylphenol (4-NP) was investigated in three hydrologically distinct streams impacted by wastewater treatment plants (WWTPs) in the United States. Microcosms were prepared with sediments from each site and amended with [U-ring-14C]4-n-nonylphenol (4-n-NP) as a model test substrate. Microcosms prepared with sediment collected upstream of the WWTP outfalls and incubated under oxic conditions showed rapid and complete mineralization of [U-ring-14C]4- n-NP to 14CO2 in all three systems. In contrast, no mineralization of [U-ring-14C]4-n-NP was observed in these sediments under anoxic (methanogenic) conditions. The initial linear rate of [U-ring-14C]4-n-NP mineralization in sediments from upstream and downstream of the respective WWTP outfalls was inversely correlated with the biochemical oxygen demand (BOD) of the streambed sediments. These results suggest that the net supply of dissolved oxygen to streambed sediments is a key determinant of the rate and extent of 4-NP biodegradation in stream systems. In the stream systems considered by the present study, dissolved oxygen concentrations in the overlying water column (8–10 mg/L) and in the bed sediment pore water (1–3 mg/L at a depth of 10 cm below the sediment–water interface) were consistent with active in situ 4-NP biodegradation. These results suggest WWTP procedures that maximize the delivery of dissolved oxygen while minimizing the release of BOD to stream receptors favor efficient biodegradation of 4-NP contaminants in wastewater-impacted stream environments.

  14. Atomistic aspects of ductile responses of cubic silicon carbide during nanometric cutting

    PubMed Central

    2011-01-01

    Cubic silicon carbide (SiC) is an extremely hard and brittle material having unique blend of material properties which makes it suitable candidate for microelectromechanical systems and nanoelectromechanical systems applications. Although, SiC can be machined in ductile regime at nanoscale through single-point diamond turning process, the root cause of the ductile response of SiC has not been understood yet which impedes significant exploitation of this ceramic material. In this paper, molecular dynamics simulation has been carried out to investigate the atomistic aspects of ductile response of SiC during nanometric cutting process. Simulation results show that cubic SiC undergoes sp3-sp2 order-disorder transition resulting in the formation of SiC-graphene-like substance with a growth rate dependent on the cutting conditions. The disorder transition of SiC causes the ductile response during its nanometric cutting operations. It was further found out that the continuous abrasive action between the diamond tool and SiC causes simultaneous sp3-sp2 order-disorder transition of diamond tool which results in graphitization of diamond and consequent tool wear. PMID:22078069

  15. Supercritical CO2 generation of nanometric structure from Ocimum basilicum mucilage prepared for pharmaceutical applications.

    PubMed

    Akbari, Iman; Ghoreishi, Seyyed M; Habibi, Neda

    2015-04-01

    Plant-derived polymers are widely used in the pharmaceutical industry due to their emollient, lack of toxicity, and irritating nature and low cost. In this work, basil seed mucilage was dried using supercritical carbon dioxide phase inversion technique to form a nanometric structure. The obtained polymeric structures were characterized by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) method, and Fourier transform infrared spectroscopy (FTIR) and compared with the oven-derived sample group. It was demonstrated that the product morphology could be controlled by altering the composition of methanol which functioned as the co-solvent in the nonsolvent stream. The most homogeneous product (60-nm mean pore size diameter, 78 m(2)/g BET surface area with no agglomeration) was obtained with 2.5% methanol. The FTIR data showed that the presence of hydroxyl and carboxyl groups suggested the bioadhesive property of basil seed mucilage was good and many active pharmaceutical compounds might be loaded to the resultant nanometric structure to enhance drug release. Furthermore, the FTIR analyses indicated that the nature of the final product did not change during the supercritical drying procedure. PMID:25367001

  16. Breakup of Thin Liquid Filaments on Partially Wetting Substrates: from Micrometric to Nanometric Scales

    NASA Astrophysics Data System (ADS)

    Diez, Javier A.; González, Alejandro G.

    2016-04-01

    We present theoretical and experimental results regarding the instability of a thin liquid film in the form a long filament sitted on a solid substrate. We consider this problem in two different scenarios, namely, at submillimetric and nanometric scales, and we study their free surface instability. In the first scale, we take into account the effects due to surface tension and gravity, while in the smaller scale, we add intermolecular interaction and neglect gravity. The flows are modeled within the long wave approximation, which leads to a nonlinear fourth-order differential equation for the fluid thickness. This model equation also includes the partial wetting condition between the liquid and the solid. In the theoretical models, we analyze the linear stability of the equilibrium configurations. The linear stability analyses lead to eigenvalue problems that are solved using pseudo spectral methods in the submillimetric case, and finite differences in the nanoscale. Whenever possible, the theoretical results are compared with experiments performed on a submillimetric scale (silicon oils on glass), as well as on nanometric scale (nickel films melted by laser irradiation on SiO2 substrates).

  17. Phase transformation and nanometric flow cause extreme weakening during fault slip

    NASA Astrophysics Data System (ADS)

    Green, H. W., II; Shi, F.; Bozhilov, K.; Xia, G.; Reches, Z.

    2015-06-01

    Earthquake instability requires fault weakening during slip. The mechanism of this weakening is central to understanding earthquake sliding and, in many cases, has been attributed to fluids. It is also unclear why major faults such as the San Andreas Fault do not exhibit significant thermal anomalies due to shear heating during sliding and whether or not fault rocks that have been melted--pseudotachylytes--are rare. High-speed friction experiments on a wide variety of rock types have shown that they all exhibit extreme weakening and that the sliding surface is nanometric and contains phases not present at the start. Here we use electron microscopy to examine these two key observations in high-speed friction experiments and compare them with high-pressure faulting experiments. We show that phase transformations occur in both cases and that they are associated with profound weakening. However, fluid is not necessary for such weakening; the nanometric fault filling is inherently weak at seismic sliding rates and it flows by grain boundary sliding. These observations suggest that pseudotachylytes are rare in nature because shear-heating-induced endothermic reactions in fault zones prevent temperature rise to melting. Microstructures preserved in the Punchbowl Fault, an ancestral branch of the San Andreas Fault, suggest similar processes during natural faulting and offer an explanation for the lack of a thermal aureole around major faults.

  18. Sensing nanometric displacement of a micro-/nano-fiber induced by optical forces by use of white light interferometry

    NASA Astrophysics Data System (ADS)

    Qiu, Weiqia; Huang, Hankai; Yu, Jianhui; Dong, Huazhuo; Chen, Zhe; Lu, Huihui

    2015-07-01

    Sensing the nanometric displacement of a micro-/nano-fiber induced by optical forces is a key technology to study optical forces and optical momentum. When the gap between a micro-/nano-fiber and glass substrate becomes down to micrometer scale or less, a white light interference was observed. The gap changes when optical force arising from the propagating pump light along the micro-/nano-fiber causes a transversal nanometric displacement of a micro-/nanofiber, resulting in movement of the interferometric fringes. Therefore this movement of the interferometric fringes can be used to sense the nanometric displacement of the micro-/nano-fiber induced by optical forces. Experimental results show that the resolutions of this method can reach 7.27nm/pixel for tilted angle 0.8o between the micro-/nano-fiber and substrate. It is concluded that the white light interferometry method is suitable for measuring the weak optical force.

  19. Nanowires of Fe/multi-walled carbon nanotubes and nanometric thin films of Fe/MgO

    SciTech Connect

    Newman, Alexander; Khatiwada, Suman; Neupane, Suman; Seifu, Dereje

    2015-04-14

    We observed that nanowires of Fe grown in the lumens of multi-walled carbon nanotubes required four times higher magnetic field strength to reach saturation compared to planar nanometric thin films of Fe on MgO(100). Nanowires of Fe and nanometric thin films of Fe both exhibited two fold magnetic symmetries. Structural and magnetic properties of 1-dimensional nanowires and 2-dimensional nanometric films were studied by several magnetometery techniques. The θ-2θ x-ray diffraction measurements showed that a (200) peak of Fe appeared on thin film samples deposited at higher substrate temperatures. In these samples prepared at higher temperatures, lower coercive field and highly pronounced two-fold magnetic symmetry were observed. Our results show that maximum magnetocrystalline anisotropy occurred for sample deposited at 100 °C and it decreased at higher deposition temperatures.

  20. Conversion of 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST) from a Simple Optical Material to a Versatile Optoelectronic Material.

    PubMed

    Xu, Xiangdong; Sun, Ziqiang; Fan, Kai; Jiang, Yadong; Huang, Rui; Wen, Yuejiang; He, Qiong; Ao, Tianhong

    2015-01-01

    4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST) is an important optical material, but its poor conductivity limits applications in devices. To tackle this problem, we designed, prepared, and systematically investigated novel binary composite films that are composed of two-dimensional (2D) DAST and 2D graphene. Results indicate that both electrical and optical properties of DAST can be significantly improved by graphene addition. The negative steric effects of big DAST molecules that greatly trouble ex-situ synthesis can be efficiently overcome by in-situ synthesis, thus leading to better film quality and higher physical properties. Consequently, the in-situ composite film exhibits a low sheet resistance of 7.5 × 10(6) ohm and high temperature coefficient of resistance of -2.79% K(-1), close to the levels of the most important bolometric materials for uncooled infrared detectors. Particularly, a new low temperature reduction of graphene oxide induced by DAST, which is further enhanced by in-situ process, was discovered. This work presents valuable information about the DAST-graphene composite films, their chemical structures, mechanisms, physical properties, and comparison on in-situ and ex-situ syntheses of graphene-based composites, all of which will be helpful for not only theoretically studying the DAST and graphene materials and expanding their applications, but also for seeking new optoelectronic sensitive materials. PMID:26192068

  1. Innovative Powder Processing of Oxide Dispersion Strengthened ODS Ferritic Stainless Steels

    SciTech Connect

    Rieken, Joel; Anderson, Iver; Kramer, Matthew

    2011-04-01

    An innovative gas atomization reaction synthesis technique was employed as a viable method to dramatically lower the processing cost for precursor oxide dispersion forming ferritic stainless steel powders (i.e., Fe-Cr-(Hf,Ti)-Y). During this rapid solidification process the atomized powders were enveloped by a nano-metric Cr-enriched metastable oxide film. Elevated temperature heat treatment was used to dissociate this metastable oxide phase through oxygen exchange reactions with Y-(Hf,Ti) enriched intermetallic compound precipitates. These solid state reactions resulted in the formation of highly stable nano-metric mixed oxide dispersoids (i.e., Y-Ti-O or Y-Hf-O) throughout the alloy microstructure. Subsequent high temperature (1200 C) heat treatments were used to elucidate the thermal stability of each nano-metric oxide dispersoid phase. Transmission electron microscopy coupled with X-ray diffraction was used to evaluate phase evolution within the alloy microstructure.

  2. Degradation of 4-n-nonylphenol under nitrate reducing conditions

    PubMed Central

    Viñas, Marc; Grotenhuis, Tim; Rijnaarts, Huub H. M.; Langenhoff, Alette A. M.

    2010-01-01

    Nonylphenol (NP) is an endocrine disruptor present as a pollutant in river sediment. Biodegradation of NP can reduce its toxicological risk. As sediments are mainly anaerobic, degradation of linear (4-n-NP) and branched nonylphenol (tNP) was studied under methanogenic, sulphate reducing and denitrifying conditions in NP polluted river sediment. Anaerobic bioconversion was observed only for linear NP under denitrifying conditions. The microbial population involved herein was further studied by enrichment and molecular characterization. The largest change in diversity was observed between the enrichments of the third and fourth generation, and further enrichment did not affect the diversity. This implies that different microorganisms are involved in the degradation of 4-n-NP in the sediment. The major degrading bacteria were most closely related to denitrifying hexadecane degraders and linear alkyl benzene sulphonate (LAS) degraders. The molecular structures of alkanes and LAS are similar to the linear chain of 4-n-NP, this might indicate that the biodegradation of linear NP under denitrifying conditions starts at the nonyl chain. Initiation of anaerobic NP degradation was further tested using phenol as a structure analogue. Phenol was chosen instead of an aliphatic analogue, because phenol is the common structure present in all NP isomers while the structure of the aliphatic chain differs per isomer. Phenol was degraded in all cases, but did not affect the linear NP degradation under denitrifying conditions and did not initiate the degradation of tNP and linear NP under the other tested conditions. PMID:20640878

  3. Nano-metric Dust Particles as a Hardly Detectable Component of the Interplanetary Dust Cloud

    NASA Astrophysics Data System (ADS)

    Simonia, I.; Nabiyev, Sh.

    2015-09-01

    The present work introduces the hypothesis of existence of a hardly detectable component of the interplanetary dust cloud and demonstrates that such a component is a dust formation consisting of the dust particles of nano-metric dimensions. This work describes the main physical properties of such a kind of nano-dust, and its possible chemical and mineralogical peculiarities proposes new explanations related to reddening of the dynamically cold transneptunian objects on account of scattering their light by nano-dust of the hardly detectable component of the interplanetary dust cloud. We propose the relation for the coefficient of absorption by the nano-dust and provide results of the statistical analysis of the TNO color index-orbital inclinations. We also present a critical assessment of the proposed hypothesis.

  4. Digital Holographic Measurement of Nanometric Optical Excitation on Soft Matter by Optical Pressure and Photothermal Interactions

    NASA Astrophysics Data System (ADS)

    Clark, David C.

    In this dissertation we use digital holographic quantitative phase microscopy to observe and measure phase-only structures due to induced photothermal interactions and nanoscopic structures produced by photomechanical interactions. Our use of the angular spectrum method combined with off-axis digital holography allows for the successful hologram acquisition and processing necessary to view these phenomena with nanometric and, in many cases, subnanometric precision. We show through applications that this has significance in metrology of bulk fluid and interfacial properties. Our accurate quantitative phase mapping of the optically induced thermal lens in media leads to improved measurement of the absorption coefficient over existing methods. By combining a mathematical model describing the thermal lens with that describing the surface deformation effect of optical radiation pressure, we simulate the ability to temporally decouple the two phenomena. We then demonstrate this ability experimentally as well as the ability of digital holography to clearly distinguish the phase signatures of the two effects. Finally, we devise a pulsed excitation method to completely isolate the optical pressure effect from the thermal lensing effect. We then develop a noncontact purely optical approach to measuring the localized surface properties of an interface within a system using a single optical pressure pulse and a time-resolved digital holographic quantitative phase imaging technique to track a propagating nanometric capillary disturbance. We demonstrate the method's ability to accurately measure the surface energy of pure media and chemical monolayers formed by surfactants with good agreement to published values. We discuss the possible adaptation of this technique to applications for living biological cell membranes.

  5. Three-month performance evaluation of the Nanometrics, Inc., Libra Satellite Seismograph System in the northern California Seismic Network

    USGS Publications Warehouse

    Oppenheimer, David H.

    2000-01-01

    In 1999 the Northern California Seismic Network (NCSN) purchased a Libra satellite seismograph system from Nanometrics, Inc to assess whether this technology was a cost-effective and robust replacement for their analog microwave system. The system was purchased subject to it meeting the requirements, criteria and tests described in Appendix A. In early 2000, Nanometrics began delivery of various components of the system, such as the hub and remote satellite dish and mounting hardware, and the NCSN installed and assembled most equipment in advance of the arrival of Nanometrics engineers to facilitate the configuration of the system. The hub was installed in its permanent location, but for logistical reasons the "remote" satellite hardware was initially configured at the NCSN for testing. During the first week of April Nanometrics engineers came to Menlo Park to configure the system and train NCSN staff. The two dishes were aligned with the satellite, and the system was fully operational in 2 days with little problem. Nanometrics engineers spent the remaining 3 days providing hands-on training to NCSN staff in hardware/software operation, configuration, and maintenance. During the second week of April 2000, NCSN staff moved the entire remote system of digitizers, dish assembly, and mounting hardware to Mammoth Lakes, California. The system was reinstalled at the Mammoth Lakes water treatment plant and communications successfully reestablished with the hub via the satellite on 14 April 2000. The system has been in continuous operation since then. This report reviews the performance of the Libra system for the three-month period 20 April 2000 through 20 July 2000. The purpose of the report is to assess whether the system passed the acceptance tests described in Appendix A. We examine all data gaps reported by NCSN "gap list" software and discuss their cause.

  6. Photoactivation of the processes of formation of nanostructures by local anodic oxidation of a titanium film

    SciTech Connect

    Ageev, O. A.; Alyab'eva, N. I.; Konoplev, B. G. Polyakov, V. V.; Smirnov, V. A.

    2010-12-15

    Experimental results on the conditions of activation of probe nanolithography of a thin titanium film by means of local anodic oxidation are reported. It is established that ultraviolet stimulation reduces the geometric dimensions of nanometric oxide structures. The stimulation is accompanied by an increase in the amplitude and duration of the threshold voltage pulse, correspondingly, from 6 to 7 V and from 50 to 100 ms at the relative humidity 50%. The experimental data on the effect of the cantilever coating material and substrate temperature on the geometric dimensions of nanometric oxide structures are reported.

  7. SU-E-CAMPUS-I-01: Nanometric Organic Photovoltaic Thin Film X-Ray Detectors for Clinical KVp Beams

    SciTech Connect

    Elshahat, Bassem; Gill, Hardeep; Kumar, Jayant; Sajo, Erno; Filipyev, Ilya; Zygmanski, Piotr; Shrestha, Suman; Hesser, Jurgen; Karellas, Andrew

    2014-06-15

    Purpose: To fabricate and test nanometric organic photovoltaic (OPV) cells made of various active-layer/electrode thicknesses and sizes; to determine the optimal material combinations and geometries suitable for dose measurements in clinical kilovoltage x-ray beams. Methods: The OPV consisted of P3HT:PCBM photoactive materials sandwiched between aluminum and Indium Tin Oxide (ITO) electrodes. Direct conversion of xrays in the active layer composed of donor and acceptor semiconducting organic materials generated signal in photovoltaic mode (without external voltage bias). OPV cells were fabricated with different active layer thicknesses (150, 270, 370 nm) and electrode areas (0.4, 0.7, 0.9, 1.4, 2.6 cm{sup 2}). A series of experiments were preformed in the energy range of 60–150 kVp. The net current per unit area (nA/cm{sup 2}) was measured using 200 mAs time-integrated beam current. Results: The net OPV current as function of beam energy (kVp) was proportional to ∼E{sup 0,4} {sup 5} when adjusted for beam output. The best combination of parameters for these cells was 270 nm active layer thicknesses for 0.7 cm{sup 2} electrode area. The measured current ranged from 0.69 to 2.43 nA/cm{sup 2} as a function of x-ray energy between 60 and 150 kVp, corresponding to 0.09 – 0.06 nA/cm{sup 2}/mGy, respectively, when adjusted for the beam output. Conclusion: The experiments indicate that OPV detectors possessing 270 nm active layer and 0.7 cm{sup 2} Al electrode areas have sensitivity by a factor of 2.5 greater than commercial aSi thin film PV. Because OPV can be made flexible and they do not require highvoltage bias supply, they open the possibility for using as in-vivo detectors in radiation safety in x-ray imaging beams.

  8. NiCo2O4/N-doped graphene as an advanced electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Li, Huiyong; Wang, Haiyan; He, Kejian; Wang, Shuangyin; Tang, Yougen; Chen, Jiajie

    2015-04-01

    Developing low-cost catalyst for high-performance oxygen reduction reaction (ORR) is highly desirable. Herein, NiCo2O4/N-doped reduced graphene oxide (NiCo2O4/N-rGO) hybrid is proposed as a high-performance catalyst for ORR for the first time. The well-formed NiCo2O4/N-rGO hybrid is studied by cyclic voltammetry (CV) curves and linear-sweep voltammetry (LSV) performed on the rotating-ring-disk-electrode (RDE) in comparison with N-rGO-free NiCo2O4 and the bare N-rGO. Due to the synergistic effect, the NiCo2O4/N-rGO hybrid exhibits significant improvement of catalytic performance with an onset potential of -0.12 V, which mainly favors a direct four electron pathway in ORR process, close to the behavior of commercial carbon-supported Pt. Also, the benefits of N-incorporation are investigated by comparing NiCo2O4/N-rGO with NiCo2O4/rGO, where higher cathodic currents, much more positive half-wave potential and more electron transfer numbers are observed for the N-doping one, which should be ascribed to the new highly efficient active sites created by N incorporation into graphene. The NiCo2O4/N-rGO hybrid could be used as a promising catalyst for high power metal/air battery.

  9. Purification of stearidonic acid (18:4(n-3)) and hexadecatetraenoic acid (16:4(n-3)) from algal fatty acid with lipase and medium pressure liquid chromatography.

    PubMed

    Ishihara, K; Murata, M; Kaneniwa, M; Saito, H; Komatsu, W; Shinohara, K

    2000-11-01

    Stearidonic acid (18:4(n-3)) and hexadecatetraenoic acid (16:4(n-3)) are included in some edible marine algae such as Undaria pinnatifida and Ulva pertusa with relatively high compositions (up to 40%) of total fatty acids. In order to prepare 16:4(n-3) and 18:4(n-3) enriched fatty acid concentrates, we screened for a suitable lipase which concentrates these acids by the removal of other fatty acids in the selective esterification reaction reported by Shimada et al. (Shimada et al. (1997), J. Am. Oil Chem. Soc., 74, 1465-1470). In combination with the lipase reaction and reversed-phase medium pressure liquid chromatography, we purified 18:4(n-3) and 16:4(n-3) to more than 95% purity. PMID:11193415

  10. Effect of Nanometric Lactobacillus plantarum in Kimchi on Dextran Sulfate Sodium-Induced Colitis in Mice.

    PubMed

    Lee, Hyun Ah; Bong, Yeon-Ju; Kim, Hyunung; Jeong, Ji-Kang; Kim, Hee-Young; Lee, Kwang-Won; Park, Kun-Young

    2015-10-01

    Nanometric Lactobacillus plantarum (nLp) is a processed form of Lab. plantarum derived from kimchi and is 0.5-1.0 μm in size. This study was undertaken to determine the effect of nLp and kimchi plus nLp (K-nLp) on a dextran sulfate sodium (DSS)-induced mouse model of colitis. Animals fed nLp or K-nLp had longer colons, but lower colon weights per unit length than DSS controls. In addition, nLp- or K-nLp-fed animals showed lower levels of proinflammatory cytokines and inflammatory genes in serum and in colon tissues, lower populations of total bacteria, but higher populations of lactic acid bacteria in feces, and lower activities of fecal β-glucosidase and β-glucuronidase. Furthermore, these suppressive activities of nLp on colitis were equivalent to or higher than those of naive Lab. plantarum. Consequently, nLp was found to exhibit anticolitic effects, and the addition of nLp to kimchi was found to enhance the protective activity of kimchi against DSS-induced colitis. These results suggest that nLp might be an effective substitute for live probiotics and be useful as a functional ingredient with the anticolitic activity by the probiotic and food processing industries. PMID:26305853

  11. Multivalent Carbohydrate-Lectin Interactions: How Synthetic Chemistry Enables Insights into Nanometric Recognition.

    PubMed

    Roy, René; Murphy, Paul V; Gabius, Hans-Joachim

    2016-01-01

    Glycan recognition by sugar receptors (lectins) is intimately involved in many aspects of cell physiology. However, the factors explaining the exquisite selectivity of their functional pairing are not yet fully understood. Studies toward this aim will also help appraise the potential for lectin-directed drug design. With the network of adhesion/growth-regulatory galectins as therapeutic targets, the strategy to recruit synthetic chemistry to systematically elucidate structure-activity relationships is outlined, from monovalent compounds to glyco-clusters and glycodendrimers to biomimetic surfaces. The versatility of the synthetic procedures enables to take examining structural and spatial parameters, alone and in combination, to its limits, for example with the aim to produce inhibitors for distinct galectin(s) that exhibit minimal reactivity to other members of this group. Shaping spatial architectures similar to glycoconjugate aggregates, microdomains or vesicles provides attractive tools to disclose the often still hidden significance of nanometric aspects of the different modes of lectin design (sequence divergence at the lectin site, differences of spatial type of lectin-site presentation). Of note, testing the effectors alone or in combination simulating (patho)physiological conditions, is sure to bring about new insights into the cooperation between lectins and the regulation of their activity. PMID:27187342

  12. Nanometre-scale probing of spin waves using single-electron spins

    PubMed Central

    van der Sar, Toeno; Casola, Francesco; Walsworth, Ronald; Yacoby, Amir

    2015-01-01

    Pushing the frontiers of condensed-matter magnetism requires the development of tools that provide real-space, few-nanometre-scale probing of correlated-electron magnetic excitations under ambient conditions. Here we present a practical approach to meet this challenge, using magnetometry based on single nitrogen-vacancy centres in diamond. We focus on spin-wave excitations in a ferromagnetic microdisc, and demonstrate local, quantitative and phase-sensitive detection of the spin-wave magnetic field at ∼50 nm from the disc. We map the magnetic-field dependence of spin-wave excitations by detecting the associated local reduction in the disc's longitudinal magnetization. In addition, we characterize the spin–noise spectrum by nitrogen-vacancy spin relaxometry, finding excellent agreement with a general analytical description of the stray fields produced by spin–spin correlations in a 2D magnetic system. These complementary measurement modalities pave the way towards imaging the local excitations of systems such as ferromagnets and antiferromagnets, skyrmions, atomically assembled quantum magnets, and spin ice. PMID:26249673

  13. Auxetic tissue engineering scaffolds with nanometric features and resonances in the megahertz range

    NASA Astrophysics Data System (ADS)

    Díaz Lantada, Andrés; Muslija, Alban; Predestinación García-Ruíz, Josefa

    2015-05-01

    In this study we present an improved approach for the development of auxetics based on the use of deep reactive ion etching (DRIE) after a high-precision mask fabrication procedure. The whole process stands out for its precision (reaching nanometric detail), for the high aspect ratio (AR) attainable and for the possibility of promoting mass production. The quality of the proposed strategy is verified by the manufacture of an auxetic cantilever and bridged structures using two common planar auxetic geometries. The present process significantly increases the precision and AR of the micro-auxetics obtained when compared to state-of-the-art micromachining procedures and solves common challenges linked to structure adhesion to the substrate. The potential of the manufactured structures for the development of resonant structures is analyzed by means of finite-element-method- (FEM) based simulations, showing resonances in the megahertz range. A final application example, linked to monitoring cell culture processes upon auxetic scaffolds, is also proposed and analyzed by computational procedures. The initial cell culture results are also included and help to validate the scaffolds obtained and the materials used for future tissue engineering studies.

  14. Nanometre optical coatings based on strong interference effects in highly absorbing media

    NASA Astrophysics Data System (ADS)

    Kats, Mikhail A.; Blanchard, Romain; Genevet, Patrice; Capasso, Federico

    2013-01-01

    Optical coatings, which consist of one or more films of dielectric or metallic materials, are widely used in applications ranging from mirrors to eyeglasses and photography lenses. Many conventional dielectric coatings rely on Fabry-Perot-type interference, involving multiple optical passes through transparent layers with thicknesses of the order of the wavelength to achieve functionalities such as anti-reflection, high-reflection and dichroism. Highly absorbing dielectrics are typically not used because it is generally accepted that light propagation through such media destroys interference effects. We show that under appropriate conditions interference can instead persist in ultrathin, highly absorbing films of a few to tens of nanometres in thickness, and demonstrate a new type of optical coating comprising such a film on a metallic substrate, which selectively absorbs various frequency ranges of the incident light. These coatings have a low sensitivity to the angle of incidence and require minimal amounts of absorbing material that can be as thin as 5-20 nm for visible light. This technology has the potential for a variety of applications from ultrathin photodetectors and solar cells to optical filters, to labelling, and even the visual arts and jewellery.

  15. Nanometric thin polymeric films based on molecularly imprinted technology: towards electrochemical sensing applications.

    PubMed

    Ginzburg-Turgeman, Roni; Mandler, Daniel

    2010-09-28

    A new approach for assembling selective electrodes based on molecularly imprinted polymers (MIPs) is presented. The approach is based on the radical polymerization of a mixture of methacrylic acid (MAA) and ethyleneglycol dimethacrylate (EGDMA) in the presence of an initiator, benzoyl peroxide (BPO) and an activator, N,N'-dimethyl-p-toluidine (DMpT) at room temperature and atmospheric pressure. To form nanometric thin polymeric films the polymerization solution was spin-coated in the course of polymerization. The different physical and chemical parameters that affected the properties of the films, such as the spinning rate and the EGDMA:MAA ratio, were studied and optimized. A variety of techniques, e.g., rheoscopy, SEM, AFM, profilometry and electrochemistry, were used to characterize the films and the polymerization process. By optimizing the conditions very thin and reproducible films could be prepared and imprinted. The electrochemical behavior of the films showed that they were permeable to water-soluble electroactive species providing that either polyethylene glycol or template species were added to the polymerization mixture. Finally, we demonstrated that films imprinted with ferrocenylmethyl alcohol (Fc-MeOH) successfully extracted the imprinted species after their removal from MIPs. PMID:20668737

  16. A novel approach to dark matter search based on nanometric emulsions

    NASA Astrophysics Data System (ADS)

    Alexandrov, A.; Asada, T.; D'Ambrosio, N.; De Lellis, G.; Di Crescenzo, A.; Di Marco, N.; Furuya, S.; Gentile, V.; Hakamata, K.; Ishikawa, M.; Katsuragawa, T.; Kuwabara, K.; Machii, S.; Naka, T.; Pupilli, F.; Sirignano, C.; Tawara, Y.; Tioukov, V.; Umemoto, A.; Yoshimoto, M.

    2014-12-01

    The most convincing candidate as main constituent of the dark matter in the Universe consists of weakly interacting massive particles (WIMP). WIMPs must be electrically neutral and interact with a very low cross-section (σ < 10-40 cm2) which makes them detectable in direct searches only through the observation of nuclear recoils induced by the WIMP rare scatterings. In the experiments carried out so far, recoiled nuclei are searched for as a signal over a background produced by Compton electrons and neutron scatterings. Signal found by some experiments have not been confirmed by other techniques. None of these experiments is able to detect the track, typically less than one micron long, of the recoiled nucleus and therefore none is able to directly detect the incoming direction of WIMPs. We propose an R&D program for a new experimental method able to observe the track of the scattered nucleus based on new developments in the nuclear emulsion technique: films with nanometric silver grains, expansion of emulsions and very fast completely automated scanning systems. Nuclear emulsions would act both as the WIMP target and as the tracking detector able to reconstruct the direction of the recoiled nucleus. This unique characteristic would provide a new and unambiguous signature of the presence of the dark matter in our galaxy.

  17. Top-down fabrication of sub-nanometre semiconducting nanoribbons derived from molybdenum disulfide sheets.

    PubMed

    Liu, Xiaofei; Xu, Tao; Wu, Xing; Zhang, Zhuhua; Yu, Jin; Qiu, Hao; Hong, Jin-Hua; Jin, Chuan-Hong; Li, Ji-Xue; Wang, Xin-Ran; Sun, Li-Tao; Guo, Wanlin

    2013-01-01

    Developments in semiconductor technology are propelling the dimensions of devices down to 10 nm, but facing great challenges in manufacture at the sub-10 nm scale. Nanotechnology can fabricate nanoribbons from two-dimensional atomic crystals, such as graphene, with widths below the 10 nm threshold, but their geometries and properties have been hard to control at this scale. Here we find that robust ultrafine molybdenum-sulfide ribbons with a uniform width of 0.35 nm can be widely formed between holes created in a MoS2 sheet under electron irradiation. In situ high-resolution transmission electron microscope characterization, combined with first-principles calculations, identifies the sub-1 nm ribbon as a Mo5S4 crystal derived from MoS2, through a spontaneous phase transition. Further first-principles investigations show that the Mo5S4 ribbon has a band gap of 0.77 eV, a Young's modulus of 300GPa and can demonstrate 9% tensile strain before fracture. The results show a novel top-down route for controllable fabrication of functional building blocks for sub-nanometre electronics. PMID:23653188

  18. Top–down fabrication of sub-nanometre semiconducting nanoribbons derived from molybdenum disulfide sheets

    PubMed Central

    Liu, Xiaofei; Xu, Tao; Wu, Xing; Zhang, Zhuhua; Yu, Jin; Qiu, Hao; Hong, Jin-Hua; Jin, Chuan-Hong; Li, Ji-Xue; Wang, Xin-Ran; Sun, Li-Tao; Guo, Wanlin

    2013-01-01

    Developments in semiconductor technology are propelling the dimensions of devices down to 10 nm, but facing great challenges in manufacture at the sub-10 nm scale. Nanotechnology can fabricate nanoribbons from two-dimensional atomic crystals, such as graphene, with widths below the 10 nm threshold, but their geometries and properties have been hard to control at this scale. Here we find that robust ultrafine molybdenum-sulfide ribbons with a uniform width of 0.35 nm can be widely formed between holes created in a MoS2 sheet under electron irradiation. In situ high-resolution transmission electron microscope characterization, combined with first-principles calculations, identifies the sub-1 nm ribbon as a Mo5S4 crystal derived from MoS2, through a spontaneous phase transition. Further first-principles investigations show that the Mo5S4 ribbon has a band gap of 0.77 eV, a Young’s modulus of 300GPa and can demonstrate 9% tensile strain before fracture. The results show a novel top–down route for controllable fabrication of functional building blocks for sub-nanometre electronics. PMID:23653188

  19. Spearhead Nanometric Field-Effect Transistor Sensors for Single-Cell Analysis

    PubMed Central

    Córdoba, Ainara López; Ali, Tayyibah; Shevchuk, Andrew; Takahashi, Yasufumi; Novak, Pavel; Edwards, Christopher; Lab, Max; Gopal, Sahana; Chiappini, Ciro; Anand, Uma; Magnani, Luca; Coombes, R. Charles; Gorelik, Julia; Matsue, Tomokazu; Schuhmann, Wolfgang; Klenerman, David; Sviderskaya, Elena V.; Korchev, Yuri

    2016-01-01

    Nanometric field-effect-transistor (FET) sensors are made on the tip of spear-shaped dual carbon nanoelectrodes derived from carbon deposition inside double-barrel nanopipettes. The easy fabrication route allows deposition of semiconductors or conducting polymers to comprise the transistor channel. A channel from electrodeposited poly pyrrole (PPy) exhibits high sensitivity toward pH changes. This property is exploited by immobilizing hexokinase on PPy nano-FETs to give rise to a selective ATP biosensor. Extracellular pH and ATP gradients are key biochemical constituents in the microenvironment of living cells; we monitor their real-time changes in relation to cancer cells and cardiomyocytes. The highly localized detection is possible because of the high aspect ratio and the spear-like design of the nano-FET probes. The accurately positioned nano-FET sensors can detect concentration gradients in three-dimensional space, identify biochemical properties of a single living cell, and after cell membrane penetration perform intracellular measurements. PMID:26816294

  20. Spearhead Nanometric Field-Effect Transistor Sensors for Single-Cell Analysis.

    PubMed

    Zhang, Yanjun; Clausmeyer, Jan; Babakinejad, Babak; López Córdoba, Ainara; Ali, Tayyibah; Shevchuk, Andrew; Takahashi, Yasufumi; Novak, Pavel; Edwards, Christopher; Lab, Max; Gopal, Sahana; Chiappini, Ciro; Anand, Uma; Magnani, Luca; Coombes, R Charles; Gorelik, Julia; Matsue, Tomokazu; Schuhmann, Wolfgang; Klenerman, David; Sviderskaya, Elena V; Korchev, Yuri

    2016-03-22

    Nanometric field-effect-transistor (FET) sensors are made on the tip of spear-shaped dual carbon nanoelectrodes derived from carbon deposition inside double-barrel nanopipettes. The easy fabrication route allows deposition of semiconductors or conducting polymers to comprise the transistor channel. A channel from electrodeposited poly pyrrole (PPy) exhibits high sensitivity toward pH changes. This property is exploited by immobilizing hexokinase on PPy nano-FETs to give rise to a selective ATP biosensor. Extracellular pH and ATP gradients are key biochemical constituents in the microenvironment of living cells; we monitor their real-time changes in relation to cancer cells and cardiomyocytes. The highly localized detection is possible because of the high aspect ratio and the spear-like design of the nano-FET probes. The accurately positioned nano-FET sensors can detect concentration gradients in three-dimensional space, identify biochemical properties of a single living cell, and after cell membrane penetration perform intracellular measurements. PMID:26816294

  1. Energy landscape exploration of sub-nanometre copper-silver clusters.

    PubMed

    Heard, Christopher J; Johnston, Roy L; Schön, J Christian

    2015-05-18

    The energy landscapes of sub-nanometre bimetallic coinage metal clusters are explored with the Threshold Algorithm coupled with the Birmingham Cluster Genetic Algorithm. Global and energetically low-lying minima along with their permutational isomers are located for the Cu(4)Ag(4) cluster with the Gupta potential and density functional theory (DFT). Statistical tools are employed to map the connectivity of the energy landscape and the growth of structural basins, while the thermodynamics of interconversion are probed, based on probability flows between minima. Asymmetric statistical weights are found for pathways across dividing states between stable geometries, while basin volumes are observed to grow independently of the depth of the minimum. The DFT landscape is found to exhibit significantly more frustration than that of the Gupta potential, including several open, pseudo-planar geometries which are energetically competitive with the global minimum. The differences in local minima and their transition barriers between the two levels of theory indicate the importance of explicit electronic structure for even simple, closed shell clusters. PMID:25784077

  2. Live-cell protein labelling with nanometre precision by cell squeezing

    PubMed Central

    Kollmannsperger, Alina; Sharei, Armon; Raulf, Anika; Heilemann, Mike; Langer, Robert; Jensen, Klavs F.; Wieneke, Ralph; Tampé, Robert

    2016-01-01

    Live-cell labelling techniques to visualize proteins with minimal disturbance are important; however, the currently available methods are limited in their labelling efficiency, specificity and cell permeability. We describe high-throughput protein labelling facilitated by minimalistic probes delivered to mammalian cells by microfluidic cell squeezing. High-affinity and target-specific tracing of proteins in various subcellular compartments is demonstrated, culminating in photoinduced labelling within live cells. Both the fine-tuned delivery of subnanomolar concentrations and the minimal size of the probe allow for live-cell super-resolution imaging with very low background and nanometre precision. This method is fast in probe delivery (∼1,000,000 cells per second), versatile across cell types and can be readily transferred to a multitude of proteins. Moreover, the technique succeeds in combination with well-established methods to gain multiplexed labelling and has demonstrated potential to precisely trace target proteins, in live mammalian cells, by super-resolution microscopy. PMID:26822409

  3. Electrical and electroluminescent characterization of nanometric multilayers of SiOX/SiOY obtained by LPCVD including non-normal emission

    NASA Astrophysics Data System (ADS)

    Alarcón-Salazar, J.; Zaldívar-Huerta, I. E.; Aceves-Mijares, M.

    2016-06-01

    This work describes the analysis and fabrication by Low Pressure Chemical Vapor Deposition of two light-emitting capacitors (LECs) constituted by nanometric multilayers of silicon-rich oxide. For both structures, seven layers were used: three light emitting layers with 6% silicon excess and four conductive layers with 12% silicon excess for one LEC and the other with 14% silicon excess. Both LECs were annealed at 1100 °C. Both multilayers demonstrate a substantially improved photoluminescent response compared to single emitting layers. A dielectric constant of 4.1 and a trap density of 1016 cm-3 were obtained from capacitance-voltage curves. Analysis of current-voltage and electroluminescence-voltage (EL-V) characteristics indicates that EL initiates under the space-charge-limited current mechanism, and the required voltage to turn on the emission is 38 V which is the trap-free limit voltage. However, EL increases exponentially under the impact ionization and trap-assisted tunneling conduction mechanisms. The electroluminescence spectra for both multilayers show two emission peaks centered in 450 and 700 nm attributed to oxygen defects. Also, the LEC non-normal emission was measured and it behaves like a Lambertian optical source. Both multilayers obtain the values of efficiency in the order of 10-6 which is in good agreement with the values reported in the literature.

  4. Breakdown of magnetism in sub-nanometric Ni clusters embedded in Ag.

    PubMed

    García-Prieto, A; Arteche, A; Aguilera-Granja, F; Torres, M B; Orue, I; Alonso, J; Barquín, L Fernández; Fernández-Gubieda, M L

    2015-11-13

    Downsizing to the nanoscale has opened up a spectrum of new magnetic phenomena yet to be discovered. In this context, we investigate the magnetic properties of Ni clusters embedded in a metallic Ag matrix. Unlike in Ni free-standing clusters, where the magnetic moment increases towards the atomic value when decreasing the cluster size, we show, by tuning the Ni cluster size down to the sub-nanoscale, that there is a size limit below which the clusters become non-magnetic when embedded in Ag. To this end, we have fabricated by DC-sputtering a system composed of sub-nanometer sized and non interacting Ni clusters embedded into a Ag matrix. A thorough experimental characterization by means of structural techniques (x-ray diffraction, x-ray absorption spectroscopy) and DC-magnetization confirms that the cluster size is in the sub-nanometric range and shows that the magnetization of the system is dramatically reduced, reaching only 38% of the bulk value. The experimental system has been reproduced by density functional theory calculations on Ni m clusters (m = 1-6, 10 and 13) embedded in Ag. The combination of the experimental and theoretical analysis points out that there is a breakdown of magnetism occurring below a cluster size of six atoms. According to our results, the loss of magnetic moment is not due to Ag-Ni hybridization but to charge transfer between the Ni sp and d orbitals, and the reduced magnetization observed experimentally is explained on the basis of the presence of a narrow cluster size-distribution where magnetic and non-magnetic clusters coexist. PMID:26487422

  5. Diffraction pattern by nanometric thin films under illumination of an orbital angular momentum beam with integer topological charge

    NASA Astrophysics Data System (ADS)

    Mendoza, J. H.; Díaz, C. F.; Acevedo, C. H.; Torres, Y.

    2016-02-01

    The orbital angular momentum of light has a big contribution in many engineering applications like optical communications, because this physical property allows eigenstates characteristic of the wavefront rotation when the beam is propagated. The nature of these eigenstates allows that information can be encoded and gives immunity to electromagnetic interference, allowing an increase of bandwidth, cadence and capacity of the communication channel. This work shown the methodology using nanometric thin films like Titanium based (TiO2) grown over strontium titanate (SrTiO3) support, to distinguish and discriminate a well- defined integer value of the topological charge of an OAM beam.

  6. Purification and characterization of 4-N-trimethylamino-1-butanol dehydrogenase from Fusarium merismoides var. acetilereum.

    PubMed

    Fujimitsu, Hiroshi; Taniyama, Yuko; Tajima, Sae; Mohamed Ahmed, Isam A; Arima, Jiro; Mori, Nobuhiro

    2016-09-01

    From investigation of 60 filamentous fungi, we identified Fusarium merismoides var. acetilereum, which uses 4-N-trimethylamino-1-butanol (TMA-butanol) as the sole source of carbon and nitrogen. The fungus produced NAD(+)-dependent TMA-butanol dehydrogenase (DH) when it was cultivated in medium containing TMA-butanol. The enzyme showed molecular mass of 40 kDa by SDS-PAGE and 160 kDa by gel filtration, suggesting that it is a homotetramer. TMA-butanol DH is stable at pH 7.5-9.0. It exhibits moderate stability with respect to temperature (up to 30 °C). Additionally, it has optimum activity at 45 °C and at pH 9.5. The enzyme has broad specificity to various alkyl alcohols and amino alkyl alcohols, and the carbon chains of which are longer than butanol. Moreover, the activity is strongly inhibited by oxidizing agents, carbonyl and thiol modulators, and chelating agents. This report is the first study examining TMA-butanol DH from eukaryotic microbes. PMID:27121905

  7. Deposition of nanometric double layers Ru/Au, Ru/Pd, and Pd/Au onto CdZnTe by the electroless method

    NASA Astrophysics Data System (ADS)

    Zheng, Q.; Dierre, F.; Corregidor, V.; Fernández-Ruiz, R.; Crocco, J.; Bensalah, H.; Alves, E.; Diéguez, E.

    2012-11-01

    Nanometric double layer properties of different metal-semiconductor-metal (MSM) depositions onto CdZnTe produced by electroless method are investigated. The mechanisms of the deposition are discussed and the theoretical chemical equations implied in the process are presented. The solutions for different time of deposition and the deposited layers are analysed by TXRF to test the proposed reactions. RBS was used to determine the thickness, the depth profiles and the composition of the layers deposited at the surface. This work showed the feasibility of depositing nanometric double layers using electroless technique.

  8. Constructing optimal entanglement witnesses. II. Witnessing entanglement in 4Nx4N systems

    SciTech Connect

    Chruscinski, Dariusz; Pytel, Justyna

    2010-11-15

    We provide a class of optimal nondecomposable entanglement witnesses for 4Nx4N composite quantum systems or, equivalently, another construction of nondecomposable positive maps in the algebra of 4Nx4N complex matrices. This construction provides natural generalization of the Robertson map. It is shown that their structural physical approximations give rise to entanglement breaking channels.

  9. Sub-nanometre resolution imaging of polymer–fullerene photovoltaic blends using energy-filtered scanning electron microscopy

    PubMed Central

    Masters, Robert C.; Pearson, Andrew J.; Glen, Tom S.; Sasam, Fabian-Cyril; Li, Letian; Dapor, Maurizio; Donald, Athene M.; Lidzey, David G.; Rodenburg, Cornelia

    2015-01-01

    The resolution capability of the scanning electron microscope has increased immensely in recent years, and is now within the sub-nanometre range, at least for inorganic materials. An equivalent advance has not yet been achieved for imaging the morphologies of nanostructured organic materials, such as organic photovoltaic blends. Here we show that energy-selective secondary electron detection can be used to obtain high-contrast, material-specific images of an organic photovoltaic blend. We also find that we can differentiate mixed phases from pure material phases in our data. The lateral resolution demonstrated is twice that previously reported from secondary electron imaging. Our results suggest that our energy-filtered scanning electron microscopy approach will be able to make major inroads into the understanding of complex, nano-structured organic materials. PMID:25906738

  10. Sub-nanometre resolution imaging of polymer-fullerene photovoltaic blends using energy-filtered scanning electron microscopy.

    PubMed

    Masters, Robert C; Pearson, Andrew J; Glen, Tom S; Sasam, Fabian-Cyril; Li, Letian; Dapor, Maurizio; Donald, Athene M; Lidzey, David G; Rodenburg, Cornelia

    2015-01-01

    The resolution capability of the scanning electron microscope has increased immensely in recent years, and is now within the sub-nanometre range, at least for inorganic materials. An equivalent advance has not yet been achieved for imaging the morphologies of nanostructured organic materials, such as organic photovoltaic blends. Here we show that energy-selective secondary electron detection can be used to obtain high-contrast, material-specific images of an organic photovoltaic blend. We also find that we can differentiate mixed phases from pure material phases in our data. The lateral resolution demonstrated is twice that previously reported from secondary electron imaging. Our results suggest that our energy-filtered scanning electron microscopy approach will be able to make major inroads into the understanding of complex, nano-structured organic materials. PMID:25906738

  11. Deceleration of single-stranded DNA passing through a nanopore using a nanometre-sized bead structure

    NASA Astrophysics Data System (ADS)

    Goto, Yusuke; Haga, Takanobu; Yanagi, Itaru; Yokoi, Takahide; Takeda, Ken-Ichi

    2015-11-01

    DNA sequencing with a solid-state nanopore requires a reduction of the translocation speeds of single-stranded DNA (ssDNA) over 10 μs/base. In this study, we report that a nanometre-sized bead structure constructed around a nanopore can reduce the moving speed of ssDNA to 270 μs/base by adjusting the diameter of the bead and its surface chemical group. This decelerating effect originates from the strong interaction between ssDNA and the chemical group on the surface of the bead. This nanostructure was simply prepared by dip coating in which a substrate with a nanopore was immersed in a silica bead solution and then dried in an oven. As compared with conventional approaches, our novel method is less laborious, simpler to perform and more effective in reducing ssDNA translocation speed.

  12. Deceleration of single-stranded DNA passing through a nanopore using a nanometre-sized bead structure

    PubMed Central

    Goto, Yusuke; Haga, Takanobu; Yanagi, Itaru; Yokoi, Takahide; Takeda, Ken-ichi

    2015-01-01

    DNA sequencing with a solid-state nanopore requires a reduction of the translocation speeds of single-stranded DNA (ssDNA) over 10 μs/base. In this study, we report that a nanometre-sized bead structure constructed around a nanopore can reduce the moving speed of ssDNA to 270 μs/base by adjusting the diameter of the bead and its surface chemical group. This decelerating effect originates from the strong interaction between ssDNA and the chemical group on the surface of the bead. This nanostructure was simply prepared by dip coating in which a substrate with a nanopore was immersed in a silica bead solution and then dried in an oven. As compared with conventional approaches, our novel method is less laborious, simpler to perform and more effective in reducing ssDNA translocation speed. PMID:26559466

  13. Revealing the mechanism of passive transport in lipid bilayers via phonon-mediated nanometre-scale density fluctuations

    PubMed Central

    Zhernenkov, Mikhail; Bolmatov, Dima; Soloviov, Dmitry; Zhernenkov, Kirill; Toperverg, Boris P.; Cunsolo, Alessandro; Bosak, Alexey; Cai, Yong Q.

    2016-01-01

    The passive transport of molecules through a cell membrane relies on thermal motions of the lipids. However, the nature of transmembrane transport and the precise mechanism remain elusive and call for a comprehensive study of phonon excitations. Here we report a high resolution inelastic X-ray scattering study of the in-plane phonon excitations in 1,2-dipalmitoyl-sn-glycero-3-phosphocholine above and below the main transition temperature. In the gel phase, for the first time, we observe low-frequency transverse modes, which exhibit a phonon gap when the lipid transitions into the fluid phase. We argue that the phonon gap signifies the formation of short-lived nanometre-scale lipid clusters and transient pores, which facilitate the passive molecular transport across the bilayer plane. Our findings suggest that the phononic motion of the hydrocarbon tails provides an effective mechanism of passive transport, and illustrate the importance of the collective dynamics of biomembranes. PMID:27175859

  14. Revealing the mechanism of passive transport in lipid bilayers via phonon-mediated nanometre-scale density fluctuations

    NASA Astrophysics Data System (ADS)

    Zhernenkov, Mikhail; Bolmatov, Dima; Soloviov, Dmitry; Zhernenkov, Kirill; Toperverg, Boris P.; Cunsolo, Alessandro; Bosak, Alexey; Cai, Yong Q.

    2016-05-01

    The passive transport of molecules through a cell membrane relies on thermal motions of the lipids. However, the nature of transmembrane transport and the precise mechanism remain elusive and call for a comprehensive study of phonon excitations. Here we report a high resolution inelastic X-ray scattering study of the in-plane phonon excitations in 1,2-dipalmitoyl-sn-glycero-3-phosphocholine above and below the main transition temperature. In the gel phase, for the first time, we observe low-frequency transverse modes, which exhibit a phonon gap when the lipid transitions into the fluid phase. We argue that the phonon gap signifies the formation of short-lived nanometre-scale lipid clusters and transient pores, which facilitate the passive molecular transport across the bilayer plane. Our findings suggest that the phononic motion of the hydrocarbon tails provides an effective mechanism of passive transport, and illustrate the importance of the collective dynamics of biomembranes.

  15. Revealing the mechanism of passive transport in lipid bilayers via phonon-mediated nanometre-scale density fluctuations.

    PubMed

    Zhernenkov, Mikhail; Bolmatov, Dima; Soloviov, Dmitry; Zhernenkov, Kirill; Toperverg, Boris P; Cunsolo, Alessandro; Bosak, Alexey; Cai, Yong Q

    2016-01-01

    The passive transport of molecules through a cell membrane relies on thermal motions of the lipids. However, the nature of transmembrane transport and the precise mechanism remain elusive and call for a comprehensive study of phonon excitations. Here we report a high resolution inelastic X-ray scattering study of the in-plane phonon excitations in 1,2-dipalmitoyl-sn-glycero-3-phosphocholine above and below the main transition temperature. In the gel phase, for the first time, we observe low-frequency transverse modes, which exhibit a phonon gap when the lipid transitions into the fluid phase. We argue that the phonon gap signifies the formation of short-lived nanometre-scale lipid clusters and transient pores, which facilitate the passive molecular transport across the bilayer plane. Our findings suggest that the phononic motion of the hydrocarbon tails provides an effective mechanism of passive transport, and illustrate the importance of the collective dynamics of biomembranes. PMID:27175859

  16. On the interaction of an ultra-fast laser with a nanometric tip by laser assisted atom probe tomography: a review.

    PubMed

    Vella, A

    2013-09-01

    The evaporation mechanisms of surface atoms in laser assisted atom probe tomography (LA-APT) are reviewed with an emphasis on the changes in laser-matter interaction when the sample is a nanometric tip submitted to a high electric field. The nanometric dimensions induce light diffraction, the tip shape induces field enhancement and these effects together completely change the absorption properties of the sample from those of macroscopic bulk materials. Moreover, the high electric field applied to the sample during LA-APT analysis strongly modifies the surface optical properties of band gap materials, due to the band bending induced at the surface. All these effects are presented and studied in order to determine the physical mechanisms of atoms evaporation in LA-APT. Moreover, LA-APT is used as an original experimental setup to study: (a) the absorption of nanometric tips; (b) the contribution of the standing field to this laser energy absorption and (c) the heating and cooling process of nanometric sample after the interaction with ultra fast laser. PMID:23822883

  17. 4-n-butylresorcinol, a depigmenting agent used in cosmetics, reacts with tyrosinase.

    PubMed

    Garcia-Jimenez, Antonio; Teruel-Puche, Jose Antonio; Ortiz-Ruiz, Carmen Vanessa; Berna, Jose; Tudela, Jose; Garcia-Canovas, Francisco

    2016-08-01

    4-n-Butylresorcinol (BR) is considered the most potent inhibitor of tyrosinase, which is why it is used in cosmetics as a depigmenting agent. However, this work demonstrates that BR is a substrate of this enzyme. The Em (met-tyrosinase) form is not active on BR, but Eox (oxy-tyrosinase) can act on this molecule, hydroxylating it to o-diphenol. In turn, this is oxidized to an o-quinone, which isomerizes to a red p-quinone. Thus, for tyrosinase to act on this compound, a mechanism to generate Eox in the medium is required, which can be achieved by means of hydrogen peroxide or ascorbic acid. A kinetic analysis of the proposed mechanism allows its kinetic characterization: catalytic constant kcatBR (8.49 ± 0.20 s(-1) ) and Michaelis-constant KMBR (60.26 ± 8.76 μM). These findings are compared with those for other monophenolic substrates of tyrosinase. Studies of BR docking to the Em form of the enzyme show that the hydroxyl group in C-1 position is oriented toward the copper atom A (CuA), as in it is L-tyrosine. As regards Eox , BR is oriented with the carbon in C-6 position ready to be hydroxylated. The reaction of BR originates o-quinones, which isomerize to p-quinones, which in turn, could react with thiol compounds, a finding that could have important implications for pharmacology and the cosmetic industry. © 2016 IUBMB Life, 68(8):663-672, 2016. PMID:27342394

  18. Synthesis of two-dimensional titanium nitride Ti4N3 (MXene)

    NASA Astrophysics Data System (ADS)

    Urbankowski, Patrick; Anasori, Babak; Makaryan, Taron; Er, Dequan; Kota, Sankalp; Walsh, Patrick L.; Zhao, Mengqiang; Shenoy, Vivek B.; Barsoum, Michel W.; Gogotsi, Yury

    2016-06-01

    We report on the synthesis of the first two-dimensional transition metal nitride, Ti4N3-based MXene. In contrast to the previously reported MXene synthesis methods - in which selective etching of a MAX phase precursor occurred in aqueous acidic solutions - here a molten fluoride salt is used to etch Al from a Ti4AlN3 powder precursor at 550 °C under an argon atmosphere. We further delaminated the resulting MXene to produce few-layered nanosheets and monolayers of Ti4N3Tx, where T is a surface termination (F, O, or OH). Density functional theory calculations of bare, non-terminated Ti4N3 and terminated Ti4N3Tx were performed to determine the most energetically stable form of this MXene. Bare and functionalized Ti4N3 are predicted to be metallic. Bare Ti4N3 is expected to show magnetism, which is significantly reduced in the presence of functional groups.We report on the synthesis of the first two-dimensional transition metal nitride, Ti4N3-based MXene. In contrast to the previously reported MXene synthesis methods - in which selective etching of a MAX phase precursor occurred in aqueous acidic solutions - here a molten fluoride salt is used to etch Al from a Ti4AlN3 powder precursor at 550 °C under an argon atmosphere. We further delaminated the resulting MXene to produce few-layered nanosheets and monolayers of Ti4N3Tx, where T is a surface termination (F, O, or OH). Density functional theory calculations of bare, non-terminated Ti4N3 and terminated Ti4N3Tx were performed to determine the most energetically stable form of this MXene. Bare and functionalized Ti4N3 are predicted to be metallic. Bare Ti4N3 is expected to show magnetism, which is significantly reduced in the presence of functional groups. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr02253g

  19. A study of the self-aligned nanometre scale palladium clusters on silicon formation process

    NASA Astrophysics Data System (ADS)

    Gavrilov, S.; Lemeshko, S.; Shevyakov, V.; Roschin, V.

    1999-06-01

    The possibility of the self-aligned formation of Pd/Pd2Si/Si nanostructures on a single-crystal silicon substrate is shown. A porous anodic oxide film of Al was used as a mask which determines the size and shape of the nanostructures. A thin Al film was first deposited on the silicon substrate and then transformed in a nanoporous oxide by the well known anodic treatment procedure in a sulfuric acid and water solution. It is shown by atomic force microscopy that nanoscale Pd clusters with diameters equal to the size of pores in anodic Al remain at the surface of silicon substrate after cathode deposition of Pd into the pores, vacuum thermal annealing and chemical etching of the Al2O3 mask. In addition, we determine the dependencies of the size and shape of the nanoclusters on the mask formation regimes and the Pd deposition conditions.

  20. The Importance of Nanometric Passivating Films on Cathodes forLi - Air Batteries

    SciTech Connect

    Adams, Brian D.; Black, Robert; Radtke, Claudio; Williams, Zach; Mehdi, Beata L.; Browning, Nigel D.; Nazar, Linda F.

    2014-12-23

    Recently, there has been a transition from fully carbonaceous positive electrodes for the aprotic lithium oxygen battery to alternative materials and the use of redox mediator additives, in an attempt to lower the large electrochemical overpotentials associated with the charge reaction. However, the stabilizing or catalytic effect of these materials can become complicated due to the presence of major side-reactions observed during dis(charge). Here, we isolate the charge reaction from the discharge by utilizing electrodes prefilled with commercial lithium peroxide with a crystallite size of about 200-800 nm. Using a combination of S/TEM, online mass spectrometry, XPS, and electrochemical methods to probe the nature of surface films on carbon and conductive Ti-based nanoparticles, we show that oxygen evolution from lithium peroxide is strongly dependent on their surface properties. Insulating TiO2 surface layers on TiC and TiN - even as thin as 3 nm*can completely inhibit the charge reaction under these conditions. On the other hand, TiC, which lacks this oxide film, readily facilitates oxidation of the bulk Li2O2 crystallites, at a much lower overpotential relative to carbon. Since oxidation of lithium oxygen battery cathodes is inevitable in these systems, precise control of the surface chemistry at the nanoscale becomes of upmost importance.

  1. The importance of nanometric passivating films on cathodes for Li-air batteries.

    PubMed

    Adams, Brian D; Black, Robert; Radtke, Claudio; Williams, Zack; Mehdi, B Layla; Browning, Nigel D; Nazar, Linda F

    2014-12-23

    Recently, there has been a transition from fully carbonaceous positive electrodes for the aprotic lithium oxygen battery to alternative materials and the use of redox mediator additives, in an attempt to lower the large electrochemical overpotentials associated with the charge reaction. However, the stabilizing or catalytic effect of these materials can become complicated due to the presence of major side-reactions observed during dis(charge). Here, we isolate the charge reaction from the discharge by utilizing electrodes prefilled with commercial lithium peroxide with a crystallite size of about 200-800 nm. Using a combination of S/TEM, online mass spectrometry, XPS, and electrochemical methods to probe the nature of surface films on carbon and conductive Ti-based nanoparticles, we show that oxygen evolution from lithium peroxide is strongly dependent on their surface properties. Insulating TiO2 surface layers on TiC and TiN - even as thin as 3 nm-can completely inhibit the charge reaction under these conditions. On the other hand, TiC, which lacks this oxide film, readily facilitates oxidation of the bulk Li2O2 crystallites, at a much lower overpotential relative to carbon. Since oxidation of lithium oxygen battery cathodes is inevitable in these systems, precise control of the surface chemistry at the nanoscale becomes of upmost importance. PMID:25364863

  2. Confined phase separation in SiO{sub X} nanometric thin layers

    SciTech Connect

    Roussel, M.; Talbot, E.; Pareige, C.; Pareige, P.; Pratibha Nalini, R.; Gourbilleau, F.

    2013-11-11

    Phase separation in silicon-rich silica/silica multilayers was investigated using Atom Probe Tomography and Atomistic Kinetic Monte Carlo simulation. It is shown that the thickness of silicon-rich silicon oxide sublayers plays an important role during phase transformation. It determines the morphology of Si-rich phase formed after subsequent annealing, which is of prime interest for microelectronic and optoelectronic applications. Monte Carlo simulation reveals that the formation of isolated Si clusters can be achieved even in the case of spinodal decomposition and is directly related to the ratio between the spinodal wavelength and the sublayer thickness.

  3. Biological passivation of porous silicon by a self-assembled nanometric biofilm of proteins

    NASA Astrophysics Data System (ADS)

    de Stefano, Luca; Rea, Ilaria; de Tommasi, Eduardo; Giardina, Paola; Armenante, Annunziata; Longobardi, Sara; Giocondo, Michele; Rendina, Ivo

    2009-10-01

    Self-assembled monolayers are surfaces consisting of a single layer of molecules on a substrate: widespread examples of chemical and biological nature are alkylsiloxane, fatty acids, and alkanethiolate which can be deposited by different techniques on a large variety of substrates ranging from metals to oxides. We have found that a self-assembled biofilm of proteins can passivate porous silicon (PSi) based optical structures without affecting the transducing properties. Moreover, the protein coated PSi layer can also be used as a functionalized surface for proteomic applications.

  4. Search for resonances in 4n, 7H and 9He via transfer reactions

    SciTech Connect

    Fortier, S.; Tryggestad, E.; Rich, E.; Beaumel, D.; Becheva, E.; Blumenfeld, Y.; Delaunay, F.; Frascaria, N.; Guillot, J.; Hammache, F.; Khan, E.; Lima, V.; Scarpaci, J. A.

    2007-05-22

    Investigation of unbound nuclear systems 9He, 7H and 4n was performed at GANIL-SPIRAL using the 8He beam at 15.3 A MeV and a CD2 target. The missing mass spectra were deduced from kinetic energies and emission angles of light ejectiles detected by the Silicon array MUST. In addition to previously known low-lying narrow resonant states in 9He, the d(8He,p) reaction displays a structure just above neutron emission threshold, identified with the 'true' ground state of 9He. The analysis of angular distributions shows that the inversion of s1/2 and p1/2 neutron shells previously observed in 11Be and 10Li also exists in the lightest N=7 isotone 9He. The d(8He,3He) and d(8He,6Li) reactions were used to search for resonant states in the t+4n (7H) and 4n systems, respectively. The missing mass spectrum of the 4n system does not give evidence for the existence of a bound 'tetraneutron'. However the comparison with the results of 5-body phase-space calculations emphasizes the existence of correlations in the 4n system. The broad structure observed at {approx_equal}2 MeV above the t+4n emission threshold is proposed to be the ground state of 7H.

  5. Synthesis of two-dimensional titanium nitride Ti4N3 (MXene).

    PubMed

    Urbankowski, Patrick; Anasori, Babak; Makaryan, Taron; Er, Dequan; Kota, Sankalp; Walsh, Patrick L; Zhao, Mengqiang; Shenoy, Vivek B; Barsoum, Michel W; Gogotsi, Yury

    2016-06-01

    We report on the synthesis of the first two-dimensional transition metal nitride, Ti4N3-based MXene. In contrast to the previously reported MXene synthesis methods - in which selective etching of a MAX phase precursor occurred in aqueous acidic solutions - here a molten fluoride salt is used to etch Al from a Ti4AlN3 powder precursor at 550 °C under an argon atmosphere. We further delaminated the resulting MXene to produce few-layered nanosheets and monolayers of Ti4N3Tx, where T is a surface termination (F, O, or OH). Density functional theory calculations of bare, non-terminated Ti4N3 and terminated Ti4N3Tx were performed to determine the most energetically stable form of this MXene. Bare and functionalized Ti4N3 are predicted to be metallic. Bare Ti4N3 is expected to show magnetism, which is significantly reduced in the presence of functional groups. PMID:27211286

  6. Immobilization of Mn and NH4 (+)-N from electrolytic manganese residue waste.

    PubMed

    Chen, Hongliang; Liu, Renlong; Liu, Zuohua; Shu, Jiancheng; Tao, Changyuan

    2016-06-01

    The objective of this work was the immobilization of soluble manganese (Mn) and ammonium nitrogen (NH4 (+)-N) leached from electrolytic manganese residue (EMR). Immobilization of Mn was investigated via carbonation using carbon dioxide (CO2) and alkaline additives. NH4 (+)-N immobilization was evaluated via struvite precipitation using magnesium and phosphate sources. Results indicated that the immobilization efficiency of Mn using CO2 and quicklime (CaO) was higher than using CO2 and sodium hydroxide (NaOH). This higher efficiency was likely due to the slower release of OH(-) during CaO hydrolysis. The immobilization efficiency of Mn was >99.99 % at the CaO:EMR mass ratio of 0.05:1 for 20-min reaction time. The struvite precipitation of NH4 (+)-N was conducted in the carbonated EMR slurry and the immobilization efficiency was 89 % using MgCl2 · 6H2O + Na3PO4 · 12H2O at the Mg:P:N molar ratio of 1.5:1.5:1 for 90-min reaction time. A leaching test showed that the concentrations of Mn and NH4 (+)-N in the filtrate of the treated EMR were 0.2 and 9 mg/L, respectively. The combined immobilization of Mn and NH4 (+)-N was an effective pretreatment method in the harmless treatment of the EMR. PMID:26979316

  7. Ab initio study of thermodynamic, electronic, magnetic, structural, and elastic properties of Ni4N allotropes

    NASA Astrophysics Data System (ADS)

    Hemzalová, P.; Friák, M.; Šob, M.; Ma, D.; Udyansky, A.; Raabe, D.; Neugebauer, J.

    2013-11-01

    We have employed parameter-free density functional theory calculations to study the thermodynamic stability and structural parameters as well as elastic and electronic properties of Ni4N in eight selected crystallographic phases. In agreement with the experimental findings, the cubic structure with Pearson symbol cP5, space group Pm3¯m (221) is found to be the most stable and it is also the only thermodynamically stable structure at T=0 K with respect to decomposition to the elemental Ni crystal and N2 gas phase. We determine structural parameters, bulk moduli, and their pressure derivatives for all eight allotropes. The thermodynamic stability and bulk modulus is shown to be anticorrelated. Comparing ferromagnetic and nonmagnetic states, we find common features between the magnetism of elemental Ni and studied ferromagnetic Ni4N structures. For the ground-state Ni4N structure and other two Ni4N cubic allotropes, we predict a complete set of single-crystalline elastic constants (in the equilibrium and under hydrostatic pressure), the Young and area moduli, as well as homogenized polycrystalline elastic moduli obtained by different homogenization methods. We demonstrate that the elastic anisotropy of the ground-state Ni4N is qualitatively opposite to that in the elemental Ni, i.e., these materials have hard and soft crystallographic directions interchanged. Moreover, one of the studied metastable cubic phases is found auxetic, i.e., exhibiting negative Poisson ratio.

  8. Bacteria in the Tatahouine meteorite: nanometric-scale life in rocks.

    PubMed

    Gillet, P h; Barrat, J A; Heulin, T h; Achouak, W; Lesourd, M; Guyot, F; Benzerara, K

    2000-02-15

    We present a study of the textural signature of terrestrial weathering and related biological activity in the Tatahouine meteorite. Scanning and transmission electron microscopy images obtained on the weathered samples of the Tatahouine meteorite and surrounding soil show two types of bacteria-like forms lying on mineral surfaces: (1) rod-shaped forms (RSF) about 70-80 nm wide and ranging from 100 nm to 600 nm in length; (2) ovoid forms (OVF) with diameters between 70 and 300 nm. They look like single cells surrounded by a cell wall. Only Na, K, C, O and N with traces of P and S are observed in the bulk of these objects. The chemical analyses and electron diffraction patterns confirm that the RSF and OVF cannot be magnetite or other iron oxides, iron hydroxides, silicates or carbonates. The sizes of the RSF and OVF are below those commonly observed for bacteria but are very similar to some bacteria-like forms described in the Martian meteorite ALH84001. All the previous observations strongly suggest that they are bacteria or their remnants. This conclusion is further supported by microbiological experiments in which pleomorphic bacteria with morphology similar to the OVF and RSF objects are obtained from biological culture of the soil surrounding the meteorite pieces. The present results show that bacteriomorphs of diameter less than 100 nm may in fact represent real bacteria or their remnants. PMID:11543579

  9. A nanometric cushion for enhancing scratch and wear resistance of hard films

    PubMed Central

    Gotlib-Vainshtein, Katya; Girshevitz, Olga; Barlam, David

    2014-01-01

    Summary Scratch resistance and friction are core properties which define the tribological characteristics of materials. Attempts to optimize these quantities at solid surfaces are the subject of intense technological interest. The capability to modulate these surface properties while preserving both the bulk properties of the materials and a well-defined, constant chemical composition of the surface is particularly attractive. We report herein the use of a soft, flexible underlayer to control the scratch resistance of oxide surfaces. Titania films of several nm thickness are coated onto substrates of silicon, kapton, polycarbonate, and polydimethylsiloxane (PDMS). The scratch resistance measured by scanning force microscopy is found to be substrate dependent, diminishing in the order PDMS, kapton/polycarbonate, Si/SiO2. Furthermore, when PDMS is applied as an intermediate layer between a harder substrate and titania, marked improvement in the scratch resistance is achieved. This is shown by quantitative wear tests for silicon or kapton, by coating these substrates with PDMS which is subsequently capped by a titania layer, resulting in enhanced scratch/wear resistance. The physical basis of this effect is explored by means of Finite Element Analysis, and we suggest a model for friction reduction based on the "cushioning effect” of a soft intermediate layer. PMID:25161836

  10. A nanometric cushion for enhancing scratch and wear resistance of hard films.

    PubMed

    Gotlib-Vainshtein, Katya; Girshevitz, Olga; Sukenik, Chaim N; Barlam, David; Cohen, Sidney R

    2014-01-01

    Scratch resistance and friction are core properties which define the tribological characteristics of materials. Attempts to optimize these quantities at solid surfaces are the subject of intense technological interest. The capability to modulate these surface properties while preserving both the bulk properties of the materials and a well-defined, constant chemical composition of the surface is particularly attractive. We report herein the use of a soft, flexible underlayer to control the scratch resistance of oxide surfaces. Titania films of several nm thickness are coated onto substrates of silicon, kapton, polycarbonate, and polydimethylsiloxane (PDMS). The scratch resistance measured by scanning force microscopy is found to be substrate dependent, diminishing in the order PDMS, kapton/polycarbonate, Si/SiO2. Furthermore, when PDMS is applied as an intermediate layer between a harder substrate and titania, marked improvement in the scratch resistance is achieved. This is shown by quantitative wear tests for silicon or kapton, by coating these substrates with PDMS which is subsequently capped by a titania layer, resulting in enhanced scratch/wear resistance. The physical basis of this effect is explored by means of Finite Element Analysis, and we suggest a model for friction reduction based on the "cushioning effect" of a soft intermediate layer. PMID:25161836

  11. The Environmentally Benign form of Pesticide in Hydrodispersive Nanometric form with Improved Efficacy Against Adult Mosquitoes at Low Exposure Concentrations.

    PubMed

    Balaji, A P B; Mishra, Prabhakar; Suresh Kumar, R S; Ashu, Abhijeet; Margulis, Katherine; Magdassi, Shlomo; Mukherjee, Amitava; Chandrasekaran, Natarajan

    2015-12-01

    Permethrin, a poorly water-soluble synthetic pesticide belonging to the pyrethroid family, was formulated into water-dispersive nanometric form by rapid evaporation of pesticide loaded oil-in-water microemulsion. The mean hydrodynamic diameter of Nanopermethrin was found to be 199.01 ± 1.4 nm. The efficacy of the Nanopermethrin was comparatively investigated with its bulk form against 2-3 days old adult mosquitoes by WHO cone bioassay for 60 min. The median knockdown concentration of Culex tritaeniorhynchus, Culex quinquefasciatus and Aedes albopictus were found to be 7.20 × 10(4), 7.53 × 10(4), 0.42 × 10(3) mg/L for Bulk permethrin, and 0.98 × 10(4), 1.17 × 10(4), 0.05 × 10(3) mg/L for Nanopermethrin, respectively. The obtained results extrapolate the improved efficacy of Nanopermethrin even at low-level concentrations. Hence, the formulated Nanopermethrin will serve as an effective alternative pesticide in controlling the mosquito population with reduced environmental toxicity. PMID:26408032

  12. Oriented nanometric aggregates of partially inverted zinc ferrite: One-step processing and tunable high-frequency magnetic properties

    SciTech Connect

    Sai, Ranajit; Endo, Yasushi; Shimada, Yutaka; Yamaguchi, Masahiro; Shivashankar, S. A.

    2015-05-07

    In this work, it is demonstrated that the in situ growth of oriented nanometric aggregates of partially inverted zinc ferrite can potentially pave a way to alter and tune magnetocrystalline anisotropy that, in turn, dictates ferromagnetic resonance frequency (f{sub FMR}) by inducing strain due to aggregation. Furthermore, the influence of interparticle interaction on magnetic properties of the aggregates is investigated. Mono-dispersed zinc ferrite nanoparticles (<5 nm) with various degrees of aggregation were prepared through decomposition of metal-organic compounds of zinc (II) and iron (III) in an alcoholic solution under controlled microwave irradiation, below 200 °C. The nanocrystallites were found to possess high degree of inversion (>0.5). With increasing order of aggregation in the samples, saturation magnetization (at 5 K) is found to decrease from 38 emu/g to 24 emu/g, while coercivity is found to increase gradually by up to 100% (525 Oe to 1040 Oe). Anisotropy-mediated shift of f{sub FMR} has also been measured and discussed. In essence, the result exhibits an easy way to control the magnetic characteristics of nanocrystalline zinc ferrite, boosted with significant degree of inversion, at GHz frequencies.

  13. An enhanced photocatalytic response of nanometric TiO2 wrapping of Au nanoparticles for eco-friendly water applications

    NASA Astrophysics Data System (ADS)

    Scuderi, Viviana; Impellizzeri, Giuliana; Romano, Lucia; Scuderi, Mario; Brundo, Maria V.; Bergum, Kristin; Zimbone, Massimo; Sanz, Ruy; Buccheri, Maria A.; Simone, Francesca; Nicotra, Giuseppe; Svensson, Bengt G.; Grimaldi, Maria G.; Privitera, Vittorio

    2014-09-01

    We propose a ground-breaking approach by an upside-down vision of the Au/TiO2 nano-system in order to obtain an enhanced photocatalytic response. The system was synthesized by wrapping Au nanoparticles (~8 nm mean diameter) with a thin layer of TiO2 (~4 nm thick). The novel idea of embedding Au nanoparticles with titanium dioxide takes advantage of the presence of metal nanoparticles, in terms of electron trapping, without losing any of the TiO2 exposed surface, so as to favor the photocatalytic performance of titanium dioxide. A complete structural characterization was made by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The remarkable photocatalytic performance together with the stability of the nano-system was demonstrated by degradation of the methylene blue dye in water. The non-toxicity of the nano-system was established by testing the effect of the material on the reproductive cycle of Mytilus galloprovincialis in an aquatic environment. The originally synthesized material was also compared to conventional TiO2 with Au nanoparticles on top. The latter system showed a dispersion of Au nanoparticles in the liquid environment, due to their instability in the aqueous solution that clearly represents an environmental contamination issue. Thus, the results show that nanometric TiO2 wrapping of Au nanoparticles has great potential in eco-friendly water/wastewater purification.

  14. Nanometric Gap Structure with a Fluid Lipid Bilayer for the Selective Transport and Detection of Biological Molecules.

    PubMed

    Ando, Koji; Tanabe, Masashi; Morigaki, Kenichi

    2016-08-01

    The biological membrane is a natural biosensing platform that can detect specific molecules with extremely high sensitivity. We developed a biosensing methodology by combining a model biological membrane and a nanometer-sized gap structure on a glass substrate. The model membrane comprised lithographically patterned polymeric and fluid lipid bilayers. The polymeric bilayer was bonded to a poly(dimethylsiloxane) (PDMS) sheet by using an adhesion layer with a defined thickness (lipid vesicles). Extruded lipid vesicles having a biotin moiety on the surface were used as the adhesion layer in conjunction with the biotin-streptavidin linkage. A gap structure was formed between the fluid bilayer and PDMS (nanogap junction). The thickness of the gap structure was several tens of nanometers, as determined by the thickness of the adhesion layer. The nanogap junction acted as a sensitive biosensing platform. From a mixture of proteins (cholera toxin and albumin), the target protein (cholera toxin) was selectively transported into the gap by the specific binding to a glycolipid (GM1) in the fluid bilayer and lateral diffusion. The target protein molecules were then detected with an elevated signal-to-noise ratio due to the reduced background noise in the nanometric gap. The combination of selective transport and reduced background noise drastically enhanced the sensitivity toward the target protein. The nanogap junction should have broad biomedical applications by realizing highly selective and sensitive biosensing in samples having diverse coexisting molecules. PMID:27427950

  15. Oriented nanometric aggregates of partially inverted zinc ferrite: One-step processing and tunable high-frequency magnetic properties

    NASA Astrophysics Data System (ADS)

    Sai, Ranajit; Endo, Yasushi; Shimada, Yutaka; Yamaguchi, Masahiro; Shivashankar, S. A.

    2015-05-01

    In this work, it is demonstrated that the in situ growth of oriented nanometric aggregates of partially inverted zinc ferrite can potentially pave a way to alter and tune magnetocrystalline anisotropy that, in turn, dictates ferromagnetic resonance frequency (fFMR) by inducing strain due to aggregation. Furthermore, the influence of interparticle interaction on magnetic properties of the aggregates is investigated. Mono-dispersed zinc ferrite nanoparticles (<5 nm) with various degrees of aggregation were prepared through decomposition of metal-organic compounds of zinc (II) and iron (III) in an alcoholic solution under controlled microwave irradiation, below 200 °C. The nanocrystallites were found to possess high degree of inversion (>0.5). With increasing order of aggregation in the samples, saturation magnetization (at 5 K) is found to decrease from 38 emu/g to 24 emu/g, while coercivity is found to increase gradually by up to 100% (525 Oe to 1040 Oe). Anisotropy-mediated shift of fFMR has also been measured and discussed. In essence, the result exhibits an easy way to control the magnetic characteristics of nanocrystalline zinc ferrite, boosted with significant degree of inversion, at GHz frequencies.

  16. Raster microdiffraction with synchrotron radiation of hydrated biopolymers with nanometre step-resolution: case study of starch granules

    PubMed Central

    Riekel, C.; Burghammer, M.; Davies, R. J.; Di Cola, E.; König, C.; Lemke, H.T.; Putaux, J.-L.; Schöder, S.

    2010-01-01

    X-ray radiation damage propagation is explored for hydrated starch granules in order to reduce the step resolution in raster-microdiffraction experiments to the nanometre range. Radiation damage was induced by synchrotron radiation microbeams of 5, 1 and 0.3 µm size with ∼0.1 nm wavelength in B-type potato, Canna edulis and Phajus grandifolius starch granules. A total loss of crystallinity of granules immersed in water was found at a dose of ∼1.3 photons nm−3. The temperature dependence of radiation damage suggests that primary radiation damage prevails up to about 120 K while secondary radiation damage becomes effective at higher temperatures. Primary radiation damage remains confined to the beam track at 100 K. Propagation of radiation damage beyond the beam track at room temperature is assumed to be due to reactive species generated principally by water radiolysis induced by photoelectrons. By careful dose selection during data collection, raster scans with 500 nm step-resolution could be performed for granules immersed in water. PMID:20975219

  17. Bottom-up substitution assembly of AuF4-n0,-+nPO3 (n = 1-4): a theoretical study of novel oxyfluoride hyperhalogen molecules and anions AuF4-n(PO3)n0,-

    NASA Astrophysics Data System (ADS)

    Yang, Yi-fan; Cui, Zhong-hua; Ding, Yi-hong

    2014-06-01

    Compounds with high electron affinity, i.e. superhalogens, have continued to attract chemists' attention, due to their potential importance in fundamental chemistry and materials science. It has now proven very effective to build up novel superhalogens with multi-positively charged centres, which are usually called 'hyperhalogens'. Herein, using AuF4- and PO3 as the model building blocks, we made the first attempt to design the Au,P-based hyperhalogen anions AuF4-n(PO3)n- (n = 1-4) at the B3LYP/6-311+G(d)&SDD and CCSD(T)/6-311+G(d)&SDD (single-point) levels (6-311+G(d) for O, F, P and SDD for Au). Notably, for all the considered Au,P systems, the ground state bears a dioxo-bonded structure with n ≤ 3, which is significantly more stable than the usually presumed mono-oxo-bonded one. Moreover, the clustering of the -PO3 moieties becomes energetically favoured for n ≥ 3. The ground states of AuP4O120,- are the first reported cage-like oxide hyperhalogens. Thus, the -PO3 moiety cannot be retained during the 'bottom-up' assembly. The vertical detachment energy (VDE) value of the most stable AuF4-n(PO3)n- (n = 1-4) ranges from 7.16 to 8.20 eV, higher than the VDE values of the corresponding building blocks AuF4- (7.08 eV) and PO3- (4.69 eV). The adiabatic detachment energy values of these four hyperhalogens exceed 6.00 eV. Possible generation routes for AuF4-n(PO3)n- (n = 1-4) were discussed. The presently designed oxyfluorides not only enriches the family of hyperhalogens, but also demonstrates the great importance of considering the structural transformation during the superhalogen → hyperhalogen design such as for the present Au-P based systems.

  18. Synthesis and electromagnetic properties of nanodendritic γ‧-Fe4N

    NASA Astrophysics Data System (ADS)

    Zhu, Mengna; Yu, Meijie; Mao, Qiong; Li, Fazhan; Wang, Chengguo

    2016-02-01

    Nanodendritic γ‧-Fe4N was successfully synthesized through a nitriding process from dendritic α-Fe2O3, which was prepared by hydrothermal method using potassium ferricyanide (K3[Fe(CN)6]) as iron source. The structure and electromagnetic properties of this material were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and vector network analyzer (VNA). The results revealed that the dendritic morphology can be mostly inherited from α-Fe2O3 to γ‧-Fe4N by controlling the nitriding temperature, duration and nitrogen potential precisely. The dendritic γ‧-Fe4N has the saturation magnetization of 146emu/g and the coercive force of 94Oe at 300K. The maximum reflection loss is ‑12dB at 3GHz with the thickness of 3.0mm for the composite sample.

  19. Nanometric dispersion of a Mg/Al layered double hydroxide into a chemically modified polycaprolactone.

    PubMed

    Mangiacapra, Pasqualina; Raimondo, Marialuigia; Tammaro, Loredana; Vittoria, Vittoria; Malinconico, Mario; Laurienzo, Paola

    2007-03-01

    Polycaprolactone (PCL) was chemically modified by grafting maleic anhydride on it, through a radical reaction induced by benzoyl peroxide as initiator. To improve the grafting degree, a second unsaturated comonomer such as glycidyl methacrylate (GMA) has been added, demonstrating a good reactivity in melt grafting without leading to long grafted chains. The quantitative determination of grafted maleic anhydride, performed by FTIR analysis, revealed a grafting weight percentage of 9.5 +/- 0.9, and the NMR characterization made it possible to propose a structure for the grafted polymer (PCLgMA). The modified polymer was analyzed by DSC and X-ray diffraction, showing a structural organization even better than that of the pristine polymer. An exchange reaction with a layered double hydroxide (LDH), hydrotalcite-like solid in the nitrate form, led to the disappearance of the crystalline basal peak of LDH in the X-ray diffractograms, suggesting a possible exfoliation of the inorganic sample. An oxidative etching on the composite surface followed by atomic force microscopy analysis made it possible to enlighten the lamellar structure in the pristine sample. In the composite sample, the well identifiable narrow fissures homogeneously distributed on the surface demonstrate that nanometer stacks of LDH sheets, embedded in a highly textured PCLgMA matrix, are present in the composite sample. The comparison of X-ray diffractograms and AFM analysis suggests either a partial exfoliation or an intercalation of the polymer in a lamellar texture with a basal spacing higher than 5 nm. In any case, the process of ionic exchange between nitrate LDH and PCLgMA led to the formation of nanocomposites, in which no large hydrotalcite aggregates are present. This is an interesting method to obtain a direct intercalation of the modified polymer into the inorganic solid with a simple ionic exchange reaction. PMID:17319719

  20. Polybacterial Periodontal Pathogens Alter Vascular and Gut BH4/nNOS/NRF2-Phase II Enzyme Expression.

    PubMed

    Gangula, Pandu; Ravella, Kalpana; Chukkapalli, Sasanka; Rivera, Mercedes; Srinivasan, Shanthi; Hale, Ashley; Channon, Keith; Southerland, Janet; Kesavalu, Lakshmyya

    2015-01-01

    Periodontal disease is a highly prevalent chronic inflammatory disease and is associated with complex microbial infection in the subgingival cavity. Recently, American Heart Association supported a century old association between periodontal disease and atherosclerotic vascular disease. We have recently shown that polybacterial periodontal infection led to aortic atherosclerosis and modulation of lipid profiles; however the underlying mechanism(s) has not been yet demonstrated. Altered nitric oxide (NO) synthesis and tetrahydrobiopterin (BH4), a cofactor for nitric oxide synthases (NOS) has long been shown to be associated with vascular dysfunction and gastrointestinal motility disorders. We sought to examine the mechanism of periodontal infection leading to altered vascular and gastrointestinal smooth muscle relaxation, focusing on the BH4/nNOS pathways. In addition, we also have investigated how the antioxidant system (NRF2-Phase II enzyme expression) in vascular and GI specimens is altered by oral infection. Eight week old male ApoEnull mice were either sham-infected or infected orally for 16 weeks with a mixture of major periodontal bacteria Porphyromonas gingivalis, Treponema denticola and Tannerella forsythia to induce experimental periodontitis. Serum, vascular (mesenteric), stomach, and colon specimens were collected at the end of periodontal pathogen infection. Bacterial infection induced significant (p<0.05) reductions in the levels of BH4,in ratio of BH4:BH2+B and also in nitric oxide levels compared to sham-infected controls. In addition, we identified a significant (p<0.05) reduction in eNOS dimerization, nNOS dimerization and protein expression of BH4 biosynthesis enzymes; GCH-1, DHFR and NRF2 & Phase II enzymes in infected mice versus controls in both mesenteric artery and colon tissues. However, we found no differences in nNOS/BH4 protein expression in stomach tissues of infected and sham-infected mice. This suggests that a polybacterial infection

  1. Spin Polarization Inversion at Benzene-Absorbed Fe4N Surface

    PubMed Central

    Zhang, Qian; Mi, Wenbo; Wang, Xiaocha; Wang, Xuhui

    2015-01-01

    We report a first-principle study on electronic structure and simulation of the spin-polarized scanning tunneling microscopy graphic of a benzene/Fe4N interface. Fe4N is a compound ferromagnet suitable for many spintronic applications. We found that, depending on the particular termination schemes and interface configurations, the spin polarization on the benzene surface shows a rich variety of properties ranging from cosine-type oscillation to polarization inversion. Spin-polarization inversion above benzene is resulting from the hybridizations between C pz and the out-of-plane d orbitals of Fe atom. PMID:26012892

  2. Fabrication and physical properties of [Fe/Fe4N]N multilayers with high saturation magnetization

    NASA Astrophysics Data System (ADS)

    Yu, B.; Lin, L.; Ma, B.; Zhang, Z. Z.; Jin, Q. Y.; Wang, J. P.

    2016-05-01

    [Fe/Fe4N]N multilayers with high saturation magnetization were prepared on MgO(200) substrate, by the DC reactive magnetron sputtering and then annealed at higher temperature. Their structural and magnetic properties were investigated. Epitaxial growth of α-Fe and γ'-Fe4N were demonstrated on MgO, and then excellent [Fe/Fe4N]N was obtained. Though the saturation magnetizations of the as-deposited [Fe/Fe4N]N are slightly below the average value of those of α-Fe and γ'-Fe4N, the saturation magnetization of the annealed [Fe(3.04 nm)/Fe4N(3.04 nm)]5 increases up to 1850 emu/cc, 32 % larger than that of α-Fe film. N atom diffusion from the γ'-Fe4N to the α-Fe layer at high temperature greatly improves the saturation magnetization.

  3. The Impact of Antiaromatic Subunits in [4n+2] π-Systems: Bispentalenes with [4n+2] π-Electron Perimeters and Antiaromatic Character.

    PubMed

    Cao, Jing; London, Gábor; Dumele, Oliver; von Wantoch Rekowski, Margarete; Trapp, Nils; Ruhlmann, Laurent; Boudon, Corinne; Stanger, Amnon; Diederich, François

    2015-06-10

    Three series of stable, neutral, π-extended bispentalene derivatives, with two pentalenes fused to a central benzene or naphthalene moiety, have been prepared through a modified double carbopalladation cascade reaction. While these chromophores feature skeletons with [4n+2] π-electron perimeters, the two 8 π-electron pentalene subunits strongly influence bonding and spectral properties. (1)H NMR spectra showed large upfield shifts of the protons in the pentalene moieties, comparable to antiaromatic monobenzopentalenes. Further investigations on magnetic ring currents through NICS-XY-scans suggest a global paratropic current and a local diatropic current at the central benzene ring in two of the series, while the third series, with a central naphthalene ring, showed more localized ring currents, with stronger paratropic ring currents on the pentalene moieties. X-ray diffraction analyses revealed planar bispentalene cores with large double- and single-bond alternation in the pentalene units, characteristic for antiaromaticity, and small alternation in the central aromatic rings. In agreement with TD-DFT calculations, both optical and electrochemical data showed much smaller HOMO-LUMO energy gaps compared to other neutral, acene-like hydrocarbons with the same number of fused rings. Both experimental and computational results suggest that the molecular properties of the presented bispentalenes are dominated by the antiaromatic pentalene-subunits despite the [4n+2] π-electron perimeter of the skeletons. PMID:25978774

  4. Superconductivity in Ban+2Ir4nGe12n+4 (n=1,2) with cage structure and softening of low-lying localized mode

    NASA Astrophysics Data System (ADS)

    Guo, Jiangang; Yamaura, Jun-ichi; Lei, Hechang; Matsuishi, Satoru; Qi, Yanpeng; Hosono, Hideo

    2013-10-01

    We report on new superconductors Ban+2Ir4nGe12n+4 (n = 1, 2) with critical temperatures Tc = 6.1 and 3.2 K, respectively, along with their crystal structures, electron transport, and specific heat. The compounds are composed of alternating Ba@Ir8Ge16 and Ba@Ir2Ge16 cages, both of which are larger in the n = 1 sample than in the n = 2 sample. The normal-state heat capacity reveals two low-lying vibration modes associated with guest Ba cations, and both characteristic temperatures in Ba3Ir4Ge16 are smaller than those in Ba4Ir8Ge28. Meanwhile, the density functional theory calculations reveal that the Ge-4p bands dominated the Fermi level in both samples. We propose that the softening of localized phonons due to expansion of the cage strengthens the electron-phonon coupling between Ba cations and Ge anions, leading to the higher Tc in Ba3Ir4Ge16.

  5. B4N and Fe3BN nitrides bands structure and theoretical determination of bulk modulus

    NASA Astrophysics Data System (ADS)

    dos Santos, A. V.

    2007-06-01

    With the evolution of material science there was some technological evolution as well as the need of finding new links which could be applied to diverse areas of knowledge. Thus, in this article, we study nitrides bands structures which contain boron, in two different stoichiometries Fe3BN and B4N. The choice of these compounds is meant to plan new links and to understand nitrides fundamental state properties facing these new crystalline structures. In order to resolve the compound band structure we used the method of linear Muffin Tin orbital (LMTO), with atomic sphere approximation (ASA). By using this method we obtained the energy of formation as a function of the lattice parameter as one of the results. We find the equilibrium lattice parameter of 6.9755 a.u., for the Fe3BN nitride, and in B4N, we have 6.8589 a.u. We also discuss in this article the charge transference between sites and the influence of pressure on the compound properties, as well as the Bulk modulus that is 239.82 GPa for Fe3BN and 105.48 GPa for B4N. We show the behaviour of the density of states (DOS) of the new band structure found for the proposed crystalline structure Fe3BN, in which the B atom replace the Fe atom in the corner of the structure γ‧- Fe4N.

  6. Transverse anisotropic magnetoresistance effects in pseudo-single-crystal γ'-Fe4N thin films

    NASA Astrophysics Data System (ADS)

    Kabara, Kazuki; Tsunoda, Masakiyo; Kokado, Satoshi

    2016-05-01

    Transverse anisotropic magnetoresistance (AMR) effects, for which magnetization is rotated in an orthogonal plane to the current direction, were investigated at various temperatures, in order to clarify the structural transformation from a cubic to a tetragonal symmetry in a pseudo-single-crystal Fe4N film, which is predicted from the usual in-plane AMR measurements by the theory taking into account the spin-orbit interaction and crystal field splitting of 3d bands. According to a phenomenological theory of AMR, which derives only from the crystal symmetry, a cos 2θ component ( C2 tr ) exists in transverse AMR curves for a tetragonal system but does not for a cubic system. In the Fe4N film, the C2 tr shows a positive small value (0.12%) from 300 K to 50 K. However, the C2 t r increases to negative value below 50 K and reaches to -2% at 5 K. The drastic increasing of the C2 tr demonstrates the structural transformation from a cubic to a tetragonal symmetry below 50 K in the Fe4N film. In addition, the out-of-plane and in-plane lattice constants (c and a) were precisely determined with X-ray diffraction at room temperature using the Nelson-Riely function. As a result, the positive small C2 t r above 50 K is attributed to a slightly distorted Fe4N lattice (c/a = 1.002).

  7. Comparison of performance of genetics 4N6 FLOQSwabs™ with or without surfactant to rayon swabs.

    PubMed

    Frippiat, Christophe; Noel, Fabrice

    2016-08-01

    The collection of traces is the first step in the process of forensic genetics analysis. Currently, several different techniques are used (eg. gauze). Nevertheless, swabbing appears to be the most common of these. In a second step, the sampling devices should allow the use of preliminary tests in combination with an immunological confirmatory test (e.g. Hexagon Obti or Hemdirect). Our previous study shows that sampling with Genetics 4N6FLOQswabs™ coated with surfactant reduces by a factor of at least 100 the detection threshold of blood using two immunological tests. The aim of this work was to compare the ability to recover blood trace and the compatibility with immunological confirmatory test of various Genetics 4N6FLOQswabs™ nylon flocked swabs with or without surfactant. The results obtain in this study show that Genetics 4N6FLOQswabs™ not coated with surfactant and Human DNA free FLOQswabs™ were suitable for the used in combination with immunological blood detection tests. Nevertheless, the Genetics 4N6FLOQswabs™ not surfactant coated give a better blood trace recovery. PMID:27314974

  8. Oxidation investigation of nickel nanoparticles.

    PubMed

    Song, Pengxiang; Wen, Dongsheng; Guo, Z X; Korakianitis, Theodosios

    2008-09-01

    This work reported an experimental investigation of complete oxidation of nickel nanoparticles using simultaneous thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). Nickel nanoparticles and their elemental compositions were characterized by Brunauer-Emmett-Teller (BET) analysis, transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). The oxidation experiments were performed under isoconversion conditions for seven heating rates, varying from 2 to 20 K min(-1), with temperatures up to 1000 degrees C. The experiments revealed unique oxidation behaviour of nickel at the nanometre scale, such as early oxidation and melting phenomena, variable activation energies and different oxidation kinetics between low and high conversion ratios. Unlike its bulk counterpart where the activation energy is a constant, the activation energy of nickel nanoparticles depended on the conversion ratio, ranging between 1.4 and 1.8 eV. The oxidation kinetics of nickel nanoparticles changed from the classical diffusion controlled mechanism to a pseudo-homogeneous reaction as conversion ratios were over 50%. The oxidation mechanisms of nickel nanoparticles were further discussed and future studies to enhance understanding were identified. PMID:18701953

  9. Self-assembly of organic monolayers as protective and conductive bridges for nanometric surface-mount applications.

    PubMed

    Platzman, Ilia; Haick, Hossam; Tannenbaum, Rina

    2010-09-01

    In this work, we present a novel surface-mount placement process that could potentially overcome the inadequacies of the currently used stencil-printing technology, when applied to devices in which either their lateral and/or their horizontal dimensions approach the nanometric scale. Our novel process is based on the "bottom-up" design of an adhesive layer, operative in the molecular/nanoscale level, through the use of self-assembled monolayers (SAMs) that could form protective and conductive bridges between pads and components. On the basis of previous results, 1,4-phenylene diisocyanide (PDI) and terephthalic acid (TPA) were chosen to serve as the best candidates for the achievement of this goal. The quality and stability of these SAMs on annealed Cu surfaces (Rrms=0.15-1.1 nm) were examined in detail. Measurements showed that the SAMs of TPA and PDI molecules formed on top of Cu substrates created thermally stable organic monolayers with high surface coverage (∼90%), in which the molecules were closely packed and well-ordered. Moreover, the molecules assumed a standing-up phase conformation, in which the molecules bonded to the Cu substrate through one terminal functional group, with the other terminal group residing away from the substrate. To examine the ability of these monolayers to serve as "molecular wires," i.e., the capability to provide electrical conductivity, we developed a novel fabrication method of a parallel plate junction (PPJ) in order to create symmetric Cu-SAM-Cu electrical junctions. The current-bias measurements of these junctions indicated high tunneling efficiency. These achievements imply that the SAMs used in this study can serve as conductive molecular bridges that can potentially bind circuital pads/components. PMID:20804143

  10. Endocrine-Disrupting Potential of Bisphenol A, Bisphenol A Dimethacrylate, 4-n-Nonylphenol, and 4-n-Octylphenol in Vitro: New Data and a Brief Review

    PubMed Central

    Bonefeld-Jørgensen, Eva C.; Long, Manhai; Hofmeister, Marlene V.; Vinggaard, Anne Marie

    2007-01-01

    Background An array of environmental compounds is known to possess endocrine disruption (ED) potentials. Bisphenol A (BPA) and bisphenol A dimethacrylate (BPA-DM) are monomers used to a high extent in the plastic industry and as dental sealants. Alkylphenols such as 4-n-nonylphenol (nNP) and 4-n-octylphenol (nOP) are widely used as surfactants. Objectives We investigated the effect in vitro of these four compounds on four key cell mechanisms including transactivation of a) the human estrogen receptor (ER), b) the human androgen receptor (AR), c) the aryl hydrocarbon receptor (AhR), and d) aromatase activity. Results All four compounds inhibited aromatase activity and were agonists and antagonists of ER and AR, respectively. nNP increased AhR activity concentration-dependently and further increased the 2,3,7,8-tetrachlorodibenzo-p-dioxin AhR action. nOP caused dual responses with a weak increased and a decreased AhR activity at lower (10−8 M) and higher concentrations (10−5–10−4 M), respectively. AhR activity was inhibited with BPA (10−5–10−4 M) and weakly increased with BPA-DM (10−5 M), respectively. nNP showed the highest relative potency (REP) compared with the respective controls in the ER, AhR, and aromatase assays, whereas similar REP was observed for the four chemicals in the AR assay. Conclusion Our in vitro data clearly indicate that the four industrial compounds have ED potentials and that the effects can be mediated via several cellular pathways, including the two sex steroid hormone receptors (ER and AR), aromatase activity converting testosterone to estrogen, and AhR; AhR is involved in syntheses of steroids and metabolism of steroids and xenobiotic compounds. PMID:18174953

  11. A spectral study of 2-formylimidazole 4N-substituted thiosemicarbazones and their copper(II) complexes

    NASA Astrophysics Data System (ADS)

    West, Douglas X.; Lockwood, Mark A.; Albert, Julyan N.; Liberta, Anthony E.

    1993-11-01

    Copper(II) complexes of 2-formylimidazole 4N-methyl-, 4N-dimethyl- 4N-ethyl- and 3-hexa-methyleneiminylthiosemicarbazone, along with two nickel(II) complexes of the latter thiosemicarbazone, have been synthesized. Infrared, electronic, NMR and ESR spectra have been used to characterize the complexes and the uncomplexed thiosemicarbazones. None of the complexes or thiosemicarbazones possess growth inhibitory activity against Aspergillus niger and Paecilomyces variotii.

  12. Structure determination of (Fe3O4)n+(n = 1 ‑ 3) clusters via DFT

    NASA Astrophysics Data System (ADS)

    Li, Yanhua; Cai, Congzhong; Zhao, Chengjun; Gu, Yonghong

    2016-07-01

    In virtue of the particle swarm optimization (PSO) algorithm, the global minimum candidate structures with the lowest energy for (Fe3O4)n(n = 1 ‑ 3) clusters were obtained by first-principles structural searches. The geometric structures and spin configurations of three cationic (Fe3O4)n+(n = 1 ‑ 3) clusters have been identified for the first time by comparing the experimental IR spectra with the calculated results from density functional theory by using different exchange-correlation functionals. It is found that the lowest energy structures of these clusters are of a shape of hat, boat and tower, respectively, with a ferrimagnetic arrangement of spins, and M06L functional is more suitable for Fe3O4 clusters than other ones.

  13. Extrinsic anomalous Hall effect in epitaxial Mn{sub 4}N films

    SciTech Connect

    Meng, M.; Wu, S. X. Ren, L. Z.; Zhou, W. Q.; Wang, Y. J.; Wang, G. L.; Li, S. W.

    2015-01-19

    Anomalous Hall effect (AHE) in ferrimagnetic Mn{sub 4}N epitaxial films grown by molecular-beam epitaxy is investigated. The longitudinal conductivity σ{sub xx} is within the superclean regime, indicating Mn{sub 4}N is a highly conducting material. We further demonstrate that the AHE signal in 40-nm-thick films is mainly due to the extrinsic contributions based on the analysis fitted by ρ{sub AH}=a′ρ{sub xx0}+bρ{sub xx}{sup 2} and σ{sub AH}∝σ{sub xx}. Our study not only provide a strategy for further theoretical work on antiperovskite manganese nitrides but also shed promising light on utilizing their extrinsic AHE to fabricate spintronic devices.

  14. Search for coupling in ferromagnetic/superconducting multilayers: Fe{sub 4}N/NbN

    SciTech Connect

    Mattson, J.E.; Potter, C.D.; Conover, M.J.; Sowers, C.H.; Bader, S.D.

    1997-09-01

    Structural, magnetic, and superconducting properties of ferromagnetic/superconducting multilayers of Fe{sub 4}N/NbN are examined. The onset of superconductivity occurs at NbN layer thickness of {approximately}100 {Angstrom}. Below this thickness ferromagnetism of the Fe{sub 4}N layers is observed. Above this thickness superconductivity of the NbN is also observed, but there is no evidence for interlayer magnetic or superconductive coupling. The results are used in the formulation of guidelines for future searches of novel interlayer coupling phenomena. The superconducting critical field curves are reasonably well described within the framework of the theory for ferromagnetic/superconducting multilayers. {copyright} {ital 1997 American Vacuum Society.}

  15. Pulsating strings from two-dimensional CFT on (T4)N / S (N)

    NASA Astrophysics Data System (ADS)

    Cardona, Carlos

    2015-04-01

    We propose a state from the two-dimensional conformal field theory on the orbifold (T4)N / S (N) as a dual description for a pulsating string moving in AdS3. We show that, up to first order in the deforming parameter, the energy in both descriptions has the same dependence on the mode number, but with a non-trivial function of the coupling.

  16. Anomalous Hall effects in pseudo-single-crystal γ'-Fe4N thin films

    NASA Astrophysics Data System (ADS)

    Kabara, Kazuki; Tsunoda, Masakiyo; Kokado, Satoshi

    2016-05-01

    The anomalous Hall effects (AHE) were investigated at various temperatures for the pseudo-single-crystal Fe4N films, deposited on MgO substrates with changing the degree of order (S) of the nitrogen site. Both the anomalous Hall resistivity and the longitudinal resistivity simply decrease with lowering temperature for all the specimens. The AHE of the Fe4N films is presumed to arise from an intrinsic mechanism because of the relationship between the anomalous Hall resistivity and longitudinal resistivity. The anomalous Hall conductivity, σAH, exhibits a specific behavior at low temperature. In the case of the film with S = 0.93, the σAH drastically drops below 50 K, while it simply increases with lowering temperature in the range of 50-300 K. This low-temperature anomaly decays with decreasing S of the film and nearly vanishes in the films with low S. The threshold temperature and the dependence on S of the low-temperature anomaly of the σAH well correspond to those of the anisotropic magnetoresistance effects in the Fe4N films, reported in the literatures. From these results, it is suggested that the low-temperature anomaly of the σAH originates from the crystal field effect which reflects the structural transformation from a cubic to a tetragonal symmetry below 50 K and provides a modulation of the orbital angular momentum of the 3d orbitals at the Fermi level.

  17. Nano-crystalline silicon solar cell architecture with absorption at the classical 4n2 limit

    SciTech Connect

    Biswas, Rana; Xu, Chun

    2011-07-04

    We develop a periodically patterned conformal photonic-plasmonic crystal based solar architecture for a nano-crystalline silicon solar cell, through rigorous scattering matrix simulations. The solar cell architecture has a periodic array of tapered silver nano-pillars as the back-reflector coupled with a conformal periodic structure at the top of the cell. The absorption and maximal current, averaged over the entire range of wavelengths, for this solar cell architecture is at the semi-classical 4n{sup 2} limit over a range of common thicknesses (500-1500 nm) and slightly above the 4n{sup 2} limit for a 500 nm nc-Si cell. The absorption exceeds the 4n{sup 2} limit, corrected for reflection loss at the top surface. The photonic crystal cell current is enhanced over the flat Ag back-reflector by 60%, for a thick 1000 nm nc-Si layer, where predicted currents exceed 31 mA/cm{sup 2}. The conformal structure at the top surface focuses light within the absorber layer. There is plasmonic concentration of light, with intensity enhancements exceeding 7, near the back reflector that substantially enhances absorption.

  18. Singlet oxygen plays a key role in the toxicity and DNA damage caused by nanometric TiO2 in human keratinocytes

    NASA Astrophysics Data System (ADS)

    Fenoglio, Ivana; Ponti, Jessica; Alloa, Elisa; Ghiazza, Mara; Corazzari, Ingrid; Capomaccio, Robin; Rembges, Diana; Oliaro-Bosso, Simonetta; Rossi, François

    2013-06-01

    Nanometric TiO2 has been reported to be cytotoxic and genotoxic in different in vitro models when activated by UV light. However, a clear picture of the species mediating the observed toxic effects is still missing. Here, a nanometric TiO2 powder has been modified at the surface to completely inhibit its photo-catalytic activity and to inhibit the generation of all reactive species except for singlet oxygen. The prepared powders have been tested for their ability to induce strand breaks in plasmid DNA and for their cytotoxicity and genotoxicity toward human keratinocyte (HaCaT) cells (100-500 μg mL-1, 15 min UVA/B exposure at 216-36 mJ m-2 respectively). The data reported herein indicate that the photo-toxicity of TiO2 is mainly triggered by particle-derived singlet oxygen. The data presented herein contribute to the knowledge of structure-activity relationships which are needed for the design of safe nanomaterials.Nanometric TiO2 has been reported to be cytotoxic and genotoxic in different in vitro models when activated by UV light. However, a clear picture of the species mediating the observed toxic effects is still missing. Here, a nanometric TiO2 powder has been modified at the surface to completely inhibit its photo-catalytic activity and to inhibit the generation of all reactive species except for singlet oxygen. The prepared powders have been tested for their ability to induce strand breaks in plasmid DNA and for their cytotoxicity and genotoxicity toward human keratinocyte (HaCaT) cells (100-500 μg mL-1, 15 min UVA/B exposure at 216-36 mJ m-2 respectively). The data reported herein indicate that the photo-toxicity of TiO2 is mainly triggered by particle-derived singlet oxygen. The data presented herein contribute to the knowledge of structure-activity relationships which are needed for the design of safe nanomaterials. Electronic supplementary information (ESI) available: (1) ζ potential as a function of pH; (2) crystalline phase (XRD); (3) UV

  19. Structural and dynamic properties of confined water in nanometric model porous materials (8 Å⩽∅⩽40 Å)

    NASA Astrophysics Data System (ADS)

    Floquet, N.; Coulomb, J. P.; Dufau, N.; Andre, G.; Kahn, R.

    2004-07-01

    Structural and dynamic properties of confined water have been investigated by ‘‘in situ’’ neutron-scattering experiments. In the medium confinement regime (for MCM-41 host materials: 20 Å⩽∅⩽40 Å) confined water has rather similar properties to bulk (3d) water. The major difference concerns the solidification phase transition. Strong triple-point depression Δ T3t is observed and Δ T3t increases when decreasing the pore diameter ∅ (213 K⩽Δ T3t⩽233 K). Such a confined water behaves as a supercooled liquid phase. The ultra-confinement (AlPO 4-N zeolites: 8 Å⩽∅⩽12 Å), is seen to induce the structuration of the confined water and its stability at room temperature T=300 K due to commensurability effect with the AlPO 4-5 inner surface. No wetting phenomena are observed for both host materials, the silicic MCM-41 samples and the AlPO 4-N zeolite family.

  20. High Catalytic Activity and Chemoselectivity of Sub-nanometric Pd Clusters on Porous Nanorods of CeO2 for Hydrogenation of Nitroarenes.

    PubMed

    Zhang, Sai; Chang, Chun-Ran; Huang, Zheng-Qing; Li, Jing; Wu, Zhemin; Ma, Yuanyuan; Zhang, Zhiyun; Wang, Yong; Qu, Yongquan

    2016-03-01

    Sub-nanometric Pd clusters on porous nanorods of CeO2 (PN-CeO2) with a high Pd dispersion of 73.6% exhibit the highest catalytic activity and best chemoselectivity for hydrogenation of nitroarenes to date. For hydrogenation of 4-nitrophenol, the catalysts yield a TOF of ∼44059 h(-1) and a chemoselectivity to 4-aminophenol of >99.9%. The superior catalytic performance can be attributed to a cooperative effect between the highly dispersed sub-nanometric Pd clusters for hydrogen activation and unique surface sites of PN-CeO2 with a high concentration of oxygen vacancy for an energetically and geometrically preferential adsorption of nitroarenes via nitro group. The high concentration of surface defects of PN-CeO2 and large Pd dispersion contribute to the enhanced catalytic activity for the hydrogenation reactions. The high chemoselectivity is mainly governed by the high Pd dispersion on the support. The catalysts also deliver high catalytic activity and selectivity for nitroaromatics with various reducible substituents into the corresponding aminoarenes. PMID:26828123

  1. The Radiative Transfer Of CH{sub 4}-N{sub 2} Plasma Arc

    SciTech Connect

    Benallal, R.; Liani, B.

    2008-09-23

    Any physical modelling of a circuit-breaker arc therefore requires an understanding of the radiated energy which is taken into account in the form of a net coefficient. The evaluation of the net emission coefficient is performed by the knowledge of the chemical plasma composition and the resolution of the radiative transfer equation. In this paper, the total radiation which escapes from a CH{sub 4}-N{sub 2} plasma is calculated in the temperature range between 5000 and 30000K on the assumption of a local thermodynamic equilibrium and we have studied the nitrogen effect in the hydrocarbon plasmas.

  2. Critical fields of Fe{sub 4}N/NbN ferromagnetic/superconducting multilayers

    SciTech Connect

    Mattson, J.E.; Potter, C.D.; Conover, M.J.; Sowers, C.H.; Bader, S.D.

    1997-01-01

    Structural, magnetic, and superconducting properties of ferromagnetic/superconducting multilayers of Fe{sub 4}N/NbN are explored for a variety of thickness combinations. The superconducting properties show that 11 {Angstrom} ferromagnetic layers are sufficient to decouple the superconducting layers and to yield anisotropic behavior. The upper critical field data are well described by theory for ferromagnetic/superconducting multilayers. This analysis yields an interfacial parameter which characterizes the electron scattering at the ferromagnetic/superconducting boundary. {copyright} {ital 1997} {ital The American Physical Society}

  3. Tetraalklylammonium polyoxoanionic oxidation catalysts

    DOEpatents

    Ellis, P.E.; Lyons, J.E.; Myers, H.K. Jr.; Shaikh, S.N.

    1998-10-06

    Alkanes are catalytically oxidized in air or oxygen using iron-substituted polyoxoanions (POAs) of the formula: H{sub e{minus}z}[(n-C{sub 4}H{sub 9}){sub 4}N]{sub z}(XM{sub 11}M{prime}O{sub 39}){sup {minus}e}. The M{prime} (e.g., iron(III)/iron(II)) reduction potential of the POAs is affected by selection of the central atom X and the framework metal M, and by the number of tetrabutyl-ammonium groups. Decreased Fe(III)/Fe(II) reduction potential has been found to correlate to increased oxidation activity.

  4. Tetraalykylammonium polyoxoanionic oxidation catalysts

    DOEpatents

    Ellis, Paul E.; Lyons, James E.; Myers, Jr., Harry K.; Shaikh, Shahid N.

    1998-01-01

    Alkanes are catalytically oxidized in air or oxygen using iron-substituted polyoxoanions (POAs) of the formula: H.sub.e-z ›(n-C.sub.4 H.sub.9).sub.4 N!.sub.z (XM.sub.11 M'O.sub.39).sup.-e The M' (e.g., iron(III)/iron(II)) reduction potential of the POAs is affected by selection of the central atom X and the framework metal M, and by the number of tetrabutyl-ammonium groups. Decreased Fe(III)/Fe(II) reduction potential has been found to correlate to increased oxidation activity.

  5. Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far Ultraviolet Irradiation

    PubMed Central

    Jimenez, Jose L.; Yung, Yuk L.; Toon, Owen B.; Tolbert, Margaret A.

    2012-01-01

    Abstract Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (λ<120 nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120–200 nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not initiate the formation of nitrogenated species. We examined the chemical properties of photochemical aerosol produced at far UV wavelengths, using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH4/N2 photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N2 in the irradiated gas. The aerosol mass greatly decreases when N2 is removed, which indicates that N2 plays a major role in aerosol production. Because direct dissociation of N2 is highly improbable given the immeasurably low cross section at the wavelengths studied, the chemical activation of N2 must occur via another pathway. Any chemical activation of N2 at wavelengths >120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for how we view prebiotic chemistry on early Earth and similar planets. Key Words: Titan—Photochemical aerosol—CH4-N2 photolysis—Far UV—Nitrogen activation. Astrobiology 12, 315–326. PMID:22519972

  6. Fabrication of MgAl2O4 tunnel barrier by radio frequency-sputtering method and magnetoresistance effect through it with Fe or Fe4N ferromagnetic electrode

    NASA Astrophysics Data System (ADS)

    Tsunoda, Masakiyo; Chiba, Ryoichi; Kabara, Kazuki

    2015-05-01

    Spinel MgAl2O4 thin films were deposited on MgO single-crystal substrates and epitaxial Fe (or Fe4N) thin films by RF-sputtering from a ceramic target. Epitaxial relationship was confirmed by X-ray diffraction analysis between the crystalline spinel MgAl2O4 films and the respective substrate and underlayers, while no diffraction peak was observed from the films deposited on amorphous substrates. Spin-valve type magnetic tunnel junctions (MTJs) with a stacking structure of Fe [Fe4N]/MgAl2O4/CoFeB/Ru/Fe/MnIr exhibited normal [inverse] tunnel magnetoresistance (TMR) effect, reflecting the sign of spin polarization of Fe [Fe4N]. The maximum magnitude of the TMR ratio obtained for the Fe-based and Fe4N-based MTJs was 67% and 18%, respectively. The resistance area product values of the MTJs were significantly larger than the reported values for the MTJs with a post-oxidized spinel MgAl2O4 barrier.

  7. Fabrication of MgAl{sub 2}O{sub 4} tunnel barrier by radio frequency-sputtering method and magnetoresistance effect through it with Fe or Fe{sub 4}N ferromagnetic electrode

    SciTech Connect

    Tsunoda, Masakiyo; Chiba, Ryoichi; Kabara, Kazuki

    2015-05-07

    Spinel MgAl{sub 2}O{sub 4} thin films were deposited on MgO single-crystal substrates and epitaxial Fe (or Fe{sub 4}N) thin films by RF-sputtering from a ceramic target. Epitaxial relationship was confirmed by X-ray diffraction analysis between the crystalline spinel MgAl{sub 2}O{sub 4} films and the respective substrate and underlayers, while no diffraction peak was observed from the films deposited on amorphous substrates. Spin-valve type magnetic tunnel junctions (MTJs) with a stacking structure of Fe [Fe{sub 4}N]/MgAl{sub 2}O{sub 4}/CoFeB/Ru/Fe/MnIr exhibited normal [inverse] tunnel magnetoresistance (TMR) effect, reflecting the sign of spin polarization of Fe [Fe{sub 4}N]. The maximum magnitude of the TMR ratio obtained for the Fe-based and Fe{sub 4}N-based MTJs was 67% and 18%, respectively. The resistance area product values of the MTJs were significantly larger than the reported values for the MTJs with a post-oxidized spinel MgAl{sub 2}O{sub 4} barrier.

  8. Laboratory study of CH4-N2 clathrate hydrates applied to Titan's surface conditions

    NASA Astrophysics Data System (ADS)

    Nna Mvondo, D.; Tobie, G.; Le Menn, E.; Bollengier, O.; Grasset, O.

    2013-12-01

    It is proposed that clathrate hydrates may be present at the surface of Titan (Choukroun et al., 2013, 2010). At Titan's surface pressure, pure methane and ethane hydrate (as well as other guests) could exist in the sI structure and nitrogen hydrate as sII structure. The large reservoir of several guest compounds in Titan's atmosphere is expected to result in the formation of multicomponent (compound) clathrate hydrates, as sII or sH structures, stable relative to water ice on the surface of Titan, and with faster expected growth kinetics relative to pure hydrate (Osegovic et al., 2005). Compound hydrate could be a likely sink for many chemicals occurring on Titan's surface. We note that experimental studies on the formation and thermodynamics of the methane-water system, at low and high pressures applied to Titan have been carried out (Lunine and Stevenson; 1985; Choukroun et al., 2013, 2010 and references therein). However, laboratory work on mixing of methane with other compounds in the clathrate phase (ethane, N2, CO2, etc...) applied to Titan conditions (and other icy moons) has still to be addressed. In this context, we have studied the formation and spectral signatures of CH4-N2 clathrate hydrates at temperature and pressure conditions relevant for Titan's surface. Clathrate hydrates samples have been synthesized in an autoclave combined with a cooling system and a multi-gas mixer. Few ml of deionized water was introduced in the autoclave and pressurized with the N2 and CH4 gaseous species for a couple of days, at controlled low temperature and low pressure of the formation and stability of clathrate hydrates. Their formation has been monitored by gas chromatography. Their spectral characterization at low temperature was performed by infrared (FTIR) reflectance spectroscopy. Raman spectroscopy was also used to give constraints on the composition, structure and cage occupancy of the formed clathrates. Here we present the results obtained for different mixing

  9. Carbon nanotubes in electrospun polyethylene oxide nanofibres: A potential route to conducting nanofibres

    NASA Astrophysics Data System (ADS)

    Nazhipkyzy, M.; Mohan, S. D.; Davis, F. J.; Mitchell, G. R.

    2015-10-01

    Polyethylene oxide solution containing multi-walled carbon nanotubes have been electrospun onto a rotating collector to produce highly aligned arrays of electrospun nanofibers ranging in diameters from (200 - 360) nanometres. The addition of a surfactant (Triton X-100) is highly effective in dispersing carbon nanotube within an aqueous solution of polyethylene oxide and the resulting mixture can be electrospun without excessive clumping to produce nanofibers containing high loadings of nanotubes; in this case up to 5% wt thereby providing an effective route to electrically conductive nanofibres.

  10. Multimode resistive switching in nanoscale hafnium oxide stack as studied by atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Hou, Y.; Celano, U.; Goux, L.; Liu, L.; Degraeve, R.; Cheng, Y.; Kang, J.; Jurczak, M.; Vandervorst, W.

    2016-07-01

    The nanoscale resistive switching in hafnium oxide stack is investigated by the conductive atomic force microscopy (C-AFM). The initial oxide stack is insulating and electrical stress from the C-AFM tip induces nanometric conductive filaments. Multimode resistive switching can be observed in consecutive operation cycles at one spot. The different modes are interpreted in the framework of a low defect quantum point contact theory. The model implies that the optimization of the conductive filament active region is crucial for the future application of nanoscale resistive switching devices.

  11. Cation-Cation Interactions in [(UO2)2(OH)n](4-n) Complexes

    SciTech Connect

    Odoh, Samuel O.; Govind, Niranjan; Schreckenbach, Georg; De Jong, Wibe A.

    2013-10-07

    The structures and bonding of gas-phase [(UO2)2(OH)n]4-n (n=2-6) complexes have been studied using density functional theory (DFT), MP2 and CCSD(T) methods with particular emphasis on ground state structures featuring cation-cation interactions (CCIs) between the uranyl groups. An interesting trend is observed in the stabilities of members of this series of complexes. The structures of [(UO2)2(OH)2]2+, [(UO2)2(OH)4] and [(UO2)2(OH)6]2- featuring CCIs are found at higher energies (by 3-20 kcal/mol) in comparison to their conventional μ2-dihydroxo structures. In contrast, the CCI structures of [(UO2)2(OH)3]+ and [(UO2)2(OH)5]- are respectively almost degenerate with and lower in energy than the structures with the μ2-dihydroxo format. The origin of this trend lies in the ‘symmetry’-based need to balance the coordination numbers and effective atomic charges of each uranium center. The calculated IR vibrational frequencies provide signature probes that can be used in differentiating the lowenergy structures and in experimentally confirming the existence of the structures featuring CCIs. Analysis of the bonding in the structures of [(UO2)2(OH)3]+ and [(UO2)2(OH)5]- shows that the CCIs and bridging hydroxo between the dioxo-uranium units are mainly electrostatic in nature.

  12. Early Events in the Nonadiabatic Relaxation Dynamics of 4-(N,N-Dimethylamino)benzonitrile.

    PubMed

    Kochman, Michał A; Tajti, Attila; Morrison, Carole A; Miller, R J Dwayne

    2015-03-10

    4-(N,N-Dimethylamino)benzonitrile (DMABN) is the archetypal system for dual fluorescence. Several past studies, both experimental and theoretical, have examined the mechanism of its relaxation in the gas phase following photoexcitation to the S2 state, without converging to a single description. In this contribution, we report first-principles simulations of the early events involved in this process performed using the nonadiabatic trajectory surface hopping (TSH) approach in combination with the ADC(2) electronic structure method. ADC(2) is verified to reproduce the ground- and excited-state structures of DMABN in reasonably close agreement with previous theoretical benchmarks. The TSH simulations predict that internal conversion from the S2 state to the S1 takes place as early as 8.5 fs, on average, after the initial photoexcitation, and with no significant torsion of the dimethylamino group relative to the aromatic ring. As evidenced by supporting EOM-CCSD calculations, the population transfer from S2 to S1 can be attributed to the skeletal deformation modes of the aromatic ring and the stretching of the ring-dimethylamino nitrogen bond. The non- or slightly twisted locally excited structure is the predominant product of the internal conversion, and the twisted intramolecular charge transfer structure is formed through equilibration with the locally excited structure with no change of adiabatic state. These findings point toward a new interpretation of data from previous time-resolved experiments. PMID:26579762

  13. Surface layer in composites containing 4- n-octyl-4'-cyanobiphenyl. FTIR spectroscopic characterization

    NASA Astrophysics Data System (ADS)

    Frunza, L.; Kosslick, H.; Bentrup, U.; Pitsch, I.; Fricke, R.; Frunza, S.; Schönhals, A.

    2003-06-01

    Composites containing 4- n-octyl-4'-cyanobiphenyl (8CB) either confined to nanopores of molecular sieves with very large pores or coating silica nanoparticles of aerosil type at high silica-to-8CB ratios are investigated by IR spectroscopy. Band shape analysis was performed in wavenumber regions in which the peaks due to CN stretching, CH stretching and CH out-of-plane vibrations appear. Some of molecules confined to molecular sieves show spectroscopic features characteristic to a bulk-like 8CB matter located in the centre of the pores or in the inter-grain space. Other features of the IR spectra are due to 8CB molecules located in the surface layer, mostly forming hydrogen bonds between their CN groups and surface OH groups. Another part of the 8CB molecules in the surface layer may also interact by π electrons of the aromatic rings. Hydrogen bonding is less hindered for the molecules of the surface layers onto aerosil particles than inside pores of the molecular sieves. Comparison is also made with the case of composites based on molecular sieves with small pores.

  14. Intermolecular potential energy surface and thermophysical properties of the CH4-N2 system

    NASA Astrophysics Data System (ADS)

    Hellmann, Robert; Bich, Eckard; Vogel, Eckhard; Vesovic, Velisa

    2014-12-01

    A five-dimensional potential energy surface (PES) for the interaction of a rigid methane molecule with a rigid nitrogen molecule was determined from quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the CCSD(T) level of theory was utilized to compute a total of 743 points on the PES. The interaction energies were calculated using basis sets of up to quadruple-zeta quality with bond functions and were extrapolated to the complete basis set limit. An analytical site-site potential function with nine sites for methane and five sites for nitrogen was fitted to the interaction energies. The PES was validated by calculating the cross second virial coefficient as well as the shear viscosity and binary diffusion coefficient in the dilute-gas limit for CH4-N2 mixtures. An improved PES was obtained by adjusting a single parameter of the analytical potential function in such a way that quantitative agreement with the most accurate experimental values of the cross second virial coefficient was achieved. The transport property values obtained with the adjusted PES are in good agreement with the best experimental data.

  15. [Raman spectroscopic studies on CO2-CH4-N2 mixed-gas hydrate system].

    PubMed

    Zhang, Bao-yong; Liu, Chuan-hai; Wu, Qiang; Gao, Xia

    2014-06-01

    Accurate determination of coal mine gas separation product characteristics is the key for gas separation application based on hydrate technology. Gas hydrate was synthesized from two types of gas compositions (CO2-CH4-N2). The separation products were measured by in situ Raman spectroscopy. The crystal structure of mixed-gas hydrate was determined, and the cavity occupancy and hydration index were calculated, based on the object molecular various vibrational mode, "loose cage-tight cage" model and the Raman bands area ratio, combined with the model of van der Waals-Platteeuw. The results show that the mixed-gas hydrates are both structure I for the two gas samples; Large cages of mixed-gas hydrate are nearly occupied by guest molecules, and the large cavity occupancies are 98.57% and 98.52%, respectively; but small cages are not easy to be occupied, and the small cavity occupancies are 29.93% and 33.87%, respectively; hydration index of the two gas samples hydrate is 7.14 and 6.98, respectively, which is greater than the theoretical value of structure I. PMID:25358164

  16. Intermolecular potential energy surface and thermophysical properties of the CH4-N2 system.

    PubMed

    Hellmann, Robert; Bich, Eckard; Vogel, Eckhard; Vesovic, Velisa

    2014-12-14

    A five-dimensional potential energy surface (PES) for the interaction of a rigid methane molecule with a rigid nitrogen molecule was determined from quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the CCSD(T) level of theory was utilized to compute a total of 743 points on the PES. The interaction energies were calculated using basis sets of up to quadruple-zeta quality with bond functions and were extrapolated to the complete basis set limit. An analytical site-site potential function with nine sites for methane and five sites for nitrogen was fitted to the interaction energies. The PES was validated by calculating the cross second virial coefficient as well as the shear viscosity and binary diffusion coefficient in the dilute-gas limit for CH4-N2 mixtures. An improved PES was obtained by adjusting a single parameter of the analytical potential function in such a way that quantitative agreement with the most accurate experimental values of the cross second virial coefficient was achieved. The transport property values obtained with the adjusted PES are in good agreement with the best experimental data. PMID:25494743

  17. Structural and biological evaluation of some metal complexes of vanillin-4N-(2-pyridyl) thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Yousef, T. A.; Abu El-Reash, G. M.; Al-Jahdali, M.; El-Rakhawy, El-Bastawesy R.

    2013-12-01

    The synthesis and characterization of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and U(VI)O2 complexes of vanillin-4N-(2-pyridyl) thiosemicarbazone (H2PVT) are reported. Theoretical calculations have been performed to obtain IR spectra of ligand and its complexes using AM1, Zindo/1, MM+ and PM3, methods. The Schiff base and its metal complexes have been screened for antibacterial Pseudomonas aeruginosa, Escherichia coli, Bacillus subtilis and Staphylococcus saprophyticus. H2VPT shows no apparent digestion effect on the egg albumin while Mn(II), Hg(II) and Cu(II) complexes exhibited a considerable digestion effect following the order Cu(II) > Mn(II) > Hg(II). Moreover, Ni(II) and Co(II) complexes revealed strong digestion effect. Fe(II), Mn(II), Cu(II), Zn(II) and Ni(II) acted as metal co- SOD enzyme factors, which are located in different compartments of the cell.

  18. The diverse electronic properties of C4N3 monolayer under biaxial compressive strain: a theoretical study

    NASA Astrophysics Data System (ADS)

    Wu, Haiping; Liu, Yuzhen; Kan, Erjun; Ma, Yanming; Xu, Wenjie; Li, Jie; Yan, Meichen; Lu, Ruifeng; Wei, Jianfeng; Qian, Yan

    2016-07-01

    Because of the observation of half-metallicity in graphitic carbon nitride C4N3 (g-C4N3), extensive research has recently been focused on this compound. Using density-functional calculations, herein diverse electronic properties of g-C4N3 were engineered by applying biaxial compressive strain. The calculated results demonstrate that g-C4N3 preserves ferromagnetic half-metallicity when the strain is lower than  ‑2%, accompanied by a decrease of the half-metallic gap. When the compressive strain ranges from  ‑5 to  ‑3%, the compound turns into nonmagnetic metal. By increasing the strain on the end, it becomes a nonmagnetic semiconductor. Further investigations show that all nonmagnetic semiconductors possess a direct band gap with a value of around 1.6 eV. This fact indicates that g-C4N3 can be applied in spintronic or photovoltaic fields under a strain environment.

  19. Synthesis and photophysical properties of the photoactivatable cationic porphyrin 5-(4-N-dodecylpyridyl)-10,15,20-tri(4-N-methylpyridyl)-21H,23H-porphyrin tetraiodide for anti-malaria PDT.

    PubMed

    Stallivieri, Aurélie; Le Guern, Florent; Vanderesse, Régis; Meledje, Esme; Jori, Giulio; Frochot, Céline; Acherar, Samir

    2015-07-01

    This article describes a new synthetic method for obtaining three water soluble porphyrins. The more sophisticated porphyrin [5-(4-N-dodecylpyridyl)-10,15,20-tri(4-N-methylpyridyl)-21H,23H-porphyrin tetraiodide], also named C12 porphyrin, was obtained through a three step methodology. The improvements, compared to syntheses described in the literature, mostly concern the purification procedures. The photophysical properties of the three porphyrins are described and the C12 porphyrin presents a very good (1)O2 yield compared to its chemical intermediates. This porphyrin seems to be a very promising candidate for PDT applications. PMID:26066986

  20. Growth evolution of γ‧-Fe4N films on GaN(0001) and their interfacial structure

    NASA Astrophysics Data System (ADS)

    Kimura, Masamitsu; Hasegawa, Shigehiko

    2016-05-01

    We report the growth parameter dependence of structural and magnetic properties of γ‧-Fe4N thin films on GaN(0001) grown by plasma-assisted molecular beam epitaxy, particularly focusing on their interfacial structure. Reflection high-energy electron diffraction (RHEED) and X-ray diffraction reveal that γ‧-Fe4N(111) layers are grown at the interface, while the succeeding layers are preferentially oriented to (111) or (100) depending on the growth conditions. The RHEED observation during the interface formation and the cross-sectional transmission electron microscopy observation indicate that the γ‧-Fe4N(111)/GaN interface is abrupt. On the basis of the present findings, we propose the structural model for the interface.

  1. Spin-polarization inversion at small organic molecule/Fe{sub 4}N interfaces: A first-principles study

    SciTech Connect

    Zhang, Qian; Mi, Wenbo

    2015-09-21

    We report the first-principles calculations on the electronic structure and simulation of the spin-polarized scan tunneling microscopy graphic of the small organic molecules (benzene, thiophene, and cyclopentadienyl)/Fe{sub 4}N interfaces. It is found that the plane of benzene and thiophene keeps parallel to Fe{sub 4}N surface, while that of cyclopentadienyl does not. For all the systems, the organic molecules bind strongly with Fe{sub 4}N. Due to the hybridization between molecule p{sub z} orbitals and d orbitals of Fe, i.e., Zener interaction, all the three systems realize the spin-polarization inversion, whereas the spatial spin-polarization inversion distribution shows different intensities influenced by the competition between the spin polarization of C p{sub z} and Fe d states.

  2. Positron annihilation studies of 4-n-butyl-4'-isothiocyanato-1,1'-biphenyl.

    PubMed

    Dryzek, E; Juszyńska, E; Zaleski, R; Jasińska, B; Gorgol, M; Massalska-Arodź, M

    2013-08-01

    Positron annihilation lifetime spectroscopy (PALS) measurements were performed between 93 and 293 K in order to study the supercooled smectic-E (Sm-E) phase of 4-n-butyl-4'-isothiocyanato-1,1'-biphenyl (4TCB), the ordered molecular crystal of 4TCB, and the phase transition between the Sm-E phase and the ordered molecular crystal of 4TCB. The phase transition was well reflected in the abrupt increase of the ortho-positronium (o-Ps) lifetime and intensity. The value of the o-Ps lifetime in the Sm-E liquid crystalline phase of 4TCB, i.e., 2.21 ns at room temperature, was explained by the formation of bubbles induced by Ps atoms, which are created due to a liquidlike state of the butyl chains of 4TCB molecules in the Sm-E phase. The temperature dependence of the o-Ps intensity for the supercooled Sm-E phase can be explained by thermal generation of sites where bubbles are formed; an activation energy equal to 0.30±0.02 eV was estimated. This value was compared with the activation energies of molecular motions. The o-Ps lifetime in the ordered molecular crystal was interpreted as originating from the annihilation of o-Ps confined in molecular vacancy-type imperfections in the crystal lattice. The value of the o-Ps pickoff annihilation between 1.8 and 1.9 ns is in accordance with the size of the molecular vacancy for the 4TCB crystal lattice. Its intensity is lower than 5%. The isothermal crystallization of the 4TCB Sm-E phase was observed by PALS. The low-dimensional crystal growth was concluded from the Avrami equation fitted to the time dependence of the o-Ps intensity, which resulted in an Avrami exponent equal to 1.73. PMID:24032853

  3. Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far UV Irradiation

    NASA Technical Reports Server (NTRS)

    Trainer, Melissa G.; Jimenez, Jose L.; Yung, Yuk L.; Toon, Owen B.; Tolbert, Margaret A.

    2012-01-01

    Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (lambda < 120 nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120 - 200 nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not initiate the formation of nitrogenated species. We have examined the chemical properties of photochemical aerosol produced at far UV wavelengths using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH4/N2 photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N2 in the irradiated gas. The aerosol mass greatly decreases when N2 is removed, indicating that N2 plays a major role in aerosol production. Because direct dissociation of N2 is highly improbable given the immeasurably low cross-section at the wavelengths studied, the chemical activation of N2 must occur via another pathway. Any chemical activation of N2 at wavelengths > 120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for prebiotic chemistry on the early Earth and similar planets.

  4. Structure, phase transitions, dielectric and spectroscopic studies of the 2-aminopyrimidinium salts: [(2-NH 2C 4N 2H 3) 2H][ClO 4] and [2-NH 2C 4N 2H 4][BF 4

    NASA Astrophysics Data System (ADS)

    Czupiński, O.; Wojtaś, M.; Ciunik, Z.; Jakubas, R.

    2006-01-01

    Crystal structure of the 2-aminopyrimidinium derivatives: [(2-NH 2C 4N 2H 3) 2H][ClO 4] (I) and [2-NH 2C 4N 2H 4][BF 4] (II) has been determined at 100 K (I) and 293 K (II) by means of single crystal X-ray diffraction as monoclinic space group, P2/c and P2/n, respectively. The asymmetric part of the unit cell of (I) contains two symmetry independent 2-aminopyrimidine forming one dimeric cation and one disordered perchlorate anion. The structure of (II) consists of 2-aminopyrimidinium cation, [2-NH 2C 4N 2H 4] +, protonated at a pyrimidine ring-N atom and [BF 4] - anion. Differential scanning calorimetry (DSC) on perchlorate derivative ( 1:1), [2-NH 2C 4N 2H 3][ClO 4] (III)—being isomorphic to tetrafluoroborate one (I) at room temperature, reveals two phase transitions of first order: at 250/275 K and 390/410 K (cooling-heating, respectively), whereas the analog (II) only one transition at high temperatures—343/385 K. The dielectric studies in the frequency range 75 kHz - 10 MHz disclose relaxation process at high temperatures in salt (I). Infrared spectra of polycrystalline [2-NH 2C 4N 2H 4][BF 4] have been studied in the temperature range 300-420 K. Substantial changes in the temperature evolution of frequencies of internal modes of the 2-aminopyrimidinium cations and [BF 4] - anions near 390 K are due to the variations in the motion of both moieties and hydrogen bond configuration. The experimental studies indicate that all phase transitions taking place in studied 2-aminopyrimidinium derivatives are classified as an order-disorder.

  5. tetra neutron system studied by exothermic double-charge exchange reaction 4He(8He, 8Be)4n

    NASA Astrophysics Data System (ADS)

    Kisamori, Keiichi; Sharaq06 Collaboration

    2014-09-01

    A possible existence of the tetra-neutron system as a resonance state is still an open and fascinating question, while theoretical papers using ab-initio calculation suggests that the bound tetra-neutron does not exist. We have performed a missing-mass spectroscopy of the 4n system via the exothermic double-charge exchange reaction 4He(8He,8Be)4n. The experiment was carried out at the RIBF at RIKEN using the SHARAQ spectrometer and the liquid He target system. Since the secondary beam, 8He at 190A MeV, has a large internal energy, it is possible to produce the 4n system in small momentum transfers of less than 20 MeV/c. In the present analysis, a new analytical framework to treat multi-particles under high beam rate condition (2 MHz) was developed for good statistics. At the SHARAQ spectrometer, 8Be can be identified by measuring the invariant mass of the coincident two-alpha particle with a good signal-to-noise ratio. About several tens of candidate events are obtained above the 4n threshold. We will show the preliminary result of missing-msss spectrum and discuss the shape of spectrum.

  6. Structure, phase transitions, and isotope effects in [(CH3)4N]2PuCl6

    SciTech Connect

    Wilson, Richard E.

    2015-11-02

    The single crystal X-ray diffraction structure of [(CH3)4N]2PuCl6 is presented for the first time, resolving long standing confusion and speculation regarding the structure of this compound in the literature. A temperature dependent study of this compound shows that the structure of [(CH3)4N]2PuCl6 undergoes no fewer than two phase transitions between 100 and 360 K. The phase of [(CH3)4N]2PuCl6 at room temperature is Fd-3c a = 26.012(3) Å. At 360 K, the structure is in space group Fm-3m with a = 13.088(1) Å. The plutonium octahedra and tetramethylammonium cations undergo a rotative displacement and the degree of rotation varies with temperature, giving rise to the phase transition from Fm-3m to Fd-3c as the crystal is cooled. Synthesis and structural studies of the deuterated salt [(CD3)4N]2PuCl6 suggest that there is an isotopic effect associated with this phase transition as revealed by a changing transition temperature in the deuterated versus protonated compound indicating that the donor-acceptor interactions between the tetramethylammonium cations and the hexachloroplutonate anions are driving the phase transformation.

  7. Structure, Phase Transitions, and Isotope Effects in [(CH3)4N]2PuCl6.

    PubMed

    Wilson, Richard E

    2015-11-01

    The single-crystal X-ray diffraction structure of [(CH3)4N]2PuCl6 is presented for the first time, resolving long-standing confusion and speculation regarding the structure of this compound in the literature. A temperature-dependent study of this compound shows that the structure of [(CH3)4N]2PuCl6 undergoes no fewer than two phase transitions between 100 and 360 K. The phase of [(CH3)4N]2PuCl6 at room temperature is Fd3̅c a = 26.012(3) Å. At 360 K, the structure is in space group Fm3̅m, with a = 13.088(1) Å. The plutonium octahedra and tetramethylammonium cations undergo a rotative displacement, and the degree of rotation varies with temperature, giving rise to the phase transition from Fm3̅m to Fd3̅c as the crystal is cooled. Synthesis and structural studies of the deuterated salt [(CD3)4N]2PuCl6 suggest that there is an isotopic effect associated with this phase transition, as revealed by a changing transition temperature in the deuterated versus protonated compound, indicating that the donor-acceptor interactions between the tetramethylammonium cations and the hexachloroplutonate anions are driving the phase transformation. PMID:26225472

  8. Transition from half metal to semiconductor in Li doped g-C{sub 4}N{sub 3}

    SciTech Connect

    Hashmi, Arqum; Hu, Tao; Hong, Jisang

    2014-03-28

    We have investigated the structural and magnetic properties of Li doped graphitic carbon nitride (g-C{sub 4}N{sub 3}) using the van der Waals density functional theory. A free standing g-C{sub 4}N{sub 3} was known to show a half metallic state with buckling geometry, but this feature completely disappears in the presence of Li doping. Besides this structural modification, very interestingly, we have obtained that the Li doped g-C{sub 4}N{sub 3} shows dramatic change in its electronic structure. Both ferromagnetic and nonmagnetic states are almost degenerated in one Li atom doped system. However, the transition from half metallic state to semiconductor is observed with further increase of Li concentration and the calculated energy gap is 1.97 eV. We found that Li impurity plays as a donor element and charge transfer from the Li atom to neighboring N atoms induces a band gap. Overall, we have observed that the electronic and magnetic properties of g-C{sub 4}N{sub 3} are substantially modified by Li doping.

  9. AF4 and AF4N protein complexes: recruitment of P-TEFb kinase, their interactome and potential functions

    PubMed Central

    Scholz, Bastian; Kowarz, Eric; Rössler, Tanja; Ahmad, Khalil; Steinhilber, Dieter; Marschalek, Rolf

    2015-01-01

    AF4/AFF1 and AF5/AFF4 are the molecular backbone to assemble “super-elongation complexes” (SECs) that have two main functions: (1) control of transcriptional elongation by recruiting the positive transcription elongation factor b (P-TEFb = CyclinT1/CDK9) that is usually stored in inhibitory 7SK RNPs; (2) binding of different histone methyltransferases, like DOT1L, NSD1 and CARM1. This way, transcribed genes obtain specific histone signatures (e.g. H3K79me2/3, H3K36me2) to generate a transcriptional memory system. Here we addressed several questions: how is P-TEFb recruited into SEC, how is the AF4 interactome composed, and what is the function of the naturally occuring AF4N protein variant which exhibits only the first 360 amino acids of the AF4 full-length protein. Noteworthy, shorter protein variants are a specific feature of all AFF protein family members. Here, we demonstrate that full-length AF4 and AF4N are both catalyzing the transition of P-TEFb from 7SK RNP to their N-terminal domain. We have also mapped the protein-protein interaction network within both complexes. In addition, we have first evidence that the AF4N protein also recruits TFIIH and the tumor suppressor MEN1. This indicate that AF4N may have additional functions in transcriptional initiation and in MEN1-dependend transcriptional processes. PMID:26171280

  10. Nano-sized manganese oxides as biomimetic catalysts for water oxidation in artificial photosynthesis: a review

    PubMed Central

    Najafpour, Mohammad Mahdi; Rahimi, Fahimeh; Aro, Eva-Mari; Lee, Choon-Hwan; Allakhverdiev, Suleyman I.

    2012-01-01

    There has been a tremendous surge in research on the synthesis of various metal compounds aimed at simulating the water-oxidizing complex (WOC) of photosystem II (PSII). This is crucial because the water oxidation half reaction is overwhelmingly rate-limiting and needs high over-voltage (approx. 1 V), which results in low conversion efficiencies when working at current densities required for hydrogen production via water splitting. Particular attention has been given to the manganese compounds not only because manganese has been used by nature to oxidize water but also because manganese is cheap and environmentally friendly. The manganese–calcium cluster in PSII has a dimension of about approximately 0.5 nm. Thus, nano-sized manganese compounds might be good structural and functional models for the cluster. As in the nanometre-size of the synthetic models, most of the active sites are at the surface, these compounds could be more efficient catalysts than micrometre (or bigger) particles. In this paper, we focus on nano-sized manganese oxides as functional and structural models of the WOC of PSII for hydrogen production via water splitting and review nano-sized manganese oxides used in water oxidation by some research groups. PMID:22809849

  11. Multicomponent High-Strength Low-Alloy Steel Precipitation-Strengthened by Sub-nanometric Cu Precipitates and M2C Carbides

    NASA Astrophysics Data System (ADS)

    Jain, Divya; Isheim, Dieter; Hunter, Allen H.; Seidman, David N.

    2016-05-01

    HSLA-115 is a novel high-strength low-alloy structural steel derived from martensitic Cu-bearing HSLA-100. HSLA-100 is typically used in conditions with overaged Cu precipitates, to obtain acceptable impact toughness and ductility. Present work on HSLA-115 demonstrates that incorporating sub-nanometric-sized M2C carbides along with Cu precipitates produces higher strength steels that still meet impact toughness and ductility requirements. Isothermal aging at 823 K (550 °C) precipitates M2C carbides co-located with the Cu precipitates and distributed heterogeneously at lath boundaries and dislocations. 3D atom-probe tomography is used to characterize the evolution of these precipitates at 823 K (550 °C) in terms of mean radii, number densities, and volume fractions. These results are correlated with microhardness, impact toughness, and tensile strength. The optimum combination of mechanical properties, 972 MPa yield strength, 24.8 pct elongation to failure, and 188.0 J impact toughness at 255 K (-18 °C), is attained after 3-hour aging at 823 K (550 °C). Strengthening by M2C precipitates offsets the softening due to overaging of Cu precipitates and tempering of martensitic matrix. It is shown that this extended yield strength plateau can be used as a design principle to optimize strength and toughness at the same time.

  12. Using instability of nanometric liquid Cu films on SiO2 substrates to determine the underlying van der Waals potential

    NASA Astrophysics Data System (ADS)

    González, Alejandro G.; Diez, Javier A.; Wu, Yueying; Fowlkes, Jason D.; Rack, Philip D.; Kondic, Lou

    2013-11-01

    We study the instability of nanometric Cu thin films on a SiO2 substrate. The metal is melted by means of laser pulses for some tens of nanoseconds. The free surface destabilizes during the liquid lifetime, leading to the formation of holes at first and to metal drops on the substrate in later stages. By analyzing the Fourier transforms of the SEM images obtained during the metal film evolution, we determine the emerging length scales for both early and late stages of the instability development. The results are analyzed within the framework of a long-wave hydrodynamic model, which introduces van der Waals forces by means of disjoining and conjoining pressures. These forces are characterized by a pair of exponents for the ratio h / h * , where h is the liquid thickness and h* is a residual one. We find that the pair (3 , 2) provides a good agreement for the relationship of the wavelength with maximum growth rate, λm, while other typical pairs, such as (4 , 3) and (9 , 3) do not provide accurate description of the experimental data. Supported by CONICET-Argentina grant PIP 844/2011 (AGG, JAD), and by NSF grants CBET-1235651 (PDR) and CBET-1235710 (LK).

  13. Multicomponent High-Strength Low-Alloy Steel Precipitation-Strengthened by Sub-nanometric Cu Precipitates and M2C Carbides

    NASA Astrophysics Data System (ADS)

    Jain, Divya; Isheim, Dieter; Hunter, Allen H.; Seidman, David N.

    2016-08-01

    HSLA-115 is a novel high-strength low-alloy structural steel derived from martensitic Cu-bearing HSLA-100. HSLA-100 is typically used in conditions with overaged Cu precipitates, to obtain acceptable impact toughness and ductility. Present work on HSLA-115 demonstrates that incorporating sub-nanometric-sized M2C carbides along with Cu precipitates produces higher strength steels that still meet impact toughness and ductility requirements. Isothermal aging at 823 K (550 °C) precipitates M2C carbides co-located with the Cu precipitates and distributed heterogeneously at lath boundaries and dislocations. 3D atom-probe tomography is used to characterize the evolution of these precipitates at 823 K (550 °C) in terms of mean radii, number densities, and volume fractions. These results are correlated with microhardness, impact toughness, and tensile strength. The optimum combination of mechanical properties, 972 MPa yield strength, 24.8 pct elongation to failure, and 188.0 J impact toughness at 255 K (-18 °C), is attained after 3-hour aging at 823 K (550 °C). Strengthening by M2C precipitates offsets the softening due to overaging of Cu precipitates and tempering of martensitic matrix. It is shown that this extended yield strength plateau can be used as a design principle to optimize strength and toughness at the same time.

  14. Reversible Exsolution of Nanometric Fe2O3 Particles in BaFe2-x(PO4)2 (0 ≤ x ≤ 2/3):The Logic of Vacancy Ordering in Novel Metal-Depleted Two-Dimensional Lattices

    SciTech Connect

    Alcover, Ignacio Blazquez; David, Rénald; Daviero-Minaud, Sylvie; Filimonov, Dmitry; Huvé, Marielle; Roussel, Pascal; Kabbour, Houria; Mentré, Olivier

    2015-08-12

    We show here that the exsolution of Fe2+ ions out of two-dimensional (2D) honeycomb layers of BaFe2(PO4)2 into iron-deficient BaFe2–x(PO4)2 phases and nanometric α-Fe2O3 (typically 50 nm diameter at the grain surface) is efficient and reversible until x = 2/3 in mild oxidizing/reducing conditions. It corresponds to the renewable conversion of 12 wt % of the initial mass into iron oxide. After analyzing single crystal X-ray diffraction data of intermediate members x = 2/7, x = 1/3, x = 1/2 and the ultimate Fe-depleted x = 2/3 term, we then observed a systematic full ordering between Fe ions and vacancies (VFe) that denote unprecedented easy in-plane metal diffusion driven by the Fe2+/Fe3+ redox. Besides the discovery of a diversity of original depleted triangular {Fe2/3+2–xO6} topologies, we propose a unified model correlating the x Fe-removal and the experimental Fe/VFe ordering into periodic one-dimensional motifs paving the layers, gaining insights into predictive crystahemistry of complex low dimensional oxides. When we increased the x values it led to a progressive change of the materials from 2D ferromagnets (Fe2+) to 2D ferrimagnets (Fe2/3+) to antiferromagnets for x = 2/3 (Fe3+).

  15. Gas phase dicyanoacetylene (C4N2) on Titan: New experimental and theoretical spectroscopy results applied to Cassini CIRS data

    NASA Astrophysics Data System (ADS)

    Jolly, A.; Cottini, V.; Fayt, A.; Manceron, L.; Kwabia-Tchana, F.; Benilan, Y.; Guillemin, J.-C.; Nixon, C.; Irwin, P.

    2015-03-01

    Dicyanoacetylene has not been observed so far in the gas phase in Titan's atmosphere but this molecule is still on the list of the detected species, on the basis of the correspondence between a solid phase feature measured at 478 cm-1 in the laboratory and a spectral feature observed by Voyager. In this work, the infrared spectrum of gaseous C4N2 has been investigated to improve our knowledge of the band intensities and the line parameters for this molecule. Results of previously investigated bands have been revised and the intensity of the ν9 band at 107 cm-1, measured for the first time, was found to be the strongest absorption in the whole infrared domain. We have also improved the analysis of the complex rotational and hot band structure of C4N2 in order to obtain the first line lists for both bending modes ν8 and ν9. Using our radiative transfer code including the new line list of the strong ν9 band, we have searched for the signature of C4N2 at 107 cm-1 in the atmosphere of Titan utilizing Titan CIRS far infrared spectra. Despite averaging a large number of CIRS spectra at northern latitudes during the very favorable Titan winter, no gaseous C4N2 could be detected. At the 1-σ level we obtain an abundance upper limit of 5.3 × 10-10 for the limb average which is lower than or comparable to previously inferred values. As a consequence, the absence or very low amount of gaseous C4N2 makes quite puzzling its presence in the solid phase with an abundance compatible with the observed spectral feature at 478 cm-1.

  16. Metastatic Neuroblastoma Confined to Distant Lymph Nodes (stage 4N) Predicts Outcome in Patients With Stage 4 Disease: A Study From the International Neuroblastoma Risk Group Database

    PubMed Central

    Morgenstern, Daniel A.; London, Wendy B.; Stephens, Derek; Volchenboum, Samuel L.; Hero, Barbara; Di Cataldo, Andrea; Nakagawara, Akira; Shimada, Hiroyuki; Ambros, Peter F.; Matthay, Katherine K.; Cohn, Susan L.; Pearson, Andrew D.J.; Irwin, Meredith S.

    2014-01-01

    Purpose The presence of distant metastases is one of the most powerful predictors of outcome in patients with neuroblastoma. However, the pattern of metastatic spread is not incorporated into current risk stratification systems. Small case series have suggested that patients with neuroblastoma who have metastatic disease limited to distant lymph nodes (4N disease) may have improved outcomes. Patients and Methods We analyzed retrospective data from the International Neuroblastoma Risk Group database for patients diagnosed from 1990 to 2002. 4N patients were compared with the remaining stage 4 patients (non-4N), excluding those with missing metastatic site data. Results In all, 2,250 International Neuroblastoma Staging System stage 4 patients with complete data were identified, of whom 146 (6.5%) had 4N disease. For 4N patients, event-free survival (EFS; 5-year, 77% ± 4%) and overall survival (OS; 5-year, 85% ± 3%) were significantly better than EFS (5-year, 35% ± 1%) and OS (5-year, 42% ± 1%) for non-4N stage 4 patients (P < .001). 4N patients were more likely to be younger (P < .001) and have tumors with favorable characteristics, including absence of MYCN amplification (89% v 69%; P < .001). In a multivariable analysis, 4N disease remained a significant predictor of outcome (hazard ratio for non-4N v 4N: 3.40 for EFS and 3.69 for OS). Within subgroups defined by age at diagnosis and tumor MYCN status, 4N disease was significantly associated with improved outcomes. Conclusion 4N represents a subgroup with better outcome than that of other patients with metastatic disease. These findings suggest that the biology and treatment response of 4N tumors differ from other stage 4 tumors, and less intensive therapy should be considered for this cohort. Future exploration of biologic factors determining the pattern of metastatic spread is warranted. PMID:24663047

  17. Towards the development of multifunctional chitosan-based iron oxide nanoparticles: Optimization and modelling of doxorubicin release.

    PubMed

    Soares, Paula I P; Sousa, Ana Isabel; Ferreira, Isabel M M; Novo, Carlos M M; Borges, João Paulo

    2016-11-20

    In the present work composite nanoparticles with a magnetic core and a chitosan-based shell were produced as drug delivery systems for doxorubicin (DOX). The results show that composite nanoparticles with a hydrodynamic diameter within the nanometric range are able to encapsulate more DOX than polymeric nanoparticles alone corresponding also to a higher drug release. Moreover the synthesis method of the iron oxide nanoparticles influences the total amount of DOX released and a high content of iron oxide nanoparticles inhibits DOX release. The modelling of the experimental results revealed a release mechanism dominated by Fickian diffusion. PMID:27561489

  18. Bulk size crystal growth, spectroscopic, dielectric and surface studies of 4-N,N-dimethylamino-4-N'-methylstilbazolium m-nitrobenzenesulfonate (DSMNS): A potential THz crystal of stilbazolium family.

    PubMed

    Antony Raj, A; John Sundaram, S; Gunaseelan, R; Sagayaraj, P

    2015-10-01

    The synthesis and growth of a potentially useful and efficient nonlinear optical organic single crystal of 4-N,N-dimethylamino-4-N'-methylstilbazolium m-nitrobenzenesulfonate (DSMNS) is reported. The growth experiment involved the slope nucleation method coupled with slow cooling as well as slow solvent evaporation techniques. Single crystal X-ray diffraction (XRD), Fourier transform infrared (FT-IR), FT-Raman and nuclear magnetic resonance (NMR) techniques have been employed to ascertain the structure and composition of the crystal. Second harmonic generation (SHG) efficiency of the sample has been examined by Kurtz and Perry powder test. Thermogravimetry (TG), differential thermal analysis (DTA) and differential scanning calorimetry (DSC) techniques are employed to investigate the thermal behavior of the grown crystal. The frequency/temperature dependent dielectric properties of the organic crystal of DSMNS are studied. The surface features of the grown crystal are investigated by chemical etching study and atomic force microscopy (AFM). PMID:26010563

  19. Highly efficient and ultra-broadband graphene oxide ultrathin lenses with three-dimensional subwavelength focusing

    PubMed Central

    Zheng, Xiaorui; Jia, Baohua; Lin, Han; Qiu, Ling; Li, Dan; Gu, Min

    2015-01-01

    Nanometric flat lenses with three-dimensional subwavelength focusing are indispensable in miniaturized optical systems. However, they are fundamentally challenging to achieve because of the difficulties in accurately controlling the optical wavefront by a film with nanometric thickness. Based on the unique and giant refractive index and absorption modulations of the sprayable graphene oxide thin film during its laser reduction process, we demonstrate a graphene oxide ultrathin (∼200 nm) flat lens that shows far-field three-dimensional subwavelength focusing (λ3/5) with an absolute focusing efficiency of >32% for a broad wavelength range from 400 to 1,500 nm. Our flexible graphene oxide lenses are mechanically robust and maintain excellent focusing properties under high stress. The simple and scalable fabrication approach enables wide potential applications in on-chip nanophotonics. The wavefront shaping concept opens up new avenues for easily accessible, highly precise and efficient optical beam manipulations with a flexible and integratable planar graphene oxide ultrathin film. PMID:26391504

  20. Highly efficient and ultra-broadband graphene oxide ultrathin lenses with three-dimensional subwavelength focusing.

    PubMed

    Zheng, Xiaorui; Jia, Baohua; Lin, Han; Qiu, Ling; Li, Dan; Gu, Min

    2015-01-01

    Nanometric flat lenses with three-dimensional subwavelength focusing are indispensable in miniaturized optical systems. However, they are fundamentally challenging to achieve because of the difficulties in accurately controlling the optical wavefront by a film with nanometric thickness. Based on the unique and giant refractive index and absorption modulations of the sprayable graphene oxide thin film during its laser reduction process, we demonstrate a graphene oxide ultrathin (∼200 nm) flat lens that shows far-field three-dimensional subwavelength focusing (λ(3)/5) with an absolute focusing efficiency of >32% for a broad wavelength range from 400 to 1,500 nm. Our flexible graphene oxide lenses are mechanically robust and maintain excellent focusing properties under high stress. The simple and scalable fabrication approach enables wide potential applications in on-chip nanophotonics. The wavefront shaping concept opens up new avenues for easily accessible, highly precise and efficient optical beam manipulations with a flexible and integratable planar graphene oxide ultrathin film. PMID:26391504

  1. Metallic transport and large anomalous Hall effect at room temperature in ferrimagnetic Mn{sub 4}N epitaxial thin film

    SciTech Connect

    Shen, Xi; Shigematsu, Kei; Chikamatsu, Akira Fukumura, Tomoteru; Hirose, Yasushi; Hasegawa, Tetsuya

    2014-08-18

    We report the electrical transport properties of ferrimagnetic Mn{sub 4}N (001) epitaxial thin films grown by pulsed laser deposition on MgO (001) substrates. The Mn{sub 4}N thin films were tetragonally distorted with a ratio of out-of-plane to in-plane lattice constants of 0.987 and showed perpendicular magnetic anisotropy with an effective magnetic anisotropy constant of 0.16 MJ/m{sup 3}, which is comparable with that of a recently reported molecular-beam-epitaxy-grown film. The thin films exhibited metallic transport with a room temperature resistivity of 125 μΩ cm in addition to a large anomalous Hall effect with a Hall angle tangent of 0.023.

  2. Solid-state photochemistry as a formation mechanism for Titan's stratospheric C4N2 ice clouds

    NASA Astrophysics Data System (ADS)

    Anderson, C. M.; Samuelson, R. E.; Yung, Y. L.; McLain, J. L.

    2016-04-01

    We propose that C4N2 ice clouds observed in Titan's springtime polar stratosphere arise due to solid-state photochemistry occurring within extant ice cloud particles of HCN-HC3N mixtures. This formation process resembles the halogen-induced ice particle surface chemistry that leads to condensed nitric acid trihydrate (NAT) particles and ozone depletion in Earth's polar stratosphere. As our analysis of the Cassini Composite Infrared Spectrometer 478 cm-1 ice emission feature demonstrates, this solid-state photochemistry mechanism eliminates the need for the relatively high C4N2 saturation vapor pressures required (even though they are not observed) when the ice is produced through the usual procedure of direct condensation from the vapor.

  3. Enhanced unscheduled DNA synthesis in UV-irradiated human skin explants treated with T4N5 liposomes

    SciTech Connect

    Yarosh, D.B.; Kibitel, J.T.; Green, L.A.; Spinowitz, A. )

    1991-07-01

    Epidermal keratinocytes cultured from explants of skin cancer patients, including biopsies from xeroderma pigmentosum patients, were ultraviolet light-irradiated and DNA repair synthesis was measured. Repair capacity was much lower in xeroderma pigmentosum patients than in normal patients. The extent of DNA repair replication did not decline with the age of the normal patient. Treatment with T4N5 liposomes containing a DNA repair enzyme enhanced repair synthesis in both normal and xeroderma pigmentosum keratinocytes in an irradiation- and liposome-dose dependent manner. These results provide no evidence that aging people or skin cancer patients are predisposed to cutaneous malignancy by a DNA repair deficiency, but do demonstrate that T4N5 liposomes enhance DNA repair in the keratinocytes of the susceptible xeroderma pigmentosum and skin cancer population.

  4. Growth and electrical properties on NLO crystal: 4-N,N-dimethylamino 4′-N′-methylstilbazolium iodide

    SciTech Connect

    Kumar, M. Krishna Sudhahar, S. Kumar, R. Mohan

    2014-04-24

    4-N,N-Dimethylamino-4′-N′-methylstilbazolium tosylate single crystals were grown by solution crystal growth method. The cell parameters of grown crystal have been estimated using single crystal-X-ray diffraction analysis. The variation of real (´ε) and imaginary (´ε) part of dielectric constants and dielectric loss were observed for different frequencies and temperatures. The ac and dc electrical conductivities and activation energy were determined for DMSI crystal using dielectric studies.

  5. Stereotactic body radiotherapy for T3 and T4N0M0 non–small cell lung cancer

    PubMed Central

    Eriguchi, Takahisa; Takeda, Atsuya; Sanuki, Naoko; Nishimura, Shuichi; Takagawa, Yoshiaki; Enomoto, Tatsuji; Saeki, Noriyuki; Yashiro, Kae; Mizuno, Tomikazu; Aoki, Yousuke; Oku, Yohei; Yokosuka, Tetsuya; Shigematsu, Naoyuki

    2016-01-01

    To evaluate the outcomes and feasibility of stereotactic body radiotherapy (SBRT) for cT3 and cT4N0M0 non–small cell lung cancer (NSCLC), 25 patients with localized primary NSCLC diagnosed as cT3 or cT4N0M0, given SBRT between May 2005 and July 2013, were analyzed. All patients had inoperable tumors. The major reasons for tumors being unresectable were insufficient respiratory function for curative resection, advanced age (>80 years old) or technically inoperable due to invasion into critical organs. The median patient age was 79 years (range; 60–86). The median follow-up duration was 25 months (range: 5–100 months). The 2-year overall survival rates for T3 and T4 were 57% and 69%, respectively. The 2-year local control rates for T3 and T4 were 91% and 68%, respectively. As for toxicities, Grade 0–1, Grade 2 and Grade 3 radiation pneumonitis occurred in 23, 1 and 1 patient, respectively. No other acute or symptomatic late toxicities were reported. Thirteen patients who had no local, mediastinal or intrapulmonary progression at one year after SBRT underwent pulmonary function testing. The median variation in pre-SBRT and post-SBRT forced expiratory volume in 1 s (FEV1) values was –0.1 (–0.8–0.8). This variation was not statistically significant (P = 0.56). Forced vital capacity (FVC), vital capacity (VC), %VC and %FEV1 also showed no significant differences. SBRT for cT3 and cT4N0M0 NSCLC was both effective and feasible. Considering the favorable survival and low morbidity rate, SBRT is a potential treatment option for cT3 and cT4N0M0 NSCLC. PMID:26983978

  6. Stereotactic body radiotherapy for T3 and T4N0M0 non-small cell lung cancer.

    PubMed

    Eriguchi, Takahisa; Takeda, Atsuya; Sanuki, Naoko; Nishimura, Shuichi; Takagawa, Yoshiaki; Enomoto, Tatsuji; Saeki, Noriyuki; Yashiro, Kae; Mizuno, Tomikazu; Aoki, Yousuke; Oku, Yohei; Yokosuka, Tetsuya; Shigematsu, Naoyuki

    2016-06-01

    To evaluate the outcomes and feasibility of stereotactic body radiotherapy (SBRT) for cT3 and cT4N0M0 non-small cell lung cancer (NSCLC), 25 patients with localized primary NSCLC diagnosed as cT3 or cT4N0M0, given SBRT between May 2005 and July 2013, were analyzed. All patients had inoperable tumors. The major reasons for tumors being unresectable were insufficient respiratory function for curative resection, advanced age (>80 years old) or technically inoperable due to invasion into critical organs. The median patient age was 79 years (range; 60-86). The median follow-up duration was 25 months (range: 5-100 months). The 2-year overall survival rates for T3 and T4 were 57% and 69%, respectively. The 2-year local control rates for T3 and T4 were 91% and 68%, respectively. As for toxicities, Grade 0-1, Grade 2 and Grade 3 radiation pneumonitis occurred in 23, 1 and 1 patient, respectively. No other acute or symptomatic late toxicities were reported. Thirteen patients who had no local, mediastinal or intrapulmonary progression at one year after SBRT underwent pulmonary function testing. The median variation in pre-SBRT and post-SBRT forced expiratory volume in 1 s (FEV1) values was -0.1 (-0.8-0.8). This variation was not statistically significant (P = 0.56). Forced vital capacity (FVC), vital capacity (VC), %VC and %FEV1 also showed no significant differences. SBRT for cT3 and cT4N0M0 NSCLC was both effective and feasible. Considering the favorable survival and low morbidity rate, SBRT is a potential treatment option for cT3 and cT4N0M0 NSCLC. PMID:26983978

  7. The investigation of the electrical properties of Fe3O4/n-Si heterojunctions in a wide temperature range.

    PubMed

    Deniz, Ali Rıza; Çaldıran, Zakir; Metin, Önder; Meral, Kadem; Aydoğan, Şakir

    2016-07-01

    Monodisperse 8nm Fe3O4 nanoparticles (NPs) were synthesized by the thermal decomposition of iron(III) acetylacetonate in oleylamine and then were deposited onto n-type silicon wafer having the Al ohmic contact. Next, the morphology of the Fe3O4 NPs were characterized by using TEM and XRD. The optical properties of Fe3O4 NPs film was studied by UV-Vis spectroscopoy and its band gap was calculated to be 2.16eV. Au circle contacts with 7.85×10(-3)cm(2) area were provided on the Fe3O4 film via evaporation at 10(-5)Torr and the Au/Fe3O4 NPs/n-Si/Al heterojunction device were fabricated. The temperature-dependent junction parameters of Au/Fe3O4/n-Si/Al device including ideality factor, barrier height and series resistance were calculated by using the I-V characteristics in a wide temperature range of 40-300K. The results revealed that the ideality factor and series resistance increased by the decreasing temperature while the barrier height decreases. The Richardson constant of Au/Fe3O4/n-Si/Al device was calculated to be 2.17A/K(2)cm(2) from the I-V characteristics. The temperature dependence of Au/Fe3O4/n-Si/Al heterojunction device showed a double Gaussian distribution, which is caused by the inhomogeneities characteristics of Fe3O4/n-Si heterojunction. PMID:27078739

  8. Ferromagnet / superconductor oxide superlattices

    NASA Astrophysics Data System (ADS)

    Santamaria, Jacobo

    2006-03-01

    The growth of heterostructures combining oxide materials is a new strategy to design novel artificial multifunctional materials with interesting behaviors ruled by the interface. With the (re)discovery of colossal magnetoresistance (CMR) materials, there has been renewed interest in heterostructures involving oxide superconductors and CMR ferromagnets where ferromagnetism (F) and superconductivity (S) compete within nanometric distances from the interface. In F/S/F structures involving oxides, interfaces are especially complex and various factors like interface disorder and roughness, epitaxial strain, polarity mismatch etc., are responsible for depressed magnetic and superconducting properties at the interface over nanometer length scales. In this talk I will focus in F/S/F structures made of YBa2Cu3O7 (YBCO) and La0.7Ca0.3MnO3 (LCMO). The high degree of spin polarization of the LCMO conduction band, together with the d-wave superconductivity of the YBCO make this F/S system an adequate candidate for the search of novel spin dependent effects in transport. We show that superconductivity at the interface is depressed by various factors like charge transfer, spin injection or ferromagnetic superconducting proximity effect. I will present experiments to examine the characteristic distances of the various mechanisms of superconductivity depression. In particular, I will discuss that the critical temperature of the superconductor depends on the relative orientation of the magnetization of the F layers, giving rise to a new giant magnetoresistance effect which might be of interest for spintronic applications. Work done in collaboration with V. Peña^1, Z. Sefrioui^1, J. Garcia-Barriocanal^1, C. Visani^1, D. Arias^1, C. Leon^1 , N. Nemes^2, M. Garcia Hernandez^2, S. G. E. te Velthuis^3, A. Hoffmann^3, M. Varela^4, S. J. Pennycook^4. Work supported by MCYT MAT 2005-06024, CAM GR- MAT-0771/2004, UCM PR3/04-12399 Work at Argonne supported by the Department of Energy, Basic

  9. Optical properties of g-C4N3/BN bilayer film: A first-principles study

    NASA Astrophysics Data System (ADS)

    Son, Jicheol; Hashmi, Arqum; Hong, Jisang

    2015-11-01

    Using first-principles method, we explored the frequency dependent dielectric function, refractive index, reflectivity, optical conductivity, loss function, and absorption coefficient of g-C4N3/BN bilayer system. Here, the dependences of the optical properties on the electric field polarization were also explored. Because the dielectric function strongly depended on the electric polarization, we obtained anisotropic optical properties. For instance, the dielectric function was frequency independent for perpendicular electric polarization while a frequency dependent dielectric function was observed for parallel electric polarization. A high refractive index larger than 2 was obtained for parallel polarization in the infrared and the visible frequency ranges, whereas a constant refractive index of approximately 1.5 was observed for perpendicular polarization. We found that the electromagnetic wave propagating perpendicular to the film surface had a very small reflectivity at ultraviolet frequencies, this property could be utilized for applications as anti-reflection ultraviolet coatings. In addition, the g-C4N3/BN bilayer may produce no meaningful joule heating for in-plane wave propagation because of its extremely weak optical conductivity. We propose that optical phonons may generated by incident ultraviolet waves. In addition, the bilayer system may be transparent in the visible range. Overall, we found that metal-free, transparent, half-metallic g-C4N3 films could be utilized for spintronics and optical device applications.

  10. Electronic structure and magnetic properties of Mn, Co, and Ni substitution of Fe in Fe4N

    NASA Astrophysics Data System (ADS)

    Monachesi, Patrizia; Björkman, Torbjörn; Gasche, Thomas; Eriksson, Olle

    2013-08-01

    The magnetic properties of Mn, Co, and Ni substituted Fe4N are calculated from first principles theory. It is found that the generalized gradient approximation reproduces with good accuracy the magnetic moment and equilibrium volume for the parent Fe4N structure, with the atomic moment largest for the Fe atom furthest away from the N atom (Fe I site), approaching a value of 3 μB/atom, whereas the Fe atom closer to the N atom (Fe II site) has a moment closer to that of bcc Fe. The substitution of Fe for Mn, Co, or Ni, shows an intricate behavior in which the Mn substitution clearly favors the Fe II site, Ni favors substitution on the Fe I site, and Co shows no strong preference for either lattice site. The Ni and Co substitution results in a ferromagnetic coupling to the Fe atoms, whereas Mn couples antiferromagnetically on the Fe II site and ferromagnetically on the Fe I site. For all types of doping, the total magnetic moment is enhanced compared to Fe4N only in the energetically very unfavorable case of Mn doping at the Fe I site.

  11. Microwave absorption of gamma'-Fe2.6 Ni1.4N nanoparticles derived from nitriding counterpart precursor.

    PubMed

    Huang, H; Wang, F; Lv, B; Xue, F H; Guo, D Y; Park, W J; Lee, W J; Dong, X L

    2012-04-01

    Gamma-Fe2.6Ni1.4 nanoparticles were prepared by the arc-discharge method as the precursor and its nitride counterpart of gamma'-Fe2.6Ni14N nanoparticles was synthesized directly through a thermal ammonolysis reaction at the temperature of 673 K for two hours. The resultant product was identified as a homogeneous ternary nitride with nearly spherical shape and average size of about 60.0 nm. The electromagnetic characteristics of gamma'-Fe2.6Ni1.4N derivant and gamma-Fe2.6Ni1.4 precursor have been studied in the frequency range of 2-18 GHz. Compared with the precursor, gamma'-Fe2.6Ni1.4N nanoparticles exhibits an enhanced electromagnetic absorption property resulted from the increased dielectric loss by nitriding process. The optimal reflection loss (RL) of gamma'-Fe2.6Ni1.4N nanoparticles/paraffin composite can reach -39.9 dB at 5.2 GHz in a thickness of 2.29 mm, and the frequency band corresponding RL < -10 dB is over 2.6-18 GHz in the thickness range of 0.78-4.20 mm. PMID:22849063

  12. Identification of the enzyme responsible for N-acetylation of norfloxacin by Microbacterium sp. Strain 4N2-2.

    PubMed

    Kim, Dae-Wi; Feng, Jinhui; Chen, Huizhong; Kweon, Ohgew; Gao, Yuan; Yu, Li-Rong; Burrowes, Vanessa J; Sutherland, John B

    2013-01-01

    Microbacterium sp. 4N2-2, isolated from a wastewater treatment plant, converts the antibacterial fluoroquinolone norfloxacin to N-acetylnorfloxacin and three other metabolites. Because N-acetylation results in loss of antibacterial activity, identification of the enzyme responsible is important for understanding fluoroquinolone resistance. The enzyme was identified as glutamine synthetase (GS); N-acetylnorfloxacin was produced only under conditions associated with GS expression. The GS gene (glnA) was cloned, and the protein (53 kDa) was heterologously expressed and isolated. Optimal conditions and biochemical properties (K(m) and V(max)) of purified GS were characterized; the purified enzyme was inhibited by Mn(2+), Mg(2+), ATP, and ADP. The contribution of GS to norfloxacin resistance was shown by using a norfloxacin-sensitive Escherichia coli strain carrying glnA derived from Microbacterium sp. 4N2-2. The GS of Microbacterium sp. 4N2-2 was shown to act as an N-acetyltransferase for norfloxacin, which produced low-level norfloxacin resistance. Structural and docking analysis identified potential binding sites for norfloxacin at the ADP binding site and for acetyl coenzyme A (acetyl-CoA) at a cleft in GS. The results suggest that environmental bacteria whose enzymes modify fluoroquinolones may be able to survive in the presence of low fluoroquinolone concentrations. PMID:23104417

  13. Master curve characterization of the fracture toughness behavior in SA508 Gr.4N low alloy steels

    NASA Astrophysics Data System (ADS)

    Lee, Ki-Hyoung; Kim, Min-Chul; Lee, Bong-Sang; Wee, Dang-Moon

    2010-08-01

    The fracture toughness properties of the tempered martensitic SA508 Gr.4N Ni-Mo-Cr low alloy steel for reactor pressure vessels were investigated by using the master curve concept. These results were compared to those of the bainitic SA508 Gr.3 Mn-Mo-Ni low alloy steel, which is a commercial RPV material. The fracture toughness tests were conducted by 3-point bending with pre-cracked charpy (PCVN) specimens according to the ASTM E1921-09c standard method. The temperature dependency of the fracture toughness was steeper than those predicted by the standard master curve, while the bainitic SA508 Gr.3 steel fitted well with the standard prediction. In order to properly evaluate the fracture toughness of the Gr.4N steels, the exponential coefficient of the master curve equation was changed and the modified curve was applied to the fracture toughness test results of model alloys that have various chemical compositions. It was found that the modified curve provided a better description for the overall fracture toughness behavior and adequate T0 determination for the tempered martensitic SA508 Gr.4N steels.

  14. Identification of the Enzyme Responsible for N-Acetylation of Norfloxacin by Microbacterium sp. Strain 4N2-2

    PubMed Central

    Kim, Dae-Wi; Feng, Jinhui; Chen, Huizhong; Kweon, Ohgew; Gao, Yuan; Yu, Li-Rong; Burrowes, Vanessa J.

    2013-01-01

    Microbacterium sp. 4N2-2, isolated from a wastewater treatment plant, converts the antibacterial fluoroquinolone norfloxacin to N-acetylnorfloxacin and three other metabolites. Because N-acetylation results in loss of antibacterial activity, identification of the enzyme responsible is important for understanding fluoroquinolone resistance. The enzyme was identified as glutamine synthetase (GS); N-acetylnorfloxacin was produced only under conditions associated with GS expression. The GS gene (glnA) was cloned, and the protein (53 kDa) was heterologously expressed and isolated. Optimal conditions and biochemical properties (Km and Vmax) of purified GS were characterized; the purified enzyme was inhibited by Mn2+, Mg2+, ATP, and ADP. The contribution of GS to norfloxacin resistance was shown by using a norfloxacin-sensitive Escherichia coli strain carrying glnA derived from Microbacterium sp. 4N2-2. The GS of Microbacterium sp. 4N2-2 was shown to act as an N-acetyltransferase for norfloxacin, which produced low-level norfloxacin resistance. Structural and docking analysis identified potential binding sites for norfloxacin at the ADP binding site and for acetyl coenzyme A (acetyl-CoA) at a cleft in GS. The results suggest that environmental bacteria whose enzymes modify fluoroquinolones may be able to survive in the presence of low fluoroquinolone concentrations. PMID:23104417

  15. Conversion of 4-N,N-dimethylamino-4’-N’-methyl-stilbazolium tosylate (DAST) from a Simple Optical Material to a Versatile Optoelectronic Material

    PubMed Central

    Xu, Xiangdong; Sun, Ziqiang; Fan, Kai; Jiang, Yadong; Huang, Rui; Wen, Yuejiang; He, Qiong; Ao, Tianhong

    2015-01-01

    4-N,N-dimethylamino-4’-N’-methyl-stilbazolium tosylate (DAST) is an important optical material, but its poor conductivity limits applications in devices. To tackle this problem, we designed, prepared, and systematically investigated novel binary composite films that are composed of two-dimensional (2D) DAST and 2D graphene. Results indicate that both electrical and optical properties of DAST can be significantly improved by graphene addition. The negative steric effects of big DAST molecules that greatly trouble ex-situ synthesis can be efficiently overcome by in-situ synthesis, thus leading to better film quality and higher physical properties. Consequently, the in-situ composite film exhibits a low sheet resistance of 7.5 × 106 ohm and high temperature coefficient of resistance of −2.79% K−1, close to the levels of the most important bolometric materials for uncooled infrared detectors. Particularly, a new low temperature reduction of graphene oxide induced by DAST, which is further enhanced by in-situ process, was discovered. This work presents valuable information about the DAST–graphene composite films, their chemical structures, mechanisms, physical properties, and comparison on in-situ and ex-situ syntheses of graphene–based composites, all of which will be helpful for not only theoretically studying the DAST and graphene materials and expanding their applications, but also for seeking new optoelectronic sensitive materials. PMID:26192068

  16. A novel one-step strategy toward ZnMn2O4/N-doped graphene nanosheets with robust chemical interaction for superior lithium storage

    NASA Astrophysics Data System (ADS)

    Wang, Dong; Zhou, Weiwei; Zhang, Yong; Wang, Yali; Wu, Gangan; Yu, Kun; Wen, Guangwu

    2016-01-01

    Ingenious hybrid electrode design, especially realized with a facile strategy, is appealing yet challenging for electrochemical energy storage devices. Here, we report the synthesis of a novel ZnMn2O4/N-doped graphene (ZMO/NG) nanohybrid with sandwiched structure via a facile one-step approach, in which ultrafine ZMO nanoparticles with diameters of 10-12 nm are well dispersed on both surfaces of N-doped graphene (NG) nanosheets. Note that one-step synthetic strategies are rarely reported for ZMO-based nanostructures. Systematical control experiments reveal that the formation of well-dispersed ZMO nanoparticles is not solely ascribed to the restriction effect of the functional groups on graphene oxide (GO), but also to the presence of ammonia. Benefitting from the synergistic effects and robust chemical interaction between ZMO nanoparticles and N-doped graphene nanosheets, the ZMO/NG hybrids deliver a reversible capacity up to 747 mAh g-1 after 200 cycles at a current density of 500 mA g-1. Even at a high current density of 3200 mA g-1, an unrivaled capacity of 500 mAh g-1 can still be retained, corroborating the good rate capability.

  17. A novel one-step strategy toward ZnMn2O4/N-doped graphene nanosheets with robust chemical interaction for superior lithium storage.

    PubMed

    Wang, Dong; Zhou, Weiwei; Zhang, Yong; Wang, Yali; Wu, Gangan; Yu, Kun; Wen, Guangwu

    2016-01-29

    Ingenious hybrid electrode design, especially realized with a facile strategy, is appealing yet challenging for electrochemical energy storage devices. Here, we report the synthesis of a novel ZnMn2O4/N-doped graphene (ZMO/NG) nanohybrid with sandwiched structure via a facile one-step approach, in which ultrafine ZMO nanoparticles with diameters of 10-12 nm are well dispersed on both surfaces of N-doped graphene (NG) nanosheets. Note that one-step synthetic strategies are rarely reported for ZMO-based nanostructures. Systematical control experiments reveal that the formation of well-dispersed ZMO nanoparticles is not solely ascribed to the restriction effect of the functional groups on graphene oxide (GO), but also to the presence of ammonia. Benefitting from the synergistic effects and robust chemical interaction between ZMO nanoparticles and N-doped graphene nanosheets, the ZMO/NG hybrids deliver a reversible capacity up to 747 mAh g(-1) after 200 cycles at a current density of 500 mA g(-1). Even at a high current density of 3200 mA g(-1), an unrivaled capacity of 500 mAh g(-1) can still be retained, corroborating the good rate capability. PMID:26658114

  18. Macrocyclic Se4N2[7,7]ferrocenophane and Se2N[10]ferrocenophane containing benzyl unit: synthesis, complexation, crystal structures, electrochemical and optical properties.

    PubMed

    Qu, Jian; Song, Yinglin; Ji, Wei; Jing, Su; Zhu, Dunru; Huang, Wei; Zheng, Mengxi; Li, Yanle; Ma, Jing

    2016-02-28

    Two novel macrocyclic polyselena[n]ferrocenophanes containing a pendent benzyl unit, 20-membered Se4N2[7,7]ferrocenophane (L1) and 10-membered Se2N[10]ferrocenophane (L2), were designed and synthesized. The reaction of L1 with two molar amounts of metal salts (M = Cu(+), Cu(2+), Pd(2+) and Hg(2+)) led to six dimetallic complexes 1-6. A crystallographic study revealed that each metal center in 1-5 was tetracoordinated to two selenium atoms from different ferrocene units, one aliphatic nitrogen atom and one co-ligand. The structures of the complexes contain a two-fold axis perpendicular to the molecular plane with two pendant benzyl moieties in an anti-conformation. Macrocycle L1 gives significant electrochemical, linear and third-order nonlinear optical responses to Cu(2+) and Hg(2+). The DFT/B3LYP calculations of 4 demonstrated a small HOMO-LUMO energy gap and delocalization of the π-electron cloud in the frontier molecular orbitals, which led to the enhancement of molecular NLO properties after complexation. The results show that the oxidation state of the ferrocene unit is accompanied by significant differences in the corresponding absorption spectra and third-order NLO properties. PMID:26790582

  19. Microwave assisted synthesis of copper oxide and its application in electrochemical sensing

    NASA Astrophysics Data System (ADS)

    Felix, S.; Bala Praveen Chakkravarthy, R.; Nirmala Grace, A.

    2015-02-01

    Copper oxide nanopowders were prepared using copper acetate as the precursor and polyethylene glycol (PEG) as stabilizer in ethanol medium. The mixture containing copper acetate, sodium hydroxide and PEG was irradiated with microwave and nanometric copper oxide particles were formed within 8 min. The prepared nanoparticles were characterized using x-ray diffraction, UV-vis spectroscopy and scanning electron microscopy. The average particle size was found to be ~ 4 nm. This was used to modify glassy carbon electrode with PVDF & DMF as binder and used for sensing of carbohydrates (glucose and sucrose) and H2O2. The copper oxide nanoparticles showed excellent sensitivity in the range of 0.1 mM to 1 mM when choronoamperometry was carried out at 0.6 V Vs. Ag/AgCl. The observed sensitivity is much higher when compared with conventional micron sized copper oxide particles.

  20. Zirconium oxidation on the atomic scale.

    PubMed

    Hudson, Daniel; Cerezo, Alfred; Smith, George D W

    2009-04-01

    Zirconium alloys are used in the nuclear industry as fuel rod cladding. They are chosen for this role because of their good mechanical properties and low thermal neutron absorption. Oxidation of these alloys by coolant is one of the chief limiting factors of the fuel burn-up efficiency. The aim of the present study is to understand these oxidation mechanisms. As a first step, a fundamental study of the oxidation of commercially pure zirconium has been conducted using the 3D atom probe (3DAP). The current generation of 3DAPs allows both voltage and laser pulsing, providing data sets of many millions of ions. According to the literature the only stable oxide of zirconium is ZrO(2). However, the 3DAP shows that an initial layer a few nanometres thick forms with a composition of ZrO(1-)(x) when subjected to light oxidation. This result confirms and extends the work of Wadman et al. [Colloque de Physique 50 (1989) C8 303; Journal de Physique, 11 (1988) C6 49] and Wadman and Andrén [in: C.M. Euchen, A.M. Garde (Eds.), Zirconium in the Nuclear Industry: Ninth Symposium, ASTM STP 1132, ASTM, USA, 1991, p. 461], who used 1DAP techniques, obtaining reduced data sets. Segregation of hydrogen to the metal-oxide interface and a distinct ZrH phase were observed in this study. A novel kinetics study of the room temperature oxidation of zirconium showed the ZrO layer to be non-protective over the time period investigated (up to 1h). PMID:19101084

  1. Preparation, structure and photoluminescence properties of Eu{sup 2+} and Ce{sup 3+}-doped SrYSi{sub 4}N{sub 7}

    SciTech Connect

    Li, Y.Q. . E-mail: y.q.li@tue.nl; Fang, C.M.; With, G. de; Hintzen, H.T. . E-mail: h.t.hintzen@tue.nl

    2004-12-01

    Undoped and Eu{sup 2+} or Ce{sup 3+}-doped SrYSi{sub 4}N{sub 7} were synthesized by solid-state reaction method at 1400-1660{sup o}C under nitrogen/hydrogen atmosphere. The crystal structure was refined from the X-ray powder diffraction data by the Rietveld method. SrYSi{sub 4}N{sub 7} and EuYSi{sub 4}N{sub 7}, being isotypic with the family of compounds MYbSi{sub 4}N{sub 7} (M=Sr, Eu, Ba) and BaYSi{sub 4}N{sub 7,} crystallize with the hexagonal symmetry: space group P6{sub 3}mc (No. 186), Z=2, a=6.0160 (1)A, c=9.7894 (1)A, V=306.83(3)A{sup 3}; and a=6.0123 (1)A, c=9.7869 (1)A, V=306.37(1)A{sup 3}, respectively. Photoluminescence properties have been studied for Sr{sub 1-x}Eu{sub x}YSi{sub 4}N{sub 7} (x=0-1) and SrY{sub 1-x}Ce{sub x}Si{sub 4}N{sub 7} (x=0-0.03) at room temperature. Eu{sup 2+}-doped SrYSi{sub 4}N{sub 7} shows a broad yellow emission band peaking around 548-570nm, while Ce{sup 3+}-doped SrYSi{sub 4}N{sub 7} exhibits a blue emission band with a maximum at about 450nm. SrYSi{sub 4}N{sub 7}:Eu{sup 2+} can be very well excited by 390nm radiation, which makes this material attractive as conversion phosphor for LED lighting applications.

  2. The mitigating effect of calcification-dependent of utilization of inorganic carbon of Chara vulgaris Linn on NH4-N toxicity.

    PubMed

    Wang, Heyun; Ni, Leyi; Xie, Ping

    2013-09-01

    Increased ammonium (NH4-N) concentrations in water bodies have been reported to adversely affect the dominant species of submersed vegetation in meso-eutrophic waters worldwide. However calcareous plants were lowly sensitive to NH4-N toxicity. In order to make clear the function of calcification in the tolerance of calcareous plants to NH4-N stress, we studied the effects of increased HCO3(-) and additional NH4-N on calcification and utilization of dissolve inorganic carbon (DIC) in Chara vulgaris Linn in a 7-d sub-acute experiment (light:dark 12:12h) carried out in an open experimental system in lab. Results revealed that calcification was dependent of utilization of dissolve inorganic carbon. Additional HCO3(-) significantly decreased the increase of pH while additional NH4-N did not. And additional HCO3(-) significantly improved calcification while NH4-N did in versus in relation to the variation of DIC concentration. However, addition of both HCO3(-) and NH4-N increased utilization of DIC. This resulted in calcification to utilization of DIC ratio decreased under additional NH4-N condition while increased under additional HCO3(-) conditions in response to the variation of solution pH. In the present study, external HCO3(-) decreased the increase of solution pH by increasing calcification, which correspondingly mitigated the toxic effect of high NH4-N. And we argue that the mitigating effect of increased HCO3(-) on NH4-N toxicity is dependent of plant calcification, and it is a positive feedback mechanism, potentially leading to the dominance of calcareous plants in meso-eutrophic water bodies. PMID:23755986

  3. Molecular characterization of an influenza A virus (H4N2) isolated from waterfowl habitats in the State of Mexico.

    PubMed

    Ornelas-Eusebio, Erika; Obregón-Ascencio, Alejandro; Chávez-Maya, Fernando; García-Espinosa, Gary

    2015-03-01

    Wild waterfowl and their habitats are the main reservoirs of influenza A virus (IAV) mainly during the breeding season and prior to migration. This study describes the molecular characterization of an IAV isolated from 240 water samples of a small wetland during non-breeding season of migratory wild ducks in the State of Mexico, Mexico. The results showed that the virus belongs to the H4N2 subtype and each of its eight segments of the viral genome has similarity to IAV isolated from ducks in North America. This study suggests that IAV can be isolated from small wetland during non-breeding season of migrating waterfowl. PMID:25482497

  4. Electronic structure and pair potential energy analysis of 4-n-methoxy-4'-cyanobiphenyl: A nematic liquid crystal

    NASA Astrophysics Data System (ADS)

    Sharma, Dipendra; Dwivedi, M. K.; Tiwari, S. N.

    2016-05-01

    Electronic structure properties of 4-n-methoxy-4'-cyanobiphenyl, a pure nematic liquid crystal have been examined using an ab‒initio, HF/6‒31G(d,p) technique with GAMESS program. Conformational and charge distribution analysis have been carried out. MEP, HOMO and LUMO surfaces have been scanned. Ionization potential, electron affinity, electronegativity, global hardness and softness of the liquid crystal molecule have been calculated. Further, stacking, side by side and end to end interactions between a molecular pair have been evaluated. Results have been used to elucidate the physico-chemical and liquid crystalline properties of the system.

  5. Interaction peculiarities of 5,10,15,20-tetrakis(4-N-methylpyridil) tetra iodide porphyrin with albumin

    NASA Astrophysics Data System (ADS)

    Lebedeva, N. Sh.; Malkova, E. A.; Popova, T. E.; Kutyrev, A. E.; Syrbu, S. A.; Parfenyuk, E. V.; Vyugin, A. I.

    2014-01-01

    In present work interactions of bovine serum albumin with 5,10,15,20-tetrakis(4-N-methylpyridil) tetra iodide porphyrin have been studied by electron absorption and fluorescence spectroscopy. The studies were carried out in aqueous media at different pH and in water-dimethylformamide mixtures containing up to 0.19 M of the organic solvent. It has been demonstrated that the porphyrin forms stable complexes with BSA in which the porphyrin is located subdomains IB and IIA. The stability constants of the complexes is practically independent of pH.

  6. Photophysics of 4- N, N-dimethylamino cinnamaldehyde in AOT reverse micelles and exploration of its position and orientation

    NASA Astrophysics Data System (ADS)

    Panja, Subhasis; Chakravorti, Sankar

    2003-01-01

    An attempt has been made in this Letter to locate the position and orientation of 4- N, N-dimethylamino cinnamaldehyde (DMACA) inside sodium bis(2-ethylhexyl) sulfosuccinate (AOT)- n-heptane reverse micelle based on change in photophysical properties of DMACA compared to that in n-heptane. It has been proposed that the possibility of finding the donor moiety inside the small water pool of reverse micelle is maximum while the acceptor group straddles in the remaining part of the reverse micelle. The micropolarity in the vicinity of the donor moiety has been computed in terms of dielectric constant with varying water pool size.

  7. 3D Visualization of the Iron Oxidation State in FeO/Fe3O4 Core-Shell Nanocubes from Electron Energy Loss Tomography.

    PubMed

    Torruella, Pau; Arenal, Raúl; de la Peña, Francisco; Saghi, Zineb; Yedra, Lluís; Eljarrat, Alberto; López-Conesa, Lluís; Estrader, Marta; López-Ortega, Alberto; Salazar-Alvarez, Germán; Nogués, Josep; Ducati, Caterina; Midgley, Paul A; Peiró, Francesca; Estradé, Sonia

    2016-08-10

    The physicochemical properties used in numerous advanced nanostructured devices are directly controlled by the oxidation states of their constituents. In this work we combine electron energy-loss spectroscopy, blind source separation, and computed tomography to reconstruct in three dimensions the distribution of Fe(2+) and Fe(3+) ions in a FeO/Fe3O4 core/shell cube-shaped nanoparticle with nanometric resolution. The results highlight the sharpness of the interface between both oxides and provide an average shell thickness, core volume, and average cube edge length measurements in agreement with the magnetic characterization of the sample. PMID:27383904

  8. Temperature profile of a stoichiometric ch4/N2O flame from laser excited fluorescence measurements on OH

    SciTech Connect

    Anderson, W.R.; Decker, L.J.; Kotlar, A.J.

    1982-07-01

    The temperature profile of a stoichiometric CH/sub 4//N/sub 2/O flame over a porous plug, atmospheric-pressure burner has been measured using laser excited fluorescence of the OH radical. The technique of rotationally resolved fluorescence excitation scans was extended to the (1,1) vibrational band of the A doublet sigma plus - X doublet pi system to avoid problems of laser beam depletion and self-absorption encountered by this group and previous workers using the (O,O) band. Absorption spectra were obtained in addition to fluorescence spectra. A least squares curve-fitting technique which accounts for the various types of line broadening was developed and applied to two absorption lines in the (O,O) band. The resulting temperature profile is compared to that from fluorescence data reduced using Boltzmann plots. The more complicated curve-fitting approach was later applied to five lines in the spectrum using several combinations of fluorescence and absorption data. Results of all the aforementioned methods were compared to those from OH band reversal and N2 vibrational Raman measurements at the same point in the post flame gases. Excellent agreement was achieved. The results are discussed with emphasis on both the fluorescence diagnostics and the characteristics of the CH/sub 4//N/sub 2/O flame on the porous-plug burner.

  9. Microstructural Aspects of Irradiation Damage in A508 Gr 4N Forging Steel: Composition and Flux Effects

    SciTech Connect

    M.G. Burke; R.J. Stofanak; J.M. Hyde; C.A. English; W.L. Server

    2002-10-09

    Neutron irradiation can promote significant changes in the microstructure and associated mechanical properties of low alloy steels. In particular, irradiation can induce the formation of non-equilibrium phases and segregation, which may lead to a degradation in toughness. In this study, the microstructural changes caused by neutron irradiation have been characterized in A508 Grade (Gr) 4N-type steels ({approx}3.5% Ni) using a variety of state-of-the-art analytical techniques including 3D-Atom Probe Field-Ion Microscopy and Small Angle Neutron Scattering, along with post-irradiation annealing studies combining Positron Annihilation Lineshape Analysis and hardness measurements. Important differences between conventional and ''superclean'' A508 Gr 4N steel have been identified in this investigation. The data indicate that Ni is not the controlling factor in the irradiation damage behavior of these materials; rather, the Mn content of the steel is a dominant factor in the irradiation-induced microstructural development of solute-related hardening features.

  10. Inhibitory effect of high NH4(+)-N concentration on anaerobic biotreatment of fresh leachate from a municipal solid waste incineration plant.

    PubMed

    Liu, Zhao; Dang, Yan; Li, Caihua; Sun, Dezhi

    2015-09-01

    Fresh leachate from municipal solid waste (MSW) incineration plants generally contains extremely high NH4(+)-N concentration which could inhibit the bioactivity of microorganisms. The inhibitory effect of high NH4(+)-N concentration on anaerobic biotreatment of fresh leachate from a MSW incineration plant in China has been investigated in this study. The inhibition processes was studied by both static tests and a laboratory-scale expanded granular sludge bed (EGSB) reactor. The specific methanogenic activity (SMA) of the microorganisms in anaerobic granular sludge was inhibited with the NH4(+)-N concentration increasing to 1000mg/L in static tests. As well the chemical oxygen demand (COD) removal efficiency and the methane yield decreased in the EGSB reactor, while the volatile fatty acids (VFAs) accumulated and extracellular polymeric substances (EPS) of the anaerobic granular sludge increased with NH4(+)-N concentration rising to 1000mg/L, without any rebounding during 30days of operation. Decreasing NH4(+)-N concentration to 500mg/L in influent, the COD removal efficiency recovered to about 85% after 26days. 1000mg/L of NH4(+)-N in leachate was suggested to be the inhibition threshold in EGSB reactor. High-throughput sequencing results showed little changes in microbial communities of the sludge for a high NH4(+)-N concentration, indicating that the survival of most microorganisms was not affected under such a condition. It inhibited the bioactivity of the microorganisms, resulting in decrease of the COD removal efficiency. PMID:26139135

  11. Self-limiting and complete oxidation of silicon nanostructures produced by laser ablation in water

    NASA Astrophysics Data System (ADS)

    Vaccaro, L.; Popescu, R.; Messina, F.; Camarda, P.; Schneider, R.; Gerthsen, D.; Gelardi, F. M.; Cannas, M.

    2016-07-01

    Oxidized Silicon nanomaterials produced by 1064 nm pulsed laser ablation in deionized water are investigated. High-resolution transmission electron microscopy coupled with energy dispersive X-ray spectroscopy allows to characterize the structural and chemical properties at a sub-nanometric scale. This analysis clarifies that laser ablation induces both self-limiting and complete oxidation processes which produce polycrystalline Si surrounded by a layer of SiO2 and amorphous fully oxidized SiO2, respectively. These nanostructures exhibit a composite luminescence spectrum which is investigated by time-resolved spectroscopy with a tunable laser excitation. The origin of the observed luminescence bands agrees with the two structural typologies: Si nanocrystals emit a μs-decaying red band; defects of SiO2 give rise to a ns-decaying UV band and two overlapping blue bands with lifetime in the ns and ms timescale.

  12. Magnetic iron oxide nanoparticles as drug delivery system in breast cancer

    NASA Astrophysics Data System (ADS)

    Marcu, A.; Pop, S.; Dumitrache, F.; Mocanu, M.; Niculite, C. M.; Gherghiceanu, M.; Lungu, C. P.; Fleaca, C.; Ianchis, R.; Barbut, A.; Grigoriu, C.; Morjan, I.

    2013-09-01

    Present work was focused on producing improved iron oxide nanoparticles for targeted drug delivery in breast cancer. Nanometric-sized iron oxide particles were synthesized by laser pyrolysis and were morphologically/structurally characterized. These new nanoparticles were compared with some commercial, chemically prepared iron oxide ones. Cytotoxicity and the anti-proliferation effects of nanoparticles were tested in vitro on the breast adenocarcinoma cell line MCF-7. Nanoparticles were further coated with the antracyclinic antibiotic Violamycine B1 and tested for the anti-tumor effect on MCF-7 cells. The nanoparticles produced by us seem more effective in vitro than the commercial ones, with respect to cellular uptake and VB1 delivery. Violamycine B1 bound on nanoparticles is as efficient as the free form, but is better delivered into tumor cells.

  13. Continuously controlled optical band gap in oxide semiconductor thin films

    DOE PAGESBeta

    Herklotz, Andreas; Rus, Stefania Florina; Ward, Thomas Zac

    2016-02-02

    The optical band gap of the prototypical semiconducting oxide SnO2 is shown to be continuously controlled through single axis lattice expansion of nanometric films induced by low-energy helium implantation. While traditional epitaxy-induced strain results in Poisson driven multidirectional lattice changes shown to only allow discrete increases in bandgap, we find that a downward shift in the band gap can be linearly dictated as a function of out-of-plane lattice expansion. Our experimental observations closely match density functional theory that demonstrates that uniaxial strain provides a fundamentally different effect on the band structure than traditional epitaxy-induced multiaxes strain effects. In conclusion, chargemore » density calculations further support these findings and provide evidence that uniaxial strain can be used to drive orbital hybridization inaccessible with traditional strain engineering techniques.« less

  14. Continuously Controlled Optical Band Gap in Oxide Semiconductor Thin Films.

    PubMed

    Herklotz, Andreas; Rus, Stefania Florina; Ward, Thomas Zac

    2016-03-01

    The optical band gap of the prototypical semiconducting oxide SnO2 is shown to be continuously controlled through single axis lattice expansion of nanometric films induced by low-energy helium implantation. While traditional epitaxy-induced strain results in Poisson driven multidirectional lattice changes shown to only allow discrete increases in bandgap, we find that a downward shift in the band gap can be linearly dictated as a function of out-of-plane lattice expansion. Our experimental observations closely match density functional theory that demonstrates that uniaxial strain provides a fundamentally different effect on the band structure than traditional epitaxy-induced multiaxes strain effects. Charge density calculations further support these findings and provide evidence that uniaxial strain can be used to drive orbital hybridization inaccessible with traditional strain engineering techniques. PMID:26836282

  15. Reconstructing fluid-flow events in Lower-Triassic sandstones of the eastern Paris Basin by elemental tracing and isotopic dating of nanometric illite crystals

    NASA Astrophysics Data System (ADS)

    Blaise, Thomas; Clauer, Norbert; Cathelineau, Michel; Boiron, Marie-Christine; Techer, Isabelle; Boulvais, Philippe

    2016-03-01

    Lower- to Middle-Triassic sandstones from eastern Paris Basin were buried to a maximum depth of 2500 m at a paleo-temperature of about 100 °C. They contain extensive amounts of authigenic platy and filamentous illite particles similar to those reported in reservoirs generally buried at 3000 to -5000 m and subjected to temperatures of 120 to -150 °C. To evaluate this unexpected occurrence, such sandstones were collected from drill cores between 1825 and 2000 m depth, and nanometric-sized sub-fractions were separated. The illite crystals were identified by XRD, observed by SEM and TEM, analyzed for their major, trace, rare-earth elements and oxygen isotope compositions, and dated by K-Ar and Rb-Sr. Illite particles display varied growth features in the rock pore-space and on authigenic quartz and adularia that they postdate. TEM-EDS crystal-chemical in situ data show that the illite lath/fiber and platelet morphologies correspond at least to two populations with varied interlayer charges: between 0.7 and 0.9 for the former and between 0.8 and 1.0 for the latter, the Fe/Fe + Mg ratio being higher in the platelets. Except for the deeper conglomerate, the PAAS-normalized REE patterns of the illite crystals are bell-shaped, enriched in middle REEs. Ca-carbonates and Ca-phosphates were detected together with illite in the separates. These soluble components yield 87Sr/86Sr ratios that are not strictly in chemical equilibrium with the illite crystals, suggesting successive fluids flows with different chemical compositions. The K-Ar data of finer <0.05 μm illite separates confirm two crystallization events at 179.4 ± 4.5 and 149.4 ± 2.5 Ma during the Early and Late Jurassic. The slightly coarser fractions contain also earlier crystallized or detrital K-bearing minerals characterized by lower δ18O values. The δ18O of the finest authigenic illite separates tends to decrease slightly with depth, from 18.2 (±0.2) to 16.3 (±0.2)‰, suggesting different but

  16. Electronic structure and magnetism in g-C{sub 4}N{sub 3} controlled by strain engineering

    SciTech Connect

    Liu, L. Z.; Liu, X. X.; Wu, X. L. E-mail: paul.chu@cityu.edu.hk; Chu, Paul K. E-mail: paul.chu@cityu.edu.hk

    2015-03-30

    Regulation of magnetism and half-metallicity has attracted much attention because of its potential in spintronics. The magnetic properties and electronic structure of graphitic carbon nitride (g-C{sub 4}N{sub 3}) with external strain are determined theoretically based on the density function theory and many-body perturbation theory (G{sub 0}W{sub 0}). Asymmetric deformation induced by uniaxial strain not only regulates the magnetic characteristics but also leads to a transformation from half-metallicity to metallicity. However, this transition cannot occur in the structure with symmetric deformation induced by biaxial strain. Our results suggest the use of strain engineering in metal-free spintronics applications.

  17. Feature Scale Simulation of PECVD of SiO2 in SiH4/N2O Mixture

    NASA Astrophysics Data System (ADS)

    Liu, Xuan; Ge, Jie; Yang, Yi; Song, Yixu; Ren, Tianling

    2014-04-01

    In this paper, to simulate the process of PECVD (plasma enhanced chemical vapor deposition) of SiO2, the plasma chemistry and plasma density of SiH4/N2O mixture have been studied with an inductive coupled plasma model, and the level set methodology has been used to obtain the feature scale variation during the process. In this simulation, the goal is to fill a trench. We studied how ion sputtering and chamber pressure affect the feature scale model. After the simulation, we found that the trench will close up at the top after a few steps, and if we add the ion sputtering into the surface reactions, the trench top will close up a little later. When the chamber pressure is improved, the plasma density will increase, so the trench top will close up earlier. In semiconductor device manufacture, people can control the trench's feature scale through adjusting these two parameters.

  18. Two-dimensional shape memory graphene oxide

    PubMed Central

    Chang, Zhenyue; Deng, Junkai; Chandrakumara, Ganaka G.; Yan, Wenyi; Liu, Jefferson Zhe

    2016-01-01

    Driven by the increasing demand for micro-/nano-technologies, stimuli-responsive shape memory materials at nanoscale have recently attracted great research interests. However, by reducing the size of conventional shape memory materials down to approximately nanometre range, the shape memory effect diminishes. Here, using density functional theory calculations, we report the discovery of a shape memory effect in a two-dimensional atomically thin graphene oxide crystal with ordered epoxy groups, namely C8O. A maximum recoverable strain of 14.5% is achieved as a result of reversible phase transition between two intrinsically stable phases. Our calculations conclude co-existence of the two stable phases in a coherent crystal lattice, giving rise to the possibility of constructing multiple temporary shapes in a single material, thus, enabling highly desirable programmability. With an atomic thickness, excellent shape memory mechanical properties and electric field stimulus, the discovery of a two-dimensional shape memory graphene oxide opens a path for the development of exceptional micro-/nano-electromechanical devices. PMID:27325441

  19. Two-dimensional shape memory graphene oxide

    NASA Astrophysics Data System (ADS)

    Chang, Zhenyue; Deng, Junkai; Chandrakumara, Ganaka G.; Yan, Wenyi; Liu, Jefferson Zhe

    2016-06-01

    Driven by the increasing demand for micro-/nano-technologies, stimuli-responsive shape memory materials at nanoscale have recently attracted great research interests. However, by reducing the size of conventional shape memory materials down to approximately nanometre range, the shape memory effect diminishes. Here, using density functional theory calculations, we report the discovery of a shape memory effect in a two-dimensional atomically thin graphene oxide crystal with ordered epoxy groups, namely C8O. A maximum recoverable strain of 14.5% is achieved as a result of reversible phase transition between two intrinsically stable phases. Our calculations conclude co-existence of the two stable phases in a coherent crystal lattice, giving rise to the possibility of constructing multiple temporary shapes in a single material, thus, enabling highly desirable programmability. With an atomic thickness, excellent shape memory mechanical properties and electric field stimulus, the discovery of a two-dimensional shape memory graphene oxide opens a path for the development of exceptional micro-/nano-electromechanical devices.

  20. Two-dimensional shape memory graphene oxide.

    PubMed

    Chang, Zhenyue; Deng, Junkai; Chandrakumara, Ganaka G; Yan, Wenyi; Liu, Jefferson Zhe

    2016-01-01

    Driven by the increasing demand for micro-/nano-technologies, stimuli-responsive shape memory materials at nanoscale have recently attracted great research interests. However, by reducing the size of conventional shape memory materials down to approximately nanometre range, the shape memory effect diminishes. Here, using density functional theory calculations, we report the discovery of a shape memory effect in a two-dimensional atomically thin graphene oxide crystal with ordered epoxy groups, namely C8O. A maximum recoverable strain of 14.5% is achieved as a result of reversible phase transition between two intrinsically stable phases. Our calculations conclude co-existence of the two stable phases in a coherent crystal lattice, giving rise to the possibility of constructing multiple temporary shapes in a single material, thus, enabling highly desirable programmability. With an atomic thickness, excellent shape memory mechanical properties and electric field stimulus, the discovery of a two-dimensional shape memory graphene oxide opens a path for the development of exceptional micro-/nano-electromechanical devices. PMID:27325441

  1. A Termolecular Reaction Mechanism for Nitrogen Incorporation in Aerosol Produced by Far UV Irradiation of CH4-N2 Atmospheres

    NASA Astrophysics Data System (ADS)

    Hicks, R. K.; Trainer, M. G.; Jimenez, J. L.; Yung, Y. L.; Toon, O. B.; Tolbert, M. A.

    2012-12-01

    Results from the Aerosol Collector and Pyrolyser located onboard the Huygens lander reveal the presence of carbon and nitrogen in Titan's aerosols. Nitrogen incorporation is thought to be initiated by energy sources strong enough to break the N-N triple bond of molecular nitrogen (9.8eV). Such energy sources include extreme UV photons (λ <120 nm) and electrons from Saturn's magnetosphere. Less energetic photons in the far UV (120-200 nm) penetrate to the stratosphere of Titan and are only expected to affect hydrocarbon photochemistry there. However, recent results from our laboratory indicate a surprising amount of nitrogen incorporation- up to 16% by mass- in Titan aerosol analog produced by photochemistry initiated by far UV irradiation of CH4/N2 mixtures. The termolecular reaction CH + N2 + M --> HCN2 has been proposed to account for this observation. Here, we test this hypothesis by using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) to measure the mass loading and chemical composition of aerosol produced at a range of pressures from roughly 0.1 to 1 atm. Even though these gas mixtures spanned an order of magnitude in pressure, they experienced the same residence time in the photochemical chamber and had the same methane optical depth. We report a 150% increase in aerosol mass loading across the range of pressures studied, indicating that the mechanism controlling the total mass produced depends on pressure. We also report an overall increase with pressure in the ratio of nitrogen-bearing organic species to hydrocarbon-only species. These observations support the hypothesis that the termolecular reaction above is responsible for the incorporation of nitrogen into Titan aerosol analog produced from CH4/N2 gas mixtures irradiated in the far UV. These findings have implications for our understanding of the evolution of Titan's atmosphere, and the atmospheric synthesis of biologically relevant N-containing molecules.

  2. Shedding Light on Avian Influenza H4N6 Infection in Mallards: Modes of Transmission and Implications for Surveillance

    PubMed Central

    VanDalen, Kaci K.; Franklin, Alan B.; Mooers, Nicole L.; Sullivan, Heather J.; Shriner, Susan A.

    2010-01-01

    Background Wild mallards (Anas platyrhychos) are considered one of the primary reservoir species for avian influenza viruses (AIV). Because AIV circulating in wild birds pose an indirect threat to agriculture and human health, understanding the ecology of AIV and developing risk assessments and surveillance systems for prevention of disease is critical. Methodology/Principal Findings In this study, mallards were experimentally infected with an H4N6 subtype of AIV by oral inoculation or contact with an H4N6 contaminated water source. Cloacal swabs, oropharyngeal swabs, fecal samples, and water samples were collected daily and tested by real-time RT-PCR (RRT-PCR) for estimation of viral shedding. Fecal samples had significantly higher virus concentrations than oropharyngeal or cloacal swabs and 6 month old ducks shed significantly more viral RNA than 3 month old ducks regardless of sample type. Use of a water source contaminated by AIV infected mallards, was sufficient to transmit virus to naïve mallards, which shed AIV at higher or similar levels as orally-inoculated ducks. Conclusions Bodies of water could serve as a transmission pathway for AIV in waterfowl. For AIV surveillance purposes, water samples and fecal samples appear to be excellent alternatives or additions to cloacal and oropharyngeal swabbing. Furthermore, duck age (even within hatch-year birds) may be important when interpreting viral shedding results from experimental infections or surveillance. Differential shedding among hatch-year mallards could affect prevalence estimates, modeling of AIV spread, and subsequent risk assessments. PMID:20877466

  3. Influence of the substitution of the manganese for iron in the Fe sub 4 N lattice on particle formation and magnetic properties

    SciTech Connect

    Siberchicot, B.; Matar, S.F.; Fournes, L.; Demazeau, G.; Hagenmuller, P. )

    1990-01-01

    Moessbauer resonance studies on Mn-substituted Fe{sub 4}N show that manganese occupies statistically both iron sites in the lattice. Replacement of Fe by Mn modifies the crystal growth process of Fe{sub 4}N magnetic particles and leads to improvement of the extrinsic magnetic properties, i.e., H{sub c} and {sigma}{sub r}/{sigma}{sub s}, required for magnetic recording applications.

  4. Structural characterisation of human galectin-4 N-terminal carbohydrate recognition domain in complex with glycerol, lactose, 3'-sulfo-lactose, and 2'-fucosyllactose.

    PubMed

    Bum-Erdene, Khuchtumur; Leffler, Hakon; Nilsson, Ulf J; Blanchard, Helen

    2016-01-01

    Galectin-4 is a tandem-repeat galectin with two distinct carbohydrate recognition domains (CRD). Galectin-4 is expressed mainly in the alimentary tract and is proposed to function as a lipid raft and adherens junction stabilizer by its glycan cross-linking capacity. Galectin-4 plays divergent roles in cancer and inflammatory conditions, either promoting or inhibiting each disease progression, depending on the specific pathological condition. The study of galectin-4's ligand-binding profile may help decipher its roles under specific conditions. Here we present the X-ray structures of human galectin-4 N-terminal CRD (galectin-4N) bound to different saccharide ligands. Galectin-4's overall fold and its core interactions to lactose are similar to other galectin CRDs. Galectin-4N recognises the sulfate cap of 3'-sulfated glycans by a weak interaction through Arg45 and two water-mediated hydrogen bonds via Trp84 and Asn49. When galectin-4N interacts with the H-antigen mimic, 2'-fucosyllactose, an interaction is formed between the ring oxygen of fucose and Arg45. The extended binding site of galectin-4N may not be well suited to the A/B-antigen determinants, α-GalNAc/α-Gal, specifically due to clashes with residue Phe47. Overall, galectin-4N favours sulfated glycans whilst galectin-4C prefers blood group determinants. However, the two CRDs of galectin-4 can, to a less extent, recognise each other's ligands. PMID:26828567

  5. Solid-state combinatorial screening of ARSi4N7:Eu2+ (A = Sr, Ba, Ca; R = Y, La, Lu) phosphors.

    PubMed

    Park, Woon Bae; Son, Kyung Hyun; Singh, Satendra Pal; Sohn, Kee-Sun

    2012-10-01

    A double-ternary combinatorial chemistry (combi-chem) library was visualized in terms of structure, PL intensity, and color chromaticity for a nitride phosphor system, ARSi4N7:Eu(2+) (A = Sr, Ca, Ba; R = Y, La, Lu), so as to obtain a quantitative structure and property relationship (QSPR) in a systematic manner. Most of the samples constituting the double-ternary combi-chem library turned out to have ARSi4N7 structures with a P63mc space group. However, several phases such as Ca2Si5N8 with a Cc space group, LaSi3N5 with a P212121 space group, R6Si11N20O with a P31c space group, etc., coexisted. Aside from the green luminescence from the well-known SrYSi4N7:Eu(2+) and BaYSi4N7:Eu(2+) phosphors, their solid solutions (Sr,Ba)Si4N7:Eu(2+) proved to possess better PL properties. In addition, novel phosphors with an acceptable green PL intensity and color chromaticity were discovered in the ALuSi4N7:Eu(2+) side of the double-ternary combi-chem library. The Ca-rich side did not constitute a single-phase ARSi4N7 structure with a P63mc space group, and therefore the red emission in the Ca-rich side proved to originate from well-known Ca2Si5N8:Eu(2+) phosphors, which resided in the sample as a minor phase. PMID:22920282

  6. Diffusion bonding of the oxide dispersion strengthened steel PM2000

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  7. Transition metal complexes of Vanillin- 4N-(2-pyridyl) thiosemicarbazone (H 2VPT); thermal, structural and spectroscopic studies

    NASA Astrophysics Data System (ADS)

    El-Reash, Gaber Abu; El-Ayaan, Usama; Gabr, I. M.; El-Rachawy, El-Bastawesy

    2010-04-01

    The present work carried out a study on the ligational behavior of the new ligand, Vanillin- 4N-(2-pyridyl) thiosemicarbazone (H 2VPT) 1 towards some transition metal ions namely, Mn 2+, Co 2+, Ni 2+, Cu 2+, Zn 2+,Cd 2+, Hg 2+ and U 6+. These complexes namely [Mn(HVPT)Cl] 2, [Co(VPT)(H 2O)] 2H 2O 3, [Ni(HVPT)Cl(H 2O)] 4, [Cu(HVPT)Cl(H 2O)] 5, [Zn(VPT)(H 2O)]H 2O 6, [Cd(HVPT)Cl(H 2O)] 7, [Hg(VPT)(H 2O)]H 2O 8 and [UO 2(H 2VPT)(OAc) 2]H 2O 9, were characterized by elemental analysis, spectral (IR, 1H NMR and UV-vis) and magnetic moment measurements. The suggested structures were confirmed by applying geometry optimization and conformational analysis. Thermal properties and decomposition kinetics of all compounds are investigated. The interpretation, mathematical analysis and evaluation of kinetic parameters ( E, A, Δ H, Δ S and Δ G) of all thermal decomposition stages have been evaluated using Coats-Redfern equation. ESR spectra of [Cu(HVPT)Cl]H 2O at room temperature show broad signal, indicating spin-exchange interactions between copper(II) ions.

  8. A novel cobalt(II)-selective potentiometric sensor based on p-(4-n-butylphenylazo)calix[4]arene.

    PubMed

    Kumar, Pankaj; Shim, Yoon-Bo

    2009-01-15

    A new poly(vinyl chloride)-based membranes containing p-(4-n-butylphenylazo)calix[4]arene (I) as an electroactive material along with sodiumtetraphenylborate (NaTPB), and dibutyl(butyl)phosphonate in the ratio 10:100:1:200 (I:DBBP:NaTPB:PVC) (w/w) was used to fabricate a new cobalt(II)-selective sensor. It exhibited a working concentration range of 9.2 x 10(-6) to 1.0 x 10(-1)M, with a Nernstian slope of 29.0+/-1.0 mV/decade of activity and the response time of 25s. This sensor shows the detection limit of 4.0 x 10(-6)M. Its potential response remains unaffected of pH in the range, 4.0-7.2, and the cell assembly can be used successfully in partially non-aqueous medium (up to 10%, v/v) without significant change in the slope of working concentration range. The sensor has a lifetime of about 3 months and exhibits excellent selectivity over a number of mono-, bi-, and tri-valent cations including alkali, alkaline earth metal, heavy and transition metal ions. It can be used as an indicator electrode for the end point determination in the potentiometric titration of cobalt ions against ethylenediaminetetraacetic acid (EDTA) as well as for the determination of cobalt ion concentration in real samples. PMID:19064091

  9. Competitive sorption between 17alpha-ethinyl estradiol and bisphenol A/4-n-nonylphenol by soils.

    PubMed

    Li, Jianzhong; Jiang, Lu; Xiang, Xi; Xu, Shuang; Wen, Rou; Liu, Xiang

    2013-06-01

    The sorption of 17alpha-ethinyl estradiol (EE2), bisphenol A (BPA), and 4-n-nonylphenol (NP) in single systems and the sorption of EE2 with different initial aqueous concentrations of BPA or NP were examined using three soils. Results showed that all sorption isotherms were nonlinear and fit the Freundlich model. The degree of nonlinearity was in the order BPA (0.537-0.686) > EE2 (0.705-0.858) > NP (0.875-0.0.951) in single systems. The isotherm linearity index of EE2 sorption calculated by the Freundlich model for Loam, Silt Loam and Silt increased from 0.758, 0.705 and 0.858, to 0.889, 0.910 and 0.969, respectively, when BPA concentration increased from 0 to 1000 microg/L, but the effect of NP was comparably minimal. Additionally, EE2 significantly suppressed the sorption of BPA, but insignificantly suppressed that of NP. These findings can be attributed to the difference of sorption affinity of EE2, NP and BPA on the hard carbon (e.g., black carbon) of soil organic matter that dominated the sorption in the low equilibrium aqueous concentration range of endocrine-disrupting chemicals (EDCs). Competitive sorption among EDCs presents new challenges for predicting the transport and fate of EDCs under the influence of co-solutes. PMID:24191605

  10. Synthesis, characterization and magnetic properties of copper(II) complexes with 4-N-(2‧-pyridylimine)benzoic acid

    NASA Astrophysics Data System (ADS)

    Jiang, Chun-Fang; Liang, Fu-Pei; Li, Yan; Wang, Xiu-Jian; Chen, Zi-Lu; Bian, He-Dong

    2007-10-01

    Four Cu(II) complexes with 4- N-(2'-pyridylimine)benzoic acid ( HL), [Cu(HL) 2] · (ClO 4) 2 ( 1), [Cu(HL) 2(SO 4)] · 3H 2O ( 2), [Cu 2(L) 2Cl 2] n · 3H 2O ( 3), and [Cu 4(L) 2(HL) 2Cl 4] · (CH 3OH) 2 · (ClO 4) 2 ( 4), have been synthesized and structurally characterized by X-ray crystallography. Complexes ( 1) and ( 2) both exhibit a mononuclear structure with a four-coordinated Cu(II) ion by the pyridine- N and imine- N atoms of the ligands for ( 1) and a penta-coordinated Cu(II) ion by pyridine- N, imine- N atoms of the ligands and one oxygen atom of SO42- for ( 2). Complex ( 3) consists of a two-dimensional Cu(II) layer formed by deprotonated HL ligand linking four-membered Cu 2Cl 2 units. Complex ( 4) contains a tetranuclear Cu(II) coordination cation in which the Cu(II) ions are penta-coordinated in square pyramidal geometry by two bridging chloride atoms, two nitrogen atoms of HL ligand with undeprotonated carboxylic group, and one oxygen atom of syn,syn-carboxylato bridge. Magnetic susceptibility data show a weak ferromagnetic coupling between the Cu centers in ( 3) ( J = 4.95 cm -1) and a weak antiferromagnetic interaction in ( 4) ( J = -16.85 cm -1), respectively.

  11. CH 4/N 2/H 2-spark hydrophobic tholins: A systematic approach to the characterisation of tholins. Part II

    NASA Astrophysics Data System (ADS)

    Ruiz-Bermejo, Marta; Menor-Salván, César; de la Fuente, José Luis; Mateo-Martí, Eva; Osuna-Esteban, Susana; Martín-Gago, José Ángel; Veintemillas-Verdaguer, Sabino

    2009-12-01

    Two different simulation experiments of prebiotic synthesis were carried out in a CH 4/N 2/H 2 atmosphere with spark discharge activation of aqueous aerosols and liquid water. In both cases, a hydrophilic tholin and a hydrophobic tholin were obtained. The methodology developed by our group for the characterisation of hydrophilic tholins [Ruiz-Bermejo, M., Menor-Salván, C., Mateo-Martí, E., Osuna-Esteban, S., Martín-Gago, J.A., Veintemillas-Verdaguer, S., 2008. Icarus 198, 232-241] was used in order to study the hydrophobic tholins. The gas precursors of the tholins from mixtures containing CH 4, with and without H 2, were studied. We propose that the formation of the hydrophobic tholins involves the formation of unsaturated oligomeric hydrocarbon chains from vinyl and acetylene monomers, as well as allene derivatives formed in the gas phase after the incorporation of polar groups into these hydrocarbon chains. Finally, we compare our results concerning hydrophobic tholins with HCN polymers, since it is generally suggested that the polymeric material formed in spark experiments are possible oligomers of HCN, and that Titan's tholins could be poly-HCN.

  12. A "high 4He/3He" mantle material detected under the East Pacific Rise (15°4'N)

    NASA Astrophysics Data System (ADS)

    Mougel, Berengere; Moreira, Manuel; Agranier, Arnaud

    2015-03-01

    We investigate in details helium isotope data reported in Mougel et al. (2014) for 14 basaltic samples collected on the East Pacific Rise by submersible (15°4'N) where the ridge interacts with the Mathematician seamounts. Samples locations are separated by only few hundred meters across a 15 km along-axis profile. The data reveal a strong geochemical variability that has never been observed at such high spatial resolution for helium isotope compositions. Moreover, they reveal an unusually high 4He/3He mantle component also characterized by unradiogenic lead, atypical in oceanic basalts. He-Pb systematics suggests a mixture between a nonradiogenic lead and radiogenic helium pyroxenitic component, recycled from the deep continental lithosphere and the ambient peridotitic mantle. The He isotope difference between these two end-members can be interpreted as a time evolution of two distinct mantle sources after a slight (U + Th)/3He fractionation, likely due to some ancient degassing during the formation of deep continental pyroxenites.

  13. Optimized deglycosylation of glycoproteins by peptide-N4-(N-acetyl-beta-glucosaminyl)-asparagine amidase from Flavobacterium meningosepticum.

    PubMed

    Nuck, R; Zimmermann, M; Sauvageot, D; Josi D; Reutter, W

    1990-01-01

    Peptide-N4-(N-acetyl-beta-glucosaminyl)asparagine amidase F(PNGase F) from Flavobacterium meningosepticum is a highly useful enzyme for the structural analysis of N (asparagine)-linked carbohydrate chains derived from glycoproteins. The enzyme was enriched using a published procedure [Tarentino AL, Gomez CM, Plummer TH, Jr (1984) Biochemistry 1985:4665-71; Tarentino AL, Plummer TH, Jr (1987) Methods Enzymol 138:770-78] and further purified by hydrophobic interaction HPLC on a weak hydrophobic TSK-Ether column from which it was eluted by a decreasing gradient of 1.7 M ammonium sulphate in 100 mM sodium phosphate, pH 7.0, containing 5 mM EDTA. To determine the optimal conditions for a complete deglycosylation of glycoproteins by PNGase F, experiments were performed with human alpha 1-acid glycoprotein, because the five complex type carbohydrate chains are quite resistant to enzymic hydrolysis. The influence of different detergents on the enzyme reaction was studied. Complete deglycosylation of human alpha 1-acid glycoprotein was achieved by the use of 60 mU/ml PNGase F in 0.25 M sodium phosphate buffer, pH 8.6, containing 0.2% (w/v) SDS, 20 mM mercaptoethanol and 0.5% Mega-10. PMID:2136346

  14. Observation of Cu nanometre scale clusters formed in Fe85Si2B8P4Cu1 nanocrystalline soft magnetic alloy by a spherical aberration-corrected TEM/STEM

    NASA Astrophysics Data System (ADS)

    Nishijima, Masahiko; Matsuura, Makoto; Zhang, Yan; Makino, Akihiro

    2015-05-01

    Microstructure of a nanocrystalline soft magnetic Fe85Si2B8P4Cu1 alloy (NANOMET®) was investigated by the state of the art spherical aberration-corrected TEM/STEM. Observation by TEM shows that the microstructure of NANOMET® heat treated at 738 K for 600 s which exhibits the optimum soft magnetic properties has homogeneously distributed bcc-Fe nanocrystallites with the average grain size of 30 nm embedded in an amorphous matrix. Elemental mappings indicate that P is excluded from bcc-Fe grains and enriched outside the grains, which causes to retard the grain growth of bcc-Fe crystallites. The aberration-corrected STEM-EDS analysis with the ultrafine electron probe successfully proved that Cu atoms form nanometre scale clusters inside and/or outside the bcc-Fe nanocrystallites.

  15. K-Ar dating and delta O-18-delta D characterization of nanometric illite from Ordovician K-bentonites of the Appalachians: illitization and the Acadian-Alleghenian tectonic activity

    USGS Publications Warehouse

    Clauer, Norbert; Fallick, Anthony E.; Eberl, Dennis D.; Honty, Miroslav; Huff, Warren D.; Auberti, Amelie

    2013-01-01

    Nanometric (2 diagram that illitization occurred in all fractions by simultaneous nucleation and crystal growth, except for one sample. In that sample, a period of growth without nucleation was detected on top of the nucleation and growth episode. The K-Ar ages organize into two isochrons, the first at 319.9 ± 2.0 Ma with an initial 40Ar/36Ar ratio of 271 ± 66 Ma, and the second at 284.9 ± 1.2 Ma with an initial 40Ar/36Ar ratio of 310 ± 44. One data point above the older isochron and three between the two isochrons suggest a detrital contamination for the former separate and a possible further generation of nanoparticles for the three others. The samples with the older crystallization age consist of illite and illite-rich mixed-layers, and those with the younger age contain smectite-rich mixed-layers without illite, or illite-enriched illite-smectite mixed-layers. The K-Ar ages fit the age trends published previously for similar K-bentonites with regional age patterns between 240 and 270 Ma in the southwestern region, between 270 and 300 Ma in the central zone and the southern Appalachians, and between 315 and 370 Ma in the northernmost. Each of the two generations of illite crystals yields very consistent δ18O (V-SMOW) values at 17 ± 1‰ for the older and at 21 ± 1‰ for the younger. If crystallization temperatures of the nanometric illite were between 100 and 200 °C, as suggested by microthermometric determinations, the hydrothermal fluids had δ18O values of 4 ± 1‰ in the Dalton district and of 8 ± 1‰ in the Lafayette, Trenton, and Dirtseller districts at 100 °C, and of 11 ± 1 and 15 ± 1‰ in the same locations at 200 °C, probably because the water-rock isotope exchanges at elevated temperature occurred in rock-dominated systems. The δ18O of the fluids remained unchanged during local crystal growth, but varied depending on the geographic location of the samples and timing of illitization. The δD (V-SMOW) values of the different size

  16. Contrasting behaviour of the co-activators in the luminescence spectra of Y2O2S:Tb3+,Er3+ nanometre sized particles under UV and red light excitation

    NASA Astrophysics Data System (ADS)

    Yan, Xiao; Fern, George R.; Withnall, Robert; Silver, Jack

    2013-01-01

    Nanometre sized particles of terbium and erbium co-doped yttrium oxysulfide up-converting phosphors were prepared by a urea homogeneous-precipitation method. Results from X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and photoluminescence spectroscopy studies on the microstructure and luminescent properties of the materials are reported. Upconversion emission was observed from the Er3+ cations when particles were excited with laser light of 632.8 nm wavelength. Under these conditions no interactions between the Er3+ cations and the Tb3+ cations were observed. In contrast there was evidence from the Stokes emission of the Er3+ cations under 254 nm excitation for an interaction between the Er3+ and Tb3+ cations reducing intensity of the latter's blue and green emission bands by cross relaxation processes.

  17. Contrasting behaviour of the co-activators in the luminescence spectra of Y2O2S:Tb3+,Er3+ nanometre sized particles under UV and red light excitation.

    PubMed

    Yan, Xiao; Fern, George R; Withnall, Robert; Silver, Jack

    2013-02-01

    Nanometre sized particles of terbium and erbium co-doped yttrium oxysulfide up-converting phosphors were prepared by a urea homogeneous-precipitation method. Results from X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and photoluminescence spectroscopy studies on the microstructure and luminescent properties of the materials are reported. Upconversion emission was observed from the Er(3+) cations when particles were excited with laser light of 632.8 nm wavelength. Under these conditions no interactions between the Er(3+) cations and the Tb(3+) cations were observed. In contrast there was evidence from the Stokes emission of the Er(3+) cations under 254 nm excitation for an interaction between the Er(3+) and Tb(3+) cations reducing intensity of the latter's blue and green emission bands by cross relaxation processes. PMID:23263157

  18. Investigation of Seasonal Cycles of CO, CH4, N2O, and O3 in the High Arctic at Eureka, Canada and Barrow, Alaska using Infrared Emission Spectroscopy

    NASA Astrophysics Data System (ADS)

    Tran, S.; Mariani, Z.; Conway, S. A.; Lutsch, E.; Rowe, P. M.; Kasai, Y.; Strong, K.

    2015-12-01

    The High Arctic experiences prolonged periods of total darkness in the winter and continuous daylight in the summer, influencing the atmosphere and its composition in ways that are still not fully understood. Making atmospheric measurements in this remote region is challenging, particularly during polar night when solar-viewing instruments are not operational. By using infrared emission spectroscopy, which is independent of sunlight, we are able to document year-round the total column abundances of carbon monoxide (CO), methane (CH4), nitrous oxide (N2O), and ozone (O3). Measurements made at two Arctic sites are presented in this study: the Polar Environment Atmospheric Research Laboratory (PEARL, Eureka, Nunavut, Canada, 80.05°N, 86.42°W) and the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) facility on the North Slope of Alaska (NSA, Barrow, Alaska, 71.19°N, 156.36°W). At both sites, Extended-range Atmospheric Emitted Radiance Interferometers (E-AERIs), are used to measure the absolute downwelling infrared emission from the atmosphere between 400 and 3000 cm-1. The E-AERI has a moderate resolution of 1 cm-1 and provides information about trace gases columns with high sensitivity to the lower troposphere. At PEARL, the instrument was installed in October 2008. In addition, a similar instrument, the University of Idaho's Polar AERI (P-AERI) was installed at PEARL from March 2006 to June 2009. At NSA, the E-AERI has been operating since February 1998. Total columns of CO, CH4, N2O and O3 have been retrieved from 2006 to 2015 at PEARL and from 1998 to 2014 at NSA using the SFIT4 algorithm. These two datasets will be compared along with measurements made by high-resolution solar-viewing infrared spectrometers located at PEARL and at Poker Flat, Alaska (65.12°N, 147.47°W) to validate our results. These measurements will be used to present the annual, seasonal and diurnal variabilities of trace gases in the high Arctic at two different

  19. Effect of Ascorbate on the Cyanide-Scavenging Capability of Cobalt(III) meso-Tetra(4-N-methylpyridyl)porphine Pentaiodide: Deactivation by Reduction?

    PubMed

    Benz, Oscar S; Yuan, Quan; Cronican, Andrea A; Peterson, Jim; Pearce, Linda L

    2016-03-21

    The Co(III)-containing water-soluble metalloporphyrin cobalt(III) meso-tetra(4-N-methylpyridyl)porphine pentaiodide (Co(III)TMPyP) is a potential cyanide-scavenging agent. The rate of reduction of Co(III)TMPyP by ascorbate is facile enough that conversion to the Co(II)-containing Co(II)TMPyP should occur within minutes at prevailing in vivo levels of the reductant. It follows that any cyanide-decorporating capability of the metalloporphyrin should depend more on the cyanide-binding characteristics of Co(II)TMPyP than those of the administered form, Co(III)TMPyP. Addition of cyanide to buffered aqueous solutions of Co(II)TMPyP (pH 7.4, 25-37 °C) results in quite rapid (k2 = ∼10(3) M(-1) s(-1)) binding/substitution of cyanide anion in the two available axial positions with high affinity (K'β = 10(10) to 10(11)). Electron paramagnetic resonance spectroscopic measurements and cyclic voltammetry indicate that cyanide induces oxidation to the Co(III)-containing dicyano species. The constraints that these observations put on plausible mechanisms for the reaction of Co(II)TMPyP with cyanide are discussed. Experiments in which Co(III)TMPyP and cyanide were added to freshly drawn mouse blood showed the same sequence of reactions (metalloporphyrin reduction → cyanide binding/substitution → reoxidation) to occur. Therefore, in cyanide-scavenging applications with this metalloporphyrin, we should be taking advantage of both the improved rate of ligand substitution at Co(II) compared to that at Co(III) and the increased affinity of Co(III) for anionic ligands compared to that of Co(II). Finally, using an established sublethal mouse model for cyanide intoxication, Co(III)TMPyP, administered either 5 min before (prophylaxis) or 1 min after the toxicant, is shown to have very significant antidotal capability. Possible explanations for the results of a previous contradictory study, which failed to find any prophylactic effect of Co(III)TMPyP toward cyanide intoxication, are

  20. Evidence of electronic phase arrest and glassy ferromagnetic behaviour in (Nd0.4Gd0.3)Sr0.3MnO3 manganite: comparative study between bulk and nanometric samples

    NASA Astrophysics Data System (ADS)

    Kundu, S.; Nath, T. K.

    2011-09-01

    The effect of the doping of rare earth Gd3+ ions replacing Nd3+ in Nd0.7Sr0.3MnO3 is investigated in detail. Measurements of resistivity, magnetoresistance, magnetization, and linear and nonlinear ac magnetic susceptibility on chemically synthesized (Nd0.7-xGdx)Sr0.3MnO3 show various interesting features with doping level x = 0.3. A comparative study has been carried out between a bulk and a nanometric sample (grain size ˜60 nm) synthesized from the same as a prepared powder to maintain an identical stoichiometry. The resistivity of the samples shows strong dependence on the magnetic field-temperature history. The magnetoresistance of the samples also shows strong irreversibility with respect to sweeping of the field between the highest positive and negative values. Moreover, the resistivity is found to increase with time after field cooling and then switching off the field. All these phenomena have been attributed to phase separation effects and the arrest of phases in the samples. Furthermore, the bulk sample displays a spin glass like behaviour as evident from the frequency dependence of linear ac magnetic susceptibility and critical divergence of the nonlinear ac magnetic susceptibility. The experimentally obtained characteristic time τ0 after dynamical scaling analysis of the frequency dependence of the ac susceptibility is found to be 10-17 s which implies that the system is different from a canonical spin glass. An unusual frequency dependence of the second harmonic of ac susceptibility around the magnetic transition temperature led us to designate the magnetic state of the sample to be glassy ferromagnetic. On reduction of the grain size low field magnetoresistance and phase arrest phenomena are found to enhance but the glassy state is observed to be destabilized in the nanometric sample.

  1. Dual Electrospray Pyrolysis for Mixed Metal Oxide (and Carbon) Composite Nanoparticle Synthesis with Applications in Energy Storage

    NASA Astrophysics Data System (ADS)

    Tang, Justin; Liu, Wen; Wang, Hailiang; Gomez, Alessandro

    We present a novel approach to synthesizing mixed metal oxide nanoparticles with a continuous, scalable aerosol flow process using the electrospray. The electrospray is a liquid atomization technique that generates a monodisperse population of highly charged liquid droplets over a broad size range (nanometric to tens of microns). Each liquid droplet serves as a micro-reactor, containing a payload of suitable precursors (such as metal nitrides), allowing for precise control over particle composition and size. By using two electrosprays of opposite polarities, the two highly charged droplets plumes are electrostatically mixed to produce a charge-neutral aerosol. Electrostatically driven droplet-droplet collisions can also be used to control morphology to some degree. This aerosol is passed through a tubular furnace via carrier gas, pyrolizing the precursors to synthesize nanomaterials. We apply this approach to manganese oxide, cobalt oxide, and carbon composite nanoparticles for use in energy storage applications.

  2. Inorganic halogen oxidizers

    NASA Astrophysics Data System (ADS)

    Christe, K. O.; Wilson, W. W.

    1994-09-01

    A research program was carried out in novel energetic materials. This program was highly successful and resulted in 28 major publications. Highlights of this effort include: the characterization of the XeF5(-) anion which is the first example of a pentagonal planar XY5 structure, completion of our work on a quantitative oxidizer strength scale, the synthesis and characterization of new compounds at the limits of coordination and oxidation, such as XeOF5(-), TeOF6(2-), IOF6(-), IF8(-), TeF8(2-), TeF7(-), and XeF7(+), the study of fluxionality and steric repulsion effects in hexa- and hepta- coordinated species, such as IF7, HPF5(-), HSF5, and IOF5, the controlled replacement of two fluorine ligands by one doubly bonded oxygen ligand, studies of the thermal instability of NF5 and the F3(-) anion, the characterization of the N2F(+) cation N(CH3)4N3, H2N3(+) cation and the SF4(-) and SOF4(-) radical anions, the synthesis and characterization of a new Os(+VIII) compound, OsF4O2, theoretical studies on ONOF and a new family of polynitrogen compounds, the synthesis and characterization of the novel PF4(-) anion and it hydrolysis products, and the electrophilic fluorination of CH4 with F(+) equivalent N2F(+) and NF4(+) salts.

  3. Magnetic properties of nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N phases synthesized by newer precursor route

    SciTech Connect

    Theerthagiri, J.; Dalavi, Shankar B.; Manivel Raja, M.; Panda, R.N.

    2013-11-15

    Graphical abstract: Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized first time by newer chemical routes. The ε-Fe{sub 3}N phase crystallizes in hexagonal structure with unit cell parameters, a = 4.76 Å and c = 4.41 Å. The Co{sub 4}N phase crystallizes in face centred cubic (fcc) structure with unit cell parameters, a = 3.55 Å. The estimated crystallite size for ε-Fe{sub 3}N and Co{sub 4}N phases are 29 nm and 22 nm, respectively. The values of saturation magnetization for ε-Fe{sub 3}N and Co{sub 4}N phases are found to be 28.1 emu/g and 123.6 emu/g respectively. The reduction of magnetic moments in ultrafine materials compared to bulk materials has been explained by fine particle size and surface effects. We have synthesized the high moment ε-Fe{sub 3}N and Co{sub 4}N nitride with reduced coercivity which may find applications as soft magnetic materials. - Highlights: • Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized. • The ε-Fe{sub 3}N and Co{sub 4}N crystallizes in hexagonal and fcc structure respectively. • The observed magnetic parameters indicate soft magnetic properties. • The magnetic properties have been explained on the basis of fine particle magnetism. - Abstract: Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized first time by using tris(1,2-diaminoethane)iron(II) chloride and tris(1,2-diaminoethane)cobalt(III) chloride precursors, respectively. To prepare ε-Fe{sub 3}N and Co{sub 4}N nitride phases, the synthesized precursors were mixed with urea in 1:12 ratio and heat treated at various temperatures in the range of 450–900 °C under the ultrapure nitrogen gas atmosphere. The precursors are confirmed by FT-IR study. The ε-Fe{sub 3}N phase crystallizes in hexagonal structure with unit cell parameters, a = 4.76 Å and c = 4.41 Å. The Co{sub 4}N phase crystallizes in face centred cubic (fcc) structure with unit cell parameters, a = 3.55 Å. The

  4. Enhanced inverse spin-Hall voltage in (001) oriented Fe4N/Pt polycrystalline films without contribution of planar-Hall effect

    NASA Astrophysics Data System (ADS)

    Isogami, Shinji; Tsunoda, Masakiyo

    2016-04-01

    In this study, the output DC electric voltage (V out) generated by a Pt-capped Fe4N bilayer film (Fe4N/Pt) under ferromagnetic resonance conditions at room temperature was assessed. The contributions from the inverse spin-Hall effect (ISHE), the planar-Hall effect (PHE) and the anomalous-Hall effect (AHE) were separated from the output voltage by analysis of V out values determined at varying external field polar angles. The results showed that the polarity of the ISHE (V ISHE) component of V out was opposite to that of the PHE (V PHE). As a result, the magnitude of the intrinsic V ISHE was beyond V out by as much as the magnitude of V PHE. The X-ray diffraction structural analysis revealed the polycrystal of the Fe4N/Pt with (001) orientation, which might be one of the possible mechanisms for enhanced intrinsic V ISHE.

  5. Perpendicular magnetic anisotropy in CoxMn4-xN (x = 0 and 0.2) epitaxial films and possibility of tetragonal Mn4N phase

    NASA Astrophysics Data System (ADS)

    Ito, Keita; Yasutomi, Yoko; Kabara, Kazuki; Gushi, Toshiki; Higashikozono, Soma; Toko, Kaoru; Tsunoda, Masakiyo; Suemasu, Takashi

    2016-05-01

    We grow 25-nm-thick Mn4N and Co0.2Mn3.8N epitaxial films on SrTiO3(001) by molecular beam epitaxy. These films show the tetragonal structure with a tetragonal axial ratio c/a of approximately 0.99. Their magnetic properties are measured at 300 K, and perpendicular magnetic anisotropy is confirmed in both films. There is a tendency that as the Co composition increases, an anisotropy field increases, whereas saturation magnetization and uniaxial magnetic anisotropy energy decrease. First-principles calculation predicts the existence of tetragonal Mn4N phase. This explains the c/a ˜ 0.99 in the Mn4N films regardless of their film thickness and lattice mismatch with substrates used.

  6. Origin of iron oxide spherules in the banded iron formation of the Bababudan Group, Dharwar Craton, Southern India

    NASA Astrophysics Data System (ADS)

    Orberger, Beate; Wagner, Christiane; Wirth, Richard; Quirico, Eric; Gallien, Jean Paul; Derré, Colette; Montagnac, Gilles; Noret, Aurélie; Jayananda, Mudlappa; Massault, Marc; Rouchon, Virgile

    2012-06-01

    The banded iron formation of the Bababudan Group (Western Dharwar Craton, India) is composed of millimetric to centimetric alternating quartz and grey to red Fe-oxide bands. Major phases are quartz and martite (hematized magnetite) with minor Fe-sulfides and Ca-Mg-Fe-carbonates. Micrometric Fe-oxide spherules fill cavities in discontinuous micrometric layers of Fe-oxides that occur in the massive quartz layers and at the interface of massive Fe-oxide and quartz layers. The spherules are composed of micrometric radial plates of hematite intergrown with nanometric magnetite. These spherules contain carbonaceous matter (CM) with nanometric Fe-particles and have low N contents (˜900 ppm; CM1). The spherule formation is attributed to a low temperature hydrothermal process (150-200 °C) at around 2.52 Ga, possibly favored by the presence of CM. These hydrothermal fluids dissolved diagenetic interstitial sulfides or carbonates creating cavities which, provided space for the spherule precipitation. Carbonaceous matter of semi-anthracite maturity is encapsulated in quartz grains adjacent to the Fe-oxide spherules (CM2) and it is thus concluded that CM1 and CM2 are most likely contemporaneous and of the same origin, either incorporated at the time of BIF formation or during the hydrothermal event at 2.52 Ga from the underlying phyllitised black shales. Carbonaceous matter (CM3) was also found around the Fe-oxide spherules and the martite grains. CM3 has much higher N contents (>5000 ppm), is of a lower maturity than CM1 and CM2, and is related to weathering, which is also indicated by the presence of goethite and kaolinite. The δ13C of all CMs varies from -19.4 to -24.7‰, similar to values measured in the underlying phyllitised black shales and likely reflect denitrifying microbial activity.

  7. Solvent sensitive intramolecular charge transfer dynamics in the excited states of 4-N,N-dimethylamino-4'-nitrobiphenyl.

    PubMed

    Ghosh, Rajib; Nandi, Amitabha; Palit, Dipak K

    2016-03-21

    Organic molecules substituted with the nitro group show efficient nonlinear optical (NLO) properties, which are a consequence of the strong intramolecular charge transfer (ICT) character of the molecules because of the strong electron withdrawing nature of the nitro group and rapid responsiveness because of highly movable π-electrons. Dynamics of the ICT process in the excited states of a push-pull biphenyl derivative, namely, 4-N,N-dimethylamino-4'-nitrobiphenyl (DNBP), an efficient NLO material, has been investigated using ultrafast transient absorption spectroscopy. The experimental results have been corroborated with DFT and TDDFT calculations. In solvents of large polarity, e.g. acetonitrile, the ultrafast ICT process of DNBP is associated with the barrierless twisting of the N,N-dimethylaniline (DMA) group with respect to the nitrobenzene moiety to populate the twisted ICT (or TICT) state, and the rate of this process is solely governed by the viscosity of the medium. In solvents of moderate polarity, e.g. ethyl acetate, the rate of the twisting process is significantly slowed down and the LE and TICT states remain in equilibrium because of a low energy barrier for interconversion between these two states. By further lowering the polarity of the solvent, e.g. in dioxane, the twisting process is completely retarded. In nonpolar solvents, e.g. cyclohexane, a reverse twisting motion towards the planar geometry (i.e. the PICT process) has been evident in the excited state dynamics. In this solvent, the S1 state undergoes an ultrafast intersystem crossing to the triplet state because of its close proximity with the T2 state. PMID:26907751

  8. Capacitance and conductance characterization of nano-ZnGa{sub 2}Te{sub 4}/n-Si diode

    SciTech Connect

    Fouad, S.S.; Sakr, G.B.; Yahia, I.S.; Abdel-Basset, D.M.; Yakuphanoglu, F.

    2014-01-01

    Graphical abstract: - Highlights: • XRD and DTA micrographs were used to study the structure of ZnGa{sub 2}Te{sub 4}. • C–V, G–V and R{sub s}–V of the diode characteristics have been analyzed for the first time. • Dielectric constant, dielectric loss, loss tangent and ac conductivity were determined. • The interfaces states were determined using conductance–voltage technique. • ZnGa{sub 2}Te{sub 4} is a good candidate for electronic device applications. - Abstract: Capacitance–voltage (C–V) and conductance–voltage (G–V) characteristics of p-ZnGa{sub 2}Te{sub 4}/n-Si HJD were studied over a wide frequency and temperature. Both the interface states density N{sub ss} and series resistance R{sub s} were strongly frequency and temperature dependent. The interface states density N{sub ss} is decreased with increasing frequency and increase with increasing temperature. The values of the built-in potential (V{sub bi}) were calculated and found to increase with increasing temperature and frequency. The values of capacitance C, conductance G, series resistance R{sub s}, corrected capacitance C{sub ADJ}, corrected conductance G{sub ADJ}, dielectric constant (ε′), dielectric loss (ε″), loss tangent (tan δ) and the AC conductivity (σ{sub ac}) are strongly dependent on the applied frequency, voltage and temperature. The obtained results show that the locations of N{sub ss} and R{sub s} have a significant effect on the electrical characteristics of the studied diode.

  9. Variations of atmospheric CH4, N2O and SF6 over Japan and the East China Sea

    NASA Astrophysics Data System (ADS)

    Ishijima, K.; Goto, D.; Ishidoya, S.; Yashiro, H.; Umezawa, T.; Sugawara, S.; Patra, P. K.; Muromachi, A.; Elkins, J. W.; Dutton, G. S.; Dlugokencky, E. J.; Morimoto, S.; Aoki, S.; Nakazawa, T.

    2013-12-01

    East Asia is one of the most important regions for anthropogenic sources of both short-lived air pollutants and long-lived greenhouse gases (GHGs). According to recent estimates from an emission database, China has become the largest emitter of long-lived GHGs. Since Japan and the East China Sea are located at the east end of Eurasia, atmospheric species emitted from the continent are transported over them throughout the year. Particularly in winter to spring, outflow of the emitted species is enhanced over the East China Sea due to the East Asian Monsoon. To monitor temporal and spatial variability of atmospheric GHGs in the East Asian region, we conducted systematic GHG observations during 2003-2012 from flask samples collected onboard four different commercial ferry boats, which connected between Wakkanai and Rishiri islands (WAK ; 45.4°N, 141.5°E), between Sakaiminato and Oki islands (OKI ; 35.8°N, 133.2°E), between Kagoshima and Okinawa islands (RYU ; 30.0°N, 130.0°E), and between Ishigaki and Hateruma islands (HTR ; 24.0°N, 124.0°E). Air samples were collected almost weekly, and they were sent to Tohoku University and analyzed for GHGs and related gases. In this study, we present analyses of observed CH4, N2O and SF6 concentrations in comparison with simulations by the Atmospheric general circulation model-based Chemistry Transport model (ACTM). The observed three species predictably show higher concentrations than those observed at Cape Kumukahi (KUM), which is a NOAA air sampling site located in the Central Pacific, reflecting strong outflow of the species from East Asia. Annual mean latitudinal gradients found from the four locations as well as decrease toward KUM are generally reproduced by the ACTM. This is mostly because of reasonable spatial distributions in GHG emissions given in the ACTM. The three species also show discernible seasonal cycles. ACTM simulates seasonal cycles of CH4 and SF6 relatively well, but not for N2O, suggesting

  10. On the mechanism of photochromism of 4'-N,N-dimethylamino-7-hydroxyflavylium in pluronic F127.

    PubMed

    Gomes, Raquel; Laia, César A T; Pina, Fernando

    2009-08-13

    The photochromism of the compound 4'-N,N-dimethylamino-7-hydroxyflavylium incorporated in Pluronic F127 micelles and gels was studied in great detail. The red flavylium ion (AH(+)) or the quinoidal base (A), depending on pH, are the irradiation products of the colorless trans-chalcone (Ct). Absorption and fluorescence (steady-state, time-resolved, and anisotropy), pH jumps, and flash photolysis were used to characterize the system. At moderately acidic to neutral pH values, the Ct species is distributed between the core and corona of the Pluronic micelle, as well as in the aqueous phase. At acidic pH values, AH(+) remains most probably in the water phase. The Ct maximum absorption wavelength constitutes a good sensor for the critical micelle concentration (CMC) or critical micelle temperature (CMT). The apparent acidity constant pK'(a) was found to be a relatively good sensor for CMC and also for detection of the sol-gel critical temperature. The Ct photochromic mechanism was analyzed by comparing the photophysics in pure solvents and the pluronic media. Solvatochromic effects show a lack of solvent polarity dependence of the Stokes shift, indicating a low dipolar moment change between the ground and the locally excited state. An internal charge transfer nonradiative process (ICT) competes with Ct photoisomerization and is the dominant process in highly polar solvents, preventing the appearance of photochromism, in contrast with lower polar environments, such as micelles and ethanol. In high viscous environments as those found in the core of the Pluronic F127 micelles or glycerol, both ICT and photoisomerization are reduced, enhancing the Ct fluorescence quantum yield. According to the data from fluorescence measurements and pH jumps, evidence for the Ct distribution among different sites within the pluronic aggregate was found, (i) a hydrophilic/fluid region where Ct has poor fluorescence and isomerization yields, bulk region; (ii) the corona of the micelle where

  11. Missing-Mass Spectroscopy of the 4-Neutron System by Exothermic Double-Charge Exchange Reaction 4He(8He,8Be)4n

    NASA Astrophysics Data System (ADS)

    Kisamori, Keiichi; Shimoura, Susumu; Miya, Hiroyuki; Assie, Marlene; Baba, Hidetada; Baba, Tatsuo; Beaumel, Didier; Dozono, Masanori; Fujii, Toshihiko; Fukuda, Naoki; Go, Shintaro; Hammache, Fariouz; Ideguchi, Eiji; Inabe, Naohiro; Itoh, Masatoshi; Kameda, Daisuke; Kawase, Shoichiro; Kawabata, Takahiro; Kobayashi, Motoki; Kondo, Yosuke; Kubo, Toshiyuki; Kubota, Yuki; Kurata-Nishimura, Mizuki; Lee, CheongSoo; Maeda, Yukie; Matsubara, Hiroaki; Michimasa, Shin'ichiro; Miki, Kenjiro; Nishi, Takahiro; Noji, Shumpei; Ota, Shinsuke; Sakaguchi, Satoshi; Sakai, Hideyuki; Sasamoto, Yoshiko; Sasano, Masaki; Sato, Hiromi; Shimizu, Yohei; Stolz, Andreas; Suzuki, Hiroshi; Takaki, Motonobu; Takeda, Hiroyuki; Takeuchi, Satoshi; Tamii, Atsushi; Tang, Leung; Tokieda, Hiroshi; Tsumura, Miho; Uesaka, Tomohiro; Yako, Kentaro; Yanagisawa, Yoshiyuki; Yokoyama, Rin

    A possible existence of the tetra-neutron system as a resonance state is still an open and fascinating question, while theoretical papers using ab-initio calculation suggests that the bound tetra-neutron does not exist. We have performed a missing-mass spectroscopy of the 4n system via the exothermic double-charge exchange reaction 4He(8He,8Be)4n. The experiment was carried out at the RIBF at RIKEN using the SHARAQ spectrometer. Since the secondary beam, 8He at 190 A MeV, has a large internal energy, it is possible to produce the 4n system with small momentum transfers of less than 20 MeV/c. In the present analysis, a new analytical framework to treat multi-particles under high beam rate condition (2 MHz) was developed for good statistics. At the SHARAQ spectrometer, 8Be can be identified by measuring the invariant mass of the coincident two alpha particles with a good signal-to-noise ratio. About several tens of candidate events are obtained above the 4n threshold.

  12. Development of ferret as a human lung cancer model by injecting4-(N-methyl-N-nitrosamino)-1-(3-pyridyl)-1-butanone (NNK)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Development of new animal lung cancer models that are relevant to human lung carcinogenesis is important for lung cancer research. Previously we have shown the induction of lung tumor in ferrets (Mustela putorius furo) exposed to both tobacco smoke and a tobacco carcinogen (4-(N-methyl-N-nitrosamino...

  13. Characteristics of urban-ecosystem atmosphere fluxes of CO2, CH4, N2O, and et over Denver, Colorado

    USGS Publications Warehouse

    Anderson, D.E.; Alvarez, C.; Thienelt, T.

    2004-01-01

    The characteristics of urban ecosystems fluxes of carbon dioxide, methane, nitrous oxide, and evapotranspiration (ET) over Denver, Colorado were discussed. These atmospheric fluxes were measured using a methodology that included a combination of eddy covariance sensors at two levels on a tall tower and chamber measurements at 33 locations on the soil surface. There was both strong temporal and spatial heterogeneity of fluxes owing to characteristics of natural and anthropogenic ecosystem components. Although the urban ecosystem was a net carbon dioxide source, tower-based eddy covariance measurements showed it to be a net vegetative sink during the majority of mid-say summer hours.

  14. Synthesis and characterization of rhenium(III) organohydrazide compounds. Crystal and molecular structures of [ReCl(PPh{sub 3}){sub 2}(NHNC{sub 5}H{sub 4}N)(HNNC{sub 5}H{sub 4}N)]Cl{sub 2}, [Re{l_brace}2-(Ph{sub 2}P)C{sub 6}H{sub 4}S{r_brace}{l_brace}2-(Ph{sub 2}PO)C{sub 6}H{sub 4}S{r_brace}(NNC{sub 5}H{sub 4}N)(HNNC{sub 5}H{sub 4}N)], and [Re{l_brace}2-(Ph{sub 2}P)C{sub 6}H{sub 4}S{r_brace}{sub 2}(NNC{sub 5}H{sub 4}N)

    SciTech Connect

    Perez-Lourido, P.; Romero, J.; Garcia-Vazquez, J.A.; Sousa, A.; Maresca, K.P.; Zubieta, J.

    1999-04-05

    The reduction of ReO{sub 4}{sup {minus}} with 2-hydrazinopyridine dihydrochloride and PPh{sub 3} gives [ReCl(PPh{sub 3}){sub 2}(NHNC{sub 5}H{sub 4}N)-(HNNC{sub 5}H{sub 4}N)]Cl{sub 2} (2). A similar reaction using 2-hydrazino-2-imidazoline and PPh{sub 3} in methanol hydrochloric acid allows the preparation of [ReCl{sub 3}(PPh{sub 3}){sub 2}(NNC{sub 3}H{sub 4}N{sub 2})] (3). The reaction of the Re(III) complex [ReCl{sub 3}(NNC{sub 5}H{sub 4}NH)(HNNC{sub 5}H{sub 4}N)] (1), with 2-(Ph{sub 2}P)C{sub 6}H{sub 4}SH in methanol yields [Re{l_brace}2-(Ph{sub 2}P)C{sub 6}H{sub 4}S{r_brace}-{l_brace}2-(Ph{sub 2}PO)C{sub 6}H{sub 4}S{r_brace}(NNC{sub 5}H{sub 4}N)(HNNC{sub 5}H{sub 4}N)] (4) and [Re{l_brace}2-(Ph{sub 2}P)C{sub 6}H{sub 4}S{r_brace}{sub 2}(NNC{sub 5}H{sub 4}N)] (5). The same precursor with 2-(Ph{sub 2}PO)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}SH gives [ReCl{l_brace}2-(Ph{sub 2}PO)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}S{r_brace}(NNC{sub 5}H{sub 4}N)(HNNC{sub 5}H{sub 4}N)] (6) and with PhP(C{sub 6}H{sub 4}SH-2){sub 2} yields [Re{l_brace}PhP(C{sub 6}H{sub 4}S-2){sub 2}{r_brace}(NNC{sub 5}H{sub 4}N)(HNNC{sub 5}H{sub 4}N)] (7).

  15. Plasticity and ab initio characterizations on Fe 4N produced on the surface of nanocrystallized 18Ni-maraging steel plasma nitrided at lower temperature

    NASA Astrophysics Data System (ADS)

    Yan, M. F.; Wu, Y. Q.; Liu, R. L.

    2009-08-01

    18Ni-maraging steel has been entirely nanocrystallized by a series of processes including solution treatment, hot-rolling deformation, cold-drawn deformation and direct electric heating. The plasma nitriding of nanocrystallized 18Ni-maraging steel was carried out at 410 °C for 3 h and 6 h in a mixture gas of 20% N 2 + 80% H 2 with a pressure of 400 Pa. The surface phase constructions and nitrogen concentration profile in surface layer were analyzed using an X-ray diffractometer (XRD) and the glow discharge spectrometry (GDS), respectively. The results show that an about 2 μm thick compound layer (mono-phase γ'-Fe 4N) can be produced on the top of the surface layer of nanocrystallized 18Ni-maraging steel plasma nitrided at 410 °C for 6 h. The measured hardness value of the nitrided surface is 11.6 GPa. More importantly, the γ'-Fe 4N phase has better plasticity, i.e., its plastic deformation energy calculated from the load-displacement curve obtained by nano-indentation tester is close to that of nanocrystallized 18Ni-maraging steel. Additionally, the mechanical properties of γ'-Fe 4N phase were also characterized by first-principles calculations. The calculated results indicate that the hardness value and the ratio of bulk to shear modulus ( B/ G) of the γ'-Fe 4N phase are 10.15 GPa and 3.12 (>1.75), respectively. This demonstrates that the γ'-Fe 4N phase has higher hardness and better ductility.

  16. The Scope of Direct Alkylation of Gold Surface with Solutions of C1–C4n-Alkylstannanes

    PubMed Central

    2015-01-01

    Treatment of cleaned gold surfaces with dilute tetrahydrofuran or chloroform solutions of tetraalkylstannanes (alkyl = methyl, ethyl, n-propyl, n-butyl) or di-n-butylmethylstannyl tosylate under ambient conditions causes a self-limited growth of disordered monolayers consisting of alkyls and tin oxide. Extensive use of deuterium labeling showed that the alkyls originate from the stannane and not from ambient impurities, and that trialkylstannyl groups are absent in the monolayers, contrary to previous proposals. Methyl groups attached to the Sn atom are not transferred to the surface. Ethyl groups are transferred slowly, and propyl and butyl rapidly. In all cases, tin oxide is codeposited in submonolayer amounts. The monolayers were characterized by ellipsometry, contact angle goniometry, polarization modulated IR reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy with ferrocyanide/ferricyanide, which revealed a very low charge-transfer resistance. The thermal stability of the monolayers and their resistance to solvents are comparable with those of an n-octadecanethiol monolayer. A preliminary examination of the kinetics of monolayer deposition from a THF solution of tetra-n-butylstannane revealed an approximately half-order dependence on the bulk solution concentration of the stannane, hinting that more than one alkyl can be transferred from a single stannane molecule. A detailed structure of the attachment of the alkyl groups is not known, and it is proposed that it involves direct single or multiple bonding of one or more C atoms to one or more Au atoms. PMID:26327466

  17. New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses, X-ray diffraction structures of TaCl(NMe2)(3)[N(TMS)NMe2] and Ta(NMe2)(4)[N(TMS)NMe2], and fluxional behavior of the amido and hydrazido ligands in solution

    SciTech Connect

    Huang, Shih-Huang Huang; Pilvi, Tero; Wang, Xiaoping; Leskela,, Markku; Richmond, Michael G.

    2010-01-01

    The synthesis and structural characterization of new tantalum(V) compounds containing a single hydrazido(1) ligand are reported. Hydrazinolysis of TaCl(NMe2)(4) using trimethylsilyl(dimethyl)hydrazine affords the compound TaCl(NMe2)(3)[N(TMS)NMe2] in essentially quantitative yield. Metathetical replacement of the chloride ligand in TaCl(NMe2)(3)]N(TMS)NMe2] by LiNMe2 gives the all-nitrogen coordinated compound Ta(NMe2)(4)[N(TMS)NMe2]. VT H-1 NMR studies support the existence of low-energy pathways involving rotation about the Ta-N bonds of the ancillary amido and hydrazido ligands in both hydrazido-substituted compounds. X-ray crystallographic analyses confirm the octahedral disposition about the tantalum metal in TaCl(NMe2)(3)[N(TMS)NMe2] and Ta(NMe2)(4)[N(TMS)NMe2] and the presence of an mu(2)-hydrazido(1) ligand. Preliminary data using Ta(NMe2)(4)[N(TMS)NMe2] as an ALD precursor for the preparation of tantalum nitride and tantalum oxide thin films are presented.

  18. 'Clicking' on the nanoscale: 1,3-dipolar cycloaddition of terminal acetylenes on azide functionalized, nanometric surface templates with nanometer resolution

    NASA Astrophysics Data System (ADS)

    Haensch, Claudia; Hoeppener, Stephanie; Schubert, Ulrich S.

    2009-04-01

    Electro-oxidative lithography is used as a tool to create chemical nanostructures on an n-octadecyltrichlorosilane (OTS) monolayer self-assembled on silicon. The use of a bromine precursor molecule, which is exclusively assembled on these chemical templates, can be used to further functionalize the nanostructures by the site-selective generation of azide functions and performing the highly effective 1,3-dipolar cycloaddition reaction with acetylene functionalized molecules. The versatility of this reaction scheme provides the potential to integrate a large variety of functional molecules, to tailor the surface properties of the nanostructures or to anchor molecular building blocks or particles in confined, pre-defined surface areas. The results demonstrated in the present study introduce a conceivable route towards the functionalization of chemically active surface templates with high fidelity and reliability. It is demonstrated that surface features with a lateral resolution of 50 nm functionalized with propargyl alcohol can be fabricated.

  19. Cloning and expression of porcine β1,4 N-acetylgalactosaminyl transferase encoding a new xenoreactive antigen

    PubMed Central

    Byrne, Guerard W; Du, Zeji; Stalboerger, Paul; Kogelberg, Heide; McGregor, Christopher G A

    2014-01-01

    Background Xenograft rejection of pigs organs with an engineered mutation in the GGTA-1 gene (GTKO) remains a predominantly antibody mediated process which is directed to a variety of non-Gal protein and carbohydrate antigens. We previously used an expression library screening strategy to identify six porcine endothelial cell cDNAs which encode pig antigens that bind to IgG induced after pig-to-primate cardiac xenotransplantation. One of these gene products was a glycosyltransferase with homology to the bovine β1,4 N-acetylgalactosaminyltransferase (B4GALNT2). We now characterize the porcine B4GALNT2 gene sequence, genomic organization, expression, and functional significance. Methods The porcine B4GALNT2 cDNA was recovered from the original library isolate, subcloned, sequenced, and used to identify a bacterial artificial chromosome (BAC) containing the entire B4GALNT2 locus from the Children's Hospital Oakland Research Institute BACPAC Resource Centre (#AC173453). PCR primers were designed to map the intron/exon genomic organization in the BAC clone. A stable human embryonic kidney (HEK) cell line expressing porcine B4GALNT2 (HEK-B4T) was produced. Expression of porcine B4GALNT2 in HEK-B4T cells was characterized by immune staining and siRNA transfection. The effects of B4GALNT2 expression in HEK-B4T cells was measured by flow cytometry and complement mediated lysis. Antibody binding to HEK and HEK-B4T cells was used to detect an induced antibody response to the B4GALNT2 produced glycan and the results were compared to GTKO PAEC specific non-Gal antibody induction. Expression of porcine B4GALNT2 in pig cells and tissues was measured by qualitative and quantitative real time reverse transcriptase PCR and by Dolichos biflorus agglutinin (DBA) tissue staining. Results The porcine B4GALNT2 gene shares a conserved genomic organization and encodes an open reading frame with 76 and 70% amino acid identity to the human and murine B4GALNT2 genes, respectively. The B4

  20. Redox intercalation of alkylammonium IONS into VOAsO/sub 4/. nH/sub 2/O

    SciTech Connect

    Lara, M.M.; Bruque, S.; Casal, B.; Lopez, A.J.; Real, L.M.; Ruiz-Hitzky, E.

    1985-05-01

    The layered, mixed-oxide hydrates, V /SUP v/ OAsO/sub 4/ . 3H/sub 2/O and V /SUP v/ OPO/sub 4/ . 2H/sub 2/O react with alkylammonium iodides to form (RNH/sub 3/) /SUB x/ V /SUB x/ /SUP 1v/ V /SUP v/ /SUB 1-x/ OAO/sub 4/ . H/sub 2/O, where R=PhCH/sub 2/, or C /SUB n/ H /SUB 2n+1/ (n=3 to 8), and x= .4 to .6 The intercalate materials exhibit a layered structure derived from the starting solids. After reaction the latter undergo a lamellar swelling which is in agreement with a ''pillar'' arrangement of alkylchains.

  1. Assessment of efficacy, safety, and tolerability of 4-n-butylresorcinol 0.3% cream: an Indian multicentric study on melasma

    PubMed Central

    Madan Mohan, NT; Gowda, Adarsh; Jaiswal, Ashok Kumar; Sharath Kumar, BC; Shilpashree, P; Gangaboraiah, Bilugumba; Shamanna, Manjula

    2016-01-01

    Introduction Melasma is one of the commonly reported pigmentory disorders in the Indian population. Numerous therapeutic modalities are available. However, very few have produced complete satisfactory response. 4-n-Butylresorcinol 0.3% cream has recently been introduced in India as a new hypopigmenting agent. It is a resorcinol derivative and acts by inhibiting both tyrosinase and tyrosinase-related protein-1. Objective The available published literatures are with 4-n-butylresorcinol 0.1% cream, and there is paucity of clinical studies with 4-n-butylresorcinol 0.3% cream. Furthermore, considering the fact that Indian skin is more prone to irritation with hypopigmenting agents, our study explores the efficacy, safety, and tolerability of 4-n-butylresorcinol 0.3% cream in Indian subjects with melasma. Methods Fifty-two subjects with melasma participated in this open-label, single arm, observational study. All the patients were advised twice daily application of 4-n-butylresorcinol 0.3% cream for 8 weeks over the areas of melasma. Assessment parameters included modified Melasma Area Severity Index (mMASI) score. Digital photographs of all the patients at baseline, week 4, and week 8 were taken. During this 8-week study period, all the adverse events were observed and recorded. Results All the 52 subjects completed the study. Out of 52 subjects, 90.38% were females. The mean age of patients was 38.5±7.8 years. Mean ± standard error of MASI score measurements showed a significant decrease from baseline score of 14.73±0.59 to 11.09±0.53 after week 4 (P<0.001) and 6.48±0.43 at week 8 (P<0.001). The digital photographs of the study subjects taken at week 4 and week 8 also showed decrease in melasma pigmentation compared to baseline photograph and correlated with the changes in the mMASI score. The treatment was well tolerated by all the study subjects. No adverse reactions were reported throughout the study period. Conclusion Our data suggest that the 4-n

  2. Synthesis, DNA binding and cleavage activities of copper (II) thiocyanate complex with 4-( N, N-dimethylamino)pyridine and N, N-dimethylformamide

    NASA Astrophysics Data System (ADS)

    Chen, Feng-juan; Xu, Min; Xi, Pin-xian; Liu, Hong-yang; Zeng, Zheng-zhi

    2011-10-01

    Two novel copper(II) thiocyanate complexes with 4-( N, N-dimethylamino) pyridine and N, N-dimethylformamide( 1) and with4-( N, N-dimethylamino) pyridine ( 2) have been synthesized and characterized. The crystal and molecular structures of complexes 1 and 2 were determined by single-crystal X-ray diffraction. Antioxidative activity tests in vitro showed that complex 1 has significant antioxidative activity against hydroxyl free radicals from the Fenton reaction and also oxygen free radicals, which is better than standard antioxidants like vitamin C and mannitol. The interaction of complex 1 with calf thymus DNA was investigated by spectroscopic, cyclic voltammetry, and viscosity measurements. Results suggest that complex 1 can bind to DNA via partial intercalation mode. Moreover, complex 1 has been found to cleavage of plasmid DNA pBR322.

  3. Synthesis, DNA binding and cleavage activities of copper (II) thiocyanate complex with 4-(N,N-dimethylamino)pyridine and N,N-dimethylformamide.

    PubMed

    Chen, Feng-juan; Xu, Min; Xi, Pin-xian; Liu, Hong-yang; Zeng, Zheng-zhi

    2011-10-15

    Two novel copper(II) thiocyanate complexes with 4-(N,N-dimethylamino) pyridine and N,N-dimethylformamide (1) and with 4-(N,N-dimethylamino) pyridine (2) have been synthesized and characterized. The crystal and molecular structures of complexes 1 and 2 were determined by single-crystal X-ray diffraction. Antioxidative activity tests in vitro showed that complex 1 has significant antioxidative activity against hydroxyl free radicals from the Fenton reaction and also oxygen free radicals, which is better than standard antioxidants like vitamin C and mannitol. The interaction of complex 1 with calf thymus DNA was investigated by spectroscopic, cyclic voltammetry, and viscosity measurements. Results suggest that complex 1 can bind to DNA via partial intercalation mode. Moreover, complex 1 has been found to cleavage of plasmid DNA pBR322. PMID:21723777

  4. Perpendicular magnetic anisotropy of Mn{sub 4}N films on MgO(001) and SrTiO{sub 3}(001) substrates

    SciTech Connect

    Yasutomi, Yoko; Ito, Keita; Sanai, Tatsunori; Toko, Kaoru; Suemasu, Takashi

    2014-05-07

    We grew Mn{sub 4}N epitaxial thin films capped with Au layers on MgO(001) and SrTiO{sub 3}(001) substrates by molecular beam epitaxy. Perpendicular magnetic anisotropy (PMA) was confirmed in all the samples at room temperature from the magnetization versus magnetic field curves using superconducting quantum interference device magnetometer. From the ω-2θ x-ray diffraction (XRD) and ϕ-2θ{sub χ} XRD patterns, the ratios of perpendicular lattice constant c to in-plane lattice constant a, c/a, were found to be about 0.99 for all the samples. These results imply that PMA is attributed to the in-plane tensile strain in the Mn{sub 4}N films.

  5. The first quaternary lanthanide(III) nitride iodides: NaM{sub 4}N{sub 2}I{sub 7} (M=La-Nd)

    SciTech Connect

    Schurz, Christian M.; Schleid, Thomas

    2010-10-15

    In attempts to synthesize lanthanide(III) nitride iodides with the formula M{sub 2}NI{sub 3} (M=La-Nd), moisture-sensitive single crystals of the first quaternary sodium lanthanide(III) nitride iodides NaM{sub 4}N{sub 2}I{sub 7} (orthorhombic, Pna2{sub 1}; Z=4; a=1391-1401, b=1086-1094, c=1186-1211 pm) could be obtained. The dominating structural features are {sup 1}{sub {infinity}}{l_brace}[NM{sub 4/2}{sup e}]{sup 3+}{r_brace} chains of trans-edge linked [NM{sub 4}]{sup 9+} tetrahedra, which run parallel to the polar 2{sub 1}-axis [001]. Between the chains, direct bonding via special iodide anions generates cages, in which isolated [NaI{sub 6}]{sup 5-} octahedra are embedded. The IR spectrum of NaLa{sub 4}N{sub 2}I{sub 7} recorded from 100 to 1000 cm{sup -1} shows main bands at {upsilon}=337, 373 and 489 cm{sup -1}. With decreasing radii of the lanthanide trications these bands, which can be assigned as an influence of the vibrations of the condensed [NM{sub 4}]{sup 9+} tetrahedra, are shifted toward higher frequencies for the NaM{sub 4}N{sub 2}I{sub 7} series (M=La-Nd), following the lanthanide contraction. - Abstract: View at the main structural features of the NaM{sub 4}N{sub 2}I{sub 7} series (M=La-Nd): The {sup 1}{sub {infinity}}{l_brace}[NM{sub 4/2}{sup e}]{sup 3+}{r_brace} chains, consisting of trans-edge connected [NM{sub 4}]{sup 9+} tetrahedra, and the special kind of iodide anions, namely (I7){sup -}, form cages, in which isolated [NaI{sub 6}]{sup 5-} octahedra are embedded.

  6. Synthesis and characterization of a cadmium bipyridinium compound (CdCl{sub 4})(N,N'-dimethyl-2,2'-bipyridinium)

    SciTech Connect

    Luo, Hui; Zhu, Li-Cheng; Wang, Qi

    2015-12-15

    A cadmium bipyridinium compound (CdCl{sub 4})(N,N'-dimethyl-2,2'-bipyridinium), in which the (N,N'-dimethyl-2,2'-bipyridinium){sup 2+} moieties were generated in situ, has been prepared via solvothermal reactions and structurally characterized with single crystal X-ray diffraction method. Fluorescence measurement revealed a broad and strong emission band in the blue region.

  7. Synthesis and evaluation of substituted 4-(N-benzylamino)cinnamate esters as potential anti-cancer agents and HIV-1 integrase inhibitors.

    PubMed

    Faridoon; Edkins, Adrienne L; Isaacs, Michelle; Mnkandhla, Dumisani; Hoppe, Heinrich C; Kaye, Perry T

    2016-08-01

    Encouraging selectivity and low micromolar activity against HeLa cervical carcinoma (IC50⩾3.0μM) and the aggressive MDA-MB-231 triple negative breast carcinoma (IC50⩾9.6μM) cell lines has been exhibited by a number of readily accessible 4-(N-benzylamino)cinnamate esters. The potential of the ligands as HIV-1 integrase inhibitors has also been examined. PMID:27317645

  8. Evaluation of four mathematical models to describe dissipation kinetics of 4-n-nonylphenol and bisphenol-A in groundwater-aquifer material slurry.

    PubMed

    Sarmah, Ajit K; Rohan, Maheswaran

    2011-01-01

    The performance of four mathematical models (hockey stick, biexponential, first-order double exponential decay, and first-order two-compartment) was evaluated to describe the dissipation kinetics for 4-n-nonylphenol (4-n-NP) and bisphenol-A (BPA) in groundwater-aquifer material slurry under aerobic and anaerobic conditions conducted under controlled laboratory conditions. The fit of each model to the measured values under both conditions was tested using an array of statistical indices to judge the model's ability to fit the measured datasets. Corresponding 50% (DT(50)) and 90% (DT(90)) dissipation values for each compound were numerically obtained and compared against each model. The model derived DT(50) values in groundwater-aquifer material ranged from 1.06 to 1.24 (4-n-NP) and 0.341 to 0.568 days (BPA) under aerobic condition, while they were 2- to 4-fold higher under anoxic condition. DT(90) values for 4-n-NP ranged anywhere between 2.3 and 4.45 days under both conditions, while DT(90) values for BPA ranged from around 1 day to as high as 12 days under both conditions tested. A visual examination of the measured and fitted plots as well as the statistical indices showed that, with the exception of the hockey stick model, the models performed satisfactorily. Despite having only 3 parameters, the biexponential model could describe the dissipation kinetics very well and this was supported by the statistical indices generated for each case. PMID:21069247

  9. Pharmacological stress is required for the anti-alcohol effect of the α3β4* nAChR partial agonist AT-1001

    PubMed Central

    Cippitelli, Andrea; Brunori, Gloria; Gaiolini, Kelly A.; Zaveri, Nurulain T.; Toll, Lawrence

    2015-01-01

    Alcohol and nicotine are often taken together. The mechanisms underlying this frequent co-abuse are not well known. Genetic and pharmacological evidence suggests that the nicotinic acetylcholine receptors (nAChRs) containing the α3 and β4 subunits play a role in alcohol as well as nicotine addiction. AT-1001 is a high affinity α3β4 nAChR partial agonist recently found to block nicotine self-administration and relapse-like behavior in rats. Here, to study the involvement of α3β4 nAChRs in the mechanisms that regulate alcohol abuse we evaluated the effects of AT-1001 on alcohol taking and seeking in Sprague-Dawley rats. AT-1001 reduced operant alcohol self-administration at the highest dose examined (3.0 mg/kg), an effect also observed for food self-administration. A dose of 1.5 mg/kg AT-1001, which had no effect on alcohol or food self-administration, essentially eliminated reinstatement of alcohol seeking induced by yohimbine (0.625 mg/kg) whereas, reinstatement induced by alcohol-associated cues was not altered, nor did AT-1001 induce reinstatement of extinguished self-administration on its own. Finally, AT-1001 showed an anxiolytic activity when measured in the presence or absence of yohimbine stress in the elevated plus maze paradigm. Together, these observations do not support a specific involvement of the α3β4 nAChR in mediating alcohol reward or cue-induced relapse to alcohol seeking but rather indicate that the α3β4 nAChR partial agonism may constitute an attractive approach for treating alcohol use disorders exacerbated by elevated stress response. PMID:25689019

  10. Pharmacological stress is required for the anti-alcohol effect of the α3β4* nAChR partial agonist AT-1001.

    PubMed

    Cippitelli, Andrea; Brunori, Gloria; Gaiolini, Kelly A; Zaveri, Nurulain T; Toll, Lawrence

    2015-06-01

    Alcohol and nicotine are often taken together. The mechanisms underlying this frequent co-abuse are not well known. Genetic and pharmacological evidence suggests that the nicotinic acetylcholine receptors (nAChRs) containing the α3 and β4 subunits play a role in alcohol as well as nicotine addiction. AT-1001 is a high affinity α3β4 nAChR partial agonist recently found to block nicotine self-administration and relapse-like behavior in rats. Here, to study the involvement of α3β4 nAChRs in the mechanisms that regulate alcohol abuse we evaluated the effects of AT-1001 on alcohol taking and seeking in Sprague-Dawley rats. AT-1001 reduced operant alcohol self-administration at the highest dose examined (3.0 mg/kg), an effect also observed for food self-administration. A dose of 1.5 mg/kg AT-1001, which had no effect on alcohol or food self-administration, essentially eliminated reinstatement of alcohol seeking induced by yohimbine (0.625 mg/kg) whereas, reinstatement induced by alcohol-associated cues was not altered, nor did AT-1001 induce reinstatement of extinguished self-administration on its own. Finally, AT-1001 showed an anxiolytic activity when measured in the presence or absence of yohimbine stress in the elevated plus maze paradigm. Together, these observations do not support a specific involvement of the α3β4 nAChR in mediating alcohol reward or cue-induced relapse to alcohol seeking but rather indicate that the α3β4 nAChR partial agonism may constitute an attractive approach for treating alcohol use disorders exacerbated by elevated stress response. PMID:25689019

  11. Coexistence of Three Ferroic Orders in the Multiferroic Compound [(CH3 )4 N][Mn(N3 )3 ] with Perovskite-Like Structure.

    PubMed

    Gómez-Aguirre, L Claudia; Pato-Doldán, Breogán; Stroppa, Alessandro; Yang, Li-Ming; Frauenheim, Thomas; Mira, Jorge; Yáñez-Vilar, Susana; Artiaga, Ramón; Castro-García, Socorro; Sánchez-Andújar, Manuel; Señarís-Rodríguez, María Antonia

    2016-06-01

    The perovskite azido compound [(CH3 )4 N][Mn(N3 )3 ], which undergoes a first-order phase change at Tt =310 K with an associated magnetic bistability, was revisited in the search for additional ferroic orders. The driving force for such structural transition is multifold and involves a peculiar cooperative rotation of the [MnN6 ] octahedral as well as order/disorder and off-center shifts of the [(CH3 )4 N](+) cations and bridging azide ligands, which also bend and change their coordination mode. According to DFT calculations the latter two give rise to the appearance of electric dipoles in the low-temperature (LT) polymorph, the polarization of which nevertheless cancels out due to their antiparallel alignment in the crystal. The conversion of this antiferroelectric phase to the paraelectric phase could be responsible for the experimental dielectric anomaly detected at 310 K. Additionally, the structural change involves a ferroelastic phase transition, whereby the LT polymorph exhibits an unusual and anisotropic thermal behavior. Hence, [(CH3 )4 N][Mn(N3 )3 ] is a singular material in which three ferroic orders coexist even above room temperature. PMID:27072487

  12. Calculation of the thermal conductivity of low-density CH4-N2 gas mixtures using an improved kinetic theory approach

    NASA Astrophysics Data System (ADS)

    Hellmann, Robert; Bich, Eckard; Vesovic, Velisa

    2016-04-01

    The thermal conductivity of low-density CH4-N2 gas mixtures has been calculated by means of the classical trajectory method using state-of-the-art intermolecular potential energy surfaces for the CH4-CH4, N2-N2, and CH4-N2 interactions. Results are reported in the temperature range from 70 K to 1200 K. Since the thermal conductivity is influenced by the vibrational degrees of freedom of the molecules, which are not included in the rigid-rotor classical trajectory computations, a new correction scheme to account for vibrational degrees of freedom in a dilute gas mixture is presented. The calculations show that the vibrational contribution at the highest temperature studied amounts to 46% of the total thermal conductivity of an equimolar mixture compared to 13% for pure nitrogen and 58% for pure methane. The agreement with the available experimental thermal conductivity data at room temperature is good, within ±1.4%, whereas at higher temperatures, larger deviations up to 4.5% are observed, which can be tentatively attributed to deteriorating performance of the measuring technique employed. Results are also reported for the magnitude and temperature dependence of the rotational collision number, Zrot, for CH4 relaxing in collisions with N2 and for N2 relaxing in collisions with CH4. Both collision numbers increase with temperature, with the former being consistently about twice the value of the latter.

  13. Calculation of the thermal conductivity of low-density CH4-N2 gas mixtures using an improved kinetic theory approach.

    PubMed

    Hellmann, Robert; Bich, Eckard; Vesovic, Velisa

    2016-04-01

    The thermal conductivity of low-density CH4-N2 gas mixtures has been calculated by means of the classical trajectory method using state-of-the-art intermolecular potential energy surfaces for the CH4-CH4, N2-N2, and CH4-N2 interactions. Results are reported in the temperature range from 70 K to 1200 K. Since the thermal conductivity is influenced by the vibrational degrees of freedom of the molecules, which are not included in the rigid-rotor classical trajectory computations, a new correction scheme to account for vibrational degrees of freedom in a dilute gas mixture is presented. The calculations show that the vibrational contribution at the highest temperature studied amounts to 46% of the total thermal conductivity of an equimolar mixture compared to 13% for pure nitrogen and 58% for pure methane. The agreement with the available experimental thermal conductivity data at room temperature is good, within ±1.4%, whereas at higher temperatures, larger deviations up to 4.5% are observed, which can be tentatively attributed to deteriorating performance of the measuring technique employed. Results are also reported for the magnitude and temperature dependence of the rotational collision number, Z(rot), for CH4 relaxing in collisions with N2 and for N2 relaxing in collisions with CH4. Both collision numbers increase with temperature, with the former being consistently about twice the value of the latter. PMID:27059564

  14. Local electronic states of Fe{sub 4}N films revealed by x-ray absorption spectroscopy and x-ray magnetic circular dichroism

    SciTech Connect

    Ito, Keita; Toko, Kaoru; Suemasu, Takashi; Takeda, Yukiharu; Saitoh, Yuji; Oguchi, Tamio; Kimura, Akio

    2015-05-21

    We performed x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) measurements at Fe L{sub 2,3} and N K-edges for Fe{sub 4}N epitaxial films grown by molecular beam epitaxy. In order to clarify the element specific local electronic structure of Fe{sub 4}N, we compared experimentally obtained XAS and XMCD spectra with those simulated by a combination of a first-principles calculation and Fermi's golden rule. We revealed that the shoulders observed at Fe L{sub 2,3}-edges in the XAS and XMCD spectra were due to the electric dipole transition from the Fe 2p core-level to the hybridization state generated by σ* anti-bonding between the orbitals of N 2p at the body-centered site and Fe 3d on the face-centered (II) sites. Thus, the observed shoulders were attributed to the local electronic structure of Fe atoms at II sites. As to the N K-edge, the line shape of the obtained spectra was explained by the dipole transition from the N 1s core-level to the hybridization state formed by π* and σ* anti-bondings between the Fe 3d and N 2p orbitals. This hybridization plays an important role in featuring the electronic structures and physical properties of Fe{sub 4}N.

  15. Spectroscopic studies of non-volatile residue formed by photochemistry of solid C4N2: A model of condensed aerosol formation on Titan

    NASA Astrophysics Data System (ADS)

    Couturier-Tamburelli, Isabelle; Gudipati, Murthy S.; Lignell, Antti; Jacovi, Ronen; Piétri, Nathalie

    2014-05-01

    Following our recent communication (Gudipati, M.S. et al. [2013]. Nat. Commun. 4, 1648. http://dx.doi.org/10.1038/ncomms2649) on the discovery of condensed-phase non-volatile polymeric material with similar spectral features as tholins, we present here a comprehensive spectroscopic study of photochemical formation of polymeric material from condensed dicyanoacetylene (C4N2) ice films. C4N2 is chosen as starting material for the laboratory simulations because of the detection of this and similar molecules (nitriles and cyanoacetylenes) in Titan’s atmosphere. UV-Vis and infrared spectra obtained during long-wavelength (>300 nm) photon irradiation and subsequent warming of the ice films are used to analyze changes in C4N2 ice, evolution of tholins, and derive photopolymerization mechanisms. Our data analysis revealed that many processes occur during the photolysis of condensed Titan’s aerosol analogs, including isomerization and polymerization leading to the formation of long-chain as well as aromatic cyclic polymer molecules. In the light of tremendous new data from the Cassini mission on the seasonal variations in Titan’s atmosphere, our laboratory study and its results provide fresh insight into the formation and evolution of aerosols and haze in Titan’s atmosphere.

  16. Structural and magnetic properties of ferrimagnetic ε-phase Mn4N and antiferromagnetic ζ-phase Mn10N thin films on MgO(001)

    NASA Astrophysics Data System (ADS)

    Foley, Andrew; Corbett, Joseph; Richard, Andrea L.; Alam, Khan; Ingram, David C.; Smith, Arthur R.

    2016-07-01

    Single phase ε-Mn4N and ζ-Mn10N thin films are grown on MgO(001) using molecular beam epitaxy. The films are identified and characterized using reflection high-energy electron diffraction, x-ray diffraction, back scattered electron scanning electron microscopy, atomic/magnetic force microscopy and Rutherford backscattering spectrometry. These films are found to be highly smooth with root-mean-squared roughnesses 3.39 nm and below. The quality of ε-Mn4N grown is strongly dependent on substrate temperature during growth. Epitaxial growth of substantial grains composed of the antiferromagnetic η-phase Mn3N2 side by side with ferrimagnetic ε-phase grains is observed when growth temperature is below 480 °C. Ising domains isolated within areas roughly 0.5 μm across are observed in the ferrimagnetic ε-phase grains of samples consisting of a mix of η- and ε-phase grains. Magnetic domains following semi-continuous paths, which are 0.7-7.2 μm across, are observed in single phase ε-Mn4N. Measurements of the ζ-phase detail the structure and magnetism of the material as high Mn content γ-type ζ-phase with a regular surface corrugation along the [100]-direction and antiferromagnetic.

  17. Adsorptive performance and catalytic activity of superparamagnetic Fe3O4@nSiO2@mSiO2 core-shell microspheres towards DDT.

    PubMed

    Liu, Feng; Tian, Hua; He, Junhui

    2014-04-01

    Due to specific properties, core-shell Fe3O4@SiO2 and core-shell-shell Fe3O4@nSiO2@mSiO2 nanostructures have been extensively investigated for the contamination treatment of wastewater. However, these reported materials were usually used as advanced adsorbents or catalyst-supports. In this study, we demonstrate that magnetic mesoporous silica Fe3O4@nSiO2@mSiO2 microspheres can not only exhibit excellent adsorptive performance for removal of DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane) from aqueous media, but also display high catalytic activity. Over 97% of DDT could be quickly removed from aqueous media in 60 min. At 60°C the DDE (1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene) content increases greatly as DDT disappears completely, and is decomposed completely after thermal treatment at a relatively low temperature of 450°C. The obtained magnetic mesoporous silica nanoparticles were characterized by X-ray diffraction, transmission electron microscopy, nitrogen adsorption-desorption measurements and vibrating sample magnetometer. The results indicate that Fe3O4@nSiO2@mSiO2 microspheres show strong superparamagnetism and have high specific surface area (577 m(2) g(-1)). PMID:24491332

  18. Thermodynamic stability, spectroscopic identification, and gas storage capacity of CO2-CH4-N2 mixture gas hydrates: implications for landfill gas hydrates.

    PubMed

    Lee, Hyeong-Hoon; Ahn, Sook-Hyun; Nam, Byong-Uk; Kim, Byeong-Soo; Lee, Gang-Woo; Moon, Donghyun; Shin, Hyung Joon; Han, Kyu Won; Yoon, Ji-Ho

    2012-04-01

    Landfill gas (LFG), which is primarily composed of CH(4), CO(2), and N(2), is produced from the anaerobic digestion of organic materials. To investigate the feasibility of the storage and transportation of LFG via the formation of hydrate, we observed the phase equilibrium behavior of CO(2)-CH(4)-N(2) mixture hydrates. When the specific molar ratio of CO(2)/CH(4) was 40/55, the equilibrium dissociation pressures were gradually shifted to higher pressures and lower temperatures as the mole fraction of N(2) increased. X-ray diffraction revealed that the CO(2)-CH(4)-N(2) mixture hydrate prepared from the CO(2)/CH(4)/N(2) (40/55/5) gas mixture formed a structure I clathrate hydrate. A combination of Raman and solid-state (13)C NMR measurements provided detailed information regarding the cage occupancy of gas molecules trapped in the hydrate frameworks. The gas storage capacity of LFG hydrates was estimated from the experimental results for the hydrate formations under two-phase equilibrium conditions. We also confirmed that trace amounts of nonmethane organic compounds do not affect the cage occupancy of gas molecules or the thermodynamic stability of LFG hydrates. PMID:22380606

  19. Electronic structure, molecular interaction, and stability of the CH4-nH2O complex, for n = 1-21.

    PubMed

    Bravo-Pérez, Graciela; Cruz-Torres, Armando; Romero-Martínez, Ascención

    2008-09-18

    Molecular calculations were carried out with four different methodologies to study the CH 4- nH 2O complex, for n = 1-21. The HF and MP2 methods used considered the O atom with pseudopotential to freeze the 1s shell. The other methodologies applied the Bhandhlyp and B3lyp exchange and correlation functionals. The optimized CH 4- nH 2O structures are reported, specifying the number and type of H 2O subunits (triangle, square, pentagon, etc.) that comprised the nH 2O counterpart cluster or cage, that interacted with the CH 4 molecule, and, in the latter case, that provided its confinement. Results are focused to understand the stability of the CH 4- nH 2O complex. The quality of the electron correlation effect, as well as the size of the nH 2O cage to confine the guest molecule, and the number and type of H 2O subunits comprising the nH 2O cluster or cage are the most important factors to provide the stability of the complex and also dictate the particular n value at which the CH 4 molecule confinement occurs. This number was 14 for the HF, Bhandhlyp, and B3Lyp methods and 16 for the MP2 method. The reported hydrate structures for n < 20 could be predictive for future experiments. PMID:18714955

  20. Long-term measurements of atmospheric trace gases (CO2, CH4, N2O, SF6, CO, H2), O2, and δ13CH4 isotopes at Weybourne Atmospheric Observatory, UK: past, present and future

    NASA Astrophysics Data System (ADS)

    Manning, Andrew C.; Forster, Grant L.; Oram, David E.; Reeves, Claire E.; Pickers, Penelope A.; Barningham, S. Thomas; Sturges, William T.; Bandy, Brian; Nisbet, Euan G.; Lowry, David; Fisher, Rebecca; Fleming, Zoe

    2016-04-01

    The Weybourne Atmospheric Observatory (WAO) is situated on the north Norfolk Coast (52.95°N, 1.13°E) in the United Kingdom and is run by the University of East Anglia (UEA), with support from the UK National Centre for Atmospheric Science (NCAS). In 2016, the WAO became a UK-ICOS (Integrated Carbon Observing System) monitoring station. Since 2008, we have been collecting high-precision long-term in situ measurements of atmospheric carbon dioxide (CO2), oxygen (O2), carbon monoxide (CO) and molecular hydrogen (H2), as well as regular bag sampling for δ13CH4. In early 2013, the measurement of atmospheric methane (CH4) commenced, and nitrous oxide (N2O) and sulphur hexafluoride (SF6) began in 2014. We summarise the CO2, O2, CH4, N2O, SF6, CO, H2 and δ13CH4 measurements made to date and highlight some key features observed (e.g. seasonal cycles, long-term trends, pollution events and deposition events). We summarise how the long-term measurements fit into other broader projects which have helped to support the long term time-series at WAO over the years, and highlight how we contribute to broader global atmospheric observation networks.

  1. Energy and charge transfers between (Bu{sub 4}N){sub 2}(Ru)(dcbpyH){sub 2}(NCS){sub 2} (N719) and ZnO thin films

    SciTech Connect

    Ni Manman; Cheng Qiang; Zhang, W. F.

    2010-03-15

    ZnO thin films and (Bu{sub 4}N){sub 2}(Ru)(dcbpyH){sub 2}(NCS){sub 2} (called N719) sensitized ZnO thin films are grown on fluorine-doped tin oxide (FTO) conducting glass substrates using laser molecular beam epitaxy. Ultraviolet-visible absorption, photoluminescence (PL), surface photovoltage spectroscopy, and Raman scattering are employed to probe into the transition process of photogenerated charges and the interaction between ZnO and N719. The experimental results indicate that there is a significant electronic interaction between N719 and ZnO through chemiadsorption. The interaction greatly enhances the photogenerated charge separation and thus the photovoltaic response of the ZnO film but remarkedly weakens its radiative recombination, i.e., PL, implying strong energy and charge transfer occurring between N719 and ZnO. In addition, a new PL peak observed at about 720 nm in N719 sensitized ZnO/FTO is attributed to the electron-hole recombination of N719.

  2. Graphene growth from reduced graphene oxide by chemical vapour deposition: seeded growth accompanied by restoration.

    PubMed

    Chang, Sung-Jin; Hyun, Moon Seop; Myung, Sung; Kang, Min-A; Yoo, Jung Ho; Lee, Kyoung G; Choi, Bong Gill; Cho, Youngji; Lee, Gaehang; Park, Tae Jung

    2016-01-01

    Understanding the underlying mechanisms involved in graphene growth via chemical vapour deposition (CVD) is critical for precise control of the characteristics of graphene. Despite much effort, the actual processes behind graphene synthesis still remain to be elucidated in a large number of aspects. Herein, we report the evolution of graphene properties during in-plane growth of graphene from reduced graphene oxide (RGO) on copper (Cu) via methane CVD. While graphene is laterally grown from RGO flakes on Cu foils up to a few hundred nanometres during CVD process, it shows appreciable improvement in structural quality. The monotonous enhancement of the structural quality of the graphene with increasing length of the graphene growth from RGO suggests that seeded CVD growth of graphene from RGO on Cu surface is accompanied by the restoration of graphitic structure. The finding provides insight into graphene growth and defect reconstruction useful for the production of tailored carbon nanostructures with required properties. PMID:26961409

  3. Graphene growth from reduced graphene oxide by chemical vapour deposition: seeded growth accompanied by restoration

    NASA Astrophysics Data System (ADS)

    Chang, Sung-Jin; Hyun, Moon Seop; Myung, Sung; Kang, Min-A.; Yoo, Jung Ho; Lee, Kyoung G.; Choi, Bong Gill; Cho, Youngji; Lee, Gaehang; Park, Tae Jung

    2016-03-01

    Understanding the underlying mechanisms involved in graphene growth via chemical vapour deposition (CVD) is critical for precise control of the characteristics of graphene. Despite much effort, the actual processes behind graphene synthesis still remain to be elucidated in a large number of aspects. Herein, we report the evolution of graphene properties during in-plane growth of graphene from reduced graphene oxide (RGO) on copper (Cu) via methane CVD. While graphene is laterally grown from RGO flakes on Cu foils up to a few hundred nanometres during CVD process, it shows appreciable improvement in structural quality. The monotonous enhancement of the structural quality of the graphene with increasing length of the graphene growth from RGO suggests that seeded CVD growth of graphene from RGO on Cu surface is accompanied by the restoration of graphitic structure. The finding provides insight into graphene growth and defect reconstruction useful for the production of tailored carbon nanostructures with required properties.

  4. Graphene growth from reduced graphene oxide by chemical vapour deposition: seeded growth accompanied by restoration

    PubMed Central

    Chang, Sung-Jin; Hyun, Moon Seop; Myung, Sung; Kang, Min-A; Yoo, Jung Ho; Lee, Kyoung G.; Choi, Bong Gill; Cho, Youngji; Lee, Gaehang; Park, Tae Jung

    2016-01-01

    Understanding the underlying mechanisms involved in graphene growth via chemical vapour deposition (CVD) is critical for precise control of the characteristics of graphene. Despite much effort, the actual processes behind graphene synthesis still remain to be elucidated in a large number of aspects. Herein, we report the evolution of graphene properties during in-plane growth of graphene from reduced graphene oxide (RGO) on copper (Cu) via methane CVD. While graphene is laterally grown from RGO flakes on Cu foils up to a few hundred nanometres during CVD process, it shows appreciable improvement in structural quality. The monotonous enhancement of the structural quality of the graphene with increasing length of the graphene growth from RGO suggests that seeded CVD growth of graphene from RGO on Cu surface is accompanied by the restoration of graphitic structure. The finding provides insight into graphene growth and defect reconstruction useful for the production of tailored carbon nanostructures with required properties. PMID:26961409

  5. Effects of substrates on N2O emissions in an anaerobic ammonium oxidation (anammox) reactor.

    PubMed

    Jin, Yue; Wang, Dunqiu; Zhang, Wenjie

    2016-01-01

    N2O emission in the anaerobic ammonium oxidation (anammox) process is of growing concern. In this study, effects of substrate concentrations on N2O emissions were investigated in an anammox reactor. Extremely high N2O emissions of 1.67 % were led by high NH4-N concentrations. Results showed that N2O emissions have a positive correlation with NH4-N concentrations in the anammox reactor. Reducing NH4-N concentrations by recycling pump resulted in decreasing N2O emissions. In addition, further studies were performed to identify a key biological process that is contributed to N2O emissions from the anammox reactor. Based on the results obtained, Nitrosomonas, which can oxidize ammonia to nitrite, was deemed as the main sources of N2O emissions. PMID:27376009

  6. Selective liquid phase oxidation of benzyl alcohol catalyzed by copper aluminate nanostructures

    NASA Astrophysics Data System (ADS)

    Ragupathi, C.; Judith Vijaya, J.; Thinesh Kumar, R.; John Kennedy, L.

    2015-01-01

    In this paper, a simple and economic route for the preparation of CuAl2O4 is proposed. The method was developed with the objective of obtaining a material with greater surface area, when compared to the spinel prepared by conventional combustion method (CCM). The catalytic properties of CuAl2O4 spinel prepared by CCM are compared with the one prepared microwave combustion method (MCM). Nano-sized CuAl2O4 were synthesized by both CCM and MCM using Opuntia dillenii haw as the plant extract, and were characterized by X-ray diffraction analysis (XRD), high resolution scanning electron microscopy (HR-SEM), N2 adsorption/desorption isotherms, and diffuse reflectance spectroscopy (DRS). Oxidation to their corresponding carbonyl compounds, high selectivity, and inexpensive precursors make this catalytic system a useful oxidation method for benzyl alcohol. The XRD results confirmed the formation of a cubic CuAl2O4. The formation of CuAl2O4 nanorices and nanorods structures were confirmed by HR-SEM. Through MCM method, CuAl2O4 (sample B) with a high specific surface area of was obtained. The band gap values of the (2.30 and 2.35 eV) for the obtained oxides are due to the nanometric dimensions of the nanostructures. The effect of the solvent, temperature, and oxidant on the oxidation of benzyl alcohol is reported.

  7. Nanoscale analysis of surface oxides on ZnMgAl hot-dip-coated steel sheets.

    PubMed

    Arndt, M; Duchoslav, J; Itani, H; Hesser, G; Riener, C K; Angeli, G; Preis, K; Stifter, D; Hingerl, K

    2012-05-01

    In this work, the first few nanometres of the surface of ZnMgAl hot-dip-galvanised steel sheets were analysed by scanning Auger electron spectroscopy, angle-resolved X-ray photoelectron spectroscopy and atomic force microscopy. Although the ZnMgAl coating itself is exhibiting a complex micro-structure composed of several different phases, it is shown that the topmost surface is covered by a smooth, homogeneous oxide layer consisting of a mixture of magnesium oxide and aluminium oxide, exhibiting a higher amount of magnesium than aluminium and a total film thickness of 4.5 to 5 nm. Especially by the combined analytical approach of surface-sensitive methods, it is directly demonstrated for the first time that within surface imprints--created by industrial skin rolling of the steel sheet which ensures a smooth surface appearance as well as reduced yield-point phenomenon--the original, smooth oxide layer is partly removed and that a layer of native oxides, exactly corresponding to the chemical structure of the underlying metal phases, is formed. PMID:22086398

  8. Chemical degradation of trimethyl phosphate as surrogate for organo-phosporus pesticides on nanostructured metal oxides

    SciTech Connect

    Štengl, Václav Henych, Jiří; Grygar, Tomáš; Pérez, Raúl

    2015-01-15

    Nanostructured TiO{sub 2} and mixed oxides of Ti and Fe, Hf, In, Mn or Zr -were prepared by homogeneous hydrolysis of aqueous solution of metal sulphates with urea. The oxides were characterised by X-ray powder diffraction (XRD), scanning electron microscopy, particle size distribution, surface area and porosity. The oxide materials consists of a few nanometre primary crystals (mainly anatase) arranged in a few micrometre regular spherical agglomerates with specific surface area 133–511 m{sup 2} g{sup −1}. The FTIR diffuse spectroscopy was used for monitoring chemical degradation of trimethylphosphate (TMP) as a surrogate for organo-phosphorus pesticides under ambient and higher temperatures. Undoped TiO{sub 2} and Ti,Mn-mixed oxide were most active in cleavage (hydrolysis) of CH{sub 3}O from TMP at room temperature and 100 °C. Cleavage of CH{sub 3}O in the other studied mixed oxides was not complete until temperature exceeds the boiling point of TMP.

  9. Penetrating the Elusive Mechanism of Copper-Mediated Fluoromethylation in the Presence of Oxygen through the Gas-Phase Reactivity of Well-Defined [LCuO](+) Complexes with Fluoromethanes (CH(4-n)Fn, n = 1-3).

    PubMed

    Rijs, Nicole J; González-Navarrete, Patricio; Schlangen, Maria; Schwarz, Helmut

    2016-03-01

    Traveling wave ion mobility spectrometry (TWIMS) isomer separation was exploited to react the particularly well-defined ionic species [LCuO](+) (L = 1,10-phenanthroline) with the neutral fluoromethane substrates CH(4-n)Fn (n = 1-3) in the gas phase. Experimentally, the monofluoromethane substrate (n = 1) undergoes both hydrogen-atom transfer, forming the copper hydroxide complex [LCuOH](•+) and concomitantly a CH2F(•) radical, and oxygen-atom transfer, yielding the observable ionic product [LCu](+) plus the neutral oxidized substrate [C,H3,O,F]. DFT calculations reveal that the mechanism for both product channels relies on the initial C-H bond activation of the substrate. Compared to nonfluorinated methane, the addition of fluorine to the substrate assists the reactivity through a lowering of the C-H bond energy and reaction preorganization (through noncovalent interaction in the encounter complex). A two-state reactivity scenario is mandatory for the oxidation, which competitively results in the unusual fluoromethanol product, CH2FOH, or the decomposed products, CH2O and HF, with the latter channel being kinetically disfavored. Difluoromethane (n = 2) is predicted to undergo the analogous reactions at room temperature, although the reactions are less favored than those of monofluoromethane. The reaction of trifluoromethane (n = 3, fluoroform) through C-H activation is kinetically hindered under ambient conditions but might be expected to occur in the condensed phase upon heating or with further lowering of reaction barriers through templation with counterions, such as potassium. Overall, formation of CH(3-n)Fn(•) and CH(3-n)FnOH occurs under relatively gentle energetic conditions, which sheds light on their potential as reactive intermediates in fluoromethylation reactions mediated by copper in the presence of oxygen. PMID:26859159

  10. A MALDI-TOF MS analysis study of the binding of 4-(N,N-dimethylamino)pyridine to amine-bis(phenolate) chromium(III) chloride complexes: mechanistic insight into differences in catalytic activity for CO2/epoxide copolymerization.

    PubMed

    Kozak, Christopher M; Woods, April M; Bottaro, Christina S; Devaine-Pressing, Katalin; Ni, Kaijie

    2015-01-01

    Amine-bis(phenolato)chromium(III) chloride complexes, [LCrCl], are capable of catalyzing the copolymerization of cyclohexene oxide with carbon dioxide to give poly(cyclohexane) carbonate. When combined with 4-(N,N-dimethylamino)pyridine (DMAP) these catalyst systems yield low molecular weight polymers with moderately narrow polydispersities. The coordination chemistry of DMAP with five amine-bis(phenolato)chromium(III) chloride complexes was studied by matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The amine-bis(phenolato) ligands were varied in the nature of their neutral pendant donor-group and include oxygen-containing tetrahydrofurfuryl and methoxyethyl moieties, or nitrogen-containing N,N-dimethylaminoethyl or 2-pyridyl moieties. The relative abundance of mono and bis(DMAP) adducts, as well as DMAP-free ions is compared under various DMAP : Cr complex ratios. The [LCr](+) cations show the ability to bind two DMAP molecules to form six-coordinate complex ions in all cases, except when the pendant group is N,N-dimethylaminoethyl (compound ). Even in the presence of a 4 : 1 ratio of DMAP to Cr, no ions corresponding to [L3Cr(DMAP)2](+) were observed for the complex containing the tertiary sp(3)-hybridized amino donor in the pendant arm. The difference in DMAP-binding ability of these compounds results in differences in catalytic activity for alternating copolymerization of CO2 and cyclohexene oxide. Kinetic investigations by infrared spectroscopy of compounds 2 and 3 show that polycarbonate formation by 3 is twice as fast as that of compound 2 and that no initiation time is observed. PMID:26388443

  11. Magnesium Oxide

    MedlinePlus

    ... repeatedly. Magnesium oxide also is used as a dietary supplement when the amount of magnesium in the diet ... any products such as vitamins, minerals, or other dietary supplements. You should bring this list with you each ...

  12. Yttrium oxide stabilized zirconium oxide

    SciTech Connect

    Ritsko, J.E.; Houck, D.L.; Acla, H.L.R.

    1987-09-22

    This patent describes a process comprising: (a) forming a solution by mixing yttrium hydroxide and a sufficient amount of an aqueous solution of acetic acid to dissolve the yttrium hydroxide. The solution has a concentration of yttrium ion of about 5% to about 20% by weight of the solution, (b) adding from about 80% to about 95% by weight of zirconium oxide having a particle size range from about 1 to about 5 microns to yield a Zr to Y weight ratio of from about 4:1 to about 19:1 and thereby forming a slurry, (c) spray drying the slurry to form spherical agglomerates consisting essentially of zirconium oxide and a relatively uniform distribution of yttrium acetate whereby the agglomerates have a size from about 20 to about 200 micrometers, (d) heating the agglomerates to about 600/sup 0/C to about 700/sup 0/C in a neutral or oxidizing atmosphere to convert yttrium acetate to yttrium oxide to thereby form zirconium oxide yttrium oxide agglomerates with about 5% to about 20% by weight of yttrium oxide.

  13. Diffusion of ion-implanted group 4 n-type dopants in gallium arsenide and gallium/arsenide-based superlattices

    NASA Astrophysics Data System (ADS)

    Allen, Emily Lin

    1992-09-01

    As semiconductor device dimensions shrink, understanding and controlling dopant diffusion becomes increasingly important. For submicron FET's made in GaAs, dopant diffusion during post-implant anneal is undesirable. In addition, impurity induced intermixing of III-V heterostructures for optoelectronic devices requires a series of carefully controlled diffusion steps. A more complete understanding of the diffusion mechanisms of dopants and point defects in both GaAs and Al(x)Ga(1-x)As is thus required for several advanced technologies. Most of the published parameters for diffusion of dopants in III-V compound semiconductors are from thin film or vapor source diffusions. The effect of implant damage and extended defects on diffusion of implanted dopants in GaAs and Al(x)Ga(1-x)As has not been extensively studied. In this work we measure the carrier concentrations and diffusivities of the ion-implanted Group IV dopants Sn, Ge and Si in GaAs and Al(x)Ga(1-x)As, using SIMS, polaron and SUPREM 3.5 simulations. In the substrate, diffusion is modeled by an effective diffusivity which depends on the square of the electron concentration (n), due to enhancement of the negatively charged Ga vacancy concentration by the n-type doping. In the near-surface implanted region diffusion is suppressed for doses greater than 1 x 10(exp 14)/sq cm. The carrier concentrations for Sn implants are anomalously high in this region, and anomalously low for Ge and Si. Transmission electron microscopy shows that precipitates and dislocations form in the implanted region during annealing for doses greater than 1 x 10(exp 14)/sq cm. These extended defects may influence dopant diffusion by controlling the generation and recombination of point defects. The carrier concentration-dependent diffusion model is applied to interdiffusion of Al and Ga in AlAs/Al(x)Ga(1-x)As superlattice structures. We show that interdiffusion is enhanced more under an oxide film than under a nitride film, while a tungsten

  14. Alkene oxidation catalyzed by a ruthenium-substituted heteropolyanion, SiRu(L)W sub 11 O sub 39 : The mechanism of the periodate mediated oxidative cleavage

    SciTech Connect

    Neumann, R.; Abu-Gnim, C. )

    1990-08-01

    A ruthenium-substituted heteropolyanion SiRu(H{sub 2}O)W{sub 11}O{sub 39}{sup 5{minus}} was synthesized and characterized. The hydrophobic quaternary ammonium salt of the heteropolyanion ((C{sub 6}H{sub 13}){sub 4}N){sub 5}SiRu{sup III}(H{sub 2}O)W{sub 11}O{sub 39} was used as a catalyst for the oxidation of alkenes with tert-butyl hydroperoxide, potassium persulfate, iodosobenzene, and sodium periodate as primary oxidants. Reactivity and selectivity were found to be dependent on the oxidant used; several different types of oxidation processes could be identified including allylic oxidation, epoxidation, and oxidative cleavage. Use of sodium periodate as oxidant enabled selective bond cleavage with aldehydes as the exclusive product.

  15. Epitaxial V{sub 0.6}W{sub 0.4}N/MgO(001): Evidence for ordering on the cation sublattice

    SciTech Connect

    Kindlund, H.; Lu, J.; Jensen, J.; Hultman, L.; Petrov, I.; Greene, J. E.

    2013-07-15

    V{sub 0.6}W{sub 0.4}N alloys are grown on MgO(001) by ultrahigh vacuum reactive magnetron sputtering from V and W targets in 10 mTorr pure-N{sub 2} atmospheres at temperatures T{sub s} ranging from 600 to 900 Degree-Sign C. Based on x-ray diffraction and transmission electron microscopy results, all films have the B1-NaCl crystal structure and grow with a cube-on-cube epitaxial relationship to the substrate, (001){sub VWN} Double-Vertical-Line (001){sub MgO} and [100]{sub VWN} Double-Vertical-Line [100]{sub MgO}. Rutherford backscattering spectrometry analyses show that the N content in V{sub 0.6}W{sub 0.4}N{sub x} alloys decreases with increasing T{sub s} from overstoichiometric with x = 1.13 at 600 Degree-Sign C, to approximately stoichiometric with x = 1.08 at 700 Degree-Sign C, to understoichiometric at 800 Degree-Sign C (x = 0.80) and 900 Degree-Sign C (x = 0.75). High-resolution scanning transmission electron microscopy, Z-contrast, and selected-area electron diffraction investigations of V{sub 0.6}W{sub 0.4}N(001) alloys grown at 600 and 700 Degree-Sign C reveal the onset of W ordering on adjacent 111 planes of the metal sublattice; no ordering is observed for understoichiometric films grown at higher temperatures.

  16. Definitive radiotherapy with or without chemotherapy for clinical stage T4N0-1 non-small cell lung cancer

    PubMed Central

    Kim, Yeon Joo; Jeong, Seong-Yun; Kim, Sang We; Lee, Jung-Shin; Kim, Su Ssan; Choi, Wonsik; Choi, Eun Kyung

    2015-01-01

    Purpose To determine failure patterns and survival outcomes of T4N0-1 non-small cell lung cancer (NSCLC) treated with definitive radiotherapy. Materials and Methods Ninety-five patients with T4N0-1 NSCLC who received definitive radiotherapy with or without chemotherapy from May 2003 to October 2014 were retrospectively reviewed. The standard radiotherapy scheme was 66 Gy in 30 fractions. The main concurrent chemotherapy regimen was 50 mg/m2 weekly paclitaxel combined with 20 mg/m2 cisplatin or AUC 2 carboplatin. The primary outcome was overall survival (OS). Secondary outcomes were failure patterns and toxicities. Results The median age was 64 years (range, 34 to 90 years). Eighty-eight percent of patients (n = 84) had an Eastern Cooperative Oncology Group performance status of 0-1, and 42% (n = 40) experienced pretreatment weight loss. Sixty percent of patients (n = 57) had no metastatic regional lymph nodes. The median radiation dose was EQD2 67.1 Gy (range, 56.9 to 83.3 Gy). Seventy-one patients (75%) were treated with concurrent chemotherapy; of these, 13 were also administered neoadjuvant chemotherapy. At a median follow-up of 21 months (range, 1 to 102 months), 3-year OS was 44%. The 3-year cumulative incidences of local recurrence and distant recurrence were 48.8% and 36.3%, respectively. Pretreatment weight loss and combined chemotherapy were significant factors for OS. Acute esophagitis over grade 3 occurred in three patients and grade 3 chronic esophagitis occurred in one patient. There was no grade 3-4 radiation pneumonitis. Conclusion Definitive radiotherapy for T4N0-1 NSCLC results in favorable survival with acceptable toxicity rates. Local recurrence is the major recurrence pattern. Intensity modulated radiotherapy and radio-sensitizing agents would be needed to improve local tumor control. PMID:26756028

  17. Second hyperpolarizability of the calcium-doped lithium salt of pyridazine Li-H3C4N2 ⋯ Ca

    NASA Astrophysics Data System (ADS)

    Marques, Suélio; Castro, Marcos A.; Leão, Salviano A.; Fonseca, Tertius L.

    2016-08-01

    In this work we report results of coupled cluster calculations for the second hyperpolarizability of the calcium-doped lithium salt of pyridazine (Li-H3C4N2 ⋯ Ca) molecule. In the static limit an unusual value of 4.34 ×106 au was obtained at the CCSD level of calculation. Results obtained for the dc-Kerr effect through SCF, CCS and CCSD methods show that γ (- ω; ω, 0, 0) is strongly dependent of the electron correlation treatment. Dynamic results obtained at the CCSD level are also reported for the IDRI, dc-SHG and THG nonlinear optical processes.

  18. Synthesis, spectral characteristics, and the crystal and molecular structures of 2,3-dimethyl-1-phenyl-4-(N-phthalimido)pyrazolone-5

    SciTech Connect

    Sokol, V. I.; Strashnova, S. B. Kovalchukova, O. V.; Sergienko, V. S.; Davydov, V. V.; Zaitsev, B. E.; Evtushenko, Yu. M.

    2008-11-15

    2,3-Dimethyl-1-phenyl-4-(N-phthalimido)pyrazolone-5 (I) is synthesized and isolated in the form of single crystals. The crystal structure of compound I is determined using X-ray diffraction. The phthalimide and pyrazolone rings in the molecule are not coplanar: the angle between their median planes is 56.4{sup o}. The bond lengths in the rings level off, which indicates the delocalization of the electron density. The spectral characteristics (IR and electronic spectra) of molecule I are determined.

  19. Synthesis, spectral characteristics, and the crystal and molecular structures of 2,3-dimethyl-1-phenyl-4-( N-phthalimido)pyrazolone-5

    NASA Astrophysics Data System (ADS)

    Sokol, V. I.; Strashnova, S. B.; Kovalchukova, O. V.; Sergienko, V. S.; Davydov, V. V.; Zaĭtsev, B. E.; Evtushenko, Yu. M.

    2008-11-01

    2,3-Dimethyl-1-phenyl-4-( N-phthalimido)pyrazolone-5 ( I) is synthesized and isolated in the form of single crystals. The crystal structure of compound I is determined using X-ray diffraction. The phthalimide and pyrazolone rings in the molecule are not coplanar: the angle between their median planes is 56.4°. The bond lengths in the rings level off, which indicates the delocalization of the electron density. The spectral characteristics (IR and electronic spectra) of molecule I are determined.

  20. Fine specificity of domain-I of recombinant tandem-repeat-type galectin-4 from rat gastrointestinal tract (G4-N).

    PubMed Central

    Wu, Albert M; Wu, June H; Tsai, Ming-Sung; Liu, Jia-Hau; André, Sabine; Wasano, Kojiro; Kaltner, Herbert; Gabius, Hans-Joachim

    2002-01-01

    Galectins, a family of beta-galactoside-specific endogenous lectins, are involved in regulating diverse activities such as proliferation/apoptosis, cell-cell (matrix) interaction and cell migration. It is presently unclear to what extent the carbohydrate fine specificities of the combining sites of mammalian galectins overlap. To address this issue, we performed an analysis of the carbohydrate-recognition domain (CRD-I) near the N-terminus of recombinant rat galectin-4 (G4-N) by the biotin/avidin-mediated microtitre plate lectin-binding assay with natural glycoproteins (gps)/polysaccharide and by the inhibition of galectin-glycan interactions with a panel of glycosubstances. Among the 35 glycans tested for lectin binding, G4-N reacted best with human blood group ABH precursor gps, and asialo porcine salivary gps, which contain high densities of the blood group Ii determinants Galbeta1-3GalNAc (the mucin-type sugar sequence on the human erythrocyte membrane) and/or GalNAcalpha1-Ser/Thr ( Tn ), whereas this lectin domain reacted weakly or not at all with most sialylated gps. Among the oligosaccharides tested by the inhibition assay, Galbeta1-3GlcNAcbeta1-3Galbeta1-4Glc was the best. It was 666.7 and 33.3 times more potent than Gal and Galbeta1-3GlcNAc, respectively. G4-N has a preference for the beta-anomer of Gal at the non-reducing ends of oligosaccharides with a Galbeta1-3 linkage, over Galbeta1-4 and Galbeta1-6. The fraction of Tn glycopeptide from asialo ovine submandibular glycoprotein was 8.3 times more active than Galbeta1-3GlcNAc. The overall carbohydrate specificity of G4-N can be defined as Galbeta1-3GlcNAcbeta1-3Galbeta1-4Glc (lacto- N -tetraose)>Galbeta1-4GlcNAcbeta1-3Galbeta1-4Glc (lacto- N -neo-tetraose) and Tn clusters>Galbeta1-4Glc and GalNAcbeta1-3Gal>Galbeta1-3GalNAc>Galbeta1-3GlcNAc>Galbeta1-4GlcNAc>GalNAc>Gal. The definition of this binding profile provides the basis to detect differential binding properties relative to the other galectins with

  1. Rapid thermal chemical vapor deposition of thin silicon oxide films using silane and nitrous oxide

    NASA Astrophysics Data System (ADS)

    Xu, X. L.; Kuehn, R. T.; Wortman, J. J.; Öztürk, M. C.

    1992-06-01

    Thin (80-200 Å) silicon dioxide (SiO2) films have been deposited by low pressure rapid thermal chemical vapor deposition (RTCVD), using silane (SiH4) and nitrous oxide (N2O) as the reactive gases for the first time. A deposition rate of 55 Å/min has been achieved at 800 °C with a SiH4/N2O flow rate ratio of 2%. Auger electron spectroscopy (AES) and Rutherford back scattering spectroscopy (RBS) have shown a uniform and stoichiometric composition throughout the deposited oxide films. Electrical characterization of the films have shown an average catastrophic breakdown field of 13 MV/cm and a midgap interface trap density (Dit) of equal to or less than 5×1010 eV-1 cm-2. The results suggest that the deposited RTCVD SiO2 films using SiH4-N2O gas system may have the potential to be used as the gate dielectric in future low-temperature metal oxide semiconductor (MOS) device processes for ultralarge scale integration (ULSI).

  2. Gas Atomization Precursor Powder Approach for Simplified Large-Scale Production of Oxide Dispersion

    SciTech Connect

    Meyer, John; Anderson, Iver; Rieken, Joel; Byrd, David

    2011-04-01

    Oxide dispersion strengthened (ODS) Ni-based alloys show promise for future energy applications that require high-temperature and oxidation resistant properties. Gas atomization reaction synthesis (GARS), with a mixed (Ar/O{sub 2}) atomization gas, is being developed as a simplified route for producing ODS precursor powders. Internal oxidation studies determined Ni-Cr-Y-(Hf or Ti) containing systems are suitable for production of ODS alloys via hot consolidation, which is used to encourage oxygen exchange between the less stable surface oxide phase and reactive alloying elements, resulting in highly stable nano-metric dispersoid formation. Size control of powders is key to optimizing microstructural and strengthening features. Aspiration and, previously, water modeling experiments were used to develop atomization process parameters that encourage controlled powder production while maintaining reduced operating costs when implemented on an industrial scale. For an increase in pour tube extension: aspiration base pressure at any given operating pressure was found to decrease while wake closure pressure was found to increase. Aspiration hysteresis was observed as recorded previously in the literature. Light emission was observed above wake closure pressures.

  3. Oxidation catalyst

    DOEpatents

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  4. Oxide Thermoelectrics

    SciTech Connect

    Singh, David J

    2008-01-01

    Thermoelectricity in oxides, especially NaxCoO2 and related materials, is discussed from the point of view of first principles calculations and Boltzmann transport theory. The electronic structure of this material is exceptional in that it has a combination of very narrow bands and strong hybridization between metal d states and ligand p states. As shown within the framework of conventional Boltzmann transport theory, this leads to high Seebeck coefficients even at metallic carrier densities. This suggests a strategy of searching for other narrow band oxides that can be doped metallic with mobile carriers. Some possible avenues for finding such materials are suggested.

  5. Influence of bulking agents on CH4, N2O, and NH3 emissions during rapid composting of pig manure from the Chinese Ganqinfen system*

    PubMed Central

    Sun, Xiang-ping; Lu, Peng; Jiang, Tao; Schuchardt, Frank; Li, Guo-xue

    2014-01-01

    Mismanagement of the composting process can result in emissions of CH4, N2O, and NH3, which have caused severe environmental problems. This study was aimed at determining whether CH4, N2O, and NH3 emissions from composting are affected by bulking agents during rapid composting of pig manure from the Chinese Ganqinfen system. Three bulking agents, corn stalks, spent mushroom compost, and sawdust, were used in composting with pig manure in 60 L reactors with forced aeration for more than a month. Gas emissions were measured continuously, and detailed gas emission patterns were obtained. Concentrations of NH3 and N2O from the composting pig manure mixed with corn stalks or sawdust were higher than those from the spent mushroom compost treatment, especially the sawdust treatment, which had the highest total nitrogen loss among the three runs. Most of the nitrogen was lost in the form of NH3, which accounts for 11.16% to 35.69% of the initial nitrogen. One-way analysis of variance for NH3 emission showed no significant differences between the corn stalk and sawdust treatments, but a significant difference was noted between the spent mushroom compost and sawdust treatments. The introduction of sawdust reduced CH4 emission more than the corn stalks and spent mushroom compost. However, there were no significant differences among the three runs for total carbon loss. All treatments were matured after 30 d. PMID:24711356

  6. Removal of ZnO nanoparticles in simulated wastewater treatment processes and its effects on COD and NH(4)(+)-N reduction.

    PubMed

    Hou, Linlin; Xia, Jing; Li, Kaiyang; Chen, Jian; Wu, Xiaolei; Li, Xiqing

    2013-01-01

    For many engineered nanoparticles, the primary pathway of release into the environment is via sewage and industrial wastewater discharges. In this work, the removal of uncoated ZnO nanoparticles (ZnO NPs) during simulated wastewater treatment processes and its impact on treatment performance were examined. Simulated primary clarification removed the majority (about 70%) of the dosed ZnO NPs. During simulated sequencing batch reactor (SBR) processes, ZnO NPs were completely removed in each cycle throughout the 11-day experimental duration (two cycles per day). Continuous input of ZnO NPs into the wastewater (at concentrations up to 5 mg L(-1)) did not reduce chemical oxygen demand (COD) removal. NH(4)(+)-N removal was reduced at a dosing concentration of 5 mg L(-1) ZnO NPs per cycle. Inhibition of respiration of nitrifying microorganisms by ZnO NPs corroborated the reduction of NH(4)(+)-N removal. These results indicate that if the wastewater is treated, the release of ZnO NPs into receiving water bodies would be minimal and ZnO NPs would mainly accumulate in biosolids. Uncoated ZnO NPs in wastewater at very high concentrations may have some adverse effects on activated sludge process. PMID:23168621

  7. Li3VO4/N-doped graphene with high capacity and excellent cycle stability as anode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Ni, Shibing; Zhang, Jicheng; Ma, Jianjun; Yang, Xuelin; Zhang, Lulu

    2015-11-01

    Li3VO4/N-doped graphene with unique architecture of Li3VO4 nanoparticles embed in N-doped graphene is successfully prepared via a facile method, which shows superior electrochemical performance as anode for Li-ion batteries. At a specific current of 0.15 A g-1, it delivers discharge and charge capacities of 550 and 429 mAh g-1 in the initial cycle, which maintain of 478 and 476 mAh g-1 after 100 cycles. After 150 cycles at various specific currents from 0.1 to 2.0 A g-1, the discharge capacity can restore to 487 mAh g-1 when reverting the specific current to 0.1 A g-1. Meanwhile, even after 900 cycles at a specific current of 2.0 A g-1, the Li3VO4/N-doped graphene electrode can deliver discharge and charge capacities of 195 and 193 mAh g-1.

  8. Cytocompatibility of amorphous hydrogenated carbon nitride films deposited by CH4/N2 dielectric barrier discharge plasmas with respect to cell lines

    NASA Astrophysics Data System (ADS)

    Majumdar, Abhijit; Schröder, Karsten; Hippler, Rainer

    2008-10-01

    Special amorphous hydrogenated carbon nitride (a-H-CNx) films have been prepared on glass substrates for the investigation of adhesion and proliferation of different mammalian cell lines. CH4/N2 dielectric barrier discharge plasmas were applied to deposit a-H-CNx coatings at half of the atmospheric pressure. Film quality was modified by varying the CH4:N2 ratio and deposition duration. Chemical composition was determined by x-ray photoelectron spectroscopy and Fourier transformed infrared spectroscopy. The N/C ratio was in the range of 0.20-0.55. A very small surface roughness was verified by atomic force microscopy. Human embryonic kidney (HEK) and rat adrenal pheochromocytoma (PC12) cells were cultivated on the a-H-CNx films to investigate the cytocompatibility of these surfaces. The microscopic images show that both kinds of cells lines were unable to survive. The cells did not adhere to the surfaces, and most of the cells died after certain time spans. Increased amounts of nitrogen in the film induce an accelerated cell death. It is concluded, that the deposited CNx film behaves cytotoxic to HEK and PC12 cell lines.

  9. Merphos oxide

    Integrated Risk Information System (IRIS)

    Merphos oxide ; CASRN 78 - 48 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effe

  10. Propylene oxide

    Integrated Risk Information System (IRIS)

    Propylene oxide ; CASRN 75 - 56 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

  11. Thallium oxide

    Integrated Risk Information System (IRIS)

    Thallium oxide ; CASRN 1314 - 32 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

  12. Nitric oxide

    Integrated Risk Information System (IRIS)

    Nitric oxide ; CASRN 10102 - 43 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

  13. ALTERNATIVE OXIDANTS

    EPA Science Inventory

    This chapter reports on the efforts of the USEPA to study chloramines, chlorine dioxide and ozone as alternative oxidants/disinfectants to chlorine for the control of disinfection by-rpdocuts (DBPs) in drinking water. It examines the control of DBPs like trihalomethanes and haloa...

  14. The Grapevine Root-Specific Aquaporin VvPIP2;4N Controls Root Hydraulic Conductance and Leaf Gas Exchange under Well-Watered Conditions But Not under Water Stress1[W

    PubMed Central

    Perrone, Irene; Gambino, Giorgio; Chitarra, Walter; Vitali, Marco; Pagliarani, Chiara; Riccomagno, Nadia; Balestrini, Raffaella; Kaldenhoff, Ralf; Uehlein, Norbert; Gribaudo, Ivana; Schubert, Andrea; Lovisolo, Claudio

    2012-01-01

    We functionally characterized the grape (Vitis vinifera) VvPIP2;4N (for Plasma membrane Intrinsic Protein) aquaporin gene. Expression of VvPIP2;4N in Xenopus laevis oocytes increased their swelling rate 54-fold. Northern blot and quantitative reverse transcription-polymerase chain reaction analyses showed that VvPIP2;4N is the most expressed PIP2 gene in root. In situ hybridization confirmed root localization in the cortical parenchyma and close to the endodermis. We then constitutively overexpressed VvPIP2;4N in grape ‘Brachetto’, and in the resulting transgenic plants we analyzed (1) the expression of endogenous and transgenic VvPIP2;4N and of four other aquaporins, (2) whole-plant, root, and leaf ecophysiological parameters, and (3) leaf abscisic acid content. Expression of transgenic VvPIP2;4N inhibited neither the expression of the endogenous gene nor that of other PIP aquaporins in both root and leaf. Under well-watered conditions, transgenic plants showed higher stomatal conductance, gas exchange, and shoot growth. The expression level of VvPIP2;4N (endogenous + transgene) was inversely correlated to root hydraulic resistance. The leaf component of total plant hydraulic resistance was low and unaffected by overexpression of VvPIP2;4N. Upon water stress, the overexpression of VvPIP2;4N induced a surge in leaf abscisic acid content and a decrease in stomatal conductance and leaf gas exchange. Our results show that aquaporin-mediated modifications of root hydraulics play a substantial role in the regulation of water flow in well-watered grapevine plants, while they have a minor role upon drought, probably because other signals, such as abscisic acid, take over the control of water flow. PMID:22923680

  15. Role of hydrogen on the deposition and properties of fluorinated silicon-nitride films prepared by inductively coupled plasma enhanced chemical vapor deposition using SiF{sub 4}/N{sub 2}/H{sub 2} mixtures

    SciTech Connect

    Fandino, J.; Santana, G.; Rodriguez-Fernandez, L.; Cheang-Wong, J.C.; Ortiz, A.; Alonso, J.C.

    2005-03-01

    Fluorinated silicon-nitride films have been prepared at low temperature (250 deg. C) by remote plasma enhanced chemical vapor deposition using mixtures of SiF{sub 4}, N{sub 2}, Ar, and various H{sub 2} flow rates. The deposited films were characterized by means of single wavelength ellipsometry, infrared transmission, resonant nuclear reactions, Rutherford backscattering analysis, and current-voltage measurements. It was found that films deposited without hydrogen grow with the highest deposition rate, however, they result with the highest fluorine content ({approx}27 at. %) and excess of silicon (Si/N ratio{approx_equal}1.75). These films also have the lowest refractive index and the highest etch rate, and exhibit very poor dielectric properties. As a consequence of the high fluorine content, these films hydrolize rapidly upon exposure to the ambient moisture, forming Si-H and N-H bonds, however, they do not oxidize completely. The addition of hydrogen to the deposition process reduces the deposition rate but improves systematically the stability and insulating properties of the films by reducing the amount of both silicon and fluorine incorporated during growth. All the fluorinated silicon-nitride films deposited at hydrogen flow rates higher than 3.5 sccm resulted free of Si-H bonds. In spite of the fact that films obtained at the highest hydrogen flow rate used in this work are still silicon rich (Si/N ratio{approx_equal}1.0) and contain a considerable amount of fluorine ({approx}16 at. %), they are chemically stable and show acceptable dielectric properties.

  16. Direct Observation, Molecular Structure, and Location of Oxidation Debris on Graphene Oxide Nanosheets.

    PubMed

    Chen, Xiaoxiao; Chen, Baoliang

    2016-08-16

    The presence of oxidation debris (OD) complicates the structures and properties of graphene oxide (GO) nanosheets, thereby impacting their potential applications. However, the origin of OD is still in dispute. Moreover, characterizing the structure and location of supposed OD on nanosheets of GO produced during the oxidation process is difficult. Herein, the attached state and size of OD on graphene oxide nanosheets were directly observed using HRTEM, the molecular structure of OD was initially proposed based on the spectroscopic characterization and Q-TOF mass spectrometry, and the locations of OD on the GO nanosheets were detected through the adsorption of probe molecules onto as-prepared GO (a-GO) and base-washed GO (bw-GO). The results indicated that OD possesses a highly crystalline structure and can be defined as several nanometre-sized polyaromatic molecules with a considerable number of oxygen-containing functional groups attached on the edges. The dark nanodot seated on a-GO was clearly observed in the HRTEM images, whereas it appeared as a clean nanosheet in the image of bw-GO, indicating that OD is removed by base-washing treatment. Following the base-washing treatment, the contents of carboxyl groups on bw-GO unexpectedly increased and subsequently contributed to the desorption of OD from a-GO due to the electrostatic repulsion being stronger than primary π-π interactions. Compared with a-GO, the adsorption of phenanthrene, as an aromatic probe, onto bw-GO increased by 6-fold via π-π stacking interactions, whereas the increase in the adsorption of m-dinitrobenzene, as a defect probe, was not as remarkable as that of phenanthrene. Reasonably, the OD nanoparticles were primarily located at the sp(2) structures on the GO nanosheets through π-π interactions rather than attached on defects/edges. The insights regarding the existence, molecular structures and attached sites of OD nanoparticles on GO nanosheets provide a theoretical basis for preparing

  17. Fabrication of thin yttria-stabilized-zirconia dense electrolyte layers by inkjet printing for high performing solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Esposito, Vincenzo; Gadea, Christophe; Hjelm, Johan; Marani, Debora; Hu, Qiang; Agersted, Karsten; Ramousse, Severine; Jensen, Søren Højgaard

    2015-01-01

    In this work, we present how a low-cost HP Deskjet 1000 inkjet printer was used to fabricate a 1.2 μm thin, dense and gas tight 16 cm2 solid oxide fuel cells (SOFC) electrolyte. The electrolyte was printed using an ink made of highly diluted (<4 vol.%) nanometric yttria stabilized zirconia (YSZ) powders (50 nm in size) in an aqueous medium. The ink was designed to be a highly dispersed, long term stable colloidal suspension, with optimal printability characteristics. The electrolyte was made by a multiple printing procedure, which ensures coverage of the several flaws occurring in a single printing pass. Together with an optimized sintering procedure this resulted in good adhesion and densification of the electrolyte. The SOFC exhibited a close-to-theoretical open circuit voltage and a remarkable peak power density above 1.5 W cm-2 at 800 °C.

  18. Three-dimensional patterning of solid microstructures through laser reduction of colloidal graphene oxide in liquid-crystalline dispersions.

    PubMed

    Senyuk, Bohdan; Behabtu, Natnael; Martinez, Angel; Lee, Taewoo; Tsentalovich, Dmitri E; Ceriotti, Gabriel; Tour, James M; Pasquali, Matteo; Smalyukh, Ivan I

    2015-01-01

    Graphene materials and structures have become an essential part of modern electronics and photovoltaics. However, despite many production methods, applications of graphene-based structures are hindered by high costs, lack of scalability and limitations in spatial patterning. Here we fabricate three-dimensional functional solid microstructures of reduced graphene oxide in a lyotropic nematic liquid crystal of graphene oxide flakes using a pulsed near-infrared laser. This reliable, scalable approach is mask-free, does not require special chemical reduction agents, and can be implemented at ambient conditions starting from aqueous graphene oxide flakes. Orientational ordering of graphene oxide flakes in self-assembled liquid-crystalline phases enables laser patterning of complex, three-dimensional reduced graphene oxide structures and colloidal particles, such as trefoil knots, with 'frozen' orientational order of flakes. These structures and particles are mechanically rigid and range from hundreds of nanometres to millimetres in size, as needed for applications in colloids, electronics, photonics and display technology. PMID:25994393

  19. Heat of combustion of tantalum-tungsten oxide thermite composites

    SciTech Connect

    Cervantes, Octavio G.; Kuntz, Joshua D.; Gash, Alexander E.; Munir, Zuhair A.

    2010-12-15

    The heat of combustion of two distinctly synthesized stoichiometric tantalum-tungsten oxide energetic composites was investigated by bomb calorimetry. One composite was synthesized using a sol-gel (SG) derived method in which micrometric-scale tantalum is immobilized in a tungsten oxide three-dimensional nanostructured network structure. The second energetic composite was made from the mixing of micrometric-scale tantalum and commercially available (CA) nanometric tungsten oxide powders. The energetic composites were consolidated using the spark plasma sintering (SPS) technique under a 300 MPa pressure and at temperatures of 25, 400, and 500 C. For samples consolidated at 25 C, the density of the CA composite is 61.65 {+-} 1.07% in comparison to 56.41 {+-} 1.19% for the SG derived composite. In contrast, the resulting densities of the SG composite are higher than the CA composite for samples consolidated at 400 and 500 C. The theoretical maximum density for the SG composite consolidated to 400 and 500 C are 81.30 {+-} 0.58% and 84.42 {+-} 0.62%, respectively. The theoretical maximum density of the CA composite consolidated to 400 and 500 C are 74.54 {+-} 0.80% and 77.90 {+-} 0.79%, respectively. X-ray diffraction analyses showed an increase of pre-reaction of the constituents with an increase in the consolidation temperature. The increase in pre-reaction results in lower stored energy content for samples consolidated to 400 and 500 C in comparison to samples consolidated at 25 C. (author)

  20. Methane Oxidation by Nitrosococcus oceanus and Nitrosomonas europaea†

    PubMed Central

    Jones, Ronald D.; Morita, Richard Y.

    1983-01-01

    Chemolithotrophic ammonium-oxidizing and nitrite-oxidizing bacteria including Nitrosomonas europaea, Nitrosococcus oceanus, Nitrobacter sp., Nitiospina gracilis, and Nitrococcus mobilis were examined as to their ability to oxidize methane in the absence of ammonium or nitrite. All ammonium oxidizers tested had the ability to oxidize significant amounts of methane to CO2 and incorporate various amounts into cellular components. None of the nitrite-oxidizing bacteria were capable of methane oxidation. The methane-oxidizing capabilities of Nitrosococcus oceanus and Nitrosomonas europaea were examined with respect to ammonium and methane concentrations, nitrogen source, and pH. The addition of ammonium stimulated both CO2 production and cellular incorporation of methane-carbon by both organisms. Less than 0.1 mM CH4 in solution inhibited the oxidation of ammonium by Nitrosococcus oceanus by 87%. Methane concentrations up to 1.0 mM had no inhibitory effects on ammonium oxidation by Nitrosomonas europaea. In the absence of NH4-N, Nitrosococcus oceanus achieved a maximum methane oxidation rate of 2.20 × 10−2 μmol of CH4 h−1 mg (dry weight) of cells−1, which remained constant as the methane concentration was increased. In the presence of NH4-N (10 ppm [10 μg/ml]), its maximum rate was 26.4 × 10−2 μmol of CH4 h−1 mg (dry weight) of cells−1 at a methane concentration of 1.19 × 10−2 mM. Increasing the methane concentration above this level decreased CO2 production, whereas cellular incorporation of methane-carbon continued to increase. Nitrosomonas europaea showed a linear response throughout the test range, with an activity of 196.0 × 10−2 μmol of CH4 h−1 mg (dry weight) of cells −1 at a methane concentration of 1.38 × 10−1 mM. Both nitrite and nitrate stimulated the oxidation of methane. The pH range was similar to that for ammonium oxidation, but the points of maximum activity were at lower values for the oxidation of methane. PMID:16346190

  1. An innovative architectural design to enhance the electrochemical performance of La2NiO4+δ cathodes for solid oxide fuel cell applications

    NASA Astrophysics Data System (ADS)

    Sharma, Rakesh K.; Burriel, Mónica; Dessemond, Laurent; Martin, Vincent; Bassat, Jean-Marc; Djurado, Elisabeth

    2016-06-01

    An architectural design of the cathode microstructure based on combining electrostatic spray deposition (ESD) and screen-printing (SP) techniques has demonstrated to be an innovative strategy to enhance the electrochemical properties of La2NiO4+δ (LNO) as oxygen electrode on Ce0.9Gd0.1O2-δ (CGO) electrolyte for solid oxide fuel cells. For this purpose, the influence of the ESD process parameters on the microstructure has been systematically investigated. Electrochemical performances of four selected cathode microstructures are investigated: (i) 3-D coral nanocrystalline (average particle size ∼ 100 nm) LNO film grown by ESD; (ii) 3-D coral nanocrystalline film (average particle size ∼ 150 nm) grown by ESD with a continuous nanometric dense interface; (iii) porous screen-printed LNO film (average particle size ∼ 400 nm); and (iv) 3-D coral nanocrystalline film (average particle size ∼ 150 nm) with a continuous nanometric dense interface prepared by ESD topped by a LNO current collector prepared by SP. A significant reduction in the polarization resistance (Rpol) is obtained (0.08 Ω cm2 at 700 °C) for 3-D coral topped by the SP layer. Moreover LNO is found to be stable and compatible with CGO up to 800 °C for only 10 days duration in air, making it potentially suitable for SOFCs cathode application.

  2. Crystal structures of (1,4,7,10-tetra­aza­cyclo­dodecane-κ4 N)bis­(tri­cyano­methanido-κN)nickel and (1,4,7,10-tetra­aza­cyclo­dodecane-κ4 N)(tri­cyano­methanido-κN)copper tri­cyano­methanide

    PubMed Central

    Luo, Jun; Zhang, Xin-Rong; Qiu, Li-Juan; Yang, Feng; Liu, Bao-Shu

    2015-01-01

    The structures of two mononuclear transition-metal complexes with tri­cyano­methanide (tcm−) and 1,4,7,10-tetra­aza­cyclo­dodecane (cyclen) ligands, [Ni(C4N3)2(C8H20N4)], (I), and [Cu(C4N3)(C8H20N4)](C4N3), (II), are reported. In the neutral complex (I), the nickel cation is coordinated by one cyclen ligand and two monodentate N-bound tcm− anions in a distorted octa­hedral geometry. The tcm− ligands are mutually cis. The CuII atom in (II) displays a distorted tetra­gonal–pyramidal geometry, with the four N-donor atoms of the cyclen ligand in the equatorial plane, and one tcm− anion bound through a single N atom in an axial site, forming a monocation. The second tcm− molecule acts as a counter-ion not directly coordinating to the copper cation. In both (I) and (II), extensive series of N—H⋯N and C—H⋯N hydrogen bonds generate three-dimensional network structures. PMID:26090153

  3. Trapping of Li(+) Ions by [ThFn](4-n) Clusters Leading to Oscillating Maxwell-Stefan Diffusivity in the Molten Salt LiF-ThF4.

    PubMed

    Chakraborty, Brahmananda; Kidwai, Sharif; Ramaniah, Lavanya M

    2016-08-18

    A molten salt mixture of lithium fluoride and thorium fluoride (LiF-ThF4) serves as a fuel as well as a coolant in the most sophisticated molten salt reactor (MSR). Here, we report for the first time dynamic correlations, Onsager coefficients, Maxwell-Stefan (MS) diffusivities, and the concentration dependence of density and enthalpy of the molten salt mixture LiF-ThF4 at 1200 K in the composition range of 2-45% ThF4 and also at eutectic composition in the temperature range of 1123-1600 K using Green-Kubo formalism and equilibrium molecular dynamics simulations. We have observed an interesting oscillating pattern for the MS diffusivity for the cation-cation pair, in which ĐLi-Th oscillates between positive and negative values with the amplitude of the oscillation reducing as the system becomes rich in ThF4. Through the velocity autocorrelation function, vibrational density of states, radial distribution function analysis, and structural snapshots, we establish an interplay between the local structure and multicomponent dynamics and predict that formation of negatively charged [ThFn](4-n) clusters at a higher ThF4 mole % makes positively charged Li(+) ions oscillate between different clusters, with their range of motion reducing as the number of [ThFn](4-n) clusters increases, and finally Li(+) ions almost get trapped at a higher ThF4% when the electrostatic force on Li(+) exerted by various surrounding clusters gets balanced. Although reports on variations of density and enthalpy with temperature exist in the literature, for the first time we report variations of the density and enthalpy of LiF-ThF4 with the concentration of ThF4 (mole %) and fit them with the square root function of ThF4 concentration, which will be very useful for experimentalists to obtain data over a range of concentrations from fitting the formula for design purposes. The formation of [ThFn](4-n) clusters and the reduction in the diffusivity of the ions at a higher ThF4% may limit the

  4. Nanometrization of Lanthanide-Based Coordination Polymers.

    PubMed

    Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

    2015-11-23

    Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers. PMID:26471940

  5. Modern steels at atomic and nanometre scales

    DOE PAGESBeta

    Caballero, F. G.; Garcia-Mateo, C.; Miller, M. K.

    2014-10-10

    Processing bulk nanocrystalline materials for structural applications still poses a difficult challenge, particularly in achieving an industrially viable process. Recent work in ferritic steels has proved that it is possible to move from ultrafine to nanoscale by exploiting the bainite reaction without the use of severe deformation, rapid heat treatment or mechanical processing. This new generation of steels has been designed in which transformation at low temperature leads to a nanoscale structure consisting of extremely fine, 20–40 nm thick plates of bainitic ferrite and films of retained austenite. Finally, a description of the characteristics and significance of this remarkable microstructuremore » is provided here.« less

  6. Modern steels at atomic and nanometre scales

    SciTech Connect

    Caballero, F. G.; Garcia-Mateo, C.; Miller, M. K.

    2014-10-10

    Processing bulk nanocrystalline materials for structural applications still poses a difficult challenge, particularly in achieving an industrially viable process. Recent work in ferritic steels has proved that it is possible to move from ultrafine to nanoscale by exploiting the bainite reaction without the use of severe deformation, rapid heat treatment or mechanical processing. This new generation of steels has been designed in which transformation at low temperature leads to a nanoscale structure consisting of extremely fine, 20–40 nm thick plates of bainitic ferrite and films of retained austenite. Finally, a description of the characteristics and significance of this remarkable microstructure is provided here.

  7. Coordination Chemistry of [Co(acac)2 ] with N-Doped Graphene: Implications for Oxygen Reduction Reaction Reactivity of Organometallic Co-O4 -N Species.

    PubMed

    Han, Jongwoo; Sa, Young Jin; Shim, Yeonjun; Choi, Min; Park, Noejung; Joo, Sang Hoon; Park, Sungjin

    2015-10-19

    Hybridization of organometallic complexes with graphene-based materials can give rise to enhanced catalytic performance. Understanding the chemical structures within hybrid materials is of primary importance. In this work, archetypical hybrid materials are synthesized by the reaction of an organometallic complex, [Co(II) (acac)2 ] (acac=acetylacetonate), with N-doped graphene-based materials at room temperature. Experimental characterization of the hybrid materials and theoretical calculations reveal that the organometallic cobalt-containing species is coordinated to heterocyclic groups in N-doped graphene as well as to its parental acac ligands. The hybrid material shows high electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media, and superior durability and methanol tolerance to a Pt/C catalyst. Based on the chemical structures and ORR experiments, the catalytically active species is identified as a Co-O4 -N structure. PMID:26331625

  8. Butterfly hysteresis and slow relaxation of the magnetization in (Et 4N) 3Fe 2F 9: manifestations of a single-molecule magnet

    NASA Astrophysics Data System (ADS)

    Schenker, Ralph; Leuenberger, Michael N.; Chaboussant, Grégory; Güdel, Hans U.; Loss, Daniel

    2002-06-01

    (Et 4N) 3Fe 2F 9 exhibits a butterfly-shaped hysteresis below 5 K when the magnetic field is parallel to the threefold axis, in accordance with a very slow magnetization relaxation in the timescale of minutes. This is attributed to an energy barrier Δ=2.40 K resulting from the S=5 dimer ground state of [Fe 2F 9] 3- and a negative axial anisotropy. The relaxation partly occurs via thermally assisted quantum tunneling. These features of a single-molecule magnet are observable at temperatures comparable to the barrier height, due to an extremely inefficient energy exchange between the spin system and the phonons. The butterfly shape of the hysteresis arises from a phonon avalanche effect.

  9. A bowl-shaped circular trinuclear helicate generated from a TiO4 N2 motif by a multicomponent self-assembly approach.

    PubMed

    Mobian, Pierre; Baradel, Nathalie; Kyritsakas, Nathalie; Khalil, Georges; Henry, Marc

    2015-02-01

    The synthesis of a bowl-shaped trinuclear circular titanium-based helicate is reported. The strategy allowing access to this neutral architecture is based on a multicomponent self-assembly approach in which the ligands involved in the process are a bis-biphenol strand and 2,2'- bipyrimidine. By reacting the bis-biphenol ligand and 2,2'-bipyrimidine with an equimolar amount [Ti(OiPr)4 ], a bowl-shaped architecture is obtained through the formation of 18 new coordination bonds. This aggregate built from three octahedral TiO4 N2 nodes displays an unusually high stability in solution compared to related species. In addition, by modifying the stoichiometry of the initial components, two assemblies incorporating two titanium centers bridged by a 2,2'-bipyrimidine ligand are obtained. The crystal structures of these species are reported. PMID:25490957

  10. Antimutagenic and anticarcinogenic effects of betel leaf extract against the tobacco-specific nitrosamine 4-(N-nitrosomethylamino)-1-(3-pyridyl)-1-butanone (NNK).

    PubMed

    Bhide, S V; Padma, P R; Amonkar, A J

    1991-01-01

    Earlier studies showed that betel leaf inhibits the mutagenic action of standard mutagens like benzo[a]pyrene and dimethylbenz[a]anthracene. Since tobacco-specific nitrosamines are the major carcinogens present in unburnt forms of tobacco, we studied the effect of an extract of betel leaf on the mutagenic and carcinogenic actions of one of the most potent, 4-(N-nitrosomethylamino)-1-(3-pyridyl)-1-butanone (NNK). Betel-leaf extract and hydroxychavicol suppressed the mutagenicity of NNK in both the Ames and the micronucleus test. In studies in mice, betel-leaf extract reduced the tumorigenic effects of NNK by 25%. Concurrent treatment with the extract also inhibited the decreases in levels of vitamin A in liver and plasma induced by NNK. Betel leaf thus has protective effects against the mutagenic, carcinogenic and adverse metabolic effects of NNK in mice. PMID:1855909

  11. Triple quadrupole mass spectrometry as applied to flame diagnostics: study of the C2H 4/N 2O/Ar flame.

    PubMed

    Howard, S L; Newberry, J E; Sausa, R C; Miziolek, A W

    1993-02-01

    A recently developed research apparatus for characterization of low-pressure premixed flames has been developed and was used to characterize the C2H4/N2O/Ar flame at 20 torr. This instrument incorporates several diagnostic techniques in one apparatus so that individual techniques can be quantitatively compared and the usable detection range (both in terms of resolution and species detection) expanded. Results discussed in this report include mass analysis by triple quadrupole mass spectrometer and temperature measurement by thermocouple. Concentration profiles in the one-dimensional flame include CO, N2, and C2H4, at nominal m/z 28 as well as CO2 and N2O at m/z 44. PMID:24234794

  12. Using Raman spectroscopy to understand the origin of the phase transitions observed in [(C3H7)4N]2Zn2Cl6 compound

    NASA Astrophysics Data System (ADS)

    Ben Gzaiel, M.; Oueslati, A.; Chaabane, I.; Bulou, A.; Hlel, F.; Gargouri, M.

    2015-06-01

    Phase transitions of the centrosymmetric compound, [(C3H7)4N]2Zn2Cl6, were studied by differential scanning calorimetry (DSC), X-ray diffraction, Raman spectroscopy and dielectric measurements. Two reversible order-disorder and displacive phase transitions are observed at T1 = 327 K and T2 = 347 K with 3 K and 4 K hysteresis respectively, indicating a first order character. The evolution of Raman line shifts, "ν", and the half-width, "Δν", versus temperature show some singularities associated with the transitions, suggesting that they are governed by the reorientational and the displacement of the organic part. Besides the results of the dielectric permittivity study confirms the conclusion drawn from the calorimetric and Raman measurements that the phase transition located in the vicinity of the temperature of the dielectric proprieties is characterized by change of dynamical state of cation.

  13. Intramolecular charge delocalization and nonlinear optical properties of push-pull chromophore 1-(4-N,N-dimethylaminopyridinium) acetic acid bromide monohydrate from vibrational spectra.

    PubMed

    John, C Jesintha; Amalanathan, M; Sajan, D; Lakshmi, K Udaya; Joe, I Hubert

    2011-01-01

    FT-Raman and FT-IR spectra of the nonlinear optical crystal 1-(4-N,N-dimethylaminopyridinium) acetic acid bromide monohydrate have been recorded and analyzed. The equilibrium geometry, vibrational wavenumbers and the first order hyperpolarizability of the crystal have been calculated with the help of density functional theory computations. The assignments of the vibrational spectra have been carried out with the help of Scaled Quantum Mechanic force field theory. Optimized geometry gives the charge transfer interaction of the pyridine ring and the amino group in the electron-donor side of the nonlinear optic chromophore. Electron-phonon coupling and O-H⋯O interactions in making the molecule nonlinear optical active have been analyzed based on the vibrational spectral features. The Natural Bond Orbital analysis confirms the occurrence of strong intermolecular O-H⋯O hydrogen bonding. PMID:21036101

  14. Sectoral CO 2, CH 4, N 2O and SO 2 emissions from fossil fuel consumption in Nagpur City of Central India

    NASA Astrophysics Data System (ADS)

    Majumdar, Deepanjan; Gajghate, D. G.

    2011-08-01

    Emission inventory of CO 2, CH 4, N 2O and SO 2 has been prepared for Nagpur city in Central India for the year 2004. Data on fossil fuel (coal, light diesel oil, high speed diesel, petrol/gasoline, low sulphur heavy stock, furnace oil and kerosene) consumption in thermal power, industrial, transport and domestic sectors were collected. Thermal power sector had the maximum coal consumption followed by the industrial and domestic sectors, whereas kerosene, liquefied petroleum gas (LPG), diesel and gasoline were used only in any single sector. Total annual CO 2, CH 4, N 2O and SO 2 emissions from these fuels in Nagpur city for the year 2004 was found to be 14792418 MT (14.8 Tg), 4649 (4.6 Tg), 1529 (1.5 Tg) and 69093 (6.9 Tg), respectively, in which thermal power and domestic sector had the maximum share. Coal was found to be the major contributor to Green House Gas (GHG) and SO 2 emissions in all the sectors barring transport and domestic sectors. Carbon dioxide was the predominant GHG emitted by the selected sectors in terms of absolute emissions and also global warming contribution (GWC), though the share in the latter was lesser in magnitude due to higher global warming potential (GWP) of CH 4 and N 2O than CO 2. Thermal power sector had a share of 51% in total CO 2 emissions from all the sectors, followed by domestic, industrial and transport sectors having 27, 12 and 10% contributions, respectively. Share of thermal power sector in total SO 2 emissions was 61%, followed by 24% from industrial, 10% from domestic and 5% from transport sector.

  15. Imaging the Three-Dimensional Conductive Channel in Filamentary-Based Oxide Resistive Switching Memory.

    PubMed

    Celano, Umberto; Goux, Ludovic; Degraeve, Robin; Fantini, Andrea; Richard, Olivier; Bender, Hugo; Jurczak, Malgorzata; Vandervorst, Wilfried

    2015-12-01

    Filamentary-based oxide resistive memory is considered as a disruptive technology for nonvolatile data storage and reconfigurable logic. Currently accepted models explain the resistive switching in these devices through the presence/absence of a conductive filament (CF) that is described as a reversible nanosized valence-change in an oxide material. During device operation, the CF cycles billion of times at subnanosecond speed, using few tens of microamperes as operating current and thus determines the whole device's performance. Despite its importance, the CF observation is hampered by the small filament size and its minimal compositional difference with the surrounding material. Here we show an experimental solution to this problem and provide the three-dimensional (3D) characterization of the CF in a scaled device. For this purpose we have recently developed a tomography technique which combines the high spatial resolution of scanning probe microscopy with subnanometer precision in material removal, leading to a true 3D-probing metrology concept. We locate and characterize in three-dimensions the nanometric volume of the conductive filament in state-of-the-art bipolar oxide-based devices. Our measurements demonstrate that the switching occurs through the formation of a single conductive filament. The filaments exhibit sizes below 10 nm and present a constriction near the oxygen-inert electrode. Finally, different atomic-size contacts are observed as a function of the programming current, providing evidence for the filament's nature as a defects modulated quantum contact. PMID:26523952

  16. PREFACE: Semiconducting oxides Semiconducting oxides

    NASA Astrophysics Data System (ADS)

    Catlow, Richard; Walsh, Aron

    2011-08-01

    Semiconducting oxides are amongst the most widely studied and topical materials in contemporary condensed matter science, with interest being driven both by the fundamental challenges posed by their electronic and magnetic structures and properties, and by the wide range of applications, including those in catalysis and electronic devices. This special section aims to highlight recent developments in the physics of these materials, and to show the link between developing fundamental understanding and key application areas of oxide semiconductors. Several aspects of the physics of this wide and expanding range of materials are explored in this special section. Transparent semiconducting oxides have a growing role in several technologies, but challenges remain in understanding their electronic structure and the physics of charge carriers. A related problem concerns the nature of redox processes and the reactions which interconvert defects and charge carriers—a key issue which may limit the extent to which doping strategies may be used to alter electronic properties. The magnetic structures of the materials pose several challenges, while surface structures and properties are vital in controlling catalytic properties, including photochemical processes. The field profits from and exploits a wide range of contemporary physical techniques—both experimental and theoretical. Indeed, the interplay between experiment and computation is a key aspect of contemporary work. A number of articles describe applications of computational methods whose use, especially in modelling properties of defects in these materials, has a long and successful history. Several papers in this special section relate to work presented at a symposium within the European Materials Research Society (EMRS) meeting held in Warsaw in September 2010, and we are grateful to the EMRS for supporting this symposium. We would also like to thank the editorial staff of Journal of Physics: Condensed Matter for

  17. Layer structure: The oxides A 3Ti 5MO 14

    NASA Astrophysics Data System (ADS)

    Hervieu, M.; Rebbah, H.; Desgardin, G.; Raveau, B.

    1980-11-01

    Five new oxides, K 3Ti 5MO 14, Rb 3Ti 5MO 14 ( M = Ta, Nb), and Tl 3Ti 5NbO 14, have been synthesized. The structure of these oxides consists of octahedral layers similar to those observed for Na 2Ti 3O 7 and held together by monovalent ions; the sheets consist of blocks of 2 × 3 edge-sharing octahedra, which are then joined to each other by the corners of the octahedra. The relative disposition of the layers is similar to that observed for Tl 2Ti 4O 9. These oxides can be considered as the member n = 3 of a series of closely related structures with formula AnB2 nO 4 n+2 , where n indicates the number of octahedra which determines the width of the blocks of 2 × n octahedra.

  18. [Comparison of heterotrophic nitrification and aerobic denitrification system by strain qy37 and its accelerating removal characteristic of NH4+ -N].

    PubMed

    Zhang, Pei-yu; Qu, Yang; Yu, De-shuang; Guo, Sha-sha; Yang, Rui-xia

    2010-08-01

    The characterization in nitrogen removal of a heterotrophic nitrification-aerobic denitrification bacteria (qy37) was studied. A strain coded as qy37 which had simultaneous heterotrophic nitrifying and aerobic denitrifying ability was screened. In the light of its morphological and physiological characters as well as their sequence analysis of the 16S rDNA, strain qy37 was identified as Pseudomonas sp.. In heterotrophic nitrifying system utilized ammonium chloride as nitrogen source, the concentration of NH4+ -N reduced from 138.52 mg/L to 7.88 mg/L and COD reduced from 2408.39 to 1177.49 mg/L by strain qy37 in 32 hours, the maximum accumulation of NH2OH and NO2- -N were 9.42 mg/L and 0.02 mg/L respectively, it was speculated that NH2OH was transformed to N2O and N2 directly by strain qy37. In aerobic denitrifying system utilized sodium nitrite as nitrogen source, the concentration of NO2- -N reduced from 109.25 mg/L to 2.59 mg/L by strain qy37 in 24 hours, and the maximum accumulation of NH2OH was 3.28 mg/L. Compared with heterotrophic nitrifying system, aerobic denitrifying system had a higher bacterial growth whereas the lower removal rate of TN and COD, as well as the accumulation of NH2OH. NO3- -N was also detected in aerobic denitrifying system. It is considered that the upgrowth of bacterium and utilization of energy in aerobic denitrifying system were more efficient than that in heterotrophic nitrifying system. In heterotrophic nitrification-aerobic denitrification system, the removal rate of NH4+ -N improved 37.31% in 16 hours than that in heterotrophic nitrifying system, the accumulation of NH2OH was less but N2O was higher than that in both heterotrophic nitrifying system and aerobic denitrifying system. PMID:21090299

  19. Determination of medroxyprogesterone acetate in serum by HPLC with peroxyoxalate chemiluminescence detection using a fluorogenic reagent, 4-(N,N-dimethylaminosulphonyl)-7-hydrazino-2,1,3-benzoxadiazole.

    PubMed

    Uzu, S; Imai, K; Nakashima, K; Akiyama, S

    1992-01-01

    The high-performance liquid chromatographic determination of medroxyprogesterone acetate (MPA) with peroxyoxalate chemiluminescence (PO-CL) detection is described. The spiked serum containing MPA was extracted on Bond-Elut C18 columns and derivatized with 4-(N,N-dimethylaminosulphonyl)-7-hydrazino-2,1,3-benzoxadiazole (DBD-H). The hydrazone of MPA with DBD-H was confirmed to be a mono-DBD-derivative. The reaction mixture was separated by direct injection onto a C18 analytical column, and quantified by PO-CL detection. The linear range of the standard curve, in serum, was 15.6-96.6 ng ml-1 with a detection limit of 9 ng ml-1 using only 100 microliters of serum, while the detection limit of standard MPA derivatized with DBD-H was 8.7 fmol per injection. The relative standard deviation of the method was 7.4% at 19.3 ng and 1.7% at 77.3 ng ml-1. PMID:1298405

  20. The Drosophila melanogaster homologue of the human histo-blood group Pk gene encodes a glycolipid-modifying α1,4-N-acetylgalactosaminyltransferase

    PubMed Central

    2004-01-01

    Insects express arthro-series glycosphingolipids, which contain an α1,4-linked GalNAc residue. To determine the genetic basis for this linkage, we cloned a cDNA (CG17223) from Drosophila melanogaster encoding a protein with homology to mammalian α1,4-glycosyltransferases and expressed it in the yeast Pichia pastoris. Culture supernatants from the transformed yeast were found to display a novel UDP-GalNAc:GalNAcβ1,4GlcNAcβ1-R α-N-acetylgalactosaminyltransferase activity when using either a glycolipid, p-nitrophenylglycoside or an N-glycan carrying one or two terminal β-N-acetylgalactosamine residues. NMR and MS in combination with glycosidase digestion and methylation analysis indicate that the cloned cDNA encodes an α1,4-N-acetylgalactosaminyltransferase. We hypothesize that this enzyme and its orthologues in other insects are required for the biosynthesis of the N5a and subsequent members of the arthro-series of glycolipids as well as of N-glycan receptors for Bacillus thuringiensis crystal toxin Cry1Ac. PMID:15130086

  1. Molecular Simulation Studies of Separation of CO2/N2, CO2/CH4, and CH4/N2 by ZIFs

    SciTech Connect

    Liu, Bei; Smit, Berend

    2010-05-13

    In this work, molecular simulations were performed to evaluate the separation performance of two typical zeolitic imidazolate frameworks (ZIFs), ZIF-68 and ZIF-69, for CO{sub 2}/N{sub 2}, CO{sub 2}/CH{sub 4}, and CH{sub 4}/N{sub 2} mixtures. To do this, we first identified a suitable force field for describing CO{sub 2}, N{sub 2}, and CH{sub 4} adsorption in ZIFs. On the basis of the validated force field, adsorption selectivities of the three mixtures in these ZIFs were simulated then. The results show that ZIF-69 is more beneficial for separating CO{sub 2} from CO{sub 2}-related mixtures than ZIF-68, mainly due to the presence of chlorine atoms in cbIM linkers in the former for the pressures we have considered. The overall separation performances of these two ZIFs for separating the chosen mixtures are comparable to typical MOFs and zeolites. In addition, this work demonstrates that the electrostatic interactions produced by the frameworks are very important for achieving high adsorption separation selectivities in ZIFs, and ideal adsorbed solution theory (IAST) may be applicable to ZIFs. Furthermore, the effect of water on the separation performance of the two ZIFs was also investigated.

  2. Electrical properties and conduction mechanism of [N(C2H5)4][N(CH3)4]CuCl4 compound

    NASA Astrophysics Data System (ADS)

    Drissi, N.; Karoui, K.; Jomni, F.; Rhaiem, A. Ben

    2016-09-01

    The [N(CH3)4][N(C2H5)4]CuCl4 single crystal has been synthetized in order to determinate the temperatures transition and to study the electrical properties and the conduction mechanism. At room temperature, this compound crystallizes in the tetragonal system with P-421m space group. The calorimetric study shows three anomalies at 248, 284 and 326 K. Electrical conduction and dielectrical relaxation mechanisms at various frequencies and temperatures were analyzed by impedance spectroscopy and the equivalent circuit based on the Z-View-software was proposed. The variation of fp relaxation determinate by the modulus study and σdc specific to the AC conductivity as a function of temperature and confirm the all transitions for our sample. The values of the activation energy are determined and compared by those, which are found in the similar compound. Frequencies dependence of alternative current (AC) conductivity is interpreted in terms of Jonscher's law and the conduction mechanisms for each phase are determined with the Elliot's theory.

  3. Synthesis, crystal structure, thermal analysis and dielectric properties of [(C4H9)4N]3Bi2Cl9 compound

    NASA Astrophysics Data System (ADS)

    Trigui, W.; Oueslati, A.; Chaabane, I.; Hlel, F.

    2015-07-01

    A new organic-inorganic tri-tetrabutylammonium nonachlorobibismuthate(III) compound was prepared. It was found to crystallize in the monoclinic system (P21/n space group) with the following lattice parameters: a=11.32(2) Å, b=22.30(3) Å, c=28.53(2) Å and β=96.52(0)°. The [Bi2Cl9]3- anions are surrounded by six [(C4H9)N]+ cations, forming an octahedral configuration. These octahedra are sharing corners in order to provide the tri-dimensional network cohesion. The differential scanning calorimetry reveals four order-disorder reversible phase transitions located at 214, 238, 434 and 477 K. The Raman and infrared spectra confirm the presence of both cationic [(C4H9)N]+ and anionic [Bi2Cl9]3- parts. The dielectric parameters, real and imaginary dielectric permittivity (ε‧ and ε″), and dielectric loss tangent (tg δ), were measured in the frequency range of 209 kHz-5 MHz at different temperatures. The variations of dielectric dispersion (ε') and dielectric absorption (ε″) with frequency show a distribution of relaxation times, which is probably related to the change in the dynamical state of the [(C4H9)4N]+ cations and the [Bi2Cl9]3- anions.

  4. Electrorheological characterization of dispersions in silicone oil of encapsulated liquid crystal 4-n-penthyl-4‧-cyanobiphenyl in polyvinyl alcohol and in silica

    NASA Astrophysics Data System (ADS)

    Brehm, T.; Pereira, G.; Leal, C. R.; Gonçalves, C.; Borges, J. P.; Cidade, M. T.

    2015-03-01

    The electrorheological (ER) effect is known as the change in the apparent viscosity upon the application of an external electric field perpendicular to the flow direction. In this work we present the electrorheological behaviour of suspensions in silicone oil of two different dispersed phases: foams of liquid crystal 4-n-penthyl-4‧-cyanobiphenyl (5CB) encapsulated in polyvinyl alcohol (PVA) and nano/microspheres of 5CB encapsulated in silica. We will present the viscosity curves under the application of an electric field ranging between 0 and 3 kV mm-1. The ER effect was observed for the suspensions of 5CB/PVA but not in the case of 5CB/silica. For the case of the suspensions of 5CB/PVA, the effect of the viscosity of the continuum phase and the concentration of the dispersed phase was analysed, showing that the enhancement of the viscosity of the suspension increases with the concentration, as expected, however the continuum phase viscosity has no significant effect, at least in the investigated viscosity range.

  5. beta1,4-N-Acetylglucosaminyltransferase III potentiates beta1 integrin-mediated neuritogenesis induced by serum deprivation in Neuro2a cells.

    PubMed

    Shigeta, Masaki; Shibukawa, Yukinao; Ihara, Hideyuki; Miyoshi, Eiji; Taniguchi, Naoyuki; Gu, Jianguo

    2006-06-01

    Aspects of the biological significance of the bisecting N-acetylglucosamine (GlcNAc) structure on N-glycans introduced by beta1,4-N-acetylglucosaminyltransferase III (GnT-III) in Neuro2a cell differentiation are demonstrated. The overexpression of GnT-III in the cells led to the induction of axon-like processes with numerous neurites and swellings, in which beta1 integrin was localized, under conditions of serum starvation. This enhancement in neuritogenesis was suppressed by either the addition of a bisecting GlcNAc-containing N-glycan or erythroagglutinating phytohemagglutinin (E(4)-PHA), which preferentially recognizes the bisecting GlcNAc. GnT-III-promoted neuritogenesis was also significantly perturbed by treatment with a functional blocking anti-beta1 integrin antibody. In fact, beta1 integrin was found to be one of the target proteins of GnT-III, as confirmed by a pull-down assay with E(4)-PHA. These data suggest that N-glycans with a bisecting GlcNAc on target molecules, such as beta1 integrin, play important roles in the regulation of neuritogenesis. PMID:16531477

  6. Use of vibrational spectroscopy to study 2-[4-(N-dodecanoylamino)phenyl]-5-(4-nitrophenyl)-1,3,4-oxadiazole: a combined theoretical and experimental approach.

    PubMed

    Bee, Saba; Agarwal, Parag; Gupta, Archana; Tandon, Poonam

    2013-10-01

    Quantum chemical calculations of geometric structure and vibrational wavenumbers of 2-[4-(N-dodecanoylamino)phenyl]-5-(4-nitrophenyl)-1,3,4-oxadiazole (AF51) were carried out by using density functional theory (DFT/B3LYP/6-311G(d,p) method. The fundamental vibrational modes were characterized depending on their potential energy distribution (PED). In order to predict the reactive sites for electrophilic and nucleophilic attacks of the title molecule, electrostatic potential surface has been plotted. The UV absorption spectrum was examined in chloroform solvent and compared with the calculated one in gas phase as well as in solvent environment using TD-DFT/ PCM approach. The (1)H NMR spectra was recorded. Comparison between the experimental and the theoretical results is satisfactory. The thermodynamic properties of the title compound at different temperatures have been calculated. A relationship between molecular structural features, non-linear responses and hyperpolarizability of AF51 has been established using vibrational spectra with emphasis on the role of intramolecular charge transfer mechanism in such organic NLO materials. PMID:23770512

  7. 1D μ-glycine-briged copper (II) chain in complex [Cu(μ-Gly)Im(ClO4)]n and ferromagnetic interactions among copper (II)

    NASA Astrophysics Data System (ADS)

    Pan, Lu; Lv, Xue-Chuan; Luo, Guan-Hua; Gao, Xiao-Han; Tan, Zhi-Cheng

    2016-12-01

    Complex [Cu(μ-Gly)Im(ClO4)]n(Im = imidazole, and Gly = glycine) with μ-glycine-briged copper (II) chain, containing six-coordination distorted elongated octahedron, was synthesized and characterized. The complex belongs to space group P 21/c measured by X-ray single crystal diffraction. In the cluster, each Cu2+ ion are six-coordination by one nitrogen atom and two oxygen atoms of glycine, one nitrogen atoms of imidazole, and two of oxygen atoms of two perchlorate. Each Cu2+ ion has an N2O4 donor set, which forms the distorted elongated octahedron due to the Jahn-Teller (JT) effect. The magnetic and thermodynamic properties were researched. Magnetic susceptibilities of the complex showed that ferromagnetic interactions occurred between the Cu (II) atoms. The Curie-Weiss constant C = 0.565 cm3 K·mol-1 and the Weiss constant θ = 1.0585 K were given by the Curie-Weiss law The ferromagnetic nature of the interaction could be deduced as the exchange pathway of Cusbnd Osbnd Csbnd Osbnd Cu, which involved an equatorial position at one copper (II) ion and an axial position of the nearest copper (II). The complex decomposed from 511 to 538 K as two steps.

  8. Seasonal changes of CO2, CH4, N2O, and SF6 in the upper troposphere/lower stratosphere over the Eurasian continent observed by commercial airliner

    NASA Astrophysics Data System (ADS)

    Sawa, Yousuke; Machida, Toshinobu; Matsueda, Hidekazu; Niwa, Yosuke; Tsuboi, Kazuhiro; Murayama, Shohei; Morimoto, Shinji; Aoki, Shuji

    2015-03-01

    The seasonal variations of greenhouse gases at about 11 km altitude were analyzed from monthly air samples collected aboard a commercial airliner flying between Europe and Japan from April 2012 to March 2014. Compared to lower latitudes, the upper troposphere between 50 and 70°N showed higher CH4 and SF6 and an earlier seasonal phase of CO2. However, N2O values were similar to those in the subtropics. CH4, N2O, and SF6 in the lower stratosphere with potential temperature of up to 50 K above the tropopause showed seasonal variations with maxima in November/December and minima in April/May. At potential temperatures of 37.5-50 K above the tropopause, SF6 age was estimated to be about 22 months in May and 9 months in November. This strong seasonal variation is explained by the subsidence of high-stratospheric air in spring and the effective flushing of the lowermost stratospheric air with tropospheric air in autumn.

  9. Measurements of CH4, N2O, CO, H2O and O3 in the middle atmosphere by the ATMOS experiment on Spacelab 3

    NASA Technical Reports Server (NTRS)

    Gunson, M. R.; Farmer, C. B.; Norton, R. H.; Zander, R.; Rinsland, C. P.; Shaw, J. H.; Gao, Bo-Cai

    1989-01-01

    The volume mixing ratios of five minor gases (CH4, N2O, CO, H2O, and O3) were retrieved through the middle atmosphere from the analysis of 0.01/cm resolution infrared solar occultation spectra recorded near 28 N and 48 S latitudes with the ATMOS (Atmospheric Trace Molecule Spectroscopy) instrument, flown on board Spacelab 3. The results, which constitute the first simultaneous observations of continuous profiles through the middle atmosphere for these gases, are in general agreement with reported measurements from ground, balloon and satellite-based instruments for the same seasons. In detail, the vertical profiles of these gases show the effects of the upper and middle atmospheric transport patterns dominant during the season of these observations. The profiles inferred at different longitudes around 28 N suggest a near-uniform zonal distribution of these gases. Although based on fewer observations, the sunrise occultation measurements point to a larger variability in the vertical distribution of these gases at 48 S.

  10. Infusion of Sulfosuccinimidyl-4-[N-maleimidomethyl]cyclohexane-1-carboxylate-Conjugated MOG35–55-Coupled Spleen Cells Effectively Prevents and Reverses Experimental Autoimmune Encephalomyelitis in Mice

    PubMed Central

    Zhang, Lanfang; Guo, Yixian; Xia, Chang-Qing

    2015-01-01

    In this study, we have evaluated our recently developed method for antigen-cell coupling using sulfosuccinimidyl-4-[N-maleimidomethyl]cyclohexane-1-carboxylate (sulfo-SMCC) heterobifunctional crosslinker in prevention and reversal of experimental autoimmune encephalomyelitis (EAE). We demonstrate that infusion of MOG35–55-coupled spleen cells (MOG-SP) significantly prevents and reverses EAE. Further studies show that the protected animals exhibit significantly delayed EAE upon EAE reinduction. Moreover, adoptive transfer of CD4+ T cells from the protected mice to naïve syngeneic mice renders the recipient mice resistant to EAE induction. Unexpectedly, CD4+ T cell proliferation is similar upon ex vivo stimulation by MOG35–55 amongst all groups. However, further analysis of those proliferating CD4+ T cells shows remarkable differences in Foxp3+ regulatory T cells (70% in MOG-SP groups versus 10–25% in control groups) and in IL-17+ cells (2-3% in MOG-SP groups versus 6–9% in control groups). In addition, we discover that MOG-SP treatment also significantly attenuates MOG35–55-responding IFN-γ-producing Th1 cells. These findings suggest that MOG-SP treatment induces EAE protective MOG35–55-specific regulatory T cells and suppresses EAE pathogenic Th17 and Th1 cells. Our study provides a novel approach for antigen-based EAE immunotherapy, which can potentially be translated into clinical application for immunotherapy of multiple sclerosis. PMID:26258148

  11. Low Temperature Heat Capacities and Standard Molar Enthalpy of Formation of 2-Pyrazinecarboxylic Acid (C5H4N2O2)(s).

    PubMed

    Kong, Yu-Xia; Di, You-Ying; Yang, Wei-Wei; Gao, Sheng-Li; Tan, Zhi-Cheng

    2010-06-01

    Low-temperature heat capacities of 2-pyrazinecarboxylic acid (C5H4N2O2)(s) were measured by a precision automated adiabatic calorimeter over the temperature range from 78 to 400 K. A polynomial equation of heat capacities as a function of temperature was fitted by least squares method. Based on the fitted polynomial, the smoothed heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15 K were calculated and tabulated at 10 K intervals. The constant-volume energy of combustion of the compound at T = 298.15 K was measured by a precision rotating-bomb combustion calorimeter to be ΔcU = -(17839.40 ± 7.40) J g-1. The standard molar enthalpy of combustion of the compound was determined to be ΔcH0m = -(2211.39 ± 0.92) KJ mol-1, according to the definition of combustion enthalpy. Finally, the standard molar enthalpy of formation of the compound was calculated to be ΔfH0m = -(327.82 ± 1.13) kJ mol-1 in accordance with Hess law. PMID:24061733

  12. Methylated 4-N,N dimethyl aminobenzyl N,O carboxymethyl chitosan as a new chitosan derivative: Synthesis, characterization, cytotoxicity and antibacterial activity.

    PubMed

    Rahmani, Soheila; Mohammadi, Zohreh; Amini, Mohsen; Isaei, Elham; Taheritarigh, Sadegh; Rafiee Tehrani, Niyousha; Rafiee Tehrani, Morteza

    2016-09-20

    Chitosan, as a biocompatible polymer, is very attractive for biomedical applications. Continues studies are performing for improving its physicochemical features in order to make it more suitable for such approaches. In this study, methylated 4-N,N dimethyl aminobenzyl N,O carboxymethyl chitosan (MABCC) was synthesized,as a new chitosan derivative, in three steps. The investigations were carried out using FTIR, NMR, TGA and zeta potential measurement. Antibacterial and cell viability assessments were performed on four bacterial strains and two cell lines respectively. FTIR and NMR results showed that all substitution reactions were successfully carried out. Zeta potential of MABCC at various pH especially alkaline pH was greater than chitosan and it revealed increasing the solubility of the derivative. Antibacterial activity of MABCC was extremely greater than chitosan especially in Gram positive bacteria.Furthermore,it had no significant cytotoxicity against MCF-7 and Skov-3 cell lines in comparison to chitosan. These findings confirm that this new derivative can be introduced as a suitable compound for biomedical purposes. PMID:27261738

  13. A new method of testing pancreatin therapy in vivo by the use of a peroral chymotrypsin substrate 4-(N-acetyl-L-tyrosyl)aminobenzoic acid.

    PubMed

    Fric, P; Malis, F; Kasafírek, E; Slabý, J

    1980-06-01

    The efficacy of pancreatin in vivo was determined in 14 patients with advanced pancreatic insufficiency using a peroral test with 2 g of chymotrypsin substrate, 4-(N-acetyl-L-tyrosyl)aminobenzoic acid, the Lundh test meal and 1000 ml tea. Chymotrypsin hydrolysis was quantified by 4-aminobenzoic acid excreted in 6-hr or 8-hr urine samples. After a control test without pancreatin, one or two tablets of Panpur (Nordmark-700 mg of pancreatin and 50 mg of bile per tablet) were applied simultaneously with the Lundh meal on repeated examinations. The urinary excretion of 4-aminobenzoic acid was restored to normal values in 5 subjects during both sampling periods. With this method, stimulated and substituted chymotrypsin is measured at the same time. The conditions of the tests, both with and without pancreatin replacement, are fully comparable and thus the significance of factors modifying the activity of enzymic components in the digestive tube is limited. The method appears appropriate for the institution of an effect pancreatin therapy and its control in vivo. PMID:6970159

  14. Measurements of CCl3F, CCl2F2, CCl4, N2O and SF6 in the Northern Hemisphere stratosphere

    NASA Technical Reports Server (NTRS)

    Leifer, R.; Juzdan, R.

    1985-01-01

    An overview of the Department of Energy's High Altitude Sampling Program and some recent trace gas measurement results are presented. Analysis of whole air samples, collected in pressurized bottles, provides information on stratospheric inventories and distributions for CCl3F, CCl2F2, CCl4, N2O and SF6 in the Northern Hemisphere. Based on a linear regression analysis of the data the estimated mean Northern Hemisphere stratospheric concentration of each gas increased as follows: CCl3F changed from 54 to 142 p1/1 (4/74-11/83); CCl2F2 changed from 133 to 268 p1/1 (4/76-11/83); SF6 changed from 160 to 480 f1/1 (4/74-11/83); CC1, changed from 58 to 91 p1/1 (4/75-11/83); N2O changed from 246 to 261 n1/1 (4/76-11/83). The calculated mean Northern Hemisphere stratospheric concentrations of N2O, CCl3F, CCl2F2, and CCl4 after 1980 show larger than expected fluctuations with time. Recent volcanic activity may be a partial cause for these fluctuations through induced changes in stratospheric dynamical processes.

  15. Cross section limits for the {sup 248}Cm({sup 25}Mg,4n-5n){sup 268,269}Hs reactions

    SciTech Connect

    Dvorak, J.; Dvorakova, Z.; Schuber, R.; Tuerler, A.; Yakushev, A.; Bruechle, W.; Duellmann, Ch. E.; Jaeger, E.; Schaedel, M.; Schausten, B.; Schimpf, E.; Eberhardt, K.; Thoerle, P.; Eichler, R.; Nagame, Y.; Qin, Z.; Semchenkov, A.; Wegrzecki, M.

    2009-03-15

    We report on an attempt to produce and detect {sup 268}Hs and {sup 269}Hs in the nuclear fusion reaction {sup 25}Mg+{sup 248}Cm using the gas phase chemistry apparatus COMPACT. No decay chains attributable to the decay of hassium isotopes were observed during the course of this experiment. From the nonobservation of {sup 269}Hs we derive a cross section limit of 0.4 pb (63% confidence limit) for the reaction {sup 248}Cm({sup 25}Mg,4n){sup 269}Hs at a center-of-target beam energy of 140 MeV. The evaluated cross section limit for the {sup 248}Cm({sup 25}Mg,5n){sup 268}Hs reaction depends on the assumed half-life of unknown {sup 268}Hs. Current systematics of the half-lives for even-even Hs isotopes suggests a value of 0.5 s, resulting in a cross section limit of 1.3 pb.

  16. Evaluation of 4-(N-methylnitrosamino)-4-(3-pyridyl)butyric acid as a potential monitor of endogenous nitrosation of nicotine and its metabolites.

    PubMed

    Tricker, A R; Scherer, G; Conze, C; Adlkofer, F; Pachinger, A; Klus, H

    1993-07-01

    The potential endogenous nitrosation of nicotine and cotinine to yield 4-(N-methylnitrosamino)-4-(3-pyridyl)butyric acid (Iso-NNAC) has been studied in smokers and non-smokers. Following i.v. administration of 100 micrograms Iso-NNAC to rats, excretion in urine (67.4 +/- 25.4%) and feces (6.1 +/- 1.6%) occurred within 24 h. The urinary excretion of nitrate, nicotine, cotinine and Iso-NNAC were determined in 24 h urine samples from 19 smokers and 10 non-smokers. Iso-NNAC excretion was found on four occasions (44, 65, 74 and 163 ng/day) in smokers; non-smokers did not excrete Iso-NNAC. Oral administration of nicotine (n = 8; 12-40 mg) and cotinine (n = 3; 40-60 mg) to abstinent smokers did not result in Iso-NNAC excretion, even after oral nitrate (150 mg) supplementation. However, Iso-NNAC was found in cigarette tobacco (10-330 ng/g) and mainstream cigarette smoke (1.1-5.5 ng/cig.). Our studies suggest that the occasional presence of Iso-NNAC in smokers' urine results from exogenous exposure to the preformed compound in mainstream cigarette smoke and not from endogenous nitrosation of nicotine and its metabolites. PMID:8330358

  17. Ring-strain release in neutral and dicationic 7,8,17,18-tetra-bromo-5,10,15,20-tetra-phenyl-porphyrin: crystal structures of C44H26Br4N4 and C44H28Br4N4 (2+)·2ClO4 (-)·3CH2Cl2.

    PubMed

    Scheidt, W Robert; Duval, Hugues F; Oliver, Allen G

    2016-06-01

    Two porphyrin complexes were studied to determine the effects of protonation on ring deformation within the porphyrin. The porphyrin 7,8,17,18-tetra-bromo-5,10,15,20-tetra-phenyl-porphyrin, C44H26Br4N4, was selected because the neutral species is readily doubly protonated to yield a dication, which was crystallized here with perchlorate counter-ions as a di-chloro-methane tris-olvate, C44H28Br4N4 (2+)·2ClO4 (-)·3CH2Cl2. The centrosymmetric neutral species is observed to have a mild 'ruffling' of the pyrrole rings and is essentially planar throughout; intra-molecular N-H⋯N hydrogen bonds occur. In contrast, the dication exhibits considerable deformation, with the pyrrole rings oriented well out of the plane of the porphyrin, resulting in a 'saddle' conformation of the ring. The charged species forms N-H⋯O hydrogen bonds to the perchlorate anions, which lie above and below the plane of the porphyrin ring. Distortions to the planarity of the pyrrole rings in both cases are very minor. The characterization of the neutral species represents a low-temperature redetermination of the previous room-temperature analyses [Zou et al. (1995 ▸). Acta Cryst. C51, 760-761; Rayati et al. (2008 ▸). Polyhedron, pp. 2285-2290], which showed disorder and physically unrealistic displacement parameters. PMID:27308051

  18. Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.

    PubMed

    Doro, Fabio G; Pepe, Iuri M; Galembeck, Sergio E; Carlos, Rose M; da Rocha, Zenis N; Bertotti, Mauro; Tfouni, Elia

    2011-06-28

    Chemical reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam, fac-[Ru(NO)Cl(2)(κ(3)N(4),N(8),N(11)(1-carboxypropyl)cyclam)]Cl·H(2)O ((1-carboxypropyl)cyclam = 3-(1,4,8,11-tetraazacyclotetradecan-1-yl)propionic acid)), (I) are described. Chloride ligands do not undergo aquation reactions (at 25 °C, pH 3). The rate of nitric oxide (NO) dissociation (k(obs-NO)) upon reduction of I is 2.8 s(-1) at 25 ± 1 °C (in 0.5 mol L(-1) HCl), which is close to the highest value found for related complexes. The uncoordinated carboxyl of I has a pK(a) of ∼3.3, which is close to that of the carboxyl of the non coordinated (1-carboxypropyl)cyclam (pK(a) = 3.4). Two additional pK(a) values were found for I at ∼8.0 and ∼11.5. Upon electrochemical reduction or under irradiation with light (λ(irr) = 350 or 520 nm; pH 7.4), I releases NO in aqueous solution. The cyclam ring N bound to the carboxypropyl group is not coordinated, resulting in a fac configuration that affects the properties and chemical reactivities of I, especially as NO donor, compared with analogous trans complexes. Among the computational models tested, the B3LYP/ECP28MDF, cc-pVDZ resulted in smaller errors for the geometry of I. The computational data helped clarify the experimental acid-base equilibria and indicated the most favourable site for the second deprotonation, which follows that of the carboxyl group. Furthermore, it showed that by changing the pH it is possible to modulate the electron density of I with deprotonation. The calculated NO bond length and the Ru/NO charge ratio indicated that the predominant canonical structure is [Ru(III)NO], but the Ru-NO bond angles and bond index (b.i.) values were less clear; the angles suggested that [Ru(II)NO(+)] could contribute to the electronic structure of I and b.i. values indicated a contribution from [Ru(IV)NO(-)]. Considering that some experimental data are consistent with a [Ru

  19. Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

    PubMed

    De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

    2014-03-28

    New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed. PMID:24468910

  20. PREFACE: Semiconducting oxides Semiconducting oxides

    NASA Astrophysics Data System (ADS)

    Catlow, Richard; Walsh, Aron

    2011-08-01

    Semiconducting oxides are amongst the most widely studied and topical materials in contemporary condensed matter science, with interest being driven both by the fundamental challenges posed by their electronic and magnetic structures and properties, and by the wide range of applications, including those in catalysis and electronic devices. This special section aims to highlight recent developments in the physics of these materials, and to show the link between developing fundamental understanding and key application areas of oxide semiconductors. Several aspects of the physics of this wide and expanding range of materials are explored in this special section. Transparent semiconducting oxides have a growing role in several technologies, but challenges remain in understanding their electronic structure and the physics of charge carriers. A related problem concerns the nature of redox processes and the reactions which interconvert defects and charge carriers—a key issue which may limit the extent to which doping strategies may be used to alter electronic properties. The magnetic structures of the materials pose several challenges, while surface structures and properties are vital in controlling catalytic properties, including photochemical processes. The field profits from and exploits a wide range of contemporary physical techniques—both experimental and theoretical. Indeed, the interplay between experiment and computation is a key aspect of contemporary work. A number of articles describe applications of computational methods whose use, especially in modelling properties of defects in these materials, has a long and successful history. Several papers in this special section relate to work presented at a symposium within the European Materials Research Society (EMRS) meeting held in Warsaw in September 2010, and we are grateful to the EMRS for supporting this symposium. We would also like to thank the editorial staff of Journal of Physics: Condensed Matter for

  1. Preparation of periodic mesoporous silica-included divacant Keggin units for the catalytic oxidation of styrene to synthesize styrene oxide

    NASA Astrophysics Data System (ADS)

    Yu, Xiaodan; Xu, Leilei; Yang, Xia; Guo, Yingna; Li, Kexin; Hu, Jianglei; Li, Wei; Ma, Fengyan; Guo, Yihang

    2008-05-01

    Periodic mesoporous composite catalysts, [( n-C 4H 9) 4N] 4[γ-SiW 10O 34(H 2O) 2]/SBA-15 (TBA-1*/SBA-15, where TBA-1* = [( n-C 4H 9) 4N] 4[γ-SiW 10O 34(H 2O) 2]), with TBA-1* loadings of 4.3-14.8% were prepared by simultaneous hydrolysis and co-condensation of the tetraethoxysilane (TEOS) in the presence of divacant Keggin-type polyoxometalate and triblock copolymer surfactant (P123) followed by hydrothermal treatment process. Structure integrity of the Keggin unit in as-prepared composites was studied by Fourier transform infrared spectroscopy (FT-IR), Raman scattering spectra, and 29Si magic-angle spinning (MAS) NMR. Periodic mesoporous structure of the composites was evaluated by low-angle X-ray powder diffraction (LXRD) patterns, nitrogen porosimetry, and transmission electron microscope (TEM) measurements. As-prepared TBA-1*/SBA-15 was used as an heterogeneous oxidation catalyst for the styrene epoxidation reaction to synthesize styrene oxide in the presence of dilute H 2O 2 (30%), and influences of solvent, molar ratio of styrene to H 2O 2, TBA-1* loading on the styrene conversion, styrene oxide yield and selectivity were considered.

  2. Synthesis and Structural Elucidation of Triazolylmolybdenum(VI) Oxide Hybrids and Their Behavior as Oxidation Catalysts.

    PubMed

    Lysenko, Andrey B; Senchyk, Ganna A; Domasevitch, Konstantin V; Hauser, Jürg; Fuhrmann, Daniel; Kobalz, Merten; Krautscheid, Harald; Neves, Patrícia; Valente, Anabela A; Gonçalves, Isabel S

    2015-09-01

    A large family of bifunctional 1,2,4-triazole molecular tectons (tr) has been explored for engineering molybdenum(VI) oxide hybrid solids. Specifically, tr ligands bearing auxiliary basic or acidic groups were of the type amine, pyrazole, 1H-tetrazole, and 1,2,4-triazole. The organically templated molybdenum(VI) oxide solids with the general compositions [MoO3(tr)], [Mo2O6(tr)], and [Mo2O6(tr)(H2O)2] were prepared under mild hydrothermal conditions or by refluxing in water. Their crystal structures consist of zigzag chains, ribbons, or helixes of alternating cis-{MoO4N2} or {MoO5N} polyhedra stapled by short [N-N]-tr bridges that for bitriazole ligands convert the motifs into 2D or 3D frameworks. The high thermal (235-350 °C) and chemical stability observed for the materials makes them promising for catalytic applications. The molybdenum(VI) oxide hybrids were successfully explored as versatile oxidation catalysts with tert-butyl hydroperoxide (TBHP) or aqueous H2O2 as an oxygen source, at 70 °C. Catalytic performances were influenced by the different acidic-basic properties and steric hindrances of coordinating organic ligands as well as the structural dimensionality of the hybrid. PMID:26280712

  3. Nanostructured indium tin oxide slides for small-molecule profiling and imaging mass spectrometry of metabolites by surface-assisted laser desorption ionization MS.

    PubMed

    López de Laorden, Carlos; Beloqui, Ana; Yate, Luis; Calvo, Javier; Puigivila, Maria; Llop, Jordi; Reichardt, Niels-Christian

    2015-01-01

    Due to their electrical conductivity and optical transparency, slides coated with a thin layer of indium tin oxide (ITO) are the standard substrate for protein imaging mass spectrometry on tissue samples by MALDI-TOF MS. We have now studied the rf magnetron sputtering deposition parameters to prepare ITO thin films on glass substrates with the required nanometric surface structure for their use in the matrix-free imaging of metabolites and small-molecule drugs, without affecting the transparency required for classical histology. The custom-made surfaces were characterized by atomic force microscopy, scanning electron microscopy, ellipsometry, UV, and laser desorption ionization MS (LDI-MS) and employed for the LDI-MS-based analysis of glycans and druglike molecules, the quantification of lactose in milk by isotopic dilution, and metabolite imaging on mouse brain tissue samples. PMID:25411795

  4. One-pot synthesis and Nb4N5 surface modification of Nb(4+) self-doped KNbO3 nanorods for enhanced visible-light-driven hydrogen production.

    PubMed

    Wang, Jianqiang; Wang, Xia; Cui, Zhentao; Liu, Bing; Cao, Minhua

    2015-06-01

    Herein, rhombohedral self-doped KNbO3 (S-KN) nanorods were fabricated via a one pot, solvothermal method without using any surfactant. The presence of Nb(4+) in S-KN greatly narrows its band gap and thus extends its photoresponse from UV to the visible light region. Moreover, S-KN/Nb4N5 nanorod heterostructures were obtained by nitriding S-KN nanorods for different times, which exhibited significantly enhanced photocatalytic activity for hydrogen production under visible light irradiation. The junction formed between S-KN and Nb4N5 and the Nb(4+) self-doping of KN are supposed to be responsible for the enhanced photocatalytic activity of S-KN/Nb4N5. This study also paves the way for the synthesis of other similar photocatalysts. PMID:25960360

  5. Study of uranium oxide milling in order to obtain nanostructured UCx target

    NASA Astrophysics Data System (ADS)

    Guillot, Julien; Tusseau-Nenez, Sandrine; Roussière, Brigitte; Barré-Boscher, Nicole; Brisset, François; Mhamed, Maher Cheikh; Lau, Christophe; Nowak, Sophie

    2016-05-01

    A R&D program is developed at the ALTO facility to provide new beams of exotic neutron-rich nuclei, as intense as possible. In the framework of European projects, it has been shown that the use of refractory targets with nanometric structure allows us to obtain beams of nuclei unreachable until now. The first parameter to be controlled in the processing to obtain targets with a homogeneous nanostructure is the grinding of uranium dioxide, down to 100 nm grain size. In this study, dry and wet grinding routes are studied and the powders are analyzed in terms of phase stabilization, specific surface area and grain morphology. It appears that the grinding, as well dry as wet, leads to the decrease of the particle size. The oxidation of UO2 is observed whatever the grinding. However, the dry grinding is the most efficient and leads to the oxidation of UO2 into U4O9 and U3O7 whose quantities increase with the grinding time while crystallite sizes decrease.

  6. Assisted deposition of nano-hydroxyapatite onto exfoliated carbon nanotube oxide scaffolds.

    PubMed

    Zanin, H; Rosa, C M R; Eliaz, N; May, P W; Marciano, F R; Lobo, A O

    2015-06-14

    Electrodeposited nano-hydroxyapatite (nHAp) is more similar to biological apatite in terms of microstructure and dimension than apatites prepared by other processes. Reinforcement with carbon nanotubes (CNTs) enhances its mechanical properties and increases adhesion of osteoblasts. Here, we carefully studied nHAp deposited onto vertically aligned multi-walled CNT (VAMWCNT) scaffolds by electrodeposition and soaking in a simulated body fluid (SBF). VAMWCNTs are porous biocompatible scaffolds with nanometric porosity and exceptional mechanical and chemical properties. The VAMWCNT films were prepared on a Ti substrate by a microwave plasma chemical vapour deposition method, and then oxidized and exfoliated by oxygen plasma etching (OPE) to produce graphene oxide (GO) at the VAMWCNT tips. The attachment of oxygen functional groups was found to be crucial for nHAp nucleation during electrodeposition. A thin layer of plate-like and needle-like nHAp with high crystallinity was formed without any need for thermal treatment. This composite (henceforth referred to as nHAp-VAMWCNT-GO) served as the scaffold for in vitro biomineralization when soaked in the SBF, resulting in the formation of both carbonate-rich and carbonate-poor globular-like nHAp. Different steps in the deposition of biological apatite onto VAMWCNT-GO and during the short-term biomineralization process were analysed. Due to their unique structure and properties, such nano-bio-composites may become useful in accelerating in vivo bone regeneration processes. PMID:25990927

  7. Assisted deposition of nano-hydroxyapatite onto exfoliated carbon nanotube oxide scaffolds

    NASA Astrophysics Data System (ADS)

    Zanin, H.; Rosa, C. M. R.; Eliaz, N.; May, P. W.; Marciano, F. R.; Lobo, A. O.

    2015-05-01

    Electrodeposited nano-hydroxyapatite (nHAp) is more similar to biological apatite in terms of microstructure and dimension than apatites prepared by other processes. Reinforcement with carbon nanotubes (CNTs) enhances its mechanical properties and increases adhesion of osteoblasts. Here, we carefully studied nHAp deposited onto vertically aligned multi-walled CNT (VAMWCNT) scaffolds by electrodeposition and soaking in a simulated body fluid (SBF). VAMWCNTs are porous biocompatible scaffolds with nanometric porosity and exceptional mechanical and chemical properties. The VAMWCNT films were prepared on a Ti substrate by a microwave plasma chemical vapour deposition method, and then oxidized and exfoliated by oxygen plasma etching (OPE) to produce graphene oxide (GO) at the VAMWCNT tips. The attachment of oxygen functional groups was found to be crucial for nHAp nucleation during electrodeposition. A thin layer of plate-like and needle-like nHAp with high crystallinity was formed without any need for thermal treatment. This composite (henceforth referred to as nHAp-VAMWCNT-GO) served as the scaffold for in vitro biomineralization when soaked in the SBF, resulting in the formation of both carbonate-rich and carbonate-poor globular-like nHAp. Different steps in the deposition of biological apatite onto VAMWCNT-GO and during the short-term biomineralization process were analysed. Due to their unique structure and properties, such nano-bio-composites may become useful in accelerating in vivo bone regeneration processes.

  8. In-situ X-ray diffraction analysis of zirconia layer formed on zirconium alloys oxidized at high temperature

    NASA Astrophysics Data System (ADS)

    Gosset, D.; Le Saux, M.

    2015-03-01

    In the case of a hypothetical loss of primary coolant accident (LOCA) in a light water reactor, the zirconium alloys fuel cladding would be oxidized in steam at high temperature, typically in the range 800-1200 °C. The monoclinic to tetragonal phase martensitic transition of zirconia occurs within this temperature range and complex phenomena possibly having an impact on the oxidation kinetics are then to be expected. In order to provide an accurate description of the structure and microstructure of the oxide layers, systematic X-ray diffraction analyses have been performed in-situ under oxidizing atmosphere at high temperature (between 800 and 1100 °C) on Zircaloy-4 and M5™ sheet samples. It was confirmed that the volume fraction of the tetragonal and monoclinic zirconia phases formed during oxide growth drastically depends on the oxidation temperature. For example, the few outer microns of the oxide are fully tetragonal above 1050 °C and contain only 20% of tetragonal phase at 800 °C. It was also shown that cooling after oxidation induces irreversible phase transitions within the oxide. As a consequence, both the structure and the microstructure of the growing oxide cannot be observed post-facto, neither at room temperature nor after reheating at the prior oxidation temperature. It has been deduced from microstructural analyses that the grain size of the tetragonal zirconia phase is nanometric, about 100 nm during oxidation at 1100 °C down to 20 nm after cooling down to room temperature. This small grain size allows the stabilization of the tetragonal phase. The lattice parameters of the monoclinic and tetragonal zirconia phases have been analyzed, during both high temperature oxidation and cooling. In both cases, it appears the 'a' and 'b' cell parameters of the monoclinic phase are strongly constrained by the tetragonal 'a' one. The structural characteristics of the oxide formed at high temperature on Zircaloy-4 and M5™ are quite similar. All those

  9. Identification of Transient Radical Anions (LiClO4)(n)(-) (n = 1-3) in THF Solutions: Experimental and Theoretical Investigation on Electron Localization in Oligomers.

    PubMed

    Ma, Jun; Archirel, Pierre; Pernot, Pascal; Schmidhammer, Uli; Le Caër, Sophie; Mostafavi, Mehran

    2016-02-01

    Picosecond pulse radiolysis measurements of tetrahydrofuran (THF) solutions containing LiClO4 over a wide range of concentration are performed to investigate the formation of transient species. The (35)Cl NMR measurements of these solutions prior to irradiation show that the salt is in the form of (LiClO4)n oligomers. Kinetics and transient absorption spectra of intermediates in each solution are obtained on the time scale from 10 to 3800 ps. A global spectro-kinetic matrix of the data is analyzed by the multicurve resolution alternated least-squares (MCR-ALS) method. It shows the presence of 3 transient species induced by electron pulse, in addition to the solvated electron. A hybrid Monte Carlo/DFT molecular simulation method is elaborated, using the MPW1K functional for the configuration sampling and B3LYP for the spectra calculations. The maximum of the absorption band of the monomer (LiClO4)(-), dimer (LiClO4)2(-), trimer (LiClO4)3(-), and tetramer (LiClO4)4(-) anions are deduced from the simulations. They enable one to label the MCR-ALS spectra (differences are below 0.1 eV) and to interpret the kinetic data. The simulations show also that Li(I) ion catalyzes the reduction of perchlorate by excess electrons. Only the dimer anion, due to its unique structure with a stable Li2(+) core and two nonbridging perchlorates, presents higher stability toward ClO4(-) reduction into ClO3(-). It corresponds to the long-lived species observed in the experiments. PMID:26741165

  10. Conformational analysis of antineoplastic antifolates: the crystal structure of trimetrexate and the aminopterine derivative 4-[N-[(2,4-diamino-6-pteridinyl)methyl]amino]benzoic acid.

    PubMed

    Sutton, P A; Cody, V

    1987-10-01

    The crystal structures of trimetrexate (TMQ) (2,4-diamino-5-methyl-6-[(3,4,5-trimethoxyanilino)methyl]quinazoli ne) and 4-[N-[(2,4-diamino-6-pteridinyl)methyl]amino]benzoic acid (PMAB) were determined to examine their conformational features with respect to the enzyme-bound form of methotrexate (MTX). TMQ and MTX are antineoplastic drugs that act by inhibiting the enzyme dihydrofolate reductase. The molecular conformation of TMQ is extended with the trimethoxyanilino ring twisted 89 degrees from the quinazoline plane, and the molecular conformation of PMAB is completely planar. The geometry of the 2,4-diaminopteridine and 2,4-diaminoquinazoline rings are sensitive to protonation, and both TMQ and PMAB have geometries characteristic to a free base. TMQ crystallizes as a dimethyl sulfoxide hydrate. The quinazoline ring forms an antiparallel stacking arrangement in the lattice and forms a network of N...O hydrogen bonds with the solvent molecules. In PMAB there are both pteridine-benzoic acid (N...O) hydrogen bonds and pteridine-pteridine (N...N) hydrogen bonds. Although the molecular conformation of TMQ and PMAB differ from enzyme-bound MTX, rotational energy barriers calculated using CAMSEQ indicate that they can adopt a similar conformation to that seen for MTX complexed with dihydrofolate reductase. These energy calculations show that PMAB is quite flexible and further suggest that the 5-methyl in TMQ reduces its conformational flexibility in a different manner than the N(10)-methyl in MTX. These structural data also show that full geometry optimization and proper parameterization of electronic effects at N(10) are required to accurately represent antifolate conformational preferences for enzyme binding. PMID:2958629

  11. A single gas chromatograph for accurate atmospheric mixing ratio measurements of CO2, CH4, N2O, SF6 and CO

    NASA Astrophysics Data System (ADS)

    van der Laan, S.; Neubert, R. E. M.; Meijer, H. A. J.

    2009-09-01

    We present an adapted gas chromatograph capable of measuring simultaneously and semi-continuously the atmospheric mixing ratios of the greenhouse gases CO2, CH4, N2O and SF6 and the trace gas CO with high precision and long-term stability. The novelty of our design is that all species are measured with only one device, making it a very cost-efficient system. No time lags are introduced between the measured mixing ratios. The system is designed to operate fully autonomously which makes it ideal for measurements at remote and unmanned stations. Only a small amount of sample air is needed, which makes this system also highly suitable for flask air measurements. In principle, only two reference cylinders are needed for daily operation and only one calibration per year against international WMO standards is sufficient to obtain high measurement precision and accuracy. The system described in this paper is in use since May 2006 at our atmospheric measurement site Lutjewad near Groningen, The Netherlands at 6°21´ E, 53°24´N, 1 m a.s.l. Results show the long-term stability of the system. Observed measurement precisions at our remote research station Lutjewad were: ±0.04 ppm for CO2, ±0.8 ppb for CH4, ±0.8 ppb for CO, ±0.3 ppb for N2O, and ±0.1 ppt for SF6. The ambient mixing ratios of all measured species as observed at station Lutjewad for the period of May 2007 to August 2008 are presented as well.

  12. A single gas chromatograph for accurate atmospheric mixing ratio measurements of CO2, CH4, N2O, SF6 and CO

    NASA Astrophysics Data System (ADS)

    van der Laan, S.; Neubert, R. E. M.; Meijer, H. A. J.

    2009-05-01

    We present an adapted gas chromatograph capable of measuring simultaneously and semi-continuously the atmospheric mixing ratios of the greenhouse gases CO2, CH4, N2O and SF6 and the trace gas CO with high precision and long-term stability. The novelty of our design is that all species are measured with only one device, making it a very cost-efficient system. No time lags are introduced between the measured mixing ratios. The system is designed to operate fully autonomously which makes it ideal for measurements at remote and unmanned stations. Only a small amount of sample air is needed, which makes this system also highly suitable for flask air measurements. In principle, only two reference cylinders are needed for daily operation and only one calibration per year against international WMO standards is sufficient to obtain high measurement precision and accuracy. The system described in this paper is in use since May 2006 at our atmospheric measurement site Lutjewad near Groningen, The Netherlands at 6°21' E, 53°24' N, 1 m a.s.l. Results show the long-term stability of the system. Observed measurement precisions at our remote research station Lutjewad were: ±0.04 ppm for CO2, ±0.8 ppb for CH4, ±0.8 ppb for CO, ±0.3 ppb for N2O, and ±0.1 ppt for SF6. The ambient mixing ratios of all measured species as observed at station Lutjewad for the period of May 2007 to August 2008 are presented as well.

  13. Nano-crystalline p-ZnGa{sub 2}Te{sub 4}/n-Si as a new heterojunction diode

    SciTech Connect

    Sakr, G.B.; Fouad, S.S.; Yahia, I.S.; Abdel Basset, D.M.; Yakuphanoglu, F.

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► ZnGa{sub 2}Te{sub 4}/Si thin film was prepared by thermal evaporation technique. ► XRD and AFM graphs support the nano-crystalline of the studied device. ► Dark current–voltage characteristics of the heterojunction diode were investigated. ► Electrical parameters and conduction mechanism were determined. ► Conduction mechanisms were controlled by TE, SCLC and TCLC. -- Abstract: In this communication, ZnGa{sub 2}Te{sub 4} thin film was prepared by thermal evaporation technique on n-Si substrate. P-ZnGa{sub 2}Te{sub 4}/n-Si heterojunction diode was fabricated. The structure of ZnGa{sub 2}Te{sub 4} thin film was checked by XRD pattern and confirmed by AFM micrographs. The dark current–voltage characteristics of the heterojunction diode were investigated to determine the electrical parameters and conduction mechanism as a function of forward and reverse biasing conditions in the range (−10 V to 10 V) at temperature interval (303–423 K). The conduction mechanism was controlled by thermionic emission, space charge limited (SCLC) and trap-charge limited current (TCLC) mechanisms. The basic parameters such as the series resistance R{sub s}, the shunt resistance R{sub sh}, the ideality factor n and the barrier height φ{sub b} of the diode, the total density of trap states N{sub 0} and the exponential trapping distribution P{sub o} were determined. The obtained results showed that ZnGa{sub 2}Te{sub 4} is a good candidate for the applications of electronic devices.

  14. Radical Prostatectomy versus External Beam Radiotherapy for cT1-4N0M0 Prostate Cancer: Comparison of Patient Outcomes Including Mortality

    PubMed Central

    Taguchi, Satoru; Fukuhara, Hiroshi; Shiraishi, Kenshiro; Nakagawa, Keiichi; Morikawa, Teppei; Kakutani, Shigenori; Takeshima, Yuta; Miyazaki, Hideyo; Fujimura, Tetsuya; Nakagawa, Tohru; Kume, Haruki; Homma, Yukio

    2015-01-01

    Background Although radical prostatectomy (RP) and external beam radiotherapy (EBRT) have been considered as comparable treatments for localized prostate cancer (PC), it is controversial which treatment is better. The present study aimed to compare outcomes, including mortality, of RP and EBRT for localized PC. Methods We retrospectively analyzed 891 patients with cT1-4N0M0 PC who underwent either RP (n = 569) or EBRT (n = 322) with curative intent at our single institution between 2005 and 2012. Of the EBRT patients, 302 (93.8%) underwent intensity-modulated radiotherapy. Primary endpoints were overall survival (OS) and cancer-specific survival (CSS). Related to these, other-cause mortality (OCM) was also calculated. Biochemical recurrence-free survival was assessed as a secondary endpoint. Cox proportional hazards model was used for multivariate analysis. Results Median follow-up durations were 53 and 45 months, and median ages were 66 and 70 years (P <0.0001), in the RP and EBRT groups, respectively. As a whole, significantly better prognoses of the RP group than the EBRT group were observed for both OS and CSS, although OCM was significantly higher in the EBRT group. There was no death from PC in men with low and intermediate D’Amico risks, except one with intermediate-risk in the EBRT group. In high-risk patients, significantly more patients died from PC in the EBRT group than the RP group. Multivariate analysis demonstrated the RP group to be an independent prognostic factor for better CSS. On the other hand, the EBRT group had a significantly longer biochemical recurrence-free survival than the RP group. Conclusions Mortality outcomes of both RP and EBRT were generally favorable in low and intermediate risk patients. Improvement of CSS in high risk patients was seen in patients receiving RP over those receiving EBRT. PMID:26506569

  15. Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien)2(μ-1κ,2κ2-AsS4)]n (Ln==Sm, Eu, Gd) and [Ln(dien)2(1κ2-AsS4)] (Ln==Tb, Dy, Ho)

    NASA Astrophysics Data System (ADS)

    Wang, Fang; Tang, Chunying; Chen, Ruihong; Zhang, Yong; Jia, Dingxian

    2013-10-01

    Solvothermal reactions of Ln2O3, As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien)2(μ-1κ,2κ2-AsS4)]n [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien)2(1κ2-AsS4)] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln2O3 oxides were converted to [Ln(dien)2]3+ complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS4 unit. In 1-3, the AsS4 units interconnect the [Ln(dien)2]3+ cations via Ln-S bonds as tridentate μ-1κ,2κ2-AsS4 bridging ligands, resulting in the neutral coordination polymers [Ln(dien)2(μ-1κ,2κ2-AsS4)]n (Ln1). In 4-6, the AsS4 units coordinate with the Ln3+ ion of [Ln(dien)2]3+ as 1κ2-AsS4 chelating ligands to form neutral coordination compounds [Ln(dien)2(1κ2-AsS4)] (Ln2). The Ln3+ ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln3+ ions. Optical absorption spectra showed that 1-6 have potential use as semiconductors with the band gaps in the range 2.18-3.21 eV.

  16. Oxidation at Surfaces of Uranium Oxide Particles

    NASA Astrophysics Data System (ADS)

    Schueneman, Richard; Burgraff, Larry

    2001-04-01

    Uranium dioxide (UO2 (S)) is unstable in an oxidizing environment and oxidizes until covered with a layer of uranium trioxide (UO3 (C)). During the oxidation process, uranium cations change from U+4 to U+6 and the oxide crystal structure changes from face centered cubic to orthorhombic. Seven UO2(S) samples were prepared by pressing UO2 (S) powder into a tungsten screen and then subjected to five different temperatures and three partial pressures of oxygen. UO2 (S) oxidation was monitored with in situ photoluminescence (PL) spectroscopy. Quantitative oxidation data was obtained with secondary ion mass spectrometry (SIMS) and x-ray photoelectron spectroscopy (XPS). The in situ PL spectra did not identify UO3 (C) forming on the sample surfaces however, a new PL signature not associated with uranyl was observed. SIMS and XPS data from oxidized UO2 (S) samples indicated that at low temperatures, surface oxidation is kinetically limited and at high temperatures, surface oxidation is limited by diffusion. A model for the oxidation rate to UO3 (C) was not developed due to the temperature dependant oxidation process and high vacuum reduction of amorphous UO3 (A) present on the UO2 (S) sample surfaces prior to oxidation. A PL emission spectra intensity reduction was noticed on a UO3 (C) sample at room temperature under high vacuum. A reduction and re-oxidation of three additional UO3 (C) samples identified a kinetically irreversible reduction process for UO3(C) under high vacuum. A SIMS surface scan was performed on a fourth UO3(C) sample before and after exposure to ultra-high vacuum (10-8 torr) and the results suggest the reduction of UO3(C) to lower oxides (U3O8, U3O7 and UO2) at room temperature.

  17. Ring-strain release in neutral and dicationic 7,8,17,18-tetra­bromo-5,10,15,20-tetra­phenyl­porphyrin: crystal structures of C44H26Br4N4 and C44H28Br4N4 2+·2ClO4 −·3CH2Cl2

    PubMed Central

    Scheidt, W. Robert; Duval, Hugues F.; Oliver, Allen G.

    2016-01-01

    Two porphyrin complexes were studied to determine the effects of protonation on ring deformation within the porphyrin. The porphyrin 7,8,17,18-tetra­bromo-5,10,15,20-tetra­phenyl­porphyrin, C44H26Br4N4, was selected because the neutral species is readily doubly protonated to yield a dication, which was crystallized here with perchlorate counter-ions as a di­chloro­methane tris­olvate, C44H28Br4N4 2+·2ClO4 −·3CH2Cl2. The centrosymmetric neutral species is observed to have a mild ‘ruffling’ of the pyrrole rings and is essentially planar throughout; intra­molecular N—H⋯N hydrogen bonds occur. In contrast, the dication exhibits considerable deformation, with the pyrrole rings oriented well out of the plane of the porphyrin, resulting in a ‘saddle’ conformation of the ring. The charged species forms N—H⋯O hydrogen bonds to the perchlorate anions, which lie above and below the plane of the porphyrin ring. Distortions to the planarity of the pyrrole rings in both cases are very minor. The characterization of the neutral species represents a low-temperature redetermination of the previous room-temperature analyses [Zou et al. (1995 ▸). Acta Cryst. C51, 760–761; Rayati et al. (2008 ▸). Polyhedron, pp. 2285–2290], which showed disorder and physically unrealistic displacement parameters. PMID:27308051

  18. Oxidation resistance of silicon ceramics

    NASA Technical Reports Server (NTRS)

    Yasutoshi, H.; Hirota, K.

    1984-01-01

    Oxidation resistance, and examples of oxidation of SiC, Si3N4 and sialon are reviewed. A description is given of the oxidation mechanism, including the oxidation product, oxidation reaction and the bubble size. The oxidation reactions are represented graphically. An assessment is made of the oxidation process, and an oxidation example of silicon ceramics is given.

  19. Signal transduction pathways in erythrocyte nitric oxide metabolism under high fibrinogen levels

    NASA Astrophysics Data System (ADS)

    Saldanha, Carlota; Freitas, T.; Lopez de Almeida, J. P.; Silva-Herdade, A.

    2014-05-01

    Previous studies show that the fibrinogen molecule modulates the metabolism of nitric oxide (NO) in erythrocyte. The in vitro induced hiperfibrinogenemia interferes in the metabolism of the NO in the erythrocyte in dependence of the phosphorylation degree of the band 3. The soluble form of fibrinogen binds into CD47 protein present in the erythrocyte membrane. The soluble thrombomodulin is an inflammatory marker that binds to the erythrocyte CD47 in a site with a sequence peptide known as 4N1K. A study done in vitro shows that when hiperfibrinogenemia was induced in the presence of the peptide 4N1K agonist of CD47 it were observed variations in the efflux of NO from erythrocyte and an increase in the concentrations of GSNO, peroxinitrite, nitrite and nitrate of the erythrocytes. The aim of this work was to study the influence of the peptide 4N1K, on the metabolism of NO in the erythrocyte under high fibrinogen concentration and in the presence of inhibitors of the status of phosphorylation of protein band 3. In this in vitro study, whole blood samples were harvested from healthy subjects and NO, peroxynitrite, nitrite, nitrate and S-nitro-glutathione (GSNO) were determined in presence of 4N1K, calpeptine, Syk inhibitor and under high fibrinogen concentrations. The results obtained in erythrocytes under high fibrinogen levels when 4N1K is present with the Syk inhibitor or with calpeptine, showed in relation to the control samples increased significant concentrations of efflux of NO and of peroxynitrite, nitrite, nitrate and GSNO. In conclusion it was verified that in the in vitro model of hiperfibrinogenemia the peptide 4N1K, agonist of CD47, induces mobilization of NO in the erythrocyte in dependence of the status of phosphorylation of protein band 3.

  20. Electrochemical oxidation of cholesterol

    PubMed Central

    2015-01-01

    Summary Indirect cholesterol electrochemical oxidation in the presence of various mediators leads to electrophilic addition to the double bond, oxidation at the allylic position, oxidation of the hydroxy group, or functionalization of the side chain. Recent studies have proven that direct electrochemical oxidation of cholesterol is also possible and affords different products depending on the reaction conditions. PMID:25977713

  1. Thermally exfoliated graphite oxide

    NASA Technical Reports Server (NTRS)

    Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Abdala, Ahmed (Inventor)

    2011-01-01

    A modified graphite oxide material contains a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the thermally exfoliated graphite oxide displays no signature of the original graphite and/or graphite oxide, as determined by X-ray diffraction.

  2. Nitric oxide inhibition strategies

    PubMed Central

    Wong, Vivian (Wai Chong); Lerner, Ethan

    2015-01-01

    Nitric oxide is involved in many physiologic processes. There are efforts, described elsewhere in this volume, to deliver nitric oxide to tissues as a therapy. Nitric oxide also contributes to pathophysiologic processes. Inhibiting nitric oxide or its production can thus also be of therapeutic benefit. This article addresses such inhibitory strategies. PMID:26634146

  3. Lorentz transmission electron microscopy on nanometric magnetic bubbles and skyrmions in bilayered manganites La{sub 1.2}Sr{sub 1.8}(Mn{sub 1−y}Ru{sub y}){sub 2}O{sub 7} with controlled magnetic anisotropy

    SciTech Connect

    Morikawa, D.; Yu, X. Z.; Kaneko, Y.; Tokunaga, Y.; Arima, T.; Nagai, T.; Kimoto, K.; Tokura, Y.

    2015-11-23

    We have investigated nanometric magnetic textures in thin (<150 nm) plates of Ru-doped bilayered manganites La{sub 1.2}Sr{sub 1.8}(Mn{sub 1−y}Ru{sub y}){sub 2}O{sub 7}. Ru substitution for Mn site changes the magnetic anisotropy from in-plane to out-of-plane easy axis type without any significant change of global magnetic and crystal structures. The combination of conventional and Lorentz transmission electron microscopy observations confirms the emergence of magnetic bubbles and skyrmions in the absence of magnetic field. With the changing Ru concentration, systematic changes in the type of magnetic bubbles are observed. A tiny residual magnetic field also affects the generation and the type-change of magnetic bubbles.

  4. Strength by atomic force microscopy (AFM): Molecular dynamics of water layer squeezing on magnesium oxide

    NASA Astrophysics Data System (ADS)

    Kendall, K.; Dhir, Aman; Yong, Chin W.

    2010-11-01

    Localised strength testing of materials is often carried out in an atomic force microscope (AFM), as foreseen by Kelly in his book Strong Solids (Clarendon Press, Oxford, 1966). During AFM indentation experiments, contamination can strongly influence the observed strength and theoretical interpretation of the results is a major problem. Here, we use molecular dynamics computer modelling to describe the contact of NaCl and MgO crystal probes onto surfaces, comparable to an AFM experiment. Clean NaCl gave elastic, brittle behaviour in contact simulations at 300 K, whereas MgO was more plastic, leading to increased toughness. This paper also considers the strength of an oxide substrate contaminated by water molecules and tested by indentation with a pyramidal probe of oxide crystal. Recent theory on the effect of liquid contaminant layers on surface strength has been mainly focussed on Lennard Jones (LJ) molecules with some studies on alcohols and water, described by molecular dynamics, which allows the molecules to be squeezed out as the crystal lattice is deformed. In this work, we have focused on water by studying the forces between a magnesium oxide (MgO) atomic force microscope (AFM) probe and an MgO slab. Force versus separation has been plotted as the AFM probe was moved towards and away from the substrate. Simulation results showed that the water layers could be removed in steps, giving up to four force peaks. The last monolayer of water could not be squeezed out, even at pressures where MgO deformed plastically. Interestingly, with water present, strength was reduced, but more in tensile than compressive measurements. In conclusion, water contaminating the oxide surface in AFM strength testing is structured. Water layer squeezing removal can be predicted by molecular modelling, which may be verified by AFM experiments to show that water can influence the strength of perfect crystals at the nanometre scale.

  5. Solvothermal synthesis of perovskites and pyrochlores: crystallisation of functional oxides under mild conditions.

    PubMed

    Modeshia, Deena R; Walton, Richard I

    2010-11-01

    In this critical review we consider the large literature that has accumulated in the past 5-10 years concerning solution-mediated crystallisation of complex oxide materials using hydrothermal, or more generally solvothermal, reaction conditions. The aim is to show how the synthesis of dense, mixed-metal oxide materials, usually prepared using the high temperatures associated with solid-chemistry, is perfectly feasible from solution in one step reactions, typically at temperatures as low as 200 °C, and that important families of oxide materials have now been reported to crystallise using such synthetic approaches. We will focus on two common structures seen in oxide chemistry, ABO(3) perovskites and A(2)B(2)O(6)O' pyrochlores, and include a systematic survey of the variety of chemical elements now included in these two prototypical structure types, from transition metals, in families of materials that include titanates, niobates, manganites and ferrites, to main-group elements in stannates, plumbates and bismuthates. The significant advantages of solution-mediated crystallisation are well illustrated by the recent literature: examples are provided of elegant control of crystal form from the nanometre to the micron length scale to give thin films, anisotropic crystal morphologies, or hierarchical structures of materials with properties desirable for many important contemporary applications. In addition, new metastable materials have been reported, not stable once high temperatures and pressures are applied and hence not amenable using conventional synthesis. We critically discuss the possible control offered by solvothermal synthesis from crystal chemistry to crystal form and how the discovery of new materials may be achieved. Computer simulation, combinatorial synthesis approaches and in situ methods to follow crystallisation will be vital in providing the predictability in synthesis that is needed for rational design of new materials (232 references). PMID

  6. Drivers of small scale variability in soil-atmosphere fluxes of CH4, N2O and CO2 in a forest soil

    NASA Astrophysics Data System (ADS)

    Maier, Martin; Nicolai, Clara; Wheeler, Denis; Lang, Friedeike; Paulus, Sinikka

    2016-04-01

    Soil-atmosphere fluxes of CH4, N2O and CO2 can vary on different spatial scales, on large scales between ecosystems but also within apparently homogenous sites. While CO2 and CH4 consumption is rather evenly distibuted in well aerated soils, the production of N2O and CH4 seems to occur at hot spots that can be associated with anoxic or suboxic conditions. Small-scale variability in soil properties is well-known from field soil assesment, affecting also soil aeration and thus theoretically, greenhouse gas fluxes. In many cases different plant species are associated with different soil conditions and vegetation mapping should therefor combined with soil mapping. Our research objective was explaining the small scale variability of greenhouse gas fluxes in an apparently homogeneous 50 years old Scots Pine stand in a former riparian flood plain.We combined greenhouse gas measurements and soil physical lab measurments with field soil assessment and vegetation mapping. Measurements were conducted with at 60 points at a plot of 30 X 30 m at the Hartheim monitoring site (SW Germany). For greenhouse gas measurements a non-steady state chamber system and laser analyser, and a photoacoustic analyser were used. Our study shows that the well aerated site was a substantial sink for atmospheric CH4 (-2.4 nmol/m² s) and also a for N2O (-0.4 nmol/m² s), but less pronounced, whereas CO2 production was a magnitude larger (2.6 μmol/m² s). The spatial variability of the CH4 consumption of the soils could be explained by the variability of the soil gas diffusivity (measured in situ + using soil cores). Deviations of this clear trend were only observed at points where decomposing woody debris was directly under the litter layer. Soil texture ranged from gravel, coarse sand, fine sand to pure silt, with coarser texture having higher soil gas diffusivity. Changes in texture were rather abrupt at some positions or gradual at other positions, and were well reflected in the vegetation

  7. Relativistic effects on nuclear magnetic shieldings of CHnX4-n and CHXYZ (X, Y, Z = H, F, Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Melo, Juan I.; Maldonado, Alejandro F.; Aucar, Gustavo A.

    2012-12-01

    Nuclear magnetic shieldings of both carbon and hydrogen atoms of haluro methyl molecules are highly influenced by the substitution of one or more hydrogen by halogen heavy atoms. We applied the linear response elimination of small components, LRESC, formalism to calculate such shieldings and learn whether including only few terms is enough for getting quantitative reproduction of the total shieldings or not. First, we discuss the contribution of all leading relativistic corrections to σ(C), in CHX2I molecular models with X = H, F, and Cl, and show that spin-orbit (SO) effects are the main ones. After adding the SO effects to the non-relativistic (NR) results, we obtain ˜ 97% (93%) of the total LRESC values for σ(C) (σ(H)). The magnitude of SO terms increases when the halogen atom becomes heavier. In this case, such contributions to σ(C) can be extrapolated as a function of Z, the halogen atomic number. Furthermore, when paramagnetic spin-orbit (PSO) contributions are also considered, we obtain results that are within 1% of the total LRESC value. Then we study in detail the main electronic mechanisms involved to contribute C and H shieldings on CHnX4 - n (n = 1, 3), and CHXYZ (X, Y, Z = F, Cl, Br, I) model compounds. The pattern of σ(C) for all series of compounds follows a normal halogen dependence (NHD), though with different rate of increase. A special family of compounds is that of CHF2X for which σnr(C) follows an inverse halogen dependence though the total shielding have a NHD due to the SO contributions. For the series CH3X (X = F, Cl, Br and I), we found that σSO ˜ Z_X^{2.53}. Another important finding of this work is the logarithmic dependence of σSO(C) with the substituent atomic number: ln σSO(C) = A_X + a_X Z_Y for both family of compounds CH2XY and CHX2Y. We also performed four-component calculations using the spin-free Hamiltonian to obtain SO contributions within a four-component framework.

  8. Cellular and humoral mediated immunity and distribution of viral antigen in chickens after infection with a low pathogenic avian influenza virus (H4N6) isolated from wild ducks

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Four-week-old commercial chickens were intranasally inoculated with an H4N6 low pathogenicity avian influenza virus (LPAIV) isolated from a duck in Ukraine. Cecum, spleen, lung, and trachea samples were collected from birds from 1 to 21 days post inoculation (dpi) and examined by immunohistochemica...

  9. The Reaction of DABCO with 4-Chloro-5H-1,2,3-dithiazoles: Synthesis and Chemistry of 4-[N-(2-Chloroethyl)piperazin-1-yl]-5H-1,2,3-dithiazoles.

    PubMed

    Koyioni, Maria; Manoli, Maria; Koutentis, Panayiotis A

    2016-01-15

    N-(4-Chloro-5H-1,2,3-dithiazol-5-ylidene)anilines react with DABCO in hot PhCl to give N-{4-[N-(2-chloroethyl)piperazin-1-yl]-5H-1,2,3-dithiazol-5-ylidene}anilines in high yields (70-92%). The reaction also works with 4-chloro-5H-1,2,3-dithiazol-5-one and -thione, giving the corresponding products in 85% and 76% yields, respectively. While the reaction of several (4-chloro-5H-1,2,3-dithiazol-5-ylidene)methanes with DABCO failed to give {4-[N-(2-chloroethyl)piperazin-1-yl]-5H-1,2,3-dithiazol-5-ylidene}methanes, these can be prepared in moderate yields via classical cycloaddition-retrocycloaddition strategies from 4-[N-(2-chloroethyl)piperazin-1-yl]-5H-1,2,3-dithiazole-5-thione. The 2-chloroethyl moiety on selected dithiazoles was also modified without cleavage of the 1,2,3-dithiazole by reaction with various nucleophiles, giving access to 4-[N-(2-substituted)piperazin-1-yl]-5H-1,2,3-dithiazoles in moderate to high yields. PMID:26671065

  10. Micro-arc oxidation as a tool to develop multifunctional calcium-rich surfaces for dental implant applications.

    PubMed

    Ribeiro, A R; Oliveira, F; Boldrini, L C; Leite, P E; Falagan-Lotsch, P; Linhares, A B R; Zambuzzi, W F; Fragneaud, B; Campos, A P C; Gouvêa, C P; Archanjo, B S; Achete, C A; Marcantonio, E; Rocha, L A; Granjeiro, J M

    2015-09-01

    Titanium (Ti) is commonly used in dental implant applications. Surface modification strategies are being followed in last years in order to build Ti oxide-based surfaces that can fulfill, simultaneously, the following requirements: induced cell attachment and adhesion, while providing a superior corrosion and tribocorrosion performance. In this work micro-arc oxidation (MAO) was used as a tool for the growth of a nanostructured bioactive titanium oxide layer aimed to enhance cell attachment and adhesion for dental implant applications. Characterization of the surfaces was performed, in terms of morphology, topography, chemical composition and crystalline structure. Primary human osteoblast adhesion on the developed surfaces was investigated in detail by electronic and atomic force microscopy as well as immunocytochemistry. Also an investigation on the early cytokine production was performed. Results show that a relatively thick hybrid and graded oxide layer was produced on the Ti surface, being constituted by a mixture of anatase, rutile and amorphous phases where calcium (Ca) and phosphorous (P) were incorporated. An outermost nanometric-thick amorphous oxide layer rich in Ca was present in the film. This amorphous layer, rich in Ca, improved fibroblast viability and metabolic activity as well as osteoblast adhesion. High-resolution techniques allowed to understand that osteoblasts adhered less in the crystalline-rich regions while they preferentially adhere and spread over in the Ca-rich amorphous oxide layer. Also, these surfaces induce higher amounts of IFN-γ cytokine secretion, which is known to regulate inflammatory responses, bone microarchitecture as well as cytoskeleton reorganization and cellular spreading. These surfaces are promising in the context of dental implants, since they might lead to faster osseointegration. PMID:26046283

  11. Photo-oxidation catalysts

    DOEpatents

    Pitts, J. Roland; Liu, Ping; Smith, R. Davis

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  12. A novel yellow-emitting SrAlSi{sub 4}N{sub 7}:Ce{sup 3+} phosphor for solid state lighting: Synthesis, electronic structure and photoluminescence properties

    SciTech Connect

    Ruan, Jian; Xie, Rong-Jun; Funahashi, Shiro; Tanaka, Yoshinori; Takeda, Takashi; Suehiro, Takayuki; Hirosaki, Naoto; Li, Yuan-Qiang

    2013-12-15

    Ce{sup 3+}-doped and Ce{sup 3+}/Li{sup +}-codoped SrAlSi{sub 4}N{sub 7} phosphors were synthesized by gas pressure sintering of powder mixtures of Sr{sub 3}N{sub 2}, AlN, α-Si{sub 3}N{sub 4}, CeN and Li{sub 3}N. The phase purity, electronic crystal structure, photoluminescence properties of SrAlSi{sub 4}N{sub 7}:Ce{sup 3+}(Ce{sup 3+}/Li{sup +}) were investigated in this work. The band structure calculated by the DMol{sup 3} code shows that SrAlSi{sub 4}N{sub 7} has a direct band gap of 3.87 eV. The single crystal analysis of Ce{sup 3+}-doped SrAlSi{sub 4}N{sub 7} indicates a disordered Si/Al distribution and nitrogen vacnacy defects. SrAlSi{sub 4}N{sub 7} was identified as a major phase of the fired powders, and Sr{sub 5}Al{sub 5}Si{sub 21}N{sub 35}O{sub 2} and AlN as minor phases. Both Ce{sup 3+} and Ce{sup 3+}/Li{sup +} doped SrAlSi{sub 4}N{sub 7} phosphors can be efficiently excited by near-UV or blue light and show a broadband yellow emission peaking around 565 nm. A highest external quantum efficiency of 38.3% under the 450 nm excitation was observed for the Ce{sup 3+}/Li{sup +}-doped SrAlSi{sub 4}N{sub 7} (5 mol%). A white light LED lamp with color temperature of 6300 K and color rendering index of Ra=78 was achieved by combining Sr{sub 0.97}Al{sub 1.03}Si{sub 3.997}N/94/maccounttest14=t0005{sub 1}8193 {sub 7}:Ce{sup 3+}{sub 0.03} with a commercial blue InGaN chip. It indicates that SrAlSi{sub 4}N{sub 7}:Ce{sup 3+} is a promising yellow emitting down-conversion phosphor for white LEDs. - Graphical abstract: One-phosphor converted white light-emitting diode (LED) was fabricated by combining a blue LED chip and a yellow-emitting SrAlSi4N7:Ce{sup 3+} phosphor (see inset), which has the color rendering index of 78 and color temperature of 6300 K. - Highlights: • We reported a new yellow nitride phosphor suitable for solid state lighting. • We solved the crystal structure and evidenced a disordered Si/Al distribution. • We fabricated a high color rendering

  13. The Enzymatic Oxidation of Graphene Oxide

    PubMed Central

    Kotchey, Gregg P.; Allen, Brett L.; Vedala, Harindra; Yanamala, Naveena; Kapralov, Alexander A.; Tyurina, Yulia Y.; Klein-Seetharaman, Judith; Kagan, Valerian E.; Star, Alexander

    2011-01-01

    Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. Here, we reported a new phenomenon – the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). In the presence of low concentrations of hydrogen peroxide (~40 µM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). The enzymatic oxidation was characterized by Raman, UV-Vis, EPR and FT-IR spectroscopy, TEM, AFM, SDS-PAGE, and GC-MS. Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. Due to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors. PMID:21344859

  14. Improvement of the electron collection efficiency in porous hematite using a thin iron oxide underlayer: towards efficient all-iron based photoelectrodes.

    PubMed

    Dalle Carbonare, Nicola; Carli, Stefano; Argazzi, Roberto; Orlandi, Michele; Bazzanella, Nicola; Miotello, Antonio; Caramori, Stefano; Bignozzi, Carlo A

    2015-11-28

    Different approaches have been explored to increase the water oxidation activity of nanostructured hematite (α-Fe2O3) photoanodes, including doping with various elements, surface functionalization with both oxygen evolving catalysts (OEC) and functional overlayers and, more recently, the introduction of ultrathin oxide underlayers as tunneling back contacts. Inspired by this latter strategy, we present here a photoanode design with a nanometric spin-coated iron oxide underlayer coupled with a mesoporous hematite film deposited by electrophoresis. The electrodes equipped with the thin underlayer exhibit a four-fold improvement in photoactivity over the simple hematite porous film, reaching a stable photocurrent density of ca. 1 mA cm(-2) at 0.65 V versus the saturated calomel electrode (SCE) at pH 13.3 (NaOH 0.1 M) under air mass (AM) 1.5G illumination. A further improvement to 1.5 mA cm(-2) is observed after decoration of the hematite surface with a Fe(iii)-OEC. These results demonstrate that by combining different iron oxide morphologies, it is possible to improve the selectivity of the interfaces towards both electron collection at the back contact and hole transfer to the electrolyte, obtaining an efficient all-iron based photoelectrode entirely realized with simple wet solution scalable procedures. PMID:26477966

  15. The Significance of Myriophyllum elatinoides for Swine Wastewater Treatment: Abundance and Community Structure of Ammonia-Oxidizing Microorganisms in Sediments

    PubMed Central

    Li, Xi; Zhang, Miaomiao; Liu, Feng; Li, Yong; He, Yang; Zhang, Shunan; Wu, Jinshui

    2015-01-01

    Myriophyllum elatinoides was reported to effectively treat wastewater by removing nitrogen (N) and phosphorus (P). However, little is known about the abundance and community structure of ammonia-oxidizing microorganisms associated with M. elatinoides purification systems. The objective of this research was to characterize the abundance and community structure of ammonia-oxidizing microorganisms in swine wastewater and determine the main nitrogen removal pathways. In this study, five different waters were treated by M. elatinoides in microcosms for one month. The five waters included tap water (Control), swine wastewater (SW), 50% diluted swine wastewater (50% SW), and two synthetic wastewaters: 200 mg NH4+-N L−1 (200 NH4+-N) and 400 mg NH4+-N L−1 (400 NH4+-N). The most dramatic changes were in NH4+-N and total N (TN) concentrations, with average removal rates of 84% and 90%, respectively, in the treatments containing swine wastewater. On days 7, 14, and 28, the dissolved oxygen (DO) increased by 81.8%, 210.4% and 136.5%, respectively, compared with on day 0, in the swine wastewater. The results also showed that the bacterial amoA (AOB) copy numbers in the sediments of the treatments were significantly higher than those of archaeal amoA (AOA) copy numbers (p = 0.015). In addition, the high DO concentrations in swine wastewater responded well to the high abundance of AOB. The AOA and AOB community distributions were positively related with NO3-N and were negatively related with DO in swine wastewater treatments. In summary, our experimental results suggested that the M. elatinoides purification system could improve the activity of ammonia-oxidizing microorganisms and consequently might contribute to the significant N removal from the swine wastewater. PMID:26444015

  16. Spatial variability of greenhouse gases emissions (CO2, CH4, N2O) in a tropical hydroelectric reservoir flooding primary forest (Petit Saut Reservoir, French Guiana)

    NASA Astrophysics Data System (ADS)

    Cailleaud, Emilie; Guérin, Frédéric; Bouillon, Steven; Sarrazin, Max; Serça, Dominique

    2014-05-01

    At the Petit Saut Reservoir (PSR, French Guiana, South America), vertical profiles were performed at 5 stations in the open waters (OW) and 6 stations in two shallow flooded forest (FF) areas between April 2012 and September 2013. Measurements included physico-chemical parameters, ammonium, nitrate and dissolved greenhouse gas (CO2, CH4, N2O) concentrations, dissolved and particulate organic carbon (DOC, POC) and nitrogen (PN), δ13C-POC and δ15N-PN . The diffusive fluxes were calculated from surface concentrations. The aim of this study was to estimate the spatial variations of greenhouse gas emissions at a dentrical hydroelectric reservoir located in the tropics and flooding primary forest. Twenty years after impoundment, the water column of the PSR is permanently and tightly stratified thermally in the FF whereas in the OW, the thermal gradients are not as stable. The different hydrodynamical behaviours between the two different zones have significant consequences on the biogeochemistry: oxygen barely diffuses down to the hypolimnion in the FF whereas destratification occurs sporadically during the rainy season in the OW. Although we found the same range of POC in the FF and the OW (2.5-29 μmol L-1) and 20% more DOC at the bottom of OW than in the FF (229-878 μmol L-1), CO2 and CH4 concentrations were always significantly higher in the FF (CO2: 11-1412 μmol L-1, CH4: 0.001-1015 μmol L-1) than in the OW. On average, the CO2 concentrations were 30-40% higher in the FF than in the OW and the CH4 concentrations were three times higher in the FF than in the OW. The δ13C-POC and C:N values did not suggest substantial differences in the sources of OM between the FF and OW. At all stations, POC at the bottom has an isotopic signature slightly lighter than the terrestrial OM in the surrounding forest whereas the isotopic signature of surface POM would result from phytoplankton and methanotrophs. The vertical profiles of nitrogen compounds reveal that the main

  17. Ionic liquids as unique solvents in one-pot synthesis of 4-(n,2,2,2-tetranitroethylamino)-3-R-furazans.

    PubMed

    Sheremetev, Aleksei B; Aleksandrova, Nataly S; Palysaeva, Nadezhda V; Struchkova, Marina I; Tartakovsky, Vladimir A; Suponitsky, Kyrill Yu

    2013-09-01

    An efficient two-step one-pot protocol for the synthesis of N-nitrated trinitroethylamino furazans in an ionic liquid has been developed involving the condensation of aminofurazans with trinitroethanol and the N-nitration of an intermediate Mannich base. Trinitroethylnitramino derivatives have been synthesized and characterized by multinuclear NMR spectroscopy and X-ray crystallography. A role of the N,2,2,2-tetranitroethylamino group for stabilization of the high-density crystal-packing motif is described. The performance calculations gave detonation pressures and velocities for the furazan derivatives in a range of about 31-36 GPa and 8330-8745 ms(-1), respectively, which makes them competitive energetic materials. Furthermore, due to the positive oxygen balance, the compounds could be potential oxidizers for energetic formulations. PMID:23897761

  18. Structure of the Escherichia coli ArnA N-formyltransferase domain in complex with N(5) -formyltetrahydrofolate and UDP-Ara4N.

    PubMed

    Genthe, Nicholas A; Thoden, James B; Holden, Hazel M

    2016-08-01

    ArnA from Escherichia coli is a key enzyme involved in the formation of 4-amino-4-deoxy-l-arabinose. The addition of this sugar to the lipid A moiety of the lipopolysaccharide of pathogenic Gram-negative bacteria allows these organisms to evade the cationic antimicrobial peptides of the host immune system. Indeed, it is thought that such modifications may be responsible for the repeated infections of cystic fibrosis patients with Pseudomonas aeruginosa. ArnA is a bifunctional enzyme with the N- and C-terminal domains catalyzing formylation and oxidative decarboxylation reactions, respectively. The catalytically competent cofactor for the formylation reaction is N(10) -formyltetrahydrofolate. Here we describe the structure of the isolated N-terminal domain of ArnA in complex with its UDP-sugar substrate and N(5) -formyltetrahydrofolate. The model presented herein may prove valuable in the development of new antimicrobial therapeutics. PMID:27171345

  19. Applications of tunable diode laser spectroscopy for the detection of exhaled endogenous gases: CO, NH3, CH4, N20, and CO2

    NASA Astrophysics Data System (ADS)

    Kouznetsov, Andrian I.; Stepanov, Eugene V.

    1996-04-01

    Tunable diode laser spectroscopy (TDLS) is proposed for content measurements of trace gases like CO, carbon-dioxide, NH3, CH4, NO, NO2 in human and animal's exhalation. High sensitivity and wide dynamic range of the method ensure fast detection of these gases at ppb level and within the accuracy better than 10%. One-expiration sample is enough to reach these parameters. There is no need for any preliminary preparations of tested samples. Some pairs of the gases, for instance, CO and carbon-dioxide, NH3 and carbon- dioxide, or CO and nitrous oxide, can be measured simultaneously by one laser providing complex studies. The high sensitive gas analysis could provide necessary background to the noninvasive diagnostics in a wide variety of medical problems. Perspectives of the TDLS methods in application to medicine diagnostics are demonstrated by the first results of exhalation tests.

  20. Quantification of syntrophic acetate-oxidizing microbial communities in biogas processes

    PubMed Central

    Westerholm, Maria; Dolfing, Jan; Sherry, Angela; Gray, Neil D; Head, Ian M; Schnürer, Anna

    2011-01-01

    Changes in communities of syntrophic acetate-oxidizing bacteria (SAOB) and methanogens caused by elevated ammonia levels were quantified in laboratory-scale methanogenic biogas reactors operating at moderate temperature (37°C) using quantitative polymerase chain reaction (qPCR). The experimental reactor was subjected to gradually increasing ammonia levels (0.8–6.9 g NH4+-N l−1), whereas the level of ammonia in the control reactor was kept low (0.65–0.90 g NH4+-N l−1) during the entire period of operation (660 days). Acetate oxidation in the experimental reactor, indicated by increased production of 14CO2 from acetate labelled in the methyl carbon, occurred when ammonia levels reached 5.5 and 6.9 g NH4+-N l−1. Syntrophic acetate oxidizers targeted by newly designed qPCR primers were Thermacetogenium phaeum, Clostridium ultunense, Syntrophaceticus schinkii and Tepidanaerobacter acetatoxydans. The results showed a significant increase in abundance of all these bacteria except T. phaeum in the ammonia-stressed reactor, coincident with the shift to syntrophic acetate oxidation. As the abundance of the bacteria increased, a simultaneous decrease was observed in the abundance of aceticlastic methanogens from the families Methanosaetaceae and Methanosarcinaceae. qPCR analyses of sludge from two additional high ammonia processes, in which methane production from acetate proceeded through syntrophic acetate oxidation (reactor SB) or through aceticlastic degradation (reactor DVX), demonstrated that SAOB were significantly more abundant in the SB reactor than in the DVX reactor. PMID:23761313

  1. Electrolytic oxidation of anthracite

    USGS Publications Warehouse

    Senftle, F.E.; Patton, K.M.; Heard, I., Jr.

    1981-01-01

    An anthracite slurry can be oxidized only with difficulty by electrolytic methods in which aqueous electrolytes are used if the slurry is confined to the region of the anode by a porous pot or diaphragm. However, it can be easily oxidized if the anthracite itself is used as the anode. No porous pot or diaphragm is needed. Oxidative consumption of the coal to alkali-soluble compounds is found to proceed preferentially at the edges of the aromatic planes. An oxidation model is proposed in which the chief oxidants are molecular and radical species formed by the electrolytic decomposition of water at the coal surface-electrolyte interface. The oxidation reactions proposed account for the opening of the aromatic rings and the subsequent formation of carboxylic acids. The model also explains the observed anisotropic oxidation and the need for the porous pot or diaphragm used in previous studies of the oxidation of coal slurries. ?? 1981.

  2. Oxidation-resistant cermet

    NASA Technical Reports Server (NTRS)

    Phillips, W. M.

    1977-01-01

    Chromium metal alloys and chromium oxide ceramic are combined to produce cermets with oxidation-resistant properties. Application of cermets includes use in hot corrosive environments requiring strong resistive materials.

  3. Bridged graphite oxide materials

    NASA Technical Reports Server (NTRS)

    Herrera-Alonso, Margarita (Inventor); McAllister, Michael J. (Inventor); Aksay, Ilhan A. (Inventor); Prud'homme, Robert K. (Inventor)

    2010-01-01

    Bridged graphite oxide material comprising graphite sheets bridged by at least one diamine bridging group. The bridged graphite oxide material may be incorporated in polymer composites or used in adsorption media.

  4. Zinc oxide overdose

    MedlinePlus

    Zinc oxide is an ingredient in many products. Some of these are certain creams and ointments used ... prevent or treat minor skin burns and irritation. Zinc oxide overdose occurs when someone eats one of ...

  5. Studies in zirconium oxidation

    NASA Technical Reports Server (NTRS)

    Draley, J. E.; Drunen, C. J.; Levitan, J.

    1968-01-01

    Study provides insight into the oxidation mechanism of zirconium by combining electrical measurements with oxidation data. The measurement of electrical potential across growing scale on zirconium and the determination of conventional weight-change oxidation data were carried out at 550, 700, and 800 degrees C.

  6. Online technique for isotope and mixing ratios of CH4, N2O, Xe and mixing ratios of organic trace gases on a single ice core sample

    NASA Astrophysics Data System (ADS)

    Schmitt, J.; Seth, B.; Bock, M.; Fischer, H.

    2014-03-01

    Polar ice cores enclosing trace gas species offer a unique archive to study changes in the past atmosphere and in terrestrial/marine source regions. Here we present a new online technique for ice core and air samples to measure a suite of isotope ratios and mixing ratios of trace gas species on a single small sample. Isotope ratios are determined on methane, nitrous oxide and xenon with reproducibilities for ice core samples of 0.15‰ for δ13C-CH4, 0.22‰ for δ15N-N2O, 0.34 ‰ for δ18O-N2O, and 0.05‰ for δ136Xe. Mixing ratios are determined on methane, nitrous oxide, xenon, ethane, propane, methyl chloride and dichloro-difluoromethane with reproducibilities of 7 ppb for CH4, 3 ppb for N2O, 50 ppt for 136Xe, 70 ppt for C2H6, 70 ppt for C3H8, 20 ppt for CH3Cl, and 2 ppt for CCl2F2. The system consists of a vacuum extraction device, a preconcentration unit and a gas chromatograph coupled to an isotope ratio mass spectrometer. CH4 is combusted to CO2 prior to detection while we bypassed the oven for all other species. The highly automated system uses only ~160 g ice, equivalent to ~16 mL air, which is less than previous methods. This large suite of parameters on a single ice sample is new and helpful to study phase relationships of parameters which are usually not measured together. A multi-parameter dataset is also key to understand in situ production processes of organic species in the ice, a critical issue observable in many organic trace gases. Novel is the determination of xenon isotope ratios using doubly charged Xe ions. The attained precision for δ136Xe is suitable to correct the isotopic ratios and mixing ratios for gravitational firn effects, with the benefit that this information is derived from the same sample. Lastly, anomalies in the Xe mixing ratio, δXe/air, can be used to detect melt layers.

  7. Online technique for isotope and mixing ratios of CH4, N2O, Xe and mixing ratios of organic trace gases on a single ice core sample

    NASA Astrophysics Data System (ADS)

    Schmitt, J.; Seth, B.; Bock, M.; Fischer, H.

    2014-08-01

    Firn and polar ice cores enclosing trace gas species offer a unique archive to study changes in the past atmosphere and in terrestrial/marine source regions. Here we present a new online technique for ice core and air samples to measure a suite of isotope ratios and mixing ratios of trace gas species on a single sample. Isotope ratios are determined on methane, nitrous oxide and xenon with reproducibilities for ice core samples of 0.15‰ for δ13C-CH4, 0.22‰ for δ15N-N2O, 0.34‰ for δ18O-N2O, and 0.05‰ per mass difference for δ136Xe for typical concentrations of glacial ice. Mixing ratios are determined on methane, nitrous oxide, xenon, ethane, propane, methyl chloride and dichlorodifluoromethane with reproducibilities of 7 ppb for CH4, 3 ppb for N2O, 70 ppt for C2H6, 70 ppt for C3H8, 20 ppt for CH3Cl, and 2 ppt for CCl2F2. However, the blank contribution for C2H6 and C3H8 is large in view of the measured values for Antarctic ice samples. The system consists of a vacuum extraction device, a preconcentration unit and a gas chromatograph coupled to an isotope ratio mass spectrometer. CH4 is combusted to CO2 prior to detection while we bypass the oven for all other species. The highly automated system uses only ~ 160 g of ice, equivalent to ~ 16 mL air, which is less than previous methods. The measurement of this large suite of parameters on a single ice sample is new and key to understanding phase relationships of parameters which are usually not measured together. A multi-parameter data set is also key to understand in situ production processes of organic species in the ice, a critical issue observed in many organic trace gases. Novel is the determination of xenon isotope ratios using doubly charged Xe ions. The attained precision for δ136Xe is suitable to correct the isotopic ratios and mixing ratios for gravitational firn diffusion effects, with the benefit that this information is derived from the same sample. Lastly, anomalies in the Xe mixing ratio,

  8. New Main-Group-Element-Rich nido-Octahedral Cluster System: Synthesis and Characterization of [Et4N][Fe2(CO)6(μ3-As){μ3-EFe(CO)4}2].

    PubMed

    Schipper, Desmond E; Ikhlef, Djamila; Khalal, Samila; Saillard, Jean-Yves; Whitmire, Kenton H

    2016-07-01

    A series of clusters of the form [Et4N][Fe2(CO)6(μ3-As)}(μ3-EFe(CO)4)], where E is either P or As, were synthesized from [Et4N]2[HAs{Fe(CO)4}3] and ECl3. AsCl3 gives the As-only compound; PCl3 produces compounds having two As atoms with one P atom, or one As atom and two P atoms, and they can exist as two possible isomers, one of which is chiral. The As2P and AsP2 clusters cocrystallize, and their structure as determined by single-crystal X-ray diffraction is given along with the structure of the As-only cluster. Analytical data as well as density functional theory calculations support the formation and geometries of the new molecules. PMID:27310439

  9. An innovative architectural design to enhance the electrochemical performance of La2NiO4+δ cathodes for solid oxide fuel cell applications

    NASA Astrophysics Data System (ADS)

    Sharma, Rakesh K.; Burriel, Mónica; Dessemond, Laurent; Martin, Vincent; Bassat, Jean-Marc; Djurado, Elisabeth

    2016-06-01

    An architectural design of the cathode microstructure based on combining electrostatic spray deposition (ESD) and screen-printing (SP) techniques has demonstrated to be an innovative strategy to enhance the electrochemical properties of La2NiO4+δ (LNO) as oxygen electrode on Ce0.9Gd0.1O2-δ (CGO) electrolyte for solid oxide fuel cells. For this purpose, the influence of the ESD process parameters on the microstructure has been systematically investigated. Electrochemical performances of four selected cathode microstructures are investigated: (i) 3-D coral nanocrystalline (average particle size ∼ 100 nm) LNO film grown by ESD; (ii) 3-D coral nanocrystalline film (average particle size ∼ 150 nm) grown by ESD with a continuous nanometric dense interface; (iii) porous screen-printed LNO film (average particle size ∼ 400 nm); and (iv) 3-D coral nanocrystalline film (average particle size ∼ 150 nm) with a continuous nanometric dense interface prepared by ESD topped by a LNO current collector prepared by SP. A significant reduction in the polarization resistance (Rpol) is obtained (0.08 Ω cm2 at 700 °C) for 3-D coral topped by the SP layer. Moreover LNO is found to be stable and compatible with CGO up to 800 °C for only 10 days duration in air, making it potentially suitable for SOFCs cathode application.

  10. High-temperature interface superconductivity between metallic and insulating copper oxides.

    PubMed

    Gozar, A; Logvenov, G; Kourkoutis, L Fitting; Bollinger, A T; Giannuzzi, L A; Muller, D A; Bozovic, I

    2008-10-01

    The realization of high-transition-temperature (high-T(c)) superconductivity confined to nanometre-sized interfaces has been a long-standing goal because of potential applications and the opportunity to study quantum phenomena in reduced dimensions. This has been, however, a challenging target: in conventional metals, the high electron density restricts interface effects (such as carrier depletion or accumulation) to a region much narrower than the coherence length, which is the scale necessary for superconductivity to occur. By contrast, in copper oxides the carrier density is low whereas T(c) is high and the coherence length very short, which provides an opportunity-but at a price: the interface must be atomically perfect. Here we report superconductivity in bilayers consisting of an insulator (La(2)CuO(4)) and a metal (La(1.55)Sr(0.45)CuO(4)), neither of which is superconducting in isolation. In these bilayers, T(c) is either approximately 15 K or approximately 30 K, depending on the layering sequence. This highly robust phenomenon is confined within 2-3 nm of the interface. If such a bilayer is exposed to ozone, T(c) exceeds 50 K, and this enhanced superconductivity is also shown to originate from an interface layer about 1-2 unit cells thick. Enhancement of T(c) in bilayer systems was observed previously but the essential role of the interface was not recognized at the time. PMID:18843365

  11. Nucleation and growth of intragranular defect and insoluble atom clusters in nuclear oxide fuels

    NASA Astrophysics Data System (ADS)

    Garcia, P.; Martin, G.; Sabathier, C.; Carlot, G.; Michel, A.; Martin, P.; Dorado, B.; Freyss, M.; Bertolus, M.; Skorek, R.; Noirot, J.; Noirot, L.; Kaitasov, O.; Maillard, S.

    2012-04-01

    Uranium and plutonium oxides are subjected to high levels of radiation damage due to the slowing of fission fragments. In addition the composition of the material evolves over time as a result of fission events. Rare gases which constitute an abundant class of fission products are particularly insoluble and therefore tend either to be released from the fuel or form small nanometre size clusters. Bubbles are liable to grow and become trapping sites for migrating defects or other insoluble atoms. Interactions between migrating atoms, defects and existing clusters will determine the rate and extent to which clusters grow. Because the transfer of gas from within the grain to the grain boundaries is thought of as being the rate limiting process for fission gas release, a review of phenomena occurring on the sub-grain scale is carried out. The microstructural modifications induced by neutron irradiations of UO2 fuels are discussed with an emphasis on their relation to fission gas release. Based mainly on TEM studies, the phenomena which are usually taken into account in fission gas behaviour models are looked at and the limitations of these models outlined. More recent experimental and modelling approaches involving ion-irradiation experiments and atomic scale modelling are presented. It is shown that combining these approaches may lead, despite the complexity inherent to the system, to a better understanding of basic radiation induced microstructural changes, clustering events, and rare gas behaviour.

  12. The electrochemiluminescence of luminol on titania nanotubes functionalised indium tin oxide glass for flow injection analysis.

    PubMed

    Zhao, Qun; Xiao, Changbin; Tu, Yifeng

    2015-10-01

    The titania nanotubes (TiNTs) had been immobilised onto the indium tin oxide (ITO) coated glass to intensify the electrochemiluminescence (ECL) of luminol. The morphology, structure and properties such as specific surface area and transmittance of synthesised TiNTs were characterised. The results indicated that the TiNTs was several hundred nanometres in length with the diameter of 20 nm. In flow injection analysis (FIA) mode, the TiNTs dramatically enhanced the ECL emission of luminol for about 25 multiple, meanwhile decreased the requirement of buffer pH and exciting potential. The ECL emission of luminol on functionalised ITO electrode has sensitive response toward hydrogen peroxide, and extraordinarily responsive toward the antioxidant. Under the optimal conditions, the ECL emission exhibited a linear response within the concentration range from 0.1 mg L(-1) to 30 mg L(-1) and an absolute detection limit of 1.65×10(-10) g of resveratrol. The gross antioxidant activity of blueberry and kiwi were determined with satisfactory recoveries. PMID:26078133

  13. Diversity and distribution of planktonic anaerobic ammonium-oxidizing bacteria in the Dongjiang River, China.

    PubMed

    Sun, Wei; Xia, Chunyu; Xu, Meiying; Guo, Jun; Wang, Aijie; Sun, Guoping

    2014-12-01

    Anaerobic ammonium-oxidizing (anammox) process has recently been recognized as an important pathway for removing fixed nitrogen (N) from aquatic ecosystems. Anammox organisms are widely distributed in freshwater environments. However, little is known about their presence in the water column of riverine ecosystems. Here, the existence of a diverse anammox community was revealed in the water column of the Dongjiang River by analyzing 16S rRNA and hydrazine oxidation (hzo) genes of anammox bacteria. Phylogenetic analyses of hzo genes showed that Candidatus Jettenia related clades of anammox bacteria were dominant in the river, suggesting the ecological microniche distinction from freshwater/estuary and marine anammox bacteria with Ca. Brocadia and Kuenenia genera mainly detected in freshwater/estuary ecosystems, and Ca. Scalindua genus mainly detected in marine ecosystems. The abundance and diversity of anammox bacteria along the river were both significantly correlated with concentrations of NH4(+)-N based on Pearson and partial correlation analyses. Redundancy analyses showed the contents of NH4(+)-N, NO3(-)-N and the ratio of NH4(+)-N to NO2(-)-N significantly influenced the spatial distributions of anammox bacteria in the water column of the Dongjiang River. These results expanded our understanding of the distribution and potential roles of anammox bacteria in the water column of the river ecosystem. PMID:24932882

  14. Dielectric barrier discharge plasma treatment on E. coli: Influence of CH{sub 4}/N{sub 2}, O{sub 2}, N{sub 2}/O{sub 2}, N{sub 2}, and Ar gases

    SciTech Connect

    Majumdar, Abhijit; Hippler, Rainer; Singh, Rajesh Kumar; Palm, Gottfried J.

    2009-10-15

    Atmospheric pressure dielectric barrier discharge (DBD) plasma has been employed on Gram-negative bacteria, Escherichia coli BL21. Treatment was carried out using plasma generated with different compositions of gases: CH{sub 4}/N{sub 2} (1:2), O{sub 2}, N{sub 2}/O{sub 2} (1:1), N{sub 2}, and Ar, and by varying plasma power and treatment time. E. coli cells were exposed under the DBD plasma in triplicates, and their surviving numbers were observed in terms of colony forming units. It has been observed that the CH{sub 4}/N{sub 2} plasma exhibits relatively higher sterilization property toward E. coli compared to plasma generated by using O{sub 2}, N{sub 2}/O{sub 2}, N{sub 2}, and Ar gas mixtures. The time to kill up to 90% of the initial population of the E. coli cells was found to be about 2-3 min for CH{sub 4}/N{sub 2} and O{sub 2} gas mixture DBD plasma. A prolongation of treatment time and an increase in the dissipated power significantly improved the E. coli killing efficiency of the atmospheric pressure DBD plasma.

  15. [Effects of application time and basal/topdressing ratio of nitrogen fertilizer on the spatiotemporal variation of soil NO3- -N and NH4+ -N contents and the grain yield and its quality of wheat].

    PubMed

    Wu, Ji; Guo, Xi-sheng; Yang, Xiao-hu; Huang, Xiao-rong

    2008-11-01

    Field trials were conducted to study the effects of different application time and basal/topdressing ratio of nitrogen fertilizer on the spatiotemporal variation of soil NO3- -N and NH4+ -N contents and the grain yield and its quality of wheat. The results showed that soil NO3- -N and NH4+ -N contents decreased with increasing soil depth. Both the application time and the basal/topdressing ratio of nitrogen fertilizer had significant effects on the NO3- -N and NH4+ -N contents in 0-20 cm soil layer. Compared with basal application, later fertilization and higher topdressing ratio could promote the nitrogen uptake by wheat plant and increase the plant nitrogen recovery significantly, decrease the soil nitrogen recovery during wheat growth, and improve the grain quality significantly, while had less effects on the grain yield. Topdressing too much nitrogen fertilizer at booting stage could result in a significant decrease of grain yield. Under the condition of this experiment, the optimal nitrogen fertilization mode for good wheat grain yield and its quality and good ecological benefits was 5:3:2 of basal application: topdressing at jointing stage: topdressing at booting stage. PMID:19238836

  16. Could a first-trimester blood phosphatidylethanol concentration ⩾4 nM be useful to identify women with moderate-to-heavy prenatal alcohol exposure who are at high risk of adverse pregnancy outcomes?

    PubMed

    Yang, Jun-Young; Kwak, Ho-Seok; Han, Jung-Yeol; Choi, June-Seek; Ahn, Hyun-Kyong; Oh, Young-Jun; Velázquez-Armenta, E Yadira; Nava-Ocampo, Alejandro A

    2015-12-01

    It is accepted that blood phosphatidylethanol (PEth) concentrations are reliable biomarkers of ethanol (alcohol) exposure. We therefore conducted a preliminary study to test the hypothesis that elevated blood PEth concentrations can help to identifying women with prenatal alcohol exposure who are at higher risk of adverse pregnancy outcomes. The study included 35 first-trimester pregnant women who self-reported alcohol ingestion and had PEth blood concentration ⩾4 nM at recruitment. As a control group, 233 first-trimester pregnant women who self-reported as being either abstainers or light alcohol drinkers and had blood PEth concentrations <4 nM, were also included. All participants were followed up until completion of their pregnancies. Women with prenatal alcohol exposure and PEth concentrations ⩾4 nM had a risk ratio of spontaneous abortions of 3.21 (95%CI 0.93-11.06; P=0.074). Because of the potential implications in the prenatal care of women reporting risky alcohol exposure, the preliminary results from the present study indicate the need for testing the hypothesis in a more definitive approach. PMID:26365248

  17. Rhodium oxides in unusual oxidation states

    NASA Astrophysics Data System (ADS)

    Reisner, Barbara Alice

    Mixed valence RhIII/RhIV oxides have been proposed as a promising class of candidate compounds for superconductivity. Unfortunately, it is difficult to stabilize rhodates with a formal oxidation state approaching RhIV, as other techniques used for the synthesis of rhodium. oxides favor the most commonly observed formal oxidation state, RhIII. One technique which has been used to stabilize metal oxides in high formal oxidation states is crystallization from molten hydroxides. This thesis explores the use of molten hydroxides to enhance the reactivity of rhodium oxides in order to synthesize rhodates with high formal oxidation states. K0.5RhO2, Rb0.2RhO2, and CsxRhO2 were synthesized from pure alkali metal hydroxides. All crystallized with a previously unobserved polytype in the alkali metal rhodate system. Due to the low activity of dissolved oxygen species in LiOH and NaOH, LiRhO2 and NaRhO2 cannot be crystallized. The formal oxidation state of rhodium in AxRhO2 (A = K, Rb, Cs) is a function of the alkali metal hydroxide used to synthesize these oxides. These materials exhibit remarkable stability for layered metal oxides containing the heavier alkali metals, but all phases are susceptible to intercalation by water. The synthesis, structural characterization, magnetic susceptibility, and reactivity of these oxides are reported. Sr2RhO4 and a new rhodate were crystallized from a KOH-Sr(OH)2 flux. The synthesis and characterization of these materials is reported. Efforts to substitute platinum for rhodium in Sr 2RhO4 are also discussed. Mixed alkali metal-alkaline earth metal hydroxide fluxes were used to crystallize LiSr3RhO6, and NaSr3RhO 6. The synthesis of LiSr3RhO6 and NaSr3RhO 6 represents the first example of the stabilization of a rhodium oxide with a formal oxidation state approaching RhV. X-ray diffraction, electron beam microprobe analysis, thermogravimetric analysis, potentiometric titrations, X-ray photoelectron spectroscopy, and magnetic susceptibility

  18. A Microscale Oxidation Puzzle

    NASA Astrophysics Data System (ADS)

    Pelter, Michael W.; Macudzinski, Rebecca M.; Passarelli, Mary Ellen

    2000-11-01

    We have adapted oxidation of an alcohol with sodium hypochlorite solution to a "puzzle" approach by using a diol as the substrate for oxidation. The diols under investigation have both a primary and a secondary hydroxyl group. There are three possible outcomes to the reaction: (i) only the primary alcohol is oxidized to the aldehyde (or carboxylic acid); (ii) only the secondary alcohol is oxidized to the ketone; or (iii) both alcohols are oxidized. The assignment is to perform the reaction and determine the structure of the product through interpretation of the IR spectrum. Examples using two commercially available diols are shown.

  19. 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.

  20. Extension of the T{sub z} = {minus}3/2, A = 4n + 1 series of beta-delayed proton emitters to {sup 65}Se and {sup 73}Sr, and low energy beta-delayed proton emission from the T{sub z} = {minus}3/2, A = 4n + 3 nucleus {sup 23}Al

    SciTech Connect

    Batchelder, J.C.

    1993-12-01

    The series of known Tz = {minus}3/2, A = 4n + 1 nuclei has been extended to include the previously undiscovered isotopes {sup 65}Se and {sup 73}Sr, through the observation of beta-delayed proton emission via the isobaric analog state (IAS) of the beta-daughter (emitter). Due to the relatively large proton energies involved, these experiments were conducted using standard Si-Si {Delta}E-E telescopes. Beta-delayed protons arising from {sup 65}Se have been observed at an energy (laboratory) of 3.55 {plus_minus} 0.03 MeV, corresponding to the decay of the T = 3/2 isobaric analog state in {sup 65}As to the ground state of {sup 64}Ge. Similarly, beta-delayed protons from {sup 73}Sr at an energy of 3.75 {plus_minus} 0.04 MeV have been observed, corresponding to decay of the T = 3/2 isobaric analog state in {sup 73}Rb to the ground state of {sup 72}Kr. From the energies of these proton transitions, an improved prediction of the mass excesses of the two parent nuclei ({sup 65}Se and {sup 73}Sr) is made through the use of a Coulomb displacement formula. These predictions are {minus}33.41 {plus_minus} 0.26 and {minus}31.87 {plus_minus} 0.24 MeV for {sup 65}Se and {sup 73}Sr, respectively. Studies of low energy (down to {approximately}200 keV) beta-delayed protons from {sup 23}Al necessitated that a particle identification telescope with a low energy threshold for observation and identification of protons be developed. {sup 23}Al is of interest because of its role in the breakout of the hot CNO cycle leading to the astrophysical rp process.

  1. The study of leachate treatment by using three advanced oxidation process based wet air oxidation

    PubMed Central

    2013-01-01

    Wet air oxidation is regarded as appropriate options for wastewater treatment with average organic compounds. The general purpose of this research is to determine the efficiency of three wet air oxidation methods, wet oxidation with hydrogen peroxide and absorption with activated carbon in removing organic matter and nitrogenous compounds from Isfahan's urban leachate. A leachate sample with the volume of 1.5 liters entered into a steel reactor with the volume of three liters and was put under a 10-bar pressure, at temperatures of 100, 200, and 300° as well as three retention times of 30, 60, and 90 minutes. The sample was placed at 18 stages of leachate storage ponds in Isfahan Compost Plant with the volume of 20 liters, using three WPO, WAO methods and a combination of WAO/GAC for leachate pre-treatment. Thirty percent of pure oxygen and hydrogen peroxide were applied as oxidation agents. The COD removal efficiency in WAO method is 7.8-33.3%, in BOD is 14.7-50.6%, the maximum removal percentage (efficiency) for NH4-N is 53.3% and for NO3-N is 56.4-73.9%. The removal efficiency of COD and BOD5 is 4.6%-34 and 24%-50 respectively in WPO method. Adding GAC to the reactor, the removal efficiency of all parameters was improved. The maximum removal efficiency was increased 48% for COD, 31%-43.6 for BOD5 by a combinational method, and the ratio of BOD5/COD was also increased to 90%. In this paper, WAO and WPO process was used for Leachate pre-treatment and WAO/GAC combinational process was applied for improving the organic matter removal and leachate treatment; it was also determined that the recent process is much more efficient in removing resistant organic matter. PMID:23369258

  2. ZIRCONIUM OXIDE NANOSTRUCTURES PREPARED BY ANODIC OXIDATION

    SciTech Connect

    Dang, Y. Y.; Bhuiyan, M.S.; Paranthaman, M. P.

    2008-01-01

    Zirconium oxide is an advanced ceramic material highly useful for structural and electrical applications because of its high strength, fracture toughness, chemical and thermal stability, and biocompatibility. If highly-ordered porous zirconium oxide membranes can be successfully formed, this will expand its real-world applications, such as further enhancing solid-oxide fuel cell technology. Recent studies have achieved various morphologies of porous zirconium oxide via anodization, but they have yet to create a porous layer where nanoholes are formed in a highly ordered array. In this study, electrochemical methods were used for zirconium oxide synthesis due to its advantages over other coating techniques, and because the thickness and morphology of the ceramic fi lms can be easily tuned by the electrochemical parameters, such as electrolyte solutions and processing conditions, such as pH, voltage, and duration. The effects of additional steps such as pre-annealing and post-annealing were also examined. Results demonstrate the formation of anodic porous zirconium oxide with diverse morphologies, such as sponge-like layers, porous arrays with nanoholes ranging from 40 to 75 nm, and nanotube layers. X-ray powder diffraction analysis indicates a cubic crystallographic structure in the zirconium oxide. It was noted that increased voltage improved the ability of the membrane to stay adhered to the zirconium substrate, whereas lower voltages caused a propensity for the oxide fi lm to fl ake off. Further studies are needed to defi ne the parameters windows that create these morphologies and to investigate other important characteristics such as ionic conductivity.

  3. Zirconium Oxide Nanostructures Prepared by Anodic Oxidation

    SciTech Connect

    Dang, Ying Yi; Bhuiyan, Md S; Paranthaman, Mariappan Parans

    2008-01-01

    Zirconium oxide is an advanced ceramic material highly useful for structural and electrical applications because of its high strength, fracture toughness, chemical and thermal stability, and biocompatibility. If highly-ordered porous zirconium oxide membranes can be successfully formed, this will expand its real-world applications, such as further enhancing solid-oxide fuel cell technology. Recent studies have achieved various morphologies of porous zirconium oxide via anodization, but they have yet to create a porous layer where nanoholes are formed in a highly ordered array. In this study, electrochemical methods were used for zirconium oxide synthesis due to its advantages over other coating techniques, and because the thickness and morphology of the ceramic films can be easily tuned by the electrochemical parameters, such as electrolyte solutions and processing conditions, such as pH, voltage, and duration. The effects of additional steps such as pre-annealing and post-annealing were also examined. Results demonstrate the formation of anodic porous zirconium oxide with diverse morphologies, such as sponge-like layers, porous arrays with nanoholes ranging from 40 to 75 nm, and nanotube layers. X-ray powder diffraction analysis indicates a cubic crystallographic structure in the zirconium oxide. It was noted that increased voltage improved the ability of the membrane to stay adhered to the zirconium substrate, whereas lower voltages caused a propensity for the oxide film to flake off. Further studies are needed to define the parameters windows that create these morphologies and to investigate other important characteristics such as ionic conductivity.

  4. Oxidative Cross-Coupling of Two Different Phenols: An Efficient Route to Unsymmetrical Biphenols.

    PubMed

    More, Nagnath Yadav; Jeganmohan, Masilamani

    2015-06-19

    An efficient synthesis of unsymmetrical biphenols via the oxidative cross-coupling of two different phenols in the presence of K2S2O8 and Bu4N(+)·HSO3(-) (10 mol %) in CF3COOH at ambient conditions is described. 1:1 Cross-coupling of substituted phenols with naphthols and 1:2 cross-coupling of naphthols with phenol are also disclosed. By using Bu4N(+)·HSO3(-), the homocoupling of phenols or naphthols was controlled. In these reactions, the ortho C-H bond of two different phenols and the ortho and para C-H bond of phenols were coupled together. PMID:26023816

  5. Iron oxide superparamagnetic nanoparticles conjugated with a conformationally blocked α-Tn antigen mimetic for macrophage activation

    NASA Astrophysics Data System (ADS)

    Manuelli, Massimo; Fallarini, Silvia; Lombardi, Grazia; Sangregorio, Claudio; Nativi, Cristina; Richichi, Barbara

    2014-06-01

    Among new therapies to fight tumors, immunotherapy is still one of the most promising and intriguing. Thanks to the ongoing structural elucidation of several tumor antigens and the development of innovative antigen carriers, immunotherapy is in constant evolution and it is largely used either alone or in synergy with chemotherapy/radiotherapy. With the aim to develop fully synthetic immunostimulants we have recently developed a mimetic of the α-Tn mucin antigen, a relevant tumor antigen. The 4C1 blocked mimetic 1, unique example of an α-Tn mimetic antigen, was functionalized with an ω-phosphonate linker and used to decorate iron oxide superparamagnetic nanoparticles (MNPs), employed as multivalent carriers. MNPs, largely exploited for supporting and carrying biomolecules, like antibodies, drugs or antigens, consent to combine in the same nanometric system the main features of an inorganic magnetic core with a bioactive organic coating. The superparamagnetic glyconanoparticles obtained, named GMNPs, are indeed biocompatible and immunoactive, and they preserve suitable characteristics for use as heat mediators in the magnetic fluid hyperthermia (MFH) treatment of tumors. All together these properties make GMNPs attracting devices for innovative tumor treatment.Among new therapies to fight tumors, immunotherapy is still one of the most promising and intriguing. Thanks to the ongoing structural elucidation of several tumor antigens and the development of innovative antigen carriers, immunotherapy is in constant evolution and it is largely used either alone or in synergy with chemotherapy/radiotherapy. With the aim to develop fully synthetic immunostimulants we have recently developed a mimetic of the α-Tn mucin antigen, a relevant tumor antigen. The 4C1 blocked mimetic 1, unique example of an α-Tn mimetic antigen, was functionalized with an ω-phosphonate linker and used to decorate iron oxide superparamagnetic nanoparticles (MNPs), employed as multivalent

  6. Reduction of Metal Oxide to Metal using Ionic Liquids

    SciTech Connect

    Dr. Ramana Reddy

    2012-04-12

    A novel pathway for the high efficiency production of metal from metal oxide means of electrolysis in ionic liquids at low temperature was investigated. The main emphasis was to eliminate the use of carbon and high temperature application in the reduction of metal oxides to metals. The emphasis of this research was to produce metals such as Zn, and Pb that are normally produced by the application of very high temperatures. The reduction of zinc oxide to zinc and lead oxide to lead were investigated. This study involved three steps in accomplishing the final goal of reduction of metal oxide to metal using ionic liquids: 1) Dissolution of metal oxide in an ionic liquid, 2) Determination of reduction potential using cyclic voltammetry (CV) and 3) Reduction of the dissolved metal oxide. Ionic liquids provide additional advantage by offering a wide potential range for the deposition. In each and every step of the process, more than one process variable has been examined. Experimental results for electrochemical extraction of Zn from ZnO and Pb from PbO using eutectic mixtures of Urea ((NH2)2CO) and Choline chloride (HOC2H4N(CH3)3+Cl-) or (ChCl) in a molar ratio 2:1, varying voltage and temperatures were carried out. Fourier Transform Infra-Red (FTIR) spectroscopy studies of ionic liquids with and without metal oxide additions were conducted. FTIR and induction coupled plasma spectroscopy (ICPS) was used in the characterization of the metal oxide dissolved ionic liquid. Electrochemical experiments were conducted using EG&G potentiostat/galvanostat with three electrode cell systems. Cyclic voltammetry was used in the determination of reduction potentials for the deposition of metals. Chronoamperometric experiments were carried out in the potential range of -0.6V to -1.9V for lead and -1.4V to -1.9V for zinc. The deposits were characterized using XRD and SEM-EDS for phase, morphological and elemental analysis. The results showed that pure metal was deposited on the cathode

  7. Oxidation Resistant Graphite Studies

    SciTech Connect

    W. Windes; R. Smith

    2014-07-01

    The Very High Temperature Reactor (VHTR) Graphite Research and Development Program is investigating doped nuclear graphite grades exhibiting oxidation resistance. During a oxygen ingress accident the oxidation rates of the high temperature graphite core region would be extremely high resulting in significant structural damage to the core. Reducing the oxidation rate of the graphite core material would reduce the structural effects and keep the core integrity intact during any air-ingress accident. Oxidation testing of graphite doped with oxidation resistant material is being conducted to determine the extent of oxidation rate reduction. Nuclear grade graphite doped with varying levels of Boron-Carbide (B4C) was oxidized in air at nominal 740°C at 10/90% (air/He) and 100% air. The oxidation rates of the boronated and unboronated graphite grade were compared. With increasing boron-carbide content (up to 6 vol%) the oxidation rate was observed to have a 20 fold reduction from unboronated graphite. Visual inspection and uniformity of oxidation across the surface of the specimens were conducted. Future work to determine the remaining mechanical strength as well as graphite grades with SiC doped material are discussed.

  8. Spatial variability and temporal dynamics of greenhouse gas (CO2, CH4, N2O) concentrations and fluxes along the Zambezi River mainstem and major tributaries

    NASA Astrophysics Data System (ADS)

    Teodoru, C. R.; Nyoni, F. C.; Borges, A. V.; Darchambeau, F.; Nyambe, I.; Bouillon, S.

    2014-11-01

    Spanning over 3000 km in length and with a catchment of approximately 1.4 million km2, the Zambezi River is the fourth largest river in Africa and the largest flowing into the Indian Ocean from the African continent. As part of a~broader study on the riverine biogeochemistry in the Zambezi River basin, we present data on greenhouse gas (GHG, carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O)) concentrations and fluxes collected along the Zambezi River, reservoirs and several of its tributaries during 2012 and 2013 and over two climatic seasons (dry and wet) to constrain the interannual variability, seasonality and spatial heterogeneity along the aquatic continuum. All GHGs concentrations showed high spatial variability (coefficient of variation: 1.01 for CO2, 2.65 for CH4 and 0.21 for N2O). Overall, there was no unidirectional pattern along the river stretch (i.e. decrease or increase towards the ocean), as the spatial heterogeneity of GHGs appeared to be determined mainly by the connectivity with floodplains and wetlands, and the presence of man-made structures (reservoirs) and natural barriers (waterfalls, rapids). Highest CO2 and CH4 concentrations in the mainstream river were found downstream of extensive floodplains/wetlands. Undersaturated CO2 conditions, in contrast, were characteristic for the surface waters of the two large reservoirs along the Zambezi mainstem. N2O concentrations showed the opposite pattern, being lowest downstream of floodplains and highest in reservoirs. Among tributaries, highest concentrations of both CO2 and CH4 were measured in the Shire River whereas low values were characteristic for more turbid systems such as the Luangwa and Mazoe rivers. The interannual variability in the Zambezi River was relatively large for both CO2 and CH4, and significantly higher concentrations (up to two fold) were measured during wet seasons compared to the dry season. Interannual variability of N2O was less pronounced but generally higher

  9. Dynamics of greenhouse gases (CO2, CH4, N2O) along the Zambezi River and major tributaries, and their importance in the riverine carbon budget

    NASA Astrophysics Data System (ADS)

    Teodoru, C. R.; Nyoni, F. C.; Borges, A. V.; Darchambeau, F.; Nyambe, I.; Bouillon, S.

    2015-04-01

    Spanning over 3000 km in length and with a catchment of approximately 1.4 million km2, the Zambezi River is the fourth largest river in Africa and the largest flowing into the Indian Ocean from the African continent. We present data on greenhouse gas (GHG: carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O)) concentrations and fluxes, as well as data that allow for characterization of sources and dynamics of carbon pools collected along the Zambezi River, reservoirs and several of its tributaries during 2012 and 2013 and over two climatic seasons (dry and wet) to constrain the interannual variability, seasonality and spatial heterogeneity along the aquatic continuum. All GHG concentrations showed high spatial variability (coefficient of variation: 1.01 for CO2, 2.65 for CH4 and 0.21 for N2O). Overall, there was no unidirectional pattern along the river stretch (i.e., decrease or increase towards the ocean), as the spatial heterogeneity of GHGs appeared to be determined mainly by the connectivity with floodplains and wetlands as well as the presence of man-made structures (reservoirs) and natural barriers (waterfalls, rapids). Highest CO2 and CH4 concentrations in the main channel were found downstream of extensive floodplains/wetlands. Undersaturated CO2 conditions, in contrast, were characteristic of the surface waters of the two large reservoirs along the Zambezi mainstem. N2O concentrations showed the opposite pattern, being lowest downstream of the floodplains and highest in reservoirs. Among tributaries, highest concentrations of both CO2 and CH4 were measured in the Shire River, whereas low values were characteristic of more turbid systems such as the Luangwa and Mazoe rivers. The interannual variability in the Zambezi River was relatively large for both CO2 and CH4, and significantly higher concentrations (up to 2-fold) were measured during wet seasons compared to the dry season. Interannual variability of N2O was less pronounced, but higher values

  10. Metabolic Signatures of Oxidative Stress and Their Relationship with Erythrocyte Membrane Surface Roughness Among Workers of Manual Materials Handling (MMH)

    PubMed Central

    Ghosh, Subrata; Acharyya, Muktish; Majumder, Titlee; Bagchi, Anandi

    2015-01-01

    Background: Brickfield workers in India perform manual materials handling (MMH) and as a result, are at a high risk of developing oxidative stress. This results in an alteration of the various markers of metabolic oxidative stress at the cellular level. Since red blood cell (RBC) is the central point where oxygen, glucose-6-phosphate dehydrogenase (G-6-PD), and glutathione (GSH) are involved, the surface roughness and its alteration and modeling with respect to workers exposed to MMH may be considered as helpful determinants in predicting early damage to the cell and restoring better health to the exposed population, that is, the worker exposed to stress. Hence, nanometric analysis of the surface roughness of the RBC may serve as an early indicator of the stress-related damage in these individuals. Aims: The purpose of the study was to identify early red blood corpuscular surface damage profile in terms of linear modeling correlating various biochemical parameters. Linear modeling has been aimed to be developed in order to demonstrate how individual oxidative stress markers such as malondialdehyde (MDA), G-6-PD, and reduced GSH are related to the RBC surface roughness [root mean square (RMS)]. Materials and Methods: Conventional analysis of these biochemical responses were evaluated in MMH laborers (age varying between 18 years and 21 years) and a comparable control group of the same age group (with sedentary lifestyles). Peak expiratory flow rate (PEFR) and RBC surface analysis by atomic-force microscopy (AFM) and correlated scanning probe microscopy (SPM-analytical software) with corresponding image analysis were performed immediately after completion of standardized exercise (MMH) at the brickfield. Results: A number of correlated significances and regressive linear models were developed among MDA, G-6-PD, GSH, and RBC surface roughness. Conclusion: It appears that these linear models might be instrumental in predicting early oxidative damages related to

  11. Biomimetic Water-Oxidation Catalysts: Manganese Oxides.

    PubMed

    Kurz, Philipp

    2016-01-01

    The catalytic oxidation of water to molecular oxygen is a key process for the production of solar fuels. Inspired by the biological manganese-based active site for this reaction in the enzyme Photosystem II, researchers have made impressive progress in the last decades regarding the development of synthetic manganese catalysts for water oxidation. For this, it has been especially fruitful to explore the many different types of known manganese oxides MnOx. This chapter first offers an overview of the structural, thermodynamic, and mechanistic aspects of water-oxidation catalysis by MnOx. The different test systems used for catalytic studies are then presented together with general reactivity trends. As a result, it has been possible to identify layered, mixed Mn (III/IV)-oxides as an especially promising class of bio-inspired catalysts and an attempt is made to give structure-based reasons for the good performances of these materials. In the outlook, the challenges of catalyst screenings (and hence the identification of a "best MnOx catalyst") are discussed. There is a great variety of reaction conditions which might be relevant for the application of manganese oxide catalysts in technological solar fuel-producing devices, and thus catalyst improvements are currently still addressing a very large parameter space. Nonetheless, detailed knowledge about the biological catalyst and a solid experimental basis concerning the syntheses and water-oxidation reactivities of MnOx materials have been established in the last decade and thus this research field is well positioned to make important contributions to solar fuel research in the future. PMID:25980320

  12. Barium oxide, calcium oxide, magnesia, and alkali oxide free glass

    DOEpatents

    Lu, Peizhen Kathy; Mahapatra, Manoj Kumar

    2013-09-24

    A glass composition consisting essentially of about 10-45 mole percent of SrO; about 35-75 mole percent SiO.sub.2; one or more compounds from the group of compounds consisting of La.sub.2O.sub.3, Al.sub.2O.sub.3, B.sub.2O.sub.3, and Ni; the La.sub.2O.sub.3 less than about 20 mole percent; the Al.sub.2O.sub.3 less than about 25 mole percent; the B.sub.2O.sub.3 less than about 15 mole percent; and the Ni less than about 5 mole percent. Preferably, the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide. Preferably, the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack. The SOFC stack comprises a plurality of SOFCs connected by one or more interconnect and manifold materials and sealed by the glass. Preferably, each SOFC comprises an anode, a cathode, and a solid electrolyte.

  13. The Oxidation of Pyrrole.

    PubMed

    Howard, James K; Rihak, Kieran J; Bissember, Alex C; Smith, Jason A

    2016-01-01

    The dearomatization of heterocycles has been a powerful means for producing functional molecules in synthesis. In the case of pyrroles, reductive methods (such as the Birch reduction) have been most widely exploited, while oxidative methods are generally dismissed as too difficult or unpredictable to be useful. However, since the early twentieth century considerable research has been carried out on the controlled oxidation of pyrroles to give highly functionalized products, using a variety of oxidants. This review presents a summary of all work up until the present day in the area of pyrrole oxidation, looking at the use of peroxide, singlet oxygen, hypervalent iodine reagents, a range or organic and inorganic oxidants, and electrochemical approaches. It also offers some perspective on the potential future role of pyrrole oxidation in synthesis. PMID:26294175

  14. beta 1-4N-acetylgalactosaminyltransferase can synthesize both asialoglycosphingolipid GM2 and glycosphingolipid GM2 in vitro and in vivo: isolation and characterization of a beta 1-4N-acetylgalactosaminyltransferase cDNA clone from rat ascites hepatoma cell line AH7974F.

    PubMed Central

    Hidari, J K; Ichikawa, S; Furukawa, K; Yamasaki, M; Hirabayashi, Y

    1994-01-01

    We have cloned a cDNA encoding beta 1-4N-acetylgalactosaminyltransferase (EC 2.4.1.92) (GalNAc-T) from rat ascites hepatoma of the free-cell type AH7974F. The cell line only expressed asialo-series glycosphingolipids (GSLs) including asialo-GM2 [Taki, T., Hirabayashi, Y., Ishiwata, Y., Matsumoto, M., and Kojima, K. (1979) Biochim. Biophys. Acta 572, 113-120]. The cDNA, pGNA56, was isolated by screening AH7974F cDNA library in lambda gt10 with a probe. The probe was obtained from AH7974F cDNA by PCR using primers with the nucleotide sequence of the human GalNAc-T cDNA. The amino acid sequence deduced from the nucleotide sequence of pGNA56 exhibited 88% similarity to the human GalNAc-T sequence. The enzyme was a typical type II membrane protein, which consisted of a short N-terminal residue, a transmembrane region, and a long C-terminal residue, including the catalytic domain. The substrate specificity of rat GalNAc-T was determined using homogenates from cells into which the cDNA clone was transfected. The enzyme catalysed not only the formation of GM2 and GD2 from GM3 and GD3 respectively, but also asialo-GM2 from CDH. It also acted on GSL substrates, including GM1b, sialylparagloboside and GD1 alpha. On the other hand, the enzyme did not transfer GalNAc to soluble substrates such as glycoproteins and oligosaccharide. The GSL compositional and immunocytochemical analyses of stable transfectants obtained by transfection of the cDNA showed simultaneous expression of asialo-GM2 and GM2 on the plasma membrane. Therefore, we concluded that the formation of asialo-GM2, GM2 and GD2 was catalysed by the single GalNAc-T. Northern-blot hybridization showed that the GalNAc-T mRNA was strongly expressed in rat brain, testis, and spleen. The gene was also expressed in rat normal liver to a lesser extent. We found the GSLs in asialo- and alpha-pathways such as asialo-GM1 and GD1 alpha in the rat tissues by using a sensitive t.l.c.-immunostaining method. These observations also

  15. Superconductive ceramic oxide combination

    SciTech Connect

    Chatterjee, D.K.; Mehrotra, A.K.; Mir, J.M.

    1991-03-05

    This patent describes the combination of a superconductive ceramic oxide which degrades in conductivity upon contact of ambient air with its surface and, interposed between the ceramic oxide surface and ambient air in the amount of at least 1 mg per square meter of surface area of the superconductive ceramic oxide, a passivant polymer selected from the group consisting of a polyester ionomer and an alkyl cellulose.

  16. METAL OXIDE NANOPARTICLES

    SciTech Connect

    FERNANDEZ-GARCIA,M.; RODGRIGUEZ, J.A.

    2007-10-01

    This chapter covers the fundamental science, synthesis, characterization, physicochemical properties and applications of oxide nanomaterials. Explains fundamental aspects that determine the growth and behavior of these systems, briefly examines synthetic procedures using bottom-up and top-down fabrication technologies, discusses the sophisticated experimental techniques and state of the art theory results used to characterize the physico-chemical properties of oxide solids and describe the current knowledge concerning key oxide materials with important technological applications.

  17. Multifunctional Oxide Heterostructures

    SciTech Connect

    Tsymbal, E Y; Dagotto, Elbio R; Eom, Professor Chang-Beom; Ramesh, Ramamoorthy

    2012-01-01

    This book is devoted to the rapidly developing field of oxide thin-films and heterostructures. Oxide materials combined with atomic-scale precision in a heterostructure exhibit an abundance of macroscopic physical properties involving the strong coupling between the electronic, spin, and structural degrees of freedom, and the interplay between magnetism, ferroelectricity, and conductivity. Recent advances in thin-film deposition and characterization techniques made possible the experimental realization of such oxide heterostructures, promising novel functionalities and device concepts.

  18. Stabilizing PFAE Against Oxidation

    NASA Technical Reports Server (NTRS)

    Jones, W. R., Jr.; Paciorek, K.; Kratzer, R.

    1988-01-01

    Process makes commercial perfluoroalkylether (PFAE) hydraulic fluid more stable in presence of metals in hot oxidizing atmospheres. Consists of thermal oxidation in presence of catalyst to remove weak links, followed by transformation of newly-created functional groups into phospha-s-triazine linkages, which impart antioxidation and anticorrosion properties. A 66-percent yield of stable PFAE obtained. Fluid used as lubricant, grease, or hydraulic fluid at temperatures from -55 to +300 degree C in presence of metals in oxidizing atmosphere.

  19. Plasma oxidation of polymers

    SciTech Connect

    Moss, S.J.; Jolly, A.M.; Tighe, B.J.

    1986-12-01

    The rates of plasma oxidation have been measured for homopolymers of several monomers and for copolymers of methyl methacrylate with styrene and vinyl naphthalene. Their results show that relatively small amounts of the aromatic component in the copolymer convey substantially increased resistance to plasma oxidation. Current knowledge of the mechanisms of plasma oxidation is reviewed and new mechanistic explanations are suggested. The implications for improved design of plasma-developable resists systems are considered.

  20. OXIDATION OF TRANSURANIC ELEMENTS

    DOEpatents

    Moore, R.L.

    1959-02-17

    A method is reported for oxidizing neptunium or plutonium in the presence of cerous values without also oxidizing the cerous values. The method consists in treating an aqueous 1N nitric acid solution, containing such cerous values together with the trivalent transuranic elements, with a quantity of hydrogen peroxide stoichiometrically sufficient to oxidize the transuranic values to the hexavalent state, and digesting the solution at room temperature.

  1. Mixed oxide solid solutions

    DOEpatents

    Magno, Scott; Wang, Ruiping; Derouane, Eric

    2003-01-01

    The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

  2. UV Induced Oxidation of Nitric Oxide

    NASA Technical Reports Server (NTRS)

    Parrish, Clyde, F. (Inventor); Luecke, Dale E. (Inventor)

    2007-01-01

    Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated at least in part using in situ UV radiation sources. The sources of the oxidizing species include oxygen and/or hydrogen peroxide. The oxygen may be a component of the gaseous stream or added to the gaseous stream, preferably near a UV radiation source, and is converted to ozone by the UV irradiation. The hydrogen peroxide is decomposed through a combination of vaporization and UV irradiation. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50% by volume and increased in concentration in a continuous process preceding vaporization within the flow channel of the gaseous stream and in the presence of the UV radiation sources.

  3. Oxidants and oxidation in the Earth's atmosphere

    NASA Technical Reports Server (NTRS)

    1995-01-01

    The 1994 BOC Priestley Conference was held at Bucknell University in Lewisburg, Pennsylvania, from June 24 through June 27, 1994. This conference, managed by the American Chemical Society (ACS), was a joint celebration with the Royal Society of Chemistry (RSC) commemorating Joseph Priestley's arrival in the U.S. and his discovery of oxygen. The basic theme of the conference was 'Oxidants and Oxidation in the Earth's Atmosphere,' with a keynote lecture on the history of ozone. A distinguished group of U.S. and international atmospheric chemists addressed the issues dominating current research and policy agendas. Topics crucial to the atmospheric chemistry of global change and local and regional air pollution were discussed. The program for the conference included four technical sessions on the following topics: (1) Oxidative Fate of Atmospheric Pollutants; (2) Photochemical Smog and Ozone; (3) Stratospheric Ozone; and (4) Global Tropospheric Ozone.

  4. Thiocyanate complexes of uranium in multiple oxidation states: a combined structural, magnetic, spectroscopic, spectroelectrochemical, and theoretical study.

    PubMed

    Hashem, Emtithal; Platts, James A; Hartl, František; Lorusso, Giulia; Evangelisti, Marco; Schulzke, Carola; Baker, Robert J

    2014-08-18

    A comprehensive study of the complexes A4[U(NCS)8] (A = Cs, Et4N, (n)Bu4N) and A3[UO2(NCS)5] (A = Cs, Et4N) is described, with the crystal structures of [(n)Bu4N]4[U(NCS)8]·2MeCN and Cs3[UO2(NCS)5]·O0.5 reported. The magnetic properties of square antiprismatic Cs4[U(NCS)8] and cubic [Et4N]4[U(NCS)8] have been probed by SQUID magnetometry. The geometry has an important impact on the low-temperature magnetic moments: at 2 K, μeff = 1.21 μB and 0.53 μB, respectively. Electronic absorption and photoluminescence spectra of the uranium(IV) compounds have been measured. The redox chemistry of [Et4N]4[U(NCS)8] has been explored using IR and UV-vis spectroelectrochemical methods. Reversible 1-electron oxidation of one of the coordinated thiocyanate ligands occurs at +0.22 V vs Fc/Fc(+), followed by an irreversible oxidation to form dithiocyanogen (NCS)2 which upon back reduction regenerates thiocyanate anions coordinating to UO2(2+). NBO calculations agree with the experimental spectra, suggesting that the initial electron loss of [U(NCS)8](4-) is delocalized over all NCS(-) ligands. Reduction of the uranyl(VI) complex [Et4N]3[UO2(NCS)5] to uranyl(V) is accompanied by immediate disproportionation and has only been studied by DFT methods. The bonding in [An(NCS)8](4-) (An = Th, U) and [UO2(NCS)5](3-) has been explored by a combination of DFT and QTAIM analysis, and the U-N bonds are predominantly ionic, with the uranyl(V) species more ionic that the uranyl(VI) ion. Additionally, the U(IV)-NCS ion is more ionic than what was found for U(IV)-Cl complexes. PMID:25072532

  5. Sunscreens and T4N5 liposomes differ in their ability to protect against ultraviolet-induced sunburn cell formation, alterations of dendritic epidermal cells, and local suppression of contact hypersensitivity.

    PubMed

    Wolf, P; Cox, P; Yarosh, D B; Kripke, M L

    1995-02-01

    Exposure of skin to ultraviolet (UV) radiation can lead to diverse biologic effects, including inflammation, sunburn cell formation, alterations of cutaneous immune cells, and impaired induction of contact hypersensitivity responses. The molecular mechanisms of these UV-induced effects are not completely understood. We investigated the ability of sunscreens and liposomes containing the DNA excision repair enzyme T4 endonuclease V to prevent these effects of UV radiation. The use of T4N5 liposomes, which increase the repair of cyclobutyl pyrimidine dimers, provides an approach for assessing the role of DNA damage in the effects of UV radiation on the skin. Exposing C3H mice to 500 mJ/cm2 UVB radiation from FS40 sunlamps resulted in skin edema, sunburn cell formation, and morphologic alterations and decreased numbers of Langerhans cells and Thy-1+ dendritic epidermal T cells. In addition, the induction of contact hypersensitivity after application of 2,4-dinitrofluorobenzene on UV-irradiated skin was diminished by 80%. Applying sunscreens containing octyl-N-dimethyl-p-aminobenzoate, 2-ethylhexyl-p-methoxycinnamate, or benzophenone-3 before this dose of UV irradiation gave nearly complete protection against all of these effects of UV irradiation. In contrast, topical application of T4N5 liposomes after UV irradiation had no effect on UV-induced skin edema and only partially protected against sunburn cell formation and local suppression of contact hypersensitivity, although its ability to protect against alterations in dendritic immune cells was comparable to that of the sunscreens. These results suggest that DNA damage is involved in only some of the local effects of UV radiation on the skin. In addition, T4N5 liposomes may be a useful adjunct to sunscreens because they can reduce some of the deleterious effects of UV radiation on skin even after a sunburn has been initiated. PMID:7829886

  6. In Situ Coupling of Strung Co4N and Intertwined N-C Fibers toward Free-Standing Bifunctional Cathode for Robust, Efficient, and Flexible Zn-Air Batteries.

    PubMed

    Meng, Fanlu; Zhong, Haixia; Bao, Di; Yan, Junmin; Zhang, Xinbo

    2016-08-17

    Flexible power sources with high energy density are crucial for the realization of next-generation flexible electronics. Theoretically, rechargeable flexible zinc-air (Zn-air) batteries could provide high specific energy, while their large-scale applications are still greatly hindered by high cost and resources scarcity of noble-metal-based oxygen evolution reaction (OER)/oxygen reduction reaction (ORR) electrocatalysts as well as inferior mechanical properties of the air cathode. Combining metallic Co4N with superior OER activity and Co-N-C with perfect ORR activity on a free-standing and flexible electrode could be a good step for flexible Zn-air batteries, while lots of difficulties need to be overcome. Herein, as a proof-of-concept experiment, we first propose a strategy for in situ coupling of strung Co4N and intertwined N-C fibers, by pyrolyzation of the novel pearl-like ZIF-67/polypyrrole nanofibers network rooted on carbon cloth. Originating from the synergistic effect of Co4N and Co-N-C and the stable 3D interconnected conductive network structure, the obtained free-standing and highly flexible bifunctional oxygen electrode exhibits excellent electrocatalytic activity and stability for both OER and ORR in terms of low overpotential (310 mV at 10 mA cm(-2)) for OER, a positive half-wave potential (0.8 V) for ORR, and a stable current density retention for at least 20 h, and especially, the obtained Zn-air batteries exhibit a low discharge-charge voltage gap (1.09 V at 50 mA cm(-2)) and long cycle life (up to 408 cycles). Furthermore, the perfect bendable and twistable and rechargeable properties of the flexible Zn-air battery particularly make it a potentially power portable and wearable electronic device. PMID:27463122

  7. Synthesis and characterization of a new (2-NH{sub 2}-6-CH{sub 3}C{sub 5}H{sub 4}N)H{sub 2}XO{sub 4} (X=P, As)

    SciTech Connect

    Chtioui, A.; Jouini, A. . E-mail: amor.jouini@fsm.rnu.tn

    2006-03-09

    Crystals of 2-amino-6-methylpyridinium dihydrogenmonophosphate (denoted as 2A6MPP) and 2-amino-6-methylpyridinium dihydrogenmonoarsenate (denoted as 2A6MPAs), have been prepared and grown at room temperature. They crystallize with triclinic unit cells and are isotopic. The following unit cell parameters were found, (2-NH{sub 2}-6-CH{sub 3}C{sub 5}H{sub 4}N)H{sub 2}PO{sub 4}: a=7.5165(6), b=8.2640(5), c=8.5674(7)A, {alpha}=64.845(5), {beta}=80.156(3), {gamma}=85.783(5), Z=2, V=474.61(6)A{sup 3}; (2-NH{sub 2}-6-CH{sub 3}C{sub 5}H{sub 4}N)H{sub 2}AsO{sub 4}: a=7.6011(4), b=8.4261(6), c=8.7074(6)A, {alpha}=64.228(3), {beta}=81.047(4), {gamma}=85.972(4), Z=2, V=496.09(6)A{sup 3}. The common space group is P1-bar . We have determined the structure of the phosphate. It exhibits infinite (H{sub 2}PO{sub 4}){sub n}{sup -n} chains. The organic groups (2-NH{sub 2}-6-CH{sub 3}C{sub 5}H{sub 4}N){sup +} are anchored between adjacent polyanions through multiple hydrogen bonds. The thermal property of the compound was investigated as well as was the IR property supported by group theoretical analyses.

  8. Synthesis and Mechanical Wear Studies of Ultra Smooth Nanostructured Diamond (USND) Coatings Deposited by Microwave Plasma Chemical Vapor Deposition with He/H2/CH4/N2 Mixtures

    PubMed Central

    Chowdhury, S.; Borham, J.; Catledge, S. A.; Eberhardt, A. W.; Johnson, P. S.; Vohra, Y. K.

    2008-01-01

    Ultra smooth nanostructured diamond (USND) coatings were deposited by microwave plasma chemical vapor deposition (MPCVD) technique using He/H2/CH4/N2 gas mixture. The RMS surface roughness as low as 4 nm (2 micron square area) and grain size of 5–6 nm diamond coatings were achieved on medical grade titanium alloy. Previously it was demonstrated that the C2 species in the plasma is responsible for the production of nanocrystalline diamond coatings in the Ar/H2/CH4 gas mixture. In this work we have found that CN species is responsible for the production of USND coatings in He/H2/CH4/N2 plasma. It was found that diamond coatings deposited with higher CN species concentration (normalized by Balmer Hα line) in the plasma produced smoother and highly nanostructured diamond coatings. The correlation between CN/Hα ratios with the coating roughness and grain size were also confirmed with different set of gas flows/plasma parameters. It is suggested that the presence of CN species could be responsible for producing nanocrystallinity in the growth of USND coatings using He/H2/CH4/N2 gas mixture. The RMS roughness of 4 nm and grain size of 5–6 nm were calculated from the deposited diamond coatings using the gas mixture which produced the highest CN/Hα species in the plasma. Wear tests were performed on the OrthoPOD®, a six station pin-on-disk apparatus with ultra-high molecular weight polyethylene (UHMWPE) pins articulating on USND disks and CoCrMo alloy disk. Wear of the UHMWPE was found to be lower for the polyethylene on USND than that of polyethylene on CoCrMo alloy. PMID:19112519

  9. Infrared rectification in a nanoantenna-coupled metal-oxide-semiconductor tunnel diode.

    PubMed

    Davids, Paul S; Jarecki, Robert L; Starbuck, Andrew; Burckel, D Bruce; Kadlec, Emil A; Ribaudo, Troy; Shaner, Eric A; Peters, David W

    2015-12-01

    Direct rectification of electromagnetic radiation is a well-established method for wireless power conversion in the microwave region of the spectrum, for which conversion efficiencies in excess of 84% have been demonstrated. Scaling to the infrared or optical part of the spectrum requires ultrafast rectification that can only be obtained by direct tunnelling. Many research groups have looked to plasmonics to overcome antenna-scaling limits and to increase the confinement. Recently, surface plasmons on heavily doped Si surfaces were investigated as a way of extending surface-mode confinement to the thermal infrared region. Here we combine a nanostructured metallic surface with a heavily doped Si infrared-reflective ground plane designed to confine infrared radiation in an active electronic direct-conversion device. The interplay of strong infrared photon-phonon coupling and electromagnetic confinement in nanoscale devices is demonstrated to have a large impact on ultrafast electronic tunnelling in metal-oxide-semiconductor (MOS) structures. Infrared dispersion of SiO2 near a longitudinal optical (LO) phonon mode gives large transverse-field confinement in a nanometre-scale oxide-tunnel gap as the wavelength-dependent permittivity changes from 1 to 0, which leads to enhanced electromagnetic fields at material interfaces and a rectified displacement current that provides a direct conversion of infrared radiation into electric current. The spectral and electrical signatures of the nanoantenna-coupled tunnel diodes are examined under broadband blackbody and quantum-cascade laser (QCL) illumination. In the region near the LO phonon resonance, we obtained a measured photoresponsivity of 2.7 mA W(-1) cm(-2) at -0.1 V. PMID:26414194

  10. Artificial chemical and magnetic structure at the domain walls of an epitaxial oxide.

    PubMed

    Farokhipoor, S; Magén, C; Venkatesan, S; Íñiguez, J; Daumont, C J M; Rubi, D; Snoeck, E; Mostovoy, M; de Graaf, C; Müller, A; Döblinger, M; Scheu, C; Noheda, B

    2014-11-20

    Progress in nanotechnology requires new approaches to materials synthesis that make it possible to control material functionality down to the smallest scales. An objective of materials research is to achieve enhanced control over the physical properties of materials such as ferromagnets, ferroelectrics and superconductors. In this context, complex oxides and inorganic perovskites are attractive because slight adjustments of their atomic structures can produce large physical responses and result in multiple functionalities. In addition, these materials often contain ferroelastic domains. The intrinsic symmetry breaking that takes place at the domain walls can induce properties absent from the domains themselves, such as magnetic or ferroelectric order and other functionalities, as well as coupling between them. Moreover, large domain wall densities create intense strain gradients, which can also affect the material's properties. Here we show that, owing to large local stresses, domain walls can promote the formation of unusual phases. In this sense, the domain walls can function as nanoscale chemical reactors. We synthesize a two-dimensional ferromagnetic phase at the domain walls of the orthorhombic perovskite terbium manganite (TbMnO3), which was grown in thin layers under epitaxial strain on strontium titanate (SrTiO3) substrates. This phase is yet to be created by standard chemical routes. The density of the two-dimensional sheets can be tuned by changing the film thickness or the substrate lattice parameter (that is, the epitaxial strain), and the distance between sheets can be made as small as 5 nanometres in ultrathin films, such that the new phase at domain walls represents up to 25 per cent of the film volume. The general concept of using domain walls of epitaxial oxides to promote the formation of unusual phases may be applicable to other materials systems, thus giving access to new classes of nanoscale materials for applications in nanoelectronics and

  11. Artificial chemical and magnetic structure at the domain walls of an epitaxial oxide

    NASA Astrophysics Data System (ADS)

    Farokhipoor, S.; Magén, C.; Venkatesan, S.; Íñiguez, J.; Daumont, C. J. M.; Rubi, D.; Snoeck, E.; Mostovoy, M.; de Graaf, C.; Müller, A.; Döblinger, M.; Scheu, C.; Noheda, B.

    2014-11-01

    Progress in nanotechnology requires new approaches to materials synthesis that make it possible to control material functionality down to the smallest scales. An objective of materials research is to achieve enhanced control over the physical properties of materials such as ferromagnets, ferroelectrics and superconductors. In this context, complex oxides and inorganic perovskites are attractive because slight adjustments of their atomic structures can produce large physical responses and result in multiple functionalities. In addition, these materials often contain ferroelastic domains. The intrinsic symmetry breaking that takes place at the domain walls can induce properties absent from the domains themselves, such as magnetic or ferroelectric order and other functionalities, as well as coupling between them. Moreover, large domain wall densities create intense strain gradients, which can also affect the material's properties. Here we show that, owing to large local stresses, domain walls can promote the formation of unusual phases. In this sense, the domain walls can function as nanoscale chemical reactors. We synthesize a two-dimensional ferromagnetic phase at the domain walls of the orthorhombic perovskite terbium manganite (TbMnO3), which was grown in thin layers under epitaxial strain on strontium titanate (SrTiO3) substrates. This phase is yet to be created by standard chemical routes. The density of the two-dimensional sheets can be tuned by changing the film thickness or the substrate lattice parameter (that is, the epitaxial strain), and the distance between sheets can be made as small as 5 nanometres in ultrathin films, such that the new phase at domain walls represents up to 25 per cent of the film volume. The general concept of using domain walls of epitaxial oxides to promote the formation of unusual phases may be applicable to other materials systems, thus giving access to new classes of nanoscale materials for applications in nanoelectronics and

  12. Infrared rectification in a nanoantenna-coupled metal-oxide-semiconductor tunnel diode

    NASA Astrophysics Data System (ADS)

    Davids, Paul S.; Jarecki, Robert L.; Starbuck, Andrew; Burckel, D. Bruce; Kadlec, Emil A.; Ribaudo, Troy; Shaner, Eric A.; Peters, David W.

    2015-12-01

    Direct rectification of electromagnetic radiation is a well-established method for wireless power conversion in the microwave region of the spectrum, for which conversion efficiencies in excess of 84% have been demonstrated. Scaling to the infrared or optical part of the spectrum requires ultrafast rectification that can only be obtained by direct tunnelling. Many research groups have looked to plasmonics to overcome antenna-scaling limits and to increase the confinement. Recently, surface plasmons on heavily doped Si surfaces were investigated as a way of extending surface-mode confinement to the thermal infrared region. Here we combine a nanostructured metallic surface with a heavily doped Si infrared-reflective ground plane designed to confine infrared radiation in an active electronic direct-conversion device. The interplay of strong infrared photon-phonon coupling and electromagnetic confinement in nanoscale devices is demonstrated to have a large impact on ultrafast electronic tunnelling in metal-oxide-semiconductor (MOS) structures. Infrared dispersion of SiO2 near a longitudinal optical (LO) phonon mode gives large transverse-field confinement in a nanometre-scale oxide-tunnel gap as the wavelength-dependent permittivity changes from 1 to 0, which leads to enhanced electromagnetic fields at material interfaces and a rectified displacement current that provides a direct conversion of infrared radiation into electric current. The spectral and electrical signatures of the nanoantenna-coupled tunnel diodes are examined under broadband blackbody and quantum-cascade laser (QCL) illumination. In the region near the LO phonon resonance, we obtained a measured photoresponsivity of 2.7 mA W-1 cm-2 at -0.1 V.

  13. Force modulation atomic force microscopy: background, development and application to electrodeposited cerium oxide films

    NASA Astrophysics Data System (ADS)

    Li, Feng-Bin; Thompson, G. E.; Newman, R. C.

    1998-04-01

    In force modulation atomic force microscopy (FMAFM), vertical oscillation of the scanning tip of the AFM is added purposely and the deflection of the tip, which is influenced by surface features of the sample, is used as the z dimension to construct images. FMAFM represents a powerful technique for scientific research, but its merit has not been realized adequately to date. In this paper, the basic principles and particular features, as well as potential drawbacks of the technique, are presented and demonstrated systematically, through its application to electrochemically deposited cerium oxide films. Comparisons are also made with the more familiar contact mode AFM (CMAFM) and tapping mode AFM (TMAFM). It is shown that FMAFM reveals the major topographic features of CMAFM, but affords (i) greater resolution for sample features that are difficult in CMAFM, and (ii) continuous two-dimensional mapping of local mechanical properties on a scale of nanometres that the CMAFM, TMAFM and any other techniques, are not capable of sensing. This information can be used to elucidate other properties of the investigated surface, such as crystallinity variation, phase separation and distribution, and mechanisms of formation of deposited films. Major artifacts associated with the technique include `wedge cavity effect' and `tip slip effect', for which a geometric model is proposed to elucidate their origins. The cerium oxide films are shown to be composed of relatively hard crystalline grains, of well-defined individual geometry and comparatively regular packing, alongside relatively soft amorphous patches, devoid of distinct geometry and assembled disorderly. These features are consistent with a nucleation and growth mechanism of the deposition, in which crystalline nuclei arise and grow from an intermediate cerium gel mass, produced in the interfacial region during deposition.

  14. Oxidative Remobilization of Technetium Sequestered by Sulfide-Transformed Nano Zerovalent Iron

    SciTech Connect

    Fan, Dimin; Anitori, Roberto; Tebo, Bradley M.; Tratnyek, P. G.; Lezama Pacheco, Juan S.; Kukkadapu, Ravi K.; Kovarik, Libor; Engelhard, Mark H.; Bowden, Mark E.

    2014-06-02

    The dissolution of Tc(IV) sulfide and concurrent transformation of sulfidated ZVI during 2 oxidation were examined. Kinetic data obtained with 10 mL batch reactors showed that Tc(VII) 3 reduced by sulfidated nZVI has significantly slower reoxidation rates than Tc(VII) reduced by 4 nZVI only. In a 50 mL batch reactor, initial inhibition of Tc(IV) dissolution was apparent and 5 lasted until 120 hours at S/Fe = 0.112, presumably due to the redox buffer capacity of FeS. This 6 is evidenced by the parallel trends in oxidation-reduction potentials (ORP) and Tc dissolution 7 kinetics. Mӧssbauer spectra and micro X-ray diffraction of S/Fe = 0.112 suggested the 8 persistence of FeS after 24-h oxidation although X-ray photoelectron spectroscopy indicated 9 substantial surface oxidation. After 120-h oxidation, all characterizations showed complete 10 oxidation of FeS, which further indicates that FeS inhibits Tc oxidation. X-ray absorption 11 spectroscopy for S/Fe = 0.011 showed significantly increasing percentage of TcS2 in the solid 12 phase after 24-h oxidation, indicating TcS2 is more resistant to oxidation than TcO2. At S/Fe = 13 0.112, the XAS results revealed significant transformation of Tc speciation from TcS2 to TcO2 14 after 120-h oxidation at S/Fe = 0.112. Given that no apparent Tc dissolution occurred during this 15 period, the speciation transformation might play a secondary role in hindering Tc oxidation, 16 especially as redox buffer capacity approached depletion.

  15. Catalytic process for formaldehyde oxidation

    NASA Technical Reports Server (NTRS)

    Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); D'Ambrosia, Christine M. (Inventor)

    1996-01-01

    Disclosed is a process for oxidizing formaldehyde to carbon dioxide and water without the addition of energy. A mixture of formaldehyde and an oxidizing agent (e.g., ambient air containing formaldehyde) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

  16. Lagoons and Oxidation Ponds.

    ERIC Educational Resources Information Center

    O'Brien, W. J.

    1978-01-01

    Presents the 1978 literature review of wastewater treatment. This review covers lagoons and oxidation ponds, and it includes some areas such as improving the effluents from ponds, stabilization ponds, aerated lagoons, and oxidation ditches. A list of 36 references is also presented. (HM)

  17. OXIDANT-PRECURSOR RELATIONSHIPS

    EPA Science Inventory

    New methods of ambient air analysis were used to define more clearly the relationships between oxidants and their precursors. Non-methane hydrocarbons, NOx, O2, and oxidants were measured at the same time and location (Riverside, California). The ambient air data presented in thi...

  18. Monolithic metal oxide transistors.

    PubMed

    Choi, Yongsuk; Park, Won-Yeong; Kang, Moon Sung; Yi, Gi-Ra; Lee, Jun-Young; Kim, Yong-Hoon; Cho, Jeong Ho

    2015-04-28

    We devised a simple transparent metal oxide thin film transistor architecture composed of only two component materials, an amorphous metal oxide and ion gel gate dielectric, which could be entirely assembled using room-temperature processes on a plastic substrate. The geometry cleverly takes advantage of the unique characteristics of the two components. An oxide layer is metallized upon exposure to plasma, leading to the formation of a monolithic source-channel-drain oxide layer, and the ion gel gate dielectric is used to gate the transistor channel effectively at low voltages through a coplanar gate. We confirmed that the method is generally applicable to a variety of sol-gel-processed amorphous metal oxides, including indium oxide, indium zinc oxide, and indium gallium zinc oxide. An inverter NOT logic device was assembled using the resulting devices as a proof of concept demonstration of the applicability of the devices to logic circuits. The favorable characteristics of these devices, including (i) the simplicity of the device structure with only two components, (ii) the benign fabrication processes at room temperature, (iii) the low-voltage operation under 2 V, and (iv) the excellent and stable electrical performances, together support the application of these devices to low-cost portable gadgets, i.e., cheap electronics. PMID:25777338

  19. Stabilized chromium oxide film

    DOEpatents

    Nyaiesh, A.R.; Garwin, E.L.

    1986-08-04

    Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150A are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

  20. Stabilized chromium oxide film

    DOEpatents

    Garwin, Edward L.; Nyaiesh, Ali R.

    1988-01-01

    Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150.ANG. are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

  1. Reducible oxide based catalysts

    DOEpatents

    Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

    2010-04-06

    A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

  2. PROCESS OF OXIDIZING PLUTONIUM

    DOEpatents

    Coryell, C.D.

    1959-08-25

    The oxidation of plutonium to the plus six valence state is described. The oxidation is accomplished by treating the plutonium in aqueous solution with a solution above 0.01 molar in argentic ion, above 1.1 molar in nitric acid, and above 0.02 molar in argentous ion.

  3. Organic Oxidations Using Geomimicry.

    PubMed

    Yang, Ziming; Hartnett, Hilairy E; Shock, Everett L; Gould, Ian R

    2015-12-18

    Oxidations of phenylacetic acid to benzaldehyde, benzyl alcohol to benzaldehyde, and benzaldehyde to benzoic acid have been observed, in water as the solvent and using only copper(II) chloride as the oxidant. The reactions are performed at 250 °C and 40 bar, conditions that mimic hydrothermal reactions that are geochemically relevant. Speciation calculations show that the oxidizing agent is not freely solvated copper(II) ions, but complexes of copper(II) with chloride and carboxylate anions. Measurements of the reaction stoichiometries and also of substituent effects on reactivity allow plausible mechanisms to be proposed. These oxidation reactions are relevant to green chemistry in that they proceed in high chemical yield in water as the solvent and avoid the use of toxic heavy metal oxidizing reagents. PMID:26561976

  4. Oxidation State 10 Exists.

    PubMed

    Yu, Haoyu S; Truhlar, Donald G

    2016-07-25

    In a recent paper, Wang et al. found an iridium-containing compound with a formal oxidation state of 9. This is the highest oxidation state ever found in a stable compound. To learn if this is the highest chemical oxidation state possible, Kohn-Sham density functional theory was used to study various compounds, including PdO4 (2+) , PtO4 (2+) , PtO3 F2 (2+) , PtO4 OH(+) , PtO5 , and PtO4 SH(+) , in which the metal has an oxidation state of 10. It was found that PtO4 (2+) has a metastable state that is kinetically stable with a barrier height for decomposition of 31 kcal mol(-1) and a calculated lifetime of 0.9 years. All other compounds studied would readily decompose to lower oxidation states. PMID:27273799

  5. Nitric Oxide Nanoparticle Technology

    PubMed Central

    Englander, Laura

    2010-01-01

    Staphylococcus aureus infections account for the majority of skin and soft tissue infections in the United States. Staphylococcus aureus is rapidly evolving resistance to contemporary topical as well as systemic antibiotics. Alternatives to current treatment options for skin and soft tissue infections are needed for more effective treatment now and in the future. Nitric oxide's proven roles in both wound repair and as an antimicrobial agent make it an excellent candidate for the treatment of skin infections. Recent attempts at novel nitric oxide therapies, in the form of nitric oxide donors, have shown limited potential in treating cutaneous infection. However, more recent developments in nitric oxide delivery, using nitric oxide nanoparticle technology, demonstrate substantial promise in the promotion of wound repair and eradication of skin and soft tissue infections. PMID:20725551

  6. Oxidation characteristics of molybdenum-zirconium oxide cermets

    NASA Technical Reports Server (NTRS)

    Heitzinger, B.

    1984-01-01

    The oxidation of molybdenum is affected by the factors of temperature, the oxygen pressure in the oxidizing atmosphere, and the time of exposure. Studies of the oxidation characteristics of Mo show that the oxidation rate increases strongly when the temperature exceeds 600 C. Investigations of the behavior of cermets with various percentages of zirconium oxide are discussed, taking into account oxidation conditions at temperatures under and above the melting point of molybdenum trioxide.

  7. Raman spectroscopic investigation of the single-monolayer Langmuir-Blodgett film of C16NaphOH and C10AzoNaphC4N-SDS.

    PubMed

    Wu, Yuqing; Zhao, Bing; Xu, Weiqing; Li, Guowen; Li, Bofu

    2003-04-01

    Raman spectra were measured for Langmuir-Blodgett (LB) films of C(16)NaphOH and C(10)AzoNaphC(4)N-SDS on Calcium Fluorite substrate for the first time. In order to find out favorable excitation condition, Raman spectra of the single and multi-monolayer LB films excited at different lines at 244, 514, 633 and 778 nm are recorded and compared in the present study. Raman spectrum of the monolayer LB film of C(16)NaphOH excited by 244 nm demonstrate that excellent signal to noise is achieved even for one monolayer LB film with an extremely short integrating time as 60 s because of being resonantly enhanced, while no meaningful spectra were recorded under the same condition for the monolayer LB film of C(10)AzoNaphC(4)N-SDS because of burning. Using a HeNe 633 nm excitation the problem with strong substrate fluorescence was partially solved, since under these conditions this fluorescence is mainly outside the fingerprint region of the LB film molecules (1000-2000 cm(-1)). Therefore by using the HeNe laser excitation, Raman spectra with high signal to noise ratio of LB films of C(16)NaphOH were collected and shown in this paper. These findings stress again the necessity to define an appropriate Raman system for this special application of LB film diagnosis. PMID:12659885

  8. CRISPR/Cas9-Mediated Genomic Deletion of the Beta-1, 4 N-acetylgalactosaminyltransferase 1 Gene in Murine P19 Embryonal Carcinoma Cells Results in Low Sensitivity to Botulinum Neurotoxin Type C

    PubMed Central

    Tsukamoto, Kentaro; Ozeki, Chikako; Kohda, Tomoko; Tsuji, Takao

    2015-01-01

    Botulinum neurotoxins produced by Clostridium botulinum cause flaccid paralysis by inhibiting neurotransmitter release at peripheral nerve terminals. Previously, we found that neurons derived from the murine P19 embryonal carcinoma cell line exhibited high sensitivity to botulinum neurotoxin type C. In order to prove the utility of P19 cells for the study of the intracellular mechanism of botulinum neurotoxins, ganglioside-knockout neurons were generated by deletion of the gene encoding beta-1,4 N-acetylgalactosaminyltransferase 1 in P19 cells using the clustered regularly interspaced short palindromic repeats combined with Cas9 (CRISPR/Cas9) system. By using this system, knockout cells could be generated more easily than with previous methods. The sensitivity of the generated beta-1,4 N-acetylgalactosaminyltransferase 1-depleted P19 neurons to botulinum neurotoxin type C was decreased considerably, and the exogenous addition of the gangliosides GD1a, GD1b, and GT1b restored the susceptibility of P19 cells to botulinum neurotoxin type C. In particular, addition of a mixture of these three ganglioside more effectively recovered the sensitivity of knockout cells compared to independent addition of GD1a, GD1b, or GT1b. Consequently, the genome-edited P19 cells generated by the CRISPR/Cas9 system were useful for identifying and defining the intracellular molecules involved in the toxic action of botulinum neurotoxins. PMID:26177297

  9. Monitoring dehydration of the organic-inorganic [(C3H7)4N][SnCl5(H2O)]·2H2O compound using simultaneous thermal and Raman studies

    NASA Astrophysics Data System (ADS)

    Hajlaoui, S.; Chaabane, I.; Guidara, K.; Bulou, A.

    2016-07-01

    In this work we report the experimental studies of the structural phase transition in the [(C3H7)4N]SnCl5(H2O)]·2H2O compound by differential scanning calorimetric (DSC) and Raman spectroscopic. The X-ray powder diffraction study of the [(C3H7)4N][SnCl5(H2O)]·2H2O sample at room temperature showed that this compound is monoclinic and has P121/c1 space group. Differential scanning calorimetric disclosed two types of phase transitions in the temperature range 356-376 (T1) K and at 393 K (T2) characterized, by a loss of water molecules and probably a reconstruction of new anionic parts after T2 transition. The Raman scattering spectra recorded at various temperatures in the wavenumber range from 100 to 3800 cm- 1 covering the domains of existence of changes in the vicinity of the two phase transitions detected by DSC measurement. A detailed study of the spectral parameters (wave number, reduced intensity and the full width at half maximum) as a function of temperature of a chosen band, associated with (νs(Snsbnd O) + νs(Snsbnd Cl)), based on an order-disorder model allowed us to obtain information relative to the activation energy and correlation length.

  10. Volumetric properties of CO{sub 2}-CH{sub 4}-N{sub 2} fluids at 200{degree}C and 1000 bars: A comparison of equations of state and experimental data. Chapter 4

    SciTech Connect

    Seitz, J.C.; Blencoe, J.G.; Joyce, D.B.; Bodnar, R.J.

    1994-12-31

    Predictions of molar volume, excess molar volume, and isochoric P-T trajectories from 13 published equations of state are compared with one another and with preliminary volumetric data for CO{sub 2}-CH{sub 4}-N{sub 2} fluids at 200{degrees}C and 1000 bars. The equations of state investigated represent a wide variety of empirical and semi-empirical approaches to the modeling of fluids. The experimental data indicate that excess volumes of CO{sub 2}-CH{sub 4}-N{sub 2} mixtures are small (<3% of the total volume of the mixture, except near the critical point of CO{sub 2}). The NIST software package DDMIX yields volumetric properties that are most consistent with our experimental results. Differences in the calculated volumetric properties of mixtures from the different equations of state are significant For example, estimates of the equilibrium trapping temperature of a fluid inclusion (2000 bars, 60% CO{sub 2}-20% CH{sub 4}20% N{sub 2}mixture, V=59.10 cm{sup 3}/mole) calculated from various equations of state range from 462-570{degrees}C. The major source of error in calculated volumetric properties of fluid mixtures is the inability of equations of state to accurately predict the volumetric properties of the pure components.

  11. Monitoring dehydration of the organic-inorganic [(C3H7)4N][SnCl5(H2O)]·2H2O compound using simultaneous thermal and Raman studies.

    PubMed

    Hajlaoui, S; Chaabane, I; Guidara, K; Bulou, A

    2016-07-01

    In this work we report the experimental studies of the structural phase transition in the [(C3H7)4N]SnCl5(H2O)]·2H2O compound by differential scanning calorimetric (DSC) and Raman spectroscopic. The X-ray powder diffraction study of the [(C3H7)4N][SnCl5(H2O)]·2H2O sample at room temperature showed that this compound is monoclinic and has P121/c1 space group. Differential scanning calorimetric disclosed two types of phase transitions in the temperature range 356-376 (T1) K and at 393K (T2) characterized, by a loss of water molecules and probably a reconstruction of new anionic parts after T2 transition. The Raman scattering spectra recorded at various temperatures in the wavenumber range from 100 to 3800cm(-1) covering the domains of existence of changes in the vicinity of the two phase transitions detected by DSC measurement. A detailed study of the spectral parameters (wave number, reduced intensity and the full width at half maximum) as a function of temperature of a chosen band, associated with (νs(SnO)+νs(SnCl)), based on an order-disorder model allowed us to obtain information relative to the activation energy and correlation length. PMID:27070530

  12. Determination of bisphenol A, 4-n-nonylphenol, and 4-tert-octylphenol by temperature-controlled ionic liquid dispersive liquid-phase microextraction combined with high performance liquid chromatography-fluorescence detector.

    PubMed

    Zhou, Qingxiang; Gao, Yuanyuan; Xie, Guohong

    2011-09-15

    Present study described a simple, sensitive, and viable method for the determination of bisphenol A, 4-n-nonylphenol and 4-tert-octylphenol in water samples using temperature-controlled ionic liquid dispersive liquid-phase microextraction coupled to high performance liquid chromatography-fluorescence detector. In this experiment, 1-octyl-3-methylimidazolium hexafluorophosphate ([C(8)MIM][PF(6)]) was used as the extraction solvent, and bisphenol A, 4-n-nonylphenol and 4-tert-octylphenol were selected as the model analytes. Parameters affecting the extraction efficiency such as the volume of [C(8)MIM][PF(6)], dissolving temperature, extraction time, sample pH, centrifuging time and salting-out effect have been investigated in detail. Under the optimized conditions, good linear relationship was found in the concentration range of 1.0-100 μg L(-1) for BPA, 1.5-150 μg L(-1) for 4-NP, and 3-300 μg L(-1) for 4-OP, respectively. Limits of detection (LOD, S/N=3) were in the range of 0.23-0.48 μg L(-1). Intra day and inter day precisions (RSDs, n=6) were in the range of 4.6-5.5% and 8.5-13.3%, respectively. This method has been also successfully applied to analyze the real water samples at two different spiked concentrations and excellent results were obtained. PMID:21807227

  13. G-quadruplexes with (4n - 1) guanines in the G-tetrad core: formation of a G-triad·water complex and implication for small-molecule binding

    PubMed Central

    Heddi, Brahim; Martín-Pintado, Nerea; Serimbetov, Zhalgas; Kari, Teuku Mahfuzh Aufar; Phan, Anh Tuân

    2016-01-01

    G-quadruplexes are non-canonical structures of nucleic acids, in which guanine bases form planar G-tetrads (G·G·G·G) that stack on each other in the core of the structure. G-quadruplexes generally contain multiple times of four (4n) guanines in the core. Here, we study the structure of G-quadruplexes with only (4n - 1) guanines in the core. The solution structure of a DNA sequence containing 11 guanines showed the formation of a parallel G-quadruplex involving two G-tetrads and one G-triad with a vacant site. Molecular dynamics simulation established the formation of a stable G-triad·water complex, where water molecules mimic the position of the missing guanine in the vacant site. The concept of forming G-quadruplexes with missing guanines in the core broadens the current definition of G-quadruplex-forming sequences. The potential ability of such structures to bind different metabolites, including guanine, guanosine and GTP, in the vacant site, could have biological implications in regulatory functions. Formation of this unique binding pocket in the G-triad could be used as a specific target in drug design. PMID:26673723

  14. Growth of silicon-doped Al0.6Ga0.4N with low carbon concentration at high growth rate using high-flow-rate metal organic vapor phase epitaxy reactor

    NASA Astrophysics Data System (ADS)

    Ikenaga, Kazutada; Mishima, Akira; Yano, Yoshiki; Tabuchi, Toshiya; Matsumoto, Koh

    2016-05-01

    The relationship between the carbon concentration and electrical characteristics of silicon-doped AlGaN (Al > 0.5) was investigated using a high-flow-rate metal organic vapor phase epitaxy (MOVPE) reactor. The carbon concentration and electrical properties of AlGaN (Al > 0.5) were measured as a function of the growth rate, V/III ratio, and growth temperature. The growth rate of Al0.6Ga0.4N was linearly controlled up to 7.2 µm/h under a constant ammonia (NH3) flow rate. However, a decrease in V/III ratio resulted in an increase in carbon concentration to 8 × 1017 cm‑3. With increased growth temperature, the carbon concentration decreased to less than 2 × 1017 cm‑3 without showing any reduction in growth rate. As a result, n-type Al0.6Ga0.4N with a carrier concentration of 5.4 × 1018 cm‑3 and a resistivity of 2.2 × 10‑2 Ω·cm was obtained.

  15. Proximity Driven Commensurate Pinning in YBa2Cu3O7 through All-Oxide Magnetic Nanostructures.

    PubMed

    Rocci, M; Azpeitia, J; Trastoy, J; Perez-Muñoz, A; Cabero, M; Luccas, R F; Munuera, C; Mompean, F J; Garcia-Hernandez, M; Bouzehouane, K; Sefrioui, Z; Leon, C; Rivera-Calzada, A; Villegas, J E; Santamaria, J

    2015-11-11

    The design of artificial vortex pinning landscapes is a major goal toward large scale applications of cuprate superconductors. Although disordered nanometric inclusions have shown to modify their vortex phase diagram and to produce enhancements of the critical current ( MacManus-Driscoll , J. L. ; Foltyn , S. R. ; Jia , Q. X. ; Wang , H. ; Serquis , A. ; Civale , L. ; Maiorov , B. ; Hawley , M. E. ; Maley , M. P. ; Peterson , D. E. Nat. Mater. 2004 , 3 , 439 - 443 and Yamada , Y. ; Takahashi , K. ; Kobayashi , H. ; Konishi , M. ; Watanabe , T. ; Ibi , A. ; Muroga , T. ; Miyata , S. ; Kato , T. ; Hirayama , T. ; Shiohara , Y. Appl. Phys. Lett. 2005 , 87 , 1 - 3 ), the effect of ordered oxide nanostructures remains essentially unexplored. This is due to the very small nanostructure size imposed by the short coherence length, and to the technological difficulties in the nanofabrication process. Yet, the novel phenomena occurring at oxide interfaces open a wide spectrum of technological opportunities to interplay with the superconductivity in cuprates. Here, we show that the unusual long-range suppression of the superconductivity occurring at the interface between manganites and cuprates affects vortex nucleation and provides a novel vortex pinning mechanism. In particular, we show evidence of commensurate pinning in YBCO films with ordered arrays of LCMO ferromagnetic nanodots. Vortex pinning results from the proximity induced reduction of the condensation energy at the vicinity of the magnetic nanodots, and yields an enhanced friction between the nanodot array and the moving vortex lattice in the liquid phase. This result shows that all-oxide ordered nanostructures constitute a powerful, new route for the artificial manipulation of vortex matter in cuprates. PMID:26441137

  16. NEPTUNIUM OXIDE PROCESSING

    SciTech Connect

    Jordan, J; Watkins, R; Hensel, S

    2009-05-27

    The Savannah River Site's HB-Line Facility completed a campaign in which fifty nine cans of neptunium oxide were produced and shipped to the Idaho National Laboratory in the 9975 shipping container. The neptunium campaign was divided into two parts: Part 1 which consisted of oxide made from H-Canyon neptunium solution which did not require any processing prior to conversion into an oxide, and Part 2 which consisted of oxide made from additional H-Canyon neptunium solutions which required processing to purify the solution prior to conversion into an oxide. The neptunium was received as a nitrate solution and converted to oxide through ion-exchange column extraction, precipitation, and calcination. Numerous processing challenges were encountered in order make a final neptunium oxide product that could be shipped in a 9975 shipping container. Among the challenges overcome was the issue of scale: translating lab scale production into full facility production. The balance between processing efficiency and product quality assurance was addressed during this campaign. Lessons learned from these challenges are applicable to other processing projects.

  17. 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.

  18. Advanced gas atomization production of oxide dispersion strengthened (ODS) Ni-base superalloys through process and solidification control

    NASA Astrophysics Data System (ADS)

    Meyer, John Louis Lamb

    A novel gas atomization reaction synthesis (GARS) method was utilized to produce precursor Ni-Cr-Y-Ti powder with a surface oxide and an internal rare earth (RE)-containing intermetallic. Although Al is necessary for industrial superalloy production, the Ni-Cr base alloy system was selected as a simplified system more amenable to characterization. This was done in an effort to better study the effects of processing parameters. Consolidation and heat-treatment were performed to promote the exchange of oxygen from the surface oxide to the RE intermetallic to form nanometric oxide dispersoids. Alloy selection was aided by an internal oxidation and serial grinding experiment that found that Hf-containing alloys may form more stable dispersoids than Ti-containing alloys, but the Hf-containing system exhibited five different oxide phases and two different intermetallics compared to the two oxide phases and one intermetallic in the Ti-containing alloys. Since the simpler Ti-containing system was easier to characterize, and make observations on the effects of processing parameters, the Ti-containing system was used for experimental atomization trials. An internal oxidation model was used to predict the heat treatment times necessary for dispersoid formation as a function of powder size and temperature. A new high-pressure gas atomization (HPGA) nozzle was developed with the aim of promoting fine powder production at scales similar to that of the high gas-flow and melt-flow of industrial atomizers. The atomization nozzle was characterized using schlieren imaging and aspiration pressure testing to determine the optimum melt delivery tip geometry and atomization pressure to promote enhanced secondary atomization mechanisms. Six atomization trials were performed to investigate the effects of gas atomization pressure and reactive-gas concentration on the particle size distribution (PSD). Also, the effect on the rapidly solidified microstructure (as a function of powder size

  19. Bi12Sr22Fe11O56: A new form of 2 2 0 1/0 2 0 1 “terraces” like structures, term m=6, n=11 of the [BiO2]m[Sr2FeO4]n family

    NASA Astrophysics Data System (ADS)

    Allix, Mathieu; Pelloquin, Denis; Raveau, Bernard

    2005-04-01

    A new oxide, namely Bi 12Sr 22Fe 11O 56, has been isolated in the Bi-Sr-Fe-O system. The transmission electronic microscopy studies carried out have permitted to characterise it as a double collapsed member derived from the regular intergrowth 2 2 0 1/0 2 0 1 type structure Bi 2Sr 4Fe 2O 10 (J. Solid State Chem. 118 (1995) 227). It crystallises in the space group I2 /a with the following parameters: a=38.82(1)Å,b=5.731(2),c=38.35(1)Å and β=121.31(2)°. Close relationships with the collapsed structure Bi 13Ba 2Sr 25Fe 13O 66 ( m=7,n=13) are shown. This new ferrite can be described as the ( m=6,n=11) member of the [Bi 2O 2] m[Sr 2FeO 4] n family. The stairs are then 6 bismuth atoms wide and the K 2NiF 4 layers are 11 FeO 6 octahedra thick. Moreover, the high-resolution electron microscopy images show the presence of local defects leading to the ( m=7,n=11) member. Another description of this structure is also considered: it can be understood as slices of the parent structure, Bi 2Sr 4Fe 2O 10, separated by shearing zones. If the last ones seem to be the same in all the members, the thickness of the first ones can vary and so leading to different members of the new [Bi 2Sr 4Fe 2O 10] w [Bi 4Sr 6Fe 3O 16] family.

  20. Periodate oxidation of dextrans

    SciTech Connect

    Mirgorodskaya, O.A.; Poletaeva, L.V.

    1986-03-01

    The authors estimate the degree of oxidation of the thiol group in dextran with various mol. wt. and make an attempt at a kinetic description of the main parameters of the process. Polyglucin was used. The results are shown of experiments done on the estimation of the amount of products formed in the process of oxidation of polyglucin in which the reaction stopped as a result of complete exhaustion of one of the original reagents. To estimate the reactivity of the thiol group toward oxidation, the authors studied the interaction of potassium periodate with alpha-D-glucose, isolated by the monomer unit of dextran.