Reactivity of tris(acetylacetonato) iron(III) with tridentate [ONO] donor Schiff base as an access to newer mixed-ligand iron(III) complexes.

PubMed

Bhattacharjee, Chira R; Goswami, Pankaj; Pramanik, Harun A R; Paul, Pradip C; Mondal, Paritosh

2011-05-01

Two new mixed-ligand iron(III) complexes, [Fe(L(n))(acac)(C(2)H(5)OH)] incorporating coordinated ethanol from the reaction solvent were accessed from the reaction of [Fe(acac)(3)] with [ONO] donor dibasic tridentate unsymmetrical Schiff base ligands derived from condensation of 2-hydroxy-1-napthaldehyde with 2-aminophenol (H(2)L(1)) or 2-aminobenzoic acid (H(2)L(2)). The thermal study (TGA-DTA) provided evidence for weakly bound ethanol which is readily substituted by neutral N-donor molecule imidazole, benzimidazole or pyridine to produce an array of newer complexes, [Fe(L(n))(acac)X] (n=1, 2; X=Im, Bim, Py). The compounds were characterized by elemental analyses, FT-IR, UV-vis, solution electrical conductivity, FAB mass, (1)H and (13)C NMR spectroscopy. Room temperature magnetic susceptibility measurements (μ(eff)∼5.8 B.M.) are consistent with spin-free octahedral iron(III) complexes. Cyclic voltammetry of ethanol complexes revealed a quasi-reversible one electron redox response (ΔE(p)>100 mV) for the Fe(III)/Fe(II) couple. Low half wave redox potential (E(1/2)) values suggested easy redox susceptibility. The ground state geometries of the ethanol and imidazole complexes have been ascertained to be distorted octahedral by density functional theory using DMol3 program at BLYP/DNP level. Copyright © 2011 Elsevier B.V. All rights reserved.

Bulk oxides: asymmetry between p-and n-type transport properties

NASA Astrophysics Data System (ADS)

Maignan, Antioine

2015-03-01

The thermoelectric power (TEP) of transition metal oxides shows large difference depending on the sign of the charge carriers. In electron-doped oxides, the best TEs in terms of the figure of merit are heavily doped transparent conductors (as doped ZnO). The physics is very similar to that of semiconductors, though the defects chemistry differs: the existence of planar defects created by the doping elements, is far from the random distribution in semiconductors. In contrast the best p-types are layered cobaltites (CdI2 -type layers with edge-shared CoO6 octahedras). The Co cations adopt a low spin state. Both electronic correlations and spin entropy have to be considered to explain the S(T) curve for T <150K, whereas for T>150K, the spin/orbital configurations and the doping level in the generalized Heikes formula are dominating. This description supported by the results obtained for perovskite ruthenates was recently unvalidated for the quadruple perovskite ACu3Ru4O12, showing very different S(T) without S saturation up to ~ 900K. Their Pauli paramagnetism enlights the role of the spins upon thermopower. Similarly, searching for other n-types, interesting TE properties have been found in Ba1.2Mn8O16: the S(T) evidences a charge/orbital ordering in this manganite (vMn = 3.7) coupled to an abrupt change in the unit-cell volume. Ba1.2Mn8O16, although of n-type, exhibits a cst. | S | ~ 92 μV.K-1 for T>400K, explained by the generalized Heikes formula rather used for p-type. This difference with other n-type oxides is related to the Mn3+/Mn4+ magnetism and the contribution of eg orbitals for the transport properties. In this presentation, the richness of the TE properties of metal transition oxides will be emphasized focusing on the important role of the spins.

Synthesis, characterization and electrochemistry studies of iron(III) complex with curcumin ligand.

PubMed

Özbolat, Gülüzar; Yegani, Arash Alizadeh; Tuli, Abdullah

2018-05-11

Iron overload is a serious clinical condition for humans and is a key target in drug development. The aim of this study was to investigate the coordination of iron(III) ions with curcumin ligand that may be used in the treatment of iron overload. Iron(III) complex of curcumin was synthesized and structurally characterized in its solid and solution state by FT-IR, UV-Vis, elemental analysis, and magnetic susceptibility. Electrochemical behaviour of the ligand and the complexes were examined using cyclic voltammetry. The cytotoxic activities of the ligand and the iron(III) complex were evaluated by the MTT assay. Curcumin reacted with iron in high concentrations at physiological pH at room temperature. Subsequently, a brown-red complex was formed. Data regarding magnetic susceptibility showed that the complexes with a 1:2 (metal/ligand) mole ratio had octahedral geometry. The complex showed higher anti-oxidant effect towards the cell line ECV304 at IC 50 values of 4.83 compared to curcumin. The complex exhibited very high cytotoxic activity and showed a cytotoxic effect that was much better than that of the ligand. The potentials for redox were calculated as 0.180 V and 0.350 V, respectively. The electrochemistry studies showed that Fe 3+ /Fe 2+ couple redox process occurred at low potentials. This value was within the range of compounds that are expected to show superoxide dismutase activity. This finding indicates that the iron complex is capable of removing free radicals. The observed cytotoxicity could be pursued to obtain a potential drug. Further studies investigating the use of curcumin for this purpose are needed. © 2018 John Wiley & Sons Australia, Ltd.

P-type ZnO:N Films Prepared by Thermal Oxidation of Zn3N2

NASA Astrophysics Data System (ADS)

Zhang, Bin; Li, Min; Wang, Jian-Zhong; Shi, Li-Qun

2013-02-01

We prepare p-type ZnO:N films by annealing Zn3N2 films in oxygen over a range of temperatures. The prepared films are characterized by various techniques, such as Rutherford backscattering spectroscopy, x-ray diffraction, x-ray photoemission spectroscopy, the Hall effect and photoluminescence spectra. The results show that the Zn3N2 films start to transform to ZnO at 300°C and the N content decreases with an increase in annealing temperature. N has two local chemical states: zinc oxynitride (ZnO1-xNx) and substitutional NO in O-rich local environments (α -NO). The conduction type changes from n-type to p-type upon oxidation at 400-600°C, indicating that N is an effective acceptor in the ZnO film. The photoluminescence spectra show the UV emission and defect-related emissions of ZnO:N films. The mechanism and efficiency of p-type doping are briefly discussed.

Synthesis of p-type nickel oxide nanosheets on n-type titanium dioxide nanorod arrays for p-n heterojunction-based UV photosensor

NASA Astrophysics Data System (ADS)

Yusoff, M. M.; Mamat, M. H.; Malek, M. F.; Abdullah, M. A. R.; Ismail, A. S.; Saidi, S. A.; Mohamed, R.; Suriani, A. B.; Khusaimi, Z.; Rusop, M.

2018-05-01

Titanium dioxide (TiO2) nanorod arrays (TNAs) were synthesized and deposited on fluorine tin oxide (FTO)-coated glass substrate using a novel and facile immersion method in a glass container. The synthesis and deposition of p-type nickel oxide (NiO) nanosheets (NS) on the n-type TNAs was investigated in the p-n heterojunction photodiode (PD) for the application of ultraviolet (UV) photosensor. The fabricated TNAs/NiO NS based UV photosensor exhibited a highly increased photocurrent of 4.3 µA under UV radiation (365 nm, 750 µW/cm2) at 1.0 V reverse bias. In this study, the fabricated TNAs/NiO NS p-n heterojunction based photodiode showed potential applications for UV photosensor based on the stable photo-generated current attained under UV radiation.

Selection Rule of Preferred Doping Site for n-Type Oxides

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

Li, C.; Li, J.; Li, S. S.

2012-06-25

Using first-principles calculations and analysis, we show that to create shallow n-type dopants in oxides, anion site doping is preferred for more covalent oxides such as SnO{sub 2} and cation site doping is preferred for more ionic oxides such as ZnO. This is because for more ionic oxides, the conduction band minimum (CBM) state actually contains a considerable amount of O 3s orbitals, thus anion site doping can cause large perturbation on the CBM and consequently produces deeper donor levels. We also show that whether it is cation site doping or anion site doping, the oxygen-poor condition should always bemore » used.« less

p-i-n heterojunctions with BiFeO3 perovskite nanoparticles and p- and n-type oxides: photovoltaic properties.

PubMed

Chatterjee, Soumyo; Bera, Abhijit; Pal, Amlan J

2014-11-26

We formed p-i-n heterojunctions based on a thin film of BiFeO3 nanoparticles. The perovskite acting as an intrinsic semiconductor was sandwiched between a p-type and an n-type oxide semiconductor as hole- and electron-collecting layer, respectively, making the heterojunction act as an all-inorganic oxide p-i-n device. We have characterized the perovskite and carrier collecting materials, such as NiO and MoO3 nanoparticles as p-type materials and ZnO nanoparticles as the n-type material, with scanning tunneling spectroscopy; from the spectrum of the density of states, we could locate the band edges to infer the nature of the active semiconductor materials. The energy level diagram of p-i-n heterojunctions showed that type-II band alignment formed at the p-i and i-n interfaces, favoring carrier separation at both of them. We have compared the photovoltaic properties of the perovskite in p-i-n heterojunctions and also in p-i and i-n junctions. From current-voltage characteristics and impedance spectroscopy, we have observed that two depletion regions were formed at the p-i and i-n interfaces of a p-i-n heterojunction. The two depletion regions operative at p-i-n heterojunctions have yielded better photovoltaic properties as compared to devices having one depletion region in the p-i or the i-n junction. The results evidenced photovoltaic devices based on all-inorganic oxide, nontoxic, and perovskite materials.

Dynamic desorption of arsenic from polymer-supported hydrated iron(III) oxide in a wastewater treatment plant.

PubMed

Hu, Jian-Long; Yang, Xiao-Song; Liu, Ting; Shao, Li-Nan; Zhang, Wang

2017-11-01

Polymer-supported hydrated iron(III) oxide (PHIO) was successfully applied as adsorbent for arsenic removal in a wastewater treatment plant in Nandan, China. The practical PHIO adsorbent samples (PHIO-P) were collected from the adsorption column of the wastewater treatment plant, and desorption experiments of the adsorbent were carried out. Our results showed that the formation of precipitates on the surface of PHIO-P might block the porous channel of the adsorbent and decrease its arsenic adsorption capacity. In the dynamic arsenic desorption experiment, the arsenic desorption equilibrium was achieved more quickly at decreasing desorption velocity, and higher arsenic desorption efficiency was obtained at increasing NaOH concentration in regenerant. It was found that the PHIO-P adsorbent could be well regenerated at 1.0 M NaOH solution and desorption velocity of 5 BV h -1 . Comparing with the raw adsorbent, the maximum arsenic adsorption capacity of PHIO-P decreased by 41.1% after practical running for 26 months. Additionally, the frequently used waste PHIO adsorbent could be treated as non-hazardous material in the arsenic-containing wastewater treatment process after long-time use.

Influence of the type of oxidant on anion exchange properties of fibrous Cladophora cellulose/polypyrrole composites.

PubMed

Razaq, Aamir; Mihranyan, Albert; Welch, Ken; Nyholm, Leif; Strømme, Maria

2009-01-15

The electrochemically controlled anion absorption properties of a novel large surface area composite paper material composed of polypyrrole (PPy) and cellulose derived from Cladophora sp. algae, synthesized with two oxidizing agents, iron(III) chloride and phosphomolybdic acid (PMo), were analyzed in four different electrolytes containing anions (i.e., chloride, aspartate, glutamate, and p-toluenesulfonate) of varying size.The composites were characterized with scanning and transmission electron microscopy, N2 gas adsorption,and conductivity measurements. The potential-controlled ion exchange properties of the materials were studied by cyclic voltammetry and chronoamperometry at varying potentials. The surface area and conductivity of the iron(III) chloride synthesized sample were 58.8 m2/g and 0.65 S/cm, respectively, while the corresponding values for the PMo synthesized sample were 31.3 m2/g and 0.12 S/cm. The number of absorbed ions per sample mass was found to be larger for the iron(III) chloride synthesized sample than for the PMo synthesized one in all four electrolytes. Although the largest extraction yields were obtained in the presence of the smallest anion (i.e., chloride) for both samples, the relative degree of extraction for the largest ions (i.e., glutamate and p-toluenesulfonate) was higher for the PMo sample. This clearly shows that it is possible to increase the extraction yield of large anions by carrying out the PPy polymerization in the presence of large anions. The results likewise show that high ion exchange capacities, as well as extraction and desorption rates, can be obtained for large anions with high surface area composites coated with relatively thin layers of PPy.

Arsenic removal with iron(II) and iron(III) in waters with high silicate and phosphate concentrations.

PubMed

Roberts, Linda C; Hug, Stephan J; Ruettimann, Thomas; Billah, Morsaline; Khan, Abdul Wahab; Rahman, Mohammad Tariqur

2004-01-01

Arsenic removal by passive treatment, in which naturally present Fe(II) is oxidized by aeration and the forming iron(III) (hydr)oxides precipitate with adsorbed arsenic, is the simplest conceivable water treatment option. However, competing anions and low iron concentrations often require additional iron. Application of Fe(II) instead of the usually applied Fe(III) is shown to be advantageous, as oxidation of Fe(II) by dissolved oxygen causes partial oxidation of As(III) and iron(III) (hydr)oxides formed from Fe(II) have higher sorption capacities. In simulated groundwater (8.2 mM HCO3(-), 2.5 mM Ca2+, 1.6 mM Mg2+, 30 mg/L Si, 3 mg/L P, 500 ppb As(III), or As(V), pH 7.0 +/- 0.1), addition of Fe(II) clearly leads to better As removal than Fe(III). Multiple additions of Fe(II) further improved the removal of As(II). A competitive coprecipitation model that considers As(III) oxidation explains the observed results and allows the estimation of arsenic removal under different conditions. Lowering 500 microg/L As(III) to below 50 microg/L As(tot) in filtered water required > 80 mg/L Fe(III), 50-55 mg/L Fe(II) in one single addition, and 20-25 mg/L in multiple additions. With As(V), 10-12 mg/L Fe(II) and 15-18 mg/L Fe(III) was required. In the absence of Si and P, removal efficiencies for Fe(II) and Fe(III) were similar: 30-40 mg/L was required for As(II), and 2.0-2.5 mg/L was required for As(V). In a field study with 22 tubewells in Bangladesh, passive treatment efficiently removed phosphate, but iron contents were generally too low for efficient arsenic removal.

Metachelins, mannosylated and N-oxidized coprogen-type siderophores from Metarhizium robertsii

USDA-ARS?s Scientific Manuscript database

Under iron-depleted culture conditions, the entomopathogenic fungus Metarhizium robertsii (Bischoff, Humber, and Rehner) (= M. anisopliae) produces a complex of extracellular siderophores including novel O-glycosylated and/or N-oxidized coprogen-type compounds as well as the known fungal siderophore...

Large area tunnel oxide passivated rear contact n -type Si solar cells with 21.2% efficiency: Large area tunnel oxide passivated rear contact n -type Si solar cells

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

Tao, Yuguo; Upadhyaya, Vijaykumar; Chen, Chia-Wei

This paper reports on the implementation of carrier-selective tunnel oxide passivated rear contact for high-efficiency screen-printed large area n-type front junction crystalline Si solar cells. It is shown that the tunnel oxide grown in nitric acid at room temperature (25°C) and capped with n+ polysilicon layer provides excellent rear contact passivation with implied open-circuit voltage iVoc of 714mV and saturation current density J0b of 10.3 fA/cm2 for the back surface field region. The durability of this passivation scheme is also investigated for a back-end high temperature process. In combination with an ion-implanted Al2O3-passivated boron emitter and screen-printed front metal grids,more » this passivated rear contact enabled 21.2% efficient front junction Si solar cells on 239 cm2 commercial grade n-type Czochralski wafers.« less

Metal-oxide-semiconductor devices using Ga2O3 dielectrics on n-type GaN

NASA Astrophysics Data System (ADS)

Lee, Ching-Ting; Chen, Hong-Wei; Lee, Hsin-Ying

2003-06-01

Using a photoelectrochemical method involving a He-Cd laser, Ga2O3 oxide layers were directly grown on n-type GaN. We demonstrated the performance of the resultant metal-oxide-semiconductor devices based on the grown Ga2O3 layer. An extremely low reverse leakage current of 200 pA was achieved when devices operated at -20 V. Furthermore, high forward and reverse breakdown electric fields of 2.80 MV/cm and 5.70 MV/cm, respectively, were obtained. Using a photoassisted current-voltage method, a low interface state density of 2.53×1011 cm-2 eV-1 was estimated. The varactor devices permit formation of inversion layers, so that they may be applied for the fabrication of metal-oxide-semiconductor field-effect transistors.

Biochar type and factors affecting N transformation, ammonia volatilization, and nitrous oxide emissions

USDA-ARS?s Scientific Manuscript database

Soil amendment with biochar has shown the potential to improve nitrogen (N) availability for plant uptake and reduce environmental losses via ammonia (NH3) and nitrous oxide (N2O) emissions. There are still many unknowns on how biochar type and soil conditions affect N dynamics and processes associa...

Benzyl and Methyl Fatty Hydroxamic Acids Based on Palm Kernel Oil as Chelating Agent for Liquid-Liquid Iron(III) Extraction

PubMed Central

Haron, Md Jelas; Jahangirian, Hossein; Silong, Sidik; Yusof, Nor Azah; Kassim, Anuar; Rafiee-Moghaddam, Roshanak; Mahdavi, Behnam; Peyda, Mazyar; Abdollahi, Yadollah; Amin, Jamileh

2012-01-01

Liquid-liquid iron(III) extraction was investigated using benzyl fatty hydroxamic acids (BFHAs) and methyl fatty hydroxamic acids (MFHAs) as chelating agents through the formation of iron(III) methyl fatty hydroxamate (Fe-MFHs) or iron(III) benzyl fatty hydroxamate (Fe-BFHs) in the organic phase. The results obtained under optimized conditions, showed that the chelating agents in hexane extract iron(III) at pH 1.9 were realized effectively with a high percentage of extraction (97.2% and 98.1% for MFHAs and BFHAs, respectively). The presence of a large amount of Mg(II), Ni(II), Al(III), Mn(II) and Co(II) ions did affect the iron(III) extraction. Finally stripping studies for recovering iron(III) from organic phase (Fe-MFHs or Fe-BFHs dissolved in hexane) were carried out at various concentrations of HCl, HNO3 and H2SO4. The results showed that the desired acid for recovery of iron(III) was 5 M HCl and quantitative recovery of iron(III) was achieved from Fe(III)-MFHs and Fe(III)-BFHs solutions in hexane containing 5 mg/L of Fe(III). PMID:22408444

Silicon heterojunction solar cells with novel fluorinated n-type nanocrystalline silicon oxide emitters on p-type crystalline silicon

NASA Astrophysics Data System (ADS)

Dhar, Sukanta; Mandal, Sourav; Das, Gourab; Mukhopadhyay, Sumita; Pratim Ray, Partha; Banerjee, Chandan; Barua, Asok Kumar

2015-08-01

A novel fluorinated phosphorus doped silicon oxide based nanocrystalline material have been used to prepare heterojunction solar cells on flat p-type crystalline silicon (c-Si) Czochralski (CZ) wafers. The n-type nc-SiO:F:H material were deposited by radio frequency plasma enhanced chemical vapor deposition. Deposited films were characterized in detail by using atomic force microscopy (AFM), high resolution transmission electron microscopy (HRTEM), Raman, fourier transform infrared spectroscopy (FTIR) and optoelectronics properties have been studied using temperature dependent conductivity measurement, Ellipsometry, UV-vis spectrum analysis etc. It is observed that the cell fabricated with fluorinated silicon oxide emitter showing higher initial efficiency (η = 15.64%, Jsc = 32.10 mA/cm2, Voc = 0.630 V, FF = 0.77) for 1 cm2 cell area compare to conventional n-a-Si:H emitter (14.73%) on flat c-Si wafer. These results indicate that n type nc-SiO:F:H material is a promising candidate for heterojunction solar cell on p-type crystalline wafers. The high Jsc value is associated with excellent quantum efficiencies at short wavelengths (<500 nm).

Spectroscopic, potentiometric and theoretical studies on the binding properties of a novel tripodal polycatechol-imine ligand towards iron(III)

NASA Astrophysics Data System (ADS)

Kanungo, B. K.; Sahoo, Suban K.; Baral, Minati

2008-12-01

A novel multidentate tripodal ligand, cis, cis-1,3,5-tris[(2,3-dihydroxybenzylidene)aminomethyl]cyclohexane (TDBAC, L) containing one catechol unit in each arms of a tripodal amine, cis, cis-1,3,5-tris(aminomethyl)cyclohexane was investigated as a chelator for iron(III) through potentiometric and spectrophotometric methods in an aqueous medium of 0.1N ionic strength and 25 ± 1 °C as well as in ethanol by continuous variation method. From pH metric in water, three protonation constants characterized for the three-hydroxyl groups of the catechol units at ortho were used as input data to evaluate the stability constants of the complexes. Formation of monomeric complexes FeLH 3, FeLH 2, FeLH and FeL were depicted. In ethanol, formation of complexes FeL, Fe 2L and Fe 3L were characterized. Structures of the complexes were explained by using the experimental evidences and predicted through molecular modeling calculations. The ligand showed potential to coordinate iron(III) through three imine nitrogens and three catecholic oxygens at ortho to form a tris(iminocatecholate) type complex.

Perspective: n-type oxide thermoelectrics via visual search strategies

DOE PAGES

Xing, Guangzong; Sun, Jifeng; Ong, Khuong P.; ...

2016-02-12

We discuss and present search strategies for finding new thermoelectric compositions based on first principles electronic structure and transport calculations. We illustrate them by application to a search for potential n-type oxide thermoelectric materials. This includes a screen based on visualization of electronic energy isosurfaces. Lastly, we report compounds that show potential as thermoelectric materials along with detailed properties, including SrTiO 3, which is a known thermoelectric, and appropriately doped KNbO 3 and rutile TiO 2.

Perspective: n-type oxide thermoelectrics via visual search strategies

NASA Astrophysics Data System (ADS)

Xing, Guangzong; Sun, Jifeng; Ong, Khuong P.; Fan, Xiaofeng; Zheng, Weitao; Singh, David J.

2016-05-01

We discuss and present search strategies for finding new thermoelectric compositions based on first principles electronic structure and transport calculations. We illustrate them by application to a search for potential n-type oxide thermoelectric materials. This includes a screen based on visualization of electronic energy isosurfaces. We report compounds that show potential as thermoelectric materials along with detailed properties, including SrTiO3, which is a known thermoelectric, and appropriately doped KNbO3 and rutile TiO2.

Heterojunction solar cell with 6% efficiency based on an n-type aluminum-gallium-oxide thin film and p-type sodium-doped Cu2O sheet

NASA Astrophysics Data System (ADS)

Minami, Tadatsugu; Nishi, Yuki; Miyata, Toshihiro

2015-02-01

In this paper, we describe efforts to enhance the efficiency of Cu2O-based heterojunction solar cells fabricated with an aluminum-gallium-oxide (Al-Ga-O) thin film as the n-type layer and a p-type sodium (Na)-doped Cu2O (Cu2O:Na) sheet prepared by thermally oxidizing copper sheets. The optimal Al content [X; Al/(Ga + Al) atomic ratio] of an AlX-Ga1-X-O thin-film n-type layer was found to be approximately 2.5 at. %. The optimized resistivity was approximately 15 Ω cm for n-type AlX-Ga1-X-O/p-type Cu2O:Na heterojunction solar cells. A MgF2/AZO/Al0.025-Ga0.975-O/Cu2O:Na heterojunction solar cell with 6.1% efficiency was fabricated using a 60-nm-thick n-type oxide thin-film layer and a 0.2-mm-thick Cu2O:Na sheet with the optimized resistivity.

Real-time photoelectron spectroscopy study of the oxidation reaction kinetics on p-type and n-type Si (001) surfaces

NASA Astrophysics Data System (ADS)

Yu, Zhou

Silicon oxides thermally grown on Si surface are the core gate materials of metal-oxide-semiconductor field effect transistor (MOSFET). This thin oxide layer insulates the gate terminals and the transistors substrate which make MOSFET has certain advantages over those conventional junctions, such as field-effect transistor (FET) and junction field effect transistor (JFET). With an oxide insulating layer, MOSFET is able to sustain higher input impedance and the corresponding gate leakage current can be minimized. Today, though the oxidation process on Si substrate is popular in industry, there are still some uncertainties about its oxidation kinetics. On a path to clarify and modeling the oxidation kinetics, a study of initial oxidation kinetics on Si (001) surface has attracted attentions due to having a relatively low surface electron density and few adsorption channels compared with other Si surface direction. Based on previous studies, there are two oxidation models of Si (001) that extensively accepted, which are dual oxide species mode and autocatalytic reaction model. These models suggest the oxidation kinetics on Si (001) mainly relies on the metastable oxygen atom on the surface and the kinetic is temperature dependent. Professor Yuji Takakuwa's group, Surface Physics laboratory, Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, observed surface strain existed during the oxidation kinetics on Si (001) and this is the first time that strain was discovered during Si oxidation. Therefore, it is necessary to explain where the strain comes from since none of previous model research included the surface strain (defects generation) into considerations. Moreover, recent developing of complementary metal-oxide-semiconductor (CMOS) requires a simultaneous oxidation process on p- and n-type Si substrate. However, none of those previous models included the dopant factor into the oxidation kinetic modeling. All of these points that

Ferrate(VI)-induced arsenite and arsenate removal by in situ structural incorporation into magnetic iron(III) oxide nanoparticles.

PubMed

Prucek, Robert; Tuček, Jiří; Kolařík, Jan; Filip, Jan; Marušák, Zdeněk; Sharma, Virender K; Zbořil, Radek

2013-04-02

We report the first example of arsenite and arsenate removal from water by incorporation of arsenic into the structure of nanocrystalline iron(III) oxide. Specifically, we show the capability to trap arsenic into the crystal structure of γ-Fe2O3 nanoparticles that are in situ formed during treatment of arsenic-bearing water with ferrate(VI). In water, decomposition of potassium ferrate(VI) yields nanoparticles having core-shell nanoarchitecture with a γ-Fe2O3 core and a γ-FeOOH shell. High-resolution X-ray photoelectron spectroscopy and in-field (57)Fe Mössbauer spectroscopy give unambiguous evidence that a significant portion of arsenic is embedded in the tetrahedral sites of the γ-Fe2O3 spinel structure. Microscopic observations also demonstrate the principal effect of As doping on crystal growth as reflected by considerably reduced average particle size and narrower size distribution of the "in-situ" sample with the embedded arsenic compared to the "ex-situ" sample with arsenic exclusively sorbed on the iron oxide nanoparticle surface. Generally, presented results highlight ferrate(VI) as one of the most promising candidates for advanced technologies of arsenic treatment mainly due to its environmentally friendly character, in situ applicability for treatment of both arsenites and arsenates, and contrary to all known competitive technologies, firmly bound part of arsenic preventing its leaching back to the environment. Moreover, As-containing γ-Fe2O3 nanoparticles are strongly magnetic allowing their separation from the environment by application of an external magnet.

Comparison of the IN VITRO Cytotoxicities of Nitrogen Doped (p-TYPE) and n-TYPE Zinc Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Fujihara, Junko; Hashimoto, Hideki; Nishimoto, Naoki; Tongu, Miki; Fujita, Yasuhisa

The use of NPs in the health care field is increasing. Before their biological application, investigating the toxicities of both n-type ZnO nanoparticles (NPs) and nitrogen-doped (“p-type”) NPs is important. Using L929 cells, the cell viability, oxidative stress, apoptosis induction, inflammatory responses, and cellular uptake were assayed 24h after the addition of n-type ZnO NPs and nitrogen-doped NPs (which act as p-type) (25μg/mL). The ZnO NPs were fabricated using a gas evaporation method. Increased H2O2 generation and decreased levels of glutathione were more evident in with n-type than in those treated with nitrogen-doped (“p-type”) ZnO NPs. Caspase-3/-7 activity was higher in cells treated with n-type ZnO NPs than in those treated with nitrogen-doped (“p-type”) NPs. Elevated levels of TNF-α and IL-1β were observed in cell culture supernatants: IL-1β levels were higher in n-type ZnO NPs than nitrogen-doped (“p-type”) NPs. The cellular Zn uptake of n-type ZnO NPs was higher than nitrogen-doped (“p-type”) NPs. These findings show that n-type ZnO NPs have higher cytotoxicity than nitrogen-doped (“p-type”) ZnO NPs. This may be due to a reductive effect of n-type ZnO NPs that induces higher free radical production, reactive oxygen species (ROS) generation, and cellular uptake of this type of ZnO NPs.

Mechanisms and efficiency of the simultaneous removal of metals and cyanides by using ferrate(VI): crucial roles of nanocrystalline iron(III) oxyhydroxides and metal carbonates.

PubMed

Filip, Jan; Yngard, Ria A; Siskova, Karolina; Marusak, Zdenek; Ettler, Vojtech; Sajdl, Petr; Sharma, Virender K; Zboril, Radek

2011-08-29

The reaction of potassium ferrate(VI), K(2)FeO(4), with weak-acid dissociable cyanides--namely, K(2)[Zn(CN)(4)], K(2)[Cd(CN)(4)], K(2)[Ni(CN)(4)], and K(3)[Cu(CN)(4)]--results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2-line ferrihydrite, 7-line ferrihydrite, and/or goethite. Based on the results of XRD, Mössbauer and IR spectroscopies, as well as TEM, X-ray photoelectron emission spectroscopy, and Brunauer-Emmett-Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd-bearing, X-ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Real-Time Studies of Iron Oxalate-Mediated Oxidation of Glycolaldehyde as a Model for Photochemical Aging of Aqueous Tropospheric Aerosols.

PubMed

Thomas, Daniel A; Coggon, Matthew M; Lignell, Hanna; Schilling, Katherine A; Zhang, Xuan; Schwantes, Rebecca H; Flagan, Richard C; Seinfeld, John H; Beauchamp, J L

2016-11-15

The complexation of iron(III) with oxalic acid in aqueous solution yields a strongly absorbing chromophore that undergoes efficient photodissociation to give iron(II) and the carbon dioxide anion radical. Importantly, iron(III) oxalate complexes absorb near-UV radiation (λ > 350 nm), providing a potentially powerful source of oxidants in aqueous tropospheric chemistry. Although this photochemical system has been studied extensively, the mechanistic details associated with its role in the oxidation of dissolved organic matter within aqueous aerosol remain largely unknown. This study utilizes glycolaldehyde as a model organic species to examine the oxidation pathways and evolution of organic aerosol initiated by the photodissociation of aqueous iron(III) oxalate complexes. Hanging droplets (radius 1 mm) containing iron(III), oxalic acid, glycolaldehyde, and ammonium sulfate (pH ∼3) are exposed to irradiation at 365 nm and sampled at discrete time points utilizing field-induced droplet ionization mass spectrometry (FIDI-MS). Glycolaldehyde is found to undergo rapid oxidation to form glyoxal, glycolic acid, and glyoxylic acid, but the formation of high molecular weight oligomers is not observed. For comparison, particle-phase experiments conducted in a laboratory chamber explore the reactive uptake of gas-phase glycolaldehyde onto aqueous seed aerosol containing iron and oxalic acid. The presence of iron oxalate in seed aerosol is found to inhibit aerosol growth. These results suggest that photodissociation of iron(III) oxalate can lead to the formation of volatile oxidation products in tropospheric aqueous aerosols.

First principles search for n-type oxide, nitride, and sulfide thermoelectrics

PubMed Central

Garrity, Kevin F.

2016-01-01

Oxides have many potentially desirable characteristics for thermoelectric applications, including low cost and stability at high temperatures, but thus far there are few known high zT n-type oxide thermoelectrics. In this work, we use high-throughput first principles calculations to screen transition metal oxides, nitrides, and sulfides for candidate materials with high power factors and low thermal conductivity. We find a variety of promising materials, and we investigate these materials in detail in order to understand the mechanisms that cause them to have high power factors. These materials all combine a high density of states near the Fermi level with dispersive bands, reducing the trade-off between the Seebeck coefficient and the electrical conductivity, but they do so for several different reasons. In addition, our calculations indicate that many of our candidate materials have low thermal conductivity. PMID:27885361

Abrupt spin transition with thermal hysteresis of iron(III) complex [Fe(III)(Him)2(hapen)]AsF6 (Him = imidazole, H2hapen = N,N'-bis(2-hydroxyacetophenylidene)ethylenediamine).

PubMed

Fujinami, Takeshi; Koike, Masataka; Matsumoto, Naohide; Sunatsuki, Yukinari; Okazawa, Atsushi; Kojima, Norimichi

2014-02-17

The solvent-free spin crossover iron(III) complex [Fe(III)(Him)2(hapen)]AsF6 (Him = imidazole, H2hapen = N,N'-bis(2-hydroxyacetophenylidene)ethylenediamine), exhibiting thermal hysteresis, was synthesized and characterized. The Fe(III) ion has an octahedral coordination geometry, with N2O2 donor atoms of the planar tetradentate ligand (hapen) and two nitrogen atoms of two imidazoles at the axial positions. One of two imidazoles is hydrogen-bonded to the phenoxo oxygen atom of hapen of the adjacent unit to give a hydrogen-bonded one-dimensional chain, while the other imidazole group is free from hydrogen bonding. The temperature dependencies of the magnetic susceptibilities and Mössbauer spectra revealed an abrupt spin transition between the high-spin (S = 5/2) and low-spin (S = 1/2) states, with thermal hysteresis.

Molecular structure, magnetic properties, cyclic voltammetry of the low-spin iron(III) Bis(4-ethylaniline) complex with the para-chloro substituted meso-tetraphenylporphyrin

NASA Astrophysics Data System (ADS)

Dhifaoui, Selma; Mchiri, Chadlia; Quatremare, Pierre; Marvaud, Valérie; Bujacz, Anna; Nasri, Habib

2018-02-01

In this study, the preparation of a new iron(III) hexacoordinated metalloporphyrin namely the bis(4-ethylaniline){meso-tetra(para-chlorophenyl)porphyrinato}iron(III) triflate hemi-4-ethylaniline monohydrate with the formula [FeIII(TClPP)(PhEtNH2)2]SO3CF3•1/2PhEtNH2•H2O (I) was reported. This is the first example of an iron(III) metalloporphyrin bis(primary amine) with an aryl group adjacent to the amino group. This species was characterized by elemental, spectroscopic analysis including UV-visible and IR data, cyclic voltammetry, SQUID measurements and X-ray molecular structure. The mean equatorial distance between the iron(III) and the nitrogens of the porphyrin is appropriate for a low-spin (S = 1/2) iron(III) porphyrin complex. The magnetic data confirm the low-spin state of our ferric derivative while the cyclic voltammetry indicates a shift of the half potential E1/2[Fe(III)/Fe(II)] of complex (I) toward more negative value. In the crystal of (I), the [FeIII(TClPP)(PhEtNH2)2]+ ions, the triflate counterions and the water molecules are involved in a number of O__H⋯O, N__H⋯O, C-H⋯O and C__H⋯π intermolecular interactions forming a three-dimension network.

Recent progress in oxide thermoelectric materials: p-type Ca3Co4O9 and n-type SrTiO3(-).

PubMed

Ohta, Hiromichi; Sugiura, Kenji; Koumoto, Kunihito

2008-10-06

Thermoelectric energy conversion technology to convert waste heat into electricity has received much attention. In addition, metal oxides have recently been considered as thermoelectric power generation materials that can operate at high temperatures on the basis of their potential advantages over heavy metallic alloys in chemical and thermal robustness. We have fabricated high-quality epitaxial films composed of oxide thermoelectric materials that are suitable for clarifying the intrinsic "real" properties. This review focuses on the thermoelectric properties of two representative oxide epitaxial films, p-type Ca 3Co 4O 9 and n-type SrTiO 3, which exhibit the best thermoelectric figures of merit, ZT (= S (2)sigma Tkappa (-1), S = Seebeck coefficient, sigma = electrical conductivity, kappa = thermal conductivity, and T = absolute temperature) among oxide thermoelectric materials reported to date. In addition, we introduce the recently discovered giant S of two-dimensional electrons confined within a unit cell layer thickness ( approximately 0.4 nm) of SrTiO 3.

MOCVD Growth and Characterization of n-type Zinc Oxide Thin Films

NASA Astrophysics Data System (ADS)

Ben-Yaacov, Tammy

In the past decade, there has been widespread effort in the development of zinc oxide as a II-V1 semiconductor material. ZnO has potential advantages in optoelectronip device applications due to its unique electrical and optical properties. What stands out among these properties is its wide direct bandgap of 3.37 eV and its high electrical conductivity and transparency in the visible and near-UV regions of the spectrum. ZnO can be grown heteroepitaxially on GaN under near lattice-matched conditions and homoepitaxially as well, as high-quality bulk ZnO substrates are commercially available. This dissertation focuses on the development of the growth of high-quality, single crystal n-type ZnO films, control of n-type conductivity, as well as its application as a transparent contact material in GaN-based devices. The first part of this dissertation is an extensive heteroepitaxial and homoepitaxial growth study presenting the properties of ZnO(0001) layers grown on GaN(0001) templates and ZnO(0001) substrates. We show that deposition on GaN requires a two-step growth technique involving the growth of a low temperature nucleation layer before growing a high temperature epitaxial layer in order to obtain smooth ZnO films with excellent crystal quality and step-flow surface morphology. We obtained homoepitaxial ZnO(0001) films of structural quality and surface morphology that is comparable to the as-received substrates, and showed that a high growth temperature (≥1000°C) is needed in order to achieve step-flow growth mode. We performed n-type doping experiments, and established the conditions for which Indium effectively controls the n-type conductivity of ZnO films grown on GaN(0001) templates. A peak carrier concentration of 3.22x 10 19cm-3 and minimum sheet resistance of 97 O/square was achieved, while simultaneously maintaining good morphology and crystal quality. Finally, we present In-doped ZnO films implemented as p-contacts for GaN-based solar cells and LEDs

Amide-N-oxide heterosynthon and amide dimer homosynthon in cocrystals of carboxamide drugs and pyridine N-oxides.

PubMed

Babu, N Jagadeesh; Reddy, L Sreenivas; Nangia, Ashwini

2007-01-01

The carboxamide-pyridine N-oxide heterosynthon is sustained by syn(amide)N-H...O-(oxide) hydrogen bond and auxiliary (N-oxide)C-H...O(amide) interaction (Reddy, L. S.; Babu, N. J.; Nangia, A. Chem. Commun. 2006, 1369). We evaluate the scope and utility of this heterosynthon in amide-containing molecules and drugs (active pharmaceutical ingredients, APIs) with pyridine N-oxide cocrystal former molecules (CCFs). Out of 10 cocrystals in this study and 7 complexes from previous work, amide-N-oxide heterosynthon is present in 12 structures and amide dimer homosynthon occurs in 5 structures. The amide dimer is favored over amide-N-oxide synthon in cocrystals when there is competition from another H-bonding functional group, e.g., 4-hydroxybenzamide, or because of steric factors, as in carbamazepine API. The molecular organization in carbamazepine.quinoxaline N,N'-dioxide 1:1 cocrystal structure is directed by amide homodimer and anti(amide)N-H...O-(oxide) hydrogen bond. Its X-ray crystal structure matches with the third lowest energy frame calculated in Polymorph Predictor (Cerius(2), COMPASS force field). Apart from generating new and diverse supramolecular structures, hydration is controlled in one substance. 4-Picoline N-oxide deliquesces within a day, but its cocrystal with barbital does not absorb moisture at 50% RH and 30 degrees C up to four weeks. Amide-N-oxide heterosynthon has potential utility in both amide and N-oxide type drug molecules with complementary CCFs. Its occurrence probability in the Cambridge Structural Database is 87% among 27 structures without competing acceptors and 78% in 41 structures containing OH, NH, H(2)O functional groups.

FATE, TRANSFORMATION AND TOXICITY OF MANUFACTURED NANOMATERIALS IN DRINKING WATER

EPA Science Inventory

Studies were conducted using several types of commercial metal oxide nanoparticles (two types of titanium dioxide, iron(III) oxide, zinc oxide, nickel oxide, and silica in powder form or liquid suspensions), functionalized quantum dots, lab-synthesized hematite nanoparticles a...

Au-Doped Indium Tin Oxide Ohmic Contacts to p-Type GaN

NASA Astrophysics Data System (ADS)

Guo, H.; Andagana, H. B.; Cao, X. A.

2010-05-01

Indium tin oxide (ITO) thin films doped with Au, Ni, or Pt (3.5 at.% to 10.5 at.%) were deposited on p-GaN epilayers (Mg ~4 × 1019 cm-3) using direct-current (DC) sputter codeposition. It was found that undoped ITO con- tacts to p-GaN exhibited leaky Schottky behavior, whereas the incorporation of a small amount of Au (3.5 at.% to 10.5 at.%) significantly improved their ohmic characteristics. Compared with standard Ni/ITO contacts, the Au-doped ITO contacts had a similar specific contact resistance in the low 10-2 Ω cm-2 range, but were more stable above 600°C and more transparent at blue wavelengths. These results provide support for the use of Au-doped ITO ohmic contact to p-type GaN in high-brightness blue light-emitting diodes.

Cloud point extraction of iron(III) and vanadium(V) using 8-quinolinol derivatives and Triton X-100 and determination of 10(-7)moldm(-3) level iron(III) in riverine water reference by a graphite furnace atomic absorption spectroscopy.

PubMed

Ohashi, Akira; Ito, Hiromi; Kanai, Chikako; Imura, Hisanori; Ohashi, Kousaburo

2005-01-30

The cloud point extraction behavior of iron(III) and vanadium(V) using 8-quinolinol derivatives (HA) such as 8-quinolinol (HQ), 2-methyl-8-quinolinol (HMQ), 5-butyloxymethyl-8-quinolinol (HO(4)Q), 5-hexyloxymethyl-8-quinolinol (HO(6)Q), and 2-methyl-5-octyloxymethyl-8-quinolinol (HMO(8)Q) and Triton X-100 solution was investigated. Iron(III) was extracted with HA and 4% (v/v) Triton X-100 in the pH range of 1.70-5.44. Above pH 4.0, more than 95% of iron(III) was extracted with HQ, HMQ, and HMO(8)Q. Vanadium(V) was also extracted with HA and 4% (v/v) Triton X-100 in the pH range of 2.07-5.00, and the extractability increased in the following order of HMQ < HQ < HO(4)Q < HO(6)Q. The cloud point extraction was applied to the determination of iron(III) in the riverine water reference by a graphite furnace atomic absorption spectroscopy. When 1.25 x 10(-3)M HMQ and 1% (v/v) Triton X-100 were used, the found values showed a good agreement with the certified ones within the 2% of the R.S.D. Moreover, the effect of an alkyl group on the solubility of 5-alkyloxymethyl-8-quinolinol and 2-methyl-5-alkyloxymethyl-8-quinolinol in 4% (v/v) Triton X-100 at 25 degrees C was also investigated.

P-type transparent conducting oxides.

PubMed

Zhang, Kelvin H L; Xi, Kai; Blamire, Mark G; Egdell, Russell G

2016-09-28

Transparent conducting oxides constitute a unique class of materials combining properties of electrical conductivity and optical transparency in a single material. They are needed for a wide range of applications including solar cells, flat panel displays, touch screens, light emitting diodes and transparent electronics. Most of the commercially available TCOs are n-type, such as Sn doped In2O3, Al doped ZnO, and F doped SnO2. However, the development of efficient p-type TCOs remains an outstanding challenge. This challenge is thought to be due to the localized nature of the O 2p derived valence band which leads to difficulty in introducing shallow acceptors and large hole effective masses. In 1997 Hosono and co-workers (1997 Nature 389 939) proposed the concept of 'chemical modulation of the valence band' to mitigate this problem using hybridization of O 2p orbitals with close-shell Cu 3d (10) orbitals. This work has sparked tremendous interest in designing p-TCO materials together with deep understanding the underlying materials physics. In this article, we will provide a comprehensive review on traditional and recently emergent p-TCOs, including Cu(+)-based delafossites, layered oxychalcogenides, nd (6) spinel oxides, Cr(3+)-based oxides (3d (3)) and post-transition metal oxides with lone pair state (ns (2)). We will focus our discussions on the basic materials physics of these materials in terms of electronic structures, doping and defect properties for p-type conductivity and optical properties. Device applications based on p-TCOs for transparent p-n junctions will also be briefly discussed.

Detox{sup SM} wet oxidation system studies for engineering scale up

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

Robertson, D.T.; Moslander, J.E.; Zigmond, J.A.

1995-12-31

Catalyzed wet oxidation utilizing iron(III) has been shown to have promise for treating many hazardous and mixed wastes. The reaction occurs at the surface of contact between an aqueous iron(III) solution and organic material. Studies with liquid- and vapor-phase organic waste surrogates have established reaction kinetics and the limits of reaction rate based on organic concentration and iron(III) diffusion. Continuing engineering studies have concentrated on reaction vessel agitator and solids feed configurations, an improved bench scale reflux condenser and reflux condenser calculations, sparging of organic compounds from the process condensate water, filtration of solids from the process solution, and flammabilitymore » limits for volatile organic compounds in the headspace of the reaction vessel under the reaction conditions. Detailed engineering design and fabrication of a demonstration unit for treatment of mixed waste is in progress.« less

Development of p-type oxide semiconductors based on tin oxide and its alloys: application to thin film transistors

NASA Astrophysics Data System (ADS)

Barros, Ana Raquel Xarouco de

In spite of the recent p-type oxide TFTs developments based on SnOx and CuxO, the results achieved so far refer to devices processed at high temperatures and are limited by a low hole mobility and a low On-Off ratio and still there is no report on p-type oxide TFTs with performance similar to n-type, especially when comparing their field-effect mobility values, which are at least one order of magnitude higher on n-type oxide TFTs. Achieving high performance p-type oxide TFTs will definitely promote a new era for electronics in rigid and flexible substrates, away from silicon. None of the few reported p-channel oxide TFTs is suitable for practical applications, which demand significant improvements in the device engineering to meet the real-world electronic requirements, where low processing temperatures together with high mobility and high On-Off ratio are required for TFT and CMOS applications. The present thesis focuses on the study and optimization of p-type thin film transistors based on oxide semiconductors deposited by r.f. magnetron sputtering without intentional substrate heating. In this work several p-type oxide semiconductors were studied and optimized based on undoped tin oxide, Cu-doped SnOx and In-doped SnO2.

A new iron(III) complex-containing sulfadiazine inhibits the proliferation and induces cystogenesis of Toxoplasma gondii.

PubMed

Portes, Juliana de A; Azeredo, Nathália F B; Siqueira, Pedro G T; de Souza, Tatiana Guinancio; Fernandes, Christiane; Horn, Adolfo; Candela, Dalber R S; de Souza, Wanderley; DaMatta, Renato A; Seabra, Sérgio H

2018-06-22

We have previously shown that metallocomplexes can control the growth of Toxoplasma gondii, the agent that causes toxoplasmosis. In order to develop new metallodrugs to treat this disease, we investigated the influence of the coordination of sulfadiazine (SDZ), a drug used to treat toxoplasmosis, on the biological activity of the iron(III) complex [Fe(HBPClNOL)Cl 2 ]·H 2 O, 1, (H 2 BPClNOL=N-(2-hydroxybenzyl)-N-(2-pyridylmethyl)(3-chloro)(2-hydroxy)-propylamine). The new complex [(Cl)(SDZ)Fe(III)(μ-BPClNOL) 2 Fe(III)(SDZ)(Cl)]·2H 2 O, 2, which was obtained by the reaction between complex 1 and SDZ, was characterized using a range of physico-chemical techniques. The cytotoxic effect of the complexes and the ability of T. gondii to infect LLC-MK2 cells were assessed. It was found that both complexes reduced the growth of T. gondii while also causing low cytotoxicity in the host cells. After 48 h of treatment, complex 2 reduced the parasite's ability to proliferate by about 50% with an IC 50 of 1.66 μmol/L. Meanwhile, complex 1 or SDZ alone caused a 40% reduction in proliferation, and SDZ displayed an IC 50 of 5.3 μmol/L. In addition, complex 2 treatment induced distinct morphological and ultrastructural changes in the parasites and triggered the formation of cyst-like forms. These results show that the coordination of SDZ to the iron(III) complex is a good strategy for increasing the anti-toxoplasma activity of these compounds.

Binary Oxide p-n Heterojunction Piezoelectric Nanogenerators with an Electrochemically Deposited High p-Type Cu2O Layer.

PubMed

Baek, Seung Ki; Kwak, Sung Soo; Kim, Joo Sung; Kim, Sang Woo; Cho, Hyung Koun

2016-08-31

The high performance of ZnO-based piezoelectric nanogenerators (NGs) has been limited due to the potential screening from intrinsic electron carriers in ZnO. We have demonstrated a novel approach to greatly improve piezoelectric power generation by electrodepositing a high-quality p-type Cu2O layer between the piezoelectric semiconducting film and the metal electrode. The p-n heterojunction using only oxides suppresses the screening effect by forming an intrinsic depletion region, and thus sufficiently enhances the piezoelectric potential, compared to the pristine ZnO piezoelectric NG. Interestingly, a Sb-doped Cu2O layer has high mobility and low surface trap states. Thus, this doped layer is an attractive p-type material to significantly improve piezoelectric performance. Our results revealed that p-n junction NGs consisting of Au/ZnO/Cu2O/indium tin oxide with a Cu2O:Sb (cuprous oxide with a small amount of antimony) layer of sufficient thickness (3 μm) exhibit an extraordinarily high piezoelectric potential of 0.9 V and a maximum output current density of 3.1 μA/cm(2).

Iron as a catalyst of human low-density lipoprotein oxidation: Critical factors involved in its oxidant properties.

PubMed

Lapenna, Domenico; Ciofani, Giuliano; Obletter, Gabriele

2017-05-01

Iron-induced human LDL oxidation, which is relevant to atherosclerosis, has not yet been properly investigated. We addressed such issue using iron(II) and (III) basically in the presence of phosphates, which are present in vivo and influence iron oxidative properties, at pH 4.5 and 7.4, representative, respectively, of the lysosomal and plasma environment. In 10mM phosphate buffered saline (PBS), iron(II) induces substantial LDL oxidation at pH 4.5 at low micromolar concentrations, while at pH 7.4 has low oxidative effects; iron(III) promotes small LDL oxidation only at pH 4.5. In 10mM sodium acetate/NaCl buffer, pH 4.5, iron-induced LDL oxidation is far higher than in PBS, highlighting the relevance of phosphates in the inhibitory modulation of iron-induced LDL oxidation. LDL oxidation is related to iron binding to the protein and lipid moiety of LDL, and requires the presence of iron(II) bound to LDL together with iron(III). Chemical modification of LDL carboxyl groups, which could bind iron especially at pH 4.5, decreases significantly iron binding to LDL and iron-induced LDL oxidation. Hydroxyl radical scavengers are ineffective on iron-induced LDL oxidation, which is inhibited by metal chelation, scavengers of alkoxyl/peroxyl radicals, or removal of LDL lipid hydroperoxides (LOOH). Overall, substantial human LDL oxidation is induced LOOH-dependently by iron(II) at pH 4.5 even in the presence of phosphates, suggesting the occurrence of iron(II)-induced LDL oxidation in vivo within lysosomes, where pH is about 4.5, iron(II) and phosphates coexist, plasma with its antioxidants is absent, and glutathione peroxidase is poorly expressed resulting in LOOH accumulation. Copyright © 2017 Elsevier GmbH. All rights reserved.

The stability of amitriptyline N-oxide and clozapine N-oxide on treated and untreated dry blood spot cards.

PubMed

Temesi, David; Swales, John; Keene, Warren; Dick, Samuel

2013-03-25

Procedures for drug monitoring based on Dried Blood Spot (DBS) sampling are gaining acceptance for an increasing number of clinical and preclinical applications, where ease of use, small sample requirement, and improved sample stability have been shown to offer advantages over blood tube sampling. However, to-date, the vast majority of this work has described the analysis of well characterized drugs. Using amitriptyline, clozapine, and their potentially labile N-oxide metabolites as model compounds, we consider the merits of using DBS for discovery pharmacokinetic (PK) studies where the metabolic fate of test compounds are often unknown. Both N-oxide metabolites reverted to parent compound under standard drying (2hr) and extraction conditions. Card type significantly affected the outcome, with 14% and 22% degradation occurring for clozapine-N-oxide and amitriptyline-N-oxide on a brand of untreated DBS cards, compared to 59 and 88% on a brand of treated DBS cards. Enrichment of the parent compound ex vivo leads to overestimation of circulating blood concentration and inaccurate determination of the PK profile. Copyright © 2012 Elsevier B.V. All rights reserved.

Converting the Conducting Behavior of Graphene Oxides from n-Type to p-Type via Electron-Beam Irradiation.

PubMed

Mirzaei, Ali; Kwon, Yong Jung; Wu, Ping; Kim, Sang Sub; Kim, Hyoun Woo

2018-02-28

We studied the effects of electron-beam irradiation (EBI) on the structural and gas-sensing properties of graphene oxide (GO). To understand the effects of EBI on the structure and gas-sensing behavior of irradiated GO, the treated GO was compared with nonirradiated GO. Characterization results indicated an enhancement in the number of oxygen functional groups that occurs with EBI exposure at 100 kGy and then decreases with doses in the range of 100-500 kGy. Data from Raman spectra indicated that EBI could generate defects, and NO 2 -sensing results at room temperature showed a decreased NO 2 response after exposure to EBI at 100 kGy; further increasing the dose to 500 kGy resulted in p-type semiconducting conductivity. The conversion of GO from n-type to p-type via EBI is explained not only through the generation of holes but also the variation in the amount of residual functional groups, including carboxyl (COOH) and hydroxyl groups (C-OH). The obtained results suggest that EBI can be a useful tool to convert GO into a diverse range of sensing devices.

Characterization of submicrometer aqueous iron(III) colloids formed in the presence of phosphate by sedimentation field flow fractionation with multiangle laser light scattering detection.

PubMed

Magnuson, M L; Lytle, D A; Frietch, C M; Kelty, C A

2001-10-15

Iron colloids play a major role in the water chemistry of natural watersheds and of engineered drinking water distribution systems. Phosphate is frequently added to distribution systems to control corrosion problems, so iron-phosphate colloids may form through reaction of iron in water pipes. In this study, sedimentation field flow fractionation (SdFFF) is coupled on-line with multiangle laser light scattering (MALLS) detection to characterize these iron colloids formed following the oxygenation of iron(II) in the presence of phosphate. The SdFFF-MALLS data were used to calculate the hydrodynamic diameter, density, and particle size distribution of these submicrometer colloids. The system was first verified with standard polystyrene beads, and the results compared well with certified values. Iron(III) colloids were formed in the presence of phosphate at a variety of pH conditions. The colloids' hydrodynamic diameters, which ranged from 218 +/- 3 (pH 7) to 208 +/- 4 nm (pH 10), did not change significantly within the 95% confidence limit. Colloid density did increase significantly from 1.12 +/- 0.01 (pH 7) to 1.36 +/- 0.02 g/mL (pH 10). Iron(III) colloids formed at pH 10 in the presence of phosphate were compared to iron(III) colloids formed without phosphate and also to iron(III) colloids formed with silicate. The iron(III) colloids formed without phosphate or silicate were 0.46 g/mL more dense than any other colloids and were >6 times more narrowly distributed than the other colloids. The data suggest competitive incorporation of respective anions into the colloid during formation.

Association between microbiota-dependent metabolite trimethylamine-N-oxide and type 2 diabetes.

PubMed

Shan, Zhilei; Sun, Taoping; Huang, Hao; Chen, Sijing; Chen, Liangkai; Luo, Cheng; Yang, Wei; Yang, Xuefeng; Yao, Ping; Cheng, Jinquan; Hu, Frank B; Liu, Liegang

2017-09-01

Background: The association of trimethylamine- N -oxide (TMAO), a microbiota-dependent metabolite from dietary choline and carnitine, with type 2 diabetes was inconsistent. Objective: We evaluated the association of plasma TMAO with newly diagnosed type 2 diabetes and the potential modification of TMAO-generating enzyme flavin monooxygenase 3 (FMO3) polymorphisms. Design: This was an age- and sex-matched case-control study of 2694 participants: 1346 newly diagnosed cases of type 2 diabetes and 1348 controls. Concentrations of plasma TMAO were measured, and FMO3 E158K polymorphisms (rs2266782) were genotyped. Results: Medians (IQRs) of plasma TMAO concentration were 1.47 μmol/L (0.81-2.20 μmol/L) for controls and 1.77 μmol/L (1.09-2.80 μmol/L) for type 2 diabetes cases. From the lowest to the highest quartiles of plasma TMAO, the multivariable adjusted ORs of type 2 diabetes were 1.00 (reference), 1.38 (95% CI: 1.08, 1.77), 1.64 (95% CI: 1.28, 2.09), and 2.55 (95% CI: 1.99, 3.28) ( P -trend < 0.001); each SD of ln-transformed plasma TMAO was associated with a 38% (95% CI: 26%, 51%) increment in ORs of type 2 diabetes. The FMO3 rs2266782 polymorphism was not associated with type 2 diabetes. The positive association between plasma TMAO and type 2 diabetes was consistent in each rs2266782 genotype group, and no significant interaction was observed ( P = 0.093). Conclusions: Our results suggested that higher plasma TMAO was associated with increased odds of newly diagnosed type 2 diabetes and that this association was not modified by the FMO3 rs2266782 polymorphism. This study was registered at clinicaltrials.gov as NCT03130894. © 2017 American Society for Nutrition.

Redox Chemistry in Laccase-Catalyzed Oxidation of N-Hydroxy Compounds

PubMed Central

Xu, Feng; Kulys, Juozas J.; Duke, Kyle; Li, Kaichang; Krikstopaitis, Kastis; Deussen, Heinz-Josef W.; Abbate, Eric; Galinyte, Vilija; Schneider, Palle

2000-01-01

1-Hydroxybenzotriazole, violuric acid, and N-hydroxyacetanilide are three N-OH compounds capable of mediating a range of laccase-catalyzed biotransformations, such as paper pulp delignification and degradation of polycyclic hydrocarbons. The mechanism of their enzymatic oxidation was studied with seven fungal laccases. The oxidation had a bell-shaped pH-activity profile with an optimal pH ranging from 4 to 7. The oxidation rate was found to be dependent on the redox potential difference between the N-OH substrate and laccase. A laccase with a higher redox potential or an N-OH compound with a lower redox potential tended to have a higher oxidation rate. Similar to the enzymatic oxidation of phenols, phenoxazines, phenothiazines, and other redox-active compounds, an “outer-sphere” type of single-electron transfer from the substrate to laccase and proton release are speculated to be involved in the rate-limiting step for N-OH oxidation. PMID:10788380

Electronic properties and morphology of copper oxide/n-type silicon heterostructures

NASA Astrophysics Data System (ADS)

Lindberg, P. F.; Gorantla, S. M.; Gunnæs, A. E.; Svensson, B. G.; Monakhov, E. V.

2017-08-01

Silicon-based tandem heterojunction solar cells utilizing cuprous oxide (Cu2O) as the top absorber layer show promise for high-efficiency conversion and low production cost. In the present study, single phase Cu2O films have been realized on n-type Si substrates by reactive magnetron sputtering at 400 °C. The obtained Cu2O/Si heterostructures have subsequently been heat treated at temperatures in the 400-700 °C range in Ar flow and extensively characterized by x-ray diffraction (XRD) measurements, transmission electron microscopy (TEM) imaging and electrical techniques. The Cu2O/Si heterojunction exhibits a current rectification of ~5 orders of magnitude between forward and reverse bias voltages. High resolution cross-sectional TEM-images show the presence of a ~2 nm thick interfacial SiO2 layer between Cu2O and the Si substrate. Heat treatments below 550 °C result in gradual improvement of crystallinity, indicated by XRD. At and above 550 °C, partial phase transition to cupric oxide (CuO) occurs followed by a complete transition at 700 °C. No increase or decrease of the SiO2 layer is observed after the heat treatment at 550 °C. Finally, a thin Cu-silicide layer (Cu3Si) emerges below the SiO2 layer upon annealing at 550 °C. This silicide layer influences the lateral current and voltage distributions, as evidenced by an increasing effective area of the heterojunction diodes.

Immunomodulation by different types of N-oxides in the hemocytes of the marine bivalve Mytilus galloprovincialis.

PubMed

Ciacci, Caterina; Canonico, Barbara; Bilaniĉovă, Dagmar; Fabbri, Rita; Cortese, Katia; Gallo, Gabriella; Marcomini, Antonio; Pojana, Giulio; Canesi, Laura

2012-01-01

The potential toxicity of engineered nanoparticles (NPs) for humans and the environment represents an emerging issue. Since the aquatic environment represents the ultimate sink for NP deposition, the development of suitable assays is needed to evaluate the potential impact of NPs on aquatic biota. The immune system is a sensitive target for NPs, and conservation of innate immunity represents an useful basis for studying common biological responses to NPs. Suspension-feeding invertebrates, such as bivalves, are particularly at risk to NP exposure, since they have extremely developed systems for uptake of nano and microscale particles integral to intracellular digestion and cellular immunity. Evaluation of the effects of NPs on functional parameters of bivalve immunocytes, the hemocytes, may help understanding the major toxic mechanisms and modes of actions that could be relevant for different NP types in aquatic organisms.In this work, a battery of assays was applied to the hemocytes of the marine bivalve Mytilus galloprovincialis to compare the in vitro effects of different n-oxides (n-TiO(2), n-SiO(2), n-ZnO, n-CeO(2)) chosen on the basis of their commercial and environmental relevance. Physico-chemical characterization of both primary particles and NP suspensions in artificial sea water-ASW was performed. Hemocyte lysosomal and mitochondrial parameters, oxyradical and nitric oxide production, phagocytic activity, as well as NP uptake, were evaluated. The results show that different n-oxides rapidly elicited differential responses hemocytes in relation to their chemical properties, concentration, behavior in sea water, and interactions with subcellular compartments. These represent the most extensive data so far available on the effects of NPs in the cells of aquatic organisms. The results indicate that Mytilus hemocytes can be utilized as a suitable model for screening the potential effects of NPs in the cells of aquatic invertebrates, and may provide a basis for

Immunomodulation by Different Types of N-Oxides in the Hemocytes of the Marine Bivalve Mytilus galloprovincialis

PubMed Central

Ciacci, Caterina; Canonico, Barbara; Bilaniĉovă, Dagmar; Fabbri, Rita; Cortese, Katia; Gallo, Gabriella; Marcomini, Antonio; Pojana, Giulio; Canesi, Laura

2012-01-01

The potential toxicity of engineered nanoparticles (NPs) for humans and the environment represents an emerging issue. Since the aquatic environment represents the ultimate sink for NP deposition, the development of suitable assays is needed to evaluate the potential impact of NPs on aquatic biota. The immune system is a sensitive target for NPs, and conservation of innate immunity represents an useful basis for studying common biological responses to NPs. Suspension-feeding invertebrates, such as bivalves, are particularly at risk to NP exposure, since they have extremely developed systems for uptake of nano and microscale particles integral to intracellular digestion and cellular immunity. Evaluation of the effects of NPs on functional parameters of bivalve immunocytes, the hemocytes, may help understanding the major toxic mechanisms and modes of actions that could be relevant for different NP types in aquatic organisms.In this work, a battery of assays was applied to the hemocytes of the marine bivalve Mytilus galloprovincialis to compare the in vitro effects of different n-oxides (n-TiO2, n-SiO2, n-ZnO, n-CeO2) chosen on the basis of their commercial and environmental relevance. Physico-chemical characterization of both primary particles and NP suspensions in artificial sea water-ASW was performed. Hemocyte lysosomal and mitochondrial parameters, oxyradical and nitric oxide production, phagocytic activity, as well as NP uptake, were evaluated. The results show that different n-oxides rapidly elicited differential responses hemocytes in relation to their chemical properties, concentration, behavior in sea water, and interactions with subcellular compartments. These represent the most extensive data so far available on the effects of NPs in the cells of aquatic organisms. The results indicate that Mytilus hemocytes can be utilized as a suitable model for screening the potential effects of NPs in the cells of aquatic invertebrates, and may provide a basis for

Reverse osmosis membrane composition, structure and performance modification by bisulphite, iron(III), bromide and chlorite exposure.

PubMed

Ferrer, O; Gibert, O; Cortina, J L

2016-10-15

Reverse osmosis (RO) membrane exposure to bisulphite, chlorite, bromide and iron(III) was assessed in terms of membrane composition, structure and performance. Membrane composition was determined by Rutherford backscattering spectrometry (RBS) and membrane performance was assessed by water and chloride permeation, using a modified version of the solution-diffusion model. Iron(III) dosage in presence of bisulphite led to an autooxidation of the latter, probably generating free radicals which damaged the membrane. It comprised a significant raise in chloride passage (chloride permeation coefficient increased 5.3-5.1 fold compared to the virgin membrane under the conditions studied) rapidly. No major differences in terms of water permeability and membrane composition were observed. Nevertheless, an increase in the size of the network pores, and a raise in the fraction of aggregate pores of the polyamide (PA) layer were identified, but no amide bond cleavage was observed. These structural changes were therefore, in accordance with the transport properties observed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Salicylate Detection by Complexation with Iron(III) and Optical Absorbance Spectroscopy: An Undergraduate Quantitative Analysis Experiment

ERIC Educational Resources Information Center

Mitchell-Koch, Jeremy T.; Reid, Kendra R.; Meyerhoff, Mark E.

2008-01-01

An experiment for the undergraduate quantitative analysis laboratory involving applications of visible spectrophotometry is described. Salicylate, a component found in several medications, as well as the active by-product of aspirin decomposition, is quantified. The addition of excess iron(III) to a solution of salicylate generates a deeply…

Oxidizing action of purine N-oxide esters.

PubMed

Stöhrer, G; Salemnick, G

1975-01-01

A technique involving O-acetylation of purine N-oxide derivatives in buffered aqueous solutions has permitted studies of the reactivity of many compounds for which the O-acetyl derivatives are not otherwise available. The oxidizing properties of a variety of N-acetoxypurines have been measured through their ability to oxidize iodide ion ot iodine, a reaction which is representative of a more general oxidizing ability. Those esters that oxidize iodide ion also catalyze the autoxidation of sulfite, a property characteristic of radicals. The same esters also oxidize cysteine to cysteic acid and tryptophan, tyrosine, and uric acid to yet uncharacterized products. Their oxidizing reactivity was compared with the ability of the same esters to react as electrophiles in another assay that measured the rate of formation of pyridine substitution products. The sulfate ester of 3-hydroxyxanthine has been synthesized. Its reactivity is qualitatively the same as that of 3-acetoxyxanthine but proceeds at a higher rate. Syntheses of S-(8-xanthyl)-N-acetylcysteine, 8-(2-hydroxyethylthio)xanthine, and 1-methyl-8-mehtylmercaptoguanine are also described.

Selective Conversion from p-Type to n-Type of Printed Bottom-Gate Carbon Nanotube Thin-Film Transistors and Application in Complementary Metal-Oxide-Semiconductor Inverters.

PubMed

Xu, Qiqi; Zhao, Jianwen; Pecunia, Vincenzo; Xu, Wenya; Zhou, Chunshan; Dou, Junyan; Gu, Weibing; Lin, Jian; Mo, Lixin; Zhao, Yanfei; Cui, Zheng

2017-04-12

The fabrication of printed high-performance and environmentally stable n-type single-walled carbon nanotube (SWCNT) transistors and their integration into complementary (i.e., complementary metal-oxide-semiconductor, CMOS) circuits are widely recognized as key to achieving the full potential of carbon nanotube electronics. Here, we report a simple, efficient, and robust method to convert the polarity of SWCNT thin-film transistors (TFTs) using cheap and readily available ethanolamine as an electron doping agent. Printed p-type bottom-gate SWCNT TFTs can be selectively converted into n-type by deposition of ethanolamine inks on the transistor active region via aerosol jet printing. Resulted n-type TFTs show excellent electrical properties with an on/off ratio of 10 6 , effective mobility up to 30 cm 2 V -1 s -1 , small hysteresis, and small subthreshold swing (90-140 mV dec -1 ), which are superior compared to the original p-type SWCNT devices. The n-type SWCNT TFTs also show good stability in air, and any deterioration of performance due to shelf storage can be fully recovered by a short low-temperature annealing. The easy polarity conversion process allows construction of CMOS circuitry. As an example, CMOS inverters were fabricated using printed p-type and n-type TFTs and exhibited a large noise margin (50 and 103% of 1/2 V dd = 1 V) and a voltage gain as high as 30 (at V dd = 1 V). Additionally, the CMOS inverters show full rail-to-rail output voltage swing and low power dissipation (0.1 μW at V dd = 1 V). The new method paves the way to construct fully functional complex CMOS circuitry by printed TFTs.

Thermally-induced solid state transformation of β‐Fe{sub 2}O{sub 3} nanoparticles in various atmospheres

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

Malina, Ondrej, E-mail: ondrej.malina@upol.cz; Kaslik, Josef, E-mail: ondrej.malina@upol.cz; Tucek, Jiri, E-mail: ondrej.malina@upol.cz

2014-10-27

To date, iron oxides have become one of the most studied nanomaterials due to their interesting and aaplication appealing physical, chemical, and biological properties in comparison with their bulk counterparts. In general, four forms of iron(III) oxide can be distinguished depending on their crystallographic and magnetic properties. In this work, one of the rare phases of iron(III) oxide, β‐Fe{sub 2}O{sub 3}, prepared by the solid state reaction was explored for the thermal transformations in various ambient atmospheres, including O{sub 2}, N{sub 2}, and CO{sub 2} atmospheres. The thermally treated products were investigated employing X-ray powder diffraction and {sup 57}Fe Mössbauermore » spectroscopy.« less

Economically attractive route for the preparation of high quality magnetic nanoparticles by the thermal decomposition of iron(III) acetylacetonate.

PubMed

Effenberger, Fernando B; Couto, Ricardo A; Kiyohara, Pedro K; Machado, Giovanna; Masunaga, Sueli H; Jardim, Renato F; Rossi, Liane M

2017-03-17

The thermal decomposition (TD) methods are among the most successful in obtaining magnetic nanoparticles with a high degree of control of size and narrow particle size distribution. Here we investigated the TD of iron(III) acetylacetonate in the presence of oleic acid, oleylamine, and a series of alcohols in order to disclose their role and also investigate economically attractive alternatives for the synthesis of iron oxide nanoparticles without compromising their size and shape control. We have found that some affordable and reasonably less priced alcohols, such as 1,2-octanediol and cyclohexanol, may replace the commonly used and expensive 1,2-hexadecanediol, providing an economically attractive route for the synthesis of high quality magnetic nanoparticles. The relative cost for the preparation of Fe 3 O 4 NPs is reduced to only 21% and 9% of the original cost when using 1,2-octanediol and cyclohexanol, respectively.

Investigation of anodic and chemical oxides grown on p-type InP with applications to surface passivation for n(+)-p solar cell fabrication

NASA Technical Reports Server (NTRS)

Faur, Maria; Faur, Mircea; Goradia, Manju; Goradia, Chandra; Jenkins, Phillip; Jayne, Douglas; Weinberg, Irving

1991-01-01

Most of the previously reported InP anodic oxides were grown on a n-type InP with applications to fabrication of MISFET structures and were described as a mixture of In2O3 and P2O5 stoichiometric compounds or nonstoichiometric phases which have properties similar to crystalline compounds In(OH)3, InPO4, and In(PO3)3. Details of the compositional change of the anodic oxides grown under different anodization conditions were previously reported. The use of P-rich oxides grown either by anodic or chemical oxidation are investigated for surface passivation of p-type InP and as a protective cap during junction formation by closed-ampoule sulfur diffusion. The investigation is based on but not limited to correlations between PL intensity and X-ray photoelectron spectroscopy (XPS) chemical composition data.

Evolution of electronic states in n-type copper oxide superconductor via electric double layer gating

NASA Astrophysics Data System (ADS)

Jin, Kui; Hu, Wei; Zhu, Beiyi; Kim, Dohun; Yuan, Jie; Sun, Yujie; Xiang, Tao; Fuhrer, Michael S.; Takeuchi, Ichiro; Greene, Richard. L.

2016-05-01

The occurrence of electrons and holes in n-type copper oxides has been achieved by chemical doping, pressure, and/or deoxygenation. However, the observed electronic properties are blurred by the concomitant effects such as change of lattice structure, disorder, etc. Here, we report on successful tuning the electronic band structure of n-type Pr2-xCexCuO4 (x = 0.15) ultrathin films, via the electric double layer transistor technique. Abnormal transport properties, such as multiple sign reversals of Hall resistivity in normal and mixed states, have been revealed within an electrostatic field in range of -2 V to + 2 V, as well as varying the temperature and magnetic field. In the mixed state, the intrinsic anomalous Hall conductivity invokes the contribution of both electron and hole-bands as well as the energy dependent density of states near the Fermi level. The two-band model can also describe the normal state transport properties well, whereas the carrier concentrations of electrons and holes are always enhanced or depressed simultaneously in electric fields. This is in contrast to the scenario of Fermi surface reconstruction by antiferromagnetism, where an anti-correlation is commonly expected.

Nb-doped SrTiO3 glass-ceramics as high temperature stable n-type oxide thermoelectrics

NASA Astrophysics Data System (ADS)

Lingner, Julian; Jakob, Gerhard; Letz, Martin

2012-06-01

Niobium doped SrTiO3 is known for its high potential as an oxide thermoelectric material and is one of the possible candidates for the n-type site in an oxidic thermoelectric module. The high thermal conductivity [1] and the lack of high-temperature stability of the oxygen vacancies [2] limit its properties in the ceramic systems. Glass-ceramics are intrinsic nano-structured systems and provide crystal phases densely embedded in a glass matrix which prevents the material from detoriation at high temperatures. In particular, the glass-matrix prevents an uncontrolled reoxidization as well as an uncontrolled grain growth therefore retaining the nano-structure even at high temperatures. Here, measurements and results of first glass-ceramic systems are presented, which show a low thermal conductivity due to the residue glass phase. Furthermore a stable thermal cycling up to 650 °C is demonstrated.

Effect of N2 flow during deposition on p-type ZnO film

NASA Astrophysics Data System (ADS)

Lin, Chiung-Wei; Liu, Bor-Chang

2017-01-01

In this study, the influence of a nitrogen source on p-type conductive ZnO films was studied. Rapid thermal oxidation was conducted to oxidize ZnN films and convert them to ZnO films. When an as-deposited ZnN film was prepared at a high nitrogen gas flow rate, the converted ZnO film possessed many acceptors and showed stable p-type conduction. This p-type conduction was attributed to the nitrogen gas flow providing many “No” states, which act as acceptors within the processed ZnO film. It was found that the as-deposited ZnN film prepared at a high nitrogen gas flow rate is oxidized slightly so that only a few nitrogen atoms were replaced by oxygen. The carrier concentration and mobility of the optimized oxidized ZnN film were 9.76 × 1017 cm-3 and 62.78 cm2 V-1 s-1, respectively. A good rectified current-voltage characteristic with a turn-on voltage of 3.65 V was achieved for the optimized ZnO:N/ZnO junction.

Metal-Free Functionalization of N,N-Dialkylanilines via Temporary Oxidation to N,N-Dialkylaniline N-Oxides and Group Transfer

PubMed Central

2015-01-01

A simple set of protocols for the controlled elaboration of anilines is reported allowing access to a diverse array of aminophenols, aminoarylsulfonates, alkylated anilines, and aminoanilines in 29–95% yield in a single laboratory operation from easily isolable, bench-stable N,N-dialkylaniline N-oxides. The introduction of new C–O, C–C, and C–N bonds on the aromatic ring is made possible by a temporary increase in oxidation level and excision of a weak N–O bond. PMID:24992642

Process for light-driven hydrocarbon oxidation at ambient temperatures

DOEpatents

Shelnutt, John A.

1990-01-01

A photochemical reaction for the oxidation of hydrocarbons uses molecular oxygen as the oxidant. A reductive photoredox cycle that uses a tin(IV)- or antimony(V)-porphyrin photosensitizer generates the reducing equivalents required to activate oxygen. This artificial photosynthesis system drives a catalytic cycle, which mimics the cytochrome P.sub.450 reaction, to oxidize hydrocarbons. An iron(III)- or manganese(III)-porphyrin is used as the hydrocarbon-oxidation catalyst. Methylviologen can be used as a redox relay molecule to provide for electron-transfer from the reduced photosensitizer to the Fe or Mn porphyrin. The system is long-lived and may be used in photo-initiated spectroscopic studies of the reaction to determine reaction rates and intermediates.

Identification and design principles of low hole effective mass p-type transparent conducting oxides

PubMed Central

Hautier, Geoffroy; Miglio, Anna; Ceder, Gerbrand; Rignanese, Gian-Marco; Gonze, Xavier

2013-01-01

The development of high-performance transparent conducting oxides is critical to many technologies from transparent electronics to solar cells. Whereas n-type transparent conducting oxides are present in many devices, their p-type counterparts are not largely commercialized, as they exhibit much lower carrier mobilities due to the large hole effective masses of most oxides. Here we conduct a high-throughput computational search on thousands of binary and ternary oxides and identify several highly promising compounds displaying exceptionally low hole effective masses (up to an order of magnitude lower than state-of-the-art p-type transparent conducting oxides), as well as wide band gaps. In addition to the discovery of specific compounds, the chemical rationalization of our findings opens new directions, beyond current Cu-based chemistries, for the design and development of future p-type transparent conducting oxides. PMID:23939205

Immersed finger-type indium tin oxide ohmic contacts on p-GaN photoelectrodes for photoelectrochemical hydrogen generation.

PubMed

Liu, Shu-Yen; Sheu, J K; Lee, M L; Lin, Yu-Chuan; Tu, S J; Huang, F W; Lai, W C

2012-03-12

In this study, we demonstrated photoelectrochemical (PEC) hydrogen generation using p-GaN photoelectrodes associated with immersed finger-type indium tin oxide (IF-ITO) ohmic contacts. The IF-ITO/p-GaN photoelectrode scheme exhibits higher photocurrent and gas generation rate compared with p-GaN photoelectrodes without IF-ITO ohmic contacts. In addition, the critical external bias for detectable hydrogen generation can be effectively reduced by the use of IF-ITO ohmic contacts. This finding can be attributed to the greatly uniform distribution of the IF-ITO/p-GaN photoelectrode applied fields over the whole working area. As a result, the collection efficiency of photo-generated holes by electrode contacts is higher than that of p-GaN photoelectrodes without IF-ITO contacts. Microscopy revealed a tiny change on the p-GaN surfaces before and after hydrogen generation. In contrast, photoelectrodes composed of n-GaN have a short lifetime due to n-GaN corrosion during hydrogen generation. Findings of this study indicate that the ITO finger contacts on p-GaN layer is a potential candidate as photoelectrodes for PEC hydrogen generation.

Effect of photocatalytic oxidation technology on GaN CMP

NASA Astrophysics Data System (ADS)

Wang, Jie; Wang, Tongqing; Pan, Guoshun; Lu, Xinchun

2016-01-01

GaN is so hard and so chemically inert that it is difficult to obtain a high material removal rate (MRR) in the chemical mechanical polishing (CMP) process. This paper discusses the application of photocatalytic oxidation technology in GaN planarization. Three N-type semiconductor particles (TiO2, SnO2, and Fe2O3) are used as catalysts and added to the H2O2-SiO2-based slurry. By optical excitation, highly reactive photoinduced holes are produced on the surface of the particles, which can oxidize OH- and H2O absorbed on the surface of the catalysts; therefore, more OH* will be generated. As a result, GaN MRRs in an H2O2-SiO2-based polishing system combined with catalysts are improved significantly, especially when using TiO2, the MRR of which is 122 nm/h. The X-ray photoelectron spectroscopy (XPS) analysis shows the variation trend of chemical composition on the GaN surface after polishing, revealing the planarization process. Besides, the effect of pH on photocatalytic oxidation combined with TiO2 is analyzed deeply. Furthermore, the physical model of GaN CMP combined with photocatalytic oxidation technology is proposed to describe the removal mechanism of GaN.

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

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

Klobukowski, Erik

2011-01-01

This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallicmore » complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system

Structure and Magnetic Properties of a Dodecanuclear Twisted-Ring Iron(III) Cluster.

PubMed

Caneschi, Andrea; Cornia, Andrea; Fabretti, Antonio C; Gatteschi, Dante

1999-05-03

An unprecedented nonplanar structure characterizes the complex [Fe(OCH 3 ) 2 (dbm)] 12 (on the left in the picture), which contains the largest cyclic ferric cluster yet reported with chemically equivalent bridging units. It is made up of twelve high-spin, antiferromagnetically coupled iron(III) centers and neatly reacts with Na I or Li I templates in organic solution to give hexairon(III) coronates (right). Fe=•, O=○, NaI or LiI=• Hdbm=dibenzoylmethane. © 1999 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Fabrication and thermoelectric properties of n-type (Sr0.9Gd0.1)TiO3 oxides

NASA Astrophysics Data System (ADS)

Li, Liangliang; Qin, Xiaoying; Liu, Yongfei; Xin, Hongxing; Zhang, Jian; Li, Di; Song, Chunjun; Guo, Guanglei; Dou, Yunchen; Zou, Tianhua

2014-02-01

The n-type oxides (Sr0.9Gd0.1)TiO3 (SGTO) have been successfully prepared via a sol-gel process followed by solid-state sintering. The effects of sintering temperature on the thermoelectric (TE) properties of the SGTO samples have been investigated. The Seebeck coefficient showed no obvious difference, while the electrical conductivity increased with increasing sintering temperature, benefiting from an enhancement of densification. The maximum power factor (PF) value, 20.5μW/K2cm at 370 K in the metallic region, was observed for the sample sintered at 1748 K. As a result, the peak figure of merit (ZT) values for the samples sintered at higher than 1673 K were in the range of 0.28-0.30. All the results indicate that such synthetic method provides a simple and effective way to prepare TE oxides.

New Electronic Materials and CO2 Reduction.

DTIC Science & Technology

1988-02-02

REPORT DOCUMENTATION PAGE ! a ;t, C ’ SE -R .r N ’ D RE--R’tThVE "j f ’ .NUS UNCLASSIFIED APPROVED FOR PUBLIC RELEASE AD-A240 192 Lit R 11 II6 NOOO 14...by H12 have been carried out at 290C in a microreactor with a H2 /CO ration of 9/1. The catalysts studied were iron(III) oxide, iron(1I) diiron(1II...Methanation studies have been carried out at 290’C in a microreactor with a H 2 /CO ratio of 9/1. The catalysts studied were iron(III) oxide, iron(IT

The mechanisms of pyrite oxidation and leaching: A fundamental perspective

NASA Astrophysics Data System (ADS)

Chandra, A. P.; Gerson, A. R.

2010-09-01

Pyrite is the earth's most abundant sulfide mineral. Its frequent undesirable association with minerals of economic value such as sphalerite, chalcopyrite and galena, and precious metals such as gold necessitates costly separation processes such as leaching and flotation. Additionally pyrite oxidation is a major contributor to the environmental problem of acid rock drainage. The surface oxidation reactions of pyrite are therefore important both economically and environmentally. Significant variations in electrical properties resulting from lattice substitution of minor and trace elements into the lattice structure exist between pyrite from different geographical locations. Furthermore the presence of low coordination surface sites as a result of conchoidal fracture causes a reduction in the band gap at the surface compared to the bulk thus adding further electrochemical variability. Given the now general acceptance after decades of research that electrochemistry dominates the oxidation process, the geographical location, elemental composition and semi-conductor type (n or p) of pyrite are important considerations. Aqueous pyrite oxidation results in the production of sulfate and ferrous iron. However other products such as elemental sulfur, polysulfides, hydrogen sulfide, ferric hydroxide, iron oxide and iron(III) oxyhydroxide may also form. Intermediate species such as thiosulfate, sulfite and polythionates are also proposed to occur. Oxidation and leach rates are generally influenced by solution Eh, pH, oxidant type and concentration, hydrodynamics, grain size and surface area in relation to solution volume, temperature and pressure. Of these, solution Eh is most critical as expected for an electrochemically controlled process, and directly correlates with surface area normalised rates. Studies using mixed mineral systems further indicate the importance of electrochemical processes during the oxidation process. Spatially resolved surface characterisation of fresh

Deep vs shallow nature of oxygen vacancies and consequent n -type carrier concentrations in transparent conducting oxides

NASA Astrophysics Data System (ADS)

Buckeridge, J.; Catlow, C. R. A.; Farrow, M. R.; Logsdail, A. J.; Scanlon, D. O.; Keal, T. W.; Sherwood, P.; Woodley, S. M.; Sokol, A. A.; Walsh, A.

2018-05-01

The source of n -type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In2O3 ,SnO2, and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In2O3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO2, the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n -type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In2O3 , but also in SnO2 and ZnO.

Three dimensional-stacked complementary thin-film transistors using n-type Al:ZnO and p-type NiO thin-film transistors.

PubMed

Lee, Ching-Ting; Chen, Chia-Chi; Lee, Hsin-Ying

2018-03-05

The three dimensional inverters were fabricated using novel complementary structure of stacked bottom n-type aluminum-doped zinc oxide (Al:ZnO) thin-film transistor and top p-type nickel oxide (NiO) thin-film transistor. When the inverter operated at the direct voltage (V DD ) of 10 V and the input voltage from 0 V to 10 V, the obtained high performances included the output swing of 9.9 V, the high noise margin of 2.7 V, and the low noise margin of 2.2 V. Furthermore, the high performances of unskenwed inverter were demonstrated by using the novel complementary structure of the stacked n-type Al:ZnO thin-film transistor and p-type nickel oxide (NiO) thin-film transistor.

Molybdenum Oxide Nitrides of the Mo2(O,N,□)5 Type: On the Way to Mo2O5.

PubMed

Weber, Dominik; Huber, Manop; Gorelik, Tatiana E; Abakumov, Artem M; Becker, Nils; Niehaus, Oliver; Schwickert, Christian; Culver, Sean P; Boysen, Hans; Senyshyn, Anatoliy; Pöttgen, Rainer; Dronskowski, Richard; Ressler, Thorsten; Kolb, Ute; Lerch, Martin

2017-08-07

Blue-colored molybdenum oxide nitrides of the Mo 2 (O,N,□) 5 type were synthesized by direct nitridation of commercially available molybdenum trioxide with a mixture of gaseous ammonia and oxygen. Chemical composition, crystal structure, and stability of the obtained and hitherto unknown compounds are studied extensively. The average oxidation state of +5 for molybdenum is proven by Mo K near-edge X-ray absorption spectroscopy; the magnetic behavior is in agreement with compounds exhibiting Mo V O 6 units. The new materials are stable up to ∼773 K in an inert gas atmosphere. At higher temperatures, decomposition is observed. X-ray and neutron powder diffraction, electron diffraction, and high-resolution transmission electron microscopy reveal the structure to be related to VNb 9 O 24.9 -type phases, however, with severe disorder hampering full structure determination. Still, the results demonstrate the possibility of a future synthesis of the potential binary oxide Mo 2 O 5 . On the basis of these findings, a tentative suggestion on the crystal structure of the potential compound Mo 2 O 5 , backed by electronic-structure and phonon calculations from first principles, is given.

Prebiotic Oxidative Polymerization of 2,3 Dimercaptopropanol on the Surface of Iron(III) Hydroxide Oxide

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1994-01-01

The oxidation of 2,3-Dimercapto-1-propanol by ferric ions on the surface of iron (III) hydroxide oxide yielded polydisulfide polymers. This polymerization occured readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron (III) hydroxide oxide (20 mg, 160 micro mole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the mineral phase. Reactions at higher dithiol concentrations with the same ratio of dithiol to mineral gave a higher yield of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis will be discussed.

Selective sensing of submicromolar iron(III) with 3,3‧,5,5‧-tetramethylbenzidine as a chromogenic probe

NASA Astrophysics Data System (ADS)

Zhang, Lufeng; Du, Jianxiu

2016-04-01

The development of highly selective and sensitive method for iron(III) detection is of great importance both from human health as well as environmental point of view. We herein reported a simple, selective and sensitive colorimetric method for the detection of Fe(III) at submicromolar level with 3,3,‧5,5‧-tetramethylbenzidine (TMB) as a chromogenic probe. It was observed that Fe(III) could directly oxidize TMB to form a blue solution without adding any extra oxidants. The reaction has a stoichiometric ratio of 1:1 (Fe(III)/TMB) as determined by a molar ratio method. The resultant color change can be perceived by the naked eye or monitored the absorbance change at 652 nm. The method allowed the measurement of Fe(III) in the range 1.0 × 10- 7-1.5 × 10- 4 mol L- 1 with a detection limit of 5.5 × 10- 8 mol L- 1. The relative standard deviation was 0.9% for eleven replicate measurements of 2.5 × 10- 5 mol L- 1 Fe(III) solution. The chemistry showed high selectivity for Fe(III) in contrast to other common cation ions. The practically of the method was evaluated by the determination of Fe in milk samples; good consistency was obtained between the results of this method and atomic absorption spectrophotometry as indicated by statistical analysis.

Proton translocation coupled to trimethylamine N-oxide reduction in anaerobically grown Escherichia coli.

PubMed Central

Takagi, M; Tsuchiya, T; Ishimoto, M

1981-01-01

Proton translocation coupled to trimethylamine N-oxide reduction was studied in Escherichia coli grown anaerobically in the presence of trimethylamine N-oxide. Rapid acidification of the medium was observed when trimethylamine N-oxide was added to anaerobic cell suspensions of E. coli K-10. Acidification was sensitive to the proton conductor 3,5-di-tert-butyl-4-hydroxybenzylidenemalononitrile (SF6847). No pH change was shown in a strain deficient in trimethylamine N-oxide reductase activity. The apparent H+/trimethylamine N-oxide ratio in cells oxidizing endogenous substrates was 3 to 4 g-ions of H+ translocated per mol of trimethylamine N-oxide added. The addition of trimethylamine N-oxide and formate to ethylenediaminetetraacetic acid-treated cell suspension caused fluorescence quenching of 3,3'-dipropylthiacarbocyanine [diS-C3-(5)], indicating the generation of membrane potential. These results indicate that the reduction of trimethylamine N-oxide in E. coli is catalyzed by an anaerobic electron transfer system, resulting in formation of a proton motive force. Trimethylamine N-oxide reductase activity and proton extrusion were also examined in chlorate-resistant mutants. Reduction of trimethylamine N-oxide occurred in chlC, chlG, and chlE mutants, whereas chlA, chlB, and chlD mutants, which are deficient in the molybdenum cofactor, could not reduce it. Protons were extruded in chlC and chlG mutants, but not in chlA, chlB, and chlD mutants. Trimethylamine N-oxide reductase activity in a chlD mutant was restored to the wild-type level by the addition of 100 microM molybdate to the growth medium, indicating that the same molybdenum cofactor as used by nitrate reductase is required for the trimethylamine N-oxide reductase system. PMID:7031034

Recent progress in high performance and reliable n-type transition metal oxide-based thin film transistors

NASA Astrophysics Data System (ADS)

Kwon, Jang Yeon; Kyeong Jeong, Jae

2015-02-01

This review gives an overview of the recent progress in vacuum-based n-type transition metal oxide (TMO) thin film transistors (TFTs). Several excellent review papers regarding metal oxide TFTs in terms of fundamental electron structure, device process and reliability have been published. In particular, the required field-effect mobility of TMO TFTs has been increasing rapidly to meet the demands of the ultra-high-resolution, large panel size and three dimensional visual effects as a megatrend of flat panel displays, such as liquid crystal displays, organic light emitting diodes and flexible displays. In this regard, the effects of the TMO composition on the performance of the resulting oxide TFTs has been reviewed, and classified into binary, ternary and quaternary composition systems. In addition, the new strategic approaches including zinc oxynitride materials, double channel structures, and composite structures have been proposed recently, and were not covered in detail in previous review papers. Special attention is given to the advanced device architecture of TMO TFTs, such as back-channel-etch and self-aligned coplanar structure, which is a key technology because of their advantages including low cost fabrication, high driving speed and unwanted visual artifact-free high quality imaging. The integration process and related issues, such as etching, post treatment, low ohmic contact and Cu interconnection, required for realizing these advanced architectures are also discussed.

Fabrication and characterization of GaN-based light-emitting diodes without pre-activation of p-type GaN.

PubMed

Hu, Xiao-Long; Wang, Hong; Zhang, Xi-Chun

2015-01-01

We fabricated GaN-based light-emitting diodes (LEDs) without pre-activation of p-type GaN. During the fabrication process, a 100-nm-thick indium tin oxide film was served as the p-type contact layer and annealed at 500°C in N2 ambient for 20 min to increase its transparency as well as to activate the p-type GaN. The electrical measurements showed that the LEDs were featured by a lower forward voltage and higher wall-plug efficiency in comparison with LEDs using pre-activation of p-type GaN. We discussed the mechanism of activation of p-type GaN at 500°C in N2 ambient. Furthermore, x-ray photoemission spectroscopy examinations were carried out to study the improved electrical performances of the LEDs without pre-activation of p-type GaN.

Interfacial reactions of nano-structured Cu-doped indium oxide/indium tin oxide ohmic contacts to p-GaN.

PubMed

Yoon, Young Joon; Chae, S W; Kim, B K; Park, Min Joo; Kwak, Joon Seop

2010-05-01

Interfacial microstructure and elemental diffusion of Cu-doped indium oxide (CIO)/indium tin oxide (ITO) ohmic contacts to p-type GaN for light-emitting diodes (LEDs) were investigated using cross-sectional transmission electron microscopy (XTEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction. The CIO/ITO contacts gave specific contact resistances of approximately 10(-4) omegacm2 and transmittance greater than 95% at a wavelength of 405 nm when annealed at 630 degrees C for 1 min in air. After annealing at 630 degrees C, multi-component oxides composed of Ga2O3-In2O3, Ga2O3-CuO, and In2O3-CuO formed at the interface between p-GaN and ITO. Formation of multi-component oxides reduced the barrier height between p-GaN and ITO due to their higher work functions than that of ITO, and caused Ga in the GaN to diffuse into the CIO/ITO layer, followed by generation of acceptor-like Ga vacancies near the GaN surface, which lowered contact resistivity of the CIO/ITO contacts to p-GaN after the annealing.

Metal Organic Framework-Templated Chemiresistor: Sensing Type Transition from P-to-N Using Hollow Metal Oxide Polyhedron via Galvanic Replacement.

PubMed

Jang, Ji-Soo; Koo, Won-Tae; Choi, Seon-Jin; Kim, Il-Doo

2017-08-30

Facile synthesis of porous nanobuilding blocks with high surface area and uniform catalyst functionalization has always been regarded as an essential requirement for the development of highly sensitive and selective chemical sensors. Metal-organic frameworks (MOFs) are considered as one of the most ideal templates due to their ability to encapsulate ultrasmall catalytic nanoparticles (NPs) in microporous MOF structures in addition to easy removal of the sacrificial MOF scaffold by calcination. Here, we introduce a MOFs derived n-type SnO 2 (n-SnO 2 ) sensing layer with hollow polyhedron structures, obtained from p-n transition of MOF-templated p-type Co 3 O 4 (p-Co 3 O 4 ) hollow cubes during galvanic replacement reaction (GRR). In addition, the Pd NPs encapsulated in MOF and residual Co 3 O 4 clusters partially remained after GRR led to uniform functionalization of efficient cocatalysts (PdO NPs and p-Co 3 O 4 islands) on the porous and hollow polyhedron SnO 2 structures. Due to high gas accessibility through the meso- and macrosized pores in MOF-templated oxides and effective modulation of electron depletion layer assisted by the creation of numerous p-n junctions, the GRR-treated SnO 2 structures exhibited 21.9-fold higher acetone response (R air /R gas = 22.8 @ 5 ppm acetone, 90%RH) compared to MOF-templated p-Co 3 O 4 hollow structures. To the best of our knowledge, the selectivity and response amplitudes reported here for the detection of acetone are superior to those MOF derived metal oxide sensing layers reported so far. Our results demonstrate that highly active MOF-derived sensing layers can be achieved via p-n semiconducting phase transition, driven by a simple and versatile GRR process combined with MOF templating route.

Novel spin transition between S = 5/2 and S = 3/2 in highly saddled iron(III) porphyrin complexes at extremely low temperatures.

PubMed

Ohgo, Yoshiki; Chiba, Yuya; Hashizume, Daisuke; Uekusa, Hidehiro; Ozeki, Tomoji; Nakamura, Mikio

2006-05-14

A novel spin transition between S = 5/2 and S = 3/2 has been observed for the first time in five-coordinate, highly saddled iron(III) porphyrinates by EPR and SQUID measurements at extremely low temperatures.

Synaptic behaviors of thin-film transistor with a Pt/HfO x /n-type indium-gallium-zinc oxide gate stack.

PubMed

Yang, Paul; Park, Daehoon; Beom, Keonwon; Kim, Hyung Jun; Kang, Chi Jung; Yoon, Tae-Sik

2018-07-20

We report a variety of synaptic behaviors in a thin-film transistor (TFT) with a metal-oxide-semiconductor gate stack that has a Pt/HfO x /n-type indium-gallium-zinc oxide (n-IGZO) structure. The three-terminal synaptic TFT exhibits a tunable synaptic weight with a drain current modulation upon repeated application of gate and drain voltages. The synaptic weight modulation is analog, voltage-polarity dependent reversible, and strong with a dynamic range of multiple orders of magnitude (>10 4 ). This modulation process emulates biological synaptic potentiation, depression, excitatory-postsynaptic current, paired-pulse facilitation, and short-term to long-term memory transition behaviors as a result of repeated pulsing with respect to the pulse amplitude, width, repetition number, and the interval between pulses. These synaptic behaviors are interpreted based on the changes in the capacitance of the Pt/HfO x /n-IGZO gate stack, the channel mobility, and the threshold voltage that result from the redistribution of oxygen ions by the applied gate voltage. These results demonstrate the potential of this structure for three-terminal synaptic transistor using the gate stack composed of the HfO x gate insulator and the IGZO channel layer.

Synaptic behaviors of thin-film transistor with a Pt/HfO x /n-type indium–gallium–zinc oxide gate stack

NASA Astrophysics Data System (ADS)

Yang, Paul; Park, Daehoon; Beom, Keonwon; Kim, Hyung Jun; Kang, Chi Jung; Yoon, Tae-Sik

2018-07-01

We report a variety of synaptic behaviors in a thin-film transistor (TFT) with a metal-oxide-semiconductor gate stack that has a Pt/HfO x /n-type indium–gallium–zinc oxide (n-IGZO) structure. The three-terminal synaptic TFT exhibits a tunable synaptic weight with a drain current modulation upon repeated application of gate and drain voltages. The synaptic weight modulation is analog, voltage-polarity dependent reversible, and strong with a dynamic range of multiple orders of magnitude (>104). This modulation process emulates biological synaptic potentiation, depression, excitatory-postsynaptic current, paired-pulse facilitation, and short-term to long-term memory transition behaviors as a result of repeated pulsing with respect to the pulse amplitude, width, repetition number, and the interval between pulses. These synaptic behaviors are interpreted based on the changes in the capacitance of the Pt/HfO x /n-IGZO gate stack, the channel mobility, and the threshold voltage that result from the redistribution of oxygen ions by the applied gate voltage. These results demonstrate the potential of this structure for three-terminal synaptic transistor using the gate stack composed of the HfO x gate insulator and the IGZO channel layer.

Design of n - and p -type oxide thermoelectrics in LaNiO3/SrTiO3(001 ) superlattices exploiting interface polarity

NASA Astrophysics Data System (ADS)

Geisler, Benjamin; Blanca-Romero, Ariadna; Pentcheva, Rossitza

2017-03-01

We investigate the structural, electronic, transport, and thermoelectric properties of LaNiO3/SrTiO3(001 ) superlattices containing either exclusively n - or p -type interfaces or coupled interfaces of opposite polarity by using density functional theory calculations with an on-site Coulomb repulsion term. The results show that significant octahedral tilts are induced in the SrTiO3 part of the superlattice. Moreover, the La-Sr distances and Ni-O out-of-plane bond lengths at the interfaces exhibit a distinct variation by about 7 % with the sign of the electrostatic doping. In contrast to the much studied LaAlO3/SrTiO3 system, the charge mismatch at the interfaces is exclusively accommodated within the LaNiO3 layers, whereas the interface polarity leads to a band offset and to the formation of an electric field within the coupled superlattice. Features of the electronic structure indicate an orbital-selective quantization of quantum well states. The potential- and confinement-induced multiband splitting results in complex cylindrical Fermi surfaces with a tendency towards nesting that depends on the interface polarity. The analysis of the thermoelectric response reveals a particularly large positive Seebeck coefficient (135 μ V /K) and a high figure of merit (0.35) for room-temperature cross-plane transport in the p -type superlattice that is attributed to the participation of the SrTiO3 valence band. Superlattices with either n - or p -type interfaces show cross-plane Seebeck coefficients of opposite sign and thus emerge as a platform to construct an oxide-based thermoelectric generator with structurally and electronically compatible n - and p -type oxide thermoelectrics.

Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles.

PubMed

Gilbert, Benjamin; Katz, Jordan E; Huse, Nils; Zhang, Xiaoyi; Frandsen, Cathrine; Falcone, Roger W; Waychunas, Glenn A

2013-10-28

An emerging area in chemical science is the study of solid-phase redox reactions using ultrafast time-resolved spectroscopy. We have used molecules of the photoactive dye 2',7'-dichlorofluorescein (DCF) anchored to the surface of iron(III) oxide nanoparticles to create iron(II) surface atoms via photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(III) oxide nanoparticles has not been reported. We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(III)-dye complex. Following light absorption, excited state relaxation times of the dye of 115-310 fs were found for all samples. Comparison between TA dynamics on uncoated and dye-sensitized hematite nanoparticles revealed the dye de-excitation pathway to consist of a competition between electron and energy transfer to the nanoparticles. We analyzed the TA data for hematite nanoparticles using a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye-oxide energy transfer is energetically forbidden) even though the acceptor states are different. Comparison of the alignment of the excited states of the dye and the unoccupied states of these oxides showed that the dye injects into acceptor states of different symmetry (Ti t2gvs. Fe eg).

Ultrafast primary processes of an iron-(III) azido complex in solution induced with 266 nm light.

PubMed

Vennekate, Hendrik; Schwarzer, Dirk; Torres-Alacan, Joel; Krahe, Oliver; Filippou, Alexander C; Neese, Frank; Vöhringer, Peter

2012-05-14

The ultrafast photo-induced primary processes of the iron-(III) azido complex, [Fe(III)N(3)(cyclam-acetato)] PF(6) (1), in acetonitrile solution at room temperature were studied using femtosecond spectroscopy with ultraviolet (UV) excitation and mid-infrared (MIR) detection. Following the absorption of a 266 nm photon, the complex undergoes an internal conversion back to the electronic doublet ground state at a time scale below 2 ps. Subsequently, the electronic ground state vibrationally cools with a characteristic time constant of 13 ps. A homolytic bond cleavage was also observed by the appearance of ground state azide radicals, which were identified by their asymmetric stretching vibration at 1659 cm(-1). The azide radical recombines in a geminate fashion with the iron containing fragment within 20 ps. The cage escape leading to well separated fragments after homolytic Fe-N bond breakage was found to occur with a quantum yield of 35%. Finally, non-geminate recombination at nanosecond time scales was seen to further reduce the photolytic quantum yield to below 20% at a wavelength of 266 nm. This journal is © the Owner Societies 2012

Synthesis of visible-light responsive graphene oxide/TiO(2) composites with p/n heterojunction.

PubMed

Chen, Chao; Cai, Weimin; Long, Mingce; Zhou, Baoxue; Wu, Yahui; Wu, Deyong; Feng, Yujie

2010-11-23

Graphene oxide/TiO(2) composites were prepared by using TiCl(3) and graphene oxide as reactants. The concentration of graphene oxide in starting solution played an important role in photoelectronic and photocatalytic performance of graphene oxide/TiO(2) composites. Either a p-type or n-type semiconductor was formed by graphene oxide in graphene oxide/TiO(2) composites. These semiconductors could be excited by visible light with wavelengths longer than 510 nm and acted as sensitizer in graphene oxide/TiO(2) composites. Visible-light driven photocatalytic performance of graphene oxide/TiO(2) composites in degradation of methyl orange was also studied. Crystalline quality and chemical states of carbon elements from graphene oxide in graphene oxide/TiO(2) composites depended on the concentration of graphene oxide in the starting solution. This study shows a possible way to fabricate graphene oxide/semiconductor composites with different properties by using a tunable semiconductor conductivity type of graphene oxide.

Biocompatible magnetofluorescent probes: luminescent silicon quantum dots coupled with superparamagnetic iron(III) oxide.

PubMed

Erogbogbo, Folarin; Yong, Ken-Tye; Hu, Rui; Law, Wing-Cheung; Ding, Hong; Chang, Ching-Wen; Prasad, Paras N; Swihart, Mark T

2010-09-28

Luminescent silicon quantum dots (SiQDs) are gaining momentum in bioimaging applications, based on their unique combination of optical properties and biocompatibility. Here, we report the development of a multimodal probe that combines the optical properties of silicon quantum dots with the superparamagnetic properties of iron oxide nanoparticles to create biocompatible magnetofluorescent nanoprobes. Multiple nanoparticles of each type are coencapsulated within the hydrophobic core of biocompatible phospholipid-polyethyleneglycol (DSPE-PEG) micelles. The size distribution and composition of the magnetofluorescent nanoprobes were characterized by transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). Enhanced cellular uptake of these probes in the presence of a magnetic field was demonstrated in vitro. Their luminescence stability in a prostate cancer tumor model microenvironment was demonstrated in vivo. This paves the way for multimodal silicon quantum-dot-based nanoplatforms for a variety of imaging and delivery applications.

Gallium(iii) and iron(iii) complexes of quinolone antimicrobials.

PubMed

Mjos, Katja Dralle; Cawthray, Jacqueline F; Polishchuk, Elena; Abrams, Michael J; Orvig, Chris

2016-08-16

Iron is an essential nutrient for many microbes. According to the "Trojan Horse Hypothesis", biological systems have difficulties distinguishing between Fe(3+) and Ga(3+), which constitutes the antimicrobial efficacy of the gallium(iii) ion. Nine novel tris(quinolono)gallium(iii) complexes and their corresponding iron(iii) analogs have been synthesized and fully characterized. Quinolone antimicrobial agents from three drug generations were used in this study: ciprofloxacin, enoxacin, fleroxacin, levofloxacin, lomefloxacin, nalidixic acid, norfloxacin, oxolinic acid, and pipemidic acid. The antimicrobial efficacy of the tris(quinolono)gallium(iii) complexes was studied against E. faecalis and S. aureus (both Gram-positive), as well as E. coli, K. pneumonia, and P. aeruginosa (all Gram-negative) in direct comparison to the tris(quinolono)iron(iii) complexes and the corresponding free quinolone ligands at various concentrations. For the tris(quinolono)gallium(iii) complexes, no combinational antimicrobial effects between Ga(3+) and the quinolone antimicrobial agents were observed.

Hydrogen adsorption on two catalysts for the ortho- to parahydrogen conversion: Cr-doped silica and ferric oxide gel.

PubMed

Hartl, Monika; Gillis, Robert Chad; Daemen, Luke; Olds, Daniel P; Page, Katherine; Carlson, Stefan; Cheng, Yongqiang; Hügle, Thomas; Iverson, Erik B; Ramirez-Cuesta, A J; Lee, Yongjoong; Muhrer, Günter

2016-06-29

Molecular hydrogen exists in two spin-rotation coupled states: parahydrogen and orthohydrogen. Due to the variation of energy with rotational level, the occupation of ortho- and parahydrogen states is temperature dependent, with parahydrogen being the dominant species at low temperatures. The equilibrium at 20 K (99.8% parahydrogen) can be reached by natural conversion only after a lengthy process. With the use of a suitable catalyst, this process can be shortened significantly. Two types of commercial catalysts currently being used for ortho- to parahydrogen conversion are: iron(iii) oxide (Fe2O3, IONEX®), and chromium(ii) oxide doped silica catalyst (CrO·SiO2, OXISORB®). We investigate the interaction of ortho- and parahydrogen with the surfaces of these ortho-para conversion catalysts using neutron vibrational spectroscopy. The catalytic surfaces have been characterized using X-ray absorption fine structure (XAFS) and X-ray/neutron pair distribution function measurements.

Synthesis, crystal structure and magnetic properties of a novel tetranuclear oxo-bridged iron(III) butterfly

NASA Astrophysics Data System (ADS)

Arizaga, Livia; Gancheff, Jorge S.; Faccio, Ricardo; Cañón-Mancisidor, Walter; González, Ricardo; Kremer, Carlos; Chiozzone, Raúl

2014-01-01

A novel carboxylate/picolinate oxo-bridged iron(III) cluster, namely [Na2(H2O)8][Fe4(μ-O)2(O2CPh)7(pic)2]2·2H2O (1) where pic = picolinate, has been obtained by reacting "basic iron benzoate" [Fe3O(O2CPh)6(H2O)3](O2CPh) with sodium picolinate in acetonitrile. The compound has been characterized by elemental analysis and IR spectroscopy and its crystal structure has been determined by single-crystal X-ray diffraction.

All oxide semiconductor-based bidirectional vertical p-n-p selectors for 3D stackable crossbar-array electronics

PubMed Central

Bae, Yoon Cheol; Lee, Ah Rahm; Baek, Gwang Ho; Chung, Je Bock; Kim, Tae Yoon; Park, Jea Gun; Hong, Jin Pyo

2015-01-01

Three-dimensional (3D) stackable memory devices including nano-scaled crossbar array are central for the realization of high-density non-volatile memory electronics. However, an essential sneak path issue affecting device performance in crossbar array remains a bottleneck and a grand challenge. Therefore, a suitable bidirectional selector as a two-way switch is required to facilitate a major breakthrough in the 3D crossbar array memory devices. Here, we show the excellent selectivity of all oxide p-/n-type semiconductor-based p-n-p open-based bipolar junction transistors as selectors in crossbar memory array. We report that bidirectional nonlinear characteristics of oxide p-n-p junctions can be highly enhanced by manipulating p-/n-type oxide semiconductor characteristics. We also propose an associated Zener tunneling mechanism that explains the unique features of our p-n-p selector. Our experimental findings are further extended to confirm the profound functionality of oxide p-n-p selectors integrated with several bipolar resistive switching memory elements working as storage nodes. PMID:26289565

Photochemical oxidation of persistent cyanide-related compounds

NASA Astrophysics Data System (ADS)

Budaev, S. L.; Batoeva, A. A.; Khandarkhaeva, M. S.; Aseev, D. G.

2017-03-01

Kinetic regularities of the photolysis of thiocyanate solutions using of mono- and polychromatic UV radiation sources with different spectral ranges are studied. Comparative experiments aimed at investigating the role of photochemical action during the oxidation of thiocyanates with persulfates and additional catalytic activation with iron(III) ions are performed. The rate of conversion and the initial rate of thiocyanate oxidation are found to change in the order UV < UV/S2O 8 2- < S2O 8 2- /Fe3+ < UV/S2O 8 2- /Fe3+. A synergistic effect is detected when using the combined catalytic method for the destruction of thiocyanates by the UV/S2O 8 2- /Fe3+ oxidation system. This effect is due to the formation of reactive oxygen species, as a result of both the decomposition of persulfate and the reduction of inactive Fe3+ intermediates into Fe3+.

The oxidation of Inconel-690 alloy at 600 K in air

NASA Astrophysics Data System (ADS)

Allen, G. C.; Dyke, J. M.; Harris, S. J.; Morris, A.

1988-03-01

The alloy Inconel-690 has been oxidised at 600 K in air for periods varying between 30 s and 120 h and the composition of the oxide layer formed examined by scanning Auger microscopy (SAM), scanning electron microscopy with energy dispersive analysis of X-rays (SEM/EDAX), secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS). Analysis of the spectra revealed the formation of a layer of essentially α-Cr 2O 3 at room temperature. Oxidation at 600 K resulted in the formation of a duplex oxide film with a thin outer layer of iron(III) oxide. Beneath this was a mixed chromium, iron, nickel oxide. Following 8 h of oxidation at 600 K the oxide was approximately 10 nm thick but this was found to vary with the physical surface of the underlying alloy which also appeared to affect the relative rates of diffusion of the ionic species during film growth.

Unipolar n-Type Black Phosphorus Transistors with Low Work Function Contacts.

PubMed

Wang, Ching-Hua; Incorvia, Jean Anne C; McClellan, Connor J; Yu, Andrew C; Mleczko, Michal J; Pop, Eric; Wong, H-S Philip

2018-05-09

Black phosphorus (BP) is a promising two-dimensional (2D) material for nanoscale transistors, due to its expected higher mobility than other 2D semiconductors. While most studies have reported ambipolar BP with a stronger p-type transport, it is important to fabricate both unipolar p- and n-type transistors for low-power digital circuits. Here, we report unipolar n-type BP transistors with low work function Sc and Er contacts, demonstrating a record high n-type current of 200 μA/μm in 6.5 nm thick BP. Intriguingly, the electrical transport of the as-fabricated, capped devices changes from ambipolar to n-type unipolar behavior after a month at room temperature. Transmission electron microscopy analysis of the contact cross-section reveals an intermixing layer consisting of partly oxidized metal at the interface. This intermixing layer results in a low n-type Schottky barrier between Sc and BP, leading to the unipolar behavior of the BP transistor. This unipolar transport with a suppressed p-type current is favorable for digital logic circuits to ensure a lower off-power consumption.

Fabrication of visible light-triggered photocatalytic materials from the coupling of n-type zinc oxide and p-type copper oxide

NASA Astrophysics Data System (ADS)

Gorospe, A. B.; Herrera, M. U.

2017-04-01

Coupling of copper oxide (CuO) and zinc oxide (ZnO) was done by chemical precipitation method. In this method, copper sulfate pentahydrate and zinc sulfate heptahydrate salt precursors were separately dissolved in distilled water; then were mixed together. The copper sulfate-zinc sulfate solution was then combined with a sodium hydroxide solution. The precipitates were collected and washed in distilled water and ethanol several times, then filtered and dried. The dried sample was grounded, and then undergone heat treatment. After heating, the sample was grounded again. Zinc oxide powder and copper oxide powder were also fabricated using chemical precipitation method. X-Ray Diffraction measurements of the coupled CuO/ZnO powder showed the presence of CuO and ZnO in the fabricated sample. Furthermore, other peaks shown by XRD were also identified corresponding to copper, copper (II) oxide, copper sulfate and zinc sulfate. Results of the photocatalytic activity investigation show that the sample exhibited superior photocatalytic degradation of methyl orange under visible light illumination compared to copper oxide powder and zinc oxide powder. This may be attributed to the lower energy gap at the copper oxide-zinc oxide interface, compared to zinc oxide, allowing visible light to trigger its photocatalytic activity.

Hepatic Flavin-Containing Monooxygenase 3 Enzyme Suppressed by Type 1 Allergy-Produced Nitric Oxide.

PubMed

Tanino, Tadatoshi; Bando, Toru; Komada, Akira; Nojiri, Yukie; Okada, Yuna; Ueda, Yukari; Sakurai, Eiichi

2017-11-01

Flavin-containing monooxygenases (FMOs) are major mammalian non-cytochrome P450 oxidative enzymes. T helper 2 cell-activated allergic diseases produce excess levels of nitric oxide (NO) that modify the functions of proteins. However, it remains unclear whether allergy-induced NO affects the pharmacokinetics of drugs metabolized by FMOs. This study investigated alterations of hepatic microsomal FMO1 and FMO3 activities in type 1 allergic mice and further examined the interaction of FMO1 and FMO3 with allergy-induced NO. Imipramine (IMP; FMO1 substrate) N- oxidation activity was not altered in allergic mice with high serum NO and immunoglobulin E levels. At 7 days after primary sensitization (PS7) or secondary sensitization (SS7), benzydamine (BDZ; FMO1 and FMO3 substrate) N- oxygenation was significantly decreased to 70% of individual controls. The expression levels of FMO1 and FMO3 proteins were not significantly changed in the sensitized mice. Hepatic inducible NO synthase (iNOS) mRNA level increased 5-fold and 15-fold in PS7 and SS7 mice, respectively, and hepatic tumor necrosis factor- α levels were greatly enhanced. When a selective iNOS inhibitor was injected into allergic mice, serum NO levels and BDZ N- oxygenation activity returned to control levels. NO directly suppressed BDZ N- oxygenation, which was probably related to FMO3-dependent metabolism in comparison with IMP N- oxidation. In hepatic microsomes from PS7 and SS7 mice, the suppression of BDZ N- oxygenation was restored by ascorbate. Therefore, type 1 allergic mice had differentially suppressed FMO3-dependent BDZ N- oxygenation. The suppression of FMO3 metabolism related to reversible S- nitrosyl modifications of iNOS-derived NO. NO is expected to alter FMO3-metabolic capacity-limited drug pharmacokinetics in humans. Copyright © 2017 by The American Society for Pharmacology and Experimental Therapeutics.

Meat-type chickens have a higher efficiency of mitochondrial oxidative phosphorylation than laying-type chickens.

PubMed

Toyomizu, Masaaki; Kikusato, Motoi; Kawabata, Yusuke; Azad, Md Abul Kalam; Inui, Eriko; Amo, Taku

2011-05-01

Meat-type chickens show high feed efficiency and have a very rapid growth rate compared with laying-type chickens. To clarify whether the type-specific difference in feed conversion efficiency is involved in mitochondrial bioenergetics, modular kinetic analysis was applied to oxidative phosphorylation in skeletal muscle mitochondria of both type chickens. Mitochondria from skeletal muscle of meat-type chickens showed greater substrate oxidation and phosphorylating activities, and less proton leak than those of the laying-type, resulting in a higher efficiency of oxidative phosphorylation. Gene expression and protein content of uncoupling protein (avUCP) but not adenine nucleotide translocase (avANT) gene expression were lower in skeletal muscle mitochondria of meat-type chickens than the laying-type. The current results regarding a higher efficiency of oxidative phosphorylation and UCP content may partially support the high feed efficiency of meat-type chickens. Copyright © 2011 Elsevier Inc. All rights reserved.

Interface states and internal photoemission in p-type GaAs metal-oxide-semiconductor surfaces

NASA Technical Reports Server (NTRS)

Kashkarov, P. K.; Kazior, T. E.; Lagowski, J.; Gatos, H. C.

1983-01-01

An interface photodischarge study of p-type GaAs metal-oxide-semiconductor (MOS) structures revealed the presence of deep interface states and shallow donors and acceptors which were previously observed in n-type GaAs MOS through sub-band-gap photoionization transitions. For higher photon energies, internal photoemission was observed, i.e., injection of electrons to the conduction band of the oxide from either the metal (Au) or from the GaAs valence band; the threshold energies were found to be 3.25 and 3.7 + or - 0.1 eV, respectively. The measured photoemission current exhibited a thermal activation energy of about 0.06 eV, which is consistent with a hopping mechanism of electron transport in the oxide.

Fabrication and Characterization of N-Type Zinc Oxide/P-Type Boron Doped Diamond Heterojunction

NASA Astrophysics Data System (ADS)

Marton, Marián; Mikolášek, Miroslav; Bruncko, Jaroslav; Novotný, Ivan; Ižák, Tibor; Vojs, Marian; Kozak, Halyna; Varga, Marián; Artemenko, Anna; Kromka, Alexander

2015-09-01

Diamond and ZnO are very promising wide-bandgap materials for electronic, photovoltaic and sensor applications because of their excellent electrical, optical, physical and electrochemical properties and biocompatibility. In this contribution we show that the combination of these two materials opens up the potential for fabrication of bipolar heterojunctions. Semiconducting boron doped diamond (BDD) thin films were grown on Si and UV grade silica glass substrates by HFCVD method with various boron concentration in the gas mixture. Doped zinc oxide (ZnO:Al, ZnO:Ge) thin layers were deposited by diode sputtering and pulsed lased deposition as the second semiconducting layer on the diamond films. The amount of dopants within the films was varied to obtain optimal semiconducting properties to form a bipolar p-n junction. Finally, different ZnO/BDD heterostructures were prepared and analyzed. Raman spectroscopy, SEM, Hall constant and I-V measurements were used to investigate the quality, structural and electrical properties of deposited heterostructures, respectively. I-V measurements of ZnO/BDD diodes show a rectifying ratio of 55 at ±4 V. We found that only very low dopant concentrations for both semiconducting materials enabled us to fabricate a functional p-n junction. Obtained results are promising for fabrication of optically transparent ZnO/BDD bipolar heterojunction.

Measurement of n-type Dry Thermally Oxidized 6H-SiC Metal-oxide Semiconductor Diodes by Quasistatic and High-Frequency Capacitance Versus Voltage and Capacitance Transient Techniques

NASA Technical Reports Server (NTRS)

Neudeck, P.; Kang, S.; Petit, J.; Tabib-Azar, M.

1994-01-01

Dry-oxidized n-type 6H-SiC metal-oxide-semiconductor capacitors are investigated using quasistatic capacitance versus voltage (C-V), high-frequency C-V, and pulsed high-frequency capacitance transient (C-t) analysis over the temperature range from 297 to 573 K. The quasistatic C - V characteristics presented are the first reported for 6H-SiC MOS capacitors, and exhibit startling nonidealities due to nonequilibrium conditions that arise from the fact that the recombination/generation process in 6H-SiC is extraordinarily slow even at the highest measurement temperature employed. The high-frequency dark C-V characteristics all showed deep depletion with no observable hysteresis. The recovery of the high-frequency capacitance from deep depletion to inversion was used to characterize the minority-carrier generation process as a function of temperature. Zerbst analysis conducted on the resulting C-t transients, which were longer than 1000 s at 573 K, showed a generation lifetime thermal activation energy of 0.49 eV.

Near ultraviolet InGaN/AlGaN-based light-emitting diodes with highly reflective tin-doped indium oxide/Al-based reflectors.

PubMed

Choi, Chang-Hoon; Han, Jaecheon; Park, Jae-Seong; Seong, Tae-Yeon

2013-11-04

The enhanced light output power of a InGaN/AlGaN-based light-emitting diodes (LEDs) using three different types of highly reflective Sn-doped indium oxide (ITO)/Al-based p-type reflectors, namely, ITO/Al, Cu-doped indium oxide (CIO)/s-ITO(sputtered)/Al, and Ag nano-dots(n-Ag)/CIO/s-ITO/Al, is presented. The ITO/Al-based reflectors exhibit lower reflectance (76 - 84% at 365 nm) than Al only reflector (91.1%). However, unlike Al only n-type contact, the ITO/Al-based contacts to p-GaN show good ohmic characteristics. Near-UV (365 nm) InGaN/AlGaN-based LEDs with ITO/Al, CIO/s-ITO/Al, and n-Ag/CIO/s-ITO/Al reflectors exhibit forward-bias voltages of 3.55, 3.48, and 3.34 V at 20 mA, respectively. The LEDs with the ITO/Al and CIO/s-ITO/Al reflectors exhibit 9.5% and 13.5% higher light output power (at 20 mA), respectively, than the LEDs with the n-Ag/CIO/s-ITO/Al reflector. The improved performance of near UV LEDs is attributed to the high reflectance and low contact resistivity of the ITO/Al-based reflectors, which are better than those of conventional Al-based reflectors.

Hepatic microsomal N-oxidation and N-demethylation of N,N-dimethylaniline in red-winged blackbird compared with rat and other birds

USGS Publications Warehouse

Pan, H.P.; Fouts, J.R.; Devereux, T.R.

1975-01-01

Hepatic microsomes prepared from red-winged blackbirds and albino rats were incubated with N,N-dimethylaniline (DMA)_in complete incubation mixtures at pH 7.9 and 37?C for 10 min. Formaldehyde and N,N-dimethylaniline--oxide produced from DMA were measured. Redwings were found to have significantly lower N-demethylation activities than rats, and redwings had only marginal or no N-oxidation activities. Hepatic microsomes from redwings did not further metabolize the N-oxide. The N-oxidation and N-demethylation activities of brown-headed cowbirds, common grackles, and starlings were similar to those of redwings.

Phenanthridine synthesis through iron-catalyzed intramolecular N-arylation of O-acetyl oxime.

PubMed

Deb, Indubhusan; Yoshikai, Naohiko

2013-08-16

O-Acetyl oximes derived from 2'-arylacetophenones undergo N-O bond cleavage/intramolecular N-arylation in the presence of a catalytic amount of iron(III) acetylacetonate in acetic acid. In combination with the conventional cross-coupling or directed C-H arylation, the reaction offers a convenient route to substituted phenanthridines.

Production of Nitrous Oxide from Nitrite in Stable Type II Methanotrophic Enrichments.

PubMed

Myung, Jaewook; Wang, Zhiyue; Yuan, Tong; Zhang, Ping; Van Nostrand, Joy D; Zhou, Jizhong; Criddle, Craig S

2015-09-15

The coupled aerobic-anoxic nitrous decomposition operation is a new process for wastewater treatment that removes nitrogen from wastewater and recovers energy from the nitrogen in three steps: (1) NH4(+) oxidation to NO2(-), (2) NO2(-) reduction to N2O, and (3) N2O conversion to N2 with energy production. Here, we demonstrate that type II methanotrophic enrichments can mediate step two by coupling oxidation of poly(3-hydroxybutyrate) (P3HB) to NO2(-) reduction. Enrichments grown with NH4(+) and NO2(-) were subject to alternating 48-h aerobic and anoxic periods, in which CH4 and NO2(-) were added together in a "coupled" mode of operation or separately in a "decoupled mode". Community structure was stable in both modes and dominated by Methylocystis. In the coupled mode, production of P3HB and N2O was low. In the decoupled mode, significant P3HB was produced, and oxidation of P3HB drove reduction of NO2(-) to N2O with ∼ 70% conversion for >30 cycles (120 d). In batch tests of wasted cells from the decoupled mode, N2O production rates increased at low O2 or high NO2(-) levels. The results are significant for the development of engineered processes that remove nitrogen from wastewater and for understanding of conditions that favor environmental production of N2O.

Pseudomonas stutzeri N2O reductase contains CuA-type sites.

PubMed Central

Scott, R A; Zumft, W G; Coyle, C L; Dooley, D M

1989-01-01

N2O reductase (N2O----N2) is the terminal enzyme in the energy-conserving denitrification pathway of soil and marine denitrifying bacteria. The protein is composed of two identical subunits and contains eight copper ions per enzyme molecule. The magnetic circular dichroism spectrum of resting (oxidized) N2O reductase is strikingly similar to the magnetic circular dichroism spectrum of the CuA site in mammalian cytochrome c oxidase [Greenwood, C., Hull, B. C., Barber, D., Eglinton, D. G. & Thomson, A. J. (1983) Biochem. J. 215, 303-316] and is unlike the magnetic circular dichroism spectra of all other biological copper chromophores obtained to date. Sulfur (or chlorine) scatterers are required to fit the copper extended x-ray absorption fine structure data of both the oxidized and reduced forms of N2O reductase. Satisfactory fits require a Cu-N or Cu-O [denoted Cu-(N, O)] interaction at 2.0 A, a Cu-(S, Cl) interaction at 2.3 A and an additional Cu(S, Cl) interaction at approximately 2.6 A (oxidized) or approximately 2.7 A (reduced). Approximately eight sulfur ions (per eight copper ions) at approximately 2.3 A are required to fit the extended x-ray absorption fine structure data for both the oxidized and reduced N2O reductase. The 2.3-A Cu-(S, Cl) distance is nearly identical to that previously determined for the CuA site in cytochrome c oxidase. A 2.6-2.7 A Cu-(S, Cl) interaction is also present in resting and fully reduced cytochrome c oxidase. Comparison of the N2O reductase sequence, determined by translating the structural NosZ gene, with cytochrome c oxidase subunit II sequences from several sources indicates that a Gly-Xaa-Xaa-Xaa-Xaa-Xaa-Cys-Ser-Xaa-Xaa-Cys-Xaa-Xaa-Xaa-His stretch is highly conserved. This sequence contains three of the probable ligands (two cysteines and one histidine) in a CuA-type site. Collectively these data establish that Pseudomonas stutzeri N2O reductase contains CuA-type sites. PMID:2542963

Theoretical prediction of a self-forming gallium oxide layer at an n-type GaN/SiO2 interface

NASA Astrophysics Data System (ADS)

Chokawa, Kenta; Narita, Tetsuo; Kikuta, Daigo; Kachi, Tetsu; Shiozaki, Koji; Shiraishi, Kenji

2018-03-01

We examine the energy band diagram at the n-type GaN (n-GaN)/SiO2 interface and show that electron transfer from n-GaN to SiO2 leads to the formation of negatively charged oxygen vacancies in the SiO2, resulting in the self-formation of an n-GaN/Ga2O3/SiO2 structure. On the other hand, it is difficult to automatically form Ga2O3 at a p-type GaN (p-GaN)/SiO2 interface. This electron-transfer-induced self-formation of Ga2O3 causes an interface dipole, which leads to band bending, resulting in an increase in the conduction band offset between GaN and SiO2. Accordingly, by using this self-forming phenomenon, GaN MOSFETs with lower leakage current can be realized.

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

Mechanistic analysis of temperature-dependent current conduction through thin tunnel oxide in n+-polySi/SiO2/n+-Si structures

NASA Astrophysics Data System (ADS)

Samanta, Piyas

2017-09-01

We present a detailed investigation on temperature-dependent current conduction through thin tunnel oxides grown on degenerately doped n-type silicon (n+-Si) under positive bias ( VG ) on heavily doped n-type polycrystalline silicon (n+-polySi) gate in metal-oxide-semiconductor devices. The leakage current measured between 298 and 573 K and at oxide fields ranging from 6 to 10 MV/cm is primarily attributed to Poole-Frenkel (PF) emission of trapped electrons from the neutral electron traps located in the silicon dioxide (SiO2) band gap in addition to Fowler-Nordheim (FN) tunneling of electrons from n+-Si acting as the drain node in FLOating gate Tunnel OXide Electrically Erasable Programmable Read-Only Memory devices. Process-induced neutral electron traps are located at 0.18 eV and 0.9 eV below the SiO2 conduction band. Throughout the temperature range studied here, PF emission current IPF dominates FN electron tunneling current IFN at oxide electric fields Eox between 6 and 10 MV/cm. A physics based new analytical formula has been developed for FN tunneling of electrons from the accumulation layer of degenerate semiconductors at a wide range of temperatures incorporating the image force barrier rounding effect. FN tunneling has been formulated in the framework of Wentzel-Kramers-Brilloiun taking into account the correction factor due to abrupt variation of the energy barrier at the cathode/oxide interface. The effect of interfacial and near-interfacial trapped-oxide charges on FN tunneling has also been investigated in detail at positive VG . The mechanism of leakage current conduction through SiO2 films plays a crucial role in simulation of time-dependent dielectric breakdown of the memory devices and to precisely predict the normal operating field or applied floating gate (FG) voltage for lifetime projection of the devices. In addition, we present theoretical results showing the effect of drain doping concentration on the FG leakage current.

Highly efficient oxidation of amines to imines by singlet oxygen and its application in Ugi-type reactions.

PubMed

Jiang, Gaoxi; Chen, Jian; Huang, Jie-Sheng; Che, Chi-Ming

2009-10-15

A variety of secondary benzylic amines were oxidized to imines in 90% to >99% yields by singlet oxygen generated from oxygen and a porphyrin photosensitizer. On the basis of these reactions, a protocol was developed for oxidative Ugi-type reactions with singlet oxygen as the oxidant. This protocol has been used to synthesize C1- and N-functionalized benzylic amines in up to 96% yields.

Planar-type ferromagnetic tunnel junctions fabricated by SPM local oxidation

NASA Astrophysics Data System (ADS)

Tomoda, Y.; Kayashima, S.; Ogino, T.; Motoyama, M.; Takemura, Y.; Shirakashi, J.

Nanometer-scale oxide wires were fabricated by local oxidation nanolithography using scanning probe microscope (SPM). This technique was applied to the fabrication of planar-type Ni/Ni oxide/Ni ferromagnetic tunnel junctions. In order to induce magnetic shape anisotropy, asymmetrical channel structure was patterned by conventional photolithography and wet etching processes. The magnetoresistance (MR) characteristics were clearly shown in the planar-type Ni/Ni oxide/Ni ferromagnetic tunnel junctions. MR ratio of above 100% was obtained at 17 K. This result suggests that the local oxidation nanolithography using SPM is useful for the application to planar-type ferromagnetic tunnel junctions.

Addition of n-3 fatty acids to a 4-hour lipid infusion does not affect insulin sensitivity, insulin secretion, or markers of oxidative stress in subjects with type 2 diabetes mellitus.

PubMed

Mostad, Ingrid L; Bjerve, Kristian S; Basu, Samar; Sutton, Pauline; Frayn, Keith N; Grill, Valdemar

2009-12-01

Fatty acids (FA) can impair glucose metabolism to a varying degree depending on time of exposure and also of type of FA. Here we tested for acute effects of marine n-3 FA on insulin sensitivity, insulin secretion, energy metabolism, and oxidative stress. This was a randomized, double-blind, crossover study in 11 subjects with type 2 diabetes mellitus. A 4-hour lipid infusion (Intralipid [Fresenius Kabi, Halden, Norway], total of 384 mL) was compared with a similar lipid infusion partly replaced by Omegaven (Fresenius Kabi) that contributed a median of 0.1 g fish oil per kilogram body weight, amounting to 0.04 g/kg of marine n-3 FA. Insulin sensitivity was assessed by isoglycemic hyperinsulinemic clamps; insulin secretion (measured after the clamps), by C-peptide glucagon tests; and energy metabolism, by indirect calorimetry. Infusion of Omegaven increased the proportion of n-3 FA in plasma nonesterified fatty acids (NEFA) compared with Intralipid alone (20:5n-3: median, 1.5% [interquartile range, 0.6%] vs -0.2% [0.2%], P = .001; 22:6n-3: 0.8% [0.4%] vs -0.7% [0.2%], P = .001). However, glucose utilization was not affected; neither was insulin secretion or total energy production (P = .966, .210, and .423, respectively, for the differences between the lipid clamps). Omegaven tended to lower oxidation of fat (P = .062) compared with Intralipid only, correlating with the rise in individual n-3 NEFA (r = 0.627, P = .039). The effects of clamping on phospholipid FA composition, leptin, adiponectin, or F(2)-isoprostane concentrations were not affected by Omegaven. Enrichment of NEFA with n-3 FA during a 4-hour infusion of Intralipid failed to affect insulin sensitivity, insulin secretion, or markers of oxidative stress in subjects with type 2 diabetes mellitus.

Controls on the Fate and Speciation of Np(V) During Iron (Oxyhydr)oxide Crystallization.

PubMed

Bots, Pieter; Shaw, Samuel; Law, Gareth T W; Marshall, Timothy A; Mosselmans, J Frederick W; Morris, Katherine

2016-04-05

The speciation and fate of neptunium as Np(V)O2(+) during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2(+) to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.

Reduced Graphene Oxide/Single-Walled Carbon Nanotube Hybrid Films Using Various p-Type Dopants and Their Application to GaN-Based Light-Emitting Diodes.

PubMed

Lee, Byeong Ryong; Kim, Tae Geun

2017-01-01

This article reports the electrical and optical properties of the reduced graphene oxide (RGO)/single-walled carbon nanotube (SWCNT) films using various p-type dopants and their application to GaN-based light-emitting diodes. To enhance the current injection and spreading of the RGO/SWCNT films on the light-emitting diodes (LEDs), we increased the work function (Φ) of the films using chemical doping with AuCl₃, poly(3,4-ethylenedioxythiophene) oxidized with poly(4-styrenesulfonate) (PEDOT:PSS) and MoO₃; thereby reduced the Schottky barrier height between the RGO/SWCNT films and p-GaN. By comparison, LEDs fabricated with work-function-tuned RGO/SWCNT film doped with MoO₃ exhibited the decrease of the forward voltage from 5.3 V to 5.02 V at 20 mA and the increase of the output power up to 1.26 times. We also analyzed the current injection mechanism using ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy.

Reduced Graphene Oxide/Single-Walled Carbon Nanotube Hybrid Film Using Various p-Type Dopants and Its Application to GaN-Based Light-Emitting Diodes.

PubMed

Lee, Byeong Ryong; Kim, Tae Geun

2016-06-01

This paper reports the electrical and optical properties of the reduced graphene oxide (RGO)/single-walled carbon nanotube (SWNT) films using various p-type dopants and its application to GaN-based light-emitting diodes. To enhance the current injection and spreading of the RGO/SWNT films on the light-emitting diodes (LEDs), we increased the work function (φ) of the films using chemical doping with AuCl3, poly(3,4-ethylenedioxythiophene) oxidized with poly(4-styrenesulfonate) ( PSS) and MoO3; thereby reduced the Schottky barrier height between the RGO/SWNT films and p-GaN. By comparison, LEDs fabricated with work-function-tuned RGO/SWNT film doped with MoO3 exhibited the decrease of the forward voltage from 5.3 V to 5.02 V at 20 mA and the increase of the output power up to 1.26 times. We also analyzed the current injection mechanism using ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy.

Biochemical establishment and characterization of EncM's flavin-N5-oxide cofactor

PubMed Central

Teufel, Robin; Stull, Frederick; Meehan, Michael J.; Michaudel, Quentin; Dorrestein, Pieter C.; Palfey, Bruce; Moore, Bradley S.

2016-01-01

The ubiquitous flavin-dependent monooxygenases commonly catalyze oxygenation reactions by means of a transient C4a-peroxyflavin. A recent study, however, suggested an unprecedented flavin-oxygenating species - proposed as the flavin-N5-oxide (FlN5[O]) - as key to an oxidative Favorskii-type rearrangement in the biosynthesis of the bacterial polyketide antibiotic enterocin. This stable superoxidized flavin is covalently tethered to the enzyme EncM and converted into FADH2 (Flred) during substrate turnover. Subsequent reaction of Flred with molecular oxygen restores the postulated FlN5[O] via an unknown pathway. Here we provide direct evidence for the FlN5[O] species via isotope labeling, proteolytic digestion, and high-resolution tandem mass spectrometry of EncM. We propose that formation of this species occurs by hydrogen-transfer from Flred to molecular oxygen, allowing radical coupling of the formed protonated superoxide and anionic flavin semiquinone at N5, before elimination of water affords the FlN5[O] cofactor. Further biochemical and spectroscopic investigations reveal important features of the FlN5[O] species and the EncM catalytic mechanism. We speculate that flavin-N5-oxides may be intermediates or catalytically active species in other flavoproteins that form the anionic semiquinone and promote access of oxygen to N5. PMID:26067765

Is N,N-dimethylglycine N-oxide a choline and betaine metabolite?

PubMed

Lever, Michael; McEntyre, Christopher J; George, Peter M; Chambers, Stephen T

2017-06-27

Choline metabolism is by oxidation to betaine, which is demethylated to N,N-dimethylglycine; dimethylglycine is oxidatively demethylated to sarcosine. This pathway is important for osmoregulation and as a source of methyl groups. We asked whether another metabolite was involved. We synthesized the N-oxide of dimethylglycine (DMGO) by oxidizing dimethylglycine with peracetic acid, and measured DMGO in human plasma and urine by HPLC-MS/MS with positive ion detection, using two chromatography procedures, based on ion exchange and HILIC separations. The molecular ion DMGOH+ (m/z=120) yielded four significant fragments (m/z=103, 102, 58 and 42). The suspected DMGO peak in human body fluids showed all these fragments, and co-chromatographed with added standard DMGO in both HPLC systems. Typical plasma concentrations of DMGO are under 1 μmol/l. They may be lower in metabolic syndrome patients. Urine concentrations are higher, and DMGO has a higher fractional clearance than dimethylglycine, betaine and choline. It was present in all of over 80 human urine and plasma samples assayed. Plasma DMGO concentrations correlate with plasma DMG concentrations, with betaine and choline concentrations, with the osmolyte myo-inositol, and strongly with urinary DMGO excretion. We conclude that DMGO is probably a normal human metabolite.

Flavin-mediated dual oxidation controls an enzymatic Favorskii-type rearrangement

PubMed Central

Louie, Gordon; Noel, Joseph P.; Baran, Phil S.; Palfey, Bruce; Moore, Bradley S.

2013-01-01

Flavoproteins catalyze a diversity of fundamental redox reactions and are one of the most studied enzyme families1,2. As monooxygenases, they are universally thought to control oxygenation by means of a peroxyflavin species that transfers a single atom of molecular oxygen to an organic substrate1,3,4. Here we report that the bacterial flavoenzyme EncM5,6 catalyzes the peroxyflavin-independent oxygenation-dehydrogenation dual oxidation of a highly reactive poly(β-carbonyl). The crystal structure of EncM with bound substrate mimics coupled with isotope labeling studies reveal previously unknown flavin redox biochemistry. We show that EncM maintains an unanticipated stable flavin oxygenating species, proposed to be a flavin-N5-oxide, to promote substrate oxidation and trigger a rare Favorskii-type rearrangement that is central to the biosynthesis of the antibiotic enterocin. This work provides new insight into the fine-tuning of the flavin cofactor in offsetting the innate reactivity of a polyketide substrate to direct its efficient electrocyclization. PMID:24162851

High carrier concentration p-type transparent conducting oxide films

DOEpatents

Yan, Yanfa; Zhang, Shengbai

2005-06-21

A p-type transparent conducting oxide film is provided which is consisting essentially of, the transparent conducting oxide and a molecular doping source, the oxide and doping source grown under conditions sufficient to deliver the doping source intact onto the oxide.

Oxygen vacancies: The origin of n -type conductivity in ZnO

NASA Astrophysics Data System (ADS)

Liu, Lishu; Mei, Zengxia; Tang, Aihua; Azarov, Alexander; Kuznetsov, Andrej; Xue, Qi-Kun; Du, Xiaolong

2016-06-01

Oxygen vacancy (VO) is a common native point defect that plays crucial roles in determining the physical and chemical properties of metal oxides such as ZnO. However, fundamental understanding of VO is still very sparse. Specifically, whether VO is mainly responsible for the n -type conductivity in ZnO has been still unsettled in the past 50 years. Here, we report on a study of oxygen self-diffusion by conceiving and growing oxygen-isotope ZnO heterostructures with delicately controlled chemical potential and Fermi level. The diffusion process is found to be predominantly mediated by VO. We further demonstrate that, in contrast to the general belief of their neutral attribute, the oxygen vacancies in ZnO are actually +2 charged and thus responsible for the unintentional n -type conductivity as well as the nonstoichiometry of ZnO. The methodology can be extended to study oxygen-related point defects and their energetics in other technologically important oxide materials.

High-Performance Asymmetric Supercapacitors of MnCo2O4 Nanofibers and N-Doped Reduced Graphene Oxide Aerogel.

PubMed

Pettong, Tanut; Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Sukha, Phansiri; Sirisinudomkit, Pichamon; Seubsai, Anusorn; Chareonpanich, Metta; Kongkachuichay, Paisan; Limtrakul, Jumras; Sawangphruk, Montree

2016-12-14

The working potential of symmetric supercapacitors is not so wide because one type of material used for the supercapacitor electrodes prefers either positive or negative charge to both charges. To address this problem, a novel asymmetrical supercapacitor (ASC) of battery-type MnCo 2 O 4 nanofibers (NFs)//N-doped reduced graphene oxide aerogel (N-rGO AE ) was fabricated in this work. The MnCo 2 O 4 NFs at the positive electrode store the negative charges, i.e., solvated OH - , while the N-rGO AE at the negative electrode stores the positive charges, i.e., solvated K + . An as-fabricated aqueous-based MnCo 2 O 4 //N-rGO AE ASC device can provide a wide operating potential of 1.8 V and high energy density and power density at 54 W h kg -1 and 9851 W kg -1 , respectively, with 85.2% capacity retention over 3000 cycles. To understand the charge storage reaction mechanism of the MnCo 2 O 4 , the synchrotron-based X-ray absorption spectroscopy (XAS) technique was also used to determine the oxidation states of Co and Mn at the MnCo 2 O 4 electrode after being electrochemically tested. The oxidation number of Co is oxidized from +2.76 to +2.85 after charging and reduced back to +2.75 after discharging. On the other hand, the oxidation state of Mn is reduced from +3.62 to +3.44 after charging and oxidized to +3.58 after discharging. Understanding in the oxidation states of Co and Mn at the MnCo 2 O 4 electrode here leads to the awareness of the uncertain charge storage mechanism of the spinel-type oxide materials. High-performance ASC here in this work may be practically used in high-power applications.

Plasma vapor deposited n-indium tin oxide/p-copper indium oxide heterojunctions for optoelectronic device applications

NASA Astrophysics Data System (ADS)

Jaya, T. P.; Pradyumnan, P. P.

2017-12-01

Transparent crystalline n-indium tin oxide/p-copper indium oxide diode structures were fabricated on quartz substrates by plasma vapor deposition using radio frequency (RF) magnetron sputtering. The p-n heterojunction diodes were highly transparent in the visible region and exhibited rectifying current-voltage (I-V) characteristics with a good ideality factor. The sputter power during fabrication of the p-layer was found to have a profound effect on I-V characteristics, and the diode with the p-type layer deposited at a maximum power of 200 W exhibited the highest value of the diode ideality factor (η value) of 2.162, which suggests its potential use in optoelectronic applications. The ratio of forward current to reverse current exceeded 80 within the range of applied voltages of -1.5 to +1.5 V in all cases. The diode structure possessed an optical transmission of 60-70% in the visible region.

Effect of compressive stress on stability of N-doped p-type ZnO

NASA Astrophysics Data System (ADS)

Chen, Xingyou; Zhang, Zhenzhong; Yao, Bin; Jiang, Mingming; Wang, Shuangpeng; Li, Binghui; Shan, Chongxin; Liu, Lei; Zhao, Dongxu; Shen, Dezhen

2011-08-01

Nitrogen-doped p-type zinc oxide (p-ZnO:N) thin films were fabricated on a-/c-plane sapphire (a-/c-Al2O3) by plasma-assisted molecular beam epitaxy. Hall-effect measurements show that the p-type ZnO:N on c-Al2O3 degenerated into n-type after a preservation time; however, the one grown on a-Al2O3 showed good stability. The conversion of conductivity in the one grown on c-Al2O3 ascribed to the faster disappearance of NO and the growing N2(O), which is demonstrated by x-ray photoelectron spectroscopy (XPS). Compressive stress, caused by lattice misfit, was revealed by Raman spectra and optical absorption spectra, and it was regarded as the root of the instability in ZnO:N.

Potassium-doped n-type bilayer graphene

NASA Astrophysics Data System (ADS)

Yamada, Takatoshi; Okigawa, Yuki; Hasegawa, Masataka

2018-01-01

Potassium-doped n-type bilayer graphene was obtained. Chemical vapor deposited bilayer and single layer graphene on copper (Cu) foils were used. After etching of Cu foils, graphene was dipped in potassium hydroxide aqueous solutions to dope potassium. Graphene on silicon oxide was characterized by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), and Raman spectroscopy. Both XPS and EDX spectra indicated potassium incorporation into the bilayer graphene via intercalation between the graphene sheets. The downward shift of the 2D peak position of bilayer graphene after the potassium hydroxide (KOH) treatment was confirmed in Raman spectra, indicating that the KOH-treated bilayer graphene was doped with electrons. Electrical properties were measured using Hall bar structures. The Dirac points of bilayer graphene were shifted from positive to negative by the KOH treatment, indicating that the KOH-treated bilayer graphene was n-type conduction. For single layer graphene after the KOH treatment, although electron doping was confirmed from Raman spectra, the peak of potassium in the X-ray photoelectron spectroscopy (XPS) spectrum was not detected. The Dirac points of single layer graphene with and without the KOH treatment showed positive.

Bench-scale operation of the DETOX wet oxidation process for mixed waste

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

Dhooge, P.M.

1993-01-01

Waste matrices containing organics, radionuclides, and metals pose difficult problems in waste treatment and disposal when the organic compounds and/or metals are considered to be hazardous. A means of destroying hazardous organic components while safely containing and concentrating metals would be extremely useful in mixed waste volume reduction or conversion to a radioactive-only form. Previous studies have found the DETOX, a patented process utilizing a novel catalytic wet oxidation by iron(III) oxidant, cold have successful application to mixed wastes, and to many other waste types. This paper describes the results of bench scale studies of DETOX applied to the componentsmore » of liquid mixed wastes, with the goal of establishing parameters for the design of a prototype waste treatment unit. Apparent organic reaction rate orders, and the dependence of apparent reaction rate on the contact area, were measured for vacuum pump oil, scintillation fluids, and trichloroethylene. It was found that reaction rate was proportional to contact area above about 2.% w/w loading of organic. Oxidations in a 4 liter. volume, mixed bench top reactor have given destruction efficiencies of 99.9999+% for common organics. Reaction rates achieved in the mixedbench top reactor were one to two orders of magnitude greater than had been achieved in unmixed reactions; a thoroughly mixed reactor should be capable of oxidizing 10. to 100.+ grams of organic per liter-hour,depending on the nature and concentration of the organic.« less

Bench-scale operation of the DETOX wet oxidation process for mixed waste

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

Dhooge, P.M.

1993-03-01

Waste matrices containing organics, radionuclides, and metals pose difficult problems in waste treatment and disposal when the organic compounds and/or metals are considered to be hazardous. A means of destroying hazardous organic components while safely containing and concentrating metals would be extremely useful in mixed waste volume reduction or conversion to a radioactive-only form. Previous studies have found the DETOX, a patented process utilizing a novel catalytic wet oxidation by iron(III) oxidant, cold have successful application to mixed wastes, and to many other waste types. This paper describes the results of bench scale studies of DETOX applied to the componentsmore » of liquid mixed wastes, with the goal of establishing parameters for the design of a prototype waste treatment unit. Apparent organic reaction rate orders, and the dependence of apparent reaction rate on the contact area, were measured for vacuum pump oil, scintillation fluids, and trichloroethylene. It was found that reaction rate was proportional to contact area above about 2.% w/w loading of organic. Oxidations in a 4 liter. volume, mixed bench top reactor have given destruction efficiencies of 99.9999+% for common organics. Reaction rates achieved in the mixedbench top reactor were one to two orders of magnitude greater than had been achieved in unmixed reactions; a thoroughly mixed reactor should be capable of oxidizing 10. to 100.+ grams of organic per liter-hour,depending on the nature and concentration of the organic.« less

Complexation equilibria and spectrophotometric determination of iron(III) with 1-amino-4-hydroxyanthraquinone.

PubMed

Abu-Bakr, M S; Sedaira, H; Hashem, E Y

1994-10-01

The complex equilibria of iron(III) with 1-amino-4-hydroxyanthraquinone (AMHA) were studied spectrophotometrically in 40% (v/v) ethanol and an ionic strength of 0.1M (NaClO(4)). The complexation reactions were demonstrated and characterized using graphical logarithmic analysis of the absorbance-pH graphs. A simple, rapid, selective and sensitive method for the spectrophotometric determination of trace amounts of Fe(III) is developed based on the formation of Fe(AMHA) complex at pH 2.5 (lambda(max) = 640 nm, epsilon approximately = 2.1 x 10(4) L. mol(-1) . cm(-1)) in the presence of a large number of foreign ions. Interferences caused by palladium(II) was masked by the addition of cyanide ions. The method has been applied to the determination of iron in some synthetic samples and polymetallic iron ores.

Heterocyclic N-Oxides – An Emerging Class of Therapeutic Agents

PubMed Central

Mfuh, Adelphe M.; Larionov, Oleg V.

2016-01-01

Heterocyclic N-oxides have emerged as potent compounds with anticancer, antibacterial, antihypertensive, antiparasitic, anti-HIV, anti-inflammatory, herbicidal, neuroprotective, and procognitive activities. The N-oxide motif has been successfully employed in a number of recent drug development projects. This review surveys the emergence of this scaffold in the mainstream medicinal chemistry with a focus on the discovery of the heterocyclic N-oxide drugs, N-oxide-specific mechanisms of action, drug-receptor interactions and synthetic avenues to these compounds. As the first review on this subject that covers the developments since 1950s to date, it is expected that it will inspire wider implementation of the heterocyclic N-oxide motif in the rational design of new medicinal agents. PMID:26087764

Characterization of moclobemide N-oxidation in human liver microsomes.

PubMed

Hoskins, J; Shenfield, G; Murray, M; Gross, A

2001-07-01

1. Moclobemide underdergoes morpholine ring N-oxidation to form a major metabolite in plasma Rol2-5637. 2. The kinetics of moclobemide N-oxidation in human liver microsomes (HLM) (n = 6) have been investigated and the mixed-function oxidase enzymes catalysing this reaction have been identified using inhibition, enzyme correlation, altered pH and heat pretreatment experiments. 3. N-oxidation followed single enzyme Michealis-Menten kinetics (0.02-4.0 mm). Km app and Vmax ranged from 0.48 to 1.35 mM (mean +/- SD) 0.77 +/- 0.34 mM) and 0.22 to 2.15 nmol mg(-1) min(-1) (1.39 +/- 0.80 nmol mg(-1) respectively. 4. The N-oxidation of moclobemide strongly correlated with benzydamine N-oxidation a probe reaction for flavin-containing monoxygenase (FMO) activity (0.1 mM moclobemide, rs = 0.81, p < 0.005; 4 mM moclobemide, rs = 0.94, p = 0.0001). Correlations were observed between moclobemide N-oxidation and specific cytochromre P450 (CYP) activities at both moclobemide concentrations (0.1 mM moclobemide, CYP2C19 0.66, p < 0.05; 4 mM moclobemide, CYP2E1 rs = 0.56, p < 0.05). 5. The general P450 inhibitor, N-benzylimidazole, did not affect the rate of Rol2-5637 formation (0% inhibition versus control) (at 1.3 mM moclobemide. Furthermore, the rate of Ro12-5637 formation in HLM was unaffected by inhibitors Or substrates of specific P450s (< 10% inhibition versus control). 6. Heat pretreatment of HLM in the absence of NADPH (inactivating FMOs) resulted in 97% inhibition of Ro12-5637 formation. N-oxidation activity was greatest when incubated at pH 8.5. These results ilre consistent with the reaction being FMO medialtetd . 7. In conclusion, moclobemide N-oxidation activity has been observed in HLM in vitro and the reaction is predominantly catalysed by FMOs with a potentially small contribution from cytochrome P450 isoforms.

Evaluation of metal/indium-tin-oxide for transparent low-resistance contacts to p-type GaN.

PubMed

Hou, Wenting; Stark, Christoph; You, Shi; Zhao, Liang; Detchprohm, Theeradetch; Wetzel, Christian

2012-08-10

In search of a better transparent contact to p-GaN, we analyze various metal/indium-tin-oxide (ITO) (Ag/ITO, AgCu/ITO, Ni/ITO, and NiZn/ITO) contact schemes and compare to Ni/Au, NiZn/Ag, and ITO. The metal layer boosts conductivity while the ITO thickness can be adjusted to constructive transmission interference on GaN that exceeds extraction from bare GaN. We find a best compromise for an Ag/ITO (3 nm/67 nm) ohmic contact with a relative transmittance of 97% of the bare GaN near 530 nm and a specific contact resistance of 0.03 Ω·cm2. The contact proves suitable for green light-emitting diodes in epi-up geometry.

Azido and tetrazolo 1,2,4,5-tetrazine N-oxides

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

Chavez, David E.; Parrish, Damon A.; Mitchell, Lauren

2017-02-23

This paper presents the synthesis and characterization of the oxidation products of 3,6-diazido-1,2,4,5-tetrazine (1) and 6-amino-[1,5-b]tetrazolo-1,2,4,5-tetrazine (2). 3,6-Diazido-1,2,4,5-tetrazine-1,4-dioxide was produced from oxidation with peroxytrifluoroacetic acid, and more effectively using hypofluorous acid, and 2 can be oxidized to two different products, 6-amino-[1,5-b]tetrazolo-1,2,4,5-tetrazine mono-N-oxide and di-N-oxide. These N-oxide compounds display promising performance properties as energetic materials.

From iron coordination compounds to metal oxide nanoparticles.

PubMed

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel; Cazacu, Maria

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe 2 III Fe II O(CH 3 COO) 6 (H 2 O) 3 ]·2H 2 O (FeAc1), μ 3 -oxo trinuclear iron(III) acetate, [Fe 3 O(CH 3 COO) 6 (H 2 O) 3 ]NO 3 ∙4H 2 O (FeAc2), iron furoate, [Fe 3 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeF), iron chromium furoate, FeCr 2 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles.

From iron coordination compounds to metal oxide nanoparticles

PubMed Central

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe2 IIIFeIIO(CH3COO)6(H2O)3]·2H2O (FeAc1), μ3-oxo trinuclear iron(III) acetate, [Fe3O(CH3COO)6(H2O)3]NO3∙4H2O (FeAc2), iron furoate, [Fe3O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeF), iron chromium furoate, FeCr2O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles. PMID:28144555

Physical and electrical characterizations of AlGaN/GaN MOS gate stacks with AlGaN surface oxidation treatment

NASA Astrophysics Data System (ADS)

Yamada, Takahiro; Watanabe, Kenta; Nozaki, Mikito; Shih, Hong-An; Nakazawa, Satoshi; Anda, Yoshiharu; Ueda, Tetsuzo; Yoshigoe, Akitaka; Hosoi, Takuji; Shimura, Takayoshi; Watanabe, Heiji

2018-06-01

The impacts of inserting ultrathin oxides into insulator/AlGaN interfaces on their electrical properties were investigated to develop advanced AlGaN/GaN metal–oxide–semiconductor (MOS) gate stacks. For this purpose, the initial thermal oxidation of AlGaN surfaces in oxygen ambient was systematically studied by synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS) and atomic force microscopy (AFM). Our physical characterizations revealed that, when compared with GaN surfaces, aluminum addition promotes the initial oxidation of AlGaN surfaces at temperatures of around 400 °C, followed by smaller grain growth above 850 °C. Electrical measurements of AlGaN/GaN MOS capacitors also showed that, although excessive oxidation treatment of AlGaN surfaces over around 700 °C has an adverse effect, interface passivation with the initial oxidation of the AlGaN surfaces at temperatures ranging from 400 to 500 °C was proven to be beneficial for fabricating high-quality AlGaN/GaN MOS gate stacks.

Oxidant/antioxidant status in obese children compared to pediatric patients with type 1 diabetes mellitus.

PubMed

Codoñer-Franch, Pilar; Pons-Morales, Sara; Boix-García, Laura; Valls-Bellés, Victoria

2010-06-01

Type 1 diabetes (T1D) mellitus and obesity are recognized risk factors for cardiovascular disease (CVD). A common mechanism underlying an increased risk for endothelial dysfunction in these two metabolic diseases is oxidative stress. To evaluate and compare the oxidant/antioxidant defense systems in children affected with T1D or obesity in order to determine the importance of oxidative stress before the emergence of complications. Children with T1D (n = 20) or obesity (n = 22), without comorbidities, and age- and sex-matched controls (n = 16). We assessed lipid peroxidation by circulating levels of lipoperoxides and malondialdehyde, as well as protein oxidation by the concentration of plasma carbonyl groups. The endogenous antioxidative defense system was evaluated by the red cell glutathione peroxidase and reduced glutathione. The serum levels of alpha-tocopherol and beta-carotene were determined to assess exogenous antioxidants. Lipid peroxidation was significantly higher in both T1D and obese children when compared with control children. However, T1D patients showed a more elevated level, because their malondialdehyde values were significantly increased with respect to obese children. Protein oxidation was present in both groups of children and did not differ between them. With respect to obese children, the glutathione peroxidase activity and exogenous antioxidants were decreased in T1D patients. Oxidative stress is present in both children with T1D and obesity, although it is more pronounced in the former. Obese children may suffer an additional oxidative stress in the case of developing impaired glucose metabolism.

Superparamagnetic iron oxide nanoparticles with variable size and an iron oxidation state as prospective imaging agents.

PubMed

Kucheryavy, Pavel; He, Jibao; John, Vijay T; Maharjan, Pawan; Spinu, Leonard; Goloverda, Galina Z; Kolesnichenko, Vladimir L

2013-01-15

Magnetite nanoparticles in the size range of 3.2-7.5 nm were synthesized in high yields under variable reaction conditions using high-temperature hydrolysis of the precursor iron(II) and iron(III) alkoxides in diethylene glycol solution. The average sizes of the particles were adjusted by changing the reaction temperature and time and by using a sequential growth technique. To obtain γ-iron(III) oxide particles in the same range of sizes, magnetite particles were oxidized with dry oxygen in diethylene glycol at room temperature. The products were characterized by DLS, TEM, X-ray powder diffractometry, TGA, chemical analysis, and magnetic measurements. NMR r(1) and r(2) relaxivity measurements in water and diethylene glycol (for OH and CH(2) protons) have shown a decrease in the r(2)/r(1) ratio with the particle size reduction, which correlates with the results of magnetic measurements on magnetite nanoparticles. Saturation magnetization of the oxidized particles was found to be 20% lower than that for Fe(3)O(4) with the same particle size, but their r(1) relaxivities are similar. Because the oxidation of magnetite is spontaneous under ambient conditions, it was important to learn that the oxidation product has no disadvantages as compared to its precursor and therefore may be a better prospective imaging agent because of its chemical stability.

GaN-based flip-chip LEDs with highly reflective ITO/DBR p-type and via hole-based n-type contacts for enhanced current spreading and light extraction

NASA Astrophysics Data System (ADS)

Zhou, Shengjun; Zheng, Chenju; Lv, Jiajiang; Gao, Yilin; Wang, Ruiqing; Liu, Sheng

2017-07-01

We demonstrate GaN-based double-layer electrode flip-chip light-emitting diodes (DLE-FCLED) with highly reflective indium-tin oxide (ITO)/distributed bragg reflector (DBR) p-type contact and via hole-based n-type contacts. Transparent thin ITO in combination with TiO2/SiO2 DBR is used for reflective p-type ohmic contact, resulting in a significant reduction in absorption of light by opaque metal electrodes. The finely distributed via hole-based n-type contacts are formed on the n-GaN layer by etching via holes through p-GaN and multiple quantum well (MQW) active layer, leading to reduced lateral current spreading length, and hence alleviated current crowding effect. The forward voltage of the DLE-FCLED is 0.31 V lower than that of the top-emitting LED at 90 mA. The light output power of DLE-FCLED is 15.7% and 80.8% higher than that of top-emitting LED at 90 mA and 300 mA, respectively. Compared to top- emitting LED, the external quantum efficiency (EQE) of DLE-FCLED is enhanced by 15.4% and 132% at 90 mA and 300 mA, respectively. The maximum light output power of the DLE-FCLED obtained at 195.6 A/cm2 is 1.33 times larger than that of the top-emitting LED obtained at 93 A/cm2.

Impedance of Barrier-Type Oxide Layer on Aluminum

NASA Astrophysics Data System (ADS)

Oh, Han-Jun; Kim, Jung-Gu; Jeong, Yong-Soo; Chi, Choong-Soo

2000-12-01

The impedance characteristics of barrier-type oxide layers on aluminum was studied using impedance spectroscopy. Since anodic films on Al have a variable stoichiometry with a gradual reduction of oxygen deficiency towards the oxide-electrolyte interface, the interpretation of impedance spectra for oxide layers is complex and the impedance of surface layers differs from those of ideal capacitors. This frequency response of the layer with conductance gradients cannot be described by a single resistance-capacitance (RC) element. The oxide layers of Al are properly described by the Young model of dielectric constant with a vertical decay of conductivity.

Effect of the introduction of oxide ion vacancies into cubic fluorite-type rare earth oxides on the NO decomposition catalysis

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

Masui, Toshiyuki; Nagai, Ryosuke; Imanaka, Nobuhito, E-mail: imanaka@chem.eng.osaka-u.ac.jp

2014-12-15

Cubic fluorite-type solid solutions based on Pr{sub 6}O{sub 11} and CeO{sub 2} were synthesized and oxide anion vacancies were intentionally introduced into the cubic fluorite-type lattice through the charge compensating mechanism by Mg{sup 2+} and/or Ca{sup 2+} doping into their lattices. The oxide anion vacancies bring about positive effect on NO decomposition catalysis. The reason for the increase in the catalytic activity was attributed to defect fluorite-type structures close to the C-type cubic one, because C-type cubic rare earth oxides, in which one-quarter of the oxygen atoms in the fluorite-type structure are removed, show high NO decomposition activity. In particular,more » the positive effect of the formation of oxide anion vacancies was significant for Pr{sub 6}O{sub 11} and its solid solutions, because the molar volume of Pr{sub 6}O{sub 11} is larger than that of CeO{sub 2}, and Pr{sub 6}O{sub 11} contains Pr{sup 3+} as well as Pr{sup 4+} and thereby a small amount of oxide anion vacancies exist inherently in the lattice. - Graphical abstract: Oxide anion vacancies intentionally introduced into the cubic fluorite-type lattice bring about positive effect on NO decomposition catalysis. - Highlights: • Cubic fluorite-type solid solutions were synthesized. • Oxide anion vacancies were intentionally introduced into the cubic fluorite-type lattice. • The oxide anion vacancies bring about positive effect on NO decomposition catalysis. • The activity was enhanced by making the structure close to the C-type cubic one.« less

p-type Mesoscopic nickel oxide/organometallic perovskite heterojunction solar cells.

PubMed

Wang, Kuo-Chin; Jeng, Jun-Yuan; Shen, Po-Shen; Chang, Yu-Cheng; Diau, Eric Wei-Guang; Tsai, Cheng-Hung; Chao, Tzu-Yang; Hsu, Hsu-Cheng; Lin, Pei-Ying; Chen, Peter; Guo, Tzung-Fang; Wen, Ten-Chin

2014-04-23

In this article, we present a new paradigm for organometallic hybrid perovskite solar cell using NiO inorganic metal oxide nanocrystalline as p-type electrode material and realized the first mesoscopic NiO/perovskite/[6,6]-phenyl C61-butyric acid methyl ester (PC61BM) heterojunction photovoltaic device. The photo-induced transient absorption spectroscopy results verified that the architecture is an effective p-type sensitized junction, which is the first inorganic p-type, metal oxide contact material for perovskite-based solar cell. Power conversion efficiency of 9.51% was achieved under AM 1.5 G illumination, which significantly surpassed the reported conventional p-type dye-sensitized solar cells. The replacement of the organic hole transport materials by a p-type metal oxide has the advantages to provide robust device architecture for further development of all-inorganic perovskite-based thin-film solar cells and tandem photovoltaics.

p-type Mesoscopic Nickel Oxide/Organometallic Perovskite Heterojunction Solar Cells

PubMed Central

Wang, Kuo-Chin; Jeng, Jun-Yuan; Shen, Po-Shen; Chang, Yu-Cheng; Diau, Eric Wei-Guang; Tsai, Cheng-Hung; Chao, Tzu-Yang; Hsu, Hsu-Cheng; Lin, Pei-Ying; Chen, Peter; Guo, Tzung-Fang; Wen, Ten-Chin

2014-01-01

In this article, we present a new paradigm for organometallic hybrid perovskite solar cell using NiO inorganic metal oxide nanocrystalline as p-type electrode material and realized the first mesoscopic NiO/perovskite/[6,6]-phenyl C61-butyric acid methyl ester (PC61BM) heterojunction photovoltaic device. The photo-induced transient absorption spectroscopy results verified that the architecture is an effective p-type sensitized junction, which is the first inorganic p-type, metal oxide contact material for perovskite-based solar cell. Power conversion efficiency of 9.51% was achieved under AM 1.5 G illumination, which significantly surpassed the reported conventional p-type dye-sensitized solar cells. The replacement of the organic hole transport materials by a p-type metal oxide has the advantages to provide robust device architecture for further development of all-inorganic perovskite-based thin-film solar cells and tandem photovoltaics. PMID:24755642

Variation of betaine, N,N-dimethylglycine, choline, glycerophosphorylcholine, taurine and trimethylamine-N-oxide in the plasma and urine of overweight people with type 2 diabetes over a two-year period.

PubMed

McEntyre, Christopher J; Lever, Michael; Chambers, Stephen T; George, Peter M; Slow, Sandy; Elmslie, Jane L; Florkowski, Christopher M; Lunt, Helen; Krebs, Jeremy D

2015-05-01

Plasma betaine concentrations and urinary betaine excretions have high test-retest reliability. Abnormal betaine excretion is common in diabetes. We aimed to confirm the individuality of plasma betaine and urinary betaine excretion in an overweight population with type 2 diabetes and compare this with the individuality of other osmolytes, one-carbon metabolites and trimethylamine-N-oxide (TMAO), thus assessing their potential usefulness as disease markers. Urine and plasma were collected from overweight subjects with type 2 diabetes at four time points over a two-year period. We measured the concentrations of the osmolytes: betaine, glycerophosphorylcholine (GPC) and taurine, as well as TMAO, and the one-carbon metabolites, N,N-dimethylglycine (DMG) and free choline. Samples were measured using tandem mass spectrometry (LC-MS/MS). Betaine showed a high degree of individuality (or test-retest reliability) in the plasma (index of individuality = 0.52) and urine (index of individuality = 0.45). Betaine in the plasma had positive and negative log-normal reference change values (RCVs) of 54% and -35%, respectively. The other osmolytes, taurine and GPC were more variable in the plasma of individuals compared to the urine. DMG and choline showed high individuality in the plasma and urine. TMAO was highly variable in the plasma and urine (log-normal RCVs ranging from 403% to -80% in plasma). Betaine is highly individual in overweight people with diabetes. Betaine, its metabolite DMG, and precursor choline showed more reliability than the osmolytes, GPC and taurine. The low reliability of TMAO suggests that a single TMAO measurement has low diagnostic value. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Structural & oxidation behavior of TiN & AlxTi1-xN coatings deposited by CA-PVD technique

NASA Astrophysics Data System (ADS)

Thorat, Nirmala; Mundotia, Rajesh; Varma, Ranjana; Kale, Ashwin; Mhatre, Umesh; Patel, Nainesh

2018-04-01

Coatings with thermal stability at elevated temperatures are prerequisite for various high speed machining and high temperature applications. The present work compares the oxidation behavior of the AlxTi1-xN coating prepared with different Al composition. Coated samples were tested at different temperatures in the range of 400 - 800 C to study their oxidation behavior. Percentage weight gain of all the samples were evaluated using high accuracy weighing balance. The depth of oxide layers were studied using Calo-test instrument. The XRD analysis was carried out to specify the phase structure. Higher oxidation rate was observed for TiN coating at all the oxidation temperatures. Oxidation rate was higher for Al13Ti87N and Al70Ti30N coatings compared to Al60Ti40N and Al50Ti50N coatings which exhibits better oxygen diffusion barrier at all the temperature.

Nicotine N-glucuronidation relative to N-oxidation and C-oxidation and UGT2B10 genotype in five ethnic/racial groups

PubMed Central

Murphy, Sharon E.; Park, Sung-Shim L.; Thompson, Elizabeth F.; Wilkens, Lynne R.; Patel, Yesha; Stram, Daniel O.; Le Marchand, Loic

2014-01-01

Nicotine metabolism influences smoking behavior and differences in metabolism probably contribute to ethnic variability in lung cancer risk. We report here on the proportion of nicotine metabolism by cytochrome P450 2A6-catalyzed C-oxidation, UDP-glucuronosyl transferase 2B10 (UGT2B10)-catalyzed N-glucuronidation and flavin monooxygenase 3-catalyzed N-oxidation in five ethnic/racial groups and the role of UGT2B10 genotype on the metabolic patterns observed. Nicotine and its metabolites were quantified in urine from African American (AA, n = 364), Native Hawaiian (NH, n = 311), White (n = 437), Latino (LA, n = 453) and Japanese American (JA, n = 674) smokers. Total nicotine equivalents, the sum of nicotine and six metabolites, and nicotine metabolism phenotypes were calculated. The relationship of UGT2B10 genotype to nicotine metabolic pathways was determined for each group; geometric means were computed and adjusted for age, sex, creatinine, and body mass index. Nicotine metabolism patterns were unique across the groups, C-oxidation was lowest in JA and NH (P < 0.0001), and N-glucuronidation lowest in AA (P < 0.0001). There was no difference in C-oxidation among Whites and AA and LA. Nicotine and cotinine glucuronide ratios were 2- and 3-fold lower in AA compared with Whites. Two UGT variants, a missense mutation (Asp67Tyr, rs61750900) and a splice variant (rs116294140) accounted for 33% of the variation in glucuronidation. In AA, the splice variant accounted for the majority of the reduced nicotine glucuronidation. UGT2B10 variant allele carriers had increased levels of C-oxidation (P = 0.0099). Our data indicate that the relative importance of nicotine metabolic pathways varies by ethnicity, and all pathways should be considered when characterizing the role of nicotine metabolism on smoking behavior and cancer risk. PMID:25233931

Oxidative Stress, DNA Damage and DNA Repair in Female Patients with Diabetes Mellitus Type 2

PubMed Central

Grindel, Annemarie; Guggenberger, Bianca; Eichberger, Lukas; Pöppelmeyer, Christina; Gschaider, Michaela; Tosevska, Anela; Mare, George; Briskey, David; Brath, Helmut; Wagner, Karl-Heinz

2016-01-01

Background Diabetes mellitus type 2 (T2DM) is associated with oxidative stress which in turn can lead to DNA damage. The aim of the present study was to analyze oxidative stress, DNA damage and DNA repair in regard to hyperglycemic state and diabetes duration. Methods Female T2DM patients (n = 146) were enrolled in the MIKRODIAB study and allocated in two groups regarding their glycated hemoglobin (HbA1c) level (HbA1c≤7.5%, n = 74; HbA1c>7.5%, n = 72). In addition, tertiles according to diabetes duration (DD) were created (DDI = 6.94±3.1 y, n = 49; DDII = 13.35±1.1 y, n = 48; DDIII = 22.90±7.3 y, n = 49). Oxidative stress parameters, including ferric reducing ability potential, malondialdehyde, oxidized and reduced glutathione, reduced thiols, oxidized LDL and F2-Isoprostane as well as the activity of antioxidant enzymes superoxide dismutase, catalase and glutathione peroxidase were measured. Damage to DNA was analyzed in peripheral blood mononuclear cells and whole blood with single cell gel electrophoresis. DNA base excision repair capacity was tested with the modified comet repair assay. Additionally, mRNA expressions of nine genes related to base excision repair were analyzed in a subset of 46 matched individuals. Results No significant differences in oxidative stress parameters, antioxidant enzyme activities, damage to DNA and base excision repair capacity, neither between a HbA1c cut off />7.5%, nor between diabetes duration was found. A significant up-regulation in mRNA expression was found for APEX1, LIG3 and XRCC1 in patients with >7.5% HbA1c. Additionally, we observed higher total cholesterol, LDL-cholesterol, LDL/HDL-cholesterol, triglycerides, Framingham risk score, systolic blood pressure, BMI and lower HDL-cholesterol in the hyperglycemic group. Conclusion BMI, blood pressure and blood lipid status were worse in hyperglycemic individuals. However, no major disparities regarding oxidative stress, damage to DNA and DNA repair were present which

Oxidative Stress, DNA Damage and DNA Repair in Female Patients with Diabetes Mellitus Type 2.

PubMed

Grindel, Annemarie; Guggenberger, Bianca; Eichberger, Lukas; Pöppelmeyer, Christina; Gschaider, Michaela; Tosevska, Anela; Mare, George; Briskey, David; Brath, Helmut; Wagner, Karl-Heinz

2016-01-01

Diabetes mellitus type 2 (T2DM) is associated with oxidative stress which in turn can lead to DNA damage. The aim of the present study was to analyze oxidative stress, DNA damage and DNA repair in regard to hyperglycemic state and diabetes duration. Female T2DM patients (n = 146) were enrolled in the MIKRODIAB study and allocated in two groups regarding their glycated hemoglobin (HbA1c) level (HbA1c≤7.5%, n = 74; HbA1c>7.5%, n = 72). In addition, tertiles according to diabetes duration (DD) were created (DDI = 6.94±3.1 y, n = 49; DDII = 13.35±1.1 y, n = 48; DDIII = 22.90±7.3 y, n = 49). Oxidative stress parameters, including ferric reducing ability potential, malondialdehyde, oxidized and reduced glutathione, reduced thiols, oxidized LDL and F2-Isoprostane as well as the activity of antioxidant enzymes superoxide dismutase, catalase and glutathione peroxidase were measured. Damage to DNA was analyzed in peripheral blood mononuclear cells and whole blood with single cell gel electrophoresis. DNA base excision repair capacity was tested with the modified comet repair assay. Additionally, mRNA expressions of nine genes related to base excision repair were analyzed in a subset of 46 matched individuals. No significant differences in oxidative stress parameters, antioxidant enzyme activities, damage to DNA and base excision repair capacity, neither between a HbA1c cut off />7.5%, nor between diabetes duration was found. A significant up-regulation in mRNA expression was found for APEX1, LIG3 and XRCC1 in patients with >7.5% HbA1c. Additionally, we observed higher total cholesterol, LDL-cholesterol, LDL/HDL-cholesterol, triglycerides, Framingham risk score, systolic blood pressure, BMI and lower HDL-cholesterol in the hyperglycemic group. BMI, blood pressure and blood lipid status were worse in hyperglycemic individuals. However, no major disparities regarding oxidative stress, damage to DNA and DNA repair were present which might be due to good medical treatment

Effects of valsartan and amlodipine on oxidative stress in type 2 diabetic patients with hypertension: a randomized, multicenter study

PubMed Central

Kim, Hae Jin; Han, Seung Jin; Kim, Dae Jung; Jang, Hak Chul; Lim, Soo; Choi, Sung Hee; Kim, Yong Hyun; Shin, Dong Hyun; Kim, Se Hwa; Kim, Tae Ho; Ahn, Yu Bae; Ko, Seung Hyun; Kim, Nan Hee; Seo, Ji A; Kim, Ha Young; Lee, Kwan Woo

2017-01-01

Background/Aims Oxidative stress plays an important role in the pathogenesis and progression of diabetic complications and antagonists of renin-angiotensin system and amlodipine have been reported previously to reduce oxidative stress. In this study, we compared the changes in oxidative stress markers after valsartan and amlodipine treatment in type 2 diabetic patients with hypertension and compared the changes in metabolic parameters. Methods Type 2 diabetic subjects with hypertension 30 to 80 years of age who were not taking antihypertensive drugs were randomized into either valsartan (n = 33) or amlodipine (n = 35) groups and treated for 24 weeks. We measured serum nitrotyrosine levels as an oxidative stress marker. Metabolic parameters including serum glucose, insulin, lipid profile, and urine albumin and creatinine were also measured. Results After 24 weeks of valsartan or amlodipine treatment, systolic and diastolic blood pressure decreased, with no significant difference between the groups. Both groups showed a decrease in serum nitrotyrosine (7.74 ± 7.30 nmol/L vs. 3.95 ± 4.07 nmol/L in the valsartan group and 8.37 ± 8.75 nmol/L vs. 2.68 ± 2.23 nmol/L in the amlodipine group) with no significant difference between the groups. Other parameters including glucose, lipid profile, albumin-to-creatinine ratio, and homeostasis model assessment of insulin resistance showed no significant differences before and after treatment in either group. Conclusions Valsartan and amlodipine reduced the oxidative stress marker in type 2 diabetic patients with hypertension. PMID:28490725

Effects of valsartan and amlodipine on oxidative stress in type 2 diabetic patients with hypertension: a randomized, multicenter study.

PubMed

Kim, Hae Jin; Han, Seung Jin; Kim, Dae Jung; Jang, Hak Chul; Lim, Soo; Choi, Sung Hee; Kim, Yong Hyun; Shin, Dong Hyun; Kim, Se Hwa; Kim, Tae Ho; Ahn, Yu Bae; Ko, Seung Hyun; Kim, Nan Hee; Seo, Ji A; Kim, Ha Young; Lee, Kwan Woo

2017-05-01

Oxidative stress plays an important role in the pathogenesis and progression of diabetic complications and antagonists of renin-angiotensin system and amlodipine have been reported previously to reduce oxidative stress. In this study, we compared the changes in oxidative stress markers after valsartan and amlodipine treatment in type 2 diabetic patients with hypertension and compared the changes in metabolic parameters. Type 2 diabetic subjects with hypertension 30 to 80 years of age who were not taking antihypertensive drugs were randomized into either valsartan (n = 33) or amlodipine (n = 35) groups and treated for 24 weeks. We measured serum nitrotyrosine levels as an oxidative stress marker. Metabolic parameters including serum glucose, insulin, lipid profile, and urine albumin and creatinine were also measured. After 24 weeks of valsartan or amlodipine treatment, systolic and diastolic blood pressure decreased, with no significant difference between the groups. Both groups showed a decrease in serum nitrotyrosine (7.74 ± 7.30 nmol/L vs. 3.95 ± 4.07 nmol/L in the valsartan group and 8.37 ± 8.75 nmol/L vs. 2.68 ± 2.23 nmol/L in the amlodipine group) with no significant difference between the groups. Other parameters including glucose, lipid profile, albumin-to-creatinine ratio, and homeostasis model assessment of insulin resistance showed no significant differences before and after treatment in either group. Valsartan and amlodipine reduced the oxidative stress marker in type 2 diabetic patients with hypertension.

Improvements of electronic and optical characteristics of n-GaN-based structures by photoelectrochemical oxidation in glycol solution

NASA Astrophysics Data System (ADS)

Shiozaki, Nanako; Hashizume, Tamotsu

2009-03-01

Surface control of n-GaN was performed by applying a photoelectrochemical oxidation method in a glycol solution to improve the optical and electronic characteristics. The fundamental properties of the oxidation were investigated. The oxidation, chemical composition, and bonding states were analyzed by x-ray photoelectron spectroscopy and micro-Auger electron spectroscopy, in which confirmed the formation of gallium oxide on the surface. The oxide formation rate was about 8 nm/min under UV illumination of 4 mW/cm2. After establishing the basic properties for control of n-GaN oxidation, the surface control technique was applied to achieve low-damage etching, enhancement of the photoluminescence intensity, and selective passivation of the air-exposed sidewalls in an AlGaN/GaN high electron mobility transistor wire structure. The capacitance-voltage measurement revealed the minimum interface-state density between GaN and anodic oxide to be about 5×1011 cm-2 eV-1, which is rather low value for compound semiconductors.

Nanoscale electrical and structural modification induced by rapid thermal oxidation of AlGaN/GaN heterostructures.

PubMed

Greco, Giuseppe; Fiorenza, Patrick; Giannazzo, Filippo; Alberti, Alessandra; Roccaforte, Fabrizio

2014-01-17

In this paper, the structural and electrical modifications induced, in the nanoscale, by a rapid thermal oxidation process on AlGaN/GaN heterostructures, are investigated. A local rapid oxidation (900 ° C in O2, 10 min) localized under the anode region of an AlGaN/GaN diode enabled a reduction of the leakage current with respect to a standard Schottky contact. The insulating properties of the near-surface oxidized layer were probed by a nanoscale electrical characterization using scanning probe microscopy techniques. The structural characterization indicated the formation of a thin uniform oxide layer on the surface, with preferential oxidation paths along V-shaped defects penetrating through the AlGaN/GaN interface. The oxidation process resulted in an expansion of the lattice parameters due to the incorporation of oxygen atoms, accompanied by an increase of the crystal mosaicity. As a consequence, a decrease of the sheet carrier density of the two-dimensional electron gas and a positive shift of the threshold voltage are observed. The results provide useful insights for a possible future integration of rapid oxidation processes during GaN device fabrication.

Origins of n -type doping difficulties in perovskite stannates

NASA Astrophysics Data System (ADS)

Weston, L.; Bjaalie, L.; Krishnaswamy, K.; Van de Walle, C. G.

2018-02-01

The perovskite stannates (A SnO3 ; A = Ba, Sr, Ca) are promising for oxide electronics, but control of n -type doping has proved challenging. Using first-principles hybrid density functional calculations, we investigate La dopants and explore the formation of compensating acceptor defects. We find that La on the A site always behaves as a shallow donor, but incorporation of La on the Sn site can lead to self-compensation. At low La concentrations and in O-poor conditions, oxygen vacancies form in BaSnO3. A -site cation vacancies are found to be dominant among the native compensating centers. Compared to BaSnO3, charge compensation is a larger problem for the wider-band-gap stannates, SrSnO3 and CaSnO3, a trend we can explain based on conduction-band alignments. The formation of compensating acceptor defects can be inhibited by choosing oxygen-poor (cation-rich) growth or annealing conditions, thus providing a pathway for improved n -type doping.

Quantitative determination of some pharmaceutical piperazine derivatives through complexation with iron(III) chloride.

PubMed

Abou-Attia, F M; Issa, Y M; Abdel-Gawad, F M; Abdel-Hamid, S M

2003-08-01

A simple, accurate and sensitive spectrophotometric method has been developed for the determination of three pharmaceutical piperazine derivatives, namely ketoconazole (KC), trimetazidine hydrochloride (TMH) and piribedil (PD). This method is based on the formation of yellow orange complexes between iron(III) chloride and the investigated drugs. The optimum reaction conditions, spectral characteristics, conditional stability constants and composition of the water soluble complexes have been established. The method permits the determination of KC, TMH and PD over a concentration range 1-15, 1-12 and 1-12 microg ml(-1), respectively. Sandell sensitivity is found to be 0.016, 0.013 and 0.013 microg cm(-2) for KC, TMH and PD, respectively. The method was sensitive, simple, reproducible and accurate within +/-1.5%. The method is applicable to the assay of the three drugs under investigation in different dosage forms and the results are in good agreement with those obtained by the official methods (USP and JP).

Dehydroepiandrosterone administration counteracts oxidative imbalance and advanced glycation end product formation in type 2 diabetic patients.

PubMed

Brignardello, Enrico; Runzo, Cristina; Aragno, Manuela; Catalano, Maria Graziella; Cassader, Maurizio; Perin, Paolo Cavallo; Boccuzzi, Giuseppe

2007-11-01

Dehydroepiandrosterone (DHEA) has been shown to prevent oxidative stress in several in vivo and in vitro models. This study aimed to evaluate the effects of DHEA administration on oxidative stress, pentosidine concentration, and tumor necrosis factor (TNF)-alpha/TNF-alpha receptor system activity in patients with type 2 diabetes. Twenty patients were enrolled in the study and randomly assigned to the DHEA (n = 10) or placebo (n = 10) group. Twenty healthy sex- and age-matched subjects with normal glucose levels served as control subjects. DHEA was given as a single daily dose of 50 mg for 12 weeks. Oxidative stress parameters were significantly higher in diabetic patients versus control subjects. Pentosidine levels, as well as soluble TNF receptor (sTNF-R)I and sTNF-RII, were also higher in diabetic patients. After DHEA, plasma levels of reactive oxygen species and hydroxynonenal dropped by 53 and 47%, respectively, whereas the nonenzymatic antioxidants glutathione and vitamin E increased (+38 and +76%, respectively). The same changes in oxidative parameters were detected in peripheral blood mononuclear cells (PBMCs). DHEA treatment also induced a marked decrease of pentosidine plasma concentration in diabetic patients (-50%). Moreover, the TNF-alpha/TNF-alpha receptor system was shown to be less activated after DHEA treatment, in both plasma and PBMCs. Data indicate that DHEA treatment ameliorates the oxidative imbalance induced by hyperglycemia, downregulates the TNF-alpha/TNF-alpha receptor system, and prevents advanced glycation end product formation, suggesting a beneficial effect on the onset and/or progression of chronic complications in type 2 diabetic patients.

Flexible CMOS-Like Circuits Based on Printed P-Type and N-Type Carbon Nanotube Thin-Film Transistors.

PubMed

Zhang, Xiang; Zhao, Jianwen; Dou, Junyan; Tange, Masayoshi; Xu, Weiwei; Mo, Lixin; Xie, Jianjun; Xu, Wenya; Ma, Changqi; Okazaki, Toshiya; Cui, Zheng

2016-09-01

P-type and n-type top-gate carbon nanotube thin-film transistors (TFTs) can be selectively and simultaneously fabricated on the same polyethylene terephthalate (PET) substrate by tuning the types of polymer-sorted semiconducting single-walled carbon nanotube (sc-SWCNT) inks, along with low temperature growth of HfO 2 thin films as shared dielectric layers. Both the p-type and n-type TFTs show good electrical properties with on/off ratio of ≈10 5 , mobility of ≈15 cm 2 V -1 s -1 , and small hysteresis. Complementary metal oxide semiconductor (CMOS)-like logic gates and circuits based on as-prepared p-type and n-type TFTs have been achieved. Flexible CMOS-like inverters exhibit large noise margin of 84% at low voltage (1/2 V dd = 1.5 V) and maximum voltage gain of 30 at V dd of 1.5 V and low power consumption of 0.1 μW. Both of the noise margin and voltage gain are one of the best values reported for flexible CMOS-like inverters at V dd less than 2 V. The printed CMOS-like inverters work well at 10 kHz with 2% voltage loss and delay time of ≈15 μs. A 3-stage ring oscillator has also been demonstrated on PET substrates and the oscillation frequency of 3.3 kHz at V dd of 1 V is achieved. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Geobacter bemidjiensis sp. nov. and Geobacter psychrophilus sp. nov., two novel Fe(III)-reducing subsurface isolates

USGS Publications Warehouse

Nevin, Kelly P.; Holmes, Dawn E.; Woodard, Trevor L.; Hinlein, Erich S.; Ostendorf, David W.; Lovely, Derek R.

2005-01-01

Fe(III)-reducing isolates were recovered from two aquifers in which Fe(III) reduction is known to be important. Strain BemT was enriched from subsurface sediments collected in Bemidji, MN, USA, near a site where Fe(III) reduction is important in aromatic hydrocarbon degradation. Strains P11, P35T and P39 were isolated from the groundwater of an aquifer in Plymouth, MA, USA, in which Fe(III) reduction is important because of long-term inputs of acetate as a highway de-icing agent to the subsurface. All four isolates were Gram-negative, slightly curved rods that grew best in freshwater media. Strains P11, P35T and P39 exhibited motility via means of monotrichous flagella. Analysis of the 16S rRNA and nifD genes indicated that all four strains are δ-proteobacteria and members of the Geobacter cluster of the Geobacteraceae. Differences in phenotypic and phylogenetic characteristics indicated that the four isolates represent two novel species within the genus Geobacter. All of the isolates coupled the oxidation of acetate to the reduction of Fe(III) [iron(III) citrate, amorphous iron(III) oxide, iron(III) pyrophosphate and iron(III) nitrilotriacetate]. All four strains utilized ethanol, lactate, malate, pyruvate and succinate as electron donors and malate and fumarate as electron acceptors. Strain BemT grew fastest at 30 °C, whereas strains P11, P35T and P39 grew equally well at 17, 22 and 30 °C. In addition, strains P11, P35T and P39 were capable of growth at 4 °C. The names Geobacter bemidjiensis sp. nov. (type strain BemT=ATCC BAA-1014T=DSM 16622T=JCM 12645T) and Geobacter psychrophilus sp. nov. (strains P11, P35T and P39; type strain P35T=ATCC BAA-1013T=DSM 16674T=JCM 12644T) are proposed.

The simple preparation of birnessite-type manganese oxide with flower-like microsphere morphology and its remarkable capacity retention

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

Zhu, Gang; Deng, Lingjuan; Wang, Jianfang

Graphical abstract: Flower-like birnessite-type manganese oxide microspheres with large specific surface area and excellent electrochemical properties have been prepared by a facile hydrothermal method. Highlights: ► Birnessite-type manganese oxide with flower-like microsphere morphology and large specific surface area. ► A facile low-temperature hydrothermal method. ► Novel flower-like microsphere consists of the thin nano-platelets. ► Birnessite-type manganese oxide exhibits an ideal capacitive behavior and excellent cycling stability. -- Abstract: Birnessite-type manganese oxide with flower-like microsphere morphology and large specific surface area has been prepared by hydrothermal treating a mixture solution of KMnO{sub 4} and (NH{sub 4}){sub 2}SO{sub 4} at 90 °Cmore » for 24 h. The obtained material is characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N{sub 2} adsorption–desorption. Results indicate that the birnessite-type manganese oxide shows novel flower-like microsphere morphology and a specific surface area of 280 m{sup 2} g{sup −1}, and the flower-like microsphere consists of the thin nano-platelets. Electrochemical characterization indicates that the prepared material exhibits an ideal capacitive behavior with a capacitance value of 278 F g{sup −1} in 1 mol L{sup −1} Na{sub 2}SO{sub 4} aqueous solution at a scan rate of 5 mV s{sup −1}. Moreover, the prepared manganese oxide electrode shows excellent cycle stability, and the specific capacitance can maintain 98.6% of the initial one after 5000 cycles.« less

Biogenic uraninite precipitation and its reoxidation by iron(III) (hydr)oxides: A reaction modeling approach

NASA Astrophysics Data System (ADS)

Spycher, Nicolas F.; Issarangkun, Montarat; Stewart, Brandy D.; Sevinç Şengör, S.; Belding, Eileen; Ginn, Tim R.; Peyton, Brent M.; Sani, Rajesh K.

2011-08-01

One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO 2). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO 2, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO 2 and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO 2, and for this reason the relative rates of sulfide and UO 2 oxidation play a key role on whether or not UO 2 reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe +2 activity in solution and increasing the potential for both sulfide and UO 2 reoxidation. The greater (and unintuitive) UO 2 reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO 2 reoxidation through formation of uranyl carbonate aqueous complexes.

Influence of experimental parameters on iron oxide nanoparticle properties synthesized by thermal decomposition: size and nuclear magnetic resonance studies

NASA Astrophysics Data System (ADS)

Belaïd, Sarah; Stanicki, Dimitri; Vander Elst, Luce; Muller, Robert N.; Laurent, Sophie

2018-04-01

A study of the experimental conditions to synthesize monodisperse iron oxide nanocrystals prepared from the thermal decomposition of iron(III) acetylacetonate was carried out in the presence of surfactants and a reducing agent. The influence of temperature, synthesis time and surfactant amounts on nanoparticle properties is reported. This investigation combines relaxometric characterization and size properties. The relaxometric behavior of the nanomaterials depends on the selected experimental parameters. The synthesis of iron oxide nanoparticles with a high relaxivity and a high saturation magnetization can be obtained with a short reaction time at high temperature. Moreover, the influence of surfactant concentrations determines the optimal value in order to produce iron oxide nanoparticles with a narrow size distribution. The optimized synthesis is rapid, robust and reproductive, and produces nearly monodisperse magnetic nanocrystals.

DDT degradation efficiency and ecotoxicological effects of two types of nano-sized zero-valent iron (nZVI) in water and soil.

PubMed

El-Temsah, Yehia S; Sevcu, Alena; Bobcikova, Katerina; Cernik, Miroslav; Joner, Erik J

2016-02-01

Nano-scale zero-valent iron (nZVI) has been conceived for cost-efficient degradation of chlorinated pollutants in soil as an alternative to e.g permeable reactive barriers or excavation. Little is however known about its efficiency in degradation of the ubiquitous environmental pollutant DDT and its secondary effects on organisms. Here, two types of nZVI (type B made using precipitation with borohydride, and type T produced by gas phase reduction of iron oxides under H2) were compared for efficiency in degradation of DDT in water and in a historically (>45 years) contaminated soil (24 mg kg(-1) DDT). Further, the ecotoxicity of soil and water was tested on plants (barley and flax), earthworms (Eisenia fetida), ostracods (Heterocypris incongruens), and bacteria (Escherichia coli). Both types of nZVI effectively degraded DDT in water, but showed lower degradation of aged DDT in soil. Both types of nZVI had negative impact on the tested organisms, with nZVI-T giving least adverse effects. Negative effects were mostly due to oxidation of nZVI, resulting in O2 consumption and excess Fe(II) in water and soil. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Inulin Supplementation Does Not Reduce Plasma Trimethylamine N-Oxide Concentrations in Individuals at Risk for Type 2 Diabetes.

PubMed

Baugh, Mary Elizabeth; Steele, Cortney N; Angiletta, Christopher J; Mitchell, Cassie M; Neilson, Andrew P; Davy, Brenda M; Hulver, Matthew W; Davy, Kevin P

2018-06-20

Trimethylamine N -oxide (TMAO) is associated with type 2 diabetes (T2DM) and increased risk of adverse cardiovascular events. Prebiotic supplementation has been purported to reduce TMAO production, but whether prebiotics reduce fasting or postprandial TMAO levels is unclear. Sedentary, overweight/obese adults at risk for T2DM ( n = 18) were randomized to consume a standardized diet (55% carbohydrate, 30% fat) with 10 g/day of either an inulin supplement or maltodextrin placebo for 6 weeks. Blood samples were obtained in the fasting state and hourly during a 4-h high-fat challenge meal (820 kcal; 25% carbohydrate, 63% fat; 317.4 mg choline, 62.5 mg betaine, 8.1 mg l-carnitine) before and after the diet. Plasma TMAO and trimethylamine (TMA) moieties (choline, l-carnitine, betaine, and γ-butyrobetaine) were measured using isocratic ultraperformance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). There were no differences in fasting or postprandial TMAO or TMA moieties between the inulin and placebo groups at baseline (all p > 0.05). There were no significant changes in fasting or postprandial plasma TMAO or TMA moiety concentrations following inulin or placebo. These findings suggest that inulin supplementation for 6 weeks did not reduce fasting or postprandial TMAO in individuals at risk for T2DM. Future studies are needed to identify efficacious interventions that reduce plasma TMAO concentrations.

High-voltage SPM oxidation of ZrN: materials for multiscale applications

NASA Astrophysics Data System (ADS)

Farkas, N.; Comer, J. R.; Zhang, G.; Evans, E. A.; Ramsier, R. D.; Dagata, J. A.

2005-02-01

Scanning probe microscope (SPM) oxidation was used to form zirconium oxide features on 200 nm thick ZrN films. The features exhibit rapid yet controlled growth kinetics, even in contact mode with 70 V dc applied between the probe tip and substrate. The features grown for times longer than 10 s are higher than 200 nm, and reach more than 1000 nm in height after 300 s. Long-time oxidation experiments and selective etching of the oxides and nitrides lead us to propose that as the oxidation reaches the silicon substrate, delamination occurs with the simultaneous formation of a thin layer of new material at the ZrN/Si interface. High-voltage oxide growth on ZrN is fast and sustainable, and the robust oxide features are promising candidates for multiscale (nanometre-to-micrometre) applications.

Oxidative Folding and N-terminal Cyclization of Onconase+

PubMed Central

Welker, Ervin; Hathaway, Laura; Xu, Guoqiang; Narayan, Mahesh; Pradeep, Lovy; Shin, Hang-Cheol; Scheraga, Harold A.

2008-01-01

Cyclization of the N-terminal glutamine residue to pyroglutamic acid in onconase, an anti-cancer chemotherapeutic agent, increases the activity and stability of the protein. Here, we examine the correlated effects of the folding/unfolding process and the formation of this N-terminal pyroglutamic acid. The results in this study indicate that cyclization of the N-terminal glutamine has no significant effect on the rate of either reductive unfolding or oxidative folding of the protein. Both the cyclized and uncyclized proteins seem to follow the same oxidative folding pathways; however, cyclization altered the relative flux of the protein in these two pathways by increasing the rate of formation of a kinetically trapped intermediate. Glutaminyl cyclase (QC) catalyzed the cyclization of the unfolded, reduced protein, but had no effect on the disulfide-intact, uncyclized, folded protein. The structured intermediates of uncyclized onconase were also resistant to QC-catalysis, consistent with their having a native-like fold. These observations suggest that, in vivo, cyclization takes place during the initial stages of oxidative folding, specifically, before the formation of structured intermediates. The competition between oxidative folding and QC-mediated cyclization suggests that QC-catalyzed cyclization of the N-terminal glutamine in onconase occurs in the endoplasmic reticulum, probably co-translationally. PMID:17439243

Atomic Layer Deposition of Metastable β-Fe 2 O 3 via Isomorphic Epitaxy for Photoassisted Water Oxidation

DOE PAGES

Emery, Jonathan D.; Schlepütz, Christian M.; Guo, Peijun; ...

2014-12-09

Here, we report the growth and photoelectrochemical (PEC) characterization of the uncommon bibyite phase of iron(III) oxide (β-Fe 2O 3) epitaxially stabilized via atomic layer deposition on an conductive, transparent, and isomorphic template (Sn-doped In 2O 3). Furthermore, as a photoanode, unoptimized β-Fe 2O 3 ultrathin films perform similarly to their ubiquitous α-phase (hematite) counterpart, but reveal a more ideal bandgap (1.8 eV), a ~0.1 V improved photocurrent onset potential, and longer wavelength (>600 nm) spectral response. Finally, stable operation under basic water oxidation justifies further exploration of this atypical phase and motivates the investigation of other unexplored metastable phasesmore » as new PEC materials.« less

Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

PubMed

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

Aerobic nitrous oxide production through N-nitrosating hybrid formation in ammonia-oxidizing archaea.

PubMed

Stieglmeier, Michaela; Mooshammer, Maria; Kitzler, Barbara; Wanek, Wolfgang; Zechmeister-Boltenstern, Sophie; Richter, Andreas; Schleper, Christa

2014-05-01

Soil emissions are largely responsible for the increase of the potent greenhouse gas nitrous oxide (N2O) in the atmosphere and are generally attributed to the activity of nitrifying and denitrifying bacteria. However, the contribution of the recently discovered ammonia-oxidizing archaea (AOA) to N2O production from soil is unclear as is the mechanism by which they produce it. Here we investigate the potential of Nitrososphaera viennensis, the first pure culture of AOA from soil, to produce N2O and compare its activity with that of a marine AOA and an ammonia-oxidizing bacterium (AOB) from soil. N. viennensis produced N2O at a maximum yield of 0.09% N2O per molecule of nitrite under oxic growth conditions. N2O production rates of 4.6±0.6 amol N2O cell(-1) h(-1) and nitrification rates of 2.6±0.5 fmol NO2(-) cell(-1) h(-1) were in the same range as those of the AOB Nitrosospira multiformis and the marine AOA Nitrosopumilus maritimus grown under comparable conditions. In contrast to AOB, however, N2O production of the two archaeal strains did not increase when the oxygen concentration was reduced, suggesting that they are not capable of denitrification. In (15)N-labeling experiments we provide evidence that both ammonium and nitrite contribute equally via hybrid N2O formation to the N2O produced by N. viennensis under all conditions tested. Our results suggest that archaea may contribute to N2O production in terrestrial ecosystems, however, they are not capable of nitrifier-denitrification and thus do not produce increasing amounts of the greenhouse gas when oxygen becomes limiting.

Stabilization of n-type semiconductors to photoanodic dissolution by competitive electron transfer processes

NASA Technical Reports Server (NTRS)

Wrighton, M. S.; Bocarsly, A. B.; Bolts, J. M.; Ellis, A. B.; Legg, K. D.

1977-01-01

The behavior of n-type CdX (X = S, Se, Te) and GaP, GaAs, and InP in alkaline electrolytes containing X(--) and X sub n(--) ions is reviewed. Of the 18 combinations of electrode and electrolyte, 12 alliances are completely stable to photoanodic dissolution of the n-type photoanode. In each case the oxidation of the chalcogenide species at the photoanode is reversed at the cathode to complete an electrochemical cycle involving no net chemical change. The best system in terms of light-to-electric energy conversion seems to be the CdTe-based cell employing the Te(--)/Te2(--) electrolyte, with roughly 10% efficiency at an output voltage of 0.35 V for monochromatic 633 nm input optical energy at about 25 mW/sq cm.

Solvent free oxidation of primary alcohols and diols using thymine iron(III) catalyst.

PubMed

Al-Hunaiti, Afnan; Niemi, Teemu; Sibaouih, Ahlam; Pihko, Petri; Leskelä, Markku; Repo, Timo

2010-12-28

In this study, we developed an efficient and selective iron-based catalyst system for the synthesis of ketones from secondary alcohols and carboxylic acids from primary alcohol. In situ generated iron catalyst of thymine-1-acetate (THA) and FeCl(3) under solvent-free condition exhibits high activity. As an example, 1-octanol and 2-octanol were oxidized to 1-octanoic acid and 2-octanone with 89% and 98% yields respectively.

Codoping method for the fabrication of low-resistivity wide band-gap semiconductors in p-type GaN, p-type AlN and n-type diamond: prediction versus experiment

NASA Astrophysics Data System (ADS)

Katayama-Yoshida, H.; Nishimatsu, T.; Yamamoto, T.; Orita, N.

2001-10-01

We review our new valence control method of a co-doping for the fabrication of low-resistivity p-type GaN, p-type AlN and n-type diamond. The co-doping method is proposed based upon ab initio electronic structure calculation in order to solve the uni-polarity and the compensation problems in the wide band-gap semiconductors. In the co-doping method, we dope both the acceptors and donors at the same time by forming the meta-stable acceptor-donor-acceptor complexes for the p-type or donor-acceptor-donor complexes for the n-type under thermal non-equilibrium crystal growth conditions. We propose the following co-doping method to fabricate the low-resistivity wide band-gap semiconductors; p-type GaN: [Si + 2 Mg (or Be)], [H + 2 Mg (or Be)], [O + 2 Mg (or Be)], p-type AlN: [O + 2 C] and n-type diamond: [B + 2 N], [H + S], [H + 2 P]. We compare our prediction of the co-doping method with the recent successful experiments to fabricate the low-resistivity p-type GaN, p-type AlN and n-type diamond. We show that the co-doping method is the efficient and universal doping method by which to avoid carrier compensation with an increase of the solubility of the dopant, to increase the activation rate by decreasing the ionization energy of acceptors and donors, and to increase the mobility of the carrier.

Positron beam study of indium tin oxide films on GaN

NASA Astrophysics Data System (ADS)

Cheung, C. K.; Wang, R. X.; Beling, C. D.; Djurisic, A. B.; Fung, S.

2007-02-01

Variable energy Doppler broadening spectroscopy has been used to study open-volume defects formed during the fabrication of indium tin oxide (ITO) thin films grown by electron-beam evaporation on n-GaN. The films were prepared at room temperature, 200 and 300 °C without oxygen and at 200 °C under different oxygen partial pressures. The results show that at elevated growth temperatures the ITO has fewer open volume sites and grows with a more crystalline structure. High temperature growth, however, is not sufficient in itself to remove open volume defects at the ITO/GaN interface. Growth under elevated temperature and under partial pressure of oxygen is found to further reduce the vacancy type defects associated with the ITO film, thus improving the quality of the film. Oxygen partial pressures of 6 × 10-3 mbar and above are found to remove open volume defects associated with the ITO/GaN interface. The study suggests that, irrespective of growth temperature and oxygen partial pressure, there is only one type of defect in the ITO responsible for trapping positrons, which we tentatively attribute to the oxygen vacancy.

Saturated amine oxides: Part 8. Hydroacridines: Part 27. Effects of N-oxidation and of N-quaternization on the 15N NMR chemical shifts of N-methylpiperidine-derived mono-, bi-, and tricycloaliphatic tertiary amines.

PubMed

Potmischil, Francisc; Duddeck, Helmut; Nicolescu, Alina; Deleanu, Calin

2007-03-01

The (15)N chemical shifts of 13 N-methylpiperidine-derived mono-, bi- and tricycloaliphatic tertiary amines, their methiodides and their N-epimeric pairs of N-oxides were measured, and the contributions of specific structural parameters to the chemical shifts were determined by multilinear regression analysis. Within the examined compounds, the effects of N-oxidation upon the (15)N chemical shifts of the amines vary from +56 ppm to +90 ppm (deshielding), of which approx. +67.7 ppm is due to the inductive effect of the incoming N(+)--O(-) oxygen atom, whereas the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The effects of quaternization vary from -3.1 ppm to +29.3 ppm, of which approx. +8.9 ppm is due to the inductive effect of the incoming N(+)--CH(3) methyl group, and the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The shift effects of the C-alkyl substituents in the amines, the N-oxides and the methiodides are discussed. Copyright (c) 2007 John Wiley & Sons, Ltd.

The ground states of iron(III) porphines: role of entropy-enthalpy compensation, Fermi correlation, dispersion, and zero-point energies.

PubMed

Kepp, Kasper P

2011-10-01

Porphyrins are much studied due to their biochemical relevance and many applications. The density functional TPSSh has previously accurately described the energy of close-lying electronic states of transition metal systems such as porphyrins. However, a recent study questioned this conclusion based on calculations of five iron(III) porphines. Here, we compute the geometries of 80 different electronic configurations and the free energies of the most stable configurations with the functionals TPSSh, TPSS, and B3LYP. Zero-point energies and entropy favor high-spin by ~4kJ/mol and 0-10kJ/mol, respectively. When these effects are included, and all electronic configurations are evaluated, TPSSh correctly predicts the spin of all the four difficult phenylporphine cases and is within the lower bound of uncertainty of any known theoretical method for the fifth, iron(III) chloroporphine. Dispersion computed with DFT-D3 favors low-spin by 3-53kJ/mol (TPSSh) or 4-15kJ/mol (B3LYP) due to the attractive r(-6) term and the shorter distances in low-spin. The very large and diverse corrections from TPSS and TPSSh seem less consistent with the similarity of the systems than when calculated from B3LYP. If the functional-specific corrections are used, B3LYP and TPSSh are of equal accuracy, and TPSS is much worse, whereas if the physically reasonable B3LYP-computed dispersion effect is used for all functionals, TPSSh is accurate for all systems. B3LYP is significantly more accurate when dispersion is added, confirming previous results. Copyright © 2011 Elsevier Inc. All rights reserved.

Cytotoxicity, permeability, and inflammation of metal oxide nanoparticles in human cardiac microvascular endothelial cells: cytotoxicity, permeability, and inflammation of metal oxide nanoparticles.

PubMed

Sun, Jing; Wang, Shaochuang; Zhao, Dong; Hun, Fei Han; Weng, Lei; Liu, Hui

2011-10-01

Wide applications and extreme potential of metal oxide nanoparticles (NPs) increase occupational and public exposure and may yield extraordinary hazards for human health. Exposure to NPs has a risk for dysfunction of the vascular endothelial cells. The objective of this study was to assess the cytotoxicity of six metal oxide NPs to human cardiac microvascular endothelial cells (HCMECs) in vitro. Metal oxide NPs used in this study included zinc oxide (ZnO), iron(III) oxide (Fe(2)O(3)), iron(II,III) oxide (Fe(3)O(4)), magnesium oxide (MgO), aluminum oxide (Al(2)O(3)), and copper(II) oxide (CuO). The cell viability, membrane leakage of lactate dehydrogenase, intracellular reactive oxygen species, permeability of plasma membrane, and expression of inflammatory markers vascular cell adhesion molecule-1, intercellular adhesion molecule-1, macrophage cationic peptide-1, and interleukin-8 in HCMECs were assessed under controlled and exposed conditions (12-24 h and 0.001-100 μg/ml of exposure). The results indicated that Fe(2)O(3), Fe(3)O(4), and Al(2)O(3) NPs did not have significant effects on cytotoxicity, permeability, and inflammation response in HCMECs at any of the concentrations tested. ZnO, CuO, and MgO NPs produced the cytotoxicity at the concentration-dependent and time-dependent manner, and elicited the permeability and inflammation response in HCMECs. These results demonstrated that cytotoxicity, permeability, and inflammation in vascular endothelial cells following exposure to metal oxide nanoparticles depended on particle composition, concentration, and exposure time. © Springer Science+Business Media B.V. 2011

Low temperature processed complementary metal oxide semiconductor (CMOS) device by oxidation effect from capping layer.

PubMed

Wang, Zhenwei; Al-Jawhari, Hala A; Nayak, Pradipta K; Caraveo-Frescas, J A; Wei, Nini; Hedhili, M N; Alshareef, H N

2015-04-20

In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190 °C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field.

Potential Role of Nitrite for Abiotic Fe(II) Oxidation and Cell Encrustation during Nitrate Reduction by Denitrifying Bacteria

PubMed Central

Klueglein, Nicole; Zeitvogel, Fabian; Stierhof, York-Dieter; Floetenmeyer, Matthias; Konhauser, Kurt O.; Obst, Martin

2014-01-01

Microorganisms have been observed to oxidize Fe(II) at neutral pH under anoxic and microoxic conditions. While most of the mixotrophic nitrate-reducing Fe(II)-oxidizing bacteria become encrusted with Fe(III)-rich minerals, photoautotrophic and microaerophilic Fe(II) oxidizers avoid cell encrustation. The Fe(II) oxidation mechanisms and the reasons for encrustation remain largely unresolved. Here we used cultivation-based methods and electron microscopy to compare two previously described nitrate-reducing Fe(II) oxidizers ( Acidovorax sp. strain BoFeN1 and Pseudogulbenkiania sp. strain 2002) and two heterotrophic nitrate reducers (Paracoccus denitrificans ATCC 19367 and P. denitrificans Pd 1222). All four strains oxidized ∼8 mM Fe(II) within 5 days in the presence of 5 mM acetate and accumulated nitrite (maximum concentrations of 0.8 to 1.0 mM) in the culture media. Iron(III) minerals, mainly goethite, formed and precipitated extracellularly in close proximity to the cell surface. Interestingly, mineral formation was also observed within the periplasm and cytoplasm; intracellular mineralization is expected to be physiologically disadvantageous, yet acetate consumption continued to be observed even at an advanced stage of Fe(II) oxidation. Extracellular polymeric substances (EPS) were detected by lectin staining with fluorescence microscopy, particularly in the presence of Fe(II), suggesting that EPS production is a response to Fe(II) toxicity or a strategy to decrease encrustation. Based on the data presented here, we propose a nitrite-driven, indirect mechanism of cell encrustation whereby nitrite forms during heterotrophic denitrification and abiotically oxidizes Fe(II). This work adds to the known assemblage of Fe(II)-oxidizing bacteria in nature and complicates our ability to delineate microbial Fe(II) oxidation in ancient microbes preserved as fossils in the geological record. PMID:24271182

Selective reduction of N-oxides to amines: application to drug metabolism.

PubMed

Kulanthaivel, Palaniappan; Barbuch, Robert J; Davidson, Rita S; Yi, Ping; Rener, Gregory A; Mattiuz, Edward L; Hadden, Chad E; Goodwin, Lawrence A; Ehlhardt, William J

2004-09-01

Phase I oxidative metabolism of nitrogen-containing drug molecules to their corresponding N-oxides is a common occurrence. There are instances where liquid chromatography/tandem mass spectometry techniques are inadequate to distinguish this pathway from other oxidation processes, including C-hydroxylations and other heteroatom oxidations, such as sulfur to sulfoxide. Therefore, the purpose of the present study was to develop and optimize an efficient and practical chemical method to selectively convert N-oxides to their corresponding amines suitable for drug metabolism applications. Our results indicated that efficient conversion of N-oxides to amines could be achieved with TiCl(3) and poly(methylhydrosiloxane). Among them, we found TiCl(3) to be a facile and easy-to-use reagent, specifically applicable to drug metabolism. There are a few reports describing the use of TiCl(3) to reduce N-O bonds in drug metabolism studies, but this methodology has not been widely used. Our results indicated that TiCl(3) is nearly as efficient when the reductions were carried out in the presence of biological matrices, including plasma and urine. Finally, we have shown a number of examples where TiCl(3) can be successfully used to selectively reduce N-oxides in the presence of sulfoxides and other labile groups.

Metabolism of clebopride in vitro. Identification of N-oxidized products.

PubMed

Huizing, G; Beckett, A H

1980-01-01

1. N-(1'-Benzyl-4'-piperidyl-N-oxide)-4-amino-5-chloro-2-methoxybenzamide, N-(4'-(N-hydroxylpiperidyl)-4-amino-5-chloro-2-methoxybenzamide and N-(4'-(delta 1'-piperidyl-N-oxide))-4-amino-5-chloro-2-methoxybenzamide were obtained from chloroform extracts of incubation mixtures of clebopride or desbenzyl clebopride with 9000 g supernatant of liver homogenates of male NZW rabbits. 2. These metabolites were identified using electron impact (low and high resolution) and field desorption mass spectrometry, and computer averaged time proton magnetic resonance spectroscopy.

Relevance of GaAs(001) surface electronic structure for high frequency dispersion on n-type accumulation capacitance

NASA Astrophysics Data System (ADS)

Pi, T. W.; Chen, W. S.; Lin, Y. H.; Cheng, Y. T.; Wei, G. J.; Lin, K. Y.; Cheng, C.-P.; Kwo, J.; Hong, M.

2017-01-01

This study investigates the origin of long-puzzled high frequency dispersion on the accumulation region of capacitance-voltage characteristics in an n-type GaAs-based metal-oxide-semiconductor. Probed adatoms with a high Pauling electronegativity, Ag and Au, unexpectedly donate charge to the contacted As/Ga atoms of as-grown α2 GaAs(001)-2 × 4 surfaces. The GaAs surface atoms behave as charge acceptors, and if not properly passivated, they would trap those electrons accumulated at the oxide and semiconductor interface under a positive bias. The exemplified core-level spectra of the Al2O3/n-GaAs(001)-2 × 4 and the Al2O3/n-GaAs(001)-4 × 6 interfaces exhibit remnant of pristine surface As emission, thereby causing high frequency dispersion in the accumulation region. For the p-type GaAs, electrons under a negatively biased condition are expelled from the interface, thereby avoiding becoming trapped.

Distinctive functions of Syk N-terminal and C-terminal SH2 domains in the signaling cascade elicited by oxidative stress in B cells.

PubMed

Ding, J; Takano, T; Hermann, P; Gao, S; Han, W; Noda, C; Yanagi, S; Yamamura, H

2000-05-01

Syk plays a crucial role in the transduction of oxidative stress signaling. In this paper, we investigated the roles of Src homology 2 (SH2) domains of Syk in oxidative stress signaling, using Syk-negative DT40 cells expressing the N- or C-terminal SH2 domain mutant [mSH2(N) or mSH2(C)] of Syk. Tyrosine phosphorylation of Syk in cells expressing mSH2(N) Syk after H(2)O(2) treatment was higher than that in cells expressing wild-type Syk or mSH2(C) Syk. The tyrosine phosphorylation of wild-type Syk and mSH2(C) Syk, but not that of mSH2(N), was sensitive to PP2, a specific inhibitor of Src-family protein-tyrosine kinase. In oxidative stress, the C-terminal SH2 domain of Syk was demonstrated to be required for induction of tyrosine phosphorylation of cellular proteins, phospholipase C (PLC)-gamma2 phosphorylation, inositol 1,4, 5-triphosphate (IP(3)) generation, Ca(2)(+) release from intracellular stores, and c-Jun N-terminal kinase activation. In contrast, in mSH2(N) Syk-expressing cells, tyrosine phosphorylation of intracellular proteins including PLC-gamma2 was markedly induced in oxidative stress. The enhanced phosphorylation of mSH2(N) Syk and PLC-gamma2, however, did not link to Ca(2)(+) mobilization from intracellular pools and IP(3) generation. Thus, the N- and C-terminal SH2 domains of Syk possess distinctive functions in oxidative stress signaling.

Aerosol jet printed p- and n-type electrolyte-gated transistors with a variety of electrode materials: exploring practical routes to printed electronics.

PubMed

Hong, Kihyon; Kim, Se Hyun; Mahajan, Ankit; Frisbie, C Daniel

2014-11-12

Printing electrically functional liquid inks is a promising approach for achieving low-cost, large-area, additive manufacturing of flexible electronic circuits. To print thin-film transistors, a basic building block of thin-film electronics, it is important to have several options for printable electrode materials that exhibit high conductivity, high stability, and low-cost. Here we report completely aerosol jet printed (AJP) p- and n-type electrolyte-gated transistors (EGTs) using a variety of different electrode materials including highly conductive metal nanoparticles (Ag), conducting polymers (polystyrenesulfonate doped poly(3,4-ethylendedioxythiophene, PEDOT:PSS), transparent conducting oxides (indium tin oxide), and carbon-based materials (reduced graphene oxide). Using these source-drain electrode materials and a PEDOT:PSS/ion gel gate stack, we demonstrated all-printed p- and n-type EGTs in combination with poly(3-hexythiophene) and ZnO semiconductors. All transistor components (including electrodes, semiconductors, and gate insulators) were printed by AJP. Both kinds of devices showed typical p- and n-type transistor characteristics, and exhibited both low-threshold voltages (<2 V) and high hole and electron mobilities. Our assessment suggests Ag electrodes may be the best option in terms of overall performance for both types of EGTs.

Impaired fat oxidation after a single high-fat meal in insulin-sensitive nondiabetic individuals with a family history of type 2 diabetes.

PubMed

Heilbronn, Leonie K; Gregersen, Søren; Shirkhedkar, Deepali; Hu, Dachun; Campbell, Lesley V

2007-08-01

Individuals with insulin resistance and type 2 diabetes have an impaired ability to switch appropriately between carbohydrate and fatty acid oxidation. However, whether this is a cause or consequence of insulin resistance is unclear, and the mechanism(s) involved in this response is not completely elucidated. Whole-body fat oxidation and transcriptional regulation of genes involved in lipid metabolism in skeletal muscle were measured after a prolonged fast and after consumption of either high-fat (76%) or high-carbohydrate (76%) meals in individuals with no family history of type 2 diabetes (control, n = 8) and in age- and fatness-matched individuals with a strong family history of type 2 diabetes (n = 9). Vastus lateralis muscle biopsies were performed before and 3 h after each meal. Insulin sensitivity and fasting measures of fat oxidation were not different between groups. However, subjects with a family history of type 2 diabetes had an impaired ability to increase fatty acid oxidation in response to the high-fat meal (P < 0.05). This was related to impaired activation of genes involved in lipid metabolism, including those for peroxisome proliferator-activated receptor coactivator-1alpha (PGC1alpha) and fatty acid translocase (FAT)/CD36 (P < 0.05). Of interest, adiponectin receptor-1 expression decreased 23% after the high-fat meal in both groups, but it was not changed after the high-carbohydrate meal. In conclusion, an impaired ability to increase fatty acid oxidation precedes the development of insulin resistance in genetically susceptible individuals. PGC1alpha and FAT/CD36 are likely candidates in mediating this response.

The Oxidation of AlN in Dry and Wet Oxygen

NASA Technical Reports Server (NTRS)

Opila, Elizabeth; Humphrey, Donald; Jacobson, Nathan; Yoshio, Tetsuo; Oda, Kohei

1998-01-01

The oxidation kinetics of AlN containing 3.5 wt% Y2O3 were studied by thermogravimetric analysis in dry oxygen and 10% H2O/balance oxygen at temperatures between 1000 and 1200 C for times between 48 and 100 h. The oxidation kinetics for AlN in dry oxygen were parabolic and of approximately the same magnitude and temperature dependence as other alumina forming materials. In this case, diffusion of oxygen and/or aluminum through the alumina scale is the rate limiting mechanism. The oxidation kinetics for AlN in wet oxygen were nearly linear and much more rapid than rates observed in dry oxygen. Numerous micropores were observed in the alumina formed on AIN in wet oxygen. These pores provide a fast path for oxygen transport. The linear kinetics observed in this case suggest that the interface reaction rate of AlN with wet oxygen is the oxidation rate limiting step.

Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

PubMed Central

Wang, Zhenwei; Al-Jawhari, Hala A.; Nayak, Pradipta K.; Caraveo-Frescas, J. A.; Wei, Nini; Hedhili, M. N.; Alshareef, H. N.

2015-01-01

In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190°C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field. PMID:25892711

Antioxidant, pro-oxidant and cytotoxic properties of parsley.

PubMed

Dorman, H J Damien; Lantto, Tiina A; Raasmaja, Atso; Hiltunen, Raimo

2011-06-01

Parsley (Petroselinum crispum) leaves were macerated with a mixture of methanol: water: acetic acid to produce a crude extract which was then defatted with (40°-60°) petrol. Antioxidant activity of the extract was evaluated using a battery of in vitro assays, viz., iron(iii) reduction, iron(ii) chelation and free radical scavenging assays. Evaluation of the pro-oxidant activity of the extract was based upon its effects upon DNA fragmentation and protein carbonylation. Cytotoxicity and apoptotic effects of the extract were determined in non-cancerous CV1-P fibroblast and cancerous A375 melanoma cells using MTT and LDH tests and caspase 3-like activity assay. The highest concentration, 2.0 mg ml(-1), decreased the viability of both cell lines, however, the cancerous melanoma cells were slightly susceptible to the effects. The observed cytotoxicity was not due to the caspase 3 activity. In conclusion, the toxicity might be explained by the pro-oxidative activity of components within the extract against proteins and/or DNA but it is not related to caspase 3-dependent apoptosis within cells.

Pseudo 2-transistor active pixel sensor using an n-well/gate-tied p-channel metal oxide semiconductor field eeffect transistor-type photodetector with built-in transfer gate

NASA Astrophysics Data System (ADS)

Seo, Sang-Ho; Seo, Min-Woong; Kong, Jae-Sung; Shin, Jang-Kyoo; Choi, Pyung

2008-11-01

In this paper, a pseudo 2-transistor active pixel sensor (APS) has been designed and fabricated by using an n-well/gate-tied p-channel metal oxide semiconductor field effect transistor (PMOSFET)-type photodetector with built-in transfer gate. The proposed sensor has been fabricated using a 0.35 μm 2-poly 4-metal standard complementary metal oxide semiconductor (CMOS) logic process. The pseudo 2-transistor APS consists of two NMOSFETs and one photodetector which can amplify the generated photocurrent. The area of the pseudo 2-transistor APS is 7.1 × 6.2 μm2. The sensitivity of the proposed pixel is 49 lux/(V·s). By using this pixel, a smaller pixel area and a higher level of sensitivity can be realized when compared with a conventional 3-transistor APS which uses a pn junction photodiode.

Reversible and Precisely Controllable p/n-Type Doping of MoTe2 Transistors through Electrothermal Doping.

PubMed

Chang, Yuan-Ming; Yang, Shih-Hsien; Lin, Che-Yi; Chen, Chang-Hung; Lien, Chen-Hsin; Jian, Wen-Bin; Ueno, Keiji; Suen, Yuen-Wuu; Tsukagoshi, Kazuhito; Lin, Yen-Fu

2018-03-01

Precisely controllable and reversible p/n-type electronic doping of molybdenum ditelluride (MoTe 2 ) transistors is achieved by electrothermal doping (E-doping) processes. E-doping includes electrothermal annealing induced by an electric field in a vacuum chamber, which results in electron (n-type) doping and exposure to air, which induces hole (p-type) doping. The doping arises from the interaction between oxygen molecules or water vapor and defects of tellurium at the MoTe 2 surface, and allows the accurate manipulation of p/n-type electrical doping of MoTe 2 transistors. Because no dopant or special gas is used in the E-doping processes of MoTe 2 , E-doping is a simple and efficient method. Moreover, through exact manipulation of p/n-type doping of MoTe 2 transistors, quasi-complementary metal oxide semiconductor adaptive logic circuits, such as an inverter, not or gate, and not and gate, are successfully fabricated. The simple method, E-doping, adopted in obtaining p/n-type doping of MoTe 2 transistors undoubtedly has provided an approach to create the electronic devices with desired performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Emissions of nitrous acid (HONO), nitric oxide (NO) and nitrous oxide (N2O) from boreal agricultural soil - Effect of N fertilization

NASA Astrophysics Data System (ADS)

Bhattarai, Hem Raj; Virkajärvi, Perttu; -Yli Pirilä, Pasi; Maljanen, Marja

2017-04-01

There is no doubt that nitrogen (N) fertilization has crucial role in increasing food production. However, in parallel it can cause severe impact in environment such as eutrophication, surface/groundwater pollution via nitrate (NO3-) leaching and emissions of N trace gases. Fertilization increases the emissions of nitrous oxide (N2O) which is 260 stronger greenhouse gas than carbon dioxide (CO2). It also enhances the emissions of nitric oxide (NO); an oxidized and very reactive form of nitrogen which can fluctuate the ozone (O3) concentration in atmosphere and cause acidification. The effects of N- fertilization on the emission of N2O and NO from agricultural soil are well known. However, the effects of N fertilization on nitrous acid (HONO) emissions are unknown. Few studies have shown that HONO is emitted from soil but they lack to interlink fertilization and HONO emission. HONO accounts for 17-34 % of hydroxyl (OH-) radical production? in the atmosphere, OH- radicals have vital role in atmospheric chemistry; they can cause photochemical smog, form O3, oxidize volatile organic compounds and also atmospheric methane (CH4). We formulated hypothesis that N fertilization will increase the HONO emissions as it does for N2O and NO. To study this, we took soil samples from agricultural soil receiving different amount of N-fertilizer (0, 250 and 450 kg ha-1) in eastern Finland. HONO emissions were measured by dynamic chamber technique connected with LOPAP (Quma Elektronik & Analytik GmbH), NO by NOx analyzer (Thermo scientific) and static chamber technique and gas chromatograph was used for N2O gas sampling and analysis. Several soil parameters were also measured to establish the relationship between the soil properties, fertilization rate and HONO emission. This study is important because eventually it will open up more questions regarding the forms of N loss from soils and impact of fertilization on atmospheric chemistry.

Ultraviolet GaN photodetectors on Si via oxide buffer heterostructures with integrated short period oxide-based distributed Bragg reflectors and leakage suppressing metal-oxide-semiconductor contacts

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

Szyszka, A., E-mail: szyszka@ihp-microelectronics.com, E-mail: adam.szyszka@pwr.wroc.pl; Faculty of Microsystem Electronics and Photonics, Wroclaw University of Technology, Janiszewskiego 11/17, 50-372 Wroclaw; Lupina, L.

2014-08-28

Based on a novel double step oxide buffer heterostructure approach for GaN integration on Si, we present an optimized Metal-Semiconductor-Metal (MSM)-based Ultraviolet (UV) GaN photodetector system with integrated short-period (oxide/Si) Distributed Bragg Reflector (DBR) and leakage suppressing Metal-Oxide-Semiconductor (MOS) electrode contacts. In terms of structural properties, it is demonstrated by in-situ reflection high energy electron diffraction and transmission electron microscopy-energy dispersive x-ray studies that the DBR heterostructure layers grow with high thickness homogeneity and sharp interface structures sufficient for UV applications; only minor Si diffusion into the Y{sub 2}O{sub 3} films is detected under the applied thermal growth budget. Asmore » revealed by comparative high resolution x-ray diffraction studies on GaN/oxide buffer/Si systems with and without DBR systems, the final GaN layer structure quality is not significantly influenced by the growth of the integrated DBR heterostructure. In terms of optoelectronic properties, it is demonstrated that—with respect to the basic GaN/oxide/Si system without DBR—the insertion of (a) the DBR heterostructures and (b) dark current suppressing MOS contacts enhances the photoresponsivity below the GaN band-gap related UV cut-off energy by almost up to two orders of magnitude. Given the in-situ oxide passivation capability of grown GaN surfaces and the one order of magnitude lower number of superlattice layers in case of higher refractive index contrast (oxide/Si) systems with respect to classical III-N DBR superlattices, virtual GaN substrates on Si via functional oxide buffer systems are thus a promising robust approach for future GaN-based UV detector technologies.« less

Degradation of superconducting Nb/NbN films by atmospheric oxidation

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

Henry, M. David; Wolfley, Steve; Young, Travis

2017-03-01

Niobium and niobium nitride thin films are transitioning from fundamental research toward wafer scale manufacturing with technology drivers that include superconducting circuits and electronics, optical single photon detectors, logic, and memory. Successful microfabrication requires precise control over the properties of sputtered superconducting films, including oxidation. Previous work has demonstrated the mechanism in oxidation of Nb and how film structure could have deleterious effects upon the superconducting properties. This study provides an examination of atmospheric oxidation of NbN films. By examination of the room temperature sheet resistance of NbN bulk oxidation was identified and confirmed by secondary ion mass spectrometry. Asmore » a result, Meissner magnetic measurements confirmed the bulk oxidation not observed with simple cryogenic resistivity measurements.« less

Fabrication of DC inorganic electroluminescent thin-film devices with novel n-p-n type structure

NASA Astrophysics Data System (ADS)

Ishimura, Takuyoshi; Matsumoto, Hironaga

2014-04-01

Inorganic electroluminescent (iEL) thin films are used in light-emitting devices and are functional under alternating current conditions only. Stable luminescent light has yet to be obtained under direct current conditions. We postulated that thin-film iEL light emission occurs when an injected electron occupies the excited state of a luminescent center and then recombines radiatively. From this perspective, we fabricated a novel stacked n-p-n type thin-film iEL device composed of indium tin oxide (ITO)-ZnO-CuAlO2-ZnS-ZnS:TbF3-Al thin films and obtained stable luminescence using a low-voltage DC power supply. The overall luminescent color of the device depended on only the dopant in the luminescent layer, not the band gap or thin-film material.

Chemical-free n-type and p-type multilayer-graphene transistors

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

Dissanayake, D. M. N. M., E-mail: nandithad@voxtel-inc.com; Eisaman, M. D.; Department of Electrical and Computer Engineering, Stony Brook University, Stony Brook, New York 11794

A single-step doping method to fabricate n- and p-type multilayer graphene (MG) top-gate field effect transistors (GFETs) is demonstrated. The transistors are fabricated on soda-lime glass substrates, with the n-type doping of MG caused by the sodium in the substrate without the addition of external chemicals. Placing a hydrogen silsesquioxane (HSQ) barrier layer between the MG and the substrate blocks the n-doping, resulting in p-type doping of the MG above regions patterned with HSQ. The HSQ is deposited in a single fabrication step using electron beam lithography, allowing the patterning of arbitrary sub-micron spatial patterns of n- and p-type doping.more » When a MG channel is deposited partially on the barrier and partially on the glass substrate, a p-type and n-type doping profile is created, which is used for fabricating complementary transistors pairs. Unlike chemically doped GFETs in which the external dopants are typically introduced from the top, these substrate doped GFETs allow for a top gate which gives a stronger electrostatic coupling to the channel, reducing the operating gate bias. Overall, this method enables scalable fabrication of n- and p-type complementary top-gated GFETs with high spatial resolution for graphene microelectronic applications.« less

First evidence of pyrrolizidine alkaloid N-oxide-induced hepatic sinusoidal obstruction syndrome in humans.

PubMed

Yang, Mengbi; Ruan, Jianqing; Gao, Hong; Li, Na; Ma, Jiang; Xue, Junyi; Ye, Yang; Fu, Peter Pi-Cheng; Wang, Jiyao; Lin, Ge

2017-12-01

Pyrrolizidine alkaloids (PAs) are among the most potent phytotoxins widely distributed in plant species around the world. PA is one of the major causes responsible for the development of hepatic sinusoidal obstruction syndrome (HSOS) and exerts hepatotoxicity via metabolic activation to form the reactive metabolites, which bind with cellular proteins to generate pyrrole-protein adducts, leading to hepatotoxicity. PA N-oxides coexist with their corresponding PAs in plants with varied quantities, sometimes even higher than that of PAs, but the toxicity of PA N-oxides remains unclear. The current study unequivocally identified PA N-oxides as the sole or predominant form of PAs in 18 Gynura segetum herbal samples ingested by patients with liver damage. For the first time, PA N-oxides were recorded to induce HSOS in human. PA N-oxide-induced hepatotoxicity was further confirmed on mice orally dosed of herbal extract containing 170 μmol PA N-oxides/kg/day, with its hepatotoxicity similar to but potency much lower than the corresponding PAs. Furthermore, toxicokinetic study after a single oral dose of senecionine N-oxide (55 μmol/kg) on rats revealed the toxic mechanism that PA N-oxides induced hepatotoxicity via their biotransformation to the corresponding PAs followed by the metabolic activation to form pyrrole-protein adducts. The remarkable differences in toxicokinetic profiles of PAs and PA N-oxides were found and attributed to their significantly different hepatotoxic potency. The findings of PA N-oxide-induced hepatotoxicity in humans and rodents suggested that the contents of both PAs and PA N-oxides present in herbs and foods should be regulated and controlled in use.

N-Hydroxylation of 4-Aminobiphenyl by CYP2E1 Produces Oxidative Stress in a Mouse Model of Chemically Induced Liver Cancer

PubMed Central

Wang, Shuang; Sugamori, Kim S.; Tung, Aveline; McPherson, J. Peter; Grant, Denis M.

2015-01-01

4-Aminobiphenyl (ABP) is a trace component of cigarette smoke and hair dyes, a suspected human carcinogen and a potent rodent liver carcinogen. Postnatal exposure of mice to ABP results in a higher incidence of liver tumors in males than in females, paralleling the sex difference in human liver cancer incidence. A traditional model of ABP tumorigenesis involves initial CYP1A2-mediated N-hydroxylation, which eventually leads to production of mutagenic ABP-DNA adducts that initiate tumor growth. However, several studies have found no correlation between sex or CYP1A2 function and the DNA-damaging, mutagenic, or tumorigenic effects of ABP. Oxidative stress may be an important etiological factor for liver cancer, and it has also been linked to ABP exposure. The goals of this study were to identify novel enzyme(s) that contribute to ABP N-oxidation, and to investigate a potential role for oxidative stress in ABP liver tumorigenicity. Isozyme-selective inhibition experiments using liver microsomes from wild-type and genetically modified mice identified CYP2E1 as a major ABP N-hydroxylating enzyme. The N-hydroxylation of ABP by transiently expressed CYP2E1 produced oxidative stress in cultured mouse hepatoma cells. In vivo postnatal exposure of mice to a tumorigenic dose of ABP also produced oxidative stress in male wild-type mice, but not in male Cyp2e1(−/−) mice or in female mice. However, a stronger NRF2-associated antioxidant response was observed in females. Our results identify CYP2E1 as a novel ABP-N-oxidizing enzyme, and suggest that sex differences in CYP2E1-dependent oxidative stress and antioxidant responses to ABP may contribute to the observed sex difference in tumor incidence. PMID:25601990

Electronic conduction in La-based perovskite-type oxides

PubMed Central

Ohbayashi, Kazushige; Koumoto, Kunihito

2015-01-01

A systematic study of La-based perovskite-type oxides from the viewpoint of their electronic conduction properties was performed. LaCo0.5Ni0.5O3±δ was found to be a promising candidate as a replacement for standard metals used in oxide electrodes and wiring that are operated at temperatures up to 1173 K in air because of its high electrical conductivity and stability at high temperatures. LaCo0.5Ni0.5O3±δ exhibits a high conductivity of 1.9 × 103 S cm−1 at room temperature (R.T.) because of a high carrier concentration n of 2.2 × 1022 cm−3 and a small effective mass m∗ of 0.10 me. Notably, LaCo0.5Ni0.5O3±δ exhibits this high electrical conductivity from R.T. to 1173 K, and little change in the oxygen content occurs under these conditions. LaCo0.5Ni0.5O3±δ is the most suitable for the fabrication of oxide electrodes and wiring, though La1−xSrxCoO3±δ and La1−xSrxMnO3±δ also exhibit high electronic conductivity at R.T., with maximum electrical conductivities of 4.4 × 103 S cm−1 for La0.5Sr0.5CoO3±δ and 1.5 × 103 S cm−1 for La0.6Sr0.4MnO3±δ because oxygen release occurs in La1−xSrxCoO3±δ as elevating temperature and the electrical conductivity of La0.6Sr0.4MnO3±δ slightly decreases at temperatures above 400 K. PMID:27877778

Simplified Synthesis of Isotopically Labeled 5,5-Dimethyl-pyrroline N-Oxide

PubMed Central

Leinisch, Fabian; Jiang, JinJie; Deterding, Leesa J.; Mason, Ronald P.

2011-01-01

5,5-Dimethylpyrroline N-oxide (15N) and 5,5-di(trideuteromethyl)pyrroline N-oxide were synthesized from the respective isotopically labeled 2-nitropropane analogs obtained from the reaction of sodium nitrate with 2-halopropanes. This facile, straightforward process allows synthesizing isotopically labeled DMPO analogs in a 4-step reaction without special equipment. PMID:21986521

Reduction of Charge Traps and Stability Enhancement in Solution-Processed Organic Field-Effect Transistors Based on a Blended n-Type Semiconductor.

PubMed

Campos, Antonio; Riera-Galindo, Sergi; Puigdollers, Joaquim; Mas-Torrent, Marta

2018-05-09

Solution-processed n-type organic field-effect transistors (OFETs) are essential elements for developing large-area, low-cost, and all organic logic/complementary circuits. Nonetheless, the development of air-stable n-type organic semiconductors (OSCs) lags behind their p-type counterparts. The trapping of electrons at the semiconductor-dielectric interface leads to a lower performance and operational stability. Herein, we report printed small-molecule n-type OFETs based on a blend with a binder polymer, which enhances the device stability due to the improvement of the semiconductor-dielectric interface quality and a self-encapsulation. Both combined effects prevent the fast deterioration of the OSC. Additionally, a complementary metal-oxide semiconductor-like inverter is fabricated depositing p-type and n-type OSCs simultaneously.

Hydroperoxide Measurements During Low-Temperature Gas-Phase Oxidation of n-Heptane and n-Decane.

PubMed

Rodriguez, Anne; Herbinet, Olivier; Meng, Xiangzan; Fittschen, Christa; Wang, Zhandong; Xing, Lili; Zhang, Lidong; Battin-Leclerc, Frédérique

2017-03-09

A wide range of hydroperoxides (C 1 -C 3 alkyl hydroperoxides, C 3 -C 7 alkenyl hydroperoxides, C 7 ketohydroperoxides, and hydrogen peroxide (H 2 O 2 )), as well as ketene and diones, have been quantified during the gas-phase oxidation of n-heptane. Some of these species, as well as C 10 alkenyl hydroperoxides and ketohydroperoxides, were also measured during the oxidation of n-decane. These experiments were performed using an atmospheric-pressure jet-stirred reactor at temperatures from 500 to 1100 K and one of three analytical methods, time-of-flight mass spectrometry combined with tunable synchrotron photoionization with a molecular beam sampling: time-of-flight mass spectrometry combined with laser photoionization with a capillary tube sampling, continuous wave cavity ring-down spectroscopy with sonic probe sampling. The experimental temperature at which the maximum mole fraction is observed increases significantly for alkyl hydroperoxides, alkenyl hydroperoxides, and then more so again for hydrogen peroxide, compared to ketohydroperoxides. The influence of the equivalence ratio from 0.25 to 4 on the formation of these peroxides has been studied during n-heptane oxidation. The up-to-date detailed kinetic oxidation models for n-heptane and for n-decane found in the literature have been used to discuss the possible pathways by which these peroxides, ketene, and diones are formed. In general, the model predicts well the reactivity of the two fuels, as well as the formation of major intermediates.

The Expression of Type-1 and Type-2 Nitric Oxide Synthase in Selected Tissues of the Gastrointestinal Tract during Mixed Mycotoxicosis

PubMed Central

Gajęcka, Magdalena; Stopa, Ewa; Tarasiuk, Michał; Zielonka, Łukasz; Gajęcki, Maciej

2013-01-01

The aim of the study was to verify the hypothesis that intoxication with low doses of mycotoxins leads to changes in the mRNA expression levels of nitric oxide synthase-1 and nitric oxide synthase-2 genes in tissues of the gastrointestinal tract and the liver. The experiment involved four groups of immature gilts (with body weight of up to 25 kg) which were orally administered zearalenone in a daily dose of 40 μg/kg BW (group Z, n = 18), deoxynivalenol at 12 μg/kg BW (group D, n = 18), zearalenone and deoxynivalenol (group M, n = 18) or placebo (group C, n = 21) over a period of 42 days. The lowest mRNA expression levels of nitric oxide synthase-1 and nitric oxide synthase-2 genes were noted in the sixth week of the study, in particular in group M. Our results suggest that the presence of low mycotoxin doses in feed slows down the mRNA expression of both nitric oxide synthase isomers, which probably lowers the concentrations of nitric oxide, a common precursor of inflammation. PMID:24284830

Thermo-mechanical characterization of siliconized E-glass fiber/hematite particles reinforced epoxy resin hybrid composite

NASA Astrophysics Data System (ADS)

V. R., Arun prakash; Rajadurai, A.

2016-10-01

In this present work hybrid polymer (epoxy) matrix composite has been strengthened with surface modified E-glass fiber and iron(III) oxide particles with varying size. The particle sizes of 200 nm and <100 nm has been prepared by high energy ball milling and sol-gel methods respectively. To enhance better dispersion of particles and improve adhesion of fibers and fillers with epoxy matrix surface modification process has been done on both fiber and filler by an amino functional silane 3-Aminopropyltrimethoxysilane (APTMS). Crystalline and functional groups of siliconized iron(III) oxide particles were characterized by XRD and FTIR spectroscopy analysis. Fixed quantity of surface treated 15 vol% E-glass fiber was laid along with 0.5 and 1.0 vol% of iron(III) oxide particles into the matrix to fabricate hybrid composites. The composites were cured by an aliphatic hardener Triethylenetetramine (TETA). Effectiveness of surface modified particles and fibers addition into the resin matrix were revealed by mechanical testing like tensile testing, flexural testing, impact testing, inter laminar shear strength and hardness. Thermal behavior of composites was evaluated by TGA, DSC and thermal conductivity (Lee's disc). The scanning electron microscopy was employed to found shape and size of iron(III) oxide particles adhesion quality of fiber with epoxy matrix. Good dispersion of fillers in matrix was achieved with surface modifier APTMS. Tensile, flexural, impact and inter laminar shear strength of composites was improved by reinforcing surface modified fiber and filler. Thermal stability of epoxy resin was improved when surface modified fiber was reinforced along with hard hematite particles. Thermal conductivity of epoxy increased with increase of hematite content in epoxy matrix.

Aerobic and Electrochemical Oxidations with N-Oxyl Reagents

NASA Astrophysics Data System (ADS)

Miles, Kelsey C.

Selective oxidation of organic compounds represents a significant challenge for chemical transformations. Oxidation methods that utilize nitroxyl catalysts have become increasingly attractive and include Cu/nitroxyl and nitroxyl/NO x co-catalyst systems. Electrochemical activation of nitroxyls is also well known and offers an appealing alternative to the use of chemical co-oxidants. However, academic and industrial organic synthetic communities have not widely adopted electrochemical methods. Nitroxyl catalysts facilitate effective and selective oxidation of alcohols and aldehydes to ketones and carboxylic acids. Selective benzylic, allylic, and alpha-heteroatom C-H abstraction can also be achieved with nitroxyls and provides access to oxygenated products when used in combination with molecular oxygen as a radical trap. This thesis reports various chemical and electrochemical oxidation methods that were developed using nitroxyl mediators. Chapter 1 provides a short review on practical aerobic alcohol oxidation with Cu/nitroxyl and nitroxyl/NO x systems and emphasizes the utility of bicyclic nitroxyls as co-catalysts. In Chapter 2, the combination of these bicyclic nitroxyls with NOx is explored for development of a mild oxidation of alpha-chiral aryl aldehydes and showcases a sequential asymmetric hydroformylation/oxidation method. Chapter 3 reports the synthesis and characterization of two novel Cu/bicyclic nitroxyl complexes and the electronic structure analysis of these complexes. Chapter 4 highlights the electrochemical activation of various nitroxyls and reports an in-depth study on electrochemical alcohol oxidation and compares the reactivity of nitroxyls under electrochemical or chemical activation. N-oxyls can also participate in selective C-H abstraction, and Chapter 5 reports the chemical and electrochemical activation of N-oxyls for radical-mediated C-H oxygenation of (hetero)arylmethanes. For these electrochemical transformations, the development of

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

NASA Astrophysics Data System (ADS)

Tomyn, Stefania; Shylin, Sergii I.; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O.

2017-01-01

In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge.

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation.

PubMed

Tomyn, Stefania; Shylin, Sergii I; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O

2017-01-19

In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge.

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

PubMed Central

Tomyn, Stefania; Shylin, Sergii I.; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O.

2017-01-01

In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge. PMID:28102364

Design Rules for Oxygen Evolution Catalysis at Porous Iron Oxide Electrodes: A 1000-Fold Current Density Increase.

PubMed

Haschke, Sandra; Pankin, Dmitrii; Petrov, Yuri; Bochmann, Sebastian; Manshina, Alina; Bachmann, Julien

2017-09-22

Nanotubular iron(III) oxide electrodes are optimized for catalytic efficiency in the water oxidation reaction at neutral pH. The nanostructured electrodes are prepared from anodic alumina templates, which are coated with Fe 2 O 3 by atomic layer deposition. Scanning helium ion microscopy, X-ray diffraction, and Raman spectroscopy are used to characterize the morphologies and phases of samples submitted to various treatments. These methods demonstrate the contrasting effects of thermal annealing and electrochemical treatment. The electrochemical performances of the corresponding electrodes under dark conditions are quantified by steady-state electrolysis and electrochemical impedance spectroscopy. A rough and amorphous Fe 2 O 3 with phosphate incorporation is critical for the optimization of the water oxidation reaction. For the ideal pore length of 17 μm, the maximum catalytic turnover is reached with an effective current density of 140 μA cm -2 at an applied overpotential of 0.49 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of p-type GaN nanowires.

PubMed

Kim, Sung Wook; Park, Youn Ho; Kim, Ilsoo; Park, Tae-Eon; Kwon, Byoung Wook; Choi, Won Kook; Choi, Heon-Jin

2013-09-21

GaN has been utilized in optoelectronics for two decades. However, p-type doping still remains crucial for realization of high performance GaN optoelectronics. Though Mg has been used as a p-dopant, its efficiency is low due to the formation of Mg-H complexes and/or structural defects in the course of doping. As a potential alternative p-type dopant, Cu has been recognized as an acceptor impurity for GaN. Herein, we report the fabrication of Cu-doped GaN nanowires (Cu:GaN NWs) and their p-type characteristics. The NWs were grown vertically via a vapor-liquid-solid (VLS) mechanism using a Au/Ni catalyst. Electrical characterization using a nanowire-field effect transistor (NW-FET) showed that the NWs exhibited n-type characteristics. However, with further annealing, the NWs showed p-type characteristics. A homo-junction structure (consisting of annealed Cu:GaN NW/n-type GaN thin film) exhibited p-n junction characteristics. A hybrid organic light emitting diode (OLED) employing the annealed Cu:GaN NWs as a hole injection layer (HIL) also demonstrated current injected luminescence. These results suggest that Cu can be used as a p-type dopant for GaN NWs.

Influences of Land Use/Cover Types on Nitrous Oxide Emissions during Freeze-Thaw Periods from Waterlogged Soils in Inner Mongolia.

PubMed

Lu, Zedong; Du, Rui; Du, Pengrui; Qin, Saisai; Liang, Zongmin; Li, Ziming; Wang, Yaling; Wang, Yanfen

2015-01-01

Nitrous oxide emissions during freeze/thaw periods contribute significantly to annual soil N2O emissions budgets in middle- and high-latitude areas; however, the freeze/thaw-related N2O emissions from waterlogged soils have hardly been studied in the Hulunber Grassland, Inner Mongolia. For this study, the effects of changes in land use/cover types on N2O emissions during freeze-thaw cycles were investigated to more accurately quantify the annual N2O emissions from grasslands. Soil cores from six sites were incubated at varying temperature (ranging from -15 to 10°C) to simulate freeze-thaw cycles. N2O production rates were low in all soil cores during freezing periods, but increased markedly after soil thawed. Mean rates of N2O production differed by vegetation type, and followed the sequence: Leymus chinensis (LC) and Artemisia tanacetifolia (AT) steppes > LC steppes ≥ Stipa baicalensis (SB) steppes. Land use types (mowing and grazing) had differing effects on freeze/thaw-related N2O production. Grazing significantly reduced N2O production by 36.8%, while mowing enhanced production. The production of N2O was related to the rate at which grassland was mowed, in the order: triennially (M3) > once annually (M1) ≥ unmown (UM). Compared with the UM control plot, the M3 and M1 mowing regimes enhanced N2O production by 57.9% and 13.0% respectively. The results of in situ year-round measurements showed that large amounts of N2O were emitted during the freeze-thaw period, and that annual mean fluxes of N2O were 9.21 μg N2O-N m-2 h-1 (ungrazed steppe) and 6.54 μg N2O-N m-2 h-1 (grazed steppe). Our results further the understanding of freeze/thaw events as enhancing N2O production, and confirm that different land use/cover types should be differentiated rather than presumed to be equivalent, regarding nitrous oxide emission. Even so, further research involving multi-year and intensive measurements of N2O emission is still needed.

Cyclic oxidation resistance of a reaction milled NiAl-AlN composite

NASA Technical Reports Server (NTRS)

Lowell, Carl E.; Barrett, Charles A.; Whittenberger, J. D.

1990-01-01

Based upon recent mechanical property tests a NiAl-AlN composite produced by cryomilling has very attractive high temperature strength. This paper focuses on the oxidation resistance of the NiAl-AlN composite at 1473 and 1573 K as compared to that of Ni-47Al-0.15Zr, one of the most oxidation resistant intermetallics. The results of cyclic oxidation tests show that the NiAl-AlN composite has excellent properties although not quite as good as those of Ni-47Al-0.15Zr. The onset of failure of the NiAl-AlN was unique in that it was not accompanied by a change in scale composition from alumina to less protective oxides. Failure in the composite appears to be related to the entrapment of AlN particles within the alumina scale.

A novel sensor for monitoring of iron(III) ions based on porphyrins.

PubMed

Vlascici, Dana; Fagadar-Cosma, Eugenia; Popa, Iuliana; Chiriac, Vlad; Gil-Agusti, Mayte

2012-01-01

Three A(3)B porphyrins with mixed carboxy-, phenoxy-, pyridyl-, and dimethoxy-substituent functionalization on the meso-phenyl groups were obtained by multicomponent synthesis, fully characterized and used as ionophores for preparing PVC-based membrane sensors selective to iron(III). The membranes have an ionophore:PVC:plasticizer composition ratio of 1:33:66. Sodium tetraphenylborate was used as additive (20 mol% relative to ionophore). The performance characteristics (linear concentration range, slope and selectivity) of the sensors were investigated. The best results were obtained for the membrane based on 5-(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin plasticized with bis(2-ethylhexyl)sebacate, in a linear range from 1 × 10(-7)-1 × 10(-1) M with a slope of 21.6 mV/decade. The electrode showed high selectivity with respect to alkaline and heavy metal ions and a response time of 20 s. The influence of pH on the sensor response was studied. The sensor was used for a period of six weeks and the utility has been tested for the quantitative determination of Fe(III) in recovered solutions from spent lithium ion batteries and for the quantitative determination of Fe(III) in tap water samples.

A Novel Sensor for Monitoring of Iron(III) Ions Based on Porphyrins

PubMed Central

Vlascici, Dana; Fagadar-Cosma, Eugenia; Popa, Iuliana; Chiriac, Vlad; Gil-Agusti, Mayte

2012-01-01

Three A3B porphyrins with mixed carboxy-, phenoxy-, pyridyl-, and dimethoxy-substituent functionalization on the meso-phenyl groups were obtained by multicomponent synthesis, fully characterized and used as ionophores for preparing PVC-based membrane sensors selective to iron(III). The membranes have an ionophore:PVC:plasticizer composition ratio of 1:33:66. Sodium tetraphenylborate was used as additive (20 mol% relative to ionophore). The performance characteristics (linear concentration range, slope and selectivity) of the sensors were investigated. The best results were obtained for the membrane based on 5-(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin plasticized with bis(2-ethylhexyl)sebacate, in a linear range from 1 × 10−7–1 × 10−1 M with a slope of 21.6 mV/decade. The electrode showed high selectivity with respect to alkaline and heavy metal ions and a response time of 20 s. The influence of pH on the sensor response was studied. The sensor was used for a period of six weeks and the utility has been tested for the quantitative determination of Fe(III) in recovered solutions from spent lithium ion batteries and for the quantitative determination of Fe(III) in tap water samples. PMID:22969395

Catalytic determination of molybdenum(VI) by means of an iodide ion-selective electrode and a landolt-type hydrogen peroxide-iodide reaction.

PubMed

Kataoka, M; Nishimura, K; Kambara, T

1983-12-01

A trace amount of molybdenum(VI) can be determined by using its catalytic effect on the oxidation of iodide to iodine by hydrogen peroxide in acidic medium. Addition of ascorbic acid added to the reaction mixture produces the Landolt effect, i.e., the iodine produced by the indicator reaction is reduced immediately by the ascorbic add. Hence the concentration of iodide begins to decrease once all the ascorbic acid has been consumed. The induction period is measured by monitoring the concentration of iodide ion with an iodide ion-selective electrode. The reciprocal of the induction period varies linearly with the concentration of molybdenum(VI). The most suitable pH and concentrations of hydrogen peroxide and potassium iodide are found to be 1.5, 5 and 10mM, respectively. An appropriate amount of ascorbic acid is added to the reaction mixture according to the concentration of molybdenum(VI) in the sample solution. A calibration graph with good proportionality is obtained for the molybdenum(VI) concentration range from 0.1 to 160 muM. Iron(III), vanadium(IV), zirconium(IV), tungsten(VI), copper(II) and chromium(VI) interfere, but iron(III) and copper(II) can be masked with EDTA.

Robust p-type doping of copper oxide using nitrogen implantation

NASA Astrophysics Data System (ADS)

Jorge, Marina; Polyakov, Stanislav M.; Cooil, Simon; Schenk, Alex K.; Edmonds, Mark; Thomsen, Lars; Mazzola, Federico; Wells, Justin W.

2017-07-01

We demonstrate robust p-type doping of Cu2O using low/medium energy ion implantation. Samples are made by controlled oxidation of annealed Cu metal foils, which results in Cu2O with levels of doping close to intrinsic. Samples are then implanted with nitrogen ions using a kinetic energy in the few keV range. Using this method, we are able to produce very high levels of doping, as evidenced by a 350 meV shift in the Fermi level towards the VB maximum. The robustness of the nitrogen implanted samples are tested by exposing them to atmospheric contaminants, and elevated temperatures. The samples are found to survive an increase in temperature of many hundreds of degrees. The robustness of the samples, combined with the fact that the materials used are safe, abundant and non-toxic and that the methods used for the growth of Cu2O and N+ implantation are simple and cheap to implement industrially, underlines the potential of Cu2O:N for affordable intermediate band photovoltaics.

Long-term oxidization and phase transition of InN nanotextures

PubMed Central

2011-01-01

The long-term (6 months) oxidization of hcp-InN (wurtzite, InN-w) nanostructures (crystalline/amorphous) synthesized on Si [100] substrates is analyzed. The densely packed layers of InN-w nanostructures (5-40 nm) are shown to be oxidized by atmospheric oxygen via the formation of an intermediate amorphous In-Ox-Ny (indium oxynitride) phase to a final bi-phase hcp-InN/bcc-In2O3 nanotexture. High-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy and selected area electron diffraction are used to identify amorphous In-Ox-Ny oxynitride phase. When the oxidized area exceeds the critical size of 5 nm, the amorphous In-Ox-Ny phase eventually undergoes phase transition via a slow chemical reaction of atomic oxygen with the indium atoms, forming a single bcc In2O3 phase. PMID:21711908

Exploration of pro-oxidant and antioxidant activities of the flavonoid myricetin.

PubMed

Chobot, Vladimir; Hadacek, Franz

2011-01-01

Flavonoids are ubiquitous phenolic plant metabolites. Many of them are well known for their pro- and antioxidant properties. Myricetin has been reported to be either a potent antioxidant or a pro-oxidant depending on the conditions. The reaction conditions for the pro- and antioxidant activities were therefore investigated using variations of the deoxyribose degradation assay systems. The deoxyribose degradation assay systems were conducted as follows; H(2)O(2)/Fe(III)/ascorbic acid, H(2)O(2)/Fe(III), Fe(III)/ascorbic acid, and Fe(III). Each system was carried out in two variants, FeCl(3) (iron ions added as FeCl(3)) and FeEDTA (iron added in complex with ethylenediaminetetraacetic acid). When ascorbic acid was present, myricetin showed antioxidant properties, especially when it occurred in complex with iron. In ascorbic acid-free systems, pro-oxidant activities prevailed, which where enhanced if iron was in complex with EDTA. Myricetin's antioxidant activity depends on both the reactive oxygen species (ROS) scavenging and iron ions chelation properties. The pro-oxidative properties are caused by reduction of molecular oxygen to ROS and iron(III) to iron(II). Myricetin is able to substitute for ascorbic acid albeit less efficiently.

Ba6-3 x Nd8+2 x Ti18O54 Tungsten Bronze: A New High-Temperature n-Type Oxide Thermoelectric

NASA Astrophysics Data System (ADS)

Azough, Feridoon; Freer, Robert; Yeandel, Stephen R.; Baran, Jakub D.; Molinari, Marco; Parker, Stephen C.; Guilmeau, Emmanuel; Kepaptsoglou, Demie; Ramasse, Quentin; Knox, Andy; Gregory, Duncan; Paul, Douglas; Paul, Manosh; Montecucco, Andrea; Siviter, Jonathan; Mullen, Paul; Li, Wenguan; Han, Guang; Man, Elena A.; Baig, Hasan; Mallick, Tapas; Sellami, Nazmi; Min, Gao; Sweet, Tracy

2016-03-01

Semiconducting Ba6-3 x Nd8+2 x Ti18O54 ceramics (with x = 0.00 to 0.85) were synthesized by the mixed oxide route followed by annealing in a reducing atmosphere; their high-temperature thermoelectric properties have been investigated. In conjunction with the experimental observations, atomistic simulations have been performed to investigate the anisotropic behavior of the lattice thermal conductivity. The ceramics show promising n-type thermoelectric properties with relatively high Seebeck coefficient, moderate electrical conductivity, and temperature-stable, low thermal conductivity; For example, the composition with x = 0.27 (i.e., Ba5.19Nd8.54Ti18O54) exhibited a Seebeck coefficient of S 1000K = 210 µV/K, electrical conductivity of σ 1000K = 60 S/cm, and thermal conductivity of k 1000K = 1.45 W/(m K), leading to a ZT value of 0.16 at 1000 K.

Metal Oxide Supported Vanadium Substituted Keggin Type Polyoxometalates as Catalyst For Oxidation of Dibenzothiophene

NASA Astrophysics Data System (ADS)

Lesbani, Aldes; Novri Meilyana, Sarah; Karim, Nofi; Hidayati, Nurlisa; Said, Muhammad; Mohadi, Risfidian; Miksusanti

2018-01-01

Supported polyoxometalatate H4[γ-H2SiV2W10O40]·nH2O with metal oxide i.e. silica, titanium, and tantalum was successfully synthesized via wet impregnation method to form H4[γ-H2SiV2W10O40]·nH2O-Si, H4[γ-H2SiV2W10O40]·nH2O-Ti, and H4[γ-H2SiV2W10O40]·nH2O-Ta. Characterization was performed using FTIR spectroscopy, X-Ray analyses, and morphology analyses using SEM. All compounds were used as the catalyst for desulfurization of dibenzothiophene (DBT). Silica and titanium supported polyoxometalate H4[γ-H2SiV2W10O40]·nH2O better than tantalum due to retaining crystallinity after impregnation process. On the other hand, compound H H4[γ-H2SiV2W10O40]·nH2O-Ta showed high catalytic activity than other supported metal oxides for desulfurization of DBT. Optimization desulfurization process resulted in 99% conversion of DBT under a mild condition at 70 °C, 0.1 g catalyst, and reaction for 3 hours. Regeneration studies showed catalyst H4[γ-H2SiV2W10O40]·nH2O-Ti was remaining catalytic activity for desulfurization of DBT.

Identical acyl transfer reactions between pyridine N-oxides and their N-acylonium salts

NASA Astrophysics Data System (ADS)

Rybachenko, V. I.; Shroeder, G.; Chotii, K. Yu.; Kovalenko, V. V.; Red'Ko, A. N.; Gierzyk, B.

2007-10-01

28 identical acyl exchange reactions R-CO-Nu+, X- + Nu between pyridine N-oxides in acetonitrile were studied. Here, X- = BPh{4/-} and R = methyl, N,N-dimethylamino, N,N-diethylamino, 4-morpholino, 1-piperidino, N-methyl, N-phenylamino, or N,N-diphenylamino group. The IR and NMR spectroscopic characteristics of acyloxypyridinium salts were determined, and the quantum-chemical parameters of all reagents calculated. The results were subjected to correlation analysis. It was found that the rate of identical acyl transfer reactions was controlled by the interaction of frontier orbitals in the transition state.

Reductive reactivity of iron(III) oxides in the east china sea sediments: characterization by selective extraction and kinetic dissolution.

PubMed

Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li

2013-01-01

Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m 0 (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k' (rate constant) and γ (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m 0, k' and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m 0 at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m 0 may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m 0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases.

Reductive Reactivity of Iron(III) Oxides in the East China Sea Sediments: Characterization by Selective Extraction and Kinetic Dissolution

PubMed Central

Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li

2013-01-01

Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m 0 (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k′ (rate constant) and γ (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m 0, k′ and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m 0 at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m 0 may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m 0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases. PMID:24260377

Piezo-phototronic effect on electroluminescence properties of p-type GaN thin films.

PubMed

Hu, Youfan; Zhang, Yan; Lin, Long; Ding, Yong; Zhu, Guang; Wang, Zhong Lin

2012-07-11

We present that the electroluminescence (EL) properties of Mg-doped p-type GaN thin films can be tuned by the piezo-phototronic effect via adjusting the minority carrier injection efficiency at the metal-semiconductor (M-S) interface by strain induced polarization charges. The device is a metal-semiconductor-metal structure of indium tin oxide (ITO)-GaN-ITO. Under different straining conditions, the changing trend of the transport properties of GaN films can be divided into two types, corresponding to the different c-axis orientations of the films. An extreme value was observed for the integral EL intensity under certain applied strain due to the adjusted minority carrier injection efficiency by piezoelectric charges introduced at the M-S interface. The external quantum efficiency of the blue EL at 430 nm was changed by 5.84% under different straining conditions, which is 1 order of magnitude larger than the change of the green peak at 540 nm. The results indicate that the piezo-phototronic effect has a larger impact on the shallow acceptor states related EL process than on the one related to the deep acceptor states in p-type GaN films. This study has great significance on the practical applications of GaN in optoelectronic devices under a working environment where mechanical deformation is unavoidable such as for flexible/printable light emitting diodes.

Indium oxide/n-silicon heterojunction solar cells

DOEpatents

Feng, Tom; Ghosh, Amal K.

1982-12-28

A high photo-conversion efficiency indium oxide/n-silicon heterojunction solar cell is spray deposited from a solution containing indium trichloride. The solar cell exhibits an Air Mass One solar conversion efficiency in excess of about 10%.

Recent Advances of Solution-Processed Metal Oxide Thin-Film Transistors.

PubMed

Xu, Wangying; Li, Hao; Xu, Jian-Bin; Wang, Lei

2018-03-06

Solution-processed metal oxide thin-film transistors (TFTs) are considered as one of the most promising transistor technologies for future large-area flexible electronics. This review surveys the recent advances in solution-based oxide TFTs, including n-type oxide semiconductors, oxide dielectrics and p-type oxide semiconductors. Firstly, we provide an introduction on oxide TFTs and the TFT configurations and operating principles. Secondly, we present the recent progress in solution-processed n-type transistors, with a special focus on low-temperature and large-area solution processed approaches as well as novel non-display applications. Thirdly, we give a detailed analysis of the state-of-the-art solution-processed oxide dielectrics for low-voltage electronics. Fourthly, we discuss the recent progress in solution-based p-type oxide semiconductors, which will enable the highly desirable future low-cost large-area complementary circuits. Finally, we draw the conclusions and outline the perspectives over the research field.

Demonstration of high-performance p-type tin oxide thin-film transistors using argon-plasma surface treatments

NASA Astrophysics Data System (ADS)

Bae, Sang-Dae; Kwon, Soo-Hun; Jeong, Hwan-Seok; Kwon, Hyuck-In

2017-07-01

In this work, we investigated the effects of low-temperature argon (Ar)-plasma surface treatments on the physical and chemical structures of p-type tin oxide thin-films and the electrical performance of p-type tin oxide thin-film transistors (TFTs). From the x-ray photoelectron spectroscopy measurement, we found that SnO was the dominant phase in the deposited tin oxide thin-film, and the Ar-plasma treatment partially transformed the tin oxide phase from SnO to SnO2 by oxidation. The resistivity of the tin oxide thin-film increased with the plasma-treatment time because of the reduced hole concentration. In addition, the root-mean-square roughness of the tin oxide thin-film decreased as the plasma-treatment time increased. The p-type oxide TFT with an Ar-plasma-treated tin oxide thin-film exhibited excellent electrical performance with a high current on-off ratio (5.2 × 106) and a low off-current (1.2 × 10-12 A), which demonstrates that the low-temperature Ar-plasma treatment is a simple and effective method for improving the electrical performance of p-type tin oxide TFTs.

Kinetic studies on the oxidation of oxyhemoglobin by biologically active iron thiosemicarbazone complexes: relevance to iron-chelator-induced methemoglobinemia.

PubMed

Basha, Maram T; Rodríguez, Carlos; Richardson, Des R; Martínez, Manuel; Bernhardt, Paul V

2014-03-01

The oxidation of oxyhemoglobin to methemoglobin has been found to be facilitated by low molecular weight iron(III) thiosemicarbazone complexes. This deleterious reaction, which produces hemoglobin protein units unable to bind dioxygen and occurs during the administration of iron chelators such as the well-known 3-aminopyridine-2-pyridinecarbaldehyde thiosemicarbazone (3-AP; Triapine), has been observed in the reaction with Fe(III) complexes of some members of the 3-AP structurally-related thiosemicarbazone ligands derived from di-2-pyridyl ketone (HDpxxT series). We have studied the kinetics of this oxidation reaction in vitro using human hemoglobin and found that the reaction proceeds with two distinct time-resolved steps. These have been associated with sequential oxidation of the two different oxyheme cofactors in the α and β protein chains. Unexpected steric and hydrogen-bonding effects on the Fe(III) complexes appear to be the responsible for the observed differences in the reaction rate across the series of HDpxxT ligand complexes used in this study.

Glutathione peroxidase-1 gene (GPX1) variants, oxidative stress and risk of kidney complications in people with type 1 diabetes.

PubMed

Mohammedi, Kamel; Patente, Thiago A; Bellili-Muñoz, Naima; Driss, Fathi; Le Nagard, Hervé; Fumeron, Frédéric; Roussel, Ronan; Hadjadj, Samy; Corrêa-Giannella, Maria Lúcia; Marre, Michel; Velho, Gilberto

2016-02-01

Glutathione peroxidase (GPX) is a class of antioxidant enzymes that catalyze the reduction of hydrogen peroxide to water. GPX1 is the most abundant isoform and is expressed in all kidney cells. Isoprostane and advanced oxidation protein products (AOPP) were identified as markers of oxidative stress in patients with kidney disease. We investigated associations of GPX1 genotypes with kidney complications, and with plasma concentrations of isoprostane and AOPP in type 1 diabetic patients. Four SNPs in the GPX1 gene region were genotyped in SURGENE (n=340; 10-year follow-up); GENEDIAB (n=461) and GENESIS (n=584) cohorts of type 1 diabetic patients. Subsets of GENEDIAB (n=237) and GENESIS (n=466) participants were followed up for 9 and 5years, respectively. Plasma concentrations of isoprostane and AOPP were measured at baseline in GENEDIAB. Hazard ratios (HR) were estimated for incidence of kidney complications. In SURGENE, 98 renal events (new cases of microalbuminuria or progression to more severe stage of diabetic nephropathy) occurred during follow-up. The minor T-allele of rs3448 was associated with the incidence of renal events (HR 1.81, 95% CI 1.16-2.84, p=0.008). In GENESIS/GENEDIAB pooled study, end stage renal disease (ESRD) occurred during follow-up in 52 individuals. The same variant was associated with the incidence of ESRD (HR 3.34, 95% CI, 1.69-6.98, p=0.0004). The variant was also associated with higher plasma isoprostane concentration in GENEDIAB cohort: 2.02±0.12 (TT+CT) vs 1.75±0.13 (CC) ng/mL (p=0.009), and with higher plasma AOPP in the subset of participants with the baseline history of ESRD (TT+CT 67±6 vs CC 48±6μmol/L, p=0.006). The minor T-allele of rs3448 was associated with kidney complications (incidences of microalbuminuria, renal events and ESRD) in patients with type 1 diabetes. The risk allele was associated with higher plasma concentrations of isoprostane and AOPP. Our results are consistent with the implication of GPX1 in the

Porous nanoarchitectures of spinel-type transition metal oxides for electrochemical energy storage systems.

PubMed

Park, Min-Sik; Kim, Jeonghun; Kim, Ki Jae; Lee, Jong-Won; Kim, Jung Ho; Yamauchi, Yusuke

2015-12-14

Transition metal oxides possessing two kinds of metals (denoted as AxB3-xO4, which is generally defined as a spinel structure; A, B = Co, Ni, Zn, Mn, Fe, etc.), with stoichiometric or even non-stoichiometric compositions, have recently attracted great interest in electrochemical energy storage systems (ESSs). The spinel-type transition metal oxides exhibit outstanding electrochemical activity and stability, and thus, they can play a key role in realising cost-effective and environmentally friendly ESSs. Moreover, porous nanoarchitectures can offer a large number of electrochemically active sites and, at the same time, facilitate transport of charge carriers (electrons and ions) during energy storage reactions. In the design of spinel-type transition metal oxides for energy storage applications, therefore, nanostructural engineering is one of the most essential approaches to achieving high electrochemical performance in ESSs. In this perspective, we introduce spinel-type transition metal oxides with various transition metals and present recent research advances in material design of spinel-type transition metal oxides with tunable architectures (shape, porosity, and size) and compositions on the micro- and nano-scale. Furthermore, their technological applications as electrode materials for next-generation ESSs, including metal-air batteries, lithium-ion batteries, and supercapacitors, are discussed.

Temperature-dependent thermal and thermoelectric properties of n -type and p -type S c1 -xM gxN

NASA Astrophysics Data System (ADS)

Saha, Bivas; Perez-Taborda, Jaime Andres; Bahk, Je-Hyeong; Koh, Yee Rui; Shakouri, Ali; Martin-Gonzalez, Marisol; Sands, Timothy D.

2018-02-01

Scandium Nitride (ScN) is an emerging rocksalt semiconductor with octahedral coordination and an indirect bandgap. ScN has attracted significant attention in recent years for its potential thermoelectric applications, as a component material in epitaxial metal/semiconductor superlattices, and as a substrate for defect-free GaN growth. Sputter-deposited ScN thin films are highly degenerate n -type semiconductors and exhibit a large thermoelectric power factor of ˜3.5 ×10-3W /m -K2 at 600-800 K. Since practical thermoelectric devices require both n- and p-type materials with high thermoelectric figures-of-merit, development and demonstration of highly efficient p-type ScN is extremely important. Recently, the authors have demonstrated p-type S c1 -xM gxN thin film alloys with low M gxNy mole-fractions within the ScN matrix. In this article, we demonstrate temperature dependent thermal and thermoelectric transport properties, including large thermoelectric power factors in both n- and p-type S c1 -xM gxN thin film alloys at high temperatures (up to 850 K). Employing a combination of temperature-dependent Seebeck coefficient, electrical conductivity, and thermal conductivity measurements, as well as detailed Boltzmann transport-based modeling analyses of the transport properties, we demonstrate that p-type S c1 -xM gxN thin film alloys exhibit a maximum thermoelectric power factor of ˜0.8 ×10-3W /m -K2 at 850 K. The thermoelectric properties are tunable by adjusting the M gxNy mole-fraction inside the ScN matrix, thereby shifting the Fermi energy in the alloy films from inside the conduction band in case of undoped n -type ScN to inside the valence band in highly hole-doped p -type S c1 -xM gxN thin film alloys. The thermal conductivities of both the n- and p-type films were found to be undesirably large for thermoelectric applications. Thus, future work should address strategies to reduce the thermal conductivity of S c1 -xM gxN thin-film alloys, without affecting

Radiation Effects on the Electrical Properties of Hafnium Oxide Based MOS Capacitors

DTIC Science & Technology

2011-03-01

Figures Figure Page 1. Conceptual illustration of the creation of electron-hole pairs and displacement damage in a n -type silicon metal-oxide-silicon...Illustration of the effect, in a CV plot, of oxide trapped charge for a hypothetical n -type device...8 5. Illustration of the effect, in a CV plot, of interface trapped charge for a hypothetical n -type device

The kinetics of the reaction of nitrogen dioxide with iron(II)- and iron(III) cytochrome c.

PubMed

Domazou, Anastasia S; Gebicka, Lidia; Didik, Joanna; Gebicki, Jerzy L; van der Meijden, Benjamin; Koppenol, Willem H

2014-04-01

The reactions of NO2 with both oxidized and reduced cytochrome c at pH 7.2 and 7.4, respectively, and with N-acetyltyrosine amide and N-acetyltryptophan amide at pH 7.3 were studied by pulse radiolysis at 23 °C. NO2 oxidizes N-acetyltyrosine amide and N-acetyltryptophan amide with rate constants of (3.1±0.3)×10(5) and (1.1±0.1)×10(6) M(-1) s(-1), respectively. With iron(III)cytochrome c, the reaction involves only its amino acids, because no changes in the visible spectrum of cytochrome c are observed. The second-order rate constant is (5.8±0.7)×10(6) M(-1) s(-1) at pH 7.2. NO2 oxidizes iron(II)cytochrome c with a second-order rate constant of (6.6±0.5)×10(7) M(-1) s(-1) at pH 7.4; formation of iron(III)cytochrome c is quantitative. Based on these rate constants, we propose that the reaction with iron(II)cytochrome c proceeds via a mechanism in which 90% of NO2 oxidizes the iron center directly-most probably via reaction at the solvent-accessible heme edge-whereas 10% oxidizes the amino acid residues to the corresponding radicals, which, in turn, oxidize iron(II). Iron(II)cytochrome c is also oxidized by peroxynitrite in the presence of CO2 to iron(III)cytochrome c, with a yield of ~60% relative to peroxynitrite. Our results indicate that, in vivo, NO2 will attack preferentially the reduced form of cytochrome c; protein damage is expected to be marginal, the consequence of formation of amino acid radicals on iron(III)cytochrome c. Copyright © 2014 Elsevier Inc. All rights reserved.

Anaerobic nitrification-denitrification mediated by Mn-oxides in meso-tidal sediments: Implications for N2 and N2O production

NASA Astrophysics Data System (ADS)

Fernandes, Sheryl Oliveira; Javanaud, Cedric; Aigle, Axel; Michotey, Valérie D.; Guasco, Sophie; Deborde, Jonathan; Deflandre, Bruno; Anschutz, Pierre; Bonin, Patricia C.

2015-04-01

Field measurements in the Arcachon Bay (southwest France) indicated anaerobic production of NOx via nitrification, which was coupled to the reduction of Mn-oxides. To prove the occurrence of this process, laboratory microcosm experiments were set up. A 15N tracer-based approach was used to track if NOx produced through Mn-oxide-mediated anaerobic nitrification would be reduced to N2 via denitrification or anammox. We also hypothesized the generation of the potent greenhouse gas nitrous oxide (N2O) during nitrification-denitrification in the presence of Mn-oxides. The microcosms were prepared using sediment sectioned at varying depths (0-2.5, 2.5-4.5, 4.5-8.5, 8.5-12 and 12-17 cm) during two sampling campaigns in October (fall) and January (winter). Labeling with 15NO3- revealed low N2 production originating from NO3- in the water column (Pw), which did not increase significantly on amendment with Mn-oxides during both sampling periods. However, for both seasons, a significant increase of N2 produced via nitrification (Pn) was observed upon addition of Mn-oxides reaching 76-fold enhancement at ≤ 2.5 cm. To support these results, sediment slurries of October were subjected to amendment of 15NH4+, 14NO3- with or without addition of Mn-oxides. A substantial production of P15 (N2 production from 15NH4+) within 0-17 cm provided further evidence on nitrification-denitrification mediated by Mn-oxides probably with minimal intervention of anammox. In organically rich sediments, anaerobic nitrification-denitrification mediated by Mn-oxides could play an important role in lowering re-mineralized NH4+ levels in the benthic system. As hypothesized, significant production of N2O through the pathway was observed revealing newer mechanisms leading to the generation of the radiative gas.

Oxidation of Alkyl-substituted Cyclic Hydrocarbons by a Nocardia during Growth on n-Alkanes

PubMed Central

Davis, J. B.; Raymond, R. L.

1961-01-01

Nocardia 107-332, a soil isolate, oxidizes short-chain alkyl-substituted cyclic hydrocarbons to cyclic acids while growing on n-alkanes. Cyclic acids are produced also from relatively long-chain alkyl-substituted cyclics such as n-nonylbenzene or n-dodecylbenzene which alone support growth in a mineral-salts medium. ω-Oxidation of the alkyl substituents is followed by β-oxidation. It is of particular interest that cyclic acids such as cyclohexaneacetic and phenylacetic with C2 residual carboxylic acid substituents are resistant to further oxidation by the nocardia but cyclic acids with C1 or C3 substituents are readily oxidized and utilized for growth. The specificity of microbial oxidations is demonstrated by the conversion of p-isopropyltoluene (p-cymene) to p-isopropylbenzoic acid in n-alkane, growth-supported nocardia cultures. PMID:13720182

Comparative study on nitridation and oxidation plasma interface treatment for AlGaN/GaN MIS-HEMTs with AlN gate dielectric

NASA Astrophysics Data System (ADS)

Zhu, Jie-Jie; Ma, Xiao-Hua; Hou, Bin; Chen, Li-Xiang; Zhu, Qing; Hao, Yue

2017-02-01

This paper demonstrated the comparative study on interface engineering of AlN/AlGaN/GaN metal-insulator-semiconductor high-electron-mobility transistors (MIS-HEMTs) by using plasma interface pre-treatment in various ambient gases. The 15 nm AlN gate dielectric grown by plasma-enhanced atomic layer deposition significantly suppressed the gate leakage current by about two orders of magnitude and increased the peak field-effect mobility by more than 50%. NH3/N2 nitridation plasma treatment (NPT) was used to remove the 3 nm poor-quality interfacial oxide layer and N2O/N2 oxidation plasma treatment (OPT) to improve the quality of interfacial layer, both resulting in improved dielectric/barrier interface quality, positive threshold voltage (V th) shift larger than 0.9 V, and negligible dispersion. In comparison, however, NPT led to further decrease in interface charges by 3.38 × 1012 cm-2 and an extra positive V th shift of 1.3 V. Analysis with fat field-effect transistors showed that NPT resulted in better sub-threshold characteristics and transconductance linearity for MIS-HEMTs compared with OPT. The comparative study suggested that direct removing the poor interfacial oxide layer by nitridation plasma was superior to improving the quality of interfacial layer by oxidation plasma for the interface engineering of GaN-based MIS-HEMTs.

A study on the thermal conversion of scheelite-type ABO4 into perovskite-type AB(O,N)3.

PubMed

Li, Wenjie; Li, Duan; Gao, Xin; Gurlo, Aleksander; Zander, Stefan; Jones, Philip; Navrotsky, Alexandra; Shen, Zhijian; Riedel, Ralf; Ionescu, Emanuel

2015-05-07

Phase-pure scheelite AMoO4 and AWO4 (A = Ba, Sr, Ca) were thermally treated under an ammonia atmosphere at 400 to 900 °C. SrMoO4 and SrWO4 were shown to convert into cubic perovskite SrMoO2N and SrWO1.5N1.5, at 700 °C and 900 °C respectively, and to form metastable intermediate phases (scheelite SrMoO4-xNx and SrWO4-xNx), as revealed by X-ray diffraction (XRD), elemental analysis and FTIR spectroscopy. High-temperature oxide melt solution calorimetry reveals that the enthalpy of formation for SrM(O,N)3 (M = Mo, W) perovskites is less negative than that of the corresponding scheelite oxides, though the conversion of the scheelite oxides into perovskite oxynitrides is thermodynamically favorable at moderate temperatures. The reaction of BaMO4 with ammonia leads to the formation of rhombohedral Ba3M2(O,N)8 and the corresponding binary metal nitrides Mo3N2 and W4.6N4; similar behavior was observed for CaMO4, which converted upon ammonolysis into individual oxides and nitrides. Thus, BaMO4 and CaMO4 were shown to not provide access to perovskite oxynitrides. The influence of the starting scheelite oxide precursor, the structure distortion and the degree of covalency of the B-site-N bond are discussed within the context of the formability of perovskite oxynitrides.

Uncertainty quantification in (α,n) neutron source calculations for an oxide matrix

DOE PAGES

Pigni, M. T.; Croft, S.; Gauld, I. C.

2016-04-25

Here we present a methodology to propagate nuclear data covariance information in neutron source calculations from (α,n) reactions. The approach is applied to estimate the uncertainty in the neutron generation rates for uranium oxide fuel types due to uncertainties on 1) 17,18O( α,n) reaction cross sections and 2) uranium and oxygen stopping power cross sections. The procedure to generate reaction cross section covariance information is based on the Bayesian fitting method implemented in the R-matrix SAMMY code. The evaluation methodology uses the Reich-Moore approximation to fit the 17,18O(α,n) reaction cross-sections in order to derive a set of resonance parameters andmore » a related covariance matrix that is then used to calculate the energydependent cross section covariance matrix. The stopping power cross sections and related covariance information for uranium and oxygen were obtained by the fit of stopping power data in the -energy range of 1 keV up to 12 MeV. Cross section perturbation factors based on the covariance information relative to the evaluated 17,18O( α,n) reaction cross sections, as well as uranium and oxygen stopping power cross sections, were used to generate a varied set of nuclear data libraries used in SOURCES4C and ORIGEN for inventory and source term calculations. The set of randomly perturbed output (α,n) source responses, provide the mean values and standard deviations of the calculated responses reflecting the uncertainties in nuclear data used in the calculations. Lastly, the results and related uncertainties are compared with experiment thick target (α,n) yields for uranium oxide.« less

Method for producing high carrier concentration p-Type transparent conducting oxides

DOEpatents

Li, Xiaonan; Yan, Yanfa; Coutts, Timothy J.; Gessert, Timothy A.; Dehart, Clay M.

2009-04-14

A method for producing transparent p-type conducting oxide films without co-doping plasma enhancement or high temperature comprising: a) introducing a dialkyl metal at ambient temperature and a saturated pressure in a carrier gas into a low pressure deposition chamber, and b) introducing NO alone or with an oxidizer into the chamber under an environment sufficient to produce a metal-rich condition to enable NO decomposition and atomic nitrogen incorporation into the formed transparent metal conducting oxide.

Exercise Training at Maximal Fat Oxidation Intensity for Older Women with Type 2 Diabetes.

PubMed

Tan, Sijie; Du, Ping; Zhao, Wanting; Pang, Jiaqi; Wang, Jianxiong

2018-05-01

The purpose of this study was to investigate the pleiotropic effects of 12 weeks of supervised exercise training at maximal fat oxidation (FATmax) intensity on body composition, lipid profile, glycemic control, insulin sensitivity and serum adipokine levels in older women with type 2 diabetes. Thirty-one women with type 2 diabetes, aged 60 to 69 years, were randomly allocated into exercise and control groups. Body composition, lipid profile, blood glucose, insulin resistance and serum leptin and adiponectin concentrations were measured before and after the intervention. Exercise group (n=16) walked at individualized FATmax intensities for 1 h/day for 3 days/week over 12 weeks. No dietary intervention was introduced during the experimental period. Maximal fat oxidation rate was 0.37±0.10 g/min, and occurred at 37.3±7.3% of the estimated VO 2 max. Within the exercise group, significant improvements were observed for most of the measured variables compared to non-exercising controls; in particular, the FATmax program reduced body fat% (p<0.001), visceral fat% (p<0.001), and insulin resistance (p<0.001). There was no significant change in daily energy intake for all participants during the intervention period. These results suggest that individualized FATmax training is an effective exercise training intensity for managing type 2 diabetes in older women. © Georg Thieme Verlag KG Stuttgart · New York.

Arsenic mobilization and immobilization in paddy soils

NASA Astrophysics Data System (ADS)

Kappler, A.; Hohmann, C.; Zhu, Y. G.; Morin, G.

2010-05-01

Arsenic is oftentimes of geogenic origin and in many cases bound to iron(III) minerals. Iron(III)-reducing bacteria can harvest energy by coupling the oxidation of organic or inorganic electron donors to the reduction of Fe(III). This process leads either to dissolution of Fe(III)-containing minerals and thus to a release of the arsenic into the environment or to secondary Fe-mineral formation and immobilisation of arsenic. Additionally, aerobic and anaerobic iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II) oxidation at neutral pH that is usually followed by iron(III) mineral precipitation. We are currently investigating arsenic immobilization by Fe(III)-reducing bacteria and arsenic co-precipitation and immobilization by anaerobic iron(II)-oxidizing bacteria in batch, microcosm and rice pot experiments. Co-precipitation batch experiments with pure cultures of nitrate-dependent Fe(II)-oxidizing bacteria are used to quantify the amount of arsenic that can be immobilized during microbial iron mineral precipitation, to identify the minerals formed and to analyze the arsenic binding environment in the precipitates. Microcosm and rice pot experiments are set-up with arsenic-contaminated rice paddy soil. The microorganisms (either the native microbial population or the soil amended with the nitrate-dependent iron(II)-oxidizing Acidovorax sp. strain BoFeN1) are stimulated either with iron(II), nitrate, or oxygen. Dissolved and solid-phase arsenic and iron are quantified. Iron and arsenic speciation and redox state in batch and microcosm experiments are determined by LC-ICP-MS and synchrotron-based methods (EXAFS, XANES).

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

PubMed Central

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

2015-01-01

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

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

PubMed

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

2015-01-14

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

Optoelectronic properties of dicyanofluorene-based n-type polymers.

PubMed

Vijayakumar, Chakkooth; Saeki, Akinori; Seki, Shu

2012-08-01

Three new donor-acceptor-type copolymers (P1-P3) consisting of dicyanofluorene as acceptor and various donor moieties were designed and synthesized. Optoelectronic properties were studied in detail by means of UV-visible absorption and fluorescence spectroscopy, cyclic voltammetry, space-charge-limited current (SCLC), flash-photolysis time-resolved microwave conductivity (FP-TRMC), and density functional theory (DFT). All polymers showed strong absorption in the UV-visible region and the absorption maximum undergoes redshift with an increasing number of thiophene units in the polymer backbone. SCLC analysis showed that the electron mobilities of the polymers in the bulk state were 1 to 2 orders higher than that of the corresponding hole mobilities, which indicated the n-type nature of the materials. By using FP-TRMC, the intrapolymer charge-carrier mobility was assessed and compared with the interpolymer mobility obtained by SCLC. The polymers exhibited good electron-accepting properties sufficiently high enough to oxidize the excited states of regioregular poly(3-hexylthiophene) (P3HT (donor)), as evident from the FP-TRMC analysis. The P3 polymer exhibited the highest FP-TRMC transients in the pristine form as well as when blended with P3HT. Use of these polymers as n-type materials in all-polymer organic solar cells was also explored in combination with P3HT. In accordance with the TRMC results, P3 exhibited superior electron-transport and photovoltaic properties to the other two polymers, which is explained by the distribution of the energy levels of the polymers by using DFT calculations. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidative stress, insulin resistance, dyslipidemia and type 2 diabetes mellitus

PubMed Central

Tangvarasittichai, Surapon

2015-01-01

Oxidative stress is increased in metabolic syndrome and type 2 diabetes mellitus (T2DM) and this appears to underlie the development of cardiovascular disease, T2DM and diabetic complications. Increased oxidative stress appears to be a deleterious factor leading to insulin resistance, dyslipidemia, β-cell dysfunction, impaired glucose tolerance and ultimately leading to T2DM. Chronic oxidative stress, hyperglycemia and dyslipidemia are particularly dangerous for β-cells from lowest levels of antioxidant, have high oxidative energy requirements, decrease the gene expression of key β-cell genes and induce cell death. If β-cell functioning is impaired, it results in an under production of insulin, impairs glucose stimulated insulin secretion, fasting hyperglycemia and eventually the development of T2DM. PMID:25897356

Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

PubMed

Cama, Christina A; Pelliccione, Christopher J; Brady, Alexander B; Li, Jing; Stach, Eric A; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

2016-06-22

Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

Controlling interface oxygen for forming Ag ohmic contact to semi-polar (1 1 -2 2) plane p-type GaN

NASA Astrophysics Data System (ADS)

Park, Jae-Seong; Han, Jaecheon; Seong, Tae-Yeon

2014-11-01

Low-resistance Ag ohmic contacts to semi-polar (1 1 -2 2) p-GaN were developed by controlling interfacial oxide using a Zn layer. The 300 °C-annealed Zn/Ag samples showed ohmic behavior with a contact resistivity of 6.0 × 10-4 Ω cm2 better than that of Ag-only contacts (1.0 × 10-3 Ω cm2). The X-ray photoemission spectroscopy (XPS) results showed that annealing caused the indiffusion of oxygen at the contact/GaN interface, resulting in the formation of different types of interfacial oxides, viz. Ga-oxide and Ga-doped ZnO. Based on the XPS and electrical results, the possible mechanisms underlying the improved electrical properties of the Zn/Ag samples are discussed.

n-Type diamond and method for producing same

DOEpatents

Anderson, Richard J.

2002-01-01

A new n-type semiconducting diamond is disclosed, which is doped with n-type dopant atoms. Such diamond is advantageously formed by chemical vapor deposition from a source gas mixture comprising a carbon source compound for the diamond, and a volatile hot wire filament for the n-type impurity species, so that the n-type impurity atoms are doped in the diamond during its formation. A corresponding chemical vapor deposition method of forming the n-type semiconducting diamond is disclosed. The n-type semiconducting diamond of the invention may be usefully employed in the formation of diamond-based transistor devices comprising pn diamond junctions, and in other microelectronic device applications.

Novel antiprotozoal products: imidazole and benzimidazole N-oxide derivatives and related compounds.

PubMed

Aguirre, Gabriela; Boiani, Mariana; Cerecetto, Hugo; Gerpe, Alejandra; González, Mercedes; Sainz, Yolanda Fernández; Denicola, Ana; De Ocáriz, Carmen Ochoa; Nogal, Juan José; Montero, David; Escario, José Antonio

2004-05-01

The syntheses and biological evaluation of the first anti-protozoa imidazole N-oxide and benzimidazole N-oxide and their derivatives are reported. They were tested in vitro against two different protozoa, Trypanosoma cruzi and Trichomonas vaginalis. Derivative 7c, ethyl-1-(i-butyloxycarbonyloxy)-6-nitrobenzimid-azole-2-carboxylate, displayed activity on both protozoa. Lipophilicity and redox potential were experimentally determined in order to study the relationship with activity of the compounds. These properties are well related with the observed bioactivity. Imidazole and benzimidazole N-oxide derivatives are becoming leaders for further chemical modifications and advanced biological studies.

Structure of indazole N1-oxide derivatives studied by X-ray, theoretical methods, 1H, 13C, 15N NMR and EI/MS

NASA Astrophysics Data System (ADS)

Gerpe, Alejandra; Piro, Oscar E.; Cerecetto, Hugo; González, Mercedes

2007-12-01

A series of indazole N1-oxide derivatives has been spectroscopically studied in solution using 1H, 13C, and 15N NMR based on pulsed field gradient selected PFG 1H sbnd X (X = 13C and 15N) gHMQC and gHMBC experiments. Some indazoles were prepared using a new methodology to compare its spectral and structural data with the indazole N1-oxide parent compounds. The 13C resonances of the indazole N1-oxide carbon 3 and 7a demonstrate the N-oxide push-electron capability. The 15N resonances of the indazole N-oxide, nitrogen 1, are near to 30 ppm more shielded than the corresponding values in the indazole heterocycle (deoxygenated form). Moreover, the structures of one indazole and one indazole N-oxide were unambiguously confirmed by X-ray crystallography. The solid state structures were contrasted with the theoretical ones obtained in vacuo at different calculus level. The aromaticity of the derivatives was studied analyzing the H sbnd H coupling constants of indazole's aromatic hydrogens and measuring C sbnd C distances in the solid state. The fragmentation that takes place in EI/MS was gathered for all the indazole N-oxide derivatives and the general fragmentation pattern analyzed.

N-acetylcysteine is able to reduce the oxidation status and the endothelial activation after a high-glucose content meal in patients with Type 2 diabetes mellitus.

PubMed

Masha, A; Brocato, L; Dinatale, S; Mascia, C; Biasi, F; Martina, V

2009-04-01

Post-prandial hyperglycemia seems to play a pivotal role in the pathogenesis of the cardiovascular complications of diabetes mellitus, as it leads to an oxidative stress which in turn causes a reduced NO bioavailability. These conditions produce an endothelial activation. The aim of this study was to assure that the administration of N-acetylcysteine (NAC), thiolic antioxidant, is able to decrease the oxidation status and endothelial activation after a high-glucose content meal. Ten patients with Type 2 diabetes mellitus (DMT2) (Group 1) and 10 normal subjects (Group 2) were studied. They assumed a high-glucose content meal without (phase A) or after (phase B) the administration of NAC. Glycemia, insulinemia, intercellular adhesion molecule 1, vascular adhesion molecule 1 (VCAM-1), E-selectin, malonaldehyde (MDA), and 4-hydroxynonenal (HNE) were assessed at -30, 0, +30, +60, +90, +120, and +180 min with respect to the meal consumption. During the phase A in Group 1, only HNE and MDA levels increased after the meal assumption; all parameters remained unchanged in Group 2. During the phase B, in Group 1, HNE, MDA, VCAM-1, and E-selectin levels after the meal were lower than those in phase A, while no change for all variables were observed in Group 2. A high-glucose meal produces an increase in oxidation parameters in patients with DMT2. The administration of NAC reduces the oxidative stress and, by doing so, reduces the endothelial activation. In conclusion, NAC could be efficacious in the slackening of the progression of vascular damage in DMT2.

Aluminum Complexes of N2O23- Formazanate Ligands Supported by Phosphine Oxide Donors.

PubMed

Maar, Ryan R; Rabiee Kenaree, Amir; Zhang, Ruizhong; Tao, Yichen; Katzman, Benjamin D; Staroverov, Viktor N; Ding, Zhifeng; Gilroy, Joe B

2017-10-16

The synthesis and characterization of a new family of phosphine oxide supported aluminum formazanate complexes (7a,b, 8a, 9a) are reported. X-ray diffraction studies showed that the aluminum atoms in the complexes adopt an octahedral geometry in the solid state. The equatorial positions are occupied by an N 2 O 2 3- formazanate ligand, and the axial positions are occupied by L-type phosphine oxide donors. UV-vis absorption spectroscopy revealed that the complexes were strongly absorbing (ε ≈ 30000 M -1 cm -1 ) between 500 and 700 nm. The absorption maxima in this region were simulated using time-dependent density functional theory. With the exception of 3-cyano-substituted complex 7b, which showed maximum luminescence intensity in the presence of excess phosphine oxide, the title complexes are nonemissive in solution and the solid state. The electrochemical properties of the complexes were probed using cyclic voltammetry. Each complex underwent sequential one-electron oxidations in potential ranges of -0.12 to 0.29 V and 0.62 to 0.97 V, relative to the ferrocene/ferrocenium redox couple. Electrochemical reduction events were observed at potentials between -1.34 and -1.75 V. In combination with tri-n-propylamine as a coreactant, complex 7b acted as an electrochemiluminescence emitter with a maximum electrochemiluminescence intensity at a wavelength of 735 nm, red-shifted relative to the photoluminescence maximum of the same compound.

Investigation of the interaction of iron(III) complexes with dAMP by ESI-MS, MALDI-MS and potentiometric titration: insights into synthetic nuclease behavior.

PubMed

Fernandes, Christiane; Oliveira Moreira, Rafaela; Lube, Leonardo M; Horn, Adolfo; Szpoganicz, Bruno; Sherrod, Stacy; Russell, David H

2010-06-07

We report herein the characterization by electrospray ionization (ESI) mass spectrometry (MS), matrix assisted laser desorption ionization (MALDI-MS) and potentiometric titration of three iron(III) compounds: [Fe(III)(HPClNOL)Cl2]·NO3 (1), [Cl(HPClNOL)Fe(III)-(μ-O)-Fe(III)(HPClNOL)Cl]·Cl2·H2O (2) and [(SO4)(HPClNOL)Fe(III)-(μ-O)-Fe(III)(HPClNOL)(SO4)]·6H2O (3), where HPClNOL= 1-(bis-pyridin-2-ylmethyl-amino)-3-chloropropan-2-ol). Despite the fact that the compounds have distinct structures in solid state and non-buffered solution, all compounds present similar ESI and MALDI mass spectra in a buffered medium (pH 7.0). At this pH, the species [(PClNOL)Fe(III)-(μ-O)-Fe(III)(PClNOL)](2+) (m/z 354) was observed for all the compounds under investigation. Potentiometric titration confirms a similar behavior for all compounds, indicating that the dihydroxo form [(OH)(HPClNOL)Fe(III)-(μ-O)-Fe(III)(HPClNOL)(OH)](2+) is the major species at pH 7.0, for all the compounds. The products of the interaction between compounds (1), (2) and (3) and dAMP (2'-deoxyadenosine-5'-monophosphate) in a buffered medium (pH 7.0) were identified by MALDI-MS/MS. The fragmentation data obtained by MS/MS allow one to identify the nature of the interaction between the iron(III) compounds and dAMP, revealing the direct interaction between the iron center and phosphate groups.

As(III) oxidation by MnO2 during groundwater treatment.

PubMed

Gude, J C J; Rietveld, L C; van Halem, D

2017-03-15

The top layer of natural rapid sand filtration was found to effectively oxidise arsenite (As(III)) in groundwater treatment. However, the oxidation pathway has not yet been identified. The aim of this study was to investigate whether naturally formed manganese oxide (MnO 2 ), present on filter grains, could abiotically be responsible for As(III) oxidation in the top of a rapid sand filter. For this purpose As(III) oxidation with two MnO 2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO 2 powder was a very pure - commercially available - natural MnO 2 powder. The second originated from a filter sand coating, produced over 22 years in a rapid filter during aeration and filtration. Jar test experiments showed that both powders oxidised As(III). However, when applying the MnO 2 in aerated, raw groundwater, As(III) removal was not enhanced compared to aeration alone. It was found that the presence of Fe(II)) and Mn(II) inhibited As(III) oxidation, as Fe(II) and Mn(II) adsorption and oxidation were preferred over As(III) on the MnO 2 surface (at pH 7). Therefore it is concluded that just because MnO 2 is present in a filter bed, it does not necessarily mean that MnO 2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO 2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigation on Tribological Properties of the Pre-oxidized Ti2AlN/TiAl Composite

NASA Astrophysics Data System (ADS)

Wang, Daqun; Sun, Dongli; Han, Xiuli; Wang, Qing; Wang, Guangwei

2018-03-01

Different oxidation layers on the Ti2AlN/TiAl substrate which was fabricated by in situ synthesis were prepared through thermal oxidation process. The microstructure, phase identification and elements distribution of the oxidation layers were analyzed. The tribological performance of pre-oxidized composites against Si3N4 ball at 25 and 600 °C, as well as the effect of pre-oxidation layers on tribological performance was systematically investigated. The results show that, compared to Ti2AlN/TiAl, the pre-oxidized composites present more excellent tribological properties, especially the wear resistance at 600 °C. It is a significant finding that, different from severe abrasive wear and plastic deformation of Ti2AlN/TiAl, the tribo-films formed by the pre-oxidation layers on the worn surface of pre-oxidized composites weaken abrasive wear and suppress the development of plastic deformation to protect the underlying composite substrate from wear. Moreover, the stable cooperation on the interface between tribo-films and Si3N4 ball results in the relatively steady friction coefficient.

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

2011-10-07

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

Increasing the availability of l-arginine and nitric oxide increases sensitivity of nitrous oxide (N2O)-insensitive inbred mice to N2O-induced antinociception.

PubMed

Chung, Eunhee; Ohgami, Yusuke; Quock, Raymond M

2016-07-01

Nitrous oxide (N2O)-induced antinociception in mice is dependent on the neuromodulator nitric oxide (NO). In contrast to C57BL/6J (B6) mice, DBA/2J (D2) mice fail to respond to N2O with a robust antinociceptive response or with an increase in brain nitric oxide synthase (NOS) enzyme activity, suggesting that failure of D2 mice to respond to N2O might result from a deficit of NO function. Therefore, it was of interest to determine whether increasing the availability of NO might increase sensitivity of D2 mice to N2O. Male D2 mice were pretreated with sub-antinociceptive intracerebroventricular doses of the NO donor 3-morpholinosydnoimine or the NO precursor l-arginine then assessed for responsiveness to N2O-induced antinociception using the acetic acid abdominal constriction test. Both pretreatments increased the antinociceptive responsiveness of D2 mice to N2O. These results indicate that the NOS enzyme in D2 mice is functional and that the deficit in NO function that obstructs sensitivity to N2O-induced antinociception may lie in availability or utilization of l-arginine. Copyright © 2016 Elsevier Inc. All rights reserved.

Fundamentals of Passive Oxidation In SiC and Si3N4

NASA Technical Reports Server (NTRS)

Thomas-Ogbuji, Linus U.

1998-01-01

The very slow oxidation kinetics of silicon carbide and silicon nitride, which derive from their adherent and passivating oxide films, has been explored at length in a broad series of studies utilizing thermogravimetric analysis, electron and optical micrography, energy dispersive spectrometry, x-ray diffractometry, micro-analytical depth profiling, etc. Some interesting microstructural phenomena accompanying the process of oxidation in the two materials will be presented. In Si3N4 the oxide is stratified, with an SiO2 topscale (which is relatively impervious to O2)underlain by a coherent subscale of silicon oxynitride which is even less permeable to O2- Such "defence in depth" endows Si3N4 with what is perhaps the highest oxidation resistance of any material, and results in a unique set of oxidation processes. In SiC the oxidation reactions are much simpler, yet new issues still emerge; for instance, studies involving controlled devitrification of the amorphous silica scale confirmed that the oxidation rate of SiC drops by more than an order of magnitude when the oxide scale fully crystallizes.

2,2,2-Trifluoroacetophenone as an organocatalyst for the oxidation of tertiary amines and azines to N-oxides.

PubMed

Limnios, Dimitris; Kokotos, Christoforos G

2014-01-07

A cheap, mild and environmentally friendly oxidation of tertiary amines and azines to the corresponding N-oxides is reported by using polyfluoroalkyl ketones as efficient organocatalysts. 2,2,2-Trifluoroacetophenone was identified as the optimum catalyst for the oxidation of aliphatic tertiary amines and azines. This oxidation is chemoselective and proceeds in high-to-quantitative yields utilizing 10 mol % of the catalyst and H2 O2 as the oxidant. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative analyses of ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB) in fields with different soil types.

PubMed

Morimoto, Sho; Hayatsu, Masahito; Takada Hoshino, Yuko; Nagaoka, Kazunari; Yamazaki, Masatsugu; Karasawa, Toshihiko; Takenaka, Makoto; Akiyama, Hiroko

2011-01-01

Soil type is one of the key factors affecting soil microbial communities. With regard to ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB), however, it has not been determined how soil type affects their community size and soil nitrification activity. Here we quantitatively analyzed the ammonia monooxygenase genes (amoA) of these ammonia oxidizers in fields with three different soil types (Low-humic Andosol [LHA], Gray Lowland Soil [GLS], and Yellow Soil [YS]) under common cropping conditions, and assessed the relationships between soil nitrification activity and the abundance of each amoA. Nitrification activity of LHA was highest, followed by that of GLS and YS; this order was consistent with that for the abundance of AOB amoA. Abundance of AOB amoA showed temporal variation, which was similar to that observed in nitrification activity, and a strong relationship (adjusted R(2)=0.742) was observed between the abundance of AOB amoA and nitrification activity. Abundance of AOA amoA also exhibited a significant relationship (adjusted R(2)=0.228) with nitrification activity, although this relationship was much weaker. Our results indicate that soil type affects the community size of AOA and AOB and the resulting nitrification activity, and that AOB are major contributors to nitrification in soils, while AOA are partially responsible.

Acidification Enhances Hybrid N2O Production Associated with Aquatic Ammonia-Oxidizing Microorganisms

PubMed Central

Frame, Caitlin H.; Lau, Evan; Nolan, E. Joseph; Goepfert, Tyler J.; Lehmann, Moritz F.

2017-01-01

Ammonia-oxidizing microorganisms are an important source of the greenhouse gas nitrous oxide (N2O) in aquatic environments. Identifying the impact of pH on N2O production by ammonia oxidizers is key to understanding how aquatic greenhouse gas fluxes will respond to naturally occurring pH changes, as well as acidification driven by anthropogenic CO2. We assessed N2O production rates and formation mechanisms by communities of ammonia-oxidizing bacteria (AOB) and archaea (AOA) in a lake and a marine environment, using incubation-based nitrogen (N) stable isotope tracer methods with 15N-labeled ammonium (15NH4+) and nitrite (15NO2−), and also measurements of the natural abundance N and O isotopic composition of dissolved N2O. N2O production during incubations of water from the shallow hypolimnion of Lake Lugano (Switzerland) was significantly higher when the pH was reduced from 7.54 (untreated pH) to 7.20 (reduced pH), while ammonia oxidation rates were similar between treatments. In all incubations, added NH4+ was the source of most of the N incorporated into N2O, suggesting that the main N2O production pathway involved hydroxylamine (NH2OH) and/or NO2− produced by ammonia oxidation during the incubation period. A small but significant amount of N derived from exogenous/added 15NO2− was also incorporated into N2O, but only during the reduced-pH incubations. Mass spectra of this N2O revealed that NH4+ and 15NO2− each contributed N equally to N2O by a “hybrid-N2O” mechanism consistent with a reaction between NH2OH and NO2−, or compounds derived from these two molecules. Nitrifier denitrification was not an important source of N2O. Isotopomeric N2O analyses in Lake Lugano were consistent with incubation results, as 15N enrichment of the internal N vs. external N atoms produced site preferences (25.0–34.4‰) consistent with NH2OH-dependent hybrid-N2O production. Hybrid-N2O formation was also observed during incubations of seawater from coastal Namibia

Synthesis and catalytic activity of Birnessite-Type Manganese Oxide synthesized by solvent-free method

NASA Astrophysics Data System (ADS)

Siregar, S. S.; Awaluddin, A.

2018-04-01

Redox reaction between KMnO4 and glucose usingsolvent-free method produces the octahedral layer birnessite-type manganese oxide. The effects of mole ratios, temperatures, and calcinations time on the structures and crystallinity of the oxides were studied throughthe X-ray powder diffraction analysis. The mole ratio of KMnO4/glucose (1:3) produces the purebirnessite with low crystallinity, whereas the mole ratio of KMnO4/glucose (3:1) yields high crystalline birnessite with minor components of hausmannite-type manganese oxide.The increasing of the temperature and calcinations times (300-700 °C and 3-7 h, respectively) willimprove the crystallinity and the purity of the as-synthesized oxide. Further experiments also showed that the as-syntesized octahedral layer birnessite-type manganese oxides have catalytic activity on the degradation of methylene blue (MB) dye with H2O2 as oxidant. The results revealed that the effective degradation could be achieved only in the presence of both the birnessite and H2O2, whereas without the addition of catalyst (H2O2only) or addition of H2O2 (catalyst only), the 3.5% and 15.5% of MB removal were obtained, respectively.

High-resolution MS and MS(n) investigation of ozone oxidation products from phenazone-type pharmaceuticals and metabolites.

PubMed

Favier, Maxime; Dewil, Raf; Van Eyck, Kwinten; Van Schepdael, Ann; Cabooter, Deirdre

2015-10-01

Phenazone-type pharmaceuticals, such as aminopyrine, metamizole, phenazone and propyphenazone, are widely used analgesics that have been detected in wastewater treatment plant effluents in μg L(-1) concentrations. Acetamido antipyrine (AAA) and formyl aminoantipyrine (FAA) - the main metabolites of aminopyrine and metamizole - have also been detected in sub μg L(-1) concentrations in environmental water bodies and in resources used to produce drinking water, suggesting their highly persistent character. In this study phenazone, propyphenazone, AAA and FAA were treated with ozone under laboratory conditions and 17 degradation products were identified by an elucidation approach based on high-resolution mass spectrometry (LTQ Orbitrap). Typical oxidation of carbon-carbon double bonds by ozone was observed among other mechanisms of ring opening. It was demonstrated that reactivity of these compounds with ozone is high (rate constants kO3 ranging from 6.5×10(4) to 2.4×10(6) M(-1) s(-1)). The toxicity of the degradation products from ozonation was estimated by quantitative structure-activity relationships (QSAR). It was shown that, when the carbon-carbon double bond is partially oxidized to an epoxy, the toxicity towards fish and daphnids is higher than that of the parent compound. By further oxidizing the molecules, a common degradation product - 1-acetyl-1-methyl-2-phenylhydrazide (AMPH) - was also found to be more toxic than its parent compounds, which is of concern since this compound has previously been reported in environmental waters. Copyright © 2015 Elsevier Ltd. All rights reserved.

Cu-catalyzed aerobic oxidative cyclizations of 3-N-hydroxyamino-1,2-propadienes with alcohols, thiols, and amines to form α-O-, S-, and N-substituted 4-methylquinoline derivatives.

PubMed

Sharma, Pankaj; Liu, Rai-Shung

2015-03-16

A one-pot, two-step synthesis of α-O-, S-, and N-substituted 4-methylquinoline derivatives through Cu-catalyzed aerobic oxidations of N-hydroxyaminoallenes with alcohols, thiols, and amines is described. This reaction sequence involves an initial oxidation of N-hydroxyaminoallenes with NuH (Nu = OH, OR, NHR, and SR) to form 3-substituted 2-en-1-ones, followed by Brønsted acid catalyzed intramolecular cyclizations of the resulting products. Our mechanistic analysis suggests that the reactions proceed through a radical-type mechanism rather than a typical nitrone-intermediate route. The utility of this new Cu-catalyzed reaction is shown by its applicability to the synthesis of several 2-amino-4-methylquinoline derivatives, which are known to be key precursors to several bioactive molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrous oxide reduction in nodules: denitrification or N/sub 2/ fixation

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

Coyne, M.S.; Focht, D.D.

1987-05-01

Detached cowpea nodules that contained a nitrous oxide reductase-positive (Nor/sup +/) rhizobium strain (8A55) and a nitrous oxide reductase-negative (Nor/sup -/) rhizobium strain (32H1) were incubated with 1% /sup 15/N/sub 2/O (95 atom% /sup 15/N) in the following three atmospheres: aerobic with C/sub 2/H/sub 2/ (10%), aerobic without C/sub 2/H/sub 2/, and anaerobic (argon atmosphere) without C/sub 2/H/sub 2/. The greatest production of /sup 15/N/sub 2/ occurred anaerobically with 8A55, yet very little was formed with 32H1. Although acetylene reduction activity was slightly higher with 32H1, about 10 times more /sup 15/N/sub 2/ was produced aerobically by 8A55 than bymore » 32H1 in the absence of acetylene. The major reductive pathway of N/sub 2/O reduction by denitrifying rhizobium strain 8A55 is by nitrous oxide reductase rather than nitrogenase.« less

AlGaN/GaN metal-oxide-semiconductor high electron mobility transistors using Sc2O3 as the gate oxide and surface passivation

NASA Astrophysics Data System (ADS)

Mehandru, R.; Luo, B.; Kim, J.; Ren, F.; Gila, B. P.; Onstine, A. H.; Abernathy, C. R.; Pearton, S. J.; Gotthold, D.; Birkhahn, R.; Peres, B.; Fitch, R.; Gillespie, J.; Jenkins, T.; Sewell, J.; Via, D.; Crespo, A.

2003-04-01

We demonstrated that Sc2O3 thin films deposited by plasma-assisted molecular-beam epitaxy can be used simultaneously as a gate oxide and as a surface passivation layer on AlGaN/GaN high electron mobility transistors (HEMTs). The maximum drain source current, IDS, reaches a value of over 0.8 A/mm and is ˜40% higher on Sc2O3/AlGaN/GaN transistors relative to conventional HEMTs fabricated on the same wafer. The metal-oxide-semiconductor HEMTs (MOS-HEMTs) threshold voltage is in good agreement with the theoretical value, indicating that Sc2O3 retains a low surface state density on the AlGaN/GaN structures and effectively eliminates the collapse in drain current seen in unpassivated devices. The MOS-HEMTs can be modulated to +6 V of gate voltage. In particular, Sc2O3 is a very promising candidate as a gate dielectric and surface passivant because it is more stable on GaN than is MgO.

Sulfate formation catalyzed by coal fly ash, mineral dust and iron(iii) oxide: variable influence of temperature and light.

PubMed

Gankanda, Aruni; Coddens, Ellen M; Zhang, Yaping; Cwiertny, David M; Grassian, Vicki H

2016-12-08

Recent atmospheric field and modeling studies have highlighted a lack of understanding of the processes responsible for high levels of sulfate aerosol in the atmosphere, ultimately arising from a dearth of experimental data on such processes. Here we investigated the effect of temperature and simulated solar radiation on the catalytic oxidation of S(iv) to S(vi) (i.e., sulfite to sulfate) in aqueous suspensions of several metal-containing, atmospherically relevant particles including coal fly ash (FA), Arizona test dust (ATD) and an iron oxide (γ-Fe 2 O 3 ). The effect of temperature and light on S(iv) oxidation was found to be very different for these three samples. For example, in the presence of FA and γ-Fe 2 O 3 the temporal evolution of dissolved Fe(ii) (formed via reductive particle dissolution) correlated with S(iv) oxidation. Accordingly, we propose that S(iv) oxidation in most of these systems initially occurs primarily at the particle surface (i.e., a heterogeneous reaction pathway), although a solution-phase (i.e., homogeneous) catalytic pathway also contributes over later timescales due to the formation and accumulation of dissolved Fe(iii) (generated via oxidation of dissolved Fe(ii) by O 2 ). It is likely that the homogeneous reaction pathway is operative at initial times in the presence of γ-Fe 2 O 3 at 25 °C. In contrast, S(iv) oxidation in the presence of ATD appears to proceed entirely via a heterogeneous reaction, which notably does not lead to any iron dissolution. In fact, the greater overall rate of S(iv) loss in the presence of ATD compared to FA and γ-Fe 2 O 3 suggests that other factors, including greater adsorption of sulfite, transition metal ion (TMI) catalysis by other metal ions (e.g., Ti), or different species of iron in ATD, play a role. Overall these studies suggest that the rate, extent and products of atmospheric S(iv) oxidation can be highly variable and dependent upon the nature of aerosol sources and ambient conditions (e

IBX-mediated oxidation of unactivated cyclic amines: application in highly diastereoselective oxidative Ugi-type and aza-Friedel-Crafts reactions.

PubMed

de Graaff, C; Bensch, L; van Lint, Matthijs J; Ruijter, E; Orru, R V A

2015-10-28

The first o-iodoxybenzoic acid (IBX) mediated oxidation of unactivated amines to imines is described. A range of meso-pyrrolidines were shown to be suitable substrates. The chemical space was further explored with one-pot oxidative Ugi-type and aza-Friedel-Crafts reactions, which proved to be highly diastereoselective.

Determination of carrier diffusion length in p- and n-type GaN

NASA Astrophysics Data System (ADS)

Hafiz, Shopan; Metzner, Sebastian; Zhang, Fan; Monavarian, Morteza; Avrutin, Vitaliy; Morkoç, Hadis; Karbaum, Christopher; Bertram, Frank; Christen, Jürgen; Gil, Bernard; Özgür, Ümit

2014-03-01

Diffusion lengths of photo-excited carriers along the c-direction were determined from photoluminescence (PL) measurements in p- and n-type GaN epitaxial layers grown on c-plane sapphire by metal-organic chemical vapor deposition. The investigated samples incorporate a 6 nm thick In0.15Ga0.85N active layer capped with either 500 nm p- GaN or 1300 nm n-GaN. The top GaN layers were etched in steps and PL from the InGaN active region and the underlying layers was monitored as a function of the top GaN thickness upon photogeneration near the surface region by above bandgap excitation. Taking into consideration the absorption in the active and underlying layers, the diffusion lengths at 295 K and at 15 K were measured to be about 92 ± 7 nm and 68 ± 7 nm for Mg-doped p-type GaN and 432 ± 30 nm and 316 ± 30 nm for unintentionally doped n-type GaN, respectively. Cross-sectional cathodoluminescence line-scan measurement was performed on a separate sample and the diffusion length in n-type GaN was measured to be 280 nm.

Low-temperature preparation of GaN-SiO2 interfaces with low defect density. II. Remote plasma-assisted oxidation of GaN and nitrogen incorporation

NASA Astrophysics Data System (ADS)

Bae, Choelhwyi; Lucovsky, Gerald

2004-11-01

Low-temperature remote plasma-assisted oxidation and nitridation processes for interface formation and passivation have been extended from Si and SiC to GaN. The initial oxidation kinetics and chemical composition of thin interfacial oxide were determined from analysis of on-line Auger electron spectroscopy features associated with Ga, N, and O. The plasma-assisted oxidation process is self-limiting with power-law kinetics similar to those for the plasma-assisted oxidation of Si and SiC. Oxidation using O2/He plasma forms nearly pure GaOx, and oxidation using 1% N2O in N2 forms GaOxNy with small nitrogen content, ~4-7 at. %. The interface and dielectric layer quality was investigated using fabricated GaN metal-oxide-semiconductor capacitors. The lowest density of interface states was achieved with a two-step plasma-assisted oxidation and nitridation process before SiO2 deposition.

N,N-Dimethyl-p-phenylenediamine dihydrochloride-based method for the measurement of plasma oxidative capacity during human aging.

PubMed

Mehdi, Mohammad Murtaza; Rizvi, Syed Ibrahim

2013-05-15

N,N-Dimethyl-p-phenylenediamine dihydrochloride (DMPD) is a compound that is normally used to measure the antioxidant potential. In the presence of Fe(3+), it gets converted to DMPD(∙+) radical, which is scavenged by antioxidant molecules present in test samples. In plasma, due to the presence of iron, this method cannot be applied for the measurement of antioxidant potential. The modified DMPD method proposed by us measures with great accuracy the oxidant potential of plasma using the oxidizing effect of plasma to oxidize DMPD into producing a stable pink color. The method is fast and reproducible. We show that plasma oxidative capacity increases significantly during human aging. Copyright © 2013 Elsevier Inc. All rights reserved.

Facile synthesis of birnessite-type manganese oxide nanoparticles as supercapacitor electrode materials.

PubMed

Liu, Lihu; Luo, Yao; Tan, Wenfeng; Zhang, Yashan; Liu, Fan; Qiu, Guohong

2016-11-15

Manganese oxides are environmentally benign supercapacitor electrode materials and, in particular, birnessite-type structure shows very promising electrochemical performance. In this work, nanostructured birnessite was facilely prepared by adding dropwise NH2OH·HCl to KMnO4 solution under ambient temperature and pressure. In order to fully exploit the potential of birnessite-type manganese oxide electrode materials, the effects of specific surface area, pore size, content of K(+), and manganese average oxidation state (Mn AOS) on their electrochemical performance were studied. The results showed that with the increase of NH2OH·HCl, the Mn AOS decreased and the corresponding pore sizes and specific surface area of birnessite increased. The synthesized nanostructured birnessite showed the highest specific capacitance of 245Fg(-1) at a current density of 0.1Ag(-1) within a potential range of 0-0.9V, and excellent cycle stability with a capacitance retention rate of 92% after 3000 cycles at a current density of 1.0Ag(-1). The present work implies that specific capacitance is mainly affected by specific surface area and pore volume, and provides a new method for the facile preparation of birnessite-type manganese oxide with excellent capacitive performance. Copyright © 2016 Elsevier Inc. All rights reserved.

The lyocell process: Cellulose solutions in N-Methylmorpholine-N-oxide (NMMO) - degradation processes and stabilizers

Treesearch

Thomas Rosenau; Thomas Elder; Antje Potthast; Sixta Herbert; Paul Kosma

2003-01-01

Homolytic (radical) reactions in the system cellulose / N-methylmorpholine-N-oxide (NMMO, 1) involve a primary, nitrogen-centered cation radical (2), and two secondary, carbon-centered radical species (3, 4). Radical formation &om NMMO is strongly promoted by transition metal ions.

Water-Gas Shift and Methane Reactivity on Reducible Perovskite-Type Oxides

PubMed Central

2015-01-01

Comparative (electro)catalytic, structural, and spectroscopic studies in hydrogen electro-oxidation, the (inverse) water-gas shift reaction, and methane conversion on two representative mixed ionic–electronic conducting perovskite-type materials La0.6Sr0.4FeO3−δ (LSF) and SrTi0.7Fe0.3O3−δ (STF) were performed with the aim of eventually correlating (electro)catalytic activity and associated structural changes and to highlight intrinsic reactivity characteristics as a function of the reduction state. Starting from a strongly prereduced (vacancy-rich) initial state, only (inverse) water-gas shift activity has been observed on both materials beyond ca. 450 °C but no catalytic methane reforming or methane decomposition reactivity up to 600 °C. In contrast, when starting from the fully oxidized state, total methane oxidation to CO2 was observed on both materials. The catalytic performance of both perovskite-type oxides is thus strongly dependent on the degree/depth of reduction, on the associated reactivity of the remaining lattice oxygen, and on the reduction-induced oxygen vacancies. The latter are clearly more reactive toward water on LSF, and this higher reactivity is linked to the superior electrocatalytic performance of LSF in hydrogen oxidation. Combined electron microscopy, X-ray diffraction, and Raman measurements in turn also revealed altered surface and bulk structures and reactivities. PMID:26045733

A new and efficient synthetic method for 15N3-labeled cytosine nucleosides: Dimroth rearrangement of cytidine N3-oxides.

PubMed

Sako, Magoichi; Kawada, Hiroyoshi

2004-11-12

The treatment of (15)N(4)-labeled cytidine N(3)-oxide and (15)N(4)-labeled 2'-deoxycytidine N(3)-oxide, prepared from the appropriate unprotected uridines in three reaction steps, with benzyl bromide in the presence of excess lithium methoxide allowed the smooth occurrence of their Dimroth rearrangement even under mild conditions leading to the corresponding (15)N(3)-labeled uridine 4-O-benzyloximes which can easily undergo the reductive N-O bond cleavage to give the desirable (15)N(3)-labeled cytosine nucleosides in high total yields.

Design of a 1200-V ultra-thin partial SOI LDMOS with n-type buried layer

NASA Astrophysics Data System (ADS)

Qiao, Ming; Wang, Yuru; Li, Yanfei; Zhang, Bo; Li, Zhaoji

2014-11-01

A novel 1200-V ultra-thin partial silicon-on-insulator (PSOI) lateral double-diffusion metal oxide semiconductor (LDMOS) with n-type buried (n-buried) layer (NBL PSOI LDMOS) is proposed in this paper. The new PSOI LDMOS features an n-buried layer underneath the n-type drift (n-drift) region close to the source side, providing a large conduction region for majority carriers and a silicon window to improve self-heating effect (SHE). A combination of uniform and linear variable doping (ULVD) profile is utilized in the n-drift region, which alleviates the inherent tradeoff between specific on-resistance (Ron,sp) and breakdown voltage (BV). With the n-drift region length of 80 μm, the NBL PSOI LDMOS obtains a high BV of 1243 V which is improved by around 105 V in comparison to the conventional SOI LDMOS with linear variable doping (LVD) profile for the n-drift region (LVD SOI LDMOS). Besides, the 1200-V NBL PSOI LDMOS has a lower maximum temperature (Tmax) of 333 K at a power (P) of 1 mW/μm which is reduced by around 61 K. Meanwhile, Ron,sp and Tmax of the NBL PSOI LDMOS are lower than those of the conventional LVD SOI LDMOS for a wide range of BV.

Mechanical writing of n-type conductive layers on the SrTiO3 surface in nanoscale

PubMed Central

Wang, Yuhang; Zhao, Kehan; Shi, Xiaolan; Li, Geng; Xie, Guanlin; Lai, Xubo; Ni, Jun; Zhang, Liuwan

2015-01-01

The fabrication and control of the conductive surface and interface on insulating SrTiO3 bulk provide a pathway for oxide electronics. The controllable manipulation of local doping concentration in semiconductors is an important step for nano-electronics. Here we show that conductive patterns can be written on bare SrTiO3 surface by controllable doping in nanoscale using the mechanical interactions of atomic force microscopy tip without applying external electric field. The conductivity of the layer is n-type, oxygen sensitive, and can be effectively tuned by the gate voltage. Hence, our findings have potential applications in oxide nano-circuits and oxygen sensors. PMID:26042679

Variation Quality and Kinetic Parameter of Commercial n-3 PUFA-Rich Oil during Oxidation via Rancimat

PubMed Central

Yang, Kai-Min; Chiang, Po-Yuan

2017-01-01

Different biological sources of n-3 polyunsaturated fatty acids (n-3 PUFA) in mainstream commercial products include algae and fish. Lipid oxidation in n-3 PUFA-rich oil is the most important cause of its deterioration. We investigated the kinetic parameters of n-3 PUFA-rich oil during oxidation via Rancimat (at a temperature range of 70~100 °C). This was done on the basis of the Arrhenius equation, which indicates that the activation energies (Ea) for oxidative stability are 82.84–96.98 KJ/mol. The chemical substrates of different oxidative levels resulting from oxidation via Rancimat at 80 °C were evaluated. At the initiation of oxidation, the tocopherols in the oil degraded very quickly, resulting in diminished protection against further oxidation. Then, the degradation of the fatty acids with n-3 PUFA-rich oil was evident because of decreased levels of PUFA along with increased levels of saturated fatty acids (SFA). The quality deterioration from n-3 PUFA-rich oil at the various oxidative levels was analyzed chemometrically. The anisidine value (p-AV, r: 0.92) and total oxidation value (TOTOX, r: 0.91) exhibited a good linear relationship in a principal component analysis (PCA), while oxidative change and a significant quality change to the induction period (IP) were detected through an agglomerative hierarchical cluster (AHC) analysis. PMID:28350348

Variation Quality and Kinetic Parameter of Commercial n-3 PUFA-Rich Oil during Oxidation via Rancimat.

PubMed

Yang, Kai-Min; Chiang, Po-Yuan

2017-03-28

Different biological sources of n -3 polyunsaturated fatty acids ( n -3 PUFA) in mainstream commercial products include algae and fish. Lipid oxidation in n -3 PUFA-rich oil is the most important cause of its deterioration. We investigated the kinetic parameters of n -3 PUFA-rich oil during oxidation via Rancimat (at a temperature range of 70~100 °C). This was done on the basis of the Arrhenius equation, which indicates that the activation energies ( E a) for oxidative stability are 82.84-96.98 KJ/mol. The chemical substrates of different oxidative levels resulting from oxidation via Rancimat at 80 °C were evaluated. At the initiation of oxidation, the tocopherols in the oil degraded very quickly, resulting in diminished protection against further oxidation. Then, the degradation of the fatty acids with n -3 PUFA-rich oil was evident because of decreased levels of PUFA along with increased levels of saturated fatty acids (SFA). The quality deterioration from n -3 PUFA-rich oil at the various oxidative levels was analyzed chemometrically. The anisidine value (p-AV, r: 0.92) and total oxidation value (TOTOX, r: 0.91) exhibited a good linear relationship in a principal component analysis (PCA), while oxidative change and a significant quality change to the induction period (IP) were detected through an agglomerative hierarchical cluster (AHC) analysis.

Systemic inflammation and oxidative stress post-lung resection: Effect of pretreatment with N-acetylcysteine.

PubMed

Bastin, Anthony J; Davies, Nathan; Lim, Eric; Quinlan, Greg J; Griffiths, Mark J

2016-01-01

N-acetylcysteine has been used to treat a variety of lung diseases, where is it thought to have an antioxidant effect. In a randomized placebo-controlled double-blind study, the effect of N-acetylcysteine on systemic inflammation and oxidative damage was examined in patients undergoing lung resection, a human model of acute lung injury. Eligible adults were randomized to receive preoperative infusion of N-acetylcysteine (240 mg/kg over 12 h) or placebo. Plasma thiols, interleukin-6, 8-isoprostane, ischaemia-modified albumin, red blood cell glutathione and exhaled breath condensate pH were measured pre- and post-operatively as markers of local and systemic inflammation and oxidative stress. Patients undergoing lung resection and one-lung ventilation exhibited significant postoperative inflammation and oxidative damage. Postoperative plasma thiol concentration was significantly higher in the N-acetylcysteine-treated group. However, there was no significant difference in any of the measured biomarkers of inflammation or oxidative damage, or in clinical outcomes, between N-acetylcysteine and placebo groups. Preoperative administration of N-acetylcysteine did not attenuate postoperative systemic or pulmonary inflammation or oxidative damage after lung resection. NCT00655928 at ClinicalTrials.gov. © 2015 Asian Pacific Society of Respirology.

Products of n-hexane oxidation with air oxygen on an activated carbon surface

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

Barkauskas, Yu.; Kareiva, A.

Products of n-hexane oxidation on an activated carbon surface have been investigated. Carbon samples have been prepared using the Plackett-Burman method of mathematical design. The influence of carbon preparation stages on the composition of products of n-hexane oxidation has been discussed.

Low resistance Ohmic contact to p-type crystalline silicon via nitrogen-doped copper oxide films

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

Zhang, Xinyu, E-mail: xinyu.zhang@anu.edu.au; Wan, Yimao; Bullock, James

2016-08-01

This work explores the application of transparent nitrogen doped copper oxide (CuO{sub x}:N) films deposited by reactive sputtering to create hole-selective contacts for p-type crystalline silicon (c-Si) solar cells. It is found that CuO{sub x}:N sputtered directly onto crystalline silicon is able to form an Ohmic contact. X-ray photoelectron spectroscopy and Raman spectroscopy measurements are used to characterise the structural and physical properties of the CuO{sub x}:N films. Both the oxygen flow rate and the substrate temperature during deposition have a significant impact on the film composition, as well as on the resulting contact resistivity. After optimization, a low contactmore » resistivity of ∼10 mΩ cm{sup 2} has been established. This result offers significant advantages over conventional contact structures in terms of carrier transport and device fabrication.« less

Assessment of nitric oxide (NO) redox reactions contribution to nitrous oxide (N2 O) formation during nitrification using a multispecies metabolic network model.

PubMed

Perez-Garcia, Octavio; Chandran, Kartik; Villas-Boas, Silas G; Singhal, Naresh

2016-05-01

Over the coming decades nitrous oxide (N2O) is expected to become a dominant greenhouse gas and atmospheric ozone depleting substance. In wastewater treatment systems, N2O is majorly produced by nitrifying microbes through biochemical reduction of nitrite (NO2(-)) and nitric oxide (NO). However it is unknown if the amount of N2O formed is affected by alternative NO redox reactions catalyzed by oxidative nitrite oxidoreductase (NirK), cytochromes (i.e., P460 [CytP460] and 554 [Cyt554 ]) and flavohemoglobins (Hmp) in ammonia- and nitrite-oxidizing bacteria (AOB and NOB, respectively). In this study, a mathematical model is developed to assess how N2O formation is affected by such alternative nitrogen redox transformations. The developed multispecies metabolic network model captures the nitrogen respiratory pathways inferred from genomes of eight AOB and NOB species. The performance of model variants, obtained as different combinations of active NO redox reactions, was assessed against nine experimental datasets for nitrifying cultures producing N2O at different concentration of electron donor and acceptor. Model predicted metabolic fluxes show that only variants that included NO oxidation to NO2(-) by CytP460 and Hmp in AOB gave statistically similar estimates to observed production rates of N2O, NO, NO2(-) and nitrate (NO3(-)), together with fractions of AOB and NOB species in biomass. Simulations showed that NO oxidation to NO2(-) decreased N2O formation by 60% without changing culture's NO2(-) production rate. Model variants including NO reduction to N2O by Cyt554 and cNor in NOB did not improve the accuracy of experimental datasets estimates, suggesting null N2O production by NOB during nitrification. Finally, the analysis shows that in nitrifying cultures transitioning from dissolved oxygen levels above 3.8 ± 0.38 to <1.5 ± 0.8 mg/L, NOB cells can oxidize the NO produced by AOB through reactions catalyzed by oxidative NirK. © 2015 Wiley Periodicals, Inc.

Oxide semiconductor thin-film transistors: a review of recent advances.

PubMed

Fortunato, E; Barquinha, P; Martins, R

2012-06-12

Transparent electronics is today one of the most advanced topics for a wide range of device applications. The key components are wide bandgap semiconductors, where oxides of different origins play an important role, not only as passive component but also as active component, similar to what is observed in conventional semiconductors like silicon. Transparent electronics has gained special attention during the last few years and is today established as one of the most promising technologies for leading the next generation of flat panel display due to its excellent electronic performance. In this paper the recent progress in n- and p-type oxide based thin-film transistors (TFT) is reviewed, with special emphasis on solution-processed and p-type, and the major milestones already achieved with this emerging and very promising technology are summarizeed. After a short introduction where the main advantages of these semiconductors are presented, as well as the industry expectations, the beautiful history of TFTs is revisited, including the main landmarks in the last 80 years, finishing by referring to some papers that have played an important role in shaping transparent electronics. Then, an overview is presented of state of the art n-type TFTs processed by physical vapour deposition methods, and finally one of the most exciting, promising, and low cost but powerful technologies is discussed: solution-processed oxide TFTs. Moreover, a more detailed focus analysis will be given concerning p-type oxide TFTs, mainly centred on two of the most promising semiconductor candidates: copper oxide and tin oxide. The most recent data related to the production of complementary metal oxide semiconductor (CMOS) devices based on n- and p-type oxide TFT is also be presented. The last topic of this review is devoted to some emerging applications, finalizing with the main conclusions. Related work that originated at CENIMAT|I3N during the last six years is included in more detail, which

High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides

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

Ding, Xun-Lei, E-mail: dingxl@ncepu.edu.cn, E-mail: chemzyx@iccas.ac.cn; Wang, Dan; Wu, Xiao-Nan

2015-09-28

The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb{sub 2}O{sub 5}){sub N}{sup +} clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb{sub 2}O{sub 5}){sub N}{sup +} clusters decreases as the N increases, and it is higher than that of (V {sub 2}O{sub 5}){sub N}{sup +} for N ≥ 4. Theoretical studies were conducted on (Nb{sub 2}O{sub 5}){sub N}{sup +} (N = 2–6) by density functional calculations. HAA reactions on these clusters are all favorablemore » thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion.« less

Inkjet-printed p-type nickel oxide thin-film transistor

NASA Astrophysics Data System (ADS)

Hu, Hailong; Zhu, Jingguang; Chen, Maosheng; Guo, Tailiang; Li, Fushan

2018-05-01

High-performance inkjet-printed nickel oxide thin-film transistors (TFTs) with Al2O3 high-k dielectric have been fabricated using a sol-gel precursor ink. The "coffee ring" effect during the printing process was facilely restrained by modifying the viscosity of the ink to control the outward capillary flow. The impacts on the device performance was studied in detail in consideration of annealing temperature of the nickel oxide film and the properties of dielectric layer. The optimized switching ability of the device were achieved at an annealing temperature of 280 °C on a 50-nm-thick Al2O3 dielectric layer, with a hole mobility of 0.78 cm2/V·s, threshold voltage of -0.6 V and on/off current ratio of 5.3 × 104. The as-printed p-type oxide TFTs show potential application in low-cost, large-area complementary electronic devices.

[Oxidation behavior and kinetics of representative VOCs emitted from petrochemical industry over CuCeOx composite oxides].

PubMed

Chen, Chang-Wei; Yu, Yan-Ke; Chen, Jin-Sheng; He, Chi

2013-12-01

CuCeOx composite catalysts were synthesized via coprecipitation (COP-CuCeO,) and incipient impregnation (IMP-CuCeOx) methods, respectively. The physicochemical properties of the samples were characterized by XRD, low-temperature N2 sorption, H2-TPR and O2-TPD. The influences of reactant composition and concentration, reaction space velocity, O2 content, H2O concentration, and catalyst type on the oxidation behaviors of benzene, toluene, and n-hexane emitted from petrochemical industry were systematically investigated. In addition, the related kinetic parameters were model fitted. Compared with IMP-CuCeOx, COP-CuCeOx had well-dispersed active phase, better low-temperature reducibility, and more active surface oxygen species. The increase of reactant concentration was unfavorable for toluene oxidation, while the opposite phenomenon could be observed in n-hexane oxidation. The inlet concentration of benzene was irrelevant to its conversion under high oxidation rate. The introduction of benzene obviously inhibited the oxidation of toluene and n-hexane, while the presence of toluene had a positive effect on beuzene conversion. The presence of n-hexane could promote the oxidation of toluene, while toluene had a negative influence on e-hexane oxidation. Both low space velocity and high oxygen concentration were beneficial for the oxidation process, and the variation of oxygen content had negligible effect on n-hexane and henzene oxidation. The presence of H2O noticeably inhibited the oxidation of toluene, while significantly accelerated the oxidation procedure of henzene and n-hexane. COP-CuCeOx had superior catalytic performance for toluene and benzene oxidation, while IMP-CuCeOx showed higher n-hexane oxidation activity under dry condition. The oxidation behaviors under different conditions could be well fitted and predicted by the pseudo first-order kinetic model.

Predictable quantum efficient detector based on n-type silicon photodiodes

NASA Astrophysics Data System (ADS)

Dönsberg, Timo; Manoocheri, Farshid; Sildoja, Meelis; Juntunen, Mikko; Savin, Hele; Tuovinen, Esa; Ronkainen, Hannu; Prunnila, Mika; Merimaa, Mikko; Tang, Chi Kwong; Gran, Jarle; Müller, Ingmar; Werner, Lutz; Rougié, Bernard; Pons, Alicia; Smîd, Marek; Gál, Péter; Lolli, Lapo; Brida, Giorgio; Rastello, Maria Luisa; Ikonen, Erkki

2017-12-01

The predictable quantum efficient detector (PQED) consists of two custom-made induced junction photodiodes that are mounted in a wedged trap configuration for the reduction of reflectance losses. Until now, all manufactured PQED photodiodes have been based on a structure where a SiO2 layer is thermally grown on top of p-type silicon substrate. In this paper, we present the design, manufacturing, modelling and characterization of a new type of PQED, where the photodiodes have an Al2O3 layer on top of n-type silicon substrate. Atomic layer deposition is used to deposit the layer to the desired thickness. Two sets of photodiodes with varying oxide thicknesses and substrate doping concentrations were fabricated. In order to predict recombination losses of charge carriers, a 3D model of the photodiode was built into Cogenda Genius semiconductor simulation software. It is important to note that a novel experimental method was developed to obtain values for the 3D model parameters. This makes the prediction of the PQED responsivity a completely autonomous process. Detectors were characterized for temperature dependence of dark current, spatial uniformity of responsivity, reflectance, linearity and absolute responsivity at the wavelengths of 488 nm and 532 nm. For both sets of photodiodes, the modelled and measured responsivities were generally in agreement within the measurement and modelling uncertainties of around 100 parts per million (ppm). There is, however, an indication that the modelled internal quantum deficiency may be underestimated by a similar amount. Moreover, the responsivities of the detectors were spatially uniform within 30 ppm peak-to-peak variation. The results obtained in this research indicate that the n-type induced junction photodiode is a very promising alternative to the existing p-type detectors, and thus give additional credibility to the concept of modelled quantum detector serving as a primary standard. Furthermore, the manufacturing of

Complexation facilitated reduction of aromatic N-oxides by aqueous Fe(II)-tiron complex: reaction kinetics and mechanisms.

PubMed

Chen, Yiling; Zhang, Huichun

2013-10-01

Rapid reduction of carbadox (CDX), olaquindox and several other aromatic N-oxides were investigated in aqueous solution containing Fe(II) and tiron. Consistent with previous work, the 1:2 Fe(II)-tiron complex, FeL2(6-), is the dominant reactive species as its concentration linearly correlates with the observed rate constant kobs under various conditions. The N-oxides without any side chains were much less reactive, suggesting direct reduction of the N-oxides is slow. UV-vis spectra suggest FeL2(6-) likely forms 5- or 7-membered rings with CDX and olaquindox through the N and O atoms on the side chain. The formed inner-sphere complexes significantly facilitated electron transfer from FeL2(6-) to the N-oxides. Reduction products of the N-oxides were identified by HPLC/QToF-MS to be the deoxygenated analogs. QSAR analysis indicated neither the first electron transfer nor N-O bond cleavage is the rate-limiting step. Calculations of the atomic spin densities of the anionic N-oxides confirmed the extensive delocalization between the aromatic ring and the side chain, suggesting complex formation can significantly affect the reduction kinetics. Our results suggest the complexation facilitated N-oxide reduction by Fe(II)-tiron involves a free radical mechanism, and the subsequent deoxygenation might also benefit from the weak complexation of Fe(II) with the N-oxide O atom.

High-performance tandem organic light-emitting diodes based on a buffer-modified p/n-type planar organic heterojunction as charge generation layer

NASA Astrophysics Data System (ADS)

Wu, Yukun; Sun, Ying; Qin, Houyun; Hu, Shoucheng; Wu, Qingyang; Zhao, Yi

2017-04-01

High-performance tandem organic light-emitting diodes (TOLEDs) were realized using a buffer-modified p/n-type planar organic heterojunction (OHJ) as charge generation layer (CGL) consisting of common organic materials, and the configuration of this p/n-type CGL was "LiF/N,N'-diphenyl-N,N'-bis(1-napthyl)-1,1'-biphenyl-4,4'-diamine (NPB)/4,7-diphenyl-1,10-phenanthroline (Bphen)/molybdenum oxide (MoOx)". The optimized TOLED exhibited a maximum current efficiency of 77.6 cd/A without any out-coupling techniques, and the efficiency roll-off was greatly improved compared to the single-unit OLED. The working mechanism of the p/n-type CGL was discussed in detail. It is found that the NPB/Bphen heterojunction generated enough charges under a forward applied voltage and the carrier extraction was a tunneling process. These results could provide a new method to fabricate high-performance TOLEDs.

Role of N-acetylcysteine on fibrosis and oxidative stress in cirrhotic rats.

PubMed

Pereira-Filho, Gustavo; Ferreira, Clarissa; Schwengber, Alex; Marroni, Cláudio; Zettler, Cláudio; Marroni, Norma

2008-01-01

Hepatic cirrhosis is the final stage of liver dysfunction, characterized by diffuse fibrosis which is the main response to the liver injury. The inhalatory carbon tetrachloride is an effective experimental model that triggers cirrhosis and allows to obtain histological and physiological modifications similar to the one seen in humans. To investigate the effects of N-acetylcysteine (NAC) on the fibrosis and oxidative stress in the liver of cirrhotic rats, analyzing liver function tests, lipoperoxidation, activity of glutathione peroxidase enzyme, collagen quantification, histopathology, as well as the nitric oxide role. The animals were randomly in three experimental groups: control (CO); cirrhotic (CCl4) and CCl4 + NAC. Evaluate the lipid peroxidation, the glutathione peroxidase enzyme, the collagen and the expression of inducible nitric oxide synthase (iNOS). The cirrhotic group treated with N-acetylcysteine showed trough the histological analysis and collagen quantification lower degrees of fibrosis. This group has also shown less damage to the cellular membranes, less decrease on the glutathione peroxidase levels and less expression of inducible nitric oxide synthase when matched with the cirrhotic group without treatment. N-acetylcysteine seams to offer protection against hepatic fibrosis and oxidative stress in cirrhotic rat livers.

Archaea produce lower yields of N2 O than bacteria during aerobic ammonia oxidation in soil.

PubMed

Hink, Linda; Nicol, Graeme W; Prosser, James I

2017-12-01

Nitrogen fertilisation of agricultural soil contributes significantly to emissions of the potent greenhouse gas nitrous oxide (N 2 O), which is generated during denitrification and, in oxic soils, mainly by ammonia oxidisers. Although laboratory cultures of ammonia oxidising bacteria (AOB) and archaea (AOA) produce N 2 O, their relative activities in soil are unknown. This work tested the hypothesis that AOB dominate ammonia oxidation and N 2 O production under conditions of high inorganic ammonia (NH 3 ) input, but result mainly from the activity of AOA when NH 3 is derived from mineralisation. 1-octyne, a recently discovered inhibitor of AOB, was used to distinguish N 2 O production resulting from archaeal and bacterial ammonia oxidation in soil microcosms, and specifically inhibited AOB growth, activity and N 2 O production. In unamended soils, ammonia oxidation and N 2 O production were lower and resulted mainly from ammonia oxidation by AOA. The AOA N 2 O yield relative to nitrite produced was half that of AOB, likely due to additional enzymatic mechanisms in the latter, but ammonia oxidation and N 2 O production were directly linked in all treatments. Relative contributions of AOA and AOB to N 2 O production, therefore, reflect their respective contributions to ammonia oxidation. These results suggest potential mitigation strategies for N 2 O emissions from fertilised agricultural soils. © 2016 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Implementing odd-axions in dimensional oxidation of 4D non-geometric type IIB scalar potential

NASA Astrophysics Data System (ADS)

Shukla, Pramod

2016-01-01

In a setup of type IIB superstring compactification on an orientifold of a T6 /Z4 sixfold, the presence of geometric flux (ω) and non-geometric fluxes (Q, R) is implemented along with the standard NS-NS and RR three-form fluxes (H, F). After computing the F/D-term contributions to the N = 1 four dimensional effective scalar potential, we rearrange the same into 'suitable' pieces by using a set of new generalized flux orbits. Subsequently, we dimensionally oxidize the various pieces of the total four dimensional scalar potential to guess their ten-dimensional origin.

N-deethylation and N-oxidation of etamiphylline: identification of etamiphylline-N-oxide in greyhound urine by high performance liquid chromatography-mass spectrometry.

PubMed

Dumasia, M C; Teale, P

2005-01-04

Millophyline-V, (etamiphylline camsylate) was administered intramuscularly to two racing greyhounds at a dose of 10 mg kg(-1). Unhydrolysed pre- and post-administration urine samples were extracted using mixed mode solid phase extraction (SPE) cartridges, the basic isolates derivatised as trimethylsilyl ethers and analysed by positive ion electron ionisation gas chromatography-mass spectrometry (GC/EI+/MS). The parent drug and one metabolite, N-desethyletamiphylline, were detected in urine for up to 72 h. For semi-quantification, urine samples were extracted on-line using a Prospekt sample handler. The analytes retained on the C2 SPE cartridge were eluted by the mobile phase directly on to the analytical high performance liquid chromatography column and analysed by positive ion atmospheric pressure chemical ionisation (LC/APCI+) MS in the multiple selective-ion recording mode. A major peak containing both ions (m/z) 280 and (m/z) 252 was observed. Full scan LC/APCI+/MS of the unknown indicated that the ion at (m/z) 280 was formed by the loss of an oxygen atom [MH+ -->(MH+-O)]. Samples were analysed by positive ion electrospray ionisation LC/MS on two different instruments and the unknown compound was identified as an N-oxide of the tert. nitrogen atom of the 2-(diethylamino)ethyl substituent on N7 of the theophylline nucleus. This compound has not been reported previously either as an in vivo or in vitro metabolite of etamiphylline in any species. Thermal decomposition of the N-oxide could lead to an increase the detection period of the parent drug during routine GC/MS screening of post-competition greyhound urine samples.

In vivo anti-radiation activities of the Ulva pertusa polysaccharides and polysaccharide-iron(III) complex.

PubMed

Shi, Jinming; Cheng, Cuilin; Zhao, Haitian; Jing, Jing; Gong, Ning; Lu, Weihong

2013-09-01

Polysaccharides with different molecular weights were extracted from Ulva pertusa and fractionated by ultrafiltration. Iron(III) complex of the low molecular-weight U. pertusa polysaccharides were synthesized. Atomic absorption spectrum showed that the iron content of iron(III)-polysaccharide complex was 27.4%. The comparison between U. pertusa polysaccharides and their iron(III) complex showed that iron chelating altered the structural characteristics of the polysaccharides. The bioactivity analysis showed that polysaccharide with low molecular weight was more effective than polysaccharide with high molecular weight in protecting mice from radiation induced damages on bone marrow cells and immune system. Results also proved that the anti-radiation and anti-oxidative activity of iron(III) complex of low molecular-weight polysaccharides were not less than that of low molecular-weight polysaccharides. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of Atmospheric Processes on the Solubility and Composition of Iron in Saharan Dust.

PubMed

Longo, Amelia F; Feng, Yan; Lai, Barry; Landing, William M; Shelley, Rachel U; Nenes, Athanasios; Mihalopoulos, Nikolaos; Violaki, Kalliopi; Ingall, Ellery D

2016-07-05

Aerosol iron was examined in Saharan dust plumes using a combination of iron near-edge X-ray absorption spectroscopy and wet-chemical techniques. Aerosol samples were collected at three sites located in the Mediterranean, the Atlantic, and Bermuda to characterize iron at different atmospheric transport lengths and time scales. Iron(III) oxides were a component of aerosols at all sampling sites and dominated the aerosol iron in Mediterranean samples. In Atlantic samples, iron(II and III) sulfate, iron(III) phosphate, and iron(II) silicates were also contributors to aerosol composition. With increased atmospheric transport time, iron(II) sulfates are found to become more abundant, aerosol iron oxidation state became more reduced, and aerosol acidity increased. Atmospheric processing including acidic reactions and photoreduction likely influence the form of iron minerals and oxidation state in Saharan dust aerosols and contribute to increases in aerosol-iron solubility.

Switching adhesion forces by crossing the metal–insulator transition in Magnéli-type vanadium oxide crystals

PubMed Central

Klemm, Matthias; Horn, Siegfried; Woydt, Mathias

2011-01-01

Summary Magnéli-type vanadium oxides form the homologous series VnO2 n -1 and exhibit a temperature-induced, reversible metal–insulator first order phase transition (MIT). We studied the change of the adhesion force across the transition temperature between the cleavage planes of various vanadium oxide Magnéli phases (n = 3 … 7) and spherical titanium atomic force microscope (AFM) tips by systematic force–distance measurements with a variable-temperature AFM under ultrahigh vacuum conditions (UHV). The results show, for all investigated samples, that crossing the transition temperatures leads to a distinct change of the adhesion force. Low adhesion corresponds consistently to the metallic state. Accordingly, the ability to modify the electronic structure of the vanadium Magnéli phases while maintaining composition, stoichiometry and crystallographic integrity, allows for relating frictional and electronic material properties at the nano scale. This behavior makes the vanadium Magnéli phases interesting candidates for technology, e.g., as intelligent devices or coatings where switching of adhesion or friction is desired. PMID:21977416

Elimination of surface band bending on N-polar InN with thin GaN capping

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

Kuzmík, J., E-mail: Jan.Kuzmik@savba.sk; Haščík, Š.; Kučera, M.

2015-11-09

0.5–1 μm thick InN (0001) films grown by molecular-beam epitaxy with N- or In-polarity are investigated for the presence of native oxide, surface energy band bending, and effects introduced by 2 to 4 monolayers of GaN capping. Ex situ angle-resolved x-ray photo-electron spectroscopy is used to construct near-surface (GaN)/InN energy profiles, which is combined with deconvolution of In3d signal to trace the presence of InN native oxide for different types of polarity and capping. Downwards surface energy band bending was observed on bare samples with native oxide, regardless of the polarity. It was found that the In-polar InN surface is mostmore » readily oxidized, however, with only slightly less band bending if compared with the N-polar sample. On the other hand, InN surface oxidation was effectively mitigated by GaN capping. Still, as confirmed by ultra-violet photo-electron spectroscopy and by energy band diagram calculations, thin GaN cap layer may provide negative piezoelectric polarization charge at the GaN/InN hetero-interface of the N-polar sample, in addition to the passivation effect. These effects raised the band diagram up by about 0.65 eV, reaching a flat-band profile.« less

N-Type delta Doping of High-Purity Silicon Imaging Arrays

NASA Technical Reports Server (NTRS)

Blacksberg, Jordana; Hoenk, Michael; Nikzad, Shouleh

2005-01-01

A process for n-type (electron-donor) delta doping has shown promise as a means of modifying back-illuminated image detectors made from n-doped high-purity silicon to enable them to detect high-energy photons (ultraviolet and x-rays) and low-energy charged particles (electrons and ions). This process is applicable to imaging detectors of several types, including charge-coupled devices, hybrid devices, and complementary metal oxide/semiconductor detector arrays. Delta doping is so named because its density-vs.-depth characteristic is reminiscent of the Dirac delta function (impulse function): the dopant is highly concentrated in a very thin layer. Preferably, the dopant is concentrated in one or at most two atomic layers in a crystal plane and, therefore, delta doping is also known as atomic-plane doping. The use of doping to enable detection of high-energy photons and low-energy particles was reported in several prior NASA Tech Briefs articles. As described in more detail in those articles, the main benefit afforded by delta doping of a back-illuminated silicon detector is to eliminate a "dead" layer at the back surface of the silicon wherein high-energy photons and low-energy particles are absorbed without detection. An additional benefit is that the delta-doped layer can serve as a back-side electrical contact. Delta doping of p-type silicon detectors is well established. The development of the present process addresses concerns specific to the delta doping of high-purity silicon detectors, which are typically n-type. The present process involves relatively low temperatures, is fully compatible with other processes used to fabricate the detectors, and does not entail interruption of those processes. Indeed, this process can be the last stage in the fabrication of an imaging detector that has, in all other respects, already been fully processed, including metallized. This process includes molecular-beam epitaxy (MBE) for deposition of three layers, including

Influence of N-Oxide Introduction on the Stability of Nitrogen-Rich Heteroaromatic Rings: A Quantum Chemical Study.

PubMed

Yuan, Jia; Long, Xinping; Zhang, Chaoyang

2016-12-01

N-Oxidization is an important strategy for enhancing the density and energy of energetic materials. Nevertheless, the influence of N + -O - introduction on molecular stability remains relatively unknown. Thus, the present work comprehensively studied 102 basic N-rich ring structures, including azoles, furazans, and azines, as well as their N-oxides by quantum chemical calculations. The introduction of N + -O - weakens molecular stability in most cases because the process elongates chemical bonds, decreases ring aromaticity, narrows the gaps between the highest occupied and lowest unoccupied molecular orbitals, and increases the photochemical reactivity. Besides, the easy H transfer to the neighboring O atom, which forms a N-OH isomer in azoles, renders the stabilization by N-oxide introduction ineffective. However, N-oxide introduction can enhance the molecular stability of 1,2,3,4-tetrazine-1,3-dioxide and tetrazino-tetrazine 1,3,6,8-tetraoxide by promoting σ-π separation and relieving lone-pair repulsion. Moreover, the alternate arrangement of positive and negative charges is another factor stabilizing the 1,2,3,4-tetrazine ring by 1,3-dioxidation. Finally, we assess the accessibility of N-oxidized azoles and azines by regarding N 2 O and H 2 O 2 as oxidizers. We find that all the oxidations were exothermic, thermodynamically spontaneous, and kinetically feasible. After an overall evaluation, we propose 19 N-oxides as basic structures for high-energy materials with considerable stability.

P-type surface effects for thickness variation of 2um and 4um of n-type layer in GaN LED

NASA Astrophysics Data System (ADS)

Halim, N. S. A. Abdul; Wahid, M. H. A.; Hambali, N. A. M. Ahmad; Rashid, S.; Ramli, M. M.; Shahimin, M. M.

2017-09-01

The internal quantum efficiency of III-Nitrides group, GaN light-emitting diode (LED) has been considerably limited due to the insufficient hole injection and this is caused by the lack of performance p-type doping and low hole mobility. The low hole mobility makes the hole less energetic, thus reduced the performance operation of GaN LED itself. The internal quantum efficiency of GaN-based LED with surface roughness (texture) can be changed by texture size, density, and thickness of GaN film or by the combined effects of surface shape and thickness of GaN film. Besides, due to lack of p-type GaN, attempts to look forward the potential of GaN LED relied on the thickness of n-type layer and surface shape of p-type GaN layer. This work investigates the characteristics of GaN LED with undoped n-GaN layer of different thickness and the surface shape of p-type layer. The LEDs performance is significantly altered by modifying the thickness and shape. Enhancement of n-GaN layer has led to the annihilation of electrical conductivity of the chip. Different surface geometry governs the emission rate extensively. Internal quantum efficiency is also predominantly affected by the geometry of n-GaN layer which subjected to the current spreading. It is recorded that the IQE droop can be minimized by varying the thickness of the active layer without amplifying the forward voltage. Optimum forward voltage (I-V), total emission rate relationship with the injected current and internal quantum efficiency (IQE) for 2,4 µm on four different surfaces of p-type layer are also reported in this paper.

Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

DOE PAGES

Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2016-06-06

Copper ferrite, CuFe 2 O 4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe 2 O 4. A phase pure tetragonal CuFe 2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structuremore » (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(II) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(III) cations to octahedral positions previously occupied by copper(II). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.« less

Resistive switching characteristics of thermally oxidized TiN thin films

NASA Astrophysics Data System (ADS)

Biju, K. P.

2018-04-01

Resistive switching characteristics of thermally oxidized TiN thin films and mechanisms were investigated.XPS results indicates Ti-O content decreases with sputter etching and Ti 2p peak shift towards lower binding energy due to formation of Ti-O-N and Ti-N. Pt/TiO2/TiON/TiN stack exhibits both clockwise switching (CWS) and counter clockwise switching(CCWS) characteristic depending on polarity of the applied voltage. However the transition from CCWS to CWS is irreversible. Two stable switching modes with opposite switching polarity and different electrical characteristics are found to coexist in the same memory cell. Clockwise switching shows filamentary characteristics that lead to faster switching with excellent retention at high temperature. Counter-clockwise switching exhibits homogeneous conduction with slower switching and moderate retention. The field-induced switching in both CCWS and CWS might be due to inhomogeneous defect distribution due to thermal oxidation.

Electrolytic photodissociation of chemical compounds by iron oxide electrodes

DOEpatents

Somorjai, Gabor A.; Leygraf, Christofer H.

1984-01-01

Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor diode having visible light as its sole source of energy. The diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.

Threshold voltage tuning in AlGaN/GaN HFETs with p-type Cu2O gate synthesized by magnetron reactive sputtering

NASA Astrophysics Data System (ADS)

Wang, Lei; Li, Liuan; Xie, Tian; Wang, Xinzhi; Liu, Xinke; Ao, Jin-Ping

2018-04-01

In present study, copper oxide films were prepared at different sputtering powers (10-100 W) using magnetron reactive sputtering. The crystalline structure, surface morphologies, composition, and optical band gap of the as-grown films are dependent on sputtering power. As the sputtering power decreasing from 100 to 10 W, the composition of films changed from CuO to quasi Cu2O domination. Moreover, when the sputtering power is 10 W, a relative high hole carrier density and high-surface-quality quasi Cu2O thin film can be achieved. AlGaN/GaN HFETs were fabricated with the optimized p-type quasi Cu2O film as gate electrode, the threshold voltage of the device shows a 0.55 V positive shift, meanwhile, a lower gate leakage current, a higher ON/OFF drain current ratio of ∼108, a higher electron mobility (1465 cm2/Vs), and a lower subthreshold slope of 74 mV/dec are also achieved, compared with the typical Ni/Au-gated HFETs. Therefore, Cu2O have a great potential to develop high performance p-type gate AlGaN/GaN HFETs.

Lifetime degradation of n-type Czochralski silicon after hydrogenation

NASA Astrophysics Data System (ADS)

Vaqueiro-Contreras, M.; Markevich, V. P.; Mullins, J.; Halsall, M. P.; Murin, L. I.; Falster, R.; Binns, J.; Coutinho, J.; Peaker, A. R.

2018-04-01

Hydrogen plays an important role in the passivation of interface states in silicon-based metal-oxide semiconductor technologies and passivation of surface and interface states in solar silicon. We have shown recently [Vaqueiro-Contreras et al., Phys. Status Solidi RRL 11, 1700133 (2017)] that hydrogenation of n-type silicon slices containing relatively large concentrations of carbon and oxygen impurity atoms {[Cs] ≥ 1 × 1016 cm-3 and [Oi] ≥ 1017 cm-3} can produce a family of C-O-H defects, which act as powerful recombination centres reducing the minority carrier lifetime. In this work, evidence of the silicon's lifetime deterioration after hydrogen injection from SiNx coating, which is widely used in solar cell manufacturing, has been obtained from microwave photoconductance decay measurements. We have characterised the hydrogenation induced deep level defects in n-type Czochralski-grown Si samples through a series of deep level transient spectroscopy (DLTS), minority carrier transient spectroscopy (MCTS), and high-resolution Laplace DLTS/MCTS measurements. It has been found that along with the hydrogen-related hole traps, H1 and H2, in the lower half of the gap reported by us previously, hydrogenation gives rise to two electron traps, E1 and E2, in the upper half of the gap. The activation energies for electron emission from the E1 and E2 trap levels have been determined as 0.12, and 0.14 eV, respectively. We argue that the E1/H1 and E2/H2 pairs of electron/hole traps are related to two energy levels of two complexes, each incorporating carbon, oxygen, and hydrogen atoms. Our results show that the detrimental effect of the C-O-H defects on the minority carrier lifetime in n-type Si:O + C materials can be very significant, and the carbon concentration in Czochralski-grown silicon is a key parameter in the formation of the recombination centers.

Azobenzene Pd(II) complexes with N^N- and N^O-type ligands

NASA Astrophysics Data System (ADS)

Nikolaeva, M. V.; Puzyk, An. M.; Puzyk, M. V.

2017-05-01

Methods of synthesis of cyclometalated azobenzene palladium(II) complexes of [Pd(N^N)Azb]ClO4 and [Pd(N^O)Azb]ClO4 types (where Azb- is the deprotonated form of azobenzene; N^N is 2NH3, ethylenediamine, or 2,2'-bipyridine; and (N^O)- is the deprotonated form of amino acid (glycine, α-alanine, β-alanine, tyrosine, or tryptophan)) are developed. The electronic absorption and the electrochemical properties of these complexes are studied.

Improvement in crystal quality and optical properties of n-type GaN employing nano-scale SiO2 patterned n-type GaN substrate.

PubMed

Jo, Min Sung; Sadasivam, Karthikeyan Giri; Tawfik, Wael Z; Yang, Seung Bea; Lee, Jung Ju; Ha, Jun Seok; Moon, Young Boo; Ryu, Sang Wan; Lee, June Key

2013-01-01

n-type GaN epitaxial layers were regrown on the patterned n-type GaN substrate (PNS) with different size of silicon dioxide (SiO2) nano dots to improve the crystal quality and optical properties. PNS with SiO2 nano dots promotes epitaxial lateral overgrowth (ELOG) for defect reduction and also acts as a light scattering point. Transmission electron microscopy (TEM) analysis suggested that PNS with SiO2 nano dots have superior crystalline properties. Hall measurements indicated that incrementing values in electron mobility were clear indication of reduction in threading dislocation and it was confirmed by TEM analysis. Photoluminescence (PL) intensity was enhanced by 2.0 times and 3.1 times for 1-step and 2-step PNS, respectively.

Influence of temperature on oxidation mechanisms of fiber-textured AlTiTaN coatings.

PubMed

Khetan, Vishal; Valle, Nathalie; Duday, David; Michotte, Claude; Delplancke-Ogletree, Marie-Paule; Choquet, Patrick

2014-03-26

The oxidation kinetics of AlTiTaN hard coatings deposited at 265 °C by DC magnetron sputtering were investigated between 700 and 950 °C for various durations. By combining dynamic secondary ion mass spectrometry (D-SIMS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) investigations of the different oxidized coatings, we were able to highlight the oxidation mechanisms involved. The TEM cross-section observations combined with XRD analysis show that a single amorphous oxide layer comprising Ti, Al, and Ta formed at 700 °C. Above 750 °C, the oxide scale transforms into a bilayer oxide comprising an Al-rich upper oxide layer and a Ti/Ta-rich oxide layer at the interface with the coated nitride layer. From the D-SIMS analysis, it could be proposed that the oxidation mechanism was governed primarily by inward diffusion of O for temperatures of ≤700 °C, while at ≥750 °C, it is controlled by outward diffusion of Al and inward diffusion of O. Via a combination of structural and chemical analysis, it is possible to propose that crystallization of rutile lattice favors the outward diffusion of Al within the AlTiTa mixed oxide layer with an increase in the temperature of oxidation. The difference in the mechanisms of oxidation at 700 and 900 °C also influences the oxidation kinetics with respect to oxidation time. Formation of a protective alumina layer decreases the rate of oxidation at 900 °C for long durations of oxidation compared to 700 °C. Along with the oxidation behavior, the enhanced thermal stability of AlTiTaN compared to that of the TiAlN coating is illustrated.

Highly reflective Ag-Cu alloy-based ohmic contact on p-type GaN using Ru overlayer.

PubMed

Son, Jun Ho; Jung, Gwan Ho; Lee, Jong-Lam

2008-12-15

We report on a metallization scheme of high reflectance, low resistance, and smooth surface morphology ohmic contact on p-type GaN. Ag-Cu alloy/Ru contact showed low contact resistivity as low as 6.2 x 10(-6) Ohms cm(2) and high reflectance of 91% at 460 nm after annealing at 400 degrees C in air ambient. The oxidation annealing promoted the out-diffusion of Ga atoms to dissolve in an Ag-Cu layer with the formation of an Ag-Ga solid solution, lowering the contact resistivity. The Ru overlayer acts as a diffusion barrier for excessive oxygen incorporation during oxidation annealing, resulting in high reflectance, good thermal stability, and smooth surface quality of the contact.

Rheological characterization of thermal, thermo-oxidative and photo-oxidative degradation of LDPE

NASA Astrophysics Data System (ADS)

Rolón-Garrido, Víctor Hugo; Wagner, Manfred Hermann

2015-04-01

Rheology has been used to study thermal degradation (V. H. Rolón-Garrido et al., Rheol. Acta 50, 519-535, 2011), thermo-oxidative degradation (V. H. Rolón-Garrido et al., Rheol. Acta 50, 519-535, 2011; V. H. Rolón-Garrido et al., J. Rheol. 57, 105-129, 2013) and photo-oxidative degradation (V. H. Rolón-Garrido and M. H. Wagner, Polym. Degrad. Stab. 99, 136-145, 2014; V. H. Rolón-Garrido and M. H. Wagner, J. Rheol. 58, 199-22 2, 2014; V. H. Rolón-Garrido et al., Polym. Degrad. Stab. 111, 46-54, 2015) of low-density polyethylene (LDPE). This contribution presents the analogies and differences between these types of degradations of LDPE on the linear (by use of van-Gurp Palmen plots) and non-linear viscoelastic properties (by use of the parameters of the MSF model, fmax2 and β), as well as on the failure mode of the samples (through the maximum strain and stress achieved experimentally). In contrast to thermal and thermo-oxidative degradation, the linear viscoelastic properties of photo-oxidated samples were more affected by degradation. In the non-linear regime, for thermal and thermo-oxidative treated samples, the elongational measurements elucidated the role of chain scission and long-chain branching (LCB) formation, while for photo-oxidated LDPE even the competition between chain scission, LCB formation, and gel formation was demonstrated. The failure behavior was found to be determined by a constant maximum strain in thermo-oxidative degradation, if the LDPE has high content in branching points, or in photo-oxidative degraded LDPE, if a considerable portion of gel structure is present. Otherwise, either the maximum strain or stress measured was found to be strain-rate dependent.

Catalytic water oxidation by ruthenium(II) quaterpyridine (qpy) complexes: evidence for ruthenium(III) qpy-N,N'''-dioxide as the real catalysts.

PubMed

Liu, Yingying; Ng, Siu-Mui; Yiu, Shek-Man; Lam, William W Y; Wei, Xi-Guang; Lau, Kai-Chung; Lau, Tai-Chu

2014-12-22

Polypyridyl and related ligands have been widely used for the development of water oxidation catalysts. Supposedly these ligands are oxidation-resistant and can stabilize high-oxidation-state intermediates. In this work a series of ruthenium(II) complexes [Ru(qpy)(L)2 ](2+) (qpy=2,2':6',2'':6'',2'''-quaterpyridine; L=substituted pyridine) have been synthesized and found to catalyze Ce(IV) -driven water oxidation, with turnover numbers of up to 2100. However, these ruthenium complexes are found to function only as precatalysts; first, they have to be oxidized to the qpy-N,N'''-dioxide (ONNO) complexes [Ru(ONNO)(L)2 ](3+) which are the real catalysts for water oxidation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effects of aerobic exercise training at two different intensities in obesity and type 2 diabetes: implications for oxidative stress, low-grade inflammation and nitric oxide production.

PubMed

Krause, Mauricio; Rodrigues-Krause, Josianne; O'Hagan, Ciara; Medlow, Paul; Davison, Gareth; Susta, Davide; Boreham, Colin; Newsholme, Philip; O'Donnell, Mark; Murphy, Colin; De Vito, Giuseppe

2014-02-01

To investigate the effect of 16 weeks of aerobic training performed at two different intensities on nitric oxide (tNOx) availability and iNOS/nNOS expression, oxidative stress (OS) and inflammation in obese humans with or without type 2 diabetes mellitus (T2DM). Twenty-five sedentary, obese (BMI > 30 kg/m2) males (52.8 ± 7.2 years); 12 controls versus 13 T2DM were randomly allocated to four groups that exercised for 30 min, three times per week either at low (Fat-Max; 30-40% VO(2max)) or moderate (T(vent); 55-65 % VO(2max)) intensity. Before and after training, blood and muscle samples (v. lateralis) were collected. Baseline erythrocyte glutathione was lower (21.8 ± 2.8 vs. 32.7 ± 4.4 nmol/ml) and plasma protein oxidative damage and IL-6 were higher in T2DM (141.7 ± 52.1 vs. 75.5 ± 41.6 nmol/ml). Plasma catalase increased in T2DM after T(vent) training (from 0.98 ± 0.22 to 1.96 ± 0.3 nmol/min/ml). T2DM groups demonstrated evidence of oxidative damage in response to training (elevated protein carbonyls). Baseline serum tNOx were higher in controls than T2DM (18.68 ± 2.78 vs. 12.34 ± 3.56 μmol/l). Training at T(vent) increased muscle nNOS and tNOx in the control group only. Pre-training muscle nNOS was higher in controls than in T2DMs, while the opposite was found for iNOS. No differences were found after training for plasma inflammatory markers. Exercise training did not change body composition or aerobic fitness, but improved OS markers, especially when performed at T(vent). Non-diabetics responded to T(vent) training by increasing muscle nNOS expression and tNOx levels in skeletal muscle while these parameters did not change in T2DM, perhaps due to higher insulin resistance (unchanged after intervention).

Effects of hydrogen treatment on ohmic contacts to p-type GaN films

NASA Astrophysics Data System (ADS)

Huang, Bohr-Ran; Chou, Chia-Hui; Ke, Wen-Cheng; Chou, Yi-Lun; Tsai, Chia-Lung; Wu, Meng-chyi

2011-06-01

This study investigated the effects of hydrogen (H 2) treatment on metal contacts to Mg-doped p-GaN films by Hall-effect measurement, current-voltage ( I- V) analyzer and X-ray photoemission spectra (XPS). The interfacial oxide layer on the p-GaN surface was found to be the main reason for causing the nonlinear I- V behavior of the untreated p-GaN films. The increased nitrogen vacancy (V N) density due to increased GaN decomposition rate at high-temperature hydrogen treatment is believed to form high density surface states on the surface of p-GaN films. Compared to untreated p-GaN films, the surface Fermi level determined by the Ga 2p core-level peak on 1000 °C H 2-treated p-GaN films lies about ˜2.1 eV closer to the conduction band edge (i.e., the surface inverted to n-type behavior). The reduction in barrier height due to the high surface state density pinned the surface Fermi level close to the conduction band edge, and allowed the electrons to easily flow over the barrier from the metal into the p-GaN films. Thus, a good ohmic contact was achieved on the p-GaN films by the surface inversion method.

Cell type-specific hypersensitivity to oxidative damage in CSB and XPA mice.

PubMed

de Waard, Harm; de Wit, Jan; Gorgels, Theo G M F; van den Aardweg, Gerard; Andressoo, Jaan Olle; Vermeij, Marcel; van Steeg, Harry; Hoeijmakers, Jan H J; van der Horst, Gijsbertus T J

2003-01-02

Mutations in the CSB gene cause Cockayne syndrome (CS), a rare inherited disorder, characterized by UV-sensitivity, severe neurodevelopmental and progeroid symptoms. CSB functions in the transcription-coupled repair (TCR) sub-pathway of nucleotide excision repair (NER), responsible for the removal of UV-induced and other helix-distorting lesions from the transcribed strand of active genes. Several lines of evidence support the notion that the CSB TCR defect extends to other non-NER type transcription-blocking lesions, notably various kinds of oxidative damage, which may provide an explanation for part of the severe CS phenotype. We used genetically defined mouse models to examine the relationship between the CSB defect and sensitivity to oxidative damage in different cell types and at the level of the intact organism. The main conclusions are: (1) CSB(-/-) mouse embryo fibroblasts (MEFs) exhibit a clear hypersensitivity to ionizing radiation, extending the findings in genetically heterogeneous human CSB fibroblasts to another species. (2) CSB(-/-) MEFs are highly sensitive to paraquat, strongly indicating that the increased cytotoxicity is due to oxidative damage. (3) The hypersenstivity is independent of genetic background and directly related to the CSB defect and is not observed in totally NER-deficient XPA MEFs. (4) Wild type embryonic stem (ES) cells display an increased sensitivity to ionizing radiation compared to fibroblasts. Surprisingly, the CSB deficiency has only a very minor additional effect on ES cell sensitivity to oxidative damage and is comparable to that of an XPA defect, indicating cell type-specific differences in the contribution of TCR and NER to cellular survival. (5) Similar to ES cells, CSB and XPA mice both display a minor sensitivity to whole-body X-ray exposure. This suggests that the response of an intact organism to radiation is largely determined by the sensitivity of stem cells, rather than differentiated cells. These findings

Thermo-Oxidative Degradation Of SiC/Si3N4 Composites

NASA Technical Reports Server (NTRS)

Baaklini, George Y.; Batt, Ramakrishna T.; Rokhlin, Stanislav I.

1995-01-01

Experimental study conducted on thermo-oxidative degradation of composite-material specimens made of silicon carbide fibers in matrices of reaction-bonded silicon nitride. In SiC/Si3N4 composites of study, interphase is 3-micrometers-thick carbon-rich coat on surface of each SiC fiber. Thermo-oxidative degradation of these composites involves diffusion of oxygen through pores of composites to interphases damaged by oxidation. Nondestructive tests reveal critical exposure times.

Synthesizing new types of ultrathin 2D metal oxide nanosheets via half-successive ion layer adsorption and reaction

NASA Astrophysics Data System (ADS)

Gao, Linjie; Li, Yaguang; Xiao, Mu; Wang, Shufang; Fu, Guangsheng; Wang, Lianzhou

2017-06-01

Two-dimensional (2D) metal oxide nanosheets have demonstrated their great potential in a broad range of applications. The existing synthesis strategies are mainly preparing 2D nanosheets from layered and specific transition metal oxides. How to prepare the other types of metal oxides as ultrathin 2D nanosheets remains unsolved, especially for metal oxides containing alkali, alkaline earth metal, and multiple metal elements. Herein, we developed a half-successive ion layer adsorption and reaction (SILAR) method, which could synthesize those types of metal oxides as ultrathin 2D nanosheets. The synthesized 2D metal oxides nanosheets are within 1 nm level thickness and 500 m2 · g-1 level surface area. This method allows us to develop many new types of ultrathin 2D metal oxides nanosheets that have never been prepared before.

High-fat diet induces skeletal muscle oxidative stress in a fiber type-dependent manner in rats.

PubMed

Pinho, Ricardo A; Sepa-Kishi, Diane M; Bikopoulos, George; Wu, Michelle V; Uthayakumar, Abinas; Mohasses, Arta; Hughes, Meghan C; Perry, Christopher G R; Ceddia, Rolando B

2017-09-01

This study investigated the effects of high-fat (HF) diet on parameters of oxidative stress among muscles with distinct fiber type composition and oxidative capacities. To accomplish that, male Wistar rats were fed either a low-fat standard chow (SC) or a HF diet for 8 weeks. Soleus, extensor digitorum longus (EDL), and epitrochlearis muscles were collected and mitochondrial H 2 O 2 (mtH 2 O 2 ) emission, palmitate oxidation, and gene expression and antioxidant system were measured. Chronic HF feeding enhanced fat oxidation in oxidative and glycolytic muscles. It also caused a significant reduction in mtH 2 O 2 emission in the EDL muscle, although a tendency towards a reduction was also found in the soleus and epitrochlearis muscles. In the epitrochlearis, HF diet increased mRNA expression of the NADPH oxidase complex; however, this muscle also showed an increase in the expression of antioxidant proteins, suggesting a higher capacity to generate and buffer ROS. The soleus muscle, despite being highly oxidative, elicited H 2 O 2 emission rates equivalent to only 20% and 35% of the values obtained for EDL and epitrochlearis muscles, respectively. Furthermore, the Epi muscle with the lowest oxidative capacity was the second highest in H 2 O 2 emission. In conclusion, it appears that intrinsic differences related to the distribution of type I and type II fibers, rather than oxidative capacity, drove the activity of the anti- and pro-oxidant systems and determine ROS production in different skeletal muscles. This also suggests that the impact of potentially deleterious effects of ROS production on skeletal muscle metabolism/function under lipotoxic conditions is fiber type-specific. Copyright © 2017. Published by Elsevier Inc.

A DFT study on NEA GaN photocathode with an ultrathin n-type Si-doped GaN cap layer

NASA Astrophysics Data System (ADS)

Xia, Sihao; Liu, Lei; Kong, Yike; Diao, Yu

2016-10-01

Due to the drawbacks of conventional negative electron affinity (NEA) GaN photocathodes activated by Cs or Cs/O, a new-type NEA GaN photocathodes with heterojunction surface dispense with Cs activation are proposed. This structure can be obtained through the coverage of an ultrathin n-type Si-doped GaN cap layer on the p-type Mg-doped GaN emission layer. The influences of the cap layer on the photocathode are calculated using DFT. This study indicates that the n-type cap layer can promote the photoemission characteristics of GaN photocathode and demonstrates the probability of the preparation of a NEA GaN photocathode with an n-type cap layer.

Quantifying the Performance of P-Type Transparent Conducting Oxides by Experimental Methods

PubMed Central

Fleischer, Karsten; Norton, Emma; Mullarkey, Daragh; Caffrey, David; Shvets, Igor V.

2017-01-01

Screening for potential new materials with experimental and theoretical methods has led to the discovery of many promising candidate materials for p-type transparent conducting oxides. It is difficult to reliably assess a good p-type transparent conducting oxide (TCO) from limited information available at an early experimental stage. In this paper we discuss the influence of sample thickness on simple transmission measurements and how the sample thickness can skew the commonly used figure of merit of TCOs and their estimated band gap. We discuss this using copper-deficient CuCrO2 as an example, as it was already shown to be a good p-type TCO grown at low temperatures. We outline a modified figure of merit reducing thickness-dependent errors, as well as how modern ab initio screening methods can be used to augment experimental methods to assess new materials for potential applications as p-type TCOs, p-channel transparent thin film transistors, and selective contacts in solar cells. PMID:28862695

Response of nitric and nitrous oxide fluxes to N fertilizer application in greenhouse vegetable cropping systems in southeast China

PubMed Central

Zhang, Yaojun; Lin, Feng; Jin, Yaguo; Wang, Xiaofei; Liu, Shuwei; Zou, Jianwen

2016-01-01

It is of great concern worldwide that active nitrogenous gases in the global nitrogen cycle contribute to regional and global-scale environmental issues. Nitrous oxide (N2O) and nitric oxide (NO) are generally interrelated in soil nitrogen biogeochemical cycles, while few studies have simultaneously examined these two gases emission from typical croplands. Field experiments were conducted to measure N2O and NO fluxes in response to chemical N fertilizer application in annual greenhouse vegetable cropping systems in southeast China. Annual N2O and NO fluxes averaged 52.05 and 14.87 μg N m−2 h−1 for the controls without N fertilizer inputs, respectively. Both N2O and NO emissions linearly increased with N fertilizer application. The emission factors of N fertilizer for N2O and NO were estimated to be 1.43% and 1.15%, with an annual background emission of 5.07 kg N2O-N ha−1 and 1.58 kg NO-N ha−1, respectively. The NO-N/N2O-N ratio was significantly affected by cropping type and fertilizer application, and NO would exceed N2O emissions when soil moisture is below 54% WFPS. Overall, local conventional input rate of chemical N fertilizer could be partially reduced to attain high yield of vegetable and low N2O and NO emissions in greenhouse vegetable cropping systems in China. PMID:26848094

Response of nitric and nitrous oxide fluxes to N fertilizer application in greenhouse vegetable cropping systems in southeast China.

PubMed

Zhang, Yaojun; Lin, Feng; Jin, Yaguo; Wang, Xiaofei; Liu, Shuwei; Zou, Jianwen

2016-02-05

It is of great concern worldwide that active nitrogenous gases in the global nitrogen cycle contribute to regional and global-scale environmental issues. Nitrous oxide (N2O) and nitric oxide (NO) are generally interrelated in soil nitrogen biogeochemical cycles, while few studies have simultaneously examined these two gases emission from typical croplands. Field experiments were conducted to measure N2O and NO fluxes in response to chemical N fertilizer application in annual greenhouse vegetable cropping systems in southeast China. Annual N2O and NO fluxes averaged 52.05 and 14.87 μg N m(-2) h(-1) for the controls without N fertilizer inputs, respectively. Both N2O and NO emissions linearly increased with N fertilizer application. The emission factors of N fertilizer for N2O and NO were estimated to be 1.43% and 1.15%, with an annual background emission of 5.07 kg N2O-N ha(-1) and 1.58 kg NO-N ha(-1), respectively. The NO-N/N2O-N ratio was significantly affected by cropping type and fertilizer application, and NO would exceed N2O emissions when soil moisture is below 54% WFPS. Overall, local conventional input rate of chemical N fertilizer could be partially reduced to attain high yield of vegetable and low N2O and NO emissions in greenhouse vegetable cropping systems in China.

Tar balls from Deep Water Horizon oil spill: environmentally persistent free radicals (EPFR) formation during crude weathering.

PubMed

Kiruri, Lucy W; Dellinger, Barry; Lomnicki, Slawo

2013-05-07

Tar balls collected from the Gulf of Mexico shores of Louisiana and Florida after the BP oil spill have shown the presence of electron paramagnetic resonance (EPR) spectra characteristic of organic free radicals as well as transition metal ions, predominantly iron(III) and manganese(II). Two types of organic radicals were distinguished: an asphaltene radical species typically found in crude oil (g = 2.0035) and a new type of radical resulting from the environmental transformations of crude (g = 2.0041-47). Pure asphaltene radicals are resonance stabilized over a polyaromatic structure and are stable in air and unreactive. The new radicals were identified as products of partial oxidation of crude components and result from the interaction of the oxidized aromatics with metal ion centers. These radicals are similar to semiquinone-type, environmentally persistent free radicals (EPFRs) previously observed in combustion-generated particulate and contaminated soils.

Tar Balls from Deep Water Horizon Oil Spill: Environmentally Persistent Free Radicals (EPFR) Formation During Crude Weathering

PubMed Central

Kiruri, Lucy W.; Dellinger, Barry; Lomnicki, Slawo

2014-01-01

Tar balls collected from the Gulf of Mexico shores of Louisiana and Florida after the BP oil spill have shown the presence of electron paramagnetic resonance (EPR) spectra characteristic of organic free radicals as well as transition metal ions, predominantly iron(III) and manganese(II). Two types of organic radicals were distinguished: an asphaltene radical species typically found in crude oil (g = 2.0035) and a new type of radical resulting from the environmental transformations of crude (g = 2.0041−47). Pure asphaltene radicals are resonance stabilized over a polyaromatic structure and are stable in air and unreactive. The new radicals were identified as products of partial oxidation of crude components and result from the interaction of the oxidized aromatics with metal ion centers. These radicals are similar to semiquinone-type, environmentally persistent free radicals (EPFRs) previously observed in combustion-generated particulate and contaminated soils. PMID:23510127

Electrocatalytic N-Doped Graphitic Nanofiber - Metal/Metal Oxide Nanoparticle Composites.

PubMed

Tang, Hongjie; Chen, Wei; Wang, Jiangyan; Dugger, Thomas; Cruz, Luz; Kisailus, David

2018-03-01

Carbon-based nanocomposites have shown promising results in replacing commercial Pt/C as high-performance, low cost, nonprecious metal-based oxygen reduction reaction (ORR) catalysts. Developing unique nanostructures of active components (e.g., metal oxides) and carbon materials is essential for their application in next generation electrode materials for fuel cells and metal-air batteries. Herein, a general approach for the production of 1D porous nitrogen-doped graphitic carbon fibers embedded with active ORR components, (M/MO x , i.e., metal or metal oxide nanoparticles) using a facile two-step electrospinning and annealing process is reported. Metal nanoparticles/nanoclusters nucleate within the polymer nanofibers and subsequently catalyze graphitization of the surrounding polymer matrix and following oxidation, create an interconnected graphite-metal oxide framework with large pore channels, considerable active sites, and high specific surface area. The metal/metal oxide@N-doped graphitic carbon fibers, especially Co 3 O 4 , exhibit comparable ORR catalytic activity but superior stability and methanol tolerance versus Pt in alkaline solutions, which can be ascribed to the synergistic chemical coupling effects between Co 3 O 4 and robust 1D porous structures composed of interconnected N-doped graphitic nanocarbon rings. This finding provides a novel insight into the design of functional electrocatalysts using electrospun carbon nanomaterials for their application in energy storage and conversion fields. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid screening of N-oxides of chemical warfare agents degradation products by ESI-tandem mass spectrometry.

PubMed

Sridhar, L; Karthikraj, R; Lakshmi, V V S; Raju, N Prasada; Prabhakar, S

2014-08-01

Rapid detection and identification of chemical warfare agents and related precursors/degradation products in various environmental matrices is of paramount importance for verification of standards set by the chemical weapons convention (CWC). Nitrogen mustards, N,N-dialkylaminoethyl-2-chlorides, N,N-dialkylaminoethanols, N-alkyldiethanolamines, and triethanolamine, which are listed CWC scheduled chemicals, are prone to undergo N-oxidation in environmental matrices or during decontamination process. Thus, screening of the oxidized products of these compounds is also an important task in the verification process because the presence of these products reveals alleged use of nitrogen mustards or precursors of VX compounds. The N-oxides of aminoethanols and aminoethylchlorides easily produce [M + H](+) ions under electrospray ionization conditions, and their collision-induced dissociation spectra include a specific neutral loss of 48 u (OH + CH2OH) and 66 u (OH + CH2Cl), respectively. Based on this specific fragmentation, a rapid screening method was developed for screening of the N-oxides by applying neutral loss scan technique. The method was validated and the applicability of the method was demonstrated by analyzing positive and negative samples. The method was useful in the detection of N-oxides of aminoethanols and aminoethylchlorides in environmental matrices at trace levels (LOD, up to 500 ppb), even in the presence of complex masking agents, without the use of time-consuming sample preparation methods and chromatographic steps. This method is advantageous for the off-site verification program and also for participation in official proficiency tests conducted by the Organization for the Prohibition of Chemical Weapons (OPCW), the Netherlands. The structure of N-oxides can be confirmed by the MS/MS experiments on the detected peaks. A liquid chromatography-mass spectrometry (LC-MS) method was developed for the separation of isomeric N-oxides of aminoethanols and

In Situ Oxidation Synthesis of p-Type Composite with Narrow-Bandgap Small Organic Molecule Coating on Single-Walled Carbon Nanotube: Flexible Film and Thermoelectric Performance.

PubMed

Gao, Caiyan; Chen, Guangming

2018-03-01

Although composites of organic polymers or n-type small molecule/carbon nanotube (CNT) have achieved significant advances in thermoelectric (TE) applications, p-type TE composites of small organic molecules as thick surface coating layers on the surfaces of inorganic nanoparticles still remain a great challenge. Taking advantage of in situ oxidation reaction of thieno[3,4-b]pyrazine (TP) into TP di-N-oxide (TPNO) on single-walled CNT (SWCNT) surface, a novel synthesis strategy is proposed to achieve flexible films of TE composites with narrow-bandgap (1.19 eV) small molecule coating on SWCNT surface. The TE performance can be effectively enhanced and conveniently tuned by poly(sodium-p-styrenesulfonate) content, TPNO/SWCNT mass ratio, and posttreatment by various polar solvents. The maximum of the composite power factor at room temperature is 29.4 ± 1.0 µW m -1 K -2 . The work presents a way to achieve flexible films of p-type small organic molecule/inorganic composites with clear surface coating morphology for TE application. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Association of Oxidative Stress and Obesity with Insulin Resistance in Type 2 Diabetes Mellitus.

PubMed

Das, P; Biswas, S; Mukherjee, S; Bandyopadhyay, S K

2016-01-01

Oxidative stress occurs due to delicate imbalance between pro-oxidant and anti oxidant forces in our system. It has been found to be associated with many morbidities but its association with obesity and insulin resistance is still controversial. Here in our study we examined 167 patients of recent onset type 2 diabetes mellitus and 60 age sex matched non-diabetic control. Body Mass Index (BMI), abdominal circumference, fasting blood glucose, serum insulin and plasma Malondealdehyde (MDA, marker for oxidative stress) were measured in them. On the basis of BMI, subjects were divided into obese (BMI≥25) and non obese (BMI<25) groups. Insulin resistance scores were calculated by Homeostatic Model Assessment-Insulin Resistance (HOMA-IR) method. Physical parameters (BMI, abdominal circumference) as well as levels of insulin and MDA were found to be significantly higher in subjects with diabetes than their non diabetic controls. The said parameters also showed significant difference in obese and non-obese sub groups. Insulin resistance score showed positive correlation with BMI, abdominal circumference, and plasma MDA, strength of association being highest with abdominal circumference. Plasma MDA was found to have positive correlation with physical parameters. Study concludes that, obesity mainly central type may predispose to insulin resistance and oxidative stress may be a crucial factor in its pathogenesis. Thus, oxidative stress may be the connecting link between obesity and type 2 diabetes mellitus, two on going global epidemics.

Mechanochemical effect in the iron(III) spin crossover complex [Fe(3-MeO-salenEt2]PF6 as studied by heat capacity calorimetry.

PubMed

Sorai, Michio; Burriel, Ramón; Westrum, Edgar F; Hendrickson, David N

2008-04-10

Magnetic and thermal properties of the iron(III) spin crossover complex [Fe(3MeO-salenEt)(2)]PF(6) are very sensitive to mechanochemical perturbations. Heat capacities for unperturbed and differently perturbed samples were precisely determined by adiabatic calorimetry at temperatures in the 10-300 K range. The unperturbed compound shows a cooperative spin crossover transition at 162.31 K, presenting a hysteresis of 2.8 K. The anomalous enthalpy and entropy contents of the transition were evaluated to be Delta(trs)H = 5.94 kJ mol(-1) and Delta(trs)S = 36.7 J K(-1) mol(-1), respectively. By mechanochemical treatments, (1) the phase transition temperature was lowered by 1.14 K, (2) the enthalpy and entropy gains at the phase transition due to the spin crossover phenomenon were diminished to Delta(trs)H = 4.94 kJ mol(-1) and Delta(trs)S = 31.1 J K(-1) mol(-1), and (3) the lattice heat capacities were larger than those of the unperturbed sample over the whole temperature range. In spite of different mechanical perturbations (grinding with a mortar and pestle and grinding in a ball-mill), two sets of heat capacity measurements provided basically the same results. The mechanochemical perturbation exerts its effect more strongly on the low-spin state than on the high-spin state. It shows a substantial increase of the number of iron(III) ions in the high-spin state below the transition temperature. The heat capacities of the diamagnetic cobalt(III) analogue [Co(3MeO-salenEt)(2)]PF(6) also were measured. The lattice heat capacity of the iron compounds has been estimated from either the measurements on the cobalt complex using a corresponding states law or the effective frequency distribution method. These estimations have been used for the evaluation of the transition anomaly.

Lactate dilates cochlear capillaries via type V fibrocyte-vessel coupling signaled by nNOS.

PubMed

Dai, Min; Yang, Yue; Shi, Xiaorui

2011-10-01

Transduction of sound in the inner ear demands tight control over delivery of oxygen and glucose. However, the mechanisms underlying the control of regional blood flow are not yet fully understood. In this study, we report a novel local control mechanism that regulates cochlear blood flow to the stria vascularis, a high energy-consuming region of the inner ear. We found that extracellular lactate had a vasodilatory effect on the capillaries of the spiral ligament under both in vitro and in vivo conditions. The lactate, acting through monocarboxylate transporter 1 (MCT1), initiated neuronal nitric oxide (NO) synthase (nNOS) and catalyzed production of NO for the vasodilation. Blocking MCT1 with the MCT blocker, α-cyano-4-hydroxycinnamate (CHC), or a suppressing NO production with either the nonspecific inhibitor of NO synthase, N(G)-nitro-L-arginine methyl ester (L-NAME), or either of two selective nNOS inhibitors, 3-bromo-7-nitroindazole or (4S)-N-(4-amino-5[aminoethyl]aminopentyl)-N'-nitroguanidine (TFA), totally abolished the lactate-induced vasodilation. Pretreatment with the selective endothelial NO synthase inhibitor, L-N(5)-(1-iminoethyl)ornithine (L-NIO), eliminated the inhibition of lactate-induced vessel dilation. With immunohistochemical labeling, we found the expression of MCT1 and nNOS in capillary-coupled type V fibrocytes. The data suggest that type V fibrocytes are the source of the lactate-induced NO. Cochlear microvessel tone, regulated by lactate, is mediated by an NO-signaled coupling of fibrocytes and capillaries.

Effect of dissolved ozone or ferric ions on photodegradation of thiacloprid in presence of different TiO2 catalysts.

PubMed

Cernigoj, Urh; Stangar, Urska Lavrencic; Jirkovský, Jaromír

2010-05-15

Combining TiO(2) photocatalysis with inorganic oxidants (such as O(3) and H(2)O(2)) or transition metal ions (Fe(3+), Cu(2+) and Ag(+)) often leads to a synergic effect. Electron transfer between TiO(2) and the oxidant is usually involved. Accordingly, the degree of synergy could be influenced by TiO(2) surface area. With this in mind, the disappearance of thiacloprid, a neonicotinoid insecticide, was studied applying various photochemical AOPs and different TiO(2) photocatalysts. In photocatalytic ozonation experiments, synergic effect of three different TiO(2) photocatalysts was quantified. Higher surface area resulted in a more pronounced synergic effect but an increasing amount of TiO(2) did not influence the degree of the synergy. This supports the theory that the synergy is a consequence of adsorption of ozone on the TiO(2) surface. No synergy was observed in photocatalytic degradation of thiacloprid in the presence of dissolved iron(III) species performed under varied experimental conditions (concentration, age of iron(III) solution, different TiO(2) films, usage of TiO(2) slurries). This goes against the literature for different organic compounds (i.e., monuron). It indicates different roles of iron(III) in the photodegradation of different organic molecules. Moreover, TiO(2) surface area did not affect photodegradation efficiency in iron(III)-based experiments which could confirm absence of electron transfer between TiO(2) photocatalyst and iron(III). Copyright (c) 2009 Elsevier B.V. All rights reserved.

Niacin supplementation increases the number of oxidative type I fibers in skeletal muscle of growing pigs

PubMed Central

2013-01-01

Background A recent study showed that niacin supplementation counteracts the obesity-induced muscle fiber switching from oxidative type I to glycolytic type II and increases the number of type I fibers in skeletal muscle of obese Zucker rats. These effects were likely mediated by the induction of key regulators of fiber transition, PGC-1α and PGC-1β, leading to muscle fiber switching and up-regulation of genes involved in mitochondrial fatty acid import and oxidation, citrate cycle, oxidative phosphorylation, mitochondrial biogenesis. The aim of the present study was to investigate whether niacin supplementation causes type II to type I muscle and changes the metabolic phenotype of skeletal muscles in growing pigs. Results 25 male, 11 wk old crossbred pigs (Danzucht x Pietrain) with an average body weight of 32.8 ± 1.3 (mean ± SD) kg were randomly allocated to two groups of 12 (control group) and 13 pigs (niacin group) which were fed either a control diet or a diet supplemented with 750 mg niacin/kg diet. After 3 wk, the percentage number of type I fibers in three different muscles (M. longissismus dorsi, M. quadriceps femoris, M. gastrocnemius) was greater in the niacin group and the percentage number of type II fibers was lower in the niacin group than in the control group (P < 0.05). The mRNA levels of PGC-1β and genes involved in mitochondrial fatty acid catabolism (CACT, FATP1, OCTN2), citrate cycle (SDHA), oxidative phosphorylation (COX4/1, COX6A1), and thermogenesis (UCP3) in M. longissimus dorsi were greater in the niacin group than in the control group (P < 0.05). Conclusions The study demonstrates that niacin supplementation induces type II to type I muscle fiber switching, and thereby an oxidative metabolic phenotype of skeletal muscle in pigs. Given that oxidative muscle types tend to develop dark, firm and dry pork in response to intense physical activity and/or high psychological stress levels preslaughter, a niacin

Oxide Structure Dependence of SiO2/SiOx/3C-SiC/n-Type Si Nonvolatile Resistive Memory on Memory Operation Characteristics

NASA Astrophysics Data System (ADS)

Yamaguchi, Yuichiro; Shouji, Masatsugu; Suda, Yoshiyuki

2012-11-01

We have investigated the dependence of the oxide layer structure of our previously proposed metal/SiO2/SiOx/3C-SiC/n-Si/metal metal-insulator-semiconductor (MIS) resistive memory device on the memory operation characteristics. The current-voltage (I-V) measurement and X-ray photoemission spectroscopy results suggest that SiOx defect states mainly caused by the oxidation of 3C-SiC at temperatures below 1000 °C are related to the hysteresis memory behavior in the I-V curve. By restricting the SiOx interface region, the number of switching cycles and the on/off current ratio are more enhanced. Compared with a memory device formed by one-step or two-step oxidation of 3C-SiC, a memory device formed by one-step oxidation of Si/3C-SiC exhibits a more restrictive SiOx interface with a more definitive SiO2 layer and higher memory performances for both the endurance switching cycle and on/off current ratio.

Role of Angiotensin II type 1 receptor on renal NAD(P)H oxidase, oxidative stress and inflammation in nitric oxide inhibition induced-hypertension.

PubMed

Rincón, J; Correia, D; Arcaya, J L; Finol, E; Fernández, A; Pérez, M; Yaguas, K; Talavera, E; Chávez, M; Summer, R; Romero, F

2015-03-01

Activation of the renin-angiotensin system (RAS), renal oxidative stress and inflammation are constantly present in experimental hypertension. Nitric oxide (NO) inhibition with N(w)-nitro-L-arginine methyl ester (L-NAME) has previously been reported to produce hypertension, increased expression of Angiotensin II (Ang II) and renal dysfunction. The use of Losartan, an Ang II type 1 receptor (AT1R) antagonist has proven to be effective reducing hypertension and renal damage; however, the mechanism by which AT1R blockade reduced kidney injury and normalizes blood pressure in this experimental model is still complete unknown. The current study was designed to test the hypothesis that AT1R activation promotes renal NAD(P)H oxidase up-regulation, oxidative stress and cytokine production during L-NAME induced-hypertension. Male Sprague-Dawley rats were distributed in three groups: L-NAME, receiving 70 mg/100ml of L-NAME, L-NAME+Los, receiving 70 mg/100ml of L-NAME and 40 mg/kg/day of Losartan; and Controls, receiving water instead of L-NAME or L-NAME and Losartan. After two weeks, L-NAME induced high blood pressure, renal overexpression of AT1R, NAD(P)H oxidase sub-units gp91, p22 and p47, increased levels of oxidative stress, interleukin-6 (IL-6) and interleukin-17 (IL-17). Also, we found increased renal accumulation of lymphocytes and macrophages. Losartan treatment abolished the renal expression of gp91, p22, p47, oxidative stress and reduced NF-κB activation and IL-6 expression. These findings indicate that NO induced-hypertension is associated with up-regulation of NADPH oxidase, oxidative stress production and overexpression of key inflammatory mediators. These events are associated with up-regulation of AT1R, as evidenced by their reversal with AT1R blocker treatment. Copyright © 2015 Elsevier Inc. All rights reserved.

Electrolytic photodissociation of chemical compounds by iron oxide photochemical diodes

DOEpatents

Somorjai, Gabor A.; Leygraf, Christofer H.

1985-01-01

Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor photochemical diode having visible light as its sole source of energy. The photochemical diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.

Charge storage mechanisms of manganese oxide nanosheets and N-doped reduced graphene oxide aerogel for high-performance asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Seubsai, Anusorn; Chanlek, Narong; Kidkhunthod, Pinit; Sangthong, Winyoo; Maensiri, Santi; Yimnirun, Rattikorn; Nilmoung, Sukanya; Pannopard, Panvika; Ittisanronnachai, Somlak; Kongpatpanich, Kanokwan; Limtrakul, Jumras; Sawangphruk, Montree

2016-11-01

Although manganese oxide- and graphene-based supercapacitors have been widely studied, their charge storage mechanisms are not yet fully investigated. In this work, we have studied the charge storage mechanisms of K-birnassite MnO2 nanosheets and N-doped reduced graphene oxide aerogel (N-rGOae) using an in situ X-ray absorption spectroscopy (XAS) and an electrochemical quart crystal microbalance (EQCM). The oxidation number of Mn at the MnO2 electrode is +3.01 at 0 V vs. SCE for the charging process and gets oxidized to +3.12 at +0.8 V vs. SCE and then reduced back to +3.01 at 0 V vs. SCE for the discharging process. The mass change of solvated ions, inserted to the layers of MnO2 during the charging process is 7.4 μg cm-2. Whilst, the mass change of the solvated ions at the N-rGOae electrode is 8.4 μg cm-2. An asymmetric supercapacitor of MnO2//N-rGOae (CR2016) provides a maximum specific capacitance of ca. 467 F g-1 at 1 A g-1, a maximum specific power of 39 kW kg-1 and a specific energy of 40 Wh kg-1 with a wide working potential of 1.6 V and 93.2% capacity retention after 7,500 cycles. The MnO2//N-rGOae supercapacitor may be practically used in high power and energy applications.

Charge storage mechanisms of manganese oxide nanosheets and N-doped reduced graphene oxide aerogel for high-performance asymmetric supercapacitors.

PubMed

Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Seubsai, Anusorn; Chanlek, Narong; Kidkhunthod, Pinit; Sangthong, Winyoo; Maensiri, Santi; Yimnirun, Rattikorn; Nilmoung, Sukanya; Pannopard, Panvika; Ittisanronnachai, Somlak; Kongpatpanich, Kanokwan; Limtrakul, Jumras; Sawangphruk, Montree

2016-11-18

Although manganese oxide- and graphene-based supercapacitors have been widely studied, their charge storage mechanisms are not yet fully investigated. In this work, we have studied the charge storage mechanisms of K-birnassite MnO 2 nanosheets and N-doped reduced graphene oxide aerogel (N-rGO ae ) using an in situ X-ray absorption spectroscopy (XAS) and an electrochemical quart crystal microbalance (EQCM). The oxidation number of Mn at the MnO 2 electrode is +3.01 at 0 V vs. SCE for the charging process and gets oxidized to +3.12 at +0.8 V vs. SCE and then reduced back to +3.01 at 0 V vs. SCE for the discharging process. The mass change of solvated ions, inserted to the layers of MnO 2 during the charging process is 7.4 μg cm -2 . Whilst, the mass change of the solvated ions at the N-rGO ae electrode is 8.4 μg cm -2 . An asymmetric supercapacitor of MnO 2 //N-rGO ae (CR2016) provides a maximum specific capacitance of ca. 467 F g -1 at 1 A g -1 , a maximum specific power of 39 kW kg -1 and a specific energy of 40 Wh kg -1 with a wide working potential of 1.6 V and 93.2% capacity retention after 7,500 cycles. The MnO 2 //N-rGO ae supercapacitor may be practically used in high power and energy applications.

Charge storage mechanisms of manganese oxide nanosheets and N-doped reduced graphene oxide aerogel for high-performance asymmetric supercapacitors

PubMed Central

Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Seubsai, Anusorn; Chanlek, Narong; Kidkhunthod, Pinit; Sangthong, Winyoo; Maensiri, Santi; Yimnirun, Rattikorn; Nilmoung, Sukanya; Pannopard, Panvika; Ittisanronnachai, Somlak; Kongpatpanich, Kanokwan; Limtrakul, Jumras; Sawangphruk, Montree

2016-01-01

Although manganese oxide- and graphene-based supercapacitors have been widely studied, their charge storage mechanisms are not yet fully investigated. In this work, we have studied the charge storage mechanisms of K-birnassite MnO2 nanosheets and N-doped reduced graphene oxide aerogel (N-rGOae) using an in situ X-ray absorption spectroscopy (XAS) and an electrochemical quart crystal microbalance (EQCM). The oxidation number of Mn at the MnO2 electrode is +3.01 at 0 V vs. SCE for the charging process and gets oxidized to +3.12 at +0.8 V vs. SCE and then reduced back to +3.01 at 0 V vs. SCE for the discharging process. The mass change of solvated ions, inserted to the layers of MnO2 during the charging process is 7.4 μg cm−2. Whilst, the mass change of the solvated ions at the N-rGOae electrode is 8.4 μg cm−2. An asymmetric supercapacitor of MnO2//N-rGOae (CR2016) provides a maximum specific capacitance of ca. 467 F g−1 at 1 A g−1, a maximum specific power of 39 kW kg−1 and a specific energy of 40 Wh kg−1 with a wide working potential of 1.6 V and 93.2% capacity retention after 7,500 cycles. The MnO2//N-rGOae supercapacitor may be practically used in high power and energy applications. PMID:27857225

[Nitrous Oxide Exposure-mediated Increases in Cuff Pressure: A Comparison of Disposable Type and Re-use Type air-Q Devices].

PubMed

Miyazaki, Yu; Komasawa, Nobuyasu; Fujiawara, Shunsuke; Majima, Nozomi; Tatsumi, Shinichi; Minami, Toshiaki

2015-02-01

BaCKGROUND: The present study aimed to compare nitrous oxide-mediated increases in cuff pressure between the disposable type air-Q (air-Q-DT) and re-use type air-Q (air-Q-RU) in a simulated adult airway model. Automated cuff pressure was adjusted to 10, 20, and 30 cmH2O. The air-Q-DT and air-Q-RU were exposed to 80% nitrous oxide and cuff pressure was measured 15 and 30 minutes later. Cuff pressure of the air-Q-DT was significantly lower than that of the air-Q-RU after 15 and 30 minutes, regardless of the initial pressure. The polyvinyl chloride-based air-Q-DT may be more effective than the silicon-based air-Q-RU in preventing hyperinflation of the tracheal tube cuff in response to nitrous oxide exposure.

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

Longo, Amelia F.; Feng, Yan; Lai, Barry

Aerosol iron was examined in Saharan dust plumes using a combination of iron near-edge X-ray absorption spectroscopy and wet-chemical techniques. Aerosol samples were collected at three sites located in the Mediterranean, the Atlantic, and Bermuda to characterize iron at different atmospheric transport lengths and time scales. Iron(III) oxides were a component of aerosols at all sampling sites and dominated the aerosol iron in Mediterranean samples. In Atlantic samples, iron(II and III) sulfate, iron(III) phosphate, and iron(II) silicates were also contributors to aerosol composition. With increased atmospheric transport time, iron(II) sulfates are found to become more abundant, aerosol iron oxidation statemore » became more reduced, and aerosol acidity increased. As a result, atmospheric processing including acidic reactions and photoreduction likely influence the form of iron minerals and oxidation state in Saharan dust aerosols and contribute to increases in aerosol-iron solubility.« less

Influence of atmospheric processes on the solubility and composition of iron in Saharan dust

DOE PAGES

Longo, Amelia F.; Feng, Yan; Lai, Barry; ...

2016-06-10

Aerosol iron was examined in Saharan dust plumes using a combination of iron near-edge X-ray absorption spectroscopy and wet-chemical techniques. Aerosol samples were collected at three sites located in the Mediterranean, the Atlantic, and Bermuda to characterize iron at different atmospheric transport lengths and time scales. Iron(III) oxides were a component of aerosols at all sampling sites and dominated the aerosol iron in Mediterranean samples. In Atlantic samples, iron(II and III) sulfate, iron(III) phosphate, and iron(II) silicates were also contributors to aerosol composition. With increased atmospheric transport time, iron(II) sulfates are found to become more abundant, aerosol iron oxidation statemore » became more reduced, and aerosol acidity increased. As a result, atmospheric processing including acidic reactions and photoreduction likely influence the form of iron minerals and oxidation state in Saharan dust aerosols and contribute to increases in aerosol-iron solubility.« less

Micro Raman and photoluminescence spectroscopy of nano-porous n and p type GaN/sapphire(0001).

PubMed

Ingale, Alka; Pal, Suparna; Dixit, V K; Tiwari, Pragya

2007-06-01

Variation of depth within a single etching spot (3 mm circular diameter) was observed in nanoporous GaN epilayer obtained on photo-assisted electrochemical etching of n and p-type GaN. The different etching depth regions were studied using microRaman and PL(yellow region) for both n-type and p-type GaN. From Raman spectroscopy, we observed that increase in disorder is accompanied by stress relaxation, as depth of etching increases for n-type GaN epilayer. This is well corroborated with scanning electron microscopy results. Contrarily, for p-type GaN epilayer we found that for minimum etching depth, stress in epilayer increases with increase in disorder. This is understood with the fact that as grown p-type GaN is more disordered compared to n-type GaN due to heavy Mg doping and further disorder leads to lattice distortion leading to increase in stress.

p × n-Type Transverse Thermoelectrics: A Novel Type of Thermal Management Material

NASA Astrophysics Data System (ADS)

Tang, Yang; Cui, Boya; Zhou, Chuanle; Grayson, Matthew

2015-06-01

In this paper we review the recently identified p × n-type transverse thermoelectrics and study the thermoelectric properties of the proposed candidate materials. Anisotropic electron and hole conductivity arise from either an artificially engineered band structure or from appropriately anisotropic crystals, and result in orthogonal p-type and n-type directional Seebeck coefficients, inducing a non-zero off-diagonal transverse Seebeck coefficient with appropriately oriented currents. Such materials have potential for new applications of thermoelectric materials in transverse Peltier cooling and transverse thermal energy harvesting. In this paper we review general transverse thermoelectric phenomena to identify advantages of p × n-type transverse thermoelectrics compared with previously studied transverse thermoelectric phenomena. An intuitive overview of the band structure of one such p × n-material, the InAs/GaSb type-II superlattice, is introduced, and the plot of thermoelectric performance as a function of superlattice structure is calculated, as an example of how band structures can be optimized for the best transverse thermoelectric performance.

Enhanced adsorption and catalytic oxidation of ciprofloxacin by an Ag/AgCl@N-doped activated carbon composite

NASA Astrophysics Data System (ADS)

Nekouei, Farzin; Nekouei, Shahram; Noorizadeh, Hossein

2018-03-01

In this study, we synthesized a new nanocomposite catalyst comprising Ag/AgCl@N-doped activated carbon (Ag/AgCl@N-AC) and demonstrated its high efficiency during the enhanced adsorptive removal and catalytic oxidation of ciprofloxacin (CIP) with peroxymonosulfate (PMS) and persulfate (PS) as oxidants in aqueous solution. The efficiency of the new nanocomposite was compared with those of both pristine AC and N-AC under the same conditions. Furthermore, the effects of oxidants on the catalytic oxidation of CIP were assessed using PMS and PS. We found that the degradation efficiency of CIP with Ag/AgCl@N-AC was higher when using PS as an oxidant, whereas the use of PMS obtained relatively better results with both AC and N-AC. The adsorption processes for AC, N-AC, and Ag/AgCl@N-AC were dominated not only by electrostatic attraction but also by π-π interactions, which had higher impacts on the adsorption processes than the specific surface area.

Nitric Oxide Regulates Skeletal Muscle Fatigue, Fiber Type, Microtubule Organization, and Mitochondrial ATP Synthesis Efficiency Through cGMP-Dependent Mechanisms.

PubMed

Moon, Younghye; Balke, Jordan E; Madorma, Derik; Siegel, Michael P; Knowels, Gary; Brouckaert, Peter; Buys, Emmanuel S; Marcinek, David J; Percival, Justin M

2017-06-10

Skeletal muscle nitric oxide-cyclic guanosine monophosphate (NO-cGMP) pathways are impaired in Duchenne and Becker muscular dystrophy partly because of reduced nNOSμ and soluble guanylate cyclase (GC) activity. However, GC function and the consequences of reduced GC activity in skeletal muscle are unknown. In this study, we explore the functions of GC and NO-cGMP signaling in skeletal muscle. GC1, but not GC2, expression was higher in oxidative than glycolytic muscles. GC1 was found in a complex with nNOSμ and targeted to nNOS compartments at the Golgi complex and neuromuscular junction. Baseline GC activity and GC agonist responsiveness was reduced in the absence of nNOS. Structural analyses revealed aberrant microtubule directionality in GC1 -/- muscle. Functional analyses of GC1 -/- muscles revealed reduced fatigue resistance and postexercise force recovery that were not due to shifts in type IIA-IIX fiber balance. Force deficits in GC1 -/- muscles were also not driven by defects in resting mitochondrial adenosine triphosphate (ATP) synthesis. However, increasing muscle cGMP with sildenafil decreased ATP synthesis efficiency and capacity, without impacting mitochondrial content or ultrastructure. GC may represent a new target for alleviating muscle fatigue and that NO-cGMP signaling may play important roles in muscle structure, contractility, and bioenergetics. These findings suggest that GC activity is nNOS dependent and that muscle-specific control of GC expression and differential GC targeting may facilitate NO-cGMP signaling diversity. They suggest that nNOS regulates muscle fiber type, microtubule organization, fatigability, and postexercise force recovery partly through GC1 and suggest that NO-cGMP pathways may modulate mitochondrial ATP synthesis efficiency. Antioxid. Redox Signal. 26, 966-985.

Ascorbate and Apple Phenolics Affect Protein Oxidation in Emulsion-Type Sausages during Storage and in Vitro Digestion.

PubMed

Rysman, Tine; Van Hecke, Thomas; De Smet, Stefaan; Van Royen, Geert

2016-05-25

The effect of sodium ascorbate and apple phenolics on the oxidative stability of emulsion-type sausages during storage and digestion was investigated. Emulsion-type sausages containing 0.05% sodium ascorbate or 3% freeze-dried apple pomace were subjected to chilled illuminated storage and subsequent in vitro digestion. Lipid oxidation was assessed as TBARS, and protein oxidation was evaluated as thiol oxidation, total carbonyls, and γ-glutamic and α-amino adipic semialdehyde. Proteolysis was measured after digestion to evaluate protein digestibility. The results suggest the presence of protein-ascorbate and protein-phenol interactions, which may decrease protein digestibility and may interfere with spectrophotometric methods for measuring oxidation.

Metal oxides for optoelectronic applications.

PubMed

Yu, Xinge; Marks, Tobin J; Facchetti, Antonio

2016-04-01

Metal oxides (MOs) are the most abundant materials in the Earth's crust and are ingredients in traditional ceramics. MO semiconductors are strikingly different from conventional inorganic semiconductors such as silicon and III-V compounds with respect to materials design concepts, electronic structure, charge transport mechanisms, defect states, thin-film processing and optoelectronic properties, thereby enabling both conventional and completely new functions. Recently, remarkable advances in MO semiconductors for electronics have been achieved, including the discovery and characterization of new transparent conducting oxides, realization of p-type along with traditional n-type MO semiconductors for transistors, p-n junctions and complementary circuits, formulations for printing MO electronics and, most importantly, commercialization of amorphous oxide semiconductors for flat panel displays. This Review surveys the uniqueness and universality of MOs versus other unconventional electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and selected applications in thin-film transistors, solar cells, diodes and memories.

Metal oxides for optoelectronic applications

NASA Astrophysics Data System (ADS)

Yu, Xinge; Marks, Tobin J.; Facchetti, Antonio

2016-04-01

Metal oxides (MOs) are the most abundant materials in the Earth's crust and are ingredients in traditional ceramics. MO semiconductors are strikingly different from conventional inorganic semiconductors such as silicon and III-V compounds with respect to materials design concepts, electronic structure, charge transport mechanisms, defect states, thin-film processing and optoelectronic properties, thereby enabling both conventional and completely new functions. Recently, remarkable advances in MO semiconductors for electronics have been achieved, including the discovery and characterization of new transparent conducting oxides, realization of p-type along with traditional n-type MO semiconductors for transistors, p-n junctions and complementary circuits, formulations for printing MO electronics and, most importantly, commercialization of amorphous oxide semiconductors for flat panel displays. This Review surveys the uniqueness and universality of MOs versus other unconventional electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and selected applications in thin-film transistors, solar cells, diodes and memories.

Defect studies in copper-based p-type transparent conducting oxides

NASA Astrophysics Data System (ADS)

Ameena, Fnu

Among other intrinsic open-volume defects, copper vacancy (VCu) has been theoretically identified as the major acceptor in p-type Cu-based semiconducting transparent oxides, which has potential as low-cost photovoltaic absorbers in semi-transparent solar cells. A series of positron annihilation experiments with pure Cu, Cu2O, and CuO presented strong presence of VCu and its complexes in the copper oxides. The lifetime data also showed that the density of VCu was becoming higher as the oxidation state of Cu increased which was consistent with the decrease in the formation energy of VCu. Doppler broadening measurements further indicated that electrons with low momentum made more contribution to the contributed as pure Cu oxidizes to copper oxides. The metastable defects are known to be generated in Cu2O upon illumination and it has been known to affect the performance of Cu2O-based hetero-junctions used in solar cells. The metastable effect was studied using positron annihilation lifetime spectroscopy and its data showed the change in the defect population upon light exposure and the minimal effect of light-induced electron density increase in the bulk of materials to the average lifetime of the positrons. The change in the defect population is concluded to be related to the dissociation and association of VCu -- V Cu complexes. For example, the shorter lifetime under light was ascribed to the annihilation with smaller size vacancies, which explains the dissociation of the complexes with light illumination. Doppler broadening of the annihilation was independent of light illumination, which suggested that the chemical nature of the defects remained without change upon their dissociation and association -- only the size distribution of copper vacancies varied. The delafossite metal oxides, CuMIIIO2 are emerging wide-bandgap p-type semiconductors. In this research, the formation energies of structural vacancies are calculated using Van Vechten cavity model as an attempt

Transition metal coordination chemistry ofN,N-bis(2-{pyrid-2-ylethyl})hydroxylamine.

PubMed

Belock, Christopher W; Cetin, Anil; Barone, Natalie V; Ziegler, Christopher J

2008-08-18

Although directly relevant to metal mediated biological nitrification as well as the coordination chemistry of peroxide, the metal complexes of hydroxylamines and their functionalized variants remain largely unexplored. The chelating hydroxylamine ligand N,N-bis(2-{pyrid-2-ylethyl})hydroxylamine can be readily generated via a solvent free reaction in high purity; however, the ligand is prone to decomposition which can hamper metal reaction. N,N-bis(2-{pyrid-2-ylethyl})hydroxylamine forms stable complexes with chromium(III), manganese(II), nickel(II), and cadmium(II) ions, coordinating in a side-on mode in the case of chromium and via the nitrogen in the case of the latter three metal ions. The hydroxylamine ligand can also be reduced to form N,N-bis(2-{pyrid-2-ylethyl})amine upon exposure to a stoichiometric amount of the metal salts cobalt(II) nitrate, vanadium(III) chloride, and iron(II) chloride. In the reaction with cobalt nitrate, the reduced ligand then chelates to the metal to form [N,N-bis(2-{pyrid-2-ylethyl})amine]dinitrocobalt(II). Upon reaction with vanadium(III) chloride and iron(III) chloride, the reduced ligand is isolated as the protonated free base, resulting from a metal-mediated decomposition reaction.

Cu2O-based solar cells using oxide semiconductors

NASA Astrophysics Data System (ADS)

Minami, Tadatsugu; Nishi, Yuki; Miyata, Toshihiro

2016-01-01

We describe significant improvements of the photovoltaic properties that were achieved in Al-doped ZnO (AZO)/n-type oxide semiconductor/p-type Cu2O heterojunction solar cells fabricated using p-type Cu2O sheets prepared by thermally oxidizing Cu sheets. The multicomponent oxide thin film used as the n-type semiconductor layer was prepared with various chemical compositions on non-intentionally heated Cu2O sheets under various deposition conditions using a pulsed laser deposition method. In Cu2O-based heterojunction solar cells fabricated using various ternary compounds as the n-type oxide thin-film layer, the best photovoltaic performance was obtained with an n-ZnGa2O4 thin-film layer. In most of the Cu2O-based heterojunction solar cells using multicomponent oxides composed of combinations of various binary compounds, the obtained photovoltaic properties changed gradually as the chemical composition was varied. However, with the ZnO-MgO and Ga2O3-Al2O3 systems, higher conversion efficiencies (η) as well as a high open circuit voltage (Voc) were obtained by using a relatively small amount of MgO or Al2O3, e.g., (ZnO)0.91-(MgO)0.09 and (Ga2O3)0.975-(Al2O3)0.025, respectively. When Cu2O-based heterojunction solar cells were fabricated using Al2O3-Ga2O3-MgO-ZnO (AGMZO) multicomponent oxide thin films deposited with metal atomic ratios of 10, 60, 10 and 20 at.% for the Al, Ga, Mg and Zn, respectively, a high Voc of 0.98 V and an η of 4.82% were obtained. In addition, an enhanced η and an improved fill factor could be achieved in AZO/n-type multicomponent oxide/p-type Cu2O heterojunction solar cells fabricated using Na-doped Cu2O (Cu2O:Na) sheets that featured a resistivity controlled by optimizing the post-annealing temperature and duration. Consequently, an η of 6.25% and a Voc of 0.84 V were obtained in a MgF2/AZO/n-(Ga2O3-Al2O3)/p-Cu2O:Na heterojunction solar cell fabricated using a Cu2O:Na sheet with a resistivity of approximately 10 Ω·cm and a (Ga0.975Al0

Mechanism of oxide thickness and temperature dependent current conduction in n+-polySi/SiO2/p-Si structures — a new analysis

NASA Astrophysics Data System (ADS)

Samanta, Piyas

2017-10-01

The conduction mechanism of gate leakage current through thermally grown silicon dioxide (SiO2) films on (100) p-type silicon has been investigated in detail under negative bias on the degenerately doped n-type polysilicon (n+-polySi) gate. The analysis utilizes the measured gate current density J G at high oxide fields E ox in 5.4 to 12 nm thick SiO2 films between 25 and 300 °C. The leakage current measured up to 300 °C was due to Fowler-Nordheim (FN) tunneling of electrons from the accumulated n +-polySi gate in conjunction with Poole Frenkel (PF) emission of trapped-electrons from the electron traps located at energy levels ranging from 0.6 to 1.12 eV (depending on the oxide thickness) below the SiO2 conduction band (CB). It was observed that PF emission current I PF dominates FN electron tunneling current I FN at oxide electric fields E ox between 6 and 10 MV/cm and throughout the temperature range studied here. Understanding of the mechanism of leakage current conduction through SiO2 films plays a crucial role in simulation of time-dependent dielectric breakdown (TDDB) of metaloxide-semiconductor (MOS) devices and to precisely predict the normal operating field or applied gate voltage for lifetime projection of the MOS integrated circuits.

Electron transport properties of degenerate n-type GaN prepared by pulsed sputtering

NASA Astrophysics Data System (ADS)

Ueno, Kohei; Fudetani, Taiga; Arakawa, Yasuaki; Kobayashi, Atsushi; Ohta, Jitsuo; Fujioka, Hiroshi

2017-12-01

We report a systematic investigation of the transport properties of highly degenerate electrons in Ge-doped and Si-doped GaN epilayers prepared using the pulsed sputtering deposition (PSD) technique. Secondary-ion mass spectrometry and Hall-effect measurements revealed that the doping efficiency of PSD n-type GaN is close to unity at electron concentrations as high as 5.1 × 1020 cm-3. A record low resistivity for n-type GaN of 0.16 mΩ cm was achieved with an electron mobility of 100 cm2 V-1 s-1 at a carrier concentration of 3.9 × 1020 cm-3. We explain this unusually high electron mobility of PSD n-type GaN within the framework of conventional scattering theory by modifying a parameter related to nonparabolicity of the conduction band. The Ge-doped GaN films show a slightly lower electron mobility compared with Si-doped films with the same carrier concentrations, which is likely a consequence of the formation of a small number of compensation centers. The excellent electrical properties presented in this letter clearly demonstrate the striking advantages of the low-temperature PSD technique for growing high-quality and highly conductive n-type GaN.

Substitution of the nitro group with Grignard reagents: facile arylation and alkenylation of pyridine N-oxides.

PubMed

Zhang, Fang; Zhang, Song; Duan, Xin-Fang

2012-11-02

The unprecedented substitution of a nitro group with aryl or alkenyl groups of Grignard reagents affords 2-aryl or alkenylpyridine N-oxides in modest to high yields with high chemoselectivity. This protocol allows a simple and clean synthesis of various 2-substituted pyridine N-oxides and the corresponding pyridine derivatives. Furthermore, straightforward one-pot iterative functionality of pyridine N-oxides could also be achieved simply by successive applications of two Grignard reagents.

Stability of Pseudobrookite-Type Titanium Oxides

NASA Technical Reports Server (NTRS)

Xirouchakis, Dimistrios

2002-01-01

Orthorhombic, (Bbmm), (Al, Fe, Cr, Ti)(sub 2) TiO5-(Mg, Fe)Ti2O5 solid solutions (pseudobrookites, s.l.) are found either as an oxidation product of ilmenite and/or spinel or a primary crystallizing phase in igneous and metamorphic rocks on Earth (e.g., basalt flows, crustal and mantle xenoliths, hornfels), and basaltic rocks on the Moon. Moreover, orthorhombic oxides are often part of the crystalline matrix in glass/ceramics with useful applications, and play a major role in the industrial production of TiO2. To fully exploit the potential of these compounds as petrogenetic indicators and/or useful materials we need to quantitatively understand the factors controlling their properties and stability, and thus, to extrapolate beyond the calibrating experiments. For that purpose, we need to combine thermochemistry, phase equilibrium, and in situ P-V-T-cation disorder experimental data that presently either are incomplete or lacking. Perhaps, the most complete data set is that for MgTi2O5 (karrooite) which allows the calibration of models for the Gibbs free energy of the MgTi2O5 as a function of pressure, temperature, and the Mg2+-Ti4+ distribution between the two nonequivalent octahedral sites. Consequently, the effect of cation disorder on MgTi2O5 stability, and the phase relations among MgTi2O5, other titanium oxides, and silicate minerals can be examined. Calculated phase relations in the Mg-Ti-Si-O system and phase equilibrium experiments in Fe-bearing compositions suggest that pseudobrookite-type oxides may be a more common in rocks than previously realized. However, homogeneous and heterogeneous equilibria, and crystallization paths likely affect their stability. For example, isobaric increases in temperature favor disordering and thus entropy-stabilization, in contrast, isothermal increases in pressure have the opposite effect. Although, currently, the potential effect of composition to cation disorder cannot be fully explored, it appears that enrichment in

[A new type of flagellar structure. Type 9+n

PubMed Central

1977-01-01

The ultrastructural study of the Eoacanthocephala sperm cell shows a variation from 0 to 5 in the number of the axial fibers in the axoneme. All the species of the order Eoacanthocephala available to us show this variation; moreover, every individual possesses simultaneously several different structural types. So, we are dealing with a new flagellar organization: 9+n, with 0 less than or equal to n less than or equal to 5. In the Quadrigyridae and the Tenuisentidae families, n varies from 0 to 4, with a maximum of 2 for most individuals, exceptionally at 1 for some individuals. In the Neoechinorhynchidae family, n varies from 0 to 5 with a conspicuous prevalence of 3 (from 84 to 99%, according to the individual). These results prompted us to reexamine the two other orders of Acanthocephala in which the structural types 9+2 or 9+0 have been considered as fixed. Indeed, we have found a few flagella the structure of which is different from the prevalent one. It seems, therefore, that the number of the central fibers of the axoneme in the Acanthocephala sperm cell is never absolutely fixed. PMID:557042

Iron porphyrin-modified PVDF membrane as a biomimetic material and its effectiveness on nitric oxide binding

NASA Astrophysics Data System (ADS)

Can, Faruk; Demirci, Osman Cahit; Dumoulin, Fabienne; Erhan, Elif; Arslan, Leyla Colakerol; Ergenekon, Pınar

2017-10-01

Nitric oxide (NO) is a reactive gas well-known as an air pollutant causing severe environmental problems. NO is also an important signaling molecule having a strong affinity towards heme proteins in the body. Taking this specialty as a model, a biomimetic membrane was developed by modification of the membrane surface with iron-porphyrin which depicts very similar structure to heme proteins. In this study, PVDF membrane was coated with synthesized (4-carboxyphenyl)-10,15,20-triphenyl-porphyrin iron(III) chloride (FeCTPP) to promote NO fixation on the surface. The coated membrane was characterized in terms of ATR-IR spectra, contact angle measurement, chemical composition, and morphological structure. Contact angle of original PVDF first decreased sharply after plasma treatment and surface polymerization steps but after incorporation of FeCTPP, the surface acquired its hydrophobicity again. NO binding capability of modified membrane surface was evaluated on the basis of X-ray Photoelectron. Upon exposure to NO gas, a chemical shift of Fe+3 and appearance of new N peak was observed due to the electron transfer from NO ligand to Fe ion with the attachment of nitrosyl group to FeCTPP. This modification brings the functionality to the membrane for being used in biological systems such as membrane bioreactor material in biological NO removal technology.

Selective-area catalyst-free MBE growth of GaN nanowires using a patterned oxide layer.

PubMed

Schumann, T; Gotschke, T; Limbach, F; Stoica, T; Calarco, R

2011-03-04

GaN nanowires (NWs) were grown selectively in holes of a patterned silicon oxide mask, by rf-plasma-assisted molecular beam epitaxy (PAMBE), without any metal catalyst. The oxide was deposited on a thin AlN buffer layer previously grown on a Si(111) substrate. Regular arrays of holes in the oxide layer were obtained using standard e-beam lithography. The selectivity of growth has been studied varying the substrate temperature, gallium beam equivalent pressure and patterning layout. Adjusting the growth parameters, GaN NWs can be selectively grown in the holes of the patterned oxide with complete suppression of the parasitic growth in between the holes. The occupation probability of a hole with a single or multiple NWs depends strongly on its diameter. The selectively grown GaN NWs have one common crystallographic orientation with respect to the Si(111) substrate via the AlN buffer layer, as proven by x-ray diffraction (XRD) measurements. Based on the experimental data, we present a schematic model of the GaN NW formation in which a GaN pedestal is initially grown in the hole.

Role of excited N2 in the production of nitric oxide

NASA Astrophysics Data System (ADS)

Campbell, L.; Cartwright, D. C.; Brunger, M. J.

2007-08-01

Excited N2 plays a role in a number of atmospheric processes, including auroral and dayglow emissions, chemical reactions, recombination of free electrons, and the production of nitric oxide. Electron impact excitation of N2 is followed by radiative decay through a series of excited states, contributing to auroral and dayglow emissions. These processes are intertwined with various chemical reactions and collisional quenching involving the excited and ground state vibrational levels. Statistical equilibrium and time step atmospheric models are used to predict N2 excited state densities and emissions (as a test against previous models and measurements) and to investigate the role of excited nitrogen in the production of nitric oxide. These calculations predict that inclusion of the reaction N2[A3Σu +] + O, to generate NO, produces an increase by a factor of up to three in the calculated NO density at some altitudes.

Vertically aligned p-type single-crystalline GaN nanorod arrays on n-type Si for heterojunction photovoltaic cells.

PubMed

Tang, Y B; Chen, Z H; Song, H S; Lee, C S; Cong, H T; Cheng, H M; Zhang, W J; Bello, I; Lee, S T

2008-12-01

Vertically aligned Mg-doped GaN nanorods have been epitaxially grown on n-type Si substrate to form a heterostructure for fabricating p-n heterojunction photovoltaic cells. The p-type GaN nanorod/n-Si heterojunction cell shows a well-defined rectifying behavior with a rectification ratio larger than 10(4) in dark. The cell has a high short-circuit photocurrent density of 7.6 mAlcm2 and energy conversion efficiency of 2.73% under AM 1.5G illumination at 100 mW/cm2. Moreover, the nanorod array may be used as an antireflection coating for solar cell applications to effectively reduce light loss due to reflection. This study provides an experimental demonstration for integrating one-dimensional nanostructure arrays with the substrate to directly fabricate heterojunction photovoltaic cells.

Oxidative Stress Parameters in Saliva and Its Association with Periodontal Disease and Types of Bacteria.

PubMed

Almerich-Silla, Jose Manuel; Montiel-Company, Jose María; Pastor, Sara; Serrano, Felipe; Puig-Silla, Miriam; Dasí, Francisco

2015-01-01

To determine the association between oxidative stress parameters with periodontal disease, bleeding, and the presence of different periodontal bacteria. A cross-sectional study in a sample of eighty-six patients, divided into three groups depending on their periodontal status. Thirty-three with chronic periodontitis, sixteen with gingivitis, and thirty-seven with periodontal healthy as control. Oxidative stress biomarkers (8-OHdG and MDA), total antioxidant capacity (TAOC), and the activity of two antioxidant enzymes (GPx and SOD) were determined in saliva. Subgingival plaque samples were obtained from the deepest periodontal pocket and PCR was used to determine the presence of the 6 fimA genotypes of Porphyromonas gingivalis, Aggregatibacter actinomycetemcomitans, Tannerella forsythia, and Treponema denticola. Periodontal disease was found to be associated with increased oxidative stress parameter levels. These levels rose according to the number and type of different periodontal bacteria found in the periodontal pockets. The presence of different types of periodontal bacteria is predictive independent variables in linear regresion models of oxidative stress parameters as dependent variable, above all 8-OHdG. Oxidative stress parameter levels are correlated with the presence of different types of bacteria. Determination of these levels and periodontal bacteria could be a potent tool for controlling periodontal disease development.

Nitrous oxide emission related to ammonia-oxidizing bacteria and mitigation options from N fertilization in a tropical soil

NASA Astrophysics Data System (ADS)

Soares, Johnny R.; Cassman, Noriko A.; Kielak, Anna M.; Pijl, Agata; Carmo, Janaína B.; Lourenço, Kesia S.; Laanbroek, Hendrikus J.; Cantarella, Heitor; Kuramae, Eiko E.

2016-07-01

Nitrous oxide (N2O) from nitrogen fertilizers applied to sugarcane has high environmental impact on ethanol production. This study aimed to determine the main microbial processes responsible for the N2O emissions from soil fertilized with different N sources, to identify options to mitigate N2O emissions, and to determine the impacts of the N sources on the soil microbiome. In a field experiment, nitrogen was applied as calcium nitrate, urea, urea with dicyandiamide or 3,4 dimethylpyrazone phosphate nitrification inhibitors (NIs), and urea coated with polymer and sulfur (PSCU). Urea caused the highest N2O emissions (1.7% of N applied) and PSCU did not reduce cumulative N2O emissions compared to urea. NIs reduced N2O emissions (95%) compared to urea and had emissions comparable to those of the control (no N). Similarly, calcium nitrate resulted in very low N2O emissions. Interestingly, N2O emissions were significantly correlated only with bacterial amoA, but not with denitrification gene (nirK, nirS, nosZ) abundances, suggesting that ammonia-oxidizing bacteria, via the nitrification pathway, were the main contributors to N2O emissions. Moreover, the treatments had little effect on microbial composition or diversity. We suggest nitrate-based fertilizers or the addition of NIs in NH4+-N based fertilizers as viable options for reducing N2O emissions in tropical soils and lessening the environmental impact of biofuel produced from sugarcane.

Nitrous oxide emission related to ammonia-oxidizing bacteria and mitigation options from N fertilization in a tropical soil

PubMed Central

Soares, Johnny R.; Cassman, Noriko A.; Kielak, Anna M.; Pijl, Agata; Carmo, Janaína B.; Lourenço, Kesia S.; Laanbroek, Hendrikus J.; Cantarella, Heitor; Kuramae, Eiko E.

2016-01-01

Nitrous oxide (N2O) from nitrogen fertilizers applied to sugarcane has high environmental impact on ethanol production. This study aimed to determine the main microbial processes responsible for the N2O emissions from soil fertilized with different N sources, to identify options to mitigate N2O emissions, and to determine the impacts of the N sources on the soil microbiome. In a field experiment, nitrogen was applied as calcium nitrate, urea, urea with dicyandiamide or 3,4 dimethylpyrazone phosphate nitrification inhibitors (NIs), and urea coated with polymer and sulfur (PSCU). Urea caused the highest N2O emissions (1.7% of N applied) and PSCU did not reduce cumulative N2O emissions compared to urea. NIs reduced N2O emissions (95%) compared to urea and had emissions comparable to those of the control (no N). Similarly, calcium nitrate resulted in very low N2O emissions. Interestingly, N2O emissions were significantly correlated only with bacterial amoA, but not with denitrification gene (nirK, nirS, nosZ) abundances, suggesting that ammonia-oxidizing bacteria, via the nitrification pathway, were the main contributors to N2O emissions. Moreover, the treatments had little effect on microbial composition or diversity. We suggest nitrate-based fertilizers or the addition of NIs in NH4+-N based fertilizers as viable options for reducing N2O emissions in tropical soils and lessening the environmental impact of biofuel produced from sugarcane. PMID:27460335

Nitrous oxide emission related to ammonia-oxidizing bacteria and mitigation options from N fertilization in a tropical soil.

PubMed

Soares, Johnny R; Cassman, Noriko A; Kielak, Anna M; Pijl, Agata; Carmo, Janaína B; Lourenço, Kesia S; Laanbroek, Hendrikus J; Cantarella, Heitor; Kuramae, Eiko E

2016-07-27

Nitrous oxide (N2O) from nitrogen fertilizers applied to sugarcane has high environmental impact on ethanol production. This study aimed to determine the main microbial processes responsible for the N2O emissions from soil fertilized with different N sources, to identify options to mitigate N2O emissions, and to determine the impacts of the N sources on the soil microbiome. In a field experiment, nitrogen was applied as calcium nitrate, urea, urea with dicyandiamide or 3,4 dimethylpyrazone phosphate nitrification inhibitors (NIs), and urea coated with polymer and sulfur (PSCU). Urea caused the highest N2O emissions (1.7% of N applied) and PSCU did not reduce cumulative N2O emissions compared to urea. NIs reduced N2O emissions (95%) compared to urea and had emissions comparable to those of the control (no N). Similarly, calcium nitrate resulted in very low N2O emissions. Interestingly, N2O emissions were significantly correlated only with bacterial amoA, but not with denitrification gene (nirK, nirS, nosZ) abundances, suggesting that ammonia-oxidizing bacteria, via the nitrification pathway, were the main contributors to N2O emissions. Moreover, the treatments had little effect on microbial composition or diversity. We suggest nitrate-based fertilizers or the addition of NIs in NH4(+)-N based fertilizers as viable options for reducing N2O emissions in tropical soils and lessening the environmental impact of biofuel produced from sugarcane.

Electro-mechanical coupling of semiconductor film grown on stainless steel by oxidation

NASA Astrophysics Data System (ADS)

Lin, M. C.; Wang, G.; Guo, L. Q.; Qiao, L. J.; Volinsky, Alex A.

2013-09-01

Electro-mechanical coupling phenomenon in oxidation film on stainless steel has been discovered by using current-sensing atomic force microscopy, along with the I-V curves measurements. The oxidation films exhibit either ohmic, n-type, or p-type semiconductor properties, according to the obtained I-V curves. This technique allows characterizing oxidation films with high spatial resolution. Semiconductor properties of oxidation films must be considered as additional stress corrosion cracking mechanisms.

Fabricate heterojunction diode by using the modified spray pyrolysis method to deposit nickel-lithium oxide on indium tin oxide substrate.

PubMed

Wu, Chia-Ching; Yang, Cheng-Fu

2013-06-12

P-type lithium-doped nickel oxide (p-LNiO) thin films were deposited on an n-type indium tin oxide (ITO) glass substrate using the modified spray pyrolysis method (SPM), to fabricate a transparent p-n heterojunction diode. The structural, optical, and electrical properties of the p-LNiO and ITO thin films and the p-LNiO/n-ITO heterojunction diode were characterized by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), UV-visible spectroscopy, Hall effect measurement, and current-voltage (I-V) measurements. The nonlinear and rectifying I-V properties confirmed that a heterojunction diode characteristic was successfully formed in the p-LNiO/n-ITO (p-n) structure. The I-V characteristic was dominated by space-charge-limited current (SCLC), and the Anderson model demonstrated that band alignment existed in the p-LNiO/n-ITO heterojunction diode.

Selective Oxidation of Alcohols Using Photoactive VO@g??C3N4

EPA Pesticide Factsheets

A photoactive VO@g-C3N4 catalyst has been developed for the selective oxidation of alcohols to the corresponding aldehydes and ketones. The visible light mediated activity of the catalyst could be attributed to photoactive graphitic carbon nitrides surface.This dataset is associated with the following publication:Verma, S., R.B. Nasir Baig, M. Nadagouda , and R. Varma. Selective oxidation of alcohols using photoactive VO@g-C3N4.. ACS Sustainable Chemistry & Engineering. American Chemical Society, Washington, DC, USA, 4(3): 1094-1098, (2015).

Integrated structural biology and molecular ecology of N-cycling enzymes from ammonia-oxidizing archaea

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

Tolar, Bradley B.; Herrmann, Jonathan; Bargar, John R.

In this paper, knowledge of the molecular ecology and environmental determinants of ammonia-oxidizing organisms is critical to understanding and predicting the global nitrogen (N) and carbon cycles, but an incomplete biochemical picture hinders in vitro studies of N-cycling enzymes. Although an integrative structural and dynamic characterization at the atomic scale would advance our understanding of function tremendously, structural knowlede of key N-cycling enzymes from ecologically-relevant ammonia oxidizers is unfortunately extremely limited. Here, we discuss the challenges and opportunities for examining the ecology of ammonia-oxidizing organisms, particularly uncultivated Thaumarchaeota, though (meta)genome-driven structural biology of the enzymes ammonia monooxygenase (AMO) andmore » nitrite reductase (NirK).« less