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Sample records for iron 56 reactions

  1. The Quasi-Elastic Region of the IRON-56+IRON-56 and IRON-56+URANIUM-238 Reactions

    NASA Astrophysics Data System (ADS)

    Weston-Dawkes, Andrew Peter

    Projectile-like fragments (PLF's) were detected for the 15-MeV/uFe+Fe and Fe+U reactions. The mass, charge and energy of the PLF's were recorded. For the Fe+Fe reaction light-charged particles were also recorded in coincidence with PLF's. Products with kinetic energies corresponding to the first 100 MeV of energy loss were studied in detail for a variety of questions that remain concerning the quasi -elastic region. PLF energy spectra clearly show the presence of structures. These structures can be classified as either narrow or broad in kinetic energy width. By use of evaporation calculations, it was shown that broad structures were due to normal evaporation processes. Narrow structures with widths of 8 to 10 MeV could not be duplicated by evaporation calculations and their origin is still unexplained. The evaporation peaks seen in the cobalt isotope energy spectra were used to determine the mean value of the excitation energy division (EED) since it was shown that this is the main determining factor in the value of the evaporation peak centroid. The results of the EED determinations indicate that many model assumptions of excitation energy division with nucleon exchange may be inapplicable during the first stages of interaction. The variance of the EED was determined for certain cobalt isotopes by use of an iteractive fitting program based on the evaporation process. For the 15-MeV/u systems it was found that the EED variance was smaller than what would be predicted by Morrissey's thermal variance. The optimum Q-values for cobalt isotopes were found to be effected by evaporation processes. After evaporation corrections to these values, it was found that Siemen's optimum Q-value model accurately predicted all values for the Fe+U system and most values for the Fe+Fe system. The exception was for the one proton transfer to ('57)Co in the Fe+Fe system, which has a much larger optimum Q-value than predicted. This may indicate a fundamental difference in proton

  2. 46 CFR 56.60-15 - Ductile iron.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... (incorporated by reference; see 46 CFR 56.01-2). (b) Ductile iron castings conforming to ASTM A 395... 395 (incorporated by reference, see 46 CFR 56.01-2) may be used within the service restrictions and... 46 Shipping 2 2011-10-01 2011-10-01 false Ductile iron. 56.60-15 Section 56.60-15 Shipping...

  3. 46 CFR 56.60-15 - Ductile iron.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... (incorporated by reference; see 46 CFR 56.01-2). (b) Ductile iron castings conforming to ASTM A 395... 395 (incorporated by reference, see 46 CFR 56.01-2) may be used within the service restrictions and... 46 Shipping 2 2012-10-01 2012-10-01 false Ductile iron. 56.60-15 Section 56.60-15 Shipping...

  4. 46 CFR 56.60-15 - Ductile iron.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... (incorporated by reference; see 46 CFR 56.01-2). (b) Ductile iron castings conforming to ASTM A 395... 395 (incorporated by reference, see 46 CFR 56.01-2) may be used within the service restrictions and... 46 Shipping 2 2014-10-01 2014-10-01 false Ductile iron. 56.60-15 Section 56.60-15 Shipping...

  5. 46 CFR 56.60-15 - Ductile iron.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... (incorporated by reference; see 46 CFR 56.01-2). (b) Ductile iron castings conforming to ASTM A 395... 395 (incorporated by reference, see 46 CFR 56.01-2) may be used within the service restrictions and... 46 Shipping 2 2013-10-01 2013-10-01 false Ductile iron. 56.60-15 Section 56.60-15 Shipping...

  6. 46 CFR 56.60-15 - Ductile iron.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... (incorporated by reference; see 46 CFR 56.01-2). (b) Ductile iron castings conforming to ASTM A 395... 395 (incorporated by reference, see 46 CFR 56.01-2) may be used within the service restrictions and... 46 Shipping 2 2010-10-01 2010-10-01 false Ductile iron. 56.60-15 Section 56.60-15 Shipping...

  7. 46 CFR 56.60-10 - Cast iron and malleable iron.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... and malleable iron fittings conforming to the specifications of 46 CFR 56.60-1, Table 56.60-1(a) may...; see 46 CFR 56.01-2) and if their service does not exceed the rating as marked on the valve. (b) Cast... 46 Shipping 2 2011-10-01 2011-10-01 false Cast iron and malleable iron. 56.60-10 Section...

  8. 46 CFR 56.60-10 - Cast iron and malleable iron.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... and malleable iron fittings conforming to the specifications of 46 CFR 56.60-1, Table 56.60-1(a) may...; see 46 CFR 56.01-2) and if their service does not exceed the rating as marked on the valve. (b) Cast... 46 Shipping 2 2010-10-01 2010-10-01 false Cast iron and malleable iron. 56.60-10 Section...

  9. 46 CFR 56.60-10 - Cast iron and malleable iron.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... and malleable iron fittings conforming to the specifications of 46 CFR 56.60-1, Table 56.60-1(a) may...; see 46 CFR 56.01-2) and if their service does not exceed the rating as marked on the valve. (b) Cast... 46 Shipping 2 2013-10-01 2013-10-01 false Cast iron and malleable iron. 56.60-10 Section...

  10. 46 CFR 56.60-10 - Cast iron and malleable iron.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... and malleable iron fittings conforming to the specifications of 46 CFR 56.60-1, Table 56.60-1(a) may...; see 46 CFR 56.01-2) and if their service does not exceed the rating as marked on the valve. (b) Cast... 46 Shipping 2 2012-10-01 2012-10-01 false Cast iron and malleable iron. 56.60-10 Section...

  11. 46 CFR 56.60-10 - Cast iron and malleable iron.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... and malleable iron fittings conforming to the specifications of 46 CFR 56.60-1, Table 56.60-1(a) may...; see 46 CFR 56.01-2) and if their service does not exceed the rating as marked on the valve. (b) Cast... 46 Shipping 2 2014-10-01 2014-10-01 false Cast iron and malleable iron. 56.60-10 Section...

  12. Mass and charge distributions in iron-induced reactions and excitation energy division between the fragments of the 672-MeV {sup 56}Fe + {sup 165}Ho reaction

    SciTech Connect

    Madani, H.

    1993-05-01

    The projectile-like and target-like fragments produced by the 12-MeV/nucleon {sup 56}Fe + {sup 165}Ho reaction were detected in coincidence. The measured parameters were the mass, charge, kinetic energy scattering angle of the projectile-like fragments, and the scattering angle of the target-like fragments. The mass and charge distributions of the projectile-like fragments were generated as a function of energy loss, and characterized by their centroids, variances, and correlation coefficients. The neutron drift of the measured projectile-like products is mostly due to evaporative processes, while the charge drift is a result of a net transfer of protons from the projectile-like fragment to the target-like fragment. The result is a weak drift of the system towards mass asymmetry. The predictions of two nucleon exchange models are compared to the experimental results of the 672-MeV {sup 56}Fe + {sup 165}Ho reaction and other Fe-induced reactions. The fairly good agreement between the experimental and theoretical variances verifies the prevalence of a nucleon exchange mechanism in these reactions. The information from the coincidence measurement and two-body kinematics are used to reconstruct the pre-evaporation masses of the projectile-like and target-like fragments of the reaction. Statistical evaporation calculations are used to translate these masses into excitation energies of the primary fragments. The ratio of excitation energy stored in the projectile-Mm fragment decreases with increasing energy loss, in qualitative agreement with previous measurements; however, higher ratios are observed for the 672-MeV {sup 56}Fe on {sup 165}Ho system.

  13. Mass and charge distributions in iron-induced reactions and excitation energy division between the fragments of the 672-MeV [sup 56]Fe + [sup 165]Ho reaction

    SciTech Connect

    Madani, H.

    1993-01-01

    The projectile-like and target-like fragments produced by the 12-MeV/nucleon [sup 56]Fe + [sup 165]Ho reaction were detected in coincidence. The measured parameters were the mass, charge, kinetic energy scattering angle of the projectile-like fragments, and the scattering angle of the target-like fragments. The mass and charge distributions of the projectile-like fragments were generated as a function of energy loss, and characterized by their centroids, variances, and correlation coefficients. The neutron drift of the measured projectile-like products is mostly due to evaporative processes, while the charge drift is a result of a net transfer of protons from the projectile-like fragment to the target-like fragment. The result is a weak drift of the system towards mass asymmetry. The predictions of two nucleon exchange models are compared to the experimental results of the 672-MeV [sup 56]Fe + [sup 165]Ho reaction and other Fe-induced reactions. The fairly good agreement between the experimental and theoretical variances verifies the prevalence of a nucleon exchange mechanism in these reactions. The information from the coincidence measurement and two-body kinematics are used to reconstruct the pre-evaporation masses of the projectile-like and target-like fragments of the reaction. Statistical evaporation calculations are used to translate these masses into excitation energies of the primary fragments. The ratio of excitation energy stored in the projectile-Mm fragment decreases with increasing energy loss, in qualitative agreement with previous measurements; however, higher ratios are observed for the 672-MeV [sup 56]Fe on [sup 165]Ho system.

  14. New reaction tester accurate within 56 microseconds

    NASA Technical Reports Server (NTRS)

    Brown, H.

    1972-01-01

    Testing device measures simple and disjunctive reaction time of human subject to light stimuli. Tester consists of reaction key, logic card, panel mounted neon indicators, and interconnecting wiring. Device is used for determining reaction times of patients undergoing postoperative neurological therapy.

  15. Role of ν-induced reactions on lead and iron in neutrino detectors

    NASA Astrophysics Data System (ADS)

    Kolbe, E.; Langanke, K.

    2001-02-01

    We have calculated cross sections and branching ratios for neutrino-induced reactions on 208Pb and 56Fe for various supernova and accelerator-relevant neutrino spectra. This was motivated by the facts that lead and iron will be used on the one hand as target materials in future neutrino detectors and, on the other hand, have been and are still used as shielding materials in accelerator-based experiments. In particular we study the inclusive 56Fe(νe,e-)56Co and 208Pb(νe,e-)208Bi cross sections and calculate the neutron energy spectra following the decay of the daughter nuclei. These reactions give a potential background signal in the KARMEN and LSND experiment and are discussed as a detection scheme for supernova neutrinos in the proposed OMNIS and LAND detectors. We also study the neutron emission following the neutrino-induced neutral-current excitation of 56Fe and 208Pb.

  16. Iron-catalyzed asymmetric haloamination reactions.

    PubMed

    Cai, Yunfei; Liu, Xiaohua; Zhou, Pengfei; Kuang, Yulong; Lin, Lili; Feng, Xiaoming

    2013-09-21

    The first iron(III)/N,N'-dioxide-catalyzed asymmetric haloamination of 3-alkylidene- and 3-arylidene-indolin-2-ones was developed, affording the corresponding chiral oxindole derivatives bearing vicinal haloamine substituents with excellent results (up to 99% yield, 99% ee, >19 : 1 dr). This iron catalyst also exhibits perfect enantioselectivity for chalcone derivatives. The cooperative activation of the substrate and the reagent in concert guarantees the high stereoselectivity. PMID:23903004

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

    NASA Technical Reports Server (NTRS)

    Napier, Mary E.; Stair, Peter C.

    1992-01-01

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

  18. Gallic Acid, Ellagic Acid and Pyrogallol Reaction with Metallic Iron

    NASA Astrophysics Data System (ADS)

    Jaén, J. A.; González, L.; Vargas, A.; Olave, G.

    2003-06-01

    The reaction between gallic acid, ellagic acid and pyrogallol with metallic iron was studied using infrared and Mössbauer spectroscopy. Most hydrolysable tannins with interesting anticorrosive or inhibition properties are structurally related to these compounds, thus they may be used as models for the study of hydrolysable tannins and related polyphenols. The interaction was followed up to 3 months. Results indicated two different behaviors. At polyphenol concentrations higher than 1% iron converts to sparingly soluble and amorphous ferric (and ferrous) polyphenolate complexes. At lower concentrations (0.1%), the hydrolysis reactions are dominant, resulting in the formation of oxyhydroxides, which can be further reduced to compounds like magnetite by the polyphenols.

  19. Measurement of pion double charge exchange on carbon-13, carbon-14, magnesium-26, and iron-56

    SciTech Connect

    Seidl, P.A.

    1985-02-01

    Cross sections for the /sup 13,14/C,/sup 26/Mg,/sup 56/Fe(..pi../sup +/,..pi../sup -/)/sup 13,14/O,/sup 26/Si,/sup 56/Ni reactions were measured with the Energetic Pion Channel and Spectrometer at the Clinton P. Anderson Meson Physics Facility for 120 less than or equal to T/sub ..pi../ less than or equal to 292 MeV and 0 less than or equal to theta less than or equal to 50. The double isobaric analog states (DIAS) are of primary interest. In addition, cross sections for transitions to /sup 14/O(0/sup +/, 5.92 MeV), /sup 14/O(2/sup +/, 7.77 MeV), /sup 56/Ni(gs), /sup 13/O(gs), and /sup 13/O(4.21 MeV) are presented. The /sup 13/O(4.21 MeV) state is postulated to have J/sup ..pi../ = 1/2/sup -/. The data are compared to previously measured double-charge-exchange cross sections on other nuclei, and the systematics of double charge exchange on T greater than or equal to 1 target nuclei leading to the DIAS are studied. Near the ..delta../sub 33/ resonance, cross sections for the DIAS transitions are in disagreement with calculations in which the reaction is treated as sequential charge exchange through the free pion-nucleon amplitude, while for T/sub ..pi../ > 200 MeV the anomalous features of the 164 MeV data are not apparent. This is evidence for significant higher order contributions to the double-charge-exchange amplitude near the reasonable energy. Two theoretical approaches that include two nucleon processes are applied to the DIAS data. 64 references.

  20. Characterization of reaction products of iron and iron salts and aqueous plant extracts

    NASA Astrophysics Data System (ADS)

    Jaén, J. A.; García de Saldaña, E.; Hernández, C.

    1999-11-01

    The complexes formed in aqueous solution as a result of a reaction of iron and iron salts (Fe2+ and Fe3+) and some plant extracts were analyzed using Mössbauer spectroscopy and Fourier transform infrared. The extracts were obtained from Opuntia elatior mill., Acanthocereus pentagonus (L.) Britton, Mimosa tenuiflora, Caesalpinia coriaria (Jacq.) Willd., Bumbacopsis quinata (Jacq.) Dugand and Acacia mangium Willd., plants growing wildly in different zones of the Isthmus of Panama. Results suggest the formation of mono- and bis-type complexes, and in some cases, the occurrence of a redox reaction. The feasibility of application of the studied extracts as atmospheric corrosion inhibitors is discussed.

  1. Molecular Epoxidation Reactions Catalyzed by Rhenium, Molybdenum, and Iron Complexes.

    PubMed

    Kück, Jens W; Reich, Robert M; Kühn, Fritz E

    2016-02-01

    Epoxidations are of high relevance in many organic syntheses, both in industry and academia. In this personal account, the development of rhenium, molybdenum, and iron complexes in molecular epoxidation catalysis is presented. Methyltrioxorhenium (MTO) is the benchmark catalyst for these reactions, with a thoroughly investigated mechanism and reactivity profile. More recently, highly active molecular molybdenum and iron catalysts have emerged, challenging the extraordinary role of MTO in epoxidation catalysis with high turnover frequencies (TOFs). This development is highlighted in its use of cheaper, more readily available metals, and the challenges of using base metals in catalysis are discussed. These results show the promise that relatively cheap and abundant metals, such as molybdenum and iron, hold for the future of epoxidation catalysis. PMID:26776087

  2. Long-term effects of irradiation with iron-56 particles on the nigrostriatal dopamine system.

    PubMed

    Rice, Onarae V; Grande, Alicia V; Dehktyar, Natasha; Bruneus, Magalie; Robinson, John K; Gatley, Samuel J

    2009-04-01

    Exposure to heavy ions during a Mars mission might damage the brain, thus compromising mission success and the quality of life of returning astronauts. Several workers have suggested that the dopamine system is particularly sensitive to heavy ion radiation, but direct evidence for this notion is lacking. We examined measures of brain dopamine viability at times up to 15 months after acute exposure of rats to (56)Fe (1.2-2.4 Gy). No effects were seen in brain sections stained for tyrosine hydroxylase, the classical marker for dopamine cells and nerve terminals. Locomotion stimulated by cocaine, which directly activates the dopamine system, was reduced at 6 months but not at 12 months. Furthermore, in a visually cued lever-pressing test, reaction times, which are prolonged by dopamine system damage, were identical in irradiated and control animals. However, learning times were increased by irradiation. Our data suggest that the midbrain dopamine system is not especially sensitive to damage by (56)Fe particles at doses much higher than would be associated with travel to and from Mars. PMID:19259693

  3. (Phenoxyimidazolyl-salicylaldimine)iron complexes: synthesis, properties and iron catalysed ethylene reactions.

    PubMed

    Yankey, Margaret; Obuah, Collins; Guzei, Ilia A; Osei-Twum, Emmanuel; Hearne, Giovanni; Darkwa, James

    2014-10-01

    The reaction of 2-{[2-(1H-imidazol-4-yl)-ethylimino]-methyl}-phenol (L1), 2,4-di-tert-butyl-6-{[2-(1H-imidazol-4-yl)-ethylimino]-methyl}-phenol (L2) or 4-tert-butyl-2-{[2-(1H-imidazol-4-yl)-ethylimino]-methyl}-phenol (L3) with iron(ii) precursors produced either iron(ii) or iron(iii) complexes, depending on the nature of the anions in the iron(ii) precursor and the ligand. When the anion is chloride and the ligand L1, the product is [(L1)2Fe][FeCl4] (1), but when the anion is triflate (OTf(-)) and the ligand is L2, the product is [(L2)2Fe][OTf]2 (2). With iron(ii) halides and tert-butyl groups on the phenoxy ligands L2 and L3, the iron(iii) complexes [(L2)FeX2] {where X = Cl (3), Br (4) and I = (5)} and [(L3)FeCl2] (6) were formed. Complexes 1-6 were characterised by a combination of elemental analyses, IR spectroscopy and mass spectrometry; and in selected cases (3 and 4) by single crystal X-ray crystallography. The crystal structures of 3 and 4 indicated that the iron(ii) precursors oxidised to iron(iii) in forming complexes 3-6; an observation that was corroborated by the magnetic properties and the (57)Fe Mössbauer spectra of 3 and 4. The iron(iii) complexes 3-6 were used as pre-catalysts for the oligomerisation and polymerisation of ethylene. Products of these ethylene reactions depended on the solvent used. In toluene ethylene oligomerised mainly to 1-butene and was followed by the 1-butene alkylating the solvent to form butyl-toluenes via a Friedel-Crafts alkylation reaction. In chlorobenzene, ethylene oligomerised mainly to a mixture of C4-C12 alkenes. Interestingly small amounts of butyl-chlorobenzenes and hexyl-chlorobenzenes were also formed via a Friedel-Crafts alkylation with butenes and hexenes from the oligomerisation of ethylene. PMID:25111396

  4. Analysis of reaction modes of low energy reactions of deuterons with (56)Fe and (27)Al nuclei

    NASA Astrophysics Data System (ADS)

    Al-Quraishi, Saleh Ibrahim

    1997-11-01

    Measurements of deuteron-induced cross sections have been made for targets of 27Al and 56Fe. Reactions studied included elastic scattering, inelastic scattering, (d,p), (d,n) and (d,/alpha). No evidence was found for either (d,3H) or (d,3He) at the two bombarding energies (5 and 7 MeV) for either target. An optical model analysis was completed for the elastic scattering at both energies for each target. A particular effort was made to cover a large angular range (10o to 140o) with small errors. From the optical model analysis, reaction cross section values are derived. Spectra for (d,p), (d,n) and (d,/alpha) are compared with Hauser-Feshbach calculations. The (d,p) and (d,n) spectra show evidence for both stripping reactions and break-up reactions. Values for the fraction of the reaction cross section, which is due to compound nuclear reactions, are derived. Comparison with values of this parameter at higher energies derived using a different technique is presented. Some systematics of the break-up cross section are discussed.

  5. Neutron capture in s-wave resonances of iron-56, nickel-58, and nickel-60

    SciTech Connect

    Wisshak, K.; Fabbri, F.; Kappeler, F.; Reffo, G.

    1984-02-01

    The neutron capture widths of s-wave resonances in /sup 56/Fe (27.7 keV), /sup 58/Ni (15.4 keV), and /sup 60/Ni (12.5 keV) have been determined using a setup completely different from previous experiments. A pulsed 3-MV Van de Graaff accelerator and a kinematically collimated neutron beam, produced via the /sup 7/Li(p,n) reaction, were used in the experiments. Capture gamma rays were observed by three Moxon-Rae detectors with graphite, bismuth-graphite, and bismuth converters, respectively. The samples were positioned at a neutron flight path of only 9 cm. Thus, events due to capture of resonance-scattered neutrons in the detectors or in surrounding materials are completely discriminated by their additional time of flight. The high neutron flux at the sample position allowed the use of very thin samples (0.15 to 0.45 mm), avoiding large multiple scattering corrections. The data obtained with the individual detectors were corrected for the efficiency of the respective converter materials. For that purpose, detailed theoretical calculations of the capture gamma-ray spectra of the measured isotopes and of gold, which was used as a standard, were performed. The final results are GAMMA /SUB lg/ (27.7 keV, /sup 56/Fe) = 1.06 + or - 0.05 eV; GAMMA..gamma..(15.4 keV, /sup 58/Ni) = 1.53 + or - 0.10 eV; and GAMMA..gamma..(12.5 keV, /sup 60/Ni) = 2.92 + or - 0.19 eV. The accuracy obtained with the present experimental method represents an improvement by a factor 3 to 6 compared to previous experiments. The investigated s-wave resonances contribute 10 to 40% to the total capture rate of the respective isotopes in a typical fast reactor.

  6. First Step in the Reaction of Zerovalent Iron with Water.

    PubMed

    Karlický, František; Otyepka, Michal

    2011-09-13

    Here we present a comprehensive quantum chemical study of the simplest model system for the reactions of nanoscale zerovalent iron, i.e., the gas-phase reaction of an iron atom with water, to identify a theoretical method that provides reasonably accurate geometries and thermochemical data for selected iron compounds along the reaction path (Fe, FeO, HFeOH, Fe(OH)2). The energies of selected stationary points on the ground electronic potential energy surface were systematically studied using HF and post-HF methods (MP2, MP3, MP4, CCSD, CCSD(T), CASSCF, MRCI) and selected DFT functionals (B3LYP, B97-1, BPW91, M06, M06-HF, M06-L, M06-2X and MPW1K) using various basis sets up to the complete basis set. Scalar relativistic effects were modeled using the Douglas-Kroll-Hess Hamiltonian up to the fourth order, and the effects of valence plus outer-core electronic correlation were also evaluated. The calculations showed that (i) dynamic electron correlation is crucial for accurate modeling of the reactions in question, (ii) the PES around the stationary points along the reaction path is rather flat, (iii) the single-point energies calculated at the CCSD(T)/CBS level are in reasonably good agreement with experimental measurements, (iv) it is difficult to interpret DFT energies in the absence of benchmarking against experimental data or results obtained at a level of theory that is known to accurately reproduce experimental results, (v) relativistic effects are relatively modest in this system but should be included if chemical accuracy is desired, and (vi) careful analysis of the multireference character of the system and potential spin contamination is important. The CCSD(T)-3s3p-DKH2/CBS method can be considered the gold standard for this reaction because calculations at this level are in good agreement with experimental atomic excitation energies and thermochemical data. The gas-phase activation energy of the reaction between Fe and H2O is 23.6 kcal/mol including the

  7. Level density and mechanism of deuteron-induced reactions on 54,58,56Fe

    NASA Astrophysics Data System (ADS)

    Ramirez, A. P. D.; Voinov, A. V.; Grimes, S. M.; Byun, Y.; Brune, C. R.; Massey, T. N.; Akhtar, S.; Dhakal, S.; Parker, C. E.

    2015-07-01

    Deuteron elastic cross sections, as well as neutron, proton, and α -particle emission spectra, from d + 54,58,56Fe reactions have been measured with deuteron beam energies of 5, 7, and 9 MeV. Optical model parameters have been tested against our experimental data. The fraction of total reaction cross section responsible for the formation of compound nuclei has been deduced from the angular distributions. The degree of discrepancy between calculated and experimental compound cross sections was found to increase with increasing neutron number. The nuclear level densities of the residual nuclei 57Co, 55Co, 57Fe, 55Fe, 52Mn, 54Mn have been deduced from the compound double differential cross sections. The Gilbert-Cameron model with Iljinov parameter systematics [A. S. Iljinov and M. V. Mebel, Nucl. Phys. A 543, 517 (1992)], 10.1016/0375-9474(92)90278-R was found to have a good agreement with our results.

  8. Level density and mechanism of deuteron-induced reactions on Fe54,56,58

    DOE PAGESBeta

    Ramirez, A. P. D.; Voinov, A. V.; Grimes, S. M.; Byun, Y.; Brune, C. R.; Massey, T. N.; Akhtar, S.; Dhakal, S.; Parker, C. E.

    2015-07-06

    Here, deuteron elastic cross sections, as well as neutron, proton, and α-particle emission spectra, from d+54,56,58Fe reactions have been measured with deuteron beam energies of 5, 7, and 9 MeV. Optical model parameters have been tested against our experimental data. The fraction of total reaction cross section responsible for the formation of compound nuclei has been deduced from the angular distributions. The degree of discrepancy between calculated and experimental compound cross sections was found to increase with increasing neutron number. The nuclear level densities of the residual nuclei 55Co, 57Co, 55Fe, 57Fe, 52Mn, and 54Mn have been deduced from themore » compound double differential cross sections. The Gilbert-Cameron model with Iljinov parameter systematics [A. S. Iljinov and M. V. Mebel, Nucl. Phys. A 543, 517 (1992)] was found to have a good agreement with our results.« less

  9. Iron Cross Reaction Control Flight Simulator - test in hangar

    NASA Technical Reports Server (NTRS)

    1956-01-01

    In the mid-1950s -- after the X-1 had exceeded the speed of sound, the D-558-II had doubled that speed, and the X-2 had flown to a speed of Mach 3.2 (3.2 times the speed of sound) -- the problem of maintaining control of a vehicle at the low dynamic pressures found at high altitudes became real. As the development of larger rocket engines than those used in the X-1, X-2, and D-558-II became a virtual certainty, travel to near-orbital and orbital velocities lay on the horizon. It became natural to investigate alternative means to control an aircraft for low dynamic pressures where aerodynamic controls would be inadequate (even absent for orbital flight outside the atmosphere). Consequently, the High-Speed Flight Station (HSFS--predecessor of the NASA Dryden Flight Research Center) began pioneering work on simulating and then flying with reaction controls in the last years of the National Advisory Committee for Aeronautics (NACA) and the first years of its successor, the National Aeronautics and Space Administration (NASA). The HSFS began a two-phase study. One phase involved a fixed-base effort with an analog computer to solve the equations of motion needed for simulation; the other used a mechanical simulator in which the 'pilot' actually experienced the motions produced by the reaction-control jets. The 'pilot' operated the simulator through a single control stick that -- unusually for the time -- controlled three axes with one device. The stick controlled pitch by fore and aft movements, roll by lateral movements, and yaw through thumb movements. The simulator, shown in the video clip, was known as the 'Iron Cross.' It simulated the X-1B, which was equipped with reaction controls. Although the X-1B flew three missions with reaction controls, it developed fatigue cracks in a propellant tank and had to be retired from flight status. Subsequently, an F-104 equipped with reaction controls flew at relatively low dynamic pressures. Between the simulation studies with

  10. Results demonstrating techniques for enhancing electrochemical reactions involving iron oxide in slags and C in liquid iron

    NASA Astrophysics Data System (ADS)

    Pal, Uday B.; MacDonald, Scott A.; Woolley, David W.; Powell, Adam C.

    2005-04-01

    Two techniques are described for the enhancement of the kinetics of reduction of iron oxide from slags by carbon in molten iron. Laboratory experiments have shown that the rate of iron oxide reduction by carbon-saturated iron can be increased by 5 to 10 times when the reaction is carried out under a reduced-pressure atmosphere. This effect is thought to be the result of the increased volumetric gas evolution through the slag layer and the associated increase in slag stirring. A model is presented, which relates the mass-transfer coefficient for ferrous ions in the slag to its stirring that is controlled by varying the ambient pressure. Additional laboratory experiments examined the electrochemical nature of iron oxide reduction from slag by carbon in liquid iron. Results indicate that the reduction of iron oxide from slag is increased in the presence of an applied electric field. The external circuit allows for the separation of the half-cell reactions associated with iron oxide reduction and decarburization and increases the reaction area available for the individual reactions. These results have significant implications for several important slag metal reactions, which occur during ironmaking and steelmaking operations.

  11. Iron oxide mineral-water interface reactions studied by AFM

    SciTech Connect

    Hawley, M.E.; Rogers, P.S.Z.

    1994-07-01

    Natural iron mineral surfaces have been examined in air by atomic force (AFM) and scanning tunneling (STM) microscopies. A number of different surface features were found to be characteristic of the native surface. Even surfaces freshly exposed by crushing larger crystals were found to have a pebbly surface texture caused by the presence of thin coatings of what might be surface precipitates. This finding is interpreted as evidence for previous exposure to water, probably through an extensive network of microfractures. Surface reactions on the goethite crystals were studied by AFM at size resolutions ranging from microns to atomic resolution before, during, and after reaction with distilled water and 0.lN HCl. Immediate and extensive surface reconfiguration occurred on contact with water. In one case, after equilibration with water for 3 days, surface reprecipitation, etching and pitting were observed. Atomic resolution images taken under water were found to be disordered. The result of surface reaction was generally to increase the surface area substantially through the extension of surface platelet arrays, present prior to reaction. This work is being done in support of the site characterization project at Yucca Mountain.

  12. Closed system Fischer-Tropsch synthesis over meteoritic iron, iron ore and nickel-iron alloy. [deuterium-carbon monoxide reaction catalysis

    NASA Technical Reports Server (NTRS)

    Nooner, D. W.; Gibert, J. M.; Gelpi, E.; Oro, J.

    1976-01-01

    Experiments were performed in which meteoritic iron, iron ore and nickel-iron alloy were used to catalyze (in Fischer-Tropsch synthesis) the reaction of deuterium and carbon monoxide in a closed vessel. Normal alkanes and alkenes and their monomethyl substituted isomers and aromatic hydrocarbons were synthesized. Iron oxide and oxidized-reduced Canyon Diablo used as Fischer-Tropsch catalysts were found to produce aromatic hydrocarbons in distributions having many of the features of those observed in carbonaceous chondrites, but only at temperatures and reaction times well above 300 C and 6-8 h.

  13. Hypersensitivity reactions to intravenous iron: guidance for risk minimization and management

    PubMed Central

    Rampton, David; Folkersen, Joergen; Fishbane, Steven; Hedenus, Michael; Howaldt, Stefanie; Locatelli, Francesco; Patni, Shalini; Szebeni, Janos; Weiss, Guenter

    2014-01-01

    Intravenous iron is widely used for the treatment of iron deficiency anemia when oral iron is inappropriate, ineffective or poorly tolerated. Acute hypersensitivity reactions during iron infusions are very rare but can be life-threatening. This paper reviews their frequency, pathogenesis and risk factors, and provides recommendations about their management and prevention. Complement activation-related pseudo-allergy triggered by iron nanoparticles is probably a more frequent pathogenetic mechanism in acute reactions to current formulations of intravenous iron than is an immunological IgE-mediated response. Major risk factors for hypersensitivity reactions include a previous reaction to an iron infusion, a fast iron infusion rate, multiple drug allergies, severe atopy, and possibly systemic inflammatory diseases. Early pregnancy is a contraindication to iron infusions, while old age and serious co-morbidity may worsen the impact of acute reactions if they occur. Management of iron infusions requires meticulous observation, and, in the event of an adverse reaction, prompt recognition and severity-related interventions by well-trained medical and nursing staff. PMID:25420283

  14. Cross sections of the 56Fe(n ,α ) 53Cr and 54Fe(n ,α ) 51Cr reactions in the MeV region

    NASA Astrophysics Data System (ADS)

    Wang, Zhimin; Fan, Xiao; Zhang, Luyu; Bai, Huaiyong; Chen, Jinxiang; Zhang, Guohui; Gledenov, Yu. M.; Sedysheva, M. V.; Krupa, L.; Khuukhenkhuu, G.

    2015-10-01

    Cross sections of the 56Fe(n ,α ) 53Cr and 54Fe(n ,α )51Cr reactions were measured at En=5.5 and 6.5 MeV and En=4.0 ,4.5 ,5.5 ,and 6.5 MeV , respectively, using a double-section gridded ionization chamber as the α -particle detector. Natural iron and enriched 56Fe and 54Fe foil samples were prepared. A deuterium gas target was used to produce monoenergetic neutrons through the 2H(d ,n )3He reaction. Two rounds of experiments were performed at the 4.5-MV Van de Graaff Accelerator of Peking University. The foreground and background were measured in separate runs. The neutron flux was monitored by a B F3 long counter, and the cross sections of the 238U(n ,f ) reaction were used as the standard. Present results are compared with those of the talys-1.6 code calculations, existing measurements, and evaluations.

  15. Relative effectiveness of HZE iron-56 particles for the induction of cytogenetic damage in vivo

    NASA Technical Reports Server (NTRS)

    Brooks, A.; Bao, S.; Rithidech, K.; Couch, L. A.; Braby, L. A.

    2001-01-01

    One of the risks of prolonged manned space flight is the exposure of astronauts to radiation from galactic cosmic rays, which contain heavy ions such as (56)Fe. To study the effects of such exposures, experiments were conducted at the Brookhaven National Laboratory by exposing Wistar rats to high-mass, high-Z, high-energy (HZE) particles using the Alternating Gradient Synchrotron (AGS). The biological effectiveness of (56)Fe ions (1000 MeV/nucleon) relative to low-LET gamma rays and high-LET alpha particles for the induction of chromosome damage and micronuclei was determined. The mitotic index and the frequency of chromosome aberrations were evaluated in bone marrow cells, and the frequency of micronuclei was measured in cells isolated from the trachea and the deep lung. A marked delay in the entry of cells into mitosis was induced in the bone marrow cells that decreased as a function of time after the exposure. The frequencies of chromatid aberrations and micronuclei increased as linear functions of dose. The frequency of chromosome aberrations induced by HZE particles was about 3.2 times higher than that observed after exposure to (60)Co gamma rays. The frequency of micronuclei in rat lung fibroblasts, lung epithelial cells, and tracheal epithelial cells increased linearly, with slopes of 7 x 10(-4), 12 x 10(-4), and 11 x 10(-4) micronuclei/binucleated cell cGy(-1), respectively. When genetic damage induced by radiation from (56)Fe ions was compared to that from exposure to (60)Co gamma rays, (56)Fe-ion radiation was between 0.9 and 3.3 times more effective than (60)Co gamma rays. However, the HZE-particle exposures were only 10-20% as effective as radon in producing micronuclei in either deep lung or tracheal epithelial cells. Using microdosimetric techniques, we estimated that 32 cells were hit by delta rays for each cell that was traversed by the primary HZE (56)Fe particle. These calculations and the observed low relative effectiveness of the exposure to HZE

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

    ERIC Educational Resources Information Center

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

    2008-01-01

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

  17. The fragmentation of 510 MeV/nucleon iron-56 in polyethylene. I. Fragment fluence spectra

    NASA Technical Reports Server (NTRS)

    Zeitlin, C.; Miller, J.; Heilbronn, L.; Frankel, K.; Gong, W.; Schimmerling, W.

    1996-01-01

    The fragmentation of 510 MeV/nucleon iron ions in several thicknesses of polyethylene has been measured. Non-interacting primary beam particles and fragments have been identified and their LETs calculated by measuring ionization energy loss in a stack of silicon detectors. Fluences, normalized to the incident beam intensity and corrected for detector effects, are presented for each fragment charge and target. Histograms of fluence as a function of LET are also presented. Some implications of these data for measurements of the biological effects of heavy ions are discussed.

  18. Iron Mineral Effects on Ketone Reactions in Hydrothermal Fluids

    NASA Astrophysics Data System (ADS)

    Yang, Z.; Gould, I. R.; Shock, E.

    2011-12-01

    Interactions in hydrothermal environments suggest that minerals participate in and alter organic compounds transformations at high temperatures and pressures [1]. Our previous experimental studies of a model ketone (dibenzyl ketone, DBK) in aqueous media under hydrothermal conditions (700 bars, 300 °C) indicate low conversion but multiple reaction pathways yielding diverse products. In the absence of minerals, DBK not only reversibly interconverts into 1,3-diphenyl-2-propanol, 1,3-diphenylpropene and 1,3-diphenylpropane along a reduction pathway, but also yields products including toluene, bibenzyl, stilbene and conjugated, dehydrogenated three- and four-ring coupling products from carbon-carbon (C-C) and carbon-hydrogen (C-H) bond-breaking pathways. Experiments involving oxide minerals that are not sensitive to redox process, such as quartz and corundum, show no effect when compared with H2O alone in changing DBK hydrothermal reactions and product distributions. In the presence of iron bearing minerals, however, we observe that the overall reaction conversion of DBK increases by orders of magnitude, and that reaction pathways are controlled or favored differently if hematite (Fe2O3), magnetite (Fe3O4) or ferrous sulfide (FeS) is present. As an example, with the same mineral surface area, Fe2O3 expedites DBK conversion from 6.4% (H2O only) to 26.4% after 168 hours, while Fe3O4 increases conversion up to 46.8%. Although more products are formed with introduction of iron oxide minerals, the major products are identical to those found in H2O alone, such as toluene, bibenzyl and a few large coupling products from the bond-breaking pathways. Hydrothermal experiments using a synthesized asymmetrical p-methyl-DBK under the same conditions conducted with Fe2O3 and Fe3O4 are consistent with those for DBK, showing higher conversion than in H2O, and more bond-breaking products like toluene, p-xylene, and three kinds of bibenzyls. This suggests that both Fe2O3 and Fe3O4

  19. Evidence for Localization of Reaction Upon Reduction of Carbon Tetrachloride by Granular Iron

    SciTech Connect

    Gaspar, Daniel J.; Lea, Alan S.; Engelhard, Mark H.; Baer, Donald R.; Miehr, R.; Tratnyek, Paul G.

    2002-10-01

    The distribution of reaction sites on iron particles exposed to water containing carbon tetrachloride has been examined by measuring the locations of reaction products. The uniformity or localization of reaction sites has implications for understanding and modeling the reduction of environmental contaminants by iron in ground water systems. Granular iron surfaces similar to those being used for environmental remediation applications were studied using surfaces analysis techniques to develop an understanding of the physical and chemical structure of the surface and oxide films. Scanning Auger microscopy and imaging time-of-flight secondary ion mass spectrometry revealed that granular iron exposed to carbon tetrachloride-saturated water exhibits chloride-enriched regions occurred at pits rather than on the passive oxide film on the metal. Understanding the nature of the local solute reduction sites will play an important role in modeling the kinetics of reaction at passive iron oxide films in environmental systems.

  20. Reactions and reaction intermediates on iron surfaces. III. Reactions of aldehydes and ketones on Fe(100)

    SciTech Connect

    Benziger, J.B.; Madix, R.J.

    1982-01-01

    The reactions of formaldehyde, acetaldehyde, and acetone on Fe(100) were studied by temperature-programmed reaction spectroscopy and X-ray photoelectron spectroscopy (XPS). Formaldehyde and acetaldehyde were observed to react with adsorbed hydrogen to form adsorbed alkoxy intermediates. These reactions occurred at low temperature (ca. 200 K). In the absence of adsorbed hydrogen, formaldehyde and acetaldehyde decomposed to adsorbed CO and hydrogen. This reaction was also observed at low temperatures. On an initially clean surface the aldehydes first decomposed, forming adsorbed hydrogen which subsequently reacted with adsorbed aldehyde to form an alkoxy intermediate. The alkoxy intermediates reacted to form CO and H/sub 2/ primarily, with lesser amounts of alcohol, aldehyde, and hydrocarbon products. Acetone reacted differently from the aldehydes and did not appear to form an alkoxy intermediate. XPS results suggested that acetone and acetaldehyde did not adsorb in their keto form on the surface and it is suggested that they adsorbed as enol intermediates. The distinct reaction behavior of acetone may be due to these enol intermediates.

  1. Reaction mechanisms involved in reduction of halogenated hydrocarbons using sulfated iron

    SciTech Connect

    Hassan, S.M.; Cipollone, M.G.; Wolfe, N.L.

    1995-12-01

    Experiments were carried out to investigate the mechanisms and pathways involved in the reduction of halogenated hydrocarbons represented by trichloroethylene (TCE) and tetrachloroethylene (PCE) with sulfated iron aqueous media. Results suggested that iron sulfide acted as the dehalogenation center. Zero-valent iron acted as a generator for molecular hydrogen through its reaction with water. Results of experiments in which iron sulfide was replaced by other transition metal sulfides and experiments in which zero-valent iron was replaced by other sources of molecular hydrogen will be reported. The main reduction product of chloroethylene derivatives was ethyne which under the catalytic reaction of zero-valent iron was reduced further to ethene and finally to ethane. Intermediate products were identified using GC-MS. Mechanisms and pathways will be presented.

  2. Spatial learning and memory deficits induced by exposure to iron-56-particle radiation

    NASA Technical Reports Server (NTRS)

    Shukitt-Hale, B.; Casadesus, G.; McEwen, J. J.; Rabin, B. M.; Joseph, J. A.

    2000-01-01

    It has previously been shown that exposing rats to particles of high energy and charge (HZE) disrupts the functioning of the dopaminergic system and behaviors mediated by this system, such as motor performance and an amphetamine-induced conditioned taste aversion; these adverse behavioral and neuronal effects are similar to those seen in aged animals. Because cognition declines with age, spatial learning and memory were assessed in the Morris water maze 1 month after whole-body irradiation with 1.5 Gy of 1 GeV/nucleon high-energy (56)Fe particles, to test the cognitive behavioral consequences of radiation exposure. Irradiated rats demonstrated cognitive impairment compared to the control group as seen in their increased latencies to find the hidden platform, particularly on the reversal day when the platform was moved to the opposite quadrant. Also, the irradiated group used nonspatial strategies during the probe trials (swim with no platform), i.e. less time spent in the platform quadrant, fewer crossings of and less time spent in the previous platform location, and longer latencies to the previous platform location. These findings are similar to those seen in aged rats, suggesting that an increased release of reactive oxygen species may be responsible for the induction of radiation- and age-related cognitive deficits. If these decrements in behavior also occur in humans, they may impair the ability of astronauts to perform critical tasks during long-term space travel beyond the magnetosphere.

  3. The Reaction between Iron(II) Iodide and Potassium Dichromate(VI) in Acidified Aqueous Solution

    ERIC Educational Resources Information Center

    Talbot, Christopher

    2013-01-01

    This "Science note" teaching lesson explores the possible reaction between the ions in a reaction mixture consisting of iron(II) iodide and potassium dichromate(VI) in acidified aqueous solution. The electrode potentials will be used to deduce any spontaneous reactions under standard thermodynamic conditions (298 K, 1 bar (approximately…

  4. Structural studies of iron and manganese in photosynthetic reaction centers

    SciTech Connect

    McDermott, A.E.

    1987-11-01

    Electron paramagnetic resonance (EPR) and x-ray absorption spectroscopy (XAS) were used to characterize components involved in the light reactions of photosynthetic reaction centers from spinach and a thermophilic cyanobacterium, Synechococcus sp.: center X, the low electron potential acceptor in Photosystem I (PS I) and the Mn complex involved in water oxidation and oxygen evolution. The dependence of its EPR amplitude on microwave power and temperature indicate an Orbach spin relaxation mechanism involving an excited state at 40 cm/sup -1/. This low energy contributes to its unusually anisotropic g-tensor. XAS of iron in PS I preparations containing ferredoxins A, B and X are consistent with a model with (4Fe-4S) ferredoxins, which are presumably centers A and B and (2Fe-2S) ferredoxins, which would be X. Illumination of dark-adapted Synechococcus PS II samples at 220 to 240 K results in the formation of the multiline EPR signal previously assigned as a Mn S/sub 2/ species, and g = 1.8 and 1.9 signals of Fe/sup 2 +/ Q/sub A//sup -/. In contrast to spinach, illumination at 110 to 160 K produces only a new EPR signal at g = 1.6 which we assign to another configuration of Fe/sup 2+ - Q/sup -/. Following illumination of a S/sub 1/ sample at 140 K or 215 K, the Mn x-ray absorption edge inflection energy changes from 6550 eV to 6551 eV, indicating an oxidation of Mn, and average valences greater than Mn(II). Concomitant changes in the shape of the pre-edge spectrum indicate oxidation of Mn(III) to Mn(IV). The Mn EXAFS spectrum of PS II from Synechococcus is similar in the S/sub 1/ and S/sub 2/ states, indicating O or N ligands at 1.75 +- 0.05 A, transition metal neighbor(s) at 2.75 +- 0.05 A, and N and O ligands at 2.2 A with heterogeneous bond lengths; these data demonstrate the presence of a di-..mu..-oxo bridged Mn structure. 202 refs., 40 figs., 7 tabs.

  5. Safe administration of iron sucrose in a patient with a previous hypersensitivity reaction to ferric gluconate.

    PubMed

    Sane, Radhika; Baribeault, David; Rosenberg, Carol L

    2007-04-01

    A 67-year-old woman with iron deficiency anemia required parenteral iron therapy and was treated with intravenous ferric gluconate. She tolerated the first dose, but after the second dose, she developed a tingling feeling all over her body, along with swelling in her hands and feet, and a rash with hives over most of her body. It was thought that she had likely experienced a hypersensitivity reaction to ferric gluconate. The decision was made to continue therapy; however, two modifications were made. The patient was given dexamethasone, diphenhydramine, and ibuprofen 1 hour before administering the third dose, and the infusion time was prolonged by 1 hour. Approximately 45 minutes after the infusion was completed, the patient developed hives on her arms and legs. At the patient's next clinic visit, it was decided that continuation of parenteral iron repletion was necessary, and the decision was made to attempt a challenge with iron sucrose. The patient was given dexamethasone 8 mg to be taken the night before and the morning of treatment. She successfully completed the iron repletion therapy with iron sucrose. Three parenteral iron products are available in the United States: iron dextran, sodium ferric gluconate complex, and iron sucrose. Iron dextran, the oldest of these products, carries the highest risk for hypersensitivity reactions. Available data suggest that either iron sucrose or ferric gluconate can be safely administered to patients with known hypersensitivity to iron dextran. Our patient's experience implies that it may be possible to safely administer iron sucrose to a patient with hypersensitivity to ferric gluconate. This finding has clinical implications and warrants confirmation in a larger population. PMID:17381390

  6. Structural and magnetic properties of iron nanowires and iron nanoparticles fabricated through a reduction reaction.

    PubMed

    Krajewski, Marcin; Lin, Wei Syuan; Lin, Hong Ming; Brzozka, Katarzyna; Lewinska, Sabina; Nedelko, Natalia; Slawska-Waniewska, Anna; Borysiuk, Jolanta; Wasik, Dariusz

    2015-01-01

    The main goal of this work is to study the structural and magnetic properties of iron nanowires and iron nanoparticles, which have been fabricated in almost the same processes. The only difference in the synthesis is an application of an external magnetic field in order to form the iron nanowires. Both nanomaterials have been examined by means of transmission electron microscopy, energy dispersive X-ray spectrometry, X-ray diffractometry and Mössbauer spectrometry to determine their structures. Structural investigations confirm that obtained iron nanowires as well as nanoparticles reveal core-shell structures and they are composed of crystalline iron cores that are covered by amorphous or highly defected phases of iron and iron oxides. Magnetic properties have been measured using a vibrating sample magnetometer. The obtained values of coercivity, remanent magnetization, saturation magnetization as well as Curie temperature differ for both studied nanostructures. Higher values of magnetizations are observed for iron nanowires. At the same time, coercivity and Curie temperature are higher for iron nanoparticles. PMID:26425415

  7. Structural and magnetic properties of iron nanowires and iron nanoparticles fabricated through a reduction reaction

    PubMed Central

    Lin, Wei Syuan; Lin, Hong Ming; Brzozka, Katarzyna; Lewinska, Sabina; Nedelko, Natalia; Slawska-Waniewska, Anna; Borysiuk, Jolanta; Wasik, Dariusz

    2015-01-01

    Summary The main goal of this work is to study the structural and magnetic properties of iron nanowires and iron nanoparticles, which have been fabricated in almost the same processes. The only difference in the synthesis is an application of an external magnetic field in order to form the iron nanowires. Both nanomaterials have been examined by means of transmission electron microscopy, energy dispersive X-ray spectrometry, X-ray diffractometry and Mössbauer spectrometry to determine their structures. Structural investigations confirm that obtained iron nanowires as well as nanoparticles reveal core–shell structures and they are composed of crystalline iron cores that are covered by amorphous or highly defected phases of iron and iron oxides. Magnetic properties have been measured using a vibrating sample magnetometer. The obtained values of coercivity, remanent magnetization, saturation magnetization as well as Curie temperature differ for both studied nanostructures. Higher values of magnetizations are observed for iron nanowires. At the same time, coercivity and Curie temperature are higher for iron nanoparticles. PMID:26425415

  8. [CURRENT HISTOCHEMICAL METHODS OF TISSUE IRON DEMONSTRATION BASED ON PERLS' REACTION].

    PubMed

    Grigoriyev, I P; Kolos, Ye A; Sukhorukova, Ye G; Korzhevskiy, D E

    2016-01-01

    The article presents the information on the modern modifications of Perls' reaction including diaminobenzidine enhancement according to R. Meguro (for various tissues). M.A. Smith (for nervous tissue), S.M. Levine (for detection of iron in oligodendrocytes and myelinated nervous fibers), and our own modification for visualization of the nucleolar iron. The analysis is performed of the advantages and disadvantages of these modifications of histochemical demonstration of iron. It is shown that the use of new methodological approaches significantly increases the sensitivity of Perls' reaction. Control procedures allow to to eliminate the possibility of artifacts. PMID:27487670

  9. Synthesis of S-(-)-5,6-Dihydrocanthin-4-ones via a Triple Cooperative Catalysis-Mediated Domino Reaction.

    PubMed

    Dighe, Shashikant U; Mahar, Rohit; Shukla, Sanjeev K; Kant, Ruchir; Srivastava, Kumkum; Batra, Sanjay

    2016-06-01

    An enantioselective synthesis of S-(-)-5,6-dihydrocanthin-4-ones via a triple cooperative catalysis-mediated domino reaction having a broad substrate scope is reported. The reaction between substituted 1-formyl-9H-β-carbolines and terminal alkynes in the presence of catalytic amounts of Jorgensen-Hayashi catalyst, copper iodide, and Hunig base proceeded via a multicascade route, affording the title compounds in good yields and excellent ees with interesting mechanistic features. These compounds were assessed for in vitro antiplasmodial activity against P. falciparum strains. Additionally, 5,6-dihydrocanthin-4-ones are demonstrated to be a versatile precursor to different fused β-carboline derivatives via simple synthetic transformations. PMID:27159615

  10. Detailed characterization of the 1087 MeV/nucleon iron-56 beam used for radiobiology at the alternating gradient synchrotron

    NASA Technical Reports Server (NTRS)

    Zeitlin, C.; Heilbronn, L.; Miller, J.

    1998-01-01

    We report beam characterization and dosimetric measurements made using a 56Fe beam extracted from the Brookhaven National Laboratory Alternating Gradient Synchrotron (AGS) with a kinetic energy of 1087 MeV/nucleon. The measurements reveal that the depth-dose distribution of this beam differs significantly from that obtained with a 600 MeV/nucleon iron beam used in several earlier radiobiology experiments at the Lawrence Berkeley National Laboratory's BEVALAC. We present detailed measurements of beam parameters relevant for radiobiology, including track- and dose-averaged linear energy transfer (LET), fragment composition and LET spectra measured behind sample holders used in irradiations of biological samples. We also report measurements of fluence behind three depths (1.94, 4.68 and 9.35 g cm(-2)) of polyethylene targets with the 1087 MeV/nucleon beam, and behind 1.94 g cm(-2) of polyethylene with a 610 MeV/nucleon beam delivered by the AGS. These results are compared to earlier measurements with the 600 MeV/nucleon beam at the BEVALAC.

  11. Reaction of iron and steel slags with refractories

    SciTech Connect

    Banerjee, S.; Anderson, M.W.

    1993-04-01

    Slag corrosion and erosion has been a major wear factor for refractories wear in contact with molten iron and steel. In blast furnace ironmaking, the slag/iron interface plays a more important role than does the slag/refractory interface. On the other hand in steelmaking, the slag in the ladles and tundish predominantly affect refractory wear. This paper presents the results of a detailed microstructural evaluation of (a) slag and slag/iron interactions with A1{sub 2}O{sub 3}-SiC-C refractories for ironmaking in blast furnaces, (b) basic oxygen furnace and ladle slag interactions with alumina spinel refractories for steelmaking, and (c) slag interactions with working refractory lining for continuous casting tundishes. Results will also be presented on refractory wear/failure due to simultaneous corrosion and penetration by the slag.

  12. Use of Moessbauer spectroscopy to study reaction products of polyphenols and iron compounds

    SciTech Connect

    Gust, J. ); Suwalski, J. )

    1994-05-01

    Moessbauer spectroscopy was used to study parameters of the reaction products of iron compounds (Fe[sup III]) and polyphenols with hydroxyl (OH) groups in ortho positions. Polyphenols used in the reaction were catechol, pyrogallol, gallic acid, and oak tannin. The Fe-containing compounds were hydrated ferric sulfate (Fe[sub 2][SO[sub 4

  13. Synthesis of multisubstituted pyrroles from doubly activated cyclopropanes using an iron-mediated oxidation domino reaction.

    PubMed

    Zhang, Zhiguo; Zhang, Wei; Li, Junlong; Liu, Qingfeng; Liu, Tongxin; Zhang, Guisheng

    2014-11-21

    An alternative route has been developed for the construction of multisubstituted pyrrole derivatives from readily available, doubly activated cyclopropanes and anilines using an iron-mediated oxidation domino reaction (i.e., sequential ring-opening, cyclization, and dehydrogenation reactions). This reaction uses readily available reactants and is tolerant of a broad range of substrates, with the desired products being formed in good to excellent yields. PMID:25330125

  14. Supernova neutrino induced inclusive reactions on {sup 56}Fe in terrestrial detectors

    SciTech Connect

    Athar, M. Sajjad; Ahmad, Shakeb; Singh, S.K.

    2005-04-01

    The calculations for the neutrino absorption cross sections for supernova neutrinos in {sup 56}Fe have been done in the local density approximation (LDA) taking into account Pauli blocking and Fermi motion effects. The renormalization of weak transition strengths in the nuclear medium and the effect of Coulomb distortion of the final lepton are taken into account. The numerical results for the cross sections averaged over the Michel spectrum of neutrinos and various supernova neutrino spectra are presented and compared with other theoretical results.

  15. Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction

    PubMed Central

    2015-01-01

    The iron(IV) nitrido complex PhB(MesIm)3Fe≡N reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide complex PhB(MesIm)3Fe(η5-C4H4N) in high yield. The mechanism of product formation is proposed to involve sequential [4 + 1] cycloaddition and retro Diels–Alder reactions. Surprisingly, reaction with 1,4-cyclohexadiene yields the same iron-containing product, albeit in substantially lower yield. The proposed reaction mechanism, supported by electronic structure calculations, involves hydrogen-atom abstraction from 1,4-cyclohexadiene to provide the cyclohexadienyl radical. This radical is an intermediate in substrate isomerization to 1,3-cyclohexadiene, leading to formation of the pyrrolide product. PMID:25068927

  16. The Reaction Specificity of Nanoparticles in Solution: Application to the Reaction of Nanoparticulate Iron and Iron-Bimetallic Compounds with Chlorinated Hydrocarbons and Oxyanions

    SciTech Connect

    2005-06-01

    The prospect for better remediation technologies using nanoparticles of iron, iron oxides, and iron with catalytic metals (i.e., bimetallics) has potentially transformative implications for environmental management of DOE sites across the country. Of particular interest is the potential to avoid undesirable products from the degradation of chlorinated solvents by taking advantage of the potential selectivity of nanoparticles to produce environmentally benign products from CCl{sub 4}. Chlorinated solvents are the most frequently reported subsurface contaminants across the whole DOE complex, and carbon tetrachloride (CCl{sub 4}) is the chlorinated solvent that is of greatest concern at Hanford (U. S. Department Energy 2001). In evaluating technologies that might be used at the site, a critical concern will be that CCl{sub 4} reduction usually occurs predominantly by hydrogenolysis to chloroform (CHCl{sub 3}) and methylene chloride (CH{sub 2}Cl{sub 2}), both of which are nearly as problematic as CCl{sub 4} (National Research Council, 1978). Competing reaction pathways produce the more desirable products carbon monoxide (CO) and/or formate (HCOO{sup -}), and possibly CO{sub 2}, but the proportion of reaction that occurs by these pathways is highly variable. Iron-based metallic and oxide nanoparticles have been shown to have enhanced reactivity towards a variety of chemical species, including chlorinated hydrocarbons and reducible oxyanions. Possibly of greater importance is the ability of nanoparticles to select for specific reaction products, potentially facilitating the formation of more environmentally acceptable products. The purpose of this study is to develop a fundamental understanding of the mechanism responsible for the overall particle reactivity and reaction selectivity of reactive metal and oxide nanoparticles. To achieve this objective the project involves the synthesis (using solution and vacuum synthesis methods) and characterization of well

  17. Sulfur reactions and cryptic cross-linkages to oxygen, iron, and carbon cyclin

    NASA Astrophysics Data System (ADS)

    Druschel, G.; Kafantaris, F. C. A.; Fike, D. A.; Schmitt-Kopplin, P.; Dvorski, S.; Oduro, H.

    2014-12-01

    Sulfur speciation in any setting is controlled by a complex series of redox reactions, polymerization, and complexation reactions that are affected by both biotic and abiotic processes. Additionally there are several crossroads of reactions with oxygen, carbon, and iron in which polysulfide molecules serve as a key reaction component that affects not only sulfur speciation, but the speciation, solubility, and bioavailability of these elements as well. Utilizing a combination of analytical approaches including electrochemistry, spectroscopy, mass spectrometry, and chromatography, we have started to unravel the interconnections between sulfur and other key elements, and how microorganisms may be either direct or indirect contributors to these chemical and mineralogical signatures. In microbial mats, we have observed microbial production of significant hydrogen peroxide under UV-stressed conditions. This peroxide interaction with hydrogen sulfide changes the kinetics and the pathways of abiotic sulfur reactions, potentially affecting the overall bioavailability and isotopic fractionations for specific reactions via a change in the linkage between oxygen and sulfur cycling. In systems containing significant iron, we have observed the production of an electroactive form of ferrous iron and sulfide (FeS(aq)) that is of a size that can be described between a dissolved molecular cluster and a small nanoparticle. This FeS(aq) can be a significant fraction of the dissolved iron or sulfide in a system, and is a key part of both the solubility of iron and sulfur and the pathways potentially important for pyritization reactions. In systems where we investigate the links between sulfur and carbon, laboratory and field experiments indicate a wide range of large and more reduced organic compounds are highly reactive towards polysulfide. Utilizing Fourier-transform ion cyclotron resonance mass spectrometry in conjunction with electrochemistry and chromatography, we are seeing a

  18. The effect of the initial exciton numbers on {sup 54,56}Fe(p, xp) Pre-Equilibrium Reactions

    SciTech Connect

    Boeluekdemir, M. H.; Tel, E.; Ayd Latin-Small-Letter-Dotless-I n, A.; Okuducu, S.; Kaplan, A.

    2011-02-15

    In pre-equilibrium nuclear reactions, the geometry-dependent hybrid model is applied with the use of the neutron and proton densities to investigate the effect of initial exciton numbers on the nucleon emission spectra. The initial exciton numbers calculated with the theoretical neutron and proton densities have been obtained within the Skryme-Hartree-Fock method with SKM* and SLy4 forces on target nuclei in the {sup 54,56}Fe(p, xp) reaction at 61.5-MeV incident proton energy by using a new calculationmethod of Tel et al. Also, the differences between the initial exciton numbers for protons and neutrons as a function of nuclear radius, focusing on systematic discrepancies correlated to differences in the proton and neutron densities have been investigated.

  19. Sorption and reaction kinetics of arsenate and arsenite from aqueous solution by waste cast iron

    NASA Astrophysics Data System (ADS)

    Kim, B. J.; Cho, k. H.; Wi, D. W.; Choi, N. C.; Park, C. Y.

    2012-04-01

    The Sorption and reaction kinetics of As(III) and As(V) from aqueous solution was investigated using waste cast iron, which is a byproduct of the iron casting process in foundries. Two types of waste cast iron were used in the experiment: grind precipitate dust (GPD) and cast iron shot (CIS). The X-ray diffraction analysis indicated the presence of Fe0 on GPD and CIS. Non-equilibrium batch experiments were performed under different concentrations of As(III) and As(V) and in the absence/presence of PO4-3 for prevention of sorption effect. Results showed that waste cast iron was effective in the removal of As(III) and As(V). The removal parameter pattern indicated that the two-stage reduction pattern type (consists of fast reduction type (sorption and reaction) and limited slow (reaction) type) was better than the first order reduction pattern at describing the experimental result. In the reduction of both As(III) and As(V), the reduction capacity of GPD was greater than CIS, mainly due to the fact that GPD had higher surface area and weight percent of Fe than CIS. The results of reduction parameter estimation revealed that In the removal of As(III) and As(V) by GPD and CIS case, both GPD and CIS were more effective at the removal of sorption and reaction than reaction under given experimental conditions. This study demonstrates that waste cast iron has potential as a reactive material to treat wastewater and groundwater containing arsenic.

  20. Heterobifunctional PEG Ligands for Bioconjugation Reactions on Iron Oxide Nanoparticles

    PubMed Central

    Bloemen, Maarten; Van Stappen, Thomas; Willot, Pieter; Lammertyn, Jeroen; Koeckelberghs, Guy; Geukens, Nick; Gils, Ann; Verbiest, Thierry

    2014-01-01

    Ever since iron oxide nanoparticles have been recognized as promising scaffolds for biomedical applications, their surface functionalization has become even more important. We report the synthesis of a novel polyethylene glycol-based ligand that combines multiple advantageous properties for these applications. The ligand is covalently bound to the surface via a siloxane group, while its polyethylene glycol backbone significantly improves the colloidal stability of the particle in complex environments. End-capping the molecule with a carboxylic acid introduces a variety of coupling chemistry possibilities. In this study an antibody targeting plasminogen activator inhibitor-1 was coupled to the surface and its presence and binding activity was assessed by enzyme-linked immunosorbent assay and surface plasmon resonance experiments. The results indicate that the ligand has high potential towards biomedical applications where colloidal stability and advanced functionality is crucial. PMID:25275378

  1. Reaction of iron with hydrogen chloride-oxygen mixtures at 550 C

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.

    1986-01-01

    The reaction of iron with 1 percent HCl/0-50 percent O2/Ar has been studied at 550 C with thermogravimetry to monitor kinetics and scanning electron microscopy to characterize product morphologies. In addition, the volatile species were identified with an atmospheric pressure sampling mass spectrometer. The reaction of 1 percent HCl/Ar produces FeCl2. The reactions of 1 percent HCl/1, 10, 50 percent O2/Ar produce Fe2O3, Fe3O4, FeCl2, and FeCl3. In each case condensed phase chlorides form at the oxide/metal interface where the oxygen potential is low. The 10 and 50 percent oxygen mixtures have kinetics in the first 3 hr similar to pure oxidation with some deviations due to iron-chloride formation. The 1 percent oxygen mixture shows enhanced reaction rates over oxidation, very likely due to the formation of a porous scale.

  2. Iron Oxides from Volcanic Soils as Potential Catalysts in the Water Gas Shift Reaction

    SciTech Connect

    Pizarro, C.; Escudey, M.; Moya, S.A.; Fabris, J.D.

    2005-04-26

    This study was focused on changes of the iron oxide mineralogy with temperature of two Chilean soils (Andisol and Ultisol) derived from volcanic materials and their use as iron-based catalysts in the water gas shift reaction (WGSR). Ultisol materials produced about twice as much hydrogen than did those from Andisol upon WGSR, but in both cases hydrogen yielding increased as the heating temperature of the soil materials increased from 124 deg. C to 500 deg. C. The room temperature Moessbauer spectra showed an increase of the relative proportion of the magnetically ordered components as temperature increased. Higher heating temperature produced a negative effect on the catalytic activity, whereas the organic matter destruction led to a positive effect, due to an increasing exposition of the iron oxide surfaces; heating the soil sample at 600 deg. C induced changes on the iron oxide mineralogy with a significant decrease of the catalytic activity.

  3. Iron Oxides from Volcanic Soils as Potential Catalysts in the Water Gas Shift Reaction

    NASA Astrophysics Data System (ADS)

    Pizarro, C.; Escudey, M.; Moya, S. A.; Fabris, J. D.

    2005-04-01

    This study was focused on changes of the iron oxide mineralogy with temperature of two Chilean soils (Andisol and Ultisol) derived from volcanic materials and their use as iron-based catalysts in the water gas shift reaction (WGSR). Ultisol materials produced about twice as much hydrogen than did those from Andisol upon WGSR, but in both cases hydrogen yielding increased as the heating temperature of the soil materials increased from 124°C to 500°C. The room temperature Mössbauer spectra showed an increase of the relative proportion of the magnetically ordered components as temperature increased. Higher heating temperature produced a negative effect on the catalytic activity, whereas the organic matter destruction led to a positive effect, due to an increasing exposition of the iron oxide surfaces; heating the soil sample at 600 °C induced changes on the iron oxide mineralogy with a significant decrease of the catalytic activity.

  4. Light-induced point defect reactions of residual iron in crystalline silicon after aluminum gettering

    SciTech Connect

    Abdelbarey, D.; Kveder, V.; Schroeter, W.; Seibt, M.

    2010-08-15

    Deep level transient spectroscopy is used to study light-induced reactions of residual iron impurities after aluminum gettering (AlG) in crystalline silicon. White-light illumination at room temperature leads to the formation of a defect which is associated with a donor level at 0.33 eV above the valence band. This defect is stable up to about 175 deg. C where it dissociates reversibly in case of small iron concentrations and irreversibly for high iron concentrations. Since marker experiments using gold and platinum diffusion show a high vacancy concentration after AlG a tentative identification of the new defect as the metastable iron-vacancy pair is proposed.

  5. Redox reactions of the non-heme iron in photosystem II: an EPR spectroscopic study.

    PubMed

    McEvoy, James P; Brudvig, Gary W

    2008-12-16

    Photosystem II (PSII) contains a non-heme ferrous ion, located on the stromal side of the protein in close proximity to quinones A and B (Q(A) and Q(B)). We used EPR spectroscopy to examine the temperature-dependent redox reactions of the iron-quinone site, using it as a probe of potentially physiologically relevant proton-coupled electron-transfer (PCET) reactions. Complete chemical oxidation of the non-heme iron at ambient temperatures was followed by cryogenic photoreduction, producing a temperature-dependent yield of Fe(2+)Q(A) (or Fe(3+)Q(A)(-))...Chl(+)/Car(+)/Y(D)(*) charge separations. These charge separations were subsequently observed to partially recombine in the dark at cryogenic temperatures. We observed no double photochemical charge separations upon illumination at temperatures iron-quinone site in PSII, one whose Fe(3+) signal is abolished by illumination at liquid helium temperatures and one whose Fe(3+) signal is abolished by illumination only above 75 K. The observation of non-heme iron photoreduction at cryogenic temperatures (possibly at liquid helium temperatures and certainly above 75 K) implies the existence of a low reorganization energy proton-transfer (ET) pathway within the protein to the non-heme iron environment, of possible relevance to the PCET reactions of Q(B) and/or the non-heme iron itself. Furthermore, we observed the partial reoxidation of the non-heme iron by charge recombination with previously oxidized chlorophyll, carotenoid, and Y(D) within PSII. This electron transfer might be important in the photoprotective transfer of oxidative power away from P(680)(+) and the oxygen-evolving complex in stressed PSII centers. PMID:19053286

  6. From vinyl pyranoses to carbasugars by an iron-catalyzed reaction complementary to classical Ferrier carbocyclization.

    PubMed

    Mac, Dinh Hung; Samineni, Ramesh; Petrignet, Julien; Srihari, Pabbaraja; Chandrasekhar, Srivari; Yadav, Jhillu Singh; Grée, René

    2009-08-21

    Starting from vinyl pyranoses an iron-catalyzed tandem isomerization-intramolecular aldolization reaction was developed to prepare cyclohexenone derivatives bearing substituents on the double bond, and it has been applied in a short synthesis of 4-epi-gabosines A and B, from d-glucose. PMID:19641820

  7. Iron-Catalyzed Stereoselective Cross-Coupling Reactions of Stereodefined Enol Carbamates with Grignard Reagents.

    PubMed

    Rivera, Ana Cristina Parra; Still, Raymond; Frantz, Doug E

    2016-06-01

    A practical and highly stereoselective iron-catalyzed cross-coupling reaction of stereodefined enol carbamates and Grignard reagents to yield tri- and tetrasubstituted acrylates is reported. A facile method for the stereoselective generation of these enol carbamates has also been developed. PMID:27088754

  8. Influence of Ionic Liquids on an Iron(III) Catalyzed Three-Component Coupling/Hydroarylation/Dehydrogenation Tandem Reaction.

    PubMed

    Muntzeck, Maren; Wilhelm, René

    2016-01-01

    A three-component oxidative dehydrogenation tandem reaction via the coupling and hydroarylation of benzaldehyde, aniline and phenylacetylene to a quinoline derivate was catalyzed by an iron-containing ionic liquid. The reaction was air mediated and could be performed under neat conditions. The iron(III) of the ionic liquid was the oxidizing species. PMID:27258264

  9. Influence of Ionic Liquids on an Iron(III) Catalyzed Three-Component Coupling/Hydroarylation/Dehydrogenation Tandem Reaction

    PubMed Central

    Muntzeck, Maren; Wilhelm, René

    2016-01-01

    A three-component oxidative dehydrogenation tandem reaction via the coupling and hydroarylation of benzaldehyde, aniline and phenylacetylene to a quinoline derivate was catalyzed by an iron-containing ionic liquid. The reaction was air mediated and could be performed under neat conditions. The iron(III) of the ionic liquid was the oxidizing species. PMID:27258264

  10. Electrode reactions of iron oxide-hydroxide colloids.

    PubMed

    Mahmoudi, Leila; Kissner, Reinhard

    2014-11-01

    Small-sized FeO(OH) colloids stabilised by sugars, commercially available for the clinical treatment of iron deficiency, show two waves during cathodic polarographic sweeps, or two current maxima with stationary electrodes, in neutral to slightly alkaline aqueous medium. Similar signals are observed with Fe(III) in alkaline media, pH > 12, containing citrate in excess. Voltammetric and polarographic responses reveal a strong influence of fast adsorption processes on gold and mercury. Visible spontaneous accumulation was also observed on platinum. The voltammetric signal at more positive potential is caused by Fe(III)→Fe(II) reduction, while the one at more negative potential has previously been assigned to Fe(II)→Fe(0) reduction. However, the involvement of adsorption phenomena leads us to the conclusion that the second cathodic current is caused again by Fe(III)→Fe(II), of species deeper inside the particles than those causing the first wave. This is further supported by X-ray photoelectron spectra obtained after FeO(OH) particle adsorption and reduction on a gold electrode surface. The same analysis suggests that sucrose stabilising the colloid is still bound to the adsorbed material, despite dilution and rinsing. PMID:25188440

  11. Iron-copper cooperative catalysis in the reactions of alkyl Grignard reagents: exchange reaction with alkenes and carbometalation of alkynes.

    PubMed

    Shirakawa, Eiji; Ikeda, Daiji; Masui, Seiji; Yoshida, Masatoshi; Hayashi, Tamio

    2012-01-11

    Iron-copper cooperative catalysis is shown to be effective for an alkene-Grignard exchange reaction and alkylmagnesiation of alkynes. The Grignard exchange between terminal alkenes (RCH═CH(2)) and cyclopentylmagnesium bromide was catalyzed by FeCl(3) (2.5 mol %) and CuBr (5 mol %) in combination with PBu(3) (10 mol %) to give RCH(2)CH(2)MgBr in high yields. 1-Alkyl Grignard reagents add to alkynes in the presence of a catalyst system consisting of Fe(acac)(3), CuBr, PBu(3), and N,N,N',N'-tetramethylethylenediamine to give β-alkylvinyl Grignard reagents. The exchange reaction and carbometalation take place on iron, whereas copper assists with the exchange of organic groups between organoiron and organomagnesium species through transmetalation with these species. Sequential reactions consisting of the alkene-Grignard exchange and the alkylmagnesiation of alkynes were successfully conducted by adding an alkyne to a mixture of the first reaction. Isomerization of Grignard reagents from 2-alkyl to 1-alkyl catalyzed by Fe-Cu also is applicable as the first 1-alkyl Grignard formation step. PMID:22128888

  12. The reactions of cobalt, iron and nickel in SO2 atmospheres Similarities and differences

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1985-01-01

    The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibit similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

  13. The reactions of cobalt, iron and nickel in SO-2 atmospheres: Similarities and differences

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1984-01-01

    The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibits similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

  14. Iron

    MedlinePlus

    Iron is a mineral that our bodies need for many functions. For example, iron is part of hemoglobin, a protein which carries ... It helps our muscles store and use oxygen. Iron is also part of many other proteins and ...

  15. Studies of the kinetics of two parallel reactions: ammonia decomposition and nitriding of iron catalyst.

    PubMed

    Arabczyk, Walerian; Pelka, Rafat

    2009-01-15

    The reaction of ammonia decomposition and nitriding reaction as an example of the parallel reactions were studied. A surface reaction was assumed as the rate limiting step. The experiments were carried out in the range of temperatures from 623 to 723 K. Mixtures of different iron nitrides (gamma'-Fe(4)N, epsilon-Fe(3-2)N) were obtained. Differential tubular reactor with thermogravimetric (TG) measurement and analysis of the gas phase composition in the reaction volume was used. Reacting gases flowing through the reactor were mixed. Effective reactor volume was determined. The rate constants for ammonia decomposition and ammonia adsorption process at critical point between alpha-Fe and gamma'-Fe(4)N phases were estimated. The number of collisions and the sticking coefficient of ammonia over alpha-Fe phase were also assessed. PMID:19086865

  16. The CIELO Collaboration: Neutron Reactions on 1H, 16O, 56Fe, 235,238U, and 239Pu

    NASA Astrophysics Data System (ADS)

    Chadwick, M. B.; Dupont, E.; Bauge, E.; Blokhin, A.; Bouland, O.; Brown, D. A.; Capote, R.; Carlson, A.; Danon, Y.; De Saint Jean, C.; Dunn, M.; Fischer, U.; Forrest, R. A.; Frankle, S. C.; Fukahori, T.; Ge, Z.; Grimes, S. M.; Hale, G. M.; Herman, M.; Ignatyuk, A.; Ishikawa, M.; Iwamoto, N.; Iwamoto, O.; Jandel, M.; Jacqmin, R.; Kawano, T.; Kunieda, S.; Kahler, A.; Kiedrowski, B.; Kodeli, I.; Koning, A. J.; Leal, L.; Lee, Y. O.; Lestone, J. P.; Lubitz, C.; MacInnes, M.; McNabb, D.; McKnight, R.; Moxon, M.; Mughabghab, S.; Noguere, G.; Palmiotti, G.; Plompen, A.; Pritychenko, B.; Pronyaev, V.; Rochman, D.; Romain, P.; Roubtsov, D.; Schillebeeckx, P.; Salvatores, M.; Simakov, S.; Soukhovitskiı˜, E. Sh.; Sublet, J. C.; Talou, P.; Thompson, I.; Trkov, A.; Vogt, R.; van der Marck, S.

    2014-04-01

    CIELO (Collaborative International Evaluated Library Organization) provides a new working paradigm to facilitate evaluated nuclear reaction data advances. It brings together experts from across the international nuclear reaction data community to identify and document discrepancies among existing evaluated data libraries, measured data, and model calculation interpretations, and aims to make progress in reconciling these discrepancies to create more accurate ENDF-formatted files. The focus will initially be on a small number of the highest-priority isotopes, namely 1H, 16O, 56Fe, 235,238U, and 239Pu. This paper identifies discrepancies between various evaluations of the highest priority isotopes, and was commissioned by the OECD's Nuclear Energy Agency WPEC (Working Party on International Nuclear Data Evaluation Co-operation) during a meeting held in May 2012. The evaluated data for these materials in the existing nuclear data libraries - ENDF/B-VII.1, JEFF-3.1, JENDL-4.0, CENDL-3.1, ROSFOND, IRDFF 1.0 - are reviewed, discrepancies are identified, and some integral properties are given. The paper summarizes a program of nuclear science and computational work needed to create the new CIELO nuclear data evaluations.

  17. Proton-Coupled Electron Transfer Reactions at a Heme-Propionate in an Iron-Protoporphyrin-IX Model Compound

    PubMed Central

    2011-01-01

    A heme model system has been developed in which the heme-propionate is the only proton donating/accepting site, using protoporphyrin IX-monomethyl esters (PPIXMME) and N-methylimidazole (MeIm). Proton-coupled electron transfer (PCET) reactions of these model compounds have been examined in acetonitrile solvent. (PPIXMME)FeIII(MeIm)2-propionate (FeIII~CO2) is readily reduced by the ascorbate derivative 5,6-isopropylidine ascorbate to give (PPIXMME)FeII(MeIm)2-propionic acid (FeII~CO2H). Excess of the hydroxylamine TEMPOH or of hydroquinone similarly reduce FeIII~CO2, and TEMPO and benzoquinone oxidize FeII~CO2H to return to FeIII~CO2. The measured equilibrium constants, and the determined pKa and E1/2 values, indicate that FeII~CO2H has an effective bond dissociation free energy (BDFE) of 67.8 ± 0.6 kcal mol–1. In these PPIX models, electron transfer occurs at the iron center and proton transfer occurs at the remote heme propionate. According to thermochemical and other arguments, the TEMPOH reaction occurs by concerted proton-electron transfer (CPET), and a similar pathway is indicated for the ascorbate derivative. Based on these results, heme propionates should be considered as potential key components of PCET/CPET active sites in heme proteins. PMID:21524059

  18. Compositional aspect of iron Fischer-Tropsch catalyst: An XPS/reaction study

    SciTech Connect

    Kuivila, C.S.; Stair, P.C.; Butt, J.B. )

    1989-08-01

    The catalytic and compositional behaviors of prereduced and unreduced iron catalysts for Fischer-Tropsch synthesis were investigated. Catalytic behavior was evaluated by measuring rates of hydrocarbon formation 3:1 H{sub 2}:CO mixture at 1 atm and 250C. Iron phases which evolved near the catalyst surfaces were characterized by X-ray photoelectron spectroscopy, and bulk phases present following reaction were determined by Moessbauer spectroscopy. At low conversion levels the prereduced catalyst was gradually converted to iron carbide with no significant oxide phase formed. Synthesis activities increased initially with the formation of active surface carbon, but eventually lost some activity due to graphitic carbon formation. At higher conversions, the prereduced catalyst showed some formation of surface oxide phases and an inhibition of the synthesis rate due to water adsorption. Surface carbon accumulation was also suppressed under these conditions. Unreduced Fe{sub 2}O{sub 3} showed no initial synthesis activity, but underwent a gradual activation to become even more active than the prereduced catalyst. The oxide catalyst was eventually completely reduced to Fe{sub 3}O{sub 4}, and any metallic phase formed was rapidly converted to iron carbide. Compared to reduced materials, the oxide catalyst accumulated considerably less surface carbon and showed no loss of activity for reaction times up to 48 h. XPS analysis suggests that Fe{sub 3}O{sub 4} is active for synthesis.

  19. Removal of contaminants from aqueous solution by reaction with iron surfaces

    SciTech Connect

    Qiu, S.R.; Lai, H.F.; Roberson, M.J.; Hunt, M.L.; Amrhein, C.; Giancarlo, L.C.; Flynn, G.W.; Yarmoff, J.A.

    2000-03-07

    Irrigation drainage and industrial wastewaters often contain elevated levels of toxic oxyanions and oxycations such as selenate, chromate, and uranyl. A potential remediation method is to react contaminated water with zero-valent iron, which transforms the mobile contaminants into immobile forms. In this work, iron foil was exposed to aqueous solutions containing the relevant ions, and the reacted surfaces were characterized by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). STM images collected in situ show that the protrusions on the foil surface associated with iron oxides are smoothed out by the reaction. XPS indicates that partially reduced Se(IV) and Cr(III) are adsorbed on the surface, while uranium is deposited as U(VI), i.e., without reduction. More Se and Cr are deposited when the atmospheric gases are removed from solution because of the elimination of a competing process in which dissolved O{sub 2} increases the thickness of the iron oxide overlayer to the point where the reduction reaction is quenched. The amount of U deposited is greatly increased when the atmospheric gases are removed because of the elimination of dissolved CO{sub 2}, which can form carbonate complexes with uranium.

  20. Rates for neutron-capture reactions on tungsten isotopes in iron meteorites. [Abstract only

    NASA Technical Reports Server (NTRS)

    Masarik, J.; Reedy, R. C.

    1994-01-01

    High-precision W isotopic analyses by Harper and Jacobsen indicate the W-182/W-183 ratio in the Toluca iron meteorite is shifted by -(3.0 +/- 0.9) x 10(exp -4) relative to a terrestrial standard. Possible causes of this shift are neutron-capture reactions on W during Toluca's approximately 600-Ma exposure to cosmic ray particles or radiogenic growth of W-182 from 9-Ma Hf-182 in the silicate portion of the Earth after removal of W to the Earth's core. Calculations for the rates of neutron-capture reactions on W isotopes were done to study the first possibility. The LAHET Code System (LCS) which consists of the Los Alamos High Energy Transport (LAHET) code and the Monte Carlo N-Particle(MCNP) transport code was used to numerically simulate the irradiation of the Toluca iron meteorite by galactic-cosmic-ray (GCR) particles and to calculate the rates of W(n, gamma) reactions. Toluca was modeled as a 3.9-m-radius sphere with the composition of a typical IA iron meteorite. The incident GCR protons and their interactions were modeled with LAHET, which also handled the interactions of neutrons with energies above 20 MeV. The rates for the capture of neutrons by W-182, W-183, and W-186 were calculated using the detailed library of (n, gamma) cross sections in MCNP. For this study of the possible effect of W(n, gamma) reactions on W isotope systematics, we consider the peak rates. The calculated maximum change in the normalized W-182/W-183 ratio due to neutron-capture reactions cannot account for more than 25% of the mass 182 deficit observed in Toluca W.

  1. Effect Of Reaction Environments On The Reactivity Of PCB (2-Chlorobiphenyl) Over Activated Carbon Impregnated With Palladized Iron

    EPA Science Inventory

    Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-...

  2. PLANT SOURCES OF DIETARY IRON: DIVERSITY IN TISSUE IRON CONCENTRATION. IN: PROCEEDINGS OF THE THIRTEENTH INTERNATIONAL SYMPOSIUM ON IRON NUTRITION AND INTERACTIONS IN PLANTS, JULY 3-7, 2006, MONTPELLIER, FRANCE. 2006. P. 56.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Iron is an essential mineral for all organisms, including humans and other animals. Iron must be obtained through dietary sources, and plant food products are an important provider of this micronutrient. Because all plants contain iron, humans consume this nutrient in all vegetable, grain, and fru...

  3. Accelerated Catalytic Fenton Reaction with Traces of Iron: An Fe-Pd-Multicatalysis Approach.

    PubMed

    Georgi, Anett; Velasco Polo, Miriam; Crincoli, Klara; Mackenzie, Katrin; Kopinke, Frank-Dieter

    2016-06-01

    An accelerated catalytic Fenton (ACF) reaction was developed based upon a multicatalysis approach, facilitating efficient contaminant oxidation at trace levels of dissolved iron. Beside the Fe(II)/H2O2 catalyst/oxidant pair for production of OH-radicals, the ACF system contains Pd/H2 as catalyst/reductant pair for fast reduction of Fe(III) back to Fe(II) which accelerates the Fenton cycle and leads to faster contaminant degradation. By this means, the concentration of the dissolved iron catalyst can be reduced to trace levels (1 mg L(-1)) below common discharge limits, thus eliminating the need for iron sludge removal, which is one of the major drawbacks of conventional Fenton processes. ACF provides fast degradation of the model contaminant methyl tert-butyl ether (MTBE, C0 = 0.17 mM) with a half-life of 11 min with 1 mg L(-1) dissolved iron, 500 mg L(-1) H2O2, 5 mg L(-1) Pd (as suspended Pd/Al2O3 catalyst) and 0.1 MPa H2, pH 3. The effects of pH, H2 partial pressure and H2O2 concentration on MTBE degradation rates were studied. Results on kinetic deuterium isotope effect and quenching studies are in conformity with OH-radicals as main oxidant. The heterogeneous Pd/Al2O3 catalyst was reused within six cycles without significant loss in activity. PMID:27167833

  4. O2 reduction reaction by biologically relevant anionic ligand bound iron porphyrin complexes.

    PubMed

    Samanta, Subhra; Das, Pradip Kumar; Chatterjee, Sudipta; Sengupta, Kushal; Mondal, Biswajit; Dey, Abhishek

    2013-11-18

    Iron porphyrin complex with a covalently attached thiolate ligand and another with a covalently attached phenolate ligand has been synthesized. The thiolate bound complex shows spectroscopic features characteristic of P450, including the hallmark absorption spectrum of the CO adduct. Electrocatalytic O2 reduction by this complex, which bears a terminal alkyne group, is investigated by both physiabsorbing on graphite surfaces (fast electron transfer rates) and covalent attachment to azide terminated self-assembled monolayer (physiologically relevant electron transfer rates) using the terminal alkyne group. Analysis of the steady state electrochemical kinetics reveals that this catalyst can selectively reduce O2 to H2O with a second-order k(cat.) ~10(7) M(-1 )s(-1) at pH 7. The analogous phenolate bound iron porphyrin complex reduces O2 with a second-order rate constant of 10(5) M(-1) s(-1) under the same conditions. The anionic ligand bound iron porphyrin complexes catalyze oxygen reduction reactions faster than any known synthetic heme porphyrin analogues. The kinetic parameters of O2 reduction of the synthetic thiolate bound complex, which is devoid of any second sphere effects present in protein active sites, provide fundamental insight into the role of the protein environment in tuning the reactivity of thiolate bound iron porphyrin containing metalloenzymes. PMID:24171513

  5. Solid-State Thermal Reaction of a Molecular Material and Solventless Synthesis of Iron Oxide

    NASA Astrophysics Data System (ADS)

    Roy, Debasis; Roy, Madhusudan; Zubko, Maciej; Kusz, Joachim; Bhattacharjee, Ashis

    2016-09-01

    Solid-state thermal decomposition reaction of a molecular material {As}({C}6{H}5)4[{Fe}^{II}{Fe}^{III} ({C}2{O}4)3]}n has been studied using non-isothermal thermogravimetry (TG) in an inert atmosphere. By analyzing the TG data collected at multiple heating rates in 300 K-1300 K range, the kinetic parameters (activation energy, most probable reaction mechanism function and frequency factor) are determined using different multi-heating rate analysis programs. Activation energy and the frequency factor are found to be strongly dependent on the extent of decomposition. The decomposed material has been characterized to be hematite using physical techniques (FT-IR and powder XRD). Particle morphology has been checked by TEM. A solid-state reaction pathway leading the molecular precursor to hematite has been proposed illustrating an example of solventless synthesis of iron oxides utilizing thermal decomposition as a technique using innocuous materials.

  6. IRON

    EPA Science Inventory

    The document surveys the effects of organic and inorganic iron that are relevant to humans and their environment. The biology and chemistry of iron are complex and only partially understood. Iron participates in oxidation reduction processes that not only affect its geochemical m...

  7. Morphological transformation during activation and reaction of an iron Fischer-Tropsch catalyst

    SciTech Connect

    Jackson, N.B.; Kohler, S.; Harrington, M.

    1995-12-31

    The purpose of this project is to support the development of slurry-phase bubble column processes being studied at the La Porte Alternative Fuel Development Unit. This paper describes the aspects of Sandia`s recent work regarding the advancement and understanding of the iron catalyst used in the slurry phase process. A number of techniques were used to understand the chemical and physical effects of pretreatment and reaction on the attrition and carbon deposition characteristics of iron catalysts. Unless otherwise stated, the data discussed was derived form experiments carried out on the catalyst chosen for the summer 1994 Fischer-Tropsch run at LaPorte, UCI 1185-78-370, (an L 3950 type) that is 88% Fe{sub 2}O{sub 3}, 11% CuO, and 0.052%K{sub 2}O.

  8. The Olefin Metathesis Reactions Combined with Organo-Iron Arene Activation Towards Dendrimers, and Polymers

    NASA Astrophysics Data System (ADS)

    Astruc, Didier; Martinez, Victor

    The subjects treated in the two lectures of the North Atlantic Treaty Organization (NATO) summer course are (1) the combination of arene activation and perfunctionalization using organo-iron chemistry with olefin metathesis incuding metathesis of dendritic polyolefin molecules; (2) the synthesis of metallodendritic benzylidene complexes that catalyse ring-opening metathesis polymerization (ROMP) under ambient conditions and the formation of dendritic stars; (3) the use of stoichiometric and catalytic electron-transfer processes with standard reservoirs of electrons (reductants) or electron holes (oxidants) iron complexes to achieve noteworthy metathesis reactions or synthesize compounds that are useful in metathesis. Only the two first topics are treated in this chapter, and interested readers can find references concerning the third aspect called in the introduction and subsequently cited in the reference list.

  9. Oxidative damage to DNA constituents by iron-mediated Fenton reactions--the thymidine family.

    PubMed

    Chattopadhyaya, Rajagopal

    2014-01-01

    The degradative products formed from the exposure of derivatives of thymidine to iron-mediated Fenton reactions were identified by chromatographic resolution and analysis by UV absorption spectroscopy, radio-labeling, and positive and negative mode fast atom bombardment mass spectrometry. Fe(2+)/H2O2 and Fe(3+)/H2O2 were utilized to generate oxy-radicals and the effects of ethanol and N2-flushing were studied. Substrates included thymidine, 3'- and 5'-dTMP, TpT, oligo(dT), and oligo(dT)·poly(dA) and the results are compared to those reported for ionizing radiation. It is evident from the comparisons of the products that the damaging radical species and the product distribution are perturbed by interaction of the iron atom with the various phosphomono- and diester species that are present. PMID:23252741

  10. [Study on colour reaction of iron(II)-thibarbituric acid-nitrite system and its analytical application].

    PubMed

    Huang, X

    1998-12-01

    In this paper, the optimum conditions of colour reaction of iron (II)-thibarbituric acid-NO2(-) system, existent state and spectrophotometric characteristies of the complex were studied, and the reaction mechanism discussed. A new spectrophotometric method for the determination of trace iron was established. In a buffer solution of borate/NaOH of pH9.5, iron (II) and thibarbituric acid-NO2(-) react to form a stable blue complex anion, for which the maximum absorbance is at 645nm and the molar absorptivity is 2.66 x 10(4)L x mol(-1) x cm(-1). Beer's law is obeyed in the range of 0-40 microg/25mL for iron (II). The method is simple and rapid, shows satisfactory selectivity and precision and has been applied to determine iron in waters with satisfactory results. PMID:15825298

  11. Mononuclear Nonheme High-Spin Iron(III)-Acylperoxo Complexes in Olefin Epoxidation and Alkane Hydroxylation Reactions.

    PubMed

    Wang, Bin; Lee, Yong-Min; Clémancey, Martin; Seo, Mi Sook; Sarangi, Ritimukta; Latour, Jean-Marc; Nam, Wonwoo

    2016-02-24

    Mononuclear nonheme high-spin iron(III)-acylperoxo complexes bearing an N-methylated cyclam ligand were synthesized, spectroscopically characterized, and investigated in olefin epoxidation and alkane hydroxylation reactions. In the epoxidation of olefins, epoxides were yielded as the major products with high stereo-, chemo-, and enantioselectivities; cis- and trans-stilbenes were oxidized to cis- and trans-stilbene oxides, respectively. In the epoxidation of cyclohexene, cyclohexene oxide was formed as the major product with a kinetic isotope effect (KIE) value of 1.0, indicating that nonheme iron(III)-acylperoxo complexes prefer C═C epoxidation to allylic C-H bond activation. Olefin epoxidation by chiral iron(III)-acylperoxo complexes afforded epoxides with high enantioselectivity, suggesting that iron(III)-acylperoxo species, not high-valent iron-oxo species, are the epoxidizing agent. In alkane hydroxylation reactions, iron(III)-acylperoxo complexes hydroxylated C-H bonds as strong as those in cyclohexane at -40 °C, wherein (a) alcohols were yielded as the major products with high regio- and stereoselectivities, (b) activation of C-H bonds by the iron(III)-acylperoxo species was the rate-determining step with a large KIE value and good correlation between reaction rates and bond dissociation energies of alkanes, and (c) the oxygen atom in the alcohol product was from the iron(III)-acylperoxo species, not from molecular oxygen. In isotopically labeled water (H2(18)O) experiments, incorporation of (18)O from H2(18)O into oxygenated products was not observed in the epoxidation and hydroxylation reactions. On the basis of mechanistic studies, we conclude that mononuclear nonheme high-spin iron(III)-acylperoxo complexes are strong oxidants capable of oxygenating hydrocarbons prior to their conversion into iron-oxo species via O-O bond cleavage. PMID:26816269

  12. Iron(III) Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions.

    PubMed

    Rebelo, Susana L H; Silva, André M N; Medforth, Craig J; Freire, Cristina

    2016-01-01

    Iron(III) fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H₂TPFPP) and the corresponding iron complex [Fe(TPFPP)Cl], and the use of [Fe(TPFPP)Cl] as an oxidation catalyst in green conditions. The preparations of H₂TPFPP and [Fe(TPFPP)Cl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(III)porphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide) and green solvent (ethanol). Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed. PMID:27077840

  13. Investigation of the Transformation of a Modified Iron Oxide Structure During Redox Reaction

    NASA Astrophysics Data System (ADS)

    Anh, Luu Thi Lan; Trung, Nguyen Ngoc; Tho, Van Dinh Son

    Iron oxides can be used for the storage of hydrogen based on their redox reaction. Iron oxides were synthesized by the sol-gel method was a structure transformation of maghemite γ-Fe2O3 into hematite α-Fe2O3 during calcinations process could be observed. The addition of a Mo6+ cation by the preparation method results in the substitution of Mo6+ into the Fe2O3 structure and formation of Fe2(MoO4)3. There was a formation of two crystalline phases Fe2O3 and ZrO2 separately incase of the addition of Zr4+cation into Fe2O3.During redox reaction, the structure of Fe2O3 was converted into Fe and regenerated Fe3O4. There was a transformation of Fe2 (MoO4)3 into Fe2Mo3O8 phases after reduction. However ZrO2 was did not change its structure during redox reaction. The Zr-Fe2O3 very easy to be reduced into Fe and convenience formed hydrogen in the oxidation.

  14. The fragmentation of 510 MeV/nucleon iron-56 in polyethylene. II. Comparisons between data and a model

    NASA Technical Reports Server (NTRS)

    Zeitlin, C.; Heilbronn, L.; Miller, J.; Schimmerling, W.; Townsend, L. W.; Tripathi, R. K.; Wilson, J. W.

    1996-01-01

    The results of a Monte Carlo model for calculating fragment fluences and LET spectra are compared to data taken with 600 MeV/nucleon iron ions incident on an accelerator beamline configured for irradiation of biological samples, with no target and with 2, 5 and 8 cm of polyethylene. The model uses a multi-generation nuclear fragmentation code, coupled with a formulation of ionization energy loss based on the Bethe-Bloch equation. In the region where the data are reliable and the experimental acceptance is well understood, many of the features of the experimental spectra are well replicated by the model. To obtain good agreement with the experimental data, the model must allow for at least two generations of fragment production in the target.

  15. The fragmentation of 510 MeV/nucleon iron-56 in polyethylene. II. Comparisons between data and a model.

    PubMed

    Zeitlin, C; Heilbronn, L; Miller, J; Schimmerling, W; Townsend, L W; Tripathi, R K; Wilson, J W

    1996-06-01

    The results of a Monte Carlo model for calculating fragment fluences and LET spectra are compared to data taken with 600 MeV/nucleon iron ions incident on an accelerator beamline configured for irradiation of biological samples, with no target and with 2, 5 and 8 cm of polyethylene. The model uses a multi-generation nuclear fragmentation code, coupled with a formulation of ionization energy loss based on the Bethe-Bloch equation. In the region where the data are reliable and the experimental acceptance is well understood, many of the features of the experimental spectra are well replicated by the model. To obtain good agreement with the experimental data, the model must allow for at least two generations of fragment production in the target. PMID:8643825

  16. Solvent sublation and spectrometric determination of iron(II) and total iron using 3-(2-pyridyl)-5,6-bis(4-phenylsulfonic acid)-1,2,4-triazine and tetrabutylammonium bromide.

    PubMed

    Akl, Magda Ali; Mori, Yoshihito; Sawada, Kiyoshi

    2006-09-01

    Solvent sublation has been studied for the separation and determination of trace iron(II) in various kinds of water samples. A strongly magenta-colored anionic [Fe(FZ)3](4-) complex was formed at pH 5.0 upon adding 3-(2-pyridyl)-5,6-bis(4-phenylsulfonic acid)-1,2,4-triazine (ferrozine, FZ) to the sample solution. Tetrabutylammonium bromide (TBAB) was added in the solution to form the (TBA)4[Fe(FZ)3)] ion pair, and an oleic acid (HOL) surfactant was added. Then, the (TBA)4[Fe(FZ)3] ion pairs were floated by vigorous shaking in the flotation cell and extracted into methyl isobutyl ketone (MIBK) on the surface of the aqueous solution. The iron collected in the MIBK layer was measured directly by spectrophotometry and/or flame atomic-absorption spectrophotometry. Different experimental variables that may affect the sublation efficiency were thoroughly investigated. The molar absorptivity of the (TBA)4[Fe(FZ)3] ion pair was 2.8 x 10(4) l mol(-1) cm(-1) in the aqueous layer. Beer's law held up to 1.0 mg L(-1) Fe(II) in the aqueous as well as in the organic layers. The adopted solvent sublation method was successfully applied for the determination of Fe(II) in natural water samples with a preconcentration factor of 200. The application was extended to determine iron in pharmaceutical samples. PMID:16966804

  17. 4′-CyanoPLP presents better prospect for the experimental detection of elusive cyclic intermediate radical in the reaction of lysine 5,6-aminomutase

    SciTech Connect

    Maity, Amarendra Nath; Ke, Shyue-Chu

    2015-02-06

    Graphical abstract: The results of our calculations suggest that the reaction of 4′-cyanoPLP with lysine 5,6-aminomutase offers better prospect for the experimental detection of elusive cyclic azacyclopropylcarbinyl radical, which is proposed to be a key intermediate in the reaction of pyridoxal-5′-phosphate dependent radical aminomutases. - Highlights: • 4′-CyanoI{sup ·} is the lowest energy radical intermediate in the reaction of 5,6-LAM. • 4′-CyanoPLP offers good prospect for the experimental observation of elusive I{sup ·}. • The calculated HFCCs would help to characterize 4′-cyanoI{sup ·} by EPR. - Abstract: The results of our calculations suggest that the reaction of 4′-cyanoPLP with lysine 5,6-aminomutase offers better prospect for the experimental detection of elusive cyclic azacyclopropylcarbinyl radical (I{sup ·}), which is proposed to be a key intermediate in the reaction of pyridoxal-5′-phosphate dependent radical aminomutases. We have calculated the corresponding hyperfine coupling constants (HFCCs) for {sup 14}N and {sup 13}C of cyano group using several basis sets to help the characterization of 4′-cyanoI{sup ·}.

  18. Colorimetric determination of ozone in water based on reaction with bis(terpyridine)iron(II)

    SciTech Connect

    Tomiyasu, H.; Gordon, G.

    1984-04-01

    The analysis of aqueous ozone was studied by a colorimetric method that uses the reaction between ozone and bis(terpyridine)iron(II), Fe(terpy)/sub 2//sup 2 +/, in dilute hydrochloric acid solution. The ozone concentrations were determined from the change in absorption spectra of Fe(terpy)/sub 2//sup 2 +/ at concentrations as low as 10/sup -6/ M (0.05 mg/L) with an accuracy and precision of better than +/-3%. Direct comparisons with the Indigo method and UV spectrophotometric measurements are presented.

  19. Structure-activity relationship in high-performance iron-based electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Song, Ping; Wang, Ying; Pan, Jing; Xu, Weilin; Zhuang, Lin

    2015-12-01

    A sustainable Iron (Fe), Nitrogen (N) co-doped high performance Fe-Nx/C electrocatalyst for oxygen reduction reaction (ORR) is synthesized simply based on nitric acid oxidation of cheap carbon black. The obtained optimal nonprecious metal electrocatalyst shows high ORR performance in both alkaline and acidic conditions and possesses appreciable performance/price ratio due to its low cost. Furthermore, the structure-activity relationship of different active sites on Fe-Nx/C is revealed systematically: Fe-N4/2-C > Fe4-N-C > N-C >> Fe4-C ≥ C, from both experimental and theoretical points of view.

  20. A study of the effect of cesium loading on the phase transformation of iron in iron phosphate over the oxidative dehydrogenation reactions

    NASA Astrophysics Data System (ADS)

    Khan, Faiza B.; Dasireddy, Venkata D. B. C.; Bharuth-Ram, K.; Masenda, H.; Friedrich, H. B.

    2015-04-01

    A phase specific iron orthophosphate catalyst, FePO4, was synthesized and promoted with cesium. This catalyst was subjected to oxidative dehydrogenation reactions to form an alkyl methacrylate. The phases of the catalyst, before and after the reactions, were studied as a function of different cesium loading. Mössbauer spectra of the catalysts show the change of the catalyst precursor FePO4, to i) the tridymite-like phase, ii) the reduced form, iron(II) pyrophosphate and Fe2 P 2 O 7, and iii) the α-phase of iron phosphate which is governed by the temperatures of oxidation. X-ray diffraction and Mössbauer measurements on the spent catalyst show a transformation of the catalyst to a mixture of phases.

  1. Extraction of Gamow-Teller strength distributions from 56Ni and 55Co via the (p,n) reaction in inverse kinematics

    NASA Astrophysics Data System (ADS)

    Sasano, M.; Perdikakis, G.; Zegers, R. G. T.; Austin, Sam M.; Bazin, D.; Brown, B. A.; Caesar, C.; Cole, A. L.; Deaven, J. M.; Ferrante, N.; Guess, C. J.; Hitt, G. W.; Honma, M.; Meharchand, R.; Montes, F.; Palardy, J.; Prinke, A.; Riley, L. A.; Sakai, H.; Scott, M.; Stolz, A.; Suzuki, T.; Valdez, L.; Yako, K.

    2012-09-01

    Background: Gamow-Teller (GT) transition strength distributions in stable and unstable pf-shell isotopes are key inputs for estimating electron-capture rates important for stellar evolution. Charge-exchange experiments at intermediate beam energies have long been used to test theoretical predictions for GT strengths, but previous experiments were largely restricted to stable nuclei. Since a large fraction of the nuclei relevant for astrophysical applications (including key nuclei such as 56Ni) are unstable, new methods are needed to perform charge-exchange experiments in inverse kinematics with unstable isotopes.Purpose: The 56Ni(p,n) and 55Co(p,n) reactions were measured in inverse kinematics in order to extract GT strengths for transitions to 56Cu and 55Ni, respectively. The extracted strength distributions were compared with shell-model predictions in the pf shell using the KB3G and GXPF1J interactions. By invoking isospin symmetry, these strength distributions are relevant for electron captures on the ground states of 56Ni and 55Ni to final states in 56Co and 55Co, respectively.Method: Differential cross sections and excitation energy spectra for the 56Ni(p,n) and 55Co(p,n) reactions were determined by measuring neutrons recoiling from a liquid hydrogen target into the Low Energy Neutron Detector Array. GT contributions to the spectra were extracted by using a multipole decomposition analysis and were converted to strengths by employing the proportionality between GT strength and differential cross section at zero linear momentum transfer.Results: GT strengths from 56Ni and 55Co were extracted up to excitation energies of 8 and 15 MeV, respectively. Shell-model calculations performed in the pf shell with the GXPF1J interaction reproduced the experimental GT strength distributions better than calculations with the KB3G interaction.Conclusions: A new technique for measuring (p,n) charge-exchange reactions on unstable nuclei was successfully developed. It can be

  2. One-step synthesis of nitrogen-iron coordinated carbon nanotube catalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Choi, Woongchul; Yang, Gang; Kim, Suk Lae; Liu, Peng; Sue, Hung-Jue; Yu, Choongho

    2016-05-01

    Prohibitively expensive precious metal catalysts for oxygen reduction reaction (ORR) have been one of the major hurdles in a wide use of electrochemical cells. Recent significant efforts to develop precious metal free catalysts have resulted in excellent catalytic activities. However, complicated and time-consuming synthesis processes have negated the cost benefit. Moreover, detailed analysis about catalytically active sites and the role of each element in these high-performance catalysts containing nanomaterials for large surface areas are often lacking. Here we report a facile one-step synthesis method of nitrogen-iron coordinated carbon nanotube (CNT) catalysts without precious metals. Our catalysts show excellent long-term stability and onset ORR potential comparable to those of other precious metal free catalysts, and the maximum limiting current density from our catalysts is larger than that of the Pt-based catalysts. We carry out a series of synthesis and characterization experiments with/without iron and nitrogen in CNT, and identify that the coordination of nitrogen and iron in CNT plays a key role in achieving the excellent catalytic performances. We anticipate our one-step process could be used for mass production of precious metal free electrocatalysts for a wide range of electrochemical cells including fuel cells and metal-air batteries.

  3. An impact-induced terrestrial atmosphere and iron-water reactions during accretion of the Earth

    NASA Technical Reports Server (NTRS)

    Lange, M. A.; Ahrens, T. J.

    1985-01-01

    Shock wave data and theoretical calculations were used to derive models of an impact-generated terrestrial atmosphere during accretion of the Earth. The models showed that impacts of infalling planetesimals not only provided the entire budget of terrestrial water but also led to a continuous depletion of near-surface layers of water-bearing minerals of their structural water. This resulted in a final atmospheric water reservoir comparable to the present day total water budget of the Earth. The interaction of metallic iron with free water at the surface of the accreting Earth is considered. We carried out model calcualtions simulating these processes during accretion. It is assumed that these processes are the prime source of the terrestrial FeO component of silicates and oxides. It is demonstrated that the iron-water reaction would result in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed. In order to obtain the necessary amount of terrestrial water, slightly heterogeneous accretion with initially 36 wt% iron planetesimals, as compared with a homogeneous value of 34 wt% is required.

  4. An x-ray absorption study of the iron site in bacterial photosynthetic reaction centers.

    PubMed Central

    Bunker, G; Stern, E A; Blankenship, R E; Parson, W W

    1982-01-01

    Measurements were made of the extended x-ray absorption fine structure (EXAFS) of the iron site in photosynthetic reaction centers from the bacterium Rhodopseudomonas sphaeroides. Forms with two quinones, two quinones with added o-phenanthroline, and one quinone were studied. Only the two forms containing two quinones maintained their integrity and were analyzed. The spectra show directly that the added o-phenanthroline does not chelate the iron atom. Further analysis indicates that the iron is octahedrally coordinated by nitrogen and/or oxygen atoms located at various distances, with the average value of about 2.14 A. The analysis suggests that most of the ligands are nitrogens and that three of the nitrogen ligands belong to histidine rings. This interpretation accounts for several unusual features of the EXAFS spectrum. We speculate that the quinones are bound to the histidine rings in some manner. Qualitative features of the absorption edge spectra also are discussed and are related to the Fe-ligand distance. PMID:6977382

  5. Exploiting metal-ligand bifunctional reactions in the design of iron asymmetric hydrogenation catalysts.

    PubMed

    Morris, Robert H

    2015-05-19

    This is an Account of our development of iron-based catalysts for the asymmetric transfer hydrogenation (ATH) and asymmetric pressure hydrogenation (AH) of ketones and imines. These chemical processes provide enantiopure alcohols and amines for use in the pharmaceutical, agrochemical, fragrance, and other fine chemical industries. Fundamental principles of bifunctional reactivity obtained by studies of ruthenium catalysts by Noyori's group and our own with tetradentate ligands with tertiary phosphine and secondary amine donor groups were applied to improve the performance of these first iron(II) catalysts. In particular the correct positioning of a bifunctional H-Fe-NH unit in an iron hydride amine complex leads to exceptional catalyst activity because of the low energy barrier of dihydrogen transfer to the polar bond of the substrate. In addition the ligand structure with this NH group along with an asymmetric array of aryl groups orients the incoming substrate by hydrogen-bonding, and steric interactions provide the hydrogenated product in high enantioselectivity for several classes of substrates. Enantiomerically pure diamines or diphenylphosphino-amine compounds are used as the source of the asymmetry in the tetradentate ligands formed by the condensation of the amines with dialkyl- or diaryl-phosphinoaldehydes, a synthesis that is templated by Fe(II). The commercially available ortho-diphenylphosphinobenzaldehyde was used in the initial studies, but then diaryl-phosphinoacetaldehydes were found to produce much more effective ligands for iron(II). Once the mechanism of catalysis became clearer, the iron-templated synthesis of (S,S)-PAr2CH2CH2NHCHPhCHPhNH2 ligand precursors was developed to specifically introduce a secondary amine in the precatalyst structures. The reaction of a precatalyst with strong base yields a key iron-amido complex that reacts with isopropanol (in ATH) or dihydrogen (in AH) to generate an iron hydride with the Fe-H bond parallel to the

  6. Surface reactions of iron - enriched smectites: adsorption and transformation of hydroxy fatty acids and phenolic acids

    NASA Astrophysics Data System (ADS)

    Polubesova, Tamara; Olshansky, Yaniv; Eldad, Shay; Chefetz, Benny

    2014-05-01

    Iron-enriched smectites play an important role in adsorption and transformation of soil organic components. Soil organo-clay complexes, and in particular humin contain hydroxy fatty acids, which are derived from plant biopolymer cutin. Phenolic acids belong to another major group of organic acids detected in soil. They participate in various soil processes, and are of concern due to their allelopathic activity. We studied the reactivity of iron-enriched smectites (Fe(III)-montmorillonite and nontronite) toward both groups of acids. We used fatty acids- 9(10),16-dihydroxypalmitic acid (diHPA), isolated from curtin, and 9,10,16-trihydroxypalmitic acid (triHPA); the following phenolic acids were used: ferulic, p-coumaric, syringic, and vanillic. Adsorption of both groups of acids was measured. The FTIR spectra of fatty acid-mineral complexes indicated inner-sphere complexation of fatty acids with iron-enriched smectites (versus outer-sphere complexation with Ca(II)-montmorillonite). The LC-MS results demonstrated enhanced esterification of fatty acids on the iron-enriched smectite surfaces (as compared to Ca(II)-montmorillonite). This study suggests that fatty acids can be esterified on the iron-enriched smectite surfaces, which results in the formation of stable organo-mineral complexes. These complexes may serve as a model for the study of natural soil organo-clay complexes and humin. The reaction of phenolic acids with Fe(III)-montmorillonite demonstrated their oxidative transformation by the mineral surfaces, which was affected by molecular structure of acids. The following order of their transformation was obtained: ferulic >syringic >p-coumaric >vanillic. The LC-MS analysis demonstrated the presence of dimers, trimers, and tetramers of ferulic acid on the surface of Fe(III)-montmorillonite. Oxidation and transformation of ferulic acid were more intense on the surface of Fe(III)-montmorillonite as compared to Fe(III) in solution due to stronger complexation on

  7. Activation studies with a precipitated iron catalyst for Fischer-Tropsch synthesis. II. Reaction studies

    SciTech Connect

    Bukur, D.B.; Nowicki, L.; Manne, R.K.; Lang, Xiaosu

    1995-09-01

    Effects of pretreatment conditions on catalyst performance (activity, selectivity, and stability with time) during Fischer-Tropsch (FT) synthesis were studied in a fixed-bed reactor using a commercial precipitated iron catalyst (100 Fe/5 Cu/4.2K/25 SiO{sub 2} on a mass basis). The catalyst activity increased slightly with time-on-stream after hydrogen reductions, which was accompanied with conversion of metallic iron and part of iron oxides to {epsilon}{prime}-carbide ({epsilon}{prime}-Fe{sub 22}C). Initial activity of the H{sub 2}-reduced catalyst at 280{degrees}C for 8 or 24 h was markedly lower than that obtained in other tests. This is attributed to slow carburization of large oxide particles and partial poisoning of catalyst sites by migration of sulfur from the bulk to the surface of the catalyst during the reduction. Pretreatments with carbon monoxide and syngas resulted in partial conversion of Fe{sub 2}O{sub 3} to {chi}-carbide ({chi}-Fe{sub 5}C{sub 2}). During FT synthesis the CO- and the syngas-pretreated catalyst deactivated slowly with time-on-stream, due to partial conversion of {chi}-carbide to less active iron oxide phases and buildup of carbonaceous deposits which block the active sites. The hydrogen-reduced catalyst at 280{degrees}C, for 1-24h, produced more methane and gaseous hydrocarbons than the CO- or the syngas-pretreated catalyst and favored secondary reactions (1-olefin hydrogenation, isomerization, and readsorption). 41 refs., 5 figs., 2 tabs.

  8. Characterization of iron dinitrosyl species formed in the reaction of nitric oxide with a biological Rieske center.

    PubMed

    Tinberg, Christine E; Tonzetich, Zachary J; Wang, Hongxin; Do, Loi H; Yoda, Yoshitaka; Cramer, Stephen P; Lippard, Stephen J

    2010-12-29

    Reactions of nitric oxide with cysteine-ligated iron-sulfur cluster proteins typically result in disassembly of the iron-sulfur core and formation of dinitrosyl iron complexes (DNICs). Here we report the first evidence that DNICs also form in the reaction of NO with Rieske-type [2Fe-2S] clusters. Upon treatment of a Rieske protein, component C of toluene/o-xylene monooxygenase from Pseudomonas sp. OX1, with an excess of NO(g) or NO-generators S-nitroso-N-acetyl-D,L-pencillamine and diethylamine NONOate, the absorbance bands of the [2Fe-2S] cluster are extinguished and replaced by a new feature that slowly grows in at 367 nm. Analysis of the reaction products by electron paramagnetic resonance, Mössbauer, and nuclear resonance vibrational spectroscopy reveals that the primary product of the reaction is a thiolate-bridged diiron tetranitrosyl species, [Fe(2)(μ-SCys)(2)(NO)(4)], having a Roussin's red ester (RRE) formula, and that mononuclear DNICs account for only a minor fraction of nitrosylated iron. Reduction of this RRE reaction product with sodium dithionite produces the one-electron-reduced RRE, having absorptions at 640 and 960 nm. These results demonstrate that NO reacts readily with a Rieske center in a protein and suggest that dinuclear RRE species, not mononuclear DNICs, may be the primary iron dinitrosyl species responsible for the pathological and physiological effects of nitric oxide in such systems in biology. PMID:21133361

  9. Methionine as a potential precursor for halogenated compounds by the reaction with iron minerals

    NASA Astrophysics Data System (ADS)

    Tubbesing, C.; Krause, T.; Mulder, I.; Kotte, K.; Schöler, H. F.

    2012-04-01

    Volatile halogenated compounds (VOX) play an important role in different photochemical reactions within the troposphere and the stratosphere. Soils and sediments seem to act as a major natural source for VOX, but investigations of the reaction mechanisms are rather scarce. To get further information on potential intermediates the reaction of the amino acid methionine with the ferrous and ferric iron minerals pyrite and ferrihydrite as well as solute ferrous sulfate was studied using a gas chromatography-flame ionization detector (GC-FID). Methionine is an important amino acid in the biosynthesis of plants used as a starting compound for the messenger ethene with aminocyclopropane carboxylic acid as an intermediate product. This pathway may also occur under abiotic conditions. Ethene is assumed as precursor for various halogenated C2-compounds like vinyl chloride and dichloroethene. Due to its ubiquity by an average concentration of 10 to 290 ng/g soil and its potential to regenerate in soils and organic litter by microorganisms, methionine may be an important educt for both abiotic and biotic terrestrial halogenation processes. In laboratory tests methionine was exposed to different iron species like pyrite, iron sulfate or ferrihydrite. The oxidant H2O2 was used to start the reaction. Production values of methyl chloride and other halogenated compounds are discussed in the context of methionine as their potential precursor and several Fe-minerals as soil-borne catalysers. Several possible intermediates for the production of VOX have been detected e.g. methane, ethene or propane. A formation of isobutylene is noteworthy for some cases. In addition to VOC the production of methyl chloride and dimethyl sulfide (DMS) was observed. Only the DMS bears upon a specific mineral. The samples containing pyrite reveal the highest concentrations. To get a better assessment of methionine, respectively VOC released from methionine as precursors for halogenated compounds

  10. Reversible Dissociation and Ligand-Glutathione Exchange Reaction in Binuclear Cationic Tetranitrosyl Iron Complex with Penicillamine

    PubMed Central

    Syrtsova, Lidia; Sanina, Natalia; Lyssenko, Konstantin; Kabachkov, Evgeniy; Psikha, Boris; Shkondina, Natal'ja; Pokidova, Olesia; Kotelnikov, Alexander; Aldoshin, Sergey

    2014-01-01

    This paper describes a comparative study of the decomposition of two nitrosyl iron complexes (NICs) with penicillamine thiolic ligands [Fe2(SC5H11NO2)2(NO)4]SO4·5H2O (I) and glutathione- (GSH-) ligands [Fe2(SC10H17N3O6)2(NO)4]SO4·2H2O (II), which spontaneously evolve to NO in aqueous medium. NO formation was measured by a sensor electrode and by spectrophotometric methods by measuring the formation of a hemoglobin- (Hb-) NO complex. The NO evolution reaction rate from (I)  k1 = (4.6 ± 0.1)·10−3 s−1 and the elimination rate constant of the penicillamine ligand k2 = (1.8 ± 0.2)·10−3 s−1 at 25°C in 0.05 M phosphate buffer,  pH 7.0, was calculated using kinetic modeling based on the experimental data. Both reactions are reversible. Spectrophotometry and mass-spectrometry methods have firmly shown that the penicillamine ligand is exchanged for GS− during decomposition of 1.5·10−4 M (I) in the presence of 10−3 M GSH, with 76% yield in 24 h. As has been established, such behaviour is caused by the resistance of (II) to decomposition due to the higher affinity of iron to GSH in the complex. The discovered reaction may impede S-glutathionylation of the essential enzyme systems in the presence of (I) and is important for metabolism of NIC, connected with its antitumor activity. PMID:24790592

  11. Reversible dissociation and ligand-glutathione exchange reaction in binuclear cationic tetranitrosyl iron complex with penicillamine.

    PubMed

    Syrtsova, Lidia; Sanina, Natalia; Lyssenko, Konstantin; Kabachkov, Evgeniy; Psikha, Boris; Shkondina, Natal'ja; Pokidova, Olesia; Kotelnikov, Alexander; Aldoshin, Sergey

    2014-01-01

    This paper describes a comparative study of the decomposition of two nitrosyl iron complexes (NICs) with penicillamine thiolic ligands [Fe2(SC5H11NO2)2(NO)4]SO4 ·5H2O (I) and glutathione- (GSH-) ligands [Fe2(SC10H17N3O6)2(NO)4]SO4 ·2H2O (II), which spontaneously evolve to NO in aqueous medium. NO formation was measured by a sensor electrode and by spectrophotometric methods by measuring the formation of a hemoglobin- (Hb-) NO complex. The NO evolution reaction rate from (I)  k 1 = (4.6 ± 0.1)·10(-3) s(-1) and the elimination rate constant of the penicillamine ligand k 2 = (1.8 ± 0.2)·10(-3) s(-1) at 25°C in 0.05 M phosphate buffer,  pH 7.0, was calculated using kinetic modeling based on the experimental data. Both reactions are reversible. Spectrophotometry and mass-spectrometry methods have firmly shown that the penicillamine ligand is exchanged for GS(-) during decomposition of 1.5·10(-4) M (I) in the presence of 10(-3) M GSH, with 76% yield in 24 h. As has been established, such behaviour is caused by the resistance of (II) to decomposition due to the higher affinity of iron to GSH in the complex. The discovered reaction may impede S-glutathionylation of the essential enzyme systems in the presence of (I) and is important for metabolism of NIC, connected with its antitumor activity. PMID:24790592

  12. Studies on the Reaction of Iron(II) with NO in a Noncoordinating Ionic Liquid.

    PubMed

    Begel, Svetlana; Puchta, Ralph; Sutter, Jörg; Heinemann, Frank W; Dahlenburg, Lutz; Eldik, Rudi van

    2015-07-20

    In an earlier study we investigated the reaction of iron(II) chloride with NO in a strongly coordinating ionic liquid 1-ethyl-3-methylimidazolium dicyanamide [emim][dca] and showed that the actual reactive species in solution was [Fe(II)(dca)5Cl](4-). For the present report we investigated in detail how this reaction could proceed in a noncoordinating ionic liquid 1-ethyl-3-methylimidazolium trifluoromethylsulfonate [emim][OTf]. The donor ability of OTf(-) is much lower than that of dca(-), such that the solubility of FeCl2 in [emim][OTf] strongly depended on other donors like water or chloride ions present or added to the ionic liquid. On increasing the chloride concentration in [emim][OTf], the tetrachloridoferrate complex [emim]2[FeCl4] was formed, as verified by X-ray crystallography. This complex undergoes reversible binding of NO, for which the UV-vis spectral characteristics of the green-brown nitrosyl product resembled that found for the corresponding nitrosyl complexes formed in water and [emim][dca] as solvents. A detailed analysis of the spectra revealed that the {Fe-NO}(7) species has Fe(II)-NO(•) character in contrast to Fe(III)-NO(-) as found for the other solvents. The formation constant, however, is much higher than in [emim][dca], lying closer to the value found for water as solvent. Surprisingly, the Mössbauer spectrum found in [emim][OTf] is very unusual and unsimilar to that found in water and [emim][dca] as solvents, pointing at a different electron density distribution between Fe and NO in {Fe-NO}.7 First, the high isomer shift points to the presence of iron(II) species in solution, thus indicating that upon NO binding no oxidation to iron(III) occurs. Second, the negligible quadrupole splitting suggests a high local symmetry around the iron center. The nitrosyl product is suggested to be [Fe(II)Cl3NO](-), which is supported by electron paramagnetic resonance (EPR) and IR measurements. The nature of the Fe(II) complexes formed in [emim

  13. The role of sedimentology, oceanography, and alteration on the δ56Fe value of the Sokoman Iron Formation, Labrador Trough, Canada

    NASA Astrophysics Data System (ADS)

    Raye, Urmidola; Pufahl, Peir K.; Kyser, T. Kurtis; Ricard, Estelle; Hiatt, Eric E.

    2015-09-01

    The Sokoman Formation is a ca. 100-m-thick succession of interbedded iron formation and fine-grained siliciclastics deposited at 1.88 Ga. Accumulation occurred on a dynamic paleoshelf where oxygen stratification, coastal upwelling of hydrothermally derived Fe and Si, microbial processes, tide and storm currents, diagenesis, and low-grade prehnite-pumpellyite metamorphism controlled lithofacies character and produced complex associations of multigenerational chert, hematite, magnetite, greenalite, stilpnomelane and Fe carbonate. Hematite-rich facies were deposited along suboxic segments of the coastline where photosynthetic oxygen oases impinged on the seafloor. Hematitic, cross-stratified grainstones were formed by winnowing and reworking of freshly precipitated Fe-(oxyhydr)oxide and opal-A by waves and currents into subaqueous dunes. Magnetite-rich facies contain varying proportions of greenalite and stilpnomelane and record deposition in anoxic middle shelf environments beneath an oxygen chemocline. Minor negative Ce anomalies in hematitic facies, but prominent positive Ce and Eu anomalies and high LREE/HREE ratios in magnetite-rich facies imply the existence of a weakly oxygenated surface ocean above anoxic bottom waters. The Fe isotopic composition of 31 whole rock (-0.46 ⩽ δ56Fe ⩽ 0.47‰) and 21 magnetite samples (-0.29 ⩽ δ56Fe ⩽ 0.22‰) from suboxic and anoxic lithofacies was controlled primarily by the physical oceanography of the paleoshelf. Despite low-grade metamorphism recorded by the δ18O values of paragenetically related quartz and magnetite, the Sokoman Formation preserves a robust primary Fe isotopic signal. Coastal upwelling is interpreted to have affected the isotopic equilibria between Fe2+aq and Fe-(oxyhydr)oxide in open marine versus coastal environments, which controlled the Fe isotopic composition of lithofacies. Unlike previous work that focuses on microbial and abiotic fractionation processes with little regard for

  14. Iron

    MedlinePlus

    ... organ failure, coma, convulsions, and death. Child-proof packaging and warning labels on iron supplements have greatly ... levodopa that the body absorbs, making it less effective. Levodopa, found in Sinemet® and Stalevo®, is used ...

  15. Reaction mechanism for the highly efficient catalytic decomposition of peroxynitrite by the amphipolar iron(III) corrole 1-Fe.

    PubMed

    Avidan-Shlomovich, Shlomit; Gross, Zeev

    2015-07-21

    The amphipolar iron(III) corrole 1-Fe is one of the most efficient catalysts for the decomposition of peroxynitrite, the toxin involved in numerous diseases. This research focused on the mechanism of that reaction at physiological pH, where peroxynitrite is in equilibrium with its much more reactive conjugated acid, by focusing on the elementary steps involved in the catalytic cycle. Kinetic investigations uncovered the formation of a reaction intermediate in a process that is complete within a few milliseconds (k1 ∼ 3 × 10(7) M(-1) s(-1) at 5 °C, about 7 orders of magnitude larger than the first order rate constant for the non-catalyzed process). Multiple evidence points towards iron-catalyzed homolytic O-O bond cleavage to form nitrogen dioxide and hydroxo- or oxo-iron(iv) corrole. The iron(iv) intermediate was found to decay via multiple pathways that proceed at similar rates (k2 about 10(6) M(-1) s(-1)): reaction with nitrogen dioxide to form nitrate, nitration of the corrole macrocyclic, and dimerization to binuclear iron(iv) corrole. Catalysis in the presence of substrates affects the decay of the iron intermediate by either oxidative nitration (phenolic substrates) or reduction (ascorbate). A large enough excess of ascorbate accelerates the catalytic decomposition of PN by 1-Fe by orders of magnitude, prevents other decay routes of the iron intermediate, and eliminates nitration products as well. This suggests that the beneficial effect of the iron corrole under the reducing conditions present in most biological media might be even larger than in the purely chemical system. The acquired mechanistic insight is of prime importance for the design of optimally acting catalysts for the fast and safe decomposition of reactive oxygen and nitrogen species. PMID:25747957

  16. The Application of Copper/Iron Cocatalysis in Cross-Coupling Reactions.

    PubMed

    Mao, Jincheng; Yan, Hong; Rong, Guangwei; He, Yue; Zhang, Guoqi

    2016-06-01

    For conventional cross-couplings in organic chemistry, precious metal (such as Pd or Rh) complexes have been the preferable choices as catalysts. However, their high cost, toxicity, and potential contamination of products limit their massive applications on some occasions, particularly in the pharmaceutical industry, where close monitoring of the metal contamination of products is required. Therefore, the use of metals that are less expensive and less toxic than Pd or Rh can be greatly advantageous and earth abundant metal (such Fe or Cu) catalysts have shown promise for replacing the precious metals. Interestingly, a certain copper catalyst combined with an iron catalyst displays higher catalytic efficiency than itself in various coupling reactions. Notably, ligand-free conditions make such protocols more useful and practical in many cases. In this account, we summarize the recent progress made in this increasingly attractive topic by describing successful examples, including our own work in the literature, regarding effective copper/iron cocatalysis. In addition, a few examples involving a magnetic and readily recyclable CuFe2 O4 nanoparticle cocatalyst are also included. PMID:27027733

  17. Inorganic phosphate promotes redox cycling of iron in liver microsomes: effects on free radical reactions.

    PubMed

    Reinke, L A; Moore, D R; Rau, J M; McCay, P B

    1995-02-01

    The phosphate buffer concentration used in spin trapping experiments with liver microsomes markedly influenced rates of free radical formation from ethanol and dimethylsulfoxide, but not from carbon tetrachloride. Effects of phosphate concentration on ethanol radical formation were abolished by addition of deferoxamine or bathophenanthrolene, indicating that an iron-phosphate complex might be involved. High concentrations of phosphate stimulated rates of microsomal Fe+3 reduction and facilitated the mobilization of microsomal nonheme iron, but had little effect on a variety of microsomal monooxygenase enzyme activities. Although microsomal oxygen utilization and superoxide production were relatively unaffected by phosphate, hydrogen peroxide concentrations were markedly decreased in the presence of high concentrations of phosphate. Taken together, the data suggest that a ferric-phosphate complex may be enzymatically reduced by microsomal enzymes and NADPH. Reoxidation of ferrous ion is nonenzymatically promoted by phosphate and/or H2O2 produced by the microsomes. During the process of reoxidation, one or more oxidizing intermediates may be formed which initiate secondary free radical reactions. Although the reactivity of the intermediate(s) is similar to that of the hydroxyl radical, no spin trapping evidence was obtained to support this assignment. PMID:7864631

  18. Effect of thiamine hydrochloride on the redox reactions of iron at pyrite surface

    SciTech Connect

    Pesic, B.; Oliver, D.J.

    1990-01-01

    The present investigation is a part of our studies on the electro chemical aspects of pyrite bioleaching involving Thiobacillus ferrooxidans. Previously (1,2) we have examined the effect of T. ferrooxidans and their metabolic products on the redox reactions of Fe[sup 2+]/Fe[sup 3+] couple at the pyrite surface. Results obtained suggest that beyond 1. 5 days during their growth in a batch fermenter, the bacteria and their metabolic products completely cover the pyrite surface and shut down all electron transfer across the electrode-solution interface. In addition, it has been observed that the bacteria serve as the nucleation site for jarosite formation, which is found detrimental to bioleaching. In the present work we have focussed on the effect of the presence of vitamins on the redox chemistry of iron. Our examination of the effect of the presence of thiamine hydrochloride in the redox behavior of Fe[sup 2+]/Fe[sup 3+] at the pyrite surface has revealed that thiamine hydrochloride does not undergo chemical interaction with ferrous or ferric iron. However, it may adsorb onto the pyrite surface causing polarization of the pyrite electrode.

  19. Iron disilicide formation by Au-Si eutectic reaction on Si substrate

    NASA Astrophysics Data System (ADS)

    Akiyama, Kensuke; Kaneko, Satoru; Yokomizo, Kazuya; Itakura, Masaru

    2009-11-01

    We have investigated the growth of iron disilicide on Au-coated Si(0 0 1) substrates and its photoluminescence behaviour. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy observations revealed that the Si surface above 380 °C was melted as a result of the Au-Si eutectic reaction and that coarse island disilicide grains with sizes of several micrometres were formed on the Si surface. The full width at half maximum of 0.056° on the rocking curve of α-FeSi 2004 was observed on the sample deposited at 800 °C, and indicated the high crystal quality in perfection of orientation. The photoluminescence spectrum of β-FeSi 2 grains, which were deposited at 750 °C, was observed. The melted Si surface contributed to the improved crystallinity of α-FeSi 2 and β-FeSi 2.

  20. Release Activation of Iron Oxide Nanoparticles (REACTION): A novel environmentally sensitive MRI paradigm

    PubMed Central

    Granot, Dorit; Shapiro, Erik M.

    2011-01-01

    Smart contrast agents for MRI-based cell tracking would enable the use of MRI methodologies to not only detect the location of cells, but also gene expression. Here we report on a new enzyme/contrast agent paradigm which involves the enzymatic degradation of the polymer coating of magnetic nanoparticles to release encapsulated magnetic cores. Cells were labeled with particles coated with a polymer which is cleavable by a specific enzyme. This coat restricts the approach of water to the particle, preventing the magnetic core from efficiently relaxing protons. The reactive enzyme was delivered to cells and changes in cellular T2 and T2* relaxation times of ~ 35% and ~ 50% were achieved in vitro. Large enhancements of dark contrast volume (240%) and CNR (48%) within the contrast regions were measured, in vivo, for cells co-labeled with enzyme and particles. These results warrant exploration of genetic avenues towards achieving RElease ACTivation of Iron Oxide Nanoparticles (REACTION). PMID:21360745

  1. Gamma-resonance study of the reaction of iron ions with synthetic L-dopa melanin

    SciTech Connect

    Bagirov, R.M.; Stukan, R.A.; Lapina, V.A.; Dontsov, A.E.; Ostrovskii, M.A.

    1986-07-01

    The reaction of Fe/sup 3 +/ and Fe/sup 2 +/ ions with synthetic L-dopa melanin, which is a model compound of natural melanin (the melanoprotein granules in the pigment epithelial cells in vertebrate and human eyes), has been studied by gamma-resonance spectroscopy. The investigations showed that L-dopa melanin is capable of effectively binding iron ions and that it displays oxidative or reducing properties with respect to Fe, depending on the composition of the subsystem of the Fe ions and the ambient pH. Trivalent Fe/sup 3 +/ ions form stronger complexes with L-dopa melanin than do Fe/sup 2 +/ ions. The coordination takes place mainly with the carboxyl groups and the amino and imino groups of the polymer. The conformational state of the polymer apparently changes as the pH is varied.

  2. Heterocarbon nanosheets incorporating iron phthalocyanine for oxygen reduction reaction in both alkaline and acidic media.

    PubMed

    Hyun, Koangyong; Ueno, Tomonaga; Panomsuwan, Gasidit; Li, Oi Lun; Saito, Nagahiro

    2016-04-28

    Heterocarbon nanosheets incorporating iron phthalocyanine (FP-NCNs-SP) have been successfully synthesized by a facile one-pot solution plasma process at high repetition frequency. It was found that the Fe-N4 catalytic active sites could be preserved on the FP-NCNs-SP without degradation. The FP-NCNs-SP also possessed large surface area, good conductivity and high degree of graphitization. Electrochemical evaluations demonstrated that NCNs-SP had excellent electrocatalytic activity and selectivity toward oxygen reduction reaction (ORR) in alkaline medium through a direct four-electron pathway. Although the significant improvement in ORR activity was clearly observed in acidic medium, it was much poorer than in alkaline medium. We believe that the results presented in this work will shed light on the advanced synthesis and design of ORR electrocatalysts at room temperature with an abundance of catalytically active sites and high ORR performance. PMID:27055883

  3. [Effect of accelerated heavy ions of carbon 12C, neon 20Ne and iron 56Fe on the chromosomal apparatus of human blood lymphocytes in vitro].

    PubMed

    Repina, L A

    2011-01-01

    Cytogenetic assay of the chromosomal apparatus of human blood lymphocytes was carried out after in vitro irradiation by heavy charged particles with high LET values. Blood plasm samples enriched with lymphocytes were irradiated by accelerated ions of carbon 12C (290 MeV/nucleon and LET = 70 keV/microm), neon 20Ne (400 MeV/nucleon and LET = 70 keV/microm), and iron 56Fe (500 MeV/nucleon and LET = 200 keV/microm) in the dose range from 0.25 to 1 Gy. Rate of chromosome aberrations showed a linear dependence on doses from the densely ionizing radiations with high LET values. Frequency of dicentrics and centric rings in human lymphocytes irradiated by 12C with the energy of 290 MeV/nucleon was maximal at 1 Gy (p < 0.05) relative to the other heavy particles. It was found that relative biological effectiveness of heavy nuclei is several times higher than of 60Co gamma-radiation throughout the range of doses in this investigation. PMID:22312859

  4. Mechanism of the Iron(II)-Catalyzed Hydrosilylation of Ketones: Activation of Iron Carboxylate Precatalysts and Reaction Pathways of the Active Catalyst.

    PubMed

    Bleith, Tim; Gade, Lutz H

    2016-04-13

    A detailed mechanistic study of the catalytic hydrosilylation of ketones with the highly active and enantioselective iron(II) boxmi complexes as catalysts (up to >99% ee) was carried out to elucidate the pathways for precatalyst activation and the mechanism for the iron-catalyzed hydrosilylation. Carboxylate precatalysts were found to be activated by reduction of the carboxylate ligand to the corresponding alkoxide followed by entering the catalytic cycle for the iron-catalyzed hydrosilylation. An Eyring-type analysis of the temperature dependence of the enantiomeric ratio established a linear relationship of ln(S/R) and T(-1), indicating a single selectivity-determining step over the whole temperature range from -40 to +65 °C (ΔΔG(‡)sel, 233 K = 9 ± 1 kJ/mol). The rate law as well as activation parameters for the rate-determining step were derived and complemented by a Hammett analysis, radical clock experiments, kinetic isotope effect (KIE) measurements (kH/kD = 3.0 ± 0.2), the isolation of the catalytically active alkoxide intermediate, and DFT-modeling of the whole reaction sequence. The proposed reaction mechanism is characterized by a rate-determining σ-bond metathesis of an alkoxide complex with the silane, subsequent coordination of the ketone to the iron hydride complex, and insertion of the ketone into the Fe-H bond to regenerate the alkoxide complex. PMID:27013140

  5. The secondary coordination sphere and axial ligand effects on oxygen reduction reaction by iron porphyrins: a DFT computational study.

    PubMed

    Ohta, Takehiro; Nagaraju, Perumandla; Liu, Jin-Gang; Ogura, Takashi; Naruta, Yoshinori

    2016-09-01

    Oxygen reduction reaction (ORR) catalyzed by a bio-inspired iron porphyrin bearing a hanging carboxylic acid group over the porphyrin ring, and a tethered axial imidazole ligand was studied by DFT calculations. BP86 free energy calculations of the redox potentials and pK a's of reaction components involved in the proton coupled electron transfer (PCET) reactions of the ferric-hydroxo and -superoxo complexes were performed based on Born-Haber thermodynamic cycle in conjunction with a continuum solvation model. The comparison was made with iron porphyrins that lack either in the hanging acid group or axial ligand, suggesting that H-bond interaction between the carboxylic acid and iron-bound hydroxo, aquo, superoxo, and peroxo ligands (de)stabilizes the Fe-O bonding, resulting in the increase in the reduction potential of the ferric complexes. The axial ligand interaction with the imidazole raises the affinity of the iron-bound superoxo and peroxo ligands for proton. In addition, a low-spin end-on ferric-hydroperoxo intermediate, a key precursor for O-O cleavage, can be stabilized in the presence of axial ligation. Thus, selective and efficient ORR of iron porphyrin can be achieved with the aid of the secondary coordination sphere and axial ligand interactions. PMID:27501847

  6. Investigation into the role of the boudouard reaction in self-reducing iron oxide and carbon briquettes

    NASA Astrophysics Data System (ADS)

    Moon, Jeremy; Sahajwalla, Veena

    2006-04-01

    With increasing impetus to utilize more waste byproducts from ironmaking processes, a greater understanding of processes that utilize these wastes is required. In this article, the kinetics of reaction of briquettes consisting of ultrafine iron oxide and carbon are examined representing a progression in the understanding of methods to utilize fine iron oxide and carbon resulting from all stages of processing. More specifically, this article examines the role of the Boudouard reaction and its level of control in such reaction systems for the temperature range of 1000 °C to 1200 °C. Various techniques were used to examine this role, including investigating the effect of the surface area of the carbon used, the effect of a known Boudouard reaction catalyst, and the effect of temperature.

  7. Investigation of Some Stellar Iron Group Fusion Materials for ( n, p) Reactions

    NASA Astrophysics Data System (ADS)

    Sahan, M.; Tel, E.; Aydin, A.; Yegingil, Ilhami

    2012-02-01

    In this study, we present the results of a careful analysis of cross sections of some important iron (Fe) group target elements (20 ≤ Z≤28) for astrophysical ( n, p) reactions such as Si, Ca, Sc, Ti, V, Cr, Fe, Co and Ni used in neutron activation analysis have been investigated. The new calculations on the excitation functions of 28 Si(n, p) 28 Al, 29 Si(n, p) 29 Al, 42 Ca(n, p) 42 K, 45 Sc(n, p) 45 Ca, 46 Ti(n, p) 46 Sc, 51 V(n, p) 51 Ti, 52 Cr(n, p) 52 V, 53 Cr(n, p) 53 V, 54 Fe(n, p) 54 Mn, 57 Fe(n, p) 57 Mn, 59 Co(n, p) 59 Fe, 58 Ni(n, p) 58 Co and 60 Ni(n, p) 60 Co reactions have been carried out up to 25 MeV incident neutron energy. In these calculations, the pre-equilibrium and equilibrium effects have been investigated. Equilibrium effects are calculated according to the Weisskopf-Ewing model. The pre-equilibrium calculations involve the geometry dependent hybrid model, hybrid model and equilibrium model. Also in the present work, these reaction cross-sections have been calculated by using evaluated empirical formulas developed by Tel et al. at 14.7 MeV energy. The calculations are compared with existing experimental data as well as with evaluated data files (Experimental Nuclear Reaction Data (EXFOR). According to these calculations, we assume that these model calculations can be applied to some heavy elements, ejected into interstellar medium by dramatic supernova events.

  8. Kinetics of iron redox reaction in silicate melts: A high temperature Xanes study on an alkali basalt

    NASA Astrophysics Data System (ADS)

    Cochain, B.; Neuville, D. R.; de Ligny, D.; Roux, J.; Baudelet, F.; Strukelj, E.; Richet, P.

    2009-11-01

    In Earth and Materials sciences, iron is the most important transition element. Glass and melt properties are strongly affected by iron content and redox state with the consequence that some properties (i.e. viscosity, heat capacity, crystallization...) depend not only on the amounts of Fe2+ and Fe3+, but also on the coordination state of these ions. In this work we investigate iron redox reactions through XANES experiments at the K-edge of iron. Using a high-temperature heating device, pre-edge of XANES spectra exhibits definite advantages to make in-situ measurements and to determine the evolution of redox state with time, temperature and composition of synthetic silicate melts. In this study, new kinetics measurements are presented for a basalt melt from the 31,000-BC eruption of the Puy de Lemptegy Volcano in France. These measurements have been made between 773 K and at superliquidus temperatures up to 1923 K.

  9. Models for cytochrome P450 prosthetic heme alkylation. Reaction of diazoacetophenone with (tetraphenylporphyrinato)iron(II) chloride

    SciTech Connect

    Komives, E.A.; Tew, D.; Olmstead, M.M.; Ortiz de Montellano, P.R.

    1988-09-07

    The reaction of diazoacetophenone with (tetraphenylporphyrinato)iron(II) yields (N-(2-phenyl-2-oxoethyl)tetraphenylporphyrinato)iron(II) chloride. The structure of this product has been established by spectroscopic methods and by x-ray crystallography. The crystal structure shows that the first carbon of the N-alkyl group is 2.94 /angstrom/ from the iron atom and that the oxygen of the N-alkyl group points away from the iron. No evidence is seen for the Fe-C-N product expected from insertion of the diazo carbon into the metalloporphyrin iron-nitrogen bond or for intermediates in which the oxygen of the N-(2-phenyl-2-oxoethyl) group is coordinated to the iron. These results suggest it is unlikely that carbene-insertion or oxygen-coordinated intermediates will be detected during the N-alkylation of cytochrome P450 by diazo ketones. The results also rationalize the failure to detect iron-chelated enol species during N-alkylation of the prosthetic group of cytochrome P450 by catalytically activated phenylacetylene. 43 references, 5 figures, 4 tables.

  10. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    SciTech Connect

    Dixon, David Adams

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  11. Iron encapsulated in boron and nitrogen codoped carbon nanotubes as synergistic catalysts for Fenton-like reaction.

    PubMed

    Yao, Yunjin; Chen, Hao; Qin, Jiacheng; Wu, Guodong; Lian, Chao; Zhang, Jie; Wang, Shaobin

    2016-09-15

    Iron nanoparticles (NPs) encapsulated in B, N-codoped carbon nanotubes (Fe@C-BN) as heterogeneous Fenton-like catalysts were obtained by a simple and scalable pyrolysis method, and their performances were examined in the oxidative degradation of various organics in the presence of the different oxidants. The results showed that organic dyes can be effectively degraded by Fe@C-BN in the presence of peroxymonosulfate. Calcination temperature and mass of iron salt significantly affected the structures and performances of the catalysts. The effects of several reaction conditions, such as initial dye concentration, oxidant type (peroxymonosulfate, peroxydisulfate, and H2O2) and dosage, initial pH, inorganic anions, reaction temperature and dye types on oxidation as well as the stability of the composite were extensively evaluated in view of the practical applications. Through the investigation of reaction processes, HO(·) and SO4(·-) radicals were identified using quenching experiments. Owing to the synergistic effects between the iron NPs and B, N-doped carbon, Fe@C-BN catalysts intrinsically display an excellent catalytic activity for Fenton-like reaction. This study gives new insights into the design and preparation of iron NPs encapsulated in B, N-codoped carbon nanotubes as an effective strategy to enhance the overall catalytic activity. PMID:27267476

  12. Simple and Inexpensive Computer Interface to a Durrum Stopped-Flow Apparatus Tested Using the Iron (III)--Thiocyanate Reaction

    ERIC Educational Resources Information Center

    Hoag, Craig M.

    2005-01-01

    A simple Vernier software and Technology LabPro unit was used to interface a computer with a Durrum model 110 stopped-flow apparatus using the iron (III)--thiocyanate reaction. The software can readily be used to retrieve that data from the stopped-flow apparatus using one probe to measure the voltage and a second probe to trigger the data…

  13. A simple and efficient procedure of low valent iron- or copper-mediated Reformatsky reaction of aldehydes.

    PubMed

    Chattopadhyay, Angshuman; Dubey, Akhil Kr

    2007-11-23

    An operationally simple and very efficient procedure of Reformatsky reaction of aldehydes has been carried out in THF in the presence of low valent iron or copper which were prepared in situ employing a bimetal redox strategy through reduction of FeCl3 or CuCl2-2H2O with magnesium. PMID:17973426

  14. Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero-valent iron.

    PubMed

    Li, Huanxuan; Wan, Jinquan; Ma, Yongwen; Wang, Yan

    2016-08-15

    This study investigated reaction pathway and oxidation mechanisms of dibutyl phthalate (DBP) by persulfate (PS) activated with zero-valent iron (ZVI). The DBP degradation was studied at three pH values (acidic, neutral and basic) in the presence of different organic scavengers. Using a chemical probe method, both sulfate radical (SO4(-)) and hydroxyl radical (·OH) were found to be primary oxidants at pH3.0 and pH7.0, respectively while ·OH was the major specie to oxidize DBP at pH11.0. A similar result was found in an experiment of Electron Spin Resonance spin-trapping where in addition to OH, superoxide radical (O2(-)) was detected at pH11.0. The transformation of degradation products including dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic anhydride, and acetophenone exhibited diverse variation during the reaction processes. The phthalic anhydride concentration appeared to be maximum at all pHs. Another eleven intermediate products were also found at pH3.0 by GC-MS and HPLC analysis, and their degradation mechanisms and pathways were proposed. It was suggested that dealkylation, hydroxylation, decarboxylation and hydrogen extraction were the dominant degradation mechanisms of DBP at pH3.0. PMID:27125682

  15. Cluster dynamics models of irradiation damage accumulation in ferritic iron. II. Effects of reaction dimensionality

    SciTech Connect

    Kohnert, Aaron A.; Wirth, Brian D.

    2015-04-21

    The black dot damage features which develop in iron at low temperatures exhibit significant mobility during in situ irradiation experiments via a series of discrete, intermittent, long range hops. By incorporating this mobility into cluster dynamics models, the temperature dependence of such damage structures can be explained with a surprising degree of accuracy. Such motion, however, is one dimensional in nature. This aspect of the physics has not been fully considered in prior models. This article describes one dimensional reaction kinetics in the context of cluster dynamics and applies them to the black dot problem. This allows both a more detailed description of the mechanisms by which defects execute irradiation-induced hops while allowing a full examination of the importance of kinetic assumptions in accurately assessing the development of this irradiation microstructure. Results are presented to demonstrate whether one dimensional diffusion alters the dependence of the defect population on factors such as temperature and defect hop length. Finally, the size of interstitial loops that develop is shown to depend on the extent of the reaction volumes between interstitial clusters, as well as the dimensionality of these interactions.

  16. Synthesis of nanocrystalline yttrium iron garnet by low temperature solid state reaction

    SciTech Connect

    Yu Hongtao Zeng Liwen; Lu Chao; Zhang Wenbo; Xu Guangliang

    2011-04-15

    In this work, nanocrystalline yttrium iron garnet powders were produced by low temperature solid state reaction. The phase evolution during the procedure was determined from the thermogravimetric and differential thermal analysis, and the x-ray diffraction patterns. The results of transmission electron microscopy indicated that the prepared powders exhibited grain size at the nano-level of 20 {approx} 40 nm. Dense ceramics with a theoretical density of around 98% were obtained from the prepared powders after sintering at 1280 deg. C, a relative low sintering temperature compared with conventional ceramic processes, and the saturation magnetizations of sintered samples were also determined. - Research Highlights: {yields}No sol or gel form during the synthesis processing using nitrates and citric acid as raw materials. {yields}The synthesis method needs a low heating temperature (700 deg. C) compared with conventional solid state reaction. {yields}The product is a single phase with homogeneous size distribution and nano grains (20 {approx} 40 nm) confirmed by TEM. {yields}Dense YIG ceramic can be sintered at a low temperature (1280 deg. C) compared with that in conventional processing.

  17. Hydroxamate siderophore-promoted reactions between iron(II) and nitroaromatic groundwater contaminants

    NASA Astrophysics Data System (ADS)

    Kim, Dongwook; Duckworth, Owen W.; Strathmann, Timothy J.

    2009-03-01

    Recent studies show that ferrous iron (Fe II), which is often abundant in anaerobic soil and groundwater, is capable of abiotically reducing many subsurface contaminants. However, studies also demonstrate that Fe II redox reactivity in geochemical systems is heavily dependent upon metal speciation. This contribution examines the influence of hydroxamate ligands, including the trihydroxamate siderophore desferrioxamine B (DFOB), on Fe II reactions with nitroaromatic groundwater contaminants (NACs). Experimental results demonstrate that ring-substituted NACs are reduced to the corresponding aniline products in aqueous solutions containing Fe II complexes with DFOB and two monohydroxamate ligands (acetohydroxamic acid and salicylhydroxamic acid). Reaction rates are heavily dependent upon solution conditions and the identities of both the Fe II-complexing hydroxamate ligand and the target NAC. Trends in the observed pseudo-first-order rate constants for reduction of 4-chloronitrobenzene ( kobs, s -1) are quantitatively linked to the formation of Fe II species with standard one-electron reduction potentials, EH0 (Fe III/Fe II), below -0.3 V. Linear free energy relationships correlate reaction rates with the EH0 (Fe III/Fe II) values of different electron-donating Fe II complexes and with the apparent one-electron reduction potentials of different electron-accepting NACs, EH1'(ArNO 2). Experiments describing a redox auto-decomposition mechanism for Fe II-DFOB complexes that occurs at neutral pH and has implications for the stability of hydroxamate siderophores in anaerobic environments are also presented. Results from this study indicate that hydroxamates and other Fe III-stabilizing organic ligands can form highly redox-active Fe II complexes that may contribute to the natural attenuation and remediation of subsurface contaminants.

  18. Diversity of Contaminant Reduction Reactions by Zero-Valent Iron: Role of the Reductate

    SciTech Connect

    Miehr, R; Tratnyek, Paul G.; Bandstra, J; Scherer, Michelle; Alowitz, M; Bylaska, Eric J.

    2004-01-01

    The reactions of 8 model contaminants with 9 types of granular Fe(0) were studied in batch experiments using consistent experimental conditions. The model contaminants (herein referred to as reductates because they were reduced by the iron metal) included cations (Cu2+), anions (CrO42-; NO3-; and 5,5,7,7-indigotetrasulfonate), and neutral species (2-chloroacetophenone; 2,4,6-trinitrotoluene; carbon tetrachloride; and trichloroethene). The diversity of this range of reductates offers a uniquely broad perspective on the reactivity of Fe(0). Rate constants for disappearance of the reductates vary over as much as 4 orders of magnitude for particular reductates (due to differences in the 9 types of iron) but differences among the reductates were even larger, ranging over almost 7 orders of magnitude. Various ways of summarizing the data all suggest that relative reactivities with Fe(0) varies in the order: Cu2, I4S > 2CAP, TNT > CT, Cr6 > TCE > NO3. Although the reductate h as the largest effect on disappearance kinetics, more subtle differences in reactivity due to the type of Fe(0) suggests that removal of Cr6 and NO3 (the inorganic anions) involves adsorption to oxides on the Fe(0), whereas the disappearance kinetics of all other types of reductants is favored by reduction on comparatively oxide-free metal. Correlation analysis of the disappearance rate constants using descriptors of the reductates calculated by molecular modeling (energies of the lowest unoccupied molecular orbitals, LUMO, highest occupied molecular orbitals, HOMO, and HOMO-LUMO gaps) showed that reactivities generally increase with decreasing ELUMO and increasing EGAP (and, therefore, increasing chemical hardness h).

  19. Evidence for Ni-56 yields Co-56 yields Fe-56 decay in type Ia supernovae

    NASA Technical Reports Server (NTRS)

    Kuchner, Marc J.; Kirshner, Robert P.; Pinto, Philip A.; Leibundgut, Bruno

    1994-01-01

    In the prevailing picture of Type Ia supernovae (SN Ia), their explosive burning produces Ni-56, and the radioactive decay chain Ni-56 yields Co-56 yields Fe-56 powers the subsequent emission. We test a central feature of this theory by measuring the relative strengths of a (Co III) emission feature near 5900 A and a (Fe III) emission feature near 4700 A. We measure 38 spectra from 13 SN Ia ranging from 48 to 310 days after maximum light. When we compare the observations with a simple multilevel calculation, we find that the observed Fe/Co flux ratio evolves as expected when the Fe-56/Co-56 abundance ratio follows from Ni-56 yields Co-56 yields Fe-56 decay. From this agreement, we conclude that the cobalt and iron atoms we observe through SN Ia emission lines are produced by the radioactive decay of Ni-56, just as predicted by a wide range of models for SN Ia explosions.

  20. The stereochemical outcome of electrophilic addition reactions on the 5,6-double bond in the spinosyns.

    PubMed

    De Amicis, C V; Graupner, P R; Erickson, J A; Paschal, J W; Kirst, H A; Creemer, L C; Fanwick, P E

    2001-12-14

    The electrophilic addition of reagents to the 5,6-double bond in spinosyn A and spinosyn D systems occurred with high pi-diastereofacial selectivity. Addition occurred preferentially from the beta face of the molecule with selectivities ranging from 5:1 to better than 30:1. Various NMR properties were investigated in order to distinguish the beta and alpha isomers with the help of theoretical models of the products. These NMR properties include a (13)C gamma effect to C-11 and vicinal coupling between H-4 and H-5. To help rationalize the selectivity, computational studies on the transition states for epoxidation were calculated using density functional theory. The results indicate that beta epoxidation is favored and that the geometries of the transition structures are consistent with torsional steering being the source of the selectivity. PMID:11735521

  1. Combined reactions thermomechanical processing applied to ferromagnetic iron-palladium binary alloys

    NASA Astrophysics Data System (ADS)

    Cantando, Elizabeth Dawn

    2011-12-01

    The aim of this thesis was to use a combination of thermomechanical processing and heat treatment, including magnetic field annealing, to tailor ultra-fine microstructures with enhanced properties in ferromagnetic alloys. The combined reactions strategy involves the use of thermomechanical processing to induce two or more solid-state reactions to occur concomitantly, synergistically and / or sequentially during microstructural development, e.g. severe plastic deformation followed by recrystallization in tandem with precipitation, ordering and / or decomposition. The specific thrust is aimed at producing exchange-coupled nanocomposite structures in off-stoichiometric Fe-Pd alloys, which might be expected to form two-phase mixtures of magnetically soft ferrite (alpha) and the magnetically hard L10 intermetallic phase. The severe plastic deformation of the parent phase serves to enhance diffusion kinetics in addition to catalyzing novel reaction paths and microstructural development as the system relaxes toward equilibrium. Vibrating sample magnetometry (VSM), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were performed to investigate the microstructure and the magnetic properties of combined reactions transformed hypo-stoichiometric iron-palladium. Two distinct microstructures were observed to develop in these alloys, resulting from two different modes of solid-state transformation. Conventional aging of the solutionized alloys resulted in eutectoid decomposition whereby the ferrite and L10 phases precipitate a cellular product on a 100nm length scale that coarsens as aging progresses. In contrast, aging the deformed alloys produces a nanoscale lamellar composite structure consisting of alternate L10 and metastable FCC phases, on a scale of 10nm. The finer scale product appears to derive from pseudospinodal decomposition, while ferrite is simultaneously observed to precipitate heterogeneously on grain

  2. Porous Nickel-Iron Selenide Nanosheets as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction.

    PubMed

    Wang, Zhaoyang; Li, Jiantao; Tian, Xiaocong; Wang, Xuanpeng; Yu, Yang; Owusu, Kwadwo Asare; He, Liang; Mai, Liqiang

    2016-08-01

    Exploring non-noble and high-efficiency electrocatalysts is critical to large-scale industrial applications of electrochemical water splitting. Currently, nickel-based selenide materials are promising candidates for oxygen evolution reaction due to their low cost and excellent performance. In this work, we report the porous nickel-iron bimetallic selenide nanosheets ((Ni0.75Fe0.25)Se2) on carbon fiber cloth (CFC) by selenization of the ultrathin NiFe-based nanosheet precursor. The as-prepared three-dimensional oxygen evolution electrode exhibits a small overpotential of 255 mV at 35 mA cm(-2) and a low Tafel slope of 47.2 mV dec(-1) and keeps high stability during a 28 h measurement in alkaline solution. The outstanding catalytic performance and strong durability, in comparison to the advanced non-noble metal catalysts, are derived from the porous nanostructure fabrication, Fe incorporation, and selenization, which result in fast charge transportation and large electrochemically active surface area and enhance the release of oxygen bubbles from the electrode surface. PMID:27400679

  3. Synthesis of iron aluminide-Al{sub 2}O{sub 3} composites by in-situ displacement reactions

    SciTech Connect

    Subramanian, R.; McKamey, C.G.; Buck, L.R.; Schneibel, J.H.

    1997-09-01

    Composites consisting of an iron aluminide matrix with ceramic particle reinforcements, such as alumina, could improve the high temperature strength without compromising the oxidation resistance. In this paper, the feasibility of processing Fe-Al alloy/Al{sub 2}O{sub 3} composites by an in-situ displacement reaction between Fe-40 at.% Al and iron oxide, Fe{sub 2}O{sub 3}, is investigated. Simple powder metallurgical processing was performed without resorting to an externally applied pressures or deformations during the high temperature processing step. The microstructural features of the composites are rationalized based on results from diffusion couples. Preliminary mechanical properties such as fracture toughness, yield strength and hardness are determined and compared with the values obtained for monolithic iron aluminide - Fe-28 at.% Al. Results suggest that a significant improvement in the properties is needed and further avenues for modifications, such as changes in the interface strength and externally applied forces during processing, are suggested.

  4. Single-shell carbon-encapsulated iron nanoparticles: synthesis and high electrocatalytic activity for hydrogen evolution reaction.

    PubMed

    Tavakkoli, Mohammad; Kallio, Tanja; Reynaud, Olivier; Nasibulin, Albert G; Johans, Christoffer; Sainio, Jani; Jiang, Hua; Kauppinen, Esko I; Laasonen, Kari

    2015-04-01

    Efficient hydrogen evolution reaction (HER) through effective and inexpensive electrocatalysts is a valuable approach for clean and renewable energy systems. Here, single-shell carbon-encapsulated iron nanoparticles (SCEINs) decorated on single-walled carbon nanotubes (SWNTs) are introduced as a novel highly active and durable non-noble-metal catalyst for the HER. This catalyst exhibits catalytic properties superior to previously studied nonprecious materials and comparable to those of platinum. The SCEIN/SWNT is synthesized by a novel fast and low-cost aerosol chemical vapor deposition method in a one-step synthesis. In SCEINs the single carbon layer does not prevent desired access of the reactants to the vicinity of the iron nanoparticles but protects the active metallic core from oxidation. This finding opens new avenues for utilizing active transition metals such as iron in a wide range of applications. PMID:25683139

  5. Iron- and indium-catalyzed reactions toward nitrogen- and oxygen-containing saturated heterocycles.

    PubMed

    Cornil, Johan; Gonnard, Laurine; Bensoussan, Charlélie; Serra-Muns, Anna; Gnamm, Christian; Commandeur, Claude; Commandeur, Malgorzata; Reymond, Sébastien; Guérinot, Amandine; Cossy, Janine

    2015-03-17

    A myriad of natural and/or biologically active products include nitrogen- and oxygen-containing saturated heterocycles, which are thus considered as attractive scaffolds in the drug discovery process. As a consequence, a wide range of reactions has been developed for the construction of these frameworks, much effort being specially devoted to the formation of substituted tetrahydropyrans and piperidines. Among the existing methods to form these heterocycles, the metal-catalyzed heterocyclization of amino- or hydroxy-allylic alcohol derivatives has emerged as a powerful and stereoselective strategy that is particularly interesting in terms of both atom-economy and ecocompatibility. For a long time, palladium catalysts have widely dominated this area either in Tsuji-Trost reactions [Pd(0)] or in an electrophilic activation process [Pd(II)]. More recently, gold-catalyzed formation of saturated N- and O-heterocycles has received growing attention because it generally exhibits high efficiency and diastereoselectivity. Despite their demonstrated utility, Pd- and Au-complexes suffer from high costs, toxicity, and limited natural abundance, which can be barriers to their widespread use in industrial processes. Thus, the replacement of precious metals with less expensive and more environmentally benign catalysts has become a challenging issue for organic chemists. In 2010, our group took advantage of the ability of the low-toxicity and inexpensive FeCl3 in activating allylic or benzylic alcohols to develop iron-catalyzed N- and O-heterocylizations. We first focused on N-heterocycles, and a variety of 2,6-disubstituted piperidines as well as pyrrolidines were synthesized in a highly diastereoselective fashion in favor of the cis-compounds. The reaction was further extended to the construction of substituted tetrahydropyrans. Besides triggering the formation of heterocycles, the iron salts were shown to induce a thermodynamic epimerization, which is the key to reach the high

  6. EXAFS Study on the Reactions Between Iron And Fulvic Acid in Acid Aqueous Solutions

    SciTech Connect

    Schaik, J.W.J.van; Persson, I.; Kleja, D.B.; Gustafsson, J.P.

    2009-05-26

    Iron(III) competes with trace metals for binding sites on organic ligands. We used X-ray absorption fine structure (EXAFS) spectroscopy to determine the binding mode and oxidation state of iron in solutions initially containing only iron(III) and fulvic acid at pHs 2 and 4. EXAFS spectra were recorded at different times after sample preparation. Iron was octahedrally configured with inner-sphere Fe-O interactions at 1.98-2.10 {angstrom}, depending on the oxidation state of iron. Iron(III) formed complexes with fulvic acid within 15 min. Iron(III) was reduced to iron(II) with time at pH 2, whereas no significant reduction occurred at pH 4. No signs of dimeric/trimeric hydrolysis products were found in any of the solution samples (<0.45 {mu}m). However, the isolated precipitate of the pH 2 sample (>0.45 {mu}m) showed Fe{hor_ellipsis}Fe distances, indicating the presence of tightly packed iron(III) trimers and/or clusters of corner-sharing octahedra. It is suggested that the binding mode of iron(III) to fulvic acid at low pH may be phase-dependent: in solution mononuclear complexes predominate, whereas in the solid phase hydrolyzed polynuclear iron(III) complexes form, even at very low pH values. The observed pH dependence of iron(III) reduction was consistent with expected results based on thermodynamic calculations for model ligands.

  7. Reactions between molten iron and silicate melts at high pressure: Implications for the chemical evolution of Earth's core

    NASA Astrophysics Data System (ADS)

    Ito, E.; Morooka, K.; Ujike, O.; Katsura, T.

    1995-04-01

    Reactions between molten iron and silicate melt were investigated with mixtures of pure iron and silicates (1Fe + 3MgSiO3 enstatite and 1Fe(+) 3(Mg(sub 0.9)Fe(sub 0.1)2SiO4 olivine in volumetric ratio) as starting materials at pressures of 10-26 GPa and temperatures of about 2500 C. The results show that a certain amount of Si (up to about 2%) dissolves in molten iron from silicate melt and that the dissolution is enhanced with increasing pressure. Many small spherical blobs composed of SiO2 and FeO present in coalesced iron grains were interpreted as quenched immiscible liquid formed during cooling. Therefore O also dissolves in molten iron under the experimental conditions. No evidence for dissolution of Mg was obtained. The present study also indicates that Si and O are important light elements of Earth's core if core segregation occurred in the deep magma ocean. The chemical evolution of Earth's core is discussed on the bases of the current core formation model and the present experimental results.

  8. Transport and reaction of iron and iron stable isotopes in glacial meltwaters on Svalbard near Kongsfjorden: From rivers to estuary to ocean

    NASA Astrophysics Data System (ADS)

    Zhang, Ruifeng; John, Seth G.; Zhang, Jing; Ren, Jingling; Wu, Ying; Zhu, Zhuoyi; Liu, Sumei; Zhu, Xunchi; Marsay, Chris M.; Wenger, Fred

    2015-08-01

    Glacial meltwater has been suggested as a significant source of potentially bioavailable iron to the oceans. However, the supply of dissolved iron (dFe) in glacial meltwaters is poorly constrained as few sites have been studied, and because the chemical processing of Fe during transport from glaciers to the adjacent coastal ocean is not well understood. In order to better constrain glacial fluxes of dFe to the ocean, iron concentrations, iron stable isotopes (δ56Fe), and other supporting chemical and physical measurements were made along a ∼4 km long glacial meltwater river on Svalbard and in estuarine waters that it flows into. Dissolved iron concentrations in the Bayelva River decreased from a maximum of 734 nM near the glacier to an average value of 116 nM near the mouth of the river. Measurements in the Kongsfjorden estuary suggest that 3 to 10 nM of dFe from the Bayelva River is stabilized in glacial waters by the time it mixes into the ocean. Incubation of Bayelva River waters over two weeks in both the light and dark show similar results, with the majority of dFe being quickly precipitated and 4 to 7 nM Fe stabilized in the dissolved phase. Evidence suggests that Fe is most likely lost from the dissolved phase by aggregation and adsorption of nanoparticulate and colloidal Fe to particles. Dissolved δ56Fe was between - 0.11 ‰ and + 0.09 ‰ for all river samples and did not vary systematically with dFe concentrations. We infer that the Fe is lost from the dissolved phase by a process that fractionates Fe isotopes by less than 0.05‰, indicating that the Fe bonding environment does not change during precipitation. This is consistent with DOC loss that is much faster than predicted photo-oxidation rates, suggesting that DOC is also lost through adsorption and precipitation. Dissolved Fe concentrations in the Bayelva River (15-734 nM), and Fe concentrations which are stabilized in the dissolved phase (4-7 nM) are much lower than some previous estimates of

  9. Iron phthalocyanine and nitrogen-doped graphene composite as a novel non-precious catalyst for the oxygen reduction reaction.

    PubMed

    Zhang, Chenzhen; Hao, Rui; Yin, Han; Liu, Fei; Hou, Yanglong

    2012-12-01

    We develop a facile method for the synthesis of an iron phthalocyanine (FePc) and nitrogen-doped graphene (NG) composite as a novel and efficient non-precious catalyst in the oxygen reduction reaction (ORR). The resulting product exhibits superior ORR catalytic activity, excellent tolerance to methanol crossover, and comparable stability to commercial Pt/C, which leads to the invention of a new non-precious catalyst for ORR in fuel cells. PMID:23086132

  10. Spontaneous reaction between an uncharged lithium iron silicate cathode and a LiPF6-based electrolyte.

    PubMed

    Arthur, Zachary; Chiu, Hsien-Chieh; Lu, Xia; Chen, Ning; Emond, Vincent; Zaghib, Karim; Jiang, De-Tong; Demopoulos, George P

    2016-01-01

    The reaction between an uncharged Li2FeSiO4 (LFS) cathode and a LiPF6-EC/DMC electrolyte is revealed by in situ XANES in coin cells. This study shows clear evidence of delithiation and iron oxidation in LFS prior to cycling. Subsequent cycling appears to partially restore the original lithiation level, an observation that needs to be taken into consideration in future LFS development work. PMID:26511008

  11. Electrical conductivity of iron-bearing silicate glasses and melts. Implications for the mechanisms of iron redox reactions

    NASA Astrophysics Data System (ADS)

    Malki, M.; Magnien, V.; Pinet, O.; Richet, P.

    2015-09-01

    The electrical conductivity of a series of glasses and melts of the system SiO2-CaO-MgO-M2O-"FeO" (M = Li and Na) and of a borosilicate has been measured from room temperature to about 1820 K. For samples with predominantly reduced iron, the conductivity increases markedly upon addition of Na+ and still more of Li+, which is consistent with the increasing order Mg2+, Na+, Li+ order of cation mobility. For the oxidized samples the conductivity is in contrast almost not affected by the presence of alkali cations, which agrees with the low mobility of alkali cations that are then serving as charge compensators of tetrahedrally coordinated Al3+. The conductivity is higher for oxidized than for reduced samples. As indicated by polarization electrode phenomena and complementary continuous current measurements, this difference is due to an important contribution of electronic conduction caused by electronic charge transfer between iron species that exists in the oxidized samples. The diffusivities of oxygen and divalent cations were then determined from Eyring relationship and the measured conductivities, respectively and compared with the redox diffusivies determined for the same samples. The good agreement found between both kinds of data confirms the controlling role of divalent cations and of oxygen species in the redox kinetics near the glass transition and at high temperatures, respectively. In addition it illustrates that describing melt properties in an integrated manner is becoming possible.

  12. Cysteine Oxidation Reactions Catalyzed by a Mononuclear Non-heme Iron Enzyme (OvoA) in Ovothiol Biosynthesis

    PubMed Central

    2015-01-01

    OvoA in ovothiol biosynthesis is a mononuclear non-heme iron enzyme catalyzing the oxidative coupling between histidine and cysteine. It can also catalyze the oxidative coupling between hercynine and cysteine, yet with a different regio-selectivity. Due to the potential application of this reaction for industrial ergothioneine production, in this study, we systematically characterized OvoA by a combination of three different assays. Our studies revealed that OvoA can also catalyze the oxidation of cysteine to either cysteine sulfinic acid or cystine. Remarkably, these OvoA-catalyzed reactions can be systematically modulated by a slight modification of one of its substrates, histidine. PMID:24684381

  13. Solution phase and membrane immobilized iron-based free radical reactions: Fundamentals and applications for water treatment

    NASA Astrophysics Data System (ADS)

    Lewis, Scott Romak

    Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, a common limitation of iron(Fe(II/III))-catalyzed hydrogen peroxide (H 2O2) decomposition. The objectives of this research are to develop a membrane-based platform for the generation of free radicals, degrade toxic organic compounds using this and similar solution-based reactions, degrade toxic organic compounds in droplet form, quantify hydroxyl radical production in these reactions, and develop kinetic models for both processes. In this study, a functionalized membrane containing poly(acrylic acid) (PAA) was used to immobilize iron ions and conduct free radical reactions by permeating H2O2 through the membrane. The membrane's responsive behavior to pH and divalent cations was investigated and modeled. The conversion of Fe(II) to Fe(III) in the membrane and its effect on the decomposition of hydrogen peroxide were monitored and used to develop kinetic models for predicting H2O2 decomposition in these systems. The rate of hydroxyl radical production, and hence contaminant degradation can be varied by changing the residence time, H2O2 concentration, and/or iron loading. Using these membrane-immobilized systems, successful removal of toxic organic compounds, such as pentachlorophenol (PCP), from water

  14. Iron Reduction and Radionuclide Immobilization: Kinetic, Thermodynamic and Hydrologic controls & Reaction-Based Modeling - Final Report

    SciTech Connect

    William D. Burgos

    2004-06-18

    et al, 2003). We have demonstrated the use of a reaction-based reactive transport model (HYDROGEOCHEM) for the simulation of biological iron reduction in natural sediment columns (Burgos and Yeh, unpublished results). Finally, we have developed a preliminary reaction-based model of coupled Fe(III) oxide/U(VI) reduction that has been employed in numerical simulations of U(VI) bioreduction in bench-scale (Roden, 2003d) and field-scale (Roden and Scheibe, 2003;Roden, 2003c) systems.

  15. Polymersomes containing iron sulfide (FeS) as primordial cell model : for the investigation of energy providing redox reactions.

    PubMed

    Alpermann, Theodor; Rüdel, Kristin; Rüger, Ronny; Steiniger, Frank; Nietzsche, Sandor; Filiz, Volkan; Förster, Stephan; Fahr, Alfred; Weigand, Wolfgang

    2011-04-01

    According to Wächtershäuser's "Iron-Sulfur-World" one major requirement for the development of life on the prebiotic Earth is compartmentalization. Vesicles spontaneously formed from amphiphilic components containing a specific set of molecules including sulfide minerals may have lead to the first autotrophic prebiotic units. The iron sulfide minerals may have been formed by geological conversions in the environment of deep-sea volcanos (black smokers), which can be observed even today. Wächtershäuser postulated the evolution of chemical pathways as fundamentals of the origin of life on earth. In contrast to the classical Miller-Urey experiment, depending on external energy sources, the "Iron-Sulfur-World" is based on the catalytic and energy reproducing redox system FeS+H2S-->FeS2+H2. The energy release out of this redox reaction (∆RG°=-38 kJ/mol, pH 0) could be the cause for the subsequent synthesis of complex organic molecules and the precondition for the development of more complex units similar to cells known today. Here we show the possibility for precipitating iron sulfide inside vesicles composed of amphiphilic block-copolymers as a model system for a first prebiotic unit. Our findings could be an indication for a chemoautotrophic FeS based origin of life. PMID:20697814

  16. Polymersomes Containing Iron Sulfide (FeS) as Primordial Cell Model. For the investigation of energy providing redox reactions

    NASA Astrophysics Data System (ADS)

    Alpermann, Theodor; Rüdel, Kristin; Rüger, Ronny; Steiniger, Frank; Nietzsche, Sandor; Filiz, Volkan; Förster, Stephan; Fahr, Alfred; Weigand, Wolfgang

    2011-04-01

    According to Wächtershäuser's "Iron-Sulfur-World" one major requirement for the development of life on the prebiotic Earth is compartmentalization. Vesicles spontaneously formed from amphiphilic components containing a specific set of molecules including sulfide minerals may have lead to the first autotrophic prebiotic units. The iron sulfide minerals may have been formed by geological conversions in the environment of deep-sea volcanos (black smokers), which can be observed even today. Wächtershäuser postulated the evolution of chemical pathways as fundamentals of the origin of life on earth. In contrast to the classical Miller-Urey experiment, depending on external energy sources, the "Iron-Sulfur-World" is based on the catalytic and energy reproducing redox system FeS + {H_2}S to FeS{}_2 + {H_2} . The energy release out of this redox reaction (∆RG° = -38 kJ/mol, pH 0) could be the cause for the subsequent synthesis of complex organic molecules and the precondition for the development of more complex units similar to cells known today. Here we show the possibility for precipitating iron sulfide inside vesicles composed of amphiphilic block-copolymers as a model system for a first prebiotic unit. Our findings could be an indication for a chemoautotrophic FeS based origin of life.

  17. Reaction of C-type cytochromes with the iron hexacyanides. Mechanistic implications.

    PubMed

    Ohno, N; Cusanovich, M A

    1981-12-01

    The reaction of c-cytochromes with iron hexacyanides is similar in mechanism to the interaction of cytochromes with their physiological oxidants and reductants in that the formation of complexes precedes electron transfer. Analysis of the kinetics of oxidation and reduction of a number of c-cytochromes by solving the simultaneous differential equations defining the mechanism is possible, and allows assignment of all six rate constants describing a minimum three-step mechanism [cyto(Fe(+3)) + Fe(+2) right harpoon over left harpoon cyto (Fe(+3)) - Fe(+2) right harpoon over left harpoon cyto(Fe(+2)) - Fe(+3) right harpoon over left harpoon cyto(Fe(+2)) + Fe(+3)]. We find that the usual steady-state approximations are not valid. Furthermore, the ratio of first-order rate constants for electron transfer was approximately 1.0, and no correlation was found between any of the six rate constants and the differences in oxidation-reduction potential of the iron-hexacyanides and different cytochromes c. However, it was found that the ratio of the rate constants for complex formation between ferricytochrome c and potassium ferrocyanide and ferrocytochrome c and potassium ferricyanide was proportional to the difference in oxidation-reduction potentials. Thus the minimum three-step mechanism given above accurately describes the observed kinetic data. However, this mechanism leads to a number of conceptual difficulties. Specifically, the mechanism requires that the collision complexes formed [cyto(Fe(+3)) - Fe(CN)(6) (-4) and cyto(Fe(+2)) - Fe(CN)(6) (-3)] have very different equilibrium constants, and further requires that formation of the collision complexes be accompanied by "chemistry" to make the intermediates isoenergetic. A more complex five-step mechanism which requires that the reactants [Fe(CN)(6) (-4) and ferricytochrome c or Fe(CN)(6) (-3) and ferrocytochrome c] form a collision complex followed by a first-order process before electron transfer, was found to yield

  18. Gamow-Teller transition strengths from 56Ni.

    PubMed

    Sasano, M; Perdikakis, G; Zegers, R G T; Austin, Sam M; Bazin, D; Brown, B A; Caesar, C; Cole, A L; Deaven, J M; Ferrante, N; Guess, C J; Hitt, G W; Meharchand, R; Montes, F; Palardy, J; Prinke, A; Riley, L A; Sakai, H; Scott, M; Stolz, A; Valdez, L; Yako, K

    2011-11-11

    A new technique to measure (p,n) charge-exchange reactions in inverse kinematics at intermediate energies on unstable isotopes was successfully developed and used to study the (56)Ni(p,n) reaction at 110 MeV/u. Gamow-Teller transition strengths from (56)Ni leading to (56)Cu were obtained and compared with shell-model predictions in the pf shell using the KB3G and GXPF1A interactions. The calculations with the GXPF1A interaction reproduce the experimental strength distribution much better than the calculations that employed the KB3G interaction, indicating deficiencies in the spin-orbit and proton-neutron residual potentials for the latter. The results are important for improving the description of electron-capture rates on nuclei in the iron region, which are important for modeling the late evolution of core-collapse and thermonuclear supernovae. PMID:22181727

  19. Gamow-Teller transitions from {sup 56}Ni

    SciTech Connect

    Sasano, M.; Perdikakis, G.; Zegers, R.G.T.; and others

    2012-11-12

    A new technique to measure (p,n) charge-exchange reactions in inverse kinematics at intermediate energies on unstable isotopes was successfully developed and used to study the {sup 56}Ni(p,n) reaction at 110 MeV/u. Gamow-Teller transition strengths from {sup 56}Ni to {sup 56}Cu were obtained and compared with shell-model predictions in the pf-shell using the KB3G and GXPF1A interactions. The calculations with the GXPF1A interaction reproduce the experimental GT strength distribution much better than the calculations that employed the KB3G interaction, indicating deficiencies in the spin-orbit and proton-neutron residual potentials for the latter. The results are important for improving the description of electron-capture rates on nuclei in the iron region, which are important for modeling the late evolution of core-collapse and thermonuclear supernovae.

  20. Sulfur, trace nitrogen and iron codoped hierarchically porous carbon foams as synergistic catalysts for oxygen reduction reaction.

    PubMed

    Guo, Zhaoyan; Jiang, Congcong; Teng, Chao; Ren, Guangyuan; Zhu, Ying; Jiang, Lei

    2014-12-10

    Sulfur, trace nitrogen and iron codoped, hierarchically porous carbon foams (HPCFs) were fabricated by directly pyrolyzing sulfur-enriched conductive polymer, poly(3,4-ethylenedioxythiphene)-polystyrenesulfonic acid (PEDOT-PSS) aerogels under argon atmosphere. This simple pyrolysis treatment results in the molecular rearrangement of heteroatom sulfur, adjacent carbons and trace nitrogen/iron from oxidants to form active catalytic sites of HPCFs. At the same time, the high porosity of HPCFs provides the large surface area for the uniform distribution of active sites, and allows rapid oxygen transport and diffusion. As a result, these HPCFs exhibit the enhanced catalytic performances for oxygen reduction reaction (ORR) via a direct four-electron reduction pathway in alkaline electrolyte. Besides, they also display a higher stability and better methanol/CO tolerance than the commercial Pt/C catalyst, which makes them promising low cost, non-precious-metal ORR catalysts for practical application in fuel cells and metal-air batteries. PMID:25402945

  1. Generation of Oxidants From the Reaction of Nanoparticulate Zero-Valent Iron and Oxygen for the use in Contaminant Remediation

    NASA Astrophysics Data System (ADS)

    Keenan, C. R.; Lee, C.; Sedlak, D. L.

    2007-12-01

    The reaction of zero-valent iron (ZVI) with oxygen can lead to the formation of oxidants, which may be used to transform recalcitrant contaminants including non-polar organics and certain metals. Nanoparticulate iron might provide a practical mechanism of remediating oxygen-containing groundwater and contaminated soil. To gain insight into the reaction mechanism and to quantify the yield of oxidants, experiments were performed with model organic compounds in the presence of nanoparticulate zero-valent iron and oxygen. At pH values below 5, ZVI nanoparticles were oxidized within 30 minutes with a stoichiometry of approximately two Fe0 oxidized per O2 consumed. Using the oxidation of methanol and ethanol to formaldehyde and acetaldehyde, respectively, we found that less than 2% of the consumed oxygen was converted to reactive oxidants under acidic conditions. The yield of aldehydes increased with pH up to pH 7, with maximum oxidant yields of around 5% relative to the mass of ZVI added. The increase of aldehyde yield with pH was attributable to changes in the processes responsible for oxidant production. At pH values below 5, the corrosion of ZVI by oxygen produces hydrogen peroxide, which subsequently reacts with ferrous iron [Fe(II)] via the Fenton reaction. At higher pH values, the aldehydes are produced when Fe(II), the initial product of ZVI oxidation, reacts with oxygen. The decrease in oxidant yield at pH values above 7 may be attributable to precipitation of Fe(II). The oxidation of benzoic acid and 2-propanol to para-hydroxybenzoic acid and acetone, respectively, followed a very different trend compared to the primary alcohols. In both cases, the highest product yields (approximately 2% with respect to ZVI added) were observed at pH 3. Yields decreased with increasing pH, with no oxidized product detected at neutral pH. These results suggest that two different oxidants may be produced by the system: hydroxyl radical (OH-·) at acidic pH and a more selective

  2. Reaction of Inconel 690 and 693 in Iron Phosphate Melts: Alternative Glasses for Waste Vitrification

    SciTech Connect

    Day, Delbert E. Kim, Cheol-Woon

    2005-09-13

    The corrosion resistance of candidate materials used for the electrodes (Inconel 690 & 693) and the melt contact refractory (Monofrax K-3) in a Joule Heated Melter (JHM) has been investigated at the University of Missouri-Rolla (UMR) during the period from June 1, 2004 to August 31, 2005. This work was supported by the U.S. Department of Energy (DOE) Office of Biological and Environmental Research (DE-FG02-04ER63831). The unusual properties and characteristics of iron phosphate glasses, as viewed from the standpoint of alternative glasses for vitrifying nuclear and hazardous wastes which contain components that make them poorly suited for vitrification in borosilicate glass, were recently discovered at UMR. The expanding national and international interest in iron phosphate glasses for waste vitrification stems from their rapid melting and chemical homogenization which results in higher furnace output, their high waste loading that varies from 32 wt% up to 75 wt% for the Hanford LAW and HLW, respectively, and the outstanding chemical durability of the iron phosphate wasteforms which meets all present DOE requirements (PCT and VHT). The higher waste loading in iron phosphate glasses, compared to the baseline borosilicate glass, can reduce the time and cost of vitrification considerably since a much smaller mass of glass will be produced, for example, about 43% less glass when the LAW at Hanford is vitrified in an iron phosphate glass according to PNNL estimates. In view of the promising performance of iron phosphate glasses, information is needed for how to best melt these glasses on the scale needed for practical use. Melting iron phosphate glasses in a JHM is considered the preferred method at this time because its design could be nearly identical to the JHM now used to melt borosilicate glasses at the Defense Waste Processing Facility (DWPF), Westinghouse Savannah River Co. Therefore, it is important to have information for the corrosion of candidate electrode

  3. Kinetics of reactions in interlayer space of titanium diselenide intercalated with iron

    NASA Astrophysics Data System (ADS)

    Titov, A. N.; Shkvarina, E. G.; Zelenina, L. N.; Chusova, T. P.; Sharafutdinov, M. R.

    2016-04-01

    Decomposition of a homogeneous intercalation compound with the formation of inclusions in the interlayer space of a matrix lattice has been directly observed. In full compliance with previously advanced theoretical concepts, it has been shown that the decomposition is accompanied by metallic iron extraction, which then gradually transforms into iron selenide due to the interaction with gaseous selenium.The hierarchy of diffusion mobilities of various defects in Fe x TiSe2 intercalation compound has been determined. It has been found that the largest mobility is inherent to intrinsic defects of the TiSe2 lattice, i.e., vacancies in Ti and Se sublattices. The phenomenon of dissociation pressure oscillations as a function of time has been detected. This phenomenon has been explained by the existence of a slow decomposition stage, i.e., intercalated iron diffusion during the formation and dissolution of its inclusions as an individual phase.

  4. The Effect of Temperature and Ionic Strength on the Oxidation of Iodide by Iron(III): A Clock Reaction Kinetic Study

    ERIC Educational Resources Information Center

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

    2012-01-01

    A laboratory exercise has recently been reported in which the students use the initial rates method based on the clock reaction approach to deduce the rate law and propose a reaction mechanism for the oxidation of iodide by iron(III) ions. The same approach is used in the exercise proposed herein; the students determine the dependence of the…

  5. Characteristics of Fine Bacteria-like Texture Formed by Iron Meteorite by Atmosphere Reaction

    NASA Astrophysics Data System (ADS)

    Miura, Yas.

    2010-04-01

    -Spherule-chained texture of nano-grains with Fe, Ni, C and Cl is found in the Kuga iron meteorite, which are greatly different with the martian meteorite. Fine texture of the Kuga meteorite is example of fossil-like texture.

  6. Characteristics of Fine Bacteria-like Texture Formed by Iron Meteorite by Atmosphere Reaction

    NASA Astrophysics Data System (ADS)

    Miura, Yas.

    2010-03-01

    Spherule-chained texture of nano-grains with Fe, Ni, C and Cl is found in the Kuga iron meteorite, which are greatly different with the martian meteorite. Fine texture of the Kuga meteorite is example of fossil-like texture.

  7. Removal of EDB and 1,2-DCA by Abiotic Reaction with Iron (II) Sulfide

    EPA Science Inventory

    To properly evaluate the risk associated with exposure to EDB and 1,2-DCA in ground water from old spills of leaded gasoline, it is necessary to understand the mechanisms that may attenuate concentrations of these compounds in ground water. TCE reacts rapidly with iron (II) sulf...

  8. GEOCHEMICAL AND MICROBIAL REACTIONS AFFECTING THE LONG-TERM PERFORMANCE OF IN SITU 'IRON BARRIERS'

    EPA Science Inventory

    The in situ application of granular iron (Fe0) has become popular for the destruction of halogenated organic compounds for the immobilization of specific metals in groundwater. However, a knowledge gap exists concerning the long-term performance of the Fe0-barriers. The corrosi...

  9. Sequestration of Antimonite by Zerovalent Iron: Using Weak Magnetic Field Effects to Enhance Performance and Characterize Reaction Mechanisms.

    PubMed

    Xu, Chunhua; Zhang, Bingliang; Zhu, Liujia; Lin, Sheng; Sun, Xueping; Jiang, Zheng; Tratnyek, Paul G

    2016-02-01

    Many oxyanion-forming metals (As, Sb, Se, Tc, etc.) can be removed from water by adsorption and/or redox reactions involving iron oxides, including the oxides associated with zerovalent iron (ZVI). The rate of antimonite (Sb(III) hydrolysis species) removal by ZVI was determined in open, well-mixed batch reactors as a function of experimental factors, including aging of the ZVI, addition of Fe(II), Sb dose, mixing rate, pH, initial concentrations of Sb(III), etc. However, the largest effect observed was the roughly 6-8 fold increase in Sb(III) removal rate due to the application of a weak magnetic field (WMF) during the experiments. The WMF effect on Sb removal arises from stimulated corrosion and delayed passivation of the ZVI, as evidenced by time series correlation analysis of "geochemical" properties (DO, Fetot, Eh, and pH) measured synchronously in each experiment. The removal of Sb under the conditions of this study was mainly due to oxidation of Sb(III) to Sb(V) and adsorption and coprecipitation onto the iron oxides formed from accelerated corrosion of ZVI, as evidenced by Sb K-edge XANES, EXAFS, and XPS. The degree of the WMF enhancement for Sb(III) was found to be similar to the WMF effect reported previously for Sb(V), As(III), As(V), and Se(VI). PMID:26727297

  10. O2 Reactions at the Six-iron Active Site (H-cluster) in [FeFe]-Hydrogenase*

    PubMed Central

    Lambertz, Camilla; Leidel, Nils; Havelius, Kajsa G. V.; Noth, Jens; Chernev, Petko; Winkler, Martin; Happe, Thomas; Haumann, Michael

    2011-01-01

    Irreversible inhibition by molecular oxygen (O2) complicates the use of [FeFe]-hydrogenases (HydA) for biotechnological hydrogen (H2) production. Modification by O2 of the active site six-iron complex denoted as the H-cluster ([4Fe4S]-2FeH) of HydA1 from the green alga Chlamydomonas reinhardtii was characterized by x-ray absorption spectroscopy at the iron K-edge. In a time-resolved approach, HydA1 protein samples were prepared after increasing O2 exposure periods at 0 °C. A kinetic analysis of changes in their x-ray absorption near edge structure and extended X-ray absorption fine structure spectra revealed three phases of O2 reactions. The first phase (τ1 ≤ 4 s) is characterized by the formation of an increased number of Fe–O,C bonds, elongation of the Fe–Fe distance in the binuclear unit (2FeH), and oxidation of one iron ion. The second phase (τ2 ≈ 15 s) causes a ∼50% decrease of the number of ∼2.7-Å Fe–Fe distances in the [4Fe4S] subcluster and the oxidation of one more iron ion. The final phase (τ3 ≤ 1000 s) leads to the disappearance of most Fe–Fe and Fe–S interactions and further iron oxidation. These results favor a reaction sequence, which involves 1) oxygenation at 2FeH+ leading to the formation of a reactive oxygen species-like superoxide (O2−), followed by 2) H-cluster inactivation and destabilization due to ROS attack on the [4Fe4S] cluster to convert it into an apparent [3Fe4S]+ unit, leading to 3) complete O2-induced degradation of the remainders of the H-cluster. This mechanism suggests that blocking of ROS diffusion paths and/or altering the redox potential of the [4Fe4S] cubane by genetic engineering may yield improved O2 tolerance in [FeFe]-hydrogenase. PMID:21930709

  11. Synthesis of alkenyl sulfides through the iron-catalyzed cross-coupling reaction of vinyl halides with thiols.

    PubMed

    Lin, Yun-Yung; Wang, Yu-Jen; Lin, Che-Hung; Cheng, Jun-Hao; Lee, Chin-Fa

    2012-07-20

    We report here the iron-catalyzed cross-coupling reaction of alkyl vinyl halides with thiols. While many works are devoted to the coupling of thiols with alkyl vinyl iodides, interestingly, the known S-vinylation of vinyl bromides and chlorides is limited to 1-(2-bromovinyl)benzene and 1-(2-chlorovinyl)benzene. Investigation on the coupling reaction of challenging alkyl vinyl bromides and chlorides with thiols is rare. Since the coupling of 1-(2-bromovinyl)benzene and 1-(2-chlorovinyl)benzene with thiols can be performed in the absence of any catalyst, here we focus on the coupling of thiols with alkyl vinyl halides. This system is generally reactive for alkyl vinyl iodides and bromides to provide the products in good yields. 1-(Chloromethylidene)-4-tert-butyl-cyclohexane was also coupled with thiols, giving the targets in moderate yields. PMID:22708836

  12. Coupling of collective motions of the protein matrix to vibrations of the non-heme iron in bacterial photosynthetic reaction centers.

    PubMed

    Orzechowska, A; Lipińska, M; Fiedor, J; Chumakov, A; Zajac, M; Slezak, T; Matlak, K; Strzałka, K; Korecki, J; Fiedor, L; Burda, K

    2010-10-01

    Non-heme iron is a conservative component of type II photosynthetic reaction centers of unknown function. We found that in the reaction center from Rba. sphaeroides it exists in two forms, high and low spin ferrous states, whereas in Rsp. rubrum mostly in a low spin state, in line with our earlier finding of its low spin state in the algal photosystem II reaction center (Burda et al., 2003). The temperature dependence of the non-heme iron displacement studied by Mössbauer spectroscopy shows that the surrounding of the high spin iron is more flexible (Debye temperature ~165K) than that of the low spin atom (~207K). Nuclear inelastic scattering measurements of the collective motions in the Rba. sphaeroides reaction center show that the density of vibrational states, originating from non-heme iron, has well-separated modes between lower (4-17meV) and higher (17-25meV) energies while in the one from Rsp. rubrum its distribution is more uniform with only little contribution of low energy (~6meV) vibrations. It is the first experimental evidence that the fluctuations of the protein matrix in type II reaction center are correlated to the spin state of non-heme iron. We propose a simple mechanism in which the spin state of non-heme iron directly determines the strength of coupling between the two quinone acceptors (Q(A) and Q(B)) and fast collective motions of protein matrix that play a crucial role in activation and regulation of the electron and proton transfer between these two quinones. We suggest that hydrogen bond network on the acceptor side of reaction center is responsible for stabilization of non-heme iron in different spin states. PMID:20603098

  13. Iron-sulfur clusters as biological sensors: the chemistry of reactions with molecular oxygen and nitric oxide.

    PubMed

    Crack, Jason C; Green, Jeffrey; Thomson, Andrew J; Le Brun, Nick E

    2014-10-21

    recognized. This remarkable feature suggested that the original [4Fe-4S] cluster can be restored using persulfide as the source of sulfide ion. We have demonstrated that only iron and a source of electrons are required to promote efficient conversion back from the [2Fe-2S] to the [4Fe-4S] form. We propose this as a novel in vivo repair mechanism that does not require the intervention of an iron-sulfur cluster biogenesis pathway. A number of iron-sulfur regulators have evolved to function as sensors of NO. Although it has long been known that the iron-sulfur clusters of many phylogenetically unrelated proteins are vulnerable to attack by NO, our recent studies of Wbl proteins and FNR have provided new insights into the mechanism of cluster nitrosylation, which overturn the commonly accepted view that the product is solely a mononuclear iron dinitrosyl complex (known as a DNIC). The major reaction is a rapid, multiphase process involving stepwise addition of up to eight NO molecules per [4Fe-4S] cluster. The major iron nitrosyl product is EPR silent and has optical characteristics similar to Roussin's red ester, [Fe2(NO)4(RS)2] (RRE), although a species similar to Roussin's black salt, [Fe4(NO)7(S)3](-) (RBS) cannot be ruled out. A major future challenge will be to clarify the nature of these species. PMID:25262769

  14. Temperature trends for reaction rates, hydrogen generation, and partitioning of iron during experimental serpentinization of olivine

    NASA Astrophysics Data System (ADS)

    McCollom, Thomas M.; Klein, Frieder; Robbins, Mark; Moskowitz, Bruce; Berquó, Thelma S.; Jöns, Niels; Bach, Wolfgang; Templeton, Alexis

    2016-05-01

    A series of laboratory experiments were conducted to examine how partitioning of Fe among solid reaction products and rates of H2 generation vary as a function of temperature during serpentinization of olivine. Individual experiments were conducted at temperatures ranging from 200 to 320 °C, with reaction times spanning a few days to over a year. The extent of reaction ranged from <1% to ∼23%. Inferred rates for serpentinization of olivine during the experiments were 50-80 times slower than older studies had reported but are consistent with more recent results, indicating that serpentinization may proceed more slowly than previously thought. Reaction products were dominated by chrysotile, brucite, and magnetite, with minor amounts of magnesite, dolomite, and iowaite. The chrysotile contained only small amounts of Fe (XFe = 0.03-0.05, with ∼25% present as ferric Fe in octahedral sites), and displayed little variation in composition with reaction temperature. Conversely, the Fe contents of brucite (XFe = 0.01-0.09) increased steadily with decreasing reaction temperature. Analysis of the reaction products indicated that the stoichiometry of the serpentinization reactions varied with temperature, but remained constant with increasing reaction progress at a given temperature. The observed distribution of Fe among the reaction products does not appear to be entirely consistent with existing equilibrium models of Fe partitioning during serpentinization, suggesting improved models that include kinetic factors or multiple reaction steps need to be developed. Rates of H2 generation increased steeply from 200 to 300 °C, but dropped off at higher temperatures. This trend in H2 generation rates is attributable to a combination of the overall rate of serpentinization reactions and increased partitioning of Fe into brucite rather than magnetite at lower temperatures. The results suggest that millimolal concentration of H2 could be attained in moderately hot hydrothermal

  15. Surface chemistry and structural properties of mackinawite prepared by reaction of sulfide ions with metallic iron

    NASA Astrophysics Data System (ADS)

    Mullet, Martine; Boursiquot, Sophie; Abdelmoula, Mustapha; Génin, Jean-Marie; Ehrhardt, Jean-Jacques

    2002-03-01

    Tetragonal FeS 1- x mackinawite, has been synthesized by reacting metallic iron with a sodium sulfide solution and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), transmission Mössbauer spectroscopy (TMS) and X-ray photoelectron spectroscopy (XPS). Based on XRD and TEM analyses, synthetic mackinawite exhibits crystallization and is identical to the natural mineral. Unit cell parameters derived from XRD data are a = b = 0.3670 nm and c = 0.5049 nm. The bulk Fe:S ratio derived from the quantitative dispersive energy analysis is practically 1. XPS analyses, however, showed that mackinawite surface is composed of both Fe(II) and Fe(III) species bound to monosulfide. Accordingly, monosulfide is the dominant S species observed at the surface with lesser amount of polysulfides and elemental sulfur. TMS analysis revealed the presence of both Fe(II) and Fe(III) in the mackinawite structure, thus supporting the XPS analysis. We propose that the iron monosulfide phase synthesized by reacting metallic iron and dissolved sulfide is composed of Fe(II) and S(-II) atoms with the presence of a weathered thin layer covering the bulk material that consists of both Fe(II) and Fe(III) bound to S(-II) atoms and in a less extent of polysulfide and elemental sulfur.

  16. How low does iron go? Chasing the active species in fe-catalyzed cross-coupling reactions.

    PubMed

    Bedford, Robin B

    2015-05-19

    The catalytic cross-coupling reactions of organic halides or related substrates with organometallic nucleophiles form the cornerstone of many carbon-carbon bond-forming processes. While palladium-based catalysts typically mediate such reactions, there are increasing concerns about the long-term sustainability of palladium in synthesis. This is due to the high cost of palladium, coupled with its low natural abundance, environmentally deleterious extraction (∼6 g of metal are produced per ton of ore), toxicity, and competition for its use from the automotive and consumer electronics sectors. Therefore, there is a growing interest in replacing palladium-based catalysts with those incorporating more earth-abundant elements. With its low cost, high natural abundance, and low toxicity, iron makes a particularly appealing alternative, and accordingly, the development of iron-catalyzed cross-coupling is undergoing explosive growth. However, our understanding of the mechanisms that underpin the iron-based catalytic cycles is still very much in its infancy. Mechanistic insight into catalytic reactions is not only academically important but also allows us to maximize the efficiency of processes or even to develop entirely new transformations. Key to the development of robust mechanistic models for cross-coupling is knowing the lowest oxidation state in the cycle. Once this is established, we can explore subsequent redox processes and build the catalytic manifold. Until we know with confidence what the lowest oxidation state is, any cycles proposed are largely just guesswork. To date, Fe(-II), Fe(-I), Fe(0), Fe(I), and Fe(II) have been proposed as contenders for the lowest-oxidation-state species in the cycle in iron-catalyzed cross-coupling; the aim of this Account is to pull together the various pieces of evidence in support, or otherwise, of each of these suggestions in turn. There currently exists no direct evidence that oxidation states below Fe(0) are active in the

  17. Effect of reaction environments on the reactivity of PCB (2-chlorobiphenyl) over activated carbon impregnated with palladized iron.

    PubMed

    Choi, Hyeok; Al-Abed, Souhail R

    2010-07-15

    Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-ClBP) in the RAC system. The results were discussed in close connection to the implementation issue of the RAC system for the remediation of contaminated sites with PCBs. Adsorption event of 2-ClBP onto RAC limited the overall performance under condition with a 2-ClBP/RAC mass ratio of less than 1.0x10(-4) above which dechlorination of 2-ClBP adsorbed to RAC was the reaction rate-determining step. Acidic and basic conditions were harmful to 2-ClBP adsorption and iron stability while neutral pH showed the highest adsorption-promoted dechlorination of 2-ClBP and negligible metal leaching. Coexisting natural organic matter (NOM) slightly inhibited 2-ClBP adsorption onto RAC due to the partial partitioning of 2-ClBP into NOM in the liquid phase while the 2-ClBP absorbed into NOM, which also tended to adsorb onto RAC, was less available for the dechlorination reaction. Common anions slowed down 2-ClBP adsorption but adsorbed 2-ClBP was almost simultaneously dechlorinated. Some exceptions included strong inhibitory effect of carbonate species on 2-ClBP adsorption and severe detrimental effect of sulfite on 2-ClBP dechlorination. Results on treatment of 2-ClBP spiked to actual sediment supernatants implied site-specific reactivity of RAC. PMID:20388583

  18. Dinitrosyl iron complexes with cysteine. Kinetics studies of the formation and reactions of DNICs in aqueous solution.

    PubMed

    Pereira, José Clayston Melo; Iretskii, Alexei V; Han, Rui-Min; Ford, Peter C

    2015-01-14

    Kinetics studies provide mechanistic insight regarding the formation of dinitrosyl iron complexes (DNICs) now viewed as playing important roles in the mammalian chemical biology of the ubiquitous bioregulator nitric oxide (NO). Reactions in deaerated aqueous solutions containing FeSO4, cysteine (CysSH), and NO demonstrate that both the rates and the outcomes are markedly pH dependent. The dinuclear DNIC Fe2(μ-CysS)2(NO)4, a Roussin's red salt ester (Cys-RSE), is formed at pH 5.0 as well as at lower concentrations of cysteine in neutral pH solutions. The mononuclear DNIC Fe(NO)2(CysS)2(-) (Cys-DNIC) is produced from the same three components at pH 10.0 and at higher cysteine concentrations at neutral pH. The kinetics studies suggest that both Cys-RSE and Cys-DNIC are formed via a common intermediate Fe(NO)(CysS)2(-). Cys-DNIC and Cys-RSE interconvert, and the rates of this process depend on the cysteine concentration and on the pH. Flash photolysis of the Cys-RSE formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 5.0 solution led to reversible NO dissociation and a rapid, second-order back reaction with a rate constant kNO = 6.9 × 10(7) M(-1) s(-1). In contrast, photolysis of the mononuclear-DNIC species Cys-DNIC formed from Fe(II)/NO/cysteine mixtures in anaerobic pH 10.0 solution did not labilize NO but instead apparently led to release of the CysS(•) radical. These studies illustrate the complicated reaction dynamics interconnecting the DNIC species and offer a mechanistic model for the key steps leading to these non-heme iron nitrosyl complexes. PMID:25479566

  19. Measurement of the 58Ni(n,t)56Co, 59Co(n,p)59Fe, and 63Cu(n,{alpha})60Co Reaction Cross Sections from 14 to 20 MeV

    SciTech Connect

    Semkova, V.; Plompen, A.J.M.; Smith, D.L.

    2005-05-24

    Neutron activation cross sections for the 63Cu(n,{alpha})60Co, 59Co(n,p)59Fe, and 58Ni(n,t)56Co reactions were measured in the energy range from 13 to 21 MeV. The irradiations were carried out at the 7-MV Van de Graaff accelerator at IRMM, Geel. Quasi-monoenergetic neutrons were produced via the 3H(d,n)4He reaction at 1-, 2-, 3-, and 4-MeV incident deuteron energy. All reaction cross sections measured in the present work are referenced to the 27Al(n,{alpha})24Na standard reaction cross section. Neutron flux spectra were determined by an activation spectral index method in combination with TOF spectrum measurements. Standard {gamma}-ray spectrometry was employed for the measurement of radioactivity. The measured results are compared with work by other authors, TALYS-0.57 and EMPIRE-II model calculations, and current evaluated data files. The new results contribute substantially to the experimental database of the measured reactions. Recommendations are provided for the best evaluations for the 59Co(n,p)59Fe, and 63Cu(n,{alpha})60Co reactions. For the 58Ni(n,t)56Co reaction no current evaluation is in good agreement with all available data. For this reaction further measurements would help to guide new modeling efforts.

  20. Reaction sequence of iron sulfide minerals in bacteria and their use as biomarkers.

    PubMed

    Pósfai, M; Buseck, P R; Bazylinski, D A; Frankel, R B

    1998-05-01

    Some bacteria form intracellular nanometer-scale crystals of greigite (Fe3S4) that cause the bacteria to be oriented in magnetic fields. Transmission electron microscope observations showed that ferrimagnetic greigite in these bacteria forms from nonmagnetic mackinawite (tetragonal FeS) and possibly from cubic FeS. These precursors apparently transform into greigite by rearrangement of iron atoms over a period of days to weeks. Neither pyrrhotite nor pyrite was found. These results have implications for the interpretation of the presence of pyrrhotite and greigite in the martian meteorite ALH84001. PMID:9572727

  1. Photochemical Reactions of Tris (Oxalato) Iron (III): A First-Year Chemistry Experiment.

    ERIC Educational Resources Information Center

    Baker, A. D.; And Others

    1980-01-01

    Describes a first-year chemistry experiment that illustrates the fundamental concepts of a photoinduced reaction. Qualitative and quantitative parts of the photoreduction of potassium ferrioxalate are detailed. (CS)

  2. Inclusive cross-sections of (p,xp) and (p,x{alpha}) reactions on {sup 56}Fe at E{sub p}=29.9 MeV

    SciTech Connect

    Duisebayev, A.; Ismailov, K.M.; Boztosun, I.

    2005-11-01

    In this paper, we present new experimental data measured at E{sub p}= 29.9 MeV for the inclusive reactions (p,xp) and (p,x{alpha}) on nucleus {sup 56}Fe. We investigate the adequacy of the theoretical models in explaining the measured experimental data, and we determine the contributions of multistep direct and multistep compound processes in the formation of the cross-sections. We show that the traditional frameworks are valid for the description of the new experimental data, and our measurements agree with previous measurements for the (p,xp) and (p,x{alpha}) reactions on the {sup 54}Fe nucleus. The only exception is within the energy region of E{sub p}= 15 and 25 MeV for both reactions, where the cross-section for the {sup 56}Fe nucleus is smaller than the cross-section for the {sup 54}Fe nucleus.

  3. Fluorescent probes for tracking the transfer of iron-sulfur cluster and other metal cofactors in biosynthetic reaction pathways.

    PubMed

    Vranish, James N; Russell, William K; Yu, Lusa E; Cox, Rachael M; Russell, David H; Barondeau, David P

    2015-01-14

    Iron-sulfur (Fe-S) clusters are protein cofactors that are constructed and delivered to target proteins by elaborate biosynthetic machinery. Mechanistic insights into these processes have been limited by the lack of sensitive probes for tracking Fe-S cluster synthesis and transfer reactions. Here we present fusion protein- and intein-based fluorescent labeling strategies that can probe Fe-S cluster binding. The fluorescence is sensitive to different cluster types ([2Fe-2S] and [4Fe-4S] clusters), ligand environments ([2Fe-2S] clusters on Rieske, ferredoxin (Fdx), and glutaredoxin), and cluster oxidation states. The power of this approach is highlighted with an extreme example in which the kinetics of Fe-S cluster transfer reactions are monitored between two Fdx molecules that have identical Fe-S spectroscopic properties. This exchange reaction between labeled and unlabeled Fdx is catalyzed by dithiothreitol (DTT), a result that was confirmed by mass spectrometry. DTT likely functions in a ligand substitution reaction that generates a [2Fe-2S]-DTT species, which can transfer the cluster to either labeled or unlabeled Fdx. The ability to monitor this challenging cluster exchange reaction indicates that real-time Fe-S cluster incorporation can be tracked for a specific labeled protein in multicomponent assays that include several unlabeled Fe-S binding proteins or other chromophores. Such advanced kinetic experiments are required to untangle the intricate networks of transfer pathways and the factors affecting flux through branch points. High sensitivity and suitability with high-throughput methodology are additional benefits of this approach. We anticipate that this cluster detection methodology will transform the study of Fe-S cluster pathways and potentially other metal cofactor biosynthetic pathways. PMID:25478817

  4. Kinetics of the Fischer-Tropsch reaction on a precipitated promoted iron catalyst. 1. Experimental procedure and results

    SciTech Connect

    Lox, E.S.; Froment, G.F. )

    1993-01-01

    The Fischer-Tropsch reaction on a commercial promoted precipitated iron catalyst was studied in a tubular reactor under non-deactivating conditions of temperatures between 523 and 623 K, pressures between 0.6 and 2.1 MPa, hydrogen to carbon monoxide feed ratios between 3.0 and 6.0 mol/mol, and W/F[degree][sub CO] values between 9.2 and 63.0 kg[center dot]s/mol. The selectivity for carbon dioxide, methane, and hydrocarbons of different functionality with 2-15 carbon atoms in the molecule was obtained as a function of the carbon monoxide conversion, the reactor temperature, and the total pressure. The initial rate of formation of these products was measured as a function of the total pressure and the partial pressures of hydrogen and carbon monoxide at the reactor inlet. These experiments, combined with the information gained from the catalyst characterization, indicated that carbon dioxide is formed by the water gas shift reaction. Methane, n-paraffins, and 1-olefins with two and more carbon atoms in the molecule are all primary products of the Fischer-Tropsch reaction. The composition of the hydrocarbon product fraction, as a function of the number of carbon atoms in the hydrocarbon molecule, could be described by the Schulz-Flory distribution, although it is shown that the latter only approximately holds for the effluent of an integral reactor.

  5. Numerical investigation of the effects of iron oxidation reactions on the fume formation mechanism in arc welding

    NASA Astrophysics Data System (ADS)

    Sanibondi, Paolo

    2015-09-01

    Fume formation during arc welding has been modelled using a stochastic approach taking into account iron oxidation reactions. The model includes the nucleation and condensation of Fe and FeO vapours, the reaction of gaseous O2 and O on the nanoparticle surface, the coagulation of the nanoparticles including a sintering time as a function of temperature and composition, assuming chemical equilibrium for species in the gaseous phase. Results suggest that fumes generated in gas metal arc welding with oxidizing shielding mixtures are composed of aggregates of primary particles that are nucleated from gas-phase FeO and further oxidized to Fe3O4 and Fe2O3 in the liquid and solid phase, respectively. The composition of the fumes at the end of the formation process depends on the relative initial concentration of Fe and O2 species in the gas mixture and on the diameter of the primary particles that compose the aggregates: as the oxidation reactions are driven by deposition of oxygen on nanoparticle surface, the oxidation of larger particles is slower than that of smaller particles because of their lower surface to volume ratio. Solid-state diffusion is limiting the oxidation process at temperatures lower than 1500 K, inducing the formation of not fully oxidized particles composed of Fe3O4.

  6. From dihydrated iron(III) phosphate to monohydrated ammonium-iron(II) phosphate: Solvothermal reaction mediated by acetone-urea mixtures

    SciTech Connect

    Alfonso, Belen F.; Pique, Carmen; Blanco, Jesus A.

    2012-12-15

    By reaction between synthetic phosphosiderite FePO{sub 4}{center_dot}2H{sub 2}O, urea (NH{sub 2}){sub 2}CO, and acetone (CH{sub 3}){sub 2}CO, we report a novel solvothermal synthesis of polycrystalline NH{sub 4}FePO{sub 4}{center_dot}H{sub 2}O. The preparation of other two individual phases, NH{sub 4}Fe{sub 2}(OH)(PO{sub 4}){sub 2}{center_dot}2H{sub 2}O and NH{sub 4}Fe{sub 2}(PO{sub 4}){sub 2}, is also described. The obtained product is a function of the reaction time and the N/P molar ratio in the reagent mixture, and the existence of structural memory in the dissolution-precipitation processes is discussed. Below 25 K, NH{sub 4}FePO{sub 4}{center_dot}H{sub 2}O behaves magnetically in a complex way, because both ferromagnetic and antiferromagnetic signals are superimposed, suggesting the existence of a canting of iron(II) magnetic moments. - Graphical abstract: Solvothermal synthesis of polycrystalline NH{sub 4}FePO{sub 4}{center_dot}H{sub 2}O is presented. The preparation of other two individual phases, NH{sub 4}Fe{sub 2}(OH)(PO{sub 4}){sub 2}{center_dot}2H{sub 2}O and NH{sub 4}Fe{sub 2}(PO{sub 4}){sub 2} as a function of the N/P molar ratio in the reagent mixture and the reaction time, is also described. Highlights: Black-Right-Pointing-Pointer Solvothermal synthesis of NH{sub 4}FePO{sub 4}{center_dot}H{sub 2}O from an Fe(III) phosphate: reduction process. Black-Right-Pointing-Pointer Formation of two intermediate metastable phases: phase diagram. Black-Right-Pointing-Pointer Thermal decomposition in two steps: mass loss of both water and ammonia. Black-Right-Pointing-Pointer Magnetic behaviour: AF+constant spontaneous magnetization.

  7. Elimination of iron pigments and background staining which mask immunoperoxidase reactions.

    PubMed

    Itoiz, M E; Orrea, S

    1983-01-01

    When immunohistochemical stainings are applied to demonstration of antigens in histopathological specimens, the ferrous pigments which may be present in the tissues usually mask the final precipitates of the reaction. These pigments can be eliminated with oxalic acid or sodium dithionite after the immunohistochemical staining. These treatments also help in the bleaching of unspecific background stain. PMID:6192670

  8. Biogeochemical Reactions and Mineralogical Characteristics in an Iron Reactive Barrier at the Oak Ridge Y-12 Site

    NASA Astrophysics Data System (ADS)

    Gu, B.; Watson, D.; Phillips, D.

    2001-12-01

    A permeable iron reactive barrier was installed in late November, 1997 at the U.S. Department of Energy's Y-12 National Security Complex in Oak Ridge, Tennessee. The biogeochemical reactions and mineralogical and hydrological characteristics in the barrier were investigated over an extended field operation ( ~3 years). Results indicated that zero-valent iron (Fe0) reacts with a number of groundwater constituents such as bicarbonates, nitrate, and sulfate in addition to its effectiveness in removing contaminant metals or radionuclides such as uranium and technetium. Both nitrate and sulfate were reduced within or in the influence zone of the Fe0 with a low redox potential (i.e., low Eh). An increased anaerobic microbial population was also observed within and in the vicinity of the Fe0 barrier, and these microorganisms were at least partially responsible for the reduction of nitrate and sulfate in groundwater. Decreased concentrations of Ca2+ and bicarbonate in groundwater occurred as a result of the formation of minerals such as aragonite (CaCO3) and siderite (FeCO3), which coincided with the Fe0 corrosion and an increased groundwater pH. A suite of mineral precipitates was identified in the Fe0 barrier system, including amorphous iron oxyhydroxides, goethite, ferrous carbonates and sulfides, aragonite, and green rusts. These minerals were found to be responsible for the cementation and possibly clogging of Fe0 filings observed in a number of core samples from the barrier. Significant increases in cementation of the Fe0 occurred between two coring events conducted at ~1 year apart and appeared to correspond to the changes in an apparent decrease in hydraulic connectivity. The present study concludes that, while Fe0 may be used as an effective reactive medium for the retention or degradation of many redox-sensitive contaminants, its long-term reactivity and performance could be severely hindered by its reactions with other groundwater constituents; and groundwater

  9. Mononuclear Nonheme High-Spin (S=2) versus Intermediate-Spin (S=1) Iron(IV)-Oxo Complexes in Oxidation Reactions.

    PubMed

    Bae, Seong Hee; Seo, Mi Sook; Lee, Yong-Min; Cho, Kyung-Bin; Kim, Won-Suk; Nam, Wonwoo

    2016-07-01

    Mononuclear nonheme high-spin (S=2) iron(IV)-oxo species have been identified as the key intermediates responsible for the C-H bond activation of organic substrates in nonheme iron enzymatic reactions. Herein we report that the C-H bond activation of hydrocarbons by a synthetic mononuclear nonheme high-spin (S=2) iron(IV)-oxo complex occurs through an oxygen non-rebound mechanism, as previously demonstrated in the C-H bond activation by nonheme intermediate (S=1) iron(IV)-oxo complexes. We also report that C-H bond activation is preferred over C=C epoxidation in the oxidation of cyclohexene by the nonheme high-spin (HS) and intermediate-spin (IS) iron(IV)-oxo complexes, whereas the C=C double bond epoxidation becomes a preferred pathway in the oxidation of deuterated cyclohexene by the nonheme HS and IS iron(IV)-oxo complexes. In the epoxidation of styrene derivatives, the HS and IS iron(IV) oxo complexes are found to have similar electrophilic characters. PMID:27273456

  10. Facile synthesis of ultrathin magnetic iron oxide nanoplates by Schikorr reaction

    PubMed Central

    2013-01-01

    In this work, a very facile one-pot hydrothermal synthesis approach has been developed for the preparation of ultrathin magnetite nanoplates. The hydrothermal procedure was performed by aging ferrous hydroxide under anaerobic conditions, which is known as Schikorr reaction. Ethylene glycol (EG), which was introduced to the reaction as another solvent, played a critical role in the formation process of these nanoplates. Typically, hexagonal Fe3O4 nanoplates with a thickness of 10 to 15 nm and a side length of 150 to 200 nm have been synthesized with EG/H2O = 1:1 in experiments. Our data suggest that the thickness of Fe3O4 nanoplates decreases, and the shape of the nanoplate becomes more irregular when the concentration of EG increases. The as-prepared Fe3O4 nanoplates were highly crystallized single crystals and exhibited large coercivity and specific absorption rate coefficient. PMID:23294626

  11. Sea urchin-like cobalt-iron phosphide as an active catalyst for oxygen evolution reaction.

    PubMed

    Mendoza-Garcia, Adriana; Su, Dong; Sun, Shouheng

    2016-02-14

    Sea urchin-like (CoxFe1-x)2P shows Co/Fe-composition dependent catalysis for oxygen evolution reaction (OER) in 0.1 M KOH. The (Co0.54Fe0.46)2P is the most efficient OER catalyst, reaching 10 mA cm(-2) at an overpotential of 0.37 V (vs. RHE). The report offers a new synergistic approach to tune and optimize the electrocatalysis of OER. PMID:26810219

  12. Crystallographic snapshots of the reaction of aromatic C-H with O2 catalysed by a protein-bound iron complex

    NASA Astrophysics Data System (ADS)

    Cavazza, Christine; Bochot, Constance; Rousselot-Pailley, Pierre; Carpentier, Philippe; Cherrier, Mickaël V.; Martin, Lydie; Marchi-Delapierre, Caroline; Fontecilla-Camps, Juan C.; Ménage, Stéphane

    2010-12-01

    Chemical reactions inside single crystals are quite rare because crystallinity is difficult to retain owing to atomic rearrangements. Protein crystals in general have a high solvent content. This allows for some molecular flexibility, which makes it possible to trap reaction intermediates of enzymatic reactions without disrupting the crystal lattice. A similar approach has not yet been fully implemented in the field of inorganic chemistry. Here, we have combined model chemistry and protein X-ray crystallography to study the intramolecular aromatic dihydroxylation by an arene-containing protein-bound iron complex. The bound complex was able to activate dioxygen in the presence of a reductant, leading to the formation of catechol as the sole product. The structure determination of four of the catalytic cycle intermediates and the end product showed that the hydroxylation reaction implicates an iron peroxo, generated by reductive O2 activation, an intermediate already observed in iron monooxygenases. This strategy also provided unexpected mechanistic details such as the rearrangement of the iron coordination sphere on metal reduction.

  13. Foaming and the Rate of the Carbon-Iron Oxide Reaction in Slag

    NASA Astrophysics Data System (ADS)

    Corbari, Rodrigo; Matsuura, Hiroyuki; Halder, Sabuj; Walker, Matthew; Fruehan, Richard J.

    2009-12-01

    Foaming in the electric arc furnace is achieved by injecting carbon into slag, where the resulting reaction of the carbon with FeO dissolved in the slag generates gas (CO) that causes the slag to foam. In this research, the rate of the reaction of FeO in slag with carbon and the resulting foam height were measured. In these experiments, the FeO content of the slag ranged from 15 to 45 mass pct, and several different types of carbon were used including graphite, coals, and chars. The rate of the slag-carbon reaction and the consequent CO generation increased with FeO content of the slag from 15 to 45 mass pct. However, the slag foam height reached a maximum at about 25 mass pct FeO and decreased at higher FeO contents. The decrease in foaming is apparently due to a decrease in the foam index or foamability caused by a decrease in viscosity and an increase in density of the slag with FeO content. The results of this work indicate that the foam height is influenced more significantly by the decrease in the foam index compared to the increase in the CO gas generation rate at higher FeO contents. The decrease in the foam index with FeO agrees with that predicted from the slag properties.

  14. Ferric iron in sediments as a novel CO2 mineral trap: CO 2-SO2 reaction with hematite

    USGS Publications Warehouse

    Palandri, J.L.; Rosenbauer, R.J.; Kharaka, Y.K.

    2005-01-01

    Thermodynamic simulations of reactions among SO2-bearing CO 2-dominated gas, water and mineral phases predict that Fe III in sediments should be converted almost entirely to dissolved FeII and siderite (FeCO3), and that SO2 should simultaneously be oxidized to dissolved sulfate. The reactions are however, subject to kinetic constraints which may result in deviation from equilibrium and the precipitation of other metastable mineral phases. To test the prediction, a laboratory experiment was carried out in a well stirred hydrothermal reactor at 150??C and 300 bar with hematite, 1.0 m NaCl, 0.5 m NaOH, SO2 in quantity sufficient to reduce much of the iron, and excess CO2. The experiment produced stable siderite and metastable pyrite and elemental S. Changes in total dissolved Fe are consistent with nucleation of pyrite at ???17 h, and nucleation of siderite at ???600 h. Dissolution features present on elemental S at the conclusion of the experiment suggest nucleation early in the experiment. The experiment did not reach equilibrium after ???1400 h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that FeIII can be used to trap CO2 in siderite if partly oxidized S, as SO2, is present to reduce the Fe with CO2 in the gas phase. ?? 2005 Elsevier Ltd. All rights reserved.

  15. Tris(5,6-dimethyl-1,10-phenanthroline-κ2 N,N′)iron(II) bis­(tricyano­methanide)

    PubMed Central

    Váhovská, Lucia; Potočňák, Ivan

    2012-01-01

    The title compound, [Fe(C14H12N2)3](C4N3)2, consists of one [Fe(dimephen)3]2+ complex cation (dimephen = 5,6-dimethyl-1,10-phenanthroline) and two uncoordinating tcm anions (tcm = tricyano­methanide). In the complex cation, the FeII atom is coordinated by six N atoms from three chelating dimephen ligands at an average Fe—N distance of 1.963 (4) Å giving a distorted octa­hedral geometry. The crystal structure is stabilized by weak C—H⋯N hydrogen bonds and C N⋯π inter­actions between planar [maximum deviations of 0.024 (3) and 0.015 (3) Å] tcm anions and pyridine rings of dimephen [N2⋯centroid = 3.531 (3) and 3.726 (3) Å; C N⋯centroid = 96.4 (2) and 97.1 (2)°]. PMID:23468734

  16. A new mechanism of loop formation and transformation in bcc iron without dislocation reaction

    NASA Astrophysics Data System (ADS)

    Chen, J.; Gao, N.; Jung, P.; Sauvage, T.

    2013-10-01

    Structure and kinetics of dislocation loops in α-Fe is an active field in material science, due to their implications on fundamental understanding as well as application of structural materials in irradiation environments. Recent computer simulations provoke new conceptions, which call for experimental verification. The present investigation reports transmission electron microscopy of small interstitial dislocation loops (2.5-10 nm diameters) in bcc iron, irradiated with 25 MeV α-particles at 573 K up to 0.13 dpa. The observed <1 0 0> and ½<1 1 1> loops have habit planes of (1 0 0), and (1 1 0), (1 1 1) and (2 1 1), respectively. Furthermore it is observed that loops also contain ½<1 1 1>{2 1 1} and <1 0 0>{1 0 0} components which are considered as intermediate stages of transformation of ½<1 1 1> loops to <1 0 0>. Based on these observations, a new mechanism of loop formation and transformation by self-interstitial atoms aggregation is proposed, with concurrent molecular dynamic simulations supporting the kinetic feasibility of the proposed process.

  17. Organocatalytic Asymmetric Michael/Friedel-Crafts Cascade Reaction of 3-Pyrrolyl-oxindoles and α,β-Unsaturated Aldehydes for the Construction of Chiral Spiro[5,6-dihydropyrido[1,2-a]pyrrole-3,3'-oxindoles].

    PubMed

    You, Yong; Cui, Bao-Dong; Zhou, Ming-Qiang; Zuo, Jian; Zhao, Jian-Qiang; Xu, Xiao-Ying; Zhang, Xiao-Mei; Yuan, Wei-Cheng

    2015-06-01

    An efficient and unprecedented organocatalytic asymmetric reaction of 3-pyrrolyl-oxindoles with α,β-unsaturated aldehydes to generate spirocyclic oxindole compounds was developed. The reactions were catalyzed by diphenylprolinol silyl ether and 2-fluorobenzoic acid via an asymmetric Michael/Friedel-Crafts cascade process, followed by dehydration with p-toluenesulfonic acid to afford a wide variety of structurally diverse spiro[5,6-dihydropyrido[1,2-a]pyrrole-3,3'-oxindole] derivatives in high yields (up to 93%) and with high to excellent diastereo- and enantioselectivities (up to >99:1 dr and 97% ee). PMID:25984596

  18. Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 2: Iron- and Copper-Catalyzed Oxidation.

    PubMed

    Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

    2016-05-25

    Sulfidic off-odors arising during wine production are frequently removed by Cu(II) fining. In part 1 of this study ( 10.1021/acs.jafc.6b00641 ), the reaction of H2S and thiols with Cu(II) was examined; however, the interaction of iron and copper is also known to play an important synergistic role in mediating non-enzymatic wine oxidation. The interaction of these two metals in the oxidation of H2S and thiols (cysteine, 3-sulfanylhexan-1-ol, and 6-sulfanylhexan-1-ol) was therefore examined under wine-like conditions. H2S and thiols (300 μM) were reacted with Fe(III) (100 or 200 μM) alone and in combination with Cu(II) (25 or 50 μM), and concentrations of H2S and thiols, oxygen, and acetaldehyde were monitored over time. H2S and thiols were shown to be slowly oxidized in the presence of Fe(III) alone and were not bound to Fe(III) under model wine conditions. However, Cu(II) added to model wine containing Fe(III) was quickly reduced by H2S and thiols to form Cu(I) complexes, which then rapidly reduced Fe(III) to Fe(II). Oxidation of Fe(II) in the presence of oxygen regenerated Fe(III) and completed the iron redox cycle. In addition, sulfur-derived oxidation products were observed, and the formation of organic polysulfanes was demonstrated. PMID:27133088

  19. Sea urchin-like cobalt-iron phosphide as an active catalyst for oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Mendoza-Garcia, Adriana; Su, Dong; Sun, Shouheng

    2016-02-01

    Sea urchin-like (CoxFe1-x)2P shows Co/Fe-composition dependent catalysis for oxygen evolution reaction (OER) in 0.1 M KOH. The (Co0.54Fe0.46)2P is the most efficient OER catalyst, reaching 10 mA cm-2 at an overpotential of 0.37 V (vs. RHE). The report offers a new synergistic approach to tune and optimize the electrocatalysis of OER.Sea urchin-like (CoxFe1-x)2P shows Co/Fe-composition dependent catalysis for oxygen evolution reaction (OER) in 0.1 M KOH. The (Co0.54Fe0.46)2P is the most efficient OER catalyst, reaching 10 mA cm-2 at an overpotential of 0.37 V (vs. RHE). The report offers a new synergistic approach to tune and optimize the electrocatalysis of OER. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08763e

  20. Performance Enhancement and Side Reactions in Rechargeable Nickel-Iron Batteries with Nanostructured Electrodes.

    PubMed

    Lei, Danni; Lee, Dong-Chan; Magasinski, Alexandre; Zhao, Enbo; Steingart, Daniel; Yushin, Gleb

    2016-01-27

    We report for the first time a solution-based synthesis of strongly coupled nanoFe/multiwalled carbon nanotube (MWCNT) and nanoNiO/MWCNT nanocomposite materials for use as anodes and cathodes in rechargeable alkaline Ni-Fe batteries. The produced aqueous batteries demonstrate very high discharge capacities (800 mAh gFe(-1) at 200 mA g(-1) current density), which exceed that of commercial Ni-Fe cells by nearly 1 order of magnitude at comparable current densities. These cells also showed the lack of any "activation", typical in commercial batteries, where low initial capacity slowly increases during the initial 20-50 cycles. The use of a highly conductive MWCNT network allows for high-capacity utilization because of rapid and efficient electron transport to active metal nanoparticles in oxidized [such as Fe(OH)2 or Fe3O4] states. The flexible nature of MWCNTs accommodates significant volume changes taking place during phase transformation accompanying reduction-oxidation reactions in metal electrodes. At the same time, we report and discuss that high surface areas of active nanoparticles lead to multiple side reactions. Dissolution of Fe anodes leads to reprecipitation of significantly larger anode particles. Dissolution of Ni cathodes leads to precipitation of Ni metal on the anode, thus blocking transport of OH(-) anions. The electrolyte molarity and composition have a significant impact on the capacity utilization and cycling stability. PMID:26720271

  1. Steady-state studies of the reactions of H2O-CO and CO2-H2 mixtures with liquid iron

    NASA Astrophysics Data System (ADS)

    Sasaki, Y.; Belton, G. R.

    1998-08-01

    Studies have been made of the steady-stata composition of liquid iron exposed to high flow rates of H2O-CO mixtures at 1550 °C to 1700 °C and CO2-H2 mixtures at 1600 °C. Values of the steady-state activity of oxygen have been established by measurement of either the carbon concentration or the silicon concentration when the iron was held in a silica crucible. Additions of sulfur or selenium to the iron have been found to result in steady-state oxygen activities, which differ significantly from those expected from water-gas equilibrium. The results are interpreted to show that the ratio of the apparent first-order rate constants for the reactions of H2O and CO2 with liquid iron is about 3 at 1600 °C. It is shown that the dependencies of the rate constants on the activities of sulfur, oxygen, and selenium must, even if complex, be similar for the H2O and CO2 reactions with liquid iron, to a good approximation.

  2. Mechanochemical reactions and strengthening in epoxy-cast aluminum iron-oxide mixtures

    NASA Astrophysics Data System (ADS)

    Ferranti, Louis, Jr.

    2007-12-01

    Epoxy-cast Al+Fe2O3 thermite composites are an example of a structural energetic material that can simultaneously release chemical energy while providing structural strength. The structural/mechanical response and chemical reaction behavior are closely interlinked through characteristics of deformation and intermixing of reactants. In this work, the structural and energetic response of composites made from stoichiometric mixtures of nano- and micro-scale aluminum and hematite (Fe2O3) powders dispersed in 47 to 78 vol.% epoxy was investigated by characterizing the mechanical behavior under high-strain rate and shock loading conditions. The main focus of the work was to understand the influence of microstructure on mechanical behavior in epoxy-cast Al+Fe2O3 materials when exposed to high stress, large strain, and high rate loading conditions. The material's Hugoniot at pressures up to approximately 20 GPa for an Al+Fe2O3+78 vol.% epoxy composite and up to approximately 8 GPa for Al+Fe2O3+60 vol.% epoxy composite has been determined. The results reveal an inert pressure-relative volume (P-V) and shock-particle velocity (US-UP) response in the range of the shock-conditions explored, with the Al+Fe2O3+60 vol.% epoxy composite showing a greater shock stiffness. The addition of solid particle inclusions alters the Hugoniot response as compared to pure epoxy behavior. This is attributed to possible induced bulk damage that changes the composite's response as impact stress increases. While the 78 vol.% epoxy composition shows a transition from "undamaged" to "damaged" behavior that approaches pure epoxy response, the 60 vol.% epoxy composition exhibits a gradual toughening behavior. Impact experiments have also been conducted for characterizing the high-strain rate deformation and fracture response obtained from instrumented reverse Taylor tests using high-speed camera and velocity interferometry. The results show that these composite materials exhibit viscoelastic

  3. Preparation, structures and some reactions of novel diynyl complexes of iron and ruthenium.

    PubMed

    Bruce, Michael I; Ellis, Benjamin G; Gaudio, Maryka; Lapinte, Claude; Melino, Giovanni; Paul, Frédéric; Skelton, Brian W; Smith, Mark E; Toupet, Loic; White, Allan H

    2004-05-21

    Reactions between HC triple bond CC triple bond CSiMe3 and several ruthenium halide precursors have given the complexes Ru(C triple bond CC triple bond CSiMe3)(L2)Cp'[Cp'= Cp, L = CO (1), PPh3 (2); Cp' = Cp*, L2= dppe (3)]. Proto-desilylation of 2 and 3 have given unsubstituted buta-1,3-diyn-1-yl complexes Ru(C triple bond CC triple bond CH)(L2)Cp'[Cp'= Cp, L = PPh3 (5); Cp'= Cp*, L2 = dppe (6)]. Replacement of H in 5 or 6 with Au(PR3) groups was achieved in reactions with AuCl(PR3) in the presence of KN(SiMe3)2 to give Ru(C triple bond CC triple bond CAu(PR3)](L2)Cp'[Cp' = Cp, L = PPh3, R = Ph (7); Cp' = Cp*, L2= dppe, R = Ph (8), tol (9)]. The asymmetrically end-capped [Cp(Ph3P)2Ru]C triple bond CC triple bond C[Ru(dppe)Cp*] (10) was obtained from Ru(C triple bond CC triple bond CH)(dppe)Cp* and RuCl(PPh3)2Cp. Single-crystal X-ray structural determinations of and are reported, with a comparative determination of the structure of Fe(C triple bond CC triple bond CSiMe3)(dppe)Cp* (4), and those of a fifth polymorph of [Ru(PPh3)2Cp]2(mu-C triple bond CC triple bond C) (12), and [Ru(dppe)Cp]2(mu-C triple bond CC triple bond C) (13). PMID:15252610

  4. Theoretical Analyses and Experimental Investigations of Selective Carbothermal Reactions of Vanadium-Bearing Titanomagnetite Concentrates for Preparation of Iron-Based Wear-Resistant Material

    NASA Astrophysics Data System (ADS)

    Zhang, Guangming; Feng, Keqin; Yue, Huifang

    2016-07-01

    Based on FACTSage® software, this paper focuses on the thermodynamic calculations of selective carbothermal reactions of vanadium-bearing titanomagnetite concentrates for preparing iron-based wear-resistant material directly from vanadium-bearing titanomagnetite concentrates. The calculations show that it was most likely to generate metallic iron, titanium carbide and vanadium carbide among all possible carbothermal reactions of vanadium-bearing titanomagnetite concentrates in a vacuum of 10 Pa. The equilibrium composition calculations indicate that Fe3O4 can be reduced to metallic iron by carbon above 400°C, FeTiO3 can be converted into TiC by carbon above 800°C and V2O5 can be converted into VC by carbon above 600°C in a vacuum of 10 Pa. The investigations demonstrated that the percentage of ferrous oxides reduced to metallic iron was about 96%, the conversion percentage of FeTiO3 into TiC was about 75% and the conversion percentage of V2O5 into VC was about 94% after the selective carbothermal reactions of vanadium-bearing titanomagnetite concentrates at 1300°C for 3 h in a vacuum of 10 Pa.

  5. Augmentation of pulmonary reactions to quartz inhalation by trace amounts of iron-containing particles.

    PubMed Central

    Castranova, V; Vallyathan, V; Ramsey, D M; McLaurin, J L; Pack, D; Leonard, S; Barger, M W; Ma, J Y; Dalal, N S; Teass, A

    1997-01-01

    Fracturing quartz produces silica-based radicals on the fracture planes and generates hydroxyl radicals (.OH) in aqueous media. .OH production has been shown to be directly associated with quartz-induced cell damage and phagocyte activation in vitro. This .OH production in vitro is inhibited by desferrioxamine mesylate, an Fe chelator, indicating involvement of a Fenton-like reaction. Our objective was to determine if Fe contamination increased the ability of inhaled quartz to cause inflammation and lung injury. Male Fischer 344 rats were exposed 5 hr/day for 10 days to filtered air, 20 mg/m3 freshly milled quartz (57 ppm Fe), or 20 mg/m3 freshly milled quartz contaminated with Fe (430 ppm Fe). High Fe contamination of quartz produced approximately 57% more reactive species in water than quartz with low Fe contamination. Compared to inhalation of quartz with low Fe contamination, high Fe contamination of quartz resulted in increases in the following responses: leukocyte recruitment (537%), lavageable red blood cells (157%), macrophage production of oxygen radicals measured by electron spin resonance or chemiluminescence (32 or 90%, respectively), nitric oxide production by macrophages (71%), and lipid peroxidation of lung tissue (38%). These results suggest that inhalation of freshly fractured quartz contaminated with trace levels of Fe may be more pathogenic than inhalation of quartz alone. PMID:9400745

  6. Reaction kinetics of hydrogen peroxide with copper and iron in sea water

    SciTech Connect

    Moffett, J.W.; Zika, R.G.

    1987-08-01

    The oxidation of Fe(II) and Cu(I) and the reduction of Fe(III) and Cu(II) by hydrogen peroxide in sea water have been studied to understand their mechanisms and probable significance in the upper marine water column. At 10/sup -7/ M H/sub 2/O/sub 2/, a level commonly found in surface sea water, reaction with H/sub 2/O/sub 2/ is the dominant oxidation pathway for Fe(II). Reduction of Fe(III) by peroxide was not observed in the pH range 7-8. Reduction of Cu(II) and oxidation of Cu(I) by H/sub 2/O/sub 2/ contribute to a dynamic redox cycling of that element in the upper water column. Calculations based on these data indicate that CU(I) oxidation and FE(II) oxidation by H/sub 2/O/sub 2/ are at least as important as nitrite photolysis as a source of OH radicals in the ocean. 47 references, 6 figures, 2 tables.

  7. Reactions of xenon with iron and nickel are predicted in the Earth's inner core.

    PubMed

    Zhu, Li; Liu, Hanyu; Pickard, Chris J; Zou, Guangtian; Ma, Yanming

    2014-07-01

    Studies of the Earth's atmosphere have shown that more than 90% of the expected amount of Xe is depleted, a finding often referred to as the 'missing Xe paradox'. Although several models for a Xe reservoir have been proposed, whether the missing Xe could be contained in the Earth's inner core has not yet been answered. The key to addressing this issue lies in the reactivity of Xe with Fe/Ni, the main constituents of the Earth's core. Here, we predict, through first-principles calculations and unbiased structure searching techniques, a chemical reaction of Xe with Fe/Ni at the temperatures and pressures found in the Earth's core. We find that, under these conditions, Xe and Fe/Ni can form intermetallic compounds, of which XeFe3 and XeNi3 are energetically the most stable. This shows that the Earth's inner core is a natural reservoir for Xe storage and provides a solution to the missing Xe paradox. PMID:24950336

  8. Effect of phosphorous surface segregation on iron-zinc reaction kinetics during hot-dip galvanizing

    SciTech Connect

    Jordan, C.E.; Zuhr, R.; Marder, A.R.

    1997-12-01

    Phosphorous was ion implanted on one surface of a large grain (10 to 20 mm) low-carbon steel sheet in order to study the effect of surface segregation on the formation of Fe-Zn phases during galvanizing. Both an Al-free and a 0.20 wt pct Al-Zn bath at 450 C were used in this investigation. It was found that P surface segregation did not affect the kinetics of Fe-Zn phase growth for the total alloy layer or the individual Fe-Zn gamma, delta, and zeta phase alloy layers in the 0.00 wt pct Al-Zn baths. In the 0.20 wt pct Al-Zn bath, the Fe{sub 2}Al{sub 5} inhibition layer formed with kinetics, showing linear growth on both the P-ion implanted and non-P-ion implanted surfaces. Fe-Zn phase growth only occurred after extended reaction times on both surfaces and was found to directly correspond to the location of substrate grain boundary sites. These results indicate that P surface segregation does not affect the growth of Fe-Zn phases or the Fe{sub 2}Al{sub 5} inhibition layer. It was shown that in the 0.20 wt pct Al-Zn bath, substrate grain boundaries are the dominant steel substrate structural feature that controls the kinetics of Fe-Zn alloy phase growth.

  9. [Functions of pheophytin, plastoquinone, iron and carotenoids in plant photosystem 2 reaction centers].

    PubMed

    Klimov, V V; Dolan, E; Ke, B

    1981-01-01

    Photoreduction of the intermediary electron acceptor, pheophytin (Ph), in photosystem-2 (PS-2) reaction centers of spinach chloroplasts or subchloroplast particles (TSF-II and TSF-IIa) at 220 K and Eh approximately -450 mV produces a narrow ESR signal of Ph. (g = 2.0033; delta H approximately 13 G) and a "doublet" centered at g = 2.00 with a splitting of 52 G at 7 K. The doublet (but not the narrow signal) is eliminated after extraction of lyophylized TSF-II with hexane, containing 0.1-0.2% methanol, or after extraction of Fe with LiClO4 and o-phenantroline, and the signal is restored by reconstitution with plastoquinone-A (PQ) or Fe++, respectively. The Fe removal results also in the development of a photoinduced ESR signal of PQ. (g approximately 2.0044; delta H approximately 9.2 G). The conclusion is made that the primary electron acceptor, Q, is in fact a complex PQ-Fe++ and that the exchange interaction of Ph. with PQ. -Fe++ is responsible for the ESR doublet. Photoreduction of Ph in TSF-IIa is accompanied by the 3-fold decrease in the formation of carotenoid triplet state (measured by the characteristic flash-induced absorbance changes) which is suggested to be a result of charge recombination in the pair [P680+ .PH.]. PMID:6274422

  10. Stabilization of nickel by aluminum- and iron-rich ceramic materials: Reaction pathways and product leaching behavior

    NASA Astrophysics Data System (ADS)

    Shih, Kaimin

    The feasibility of stabilizing nickel-laden sludge with commonly available ceramic precursors was investigated. Nickel aluminate spinel (NiAl2O 4) was the immobilization phase produced when NiO was sintered with aluminum-rich precursors, including gamma-Al2O3, corundum, kaolinite and mullite. Analogously, nickel ferrite spinel (NiFe2O 4) was the stable phase produced by firing NiO with hematite, as an iron-rich precursor. By using gamma-Al2O3 as the precursor, the NiAl2O4 formation mechanism was a reaction between NiO and gamma-Al2O3 at lower temperatures (990°C), while the reaction was between NiO and corundum at higher temperatures. When sintering NiO with kaolinite, nickel can be efficiently incorporated in NiAl2O4 by two mechanisms: (i) a low temperature reaction with a defect spinel, and (ii) a high temperature reaction with mullite. Nickel-incorporation efficiency was quantitatively estimated by powder X-ray Diffraction (XRD) analysis. With 3-hours sintering, NiFe2O 4 (trevorite) formation took place above 600°C with more than 95% nickel incorporation efficiency achieved above 1000°C; while NiAl 2O4 crystallized above 1000°C with an efficiency >90% above 1250°C. In using kaolinite and mullite as precursors, nickel is not incorporated in any silicon-containing phase. The kinetic factors responsible for nickel incorporation efficiency from different precursors were revealed through investigation of product microstructures. Moreover, four raw material mixing procedures were compared, with the ball-milled slurries demonstrating the highest nickel incorporation efficiency. Prolonged leach tests of NiO, NiAl2O4, NiFe 2O4 and sintered kaolinite + NiO samples were carried out using the TCLP extraction fluids #1 and #2 to evaluate the durability of sintered products. Over longer leaching periods, spinel proved superior to NiO for immobilization of nickel, although NiFe2O4 appears slightly more leachable than NiAl2O4. With TCLP extraction fluid #1 (pH 4.9), the

  11. Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

    SciTech Connect

    Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.; Gates, B.C.

    1995-12-31

    The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.

  12. A novel iron (Ⅱ) polyphthalocyanine catalyst assembled on graphene with significantly enhanced performance for oxygen reduction reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Lin, Lin; Li, Meng; Jiang, Liqing; Li, Yongfeng; Liu, Dajun; He, Xingquan; Cui, Lili

    2014-12-01

    To realize the large-scale commercial application of direct methanol fuel cells (DMFCs), the catalysts for oxygen reduction reaction (ORR) are the crucial obstacle. Here, an efficient non-noble-metal catalyst for ORR, denoted FePPc/PSS-Gr, has been obtained by anchoring p-phenyl-bis(3,4-dicyanophenyl) ether iron(Ⅱ) polyphthalocyanine (FePPc) on poly(sodium-p-styrenesulfonate) (PSS) modified graphene (PSS-Gr) through a solvothermally assisted π-π assembling approach. The Ultraviolet-visible (UV-vis) spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results reveal the π-π interaction between FePPc and PSS-Gr. The rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) measurements show that the proposed catalyst possesses an excellent catalytic performance towards ORR comparable with the commercial Pt/C catalyst in alkaline medium, such as high onset potential (-0.08 V vs. SCE), half-wave potential (-0.19 V vs. SCE), better tolerance to methanol crossover, excellent stability (81.1%, retention after 10,000 s) and an efficient four-electron pathway. The enhanced electrocatalytic performance could be chiefly attributed to its large electrochemically accessible surface area, fast electron transfer rate of PSS-Gr, in particular, the synergistic effect between the FePPc moieties and the PSS-Gr sheets.

  13. Spin-flip (p,n) reactions on /sup 26/Mg, /sup 54/Fe, and /sup 56/Fe at selected proton bombarding energies in the range of 17 to 25 MeV

    SciTech Connect

    Aron, D.L.

    1985-06-01

    New data are presented for the /sup 26/Mg(p,n)/sup 26/Al reaction at E/sub p/ = 19.12 and 24.97 MeV, for the /sup 54/Fe(p,n)/sup 54/Co reaction at E/sub p/ = 17.20, 18.60, and 24.60 MeV, and for the /sup 56/Fe(p,n)/sup 56/Co reaction at E/sub p/ = 19.12 and 24.59 MeV. Data were taken with the LLNL Cyclograaff at 16 angles from 3.5/sup 0/ to 159.0/sup 0/. A large detector at 23.8/sup 0/ with a long neutron flight path collected high resolution spectra. This large detector also collected separate 0/sup 0/ high resolution data on the /sup 26/Mg and /sup 56/Fe(p,n) reactions at E/sub p/ = 19 MeV. Absolute differential (p,n) cross sections were extracted for 1/sup +/ states in /sup 26/Al, /sup 54/Co, and /sup 56/Co, for the 0/sup +/ isobaric analong state (IAS) in /sup 54/Co and /sup 56/Co, for a 2/sup +/ state in each residual nucleus, and for the 0.199 MeV 7/sup +/ state of /sup 54/Co. No new experimental states were identified. Only relative cross sections were extracted at 0/sup 0/. Experimental angle-integrated cross sections were obtained for all but one state. DWBA79 was used, with the G-matrix effective nucleon-nucleon interaction of Bertsch et al. (with the central triplet-odd component V/sub to/ = O) and the Livermore shell model wave functions to calculate differential (p,n) cross sections to 1/sup +/ states and to the /sup 54/Co and /sup 56/Co IAS. Normalization of the DWBA angle-integrated cross sections to measurements for the /sup 54/Co and /sup 56/Co IAS (at E/sub p/ = 24.6 MeV) yielded the renormalized V/sub tau/ = 21.4 +- 2.1 MeV. Normalization of the DWBA angle-integrated cross sections to measurements for the 24.6 MeV /sup 54/Co and /sup 56/Co 1/sup +/ states, coupled with the normalization of the wave functions to previously experimentally determined GT strength, yield the renormalized V/sub sigmatau/ = 12.3 +- 1.2 MeV. The experimental Gamow-Teller strength B(GT)/sub exp./ of the T = 1 /sup 26/Al state at 9.44 MeV was found to be 0.69; B

  14. Kinetic study for phenol degradation by ZVI-assisted Fenton reaction and related iron corrosion investigated by X-ray absorption spectroscopy.

    PubMed

    Yoon, In-Ho; Yoo, Gursong; Hong, Hye-Jin; Kim, Jungmin; Kim, Min Gyu; Choi, Wang-Kyu; Yang, Ji-Won

    2016-02-01

    In this study, we investigated phenol degradation via zero-valent iron (ZVI)-assisted Fenton reaction through kinetic and spectroscopic analysis. In batch experiments, 100 mg/L of phenol was completely degraded, and 75% of TOC was removed within 3 min under an optimal hydrogen peroxide (H2O2) concentration (50 mM) via the Fenton reaction. In the absence of H2O2, oxygen (O2) was dissolved into the solution and produced H2O2, which resulted in phenol degradation. However, phenol removal efficiency was not very high compared to external H2O2 input. The Fenton reaction rapidly occurred at the surface of ZVI, and then phenol mobility from the solution to the ZVI surface was the rate determining step of the whole reaction. The pseudo-second order adsorption kinetic model well describes phenol removal, and its rate increased according to the H2O2 concentration. X-ray absorption spectroscopic analysis revealed that iron oxide (Fe-O bonding) was formed on ZVI with [H2O2] > 50 mM. A high concentration of H2O2 led to rapid degradation of phenol and caused corrosion on the ZVI surface, indicating that Fe(2+) ions were rapidly oxidized to Fe(3+) ions due to the Fenton reaction and that Fe(3+) was precipitated as iron oxide on the ZVI surface. However, ZVI did not show corroded characteristics in the absence of H2O2 due to the insufficient ZVI-assisted Fenton reaction and oxidation of Fe(2+) to Fe(3+). PMID:26692518

  15. Iron and iron derived radicals

    SciTech Connect

    Borg, D.C.; Schaich, K.M.

    1987-04-01

    We have discussed some reactions of iron and iron-derived oxygen radicals that may be important in the production or treatment of tissue injury. Our conclusions challenge, to some extent, the usual lines of thought in this field of research. Insofar as they are born out by subsequent developments, the lessons they teach are two: Think fastexclamation Think smallexclamation In other words, think of the many fast reactions that can rapidly alter the production and fate of highly reactive intermediates, and when considering the impact of competitive reactions on such species, think how they affect the microenvironment (on the molecular scale) ''seen'' by each reactive molecule. 21 refs., 3 figs., 1 tab.

  16. Iron Sucrose Injection

    MedlinePlus

    ... stop working). Iron sucrose injection is in a class of medications called iron replacement products. It works ... hands, feet, ankles, or lower legs; loss of consciousness; or seizures. If you experience a severe reaction, ...

  17. Adaptation Reactions of Siderophilic Cyanobacteria to High and Low Levels Of Environmental Iron: Implications for Biosphere History

    NASA Technical Reports Server (NTRS)

    Brown, I. I.; Bryant, D.; Sarkisova, S.; Shen, G.; Garrison, D.; McKay, D. S.

    2009-01-01

    Of all extant environments, iron-depositing hot springs may constitute the most appropriate natural models (Pierson and Parenteau, 2000) for analysis of the ecophysiology of ancient cyanobacteria (CB) which may have emerged in association with hydrothermal activity (Brown et al., 2007) and elevated levels of environmental Fe (Rouxel et al., 2005). Elevated environmental Fe2+ posed a significant challenge to the first oxygenic phototrophs - CB - because reduced Fe2+ induces toxic Fenton reactions (Wiedenheft et al., 2005). Ancient CB could have also been stressed by occasional migrations from the Fe2+-rich Ocean to the basaltic land which was almost devoid of dissolved Fe2+. That is why the study of the adaptation reactions of siderophilic CB, which inhabit iron-depositing hot springs, to up and down shifts in levels of dissolved Fe may shed light on the paleophysiology of ancient oxygenic prokaryotes. Methods. Siderophilic CB (Brown et al., 2007) were cultivated in media with different concentrations of added Fe3+. In some cases basaltic rocks were used as a source of Fe and trace elements. The processes of Fe mineralization and rock dissolution were studied using TEM, SEM and EDS techniques. Fluorescence spectroscopy was used for checking chlorophyll-protein complexes. Results. It was found that five siderophilic isolates Chroogloeocystis siderophila, JSC-1, JSC-3, JSC-11 and JSC-12 precipitated Fe-bearing phases on the exopolymeric sheaths of their cells if [Fe3+] was approx. 400-600 M (high Fe). Same [Fe3+] was most optimal one for the cultures proliferation rate (Brown et al., 2005; Brown et al., 2007). Higher concentrations of Fe3+ repressed the growth of some siderophilic CB (Brown et al., 2005). No mineralized Fe3+ was observed on the sheath of freshwater isolates Synechocystis sp. PCC 6803 and Phormidium aa. Scanning TEM in conjunction with thin-window energy dispersive X-ray spectroscopy (EDS) revealed intracellular Fe-rich phases within all three isolates

  18. Flow-injection simultaneous determination of iron(III) and copper(II) and of iron(III) and palladium(II) based on photochemical reactions of thiocyanato-complexes.

    PubMed

    Oguma, Koichi; Yoshioka, Osamu

    2002-12-01

    The flow injection analysis systems have been developed for the simultaneous determination of iron(III) and copper(II) and of iron(III) and palladium(II) based on the photochemical reactions of their thiocyanato-complexes. In the first system, a sample solution was injected in to nitric acid solution and mixed with ammonium thiocyanate solution, followed by spectrophotometric monitoring of the thiocyanato-complexes formed. Another aliquot of the same sample solution was injected and the thiocyanato-complexes formed in the same way were irradiated by UV light before spectrophotometric monitoring. In another system, the absorbance of thiocyanato-complexes formed by each sample injection was monitored with two flow cells aligned with the same optical path before and after UV irradiation. The difference in the extent of photochemical decomposition of the thiocyanato-complexes enabled simultaneous determinations of iron(III) and copper(II) and of iron(III) and palladium(II) at levels of several mugml(-1) to some tens mugml(-1) in their admixtures. Sample throughputs are 40 and 20 h(-1) by the former and latter systems, respectively. PMID:18968842

  19. The FX iron-sulfur cluster serves as the terminal bound electron acceptor in heliobacterial reaction centers.

    PubMed

    Romberger, Steven P; Golbeck, John H

    2012-03-01

    Phototrophs of the family Heliobacteriaceae contain the simplest known Type I reaction center (RC), consisting of a homodimeric (PshA)(2) core devoid of bound cytochromes and antenna proteins. Unlike plant and cyanobacterial Photosystem I in which the F(A)/F(B) protein, PsaC, is tightly bound to P(700)-F(X) cores, the RCs of Heliobacterium modesticaldum contain two F(A)/F(B) proteins, PshBI and PshBII, which are loosely bound to P(800)-F(X) cores. These two 2[4Fe-4S] ferredoxins have been proposed to function as mobile redox proteins, reducing downstream metabolic partners much in the same manner as does [2Fe-2S] ferredoxin or flavodoxin (Fld) in PS I. Using P(800)-F(X) cores devoid of PshBI and PshBII, we show that iron-sulfur cluster F(X) directly reduces Fld without the involvement of F(A) or F(B) (Fld is used as a proxy for soluble redox proteins even though a gene encoding Fld is not identified in the H. modesticaldum genome). The reduction of Fld is suppressed by the addition of PshBI or PshBII, an effect explained by competition for the electron on F(X). In contrast, P(700)-F(X) cores require the presence of the PsaC, and hence, the F(A)/F(B) clusters for Fld (or ferredoxin) reduction. Thus, in H. modesticaldum, the interpolypeptide F(X) cluster serves as the terminal bound electron acceptor. This finding implies that the homodimeric (PshA)(2) cores should be capable of donating electrons to a wide variety of yet-to-be characterized soluble redox partners. PMID:22297911

  20. Water-Rock Interaction Simulations of Iron Oxide Mobilization and Precipitation: Implications of Cross-diffusion Reactions for Terrestrial and Mars 'Blueberry' Hematite Concretions

    NASA Astrophysics Data System (ADS)

    Park, A. J.; Chan, M. A.; Parry, W. T.

    2005-12-01

    Modeling of how terrestrial concretions form can provide valuable insights into understanding water-rock interactions that led to the formation of hematite concretions at Meridiani Planum, Mars. Numerical simulations of iron oxide concretions in the Jurassic Navajo Sandstone of southern Utah provide physical and chemical input parameters for emulating conditions that may have prevailed on Mars. In the terrestrial example, iron oxide coatings on eolian sand grains are reduced and mobilized by methane or petroleum. Precipitation of goethite or hematite occurs as Fe interacts with oxygen. Conditions that produced Navajo Sandstone concretions can range from a regional scale that is strongly affected by advection of large pore volumes of water, to small sub-meter scale features that are dominantly controlled by diffusive processes. Hematite concretions are results of a small-scale cross-diffusional process, where Fe and oxygen are supplied from two opposite sides from the 'middle' zone of mixing where concretions precipitate. This is an ideal natural system where Liesegang banding and other self-organized patterns can evolve. A complicating variable here is the sedimentologic (both mineralogic and textural) heterogeneity that, in reality, may be the key factor controlling the nucleation and precipitation habits (including possible competitive growth) of hematite concretions. Sym.8 water-rock interaction simulator program was used for the Navajo Sandstone concretions. Sym.8 is a water-rock simulator that accounts for advective and diffusive mass-transfer, and equilibrium and kinetic reactions. The program uses a dynamic composite media texture model to address changing sediment composition and texture to be consistent with the reaction progress. Initial one-dimensional simulation results indicate precipitation heterogeneity in the range of sub-meters, e.g., possible banding and distribution of iron oxide nodules may be centimeters apart for published diffusivities and

  1. Free energy distribution and hydrothermal mineral precipitation in Hadean submarine alkaline vent systems: Importance of iron redox reactions under anoxic conditions

    NASA Astrophysics Data System (ADS)

    Shibuya, Takazo; Russell, Michael J.; Takai, Ken

    2016-02-01

    Thermodynamic calculations of mixing between hypothetical seawater and hydrothermal fluid in the Hadean deep ocean were carried out to predict saturation states of mineral precipitates and redox reactions that could occur in Hadean submarine alkaline hydrothermal systems associated with the serpentinization of ultramafic rocks. In the calculations, the seawater was assumed to be weakly acidic (pH = 5.5) and to include carbon dioxide, ferrous iron and silica, with or without nitrate, while the Hadean hydrothermal fluid was assumed to be highly alkaline (pH = 11) and to contain abundant molecular hydrogen, methane and bisulfide, based on the Archean geologic record, the modern low-temperature alkaline hydrothermal vent fluid (Lost City field), and experimental and theoretical considerations. The modeling indicates that potential mineral precipitates in the mixing zone (hydrothermal chimney structures) could consist mainly of iron sulfides but also of ferrous serpentine and brucite, siderite, and ferric iron-bearing minerals such as goethite, hematite and/or magnetite as minor phases. The precipitation of ferric iron-bearing minerals suggests that chemical iron oxidation would be made possible by pH shift even under anoxic condition. In the mixing zone, comprising an inorganic barrier precipitated at the interface of the two contrasting solutions, various redox reactions release free energy with the potential to drive endergonic reactions, assuming the involvement of coupling inorganic protoenzymes. Hydrogenotrophic methanogenesis and acetogenesis - long considered the most ancient forms of biological energy metabolisms - are able to achieve higher maximum energy yield (>0.5 kJ/kg hydrothermal fluid) than those in the modern serpentinization-associated seafloor hydrothermal systems (e.g., Kairei field). Furthermore, the recently proposed methanotrophic acetogenesis pathway was also thermodynamically investigated. It is known that methanotrophic acetogenesis would

  2. Direct functionalization processes: a journey from palladium to copper to iron to nickel to metal-free coupling reactions.

    PubMed

    Mousseau, James J; Charette, André B

    2013-02-19

    , which led to the first description of a direct copper-catalyzed alkenylation onto an electron-deficient arene. This particular directing group offers two advantages: (1) it can be easily appended and removed to reveal the desired pyridine target, and (2) it can be incorporated in a cascade process in the preparation of pharmacologically relevant 2-pyrazolo[1,5-a]pyridines. This work has solved some of the challenges in the direct arylation of nonheterocyclic arenes, including reversing the reactivity often observed with such transformations. Readily convertible directing groups were applied to facilitate the transformation. We also demonstrated that iron can promote intermolecular arylations effectively and that the omission of any metal still permits intramolecular arylation reactions. Lastly, we recently discovered a nickel-catalyzed intramolecular arylation of sp(3) C-H bonds. Our mechanistic investigations of these processes have elucidated radical pathways, opening new avenues in future direct C-H functionalization reactions. PMID:23098328

  3. mRNA regulation of cardiac iron transporters and ferritin subunits in a mouse model of iron overload.

    PubMed

    Brewer, Casey J; Wood, Ruth I; Wood, John C

    2014-12-01

    Iron cardiomyopathy is the leading cause of death in iron overload. Men have twice the mortality rate of women, though the cause is unknown. In hemojuvelin-knockout mice, a model of the disease, males load more cardiac iron than females. We postulated that sex differences in cardiac iron import cause differences in cardiac iron concentration. Reverse transcription polymerase chain reaction was used to measure mRNA of cardiac iron transporters in hemojuvelin-knockout mice. No sex differences were discovered among putative importers of nontransferrin-bound iron (L-type and T-type calcium channels, ZRT/IRT-like protein 14 zinc channels). Transferrin-bound iron transporters were also analyzed; these are controlled by the iron regulatory element/iron regulatory protein (IRE/IRP) system. There was a positive relationship between cardiac iron and ferroportin mRNA in both sexes, but it was significantly steeper in females (p < 0.05). Transferrin receptor 1 and divalent metal transporter 1 were more highly expressed in females than males (p < 0.01 and p < 0.0001, respectively), consistent with their lower cardiac iron levels, as predicted by IRE/IRP regulatory pathways. Light-chain ferritin showed a positive correlation with cardiac iron that was nearly identical in males and females (R(2) = 0.41, p < 0.01; R(2) = 0.56, p < 0.05, respectively), whereas heavy-chain ferritin was constitutively expressed in both sexes. This represents the first report of IRE/IRP regulatory pathways in the heart. Transcriptional regulation of ferroportin was suggested in both sexes, creating a potential mechanism for differential set points for iron export. Constitutive heavy-chain-ferritin expression suggests a logical limit to cardiac iron buffering capacity at levels known to produce heart failure in humans. PMID:25220979

  4. Evidence of a reduction reaction of oxidized iron/cobalt by boron atoms diffused toward naturally oxidized surface of CoFeB layer during annealing

    SciTech Connect

    Sato, Soshi Honjo, Hiroaki; Niwa, Masaaki; Ikeda, Shoji; Ohno, Hideo; Endoh, Tetsuo

    2015-04-06

    We have investigated the redox reaction on the surface of Ta/CoFeB/MgO/CoFeB magnetic tunnel junction stack samples after annealing at 300, 350, and 400 °C for 1 h using angle-resolved X-ray photoelectron spectroscopy for precise analysis of the chemical bonding states. At a capping tantalum layer thickness of 1 nm, both the capping tantalum layer and the surface of the underneath CoFeB layer in the as-deposited stack sample were naturally oxidized. By comparison of the Co 2p and Fe 2p spectra among the as-deposited and annealed samples, reduction of the naturally oxidized cobalt and iron atoms occurred on the surface of the CoFeB layer. The reduction reaction was more significant at higher annealing temperature. Oxidized cobalt and iron were reduced by boron atoms that diffused toward the surface of the top CoFeB layer. A single CoFeB layer was prepared on SiO{sub 2}, and a confirmatory evidence of the redox reaction with boron diffusion was obtained by angle-resolved X-ray photoelectron spectroscopy analysis of the naturally oxidized surface of the CoFeB single layer after annealing. The redox reaction is theoretically reasonable based on the Ellingham diagram.

  5. Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: divergent reactions in the presence of organic ligands.

    PubMed

    Wang, Zhaohui; Bush, Richard T; Liu, Jianshe

    2013-11-01

    Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H2O2, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA<1:1), contrasting with the rapid oxidation of Fe(II) by O2 and H2O2 at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology. PMID:23880239

  6. Removal of As, Mn, Mo, Se, U, V and Zn from groundwater by zero-valent iron in a passive treatment cell: reaction progress modeling

    NASA Astrophysics Data System (ADS)

    Morrison, Stan J.; Metzler, Donald R.; Dwyer, Brian P.

    2002-05-01

    Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe 3O 4), calcite (CaCO 3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH) 2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO 2, V 2O 3), sulfides (As 2S 3, ZnS), iron minerals (FeSe 2, FeMoO 4) and carbonate (MnCO 3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.

  7. Role of indigenous iron in improving sludge dewaterability through peroxidation

    PubMed Central

    Zhou, Xu; Jiang, Guangming; Wang, Qilin; Yuan, Zhiguo

    2015-01-01

    Improvement of sludge dewaterability is important for reducing the total costs for the treatment and disposal of sludge in wastewater treatment plants. In this study, we investigate the use of hydrogen peroxide as an oxidizing reagent for the conditioning of waste activated sludge. Significant improvement to sludge dewaterability was attained after the addition of hydrogen peroxide at 30 mg/g TS and 28 mg/g TS under acidic conditions (pH = 3.0), with the highest reduction of capillary suction time being 68% and 56%, respectively, for sludge containing an iron concentration of 56 mg Fe/g TS and 25 mg Fe/g TS, respectively. The observations were due to Fenton reactions between the iron contained in sludge (indigenous iron) and hydrogen peroxide. For the sludge with an insufficient level of indigenous iron, the addition of ferrous chloride was found to be able to improve the sludge dewaterability. The results firstly indicated that indigenous iron can be utilized similarly as the externally supplied iron salt to improve sludge dewaterability through catalyzing the Fenton reactions. PMID:25559367

  8. Synthesis, DNA binding and complex formation reactions of 3-amino-5,6-dimethyl-1,2,4-triazine with Pd(II) and some selected biorelevant ligands.

    PubMed

    Shoukry, Azza A; Alghanmi, Reem M

    2015-03-01

    With the purpose of studying the binding behavior of Pd(II) complexes with DNA as the main biological target, and their ability to penetrate reasonably into tumour cells and destroy their replication ability, Pd(ADT)Cl2 complex was synthesized and characterized, where ADT is 3-amino-5,6-dimethyl-1,2,4-triazine. Stoichiometry and stability constants of the complexes formed between various biologically relevant ligands (amino acids, amides, DNA constituents, and dicarboxylic acids) and [Pd(ADT)(H2O)2](2+) were investigated at 25°C and at constant 0.1moldm(-3) ionic strength. The concentration distribution diagrams of the various species formed are evaluated. Further investigation of the binding properties of the diaqua complex [Pd(ADT)(H2O)2](2+) with calf thymus DNA (CT-DNA) was investigated by UV-vis spectroscopy. The intrinsic binding constants (Kb) calculated from UV-vis absorption studies was calculated to be 2.00×10(3)moldm(-3). The calculated (Kb) value was found to be of lower magnitude than that of the classical intercalator EB (Ethidium bromide) (Kb=1.23(±0.07)×10(5)moldm(-3)) suggesting an electrostatic and/or groove binding mode for the interaction with CT-DNA. Thermal denaturation has been systematically studied by spectrophotometric method and the calculated ΔTm was nearly 5°C, supporting the electrostatic and/or groove binding mode for the interaction between the complex and CT-DNA. PMID:25459605

  9. Synthesis, DNA binding and complex formation reactions of 3-amino-5,6-dimethyl-1,2,4-triazine with Pd(II) and some selected biorelevant ligands

    NASA Astrophysics Data System (ADS)

    Shoukry, Azza A.; Alghanmi, Reem M.

    2015-03-01

    With the purpose of studying the binding behavior of Pd(II) complexes with DNA as the main biological target, and their ability to penetrate reasonably into tumour cells and destroy their replication ability, Pd(ADT)Cl2 complex was synthesized and characterized, where ADT is 3-amino-5,6-dimethyl-1,2,4-triazine. Stoichiometry and stability constants of the complexes formed between various biologically relevant ligands (amino acids, amides, DNA constituents, and dicarboxylic acids) and [Pd(ADT)(H2O)2]2+ were investigated at 25 °C and at constant 0.1 mol dm-3 ionic strength. The concentration distribution diagrams of the various species formed are evaluated. Further investigation of the binding properties of the diaqua complex [Pd(ADT)(H2O)2]2+ with calf thymus DNA (CT-DNA) was investigated by UV-vis spectroscopy. The intrinsic binding constants (Kb) calculated from UV-vis absorption studies was calculated to be 2.00 × 103 mol dm-3. The calculated (Kb) value was found to be of lower magnitude than that of the classical intercalator EB (Ethidium bromide) (Kb = 1.23(±0.07) × 105 mol dm-3) suggesting an electrostatic and/or groove binding mode for the interaction with CT-DNA. Thermal denaturation has been systematically studied by spectrophotometric method and the calculated ΔTm was nearly 5 °C, supporting the electrostatic and/or groove binding mode for the interaction between the complex and CT-DNA

  10. Transient formation of the oxo-iron(IV) porphyrin radical cation during the reaction of iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin with hydrogen peroxide in aqueous solution.

    PubMed

    Saha, Tapan Kumar; Karmaker, Subarna; Tamagake, Keietsu

    2003-01-01

    The reaction of iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin (Fe(III)TMPyP) with hydrogen peroxide (H(2)O(2)) and the catalytic activity of the reaction intermediates on the luminescent peroxidation of luminol in aqueous solution were studied by using a double-mixing stopped-flow system. The observed luminescence intensities showed biphasic decay depending on the conditions. The initial flashlight decayed within <1 s followed by a sustained emission for more than 30 s. Computer deconvolution of the time-resolved absorption spectra under the same conditions revealed that the initial flashlight appeared during the formation of the oxo-iron(IV) porphyrin, TMPyPFe(IV) = O, which is responsible for the sustained emission. The absorption spectra 0.0-0.5 s did not reproduce well by a simple combination of the two spectra of Fe(III)TMPyP and TMPyPFe(IV) = O, indicating that transient species was formed at the initial stage. Addition of uric acid (UA) caused a significant delay in the initiation of the luminol emission as well as in the formation of the TMPyPFe(IV) = O. Both of them were completely diminished in the presence of UA equimolar with H(2)O(2), while mannitol had no effect at all. The delay of the light emission as well as the appearance of TMPyPFe(IV) = O was directly proportional to the [UA](0) but other kinetic profiles were not changed significantly. Based on these observations and the kinetic analysis, we confirmed the involvement of the oxo-iron(IV) porphyrin radical cation, (TMPyP)(.+)Fe(IV) = O, as an obligatory intermediate in the rate-determining step of the overall reaction, Fe(III)TMPyP + H(2)O(2) --> TMPyPFe(IV) = O, with a rate constant of k = 4.3 x 10(4)/mol/L/s. The rate constants for the reaction between the (TMPyP)(.+)Fe(IV) = O and luminol, and between the TMPyPFe(IV) = O and luminol were estimated to be 3.6 x 10(6)/mol/L/s and 1.31 x 10(4)/mol/L/s, respectively. PMID:12701092

  11. ULTRASOUND PRETREATMENT OF ELEMENTAL IRON: KINETIC STUDIES OF DEHALOGENATION REACTION ENHANCEMENT AND SURFACE EFFECTS. (R828598C743)

    EPA Science Inventory

    This work presents data showing the kinetic improvement afforded by ultrasound pretreatment and illustrates the physical and chemical changes that take place at the iron surface. First-order rate constants improved as much as 78% with 2 h of ultrasound pretreatment. Scann...

  12. Evolution of δ 56Fe in serpentinites during subduction: example in the Western Alps.

    NASA Astrophysics Data System (ADS)

    Debret, B.; Williams, H. M.; Millet, M. A.

    2014-12-01

    During subduction, prograde metamorphism leads to the disappearance of Fe3+-rich phases in serpentinites (mostly magnetite and lizardite). This redox reaction is accompanied with a decrease of Fe3+/FeTot ratio in serpentinites and a release of fluid mobile elements (e.g. B, S) but little is known about the iron mobility in fluids during subduction. We investigate this problem with an isotopic study of Fe in serpentinites from Western Alps ophiolites. These samples record different metamorphic conditions modelling a subduction gradient that allow deciphering the impact of prograde metamorphism on the Fe isotopic composition of serpentinites during subduction. At mid-oceanic ridges, ultramafic rocks are serpentinized by interaction with seawater derived fluids. This process leads to the replacement and oxidation of ferromagnesian minerals (olivine and orthopyroxene) to Fe3+-rich lizardite and magnetite (Liz-serpentinite). Mantle peridotites commonly display δ56Fe between -0.1 and +0.1 ‰ while Liz-serpentinites display a δ56Fe ranging from -0.09 to +0.04 (± 0.03)‰, which could potentially reflect interactions with low-δ56Fe hydrothermal fluids. During subduction, from greenschist to blueschist facies, the transition lizardite to antigorite leads to a progressive disappearance of magnetite and a reduction of Fe in serpentine. This redox reaction is accompanied with an increase of δ56Fe from +0.03 to +0.13‰. At eclogite facies, fully recrystallized Atg-serpentinites display a δ56Fe ranging from +0.14 to +0.20‰ while partly dehydrated serpentinites composed of antigorite, secondary olivine and chlorite display a lower δ56Fe ranging from -0.03 to +0.03‰. Our results show that, during the first 70 km of subduction, the transition lizardite to antigorite conduct to the formation of a serpentinite with a high δ56Fe value that can be accompanied with the loss of a low δ56Fe fluid. The increase of δ56Fe in serpentinites is correlated with a decrease of Fe3

  13. Characterization and thermolysis reactions of CO{sub 2} bridged iron-tin and rhenium-tin complexes. Structure-reactivity correlations

    SciTech Connect

    Gibson, D.H.; Ye, M.; Sleadd, B.A.; Mehta, J.M.; Mbadike, O.P.; Richardson, J.F.; Mashuta, M.S.

    1995-03-01

    We report here our studies of the thermolysis behavior of iron-tin complexes and related rhenium-tin complexes and new structural data which allow further correlations to be made between thermolysis activity and bonding parameters involving the CO{sub 2} ligand. All compounds have been characterized by solid-state IR spectral methods which allow a determination of the {mu}{sub 2}-{eta}{sup 2} or {mu}{sub 2}-{eta}{sup 3} bonding mode in each compound when compared with structural data on representative compounds of each type. Factors which control the ease of thermolysis and the mode of decomposition are the bonding type, the presence of electron-donating or electron-withdrawing groups on the tin atom as well as those on iron or rhenium, metal-carbon bond strength, the orientation of the bridging CO{sub 2} ligand between the two metal centers, and, most importantly, the stability of the corresponding metal (iron or rhenium) anion. Reaction mechanisms are proposed which are consistent with structural and electronic differences that lead to separate thermolysis paths. 17 refs., 7 figs., 11 tabs.

  14. Clathrochelates meet phosphorus. New thio- and phosphorylation reactions of an iron(II) dichloroclathrochelate precursor and preparation of its first phosphorus(III)-containing macrobicyclic derivative.

    PubMed

    Artyushin, Oleg I; Matveeva, Ekaterina V; Vologzhanina, Anna V; Voloshin, Yan Z

    2016-03-28

    Phosphorylation reactions of an iron(II) dichloroclathrochelate FeBd2(Cl2Gm)(BF)2 (where Bd(2-) and Cl2Gm(2-) are α-benzildioxime and dichloroglyoxime dianions, respectively) with diphenylphosphine oxide and diethyl thiophosphite were performed under phase-transfer conditions. In the case of diethyl thiophosphite as a P-nucleophile, the best yields were obtained in the dichloromethane-50% NaOH aqueous solution-5 mol% triethylbenzylammonium chloride (TEBAC) system. The use of different molar ratios of a macrobicycle precursor and this thiophosphorylating agent allowed us to obtain both the mono- and the diphosphorylated cage complexes. Nucleophilic substitution with diphenylphosphine oxide was performed in the K2CO3-acetonitrile-5 mol% TEBAC system, giving only the corresponding monophosphorylated iron(II) complex in high yield even in the presence of an excess of this P-nucleophile. The phosphorus(v)-containing clathrochelate product was reduced with an excess of silicoform to give an iron(II) macrobicycle with an inherent diphenylphosphine group in an almost quantitative yield, which was then characterized by (31)P{(1)H} NMR and single-crystal X-ray diffraction; it easily undergoes re-oxidation to the initial clathrochelate. The synthesized phosphorus(v)-containing cage complexes were characterized using elemental analysis, MALDI-TOF mass, IR, UV-Vis, (1)H, (11)B, (13)C{(1)H}, (19)F{(1)H} and (31)P{(1)H} NMR spectra, and by single-crystal X-ray diffraction. PMID:26902835

  15. Fischer-Tropsch synthesis over iron-based catalysts in slurry reactors. Reaction rates, kinetics and implications for improving hydrocarbon productivity

    SciTech Connect

    Raje, A.P.; Davis, B.H.

    1996-10-01

    The Fischer-Tropsch (FT) synthesis is carried out over a high activity precipitated iron catalyst promoted with silica and potassium in a slurry reactor. Reaction rates (FTS and water gas shift) and partial pressures are evaluated over a wide range of CO conversions (10 to 90%) and space velocities at 270{degrees}C, 175 psig and a H{sub 2}/CO ratio of 0.67. The partial pressure of water exhibits a maximum at intermediate CO conversion. Both the fraction of CO converted to hydrocarbons and the hydrocarbon space time yield decrease with increasing CO conversion. This implies that it would be beneficial to have lower conversion per pass in the reactor with recycle to achieve a high overall conversion. The data as well as experiments with water and CO{sub 2} addition enable us to determine a kinetic expression for the catalyst which shows negligible inhibition of the reaction rate by water or CO{sub 2}.

  16. Growth Kinetics of a Reaction Rim Between Iron and Graphite/Diamond and the Carbon Diffusion Mechanism at High Pressure and Temperature

    NASA Astrophysics Data System (ADS)

    Stagno, V.; Crispin, K. L.; Shahar, A.; Fei, Y.

    2014-12-01

    Thermodynamic calculations of the fo2 on modeled bulk silicate Earth mantle composition predict the formation of Fe-Ni metal alloy at about 250-300 km in depth. At such conditions the speciation of subducted carbon will be mainly affected by the local Fe(Ni)/C ratio, with diamond, Fe3C and C-bearing Fe-Ni alloys being the most likely stable phases. To date however, no data are available to determine the effect of pressure and temperature on 1) the transport of carbon by diffusion in iron metal and 2) the kinetics of formation of carbide phases. We performed multianvil experiments between 3 and 10 GPa and temperatures of 700-1200 ºC with the aim of measuring C diffusion in γ-Fe. Glassy carbon and synthetic diamond were used as diffusants, placed directly in contact with pure iron rod rods with a thickness of 800-1400 μm. FE-SEM was used for accurate analyses of the Fe-C interface and concentration profiles of carbon in iron were measured by electron microprobe. Results show that the diffusion coefficient for carbon in iron metal (~3x10-11 m2s-1) and the activation energy (~62 kJ/mol) are similar to previous data from 1 atm and suggest a small pressure effect. The activation volume (~1.5x10-6 m3/mol) determined from isothermal runs is in agreement with that determined for other elements for which an interstitial diffusion mechanism in iron has been established. At the interface between carbon and Fe the growth of a reaction rim was often observed. Time series experiments were therefore performed, to investigate the growth kinetics of iron carbide (Fe3C). Results will be used to 1) determine a model for the storage of C in metallic phases in the Earth's interior and 2) provide an experimental constraint on the formation of carbide phases during subduction, with implications for the deep carbon cycle and isotopic fractionation.

  17. Covalent entrapment of cobalt-iron sulfides in N-doped mesoporous carbon: extraordinary bifunctional electrocatalysts for oxygen reduction and evolution reactions.

    PubMed

    Shen, Mengxia; Ruan, Changping; Chen, Yan; Jiang, Chunhuan; Ai, Kelong; Lu, Lehui

    2015-01-21

    To alleviate the kinetic barriers associated with ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) in electrochemical systems, efficient nonprecious electrocatalysts are urgently required. Here we report a facile soft-template mediated approach for fabrication of nanostructured cobalt-iron double sulfides that are covalently entrapped in nitrogen-doped mesoporous graphitic carbon (Co0.5Fe0.5S@N-MC). Notably, with a positive half-wave potential (0.808 V) and a high diffusion-limiting current density, the composite material delivers unprecedentedly striking ORR electrocatalytic activity among recently reported nonprecious late transition metal chalcogenide materials in alkaline medium. Various characterization techniques, including X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction, are conducted to elucidate the correlation between structural features and catalytic activities of the composite. Moderate substitution and well-dispersion of iron in bimetallic sulfide composites are believed to have positive effect on the adsorption and activation of oxygen-containing species, thus leading to conspicuous ORR and OER catalytic enhancement compared to their monometallic counterparts. Besides, the covalent bridge between active sulfide particles and mesoporous carbon shells provides facile pathways for electron and mass transport. Beneficially, the intimate coupling interaction renders prolonged electrocatalytic performances to the composite. Our results may possibly lend a new impetus to the rational design of bi- or multimetallic sulfides encapsulated in porous carbon with improved performance for electrocatalysis and energy storage applications. PMID:25531776

  18. Level density and mechanism of deuteron-induced reactions on Fe54,56,58

    SciTech Connect

    Ramirez, A. P. D.; Voinov, A. V.; Grimes, S. M.; Byun, Y.; Brune, C. R.; Massey, T. N.; Akhtar, S.; Dhakal, S.; Parker, C. E.

    2015-07-06

    Here, deuteron elastic cross sections, as well as neutron, proton, and α-particle emission spectra, from d+54,56,58Fe reactions have been measured with deuteron beam energies of 5, 7, and 9 MeV. Optical model parameters have been tested against our experimental data. The fraction of total reaction cross section responsible for the formation of compound nuclei has been deduced from the angular distributions. The degree of discrepancy between calculated and experimental compound cross sections was found to increase with increasing neutron number. The nuclear level densities of the residual nuclei 55Co, 57Co, 55Fe, 57Fe, 52Mn, and 54Mn have been deduced from the compound double differential cross sections. The Gilbert-Cameron model with Iljinov parameter systematics [A. S. Iljinov and M. V. Mebel, Nucl. Phys. A 543, 517 (1992)] was found to have a good agreement with our results.

  19. Coal desulfurization. [using iron pentacarbonyl

    NASA Technical Reports Server (NTRS)

    Hsu, G. C. (Inventor)

    1979-01-01

    Organic sulfur is removed from coal by treatment with an organic solution of iron pentacarbonyl. Organic sulfur compounds can be removed by reaction of the iron pentacarbonyl with coal to generate CO and COS off-gases. The CO gas separated from COS can be passed over hot iron fillings to generate iron pentacarbonyl.

  20. Level densities of iron isotopes and low-energy enhancement of {gamma}-strength function

    SciTech Connect

    Voinov, A. V.; Grimes, S. M.; Brune, C. R.; Hornish, M. J.; Massey, T. N.; Agvaanluvsan, U.; Algin, E.; Belgya, T.; Guttormsen, M.; Rekstad, J.; Siem, S.; Mitchell, G. E.; Schiller, A.

    2006-03-13

    The neutron spectrum from the 55Mn(d, n)56Fe reaction has been measured at Ed = 7 MeV. The level density of 56Fe obtained from neutron evaporation spectrum has been compared to the level density obtained from Oslo-type 57Fe(3He, {alpha}{gamma})56Fe experiment. The good agreement supports the recent results including the low-energy enhancement in the {gamma}-strength function for iron isotopes. The new level density function allowed us to investigate an excitation energy dependence of this enhancement, which is shown to increase with increasing excitation energy.

  1. Iron-refractory iron deficiency anemia.

    PubMed

    Yılmaz Keskin, Ebru; Yenicesu, İdil

    2015-03-01

    Iron is essential for life because it is indispensable for several biological reactions, such as oxygen transport, DNA synthesis, and cell proliferation. Over the past few years, our understanding of iron metabolism and its regulation has changed dramatically. New disorders of iron metabolism have emerged, and the role of iron as a cofactor in other disorders has begun to be recognized. The study of genetic conditions such as hemochromatosis and iron-refractory iron deficiency anemia (IRIDA) has provided crucial insights into the molecular mechanisms controlling iron homeostasis. In the future, these advances may be exploited to improve treatment of both genetic and acquired iron disorders. IRIDA is caused by mutations in TMPRSS6, the gene encoding matriptase-2, which downregulates hepcidin expression under conditions of iron deficiency. The typical features of this disorder are hypochromic, microcytic anemia with a very low mean corpuscular volume of erythrocytes, low transferrin saturation, no (or inadequate) response to oral iron, and only a partial response to parenteral iron. In contrast to classic iron deficiency anemia, serum ferritin levels are usually low-normal, and serum or urinary hepcidin levels are inappropriately high for the degree of anemia. Although the number of cases reported thus far in the literature does not exceed 100, this disorder is considered the most common of the "atypical" microcytic anemias. The aim of this review is to share the current knowledge on IRIDA and increase awareness in this field. PMID:25805669

  2. Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

    DOE PAGESBeta

    Guo, Yu; Senanayake, Sanjaya; Gu, Dong; Jin, Zhao; Du, Pei -Pei; Si, Rui; Xu, Wen -Qian; Huang, Yu -Ying; Tao, Jing; Song, Qi -Sheng; et al

    2015-01-12

    Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reductionmore » by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.« less

  3. Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

    SciTech Connect

    Guo, Yu; Senanayake, Sanjaya; Gu, Dong; Jin, Zhao; Du, Pei -Pei; Si, Rui; Xu, Wen -Qian; Huang, Yu -Ying; Tao, Jing; Song, Qi -Sheng; Jia, Chun -Jia; Schueth, Ferdi

    2015-01-12

    Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.

  4. Neutron Spectroscopic factors of 56Ni

    NASA Astrophysics Data System (ADS)

    Sanetullaev, A.; Ghosh, T. K.; Lynch, W. G.; Bazin, D.; Chajecki, Z.; Coupland, Daniel; Hodges, R.; Lee, Jenny; Henzl, V.; Henzlova, D.; Rogers, A. M.; Sun, Z. Y.; Tsang, M. B.; Winkelbauer, J.; Youngs, M.; Famiano, M.; Clement, R. R. C.; Howard, M. E.; Cizewski, J. A.; O'Malley, P. D.; Manning, B.; Charity, R. J.; Charity, L. G.; Shapira, D.; Shmitt, K. T.

    2011-10-01

    The exact shell-structure of the unstable doubly-magic nucleus 56Ni has attracted a lot of interest recently. To test if 56Ni is a good core, 56Ni(p, d)55Ni transfer reactions were measured using 56Ni beam at two different energies, 37 MeV/u and 80 MeV/u, in inverse kinematics in two experiments. The second measurement was done in order to test the sensitivity of reaction cross sections and models to reaction energies. The measurements were performed at NSCL using HiRA array and S800 spectrometer. Spectroscopic factors have been extracted for the first experiment. The results show good agreement with shell-model calculations. Preliminary results of the measurements with 80 MeV/u beam will be presented as well. This work is funded by NSF under Grant No. PHY-0606007.

  5. Air oxidation of hydrazine. 1. Reaction kinetics on natural kaolinites, halloysites, and model substituent layers with varying iron and titanium oxide and O- center contents

    NASA Technical Reports Server (NTRS)

    Coyne, L.; Mariner, R.; Rice, A.

    1991-01-01

    Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

  6. Distinct effects of oxalate versus malonate on the iron redox chemistry: Implications for the photo-Fenton reaction.

    PubMed

    Xiao, Dongxue; Guo, Yaoguang; Lou, Xiaoyi; Fang, Changling; Wang, Zhaohui; Liu, Jianshe

    2014-05-01

    The dicarboxylic acids oxalate (Oxal) and malonate (Mal) are frequently detected as the final low-molecular-weight organic acids during oxidative degradation of aromatic compounds. Here a distinct effect of Oxal versus Mal on iron-based photocatalytic technologies was reported by testing the degradation efficiency of the dye rhodamine B. The rates of dye degradation in irradiated Fe(III) solutions depended on Fe(III/II) speciation, photoreactivities of Fe complexes and reactivities of Fe(II) complexes with H2O2. Photolysis of the Fe(III)-oxalato complex was favorable due to the formation of O2-, HO2 and OH for oxidizing the dye; however, an excess of H2O2 could quench the excited state of ferrioxalate, decreasing the degradation efficiency. In contrast, activities of UV/Fe(III) in the presence of Mal were significantly diminished because Fe(III)-Mal complexes, with much lower quantum yield of Fe(II) from photoreduction, dominated Fe(III) speciation. The results provide data for an understanding of the mechanism of iron redox (photo)chemistry mediated by diacids, which will aid in selecting appropriate Fe ligands, screening photo-Fenton conditions and designing UV/Fe(III) treatability. PMID:24359921

  7. Effect of thiamine hydrochloride on the redox reactions of iron at pyrite surface. [Fourth quarterly techical progress report, September 1990--November 1990

    SciTech Connect

    Pesic, B.; Oliver, D.J.

    1990-12-31

    The present investigation is a part of our studies on the electro chemical aspects of pyrite bioleaching involving Thiobacillus ferrooxidans. Previously (1,2) we have examined the effect of T. ferrooxidans and their metabolic products on the redox reactions of Fe{sup 2+}/Fe{sup 3+} couple at the pyrite surface. Results obtained suggest that beyond 1. 5 days during their growth in a batch fermenter, the bacteria and their metabolic products completely cover the pyrite surface and shut down all electron transfer across the electrode-solution interface. In addition, it has been observed that the bacteria serve as the nucleation site for jarosite formation, which is found detrimental to bioleaching. In the present work we have focussed on the effect of the presence of vitamins on the redox chemistry of iron. Our examination of the effect of the presence of thiamine hydrochloride in the redox behavior of Fe{sup 2+}/Fe{sup 3+} at the pyrite surface has revealed that thiamine hydrochloride does not undergo chemical interaction with ferrous or ferric iron. However, it may adsorb onto the pyrite surface causing polarization of the pyrite electrode.

  8. Effect of a weak magnetic field on the Mizoroki-Heck coupling reaction in the presence of wicker-like palladium-poly(N-vinylpyrrolidone)-iron nanocatalyst

    NASA Astrophysics Data System (ADS)

    Rafiee, Ezzat; Joshaghani, Mohammad; Abadi, Parvaneh Ghaderi-Shekhi

    2016-06-01

    The wicker-like Pd-PVP-Fe (palladium-poly(N-vinylpyrrolidone)-iron) was synthesized by the external magnetic field (EMF). The Pd-based catalyst with nano and the face-centered cubic (fcc) structure was obtained at room temperature without using any additive. The resulting composite was characterized. The results show that EMF has a great influence on morphology, particle size, and crystalline structure of the Pd-PVP-Fe composite. The resulting composite (Pd-PVP-Fe), was found to be an effective catalyst for the Mizoroki-Heck reaction while is exposed to EMF with the intensity at 486 μT. The reused catalyst for at least five repeating cycles, shows excellent activity.

  9. Dynamical cluster-decay model for hot and rotating light-mass nuclear systems applied to the low-energy {sup 32}S+{sup 24}Mg{yields}{sup 56}Ni{sup *} reaction

    SciTech Connect

    Gupta, Raj K.; Kumar, Rajesh; Singh, Dalip; Balasubramaniam, M.; Beck, C.

    2005-01-01

    The dynamical cluster-decay model (DCM) is developed further for the decay of hot and rotating compound nuclei (China) formed in light heavy-ion reactions. The model is worked out in terms of only one parameter, namely the neck-length parameter, which is related to the total kinetic energy TKE(T) or effective Q value Q{sub eff}(T) at temperature T of the hot CN and is defined in terms of the CN binding energy and ground-state binding energies of the emitted fragments. The emission of both the light particles (LP), with A{<=}4,Z{<=}2, as well as the complex intermediate mass fragments (IMF), with 42, is considered as the dynamical collective mass motion of preformed clusters through the barrier. Within the same dynamical model treatment, the LPs are shown to have different characteristics compared to those of the IMFs. The systematic variations of the LP emission cross section {sigma}{sub LP} and IMF emission cross section {sigma}{sub IMF} calculated from the present DCM match exactly the statistical fission model predictions. A nonstatistical dynamical description is developed for the first time for emission of light particles from hot and rotating CN. The model is applied to the decay of {sup 56}Ni* formed in the {sup 32}S+{sup 24}Mg reaction at two incident energies E{sub c.m.}=51.6 and 60.5 MeV. Both the IMFs and average TKE{sup lowbar} spectra are found to compare resonably well with the experimental data, favoring asymmetric mass distributions. The LPs' emission cross section is shown to depend strongly on the type of emitted particles and their multiplicities.

  10. Study of the effects of potassium addition to supported iron catalysts in the Fischer-Tropsch reaction

    SciTech Connect

    Miller, D.G.; Moskovits, M.

    1988-10-20

    The Fischer-Tropsch activity of supported iron catalysts prepared via electrochemical techniques has been evaluated as a function of potassium addition. Catalyst pretreatment in 0.09, 0.18, and 0.27 M K/sub 2/CO/sub 3/ solutions generated potassium levels of 1.7, 2.8, and 3.9 wt %, respectively. Pretreatment in 0.18 M KOH provided a catalyst with 2.3 wt% potassium and facilitated comparison of the effects of the basicity of the pretreatment solution upon catalyst activity. A maximum in catalyst activity and CO conversion was noted upon increasing K content, followed by a sharp decline in activity at potassium levels in excess of the maximum. The hydrogenation ability of the catalyst decreased, and a shift to higher molecular weight products was observed, with increasing potassium content. The type of pretreatment solution had little effect on the catalyst activity or the product selectivity.

  11. Iron Test

    MedlinePlus

    ... detect and help diagnose iron deficiency or iron overload. In people with anemia , these tests can help ... also be ordered when iron deficiency or iron overload is suspected. Early iron deficiency often goes unnoticed. ...

  12. 7 CFR 319.56-14-319.56-19 - [Reserved

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 5 2010-01-01 2010-01-01 false 319.56-14-319.56-19 Section 319.56-14-319.56-19 Agriculture Regulations of the Department of Agriculture (Continued) ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE FOREIGN QUARANTINE NOTICES Fruits and Vegetables §§ 319.56-14—319.56-19...

  13. 7 CFR 319.56-8-319.56-9 - [Reserved

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 5 2010-01-01 2010-01-01 false 319.56-8-319.56-9 Section 319.56-8-319.56-9 Agriculture Regulations of the Department of Agriculture (Continued) ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE FOREIGN QUARANTINE NOTICES Fruits and Vegetables §§ 319.56-8—319.56-9...

  14. Using nitrogen-rich polymeric network and iron(II) acetate as precursors to synthesize highly efficient electrocatalyst for oxygen reduction reaction in alkaline media

    NASA Astrophysics Data System (ADS)

    Yang, Mei; Chen, Hongbiao; Yang, Duanguang; Gao, Yong; Li, Huaming

    2016-03-01

    Carbon-supported transition metal/nitrogen (M-N/C) materials are considered as one of the most promising electrocatalysts for the oxygen reduction reaction (ORR) owing to their high ORR electrocatalytic activity, long-term stability, and excellent methanol tolerance. So far only a few examples of such catalysts are prepared from N-containing polymers. Herein, we report a novel Fe-N/C catalyst using a nitrogen-rich polymeric network and iron(II) acetate as the precursors. The porous polymeric network is fabricated by one-step Friedel-Crafts reaction of a low-cost cross-linker, formaldehyde dimethyl acetal, with 2,4,6-tripyrrol-1,3,5-triazine. Compared to commercial Pt/C catalyst, the as-prepared Fe-N/C electrocatalyst exhibits superior ORR activity in alkaline electrolyte, and comparable ORR activity in acidic medium. The results obtained are significant for the development of new Fe-N/C electrocatalysts for fuel cells.

  15. Selective extraction by dissolvable (nitriloacetic acid-nickel)-layered double hydroxide coupled with reaction with potassium thiocyanate for sensitive detection of iron(III).

    PubMed

    Tang, Sheng; Chang, Yuepeng; Shen, Wei; Lee, Hian Kee

    2016-07-01

    A highly selective method has been proposed for the determination of iron cation (Fe(3+)). (Nitriloacetic acid-nickel)-layered double hydroxide ((NTA-Ni)-LDH) was successfully synthesized and used as dissolvable sorbent in dispersive solid-phase extraction to pre-concentrate and separate Fe(3+) from aqueous phase. Since Fe(3+) has a larger formation constant with NTA compared to Ni(2+), subsequently ion exchange occurred when (NTA-Ni)-LDH was added to the sample solution. The resultant (NTA-Fe)-LDH sol was isolated and transferred in an acidic medium containing potassium thiocyanate (KSCN). Since (NTA-Fe)-LDH could be dissolved in acidic conditions, Fe(3+)was released and reacted with SCN(-) to form an Fe-SCN complex. The resulting product was measured by ultraviolet-visible spectrometry for quantitative detection of Fe(3+). Extraction factors, including sample pH, reaction pH, extraction temperature, extraction time, reaction time and concentration of KSCN were optimized. This method achieved a low limit of detection of 15.2nM and a good linear range from 0.05 to 50μM (r(2)=0.9937). A nearly 18-fold enhancement of signal intensity was achieved after selective extraction. The optimized conditions were validated by applying the method to determine Fe(3+) in seawater samples. PMID:27154694

  16. Effect of some naturally occurring iron ion chelators on the formation of radicals in the reaction mixtures of rat liver microsomes with ADP, Fe3+ and NADPH

    PubMed Central

    Minakata, Katsuyuki; Fukushima, Kazuaki; Nakamura, Masayuki; Iwahashi, Hideo

    2011-01-01

    In order to clarify the mechanism by polyphenols of protective effects against oxidative damage or by quinolinic acid of its neurotoxic and inflammatory actions, effects of polyphenols or quinolinic acid on the radical formation were examined. The ESR measurements showed that some polyphenols such as caffeic acid, catechol, gallic acid, D-(+)-catechin, L-dopa, chlorogenic acid and L-noradrenaline inhibited the formation of radicals in the reaction mixture of rat liver microsomes with ADP, Fe3+ and NADPH. The ESR measurements showed that α-picolinic acid, 2,6-pyridinedicarboxylic acid and quinolinic acid (2,3-pyridinedicarboxylic acid) enhanced the formation of radicals in the reaction mixture of rat liver microsomes with Fe3+ and NADPH. Caffeic acid and α-picolinic acid had no effects on the formation of radicals in the presence of EDTA, suggesting that the chelation of iron ion seems to be related to the inhibitory and enhanced effects. The polyphenols may exert protective effects against oxidative damage of erythrocyte membrane, ethanol-induced fatty livers, cardiovascular diseases, inflammatory and cancer through the mechanism. On the other hand, quinolinic acid may exert its neurotoxic and inflammatory effects because of the enhanced effect on the radical formation. PMID:22128221

  17. Degradation of 4-Chloro-3,5-Dimethylphenol by a Heterogeneous Fenton-Like Reaction Using Nanoscale Zero-Valent Iron Catalysts

    PubMed Central

    Xu, Lejin; Wang, Jianlong

    2013-01-01

    Abstract Degradation of 4-chloro-3,5-dimethylphenol (PCMX) by a heterogeneous Fenton-like process using nanoparticulate zero-valent iron (nZVI) and hydrogen peroxide (H2O2) at pH 6.3 was investigated. Interactive effects of three factors—initial PCMX concentration, nZVI dosage, and H2O2 concentration—were investigated using the response surface method based on the Box–Behnken design. Experimental results showed that complete decomposition of PCMX and 65% of total organic carbon removal were observed after 30 min of reaction at neutral pH under recommended reaction conditions: nZVI, 1.0 g/L; H2O2, 18 mM; and initial PCMX concentration, 0.15 g/L. Based on the effects of scavengers n-butanol and KI, removal of PCMX was mainly attributed to the attack of •OH, especially the surface-bonded •OH. A possible degradation pathway of PCMX was proposed. PMID:23781127

  18. High-performance liquid chromatography method for ferric iron chelators using a post-column reaction with Calcein Blue.

    PubMed

    Ariga, Tomoko; Ito, Kyoko; Imura, Yuki; Yoshimura, Etsuro

    2015-03-15

    Iron (Fe) is an essential element for higher plants, which take it up from the soil at the root surface and transport it to shoots through the xylem. Fe(III) chelators, such as organic acids and phytosiderophores, play important roles in the acquisition and transportation of Fe(III). Therefore, a selective and sensitive method for analyzing Fe(III) chelators is required to study the many Fe-related physiological mechanisms in plants. A novel analytical approach employing a high-performance liquid chromatography post-column method with fluorescence detection was developed to separate and detect Fe(III) chelators. This method takes advantage of the quenching of the fluorescence of Calcein Blue (CB) that occurs with the formation of an Fe(III)-CB complex and the dequenching that occurs with the release of CB as a result of competition for Fe(III) between CB and an Fe(III) chelator. This simple experimental method does not require complicated pretreatments and can selectively detect Fe(III) chelators according to their Fe(III)-chelating ability. The detection limit for citric acid using this method was 72pmol. Furthermore, this method can also detect unknown Fe(III) chelators that exhibit a high affinity for Fe(III). The method was evaluated with xylem sap of barley, which was shown to contain several Fe(III) chelators. PMID:25658515

  19. Fabrication of iron-doped cobalt oxide nanocomposite films by electrodeposition and application as electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Jingxuan; Wang, Xuemei; Qin, Dongdong; Xue, Zhonghua; Lu, Xiaoquan

    2014-11-01

    In this work, Fe-doped Co3O4 nanofilms were fabricated by electrodeposition on FTO glass substrates for the first time. The structures of the as-prepared nanofilms were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Characterization results demonstrate that Fe was doped homogeneously in the nanofilms. As the different concentration ratios of Fe2+/Co2+ were explored, nanofilm with the ratio of 1:5 exhibits the optimal performance in electrochemical properties assessments. It is considered that the difference in the catalytic activities for the ORR of the samples may be due to the fact that the joining of iron changed the catalyst surface's electric state and enhanced the acidity of cobalt centers, on the other hand, the doping process probably modified the absorption property of the nanofilms. The experimental results suggest that the Fe-doped Co3O4 nanofilms in this work exhibit favorable electrocatalytic activity toward ORR and appear to be promising cathodic electrocatalyst in alkaline fuel cells.

  20. Single Particle States in ^56Ni

    NASA Astrophysics Data System (ADS)

    Sanetullaev, Alisher; Lynch, W. G.; Tsang, M. B.; Bazin, D.; Coupland, D.; Henzl, V.; Henzlova, D.; Kilburn, M.; Lee, Jenny; Rogers, A. M.; Signoracci, A.; Sun, Z. Y.; Youngs, M.; Famiano, M.; Hudan, S.; O'Malley, P.; Peters, W. A.; Schmitt, K.; Shapira, D.; Charity, R. J.; Sobotka, L. G.

    2010-11-01

    Neutron spectroscopic factor of ^56Ni using (p, d) neutron transfer reaction has been measured using 37 MeV/u ^56Ni beam in inverse kinematics. The measurement was performed at NSCL using the high resolution silicon array, HiRA, to detect the deuterons in coincidence with the recoil residues detected in the S800 spectrometer. To test if ^56Ni is a good core, the most direct way is to measure the single particle nature of the neutrons or protons in the f7/2 orbits. Direct measurements of the spectroscopic factors of the neutron hole state in ^56Ni using the pickup (p,d) reaction will determine if the neutron f7/2 orbit is indeed a closed shell. In present work, preliminary experimental results will be presented.

  1. H2 oxidation versus organic substrate oxidation in non-heme iron mediated reactions with H2O2.

    PubMed

    Hassanpour, Azin; Acuña-Parés, Ferran; Luis, Josep M; Cusso, Olaf; Morales de la Rosa, Silvia; Campos-Martín, José Miguel; Fierro, Jose L G; Costas, Miquel; Lloret-Fillol, Julio; Mas-Ballesté, Rubén

    2015-10-18

    Herein we show that species generated upon reaction of α-[Fe(CF3SO3)2(BPMCN)] (BPMCN = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane) with H2O2 (putatively [Fe(V)(O)(OH)(BPMCN)]) is able to efficiently oxidize H2 to H2O even in the presence of organic substrates, while species formed in the presence of acetic acid (putatively [Fe(V)(O)(OAc)(BPMCN)]) prefer organic substrate oxidation over H2 activation. Mechanistic implications have been analysed with the aid of computational methods. PMID:26311021

  2. Iron toxicity in yeast.

    PubMed

    Wiśnicka, R; Krzepiłko, A; Wawryn, J; Biliński, T

    1997-01-01

    It has been found that yeast cells are sensitive to iron overload only when grown on glucose as a carbon source. Effective concentration of ferrous iron is much higher than that found in natural environments. Effects of ferrous iron are strictly oxygen dependent, what suggest that the formation of hydroxyl radicals in the Fenton reaction is a cause of the toxicity. Respiratory deficiency and pretreatment of cells with antimycin A prevent toxic effects in the late exponential phase of growth, whereas uncouplers and 2mM magnesium salts completely protect even the most vulnerable exponential cells. Generally, toxic effects correlate with the ability of cells to take up this metal. The results presented suggest that during ferrous iron overload iron is transported through the unspecific divalent cation uptake system which is known in fungi. The data suggest that recently described high and low affinity systems of iron uptake in yeast are the only source of iron in natural environments. PMID:9516981

  3. Highly effective degradation of sodium dodecylbenzene sulphonate and synthetic greywater by Fenton-like reaction over zerovalent iron-based catalyst.

    PubMed

    Zhu, Shi-Ni; Wang, Chao; Yip, Alex C K; Tsang, Daniel C W

    2015-01-01

    There is an increasing interest to recycle greywater for meeting non-portable water demand. However, linear alkylbenzene sulphonates (a form of anionic surfactants) that are commonly found in greywater are less biodegradable at moderate to high concentrations. A fenton-like system is a relatively economic advanced oxidation process that can potentially be used for surfactant degradation in greywater treatment. This study investigated the feasibility of zerovalent iron (ZVI)-mediated Fenton's oxidation of sodium dodecylbenzene sulphonate (SDBS) using Fe0/H2O2 and Fe2+/Fe0/H2O2 systems under a range of operating conditions. For the Fe0/H2O2 binary system, the initial pH value and Fe0 dosage played important roles in final degradation efficiency. For the Fe2+/Fe0/H2O2 ternary systems, a small amount of Fe2+ (0.5-1.7 mM) contributed a synergistic effect to promote iron recycling and SDBS degradation. Approximately, 90% of SDBS mineralization efficiency was accomplished within 15 min at a pH range from 3.0 to 6.5, using 18 mM Fe0 and 15 mM H2O2. However, the removal kinetics was rate-limited by Fe2+ dissolution from the ZVI surfaces. The Fenton-like process of the Fe2+/Fe0/H2O2 ternary system also presents a promising treatment method for synthetic greywater, in which 90% TOC removal was achieved within the first 10 min; 78% COD and 91% BOD5 were achieved after 120 min of reaction. PMID:25424128

  4. The ubiquity of iron.

    PubMed

    Frey, Perry A; Reed, George H

    2012-09-21

    The importance of iron in living systems can be traced to the many complexes within which it is found, to its chemical mobility in undergoing oxidation-reduction reactions, and to the abundance of iron in Earth's crust. Iron is the most abundant element, by mass, in the Earth, constituting about 80% of the inner and outer cores of Earth. The molten outer core is about 8000 km in diameter, and the solid inner core is about 2400 km in diameter. Iron is the fourth most abundant element in Earth's crust. It is the chemically functional component of mononuclear iron complexes, dinuclear iron complexes, [2Fe-2S] and [4Fe-4S] clusters, [Fe-Ni-S] clusters, iron protophorphyrin IX, and many other complexes in protein biochemistry. Metals such as nickel, cobalt, copper, and manganese are present in the crust and could in principle function chemically in place of iron, but they are scarce in Earth's crust. Iron is plentiful because of its nuclear stability in stellar nuclear fusion reactions. It seems likely that other solid planets, formed by the same processes as Earth, would also foster the evolution of life and that iron would be similarly important to life on those planets as it is on Earth. PMID:22845493

  5. Synthesis and characterization of nano-structured molybdenum-iron intermetallics by gas-solid reaction technique

    NASA Astrophysics Data System (ADS)

    El-Geassy, A. A.; Seetheraman, S.

    2016-03-01

    Ammonium molybdate and ferrous oxalate were used for the synthesis of nano-structured Mo-Fe intermetallics. Co-precipitation technique was applied to produce Mo/Fe precursors containing 58/42, 72/28 and 30/70 mass% respectively. The different phases formed were identified by XRD. The macro- and microstructures were microscopically examined by Reflected Light Microscope (RLM) and Scanning Electron Microscope (SEM) coupled with Electron Dispersion Spectroscopy (EDS). TG-DTA-DSC technique was applied to follow up the behavior of precursors up to 900oC (10K/min.). Endothermic peaks were detected at 97.8, 196.9 and 392.7oC due to the decomposition reactions to produce MoO3 and Fe2O3. The exothermic peak resulted at 427.8oC is due to the solid state reaction between these oxides to form Fe2(MoO4)3. Precursors were isothermally reduced at 600-850oC in a flow of purified H2 and the O2-weight loss from the reduction reactions was continuously recorded as a function of time. The isothermal reduction behavior of precursors was investigated. The structures of reduced products and the different phases formed were investigated and correlated with the reduction conditions. At >60% reduction extents, Fe2(MoO4)3] phase was first reduced to Fe2MoO3O8 before the formation of FeMo, while FeMoO4 and MoO2 were reduced to FeMo and Mo. In precursors containing higher content of Fe2O3, FeMo, Fe3Mo and Fe phases were produced. The visual observation of reduced samples showed that the volume was gradually shrinking with rise in temperature up to 800oC and beyond which a measurable swelling was observed reaching about 170% at 900oC.

  6. Structural features and the reaction mechanism of cytochrome oxidase: iron and copper X-ray absorption fine structure.

    PubMed Central

    Powers, L; Chance, B; Ching, Y; Angiolillo, P

    1981-01-01

    X-ray edge absorption of copper and extended fine structure studies of both copper and iron centers have been made of cytochrome oxidase from beef heart, Paracoccus dentrificans, and HB-8 thermophilic bacteria (1-2.5 mM in heme). The desired redox state (fully oxidized, reduced CO, mixed valence formate and CO) in the x-ray beam was controlled by low temperature (-140 degrees C) and was continuously monitored by simultaneous optical spectroscopy and by electron paramagnetic resonance (EPR) monitoring every 30 min of x-ray exposure. The structure of the active site, a cytochrome a3-copper pair in fully oxidized and in mixed valence formate states where they are spin coupled, contains a sulphur bridge with three ligands 2.60 +/- 0.03 A from Fea3 and 2.18 +/- 0.03 A from Cua3. The distance between Fea3 and Cua3 is 3.75 +/- 0.05 A, making the sulphur bond angle 103 degrees reasonable for sp3 sulphur bonding. The Fea3 first shell has four typical heme nitrogens (2.01 +/- 0.03 A) with a proximal nitrogen at 2.14 +/- 0.03 A. The sixth ligand is the bridging sulphur. The Cua3 first shell is identical to oxidized stellacyanin containing two nitrogens and a bridging sulphur. Upon reduction with CO, the active site is identical to reduced stellacyanin for the Cua3 first shell and contains the sulphur that forms the bridge in fully oxidized and mixed valence formate states. The Fea3 first shell is identical to oxyhemoglobin but has CO instead of O2. The other redox centers, Fea and the other "EPR detectable" Cu are not observed in higher shells of Fea3. Fea has six equidistant nitrogens and Cua has one (or two) nitrogens and three (or two) sulphurs with typical distances; these ligands change only slight on reduction. These structures afford the basis for an oxygen reduction mechanism involving oxy- and peroxy intermediates. Images FIGURE 2 PMID:6264990

  7. Phase transformations in thin iron oxide films: Spectromicroscopic study of velocity and shape of the reaction fronts

    NASA Astrophysics Data System (ADS)

    Genuzio, F.; Sala, A.; Schmidt, Th.; Menzel, D.; Freund, H.-J.

    2016-06-01

    Combining low energy electron microscopy (LEEM) with low energy electron diffraction (LEED) and x-ray photoemission electron microscopy (XPEEM), we studied the phase transformations between Fe3O4, γ-Fe2O3, and α-Fe2O3, grown as 10 nm thin oxide films on Pt(111) and Ag(111) single crystals. These transformations occur as moving reaction fronts in most cases, the shapes and velocities of which show strong dependences on temperature and oxygen pressure, but also on defects like step bunches of the supporting substrate and domain boundaries in the initial oxide film. While the non-uniform moving fronts make quantitative analysis difficult, we have extracted approximate values for the average front velocities. We discuss these as well as the qualitative information on the non-uniform fronts in terms of the known geometric situations and the likely motional steps.

  8. A highly efficient electrocatalyst for oxygen reduction reaction: phosphorus and nitrogen co-doped hierarchically ordered porous carbon derived from an iron-functionalized polymer

    NASA Astrophysics Data System (ADS)

    Deng, Chengwei; Zhong, Hexiang; Li, Xianfeng; Yao, Lan; Zhang, Huamin

    2016-01-01

    Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated.Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic

  9. Iron Chelation

    MedlinePlus

    ... iron overload and need treatment. What is iron overload? Iron chelation therapy is used when you have ... may want to perform: How quickly does iron overload happen? This is different for each person. It ...

  10. Structural basis of the divergent oxygenation reactions catalyzed by the rieske nonheme iron oxygenase carbazole 1,9a-dioxygenase.

    PubMed

    Inoue, Kengo; Usami, Yusuke; Ashikawa, Yuji; Noguchi, Haruko; Umeda, Takashi; Yamagami-Ashikawa, Aiko; Horisaki, Tadafumi; Uchimura, Hiromasa; Terada, Tohru; Nakamura, Shugo; Shimizu, Kentaro; Habe, Hiroshi; Yamane, Hisakazu; Fujimoto, Zui; Nojiri, Hideaki

    2014-05-01

    Carbazole 1,9a-dioxygenase (CARDO), a Rieske nonheme iron oxygenase (RO), is a three-component system composed of a terminal oxygenase (Oxy), ferredoxin, and a ferredoxin reductase. Oxy has angular dioxygenation activity against carbazole. Previously, site-directed mutagenesis of the Oxy-encoding gene from Janthinobacterium sp. strain J3 generated the I262V, F275W, Q282N, and Q282Y Oxy derivatives, which showed oxygenation capabilities different from those of the wild-type enzyme. To understand the structural features resulting in the different oxidation reactions, we determined the crystal structures of the derivatives, both free and complexed with substrates. The I262V, F275W, and Q282Y derivatives catalyze the lateral dioxygenation of carbazole with higher yields than the wild type. A previous study determined the crystal structure of Oxy complexed with carbazole and revealed that the carbonyl oxygen of Gly178 hydrogen bonds with the imino nitrogen of carbazole. In these derivatives, the carbazole was rotated approximately 15, 25, and 25°, respectively, compared to the wild type, creating space for a water molecule, which hydrogen bonds with the carbonyl oxygen of Gly178 and the imino nitrogen of carbazole. In the crystal structure of the F275W derivative complexed with fluorene, C-9 of fluorene, which corresponds to the imino nitrogen of carbazole, was oriented close to the mutated residue Trp275, which is on the opposite side of the binding pocket from the carbonyl oxygen of Gly178. Our structural analyses demonstrate that the fine-tuning of hydrophobic residues on the surface of the substrate-binding pocket in ROs causes a slight shift in the substrate-binding position that, in turn, favors specific oxygenation reactions toward various substrates. PMID:24584240

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

    SciTech Connect

    Klobukowski, Erik

    2011-01-01

    conditions, it was found that the oxidative dehydrogenation of dibenzylamine to Nbenzylidenebenzylamine, with N-methylmorpholine N-oxide (NMMO), was nearly quantitative (96%) within 24 h. However, the reaction with oxygen was much slower, with only a 52% yield of imine product over the same time period. Moreover, the rate of reaction was found to be influenced by the nature of the amine N-oxide. For example, the use of the weakly basic pyridine N-oxide (PyNO) led to an imine yield of only 6% after 24 h. A comparison of amine N-oxide and O2 was also examined in the oxidation of PhCH{sub 2}OH to PhCHO catalyzed by bulk gold. In this reaction, a 52% yield of the aldehyde was achieved when NMMO was used, while only a 7% product yield was afforded when O{sub 2} was the oxidant after 48 h. The bulk gold-catalyzed oxidative dehydrogenation of cyclic amines generates amidines, which upon treatment with Aerosil and water were found to undergo hydrolysis to produce lactams. Moreover, 5-, 6-, and 7-membered lactams could be prepared through a one-pot reaction of cyclic amines by treatment with oxygen, water, bulk gold, and Aerosil. This method is much more atom economical than industrial processes, does not require corrosive acids, and does not generate undesired byproducts. Additionally, the gold and Aerosil catalysts can be readily separated from the reaction mixture. The second project involved studying iron(III) tetraphenylporphyrin chloride, Fe(TPP)Cl, as a homogeneous catalyst for the generation of carbenes from diazo reagents and their reaction with heteroatom compounds. Fe(TPP)Cl, efficiently catalyzed the insertion of carbenes derived from methyl 2-phenyldiazoacetates into O-H bonds of aliphatic and aromatic alcohols. Fe(TPP)Cl was also found to be an effective catalyst for tandem N-H and O-H insertion/cyclization reactions when 1,2-diamines and 1,2-alcoholamines were treated with diazo reagents. This approach provides a one-pot process for synthesizing piperazinones and

  12. An investigation of reaction parameters on geochemical storage of non-pure CO2 streams in iron oxides-bearing formations

    SciTech Connect

    Garcia, Susana; Liu, Q.; Bacon, Diana H.; Maroto-Valer, M. M.

    2014-08-26

    Hematite deposit that is the main FeIII-bearing mineral in sedimentary red beds was proposed as a potential host repository for converting CO2 into carbonate minerals such as siderite (FeCO3), when CO2–SO2 gas mixtures are co-injected. This work investigated CO2 mineral trapping using hematite and sensitivity of the reactive systems to different parameters, including particle size, gas composition, temperature, pressure, and solid-to-liquid ratio. Experimental and modelling studies of hydrothermal experiments were conducted, which emulated a CO2 sequestration scenario by injecting CO2-SO2 gas streams into a NaCl-NaOH brine hosted in iron oxide-containing aquifer. This study provides novel information on the mineralogical changes and fluid chemistry derived from the co-injection of CO2-SO2 gas mixtures in hematite deposit. It can be concluded that the amount of siderite precipitate depends primarily on the SO2 content of the gas stream. Increasing SO2 content in the system could promote the reduction of Fe3+ from the hematite sample to Fe2+, which will be further available for its precipitation as siderite. Moreover, siderite precipitation is enhanced at low temperatures and high pressures. The influence of the solid to liquid ratio on the overall carbonation reaction suggests that the conversion increases if the system becomes more diluted.

  13. Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center

    SciTech Connect

    Burgos, W.D.

    2009-09-02

    This report summarizes research conducted in conjunction with a project entitled “Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center”, which was funded through the Integrative Studies Element of the former NABIR Program (now the Environmental Remediation Sciences Program) within the Office of Biological and Environmental Research. Dr. William Burgos (The Pennsylvania State University) was the overall PI/PD for the project, which included Brian Dempsey (Penn State), Gour-Tsyh (George) Yeh (Central Florida University), and Eric Roden (formerly at The University of Alabama, now at the University of Wisconsin) as separately-funded co-PIs. The project focused on development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. The work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and was directly aligned with the Scheibe et al. ORNL FRC Field Project at Area 2.

  14. Enhancement in Kinetics of the Oxygen Reduction Reaction on a Nitrogen-Doped Carbon Catalyst by Introduction of Iron via Electrochemical Methods.

    PubMed

    Wu, Jiajia; Zhang, Da; Niwa, Hideharu; Harada, Yoshihisa; Oshima, Masaharu; Ofuchi, Hironori; Nabae, Yuta; Okajima, Takeyoshi; Ohsaka, Takeo

    2015-05-19

    The iron (Fe) electrodeposition-electrochemical dissolution has been employed on nitrogen-doped carbon material (P-PI) prepared via multi-step pyrolysis of a polyimide precursor to achieve the introduction of Fe species, and its influence on the oxygen reduction reaction (ORR) is investigated by cyclic and rotating ring-disk electrode voltammetry in 0.5 M H2SO4. After the electrochemical treatment, the overpotential and H2O2 production percentage of ORR on the P-PI are decreased and the number of electrons transferred is increased in the meanwhile. In combination with the results of X-ray absorption fine structure spectra, the presence of Fe-Nx sites (Fe ions coordinated by nitrogen) is believed to be responsible for the improved ORR performance. Further kinetic analysis indicates that a two-electron reduction of O2 is predominant on the untreated P-PI with coexistence of a direct four-electron transformation of O2 to H2O, while the introduction of Fe species leads to a larger increase in the rate constant for the four-electron reduction than that for the two-electron process, being in good agreement with the view that Fe-Nx sites are active for four-electron ORR. PMID:25901901

  15. Mixtures of l-Amino Acids as Reaction Medium for Formation of Iron Nanoparticles: The Order of Addition into a Ferrous Salt Solution Matters

    PubMed Central

    Šišková, Karolína M.; Machala, Libor; Tuček, Jiři; Kašlík, Josef; Mojzeš, Peter; Zbořil, Radek

    2013-01-01

    Owing to Mössbauer spectroscopy, an advanced characterization technique for iron-containing materials, the present study reveals previously unknown possibilities using l-amino acids for the generation of magnetic particles. Based on our results, a simple choice of the order of l-amino acids addition into a reaction mixture containing ferrous ions leads to either superparamagnetic ferric oxide/oxyhydroxide particles, or magnetically strong Fe0-Fe2O3/FeOOH core-shell particles after chemical reduction. Conversely, when ferric salts are employed with the addition of selected l-amino acids, only Fe0-Fe2O3/FeOOH core-shell particles are observed, regardless of the addition order. We explain this phenomenon by a specific transient/intermediate complex formation between Fe2+ and l-glutamic acid. This type of complexation prevents ferrous ions from spontaneous oxidation in solutions with full air access. Moreover, due to surface-enhanced Raman scattering spectroscopy we show that the functional groups of l-amino acids are not destroyed during the borohydride-induced reduction. These functionalities can be further exploited for (i) attachment of l-amino acids to the as-prepared magnetic particles, and (ii) for targeted bio- and/or environmental applications where the surface chemistry needs to be tailored and directed toward biocompatible species. PMID:24071943

  16. Orientations of Iron-Sulfur Clusters FA and FB in the Homodimeric Type-I Photosynthetic Reaction Center of Heliobacterium modesticaldum.

    PubMed

    Kondo, Toru; Matsuoka, Masahiro; Azai, Chihiro; Itoh, Shigeru; Oh-Oka, Hirozo

    2016-05-12

    Orientations of the FA and FB iron-sulfur (FeS) clusters in a structure-unknown type-I homodimeric heriobacterial reaction center (hRC) were studied in oriented membranes of the thermophilic anaerobic photosynthetic bacterium Heliobacterium modesticaldum by electron paramagnetic resonance (EPR), and compared with those in heterodimeric photosystem I (PS I). The Rieske-type FeS center in the cytochrome b/c complex showed a well-oriented EPR signal. Illumination at 14 K induced an FB(-) signal with g-axes of gz = 2.066, gy = 1.937, and gx = 1.890, tilted at angles of 60°, 60°, and 45°, respectively, with respect to the membrane normal. Chemical reduction with dithionite produced an additional signal of FA(-), which magnetically interacted with FB(-), with gz = 2.046, gy = 1.942, and gx = 1.911 at 30°, 60°, and 90°, respectively. The angles and redox properties of FA(-) and FB(-) in hRC resemble those of FB(-) and FA(-), respectively, in PS I. Therefore, FA and FB in hRC, named after their g-value similarities, seem to be located like FB and FA, not like FA and FB, respectively, in PS I. The reducing side of hRC could resemble those in PS I, if the names of FA and FB are interchanged with each other. PMID:27101081

  17. A highly efficient electrocatalyst for oxygen reduction reaction: phosphorus and nitrogen co-doped hierarchically ordered porous carbon derived from an iron-functionalized polymer.

    PubMed

    Deng, Chengwei; Zhong, Hexiang; Li, Xianfeng; Yao, Lan; Zhang, Huamin

    2016-01-21

    Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm(2) g(-1)) and a pore volume of 1.14 cm(3) g(-1). Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated. PMID:26692228

  18. Measurement of hair iron concentration as a marker of body iron content

    PubMed Central

    SAHIN, CEM; PALA, CIGDEM; KAYNAR, LEYLAGUL; TORUN, YASEMIN ALTUNER; CETIN, AYSUN; KURNAZ, FATIH; SIVGIN, SERDAR; SAHIN, FATIH SERDAR

    2015-01-01

    The aim of the present study was to define the possible association between blood parameters and hair iron concentration in patient groups showing a difference in body iron content. The study population comprised subjects with iron deficiency anaemia and transfusion-related anaemia with different body iron contents and a healthy control group. All the cases included in the study were examined with respect to hair iron concentration, serum iron, total iron-binding capacity (TIBC), transferrin saturation and erythrocyte markers in the total blood count with ferritin values. Differences in hair iron concentration were evaluated between the groups. Correlation analysis was applied to define the association between the laboratory values used as markers of body iron content and hair iron concentration. A statistically significant difference was determined in hair iron 56Fe and 57Fe concentrations between the group with transfusion-related anaemia, the iron deficiency anaemia group and the healthy control group (P<0.001). In addition, a positive correlation was determined between hair iron 56Fe and 57Fe concentrations and serum iron, ferritin level, transferrin saturation, mean erythrocyte volume and mean erythrocyte haemoglobin values and a negative correlation with TIBC. In conclusion, the results of the present study showed a statistically significant difference in the hair iron concentrations of the patient groups with different body iron content and these values were correlated to the laboratory markers of body iron content. PMID:26137241

  19. Iron incorporation and post-malaria anaemia

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Iron supplementation is employed to treat post-malarial anaemia in environments where iron deficiency is common. Malaria induces an intense inflammatory reaction that stalls reticulo-endothelial macrophagal iron recycling from haemolysed red blood cells and inhibits oral iron absorption, but the mag...

  20. Asteroid mega-impacts and Precambrian banded iron formations: 2.63 Ga and 2.56 Ga impact ejecta/fallout at the base of BIF/argillite units, Hamersley Basin, Pilbara Craton, Western Australia

    NASA Astrophysics Data System (ADS)

    Glikson, Andrew; Vickers, John

    2007-02-01

    The temporal association between late Archaean to earliest Proterozoic asteroid impact ejecta/fallout units and overlying banded iron formations suggests that, in some instances, these impacts were closely followed by significant transformation in the nature of source terrains of the sediments. The Jeerinah Impact Layer (JIL) [B.M. Simonson, D. Davies, S.W. Hassler, Discovery of a layer of probable impact melt spherules in the late Archean Jeerinah Formation, Fortescue Group, Western Australia. Aust. J. Earth Sci. 47 (2000) 315-325; B.M. Simonson, S.W. Hassler, Revised correlations in the early Precambrian Hamersley Basin based on a horizon of resedimented impact spherules. Aust. J. Earth Sci. 44 (1997) 37-48; B.M. Simonson, B.P. Glass, Spherule layers - records of ancient impacts. Ann. Rev. Earth Planet. Sci. 32 (2004) 329-361; A.Y. Glikson, Early Precambrian asteroid impact-triggered tsunami: excavated seabed, debris flows, exotic boulders, and turbulence features associated with 3.47-2.47 Ga-old asteroid impact fallout units, Pilbara Craton, Western Australia. Astrobiology 4 (2001) 19-50; S.W. Hassler, B.M. Simonson, D.Y. Sumner, D. Murphy, Neoarchaean impact spherule layers in the Fortescue and Hamersley Groups, Western Australia: stratigraphic and depositional implications of re-correlation. Aust. J. Earth Sci. 52 (2005) 759-772; B. Rasmussen, C. Koeberl, Iridium anomalies and shocked quartz in a late Archean spherule layer from the Pilbara Craton: new evidence for a major asteroid impact at 2.63 Ga. Geology 32 (2004) 1029-1032; B. Rasmussen, T.S. Blake, I.R. Fletcher, U-Pb zircon age constraints on the Hamersley spherule beds: Evidence for a single 2.63 Ga Jeerinah-Carawine impact ejecta layer. Geology, 33 (2005) 725-728.] overlies an argillite-dominated unit (Jeerinah Formation, 2684 ± 6 Ma [A.F. Trendall, W. Compston, D.R. Nelson, J.R. deLaeter, V.C. Bennett, SHRIMP zircon ages constraining the depositional chronology of the Hamersley Group, Western

  1. Iron overdose

    MedlinePlus

    Iron is an ingredient in many mineral and vitamin supplements. Iron supplements are also sold by themselves. Types include: Ferrous sulfate (Feosol, Slow Fe) Ferrous gluconate (Fergon) Ferrous fumarate (Femiron, Feostat) Other products may also contain iron.

  2. 30 CFR 56.16012 - Storage of incompatible substances.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... substances, where such contact could cause a violent reaction or the liberation of harmful fumes or gases. ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Storage of incompatible substances. 56.16012 Section 56.16012 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL...

  3. Iron in asbestos chemistry and carcinogenicity

    SciTech Connect

    Hardy, J.A.; Aust, A.E.

    1995-01-01

    This article reviews the various aspects regarding the carcinogenicity of asbestos and associated reactions catalyzed by iron. Attention is focused on the following: structure of asbestos; physical properties of asbestos involved in carcinogenesis; reactions catalyzed by iron; reactions catalyzed by asbestos; fiber inactivation; physiological effects; and mutations and cancer. 183 refs.

  4. Enzymes of respiratory iron oxidation

    SciTech Connect

    Blake, R. II.

    1992-01-01

    This report describes experimental progress in characterizing and identifying redox proteins in a number of iron-oxidizing bacteria. Sections of the paper are entitled (1) In Situ electrolysis was explored to achieve enhanced yields of iron-oxidizing bacteria, (2)Structure/function studies were performed on redox-active biomolecules from Thiobacillus ferrooxidans, (3) Novel redox-active biomolecules were demonstrated in other iron autotrophs, and (4) New probes of metalloprotein electron-transfer reactions were synthesized and characterized.

  5. Electron capture of strongly screening nuclides 56Fe, 56Co, 56Ni, 56Mn,56Cr and 56V in pre-supernovae

    NASA Astrophysics Data System (ADS)

    Liu, Jing-Jing

    2013-08-01

    According to the shell-model Monte Carlo method, based on the random-phase approximation and linear response theory, we carried out an estimation of electron capture (EC) of the strongly screening nuclides 56Fe, 56Co, 56Ni, 56Mn,56Cr and 56V during strong electron screening (SES) in pre-supernovae. The EC rates are decreased greatly and may even exceed 21.5 per cent in the case of SES. We also compare our results with those calculated by the method of Aufderheide in the case of SES. Our results agree reasonably well with those of Aufderheide in higher density and temperature surroundings (e.g. ρ7 > 60, T9 = 15.40) and the maximum error is ˜0.5 per cent. However, the maximum error is ˜13.0 per cent in lower density surroundings (e.g. 56Cr at ρ7 = 10, T9 = 15.40, Ye = 0.41). We also compared our results for SES with those of Fuller, Fowler & Newman and Nabi, which apply to a case without SES. The comparisons show that our results are lower than those of Fuller, Fowler & Newman by more than one order of magnitude and about 7.23 per cent lower than those of Nabi.

  6. Revisiting Mitochondrial pH with an Improved Algorithm for Calibration of the Ratiometric 5(6)-carboxy-SNARF-1 Probe Reveals Anticooperative Reaction with H+ Ions and Warrants Further Studies of Organellar pH

    PubMed Central

    Żurawik, Tomasz Michał; Pomorski, Adam; Belczyk-Ciesielska, Agnieszka; Goch, Grażyna; Niedźwiedzka, Katarzyna; Kucharczyk, Róża; Krężel, Artur; Bal, Wojciech

    2016-01-01

    Fluorescence measurements of pH and other analytes in the cell rely on accurate calibrations, but these have routinely used algorithms that inadequately describe the properties of indicators. Here, we have established a more accurate method for calibrating and analyzing data obtained using the ratiometric probe 5(6)-carboxy-SNARF-1. We tested the implications of novel approach to measurements of pH in yeast mitochondria, a compartment containing a small number of free H+ ions. Our findings demonstrate that 5(6)-carboxy-SNARF-1 interacts with H+ ions inside the mitochondria in an anticooperative manner (Hill coefficient n of 0.5) and the apparent pH inside the mitochondria is ~0.5 unit lower than had been generally assumed. This result, at odds with the current consensus on the mechanism of energy generation in the mitochondria, is in better agreement with theoretical considerations and warrants further studies of organellar pH. PMID:27557123

  7. Revisiting Mitochondrial pH with an Improved Algorithm for Calibration of the Ratiometric 5(6)-carboxy-SNARF-1 Probe Reveals Anticooperative Reaction with H+ Ions and Warrants Further Studies of Organellar pH.

    PubMed

    Żurawik, Tomasz Michał; Pomorski, Adam; Belczyk-Ciesielska, Agnieszka; Goch, Grażyna; Niedźwiedzka, Katarzyna; Kucharczyk, Róża; Krężel, Artur; Bal, Wojciech

    2016-01-01

    Fluorescence measurements of pH and other analytes in the cell rely on accurate calibrations, but these have routinely used algorithms that inadequately describe the properties of indicators. Here, we have established a more accurate method for calibrating and analyzing data obtained using the ratiometric probe 5(6)-carboxy-SNARF-1. We tested the implications of novel approach to measurements of pH in yeast mitochondria, a compartment containing a small number of free H+ ions. Our findings demonstrate that 5(6)-carboxy-SNARF-1 interacts with H+ ions inside the mitochondria in an anticooperative manner (Hill coefficient n of 0.5) and the apparent pH inside the mitochondria is ~0.5 unit lower than had been generally assumed. This result, at odds with the current consensus on the mechanism of energy generation in the mitochondria, is in better agreement with theoretical considerations and warrants further studies of organellar pH. PMID:27557123

  8. Iron deficiency.

    PubMed

    Scrimshaw, N S

    1991-10-01

    The world's leading nutritional problem is iron deficiency. 66% of children and women aged 15-44 years in developing countries have it. Further, 10-20% of women of childbearing age in developed countries are anemic. Iron deficiency is identified with often irreversible impairment of a child's learning ability. It is also associated with low capacity for adults to work which reduces productivity. In addition, it impairs the immune system which reduces the body's ability to fight infection. Iron deficiency also lowers the metabolic rate and the body temperature when exposed to cold. Hemoglobin contains nearly 73% of the body's iron. This iron is always being recycled as more red blood cells are made. The rest of the needed iron does important tasks for the body, such as binds to molecules that are reservoirs of oxygen for muscle cells. This iron comes from our diet, especially meat. Even though some plants, such as spinach, are high in iron, the body can only absorb 1.4-7% of the iron in plants whereas it can absorb 20% of the iron in red meat. In many developing countries, the common vegetarian diets contribute to high rates of iron deficiency. Parasitic diseases and abnormal uterine bleeding also promote iron deficiency. Iron therapy in anemic children can often, but not always, improve behavior and cognitive performance. Iron deficiency during pregnancy often contributes to maternal and perinatal mortality. Yet treatment, if given to a child in time, can lead to normal growth and hinder infections. However, excess iron can be damaging. Too much supplemental iron in a malnourished child promotes fatal infections since the excess iron is available for the pathogens use. Many countries do not have an effective system for diagnosing, treating, and preventing iron deficiency. Therefore a concerted international effort is needed to eliminate iron deficiency in the world. PMID:1745900

  9. Degradation of chlorofluorocarbons using granular iron and bimetallic irons.

    PubMed

    Jeen, Sung-Wook; Lazar, Snezana; Gui, Lai; Gillham, Robert W

    2014-03-01

    Degradation of trichlorofluoromethane (CFC11) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113) by granular iron and bimetallic (nickel- or palladium-enhanced) irons was studied in flow-through column tests. Both compounds were rapidly degraded, following pseudo-first-order kinetics with respect to the parent compounds. The average pseudo-first-order rate constants for CFC11 were similar among different materials, except for palladium-enhanced iron (PdFe), in which the rate of degradation was about two times faster than for the other materials. In the case of CFC113, the rate constants for bimetallic irons were about two to three times greater than for the regular iron material. The smaller than expected differences in degradation rate constants of chlorofluorocarbons (CFCs) between regular iron and bimetallic irons suggested little, if any, catalytic effect of the bimetallic materials in the initial degradation step. Subsequent degradation steps involved catalytic hydrogenation, however, playing a significant role in further degradation of reaction intermediates. The degradation intermediates and final products of CFC11 and CFC113 suggested that degradation proceeded through hydrogenolysis and α/β-elimination in the presence of regular iron (Fe) and nickel-enhanced iron (NiFe). Even though there is only minor benefit in the use of bimetallic iron in terms of degradation kinetics of the parent CFCs, enhanced degradation rates of intermediates such as chlorotriflouroethene (CTFE) in subsequent reaction steps could be beneficial. PMID:24492233

  10. Dissolution reaction and surface iron speciation of UICC crocidolite in buffered solution at pH 7.4: A combined ICP-OES, XPS and TEM investigation

    NASA Astrophysics Data System (ADS)

    Pacella, Alessandro; Fantauzzi, Marzia; Turci, Francesco; Cremisini, Carlo; Montereali, Maria Rita; Nardi, Elisa; Atzei, Davide; Rossi, Antonella; Andreozzi, Giovanni B.

    2014-02-01

    The dissolution reaction and the surface modifications of crocidolite asbestos fibres incubated for 0.5, 1, 24, 48, 168 and 1440 h in a phosphate buffered solution at pH 7.4 with and without hydrogen peroxide were investigated. Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) was used to monitor the ion release into solution, X-ray Photoelectron Spectroscopy (XPS) was performed to unveil the chemistry of the leached surface, and High Resolution Transmission Electron Microscopy (HR-TEM) was carried out to monitor the structural modifications of the fibres. No significant differences were observed between dissolution experiments carried out with and without H2O2 with the exception of results after the first hour, from which it may be inferred that the dissolution proceeds faster in the presence of H2O2 but only in its very early steps. Congruent mobilization of Si and Mg from crocidolite was observed, increasing with time especially in the range between 1 and 48 h, while Ca decreased after 48 h and Fe was not detected at any incubation time. In the undersaturated conditions (0-48 h), dissolution rate of UICC crocidolite fibres has been estimated to be d(Si)/dt = 0.079 μmol h-1. The fibre surface modification is continuous with time: XPS results showed a regular depletion of Si and Mg and enrichment of Fe along dissolution. The Fe2p3/2 signal on the surface was fitted with four components at 709.0, 710.5, 711.6 and 712.8 eV binding energy values corresponding to: (i) Fe(II)-O and (ii) Fe(III)-O surrounded by oxygen atoms in the silicate structure, (iii) Fe(III)-OOH as a product of the dissolution process, and (iv) Fe in a phosphate precipitate (Fe-P), respectively. The evolution of Fe speciation on the crocidolite surface was followed by integrating the four photoemission peaks, and results showed that the oxidative environment promotes the formation of Fe(III)-O (up to 37% Fetot) and of Fe-P species (up to 16% Fetot), which are found on the fibre

  11. Magnetic bead-based enzyme-chromogenic substrate system for ultrasensitive colorimetric immunoassay accompanying cascade reaction for enzymatic formation of squaric acid-iron(III) chelate.

    PubMed

    Lai, Wenqiang; Tang, Dianping; Zhuang, Junyang; Chen, Guonan; Yang, Huanghao

    2014-05-20

    This work reports on a simple and feasible colorimetric immunoassay with signal amplification for sensitive determination of prostate-specific antigen (PSA, used as a model) at an ultralow concentration by using a new enzyme-chromogenic substrate system. We discovered that glucose oxidase (GOx), the enzyme broadly used in enzyme-linked immunosorbent assay (ELISA), has the ability to stimulate in situ formation of squaric acid (SQA)-iron(III) chelate. GOx-catalyzed oxidization of glucose leads to the formation of gluconic acid and hydrogen peroxide (H2O2). The latter can catalytically oxidize iron(II) to iron(III), which can rapidly (<1 min) coordinate with the SQA. Formation of the iron-squarate complex causes the color of the solution to change from bluish purple to bluish red accompanying the increasing absorbance with the increment of iron(III) concentration. On the basis of the SQA-iron(III) system, a new immunoassay protocol with GOx-labeled anti-PSA detection antibody can be designed for the detection of target PSA on capture antibody-functionalized magnetic immunosensing probe, monitored by recording the color or absorbance (λ = 468 nm) of the generated SQA-iron(III) chelate. The absorbance intensity shows to be dependent on the concentration of target PSA. A linear dependence between the absorbance and target PSA concentration is obtained under optimal conditions in the range from 1.0 pg mL(-1) to 30 ng mL(-1) with a detection limit (LOD) of 0.5 pg mL(-1) (0.5 ppt) estimated at the 3Sblank level. The sensitivity displays to be 3-5 orders of magnitude better than those of most commercialized human PSA ELISA kits. In addition, the developed colorimetric immunoassay was validated by assaying 12 human serum samples, receiving in good accordance with those obtained by the commercialized PSA ELISA kit. Importantly, the SQA-based immunosensing system can be further extended for the detection of other low-abundance proteins or biomarkers by controlling the target

  12. IRON-TOLERANT CYANOBACTERIA: IMPLICATIONS FOR ASTROBIOLOGY

    NASA Technical Reports Server (NTRS)

    Brown, Igor I.; Allen, Carlton C.; Mummey, Daniel L.; Sarkisova, Svetlana A.; McKay, David S.

    2006-01-01

    The review is dedicated to the new group of extremophiles - iron tolerant cyanobacteria. The authors have analyzed earlier published articles about the ecology of iron tolerant cyanobacteria and their diversity. It was concluded that contemporary iron depositing hot springs might be considered as relative analogs of Precambrian environment. The authors have concluded that the diversity of iron-tolerant cyanobacteria is understudied. The authors also analyzed published data about the physiological peculiarities of iron tolerant cyanobacteria. They made the conclusion that iron tolerant cyanobacteria may oxidize reduced iron through the photosystem of cyanobacteria. The involvement of both Reaction Centers 1 and 2 is also discussed. The conclusion that iron tolerant protocyanobacteria could be involved in banded iron formations generation is also proposed. The possible mechanism of the transition from an oxygenic photosynthesis to an oxygenic one is also discussed. In the final part of the review the authors consider the possible implications of iron tolerant cyanobacteria for astrobiology.

  13. Ligand iron catalysts for selective hydrogenation

    DOEpatents

    Casey, Charles P.; Guan, Hairong

    2010-11-16

    Disclosed are iron ligand catalysts for selective hydrogenation of aldehydes, ketones and imines. A catalyst such as dicarbonyl iron hydride hydroxycyclopentadiene) complex uses the OH on the five member ring and hydrogen linked to the iron to facilitate hydrogenation reactions, particularly in the presence of hydrogen gas.

  14. 21 CFR 520.1182 - Iron dextran suspension.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Iron dextran suspension. 520.1182 Section 520.1182... DRUGS, FEEDS, AND RELATED PRODUCTS ORAL DOSAGE FORM NEW ANIMAL DRUGS § 520.1182 Iron dextran suspension. (a) Specifications. Each milliliter (mL) of suspension contains 55.56 milligrams (mg) iron as...

  15. 21 CFR 520.1182 - Iron dextran suspension.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Iron dextran suspension. 520.1182 Section 520.1182... DRUGS, FEEDS, AND RELATED PRODUCTS ORAL DOSAGE FORM NEW ANIMAL DRUGS § 520.1182 Iron dextran suspension. (a) Specifications. Each milliliter (mL) of suspension contains 55.56 milligrams (mg) iron as...

  16. 21 CFR 520.1182 - Iron dextran suspension.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Iron dextran suspension. 520.1182 Section 520.1182... DRUGS, FEEDS, AND RELATED PRODUCTS ORAL DOSAGE FORM NEW ANIMAL DRUGS § 520.1182 Iron dextran suspension. (a) Specifications. Each milliliter (mL) of suspension contains 55.56 milligrams (mg) iron as...

  17. 21 CFR 520.1182 - Iron dextran suspension.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Iron dextran suspension. 520.1182 Section 520.1182... DRUGS, FEEDS, AND RELATED PRODUCTS ORAL DOSAGE FORM NEW ANIMAL DRUGS § 520.1182 Iron dextran suspension. (a) Specifications. Each milliliter (mL) of suspension contains 55.56 milligrams (mg) iron as...

  18. 21 CFR 520.1182 - Iron dextran suspension.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Iron dextran suspension. 520.1182 Section 520.1182... DRUGS, FEEDS, AND RELATED PRODUCTS ORAL DOSAGE FORM NEW ANIMAL DRUGS § 520.1182 Iron dextran suspension. (a) Specifications. Each milliliter (mL) of suspension contains 55.56 milligrams (mg) iron as...

  19. Level densities of iron isotopes and lower-energy enhancement of y-strength function

    SciTech Connect

    Voinov, A V; Grimes, S M; Agvaanluvsan, U; Algin, E; Belgya, T; Brune, C R; Guttormsen, M; Hornish, M J; Massey, T N; Mitchell, G; Rekstad, J; Schiller, A; Siem, S

    2005-08-30

    The neutron spectrum from the {sup 55}Mn(d,n){sup 56}Fe reaction has been measured at E{sub d} = 7 MeV. The level density of {sup 56}Fe obtained from neutron evaporation spectrum has been compared to the level density from Oslo-type {sup 57}Fe({sup 3}He, a{gamma}){sup 56}Fe experiment [1]. The good agreement supports the recent results [1, 8] including an availability of a low-energy enhancement in the {gamma}-strength function for iron isotopes. The new level density function allowed us to investigate an excitation energy dependence of this enhancement, which is shown to increase with increasing excitation energy.

  20. From allylic alcohols to aldols by using iron carbonyls as catalysts: computational study on a novel tandem isomerization-aldolization reaction.

    PubMed

    Branchadell, Vicenç; Crévisy, Christophe; Grée, René

    2004-11-01

    The tandem isomerization-aldolization reaction between allyl alcohol and formaldehyde mediated by [Fe(CO)3] was studied with the density functional B3LYP method. Starting from the key [(enol)Fe(CO)3] complex, several reaction paths for the reaction with formaldehyde were explored. The results show that the most favorable reaction path involves first an enol/allyl alcohol ligand-exchange process followed by direct condensation of formaldehyde with the free enol. During this process, formation of the new C-C bond takes place simultaneously with a proton transfer between the enol and the aldehyde. Therefore, the role of [Fe(CO)3] is to catalyze the allyl alcohol to enol isomerization affording the free enol, which adds to the aldehyde in a carbonyl-ene type reaction. Similar results were obtained for the reaction between allyl alcohol and acetaldehyde. PMID:15472940

  1. Graphitic encapsulation of MgO and Fe{sub 3}C nanoparticles in the reaction of iron pentacarbonyl with magnesium

    SciTech Connect

    Dyjak, Sławomir; Cudziło, Stanisław; Polański, Marek; Budner, Bogusław; Bystrzycki, Jerzy

    2013-07-15

    A simple method to produce highly ordered carbon nanostructures by combustion synthesis is presented. Graphite-encapsulated magnesium oxide, iron carbide nanoparticles and carbon nanobelts were synthesized by the one-step reduction of iron pentacarbonyl with magnesium. High-resolution transmission electron microscopy analysis of the products revealed nanocrystalline MgO and Fe{sub 3}C particles surrounded by a well-crystallized, tight graphite film. The possible formation mechanism is presented and discussed. - Highlights: • We present a simple method to produce highly ordered carbon nanostructures by combustion synthesis. • The cubic MgO particles are completely coated by tight graphitic shells. • The mechanism of formation a distant carbon film on MgO surface has been discussed. • The presented method can be applied to synthesis of other core-shell structures.

  2. 7 CFR 319.56-56 - Fresh pomegranates from Chile.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ....56-56 Agriculture Regulations of the Department of Agriculture (Continued) ANIMAL AND PLANT HEALTH... site where the fruit is grown must be registered with the national plant protection organization (NPPO... with a liquid soap and water solution, washed with water at high pressure, and washed with water at...

  3. 7 CFR 319.56-56 - Fresh pomegranates from Chile.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ....56-56 Agriculture Regulations of the Department of Agriculture (Continued) ANIMAL AND PLANT HEALTH... site where the fruit is grown must be registered with the national plant protection organization (NPPO... with a liquid soap and water solution, washed with water at high pressure, and washed with water at...

  4. A simple protocol for the synthesis of dinitrosyl iron complexes with glutathione: EPR, optical, chromatographic and biological characterization of reaction products.

    PubMed

    Borodulin, Rostislav R; Kubrina, Lyudmila N; Shvydkiy, Vyacheslav O; Lakomkin, Vladimir L; Vanin, Anatoly F

    2013-11-30

    The diamagnetic binuclear form of dinitrosyl iron complexes (B-DNIC) with glutathione can be easily synthesized in the air at ambient temperature. The synthetic protocol includes consecutive addition to distilled water of glutathione, which decreases the pH of the test solution to 4.0, a bivalent iron salt (e.g., ferrous sulphate) and sodium nitrite at the molar ratio of 2:1:1, with a subsequent increase in pH to neutral values. Under these conditions, the amount of B-DNIC formed is limited by initial nitrite concentration. In the novel procedure, 20mM glutathione, 10mM ferrous sulfate and 10mM sodium nitrite give 2.5mM B-DNIC with glutathione, while 5mM glutathione remains in the solution. Bivalent iron (5mM) is precipitated in the form of hydroxide complexes, which can be removed from the solution by passage through a paper filter. After the increase in рН to 11 and addition of thiols at concentrations exceeding that of DNIC tenfold, B-DNIC are converted into a mononuclear EPR-active form of DNIC (M-DNIC) with glutathione. B-DNIC preparations synthesized by using new method contain negligible amount of nitrite or S-nitrosoglutathione as a contaminations. All the steps of DNIC synthesis were characterized by using optical, EPR and HPLC methods. A long-lasting hypotensive action of DNIC formed was demonstrated. PMID:24018466

  5. The formation of Mg,Fe-silicates by reactions between amorphous magnesiosilica smoke particles and metallic iron nanograins with implications for comet silicate origins

    NASA Astrophysics Data System (ADS)

    Rietmeijer, Frans J. M.; Nuth, Joseph A.; Pun, Aurora

    2013-10-01

    This thermal annealing experiment at 1000 K for up to 167 h used a physical mixture of vapor phase-condensed magnesiosilica grains and metallic iron nanograins to test the hypothesis that a mixture of magnesiosilica grains and an Fe-source would lead to the formation of ferromagnesiosilica grains. This exploratory study found that coagulation and thermal annealing of amorphous magnesiosilica and metallic grains yielded ferromagnesiosilica grains with the Fe/(Fe + Mg) ratios in interplanetary dust particles. Furthermore, decomposition of brucite present in the condensed magnesiosilica grains was the source for water and the cause of different iron oxidation states, and the formation of amorphous Fe3+-ferrosilica, amorphous Fe3+-Mg, Fe-silicates, and magnesioferrite during thermal annealing. Fayalite and ferrosilite that formed from silica/FeO melts reacted with forsterite and enstatite to form Mg, Fe-silicates. The presence of iron in different oxidation states in extraterrestrial materials almost certainly requires active asteroid-like parent bodies. If so, the possible presence of trivalent Fe compounds in comet P/Halley suggests that Halley-type comets are a mixture of preserved presolar and processed solar nebula dust. The results from this thermal annealing experiment further suggest that the Fe-silicates detected in the impact-induced ejecta from comet 9P/Temple 1 might be of secondary origin and related to the impact experiment or to processing in a regolith.

  6. A model for Cryogenian iron formation

    NASA Astrophysics Data System (ADS)

    Cox, Grant M.; Halverson, Galen P.; Poirier, André; Le Heron, Daniel; Strauss, Justin V.; Stevenson, Ross

    2016-01-01

    The Neoproterozoic Tatonduk (Alaska) and Holowilena (South Australia) iron formations share many characteristics including their broadly coeval (Sturtian) ages, intimate association with glaciogenic sediments, and mineralogy. We show that these shared characteristics extend to their neodymium (εNd) and iron isotope (δ56Fe) systematics. In both regions δ56Fe values display a distinct up-section trend to isotopically heavier values, while εNd values are primitive and similar to non-ferruginous mudstones within these successions. The δ56Fe profiles are consistent with oxidation of ferruginous waters during marine transgression, and the εNd values imply that much of this iron was sourced from the leaching of continental margin sediments largely derived from continental flood basalts. Rare earth element data indicate a secondary hydrothermal source for this iron.

  7. Intravenous iron-containing products: EMA procrastination.

    PubMed

    2014-07-01

    A European reassessment has led to identical changes in the summaries of product characteristics (SPCs) for all intravenous iron-containing products: the risk of serious adverse effects is now highlighted, underlining the fact that intravenous iron-containing products should only be used when the benefits clearly outweigh the harms. Unfortunately, iron dextran still remains on the market despite a higher risk of hypersensitivity reactions than with iron sucrose. PMID:25162093

  8. Iron homeostasis and eye disease

    PubMed Central

    Loh, Allison; Hadziahmetovic, Majda; Dunaief, Joshua L.

    2009-01-01

    Summary Iron is necessary for life, but excess iron can be toxic to tissues. Iron is thought to damage tissues primarily by generating oxygen free radicals through the Fenton reaction. We present an overview of the evidence supporting iron's potential contribution to a broad range of eye disease using an anatomical approach. Firstly, iron can be visualized in the cornea as iron lines in the normal aging cornea as well as in diseases like keratoconus and pterygium. In the lens, we present the evidence for the role of oxidative damage in cataractogenesis. Also, we review the evidence that iron may play a role in the pathogenesis of the retinal disease age-related macular degeneration. Although currently there is no direct link between excess iron and development of optic neuropathies, ferrous iron's ability to form highly reactive oxygen species may play a role in optic nerve pathology. Lastly, we discuss recent advances in prevention and therapeutics for eye disease with antioxidants and iron chelators,. PMID:19059309

  9. The Structure of the Complex between Yeast Frataxin and Ferrochelatase: CHARACTERIZATION AND PRE-STEADY STATE REACTION OF FERROUS IRON DELIVERY AND HEME SYNTHESIS.

    PubMed

    Söderberg, Christopher; Gillam, Mallory E; Ahlgren, Eva-Christina; Hunter, Gregory A; Gakh, Oleksandr; Isaya, Grazia; Ferreira, Gloria C; Al-Karadaghi, Salam

    2016-05-27

    Frataxin is a mitochondrial iron-binding protein involved in iron storage, detoxification, and delivery for iron sulfur-cluster assembly and heme biosynthesis. The ability of frataxin from different organisms to populate multiple oligomeric states in the presence of metal ions, e.g. Fe(2+) and Co(2+), led to the suggestion that different oligomers contribute to the functions of frataxin. Here we report on the complex between yeast frataxin and ferrochelatase, the terminal enzyme of heme biosynthesis. Protein-protein docking and cross-linking in combination with mass spectroscopic analysis and single-particle reconstruction from negatively stained electron microscopic images were used to verify the Yfh1-ferrochelatase interactions. The model of the complex indicates that at the 2:1 Fe(2+)-to-protein ratio, when Yfh1 populates a trimeric state, there are two interaction interfaces between frataxin and the ferrochelatase dimer. Each interaction site involves one ferrochelatase monomer and one frataxin trimer, with conserved polar and charged amino acids of the two proteins positioned at hydrogen-bonding distances from each other. One of the subunits of the Yfh1 trimer interacts extensively with one subunit of the ferrochelatase dimer, contributing to the stability of the complex, whereas another trimer subunit is positioned for Fe(2+) delivery. Single-turnover stopped-flow kinetics experiments demonstrate that increased rates of heme production result from monomers, dimers, and trimers, indicating that these forms are most efficient in delivering Fe(2+) to ferrochelatase and sustaining porphyrin metalation. Furthermore, they support the proposal that frataxin-mediated delivery of this potentially toxic substrate overcomes formation of reactive oxygen species. PMID:27026703

  10. Decay of iron(V) nitride complexes by a N-N bond-coupling reaction in solution: a combined spectroscopic and theoretical analysis.

    PubMed

    Krahe, Oliver; Bill, Eckhard; Neese, Frank

    2014-08-11

    Cryogenically trapped Fe(V) nitride complexes with cyclam-based ligands were found to decay by bimolecular reactions, forming exclusively Fe(II) compounds. Characterization of educts and products by Mössbauer spectroscopy, mass spectrometry, and spectroscopy-oriented DFT calculations showed that the reaction mechanism is reductive nitride coupling and release of dinitrogen (2 Fe(V)≡N→Fe(II)-N=N-Fe(II)→2 Fe(II)+N2). The reaction pathways, representing an "inverse" of the Haber-Bosch reaction, were computationally explored in detail, also to judge the feasibility of yielding catalytically competent Fe(V)(N). Implications for the photolytic cleavage of Fe(III) azides used to generate high-valent Fe nitrides are discussed. PMID:24839269

  11. Iron isotopes in an Archean ocean analogue

    NASA Astrophysics Data System (ADS)

    Busigny, Vincent; Planavsky, Noah J.; Jézéquel, Didier; Crowe, Sean; Louvat, Pascale; Moureau, Julien; Viollier, Eric; Lyons, Timothy W.

    2014-05-01

    Iron isotopes have been extensively used to trace the history of microbial metabolisms and the redox evolution of the oceans. Archean sedimentary rocks display greater variability in iron isotope ratios and more markedly negative values than those deposited in the Proterozoic and Phanerozoic. This increased variability has been linked to changes in either water column iron cycling or the extent of benthic microbial iron reduction through time. We tested these contrasting scenarios through a detailed study of anoxic and ferruginous Lac Pavin (France), which can serve as a modern analogue of the Archean ocean. A depth-profile in the water column of Lac Pavin shows a remarkable increase in dissolved Fe concentration (0.1-1200 μM) and δ56Fe values (-2.14‰ to +0.31‰) across the oxic-anoxic boundary to the lake bottom. The largest Fe isotope variability is found at the redox boundary and is related to partial oxidation of dissolved ferrous iron, leaving the residual Fe enriched in light isotopes. The analysis of four sediment cores collected along a lateral profile (one in the oxic layer, one at the redox boundary, one in the anoxic zone, and one at the bottom of the lake) indicates that bulk sediments, porewaters, and reactive Fe mostly have δ56Fe values near 0.0 ± 0.2‰, similar to detrital iron. In contrast, pyrite δ56Fe values in sub-chemocline cores (60, 65, and 92 m) are highly variable and show significant deviations from the detrital iron isotope composition (δ56Fepyrite between -1.51‰ and +0.09‰; average -0.93‰). Importantly, the pyrite δ56Fe values mirror the δ56Fe of dissolved iron at the redox boundary—where near quantitative sulfate and sulfide drawdown occurs—suggesting limited iron isotope fractionation during iron sulfide formation. This finding has important implications for the Archean environment. Specifically, this work suggests that in a ferruginous system, most of the Fe isotope variability observed in sedimentary pyrites can

  12. Process to Produce Iron Nanoparticle Lunar Dust Simulant Composite

    NASA Technical Reports Server (NTRS)

    Hung, Ching-cheh; McNatt, Jeremiah

    2010-01-01

    A document discusses a method for producing nanophase iron lunar dust composite simulant by heating a mixture of carbon black and current lunar simulant types (mixed oxide including iron oxide) at a high temperature to reduce ionic iron into elemental iron. The product is a chemically modified lunar simulant that can be attracted by a magnet, and has a surface layer with an iron concentration that is increased during the reaction. The iron was found to be -iron and Fe3O4 nanoparticles. The simulant produced with this method contains iron nanoparticles not available previously, and they are stable in ambient air. These nanoparticles can be mass-produced simply.

  13. Life detection experiments of the Viking Mission on Mars can be best interpreted with a Fenton oxidation reaction composed of H2O2 and Fe2+ and iron-catalysed decomposition of H2O2

    NASA Astrophysics Data System (ADS)

    Apak, Resat

    2008-10-01

    The findings of the life detection experiments carried out during the Viking mission to Mars were reinterpreted with a chemical hypothesis. The labelled release (LR), pyrolytic release (PR) and gas exchange (GEx) experiments were interpreted with Fenton chemistry. Oxygen and carbon dioxide evolution from Martian soil upon wetting and nutrient addition could be attributed to competition reactions between the Fenton-type oxidation of organic nutrients with the aqueous (hydrogen peroxide+Fe(II)) combination and the iron-catalysed decomposition of hydrogen peroxide. A substantial evolution of radioactive gas upon addition of labelled organic nutrient solution to soil, whereas the ceasing of this gas with a heat treated sample in the LR experiments, was attributed to Fenton oxidation and hydrogen peroxide thermal decomposition, respectively. The peculiar kinetics of LR and PR experiments that cannot be fully explained by other chemical or biochemical scenarios were easily explained with this new hypothesis, i.e. limitation of the Fenton reaction may arise from the depletion of reactants, the build-up of ferric hydroxide on soil and excessive scavenging by the organic nutrients of the generated hydroxyl radicals. Reabsorption or adsorption of evolved or introduced CO2 may involve the formation of carbonate compounds (e.g., magnesium carbonate and bicarbonate) on the surface of alkalinized soil as a result of the Fenton reaction. A critical evaluation of the recent biological hypothesis assuming the utilization of a hydrogen peroxide water intracellular fluid by putative organisms (Houtkooper & Schulze-Makuch 2007) is also made.

  14. Water-gas shift reaction

    SciTech Connect

    Newsome, D.S.

    1980-01-01

    A review covers the industrial applications of the water-gas shift reaction in hydrogen manufacturing, removing CO from ammonia synthesis feeds, and detoxifying town gas; and the catalyst characteristics, reaction kinetics, and reaction mechanisms of the water-gas shift reactions catalyzed by iron-based, copper-based, or sulfided cobalt-molybdenum catalysts.

  15. Inorganic Reaction Mechanisms. Part I

    ERIC Educational Resources Information Center

    Cooke, D. O.

    1976-01-01

    Provides a collection of data on the mechanistic aspects of inorganic chemical reactions. Wherever possible includes procedures for classroom demonstration or student project work. The material covered includes gas phase reactions, reactions in solution, mechanisms of electron transfer, the reaction between iron III and iodine, and hydrolysis. (GS)

  16. The fate of aniline after a photo-fenton reaction in an aqueous system containing iron(III), humic acid, and hydrogen peroxide

    SciTech Connect

    Fukushima, Masami; Tatsumi, Kenji; Morimoto, Kengo

    2000-05-15

    The degradation of aniline (ArNH{sub 2}) was facilitated by light irradiation ({lambda} > 370 nm) of an aqueous solution, which contained Fe(III), humic acid(HA), and H{sub 2}O{sub 2}. The consumption of H{sub 2}O{sub 2} and the reduction of Fe(III) to Fe(II) was consistent with the degradation of ArNH{sub 2} via the photo-Fenton reaction, accompanied by the generation of hydroxyl radicals (HO{sm_bullet}). HPLC analysis of the reaction mixture indicated the presence of p-aminophenol, p-hydroquinone, and maleic and fumaric acids and the simultaneous release of NH{sub 4}{sup +} ion. However, the sum of the product concentrations, as determined by HPLC after the reaction, was much smaller than the ArNH{sub 2} concentration added initially. This can be attributed to the majority of the ArNH{sub 2} being incorporated into the polymeric structure in the HA after the reaction. The {sup 15}N NMR and pyrolysis-GC/MS studies indicated that, after the reaction, ArNH{sub 2} formed covalent bonds with quinone and the vinyl carbons in the HA, to form anilino-compounds, such as anilinoquinone and enaminone.

  17. X-56A Research Opportunities

    NASA Technical Reports Server (NTRS)

    Bosworth, John T.

    2012-01-01

    The X-56A vehicle presents an excellent research opportunity for NASA. The vehicle will be used to prove the concepts for integrated structural control and modeling of extremely lightweight flexible structures.

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

    PubMed

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

    2011-07-15

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

  19. Reactions of arsine with hemoglobin

    SciTech Connect

    Hatlelid, K.M.; Brailsford, C.; Carter, D.E.

    1996-02-09

    The mechanism of arsine (AsH{sub 3}) induced hemolysis was studied in vitro using isolated red blood cells (RBCs) from the rat or dog. AsH{sub 3}-induced hemolysis of dog red blood cells was completely blocked by carbon monoxide (CO) preincubation and was reduced by pure oxygen (O{sub 2}) compared to incubations in air. Since CO and O{sub 2} bind to heme and also reduced hemolysis, these results suggested a reaction between AsH{sub 3} and hemoglobin in the hemeligand binding pocket or with the heme iron. Further, sodium nitrite induction of methemoglobin (metHb) to 85% and 34% of total Hb in otherwise intact RBCs resulted in 56% and 16% decreases in hemolysis, respectively, after incubation for 4 h. This provided additional evidence for the involvement of hemoglobin in the AsH{sub 3}-induced hemolysis mechanism. Reactions between AsH{sub 3} and hemoglobin were studied in solutions of purified dog hemoglobin. Spectrophotometric studies of the reaction of AsH{sub 3} with various purified hemoglobin species revealed that AsH{sub 3} reacted with HbO{sub 2} to produce metHb and, eventually, degraded Hb characterized by gross precipitation of the protein. AsH{sub 3} did not alter the spectrum of deoxyHb and did not cause degradation of metHb in oxygen, but bound to and reduced metHb in the absence of oxygen. These data indicate that a reaction of AsH{sub 3} with oxygenated hemoglobin, HbO{sub 2}, may lead to hemolysis, but there are reactions between AsH{sub 3} and metHb that may not be directly involved in the hemolytic process. 17 refs., 6 figs.

  20. Iron refractory iron deficiency anemia

    PubMed Central

    De Falco, Luigia; Sanchez, Mayka; Silvestri, Laura; Kannengiesser, Caroline; Muckenthaler, Martina U.; Iolascon, Achille; Gouya, Laurent; Camaschella, Clara; Beaumont, Carole

    2013-01-01

    Iron refractory iron deficiency anemia is a hereditary recessive anemia due to a defect in the TMPRSS6 gene encoding Matriptase-2. This protein is a transmembrane serine protease that plays an essential role in down-regulating hepcidin, the key regulator of iron homeostasis. Hallmarks of this disease are microcytic hypochromic anemia, low transferrin saturation and normal/high serum hepcidin values. The anemia appears in the post-natal period, although in some cases it is only diagnosed in adulthood. The disease is refractory to oral iron treatment but shows a slow response to intravenous iron injections and partial correction of the anemia. To date, 40 different Matriptase-2 mutations have been reported, affecting all the functional domains of the large ectodomain of the protein. In vitro experiments on transfected cells suggest that Matriptase-2 cleaves Hemojuvelin, a major regulator of hepcidin expression and that this function is altered in this genetic form of anemia. In contrast to the low/undetectable hepcidin levels observed in acquired iron deficiency, in patients with Matriptase-2 deficiency, serum hepcidin is inappropriately high for the low iron status and accounts for the absent/delayed response to oral iron treatment. A challenge for the clinicians and pediatricians is the recognition of the disorder among iron deficiency and other microcytic anemias commonly found in pediatric patients. The current treatment of iron refractory iron deficiency anemia is based on parenteral iron administration; in the future, manipulation of the hepcidin pathway with the aim of suppressing it might become an alternative therapeutic approach. PMID:23729726

  1. Influence of Cd2+ on the spin state of non-heme iron and on protein local motions in reactions centers from purple photosynthetic bacterium Rhodospirilium rubrum

    NASA Astrophysics Data System (ADS)

    Lipińska, M.; Orzechowska, A.; Fiedor, J.; Chumakov, A. I.; Ślȩzak, T.; Zając, M.; Matlak, K.; Korecki, J.; Hałas, A.; Strzałka, K.; Fiedor, L.; Burda, K.

    2010-03-01

    Non-heme Fe is a conservative component of the Q-type photosynthetic reaction centers but its function remains unknown. Applying Mössbauer spectroscopy we show that in Rhodospirillum rubrum the non-heme Fe exists mostly in a ferrous low spin state. The binding of Cd2+ ions in the vicinity of the quinone-Fe complex changes the high spin state of the non-heme Fe into a low spin one characterized by hyperfine parameters similar to those obtained for the non-heme Fe low spin state in untreated reaction centers, as confirmed by Mössbauer measurements. The nuclear inelastic scattering of synchrotron radiation experiments show that the contribution of vibrations at low energies, between 3-15 meV, activated at 240 K are damped in the bacterial reaction centers treated with CdCl2. No influence of Cd2+ ions is observed on the soft vibrational states at 60 K. These results suggest that binding of cadmium cations within the reaction centers may enhance decoupling of the non-heme Fe from the surrounding protein matrix at temperatures higher than 200 K, what can explain the slowing down of electron transfer between the QA and QB quinones by Cd2+.

  2. Low-temperature approach to synthesize iron nitride from amorphous iron.

    PubMed

    Han, Yi; Wang, Huamin; Zhang, Minghui; Su, Ming; Li, Wei; Tao, Keyi

    2008-02-18

    Iron nitride was prepared by a nitridation reaction in NH 3 using amorphous iron as precursor. The precursor was prepared at ambient temperature through the process of reducing ferrous sulfate by potassium borohydride, followed by the nitridation at different temperatures. The nitridation reaction occurred at 548 K, and -Fe 2-3N was formed at 573 K. The reaction temperature was much lower than that using crystallized iron because of the characteristics of the amorphous materials. The existence of a small quantity of boron (1.6 wt.%) improved the stability of the amorphous precursor, which guaranteed an amorphous iron precursor at nitriding temperatures in excess of 548 K. PMID:18198828

  3. Patch testing with cement containing iron sulfate.

    PubMed

    Bruze, M; Fregert, S; Gruvberger, B

    1990-01-01

    Addition of iron sulfate to cement means transformation of water-soluble hexavalent chromium into nonwater-soluble trivalent chromium. This has been the basis for preventive measures concerning sensitization to hexavalent chromium (chromate) in cement. For some years, iron sulfate has been added to cement manufactured in the Scandinavian countries. In the present in vivo study, cements with and without iron sulfate were compared concerning their capacity to elicit allergic patch-test reactions in eight chromate-hypersensitive individuals. No patch-test reactions were obtained from a water extract of cement with iron sulfate when appropriately buffered. PMID:2137395

  4. Minocycline Attenuates Iron-Induced Brain Injury.

    PubMed

    Zhao, Fan; Xi, Guohua; Liu, Wenqaun; Keep, Richard F; Hua, Ya

    2016-01-01

    Iron plays an important role in brain injury after intracerebral hemorrhage (ICH). Our previous study found minocycline reduces iron overload after ICH. The present study examined the effects of minocycline on the subacute brain injury induced by iron. Rats had an intracaudate injection of 50 μl of saline, iron, or iron + minocycline. All the animals were euthanized at day 3. Rat brains were used for immunohistochemistry (n = 5-6 per each group) and Western blotting assay (n = 4). Brain swelling, blood-brain barrier (BBB) disruption, and iron-handling proteins were measured. We found that intracerebral injection of iron resulted in brain swelling, BBB disruption, and brain iron-handling protein upregulation (p < 0.05). The co-injection of minocycline with iron significantly reduced iron-induced brain swelling (n = 5, p < 0.01). Albumin, a marker of BBB disruption, was measured by Western blot analysis. Minocycline significantly decreased albumin protein levels in the ipsilateral basal ganglia (p < 0.01). Iron-handling protein levels in the brain, including ceruloplasmin and transferrin, were reduced in the minocycline co-injected animals. In conclusion, the present study suggests that minocycline attenuates brain swelling and BBB disruption via an iron-chelation mechanism. PMID:26463975

  5. Fe, C, and O isotope compositions of banded iron formation carbonates demonstrate a major role for dissimilatory iron reduction in ~2.5 Ga marine environments

    NASA Astrophysics Data System (ADS)

    Heimann, Adriana; Johnson, Clark M.; Beard, Brian L.; Valley, John W.; Roden, Eric E.; Spicuzza, Michael J.; Beukes, Nicolas J.

    2010-05-01

    Combined Fe, C, and O isotope measurements of ~ 2.5 Ga banded iron formation (BIF) carbonates from the Kuruman Iron Formation and underlying BIF and platform Ca-Mg carbonates of the Gamohaan Formation, South Africa, constrain the biologic and abiologic formation pathways in these extensive BIF deposits. Vertical intervals of up to 100 m were sampled in three cores that cover a lateral extent of ~ 250 km. BIF Fe carbonates have significant Fe isotope variability ( δ56Fe = + 1 to - 1‰) and relatively low δ13C (down to - 12‰) and δ18O values ( δ18O ~ + 21‰). In contrast, Gamohaan and stratigraphically-equivalent Campbellrand Ca-Mg carbonates have near-zero δ13C values and higher δ18O values. These findings argue against siderite precipitation from seawater as the origin of BIF Fe-rich carbonates. Instead, the C, O, and Fe isotope compositions of BIF Fe carbonates reflect authigenic pathways of formation in the sedimentary pile prior to lithification, where microbial dissimilatory iron reduction (DIR) was the major process that controlled the C, O, and Fe isotope compositions of siderite. Isotope mass-balance reactions indicate that the low- δ13C and low- δ18O values of BIF siderite, relative to those expected for precipitation from seawater, reflect inheritance of C and O isotope compositions of precursor organic carbon and ferric hydroxide that were generated in the photic zone and deposited on the seafloor. Carbon-Fe isotope relations suggest that BIF Fe carbonates formed through two end-member pathways: low- δ13C, low- δ56Fe Fe carbonates formed from remobilized, low- δ56Fe aqueous Fe 2+ produced by partial DIR of iron oxide, whereas low- δ13C, high- δ56Fe Fe carbonates formed by near-complete DIR of high- δ56Fe iron oxides that were residual from prior partial DIR. An important observation is the common occurrence of iron oxide inclusions in the high- δ56Fe siderite, supporting a model where such compositions reflect DIR "in place" in the soft

  6. Intravenous Iron Therapy in Patients with Iron Deficiency Anemia: Dosing Considerations.

    PubMed

    Koch, Todd A; Myers, Jennifer; Goodnough, Lawrence Tim

    2015-01-01

    Objective. To provide clinicians with evidence-based guidance for iron therapy dosing in patients with iron deficiency anemia (IDA), we conducted a study examining the benefits of a higher cumulative dose of intravenous (IV) iron than what is typically administered. Methods. We first individually analyzed 5 clinical studies, averaging the total iron deficit across all patients utilizing a modified Ganzoni formula; we then similarly analyzed 2 larger clinical studies. For the second of the larger studies (Study 7), we also compared the efficacy and retreatment requirements of a cumulative dose of 1500 mg ferric carboxymaltose (FCM) to 1000 mg iron sucrose (IS). Results. The average iron deficit was calculated to be 1531 mg for patients in Studies 1-5 and 1392 mg for patients in Studies 6-7. The percentage of patients who were retreated with IV iron between Days 56 and 90 was significantly (p < 0.001) lower (5.6%) in the 1500 mg group, compared to the 1000 mg group (11.1%). Conclusions. Our data suggests that a total cumulative dose of 1000 mg of IV iron may be insufficient for iron repletion in a majority of patients with IDA and a dose of 1500 mg is closer to the actual iron deficit in these patients. PMID:26257955

  7. Intravenous Iron Therapy in Patients with Iron Deficiency Anemia: Dosing Considerations

    PubMed Central

    Koch, Todd A.; Myers, Jennifer; Goodnough, Lawrence Tim

    2015-01-01

    Objective. To provide clinicians with evidence-based guidance for iron therapy dosing in patients with iron deficiency anemia (IDA), we conducted a study examining the benefits of a higher cumulative dose of intravenous (IV) iron than what is typically administered. Methods. We first individually analyzed 5 clinical studies, averaging the total iron deficit across all patients utilizing a modified Ganzoni formula; we then similarly analyzed 2 larger clinical studies. For the second of the larger studies (Study 7), we also compared the efficacy and retreatment requirements of a cumulative dose of 1500 mg ferric carboxymaltose (FCM) to 1000 mg iron sucrose (IS). Results. The average iron deficit was calculated to be 1531 mg for patients in Studies 1–5 and 1392 mg for patients in Studies 6-7. The percentage of patients who were retreated with IV iron between Days 56 and 90 was significantly (p < 0.001) lower (5.6%) in the 1500 mg group, compared to the 1000 mg group (11.1%). Conclusions. Our data suggests that a total cumulative dose of 1000 mg of IV iron may be insufficient for iron repletion in a majority of patients with IDA and a dose of 1500 mg is closer to the actual iron deficit in these patients. PMID:26257955

  8. Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III) Reaction Intermediate Models of Peroxidase Enzymes.

    PubMed

    Hernández Anzaldo, Samuel; Arroyo Abad, Uriel; León García, Armando; Ramírez Rosales, Daniel; Zamorano Ulloa, Rafael; Reyes Ortega, Yasmi

    2016-01-01

    The spectroscopic and kinetic characterization of two intermediates from the H₂O₂ oxidation of three dimethyl ester [(proto), (meso), (deuteroporphyrinato) (picdien)]Fe(III) complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively) pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III) quantum mixed spin (qms) ground states is described herein. The kinetic study by UV/Vis at λmax = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1-3 + guaiacol + H₂O₂ → oxidation guaiacol products). The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III) and H₂O₂, resulting in only two types of kinetics that were developed during the first 0-4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III) family with the ligand picdien [N,N'-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, ¹H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity. PMID:27355940

  9. Reactions of cationic transition metal acetonitrile complexes [M(CH3CN)n]m+ with GaCp*: novel gallium complexes of iron, cobalt, copper and silver.

    PubMed

    Bollermann, Timo; Puls, Arik; Gemel, Christian; Cadenbach, Thomas; Fischer, Roland A

    2009-02-28

    The reactions of the cationic transition metal acetonitrile complexes [M(CH3CN)n]m+ (m = 2: M = Fe, Co and m = 1: M = Cu, Ag) with GaCp* were investigated. The reaction of [Fe(CH3CN)6][BArF]2 (BAr(F) = [B{C6H3(CF3)2}4) with GaCp* leads to [Cp*Fe(GaCp*)3][BAr(F)] (1) via a redox neutral Cp* transfer and [Ga2Cp*][BAr(F)] as a by-product while the formation of [Cp*Co(GaCp*)3][BAr(F)]2 (2) from [Co(CH3CN)6][BAr(F)]2 is accompanied by oxidation of Co(II) to Co(III) with GaCp* as the oxidant. The reactions of [Cu(CH3CN)4][BAr(F)] and Ag[BPh4] with GaCp* lead to the formation of the homoleptic compounds [Cu(GaCp*)4][BAr(F)] (4) and [Ag(GaCp*)4][BPh4] (5), while treatment of Ag[CF3SO3] with GaCp* leads to the dimeric complex [Ag2(GaCp*)3(micro-GaCp*)2][CF3SO3]2 (6). All compounds were characterized by NMR spectroscopy, single crystal X-ray diffraction and elemental analysis. PMID:19462658

  10. Molecular catalysis of the oxygen reduction reaction by iron porphyrin catalysts tethered into Nafion layers: An electrochemical study in solution and a membrane-electrode-assembly study in fuel cells

    NASA Astrophysics Data System (ADS)

    He, Qinggang; Mugadza, Tawanda; Kang, Xiongwu; Zhu, Xiaobing; Chen, Shaowei; Kerr, John; Nyokong, Tebello

    2012-10-01

    This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV-Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.

  11. Theoretical investigation for the cycle reaction of N2O (x1∑+) with CO (1∑+) catalyzed by IrO(n)+ (n = 1, 2) and utilizing the energy span model to study its kinetic information.

    PubMed

    Nian, JingYan; Wang, YongCheng; Ma, WeiPeng; Ji, DaFang; Wang, CuiLan; La, MaoJi

    2011-10-13

    The mechanisms of the reactions between N(2)O and CO catalyzed by IrO(n)(+) (n = 1, 2) have been investigated using B3LYP and CCSD(T) levels of theory. Spin inversion among three reaction profiles corresponding to the quintet, triplet, and singlet multiplicities was discussed by using spin-orbit coupling (SOC) calculations. The probability of electron hopping in the vicinity of the (MECP) has been calculated by the Landau-Zener-type model. The single P(1)(ISC) and double P(2)(ISC) passes estimated at MECP1(#) (SOC = 198.61 cm(-1)) are approximately 0.11 and 0.20, respectively. Important analysis and explanations were done using molecular orbital theory and natural bonding orbital (NBO). The energetic span (δE) model coined by Kozuch was applied in this cycle. The turnover frequency (TOF)-determining transition state (TDTS) and TDI (TOF-determining intermediate) were confirmed. Finally, TOF(IrO(+))/TOF(IrO(2)(+)) = 0.38 at 298 K. PMID:21882822

  12. Optimization of the synthesis process of an iron oxide nanocatalyst supported on activated carbon for the inactivation of Ascaris eggs in water using the heterogeneous Fenton-like reaction.

    PubMed

    Morales-Pérez, Ariadna A; Maravilla, Pablo; Solís-López, Myriam; Schouwenaars, Rafael; Durán-Moreno, Alfonso; Ramírez-Zamora, Rosa-María

    2016-01-01

    An experimental design methodology was used to optimize the synthesis of an iron-supported nanocatalyst as well as the inactivation process of Ascaris eggs (Ae) using this material. A factor screening design was used for identifying the significant experimental factors for nanocatalyst support (supported %Fe, (w/w), temperature and time of calcination) and for the inactivation process called the heterogeneous Fenton-like reaction (H2O2 dose, mass ratio Fe/H2O2, pH and reaction time). The optimization of the significant factors was carried out using a face-centered central composite design. The optimal operating conditions for both processes were estimated with a statistical model and implemented experimentally with five replicates. The predicted value of the Ae inactivation rate was close to the laboratory results. At the optimal operating conditions of the nanocatalyst production and Ae inactivation process, the Ascaris ova showed genomic damage to the point that no cell reparation was possible showing that this advanced oxidation process was highly efficient for inactivating this pathogen. PMID:26942520

  13. The role of thiol and nitrosothiol compounds in the nitric oxide-forming reactions of the iron-N-methyl-d-glucamine dithiocarbamate complex.

    PubMed Central

    Tsuchiya, Koichiro; Kirima, Kazuyoshi; Yoshizumi, Masanori; Houchi, Hitoshi; Tamaki, Toshiaki; Mason, Ronald P

    2002-01-01

    The object of the present study is to investigate whether the physiologically dominant thiol compounds such as GSH and cysteine or their nitrosothiol compounds affect the formation of the iron- N -methyl-D-glucamine dithiocarbamate [(MGD)(2)Fe(2+)]-nitric oxide complex. The present study provided experimental evidence that physiological concentrations of GSH (approx. 5 mM) and L-cysteine (approx. 0.5 mM) accelerated the formation of the (MGD)(2)Fe(2+)-NO complex from nitrite by two and three times respectively. The rate constants for the reduction of (MGD)(3)Fe(3+) to (MGD)(2)Fe(2+) by GSH and cysteine were calculated as 1.3 and 2.0x10(2) M(-1).s(-1) respectively. Furthermore, depletion of GSH was demonstrated in PC12 cells, and thiol compounds enhanced the formation of reactive oxygen species by the (MGD)(2)Fe(2+) complex by accelerating its redox turnover. The main effect of the physiological concentration of thiols was the reduction of (MGD)(3)Fe(3+). S -nitrosoglutathione spontaneously reacted with (MGD)(2)Fe(2+) to produce the (MGD)(2)Fe(2+)-NO complex with a 1:2 stoichiometry. In fact, (MGD)(2)Fe(2+) was as good an indicator of nitrosothiols as it was of NO itself. The present study elucidates the difficulties of utilizing the (MGD)(2)Fe(2+) complex for the quantification of NO in biological samples, especially in vivo. PMID:12141947

  14. The structure of iron-oxyhydroxide mounds affected by iron-oxidizing bacteria at shallow submarine hydrothermal vent in Satsuma Iwo-Jima

    NASA Astrophysics Data System (ADS)

    Kuratomi, T.; Kiyokawa, S.; Ikehara, M.; Goto, S.; Hoshino, T.; Ikegami, F.; Minowa, Y.

    2014-12-01

    Satsuma Iwo-Jima, located 38km south of Kyusyu island, Japan, is preserved and identified on occurring iron precipitation at shallow ocean where can be recorded modern analogy of iron precipitation and sedimentation. This is a volcanic island in the northwestern rim of Kikai caldera. Iron- and silica-rich mounds (0.5-3m wide and 0.2-7m high) are developing with hydrothermal activity (pH=5.5, 50-60 degree Celsius), and there is high deposition rate of iron-oxides (33 cm/year). In this study, we analyzed samples (20-30 cm long) recovered from iron oxidized mounds at seafloor by the observation with CT scan, FE-SEM and thin-sectioned samples, and the chemical analysis with EDS, XRF, XRD and DNA, and found that the structure of mounds has unique information. Each mounds are formed two layers: blackish hard layer and brownish soft layer. The inside of samples is constructed from the aggregation of convex structure (3-4 cm) covered by hard layers as a rim. Petrographic observations indicate that both layers have filament-like forms, and the form in soft layer is perpendicular to that in the hard layer. The number of iron oxides particles observed on filament-like forms in soft layer increases toward hard layer. Hard layer consists of aggregation of bacillus-like form as the chain of particle (about 2 um). At soft layer, on the other hand, bacteria-like form with smaller particles (<0.5 um) is observed. Bacteria-like form could be classified into 3 types (helix, ribbon-like, twisted). Furthermore, hard layers consist of ferrihydrite and opal-A (Si: 26.8%, Fe: 56.0%) and soft one is composed by ferrihydrite, opal-A and silica mineral (Si: 36.5%, Fe: 43.5%). Mariprofundus ferrooxydansknown as iron-oxidizing bacteria belonging to Zeta-proteobacteria identified in this matter. Bacteria-like form is considered to be the stalk made by iron-oxidizing bacteria. Such neutrophilic iron-oxidizing bacteria prefers an environment of redox interface between hydrothermal water and

  15. Iron (II)-chelating activity of buffalo αS-casein hydrolysed by corolase PP, alcalase and flavourzyme.

    PubMed

    Jaiswal, Arvind; Bajaj, Rajesh; Mann, Bimlesh; Lata, Kiran

    2015-06-01

    Iron is a vital substance for human health which participates in many biochemical reactions. It also act as initiator for many harmful oxidative process. Buffalo αS-casein enriched fraction (80 %) was hydrolysed independently by corolase PP (H1), alcalase (H2), flavourzyme (H3) and sequentially by alcalase-flavourzyme (H4). After ultrafiltration (10 and 3 kDa) hydrolysates were analysed for their iron chelation activity using ferrozine. For H1 group of hydrolysates highest iron (II)-chelation activity (265.58 μM Fe(2+/)mg protein) was found after 8 h of hydrolysis for H2 (267.56 μM Fe(2+/)mg protein) and H3 group of hydrolysates (380.68 μM Fe(2+/)mg protein) after 6 h of hydrolysis. Sequential hydrolysis was not effective for iron (II)-chelation activity. 3 kDa fractions show higher iron (II)-chelation activity than 10 kDa fraction. Flavourzyme was more effective for generation of iron (II)-chelating peptides from buffalo αS-casein. PMID:26028776

  16. Removal of Metallic Iron on Oxide Slags

    NASA Astrophysics Data System (ADS)

    Shannon, George N.; Fruehan, R. J.; Sridhar, Seetharaman

    2009-10-01

    It is possible, in some cases, for ground coal particles to react with gasifier gas during combustion, allowing the ash material in the coal to form phases besides the expected slag phase. One of these phases is metallic iron, because some gasifiers are designed to operate under a reducing atmosphere ({p_{O2}} of approximately 10-4 atm). Metallic iron can become entrained in the gas stream and deposit on, and foul, downstream equipment. To improve the understanding of the reaction between different metallic iron particles and gas, which eventually oxidizes them, and the slag that the resulting oxide dissolves in, the kinetics of iron reaction on slag were predicted using gas-phase mass-transfer limitations for the reaction and were compared with diffusion in the slag; the reaction itself was observed under confocal scanning laser microscopy. The expected rates for iron droplet removal are provided based on the size and effective partial pressure of oxygen, and it is found that decarburization occurs before iron reaction, leading to an extra 30- to 100-second delay for carbon-saturated particles vs pure iron particles. A pure metallic iron particle of 0.5 mg should be removed in about 220 seconds at 1400 °C and in 160 seconds at 1600 °C.

  17. Removal of metallic iron on oxide slags

    SciTech Connect

    Shannon, G.N.; Fruehan, R.J.; Sridhar, S.

    2009-10-15

    It is possible, in some cases, for ground coal particles to react with gasifier gas during combustion, allowing the ash material in the coal to form phases besides the expected slag phase. One of these phases is metallic iron, because some gasifiers are designed to operate under a reducing atmosphere (pO{sub 2}) of approximately 10{sup -4} atm). Metallic iron can become entrained in the gas stream and deposit on, and foul, downstream equipment. To improve the understanding of the reaction between different metallic iron particles and gas, which eventually oxidizes them, and the slag that the resulting oxide dissolves in, the kinetics of iron reaction on slag were predicted using gas-phase mass-transfer limitations for the reaction and were compared with diffusion in the slag; the reaction itself was observed under confocal scanning laser microscopy. The expected rates for iron droplet removal are provided based on the size and effective partial pressure of oxygen, and it is found that decarburization occurs before iron reaction, leading to an extra 30- to 100-second delay for carbon-saturated particles vs pure iron particles. A pure metallic iron particle of 0.5 mg should be removed in about 220 seconds at 1400{sup o}C and in 160 seconds at 1600{sup o}C.

  18. Proof of Concept: Magnetic Fixation of Dendron-Functionalized Iron Oxide Nanoparticles Containing Palladium Nanoparticles for Continuous-Flow Suzuki Coupling Reactions.

    PubMed

    Rehm, Thomas H; Bogdan, Anca; Hofmann, Christian; Löb, Patrick; Shifrina, Zinaida B; Morgan, David G; Bronstein, Lyudmila M

    2015-12-16

    A new concept for the magnetic immobilization of catalytically active material has been developed for continuous-flow Suzuki cross-coupling reactions. The reversible immobilization of the magnetic catalyst material inside a novel capillary microreactor has been achieved by utilizing a newly designed reactor housing with 208 small permanent magnets. As a catalyst material, magnetic Fe3O4 nanoparticles decorated with polyphenylenepyridyl dendrons and loaded with Pd nanoparticles have been employed. Both batch and continuous-flow experiments prove the activity of the catalyst and the applicability of this new microreactor concept. PMID:26581446

  19. Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

    USGS Publications Warehouse

    Balci, N.; Bullen, T.D.; Witte-Lien, K.; Shanks, Wayne C.; Motelica, M.; Mandernack, K.W.

    2006-01-01

    Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42- and Cl- salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor ??Fe(III)aq-Fe(II)aq???1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (???1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (???1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9??? (??Fe(III)aq-Fe(II)aq ???1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments

  20. High temperature corrosion studies. A. Iron: based superalloy in SO/sub 2//O/sub 2/ atmospheres. B. Gas: solid reaction with formation of volatile species

    SciTech Connect

    Liu, T.K.

    1980-03-01

    The thermogravimetric method was used to study high temperature corrosion under SO/sub 2//O/sub 2/ atmosphere applied to Armco 18SR alloys with different heat treatment histories, Armco T310 and pure chromium between 750 and 1100/sup 0/C. The weight gain follows the parabolic rate law. The volatilization of the protective Cr/sub 2/O/sub 3/ layer via formation of CrO/sub 3/ was taken into account above 900/sup 0/C for long time runs. The parabolic rate and the volatilization rate, derived from fitting the experimental data to the modified Tedmon's non-linear model, were correlated using the Arrhenius equation. Armco 18SR-C has the best corrosion resistance of the Armco 18SR alloys. Armco T310 is not protective at high temperatures. The available rate data on the oxidation of chromium oxide, chlorination of chromium, oxidation-chlorination of chromium oxide, chlorination of nickel and chlorination of iron were found to be predictable. The calculation of high temperature volatilization rate was performed using the available fluid correlation equations and the Lennard-Jones parameters derived from the molecule with similar structure and from the low temperature viscosity measurement. The lower predicted volatilization rate is due to the use of the Chapman-Enskog equation with the Lennard-Jones parameters mostly derived from the low temperature viscosity measurement. This was substantiated by comparing the reliable high temperature diffusion rate in the literature with the above mentioned calculational method. The experimental volatilization rates of this study are compared with the other related studies and the mass transfer predictions.

  1. Iron contamination in silicon technology

    NASA Astrophysics Data System (ADS)

    Istratov, A. A.; Hieslmair, H.; Weber, E. R.

    This article continues the review of fundamental physical properties of iron and its complexes in silicon (Appl. Phys. A 69, 13 (1999)), and is focused on ongoing applied research of iron in silicon technology. The first section of this article presents an analysis of the effect of iron on devices, including integrated circuits, power devices, and solar cells. Then, sources of unintentional iron contamination and reaction paths of iron during device manufacturing are discussed. Experimental techniques to measure trace contamination levels of iron in silicon, such as minority carrier lifetime techniques (SPV, μ-PCD, and ELYMAT), deep-level transient spectroscopy (DLTS), total X-ray fluorescence (TXRF) and vapor-phase decomposition TXRF (VPD-TXRF), atomic absorption spectroscopy (AAS), mass spectrometry and its modifications (SIMS, SNMS, ICP-MS), and neutron activation analysis (NAA) are reviewed in the second section of the article. Prospective analytical tools, such as heavy-ion backscattering spectroscopy (HIBS) and synchrotron-based X-ray microprobe techniques (XPS, XANES, XRF) are briefly discussed. The third section includes a discussion of the present achievements and challenges of the electrochemistry and physics of cleaning of silicon wafers, with an emphasis on removal of iron contamination from the wafers. Finally, the techniques for gettering of iron are presented.

  2. Results from the NSCL TOF Mass Measurement of Neutron-rich Isotopes of Argon through Iron

    NASA Astrophysics Data System (ADS)

    Meisel, Zachary; George, Sebastian; NSCL TOF Collaboration

    2015-04-01

    A recent experiment at the National Superconducting Cyclotron Laboratory has resulted in an extension of the nuclear mass surface for neutron-rich isotopes of argon through iron. The time-of-flight technique was employed to experimentally determine the masses of several nuclei for the first time. Results include the identification of argon as the lowest even- Z element exhibiting the N = 28 shell closure, as well the uncovering of a relatively small odd-even mass stagger between 56 Ti and 56 Sc. The latter result yields strong Urca cooling when implemented in a state-of-the-art accreted neutron star crust reaction network. A strong 56 Ti-56 Sc Urca neutrino cooling layer makes shallow neutrino cooling in the crust of accreting neutron stars a strong and robust effect due to the copious production of A = 56 material in thermonuclear burning processes that occur at the accreted neutron star surface. This project is funded by the NSF through Grants 247 No. PHY-0822648, PHY-1102511, PHY-1404442, and 248 No. PHY-1430152. S.G. acknowledges support from 249 the DFG under Contracts No. GE2183/1-1 and No. 250 GE2183/2-1.

  3. Thermochemistry of the activation of N2 on iron cluster cations: Guided ion beam studies of the reactions of Fen+ (n=1-19) with N2

    NASA Astrophysics Data System (ADS)

    Tan, Lin; Liu, Fuyi; Armentrout, P. B.

    2006-02-01

    The kinetic energy dependences of the reactions of Fen+ (n=1-19) with N2 are studied in a guided ion beam tandem mass spectrometer over the energy range of 0-15eV. In addition to collision-induced dissociation forming Fem+ ions, which dominate the product spectra, a variety of FemN2+ and FemN+ product ions, where m ⩽n, is observed. All processes are observed to exhibit thresholds. Fem+-N and Fem+-2N bond energies as a function of cluster size are derived from the threshold analysis of the kinetic energy dependences of the endothermic reactions. The trends in this thermochemistry are compared to the isoelectronic D0(Fen+-CH), and to bulk phase values. A fairly uniform barrier of 0.48±0.03eV at 0K is observed for formation of the FenN2+ product ions (n =12, 15-19) and can be related to the rate-limiting step in the Haber process for catalytic ammonia production.

  4. Model studies in cytochrome P-450 mediated toxicity of halogenated compounds: radical processes involving iron porphyrins

    SciTech Connect

    Brault, D.

    1985-12-01

    Haloalkane toxicity originates from attack on biological targets by reactive intermediates derived from haloalkane metabolism by a hemoprotein, cytochrome P-450. Carbon-centered radicals and their peroxylderivatives are most likely involved. The reactions of iron porphyrin - a model for cytochrome P-450 - with various carbon-centered and peroxyl radicals generated by pulse radiolysis are examined. Competition between iron porphyrin and unsaturated fatty acids for attack by peroxyl radicals is pointed out. These kinetic data are used to derive a model for toxicity of haloalkanes with particular attention to carbon tetrachloride and halothane. The importance of local oxygen concentration and structural arrangement of fatty acids around cytochrome P-450 is emphasized. 56 references.

  5. The relationship between the iron isotopic composition of human whole blood and iron status parameters.

    PubMed

    Van Heghe, Lana; Delanghe, Joris; Van Vlierberghe, Hans; Vanhaecke, Frank

    2013-11-01

    As the iron status of an individual cannot be adequately assessed on the basis of the (total) Fe concentration in whole blood or serum, in medicine a number of parameters, such as the serum concentrations of ferritin, transferrin and soluble transferrin receptor and the transferrin saturation, are routinely determined instead. As previous research has shown that also the isotopic composition of Fe in blood and tissues is dependent on the metabolism, the present study assessed whether Fe isotopic composition in whole blood provides information as to an individual's iron status. Fe isotopic analysis of whole blood samples from a reference population (healthy volunteers) was carried out using multi-collector ICP-mass spectrometry (after chromatographic target element isolation) and the results obtained were investigated by statistical means as to their potential relation with the iron status parameters conventionally used in medicine. A low δ(56)Fe value was demonstrated to coincide with high iron status and a high δ(56)Fe value with low iron status, thus reflecting the response of the body to this iron status in terms of iron uptake, distribution between blood and stores and mobilization of storage iron. In a second phase, the iron isotopic composition in blood from patients treated for hemochromatosis type I and from patients with anemia of chronic disease (ACD) was determined. The results for hemochromatosis patients plotted with the values of low iron status, while those for ACD patients plotted with the values of high iron status. By taking a closer look at the aberrant iron metabolism that comes with these diseases, it can be seen that the patient samples confirm the conclusions drawn for the reference population. Patients with hemochromatosis type I have a strongly upregulated iron uptake, like healthy individuals with low iron status. The metabolism of patients suffering from ACD tries to remove iron from the circulation by downregulating the iron uptake

  6. Neutrino Energy Loss Rates due to {sup 54,55,56}Fe in Stellar Environment

    SciTech Connect

    Nabi, Jameel-Un

    2010-06-01

    Neutrino energy loss rates are required as a key nuclear physics input parameter in the simulation codes of core-collapse supernovae of massive stars. The weak interaction rates due to isotopes of iron, {sup 54,55,56}Fe, are considered to play an important role during the presupernova evolution of massive stars. Proton-neutron quasi-particle random phase approximation (pn-QRPA) theory has recently being used for a microscopic calculation of stellar weak interaction rates of iron isotopes with success. The calculation of neutrino energy loss rates due to {sup 54,55,56}Fe is presented along with a comparison with large scale shell model results.

  7. Electrochemically-Induced Redox Reactions in Basalt at High Pressure and Temperature: An Iron and Vanadium K-edge XANES Study

    NASA Astrophysics Data System (ADS)

    Kavner, A.; Walker, D.; Newville, M.; Sutton, S. R.

    2005-12-01

    An applied electric field across a silicate sample at high pressures and temperatures in a piston cylinder apparatus can generate a wide range of oxidation states of polyvalent cations within a single experiment. If two or more polyvalent cations are included, this technique can be used to cross-calibrate oxybarometers within a single experiment. The redox state of Fe and V within a partially melted basaltic silicate was manipulated in situ in a piston-cylinder experiment with a DC power supply providing a source and sink of electrons to the sample. A 1V electrical potential differential was applied across vanadium-doped and Fe-bearing synthetic basalt samples for 24 hrs. at 20 kbar and 1400°C in a specially-designed piston cylinder sample assembly. Three experiments were performed: a control sample with no applied voltage, one with bottom cathode and top anode, and a third with top cathode and bottom anode. Synchrotron-based x-ray absorption near edge structure (XANES) spectroscopy was used to provide spot analysis of iron and vanadium oxidation states with 5μm x 5μm spatial resolution throughout the recovered samples. Systematic spatial changes of increasing oxidation states of V and Fe were observed approaching the anode. The differences in oxidation states were mapped to a corresponding local effective oxygen fugacity by comparison and extension of a calibration of vanadium oxidation states as a function of controlled oxygen fugacity from a previous study (Sutton et al., 2005, GCA, vol. 69, pp. 2333-2348). The vanadium mapping indicates that a 1V potential drop across the sample induces effective oxygen fugacity perturbations in excess of ten orders of magnitude. The presence of both Fe and V within the same sample provides a wide range of oxygen fugacity cross-calibration in these recovered samples. A relationship between oxygen fugacity and electrochemical driving force is derived. The experimental results are in good agreement with the derived

  8. Two-dimensional iron-phthalocyanine (Fe-Pc) monolayer as a promising single-atom-catalyst for oxygen reduction reaction: a computational study

    NASA Astrophysics Data System (ADS)

    Wang, Yu; Yuan, Hao; Li, Yafei; Chen, Zhongfang

    2015-07-01

    Searching for low-cost non-Pt catalysts for oxygen reduction reaction (ORR) has been a key scientific issue in the development of fuel cells. In this work, the potential of utilizing the experimentally available two-dimensional (2D) Fe-phthalocyanine (Fe-Pc) monolayer with precisely-controlled distribution of Fe atoms as a catalyst of ORR was systematically explored by means of comprehensive density functional theory computations. The computations revealed that O2 molecules can be sufficiently activated on the surface of the Fe-Pc monolayer, and the subsequent ORR steps prefer to proceed on the Fe-Pc monolayer through a more efficient 4e pathway with a considerable limiting potential of 0.68 V. Especially, the Fe-Pc monolayer is more stable than the Fe-Pc molecule in acidic medium, and can present good catalytic performance for ORR on the addition of axial ligands. Therefore, the Fe-Pc monolayer is quite a promising single-atom-catalyst with high efficiency for ORR in fuel cells.Searching for low-cost non-Pt catalysts for oxygen reduction reaction (ORR) has been a key scientific issue in the development of fuel cells. In this work, the potential of utilizing the experimentally available two-dimensional (2D) Fe-phthalocyanine (Fe-Pc) monolayer with precisely-controlled distribution of Fe atoms as a catalyst of ORR was systematically explored by means of comprehensive density functional theory computations. The computations revealed that O2 molecules can be sufficiently activated on the surface of the Fe-Pc monolayer, and the subsequent ORR steps prefer to proceed on the Fe-Pc monolayer through a more efficient 4e pathway with a considerable limiting potential of 0.68 V. Especially, the Fe-Pc monolayer is more stable than the Fe-Pc molecule in acidic medium, and can present good catalytic performance for ORR on the addition of axial ligands. Therefore, the Fe-Pc monolayer is quite a promising single-atom-catalyst with high efficiency for ORR in fuel cells. Electronic

  9. METABOLISM OF IRON STORES

    PubMed Central

    SAITO, HIROSHI

    2014-01-01

    ABSTRACT Remarkable progress was recently achieved in the studies on molecular regulators of iron metabolism. Among the main regulators, storage iron, iron absorption, erythropoiesis and hepcidin interact in keeping iron homeostasis. Diseases with gene-mutations resulting in iron overload, iron deficiency, and local iron deposition have been introduced in relation to the regulators of storage iron metabolism. On the other hand, the research on storage iron metabolism has not advanced since the pioneering research by Shoden in 1953. However, we recently developed a new method for determining ferritin iron and hemosiderin iron by computer-assisted serum ferritin kinetics. Serum ferritin increase or decrease curves were measured in patients with normal storage iron levels (chronic hepatitis C and iron deficiency anemia treated by intravenous iron injection), and iron overload (hereditary hemochromatosis and transfusion dependent anemia). We thereby confirmed the existence of two iron pathways where iron flows followed the numbered order (1) labile iron, (2) ferritin and (3) hemosiderin in iron deposition and mobilization among many previously proposed but mostly unproven routes. We also demonstrated the increasing and decreasing phases of ferritin iron and hemosiderin iron in iron deposition and mobilization. The author first demonstrated here the change in proportion between pre-existing ferritin iron and new ferritin iron synthesized by removing iron from hemosiderin in the course of iron removal. In addition, the author disclosed the cause of underestimation of storage iron turnover rate which had been reported by previous investigators in estimating storage iron turnover rate of normal subjects. PMID:25741033

  10. Integrated gasification iron-air electrical system

    SciTech Connect

    Brown, J.T.

    1988-05-17

    An integrated, gasification, iron-air electrical system, capable of generating electrical energy from a carbonaceous material is described comprising: (A) a gasification means for carbonaceous materials comprising at least one gasification reactor, where a carbonaceous material is contacted and reacted with a gaseous medium containing steam and air, at a temperature and for a time effective to gasify the carbonaceous material and produce a hot gaseous reaction product comprising CO and H/sub 2/; (B) an iron-air cell containing at least one discharged iron electrode; (C) means to remove the discharged iron electrode from the cell of (B), and contact it with the gaseous reaction product produced in (A); (D) the discharged iron electrode removed from the cell of (B), containing material consisting essentially of Fe and Fe(OH)/sub 2/, which electrode is contacted with the hot gaseous reaction product produced in the gasification reactor of (A), directly, at a temperature of from about 450/sup 0/C to about 700/sup 0/C, for a time effective to convert, by reduction, discharged iron compounds consisting essentially of Fe and Fe(OH)/sub 2/ to charge iron compounds in the electrode and provide a recharged iron electrode; (E) an iron-air cell into which the recharged iron electrode provided in (D) is placed; (F) means to transport the recharged iron electrode provided in (D) to the iron-air cell of (E); and (G) electrical connection means attached to the iron-air cell of (E), providing the cell with capability of generating electrical energy.

  11. Development of iron aluminides

    SciTech Connect

    Viswanathan, S.; Sikka, V.K.; Andleigh, V.K.

    1995-06-01

    The primary reason for the poor room-temperature ductility of Fe{sub 3}Al-based alloys is generally accepted to be environmental embrittlement due to hydrogen produced by the reaction of aluminum with water vapor present in the test atmosphere. In the as-cast condition, another possible reason for the low room-temperature ductility is the large grain size (0.5 to 3 mm) of the cast material. While recent studies on iron aluminides in the wrought condition have led to higher room-temperature ductility and increased high-temperature strength, limited studies have been conducted on iron aluminides in the as-cast condition. The purpose of this study was to induce grain refinement of the as-cast alloy through alloying additions to the melt and study the effect on room-temperature ductility as measured by the strain corresponding to the maximum stress obtained in a three-point bend test. A base charge of Fe-28% Al-5% Cr alloy was used; as in previous studies this ternary alloy exhibited the highest tensile ductility of several alloys tested. Iron aluminide alloys are being considered for many structural uses, especially for applications where their excellent corrosion resistance is needed. Several alloy compositions developed at ORNL have been licensed to commercial vendors for development of scale-up procedures. With the licensees and other vendors, several applications for iron aluminides are being pursued.

  12. Directionality of Electron Transfer in Type I Reaction Center Proteins: High-Frequency EPR Study of PS I with Removed Iron-Sulfur Centers.

    PubMed

    Poluektov, Oleg G; Utschig, Lisa M

    2015-10-29

    A key step of photosynthetic solar energy conversion involves rapid light-induced sequential electron-transfer steps that result in the formation of a stabilized charge-separated state. These primary reactions take place in large integral membrane reaction center (RC) proteins, wherein a series of donor/acceptor cofactors are specifically positioned for efficient electron transfer. RCs can be divided in two classes, Type I and Type II and examples of both types, photosystem I (PS I) and photosystem II (PS II), are involved in the oxygenic photosynthesis of higher plants, cyanobacteria, and algae. High-resolution X-ray crystal structures reveal that PS I and PS II contain two nearly symmetric branches of redox cofactors, termed the A and B branches. While unidirectional ET along the A branch in Type II RCs is well established, there is still a debate of whether primary photochemistry in Type I RCs is unidirectional along the A branch or bidirectional proceeding down both of the A and B branches. Light-induced electron transfer through the B branch has been observed in genetically modified PS I and in native PS I pretreated with strong reducing conditions to reduce three [4Fe-4S] clusters, the terminal electron acceptors of PS I; however, the extent of asymmetry of ET along both cofactor branches remains an open question. To prove that bidirectional ET in PS I is not simply an artifact of a reducing environment or genetic modification and to determine the degree of PS I ET asymmetry, we have examined biochemically modified Synechococcus leopoliensis PS I RCs, wherein the [4Fe-4S] clusters FX, FA, and FB have been removed to prevent secondary ET from phylloquinones (A1A/A1B) to FX. For these Fe-removed proteins, we observe that ET along both the A and B branches occurs with a ratio close to 1. Together with previously reported data, the concomitant structural and kinetic information obtained with HF EPR unambiguously proves the bidirectional nature of ET in PS I over

  13. The Corrosion and Preservation of Iron Antiques.

    ERIC Educational Resources Information Center

    Walker, Robert

    1982-01-01

    Discusses general corrosion reactions (iron to rust), including corrosion of iron, sulfur dioxide, chlorides, immersed corrosion, and underground corrosion. Also discusses corrosion inhibition, including corrosion inhibitors (anodic, cathodic, mixed, organic); safe/dangerous inhibitors; and corrosion/inhibition in concrete/marble, showcases/boxes,…

  14. Dechlorination of TCE with palladized iron

    DOEpatents

    Fernando, Quintus; Muftikian, Rosy; Korte, Nic

    1997-01-01

    The present invention relates to various methods, such as an above-ground method and an in-ground method, of using a palladized iron bimetallic system for the dechlorination of chlorinated organic compounds from various effluents or contaminated soil containing the same. The use of palladized iron bimetallic system results in the dechlorination of the chlorinated organic compound into environmentally safe reaction products.

  15. Reduction of chromate from electroplating wastewater from pH 1 to 2 using fluidized zero valent iron process.

    PubMed

    Chen, Shiao-Shing; Cheng, Chih-Yu; Li, Chi-Wang; Chai, Pao-Hsuan; Chang, Yu-Min

    2007-04-01

    Fluidized zero valent iron (ZVI) process was conducted to reduce hexavalent chromium (chromate, CrO(4)(2-)) to trivalent chromium (Cr(3+)) from electroplating wastewater due to the following reasons: (1) Extremely low pH (1-2) for the electroplating wastewater favoring the ZVI reaction. (2) The ferric ion, produced from the reaction of Cr(VI) and ZVI, can act as a coagulant to assist the precipitation of Cr(OH)(3(s)) to save the coagulant cost. (3) Higher ZVI utilization for fluidized process due to abrasive motion of the ZVI. For influent chromate concentration of 418 mg/L as Cr(6+), pH 2 and ZVI dosage of 3g (41 g/L), chromate removal was only 29% with hydraulic detention time (HRT) of 1.2 min, but was increased to 99.9% by either increasing HRT to 5.6 min or adjusting pH to 1.5. For iron species at pH 2 and HRT of 1.2 min, Fe(3+) was more thermodynamically stable since oxidizing agent chromate was present. However, if pH was adjusted to 1.5 or 1, where chromate was completely removed, high Fe(2+) but very low Fe(3+) was present. It can be explained that ZVI reacted with chromate to produce Fe(2+) first and the presence of chromate would keep converting Fe(2+) to Fe(3+). Therefore, Fe(2+) is an indicator for complete reduction from Cr(VI) to Cr(III). X-ray diffraction (XRD) was conducted to exam the remained species at pH 2. ZVI, iron oxide and iron sulfide were observed, indicating the formation of iron oxide or iron sulfide could stop the chromate reduction reaction. PMID:16987595

  16. 42 CFR 56.403 - Project elements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Project elements. 56.403 Section 56.403 Public... SERVICES Grants for Operating Migrant Health Entities § 56.403 Project elements. A project for the... § 56.303 of this part, Provided, That the project will not be required to meet the requirements...

  17. Determining Iron Content in Foods by Spectrophotometry.

    ERIC Educational Resources Information Center

    Adams, Paul E.

    1995-01-01

    Describes a laboratory experiment for secondary school chemistry students utilizing the classic reaction between the iron(III) ion and the thiocyanate ion. The experiment also works very well in other chemistry courses as an experience in spectrophotometric analysis. (PVD)

  18. Daily supplementation with iron increases lipid peroxidation in young women with low iron stores.

    PubMed

    King, Sarah M; Donangelo, Carmen M; Knutson, Mitchell D; Walter, Patrick B; Ames, Bruce N; Viteri, Fernando E; King, Janet C

    2008-06-01

    The aim of this study was to determine whether women with low iron stores (plasma ferritin iron supplement for 8 wks at a level commonly used to treat poor iron status develop increased lipid peroxidation as measured by ethane exhalation rates and plasma malondialdehyde. The women served as their own control as pre- and post-supplementation periods were compared. Twelve women participated in the study for a 70-day period and consumed daily iron supplements (98 mg of iron as ferrous sulfate) from day 14 to day 70. Baseline blood and expired air samples were obtained on days 1 and 14; measurements during supplementation were performed on days 56 and 70, that is at 6 and 8 weeks of supplementation. Iron status improved during the iron supplementation period; biochemical indicators of lipid peroxidation also increased. After 6 wks of iron supplementation, serum ferritin almost doubled and body iron more than doubled. Hemoglobin levels increased slightly and other indicators of iron status became normal. However, plasma malondialdehyde (MDA) and breath ethane exhalation rates (BEER) increased by more than 40% between baseline and 6 wks of supplementation; these increases correlated significantly with plasma iron and ferritin levels. MDA was positively correlated with BEER. BEER increased further after 8 wks of iron supplementation. The increased indicators of lipid peroxidation with duration of supplementation and as iron status improved suggest that providing daily nearly 100 mg iron may not be a totally innocuous regimen for correcting iron depletion in women. PMID:18408148

  19. Probing the influence of the center atom coordination structure in iron phthalocyanine multi-walled carbon nanotube-based oxygen reduction reaction catalysts by X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Peng, Yingxiang; Li, Zhipan; Xia, Dingguo; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia

    2015-09-01

    Three different pentacoordinate iron phthalocyanine (FePc) electrocatalysts with an axial ligand (pyridyl group, Py) anchored to multi-walled carbon nanotubes (MWCNTs) are prepared by a microwave method as high performance composite electrocatalysts (FePc-Py/MWCNTs) for the oxygen reduction reaction (ORR). For comparison, tetracoordinate FePc electrocatalysts without an axial ligand anchored to MWCNTs (FePc/MWCNTs) are assembled in the same way. Ultraviolet-visible spectrophotometry (UV-Vis), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HRTEM) are used to characterize the obtained electrocatalysts. The electrocatalytic activity of the samples is measured by linear sweep voltammetry (LSV), and the onset potential of all of the FePc-Py/MWCNTs electrocatalysts is found to be more positive than that of their FePc/MWCNTs counterparts. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy are employed to elucidate the relationship between molecular structure and electrocatalytic activity. XPS indicates that higher concentrations of Fe3+ and pyridine-type nitrogen play critical roles in determining the electrocatalytic ORR activity of the samples. XAFS spectroscopy reveals that the FePc-Py/MWCNTs electrocatalysts have a coordination geometry around Fe that is closer to the square pyramidal structure, a higher concentration of Fe3+, and a smaller phthalocyanine ring radius compared with those of FePc/MWCNTs.

  20. Iron catalyzed coal liquefaction process

    DOEpatents

    Garg, Diwakar; Givens, Edwin N.

    1983-01-01

    A process is described for the solvent refining of coal into a gas product, a liquid product and a normally solid dissolved product. Particulate coal and a unique co-catalyst system are suspended in a coal solvent and processed in a coal liquefaction reactor, preferably an ebullated bed reactor. The co-catalyst system comprises a combination of a stoichiometric excess of iron oxide and pyrite which reduce predominantly to active iron sulfide catalysts in the reaction zone. This catalyst system results in increased catalytic activity with attendant improved coal conversion and enhanced oil product distribution as well as reduced sulfide effluent. Iron oxide is used in a stoichiometric excess of that required to react with sulfur indigenous to the feed coal and that produced during reduction of the pyrite catalyst to iron sulfide.

  1. 46 CFR 56.10-5 - Pipe.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... design limits of stress and temperature indicated in ASME B31.1 (incorporated by reference; see 46 CFR 56... 46 Shipping 2 2010-10-01 2010-10-01 false Pipe. 56.10-5 Section 56.10-5 Shipping COAST GUARD... § 56.10-5 Pipe. (a) General. Pipe and tubing shall be selected as described in Table 56.60-1(a)....

  2. Supplementing iron bioavailability enhanced mung bean.

    PubMed

    Purushothaman, Vijayalakshmi; M, Amirthaveni; Tsou, Samson C S; S, Shanmugasundaram

    2008-01-01

    Iron deficiency anaemia is a major public health problem. The high incidence is either due to insufficient intake of iron or poor bio availability. Enhancing the bio availability is as important as increasing the intake. The absorption could be enhanced by including ascorbic acid and beta carotene containing fruits and vegetables into recipes of iron containing food preparations. The effect of supplementation of iron bio-availability enhanced mung bean preparations was studied on 75 women who were compared against 75 who served as controls and another 75 who consumed regular traditional recipes. The methodology included identification of suitable mung bean variety, assessing iron in vitro bio availability, mapping the anaemic women, estimating their iron levels, supplementation for one year and studying the effect of supplementation. Mung bean supplementation had increased serum protein levels from 5.36 to 6.73 g/dl, serum iron levels had increased from 16.6 to 46.7 microg/dl. The TIBC levels decreased from 555 to 508 microg/dl while serum ferritin levels increased from 3.56 to 5.94 microg/dl and Hb levels from 7.54 to 8.29 g/dl. Thus, improving the bioavailability of iron of food preparations, will improve the iron status of women. PMID:18296312

  3. Iron Dextran Injection

    MedlinePlus

    Iron dextran injection is used to treat iron-deficiency anemia (a lower than normal number of red blood cells ... treated with iron supplements taken by mouth. Iron dextran injection is in a class of medications called ...

  4. Reactions in water: alkyl nitrile coupling reactions using Fenton's reagent.

    PubMed

    Keller, Christopher L; Dalessandro, James D; Hotz, Richard P; Pinhas, Allan R

    2008-05-01

    The coupling reaction of water-soluble alkyl nitriles using Fenton's reagent (Fe(II) and H2O2) is described. The best metal for the reaction is iron(II), and the greatest yields are obtained when the concentration of the metal is kept low. Hydrogen-atom abstraction is selective, preferentially producing the radical alpha to the nitrile. In order to increase the production of dinitrile, in situ reduction of iron(III) to iron(II), using a variety of reducing agents, was investigated. PMID:18363368

  5. Water oxidation: High five iron

    NASA Astrophysics Data System (ADS)

    Lloret-Fillol, Julio; Costas, Miquel

    2016-03-01

    The oxidation of water is essential to the sustainable production of fuels using sunlight or electricity, but designing active, stable and earth-abundant catalysts for the reaction is challenging. Now, a complex containing five iron atoms is shown to efficiently oxidize water by mimicking key features of the oxygen-evolving complex in green plants.

  6. Iron and alloys of iron. [lunar resources

    NASA Technical Reports Server (NTRS)

    Sastri, Sankar

    1992-01-01

    All lunar soil contains iron in the metallic form, mostly as an iron-nickel alloy in concentrations of a few tenths of 1 percent. Some of this free iron can be easily separated by magnetic means. It is estimated that the magnetic separation of 100,000 tons of lunar soil would yield 150-200 tons of iron. Agglutinates contain metallic iron which could be extracted by melting and made into powder metallurgy products. The characteristics and potential uses of the pure-iron and iron-alloy lunar products are discussed. Processes for working iron that might be used in a nonterrestrial facility are also addressed.

  7. Iron utilization and metabolism in plants.

    PubMed

    Briat, Jean-François; Curie, Catherine; Gaymard, Frédéric

    2007-06-01

    The solubilization and long-distance allocation of iron between organs and tissues, as well as its subcellular compartmentalization and remobilization, involve various chelation and oxidation/reduction steps, transport activities and association with soluble proteins that store and buffer this metal. Maintaining iron homeostasis is an important determinant in building prosthetic groups such as heme and Fe-S clusters, and in assembling them into apoproteins, which are major components of plant metabolism. Such processes require complex protein machineries located in mitochondria and plastids. An essential role for iron metabolism and utilization in plant productivity is evidenced by the strong iron requirement for proper photosynthetic reactions. PMID:17434791

  8. Comparison of iron isotope variations in modern and Ordovician siliceous Fe oxyhydroxide deposits

    NASA Astrophysics Data System (ADS)

    Moeller, Kirsten; Schoenberg, Ronny; Grenne, Tor; Thorseth, Ingunn H.; Drost, Kerstin; Pedersen, Rolf B.

    2014-02-01

    Fe oxyhydroxide deposits depends on comprehensive knowledge of the geological context. Furthermore, we demonstrate that very negative δ56Fe values in such samples might not be the result of microbial dissimilatory iron reduction, but could be caused instead by inorganic reactions.

  9. Prompt Proton Decay and Deformed Bands in 56Ni

    SciTech Connect

    Johansson, E. K.; Rudolph, D.; Andersson, L. L.; Torres, D. A.; Ragnarsson, I.; Andreoiu, C.; Baktash, Cyrus; Carpenter, M. P.; Charity, R. J.; Chiara, C. J.; Ekman, J.; Fahlander, C.; Hoel, C.; Pechenaya, O. L.; Reviol, W.; du Rietz, R.; Sarantites, D. G.; Seweryniak, D.; Sobotka, L. G.; Yu, Chang-Hong; Zhu, S.

    2008-06-01

    High-spin states in the doubly magic N=Z nucleus {sup 56}Ni have been investigated with three fusion-evaporation reaction experiments. New {gamma}-ray transitions are added, and a confirmation of a previously suggested prompt proton decay from a rotational band in {sup 56}Ni into the ground state of {sup 55}Co is presented. The rotational bands in {sup 56}Ni are discussed within the framework of cranked Nilsson-Strutinsky calculations.

  10. Studies of hypervalent iron

    SciTech Connect

    Bielski, B.H.J.

    1989-01-01

    The iron (IV), (V) and (VI) oxidation states are of great interest because of their role in catalytic oxidation/hydroxylation reactions. This report summarizes the information currently available on the kinetic and chemical properties of the water-soluble ions of FeO{sub 4}{sup 2{minus}}, FeO{sub 4}{sup 3{minus}} and FeO{sub 4}{sup 4{minus}}, their protonated forms, and/or simple complex derivatives. The discussion includes their radiation-induced formation, decay kinetics, reactivity with other compounds, determination of their respective pK{sub a} values as well as spectral properties. 32 refs., 3 figs., 2 tabs.

  11. Data Evaluation for 56Co epsilon + beta+ Decay

    SciTech Connect

    Baglin, Coral M.; MacMahon, T. Desmond

    2005-02-28

    Recommended values for nuclear and atomic data pertaining to the {var_epsilon} + {beta}{sup +} decay of {sup 56}Co are provided here, followed by comments on evaluation procedures and a summary of all available experimental data. {sup 56}Co is a radionuclide which is potentially very useful for Ge detector efficiency calibration because it is readily produced via the {sup 56}Fe(p,n) reaction, its half-life of 77.24 days is conveniently long, and it provides a number of relatively strong {gamma} rays with energies up to {approx}3500 keV. The transition intensities recommended here for the strongest lines will be included in the forthcoming International Atomic Energy Agency Coordinated Research Programme document ''Update of X- and Gamma-ray Decay Data Standards for Detector Calibration and Other Applications'', and the analysis for all transitions along with relevant atomic data have been provided to the Decay Data Evaluation Project.

  12. New 56Fe Evaluation for the CIELO project

    NASA Astrophysics Data System (ADS)

    Nobre, G. P. A.; Herman, M.; Brown, D.; Capote, R.; Trkov, A.; Leal, L.; Plompen, A.; Danon, Y.; Qian, Jing; Ge, Zhigang; Liu, Tingjin; Lu, Hnalin; Ruan, Xichao

    2016-03-01

    The Collaborative International Evaluated Library Organisation (CIELO) aims to provide revised and updated evaluations for 239Pu, 238,235U, 56Fe, 16O, and 1H through international collaboration. This work, which is part of the CIELO project, presents the initial results for the evaluation of the 56Fe isotope, with neutron-incident energy ranging from 0 to 20 MeV. The 56Fe(n,p) cross sections were fitted to reproduce the ones from IRDFF dosimetry file. Our preliminary file provides good cross-section agreements for the main angle-integrated reactions, as well as a reasonable overall agreement for angular distributions and double-di_erential spectra, when compared to previous evaluations.

  13. New Fe-56 Evaluation for the CIELO project

    SciTech Connect

    Nobre, G P; Herman, Micheal W; Brown, D A; Capote, R.; Leal, Luiz C; Plompen, A.; Danon, Y.; Qian, Jing; Ge, Zhigang; Liu, Tingjin; Lu, Hnalin; Ruan, Xichao

    2016-01-01

    The Collaborative International Evaluated Library Organisation (CIELO) aims to provide revised and updated evaluations for Pu-239, U-238,U-235, Fe-56, O-16, and H-1 through international collaboration. This work, which is part of the CIELO project, presents the initial results for the evaluation of the Fe-56 isotope, with neutron-incident energy ranging from 0 to 20 MeV. The Fe-56(n,p) cross sections were fitted to reproduce the ones from IRDFF dosimetry file. Our preliminary file provides good cross-section agreements for the main angle-integrated reactions, as well as a reasonable overall agreement for angular distributions and double-differential spectra, when compared to previous evaluations.

  14. Method for reducing iron losses in an iron smelting process

    DOEpatents

    Sarma, B.; Downing, K.B.

    1999-03-23

    A process of smelting iron that comprises the steps of: (a) introducing a source of iron oxide, oxygen, nitrogen, and a source of carbonaceous fuel to a smelting reactor, at least some of said oxygen being continuously introduced through an overhead lance; (b) maintaining conditions in said reactor to cause (1) at least some of the iron oxide to be chemically reduced, (2) a bath of molten iron to be created and stirred in the bottom of the reactor, surmounted by a layer of slag, and (3) carbon monoxide gas to rise through the slag; (c) causing at least some of said carbon monoxide to react in the reactor with the incoming oxygen, thereby generating heat for reactions taking place in the reactor; and (d) releasing from the reactor an offgas effluent, is run in a way that keeps iron losses in the offgas relatively low. After start-up of the process is complete, steps (a) and (b) are controlled so as to: (1) keep the temperature of the molten iron at or below about 1550 C and (2) keep the slag weight at or above about 0.8 ton per square meter. 13 figs.

  15. Method for reducing iron losses in an iron smelting process

    DOEpatents

    Sarma, Balu; Downing, Kenneth B.

    1999-01-01

    A process of smelting iron that comprises the steps of: a) introducing a source of iron oxide, oxygen, nitrogen, and a source of carbonaceous fuel to a smelting reactor, at least some of said oxygen being continuously introduced through an overhead lance; b) maintaining conditions in said reactor to cause (i) at least some of the iron oxide to be chemically reduced, (ii) a bath of molten iron to be created and stirred in the bottom of the reactor, surmounted by a layer of slag, and (iii) carbon monoxide gas to rise through the slag; c) causing at least some of said carbon monoxide to react in the reactor with the incoming oxygen, thereby generating heat for reactions taking place in the reactor; and d) releasing from the reactor an offgas effluent, is run in a way that keeps iron losses in the offgas relatively low. After start-up of the process is complete, steps (a) and (b) are controlled so as to: e) keep the temperature of the molten iron at or below about 1550.degree. C. and f) keep the slag weight at or above about 0.8 tonne per square meter.

  16. Hydroxylation of alkanes using sodium hypochlorite catalyzed by iron porphyrins

    SciTech Connect

    Sorokin, A.B.; Khenkin, A.M.

    1988-10-01

    This communication presents data about the oxidation of alkanes to alcohols with hypochlorite in the presence of Fe(III) phenylporphyrin derivatives in the system water-benzene. We used as catalysts the following compounds: tetraphenylporphyrin iron chloride, tetramesitylporphyrin iron chloride, tetra(2-fluorophenyl)porphyrin from chloride, and tetra (2-ntrophenyl)porphyrin iron chloride. The reaction products were analyzed by gas-liquid chromatography. The efficiency of the reaction was determined by the structure of the porphyrin used.

  17. 46 CFR 56.70-5 - Material.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... (incorporated by reference; see 46 CFR 56.01-2) and 46 CFR 57.02-5. (b) Backing rings. When metallic backing... 46 Shipping 2 2014-10-01 2014-10-01 false Material. 56.70-5 Section 56.70-5 Shipping COAST GUARD..., Assembly and Erection § 56.70-5 Material. (a) Filler metal. All filler metal, including consumable...

  18. 46 CFR 56.70-5 - Material.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... (incorporated by reference; see 46 CFR 56.01-2) and 46 CFR 57.02-5. (b) Backing rings. When metallic backing... 46 Shipping 2 2013-10-01 2013-10-01 false Material. 56.70-5 Section 56.70-5 Shipping COAST GUARD..., Assembly and Erection § 56.70-5 Material. (a) Filler metal. All filler metal, including consumable...

  19. 46 CFR 56.70-5 - Material.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... (incorporated by reference; see 46 CFR 56.01-2) and 46 CFR 57.02-5. (b) Backing rings. When metallic backing... 46 Shipping 2 2010-10-01 2010-10-01 false Material. 56.70-5 Section 56.70-5 Shipping COAST GUARD..., Assembly and Erection § 56.70-5 Material. (a) Filler metal. All filler metal, including consumable...

  20. Iron Hydroxy Carbonate Formation in Zerovalent Iron Permeable Reactive Barriers: Characterization and Evaluation of Phase Stability

    EPA Science Inventory

    Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently obs...

  1. 32 CFR 56.6 - Information requirements.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 32 National Defense 1 2011-07-01 2011-07-01 false Information requirements. 56.6 Section 56.6 National Defense Department of Defense OFFICE OF THE SECRETARY OF DEFENSE PERSONNEL, MILITARY AND CIVILIAN... DEFENSE § 56.6 Information requirements. (a) Each DoD Component shall maintain a log of all...

  2. 31 CFR 56.2 - Sales price.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 31 Money and Finance: Treasury 1 2014-07-01 2014-07-01 false Sales price. 56.2 Section 56.2 Money and Finance: Treasury Regulations Relating to Money and Finance MONETARY OFFICES, DEPARTMENT OF THE TREASURY DOMESTIC GOLD AND SILVER OPERATIONS SALE OF SILVER § 56.2 Sales price. Sales of silver will be...

  3. 31 CFR 56.2 - Sales price.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 31 Money and Finance: Treasury 1 2012-07-01 2012-07-01 false Sales price. 56.2 Section 56.2 Money and Finance: Treasury Regulations Relating to Money and Finance MONETARY OFFICES, DEPARTMENT OF THE TREASURY DOMESTIC GOLD AND SILVER OPERATIONS SALE OF SILVER § 56.2 Sales price. Sales of silver will be...

  4. 31 CFR 56.2 - Sales price.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 31 Money and Finance: Treasury 1 2013-07-01 2013-07-01 false Sales price. 56.2 Section 56.2 Money and Finance: Treasury Regulations Relating to Money and Finance MONETARY OFFICES, DEPARTMENT OF THE TREASURY DOMESTIC GOLD AND SILVER OPERATIONS SALE OF SILVER § 56.2 Sales price. Sales of silver will be...

  5. 46 CFR 56.70-3 - Limitations.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 2 2011-10-01 2011-10-01 false Limitations. 56.70-3 Section 56.70-3 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PIPING SYSTEMS AND APPURTENANCES Fabrication, Assembly and Erection § 56.70-3 Limitations. Backing rings. Backing strips used at...

  6. 46 CFR 56.70-3 - Limitations.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 2 2010-10-01 2010-10-01 false Limitations. 56.70-3 Section 56.70-3 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PIPING SYSTEMS AND APPURTENANCES Fabrication, Assembly and Erection § 56.70-3 Limitations. Backing rings. Backing strips used at...

  7. 46 CFR 56.20-1 - General.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... to those of ASME B31.1 (incorporated by reference; see 46 CFR 56.01-2) or Section VIII of the ASME Boiler and Pressure Vessel Code (incorporated by reference; see 46 CFR 56.01-2), if the valve shape...; see 46 CFR 56.01-2); or (iii) Other means specifically accepted by the Marine Safety Center....

  8. 46 CFR 56.20-1 - General.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... to those of ASME B31.1 (incorporated by reference; see 46 CFR 56.01-2) or section VIII of the ASME Boiler and Pressure Vessel Code (incorporated by reference; see 46 CFR 56.01-2), if the valve shape...; see 46 CFR 56.01-2); or (iii) Other means specifically accepted by the Marine Safety Center....

  9. 7 CFR 56.6 - Supervision.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 3 2010-01-01 2010-01-01 false Supervision. 56.6 Section 56.6 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards, Inspections... Grading of Shell Eggs General § 56.6 Supervision. All grading service shall be subject to supervision...

  10. 46 CFR 56.25-20 - Bolting.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... washers must comply with applicable standards and specifications listed in 46 CFR 56.60-1. Unless otherwise specified, bolting must be in accordance with ASME B16.5 (incorporated by reference; see 46 CFR 56... heavy hexagon heads in accordance with ASME B18.2.1 (incorporated by reference, see 46 CFR 56.01-2)...

  11. 46 CFR 56.25-20 - Bolting.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... washers must comply with applicable standards and specifications listed in 46 CFR 56.60-1. Unless otherwise specified, bolting must be in accordance with ASME B16.5 (incorporated by reference; see 46 CFR 56... heavy hexagon heads in accordance with ASME B18.2.1 (incorporated by reference, see 46 CFR 56.01-2)...

  12. 46 CFR 56.25-20 - Bolting.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... washers must comply with applicable standards and specifications listed in 46 CFR 56.60-1. Unless otherwise specified, bolting must be in accordance with ASME B16.5 (incorporated by reference; see 46 CFR 56... heavy hexagon heads in accordance with ASME B18.2.1 (incorporated by reference, see 46 CFR 56.01-2)...

  13. 8 CFR 1240.56 - Application.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... for voluntary departure as prescribed in 8 CFR part 1240 and section 244 of the Act. Pursuant to... 8 Aliens and Nationality 1 2013-01-01 2013-01-01 false Application. 1240.56 Section 1240.56 Aliens... Departure (for Proceedings Commenced Prior to April 1, 1997) § 1240.56 Application. Notwithstanding...

  14. 30 CFR 56.4600 - Extinguishing equipment.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Extinguishing equipment. 56.4600 Section 56... Control Welding/cutting/compressed Gases § 56.4600 Extinguishing equipment. (a) When welding, cutting... equivalent fire extinguishing equipment for the class of fire hazard present shall be at the worksite....

  15. 30 CFR 56.14214 - Train warnings.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Safety Practices and Operational Procedures § 56.14214 Train warnings. A warning that is audible above... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Train warnings. 56.14214 Section 56.14214 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL...

  16. 30 CFR 56.14214 - Train warnings.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Safety Practices and Operational Procedures § 56.14214 Train warnings. A warning that is audible above... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Train warnings. 56.14214 Section 56.14214 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL...

  17. 30 CFR 56.14214 - Train warnings.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Safety Practices and Operational Procedures § 56.14214 Train warnings. A warning that is audible above... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Train warnings. 56.14214 Section 56.14214 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL...

  18. 30 CFR 56.9200 - Transporting persons.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Transporting persons. 56.9200 Section 56.9200... Dumping Transportation of Persons and Materials § 56.9200 Transporting persons. Persons shall not be transported— (a) In or on dippers, forks, clamshells, or buckets except shaft buckets during...

  19. 30 CFR 56.9200 - Transporting persons.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Transporting persons. 56.9200 Section 56.9200... Dumping Transportation of Persons and Materials § 56.9200 Transporting persons. Persons shall not be transported— (a) In or on dippers, forks, clamshells, or buckets except shaft buckets during...

  20. 30 CFR 56.9200 - Transporting persons.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Transporting persons. 56.9200 Section 56.9200... Dumping Transportation of Persons and Materials § 56.9200 Transporting persons. Persons shall not be transported— (a) In or on dippers, forks, clamshells, or buckets except shaft buckets during...

  1. 30 CFR 56.9200 - Transporting persons.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Transporting persons. 56.9200 Section 56.9200... Dumping Transportation of Persons and Materials § 56.9200 Transporting persons. Persons shall not be transported— (a) In or on dippers, forks, clamshells, or buckets except shaft buckets during...

  2. 40 CFR 124.56 - Fact sheets.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 22 2014-07-01 2013-07-01 true Fact sheets. 124.56 Section 124.56 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER PROGRAMS PROCEDURES FOR DECISIONMAKING Specific Procedures Applicable to NPDES Permits § 124.56 Fact sheets. (Applicable to State programs, see § 123.25 (NPDES).) In addition...

  3. 30 CFR 56.6603 - Air gap.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Air gap. 56.6603 Section 56.6603 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND... § 56.6603 Air gap. At least a 15-foot air gap shall be provided between the blasting circuit and...

  4. 30 CFR 56.4331 - Firefighting drills.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Firefighting drills. 56.4331 Section 56.4331... Control Firefighting Procedures/alarms/drills § 56.4331 Firefighting drills. Emergency firefighting drills shall be held at least once every six months for persons assigned firefighting responsibilities by...

  5. 30 CFR 56.4331 - Firefighting drills.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Firefighting drills. 56.4331 Section 56.4331... Control Firefighting Procedures/alarms/drills § 56.4331 Firefighting drills. Emergency firefighting drills shall be held at least once every six months for persons assigned firefighting responsibilities by...

  6. 30 CFR 56.9100 - Traffic control.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Traffic control. 56.9100 Section 56.9100 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE... Dumping Traffic Safety § 56.9100 Traffic control. To provide for the safe movement of...

  7. 30 CFR 56.9100 - Traffic control.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Traffic control. 56.9100 Section 56.9100 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE... Dumping Traffic Safety § 56.9100 Traffic control. To provide for the safe movement of...

  8. 30 CFR 56.9100 - Traffic control.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Traffic control. 56.9100 Section 56.9100 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE... Dumping Traffic Safety § 56.9100 Traffic control. To provide for the safe movement of...

  9. 30 CFR 56.9100 - Traffic control.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Traffic control. 56.9100 Section 56.9100 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE... Dumping Traffic Safety § 56.9100 Traffic control. To provide for the safe movement of...

  10. 30 CFR 56.20008 - Toilet facilities.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Toilet facilities. 56.20008 Section 56.20008 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Miscellaneous § 56.20008 Toilet facilities. (a) Toilet facilities...

  11. 30 CFR 56.20008 - Toilet facilities.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Toilet facilities. 56.20008 Section 56.20008 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Miscellaneous § 56.20008 Toilet facilities. (a) Toilet facilities...

  12. 49 CFR 386.56 - Hearings.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 5 2011-10-01 2011-10-01 false Hearings. 386.56 Section 386.56 Transportation... and Hearings § 386.56 Hearings. (a) As soon as practicable after his/her appointment, the administrative law judge shall issue an order setting the date, time, and place for the hearing. The order...

  13. 30 CFR 56.11001 - Safe access.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Safe access. 56.11001 Section 56.11001 Mineral... HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Travelways § 56.11001 Safe access. Safe means of access shall be provided and maintained to all working places....

  14. 29 CFR 18.56 - Restricted access.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Restricted access. 18.56 Section 18.56 Labor Office of the... ADMINISTRATIVE LAW JUDGES General § 18.56 Restricted access. On his or her own motion, or on the motion of any party, the administrative law judge may direct that there be a restricted access portion of the...

  15. 29 CFR 18.56 - Restricted access.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 29 Labor 1 2011-07-01 2011-07-01 false Restricted access. 18.56 Section 18.56 Labor Office of the... ADMINISTRATIVE LAW JUDGES General § 18.56 Restricted access. On his or her own motion, or on the motion of any party, the administrative law judge may direct that there be a restricted access portion of the...

  16. 30 CFR 56.11001 - Safe access.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Safe access. 56.11001 Section 56.11001 Mineral... HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Travelways § 56.11001 Safe access. Safe means of access shall be provided and maintained to all working places....

  17. 21 CFR 56.106 - Registration.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Registration. 56.106 Section 56.106 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL INSTITUTIONAL REVIEW BOARDS Organization and Personnel § 56.106 Registration. (a) Who must register? Each IRB in the...

  18. 21 CFR 56.106 - Registration.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Registration. 56.106 Section 56.106 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL INSTITUTIONAL REVIEW BOARDS Organization and Personnel § 56.106 Registration. (a) Who must register? Each IRB in the...

  19. 7 CFR 56.15 - Political activity.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 3 2014-01-01 2014-01-01 false Political activity. 56.15 Section 56.15 Agriculture... EGGS Grading of Shell Eggs Licensed and Authorized Graders § 56.15 Political activity. Federal graders may participate in certain political activities, including management of and participation...

  20. 7 CFR 56.15 - Political activity.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 3 2013-01-01 2013-01-01 false Political activity. 56.15 Section 56.15 Agriculture... EGGS Grading of Shell Eggs Licensed and Authorized Graders § 56.15 Political activity. Federal graders may participate in certain political activities, including management of and participation...

  1. 7 CFR 56.15 - Political activity.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 3 2010-01-01 2010-01-01 false Political activity. 56.15 Section 56.15 Agriculture... EGGS Grading of Shell Eggs Licensed and Authorized Graders § 56.15 Political activity. Federal graders may participate in certain political activities, including management of and participation...

  2. 7 CFR 56.15 - Political activity.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 3 2012-01-01 2012-01-01 false Political activity. 56.15 Section 56.15 Agriculture... EGGS Grading of Shell Eggs Licensed and Authorized Graders § 56.15 Political activity. Federal graders may participate in certain political activities, including management of and participation...

  3. 7 CFR 56.15 - Political activity.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 3 2011-01-01 2011-01-01 false Political activity. 56.15 Section 56.15 Agriculture... EGGS Grading of Shell Eggs Licensed and Authorized Graders § 56.15 Political activity. Federal graders may participate in certain political activities, including management of and participation...

  4. 21 CFR 56.102 - Definitions.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Definitions. 56.102 Section 56.102 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL INSTITUTIONAL REVIEW BOARDS General Provisions § 56.102 Definitions. As used in this part: (a) Act means the Federal Food, Drug, and Cosmetic Act, as amended (secs....

  5. 21 CFR 56.102 - Definitions.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Definitions. 56.102 Section 56.102 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL INSTITUTIONAL REVIEW BOARDS General Provisions § 56.102 Definitions. As used in this part: (a) Act means the Federal Food, Drug, and Cosmetic Act, as amended (secs....

  6. 14 CFR 61.56 - Flight review.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 2 2014-01-01 2014-01-01 false Flight review. 61.56 Section 61.56... CERTIFICATION: PILOTS, FLIGHT INSTRUCTORS, AND GROUND INSTRUCTORS General § 61.56 Flight review. (a) Except as provided in paragraphs (b) and (f) of this section, a flight review consists of a minimum of 1 hour...

  7. 30 CFR 56.14101 - Brakes.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Brakes. 56.14101 Section 56.14101 Mineral... Devices and Maintenance Requirements § 56.14101 Brakes. (a) Minimum requirements. (1) Self-propelled mobile equipment shall be equipped with a service brake system capable of stopping and holding...

  8. 30 CFR 56.10004 - Brakes.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Brakes. 56.10004 Section 56.10004 Mineral... HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Aerial Tramways § 56.10004 Brakes. Positive-action-type brakes and devices which apply the brakes automatically in the event of a...

  9. 30 CFR 56.4501 - Fuel lines.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Fuel lines. 56.4501 Section 56.4501 Mineral... Installation/construction/maintenance § 56.4501 Fuel lines. Fuel lines shall be equipped with valves capable of stopping the flow of fuel at the source and shall be located and maintained to minimize fire hazards....

  10. 30 CFR 56.4501 - Fuel lines.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Fuel lines. 56.4501 Section 56.4501 Mineral... Installation/construction/maintenance § 56.4501 Fuel lines. Fuel lines shall be equipped with valves capable of stopping the flow of fuel at the source and shall be located and maintained to minimize fire hazards....

  11. 30 CFR 56.4501 - Fuel lines.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Fuel lines. 56.4501 Section 56.4501 Mineral... Installation/construction/maintenance § 56.4501 Fuel lines. Fuel lines shall be equipped with valves capable of stopping the flow of fuel at the source and shall be located and maintained to minimize fire hazards....

  12. 30 CFR 56.4501 - Fuel lines.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Fuel lines. 56.4501 Section 56.4501 Mineral... Installation/construction/maintenance § 56.4501 Fuel lines. Fuel lines shall be equipped with valves capable of stopping the flow of fuel at the source and shall be located and maintained to minimize fire hazards....

  13. 30 CFR 56.4501 - Fuel lines.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Fuel lines. 56.4501 Section 56.4501 Mineral... Installation/construction/maintenance § 56.4501 Fuel lines. Fuel lines shall be equipped with valves capable of stopping the flow of fuel at the source and shall be located and maintained to minimize fire hazards....

  14. 42 CFR 56.109 - Grant payments.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 42 Public Health 1 2011-10-01 2011-10-01 false Grant payments. 56.109 Section 56.109 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES GRANTS GRANTS FOR MIGRANT HEALTH SERVICES General Provisions § 56.109 Grant payments. The Secretary shall from time to time make payments to...

  15. 42 CFR 56.109 - Grant payments.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Grant payments. 56.109 Section 56.109 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES GRANTS GRANTS FOR MIGRANT HEALTH SERVICES General Provisions § 56.109 Grant payments. The Secretary shall from time to time make payments to...

  16. 45 CFR 1180.56 - Allowable costs.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 45 Public Welfare 3 2010-10-01 2010-10-01 false Allowable costs. 1180.56 Section 1180.56 Public... by a Grantee General Administrative Responsibilities § 1180.56 Allowable costs. (a) Determination of costs allowable under a grant is made in accordance with government-wide cost principles in...

  17. 30 CFR 56.12021 - Danger signs.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Danger signs. 56.12021 Section 56.12021 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Electricity § 56.12021 Danger...

  18. 30 CFR 56.12021 - Danger signs.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Danger signs. 56.12021 Section 56.12021 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Electricity § 56.12021 Danger...

  19. 30 CFR 56.12047 - Guy wires.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Guy wires. 56.12047 Section 56.12047 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Electricity § 56.12047 Guy wires....

  20. 30 CFR 56.12047 - Guy wires.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Guy wires. 56.12047 Section 56.12047 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Electricity § 56.12047 Guy wires....

  1. 45 CFR 86.56 - Fringe benefits.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 45 Public Welfare 1 2010-10-01 2010-10-01 false Fringe benefits. 86.56 Section 86.56 Public... Basis of Sex in Employment in Education Programs or Activities Prohibited § 86.56 Fringe benefits. (a) Fringe benefits defined. For purposes of this part, fringe benefits means: Any medical,...

  2. 7 CFR 15a.56 - Fringe benefits.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 1 2010-01-01 2010-01-01 false Fringe benefits. 15a.56 Section 15a.56 Agriculture Office of the Secretary of Agriculture EDUCATION PROGRAMS OR ACTIVITIES RECEIVING OR BENEFITTING FROM... Activities Prohibited § 15a.56 Fringe benefits. (a) “Fringe benefits” defined. For purposes of this...

  3. 30 CFR 56.20003 - Housekeeping.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Housekeeping. 56.20003 Section 56.20003 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Miscellaneous § 56.20003...

  4. 30 CFR 56.7055 - Intersecting holes.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Intersecting holes. 56.7055 Section 56.7055... Piercing Drilling § 56.7055 Intersecting holes. Holes shall not be drilled where there is a danger of intersecting a misfired hole or a hole containing explosives blasting agents, or detonators....

  5. 32 CFR 56.6 - Information requirements.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 32 National Defense 1 2012-07-01 2012-07-01 false Information requirements. 56.6 Section 56.6 National Defense Department of Defense OFFICE OF THE SECRETARY OF DEFENSE PERSONNEL, MILITARY AND CIVILIAN NONDISCRIMINATION ON THE BASIS OF HANDICAP IN PROGRAMS AND ACTIVITIES ASSISTED OR CONDUCTED BY THE DEPARTMENT OF DEFENSE § 56.6...

  6. 32 CFR 56.6 - Information requirements.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 32 National Defense 1 2014-07-01 2014-07-01 false Information requirements. 56.6 Section 56.6 National Defense Department of Defense OFFICE OF THE SECRETARY OF DEFENSE PERSONNEL, MILITARY AND CIVILIAN NONDISCRIMINATION ON THE BASIS OF HANDICAP IN PROGRAMS AND ACTIVITIES ASSISTED OR CONDUCTED BY THE DEPARTMENT OF DEFENSE § 56.6...

  7. 29 CFR 1926.56 - Illumination.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 29 Labor 8 2011-07-01 2011-07-01 false Illumination. 1926.56 Section 1926.56 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR (CONTINUED) SAFETY AND HEALTH REGULATIONS FOR CONSTRUCTION Occupational Health and Environmental Controls § 1926.56 Illumination. (a) General....

  8. 32 CFR 56.6 - Information requirements.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 32 National Defense 1 2010-07-01 2010-07-01 false Information requirements. 56.6 Section 56.6 National Defense Department of Defense OFFICE OF THE SECRETARY OF DEFENSE PERSONNEL, MILITARY AND CIVILIAN... DEFENSE § 56.6 Information requirements. (a) Each DoD Component shall maintain a log of all...

  9. 46 CFR 56.70-15 - Procedure.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... ASME B31.1 (incorporated by reference; see 46 CFR 56.01-2).) (6) As-welded surfaces are permitted... of the ASME Boiler and Pressure Vessel Code (incorporated by reference; see 46 CFR 56.01-2). (iii... reference; see 46 CFR 56.01-2) and may be examined nondestructively by an acceptable method....

  10. 46 CFR 56.70-15 - Procedure.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... ASME B31.1 (incorporated by reference; see 46 CFR 56.01-2).) (6) As-welded surfaces are permitted... of the ASME Boiler and Pressure Vessel Code (incorporated by reference; see 46 CFR 56.01-2). (iii... reference; see 46 CFR 56.01-2) and may be examined nondestructively by an acceptable method....

  11. 30 CFR 56.6902 - Excessive temperatures.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Excessive temperatures. 56.6902 Section 56.6902... Requirements § 56.6902 Excessive temperatures. (a) Where heat could cause premature detonation, explosive... an appropriate number of blasthole temperatures in order to assess the specific mine conditions...

  12. 32 CFR 56.6 - Information requirements.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 32 National Defense 1 2013-07-01 2013-07-01 false Information requirements. 56.6 Section 56.6 National Defense Department of Defense OFFICE OF THE SECRETARY OF DEFENSE PERSONNEL, MILITARY AND CIVILIAN... DEFENSE § 56.6 Information requirements. (a) Each DoD Component shall maintain a log of all...

  13. 30 CFR 56.6901 - Black powder.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Black powder. 56.6901 Section 56.6901 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Explosives General Requirements § 56.6901 Black powder. (a) Black powder...

  14. 30 CFR 56.6901 - Black powder.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Black powder. 56.6901 Section 56.6901 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Explosives General Requirements § 56.6901 Black powder. (a) Black powder...

  15. 12 CFR 229.56 - Liability.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 12 Banks and Banking 3 2012-01-01 2012-01-01 false Liability. 229.56 Section 229.56 Banks and Banking FEDERAL RESERVE SYSTEM (CONTINUED) BOARD OF GOVERNORS OF THE FEDERAL RESERVE SYSTEM AVAILABILITY OF FUNDS AND COLLECTION OF CHECKS (REGULATION CC) Substitute Checks § 229.56 Liability. (a)...

  16. 12 CFR 229.56 - Liability.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 12 Banks and Banking 3 2011-01-01 2011-01-01 false Liability. 229.56 Section 229.56 Banks and Banking FEDERAL RESERVE SYSTEM (CONTINUED) BOARD OF GOVERNORS OF THE FEDERAL RESERVE SYSTEM AVAILABILITY OF FUNDS AND COLLECTION OF CHECKS (REGULATION CC) Substitute Checks § 229.56 Liability. (a)...

  17. 12 CFR 229.56 - Liability.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 12 Banks and Banking 3 2014-01-01 2014-01-01 false Liability. 229.56 Section 229.56 Banks and Banking FEDERAL RESERVE SYSTEM (CONTINUED) BOARD OF GOVERNORS OF THE FEDERAL RESERVE SYSTEM (CONTINUED) AVAILABILITY OF FUNDS AND COLLECTION OF CHECKS (REGULATION CC) Substitute Checks § 229.56 Liability....

  18. 12 CFR 229.56 - Liability.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 12 Banks and Banking 3 2013-01-01 2013-01-01 false Liability. 229.56 Section 229.56 Banks and Banking FEDERAL RESERVE SYSTEM (CONTINUED) BOARD OF GOVERNORS OF THE FEDERAL RESERVE SYSTEM (CONTINUED) AVAILABILITY OF FUNDS AND COLLECTION OF CHECKS (REGULATION CC) Substitute Checks § 229.56 Liability....

  19. 12 CFR 229.56 - Liability.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 12 Banks and Banking 3 2010-01-01 2010-01-01 false Liability. 229.56 Section 229.56 Banks and Banking FEDERAL RESERVE SYSTEM (CONTINUED) BOARD OF GOVERNORS OF THE FEDERAL RESERVE SYSTEM AVAILABILITY OF FUNDS AND COLLECTION OF CHECKS (REGULATION CC) Substitute Checks § 229.56 Liability. (a)...

  20. 46 CFR 310.56 - Physical requirements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... facility designated by the Service Academies Central Medical Review Board. The required physical... 46 Shipping 8 2010-10-01 2010-10-01 false Physical requirements. 310.56 Section 310.56 Shipping... Training of Midshipmen at the United States Merchant Marine Academy § 310.56 Physical requirements....

  1. 30 CFR 56.4104 - Combustible waste.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Combustible waste. 56.4104 Section 56.4104... Control Prohibitions/precautions/housekeeping § 56.4104 Combustible waste. (a) Waste materials, including... properly, waste or rags containing flammable or combustible liquids that could create a fire hazard...

  2. 30 CFR 56.9200 - Transporting persons.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Transporting persons. 56.9200 Section 56.9200... Dumping Transportation of Persons and Materials § 56.9200 Transporting persons. Persons shall not be transported— (a) In or on dippers, forks, clamshells, or buckets except shaft buckets during...

  3. 30 CFR 56.19035 - Headframe design.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Headframe design. 56.19035 Section 56.19035 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE... Headframes and Sheaves § 56.19035 Headframe design. All headframes shall be constructed with suitable...

  4. 30 CFR 56.19035 - Headframe design.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Headframe design. 56.19035 Section 56.19035 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE... Headframes and Sheaves § 56.19035 Headframe design. All headframes shall be constructed with suitable...

  5. 30 CFR 56.19035 - Headframe design.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Headframe design. 56.19035 Section 56.19035 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE... Headframes and Sheaves § 56.19035 Headframe design. All headframes shall be constructed with suitable...

  6. 30 CFR 56.6204 - Hoists.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Hoists. 56.6204 Section 56.6204 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Explosives Transportation § 56.6204 Hoists. (a) Before explosive material...

  7. 46 CFR 56.25-7 - Blanks.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... requirements of 104.5.3 of ASME B31.1 (incorporated by reference; see 46 CFR 56.01-2). ... 46 Shipping 2 2011-10-01 2011-10-01 false Blanks. 56.25-7 Section 56.25-7 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PIPING SYSTEMS AND APPURTENANCES Pipe...

  8. 46 CFR 56.25-5 - Flanges.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... section VIII of the ASME Boiler and Pressure Vessel Code (incorporated by reference; see 46 CFR 56.01-2... 46 Shipping 2 2013-10-01 2013-10-01 false Flanges. 56.25-5 Section 56.25-5 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PIPING SYSTEMS AND APPURTENANCES Pipe...

  9. 46 CFR 56.25-7 - Blanks.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... requirements of 104.5.3 of ASME B31.1 (incorporated by reference; see 46 CFR 56.01-2). ... 46 Shipping 2 2013-10-01 2013-10-01 false Blanks. 56.25-7 Section 56.25-7 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PIPING SYSTEMS AND APPURTENANCES Pipe...

  10. 46 CFR 56.25-7 - Blanks.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... requirements of 104.5.3 of ASME B31.1 (incorporated by reference; see 46 CFR 56.01-2). ... 46 Shipping 2 2014-10-01 2014-10-01 false Blanks. 56.25-7 Section 56.25-7 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PIPING SYSTEMS AND APPURTENANCES Pipe...

  11. 46 CFR 56.25-7 - Blanks.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... requirements of 104.5.3 of ASME B31.1 (incorporated by reference; see 46 CFR 56.01-2). ... 46 Shipping 2 2012-10-01 2012-10-01 false Blanks. 56.25-7 Section 56.25-7 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PIPING SYSTEMS AND APPURTENANCES Pipe...

  12. 46 CFR 56.25-5 - Flanges.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... section VIII of the ASME Boiler and Pressure Vessel Code (incorporated by reference; see 46 CFR 56.01-2... 46 Shipping 2 2012-10-01 2012-10-01 false Flanges. 56.25-5 Section 56.25-5 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PIPING SYSTEMS AND APPURTENANCES Pipe...

  13. 46 CFR 56.25-5 - Flanges.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... section VIII of the ASME Boiler and Pressure Vessel Code (incorporated by reference; see 46 CFR 56.01-2... 46 Shipping 2 2014-10-01 2014-10-01 false Flanges. 56.25-5 Section 56.25-5 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PIPING SYSTEMS AND APPURTENANCES Pipe...

  14. 21 CFR 56.106 - Registration.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Registration. 56.106 Section 56.106 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL INSTITUTIONAL REVIEW BOARDS Organization and Personnel § 56.106 Registration. (a) Who must register? Each IRB in the United States that reviews clinical...

  15. 21 CFR 56.106 - Registration.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Registration. 56.106 Section 56.106 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL INSTITUTIONAL REVIEW BOARDS Organization and Personnel § 56.106 Registration. (a) Who must register? Each IRB in the United States that reviews clinical...

  16. 27 CFR 71.56 - Form.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... Citations § 71.56 Form. Citations shall be issued on the following forms: (a) Form 5000.6. “Order To Show... citations affecting § 71.56, see the List of CFR Sections Affected, which appears in the Finding Aids... 27 Alcohol, Tobacco Products and Firearms 2 2013-04-01 2013-04-01 false Form. 71.56 Section...

  17. 27 CFR 71.56 - Form.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... Citations § 71.56 Form. Citations shall be issued on the following forms: (a) Form 5000.6. “Order To Show... citations affecting § 71.56, see the List of CFR Sections Affected, which appears in the Finding Aids... 27 Alcohol, Tobacco Products and Firearms 2 2012-04-01 2011-04-01 true Form. 71.56 Section...

  18. 27 CFR 71.56 - Form.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... Citations § 71.56 Form. Citations shall be issued on the following forms: (a) Form 5000.6. “Order To Show... citations affecting § 71.56, see the List of CFR Sections Affected, which appears in the Finding Aids... 27 Alcohol, Tobacco Products and Firearms 2 2011-04-01 2011-04-01 false Form. 71.56 Section...

  19. 27 CFR 71.56 - Form.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Citations § 71.56 Form. Citations shall be issued on the following forms: (a) Form 5000.6. “Order To Show... citations affecting § 71.56, see the List of CFR Sections Affected, which appears in the Finding Aids... 27 Alcohol, Tobacco Products and Firearms 2 2010-04-01 2010-04-01 false Form. 71.56 Section...

  20. 27 CFR 71.56 - Form.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Citations § 71.56 Form. Citations shall be issued on the following forms: (a) Form 5000.6. “Order To Show... citations affecting § 71.56, see the List of CFR Sections Affected, which appears in the Finding Aids... 27 Alcohol, Tobacco Products and Firearms 2 2014-04-01 2014-04-01 false Form. 71.56 Section...

  1. 28 CFR 345.56 - Vacation pay.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 28 Judicial Administration 2 2010-07-01 2010-07-01 false Vacation pay. 345.56 Section 345.56 Judicial Administration FEDERAL PRISON INDUSTRIES, INC., DEPARTMENT OF JUSTICE FEDERAL PRISON INDUSTRIES (FPI) INMATE WORK PROGRAMS Inmate Pay and Benefits § 345.56 Vacation pay. Inmate workers are granted FPI vacation pay by the SOI when their...

  2. 42 CFR 56.603 - Project elements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... set forth in the most recent CSA Poverty Income Guidelines (42 CFR 1060.2) (except that nominal fees... 42 Public Health 1 2010-10-01 2010-10-01 false Project elements. 56.603 Section 56.603 Public... SERVICES Grants for Operating Migrant Health Programs § 56.603 Project elements. A project for operating...

  3. 42 CFR 56.703 - Project elements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Project elements. 56.703 Section 56.703 Public... SERVICES Grants for Technical Assistance § 56.703 Project elements. A project for the provision of.... (c) Where the project will provide training to the staff of a center or entity in management or...

  4. 42 CFR 56.503 - Project elements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Project elements. 56.503 Section 56.503 Public... SERVICES Grants for Planning and Developing Migrant Health Programs § 56.503 Project elements. A project... families within the project's catchment area in the calendar year in which the grant is made and the...

  5. 42 CFR 56.203 - Project elements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Project elements. 56.203 Section 56.203 Public... SERVICES Grants for Planning and Developing Migrant Health Centers § 56.203 Project elements. A project for... gradual assumption of operational status of the project so that the project will, in the judgment of...

  6. 42 CFR 56.303 - Project elements.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... the most recent CSA Poverty Income Guidelines (42 CFR 1060.2) (except that nominal fees for service... 42 Public Health 1 2010-10-01 2010-10-01 false Project elements. 56.303 Section 56.303 Public... SERVICES Grants for Operating Migrant Health Centers § 56.303 Project elements. A migrant health...

  7. 45 CFR 400.56 - Structure.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 45 Public Welfare 2 2011-10-01 2011-10-01 false Structure. 400.56 Section 400.56 Public Welfare Regulations Relating to Public Welfare OFFICE OF REFUGEE RESETTLEMENT, ADMINISTRATION FOR CHILDREN AND... § 400.56 Structure. (a) States may choose to enter into a partnership agreement with local...

  8. 50 CFR 648.56 - Scallop research.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... description of methods of data collection and analysis; a discussion of results and any relevant conclusions... 50 Wildlife and Fisheries 8 2010-10-01 2010-10-01 false Scallop research. 648.56 Section 648.56... Scallop Fishery § 648.56 Scallop research. (a) Annually, the Council and NMFS shall prepare and issue...

  9. 40 CFR 422.56 - [Reserved

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 28 2010-07-01 2010-07-01 true 422.56 Section 422.56 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS PHOSPHATE MANUFACTURING POINT SOURCE CATEGORY Defluorinated Phosphoric Acid Subcategory § 422.56...

  10. 40 CFR 422.56 - [Reserved

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 30 2013-07-01 2012-07-01 true 422.56 Section 422.56 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS PHOSPHATE MANUFACTURING POINT SOURCE CATEGORY Defluorinated Phosphoric Acid Subcategory § 422.56...

  11. 40 CFR 422.56 - [Reserved

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 29 2014-07-01 2012-07-01 true 422.56 Section 422.56 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS PHOSPHATE MANUFACTURING POINT SOURCE CATEGORY Defluorinated Phosphoric Acid Subcategory § 422.56...

  12. 40 CFR 422.56 - [Reserved

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 30 2012-07-01 2012-07-01 false 422.56 Section 422.56 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS PHOSPHATE MANUFACTURING POINT SOURCE CATEGORY Defluorinated Phosphoric Acid Subcategory § 422.56...

  13. 40 CFR 422.56 - [Reserved

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 29 2011-07-01 2009-07-01 true 422.56 Section 422.56 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS PHOSPHATE MANUFACTURING POINT SOURCE CATEGORY Defluorinated Phosphoric Acid Subcategory § 422.56...

  14. 18 CFR 701.56 - Observers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 18 Conservation of Power and Water Resources 2 2014-04-01 2014-04-01 false Observers. 701.56 Section 701.56 Conservation of Power and Water Resources WATER RESOURCES COUNCIL COUNCIL ORGANIZATION Headquarters Organization § 701.56 Observers. (a) Chairmen and Vice-Chairmen of River Basin...

  15. 18 CFR 701.56 - Observers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 18 Conservation of Power and Water Resources 2 2013-04-01 2012-04-01 true Observers. 701.56 Section 701.56 Conservation of Power and Water Resources WATER RESOURCES COUNCIL COUNCIL ORGANIZATION Headquarters Organization § 701.56 Observers. (a) Chairmen and Vice-Chairmen of River Basin...

  16. 18 CFR 701.56 - Observers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 18 Conservation of Power and Water Resources 2 2012-04-01 2012-04-01 false Observers. 701.56 Section 701.56 Conservation of Power and Water Resources WATER RESOURCES COUNCIL COUNCIL ORGANIZATION Headquarters Organization § 701.56 Observers. (a) Chairmen and Vice-Chairmen of River Basin...

  17. 46 CFR 56.20-1 - General.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... to those of ASME B31.1 (incorporated by reference; see 46 CFR 56.01-2) or Section VIII of the ASME Boiler and Pressure Vessel Code (incorporated by reference; see 46 CFR 56.01-2), if the valve shape...; see 46 CFR 56.01-2); or (iii) Other means specifically accepted by the Marine Safety Center....

  18. 29 CFR 2700.56 - Discovery; general.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 29 Labor 9 2011-07-01 2011-07-01 false Discovery; general. 2700.56 Section 2700.56 Labor... Hearings § 2700.56 Discovery; general. (a) Discovery methods. Parties may obtain discovery by one or more... upon property for inspecting, copying, photographing, and gathering information. (b) Scope of...

  19. 29 CFR 2700.56 - Discovery; general.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 29 Labor 9 2014-07-01 2014-07-01 false Discovery; general. 2700.56 Section 2700.56 Labor... Hearings § 2700.56 Discovery; general. (a) Discovery methods. Parties may obtain discovery by one or more... upon property for inspecting, copying, photographing, and gathering information. (b) Scope of...

  20. 30 CFR 56.19037 - Fleet angles.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Fleet angles. 56.19037 Section 56.19037 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND... Sheaves § 56.19037 Fleet angles. Fleet angles on hoists installed after November 15, 1979, shall not...