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Sample records for iron oxidation state

  1. Oxidation state of iron in plagioclase from lunar basalts.

    NASA Technical Reports Server (NTRS)

    Hafner, S. S.; Virgo, D.; Warburton, D.

    1971-01-01

    Determination of the oxidation state of iron in the plagioclase from the coarse-grained basalts 10044 and 12021, using Mossbauer spectroscopy. The location of iron in the crystal structure was also investigated. The spectra show that iron is in the high-spin ferrous state, and they located at least two distinct positions with different coordination numbers. Some excess resonant absorption is probably due to Fe(3+), although the Fe(3+) doublet could not be positively resolved.

  2. Oxidation state of iron in plagioclase from lunar basalts.

    NASA Technical Reports Server (NTRS)

    Hafner, S. S.; Virgo, D.; Warburton, D.

    1971-01-01

    Determination of the oxidation state of iron in the plagioclase from the coarse-grained basalts 10044 and 12021, using Mossbauer spectroscopy. The location of iron in the crystal structure was also investigated. The spectra show that iron is in the high-spin ferrous state, and they located at least two distinct positions with different coordination numbers. Some excess resonant absorption is probably due to Fe(3+), although the Fe(3+) doublet could not be positively resolved.

  3. Iron Partitioning and Oxidation State in Earth's Lower Mantle

    NASA Astrophysics Data System (ADS)

    Piet, H.; Badro, J.; Nabiei, F.; Dennenwaldt, T.; Shim, S. H. D.; Cantoni, M.; Hébert, C.; Gillet, P.

    2015-12-01

    Valence state and concentrations of iron in lower mantle phases have strong effects on their chemical and physical properties. Experimental studies have reported stark differences in iron partitioning between bridgmanite (Brg) and ferropericlase (Fp) for San Carlos olivine [1] and pyrolite [2] systems. We recently performed experiments at lower mantle conditions for an Al-rich olivine system [3] and observed an iron enrichment of the silicate phase very similar to that in pyrolite. Mössbauer studies [4] have shown that in the presence of aluminum non negligible amounts of Fe3+ could be incorporated in bridgmanite explaining the observed iron enrichment. Non negligible amounts of Fe3+ in the lower mantle could influence transport properties of the phases [5]. The evaluation of ferrous and ferric iron concentrations in lower mantle mineral assemblages is then key to a thorough understanding of geophysical observations and associated mantle dynamics. We used electron energy loss spectroscopy technique to quantify the proportions of Fe2+ and Fe3+ iron in Brg and Fp phases previously synthesized from Al-rich olivine composition [3]. The oxidation state of iron in the lower mantle will be discussed as well as ensuing implications on transport properties for relevant lower mantle compositions. References [1] Sakai et al., 2009 [2] Prescher et al., 2014 [3] Piet et al., submitted [4] McCammon et al., 1996 [5] Xu et al., 1998

  4. Microanalysis of iron oxidation state in iron oxides using X Ray Absorption Near Edge Structure (XANES)

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Delaney, J.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.

  5. Mapping the Iron Oxidation State in Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Martin, A. M.; Treimann, A. H.; Righter, K.

    2017-01-01

    Several types of Martian igneous meteorites have been identified: clinopyroxenites (nakhlites), basaltic shergottites, peridotitic shergottites, dunites (chassignites) and orthopyroxenites [1,2]. In order to constrain the heterogeneity of the Martian mantle and crust, and their evolution through time, numerous studies have been performed on the iron oxidation state of these meteorites [3,4,5,6,7,8,9]. The calculated fO2 values all lie within the FMQ-5 to FMQ+0.5 range (FMQ representing the Fayalite = Magnetite + Quartz buffer); however, discrepancies appear between the various studies, which are either attributed to the choice of the minerals/melts used, or to the precision of the analytical/calculation method. The redox record in volcanic samples is primarily related to the oxidation state in the mantle source(s). However, it is also influenced by several deep processes: melting, crystallization, magma mixing [10], assimilation and degassing [11]. In addition, the oxidation state in Martian meteorites is potentially affected by several surface processes: assimilation of sediment/ crust during lava flowing at Mars' surface, low temperature micro-crystallization [10], weathering at the surface of Mars and low temperature reequilibration, impact processes (i.e. high pressure phase transitions, mechanical mixing, shock degassing and melting), space weathering, and weathering on Earth (at atmospheric conditions different from Mars). Decoding the redox record of Martian meteorites, therefore, requires large-scale quantitative analysis methods, as well as a perfect understanding of oxidation processes.

  6. Superparamagnetic Iron Oxide Nanoparticles with Variable Size and an Iron Oxidation State as Prospective Imaging Agents

    PubMed Central

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

    2013-01-01

    Magnetite nanoparticles in the size range of 3.2-7.5 nm were synthesized in high yields under variable reaction conditions using high-temperature hydrolysis of the precursor iron(II) and iron(III) alkoxides in diethylene glycol solution. The average sizes of the particles were adjusted by changing the reaction temperature and time and by using a sequential growth technique. To obtain γ-iron(III) oxide particles in the same range of sizes, magnetite particles were oxidized with dry oxygen in diethylene glycol at room temperature. The products were characterized by DLS, TEM, X-ray powder diffractometry, TGA, chemical analysis, and magnetic measurements. NMR r1 and r2 relaxivity measurements in water and diethylene glycol (for OH and CH2 protons) have shown a decrease in the r2/r1 ratio with the particle size reduction, which correlates with the results of magnetic measurements on magnetite nanoparticles. Saturation magnetization of the oxidized particles was found to be 20% lower than that for Fe3O4 with the same particle size, but their r1 relaxivities are similar. Because the oxidation of magnetite is spontaneous under ambient conditions, it was important to learn that the oxidation product has no disadvantages as compared to its precursor and therefore may be a better prospective imaging agent because of its chemical stability. PMID:23249219

  7. GAS-PHASE FLAME SYNTHESIS AND PROPERTIES OF MAGNETIC IRON OXIDE NANOPARTICLES WITH REDUCED OXIDATION STATE

    PubMed Central

    Kumfer, Benjamin M; Shinoda, Kozo; Jeyadevan, Balachandran; Kennedy, Ian M

    2010-01-01

    Iron oxide nanoparticles of reduced oxidation state, mainly in the form of magnetite, have been synthesized utilizing a new continuous, gas-phase, nonpremixed flame method using hydrocarbon fuels. This method takes advantage of the characteristics of the inverse flame, which is produced by injection of oxidizer into a surrounding flow of fuel. Unlike traditional flame methods, this configuration allows for the iron particle formation to be maintained in a more reducing environment. The effects of flame temperature, oxygen-enrichment and fuel dilution (i.e. the stoichiometric mixture fraction), and fuel composition on particle size, Fe oxidation state, and magnetic properties are evaluated and discussed. The crystallite size, Fe(II) fraction, and saturation magnetization were all found to increase with flame temperature. Flames of methane and ethylene were used, and the use of ethylene resulted in particles containing metallic Fe(0), in addition to magnetite, while no Fe(0) was present in samples synthesized using methane. PMID:20228941

  8. Effects of iron oxidation state on viscosity, lunar composition 15555

    NASA Technical Reports Server (NTRS)

    Cukierman, M.; Uhlmann, D. R.

    1974-01-01

    The viscous flow behavior of a 9.6-kg lunar rock containing 22.5 wt.% FeO was studied in the temperature ranges from 620 to 700 C and from 1215 to 1400 C. The material was synthesized under mildy reducing conditions to simulate the Fe(2+)/total Fe ratio of the lunar environment. The effect of iron oxidation state on flow behavior in the high viscosity region is studied for specimens of the 15555 composition with Fe(2+) concentration ratios of 0.94, 0.76, and 0.20. A change in ratio from 0.94 to 0.76 had no observable effect on viscosity, whereas a change from 0.76 to 0.20 was accompanied by a drastic increase in viscosity (some three orders of magnitude) at a given temperature, but without changing the form of the variation of viscosity with temperature. The flow behavior is analyzed as a function of the structural features of the glasses.

  9. Arsenic removal from water using flame-synthesized iron oxide nanoparticles with variable oxidation states

    PubMed Central

    Abid, Aamir D.; Kanematsu, Masakazu; Young, Thomas M.; Kennedy, Ian M.

    2013-01-01

    We utilized gas-phase diffusion flame synthesis, which has potential for large-scale production of metal oxide nanoparticles, to produce iron oxide nanoparticles (IONPs) with variable oxidation states. The efficacy of these materials in removal of arsenate (As(V) ) from water was assessed. Two different flame configurations, a diffusion flame (DF) and an inverse diffusion flame (IDF), were employed to synthesize six different IONPs by controlling flame conditions. The IONPs produced in the IDF configuration (IDF-IONPs) had smaller particle diameters (4.8 – 8.2 nm) and larger surface areas (141–213 m2/g) than the IONPs produced in the DF configuration (29 nm, 36 m2/g), which resulted in their higher adsorption capacities. As(V) adsorption capacities of the IDF-IONPs increased when the IONPs were synthesized in more oxidizing conditions. The fully oxidized IDF-IONPs, maghemite (γ-Fe2O3), showed the highest As(V) adsorption capacity, comparable to that of magnetite nanocrystals synthesized by thermal decomposition of iron pentacarbonyl and equivalent to three to four times higher capacity than that of a commonly used goethite-based adsorbent. All IONPs were magnetically responsive, which is of great importance for solid−liquid separation. This study demonstrates that the IONPs synthesized in gas-phase flame, particularly IDF-IONPs, are excellent adsorbents because of their high As(V) sorption capacity, potential for large-scale production, and useful magnetic property. PMID:23645964

  10. Arsenic removal from water using flame-synthesized iron oxide nanoparticles with variable oxidation states.

    PubMed

    Abid, Aamir D; Kanematsu, Masakazu; Young, Thomas M; Kennedy, Ian M

    2013-02-01

    We utilized gas-phase diffusion flame synthesis, which has potential for large-scale production of metal oxide nanoparticles, to produce iron oxide nanoparticles (IONPs) with variable oxidation states. The efficacy of these materials in removal of arsenate (As(V) ) from water was assessed. Two different flame configurations, a diffusion flame (DF) and an inverse diffusion flame (IDF), were employed to synthesize six different IONPs by controlling flame conditions. The IONPs produced in the IDF configuration (IDF-IONPs) had smaller particle diameters (4.8 - 8.2 nm) and larger surface areas (141-213 m(2)/g) than the IONPs produced in the DF configuration (29 nm, 36 m(2)/g), which resulted in their higher adsorption capacities. As(V) adsorption capacities of the IDF-IONPs increased when the IONPs were synthesized in more oxidizing conditions. The fully oxidized IDF-IONPs, maghemite (γ-Fe2O3), showed the highest As(V) adsorption capacity, comparable to that of magnetite nanocrystals synthesized by thermal decomposition of iron pentacarbonyl and equivalent to three to four times higher capacity than that of a commonly used goethite-based adsorbent. All IONPs were magnetically responsive, which is of great importance for solid-liquid separation. This study demonstrates that the IONPs synthesized in gas-phase flame, particularly IDF-IONPs, are excellent adsorbents because of their high As(V) sorption capacity, potential for large-scale production, and useful magnetic property.

  11. Oxidation states of iron in the terrestrial planets: Evidence and implications for accretion models

    NASA Technical Reports Server (NTRS)

    Huguenin, R. L.; Harris, S. L.

    1985-01-01

    Analyses of Mars spectra reveal that primary minerals may be more iron rich than average basalts on Earth, and the oxidation state of iron in the pyroxines suggests equally high or higher oxygen fugacities on Mars than Earth. Analysis of Mercury spectra reveal that silicate iron contents are substantially lower than those on Mars. Mercury, however, probably has a substantial iron core. This is consistent with a lower oxidation state of iron on Mercury than on Mars. These findings are consistent with predictions of models of equilibrium condensation and homogeneous accretion. Those models predict that Mercury would have negligible Fe(2+) in silicates (Fe/Fe+Mg approx. 0.5). For Mercury iron should be virtually all metallic, while for Mars the iron would be all oxidized as FeS and silicate. Surface measurements of Fe/Fe+Mg on Venus, Earth, and Mars further support the predicted relative increase in Fe/Fe+Mg ratio (increased oxidation state) with distance from the Sun. The implied high oxygen fugacities on Mars (Fe(3+) in silicates) provide additional consistence with the model predictions.

  12. [Superparamagnetic iron oxide particles: current state and future development].

    PubMed

    Taupitz, M; Schmitz, S; Hamm, B

    2003-06-01

    A wide range of applications for superparamagnetic iron oxide (SPIO) particles as contrast media for MRI has emerged over the last 15 years. SPIO particles can be manufactured with different particle sizes and surface coatings. Large SPIO particles (50-150 nm) predominantly produce a signal decrease or T2 -shortening and are used as contrast media for MRI of the liver and spleen. They have a high accuracy, especially in detecting liver metastases (approved for clinical use: AMI-25 (Endorem or Ferridex), SHU-555A (Resovist)). Smaller particles (about 20 nm in diameter) show a different organ distribution and have a potential for improving noninvasive lymph node assessment or characterizing vulnerable atherosclerotic plaques (in clinical trials: AMI-227 [Sinerem or Combidex]). Particles with an optimized T1-relaxivity and prolonged intravascular circulation time can be used as blood pool contrast media for MR angiography. The currently investigated indications are MR angiography of the trunk, peripheral vessels, and coronary arteries (e.g., SHU-555 C (Supravist), VSOP-C 184). Other applications of small SPIO particles include MRI of the bone marrow and the determination of perfusion parameters in tumors or other tissues like the myocardium. SPIO particles with a modified coat can be used in so-called molecular imaging, such as receptor-directed imaging, cell labeling for in-vivo monitoring of cell migration, e.g., stem cell labeling, and labeling of gene constructs for localization in genetic therapy. In tumor therapy SPIO particles can serve as mediators for hyperthermia. SPIO is a powerful MR contrast medium with manifold applications ranging from diagnostic imaging to molecular medicine.

  13. Iron Oxides

    SciTech Connect

    Qafoku, Nikolla; Amonette, James E.

    2016-09-19

    Abstract: Fe oxides are common clay-sized oxide, oxyhydroxide and hydroxide soil minerals. They are compounds of Fe, O, and H that have structures based on close-packed arrays of O. The octahedral and tetrahedral cavities within these arrays are filled with either Fe3+ or Fe2+ to form Fe(O/OH)6, FeO6, or FeO4 structural units. All of the naturally occurring Fe oxide minerals usually undergo some degree of isomorphous substitution of other metal ions for Fe in their structures. Relatively simple techniques may be used to identify Fe oxides in the field based on their typical colors and magnetic properties. In the laboratory, a variety of instrumental techniques can be used to confirm phase identity and to quantify amount. Of these, X-ray diffraction, infrared spectroscopy, electron microscopy, thermal analysis, and Mössbauer spectroscopy are the most commonly used techniques. As oxides, the functional groups on their surfaces may have positive, negative, or no charge depending on pH and on the concentration and nature of other ions in the contact solution. A net positive surface charge usually is observed in soils because Fe oxides have a point-of-zero-charge in the neutral or slightly basic pHs. The functional groups on the surface form complexes with cations and anions from the aqueous phase. Their sorption and electron-buffering properties significantly affect the geochemical cycles of almost all elements having agronomic or environmental significance.

  14. The Effects of Iron Oxidation State on Clay Swelling,

    DTIC Science & Technology

    1983-03-07

    swelling, montmorillonite , nontronite, smectite, water, DLVO theory, surface charge, dissolution, methods, aluminum, silicon, inert atmosphere. 2G...that many physical properties of bulk water are changed when it is adsorbed between layers of Na4- montmorillonite (e.g., Oster and Low, 1964; Kolaian...Na+- montmorillonite accounted for about 13% of the total water content in the free-swelling state. We can therefore express the total water content

  15. Determination of oxidation state of iron in normal and pathologically altered human aortic valves

    NASA Astrophysics Data System (ADS)

    Czapla-Masztafiak, J.; Lis, G. J.; Gajda, M.; Jasek, E.; Czubek, U.; Bolechała, F.; Borca, C.; Kwiatek, W. M.

    2015-12-01

    In order to investigate changes in chemical state of iron in normal and pathologically altered human aortic valves X-ray absorption spectroscopy was applied. Since Fe is suspected to play detrimental role in aortic valve stenosis pathogenesis the oxidation state of this element has been determined. The experimental material consisted of 10 μm sections of valves excised during routine surgery and from autopsies. The experiment was performed at the MicroXAS beamline of the SLS synchrotron facility in Villigen (Switzerland). The Fe K-edge XANES spectra obtained from tissue samples were carefully analyzed and compared with the spectra of reference compounds containing iron in various chemical structures. The analysis of absorption edge position and shape of the spectra revealed that both chemical forms of iron are presented in valve tissue but Fe3+ is the predominant form. Small shift of the absorption edge toward higher energy in the spectra from stenotic valve samples indicates higher content of the Fe3+ form in pathological tissue. Such a phenomenon suggests the role of Fenton reaction and reactive oxygen species in the etiology of aortic valve stenosis. The comparison of pre-edge regions of XANES spectra for control and stenotic valve tissue confirmed no differences in local symmetry or spin state of iron in analyzed samples.

  16. Iron oxidation state of FeTiO[subscript 3] under high pressure

    SciTech Connect

    Wu, X.; Steinle-Neumann, G.; Narygina, O.; Kantor, I.; McCammon, C.; Pascarelli, S.; Aquilanti, G.; Prakapenka, V.; Dubrovinsky, L.

    2009-08-13

    The oxidation state of iron in FeTiO{sub 3} under high pressure was investigated by combining x-ray diffraction, Moessbauer spectroscopy, x-ray-absorption spectroscopy, and density-functional theory based calculations. Our results demonstrate that the ilmenite-to-perovskite phase transition occurs above 20 GPa at room temperature and on compression two phases coexist to 40 GPa. The Fe{sup 3+}/{Sigma}Fe ratio increases up to 16 GPa, probably attributed to the d-electron drifting of cations via the oxygen bridge in the adjacent octahedral, then decreases at higher pressure due to the ilmenite-to-perovskite phase transition accompanied by a slight decrease in iron valence state. Our ab initio calculations further show that the most significant changes in the charge distribution in FeTiO{sub 3} are associated with Ti and O.

  17. Oxidation state of iron and extensive redistribution of sulfur in thermally modified Stardust particles

    NASA Astrophysics Data System (ADS)

    Leroux, Hugues; Roskosz, Mathieu; Jacob, Damien

    2009-02-01

    Two representative thermally modified Stardust samples were investigated by analytical transmission electron microscopy in order to decipher their iron oxidation state after the strong thermal episode due to the capture in aerogel. Their dominant microstructure consists of evenly distributed rounded Fe-Ni-S nano-droplets within a silica-rich glassy matrix. The mineralogy and associated redox state of iron is assessed using a Fe-Mg-S ternary diagram on which ferromagnesian silicates, sulfides and metal can be represented and potentially compared with any other extraterrestrial material. In this diagram, all the data (bulk and local analysis of silicates, sulfide + metal) scatter along a mixing line between the Mg corner and the average composition of the iron-sulfide. There is an obvious genetic relationship between the different phases observed in such samples, further supported by the very low concentration of iron in the glassy matrix. Silicate glasses contain a significant concentration of dissolved sulfur probably present as MgS complexes. This chemical signature is typical of highly reduced environments. These secondary microstructures were established during the high temperature stage of the capture. A significant part of the Fe-droplets formed in situ by reduction at high temperature of ferromagnesian silicates (olivine and pyroxenes) during the impact. At this stage, the indigenous sulfides destabilized and sulfur readily volatilized as S 2, diffused into molten materials and condensed later onto the Fe-precipitates that formed in the silicate melt. This scenario is supported by the structure of Fe-Ni-S beads with a metal core and a sulfide rim. It will be difficult to derive reliable information on the redox state of 81P/Wild 2 particles based on bulk analyses of whole tracks because particles found along the walls of tracks suffered strong reduction reactions, contrary to terminal particles that may have preserved their pristine redox state. The capture

  18. Iron oxide surfaces

    NASA Astrophysics Data System (ADS)

    Parkinson, Gareth S.

    2016-03-01

    The current status of knowledge regarding the surfaces of the iron oxides, magnetite (Fe3O4), maghemite (γ-Fe2O3), haematite (α-Fe2O3), and wüstite (Fe1-xO) is reviewed. The paper starts with a summary of applications where iron oxide surfaces play a major role, including corrosion, catalysis, spintronics, magnetic nanoparticles (MNPs), biomedicine, photoelectrochemical water splitting and groundwater remediation. The bulk structure and properties are then briefly presented; each compound is based on a close-packed anion lattice, with a different distribution and oxidation state of the Fe cations in interstitial sites. The bulk defect chemistry is dominated by cation vacancies and interstitials (not oxygen vacancies) and this provides the context to understand iron oxide surfaces, which represent the front line in reduction and oxidation processes. Fe diffuses in and out from the bulk in response to the O2 chemical potential, forming sometimes complex intermediate phases at the surface. For example, α-Fe2O3 adopts Fe3O4-like surfaces in reducing conditions, and Fe3O4 adopts Fe1-xO-like structures in further reducing conditions still. It is argued that known bulk defect structures are an excellent starting point in building models for iron oxide surfaces. The atomic-scale structure of the low-index surfaces of iron oxides is the major focus of this review. Fe3O4 is the most studied iron oxide in surface science, primarily because its stability range corresponds nicely to the ultra-high vacuum environment. It is also an electrical conductor, which makes it straightforward to study with the most commonly used surface science methods such as photoemission spectroscopies (XPS, UPS) and scanning tunneling microscopy (STM). The impact of the surfaces on the measurement of bulk properties such as magnetism, the Verwey transition and the (predicted) half-metallicity is discussed. The best understood iron oxide surface at present is probably Fe3O4(100); the structure is

  19. Iron Stable Isotopes, Magmatic Differentiation and the Oxidation State of Mariana Arc Magmas

    NASA Astrophysics Data System (ADS)

    Williams, H. M.; Prytulak, J.; Plank, T. A.; Kelley, K. A.

    2014-12-01

    Arc magmas are widely considered to be oxidized, with elevated ferric iron contents (Fe3+/ΣFe) relative to mid-ocean ridge lavas (1, 2). However, it is unclear whether the oxidized nature of arc basalts is a primary feature, inherited from the sub-arc mantle, or the product of magmatic differentiation and/or post eruptive alteration processes (3). Iron stable isotopes can be used to trace the distribution of Fe during melting and magmatic differentiation processes (4, 5). Here we present Fe isotope data for well-characterized samples (6-8) from islands of the Central Volcanic Zone (CVZ) of the intra-oceanic Mariana Arc to explore the effect of magmatic differentiation processes on Fe isotope systematics. The overall variation in the Fe isotope compositions (δ57Fe) of samples from the CVZ islands ranges from -0.10 ±0.04 to 0.29 ± 0.01 ‰. Lavas from Anatahan are displaced to lower overall δ57Fe values (range -0.10 ±0.04 to 0.18 ±0.01 ‰) relative to other CVZ samples. Fe isotopes in the Anatahan suite (range -0.10 ±0.04 to 0.18 ±0.01 ‰) are positively correlated with SiO2 and negatively correlated with Ca, Fe2O3(t), Cr and V and are displaced to lower overall δ57Fe values relative to other CVZ samples. These correlations can be interpreted in terms of clinopyroxene and magnetite fractionation, with magnetite saturation throughout the differentiation sequence. Magnetite saturation is further supported by negative correlations between V, Fe2O3(t), Cr and MgO (for MgO <3.5 wt%). The early saturation of magnetite in the Anatahan and CVZ lavas is likely to be a function of high melt water content (9, 10) and potentially elevated melt oxidation state. Future work will focus on determining the relationships between mineral Fe isotope partitioning effects and melt composition and oxidation state. 1. R. Arculus, Lithos (1994). 2. K. A. Kelley et al., Science (2009). 3. C.-T. A. Lee et al., J. Pet. (2005). 4. N. Dauphas et al., EPSL (2014). 5. P. A. Sossi et al

  20. Oxidation state of iron in komatiitic melt inclusions indicates hot Archaean mantle

    SciTech Connect

    Berry, A.J.; Danyushevsky, L.; O'Neill, H.C.; Newville, M.; Sutton, S.R.

    2008-10-16

    Komatiites are volcanic rocks mainly of Archaean age that formed by unusually high degrees of melting of mantle peridotite. Their origin is controversial and has been attributed to either anhydrous melting of anomalously hot mantle or hydrous melting at temperatures only modestly greater than those found today. Here we determine the original Fe{sup 3+}/{Sigma}Fe ratio of 2.7-Gyr-old komatiitic magma from Belingwe, Zimbabwe, preserved as melt inclusions in olivine, to be 0.10 {+-} 0.02, using iron K-edge X-ray absorption near-edge structure spectroscopy. This value is consistent with near-anhydrous melting of a source with a similar oxidation state to the source of present-day mid-ocean-ridge basalt. Furthermore, this low Fe{sup 3+}/{Sigma}Fe value, together with a water content of only 0.2--0.3 wt%, excludes the possibility that the trapped melt contained significantly more water that was subsequently lost from the inclusions by reduction to H{sub 2} and diffusion. Loss of only 1.5 wt% water by this mechanism would have resulted in complete oxidation of iron (that is, the Fe{sup 3+}/{Sigma}Fe ratio would be {approx}1). There is also no petrographic evidence for the loss of molecular water. Our results support the identification of the Belingwe komatiite as a product of high mantle temperatures ({approx}1,700 C), rather than melting under hydrous conditions (3--5-wt% water), confirming the existence of anomalously hot mantle in the Archaean era.

  1. Iron Oxidation States and Distribution in the 4Bi2O3. PbO Glass Matrix

    NASA Astrophysics Data System (ADS)

    Simon, V.; Pop, R.; Neumann, M.; Chiuzbaian, S. G.; Coldea, M.; Simon, S.

    Magnetic susceptibility and XPS results on xFe2O3 . (100-x) [4Bi2O3 . PbO] where 0oxidation states and the distribution of iron ions in the lead-bismuthate matrix. The valence state of iron ions changes from Fe3+ to Fe2+ as the Fe2O3 content increases from 1 to 20 mol%. The XPS data indicate the migration of metallic elements in the inner part of the bulk investigated samples.

  2. The iron-oxidizing proteobacteria.

    PubMed

    Hedrich, Sabrina; Schlömann, Michael; Johnson, D Barrie

    2011-06-01

    The 'iron bacteria' are a collection of morphologically and phylogenetically heterogeneous prokaryotes. They include some of the first micro-organisms to be observed and described, and continue to be the subject of a considerable body of fundamental and applied microbiological research. While species of iron-oxidizing bacteria can be found in many different phyla, most are affiliated with the Proteobacteria. The latter can be subdivided into four main physiological groups: (i) acidophilic, aerobic iron oxidizers; (ii) neutrophilic, aerobic iron oxidizers; (iii) neutrophilic, anaerobic (nitrate-dependent) iron oxidizers; and (iv) anaerobic photosynthetic iron oxidizers. Some species (mostly acidophiles) can reduce ferric iron as well as oxidize ferrous iron, depending on prevailing environmental conditions. This review describes what is currently known about the phylogenetic and physiological diversity of the iron-oxidizing proteobacteria, their significance in the environment (on the global and micro scales), and their increasing importance in biotechnology.

  3. Oxidation state of iron in mantle-derived magmas of the Icelandic rift zone

    NASA Astrophysics Data System (ADS)

    Öskarsson, N.; Helgason, Ö.; Steinthórsson, S.

    1994-12-01

    Olivine tholeiites are mantle-derived magmas that are formed by partial melting of their deep sources and which have equilibrated with mineral assemblages at slightly different subcrustal pressure-temperature conditions prior to eruption. The minimum depth of the pre-eruptive reservoirs of these magmas is in the order of 10 15 km and their liquidus temperatures fall within the range of 1180 1240 ‡C. Three types of primitive olivine tholeiites are exposed along the rift zones in Iceland. In the present study, the ferric/ferrous ratios of natural glasses (pillow crusts) of the three types of olivine tholeiites were obtained by Mössbauer spectrometry. This technique is particularly well suited for the analysis of high-Mg glasses since it resolves microcrystallites of olivine which contribute to ferrous iron in chemical analysis. All results fall within 10 15% Fe(III). At the liquidus temperature of these glasses, this ferric/ferrous ratio corresponds to fugacity close to the fayalite-magnetite-quartz-oxygen (FMQ) buffer with an uncertainty of less than one log unit in fO2. This result confirms that there is no significant difference in the oxidation state of the three magma types.

  4. The solid state conversion reaction of cobalt oxide and iron fluoride thin films

    NASA Astrophysics Data System (ADS)

    Thorpe, Ryan

    Iron (II) fluoride and cobalt (II) oxide are candidate electrode materials for a new class of rechargeable lithium ion batteries known as conversion batteries. Although the energy storage capacity of these materials represents a significant improvement over that of conventional electrode materials, many challenges must be overcome before conversion batteries can become commercially viable. Chief among these challenges is a loss of energy storage capacity as a function of the number of charge-discharge cycles. In this study, FeF2 and CoO thin films have been studied as solid state analogues for lithium ion battery electrodes. These films were grown with different crystalline orientations and exposed to lithium in an ultra high vacuum chamber in order to simulate the discharge of a conversion electrode. The electronic structure and chemical phase of the films before and after exposure to lithium were characterized using x-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), and inverse photoemission spectroscopy (IPS). The depth and homogeneity of the conversion reaction in the thin films was measured as a function of lithium exposure using angle-resolved XPS (ARXPS). The crystalline structure and morphology were studied using scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). For polycrystalline FeF2 and CoO films, the products of the solid state conversion reactions were similar to those observed in electrochemical measurements. However, parasitic reaction pathways were identified for both reactions. The products of these reaction were found to inhibit the full conversion of the thin films, and are possibly responsible for the poor reaction kinetics in electrochemical cells. Furthermore, the diffusion of lithium into the FeF2 and CoO surfaces, and the concomitant conversion reaction, was found to depend strongly on the orientation of the surface. These differences in diffusivity could partially be

  5. Iron oxides as pedoenvironmental indicators: state of the art, answers and questions (Philippe Duchaufour Medal Lecture)

    NASA Astrophysics Data System (ADS)

    Torrent, J.

    2012-04-01

    The colour and magnetic properties of soils largely reflect the content and mineralogy of their iron oxides, which in turn relate to the physical, chemical and biological characteristics of the soil environment. For more than 50 years, soil mineralogists and chemists have collected data for iron oxides in soils formed in widely different environments and tried to understand the complex nature of the different suites and formation pathways for these minerals via laboratory experiments. The discovery of ferrihydrite —the poorly crystalline precursor of most Fe oxides— in 1971, and the recognition of its common presence in soils, raised interest in deciphering the environmental factors that affect its transformation into goethite and hematite, the two most abundant crystalline iron oxides in soil. Field observations were consistent with laboratory experiments in which temperature, water activity, pH, foreign ions and organic matter were found to play a key role in the crystallization of ferrihydrite. Thus, the hematite/(hematite + goethite) ratio increased with increasing temperature and also with the likelihood of seasonal soil drying. Exploiting this ratio as a (pedo)environment indicator is, however, not devoid of problems derived from insufficient knowledge of the interactions between the influential chemical variables, difficulties in quantifying the two minerals and changes brought about by reductive dissolution. Soil formation usually leads to magnetic enhancement as a result of the production of magnetite and/or maghemite, which are ferrimagnetic iron oxides, and, possibly, an ordered ferrimagnetic ferrihydrite, as suggested by recent laboratory experiments. The concentration of pedogenic ferrimagnets as estimated via proxies such as magnetic susceptibility or frequency-dependent magnetic susceptibility has been found to relate to climate variables [particularly (paleo)rainfall] in many studies reported over the last 30 years. However, extracting accurate

  6. Enzymes of respiratory iron oxidation

    SciTech Connect

    Blake, R. II.

    1991-01-01

    This report focuses on the progress made in three areas of research concerned with enzymes involved in respiratory iron oxidation. The three areas are as follows: development of an improved procedure for the routine large scale culture of iron oxidizing chemolithotrophs based on the in-situ electrolysis of the soluble iron in the growth medium; to perform iron oxidation kinetic studies on whole cells using the oxygen electrode; and to identify, separate, purify, and characterize the individual cellular components.

  7. Shifting redox states of the iron center partitions CDO between crosslink formation or cysteine oxidation.

    PubMed

    Njeri, Catherine W; Ellis, Holly R

    2014-09-15

    Cysteine dioxygenase (CDO) is a mononuclear iron-dependent enzyme that catalyzes the oxidation of L-cysteine to L-cysteine sulfinic acid. The mammalian CDO enzymes contain a thioether crosslink between Cys93 and Tyr157, and purified recombinant CDO exists as a mixture of the crosslinked and non crosslinked isoforms. The current study presents a method of expressing homogenously non crosslinked CDO using a cell permeative metal chelator in order to provide a comprehensive investigation of the non crosslinked and crosslinked isoforms. Electron paramagnetic resonance analysis of purified non crosslinked CDO revealed that the iron was in the EPR silent Fe(II) form. Activity of non crosslinked CDO monitoring dioxygen utilization showed a distinct lag phase, which correlated with crosslink formation. Generation of homogenously crosslinked CDO resulted in an ∼5-fold higher kcat/Km value compared to the enzyme with a heterogenous mixture of crosslinked and non crosslinked CDO isoforms. EPR analysis of homogenously crosslinked CDO revealed that this isoform exists in the Fe(III) form. These studies present a new perspective on the redox properties of the active site iron and demonstrate that a redox switch commits CDO towards either formation of the Cys93-Tyr157 crosslink or oxidation of the cysteine substrate. Copyright © 2014 Elsevier Inc. All rights reserved.

  8. L-Edge Xanes Measurements of the Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Righter, K.; Sutton, S.; Newville, M.

    2008-01-01

    Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies are inconsistent on whether W occurs as W(4+) or W(6+). It is assumed that W(4+) is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO2 is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO2 most relevant to core formation, around IW-2.

  9. Location and oxidation state of iron in Fe-substituted CuInS{sub 2} chalcopyrites

    SciTech Connect

    Burnett, Johanna D.; Xu Tianhong; Sorescu, Monica; Strohmeier, Brian R.; Sturgeon, Jacqueline; Gourdon, Olivier; Baroudi, Kristen; Yao Jinlei; Aitken, Jennifer A.

    2013-01-15

    CuIn{sub 1-x}Fe{sub x}S{sub 2}(x=0-0.30) was synthesized via high-temperature, solid-state synthesis. Phase-pure materials were found in samples where x=0-0.15, after which a secondary phase became apparent. The materials were characterized with the use of X-ray powder diffraction (XRPD), and Reitveld refinement revealed a linear decrease in unit cell volume as the amount of iron substitution increases in accordance with Vegard's Law. Inductively coupled plasma (ICP) confirms that the actual stoichiometry is close to the nominal composition of the materials. The temperature for both the chalcopyrite-to-sphalerite and the sphalerite-to-wurtzite phase transitions decreases with increasing iron substitution for indium. These findings suggest that the Fe is being randomly incorporated into the crystal structure of the CuInS{sub 2}. X-ray photoelectron spectroscopy (XPS) measurements were used to determine the oxidation state of the ions (Cu{sup 1+}, In{sup 3+,} and S{sup 2-}), and Fe{sup 57} Moessbauer spectroscopy verified that the iron is in the 3{sup +} oxidation state. Band gaps of the solid solution were estimated to be in the range of 0.70-0.85 eV. Rietveld refinement of neutron diffraction data indicates that the iron is occupying the In site within the chalcopyrite structure. - Graphical abstract: CuIn{sub 1-x}Fe{sub x}S{sub 2} samples were prepared by solid-state synthesis. X-ray photoelectron spectroscopy and Moessbauer spectroscopy indicate Cu{sup +}, In{sup 3+}, Fe{sup 3+} and S{sup 2-} in the samples. Rietveld refinement of neutron powder diffraction data shows Fe{sup 3+} residing on the indium site. The band gaps of the iron-containing samples decrease to {approx}0.7 eV. Highlights: Black-Right-Pointing-Pointer X-ray photoelectron spectroscopy confirms the presence of Cu{sup +}, In{sup 3+} and S{sup 2-}. Black-Right-Pointing-Pointer Moessbauer spectroscopy indicates the presence of Fe{sup 3+}. Black-Right-Pointing-Pointer Rietveld refinement of neutron

  10. Identification of the iron oxidation state and coordination geometry in iron oxide- and zeolite-based catalysts using pre-edge XAS analysis.

    PubMed

    Boubnov, Alexey; Lichtenberg, Henning; Mangold, Stefan; Grunwaldt, Jan Dierk

    2015-03-01

    Analysis of the oxidation state and coordination geometry using pre-edge analysis is attractive for heterogeneous catalysis and materials science, especially for in situ and time-resolved studies or highly diluted systems. In the present study, focus is laid on iron-based catalysts. First a systematic investigation of the pre-edge region of the Fe K-edge using staurolite, FePO4, FeO and α-Fe2O3 as reference compounds for tetrahedral Fe(2+), tetrahedral Fe(3+), octahedral Fe(2+) and octahedral Fe(3+), respectively, is reported. In particular, high-resolution and conventional X-ray absorption spectra are compared, considering that in heterogeneous catalysis and material science a compromise between high-quality spectroscopic data acquisition and simultaneous analysis of functional properties is required. Results, which were obtained from reference spectra acquired with different resolution and quality, demonstrate that this analysis is also applicable to conventionally recorded pre-edge data. For this purpose, subtraction of the edge onset is preferentially carried out using an arctangent and a first-degree polynomial, independent of the resolution and quality of the data. For both standard and high-resolution data, multiplet analysis of pre-edge features has limitations due to weak transitions that cannot be identified. On the other hand, an arbitrary empirical peak fitting assists the analysis in that non-local transitions can be isolated. The analysis of the oxidation state and coordination geometry of the Fe sites using a variogram-based method is shown to be effective for standard-resolution data and leads to the same results as for high-resolution spectra. This method, validated by analysing spectra of reference compounds and their well defined mixtures, is finally applied to track structural changes in a 1% Fe/Al2O3 and a 0.5% Fe/BEA zeolite catalyst during reduction in 5% H2/He. The results, hardly accessible by other techniques, show that Fe(3+) is

  11. Toxicity of iron-based nanoparticles to green algae: Effects of particle size, crystal phase, oxidation state and environmental aging.

    PubMed

    Lei, Cheng; Zhang, Luqing; Yang, Kun; Zhu, Lizhong; Lin, Daohui

    2016-11-01

    With the increasing environmental application and discharge of iron-based nanoparticles (NPs), a comprehensive understanding of their fate and ecotoxicological effect in the aquatic environment is very urgent. In this study, toxicities of 4 zero-valent iron NPs (nZVI) of different sizes, 2 Fe2O3 NPs of different crystal phases, and 1 type of Fe3O4 NPs to a green alga (Chlorella pyrenoidosa) were investigated, with a focus on the effects of particle size, crystal phase, oxidation state, and environmental aging. Results show that the algal growth inhibition of nZVI increased significantly with decreasing particle size; with similar particle sizes (20-30 nm), the algal growth inhibition decreased with oxidation of the NPs with an order of nZVI > Fe3O4 NPs > Fe2O3 NPs, and α-Fe2O3 NPs presented significantly higher toxicity than γ-Fe2O3 NPs. The NP-induced oxidative stress was the main toxic mechanism, which could explain the difference in algal toxicity of the NPs. The NP-cell heteroagglomeration and physical interactions also contributed to the nanotoxicity, whereas the effect of NP dissolution was negligible. The aging in distilled water and 3 surface water samples for 3 months increased surface oxidation of the iron-based NPs especially nZVI, which decreased the toxicity to algae. These findings will be helpful for the understanding of the fate and toxicity of iron-based NPs in the aquatic environment.

  12. Iron Oxidation States of Matrix in Carbonaceous Chondrites Acfer 094 and MIL 07687

    NASA Astrophysics Data System (ADS)

    Vaccaro, E.; King, A. J.; Schofield, P. F.; Abyaneh, M. K.; Kaulich, B.; Russell, S. S.

    2016-08-01

    STXM Fe-oxidation state study in Acfer 094 and MIL 07687 matrix revealed high Fe3+/ΣFe ratios likely to be a primordial signature. Terrestrial weathering cannot be ruled out but is unlikely to have a pervasive effect throughout entire meteorites.

  13. 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.

  14. Breakdown of Clays by Ectomycorrhizal Fungi Through Changes in Oxidation State of Iron

    NASA Astrophysics Data System (ADS)

    Arocena, J. M.; Velde, B.

    2012-04-01

    Organisms are known to play a significant role in the transformation of clay minerals in soils. In our earlier work on canola, barley and alfalfa, we reported that Glomus, an arbuscular mycorrhizae, selectively transformed biotite into 2:1 expanding clays through the oxidation of Fe (II) in biotite to Fe(III). In this presentation, we will share similar results on clay transformations mediated by ectomycorrhizal fungi colonizing the roots of coniferous trees. Clay samples were isolated from rhizosphere soils of sub-alpine fir (Abies lasiocarpa (Hook.) Nutt.) in northern British Columbia (Canada). Chemical and mineralogical properties of these soils had been reported in our earlier paper. In this study, we subjected the clay samples to iron X-ray Absorption Near Edge Spectroscopy (Fe-XANES) at the Canadian Light Source synchrotron facility in Saskatoon (Canada). Our initial results showed relatively higher amounts of Fe (III) than Fe(II) in clays collected from rhizosphere of Piloderma (an ectomycorrhizal fungus) compared to soils influenced by non-Piloderma species and Control (non-rhizosphere soil). Coupled with the results of X-ray diffraction (XRD) analysis, there seems to be a positive relationship between the relative amounts of Fe(III) and the 2:1 expanding clays. This relationship is consistent with our results on agricultural plants in laboratory experiments on biotites where we suggested that oxidation of Fe(II) to Fe(III) results in the formation of 2:1 expanding clays. In a related data set on chlorite alteration we observed that after dithionite-citrate-bicarbonate (DCB) treatment, the d-spacing of a slight portion of chloritic expanding clays shifted to higher angles indicating decreased d-spacing towards micaceous clays. The reductive process initiated through the action of the DCB treatment seems to indicate the collapsed of expandable clays upon the reduction of Fe(III) to Fe(II). Initial results from the Fe-XANES and XRD analysis of DCB

  15. Does a higher metal oxidation state necessarily imply higher reactivity toward H-atom transfer? A computational study of C-H bond oxidation by high-valent iron-oxo and -nitrido complexes.

    PubMed

    Geng, Caiyun; Ye, Shengfa; Neese, Frank

    2014-04-28

    In this work, the reactions of C-H bond activation by two series of iron-oxo ( (Fe(IV)), (Fe(V)), (Fe(VI))) and -nitrido model complexes ( (Fe(IV)), (Fe(V)), (Fe(VI))) with a nearly identical coordination geometry but varying iron oxidation states ranging from iv to vi were comprehensively investigated using density functional theory. We found that in a distorted octahedral coordination environment, the iron-oxo species and their isoelectronic nitrido analogues feature totally different intrinsic reactivities toward C-H bond cleavage. In the case of the iron-oxo complexes, the reaction barrier monotonically decreases as the iron oxidation state increases, consistent with the gradually enhanced electrophilicity across the series. The iron-nitrido complex is less reactive than its isoelectronic iron-oxo species, and more interestingly, a counterintuitive reactivity pattern was observed, i.e. the activation barriers essentially remain constant independent of the iron oxidation states. The detailed analysis using the Polanyi principle demonstrates that the different reactivities between these two series originate from the distinct thermodynamic driving forces, more specifically, the bond dissociation energies (BDEE-Hs, E = O, N) of the nascent E-H bonds in the FeE-H products. Further decomposition of the BDEE-Hs into the electron and proton affinity components shed light on how the oxidation states modulate the BDEE-Hs of the two series.

  16. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron oxides consist of any one or any combination of synthetically prepared iron oxides, including the...

  17. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron oxides consist of any one or any combination of synthetically prepared iron oxides, including the...

  18. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron oxides consist of any one or any combination of synthetically prepared iron oxides, including the...

  19. 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.

  20. High-precision determination of iron oxidation state in silicate glasses using XANES

    SciTech Connect

    Cottrell, Elizabeth; Kelley, Katherine A.; Lanzirotti, Antonio; Fischer, Rebecca A.

    2009-11-04

    Fe K-edge X-ray absorption near-edge structure (XANES) and Moessbauer spectra were collected on natural basaltic glasses equilibrated over a range of oxygen fugacity (QFM - 3.5 to QFM + 4.5). The basalt compositions and fO{sub 2} conditions were chosen to bracket the natural range of redox conditions expected for basalts from mid-ocean ridge, ocean island, back-arc basin, and arc settings, in order to develop a high-precision calibration for the determination of Fe{sup 3+}/{Sigma}Fe in natural basalts. The pre-edge centroid energy, corresponding to the 1s {yields} 3d transition, was determined to be the most robust proxy for Fe oxidation state, affording significant advantages compared to the use of other spectral features. A second-order polynomial models the correlation between the centroid and Fe{sup 3+}/{Sigma}Fe, yielding a precision of {+-} 0.0045 in Fe{sup 3+}/{Sigma}Fe for glasses with Fe{sup 3+}/{Sigma}Fe > 8%, which is comparable to the precision of wet chemistry. This high precision relies on a Si (311) monochromator to better define the Fe{sup 2+} and Fe{sup 3+} transitions, accurate and robust modeling of the pre-edge feature, dense fO{sub 2}-coverage and compositional appropriateness of reference glasses, and application of a non-linear drift correction. Through re-analysis of the reference glasses across three synchrotron beam sessions, we show that the quoted precision can be achieved (i.e., analyses are reproducible) across multiple synchrotron beam sessions, even when spectral collection conditions (detector parameters or sample geometry) change. Rhyolitic glasses were also analyzed and yield a higher centroid energy at a given Fe{sup 3+}/{Sigma}Fe than basalts, implying that major variations in melt structure affect the relationship between centroid position and Fe{sup 3+}/{Sigma}Fe, and that separate calibrations are needed for the determination of oxidation state in basalts and rhyolites.

  1. Proton Control of Oxidation and Spin State in a Series of Iron Tripodal Imidazole Complexes

    PubMed Central

    Brewer, Cynthia; Brewer, Greg; Luckett, Charles; Marbury, Gwen S.; Viragh, Carol; Beatty, Alicia M.; Scheidt, W. Robert

    2007-01-01

    Reaction of iron salts with three tripodal imidazole ligands, H3(1), H3(2), H3(3), formed from the condensation of tris(2-aminoethyl)amine (tren) with 3 equiv of an imidazole carboxaldehyde yielded eight new cationic iron(III) and iron(II), [FeH3L]3+or2+, and neutral iron(III), FeL, complexes. All complexes were characterized by EA(CHN), IR, UV, Mössbauer, mass spectral techniques and cyclic voltammetry. Structures of three of the complexes, Fe(2)·3H2O (C18H27FeN10O3, a = b = c = 20.2707(5), cubic, I4̄3d, Z = 16), Fe(3)·4.5H2O (C18H30FeN10O4.5, a = 20.9986(10), b = 11.7098(5), c = 19.9405(9), β= 109.141(1), monoclinic, P2(1)/c), Z = 8), and [FeH3(3)](ClO4)2·H2O (C18H26Cl2FeN10O9, a = 9.4848(4), b = 23.2354(9), c = 12.2048(5), β= 111.147(1)°, monoclinic, P2(1)/n, Z = 4) were determined at 100 K. The structures are similar to one another and feature an octahedral iron with facial coordination of imidazoles and imine nitrogen atoms. The iron(III) complexes of the deprotonated ligands, Fe(1), Fe(2), and Fe(3), are low-spin while the protonated iron(III) cationic complexes, [FeH3(1)](ClO4)3 and [FeH3(2)](ClO4)3, are high-spin and spin-crossover, respectively. The iron(II) cationic complexes, [FeH3(1)]S4O6, [FeH3(2)](ClO4)2, [FeH3(3)](ClO4)2, and [FeH3(3)][B(C6H5)4]2 exhibit spin-crossover behavior. Cyclic voltammetric measurements on the series of complexes show that complete deprotonation of the ligands produces a negative shift in the Fe(III)/Fe(II) reduction potential of 981 mV on average. Deprotonation in air of either cationic iron(II) or iron(III) complexes, [FeH3L]3+or2+, yields the neutral iron(III) complex, FeL. The process is reversible for Fe(3), where protonation of Fe(3) yields [FeH3(3)]2+. PMID:15046517

  2. 46 CFR 148.275 - Iron oxide, spent; iron sponge, spent.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Iron oxide, spent; iron sponge, spent. 148.275 Section... § 148.275 Iron oxide, spent; iron sponge, spent. (a) Before spent iron oxide or spent iron sponge is... been cooled and weathered for at least eight weeks. (b) Both spent iron oxide and spent iron sponge may...

  3. 46 CFR 148.275 - Iron oxide, spent; iron sponge, spent.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Iron oxide, spent; iron sponge, spent. 148.275 Section... § 148.275 Iron oxide, spent; iron sponge, spent. (a) Before spent iron oxide or spent iron sponge is... been cooled and weathered for at least eight weeks. (b) Both spent iron oxide and spent iron sponge may...

  4. 46 CFR 148.275 - Iron oxide, spent; iron sponge, spent.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Iron oxide, spent; iron sponge, spent. 148.275 Section... § 148.275 Iron oxide, spent; iron sponge, spent. (a) Before spent iron oxide or spent iron sponge is... been cooled and weathered for at least eight weeks. (b) Both spent iron oxide and spent iron sponge may...

  5. 46 CFR 148.275 - Iron oxide, spent; iron sponge, spent.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Iron oxide, spent; iron sponge, spent. 148.275 Section... § 148.275 Iron oxide, spent; iron sponge, spent. (a) Before spent iron oxide or spent iron sponge is... been cooled and weathered for at least eight weeks. (b) Both spent iron oxide and spent iron sponge may...

  6. 21 CFR 73.3125 - Iron oxides.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3125 Iron oxides. (a) Identity and specifications. The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

  7. 21 CFR 73.3125 - Iron oxides.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3125 Iron oxides. (a) Identity and specifications. The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

  8. 21 CFR 73.3125 - Iron oxides.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3125 Iron oxides. (a) Identity and specifications. The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

  9. 21 CFR 73.3125 - Iron oxides.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3125 Iron oxides. (a) Identity and specifications. The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

  10. 21 CFR 73.3125 - Iron oxides.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3125 Iron oxides. (a) Identity and specifications. The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

  11. Equation of State of Aluminum-Iron Oxide-Epoxy Composite

    DTIC Science & Technology

    2007-07-01

    We report on the measurements of the shock equation of state (Hugoniot) of an Al/Fe2O3/epoxy composite, prepared by epoxy cast curing of powder...corresponding shock propagation velocity. The results of the Hugoniot equation of state are compared with mesoscale finite-element simulations, which show good agreement.

  12. Iron oxidation by Thiobacillus ferrooxidans

    SciTech Connect

    Kang, Sunki; Sproull, R.D.

    1991-12-31

    Several investigators have shown that microorganisms are involved in many naturally occurring oxidation processes. At present, microbial leaching, which is the solubilization of metals catalyzed by microorganisms, is widely used commercially to produce copper, and to a lesser extent uranium, from low-grade mining wastes. Microbial leaching can also be used as a pretreatment step in the mining of precious metals, such as gold and silver. In this application, the solubilization of pyrite makes the precious metals more accessible for cyanide leaching. Because ferrous iron oxidation is such an important reaction in microbial leaching operations, this study was undertaken to examine factors affecting the rate of ferrous iron oxidation in the presence of T. ferrooxidans.

  13. A method for the determination of vanadium and iron oxidation states in naturally occurring oxides and silicates.

    PubMed

    Wanty, R B; Goldhaber, M B

    1985-05-01

    A valence-specific analytical method for determining V(3+) in ore minerals has been developed that involves two steps: dissolution of a mineral sample without disturbing the V(3+)/V(tot) ratio, followed by determination of V(3+) in the presence of V(4+). The samples are dissolved in a mixture of hydrofluoric and sulphuric acids at 100 degrees in Teflon-lined reaction vessels. Tervalent vanadium is then determined colorimetrically by formation of a V(3+)-thiocyanate complex in aqueous-acetone medium. Fe(3+) is measured semi-quantitatively in the same solution. The method has been tested with two naturally occurring samples containing vanadium and iron. The results obtained were supported by those obtained by other methods, including electron spin resonance spectroscopy, thermogravimetric analysis, and Mössbauer spectroscopy.

  14. A method for the determination of vanadium and iron oxidation states in naturally occurring oxides and silicates

    USGS Publications Warehouse

    Wanty, R.B.; Goldhaber, M.B.

    1985-01-01

    A valence-specific analytical method for determining V3+ in ore minerals has been developed that involves two steps: dissolution of a mineral sample without disturbing the V3+/Vtot ratio, followed by determination of V3+ in the presence of V4+. The samples are dissolved in a mixture of hydrofluoric and sulphuric acids at 100?? in Teflon-lined reaction vessels. Tervalent vanadium is then determined colorimetrically by formation of a V3+-thiocyanate complex in aqueous-acetone medium. Fe3+ is measured semi-quantitatively in the same solution. The method has been tested with two naturally occurring samples containing vanadium and iron. The results obtained were supported by those obtained by other methods, including electron spin resonance spectroscopy, thermogravimetric analysis, and Mo??ssbauer spectroscopy. ?? 1985.

  15. The Miniaturized Mössbauer Spectrometer MIMOS II for the Asteroid Redirect Mission (ARM): Quantitative Iron Mineralogy and Oxidation States

    NASA Astrophysics Data System (ADS)

    Schröder, C.; Klingelhöfer, G.; Morris, R. V.; Yen, A. S.; Renz, F.; Graff, T. G.

    2016-10-01

    We propose a fully-qualified flight-spare Mössbauer spectrometer for the asteroid redirect mission to identify Fe-bearing mineral phases and Fe oxidation states, and for quantitative distribution of Fe between mineral phases and oxidation states.

  16. High temperature oxidation of iron-iron oxide core-shell nanowires composed of iron nanoparticles.

    PubMed

    Krajewski, M; Brzozka, K; Lin, W S; Lin, H M; Tokarczyk, M; Borysiuk, J; Kowalski, G; Wasik, D

    2016-02-07

    This work describes an oxidation process of iron-iron oxide core-shell nanowires at temperatures between 100 °C and 800 °C. The studied nanomaterial was synthesized through a simple chemical reduction of iron trichloride in an external magnetic field under a constant flow of argon. The electron microscopy investigations allowed determining that the as-prepared nanowires were composed of self-assembled iron nanoparticles which were covered by a 3 nm thick oxide shell and separated from each other by a thin interface layer. Both these layers exhibited an amorphous or highly-disordered character which was traced by means of transmission electron microscopy and Mössbauer spectroscopy. The thermal oxidation was carried out under a constant flow of argon which contained the traces of oxygen. The first stage of process was related to slow transformations of amorphous Fe and amorphous iron oxides into crystalline phases and disappearance of interfaces between iron nanoparticles forming the studied nanomaterial (range: 25-300 °C). After that, the crystalline iron core and iron oxide shell became oxidized and signals for different compositions of iron oxide sheath were observed (range: 300-800 °C) using X-ray diffraction, Raman spectroscopy and Mössbauer spectroscopy. According to the thermal gravimetric analysis, the nanowires heated up to 800 °C under argon atmosphere gained 37% of mass with respect to their initial weight. The structure of the studied nanomaterial oxidized at 800 °C was mainly composed of α-Fe2O3 (∼ 93%). Moreover, iron nanowires treated above 600 °C lost their wire-like shape due to their shrinkage and collapse caused by the void coalescence.

  17. The Oxidation State Of Iron In Chromite As A Record Of Deep Earth Processes

    NASA Astrophysics Data System (ADS)

    McGowan, N.; Griffin, W. L.; Pearson, N.; O'Reilly, S. Y.; Clark, S. M.; Roque-Rosell, J.; Marcus, M.; McCammon, C. A.

    2015-12-01

    Recent work on podiform chromitite from the Luobusa massif, Tibet, suggests that a lithospheric slab containing the chromitite was driven into the Transition Zone (>400 km) after primary crystallisation at shallow depth [1]. Exsolution of coesite and pyroxenes from chromite is believed to reflect conversion from the spinel structure to the ultra-high pressure (UHP) calcium ferrite (CF) polymorph below 400 km [2]. Experimental studies report that UHP polymorphs can have a high affinity for Fe3+, leading to disproportionation of Fe2+ to Fe3+ + Fe0 [3], despite low fO2 as evidenced by inclusions of diamond, native metals and alloys, moissanite, and Cr2+-bearing chromite. Luobusa chromitites may be the first natural example of this phenomenon; one study reported a massive chromitite with higher Fe3+/∑Fe than nodular or disseminated varieties with lower modal chromite [4]. The absence of indicators of oxidation implies that the high Fe3+/∑Fe was not produced by formation or alteration of chromite at Earth's surface. A study using samples from Luobusa and the low-pressure Antalya Complex, Turkey was carried out to investigate relationships between pressure, fO2 and Fe3+/∑Fe. In the first application of μ-X-ray absorption near edge structure (μ-XANES) spectroscopy to measure chromite Fe3+/∑Fe, we constructed calibration curves for the pre-edge centroid and main edge maximum features using Fe3+/∑Fe (from Mössbauer spectroscopy) in synthetic and natural spinels. Pre-edge results show that Fe3+/∑Fe increases with vol.% chromite in chromitites from Luobusa, but not from Antalya (fig. 1). High Fe3+/∑Fe thus appears to be a consequence of crystallographic stabilisation of Fe3+ in the UHP polymorph stable below 400 km, despite low-fO2 conditions. The rapid upwelling of the Luobusa chromitite to the uppermost mantle (<10 Ma) has preserved the high Fe3+/∑Fe in samples where re-equilibration with olivine was limited. [1] McGowan et al., Geology (2015) 43, 179

  18. Iron, Oxidative Stress and Gestational Diabetes

    PubMed Central

    Zhuang, Taifeng; Han, Huijun; Yang, Zhenyu

    2014-01-01

    Both iron deficiency and hyperglycemia are highly prevalent globally for pregnant women. Iron supplementation is recommended during pregnancy to control iron deficiency. The purposes of the review are to assess the oxidative effects of iron supplementation and the potential relationship between iron nutrition and gestational diabetes. High doses of iron (~relative to 60 mg or more daily for adult humans) can induce lipid peroxidation in vitro and in animal studies. Pharmaceutical doses of iron supplements (e.g., 10× RDA or more for oral supplements or direct iron supplementation via injection or addition to the cell culture medium) for a short or long duration will induce DNA damage. Higher heme-iron intake or iron status measured by various biomarkers, especially serum ferritin, might contribute to greater risk of gestational diabetes, which may be mediated by iron oxidative stress though lipid oxidation and/or DNA damage. However, information is lacking about the effect of low dose iron supplementation (≤60 mg daily) on lipid peroxidation, DNA damage and gestational diabetes. Randomized trials of low-dose iron supplementation (≤60 mg daily) for pregnant women are warranted to test the relationship between iron oxidative stress and insulin resistance/gestational diabetes, especially for iron-replete women. PMID:25255832

  19. Oxidation Potentials in Iron and Steel Making

    NASA Astrophysics Data System (ADS)

    Matousek, J. W.

    2013-11-01

    The state of oxidation of a pyrometallurgical process given by the partial pressure of oxygen and the temperature (the oxidation potential) is one of the important properties monitored and controlled in the smelting and refining of iron and the nonferrous metals. Solid electrolyte sensors based on ZrO2 and a reference electrode such as Cr/Cr2O3 to measure the oxygen pressure found early application in the steel industry, followed soon after in copper, nickel, lead, and zinc smelting. Similar devices are installed in automobile postcombustion/exhaust trains as part of emission control systems. The current discussion reviews this technology as applied in the primary steps of iron and steel making and refining.

  20. Combined use of X-ray photoelectron and Mössbauer spectroscopic techniques in the analytical characterization of iron oxidation state in amphibole asbestos.

    PubMed

    Fantauzzi, Marzia; Pacella, Alessandro; Atzei, Davide; Gianfagna, Antonio; Andreozzi, Giovanni B; Rossi, Antonella

    2010-04-01

    Asbestos fibers are an important cause of serious health problems and respiratory diseases. The presence, structural coordination, and oxidation state of iron at the fiber surface are potentially important for the biological effects of asbestos because iron can catalyze the Haber-Weiss reaction, generating the reactive oxygen species *OH. Literature results indicate that the surface concentration of Fe(III) may play an important role in fiber-related radical formation. Amphibole asbestos were analyzed by X-ray photoelectron spectroscopy (XPS) and Mössbauer spectroscopy, with the aim of determining the surface vs. bulk Fe(III)/Fe(tot) ratios. A standard reference asbestos (Union Internationale Contre le Cancer crocidolite from South Africa) and three fibrous tremolite samples (from Italy and USA) were investigated. In addition to the Mössbauer spectroscopy study of bulk Fe(III)/Fe(tot) ratios, much work was dedicated to the interpretation of the XPS Fe2p signal and to the quantification of surface Fe(III)/Fe(tot) ratios. Results confirmed the importance of surface properties because this showed that fiber surfaces are always more oxidized than the bulk and that Fe(III) is present as oxide and oxyhydroxide species. Notably, the highest difference of surface/bulk Fe oxidation was found for San Mango tremolite--the sample that in preliminary cytotoxicity tests (MTT assay) had revealed a cell mortality delayed with respect to the other samples.

  1. Indium Sorption to Iron Oxides

    NASA Astrophysics Data System (ADS)

    White, S. J.; Sacco, S. A.; Hemond, H.; Hussain, F. A.; Runkel, R. L.; Walton-Day, K. E.; Kimball, B. A.; Shine, J. P.

    2014-12-01

    Indium is an increasingly important metal in semiconductors and electronics, and its use is growing rapidly as a semiconductive coating (as indium tin oxide) for liquid crystal displays (LCDs) and flat panel displays. It also has uses in important energy technologies such as light emitting diodes (LEDs) and photovoltaic cells. Despite its rapid increase in use, very little is known about the environmental behavior of indium, and concerns are being raised over the potential health effects of this emerging metal contaminant. One source of indium to the environment is acid mine drainage from the mining of lead, zinc, and copper sulfides. In our previous studies of a stream in Colorado influenced by acid mine drainage from lead and zinc mining activities, indium concentrations were found to be 10,000 times those found in uncontaminated rivers. However, the speciation and mobility of indium could not be reliably modeled because sorption constants to environmental sorbents have not been determined. In this study, we generate sorption constants for indium to ferrihydrite in the laboratory over a range of pHs, sorbent to sorbate ratios, and ionic strengths. Ferrihydrite is one of the most important sorbents in natural systems, and sorption to amorphous iron oxides such as ferrihydrite is thought to be one of the main removal mechanisms of metals from the dissolved phase in aqueous environments. Because of its relatively low solubility, we also find that indium hydroxide precipitation can dominate indium's partitioning at micromolar concentrations of indium. This precipitation may be important in describing indium's behavior in our study stream in Colorado, where modeling sorption to iron-oxides does not explain the complete removal of indium from the dissolved phase when the pH of the system is artificially raised to above 8. This study contributes much-needed data about indium's aqueous behavior, in order to better understand its fate, transport, and impacts in the

  2. 21 CFR 186.1374 - Iron oxides.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...) are undefined mixtures of iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron (III) oxide (CAS Reg. No. 1309-37-1, red-brown to black trigonal crystals). (b) In accordance with § 186.1(b...

  3. 21 CFR 186.1374 - Iron oxides.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...) are undefined mixtures of iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron (III) oxide (CAS Reg. No. 1309-37-1, red-brown to black trigonal crystals). (b) In accordance with § 186.1(b...

  4. 21 CFR 186.1374 - Iron oxides.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...) are undefined mixtures of iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron (III) oxide (CAS Reg. No. 1309-37-1, red-brown to black trigonal crystals). (b) In accordance with § 186.1(b...

  5. 21 CFR 186.1374 - Iron oxides.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...) are undefined mixtures of iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron (III) oxide (CAS Reg. No. 1309-37-1, red-brown to black trigonal crystals). (b) In accordance with § 186.1(b...

  6. 21 CFR 186.1374 - Iron oxides.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron (III) oxide (CAS Reg. No. 1309-37-1, red-brown to black trigonal crystals). (b) In accordance with § 186.1(b)(1), the ingredient is...

  7. Tannin biosynthesis of iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Herrera-Becerra, R.; Rius, J. L.; Zorrilla, C.

    2010-08-01

    In this work, iron oxide nanoparticles synthesized with gallic acid and tannic acid are characterized using High-Resolution Transmission Electron Microscopy (HRTEM). Its size, form, and structure are compared with nanoparticles obtained previously using alfalfa biomass in order to find a simpler, consistent, and environmentally friendly method in the production of iron oxide nanoparticles.

  8. Enzymatic iron oxidation by Leptothrix discophora: identification of an iron-oxidizing protein.

    PubMed Central

    Corstjens, P L; de Vrind, J P; Westbroek, P; de Vrind-de Jong, E W

    1992-01-01

    An iron-oxidizing factor was identified in the spent culture medium of the iron- and manganese-oxidizing bacterial strain Leptothrix discophora SS-1. It appeared to be a protein, with an apparent molecular weight of approximately 150,000. Its activity could be demonstrated after fractionation of the spent medium by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. A spontaneous mutant of L. discophora SS-1 was isolated which excreted neither manganese- nor iron-oxidizing activity, whereas excretion of other proteins seemed to be unaffected. Although the excretion of both metal-oxidizing factors was probably linked, the difference in other properties suggests that manganese and iron oxidation represent two different pathways. With a dot-blot assay, it was established that different bacterial species have different metal-oxidizing capacities. Whereas L. discophora oxidized both iron and manganese, Sphaerotilus natans oxidized only iron and two Pseudomonas spp. oxidized only manganese. Images PMID:1610168

  9. Facile and Sustainable Synthesis of Shaped Iron Oxide Nanoparticles: Effect of Iron Precursor Salts on the Shapes of Iron Oxides

    PubMed Central

    Sayed, Farheen N.; Polshettiwar, Vivek

    2015-01-01

    A facile and sustainable protocol for synthesis of six different shaped iron oxides is developed. Notably, all the six shapes of iron oxides can be synthesised using exactly same synthetic protocol, by simply changing the precursor iron salts. Several of the synthesised shapes are not reported before. This novel protocol is relatively easy to implement and could contribute to overcome the challenge of obtaining various shaped iron oxides in economical and sustainable manner. PMID:25939969

  10. Facile and sustainable synthesis of shaped iron oxide nanoparticles: effect of iron precursor salts on the shapes of iron oxides.

    PubMed

    Sayed, Farheen N; Polshettiwar, Vivek

    2015-05-05

    A facile and sustainable protocol for synthesis of six different shaped iron oxides is developed. Notably, all the six shapes of iron oxides can be synthesised using exactly same synthetic protocol, by simply changing the precursor iron salts. Several of the synthesised shapes are not reported before. This novel protocol is relatively easy to implement and could contribute to overcome the challenge of obtaining various shaped iron oxides in economical and sustainable manner.

  11. Nanosized Iron Oxide Colloids Strongly Enhance Microbial Iron Reduction▿ †

    PubMed Central

    Bosch, Julian; Heister, Katja; Hofmann, Thilo; Meckenstock, Rainer U.

    2010-01-01

    Microbial iron reduction is considered to be a significant subsurface process. The rate-limiting bioavailability of the insoluble iron oxyhydroxides, however, is a topic for debate. Surface area and mineral structure are recognized as crucial parameters for microbial reduction rates of bulk, macroaggregate iron minerals. However, a significant fraction of iron oxide minerals in the subsurface is supposed to be present as nanosized colloids. We therefore studied the role of colloidal iron oxides in microbial iron reduction. In batch growth experiments with Geobacter sulfurreducens, colloids of ferrihydrite (hydrodynamic diameter, 336 nm), hematite (123 nm), goethite (157 nm), and akaganeite (64 nm) were added as electron acceptors. The colloidal iron oxides were reduced up to 2 orders of magnitude more rapidly (up to 1,255 pmol h−1 cell−1) than bulk macroaggregates of the same iron phases (6 to 70 pmol h−1 cell−1). The increased reactivity was not only due to the large surface areas of the colloidal aggregates but also was due to a higher reactivity per unit surface. We hypothesize that this can be attributed to the high bioavailability of the nanosized aggregates and their colloidal suspension. Furthermore, a strong enhancement of reduction rates of bulk ferrihydrite was observed when nanosized ferrihydrite aggregates were added. PMID:19915036

  12. Platinum Attachments on Iron Oxide Nanoparticle Surfaces

    SciTech Connect

    Palchoudhury, Soubantika; Xu, Yaolin; An, Wei; Turner, C. H.; Bao, Yuping

    2010-04-30

    Platinum nanoparticles supported on metal oxide surfaces have shown great potential as heterogeneous catalysts to accelerate electrochemical processes, such as the oxygen reduction reaction in fuel cells. Recently, the use of magnetic supports has become a promising research topic for easy separation and recovery of catalysts using magnets, such as Pt nanoparticles supported on iron oxide nanoparticles. The attachment of Pt on iron oxide nanoparticles is limited by the wetting ability of the Pt (metal) on ceramic surfaces. A study of Pt nanoparticle attachment on iron oxide nanoparticle surfaces in an organic solvent is reported, which addresses the factors that promote or inhibit such attachment. It was discovered that the Pt attachment strongly depends on the capping molecules of the iron oxide seeds and the reaction temperature. For example, the attachment of Pt nanoparticles on oleic acid coated iron oxide nanoparticles was very challenging, because of the strong binding between the carboxylic groups and iron oxide surfaces. In contrast, when nanoparticles are coated with oleic acid/tri-n-octylphosphine oxide or oleic acid/oleylamine, a significant increase in Pt attachment was observed. Electronic structure calculations were then applied to estimate the binding energies between the capping molecules and iron ions, and the modeling results strongly support the experimental observations.

  13. The Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses: Results from W L-Edge Xanes Measurements

    NASA Technical Reports Server (NTRS)

    Danielson, Lisa R.; Righter, K.; Sutton S.; Newville, M.; Le, L.

    2007-01-01

    Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted approx. 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies (figure 1) are inconsistent on whether W occurs as W(4+) or W(6+).

  14. When Density Functional Approximations Meet Iron Oxides.

    PubMed

    Meng, Yu; Liu, Xing-Wu; Huo, Chun-Fang; Guo, Wen-Ping; Cao, Dong-Bo; Peng, Qing; Dearden, Albert; Gonze, Xavier; Yang, Yong; Wang, Jianguo; Jiao, Haijun; Li, Yongwang; Wen, Xiao-Dong

    2016-10-11

    Three density functional approximations (DFAs), PBE, PBE+U, and Heyd-Scuseria-Ernzerhof screened hybrid functional (HSE), were employed to investigate the geometric, electronic, magnetic, and thermodynamic properties of four iron oxides, namely, α-FeOOH, α-Fe2O3, Fe3O4, and FeO. Comparing our calculated results with available experimental data, we found that HSE (a = 0.15) (containing 15% "screened" Hartree-Fock exchange) can provide reliable values of lattice constants, Fe magnetic moments, band gaps, and formation energies of all four iron oxides, while standard HSE (a = 0.25) seriously overestimates the band gaps and formation energies. For PBE+U, a suitable U value can give quite good results for the electronic properties of each iron oxide, but it is challenging to accurately get other properties of the four iron oxides using the same U value. Subsequently, we calculated the Gibbs free energies of transformation reactions among iron oxides using the HSE (a = 0.15) functional and plotted the equilibrium phase diagrams of the iron oxide system under various conditions, which provide reliable theoretical insight into the phase transformations of iron oxides.

  15. 57Fe Mössbauer spectroscopy investigations of iron oxidation states in the Harmattan dust nutrient contribution to West African soils

    NASA Astrophysics Data System (ADS)

    Adetunji, Jacob

    2014-12-01

    A variety of investigations have been carried out on Harmattan dust over many decades demonstrating the continuing importance of the Harmattan dust phenomenon. The investigations have included elemental enrichment factors, mineralogical nutrient input through dust deposition on the soil, meteorological studies, etc. Harmattan dust is important, not only for its impact on radio communication and low visibility in the shipping lanes over the Atlantic, but also on the livelihood and health of people living in countries over which the dust-laden Harmattan wind blows. However, so far, the aspect of nutrient mineral deposition on the soil has not been thoroughly investigated and requires attention, since the majority of people living in West Africa rely heavily on agriculture. It is therefore relevant to know the useful nutrients in the Harmattan dust deposited on soils of the region. This study is therefore aimed at determining the ferric-ferrous ratio of the iron-bearing minerals contained in the Harmattan dust, so their nutritional contribution can be considered. The Mössbauer technique is a powerful tool for studying the ferric-ferrous ratio and has therefore been used, for the first time, to determine the oxidation states of iron in the dust samples. The results of the analysis show that the Harmattan dust is seriously deficient in ferrous iron, which is the more soluble Fe-ion, needed in the soil for healthy crops and plants in general.

  16. Immobilisation of arsenic by iron(II)-oxidizing bacteria

    NASA Astrophysics Data System (ADS)

    Kappler, A.; Hohmann, C.; Winkler, E.; Muehe, M.; Morin, G.

    2008-12-01

    Arsenic-contaminated groundwater is an environmental problem that affects about 1-2% of the world's population. As arsenic-contaminated water is also used for irrigating rice fields, the uptake of arsenic via rice is in some cases even higher than via drinking water. Arsenic is often of geogenic origin and in many cases bound to iron(III) minerals. Microbial iron(III) reduction leads to dissolution of Fe(III) minerals and thus the arsenic bound to these minerals is released to the environment. In turn, iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II) oxidation followed by iron(III) mineral formation. Here, we present work on arsenic co-precipitation and immobilization by anaerobic and aerobic iron(II)-oxidizing bacteria. Co-precipitation batch experiments with pure cultures of nitrate-dependent, phototrophic, and microaerophilic Fe(II)-oxidizing bacteria are used to quantify the amount of arsenic that can be immobilized during microbial iron mineral precipitation. Iron and arsenic speciation and redox state are determined by X- ray diffraction and synchrotron-based X-ray absorption methods (EXAFS, XANES). Microcosm experiments are set-up either with liquid media or with rice paddy soil amended with arsenic. Rice paddy soil from arsenic contaminated rice fields in China that include a natural population of Fe(II)-oxidizing microorganisms is used as inoculum. Dissolved and solid-phase arsenic and iron are quantified, Arsenic speciation is determined and the iron minerals are identified. Additionally, Arsenic uptake into the rice plant is quantified and a gene expression pattern in rice (Oryza sativa cv Gladia) is determined by microarrays as a response to the presence of Fe(II)-oxidizing bacteria.

  17. Effects of coating spherical iron oxide nanoparticles

    SciTech Connect

    Milosevic, Irena; Motte, Laurence; Aoun, Bachir; Li, Tao; Ren, Yang; Sun, Chengjun; Saboungi, Marie-Louise

    2017-01-01

    We investigate the effect of several coatings applied in biomedical applications to iron oxide nanoparticles on the size, structure and composition of the particles. The four structural techniques employed - TEM, DLS, VSM, SAXS and EXAFS - show no significant effects of the coatings on the spherical shape of the bare nanoparticles, the average sizes or the local order around the Fe atoms. The NPs coated with hydroxylmethylene bisphosphonate or catechol have a lower proportion of magnetite than the bare and citrated ones, raising the question whether the former are responsible for increasing the valence state of the oxide on the NP surfaces and lowering the overall proportion of magnetite in the particles. VSM measurements show that these two coatings lead to a slightly higher saturation magnetization than the citrate. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazu and Dr. Federica Migliardo.

  18. On the formation of iron(III) oxides via oxidation of iron(II)

    SciTech Connect

    Bongiovanni, R.; Pelizzetti, E.; Borgarello, E.; Meisel, D.

    1994-09-01

    Formation of iron oxides in aqueous salt solutions is reviewed. The discussion is focused on the oxidation of iron(II) and the following hydrolysis process that leads to the formation of a solid phase from homogeneous solutions. Results from our own studies on the kinetics of the oxidation reactions and the ensuing growth processes are presented.

  19. Chemical state mapping of heterogeneous reduction of iron ore sinter

    NASA Astrophysics Data System (ADS)

    Kimura, M.; Takeichi, Y.; Murao, R.; Obayashi, I.; Hiraoka, Y.; Liu, Y.

    2017-06-01

    Iron ore sinter constitutes the major component of the iron-bearing burden in blast furnaces, and its reduction mechanism is one of the keys to improving the productivity of ironmaking. Iron ore sinter is composed of multiple iron oxide phases and calcium ferrites (CFs), and their heterogeneous reduction was investigated in terms of changes in iron chemical state: FeIII, FeII, and Fe0 were examined macroscopically by 2D X-ray absorption and microscopically by 3D transmission X-ray microscopy (TXM). It was shown that the reduction starts at iron oxide grains rather than at calcium ferrite (CF) grains, especially those located near micropores. The heterogeneous reduction causes crack formation and deteriorates the mechanical strength of the sinter. These results help us to understand the fundamental aspects of heterogeneous reduction schemes in iron ore sinter.

  20. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron..., including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing practice...

  1. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron..., including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing practice...

  2. Water soluble dendronized iron oxide nanoparticles.

    PubMed

    Daou, T J; Pourroy, G; Greneche, J M; Bertin, A; Felder-Flesch, D; Begin-Colin, S

    2009-06-21

    The grafting of pegylated dendrons on 9(2) nm and 39(5) nm iron oxide nanoparticles in water, through a phosphonate group as coupling agent has been successfully achieved and its mechanism investigated, with a view to produce biocompatible magnetic nano-objects for biomedical applications. Grafting has been demonstrated to occur by interaction of negatively charged phosphonate groups with positively charged groups and hydroxyl at the iron oxide surface. The isoelectric point of the suspension of dendronized iron oxide nanoparticles is shifted towards lower pH as the amount of dendron increases. It reaches 4.7 for the higher grafting rate and for both particle size. Thus, the grafting of molecules using a phosphonate group allows stabilizing electrostatically the suspensions at physiological pH, a prerequisite for biomedical applications. Moreover the grafting step has been shown to preserve the magnetic properties of iron oxide nanoparticles due to super-super exchange interactions through the phosphonate group.

  3. Ultrasound assisted phytosynthesis of iron oxide nanoparticle.

    PubMed

    Sathya, K; Saravanathamizhan, R; Baskar, G

    2017-11-01

    The present work deals with the ultrasound assisted green synthesis of iron oxide nano particle using Coriandrum sativum leaf extract as a reducing agent. The synthesized iron oxide nanoparticle was confirmed by UV spectra. The characterization was done to know more about morphology and size of the particle by SEM analysis which shows spherical particles with size ranging from 20 to 90nm. The antimicrobial activity of the leaf extract and the synthesized nanoparticles was studied against the pathogens Micrococcus luteus, Staphylococcus aureus and Aspergillus niger. The ultrasound assisted iron oxide nanoparticle shows higher scavenging activity and antimicrobial activity compared with iron oxide nanoparticle synthesized by magnetic stirrer and Coriandrum sativum leaf extract. Copyright © 2017. Published by Elsevier B.V.

  4. Controlled oxidation of iron nanoparticles in chemical vapour synthesis

    NASA Astrophysics Data System (ADS)

    Ruusunen, Jarno; Ihalainen, Mika; Koponen, Tarmo; Torvela, Tiina; Tenho, Mikko; Salonen, Jarno; Sippula, Olli; Joutsensaari, Jorma; Jokiniemi, Jorma; Lähde, Anna

    2014-02-01

    In the present study, iron oxide nanoparticles (primary particle size of 80-90 nm) with controlled oxidation state were prepared via an atmospheric pressure chemical vapour synthesis (APCVS) method. Iron pentacarbonyl [Fe(CO)5], a precursor material, was thermally decomposed to iron in the APCVS reactor. Subsequently, the iron was oxidized with controlled amount of oxygen in the reactor to produce nearly pure magnetite or haematite particles depending on the oxygen concentration. Size, morphology and crystal structure of the synthesized nanoparticles were studied with scanning mobility particle sizer (SMPS), transmission electron microscopy (TEM) and X-ray diffraction (XRD). In addition, thermodynamic equilibrium calculations and computational fluid dynamics model were used to predict the oxidation state of the iron oxides and the reaction conditions during mixing. Aggregates of crystalline particles were formed, determined as magnetite at the oxygen volumetric fraction of 0.1 % and haematite at volumetric fraction of 0.5 %, according to the XRD. The geometric mean electrical mobility diameter of the aggregates increased from 110 to 155 nm when the volumetric fraction of oxygen increased from 0.1 to 0.5 %, determined using the SMPS. The aggregates were highly sintered based on TEM analyses. As a conclusion, APCVS method can be used to produce nearly pure crystalline magnetite or haematite nanoparticles with controlled oxidation in a continuous one-stage gas-phase process.

  5. Iron, oxidative stress, and redox signaling in the cardiovascular system.

    PubMed

    Gudjoncik, Aurélie; Guenancia, Charles; Zeller, Marianne; Cottin, Yves; Vergely, Catherine; Rochette, Luc

    2014-08-01

    The redox state of the cell is predominantly dependent on an iron redox couple and is maintained within strict physiological limits. Iron is an essential metal for hemoglobin synthesis in erythrocytes, for oxidation-reduction reactions, and for cellular proliferation. The maintenance of stable iron concentrations requires the coordinated regulation of iron transport into plasma from dietary sources in the duodenum, from recycled senescent red cells in macrophages, and from storage in hepatocytes. The absorption of dietary iron, which is present in heme or nonheme form, is carried out by mature villus enterocytes of the duodenum and proximal jejunum. Multiple physiological processes are involved in maintaining iron homeostasis. These include its storage at the intracellular and extracellular level. Control of iron balance in the whole organism requires communication between sites of uptake, utilization, and storage. Key protein transporters and the molecules that regulate their activities have been identified. In this field, ferritins and hepcidin are the major regulator proteins. A variety of transcription factors may be activated depending on the level of oxidative stress, leading to the expression of different genes. Major preclinical and clinical trials have shown advances in iron-chelation therapy for the treatment of iron-overload disease as well as cardiovascular and chronic inflammatory diseases. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The oxidized state of the nanocomposite Carbo-Iron® causes no adverse effects on growth, survival and differential gene expression in zebrafish.

    PubMed

    Weil, Mirco; Meißner, Tobias; Busch, Wibke; Springer, Armin; Kühnel, Dana; Schulz, Ralf; Duis, Karen

    2015-10-15

    For degradation of halogenated chemicals in groundwater Carbo-Iron®, a composite of activated carbon and nano-sized Fe(0), was developed (Mackenzie et al., 2012). Potential effects of this nanocomposite on fish were assessed. Beyond the contaminated zone Fe(0) can be expected to have oxidized and Carbo-Iron was used in its oxidized form in ecotoxicological tests. Potential effects of Carbo Iron in zebrafish (Danio rerio) were investigated using a 48 h embryo toxicity test under static conditions, a 96 h acute test with adult fish under semi-static conditions and a 34 d fish early life stage test (FELST) in a flow-through system. Particle diameters in test suspensions were determined via dynamic light scattering (DLS) and ranged from 266 to 497 nm. Particle concentrations were measured weekly in samples from the FELST using a method based on the count rate in DLS. Additionally, uptake of particles into test organisms was investigated using microscopic methods. Furthermore, effects of Carbo-Iron on gene expression were investigated by microarray analysis in zebrafish embryos. In all tests performed, no significant lethal effects were observed. Furthermore, Carbo-Iron had no significant influence on weight and length of fish as determined in the FELST. In the embryo test and the early life stage test, growth of fungi on the chorion was observed at Carbo-Iron concentrations between 6.3 and 25mg/L. Fungal growth did not affect survival, hatching success and growth. In the embryo test, no passage of Carbo-Iron particles into the perivitelline space or the embryo was observed. In juvenile and adult fish, Carbo-Iron was detected in the gut at the end of exposure. In juvenile fish exposed to Carbo-Iron for 29 d and subsequently kept for 5d in control water, Carbo-Iron was no longer detectable in the gut. Global gene expression in zebrafish embryos was not significantly influenced by Carbo-Iron.

  7. Genomic insights into microbial iron oxidation and iron uptake strategies in extremely acidic environments.

    PubMed

    Bonnefoy, Violaine; Holmes, David S

    2012-07-01

    This minireview presents recent advances in our understanding of iron oxidation and homeostasis in acidophilic Bacteria and Archaea. These processes influence the flux of metals and nutrients in pristine and man-made acidic environments such as acid mine drainage and industrial bioleaching operations. Acidophiles are also being studied to understand life in extreme conditions and their role in the generation of biomarkers used in the search for evidence of existing or past extra-terrestrial life. Iron oxidation in acidophiles is best understood in the model organism Acidithiobacillus ferrooxidans. However, recent functional genomic analysis of acidophiles is leading to a deeper appreciation of the diversity of acidophilic iron-oxidizing pathways. Although it is too early to paint a detailed picture of the role played by lateral gene transfer in the evolution of iron oxidation, emerging evidence tends to support the view that iron oxidation arose independently more than once in evolution. Acidic environments are generally rich in soluble iron and extreme acidophiles (e.g. the Leptospirillum genus) have considerably fewer iron uptake systems compared with neutrophiles. However, some acidophiles have been shown to grow as high as pH 6 and, in the case of the Acidithiobacillus genus, to have multiple iron uptake systems. This could be an adaption allowing them to respond to different iron concentrations via the use of a multiplicity of different siderophores. Both Leptospirillum spp. and Acidithiobacillus spp. are predicted to synthesize the acid stable citrate siderophore for Fe(III) uptake. In addition, both groups have predicted receptors for siderophores produced by other microorganisms, suggesting that competition for iron occurs influencing the ecophysiology of acidic environments. Little is known about the genetic regulation of iron oxidation and iron uptake in acidophiles, especially how the use of iron as an energy source is balanced with its need to take up

  8. The Irony of Iron - Biogenic Iron Oxides as an Iron Source to the Ocean.

    PubMed

    Emerson, David

    2015-01-01

    Primary productivity in at least a third of the sunlit open ocean is thought to be iron-limited. Primary sources of dissolved iron (dFe) to the ocean are hydrothermal venting, flux from the sediments along continental margins, and airborne dust. This article provides a general review of sources of hydrothermal and sedimentary iron to the ocean, and speculates upon the role that iron-cycling microbes play in controlling iron dynamics from these sources. Special attention is paid to iron-oxidizing bacteria (FeOB) that live by oxidizing iron and producing biogenic iron oxides as waste products. The presence and ubiquity of FeOB both at hydrothermal systems and in sediments is only beginning to be appreciated. The biogenic oxides they produce have unique properties that could contribute significantly to the dynamics of dFe in the ocean. Changes in the physical and chemical characteristics of the ocean due to climate change and ocean acidification will undoubtedly impact the microbial iron cycle. A better understanding of the contemporary role of microbes in the iron cycle will help in predicting how these changes could ultimately influence marine primary productivity.

  9. The Irony of Iron – Biogenic Iron Oxides as an Iron Source to the Ocean

    PubMed Central

    Emerson, David

    2016-01-01

    Primary productivity in at least a third of the sunlit open ocean is thought to be iron-limited. Primary sources of dissolved iron (dFe) to the ocean are hydrothermal venting, flux from the sediments along continental margins, and airborne dust. This article provides a general review of sources of hydrothermal and sedimentary iron to the ocean, and speculates upon the role that iron-cycling microbes play in controlling iron dynamics from these sources. Special attention is paid to iron-oxidizing bacteria (FeOB) that live by oxidizing iron and producing biogenic iron oxides as waste products. The presence and ubiquity of FeOB both at hydrothermal systems and in sediments is only beginning to be appreciated. The biogenic oxides they produce have unique properties that could contribute significantly to the dynamics of dFe in the ocean. Changes in the physical and chemical characteristics of the ocean due to climate change and ocean acidification will undoubtedly impact the microbial iron cycle. A better understanding of the contemporary role of microbes in the iron cycle will help in predicting how these changes could ultimately influence marine primary productivity. PMID:26779157

  10. Exploring Microbial Iron Oxidation in Wetland Soils

    NASA Astrophysics Data System (ADS)

    Wang, J.; Muyzer, G.; Bodelier, P. L. E.; den Oudsten, F.; Laanbroek, H. J.

    2009-04-01

    Iron is one of the most abundant elements on earth and is essential for life. Because of its importance, iron cycling and its interaction with other chemical and microbial processes has been the focus of many studies. Iron-oxidizing bacteria (FeOB) have been detected in a wide variety of environments. Among those is the rhizosphere of wetland plants roots which release oxygen into the soil creating suboxic conditions required by these organisms. It has been reported that in these rhizosphere microbial iron oxidation proceeds up to four orders of magnitude faster than strictly abiotic oxidation. On the roots of these wetland plants iron plaques are formed by microbial iron oxidation which are involved in the sequestering of heavy metals as well organic pollutants, which of great environmental significance.Despite their important role being catalysts of iron-cycling in wetland environments, little is known about the diversity and distribution of iron-oxidizing bacteria in various environments. This study aimed at developing a PCR-DGGE assay enabling the detection of iron oxidizers in wetland habitats. Gradient tubes were used to enrich iron-oxidizing bacteria. From these enrichments, a clone library was established based on the almost complete 16s rRNA gene using the universal bacterial primers 27f and 1492r. This clone library consisted of mainly α- and β-Proteobacteria, among which two major clusters were closely related to Gallionella spp. Specific probes and primers were developed on the basis of this 16S rRNA gene clone library. The newly designed Gallionella-specific 16S rRNA gene primer set 122f/998r was applied to community DNA obtained from three contrasting wetland environments, and the PCR products were used in denaturing gradient gel electrophoresis (DGGE) analysis. A second 16S rRNA gene clone library was constructed using the PCR products from one of our sampling sites amplified with the newly developed primer set 122f/998r. The cloned 16S rRNA gene

  11. Assessment of T1 and T2* effects in vivo and ex vivo using iron oxide nanoparticles in steady state--dependence on blood volume and water exchange.

    PubMed

    Bjørnerud, Atle; Johansson, Lars O; Briley-Saebø, Karen; Ahlström, Håkan K

    2002-03-01

    Accurate knowledge of the relationship between contrast agent concentration and tissue relaxation is a critical requirement for quantitative assessment of tissue perfusion using contrast-enhanced MRI. In the present study, using a pig model, the relationship between steady-state blood concentration levels of an iron oxide nanoparticle with a hydrated diameter of 12 nm (NC100150 Injection) and changes in the transverse and longitudinal relaxation rates (1/T2* and 1/T1, respectively) in blood, muscle, and renal cortex was investigated at 1.5 T. Ex vivo measurements of 1/T2* and 1/T1 were additionally performed in whole pig blood spiked with different concentrations of the iron oxide nanoparticle. In renal cortex and muscle, 1/T2* increased linearly with contrast agent concentration with slopes of 101 +/-22 s(-1)mM(-1) and 6.5 +/-0.9 s(-1)mM(-1) (mean +/- SD), respectively. In blood, 1/T2* increased as a quadratic function of contrast agent concentration, with different quadratic terms in the ex vivo vs. the in vivo experiments. In vivo, 1/T1 in blood increased linearly with contrast agent concentration, with a slope (T1-relaxivity) of 13.9 +/- 0.9 s(-1)mM(-1). The achievable increase in 1/T1 in renal cortex and muscle was limited by the rate of water exchange between the intra- and extravascular compartments and the 1/T1-curves were well described by a two-compartment water exchange limited relaxation model.

  12. A pentanuclear iron catalyst designed for water oxidation

    NASA Astrophysics Data System (ADS)

    Okamura, Masaya; Kondo, Mio; Kuga, Reiko; Kurashige, Yuki; Yanai, Takeshi; Hayami, Shinya; Praneeth, Vijayendran K. K.; Yoshida, Masaki; Yoneda, Ko; Kawata, Satoshi; Masaoka, Shigeyuki

    2016-02-01

    Although the oxidation of water is efficiently catalysed by the oxygen-evolving complex in photosystem II (refs 1 and 2), it remains one of the main bottlenecks when aiming for synthetic chemical fuel production powered by sunlight or electricity. Consequently, the development of active and stable water oxidation catalysts is crucial, with heterogeneous systems considered more suitable for practical use and their homogeneous counterparts more suitable for targeted, molecular-level design guided by mechanistic understanding. Research into the mechanism of water oxidation has resulted in a range of synthetic molecular catalysts, yet there remains much interest in systems that use abundant, inexpensive and environmentally benign metals such as iron (the most abundant transition metal in the Earth’s crust and found in natural and synthetic oxidation catalysts). Water oxidation catalysts based on mononuclear iron complexes have been explored, but they often deactivate rapidly and exhibit relatively low activities. Here we report a pentanuclear iron complex that efficiently and robustly catalyses water oxidation with a turnover frequency of 1,900 per second, which is about three orders of magnitude larger than that of other iron-based catalysts. Electrochemical analysis confirms the redox flexibility of the system, characterized by six different oxidation states between FeII5 and FeIII5; the FeIII5 state is active for oxidizing water. Quantum chemistry calculations indicate that the presence of adjacent active sites facilitates O-O bond formation with a reaction barrier of less than ten kilocalories per mole. Although the need for a high overpotential and the inability to operate in water-rich solutions limit the practicality of the present system, our findings clearly indicate that efficient water oxidation catalysts based on iron complexes can be created by ensuring that the system has redox flexibility and contains adjacent water-activation sites.

  13. A pentanuclear iron catalyst designed for water oxidation.

    PubMed

    Okamura, Masaya; Kondo, Mio; Kuga, Reiko; Kurashige, Yuki; Yanai, Takeshi; Hayami, Shinya; Praneeth, Vijayendran K K; Yoshida, Masaki; Yoneda, Ko; Kawata, Satoshi; Masaoka, Shigeyuki

    2016-02-25

    Although the oxidation of water is efficiently catalysed by the oxygen-evolving complex in photosystem II (refs 1 and 2), it remains one of the main bottlenecks when aiming for synthetic chemical fuel production powered by sunlight or electricity. Consequently, the development of active and stable water oxidation catalysts is crucial, with heterogeneous systems considered more suitable for practical use and their homogeneous counterparts more suitable for targeted, molecular-level design guided by mechanistic understanding. Research into the mechanism of water oxidation has resulted in a range of synthetic molecular catalysts, yet there remains much interest in systems that use abundant, inexpensive and environmentally benign metals such as iron (the most abundant transition metal in the Earth's crust and found in natural and synthetic oxidation catalysts). Water oxidation catalysts based on mononuclear iron complexes have been explored, but they often deactivate rapidly and exhibit relatively low activities. Here we report a pentanuclear iron complex that efficiently and robustly catalyses water oxidation with a turnover frequency of 1,900 per second, which is about three orders of magnitude larger than that of other iron-based catalysts. Electrochemical analysis confirms the redox flexibility of the system, characterized by six different oxidation states between Fe(II)5 and Fe(III)5; the Fe(III)5 state is active for oxidizing water. Quantum chemistry calculations indicate that the presence of adjacent active sites facilitates O-O bond formation with a reaction barrier of less than ten kilocalories per mole. Although the need for a high overpotential and the inability to operate in water-rich solutions limit the practicality of the present system, our findings clearly indicate that efficient water oxidation catalysts based on iron complexes can be created by ensuring that the system has redox flexibility and contains adjacent water-activation sites.

  14. Microbially Induced Iron Oxidation: What, Where, How

    SciTech Connect

    SCHIERMEYER,ELISA M.; PROVENCIO,PAULA P.; NORTHUP,DIANA E.

    2000-08-15

    From the results of the different bacterial cells seen, it is fairly certain that Gallionella is present because of the bean-shaped cells and twisted stalks found with the TEM. The authors cannot confirm, though, what other iron-oxidizing genera exist in the tubes, since the media was only preferential and not one that isolated a specific genus of bacteria. Based on the environment in which they live and the source of the water, they believe their cultures contain Gallionella, Leptothrix, and possibly Crenothrix and Sphaerotilus. They believe the genus Leptothrix rather than Sphaerotilus exist in the tubes because the water source was fresh, unlike the polluted water in which Sphaerotilus are usually found. The TEM preparations worked well. The cryogenic method rapidly froze the cells in place and allowed them to view their morphology. The FAA method, as stated previously, was the best of the three methods because it gave the best contrast. The gluteraldehyde samples did not come out as well. It is possible that the gluteraldehyde the authors prepared was still too concentrated and did not mix well. Although these bacteria were collected from springs and then cultured in an environment containing a presumably pure iron-bearing metal, it seems the tube already containing Manganese Gradient Medium could be used with a piece of metal containing these bacteria. A small piece of corroding metal could then be inserted into the test tube and cultured to study the bacteria.

  15. Oxidation state in chondrites

    NASA Technical Reports Server (NTRS)

    Rubin, Alan E.; Fegley, Bruce; Brett, Robin

    1988-01-01

    An evaluation is made of extant data on chondrite oxidation states and intrinsic O fugacities. A variety of oxidation states are exhibited by the chondritic meteorites; petrologic and chemical data may be used to arrange the major chondrite groups in order of oxidation state. The intrinsic O fugacity measurements on chondrite whole-rock samples are noted to display a corresponding ordering of oxidation states. Metamorphosed chondrites and igneous meteorites that were substantially altered by metamorphic reactions, outgassing, and igneous processes may preserve information on the oxidation state and size of their parent bodies.

  16. Thermodynamic constraints on microbial iron oxide reduction

    NASA Astrophysics Data System (ADS)

    Bonneville, S.; Behrends, T.; Haese, R.; van Cappellen, P.

    2003-04-01

    Iron oxides are ubiquitous reactive constituents of soils, sediments and aquifers. They exhibit large surface areas which bind trace metals, nutrients and organic molecules. Under suboxic conditions, iron oxides can reductively dissolve via several abiotic and microbial pathways. In particular, they serve as terminal electron acceptors for the oxidation of organic matter by iron reducing bacteria. The aim of our study was to determine the thermodynamic energy yields of dissimilatory iron reduction for different Fe(III) substrates. We used the facultative anaerobic gram-positive bacterium Shewanella putrefaciens as model iron reducing bacterium, with ferrihydrite, hematite, goethite or Fe(III)-salicylate as electron acceptor, and lactate as electron donor. Experiments were conducted in an anaerobic pH-stat batch reactor, equipped with a polarographic electrode to monitor in situ the dissolved ferrous iron activity. The stoichiometry of total Fe(II) production and acid consumption during the experiments indicated that lactate was oxidized to acetate. From the Fe(II) activity and redox potential measurements, free energy yields were calculated for Fe(III) reduction coupled to lactate oxidation. The results showed that the redox potential of the overall reaction was poised by equilibrium between the Fe(III)-substrate and aqueous Fe(II). Hence, the energy yields decreased in the order ferrihydrite > Fe(III)-salicylate > hematite > goethite. Accumulation of Fe(II) in solution only caused small decreases in the energy yields over the course of the experiments. Cessation of iron reduction, which was observed in all experiments, was therefore not due to thermodynamic limitation, but more likely reflected the decline in cell level of activity.

  17. Metal ion binding to iron oxides

    NASA Astrophysics Data System (ADS)

    Ponthieu, M.; Juillot, F.; Hiemstra, T.; van Riemsdijk, W. H.; Benedetti, M. F.

    2006-06-01

    The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

  18. The fate of arsenic adsorbed on iron oxides in the presence of arsenite-oxidizing bacteria.

    PubMed

    Zhang, Zhennan; Yin, Naiyi; Du, Huili; Cai, Xiaolin; Cui, Yanshan

    2016-05-01

    Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on its oxidation state. Arsenite [As(III)] can be oxidized by microbes and adsorbed by minerals in the soil. However, the combined effects of these abiotic and biotic processes are not well understood. In this study, the fate of arsenic in the presence of an isolated As(III)-oxidizing bacterium (Pseudomonas sp. HN-1, 10(9) colony-forming units (CFUs)·ml(-1)) and three iron oxides (goethite, hematite, and magnetite at 1.6 g L(-1)) was determined using batch experiments. The total As adsorption by iron oxides was lower with bacteria present and was higher with iron oxides alone. The total As adsorption decreased by 78.6%, 36.0% and 79.7% for goethite, hematite and magnetite, respectively, due to the presence of bacteria. As(III) adsorbed on iron oxides could also be oxidized by Pseudomonas sp. HN-1, but the oxidation rate (1.3 μmol h(-1)) was much slower than the rate in the aqueous phase (96.2 μmol h(-1)). Therefore, the results of other studies with minerals only might overestimate the adsorptive capacity of solids in natural systems; the presence of minerals might hinder As(III) oxidation by microbes. Under aerobic conditions, in the presence of iron oxides and As(III)-oxidizing bacteria, arsenic is adsorbed onto iron oxides within the adsorption capacity, and As(V) is the primary form in the solid and aqueous phases. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Iron oxide magnetic nanoparticles: A short review

    NASA Astrophysics Data System (ADS)

    Hasany, S. F.; Rehman, A.; Jose, R.; Ahmed, I.

    2012-11-01

    Magnetic nanoparticles have been enjoying great importance and wide scale applications during the last two decades due to their specific characteristics and applications. Iron oxide magnetic nanoparticles with appropriate surface chemistry have been implied in numerous applications such as biomedicine and cancer therapy, catalysis and in magnetic separation techniques. This review summarizes recent commercial, industrial and bio-engineering applications and brief study of the methods for the preparation of iron oxide magnetic nanoparticles with a control over the size, morphology and the magnetic properties. Some future applications of microwave irradiation for magnetic particle synthesis are also addressed.

  20. Iron oxides in human spleen.

    PubMed

    Kopáni, Martin; Miglierini, Marcel; Lančok, Adriana; Dekan, Július; Čaplovicová, Mária; Jakubovský, Ján; Boča, Roman; Mrazova, Hedviga

    2015-10-01

    Iron is an essential element for fundamental cell functions and a catalyst for chemical reactions. Three samples extracted from the human spleen were investigated by scanning (SEM) and transmission electron microscopy (TEM), Mössbauer spectrometry (MS), and SQUID magnetometry. The sample with diagnosis of hemosiderosis (H) differs from that referring to hereditary spherocytosis and the reference sample. SEM reveals iron-rich micrometer-sized aggregate of various structures-tiny fibrils in hereditary spherocytosis sample and no fibrils in hemochromatosis. Hematite and magnetite particles from 2 to 6 μm in TEM with diffraction in all samples were shown. The SQUID magnetometry shows different amount of diamagnetic, paramagnetic and ferrimagnetic structures in the tissues. The MS results indicate contribution of ferromagnetically split sextets for all investigated samples. Their occurrence indicates that at least part of the sample is magnetically ordered below the critical temperature. The iron accumulation process is different in hereditary spherocytosis and hemosiderosis. This fact may be the reason of different iron crystallization.

  1. Catalytic iron oxide for lime regeneration in carbonaceous fuel combustion

    DOEpatents

    Shen, Ming-Shing; Yang, Ralph T.

    1980-01-01

    Lime utilization for sulfurous oxides absorption in fluidized combustion of carbonaceous fuels is improved by impregnation of porous lime particulates with iron oxide. The impregnation is achieved by spraying an aqueous solution of mixed iron sulfate and sulfite on the limestone before transfer to the fluidized bed combustor, whereby the iron compounds react with the limestone substrate to form iron oxide at the limestone surface. It is found that iron oxide present in the spent limestone acts as a catalyst to regenerate the spent limestone in a reducing environment. With only small quantities of iron oxide the calcium can be recycled at a significantly increased rate.

  2. The Iron-Catalyzed Oxidation of Hydrazine by Nitric Acid

    SciTech Connect

    Karraker, D.G.

    2001-07-17

    To assess the importance of iron to hydrazine stability, the study of hydrazine oxidation by nitric acid has been extended to investigate the iron-catalyzed oxidation. This report describes those results.

  3. Defluoridation by Bacteriogenic Iron Oxides: Sorption Studies

    NASA Astrophysics Data System (ADS)

    Evans, K.; Ferris, F.

    2009-05-01

    At concentrations above 1 mg/L, fluoride in drinking water can lead to dental and skeletal fluorosis, a disease that causes mottling of the teeth, calcification of ligaments, crippling bone deformities and many other physiological disorders that can, ultimately, lead to death. Conservative estimates are that fluorosis afflicts tens of millions of people worldwide. As there is no treatment for fluorosis, prevention is the only means of controlling the disease. While numerous defluoridation techniques have been explored, no single method has been found to be both effective and inexpensive enough to implement widely. Our research began in India, with a large-scale geochemical study of the groundwater in a fluoride-contaminated region of Orissa. Having developed a better understanding of the geochemical relationships that exist between fluoride and other parameters present in an affected area, as well as the complex relationships that arise among those parameters that can impact the presence of fluoride, we began investigating certain remediation scenarios involving iron oxides. A common approach to remediation involves the partitioning of fluoride from groundwater by sorption onto a variety of materials, one of the most effective of which is iron oxide whose surface area acts as a scavenger for fluoride. In the presence of iron oxidizing bacteria, the oxidation rate of iron has been shown to be ˜6 times greater than in their absence; fluoride should, therefore, be removed from an aqueous environment by bacteriogenic iron oxides (BIOS) much more quickly than by abiotic iron oxides. Most recently, sorption studies have been conducted using both BIOS and synthetic hydrous ferric oxides in order to compare the behavior between biotic and abiotic sorbents. These studies have provided sorption isotherms that allow comparison of fluoride removed by sorption to BIOS versus synthetic iron oxides. Sorption affinity constants have also been determined, which allow for the

  4. 21 CFR 73.200 - Synthetic iron oxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically prepared...

  5. 21 CFR 73.1200 - Synthetic iron oxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically prepared...

  6. 21 CFR 73.200 - Synthetic iron oxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically prepared...

  7. 21 CFR 73.1200 - Synthetic iron oxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically prepared...

  8. 21 CFR 73.1200 - Synthetic iron oxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically prepared...

  9. 21 CFR 73.200 - Synthetic iron oxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically prepared...

  10. 21 CFR 73.200 - Synthetic iron oxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically prepared...

  11. 21 CFR 73.1200 - Synthetic iron oxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically prepared...

  12. 21 CFR 73.1200 - Synthetic iron oxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically prepared...

  13. 21 CFR 73.200 - Synthetic iron oxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically prepared...

  14. Chemical design of biocompatible iron oxide nanoparticles for medical applications.

    PubMed

    Ling, Daishun; Hyeon, Taeghwan

    2013-05-27

    Iron oxide nanoparticles are one of the most versatile and safe nanomaterials used in medicine. Recent progress in nanochemistry enables fine control of the size, crystallinity, uniformity, and surface properties of iron oxide nanoparticles. In this review, the synthesis of chemically designed biocompatible iron oxide nanoparticles with improved quality and reduced toxicity is discussed for use in diverse biomedical applications.

  15. Deep reduction behavior of iron oxide and its effect on direct CO oxidation

    NASA Astrophysics Data System (ADS)

    Dong, Changqing; Liu, Xinglei; Qin, Wu; Lu, Qiang; Wang, Xiaoqiang; Shi, Simo; Yang, Yongping

    2012-01-01

    Reduction of metal oxide oxygen carrier has been attractive for direct CO oxidation and CO2 separation. To investigate the reduction behaviors of iron oxide prepared by supporting Fe2O3 on γ-Al2O3 and its effect on CO oxidation, fluidized-bed combustion experiments, thermogravimetric analyzer (TGA) experiments, and density functional theory (DFT) calculations were carried out. Gas yield (γCO2) increases significantly with the increase of temperature from 693 K to 1203 K, while carbon deposition decreases with the increase of temperature from 743 K to 1203 K, where temperature is a very important factor for CO oxidation by iron oxide. Further, it were quantitatively detected that the interaction between CO and Fe2O3, breakage of O-Fe bonds and formation of new C-O bonds, and effect of reduction degree were quantitatively detected. Based on adsorptions under different temperatures and reducing processes from Fe3+ into Fe2+, Fe+ and then into Fe, it was found that Fe2+ → Fe+ was the reaction-controlling step and the high oxidation state of iron is active for CO oxidation, where efficient partial reduction of Fe2O3 into FeO rather than complete reduction into iron may be more energy-saving for CO oxidation.

  16. Acid monolayer functionalized iron oxide nanoparticle catalysts

    NASA Astrophysics Data System (ADS)

    Ikenberry, Myles

    Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide

  17. Ferrous iron oxidation by anoxygenic phototrophic bacteria

    NASA Astrophysics Data System (ADS)

    Widdel, Friedrich; Schnell, Sylvia; Heising, Silke; Ehrenreich, Armin; Assmus, Bernhard; Schink, Bernhard

    1993-04-01

    NATURAL oxidation of ferrous to ferric iron by bacteria such as Thiobacillus ferrooxidans or Gallionella ferruginea1, or by chemical oxidation2,3 has previously been thought always to involve molecular oxygen as the electron acceptor. Anoxic photochemical reactions4-6 or a photobiological process involving two photosystems7-9 have also been discussed as mechanisms of ferrous iron oxidation. The knowledge of such processes has implications that bear on our understanding of the origin of Precambrian banded iron formations10-14. The reducing power of ferrous iron increases dramatically at pH values higher than 2-3 owing to the formation of ferric hydroxy and oxyhydroxy compounds1,2,15 (Fig. 1). The standard redox potential of Fe3+/Fe2+ (E0 = +0.77 V) is relevant only under acidic conditions. At pH 7.0, the couples Fe(OH)3/Fe2+ (E'0 = -0.236V) or Fe(OH)3 + HCO-3FeCO3 (E'0 = +0.200 V) prevail, matching redox potentials measured in natural sediments9,16,17. It should thus be possible for Fe(n) around pH 7.0 to function as an electron donor for anoxygenic photosynthesis. The midpoint potential of the reaction centre in purple bacteria is around +0.45 V (ref. 18). Here we describe purple, non-sulphur bacteria that can indeed oxidize colourless Fe(u) to brown Fe(in) and reduce CO2 to cell material, implying that oxygen-independent biological iron oxidation was possible before the evolution of oxygenic photosynthesis.

  18. Nitric oxide and plant iron homeostasis.

    PubMed

    Buet, Agustina; Simontacchi, Marcela

    2015-03-01

    Like all living organisms, plants demand iron (Fe) for important biochemical and metabolic processes. Internal imbalances, as a consequence of insufficient or excess Fe in the environment, lead to growth restriction and affect crop yield. Knowledge of signals and factors affecting each step in Fe uptake from the soil and distribution (long-distance transport, remobilization from old to young leaves, and storage in seeds) is necessary to improve our understanding of plant mineral nutrition. In this context, the role of nitric oxide (NO) is discussed as a key player in maintaining Fe homeostasis through its cross talk with hormones, ferritin, and frataxin and the ability to form nitrosyl-iron complexes.

  19. Formulations for iron oxides dissolution

    DOEpatents

    Horwitz, Earl P.; Chiarizia, Renato

    1992-01-01

    A mixture of a di- or polyphosphonic acid and a reductant wherein each is present in a sufficient amount to provide a synergistic effect with respect to the dissolution of metal oxides and optionally containing corrosion inhibitors and pH adjusting agents.

  20. Planktonic Marine Iron-Oxidizers Drive Iron(III) Mineralization Under Low Oxygen Conditions

    NASA Astrophysics Data System (ADS)

    Luther, G. W., III; Field, E.; Findlay, A.; MacDonald, D. J.; Chan, C. S. Y.; Kato, S.

    2016-02-01

    Observations of modern microbes have led to several hypotheses on how microbes precipitated the extensive banded iron formations in the geologic record, but we have yet to resolve the exact microbial contributions. An initial hypotheses was that cyanobacteria produced oxygen that oxidized iron(II) abiotically; however, in modern environments such as microbial mats, where Fe(II) and O2 coexist, we commonly find microaerophilic chemolithotrophic iron(II)-oxidizing bacteria producing Fe(III) oxyhydroxides. This suggests that such iron-oxidizers could have inhabited niches in ancient coastal oceans where Fe(II) and O2 coexisted, and therefore contributed to iron deposits, but there is currently little evidence for planktonic marine iron-oxidizers in modern analogs. Here, we demonstrate successful cultivation of planktonic microaerophilic iron-oxidizing Zetaproteobacteria from the Chesapeake Bay during seasonal stratification. Iron-oxidizers were associated with low oxygen concentrations and active iron redox cycling in the oxic-anoxic transition zone (<3 µM O2, <0.2 µM H2S). While cyanobacteria were also detected in this transition zone, oxygen concentrations were too low to support significant rates of abiotic iron oxidation. Instead, cyanobacteria may be providing oxygen for microaerophilic iron(II) oxidation through a symbiotic relationship that promotes oxygen consumption rather than build-up. Our results suggest that once oxygenic photosynthesis evolved, microaerophilic chemolithotrophic iron(II)-oxidizers were likely important drivers of iron(III) mineralization in ancient oceans.

  1. Near-infrared excited state dynamics of melanins: the effects of iron content, photo-damage, chemical oxidation, and aggregate size.

    PubMed

    Simpson, Mary Jane; Wilson, Jesse W; Robles, Francisco E; Dall, Christopher P; Glass, Keely; Simon, John D; Warren, Warren S

    2014-02-13

    Ultrafast pump-probe measurements can discriminate the two forms of melanin found in biological tissue (eumelanin and pheomelanin), which may be useful for diagnosing and grading melanoma. However, recent work has shown that bound iron content changes eumelanin's pump-probe response, making it more similar to that of pheomelanin. Here we record the pump-probe response of these melanins at a wider range of wavelengths than previous work and show that with shorter pump wavelengths the response crosses over from being dominated by ground-state bleaching to being dominated by excited-state absorption. The crossover wavelength is different for each type of melanin. In our analysis, we found that the mechanism by which iron modifies eumelanin's pump-probe response cannot be attributed to Raman resonances or differences in melanin aggregation and is more likely caused by iron acting to broaden the unit spectra of individual chromophores in the heterogeneous melanin aggregate. We analyze the dependence on optical intensity, finding that iron-loaded eumelanin undergoes irreversible changes to the pump-probe response after intense laser exposure. Simultaneously acquired fluorescence data suggest that the previously reported "activation" of eumelanin fluorescence may be caused in part by the dissociation of metal ions or the selective degradation of iron-containing melanin.

  2. Near-Infrared Excited State Dynamics of Melanins: The Effects of Iron Content, Photo-Damage, Chemical Oxidation, and Aggregate Size

    PubMed Central

    2015-01-01

    Ultrafast pump–probe measurements can discriminate the two forms of melanin found in biological tissue (eumelanin and pheomelanin), which may be useful for diagnosing and grading melanoma. However, recent work has shown that bound iron content changes eumelanin’s pump–probe response, making it more similar to that of pheomelanin. Here we record the pump–probe response of these melanins at a wider range of wavelengths than previous work and show that with shorter pump wavelengths the response crosses over from being dominated by ground-state bleaching to being dominated by excited-state absorption. The crossover wavelength is different for each type of melanin. In our analysis, we found that the mechanism by which iron modifies eumelanin’s pump–probe response cannot be attributed to Raman resonances or differences in melanin aggregation and is more likely caused by iron acting to broaden the unit spectra of individual chromophores in the heterogeneous melanin aggregate. We analyze the dependence on optical intensity, finding that iron-loaded eumelanin undergoes irreversible changes to the pump–probe response after intense laser exposure. Simultaneously acquired fluorescence data suggest that the previously reported “activation” of eumelanin fluorescence may be caused in part by the dissociation of metal ions or the selective degradation of iron-containing melanin. PMID:24446774

  3. Quantitative determination of the oxidation state of iron in biotite using x-ray photoelectron spectroscopy: II. In situ analyses

    SciTech Connect

    Raeburn, S.P. |; Ilton, E.S.; Veblen, D.R.

    1997-11-01

    X-ray photoelectron spectroscopy (XPS) was used to determine Fe(III)/{Sigma}Fe in individual biotite crystals in thin sections of ten metapelites and one syenite. The in situ XPS analyses of Fe(III)/{Sigma}Fe in biotite crystals in the metapelites were compared with published Fe(III)/{Sigma}Fe values determined by Moessbauer spectroscopy (MS) for mineral separates from the same hand samples. The difference between Fe(III)/{Sigma}Fe by the two techniques was greatest for samples with the lowest Fe(III)/{Sigma}Fe (by MS). For eight metamorphic biotites with Fe(III)/{Sigma}Fe = 9-27% comparison of the two techniques yielded a linear correlation of r = 0.94 and a statistically acceptable fit of [Fe(III)/{Sigma}Fe]{sub xps} = [Fe(III)/{Sigma}Fe]{sub ms}. The difference between Fe(III)/{Sigma}Fe by the two techniques was greater for two samples with Fe(III)/{Sigma}Fe {le} 6% (by MS). For biotite in the syenite sample, Fe(III)/{Sigma}Fe determined by both in situ XPS and bulk wet chemistry/electron probe microanalysis were similar. This contribution demonstrates that XPS can be used to analyze bulk Fe(III)/{Sigma}Fe in minerals in thin sections when appropriate precautions taken to avoid oxidation of the near-surface during preparation of samples. 25 refs., 3 figs., 4 tabs.

  4. Nitric oxide and changes of iron metabolism in exercise.

    PubMed

    Qian, Zhong Ming

    2002-11-01

    Accumulated data imply that exercise itself might not lead to a true iron deficiency or 'sport anaemia' in a healthy athlete who has adequate iron intake. The higher prevalence of iron deficiency anaemia in younger female athletes might be not due to exercise itself, but probably results from dietary choices, inadequate iron intake and menstruation. These factors can also induce iron deficiency or anaemia in the general population. However, exercise does affect iron metabolism, leading to low or sub-optimal iron status. The underlying mechanism is unknown. In this review, recent advances in the study of the effect of exercise on iron metabolism and nitric oxide, and the relationship between nitric oxide and iron status in exercise are discussed. A hypothesis that increased production of nitric oxide might contribute to sub-optimal iron status in exercise is proposed.

  5. Method for preparing hydrous iron oxide gels and spherules

    DOEpatents

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

    2003-07-29

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

  6. Linear-chain assemblies of iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Dhak, Prasanta; Kim, Min-Kwan; Lee, Jae Hyeok; Kim, Miyoung; Kim, Sang-Koog

    2017-07-01

    We synthesized iron oxide nanoparticles using a simple hydrothermal approach and found several types of segments of their linear-chain self-assemblies as observed by field emission scanning electron microscopy. X-ray diffraction and transmission electron microscopy measurements confirm a well-defined single-phase FCC structure. Vibrating sample magnetometry measurements exhibit a ferromagnetic behavior. Micromagnetic numerical simulations show magnetic vortex states in the nanosphere model. Also, calculations of binding energies for different numbers of particles in the linear-chain assemblies explain a possible mechanism responsible for the self-assemblies of segments of the linear chains of nanoparticles. This work offers a step towards linear-chain self-assemblies of iron oxide nanoparticles and the effect of magnetic vortex states in individual nanoparticles on their binding energy.

  7. Optical properties of iron oxides

    NASA Astrophysics Data System (ADS)

    Musfeldt, Janice

    2012-02-01

    Magnetoelectric coupling in materials like multiferroics, dilute magnetic semiconductors, and topological insulators has attracted a great deal of attention, although most work has been done in the static limit. Optical spectroscopy offers a way to investigate the dynamics of charge-spin coupling, an area where there has been much less effort. Using these techniques, we discovered that charge fluctuation in LuFe2O4, the prototypical charge ordered multiferroic, has an onset well below the charge ordering transition, supporting the ``order by fluctuation'' mechanism for the development of charge order superstructure. Bragg splitting and large magneto-optical contrast suggest a low temperature monoclinic distortion that can be driven by both temperature and magnetic field. At the same time, dramatic splitting of the LuO2 layer phonon mode is attributed to charge-rich/poor proximity effects, and its temperature dependence reveals the antipolar nature of the W layer pattern. Using optical techniques, we also discovered that α-Fe2O3, a chemically-similar parent compound and one of the world's oldest and most iconic antiferromagnetic materials, appears more red in applied magnetic field than in zero field conditions. This effect is driven by a field-induced reorientation of magnetic order. The oscillator strength lost in the color band is partially transferred to the magnon side band, a process that also reveals a new exciton pattern induced by the modified exchange coupling. Analysis of the exciton pattern exposes C2/c monoclinic symmetry in the high field phase of hematite. Taken together, these findings advance our understanding of iron-based materials under extreme conditions. [4pt] Collaborators include: X. S. Xu, P. Chen, Q. -C. Sun, T. V. Brinzari (Tennessee); S. McGill (NHMFL); J. De Groot, M. Angst, R. P. Hermann (Julich); A. D. Christianson, B. C. Sales, D. Mandrus (ORNL); A. P. Litvinchuk (Houston); J. -W. Kim (Ames); Z. Islam (Argonne); N. Lee, S. -W. Cheong

  8. Iron Oxide Deposition from Aqueous Solution and Iron Formations on Mars

    NASA Technical Reports Server (NTRS)

    Catling, David; Moore, Jeff

    2000-01-01

    Iron formations are ancient, laminated chemical sediments containing at least 15 wt% Fe. We discuss possible mechanisms for their formation in aqueous environments on early Mars. Such iron oxide deposits may be detectable today.

  9. Promising iron oxide-based magnetic nanoparticles in biomedical engineering.

    PubMed

    Tran, Phuong Ha-Lien; Tran, Thao Truong-Dinh; Vo, Toi Van; Lee, Beom-Jin

    2012-12-01

    For the past few decades biomedical engineering has imprinted its significant impact on the map of science through its wide applications on many other fields. An important example obviously proving this fact is the versatile application of magnetic nanoparticles in theranostics. Due to preferable properties such as biocompatibility, non-toxicity compared to other metal derivations, iron oxide-based magnetic nanoparticles was chosen to be addressed in this review. Aim of this review is to give the readers a whole working window of these magnetic nanoparticles in the current context of science. Thus, preparation of magnetic iron oxide nanoparticles with the so-far techniques, methods of characterizing the nanoparticles as well as their most recent biomedical applications will be stated.

  10. Nanovectors for anticancer agents based on superparamagnetic iron oxide nanoparticles

    PubMed Central

    Douziech-Eyrolles, Laurence; Marchais, Hervé; Hervé, Katel; Munnier, Emilie; Soucé, Martin; Linassier, Claude; Dubois, Pierre; Chourpa, Igor

    2007-01-01

    During the last decade, the application of nanotechnologies for anticancer drug delivery has been extensively explored, hoping to improve the efficacy and to reduce side effects of chemotherapy. The present review is dedicated to a certain kind of anticancer drug nanovectors developed to target tumors with the help of an external magnetic field. More particularly, this work treats anticancer drug nanoformulations based on superparamagnetic iron oxide nanoparticles coated with biocompatible polymers. The major purpose is to focus on the specific requirements and technological difficulties related to controlled delivery of antitumoral agents. We attempt to state the problem and its possible perspectives by considering the three major constituents of the magnetic therapeutic vectors: iron oxide nanoparticles, polymeric coating and anticancer drug. PMID:18203422

  11. TNF-α-stimulated macrophages protect A549 lung cells against iron and oxidation.

    PubMed

    Persson, H Lennart; Vainikka, Linda K; Eriksson, Ida; Wennerström, Urban

    2013-01-01

    Previously, we have shown that TNF-α protects iron-exposed J774 macrophages against iron-catalyzed oxidative lysosomal disruption and cell death by increasing reduced glutathione and H-ferritin in cells. Because J774 cells are able to harbor large amounts of iron, which is potentially harmful in a redox-active state, we hypothesized that TNF-α-stimulated J774 macrophages will prevent iron-driven oxidative killing of alveolar epithelial A549 cells in co-culture. In the present study, iron trichloride (which is endocytosed by cells as hydrated iron-phosphate complexes) was mainly deposited inside the lysosomes of J774 macrophages, while A549 cells, equally iron exposed, accumulated much less iron. When challenged by oxidants, however, reactive lysosomal iron in A549 cells promoted lysosomal disruption and cell death, particularly in the presence of TNF-α. This effect resulted from an elevation in ROS generation by TNF-α, while a compensatory upregulation of protective molecules (H-ferritin and/or reduced glutathione) by TNF-α was absent. A549 cell death was particularly pronounced when iron and TNF-α were present in the conditioned medium during oxidant challenge; thus, iron-driven oxidative reactions in the culture medium were a much greater hazard to A549 cells than those taking place inside their lysosomes. Consequently, the iron chelator, deferoxamine, efficiently prevented A549 cell death when added to the culture medium during an oxidant challenge. In co-cultures of TNF-α-stimulated lung cells, J774 macrophages sequestered iron inside their lysosomes and protected A549 cells from oxidative reactions and cell death. Thus, the collective effect of TNF-α on co-cultured lung cells was mainly cytoprotective. Copyright © 2011 Elsevier GmbH. All rights reserved.

  12. Iron isotope constraints on the Archean and Paleoproterozoic ocean redox state.

    PubMed

    Rouxel, Olivier J; Bekker, Andrey; Edwards, Katrina J

    2005-02-18

    The response of the ocean redox state to the rise of atmospheric oxygen about 2.3 billion years ago (Ga) is a matter of controversy. Here we provide iron isotope evidence that the change in the ocean iron cycle occurred at the same time as the change in the atmospheric redox state. Variable and negative iron isotope values in pyrites older than about 2.3 Ga suggest that an iron-rich global ocean was strongly affected by the deposition of iron oxides. Between 2.3 and 1.8 Ga, positive iron isotope values of pyrite likely reflect an increase in the precipitation of iron sulfides relative to iron oxides in a redox stratified ocean.

  13. Pulsed-laser deposition of nanostructured iron oxide catalysts for efficient water oxidation.

    PubMed

    Orlandi, Michele; Caramori, Stefano; Ronconi, Federico; Bignozzi, Carlo A; El Koura, Zakaria; Bazzanella, Nicola; Meda, Laura; Miotello, Antonio

    2014-05-14

    Amorphous iron oxide nanoparticles were synthesized by pulsed-laser deposition (PLD) for functionalization of indium-tin oxide surfaces, resulting in electrodes capable of efficient catalysis in water oxidation. These electrodes, based on earth-abundant and nonhazardous iron metal, are able to sustain high current densities (up to 20 mA/cm2) at reasonably low applied potential (1.64 V at pH 11.8 vs reversible hydrogen electrode) for more than 1 h when employed as anodes for electrochemical water oxidation. The good catalytic performance proves the validity of PLD as a method to prepare nanostructured solid-state materials for catalysis, enabling control over critical properties such as surface coverage and morphology.

  14. Iron oxidation kinetics and autotrophic bacteria in acidified environments

    SciTech Connect

    Barry, R.C.

    1993-01-01

    Iron oxidation in the presence of lake sediment collected from an acidic alpine lake was three orders of magnitude faster than in filtered lakewater without sediment. When kinetic rates in the presence of sediment were normalized on a surface area basis, they fell within a narrow range, and the assumption of a first order dependence of rate on surface area was supported. The relative influence on heterogeneous rate of ferrous iron oxidation of the five metal oxides studied can be ranked SiO[sub 2] [approx] Al[sub 2]O[sub 3] [much lt] Fe[sub 2] O[sub 3] [approx] MnO[sub 2] [approx] TiO[sub 2], with a difference of three orders of magnitude separating the aluminum and iron oxides. The rate constants on a surface area basis were, respectively, 1.8 [times] 10[sup 10], 4.6 [times] 10[sup 10], 1.4 [times] 10[sup 13], 2.3 [times] 10[sup 13] and 5.3 [times] 10[sup 13]M[sup [minus]2] atm[sup [minus]1] sec[sup [minus]1]m[sup [minus]2]. Studies at low oxygen concentrations suggested that at low pO[sub 2] oxygenation may not be first order with respect to oxygen concentration. Biological processes were found to enhance oxidation kinetics by two orders of magnitude on a surface area basis in comparison with a gamma irradiated control. Oxidation rate in the presence of irradiated sediment was in turn approximately 130 times greater than for oxidation in deionized water. The importance of biological activity in environments exhibiting photoreduction of iron was further studied by development of a polyclonal antibody test for the detection of the iron oxidizing autotroph Thiobacillus ferrooxidans. T. ferrooxidans was found in the Snake River and its tributaries in the Colorado Rocky mountains. Tests for T. ferrooxidans in samples collected at Lake Cristallina, Canton Ticino, Switzerland and McDonalds Branch, Lebanon State Forest, New Jersey were negative.

  15. Water clustering on nanostructured iron oxide films.

    PubMed

    Merte, Lindsay R; Bechstein, Ralf; Peng, Guowen; Rieboldt, Felix; Farberow, Carrie A; Zeuthen, Helene; Knudsen, Jan; Lægsgaard, Erik; Wendt, Stefan; Mavrikakis, Manos; Besenbacher, Flemming

    2014-06-30

    The adhesion of water to solid surfaces is characterized by the tendency to balance competing molecule-molecule and molecule-surface interactions. Hydroxyl groups form strong hydrogen bonds to water molecules and are known to substantially influence the wetting behaviour of oxide surfaces, but it is not well-understood how these hydroxyl groups and their distribution on a surface affect the molecular-scale structure at the interface. Here we report a study of water clustering on a moiré-structured iron oxide thin film with a controlled density of hydroxyl groups. While large amorphous monolayer islands form on the bare film, the hydroxylated iron oxide film acts as a hydrophilic nanotemplate, causing the formation of a regular array of ice-like hexameric nanoclusters. The formation of this ordered phase is localized at the nanometre scale; with increasing water coverage, ordered and amorphous water are found to coexist at adjacent hydroxylated and hydroxyl-free domains of the moiré structure.

  16. Water Clustering on Nanostructured Iron Oxide Films

    SciTech Connect

    Merte, L. R.; Bechstein, Ralf; Peng, Guowen; Rieboldt, Felix; Farberow, Carrie A.; Zeuthen, Helene; Knudsen, Jan; Laegsgaard, E.; Wendt, Stefen; Mavrikakis, Manos; Besenbacher, Fleming

    2014-06-30

    The adhesion of water to solid surfaces is characterized by the tendency to balance competing molecule–molecule and molecule–surface interactions. Hydroxyl groups form strong hydrogen bonds to water molecules and are known to substantially influence the wetting behaviour of oxide surfaces, but it is not well-understood how these hydroxyl groups and their distribution on a surface affect the molecular-scale structure at the interface. Here we report a study of water clustering on a moire´-structured iron oxide thin film with a controlled density of hydroxyl groups. While large amorphous monolayer islands form on the are film, the hydroxylated iron oxide film acts as a hydrophilic nanotemplate, causing the formation of a regular array of ice-like hexameric nanoclusters. The formation of this ordered phase is localized at the nanometre scale; with increasing water coverage, ordered and amorphous water are found to coexist at adjacent hydroxylated and hydroxyl-free domains of the moire´ structure.

  17. Interactions between sub-10-nm iron and cerium oxide nanoparticles and 3T3 fibroblasts: the role of the coating and aggregation state

    NASA Astrophysics Data System (ADS)

    Safi, M.; Sarrouj, H.; Sandre, O.; Mignet, N.; Berret, J.-F.

    2010-04-01

    Recent nanotoxicity studies revealed that the physico-chemical characteristics of engineered nanomaterials play an important role in the interactions with living cells. Here, we report on the toxicity and uptake of cerium and iron oxide sub-10-nm nanoparticles by NIH/3T3 mouse fibroblasts. Coating strategies include low-molecular weight ligands (citric acid) and polymers (poly(acrylic acid), MW = 2000 g mol - 1). Electrostatically adsorbed on the surfaces, the organic moieties provide a negatively charged coating in physiological conditions. We find that most particles were biocompatible, as exposed cells remained 100% viable relative to controls. Only the bare and the citrate-coated nanoceria exhibit a slight decrease in mitochondrial activity at very high cerium concentrations (>1 g l - 1). We also observe that the citrate-coated particles are internalized/adsorbed by the cells in large amounts, typically 250 pg/cell after 24 h incubation for iron oxide. In contrast, the polymer-coated particles are taken up at much lower rates (<30 pg/cell). The strong uptake shown by the citrated particles is related to the destabilization of the dispersions in the cell culture medium and their sedimentation down to the cell membranes. In conclusion, we show that the uptake of nanomaterials by living cells depends on the coating of the particles and on its ability to preserve the colloidal nature of the dispersions.

  18. Phase Formation Behavior in Ultrathin Iron Oxide.

    PubMed

    Jõgi, Indrek; Jacobsson, T Jesper; Fondell, Mattis; Wätjen, Timo; Carlsson, Jan-Otto; Boman, Mats; Edvinsson, Tomas

    2015-11-17

    Nanostructured iron oxides, and especially hematite, are interesting for a wide range of applications ranging from gas sensors to renewable solar hydrogen production. A promising method for deposition of low-dimensional films is atomic layer deposition (ALD). Although a potent technique, ALD of ultrathin films is critically sensitive to the substrate and temperature conditions where initial formation of islands and crystallites influences the properties of the films. In this work, deposition at the border of the ALD window forming a hybrid ALD/pulsed CVD (pCVD) deposition is utilized to obtain a deposition less sensitive to the substrate. A thorough analysis of iron oxide phases formation on two different substrates, Si(100) and SiO2, was performed. Films between 3 and 50 nm were deposited and analyzed with diffraction techniques, high-resolution Raman spectroscopy, and optical spectroscopy. Below 10 nm nominal film thickness, island formation and phase dependent particle crystallization impose constraints for deposition of phase pure iron oxides on non-lattice-matching substrates. Films between 10 and 20 nm thickness on SiO2 could effectively be recrystallized into hematite whereas for the corresponding films on Si(100), no recrystallization occurred. For films thicker than 20 nm, phase pure hematite can be formed directly with ALD/pCVD with very low influence of the substrate on either Si or SiO2. For more lattice matched substrates such as SnO2:F, Raman spectroscopy indicated formation of the hematite phase already for films with 3 nm nominal thickness and clearly for 6 nm films. Analysis of the optical properties corroborated the analysis and showed a quantum confined blue-shift of the absorption edge for the thinnest films.

  19. Iron Oxide Nanozyme: A Multifunctional Enzyme Mimetic for Biomedical Applications

    PubMed Central

    Gao, Lizeng; Fan, Kelong; Yan, Xiyun

    2017-01-01

    Iron oxide nanoparticles have been widely used in many important fields due to their excellent nanoscale physical properties, such as magnetism/superparamagnetism. They are usually assumed to be biologically inert in biomedical applications. However, iron oxide nanoparticles were recently found to also possess intrinsic enzyme-like activities, and are now regarded as novel enzyme mimetics. A special term, “Nanozyme”, has thus been coined to highlight the intrinsic enzymatic properties of such nanomaterials. Since then, iron oxide nanoparticles have been used as nanozymes to facilitate biomedical applications. In this review, we will introduce the enzymatic features of iron oxide nanozyme (IONzyme), and summarize its novel applications in biomedicine. PMID:28900505

  20. Mineral resource of the month: iron oxide pigments

    USGS Publications Warehouse

    ,

    2008-01-01

    The article discusses iron oxide pigments, which have been used as colorants since human began painting as they resist color change due to sunlight exposure, have good chemical resistance and are stable under normal ambient conditions. Cyprus, Italy and Spain are among the countries that are known for the production of iron oxide pigments. Granular forms of iron oxides and nano-sized materials are cited as developments in the synthetic iron oxide pigment industry which are being used in computer disk drives and nuclear magnetic resonance imaging.

  1. Iron-oxo clusters biomineralizing on protein surfaces: Structural analysis of Halobacterium salinarum DpsA in its low- and high-iron states

    PubMed Central

    Zeth, Kornelius; Offermann, Stefanie; Essen, Lars-Oliver; Oesterhelt, Dieter

    2004-01-01

    The crystal structure of the Dps-like (Dps, DNA-protecting protein during starvation) ferritin protein DpsA from the halophile Halobacterium salinarum was determined with low endogenous iron content at 1.6-Å resolution. The mechanism of iron uptake and storage was analyzed in this noncanonical ferritin by three high-resolution structures at successively increasing iron contents. In the high-iron state of the DpsA protein, up to 110 iron atoms were localized in the dodecameric protein complex. For ultimate iron storage, the archaeal ferritin shell comprises iron-binding sites for iron translocation, oxidation, and nucleation. Initial iron–protein interactions occur through acidic residues exposed along the outer surface in proximity to the iron entry pore. This narrow pore permits translocation of ions toward the ferroxidase centers via two discrete steps. Iron oxidation proceeds by transient formation of tri-iron ferroxidase centers. Iron storage by biomineralization inside the ferritin shell occurs at two iron nucleation centers. Here, a single iron atom provides a structural seed for iron-oxide cluster formation. The clusters with up to five iron atoms adopt a geometry that is different from natural biominerals like magnetite but resembles iron clusters so far known only from bioinorganic model compounds. PMID:15365182

  2. Suspension Hydrogen Reduction of Iron Oxide Concentrates

    SciTech Connect

    H.Y. Sohn

    2008-03-31

    The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

  3. Modified iron oxide nanomaterials: Functionalization and application

    NASA Astrophysics Data System (ADS)

    Bagheri, Samira; Julkapli, Nurhidayatullaili Muhd

    2016-10-01

    Iron oxide magnetic nanoparticles have aroused the interest of researchers of materials' chemistry due to its exceptional properties such as decent magnetic, electric, catalytic, biocompatibility, and low toxicity. However, these magnetic nanoparticles are predisposed towards aggregation and forming larger particles, due to its strong anisotropic dipolar interactions, particularly in the aqueous phase, consequently depriving them of dispersibility and particular properties, ultimately degrading their performance. Hence, this review focuses on modified magnetic nanoparticles that are stable, easily synthesized, possess a high surface area and could be facile-separated via magnetic forces, and are of low toxicity and costs for applications such as catalyst/catalyst support, food security, biomedical, and pollutant remediation.

  4. Superparamagnetic iron oxide nanoparticle uptake alters M2 macrophage phenotype, iron metabolism, migration and invasion.

    PubMed

    Rojas, José M; Sanz-Ortega, Laura; Mulens-Arias, Vladimir; Gutiérrez, Lucía; Pérez-Yagüe, Sonia; Barber, Domingo F

    2016-05-01

    Superparamagnetic iron oxide nanoparticles (SPIONs) have shown promise as contrast agents and nanocarriers for drug delivery. Their impact on M2-polarised macrophages has nonetheless not been well studied. Here we explored the effects of SPIONs coated with dimercaptosuccinic acid, aminopropyl silane or aminodextran in two M2 macrophage models (murine primary IL-4-activated bone marrow-derived macrophages and human M2-like differentiated THP-1 cells). All SPIONs were internalised and no cell toxicity was observed. SPION treatment produced reactive oxygen species and activated the extracellular signal-regulated kinase and AKT pathways. After 24-h SPION incubation, M2 macrophages switched their iron metabolism towards an iron-replete state. SPION treatment in both M2 macrophage models altered their M2 activation profiles, promoted IL-10 production, and stimulated protease-dependent invasion. These results highlight the need to evaluate the interactions between SPIONs and cells to take full advantage of the intrinsic properties of these nanoparticles in biological systems. Superparamagnetic iron oxide nanoparticles (SPIONs) have been used as an MRI contrast agent in many experimental studies. The authors here investigated the effects of these nanoparticles on M2 macrophages after cellular uptake. The findings of cell activation further enhanced our current knowledge on the interaction of SPIONS with macrophages. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. A Diatom Ferritin Optimized for Iron Oxidation but Not Iron Storage*

    PubMed Central

    Pfaffen, Stephanie; Bradley, Justin M.; Abdulqadir, Raz; Firme, Marlo R.; Moore, Geoffrey R.; Le Brun, Nick E.; Murphy, Michael E. P.

    2015-01-01

    Ferritin from the marine pennate diatom Pseudo-nitzschia multiseries (PmFTN) plays a key role in sustaining growth in iron-limited ocean environments. The di-iron catalytic ferroxidase center of PmFTN (sites A and B) has a nearby third iron site (site C) in an arrangement typically observed in prokaryotic ferritins. Here we demonstrate that Glu-44, a site C ligand, and Glu-130, a residue that bridges iron bound at sites B and C, limit the rate of post-oxidation reorganization of iron coordination and the rate at which Fe3+ exits the ferroxidase center for storage within the mineral core. The latter, in particular, severely limits the overall rate of iron mineralization. Thus, the diatom ferritin is optimized for initial Fe2+ oxidation but not for mineralization, pointing to a role for this protein in buffering iron availability and facilitating iron-sparing rather than only long-term iron storage. PMID:26396187

  6. Magnetic Signatures of Several Synthetic Iron Oxides Alteration Pathways

    NASA Astrophysics Data System (ADS)

    Guyodo, Y.; Ona-Nguema, G.; Bonville, P.; Lagroix, F.

    2009-05-01

    The alteration of naturally occurring iron oxides and oxyhydroxides, under the influence of varying environmental conditions, including micro-environments and biological activity, is an important research topic because their connection to past climate variations remains to be elucidated. One approach to this subject matter is to perform laboratory experiments using synthetic iron oxides (sensus lato) subjected to specific physical and bio-chemical conditions. In our presentation, we will report on alteration experiments performed on synthetic lepidocrocite (γ-FeOOH) and maghemite (γ-Fe2O3) particles. A first approach consists in using the starting materials as electron acceptors in bio-reduction experiments involving the iron- reducing bacteria Shewanella putrefaciens and leading to the formation of magnetite (Fe3O4) particles. In a parallel approach, the starting materials are converted to magnetite by slow heating in CO/CO2 atmosphere. Further alteration can be done by slow heating in air, this time inducing aging and oxidation of the material. At various stages of our experiments, the samples are characterized using both magnetic (low-temperature, low-field and high-field magnetic measurements, Mossbaüer spectroscopy, etc.) and non-magnetic techniques (XRD, HRTEM, etc.). The various experiments conducted on these samples will allow us to study different pathways of magnetite formation and alteration in the environment, including solid-state conversion, partial or total dissolution/precipitation, and particles aggregation.

  7. Insight into the evolution of the iron oxidation pathways.

    PubMed

    Ilbert, Marianne; Bonnefoy, Violaine

    2013-02-01

    Iron is a ubiquitous element in the universe. Ferrous iron (Fe(II)) was abundant in the primordial ocean until the oxygenation of the Earth's atmosphere led to its widespread oxidation and precipitation. This change of iron bioavailability likely put selective pressure on the evolution of life. This element is essential to most extant life forms and is an important cofactor in many redox-active proteins involved in a number of vital pathways. In addition, iron plays a central role in many environments as an energy source for some microorganisms. This review is focused on Fe(II) oxidation. The fact that the ability to oxidize Fe(II) is widely distributed in Bacteria and Archaea and in a number of quite different biotopes suggests that the dissimilatory Fe(II) oxidation is an ancient energy metabolism. Based on what is known today about Fe(II) oxidation pathways, we propose that they arose independently more than once in evolution and evolved convergently. The iron paleochemistry, the phylogeny, the physiology of the iron oxidizers, and the nature of the cofactors of the redox proteins involved in these pathways suggest a possible scenario for the timescale in which each type of Fe(II) oxidation pathways evolved. The nitrate dependent anoxic iron oxidizers are likely the most ancient iron oxidizers. We suggest that the phototrophic anoxic iron oxidizers arose in surface waters after the Archaea/Bacteria-split but before the Great Oxidation Event. The neutrophilic oxic iron oxidizers possibly appeared in microaerobic marine environments prior to the Great Oxidation Event while the acidophilic ones emerged likely after the advent of atmospheric O(2). This article is part of a Special Issue entitled: The evolutionary aspects of bioenergetic systems.

  8. Gold and iron oxide associations under supergene conditions: An experimental approach

    NASA Astrophysics Data System (ADS)

    Greffié, Catherine; Benedetti, Marc F.; Parron, Claude; Amouric, Marc

    1996-05-01

    Abstract-The interaction of gold hydroxo-chloro complexes with iron oxides (ferrihydrites, goethites) during coprecipitation experiments is investigated. Chemical analyses of solids and solutions are coupled with a detailed characterization of the iron oxides with various methods, including X-ray diffraction, High Resolution Transmission Electron Microscopy (HRTEM), and Mössbauer spectroscopy. HCl solutions containing varying amounts of AuCl 4- and ferric nitrate were titrated to neutral or alkaline pH, resulting in the coprecipitation of gold and iron oxide phases (ferrihydrite or goethite). Reference titrations were performed in the absence of iron. Most of the gold was removed from solution in the presence of iron oxides whereas gold remained dissolved in the reference samples. In association with iron oxides two forms of gold have been identified by HRTEM and 197Au Mössbauer spectroscopy: metallic gold as well as chloro and/or hydroxo combined gold. This combined gold is in a trivalent state as the primary product which means that a reduction process is not a necessary step for the adsorption of gold species on iron oxides. Metallic gold characterized in these products by means of HRTEM consists mainly of colloids ranging from 3-60 nm in diameter embedded in the ferrihydrite matrix, as isolated particles or as particles associated with goethite laths. The smallest metallic gold particles detected would be almost invisible to classical observation techniques used for solid phases. In our experiments, oxidation-reduction reactions between Fe 2+ and Au 3+ are responsible for the presence of metallic gold observed on the iron phases. Photochemical reactions may also take part in the reduction process. Colloidal gold and gold complexes could be associated to the iron oxides by strong electrostatic interactions. Our results suggest that poorly ordered iron oxides are highly efficient in trapping gold from solutions thanks to their high surface area, and favor gold

  9. Battles with Iron: Manganese in Oxidative Stress Protection*

    PubMed Central

    Aguirre, J. Dafhne; Culotta, Valeria C.

    2012-01-01

    The redox-active metal manganese plays a key role in cellular adaptation to oxidative stress. As a cofactor for manganese superoxide dismutase or through formation of non-proteinaceous manganese antioxidants, this metal can combat oxidative damage without deleterious side effects of Fenton chemistry. In either case, the antioxidant properties of manganese are vulnerable to iron. Cellular pools of iron can outcompete manganese for binding to manganese superoxide dismutase, and through Fenton chemistry, iron may counteract the benefits of non-proteinaceous manganese antioxidants. In this minireview, we highlight ways in which cells maximize the efficacy of manganese as an antioxidant in the midst of pro-oxidant iron. PMID:22247543

  10. Uptake And Intracellular Distribution Of Functionalized Iron Oxide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Panariti, A.; Lettiero, B.; Morjan, I.; Alexandreascu, R.; Wang, D.; Bucci, C.; Miserocchi, G.; Rivolta, I.

    2010-10-01

    Iron oxide Nanoparticles represents promising nanocarrier for magnetic resonance imaging (MRI), targeted drug and gene delivery. In our study we investigated the interaction between lung alveolar epithelial cells and iron oxide NPs coated with L-Dihydroxyphenylalanina (L-Dopa)-TRITC. Our data suggest that particles crossed the plasma membrane with an energy-dependent process.

  11. TRACE ELEMENT BINDING DURING STRUCTURAL TRANSFORMATION IN IRON OXIDES

    EPA Science Inventory

    Iron (hydr)oxides often control the mobility of inorganic contaminants in soils and sediments. A poorly ordered form of ferrihydrite is commonly produced during rapid oxidation of ferrous iron at sharp redox fronts encountered during discharge of anoxic/suboxic waters into terre...

  12. TRACE ELEMENT BINDING DURING STRUCTURAL TRANSFORMATION IN IRON OXIDES

    EPA Science Inventory

    Iron (hydr)oxides often control the mobility of inorganic contaminants in soils and sediments. A poorly ordered form of ferrihydrite is commonly produced during rapid oxidation of ferrous iron at sharp redox fronts encountered during discharge of anoxic/suboxic waters into terre...

  13. Modified Nanoemulsions with Iron Oxide for Magnetic Resonance Imaging

    PubMed Central

    Fan, Yongyi; Guo, Rui; Shi, Xiangyang; Allen, Steven; Cao, Zhengyi; Baker, James R.; Wang, Su He

    2016-01-01

    A nanoemulsion (NE) is a surfactant-based, oil-in-water, nanoscale, high-energy emulsion with a mean droplet diameter of 400–600 nm. When mixed with antigen and applied nasally, a NE acts as a mucosal adjuvant and induces mucosal immune responses. One possible mechanism for the adjuvant effect of this material is that it augments antigen uptake and distribution to lymphoid tissues, where the immune response is generated. Biocompatible iron oxide nanoparticles have been used as a unique imaging approach to study the dynamics of cells or molecular migration. To study the uptake of NEs and track them in vivo, iron oxide nanoparticles were synthesized and dispersed in soybean oil to make iron oxide-modified NEs. Our results show that iron oxide nanoparticles can be stabilized in the oil phase of the nanoemulsion at a concentration of 30 µg/μL and the iron oxide-modified NEs have a mean diameter of 521 nm. In vitro experiments demonstrated that iron oxide-modified NEs can affect uptake by TC-1 cells (a murine epithelial cell line) and reduce the intensity of magnetic resonance (MR) images by shortening the T2 time. Most importantly, in vivo studies demonstrated that iron oxide-modified NE could be detected in mouse nasal septum by both transmission electron microscopy and MR imaging. Altogether these experiments demonstrate that iron oxide-modified NE is a unique tool that can be used to study uptake and distribution of NEs after nasal application. PMID:28335351

  14. Ecological succession among iron-oxidizing bacteria.

    PubMed

    Fleming, Emily J; Cetinić, Ivona; Chan, Clara S; Whitney King, D; Emerson, David

    2014-04-01

    Despite over 125 years of study, the factors that dictate species dominance in neutrophilic iron-oxidizing bacterial (FeOB) communities remain unknown. In a freshwater wetland, we documented a clear ecological succession coupled with niche separation between the helical stalk-forming Gallionellales (for example, Gallionella ferruginea) and tubular sheath-forming Leptothrix ochracea. Changes in the iron-seep community were documented using microscopy and cultivation-independent methods. Quantification of Fe-oxyhydroxide morphotypes by light microscopy was coupled with species-specific fluorescent in situ hybridization (FISH) probes using a protocol that minimized background fluorescence caused by the Fe-oxyhydroxides. Together with scanning electron microscopy, these techniques all indicated that Gallionellales dominated during early spring, with L. ochracea becoming more abundant for the remainder of the year. Analysis of tagged pyrosequencing reads of the small subunit ribosomal RNA gene (SSU rRNA) collected during seasonal progression supported a clear Gallionellales to L. ochracea transition, and community structure grouped according to observed dominant FeOB forms. Axis of redundancy analysis of physicochemical parameters collected from iron mats during the season, plotted with FeOB abundance, corroborated several field and microscopy-based observations and uncovered several unanticipated relationships. On the basis of these relationships, we conclude that the ecological niche of the stalk-forming Gallionellales is in waters with low organic carbon and steep redoxclines, and the sheath-forming L. ochracea is abundant in waters that contain high concentrations of complex organic carbon, high Fe and Mn content and gentle redoxclines. Finally, these findings identify a largely unexplored relationship between FeOB and organic carbon.

  15. Ecological succession among iron-oxidizing bacteria

    PubMed Central

    Fleming, Emily J; Cetinić, Ivona; Chan, Clara S; Whitney King, D; Emerson, David

    2014-01-01

    Despite over 125 years of study, the factors that dictate species dominance in neutrophilic iron-oxidizing bacterial (FeOB) communities remain unknown. In a freshwater wetland, we documented a clear ecological succession coupled with niche separation between the helical stalk-forming Gallionellales (for example, Gallionella ferruginea) and tubular sheath-forming Leptothrix ochracea. Changes in the iron-seep community were documented using microscopy and cultivation-independent methods. Quantification of Fe-oxyhydroxide morphotypes by light microscopy was coupled with species-specific fluorescent in situ hybridization (FISH) probes using a protocol that minimized background fluorescence caused by the Fe-oxyhydroxides. Together with scanning electron microscopy, these techniques all indicated that Gallionellales dominated during early spring, with L. ochracea becoming more abundant for the remainder of the year. Analysis of tagged pyrosequencing reads of the small subunit ribosomal RNA gene (SSU rRNA) collected during seasonal progression supported a clear Gallionellales to L. ochracea transition, and community structure grouped according to observed dominant FeOB forms. Axis of redundancy analysis of physicochemical parameters collected from iron mats during the season, plotted with FeOB abundance, corroborated several field and microscopy-based observations and uncovered several unanticipated relationships. On the basis of these relationships, we conclude that the ecological niche of the stalk-forming Gallionellales is in waters with low organic carbon and steep redoxclines, and the sheath-forming L. ochracea is abundant in waters that contain high concentrations of complex organic carbon, high Fe and Mn content and gentle redoxclines. Finally, these findings identify a largely unexplored relationship between FeOB and organic carbon. PMID:24225888

  16. Bio-inspired Iron Catalysts for Hydrocarbon Oxidations

    SciTech Connect

    Que, Jr., Lawrence

    2016-03-22

    Stereoselective oxidation of C–H and C=C bonds are catalyzed by nonheme iron enzymes. Inspired by these bioinorganic systems, our group has been exploring the use of nonheme iron complexes as catalysts for the oxidation of hydrocarbons using H2O2 as an environmentally friendly and atom-efficient oxidant in order to gain mechanistic insights into these novel transformations. In particular, we have focused on clarifying the nature of the high-valent iron oxidants likely to be involved in these transformations.

  17. Chronic Iron Limitation Confers Transient Resistance to Oxidative Stress in Marine Diatoms.

    PubMed

    Graff van Creveld, Shiri; Rosenwasser, Shilo; Levin, Yishai; Vardi, Assaf

    2016-10-01

    Diatoms are single-celled, photosynthetic, bloom-forming algae that are responsible for at least 20% of global primary production. Nevertheless, more than 30% of the oceans are considered "ocean deserts" due to iron limitation. We used the diatom Phaeodactylum tricornutum as a model system to explore diatom's response to iron limitation and its interplay with susceptibility to oxidative stress. By analyzing physiological parameters and proteome profiling, we defined two distinct phases: short-term (<3 d, phase I) and chronic (>5 d, phase II) iron limitation. While at phase I no significant changes in physiological parameters were observed, molecular markers for iron starvation, such as Iron Starvation Induced Protein and flavodoxin, were highly up-regulated. At phase II, down-regulation of numerous iron-containing proteins was detected in parallel to reduction in growth rate, chlorophyll content, photosynthetic activity, respiration rate, and antioxidant capacity. Intriguingly, while application of oxidative stress to phase I and II iron-limited cells similarly oxidized the reduced glutathione (GSH) pool, phase II iron limitation exhibited transient resistance to oxidative stress, despite the down regulation of many antioxidant proteins. By comparing proteomic profiles of P. tricornutum under iron limitation and metatranscriptomic data of an iron enrichment experiment conducted in the Pacific Ocean, we propose that iron-limited cells in the natural environment resemble the phase II metabolic state. These results provide insights into the trade-off between optimal growth rate and susceptibility to oxidative stress in the response of diatoms to iron quota in the marine environment. © 2016 American Society of Plant Biologists. All Rights Reserved.

  18. Oxidation inhibits iron-induced blood coagulation.

    PubMed

    Pretorius, Etheresia; Bester, Janette; Vermeulen, Natasha; Lipinski, Boguslaw

    2013-01-01

    Blood coagulation under physiological conditions is activated by thrombin, which converts soluble plasma fibrinogen (FBG) into an insoluble clot. The structure of the enzymatically-generated clot is very characteristic being composed of thick fibrin fibers susceptible to the fibrinolytic degradation. However, in chronic degenerative diseases, such as atherosclerosis, diabetes mellitus, cancer, and neurological disorders, fibrin clots are very different forming dense matted deposits (DMD) that are not effectively removed and thus create a condition known as thrombosis. We have recently shown that trivalent iron (ferric ions) generates hydroxyl radicals, which subsequently convert FBG into abnormal fibrin clots in the form of DMDs. A characteristic feature of DMDs is their remarkable and permanent resistance to the enzymatic degradation. Therefore, in order to prevent thrombotic incidences in the degenerative diseases it is essential to inhibit the iron-induced generation of hydroxyl radicals. This can be achieved by the pretreatment with a direct free radical scavenger (e.g. salicylate), and as shown in this paper by the treatment with oxidizing agents such as hydrogen peroxide, methylene blue, and sodium selenite. Although the actual mechanism of this phenomenon is not yet known, it is possible that hydroxyl radicals are neutralized by their conversion to the molecular oxygen and water, thus inhibiting the formation of dense matted fibrin deposits in human blood.

  19. Iron oxide nanoparticle enhancement of radiation cytotoxicity

    NASA Astrophysics Data System (ADS)

    Mazur, Courtney M.; Tate, Jennifer A.; Strawbridge, Rendall R.; Gladstone, David J.; Hoopes, P. Jack

    2013-02-01

    Iron oxide nanoparticles (IONPs) have been investigated as a promising means for inducing tumor cell-specific hyperthermia. Although the ability to generate and use nanoparticles that are biocompatible, tumor specific, and have the ability to produce adequate cytotoxic heat is very promising, significant preclinical and clinical development will be required for clinical efficacy. At this time it appears using IONP-induced hyperthermia as an adjunct to conventional cancer therapeutics, rather than as an independent treatment, will provide the initial IONP clinical treatment. Due to their high-Z characteristics, another option is to use intracellular IONPs to enhance radiation therapy without excitation with AMF (production of heat). To test this concept IONPs were added to cell culture media at a concentration of 0.2 mg Fe/mL and incubated with murine breast adenocarcinoma (MTG-B) cells for either 48 or 72 hours. Extracellular iron was then removed and all cells were irradiated at 4 Gy. Although samples incubated with IONPs for 48 hrs did not demonstrate enhanced post-irradiation cytotoxicity as compared to the non-IONP-containing cells, cells incubated with IONPs for 72 hours, which contained 40% more Fe than 48 hr incubated cells, showed a 25% decrease in clonogenic survival compared to their non-IONP-containing counterparts. These results suggest that a critical concentration of intracellular IONPs is necessary for enhancing radiation cytotoxicity.

  20. Multiple hearth furnace for reducing iron oxide

    DOEpatents

    Brandon, Mark M [Charlotte, NC; True, Bradford G [Charlotte, NC

    2012-03-13

    A multiple moving hearth furnace (10) having a furnace housing (11) with at least two moving hearths (20) positioned laterally within the furnace housing, the hearths moving in opposite directions and each moving hearth (20) capable of being charged with at least one layer of iron oxide and carbon bearing material at one end, and being capable of discharging reduced material at the other end. A heat insulating partition (92) is positioned between adjacent moving hearths of at least portions of the conversion zones (13), and is capable of communicating gases between the atmospheres of the conversion zones of adjacent moving hearths. A drying/preheat zone (12), a conversion zone (13), and optionally a cooling zone (15) are sequentially positioned along each moving hearth (30) in the furnace housing (11).

  1. Multifunctional iron oxide nanoparticles for biomedical applications

    NASA Astrophysics Data System (ADS)

    Bloemen, M.; Denis, C.; Van Stappen, T.; De Meester, L.; Geukens, N.; Gils, A.; Verbiest, T.

    2015-03-01

    Multifunctional nanoparticles have attracted a lot of attention since they can combine interesting properties like magnetism, fluorescence or plasmonic effects. As a core material, iron oxide nanoparticles have been the subject of intensive research. These cost-effective and non-toxic particles are used nowadays in many applications. We developed a heterobifunctional PEG ligand that can be used to introduce functional groups (carboxylic acids) onto the surface of the NP. Via click chemistry, a siloxane functionality was added to this ligand, for a subsequent covalent ligand exchange reaction. The functionalized nanoparticles have an excellent colloidal stability in complex environments like buffers and serum or plasma. Antibodies were coupled to the introduced carboxylic acids and these NP-antibody bioconjugates were brought into contact with Legionella bacteria for magnetic separation experiments.

  2. Biocompatible multishell architecture for iron oxide nanoparticles.

    PubMed

    Wotschadlo, Jana; Liebert, Tim; Clement, Joachim H; Anspach, Nils; Höppener, Stephanie; Rudolph, Tobias; Müller, Robert; Schacher, Felix H; Schubert, Ulrich S; Heinze, Thomas

    2013-01-01

    The coating of super-paramagnetic iron oxide nanoparticles (SPIONs) with multiple shells is demonstrated by building a layer assembled from carboxymethyldextran and poly(diallydimethylammonium chloride). Three shells are produced stepwise around aggregates of SPIONs by the formation of a polyelectrolyte complex. A growing particle size from 96 to 327 nm and a zeta potential in the range of +39 to -51 mV are measured. Microscopic techniques such as TEM, SEM, and AFM exemplify the core-shell structures. Magnetic force microscopy and vibrating sample magnetometer measurements confirm the architecture of the multishell particles. Cell culture experiments show that even nanoparticles with three shells are still taken up by cells.

  3. Artificial meteor ablation studies - Iron oxides.

    NASA Technical Reports Server (NTRS)

    Blanchard, M. B.

    1972-01-01

    Artificial meteor ablation was performed on natural minerals composed predominantly of magnetite and hematite by using an arc-heated plasma stream of air. Analysis indicates that most of the ablated debris was composed of two or more minerals. Wustite, a metastable mineral, was found to occur as a common product. The 'magnetite' sample, which was 80% magnetite, 14% hematite, 4% apatite, and 2% quartz, yielded ablated products consisting of more than 12 different minerals. Magnetite occurred in 91% of the specimens examined, hematite in 16%, and wustite in 30%. The 'hematite' sample, which was 96% hematite and 3% quartz, yielded ablated products consisting of more than 13 different minerals. Hematite occurred in 47% of the specimens examined, magnetite in 60%, and wustite in 28%. The more volatile elements (Si, P, and Cl) were depleted by about 50%. This study has shown that artificially created ablation products from iron oxides exhibit unique properties that can be used for identification.

  4. Controlling barrier penetration via exothermic iron oxidation.

    PubMed

    Wood, Daniel G; Brown, Marc B; Jones, Stuart A

    2011-02-14

    Exothermic iron oxidation is an elegant means to generate heat, with the potential to modulate barrier penetration if reaction kinetics can be controlled. This aim of this study was to gain a fundamental understanding of how these temperature change kinetics influenced barrier diffusion rate. Lidocaine transport through a hydrophilic carboxymethyl cellulose (CMC) gel was compared using two rapid iron oxidation reactions initiated by water (ExoRap(50), T(max)-47.7 ± 0.6 °C, t(max)-3.3 ± 0.6 min, ExoRap(60), T(max)-60.4 ± 0.3 °C, t(max)-9.3 ± 0.6 min) and a slower reaction initiated by oxygen (ExoSl(45)T(max)-ca. 44 °C, t(max) ca. 240 min). Temperature change induced by the oxygen initiated reaction (ExoSl(45)) was almost double those initiated by water (over 4h), but lidocaine diffusion was approximately 4 times higher for the latter (ExoRap(50), 555.61 ± 22.04 μg/cm(2)/h; ExoRap(60), 663.1 ± 50.95 μg/cm(2)/h; compared to ExoSl(45), 159.36 ± 29.44 μg/cm(2)/h). The large influence of temperature change kinetics on lidocaine diffusion suggested that transport was heavily dependent on temperature induced structural changes of the barrier. CMC, like many polymers adsorbs more water when exposed to moderate increases in temperature and this appeared to be a critical determinant of lidocaine barrier diffusion rate. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

    NASA Astrophysics Data System (ADS)

    Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

    2016-11-01

    Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  7. The Iron-Iron Carbide Phase Diagram: A Practical Guide to Some Descriptive Solid State Chemistry.

    ERIC Educational Resources Information Center

    Long, Gary J.; Leighly, H. P., Jr.

    1982-01-01

    Discusses the solid state chemistry of iron and steel in terms of the iron-iron carbide phase diagram. Suggests that this is an excellent way of introducing the phase diagram (equilibrium diagram) to undergraduate students while at the same time introducing the descriptive solid state chemistry of iron and steel. (Author/JN)

  8. The Iron-Iron Carbide Phase Diagram: A Practical Guide to Some Descriptive Solid State Chemistry.

    ERIC Educational Resources Information Center

    Long, Gary J.; Leighly, H. P., Jr.

    1982-01-01

    Discusses the solid state chemistry of iron and steel in terms of the iron-iron carbide phase diagram. Suggests that this is an excellent way of introducing the phase diagram (equilibrium diagram) to undergraduate students while at the same time introducing the descriptive solid state chemistry of iron and steel. (Author/JN)

  9. Identification of iron oxide impurities in earliest industrial-scale processed platinum

    SciTech Connect

    Weerd, Jaap van der; Rehren, Thilo . E-mail: th.rehren@ucl.ac.uk; Firth, Steven; Clark, Robin J.H. . E-mail: r.j.h.clark@ucl.ac.uk

    2004-09-15

    A detailed investigation of iron oxide inclusions in a 19th century Russian platinum coin is presented. Such coins represent the products of the first industrial-scale purification of platinum metal. The processed metal is far from pure, however, and two types of iron oxide inclusions are identified by electron microprobe and Raman microscopy. The results show that the inclusions mainly consist of magnetite and haematite. The Raman band of magnetite at 668 cm{sup -1} was found to shift to about 680 cm{sup -1} with an increase in the average oxidation state of the iron. It is concluded that the iron oxides are formed during the heating of the platinum metal powder in the manufacturing process.

  10. Effects of iron chelators, iron salts, and iron oxide nanoparticles on the proliferation and the iron content of oligodendroglial OLN-93 cells.

    PubMed

    Hohnholt, Michaela; Geppert, Mark; Dringen, Ralf

    2010-08-01

    The oligodendroglial cell line OLN-93 was used as model system to investigate the consequences of iron deprivation or iron excess on cell proliferation. Presence of ferric or ferrous iron chelators inhibited the proliferation of OLN-93 cells in a time and concentration dependent manner, while the application of a molar excess of ferric ammonium citrate (FAC) prevented the inhibition of proliferation by the chelator deferoxamine. Proliferation of OLN-93 cells was not affected by incubation with 300 microM iron that was applied in the form of FAC, FeCl(2), ferrous ammonium sulfate or iron oxide nanoparticles, although the cells efficiently accumulated iron during exposure to each of these iron sources. The highest specific iron content was observed for cells that were exposed to the nanoparticles. These data demonstrate that the proliferation of OLN-93 cells depends strongly on the availability of iron and that these cells efficiently accumulate iron from various extracellular iron sources.

  11. Reactive oxygen species-related activities of nano-iron metal and nano-iron oxides.

    PubMed

    Wu, Haohao; Yin, Jun-Jie; Wamer, Wayne G; Zeng, Mingyong; Lo, Y Martin

    2014-03-01

    Nano-iron metal and nano-iron oxides are among the most widely used engineered and naturally occurring nanostructures, and the increasing incidence of biological exposure to these nanostructures has raised concerns about their biotoxicity. Reactive oxygen species (ROS)-induced oxidative stress is one of the most accepted toxic mechanisms and, in the past decades, considerable efforts have been made to investigate the ROS-related activities of iron nanostructures. In this review, we summarize activities of nano-iron metal and nano-iron oxides in ROS-related redox processes, addressing in detail the known homogeneous and heterogeneous redox mechanisms involved in these processes, intrinsic ROS-related properties of iron nanostructures (chemical composition, particle size, and crystalline phase), and ROS-related bio-microenvironmental factors, including physiological pH and buffers, biogenic reducing agents, and other organic substances. Copyright © 2014. Published by Elsevier B.V.

  12. Iron Oxide as an MRI Contrast Agent for Cell Tracking

    PubMed Central

    Korchinski, Daniel J.; Taha, May; Yang, Runze; Nathoo, Nabeela; Dunn, Jeff F.

    2015-01-01

    Iron oxide contrast agents have been combined with magnetic resonance imaging for cell tracking. In this review, we discuss coating properties and provide an overview of ex vivo and in vivo labeling of different cell types, including stem cells, red blood cells, and monocytes/macrophages. Furthermore, we provide examples of applications of cell tracking with iron contrast agents in stroke, multiple sclerosis, cancer, arteriovenous malformations, and aortic and cerebral aneurysms. Attempts at quantifying iron oxide concentrations and other vascular properties are examined. We advise on designing studies using iron contrast agents including methods for validation. PMID:26483609

  13. 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.

  14. Iron photoreduction and oxidation in an acidic mountain stream

    USGS Publications Warehouse

    McKnight, D.M.; Kimball, B.A.; Bencala, K.E.

    1988-01-01

    In a small mountain stream in Colorado that receives acidic mine drainage, photoreduction of ferric iron results in a well-defined increase in dissolved ferrous iron during the day. To quantify this process, an instream injection of a conservative tracer was used to measure discharge at the time that each sample was collected. Daytime production of ferrous iron by photoreduction was almost four times as great as nighttime oxidation of ferrous iron. The photoreduction process probably involves dissolved or colloidal ferric iron species and limited interaction with organic species because concentrations of organic carbon are low in this stream.

  15. Iron photoreduction and oxidation in an acidic mountain stream.

    PubMed

    McKnight, D M; Kimball, B A; Bencala, K E

    1988-04-29

    In a small mountain stream in Colorado that receives acidic mine drainage, photoreduction of ferric iron results in a well-defined increase in dissolved ferrous iron during the day. To quantify this process, an instream injection of a conservative tracer was used to measure discharge at the time that each sample was collected. Daytime production of ferrous iron by photoreduction was almost four times as great as nighttime oxidation of ferrous iron. The photoreduction process probably involves dissolved or colloidal ferric iron species and limited interaction with organic species because concentrations of organic carbon are low in this stream.

  16. Magnetization measurements and XMCD studies on ion irradiated iron oxide and core-shell iron/iron-oxide nanomaterials

    SciTech Connect

    Kaur, Maninder; Qiang, You; Jiang, Weilin; Pearce, Carolyn; McCloy, John S.

    2014-12-02

    Magnetite (Fe3O4) and core-shell iron/iron-oxide (Fe/Fe3O4) nanomaterials prepared by a cluster deposition system were irradiated with 5.5 MeV Si2+ ions and the structures determined by x-ray diffraction as consisting of 100% magnetite and 36/64 wt% Fe/FeO, respectively. However, x-ray magnetic circular dichroism (XMCD) indicates similar surfaces in the two samples, slightly oxidized and so having more Fe3+ than the expected magnetite structure, with XMCD intensity much lower for the irradiated core-shell samples indicating weaker magnetism. X-ray absorption spectroscopy (XAS) data lack the signature for FeO, but the irradiated core-shell system consists of Fe-cores with ~13 nm of separating oxide crystallite, so it is likely that FeO exists deeper than the probe depth of the XAS (~5 nm). Exchange bias (Hex) for both samples becomes increasingly negative as temperature is lowered, but the irradiated Fe3O4 sample shows greater sensitivity of cooling field on Hex. Loop asymmetries and Hex sensitivities of the irradiated Fe3O4 sample are due to interfaces and interactions between grains which were not present in samples before irradiation as well as surface oxidation. Asymmetries in the hysteresis curves of the irradiated core/shell sample are related to the reversal mechanism of the antiferromagnetic FeO and possibly some near surface oxidation.

  17. Investigation of oxidation process of mechanically activated ultrafine iron powders

    NASA Astrophysics Data System (ADS)

    Lysenko, E. N.; Nikolaev, E. V.; Vlasov, V. A.; Zhuravkov, S. P.

    2016-02-01

    The oxidation of mechanically activated ultrafine iron powders was studied using X- ray powder diffraction and thermogravimetric analyzes. The powders with average particles size of 100 nm were made by the electric explosion of wire, and were subjected to mechanical activation in planetary ball mill for 15 and 40 minutes. It was shown that a certain amount of FeO phase is formed during mechanical activation of ultrafine iron powders. According to thermogravimetric analysis, the oxidation process of non-milled ultrafine iron powders is a complex process and occurs in three stages. The preliminary mechanical activation of powders considerably changes the nature of the iron powders oxidation, leads to increasing in the temperature of oxidation onset and shifts the reaction to higher temperatures. For the milled powders, the oxidation is more simple process and occurs in a single step.

  18. Nitric Oxide Improves Internal Iron Availability in Plants1

    PubMed Central

    Graziano, Magdalena; Beligni, María Verónica; Lamattina, Lorenzo

    2002-01-01

    Iron deficiency impairs chlorophyll biosynthesis and chloroplast development. In leaves, most of the iron must cross several biological membranes to reach the chloroplast. The components involved in the complex internal iron transport are largely unknown. Nitric oxide (NO), a bioactive free radical, can react with transition metals to form metal-nitrosyl complexes. Sodium nitroprusside, an NO donor, completely prevented leaf interveinal chlorosis in maize (Zea mays) plants growing with an iron concentration as low as 10 μm Fe-EDTA in the nutrient solution. S-Nitroso-N-acetylpenicillamine, another NO donor, as well as gaseous NO supply in a translucent chamber were also able to revert the iron deficiency symptoms. A specific NO scavenger, 2-(4-carboxy-phenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, blocked the effect of the NO donors. The effect of NO treatment on the photosynthetic apparatus of iron-deficient plants was also studied. Electron micrographs of mesophyll cells from iron-deficient maize plants revealed plastids with few photosynthetic lamellae and rudimentary grana. In contrast, in NO-treated maize plants, mesophyll chloroplast appeared completely developed. NO treatment did not increase iron content in plant organs, when expressed in a fresh matter basis, suggesting that root iron uptake was not enhanced. NO scavengers 2-(4-carboxy-phenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and methylene blue promoted interveinal chlorosis in iron-replete maize plants (growing in 250 μm Fe-EDTA). Even though results support a role for endogenous NO in iron nutrition, experiments did not establish an essential role. NO was also able to revert the chlorotic phenotype of the iron-inefficient maize mutants yellow stripe1 and yellow stripe3, both impaired in the iron uptake mechanisms. All together, these results support a biological action of NO on the availability and/or delivery of metabolically active iron within the plant. PMID:12481068

  19. Application of novel iron core/iron oxide shell nanoparticles to sentinel lymph node identification

    NASA Astrophysics Data System (ADS)

    Cousins, Aidan; Howard, Douglas; Henning, Anna M.; Nelson, Melanie R. M.; Tilley, Richard D.; Thierry, Benjamin

    2015-12-01

    Current `gold standard' staging of breast cancer and melanoma relies on accurate in vivo identification of the sentinel lymph node. By replacing conventional tracers (dyes and radiocolloids) with magnetic nanoparticles and using a handheld magnetometer probe for in vivo identification, it is believed the accuracy of sentinel node identification in nonsuperficial cancers can be improved due to increased spatial resolution of magnetometer probes and additional anatomical information afforded by MRI road-mapping. By using novel iron core/iron oxide shell nanoparticles, the sensitivity of sentinel node mapping via MRI can be increased due to an increased magnetic saturation compared to traditional iron oxide nanoparticles. A series of in vitro magnetic phantoms (iron core vs. iron oxide nanoparticles) were prepared to simulate magnetic particle accumulation in the sentinel lymph node. A novel handheld magnetometer probe was used to measure the relative signals of each phantom, and determine if clinical application of iron core particles can improve in vivo detection of the sentinel node compared to traditional iron oxide nanoparticles. The findings indicate that novel iron core nanoparticles above a certain size possess high magnetic saturation, but can also be produced with low coercivity and high susceptibility. While some modification to the design of handheld magnetometer probes may be required for particles with large coercivity, use of iron core particles could improve MRI and magnetometer probe detection sensitivity by up to 330 %.

  20. Oxidative Stress and the Homeodynamics of Iron Metabolism

    PubMed Central

    Bresgen, Nikolaus; Eckl, Peter M.

    2015-01-01

    Iron and oxygen share a delicate partnership since both are indispensable for survival, but if the partnership becomes inadequate, this may rapidly terminate life. Virtually all cell components are directly or indirectly affected by cellular iron metabolism, which represents a complex, redox-based machinery that is controlled by, and essential to, metabolic requirements. Under conditions of increased oxidative stress—i.e., enhanced formation of reactive oxygen species (ROS)—however, this machinery may turn into a potential threat, the continued requirement for iron promoting adverse reactions such as the iron/H2O2-based formation of hydroxyl radicals, which exacerbate the initial pro-oxidant condition. This review will discuss the multifaceted homeodynamics of cellular iron management under normal conditions as well as in the context of oxidative stress. PMID:25970586

  1. Atomistic simulations of uranium incorporation into iron (hydr)oxides.

    PubMed

    Kerisit, Sebastien; Felmy, Andrew R; Ilton, Eugene S

    2011-04-01

    Atomistic simulations were carried out to characterize the coordination environments of U incorporated in three Fe-(hydr)oxide minerals: goethite, magnetite, and hematite. The simulations provided information on U-O and U-Fe distances, coordination numbers, and lattice distortion for U incorporated in different sites (e.g., unoccupied versus occupied sites, octahedral versus tetrahedral) as a function of the oxidation state of U and charge compensation mechanisms (i.e., deprotonation, vacancy formation, or reduction of Fe(III) to Fe(II)). For goethite, deprotonation of first shell hydroxyls enables substitution of U for Fe(III) with a minimal amount of lattice distortion, whereas substitution in unoccupied octahedral sites induced appreciable distortion to 7-fold coordination regardless of U oxidation states and charge compensation mechanisms. Importantly, U-Fe distances of ∼3.6 Å were associated with structural incorporation of U and cannot be considered diagnostic of simple adsorption to goethite surfaces. For magnetite, the octahedral site accommodates U(V) or U(VI) with little lattice distortion. U substituted for Fe(III) in hematite maintained octahedral coordination in most cases. In general, comparison of the simulations with available experimental data provides further evidence for the structural incorporation of U in iron (hydr)oxide minerals.

  2. Atomistic Simulations of Uranium Incorporation into Iron (Hydr)Oxides

    SciTech Connect

    Kerisit, Sebastien N.; Felmy, Andrew R.; Ilton, Eugene S.

    2011-04-29

    Atomistic simulations were carried out to characterize the coordination environments of U incorporated in three Fe-(hydr)oxide minerals: goethite, magnetite, and hematite. The simulations provided information on U-O and U-Fe distances, coordination numbers, and lattice distortion for U incorporated in different sites (e.g., unoccupied versus occupied sites, octahedral versus tetrahedral) as a function of the oxidation state of U and charge compensation mechanisms (i.e., deprotonation, vacancy formation, or reduction of Fe(III) to Fe(II)). For goethite, deprotonation of first shell hydroxyls enables substitution of U for Fe(III) with a minimal amount of lattice distortion, whereas substitution in unoccupied octahedral sites induced appreciable distortion to 7-fold coordination regardless of U oxidation states and charge compensation mechanisms. Importantly, U-Fe distances of ~3.6 Å were associated with structural incorporation of U and cannot be considered diagnostic of simple adsorption to goethite surfaces. For magnetite, the octahedral site accommodates U(V) or U(VI) with little lattice distortion. U substituted for Fe(III) in hematite maintained octahedral coordination in most cases. In general, comparison of the simulations with available experimental data provides further evidence for the structural incorporation of U in iron (hydr)oxide minerals.

  3. Size- and composition-dependent radio frequency magnetic permeability of iron oxide nanocrystals.

    PubMed

    Yun, Hongseok; Liu, Xiyu; Paik, Taejong; Palanisamy, Duraivelan; Kim, Jungkwun; Vogel, William D; Viescas, Arthur J; Chen, Jun; Papaefthymiou, Georgia C; Kikkawa, James M; Allen, Mark G; Murray, Christopher B

    2014-12-23

    We investigate the size- and composition-dependent ac magnetic permeability of superparamagnetic iron oxide nanocrystals for radio frequency (RF) applications. The nanocrystals are obtained through high-temperature decomposition synthesis, and their stoichiometry is determined by Mössbauer spectroscopy. Two sets of oxides are studied: (a) as-synthesized magnetite-rich and (b) aged maghemite nanocrystals. All nanocrystalline samples are confirmed to be in the superparamagnetic state at room temperature by SQUID magnetometry. Through the one-turn inductor method, the ac magnetic properties of the nanocrystalline oxides are characterized. In magnetite-rich iron oxide nanocrystals, size-dependent magnetic permeability is not observed, while maghemite iron oxide nanocrystals show clear size dependence. The inductance, resistance, and quality factor of hand-wound inductors with a superparamagnetic composite core are measured. The superparamagnetic nanocrystals are successfully embedded into hand-wound inductors to function as inductor cores.

  4. Size- and Composition-Dependent Radio Frequency Magnetic Permeability of Iron Oxide Nanocrystals

    SciTech Connect

    Yun, H; Liu, XY; Paik, T; Palanisamy, D; Kim, J; Vogel, WD; Viescas, AJ; Chen, J; Papaefthymiou, GC; Kikkawa, JM; Allen, MG; Murray, CB

    2014-12-01

    We investigate the size- and composition-dependent ac magnetic permeability of superparamagnetic iron oxide nanocrystals for radio frequency (RF) applications. The nanocrystals are obtained through high-temperature decomposition synthesis, and their stoichiometry is determined by Mossbauer spectroscopy. Two sets of oxides are studied: (a) as-synthesized magnetite-rich and (b) aged maghemite nanocrystals. All nanocrystalline samples are confirmed to be in the superparamagnetic state at room temperature by SQUID magnetometry. Through the one-turn inductor method, the ac magnetic properties of the nanocrystalline oxides are characterized. In magnetite-rich iron oxide nanocrystals, size-dependent magnetic permeability is not observed, while maghemite iron oxide nanocrystals show clear size dependence. The inductance, resistance, and quality factor of hand-wound inductors with a superparamagnetic composite core are measured. The superparamagnetic nanocrystals are successfully embedded into hand-wound inductors to function as inductor cores.

  5. Dechlorination of polychlorinated biphenyls by iron and its oxides.

    PubMed

    Sun, Yifei; Liu, Xiaoyuan; Kainuma, Masashi; Wang, Wei; Takaoka, Masaki; Takeda, Nobuo

    2015-10-01

    The decomposition efficiency of polychlorinated biphenyls (PCBs) was determined using elemental iron (Fe) and three iron (hydr)oxides, i.e., α-Fe2O3, Fe3O4, and α-FeOOH, as catalysts. The experiments were performed using four distinct PCB congeners (PCB-209, PCB-153, and the coplanar PCB-167 and PCB-77) at temperatures ranging from 180 °C to 380 °C and under an inert, oxidizing or reducing atmosphere composed of N2, N2+O2, or N2+H2. From these three options N2 showed to provide the best reaction atmosphere. Among the iron compounds tested, Fe3O4 showed the highest activity for decomposing PCBs. The decomposition efficiencies of PCB-209, PCB-167, PCB-153, and PCB-77 by Fe3O4 in an N2 atmosphere at 230 °C were 88.5%, 82.5%, 69.9%, and 66.4%, respectively. Other inorganic chlorine (Cl) products which were measured by the amount of inorganic Cl ions represented 82.5% and 76.1% of the reaction products, showing that ring cleavage of PCBs was the main elimination process. Moreover, the dechlorination did not require a particular hydrogen donor. We used X-ray photoelectron spectroscopy to analyze the elemental distribution at the catalyst's surface. The O/Fe ratio influenced upon the decomposition efficiency of PCBs: the lower this ratio, the higher the decomposition efficiency. X-ray absorption near edge structure spectra showed that α-Fe2O3 effectively worked as a catalyst, while Fe3O4 and α-FeOOH were consumed as reactants, as their final state is different from their initial state. Finally, a decomposition pathway was postulated in which the Cl atoms in ortho-positions were more difficult to eliminate than those in the para- or meta-positions. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Magnetic Characterization of Iron Oxide Cross Linked Hydro gels

    NASA Astrophysics Data System (ADS)

    Senaratne, U.; Powell, N.; Kroll, E.; Tsoi, G.; Naik, R.; Naik, V.; Vaishnava, P. P.; Wenger, L. E.

    2004-03-01

    Magnetic hydro gels have potential applications in drug delivery, cells sorting, sensors, and actuating technologies. Iron oxide alginate nanocomposites were synthesized following the method of Kroll et al^1 by cross linking sodium alginate with Fe^2+ and Fe^3+ in methanol: water. The ion-cross linked alginate hydro gels are oxidized in an alkaline solution. The resulting hydro gel consists of iron oxide cross linked alginate. The alginate hydro gels are inert to the reaction conditions and therefore the reaction sequence can be repeated. The multiple loadings result in an increase in the amount of iron oxide and the size of the iron oxide nanoparticles in the cross linked hydro gels. The third and sixth loaded iron oxide alginate hydro gels were dried and characterized by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), and Superconducting Quantum Interference Device (SQUID) magnetometry. The XRD patterns have characteristic features of γ- Fe_2O3 or Fe_3O4 phases. The average particle size, calculated from the XRD peaks, for third loaded iron oxide alginate was 2 nm. The zero-field-cooled and field-cooled SQUID measurements show the iron oxide nanoparticles are superparamagnetic with blocking temperature (T_B) of approximately 35 K. Above the blocking temperature, the inverse susceptibility versus temperature relationship does not follow the Curie-Weiss law, indicating strong inter-particle interactions. The M vs. H data above the blocking temperature was fitted with a modified Langevin function to obtain additional information about the iron oxide particle size. Details of the relationship between coercive field and temperature as well as the particle size distribution obtained from XRD and TEM measurements will be presented. *Research supported by NSF grant # DGE ˜980720 **Supported by NSF REU grant # EEC-0097736 ^1E. Kroll, F.M. Winnik, and R.F. Ziolo, Chem. Mater, 8, 1594 (1996).

  7. Properties and suspension stability of dendronized iron oxide nanoparticles for MRI applications.

    PubMed

    Basly, B; Felder-Flesch, D; Perriat, P; Pourroy, G; Bégin-Colin, S

    2011-01-01

    Functionalized iron oxide nanoparticles have attracted an increasing interest in the last 10 years as contrast agents for MRI. One challenge is to obtain homogeneous and stable aqueous suspensions of iron oxide nanoparticles without aggregates. Iron oxide nanoparticles with sizes around 10 nm were synthesized by two methods: the particle size distribution in water suspension of iron oxide nanoparticles synthesized by the co-precipitation method was improved by a process involving two steps of ligand exchange and phase transfer and was compared with that of iron oxide nanoparticles synthesized by thermal decomposition and functionalized by the same dendritic molecule. The saturation magnetization of dendronized nanoparticles synthesized by thermal decomposition was lower than that of nanoparticles synthesized by co-precipitation. The r(2) relaxivity values were shown to decrease with the agglomeration state in suspension and high r(2) values and r(2) /r(1) ratios were obtained with nanoparticles synthesized by co-precipitation by comparison with those of commercial products. Dendronized iron oxide nanoparticles thus have potential properties as contrast agent.

  8. Biogenic Fabrication of Iron/Iron Oxide Nanoparticles and Their Application

    NASA Astrophysics Data System (ADS)

    Siddiqi, Khwaja Salahuddin; ur Rahman, Aziz; Tajuddin; Husen, Azamal

    2016-11-01

    Enshrined in this review are the biogenic fabrication and applications of coated and uncoated iron and iron oxide nanoparticles. Depending on their magnetic properties, they have been used in the treatment of cancer, drug delivery system, MRI, and catalysis and removal of pesticides from potable water. The polymer-coated iron and iron oxide nanoparticles are made biocompatible, and their slow release makes them more effective and lasting. Their cytotoxicity against microbes under aerobic/anaerobic conditions has also been discussed. The magnetic moment of superparamagnetic iron oxide nanoparticles changes with their interaction with biomolecules as a consequence of which their size decreases. Their biological efficacy has been found to be dependent on the shape, size, and concentration of these nanoparticles.

  9. Design of Fucoidan Functionalized - Iron Oxide Nanoparticles for Biomedical Applications.

    PubMed

    Tran, Khanh Nghia; Tran, Phuong Ha-Lien; Vo, Toi Van; Tran, Thao Truong-Dinh

    2016-01-01

    This research aims to develop an iron oxide nanoparticle drug delivery system utilizing a recent material discovered from ocean, fucoidan. The material has drawn much interest due to many biomedical functions that have been proven for human health. One interesting point herein is that fucoidan is not only a sulfated polysaccharide, a polymer for stabilization of iron oxide nanoparticles, but plays a role of an anticancer agent also. Various approaches were investigated to optimize the high loading efficiency and explain the mechanism of nanoparticle formations. Fucoidan was functionalized on iron oxide nanoparticles by a direct coating or via amine groups. Also, a hydrophobic part of oleic acid was conjugated to the amine groups for a more favorable loading of poorly water-soluble anticancer drugs. This study proposed a novel system and an efficient method to functionalize fucoidan on iron oxide nanoparticle systems which will lead to a facilitation of a double strength treatment of cancer.

  10. Dissolution of iron oxide nanoparticles inside polymer nanocapsules.

    PubMed

    Möller, Johannes; Cebi, Melek; Schroer, Martin A; Paulus, Michael; Degen, Patrick; Sahle, Christoph J; Wieland, D C Florian; Leick, Sabine; Nyrow, Alexander; Rehage, Heinz; Tolan, Metin

    2011-12-07

    The structure of poly(organosiloxane) nanocapsules partially filled with iron oxide cores of different sizes was revealed by small angle X-ray scattering and X-ray diffraction. The nanocapsules are synthesized by the formation of a poly(organosiloxane) shell around iron oxide nanoparticles and the simultaneous partial dissolution of these cores. Due to the high scattering contrast of the iron oxide cores compared to the polymer shell, the particle size distribution of the cores inside the capsules can be measured by small angle X-ray scattering. Additional information can be revealed by X-ray diffraction, which gives insights into the formation of the polymer network and the structure of the iron oxide cores. The study shows how the crystallinity and size of the nanoparticles as well as the shape and width of the size distribution can be altered by the synthesis parameters.

  11. Magnetic Iron Oxide Nanoparticles: Synthesis and Surface Functionalization Strategies

    PubMed Central

    2008-01-01

    Surface functionalized magnetic iron oxide nanoparticles (NPs) are a kind of novel functional materials, which have been widely used in the biotechnology and catalysis. This review focuses on the recent development and various strategies in preparation, structure, and magnetic properties of naked and surface functionalized iron oxide NPs and their corresponding application briefly. In order to implement the practical application, the particles must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of iron oxide NPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The problems and major challenges, along with the directions for the synthesis and surface functionalization of iron oxide NPs, are considered. Finally, some future trends and prospective in these research areas are also discussed. PMID:21749733

  12. Iron oxide surface-catalyzed oxidation of ferrous iron by monochloramine: implications of oxide type and carbonate on reactivity.

    PubMed

    Vikesland, Peter J; Valentine, Richard L

    2002-02-01

    The maintenance of monochloramine residuals in drinking water distribution systems is one technique often used to minimize microbial outbreaks and thereby maintain the safety of the water. Reactions between oxidizable species and monochloramine can however lead to undesirable losses in the disinfectant residual. Previous work has illustrated that the Fe(II) present within distribution systems is one type of oxidizable species that can exert a monochloramine demand. This paper extends this prior work by examining the kinetics of the reactions between Fe(II) and monochloramine in the presence of a variety of iron oxide surfaces. The identity of the iron oxide plays a significant role in the rate of these reactions. Surface area-normalized initial rate coefficients (k(init)) obtained in the presence of each oxide at pH approximately 6.9 exhibit the following trend in catalytic activity: magnetite > goethite > hematite approximately = lepidocrocite > ferrihydrite. The differences in the activity of these oxides are hypothesized to result from variations in the amount of Fe(II) sorbed to each of the oxides and to dissimilarities in the surface site densities of the oxides. The implications of carbonate on Fe(II) sorption to iron oxides are also examined. Comparing Fe(II) sorption isotherms for goethite obtained under differential carbonate concentrations, it is apparent that as the carbonate concentration (C(T,CO3)) increased from 0 to 11.7 mM that the Fe(II) sorption edge (50% sorption) shifts from a pH of approximately 5.8 to a pH of 7.8. This shift is hypothesized to be the result of the formation of aqueous and surface carbonate-Fe(II) complexes and to competition between carbonate and Fe(II) for surface sites. The implications of these changes are then discussed in light of the variable oxide studies.

  13. Long term in vivo biotransformation of iron oxide nanoparticles.

    PubMed

    Levy, Michael; Luciani, Nathalie; Alloyeau, Damien; Elgrabli, Dan; Deveaux, Vanessa; Pechoux, Christine; Chat, Sophie; Wang, Guillaume; Vats, Nidhi; Gendron, François; Factor, Cécile; Lotersztajn, Sophie; Luciani, Alain; Wilhelm, Claire; Gazeau, Florence

    2011-06-01

    The long term outcome of nanoparticles in the organism is one of the most important concerns raised by the development of nanotechnology and nanomedicine. Little is known on the way taken by cells to process and degrade nanoparticles over time. In this context, iron oxide superparamagnetic nanoparticles benefit from a privileged status, because they show a very good tolerance profile, allowing their clinical use for MRI diagnosis. It is generally assumed that the specialized metabolism which regulates iron in the organism can also handle iron oxide nanoparticles. However the biotransformation of iron oxide nanoparticles is still not elucidated. Here we propose a multiscale approach to study the fate of nanomagnets in the organism. Ferromagnetic resonance and SQUID magnetization measurements are used to quantify iron oxide nanoparticles and follow the evolution of their magnetic properties. A nanoscale structural analysis by electron microscopy complements the magnetic follow-up of nanoparticles injected to mice. We evidence the biotransformation of superparamagnetic maghemite nanoparticles into poorly-magnetic iron species probably stored into ferritin proteins over a period of three months. A putative mechanism is proposed for the biotransformation of iron-oxide nanoparticles. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Iron Oxide Nanocrystals for Magnetic Hyperthermia Applications

    PubMed Central

    Armijo, Leisha M.; Brandt, Yekaterina I.; Mathew, Dimple; Yadav, Surabhi; Maestas, Salomon; Rivera, Antonio C.; Cook, Nathaniel C.; Withers, Nathan J.; Smolyakov, Gennady A.; Adolphi, Natalie; Monson, Todd C.; Huber, Dale L.; Smyth, Hugh D. C.; Osiński, Marek

    2012-01-01

    Magnetic nanocrystals have been investigated extensively in the past several years for several potential applications, such as information technology, MRI contrast agents, and for drug conjugation and delivery. A specific property of interest in biomedicine is magnetic hyperthermia—an increase in temperature resulting from the thermal energy released by magnetic nanocrystals in an external alternating magnetic field. Iron oxide nanocrystals of various sizes and morphologies were synthesized and tested for specific losses (heating power) using frequencies of 111.1 kHz and 629.2 kHz, and corresponding magnetic field strengths of 9 and 25 mT. Polymorphous nanocrystals as well as spherical nanocrystals and nanowires in paramagnetic to ferromagnetic size range exhibited good heating power. A remarkable 30 °C temperature increase was observed in a nanowire sample at 111 kHz and magnetic field of 25 mT (19.6 kA/m), which is very close to the typical values of 100 kHz and 20 mT used in medical treatments.

  15. Anthropogenic iron oxide aerosols enhance atmospheric heating

    PubMed Central

    Moteki, Nobuhiro; Adachi, Kouji; Ohata, Sho; Yoshida, Atsushi; Harigaya, Tomoo; Koike, Makoto; Kondo, Yutaka

    2017-01-01

    Combustion-induced carbonaceous aerosols, particularly black carbon (BC) and brown carbon (BrC), have been largely considered as the only significant anthropogenic contributors to shortwave atmospheric heating. Natural iron oxide (FeOx) has been recognized as an important contributor, but the potential contribution of anthropogenic FeOx is unknown. In this study, we quantify the abundance of FeOx over East Asia through aircraft measurements using a modified single-particle soot photometer. The majority of airborne FeOx particles in the continental outflows are of anthropogenic origin in the form of aggregated magnetite nanoparticles. The shortwave absorbing powers (Pabs) attributable to FeOx and to BC are calculated on the basis of their size-resolved mass concentrations and the mean Pabs(FeOx)/Pabs(BC) ratio in the continental outflows is estimated to be at least 4–7%. We demonstrate that in addition to carbonaceous aerosols the aggregate of magnetite nanoparticles is a significant anthropogenic contributor to shortwave atmospheric heating. PMID:28508863

  16. Stem cell tracking using iron oxide nanoparticles.

    PubMed

    Bull, Elizabeth; Madani, Seyed Yazdan; Sheth, Roosey; Seifalian, Amelia; Green, Mark; Seifalian, Alexander M

    2014-01-01

    Superparamagnetic iron oxide nanoparticles (SPIONs) are an exciting advancement in the field of nanotechnology. They expand the possibilities of noninvasive analysis and have many useful properties, making them potential candidates for numerous novel applications. Notably, they have been shown that they can be tracked by magnetic resonance imaging (MRI) and are capable of conjugation with various cell types, including stem cells. In-depth research has been undertaken to establish these benefits, so that a deeper level of understanding of stem cell migratory pathways and differentiation, tumor migration, and improved drug delivery can be achieved. Stem cells have the ability to treat and cure many debilitating diseases with limited side effects, but a main problem that arises is in the noninvasive tracking and analysis of these stem cells. Recently, researchers have acknowledged the use of SPIONs for this purpose and have set out to establish suitable protocols for coating and attachment, so as to bring MRI tracking of SPION-labeled stem cells into common practice. This review paper explains the manner in which SPIONs are produced, conjugated, and tracked using MRI, as well as a discussion on their limitations. A concise summary of recently researched magnetic particle coatings is provided, and the effects of SPIONs on stem cells are evaluated, while animal and human studies investigating the role of SPIONs in stem cell tracking will be explored.

  17. Photocatalytic water oxidation with iron oxide hydroxide (rust) nanoparticles

    NASA Astrophysics Data System (ADS)

    Shelton, Timothy L.; Bensema, Bronwyn L.; Brune, Nicholas K.; Wong, Christopher; Yeh, Max; Osterloh, Frank E.

    2017-01-01

    Hematite has attracted considerable interest as a photoanode material for water oxidation under visible illumination. Here, we explore the limits of photocatalytic water oxidation activity with iron (III) oxide hydroxide nanocrystals and NaIO4 as a sacrificial electron acceptor (E=1.63 V NHE at pH=0.5). The sol was prepared by hydrolysis of FeCl3 in boiling 0.002-M HCl solution and confirmed to mainly consist of ß-FeO(OH) (akaganéite) particles with 5 to 15 nm diameter. From a 0.01 M aqueous NaIO4 solution, the sol evolves between 4.5 and 35.2 μmol O2 h-1, depending on pH, light intensity (>400 nm, 290 to 700 mW cm-2), ß-FeO(OH), and NaIO4 concentration. The activity increases with pH, and depends linearly on light intensity and photocatalyst amount, and it varies with sacrificial electron donor concentration. Under optimized conditions, the apparent quantum efficiency is 0.19% (at 400 nm and 460 mW cm-2), and the turnover number is 2.58 based on total ß-FeO(OH). Overall, the efficiency of the ß-FeO(OH)/NaIO4 photocatalytic system is limited by electron hole recombination and by particle aggregation over longer irradiation times (24 h). Lastly, surface photovoltage measurements on ß-FeO(OH) films on fluorine doped tin oxide substrate confirm a 2.15 eV effective band gap for the material.

  18. The role of crustal and eruptive processes versus source variations in controlling the oxidation state of iron in Central Andean magmas

    NASA Astrophysics Data System (ADS)

    Grocke, Stephanie B.; Cottrell, Elizabeth; de Silva, Shanaka; Kelley, Katherine A.

    2016-04-01

    The composition of the continental crust is closely tied to subduction zone magmatism. Elevated oxygen fugacity (fO2) plays a central role in fostering crystallization of oxide minerals and thereby aids in generating the calc-alkaline trend of iron depletion that characterizes the continents. Along continental margins, arc magmas erupt through continental crust and often undergo extensive differentiation that may modify magmatic fO2. The importance of the subducting slab and mantle wedge relative to the effects of this differentiation on the fO2 recorded by continental arc magmas remains relatively unconstrained. Here, we focus on the effect of differentiation on magmatic fO2 using a suite of 14 samples from the Central Volcanic Zone (CVZ) of the Andes where the continental crust is atypically thick (60-80 km). The samples range in composition from ∼55 to 74 wt% SiO2 and represent the Neogene history of the arc. Samples are basaltic andesite to rhyolite and span a range of radiogenic isotopic compositions (87Sr/86Sr = ∼0.705-0.712) that represent 30 to 100% crustal assimilation. We use several proxies to estimate the fO2 recorded by lavas, pumice, and scoria: (1) whole rock Fe3+ / Σ Fe ratios, (2) Fe3+ / Σ Fe ratios in quartz-hosted melt inclusions, and (3) Fe-Ti oxide oxygen-barometry. Comparison of the fO2 calculated from bulk Fe3+ / Σ Fe ratios (post-eruptive) with that derived from Fe-Ti oxides or melt inclusion Fe3+ / Σ Fe ratios (pre-eruptive), enables us to quantify the effect of syn- or post-eruptive alteration, and to select rocks for bulk analysis appropriate for the determination of pre-eruptive magmatic fO2 using a strict criterion developed here. Across our sample suite, and in context with samples from the literature, we do not find evidence for systematic oxidation due to crystal fractionation or crustal contamination. Less evolved samples, ranging from 55 to 61 wt% SiO2, record a range of >3 orders of magnitude in fO2, spanning the fO2 range

  19. An inorganic geochemical argument for coupled anaerobic oxidation of methane and iron reduction in marine sediments.

    PubMed

    Riedinger, N; Formolo, M J; Lyons, T W; Henkel, S; Beck, A; Kasten, S

    2014-03-01

    Here, we present results from sediments collected in the Argentine Basin, a non-steady state depositional marine system characterized by abundant oxidized iron within methane-rich layers due to sediment reworking followed by rapid deposition. Our comprehensive inorganic data set shows that iron reduction in these sulfate and sulfide-depleted sediments is best explained by a microbially mediated process-implicating anaerobic oxidation of methane coupled to iron reduction (Fe-AOM) as the most likely major mechanism. Although important in many modern marine environments, iron-driven AOM may not consume similar amounts of methane compared with sulfate-dependent AOM. Nevertheless, it may have broad impact on the deep biosphere and dominate both iron and methane cycling in sulfate-lean marine settings. Fe-AOM might have been particularly relevant in the Archean ocean, >2.5 billion years ago, known for its production and accumulation of iron oxides (in iron formations) in a biosphere likely replete with methane but low in sulfate. Methane at that time was a critical greenhouse gas capable of sustaining a habitable climate under relatively low solar luminosity, and relationships to iron cycling may have impacted if not dominated methane loss from the biosphere.

  20. Synthesis and heating effect of iron/iron oxide composite and iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Zeng, Q.; Baker, I.; Loudis, J. A.; Liao, Y. F.; Hoopes, P. J.

    2007-02-01

    Fe/Fe oxide nanoparticles, in which the core consists of metallic Fe and the shell is composed of Fe oxides, were obtained by reduction of an aqueous solution of FeCl 3 within a NaBH 4 solution, or, using a water-in-oil micro-emulsion with CTAB as the surfactant. The reduction was performed either in an inert atmosphere or in air, and passivation with air was performed to produce the Fe/Fe 3O 4 core/shell composite. Phase identification and particle size were determined by X-ray diffraction and TEM. Thermal analysis was performed using a differential scanning calorimeter. The quasistatic magnetic properties were measured using a VSM, and the specific absorption rates (SARs) of both Fe oxide and Fe/Fe 3O 4 composite nanoparticles either dispersed in methanol or in an epoxy resin were measured by Luxtron fiber temperature sensors in an alternating magnetic field of 150 Oe at 250 kHz. It was found that the preparation conditions, including the concentrations of solutions, the mixing procedure and the heat treatment, influence the particle size, the crystal structure and consequently the magnetic properties of the particles. Compared with Fe oxides, the saturation magnetization (MS) of Fe/Fe 3O 4 particles (100-190 emu/g) can be twice as high, and the coercivity (H C) can be tunable from several Oe to several hundred Oe. Hence, the SAR of Fe/Fe 3O 4 composite nanoparticles can be much higher than that of Fe oxides, with a maximum SAR of 345 W/g. The heating behavior is related to the magnetic behavior of the nanoparticles.

  1. Synthesis and heating effect of iron/iron oxide composite and iron oxide nanoparticles

    PubMed Central

    Zeng, Q.; Baker, I.; Loudis, J. A.; Liao, Y.F.; Hoopes, P.J.

    2014-01-01

    Fe/Fe oxide nanoparticles, in which the core consists of metallic Fe and the shell is composed of Fe oxides, were obtained by reduction of an aqueous solution of FeCl3 within a NaBH4 solution, or, using a water-in-oil micro-emulsion with CTAB as the surfactant. The reduction was performed either in an inert atmosphere or in air, and passivation with air was performed to produce the Fe/Fe3O4 core/shell composite. Phase identification and particle size were determined by X-ray diffraction and TEM. Thermal analysis was performed using a differential scanning calorimeter. The quasistatic magnetic properties were measured using a VSM, and the specific absorption rates (SARs) of both Fe oxide and Fe/Fe3O4 composite nanoparticles either dispersed in methanol or in an epoxy resin were measured by Luxtron fiber temperature sensors in an alternating magnetic field of 150 Oe at 250 kHz. It was found that the preparation conditions, including the concentrations of solutions, the mixing procedure and the heat treatment, influence the particle size, the crystal structure and consequently the magnetic properties of the particles. Compared with Fe oxides, the saturation magnetization (MS) of Fe/Fe3O4 particles (100–190 emu/g) can be twice as high, and the coercivity (HC) can be tunable from several Oe to several hundred Oe. Hence, the SAR of Fe/Fe3O4 composite nanoparticles can be much higher than that of Fe oxides, with a maximum SAR of 345 W/g. The heating behavior is related to the magnetic behavior of the nanoparticles. PMID:25301983

  2. Iron oxide-based nanomagnets in nanomedicine: fabrication and applications

    PubMed Central

    Meng Lin, Meng; Kim, Hyung-Hwan; Kim, Hyuck; Muhammed, Mamoun; Kyung Kim, Do

    2010-01-01

    Iron oxide-based nanomagnets have attracted a great deal of attention in nanomedicine over the past decade. Down to the nanoscale, superparamagnetic iron oxide nanoparticles can only be magnetized in the presence of an external magnetic field, which makes them capable of forming stable colloids in a physio-biological medium. Their superparamagnetic property, together with other intrinsic properties, such as low cytotoxicity, colloidal stability, and bioactive molecule conjugation capability, makes such nanomagnets ideal in both in-vitro and in-vivo biomedical applications. In this review, a chemical, physical, and biological synthetic approach to prepare iron oxide-based nanomagnets with different physicochemical properties was illustrated and compared. The growing interest in iron oxide-based nanomagnets with multifunctionalities was explored in cancer diagnostics and treatment, focusing on their combined roles in a magnetic resonance contrast agent, hyperthermia, and magnetic force assisted drug delivery. Iron oxides as magnetic carriers in gene therapy were reviewed with a focus on the sophisticated design and construction of magnetic vectors. Finally, the iron oxide-based nanomagnet also represents a very promising tool in particle/cell interfacing in controlling cellular functionalities, such as adhesion, proliferation, differentiation, and cell patterning, in stem cell therapy and tissue engineering applications. PMID:22110854

  3. Iron Oxide Silica Derived from Sol-Gel Synthesis

    PubMed Central

    Darmawan, Adi; Smart, Simon; Julbe, Anne; Diniz da Costa, João Carlos

    2011-01-01

    In this work we investigate the effect of iron oxide embedded in silica matrices as a function of Fe/Si molar ratio and sol pH. To achieve homogeneous dispersion of iron oxide particles, iron nitrate nonahydrate was dissolved in hydrogen peroxide and was mixed with tetraethyl orthosilicate and ethanol in a sol-gel synthesis method. Increasing the calcination temperature led to a reduction in surface area, although the average pore radius remained almost constant at about 10 Å, independent of the Fe/Si molar ratio or sol pH. Hence, the densification of the matrix was accompanied by similar reduction in pore volume. However, calcination at 700 °C resulted in samples with similar surface area though the iron oxide content increased from 5% to 50% Fe/Si molar ratio. As metal oxide particles have lower surface area than polymeric silica structures, these results strongly suggest that the iron oxides opposed the silica structure collapse. The effect of sol pH was found to be less significant than the Fe/Si molar ratio in the formation of molecular sieve structures derived from iron oxide silica. PMID:28879999

  4. Iron oxide nanoparticles in geomicrobiology: from biogeochemistry to bioremediation.

    PubMed

    Braunschweig, Juliane; Bosch, Julian; Meckenstock, Rainer U

    2013-09-25

    Iron oxides are important constituents of soils and sediments and microbial iron reduction is considered to be a significant anaerobic respiration process in the subsurface, however low microbial reduction rates of macroparticulate Fe oxides in laboratory studies led to an underestimation of the role of Fe oxides in the global Fe redox cycle. Recent studies show the high potential of nano-sized Fe oxides in the environment as, for example, electron acceptor for microbial respiration, electron shuttle between different microorganisms, and scavenger for heavy metals. Biotic and abiotic reactivity of iron macroparticles differ significantly from nano-sized Fe oxides, which are usually much more reactive. Factors such as particle size, solubility, ferrous iron, crystal structure, and organic molecules were identified to influence the reactivity. This review discusses factors influencing the microbial reactivity of Fe oxides. It highlights the differences between natural and synthetic Fe oxides especially regarding the presence of organic molecules such as humic acids and natural organic matter. Attention is given to the transport behavior of Fe oxides in laboratory systems and in the environment, because of the high affinity of different contaminants to Fe oxide surfaces and associated co-transport of pollutants. The high reactivity of Fe oxides and their potential as adsorbents for different pollutants are discussed with respect to application and development of remediation technologies. Copyright © 2013. Published by Elsevier B.V.

  5. Experiments with Unusual Oxidation States

    ERIC Educational Resources Information Center

    Kauffman, G. B.

    1975-01-01

    Describes four synthesis experiments, adapted for the general chemistry laboratory, in which compounds in unusual oxidation are prepared. The abnormal oxidation states involved in the synthesis products are: silver (II), chromium (II), lead (IV), and bromine (I). (MLH)

  6. Experiments with Unusual Oxidation States

    ERIC Educational Resources Information Center

    Kauffman, G. B.

    1975-01-01

    Describes four synthesis experiments, adapted for the general chemistry laboratory, in which compounds in unusual oxidation are prepared. The abnormal oxidation states involved in the synthesis products are: silver (II), chromium (II), lead (IV), and bromine (I). (MLH)

  7. Physiochemical, mineralogical, and isotopic characterization of magnetite-rich iron oxides formed by thermophilic iron-reducing bacteria

    SciTech Connect

    Zhang, Chuanlun; Liu, Shi; Phelps, T.J.; Elless, M.

    1997-11-01

    Thermophilic (45-75{degrees}C) iron-reducing bacteria obtained from two sedimentary basins in Virginia and Colorado, USA, reduced amorphous Fe(III) oxyhydroxide to form magnetite-rich (>60% in most samples) iron oxides in acetate- or H{sub 2}/CO{sub 2}-enriched cultures. The mineralogical compositions of the iron oxides were determined by X-ray diffraction and oxidation state analyses. Significantly lower Eh values (< -300 mV) occurred in the enrichment cultures than in the abiotic controls (Eh > -100 mV). The pH values in acetate-enriched cultures did not change significantly from the starting value siderite was formed in addition to magnetite. The microbial production of magnetic and siderite was consistent, on a thermodynamic basis, with Eh-pH conditions determined for these experiments. Examination of the magnetite-rich iron oxides by scanning electron microscopy showed extracellular aggregates of <200 nm and no distinguishable increase in particle size over a period of 20 days. Average values of oxygen isotope fractionation between the magnetite-rich iron oxides (io) and water (wt), expressed as 10{sup 3} ln {alpha}{sub io-wt}, ranged from -0.09% at 50{degrees}C to -1.08{per_thousand} at 70{degrees}C. These values did not differ significantly among various cultures of different growth rates, suggesting that a kinetic isotopic effect is either unimportant or reproducible during microbial magnetic formation. Results of this research indicate that studies combining microbial activity, solution chemistry, mineralogy, and oxygen isotopes can provide insight into the environmental conditions and mechanisms for biogenic iron mineral formation in natural systems. 62 refs., 6 figs., 3 tabs.

  8. Iron assimilation and utilization in anaerobic ammonium oxidizing bacteria.

    PubMed

    Ferousi, Christina; Lindhoud, Simon; Baymann, Frauke; Kartal, Boran; Jetten, Mike Sm; Reimann, Joachim

    2017-04-01

    The most abundant transition metal in biological systems is iron. It is incorporated into protein cofactors and serves either catalytic, redox or regulatory purposes. Anaerobic ammonium oxidizing (anammox) bacteria rely heavily on iron-containing proteins - especially cytochromes - for their energy conservation, which occurs within a unique organelle, the anammoxosome. Both their anaerobic lifestyle and the presence of an additional cellular compartment challenge our understanding of iron processing. Here, we combine existing concepts of iron uptake, utilization and metabolism, and cellular fate with genomic and still limited biochemical and physiological data on anammox bacteria to propose pathways these bacteria may employ. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

  9. Morphology of biogenic iron oxides records microbial physiology and environmental conditions: toward interpreting iron microfossils.

    PubMed

    Krepski, S T; Emerson, D; Hredzak-Showalter, P L; Luther, G W; Chan, C S

    2013-09-01

    Despite the abundance of Fe and its significance in Earth history, there are no established robust biosignatures for Fe(II)-oxidizing micro-organisms. This limits our ability to piece together the history of Fe biogeochemical cycling and, in particular, to determine whether Fe(II)-oxidizers played a role in depositing ancient iron formations. A promising candidate for Fe(II)-oxidizer biosignatures is the distinctive morphology and texture of extracellular Fe(III)-oxyhydroxide stalks produced by mat-forming microaerophilic Fe(II)-oxidizing micro-organisms. To establish the stalk morphology as a biosignature, morphologic parameters must be quantified and linked to the microaerophilic Fe(II)-oxidizing metabolism and environmental conditions. Toward this end, we studied an extant model organism, the marine stalk-forming Fe(II)-oxidizing bacterium, Mariprofundus ferrooxydans PV-1. We grew cultures in flat glass microslide chambers, with FeS substrate, creating opposing oxygen/Fe(II) concentration gradients. We used solid-state voltammetric microelectrodes to measure chemical gradients in situ while using light microscopy to image microbial growth, motility, and mineral formation. In low-oxygen (2.7-28 μm) zones of redox gradients, the bacteria converge into a narrow (100 μm-1 mm) growth band. As cells oxidize Fe(II), they deposit Fe(III)-oxyhydroxide stalks in this band; the stalks orient directionally, elongating toward higher oxygen concentrations. M. ferrooxydans stalks display a narrow range of widths and uniquely biogenic branching patterns, which result from cell division. Together with filament composition, these features (width, branching, and directional orientation) form a physical record unique to microaerophilic Fe(II)-oxidizer physiology; therefore, stalk morphology is a biosignature, as well as an indicator of local oxygen concentration at the time of formation. Observations of filamentous Fe(III)-oxyhydroxide microfossils from a ~170 Ma marine Fe

  10. The structure and magnetic properties of ultrafine iron particles with oxide layer

    SciTech Connect

    Gavrilyuk, A.G.; Sadykov, R.A.

    1994-12-01

    Ultrafine iron particles (UFIPs) are promising as materials for high-density magnetic recording and ferrofluids because the superparamagnetic state in these particles develops at smaller particle sizes than in conventional magnetic materials. The basic obstacle to producing UFIPs is their high reactivity, which leads to strong oxidation of these particles. Given this, effort is being devoted to extending chemical stabilization to iron particles of the smallest size possible. One possible approach involves the formation of a thin passivating oxide layer on iron particles [1-3], for example, by atmospheric-air oxidation or by oxidation in a special atmosphere. This results in the formation of an interesting structure - an ultrafine particle whose magnetic properties exhibit a marked variation from its center to the surface. The UFIP oxidized at room temperature was shown to consist of an unoxidized {alpha}-Fe core with an average diameter of 110 {Angstrom} and a 45-{Angstrom}-thick oxide layer with a spinel-type structure. The hyperfine magnetic field at the particle core coincides with the field in an infinite sample, whereas in the oxide layer, the average magnetic field was lower. Magnetic interaction between the central region of the UFIP and the oxide layer was found to suppress superparamagnetism and to result in development of a hyperfine structure in the Moessbauer subspectrum of the oxide layer. The observed shape of the Moessbauer spectrum is related to the surface state of the oxide phase and, to some extent, to the presence of defects.

  11. Synthesis of monodisperse iron oxide and iron/iron oxide core/shell nanoparticles via iron-oleylamine complex.

    PubMed

    Yu, S; Chow, G M

    2006-07-01

    Monodisperse magnetic nanoparticles are of great scientific and technical interests. This paper reports a single-step synthesis of monodisperse magnetite nanoparticles with particle size of 8 nm. Iron/maghaemite core/shell nanoparticles with particle size of 11 nm were obtained by reducing the concentration of oleylamine. TEM and in-situ FTIR results suggested that iron-oleylamine intermediate was generated in-situ and decomposed at higher temperature. Oleylamine was also found on the surface of nanoparticles, indicating its role as capping agent which provided steric protection of as-synthesized nanoparticles from agglomeration. Both magnetite and iron/maghaemite core/shell nanoparticles were superparamagnetic at room temperature with a blocking temperature at 80 K and 67 K, respectively.

  12. Oxidation-Induced Degradable Nanogels for Iron Chelation

    NASA Astrophysics Data System (ADS)

    Liu, Zhi; Wang, Yan; Purro, Max; Xiong, May P.

    2016-02-01

    Iron overload can increase cellular oxidative stress levels due to formation of reactive oxygen species (ROS); untreated, it can be extremely destructive to organs and fatal to patients. Since elevated oxidative stress levels are inherent to the condition in such patients, oxidation-induced degradable nanogels for iron chelation were rationally designed by simultaneously polymerizing oxidation-sensitive host-guest crosslinkers between β-cyclodextrin (β-CD) and ferrocene (Fc) and iron chelating moieties composed of deferoxamine (DFO) into the final gel scaffold in reverse emulsion reaction chambers. UV-Vis absorption and atomic absorption spectroscopy (AAS) was used to verify iron chelating capability of nanogels. These materials can degrade into smaller chelating fragments at rates proportional to the level of oxidative stress present. Conjugating DFO reduces the cytotoxicity of the chelator in the macrophage cells. Importantly, the nanogel can effectively reduce cellular ferritin expression in iron overloaded cells and regulate intracellular iron levels at the same time, which is important for maintaining a homeostatic level of this critical metal in cells.

  13. Oxidation-Induced Degradable Nanogels for Iron Chelation

    PubMed Central

    Liu, Zhi; Wang, Yan; Purro, Max; Xiong, May P.

    2016-01-01

    Iron overload can increase cellular oxidative stress levels due to formation of reactive oxygen species (ROS); untreated, it can be extremely destructive to organs and fatal to patients. Since elevated oxidative stress levels are inherent to the condition in such patients, oxidation-induced degradable nanogels for iron chelation were rationally designed by simultaneously polymerizing oxidation-sensitive host-guest crosslinkers between β-cyclodextrin (β-CD) and ferrocene (Fc) and iron chelating moieties composed of deferoxamine (DFO) into the final gel scaffold in reverse emulsion reaction chambers. UV-Vis absorption and atomic absorption spectroscopy (AAS) was used to verify iron chelating capability of nanogels. These materials can degrade into smaller chelating fragments at rates proportional to the level of oxidative stress present. Conjugating DFO reduces the cytotoxicity of the chelator in the macrophage cells. Importantly, the nanogel can effectively reduce cellular ferritin expression in iron overloaded cells and regulate intracellular iron levels at the same time, which is important for maintaining a homeostatic level of this critical metal in cells. PMID:26868174

  14. Photocatalysis over titania on iron oxide

    NASA Astrophysics Data System (ADS)

    Kim, Kwi Cheol; Han, Chong Soo

    2006-03-01

    Photocatalytic activity of TiO{2} deposited on spherical sub micron-sized Fe{2}O{3} particle was investigated under ultraviolet or visible light. The Fe{2}O{3} particles were prepared using a spray pyrolysis of aqueous Fe(NO{3})3 solution in air flow. TiO{2} was deposited on Fe{2}O{3} particle by irradiation of ultraviolet or visible light to the suspension of Fe{2}O{3} particle and a TiO{2} precursor. When TiO{2} was formed under visible light (TiO{2}/Fe{2}O{3}-VIS), there were reasonable trends in the phase shift of PAS signal and EDX signal of Ti. However, there was no trend for the case of ultra violet irradiation (TiO{2}/Fe{2}O{3}-UV). TiO{2}/Fe{2}O{3}-VIS showed higher rates of decomposition of organic compound, of decrease in contact angle of water drop, and of decrease in the number of E. coli under visible light than TiO{2}/Fe{2}O{3}-UV or TiO{2} film. From the results, it was suggested that TiO{2}/Fe{2}O{3}-VIS had a regular thin layer of TiO{2} compared to TiO{2}/Fe{2}O{3}-UV and the photo-generated carrier(s) in iron oxide migrated to the surface of TiO{2} in the case of TiO{2}/Fe{2}O{3}-VIS.

  15. Calcium-Iron Oxide as Energy Storage Medium in Rechargeable Oxide Batteries

    DOE PAGES

    Berger, Cornelius M.; Mahmoud, Abdelfattah; Hermann, Raphaël P.; ...

    2016-08-08

    Rechargeable oxide batteries (ROB) comprise a regenerative solid oxide cell (rSOC) and a storage medium for oxygen ions. A sealed ROB avoids pumping loss, heat loss, and gas purity expenses in comparison with conventional rSOC. However, the iron oxide base storage medium degrades during charging–discharging cycles. In comparison, CaFe3O5 has improved cyclability and a high reversible oxygen storage capacity of 22.3 mol%. In this paper, we analyzed the redox mechanism of this compound. After a solid-state synthesis of CaFe3O5, we verified the phase composition and studied the redox reaction by means of X-ray diffraction, Mössbauer spectrometry, and scanning electron microscopy.more » Finally, results show a great potential to operate the battery with this storage material during multiple charging–discharging cycles.« less

  16. Calcium-Iron Oxide as Energy Storage Medium in Rechargeable Oxide Batteries

    SciTech Connect

    Berger, Cornelius M.; Mahmoud, Abdelfattah; Braun, Waldemar; Yazhenskikh, Elena; Sohn, Yoo Jung; Menzler, Norbert H.; Guillon, Olivier; Bram, Martin

    2016-08-08

    Rechargeable oxide batteries (ROB) comprise a regenerative solid oxide cell (rSOC) and a storage medium for oxygen ions. A sealed ROB avoids pumping loss, heat loss, and gas purity expenses in comparison with conventional rSOC. However, the iron oxide base storage medium degrades during charging–discharging cycles. In comparison, CaFe3O5 has improved cyclability and a high reversible oxygen storage capacity of 22.3 mol%. In this paper, we analyzed the redox mechanism of this compound. After a solid-state synthesis of CaFe3O5, we verified the phase composition and studied the redox reaction by means of X-ray diffraction, Mössbauer spectrometry, and scanning electron microscopy. Finally, results show a great potential to operate the battery with this storage material during multiple charging–discharging cycles.

  17. Calcium-Iron Oxide as Energy Storage Medium in Rechargeable Oxide Batteries

    SciTech Connect

    Berger, Cornelius M.; Mahmoud, Abdelfattah; Braun, Waldemar; Yazhenskikh, Elena; Sohn, Yoo Jung; Menzler, Norbert H.; Guillon, Olivier; Bram, Martin

    2016-08-08

    Rechargeable oxide batteries (ROB) comprise a regenerative solid oxide cell (rSOC) and a storage medium for oxygen ions. A sealed ROB avoids pumping loss, heat loss, and gas purity expenses in comparison with conventional rSOC. However, the iron oxide base storage medium degrades during charging–discharging cycles. In comparison, CaFe3O5 has improved cyclability and a high reversible oxygen storage capacity of 22.3 mol%. In this paper, we analyzed the redox mechanism of this compound. After a solid-state synthesis of CaFe3O5, we verified the phase composition and studied the redox reaction by means of X-ray diffraction, Mössbauer spectrometry, and scanning electron microscopy. Finally, results show a great potential to operate the battery with this storage material during multiple charging–discharging cycles.

  18. Persulfate activation by iron oxide-immobilized MnO2 composite: identification of iron oxide and the optimum pH for degradations.

    PubMed

    Jo, Young-Hoon; Do, Si-Hyun; Kong, Sung-Ho

    2014-01-01

    Iron oxide-immobilized manganese oxide (MnO2) composite was prepared and the reactivity of persulfate (PS) with the composite as activator was investigated for degradation of carbon tetrachloride and benzene at various pH levels. Brunauer-Emmett-Teller (BET) surface area of the composite was similar to that of pure MnO2 while the pore volume and diameter of composite was larger than those of MnO2. Scanning electron microscopy couples with energy dispersive spectroscopy (SEM-EDS) showed that Fe and Mn were detected on the surface of the composite, and X-ray diffraction (XRD) analysis indicated the possibilities of the existence of various iron oxides on the composite surface. Furthermore, the analyses of X-ray photoelectron (XPS) spectra revealed that the oxidation state of iron was identified as 1.74. In PS/composite system, the same pH for the highest degradation rates of both carbon tetrachloride and benzene were observed and the value of pH was 9. Scavenger test was suggested that both oxidants (i.e. hydroxyl radical, sulfate radical) and reductant (i.e. superoxide anion) were effectively produced when PS was activated with the iron-immobilized MnO2. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. Stabilization and functionalization of iron oxide nanoparticles for biomedical applications

    NASA Astrophysics Data System (ADS)

    Amstad, Esther; Textor, Marcus; Reimhult, Erik

    2011-07-01

    Superparamagnetic iron oxide nanoparticles (NPs) are used in a rapidly expanding number of research and practical applications in the biomedical field, including magnetic cell labeling separation and tracking, for therapeutic purposes in hyperthermia and drug delivery, and for diagnostic purposes, e.g., as contrast agents for magnetic resonance imaging. These applications require good NP stability at physiological conditions, close control over NP size and controlled surface presentation of functionalities. This review is focused on different aspects of the stability of superparamagnetic iron oxide NPs, from its practical definition to its implementation by molecular design of the dispersant shell around the iron oxide core and further on to its influence on the magnetic properties of the superparamagnetic iron oxide NPs. Special attention is given to the selection of molecular anchors for the dispersant shell, because of their importance to ensure colloidal and functional stability of sterically stabilized superparamagnetic iron oxide NPs. We further detail how dispersants have been optimized to gain close control over iron oxide NP stability, size and functionalities by independently considering the influences of anchors and the attached sterically repulsive polymer brushes. A critical evaluation of different strategies to stabilize and functionalize core-shell superparamagnetic iron oxide NPs as well as a brief introduction to characterization methods to compare those strategies is given.Superparamagnetic iron oxide nanoparticles (NPs) are used in a rapidly expanding number of research and practical applications in the biomedical field, including magnetic cell labeling separation and tracking, for therapeutic purposes in hyperthermia and drug delivery, and for diagnostic purposes, e.g., as contrast agents for magnetic resonance imaging. These applications require good NP stability at physiological conditions, close control over NP size and controlled surface

  20. ISOLATION AND PROPERTIES OF AN IRON-OXIDIZING THIOBACILLUS

    PubMed Central

    Razzell, W. E.; Trussell, P. C.

    1963-01-01

    Razzell, W. E. (British Columbia Research Council, Vancouver, Canada) and P. C. Trussell. Isolation and properties of an iron-oxidizing Thiobacillus. J. Bacteriol. 85:595–603. 1963. — An organism isolated from acidic copper-leaching waters has been shown to oxidize ferrous ions, sulfur, and metallic sulfides but exhibit peculiar responses to thiosulfate. The name Thiobacillus ferrooxidans has been used to describe it. A pH of 2.5 is optimal for growth on iron, sulfur, and metallic sulfides, but cells free from iron can be obtained from growth at pH 1.6, and sulfur cultures adjusted to pH 5.5 readily attain a pH of 1.8. A stationary cultivation procedure appears superior to percolation techniques for studying the oxidation of finely divided metallic sulfides. Concentrations of soluble copper in excess of 1 g per liter were obtained from chalcopyrite in less than 4 weeks. Chalcocite oxidation proceeded in the absence of iron. Sodium chloride inhibits iron oxidation without preventing oxidation of metallic sulfides by the organism. PMID:14042937

  1. Synthesis of phase pure praseodymium barium copper iron oxide.

    PubMed

    Konne, Joshua L; Davis, Sean A; Glatzel, Stefan; Hall, Simon R

    2013-06-18

    The control of crystallization of praseodymium barium copper iron oxide, an intermediate temperature solid oxide fuel cell cathode material, has been demonstrated for the first time using a biotemplated sol-gel synthesis technique. The results obtained showed significant improvement in purity, synthesis time, surface area and simplicity over that previously reported.

  2. The Oxidation Of Iron In A Gel Using Consumer Chemicals

    ERIC Educational Resources Information Center

    Wright, Stephen W.; Folger, Marsha R.; Quinn, Ryan P.; Sauls, Frederick C.; Krone, Diane

    2005-01-01

    An experiment is conducted for the oxidation of iron in a gel using consumer chemicals, which is pertinent to the students' understanding of redox chemistry and of the relative oxidation potentials of various metals. The experiment can be carried out with consumer chemicals that might be purchased at a supermarket and commonly found in the home.

  3. The Oxidation Of Iron In A Gel Using Consumer Chemicals

    ERIC Educational Resources Information Center

    Wright, Stephen W.; Folger, Marsha R.; Quinn, Ryan P.; Sauls, Frederick C.; Krone, Diane

    2005-01-01

    An experiment is conducted for the oxidation of iron in a gel using consumer chemicals, which is pertinent to the students' understanding of redox chemistry and of the relative oxidation potentials of various metals. The experiment can be carried out with consumer chemicals that might be purchased at a supermarket and commonly found in the home.

  4. Rhodium oxides in unusual oxidation states

    NASA Astrophysics Data System (ADS)

    Reisner, Barbara Alice

    Mixed valence RhIII/RhIV oxides have been proposed as a promising class of candidate compounds for superconductivity. Unfortunately, it is difficult to stabilize rhodates with a formal oxidation state approaching RhIV, as other techniques used for the synthesis of rhodium. oxides favor the most commonly observed formal oxidation state, RhIII. One technique which has been used to stabilize metal oxides in high formal oxidation states is crystallization from molten hydroxides. This thesis explores the use of molten hydroxides to enhance the reactivity of rhodium oxides in order to synthesize rhodates with high formal oxidation states. K0.5RhO2, Rb0.2RhO2, and CsxRhO2 were synthesized from pure alkali metal hydroxides. All crystallized with a previously unobserved polytype in the alkali metal rhodate system. Due to the low activity of dissolved oxygen species in LiOH and NaOH, LiRhO2 and NaRhO2 cannot be crystallized. The formal oxidation state of rhodium in AxRhO2 (A = K, Rb, Cs) is a function of the alkali metal hydroxide used to synthesize these oxides. These materials exhibit remarkable stability for layered metal oxides containing the heavier alkali metals, but all phases are susceptible to intercalation by water. The synthesis, structural characterization, magnetic susceptibility, and reactivity of these oxides are reported. Sr2RhO4 and a new rhodate were crystallized from a KOH-Sr(OH)2 flux. The synthesis and characterization of these materials is reported. Efforts to substitute platinum for rhodium in Sr 2RhO4 are also discussed. Mixed alkali metal-alkaline earth metal hydroxide fluxes were used to crystallize LiSr3RhO6, and NaSr3RhO 6. The synthesis of LiSr3RhO6 and NaSr3RhO 6 represents the first example of the stabilization of a rhodium oxide with a formal oxidation state approaching RhV. X-ray diffraction, electron beam microprobe analysis, thermogravimetric analysis, potentiometric titrations, X-ray photoelectron spectroscopy, and magnetic susceptibility

  5. Heterogeneous Fenton oxidation of ofloxacin drug by iron alginate support.

    PubMed

    Titouhi, Hana; Belgaied, Jamel-Eddine

    2016-08-01

    A new catalytic wet peroxide oxidation of ofloxacin antibiotic is presented in this work. The removal was achieved using a biodegradable sodium alginate-iron material. Several parameters were studied such as iron content, drying duration of the catalytic support, temperature, solid amount and initial drug concentration. The process showed a strong oxidative ability; at optimum conditions, a nearly complete removal of the drug (around 98%) has been reached after three h of treatment. A relatively low decrease of support activity (around 10%) has been observed after three successive oxidation runs and a low iron leaching has been detected (1.2% of the incorporated quantity). The removal of the substrate has been also examined in the absence of hydrogen peroxide in order to discriminate between the contributions of simple adsorption and oxidation processes in the drug disappearance. We also discussed the influence of the studied experimental parameters on the removal kinetic.

  6. Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water

    NASA Astrophysics Data System (ADS)

    Gui, Minghui; Smuleac, Vasile; Ormsbee, Lindell E.; Sedlak, David L.; Bhattacharyya, Dibakar

    2012-05-01

    The potential for using hydroxyl radical (OH•) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H2O2 addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80-100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Mössbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H2O2 by NP surface generated OH• were investigated. Depending on the ratio of iron and H2O2, TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.

  7. Iron and oxidative stress in cardiomyopathy in thalassemia.

    PubMed

    Berdoukas, Vasilios; Coates, Thomas D; Cabantchik, Zvi Ioav

    2015-11-01

    With repeated blood transfusions, patients with thalassemia major rapidly become loaded with iron, often surpassing hepatic metal accumulation capacity within ferritin shells and infiltrating heart and endocrine organs. That pathological scenario contrasts with the physiological one, which is characterized by an efficient maintenance of all plasma iron bound to circulating transferrin, due to a tight control of iron ingress into plasma by the hormone hepcidin. Within cells, most of the acquired iron becomes protein-associated, as once released from endocytosed transferrin, it is used within mitochondria for the synthesis of protein prosthetic groups or it is incorporated into enzyme active centers or alternatively sequestered within ferritin shells. A few cell types also express the iron extrusion transporter ferroportin, which is under the negative control of circulating hepcidin. However, that system only backs up the major cell regulated iron uptake/storage machinery that is poised to maintain a basal level of labile cellular iron for metabolic purposes without incurring potentially toxic scenarios. In thalassemia and other transfusion iron-loading conditions, once transferrin saturation exceeds about 70%, labile forms of iron enter the circulation and can gain access to various types of cells via resident transporters or channels. Within cells, they can attain levels that exceed their ability to chemically cope with labile iron, which has a propensity for generating reactive oxygen species (ROS), thereby inducing oxidative damage. This scenario occurs in the heart of hypertransfused thalassemia major patients who do not receive adequate iron-chelation therapy. Iron that accumulates in cardiomyocytes forms agglomerates that are detected by T2* MRI. The labile forms of iron infiltrate the mitochondria and damage cells by inducing noxious ROS formation, resulting in heart failure. The very rapid relief of cardiac dysfunction seen after intensive iron

  8. Inverse-Photoemission Spectroscopy of Iron Oxides, Silver

    NASA Astrophysics Data System (ADS)

    Kim, Bongsoo

    1990-01-01

    I measured the inverse-photoemission spectra (IPES) of iron oxides grown on an Fe substrate, and calculated the band structure of paramagnetic FeO to analyze the IPES. The band calculation showed some overlap between Fe _3_{rm d} states and O_2_{rm p} states in the region of occupied states, and s,p-like states of Fe in the unoccupied region. Isochromatic IPES showed structures at ~2.5 eV and ~7.5 eV above the Fermi energy. I estimate the full band gap of FeO as 2.5 eV from the IPES data. Angle-resolved inverse-photoemission spectra (ARIPES) have been measured on single-crystal Ag. The results are compared with the predictions of bulk band-structure theory and a free-electron model. The latter gives good agreement for the structure with a final state near the Fermi energy. Band theory is needed for the structure 17 eV above the Fermi energy. This structure is very nondispersive, indicating the existence of a very flat band throughout the IXUL plane.

  9. Iron and iron oxide nanoparticles obtained by ultra-short laser ablation in liquid

    NASA Astrophysics Data System (ADS)

    De Bonis, A.; Lovaglio, T.; Galasso, A.; Santagata, A.; Teghil, R.

    2015-10-01

    Laser ablation of an iron target in water and acetone has been carried out using a frequency doubled Nd:glass laser source (pulse duration of 250 fs and frequency repetition rate of 10 Hz). The observation of the nanostructures formed in the laser irradiated region of the metallic target and fast shadowgraphic analysis of the laser induced cavitation bubble have been performed in order to correlate the size distribution of the obtained nanoparticles to the dynamics of the ablation process. The composition, morphology and oxidation state of the synthesized nanoproducts have been investigated by XPS (X-ray Photoelectron Spectroscopy), TEM (Transmission Electron Microscopy) and microRaman spectroscopy. The experimental data support a relationship between the nanoparticles size distribution and the femtosecond laser ablation mechanism, while the chemical and structural characteristics of the nanoparticles can be tuned by varying the liquid medium.

  10. Effect of green tea on iron status and oxidative stress in iron-loaded rats.

    PubMed

    Ounjaijean, S; Thephinlap, C; Khansuwan, U; Phisalapong, C; Fucharoen, S; Porter, J B; Srichairatanakool, S

    2008-07-01

    Plasma non-transferrin bound iron (NTBI) is potentially toxic and contributes to the generation of reactive oxygen species (ROS), consequently leading to tissue damage and organ dysfunction. Iron chelators and antioxidants are used for treatment of thalassemia patients. Green tea (GT) contains catechins derivatives that have many biological activities. The purpose of this study was to investigate the iron-chelating and free-radical scavenging capacities of green tea extract in vivo. Rats were injected ip with ferric citrate together with orally administered GT extract (GTE) for 4 months. Blood was collected monthly for measurement of iron overload and oxidative stress indicators. Plasma iron (PI) and total iron-binding capacity (TIBC) were quantified using bathophenanthroline method. Plasma NTBI was assayed with NTA chelation/HPLC. Plasma malonyldialdehyde (MDA) was determined by using the TBARS method. Erythrocyte oxidative stress was assessed using flow cytometry. Levels of PI, TIBC, NTBI and MDA, and erythrocyte ROS increased in the iron-loaded rats. Intervention with GT extract markedly decreased the PI and TIBC concentrations. It also lowered the transferrin saturation and effectively inhibited formation of NTBI. It also decreased the levels of erythrocyte ROS in week 4, 12 and 16. Therefore, green tea extract can decrease iron in plasma as well as eliminate lipid peroxidation in plasma, and destroy formation of erythrocyte ROS in the rats challenged with iron. The bifunctional effects could be beneficial in alleviating the iron and oxidative stress toxicity. In prospective, these GTE activities should be further examined in thalassemic animals or humans.

  11. A chameleon catalyst for nonheme iron-promoted olefin oxidation.

    PubMed

    Iyer, Shyam R; Javadi, Maedeh Moshref; Feng, Yan; Hyun, Min Young; Oloo, Williamson N; Kim, Cheal; Que, Lawrence

    2014-11-18

    We report the chameleonic reactivity of two nonheme iron catalysts for olefin oxidation with H2O2 that switch from nearly exclusive cis-dihydroxylation of electron-poor olefins to the exclusive epoxidation of electron-rich olefins upon addition of acetic acid. This switching suggests a common precursor to the nucleophilic oxidant proposed to Fe(III)-η(2)-OOH and electrophilic oxidant proposed to Fe(V)(O)(OAc), and reversible coordination of acetic acid as a switching pathway.

  12. Iron oxide and gold nanoparticles in cancer therapy

    NASA Astrophysics Data System (ADS)

    Gotman, Irena; Psakhie, Sergey G.; Lozhkomoev, Aleksandr S.; Gutmanas, Elazar Y.

    2016-08-01

    Continuous research activities in the field of nanomedicine in the past decade have, to a great extent, been focused on nanoparticle technologies for cancer therapy. Gold and iron oxide nanoparticles (NP) are two of the most studied inorganic nanomaterials due to their unique optical and magnetic properties. Both types of NPs are emerging as promising systems for anti-tumor drug delivery and for nanoparticle-mediated thermal therapy of cancer. In thermal therapy, localized heating inside tumors or in proximity of tumor cells can be induced, for example, with Au NPs by radiofrequency ablation heating or conversion of photon energy (photothermal therapy) and in iron oxide magnetic NPs by heat generation through relaxation in an alternating magnetic field (magnetic hyperthermia). Furthermore, the superparamagnetic properties of iron oxide nanoparticles have led to their use as potent MRI (magnetic resonance imaging) contrast agents. Surface modification/coating can produce NPs with tailored and desired properties, such as enhanced blood circulation time, stability, biocompatibility and water solubility. To target nanoparticles to specific tumor cells, NPs should be conjugated with targeting moieties on the surface which bind to receptors or other molecular structures on the cell surface. The article presents several approaches to enhancing the specificity of Au and iron oxide nanoparticles for tumor tissue by appropriate surface modification/functionalization, as well as the effect of these treatments on the saturation magnetization value of iron oxide NPs. The use of other nanoparticles and nanostructures in cancer treatment is also briefly reviewed.

  13. Iron oxide and gold nanoparticles in cancer therapy

    SciTech Connect

    Gotman, Irena Gutmanas, Elazar Y.; Psakhie, Sergey G.; Lozhkomoev, Aleksandr S.

    2016-08-02

    Continuous research activities in the field of nanomedicine in the past decade have, to a great extent, been focused on nanoparticle technologies for cancer therapy. Gold and iron oxide nanoparticles (NP) are two of the most studied inorganic nanomaterials due to their unique optical and magnetic properties. Both types of NPs are emerging as promising systems for anti-tumor drug delivery and for nanoparticle-mediated thermal therapy of cancer. In thermal therapy, localized heating inside tumors or in proximity of tumor cells can be induced, for example, with Au NPs by radiofrequency ablation heating or conversion of photon energy (photothermal therapy) and in iron oxide magnetic NPs by heat generation through relaxation in an alternating magnetic field (magnetic hyperthermia). Furthermore, the superparamagnetic properties of iron oxide nanoparticles have led to their use as potent MRI (magnetic resonance imaging) contrast agents. Surface modification/coating can produce NPs with tailored and desired properties, such as enhanced blood circulation time, stability, biocompatibility and water solubility. To target nanoparticles to specific tumor cells, NPs should be conjugated with targeting moieties on the surface which bind to receptors or other molecular structures on the cell surface. The article presents several approaches to enhancing the specificity of Au and iron oxide nanoparticles for tumor tissue by appropriate surface modification/functionalization, as well as the effect of these treatments on the saturation magnetization value of iron oxide NPs. The use of other nanoparticles and nanostructures in cancer treatment is also briefly reviewed.

  14. THE EFFECT OF PH, PHOSPHATE AND OXIDANT TYPE ON THE REMOVAL OF ARSENIC FROM DRINKING WATER DURING IRON REMOVAL

    EPA Science Inventory

    In many regions of the United States, groundwaters that contain arsenic (primarily As[III]) also contain significant amounts of iron (Fe[II]). Arsenic removal will most likely be achieved by iron removal in many of those cases which will consist of oxidization followed by filtra...

  15. THE EFFECT OF PH, PHOSPHATE AND OXIDANT TYPE ON THE REMOVAL OF ARSENIC FROM DRINKING WATER DURING IRON REMOVAL

    EPA Science Inventory

    In many regions of the United States, groundwaters that contain arsenic (primarily As[III]) also contain significant amounts of iron (Fe[II]). Arsenic removal will most likely be achieved by iron removal in many of those cases which will consist of oxidization followed by filtra...

  16. Development and use of iron oxide nanoparticles (Part 1): Synthesis of iron oxide nanoparticles for MRI

    PubMed Central

    Lodhia, J; Mandarano, G; Ferris, NJ; Eu, P; Cowell, SF

    2010-01-01

    Contrast agents, such as iron oxide, enhance MR images by altering the relaxation times of tissues in which the agent is present. They can also be used to label targeted molecular imaging probes. Unfortunately, no molecular imaging probe is currently available on the clinical MRI market. A promising platform for MRI contrast agent development is nanotechnology, where superparamagnetic iron oxide nanoparticles (SPIONS) are tailored for MR contrast enhancement, and/or for molecular imaging. SPIONs can be produced using a range of methods and the choice of method will be influenced by the characteristics most important for a particular application. In addition, the ability to attach molecular markers to SPIONS heralds their application in molecular imaging. There are many reviews on SPION synthesis for MRI; however, these tend to be targeted to a chemistry audience. The development of MRI contrast agents attracts experienced researchers from many fields including some researchers with little knowledge of medical imaging or MRI. This situation presents medical radiation practitioners with opportunities for involvement, collaboration or leadership in research depending on their level of commitment and their ability to learn. Medical radiation practitioners already possess a large portion of the understanding, knowledge and skills necessary for involvement in MRI development and molecular imaging. Their expertise in imaging technology, patient care and radiation safety provides them with skills that are directly applicable to research on the development and application of SPIONs and MRI. In this paper we argue that MRI SPIONs, currently limited to major research centres, will have widespread clinical use in the future. We believe that knowledge about this growing area of research provides an opportunity for medical radiation practitioners to enhance their specialised expertise to ensure best practice in a truly multi-disciplinary environment. This review outlines how and

  17. Recycling of a spent iron based catalyst for the complete oxidation of toluene: effect of palladium.

    PubMed

    Kim, Sang Chai; Nah, Jae Woon

    2015-01-01

    Complete oxidation of volatile organic compound (toluene) was carried out to assess the property and activity of the palladium-spent iron based catalyst. The properties of the prepared catalysts were characterized by using the Brunauer-Emmett-Teller method and by conducting temperature-programmed reduction, X-ray diffraction, X-ray photoelectron spectroscopy and field emission transmission electron microscopy. The addition of palladium to the spent iron based catalyst pretreated with oxalic acid shifted the conversion curve for the total oxidation of toluene to lower temperature. An increase in the toluene conversion due to palladium was highly related to the easier lattice oxygen mobility of the catalysts. Instrumental analysis suggested the presence of a strong interaction between palladium and iron oxide species. Moreover, in the case of reducing the Pd/Fe catalyst with hydrogen, palladium accelerated the reducing iron oxides, subsequently decreasing the toluene conversion. As a result, the oxidation states of palladium and iron had an important effect on the catalytic activity.

  18. Structure and Properties of Nanocrystalline Iron Oxide Powder Prepared by the Method of Pulsed Laser Ablation

    NASA Astrophysics Data System (ADS)

    Svetlichnyi, V. A.; Shabalina, A. V.; Lapin, I. N.

    2017-04-01

    Colloidal solution of iron oxide nanoparticles is synthesized by nanosecond pulsed laser ablation (Nd:YAG laser, 1064 nm, 7 ns, and 180 mJ) of a metallic iron target in water, and nanocrystalline powder is prepared from this solution by vacuum drying. A composition and structure of the material obtained are investigated by methods of electron microscopy, x-ray diffraction, and optical spectroscopy. It is established that oxide particles with average size of about 5 nm and Fe3O4 magnetite structure are mainly formed during ablation. Preliminary investigation of magnetic properties of the prepared nanoparticle powders shows that they can be in ferromagnetic and/or superparamagnetic states.

  19. OXIDATION OF CYCLOHEXANE WITH AIR CATALYZED BY A STERICALLY HINDERED IRON (II) COMPLEX

    EPA Science Inventory

    Oxidation of Cyclohexane with Air Catalyzed by a Sterically Hindered Iron(II) Complex.


    Thomas M. Becker, Michael A. Gonzalez*

    United States Environmental Protection Agency; National Risk Management Research Laboratory; Sustainable Technology Division; Clean Pr...

  20. Modeling of iron oxide deposition by reactive ion beam sputtering

    SciTech Connect

    Puech, Laurent; Dubarry, Christophe; Ravel, Guillaume; Vito, Eric de

    2010-03-15

    An analytic model of deposition is applied on reactive ion beam sputtering to optimize the properties of iron oxide thin films. This model will be able to predict deposition rate and phase contents. Among its hypotheses, we assume oxygen adsorption at the surface of the target to explain variations of deposition rate for oxygen flow. This hypothesis is validated by chemical analyses on iron targets. An ellipsoidal distribution of probability is introduced to model sputtered matter distribution from iron target and to calculate sputtering yield. Comparison between experimental and calculated deposition rates validates previously assumed hypotheses.

  1. Colossal super saturation of oxygen at the iron-aluminum interfaces fabricated using solid state welding

    SciTech Connect

    Sridharan, Niyanth; Isheim, D.; Seidman, David N.; Babu, Suresh S.

    2016-12-14

    Solid state joining is achieved in three steps, (i) interface asperity deformation, (ii) oxide dispersion, followed by (iii) atomic contact and bonding. Atomically clean metallic surfaces without an oxide layer bond spontaneously. Despite its importance the oxide dispersion mechanism is not well studied. In this work the first ever atom probe study of iron-aluminum solid state welds show that the oxygen concentration at the interface is 20 at.%. This is significantly lower than any equilibrium oxide concentration. Here, we therefore propose that the high-strain rate deformation at the interfaces renders the oxide unstable resulting in the observed concentration of oxygen.

  2. Safety assessment of chronic oral exposure to iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Chamorro, Susana; Gutiérrez, Lucía; Vaquero, María Pilar; Verdoy, Dolores; Salas, Gorka; Luengo, Yurena; Brenes, Agustín; José Teran, Francisco

    2015-05-01

    Iron oxide nanoparticles with engineered physical and biochemical properties are finding a rapidly increasing number of biomedical applications. However, a wide variety of safety concerns, especially those related to oral exposure, still need to be addressed for iron oxide nanoparticles in order to reach clinical practice. Here, we report on the effects of chronic oral exposure to low doses of γ-Fe2O3 nanoparticles in growing chickens. Animal observation, weight, and diet intake reveal no adverse signs, symptoms, or mortality. No nanoparticle accumulation was observed in liver, spleen, and duodenum, with feces as the main excretion route. Liver iron level and duodenal villi morphology reflect the bioavailability of the iron released from the partial transformation of γ-Fe2O3 nanoparticles in the acid gastric environment. Duodenal gene expression studies related to the absorption of iron from γ-Fe2O3 nanoparticles indicate the enhancement of a ferric over ferrous pathway supporting the role of mucins. Our findings reveal that oral administration of iron oxide nanoparticles is a safe route for drug delivery at low nanoparticle doses.

  3. Safety assessment of chronic oral exposure to iron oxide nanoparticles.

    PubMed

    Chamorro, Susana; Gutiérrez, Lucía; Vaquero, María Pilar; Verdoy, Dolores; Salas, Gorka; Luengo, Yurena; Brenes, Agustín; José Teran, Francisco

    2015-05-22

    Iron oxide nanoparticles with engineered physical and biochemical properties are finding a rapidly increasing number of biomedical applications. However, a wide variety of safety concerns, especially those related to oral exposure, still need to be addressed for iron oxide nanoparticles in order to reach clinical practice. Here, we report on the effects of chronic oral exposure to low doses of γ-Fe2O3 nanoparticles in growing chickens. Animal observation, weight, and diet intake reveal no adverse signs, symptoms, or mortality. No nanoparticle accumulation was observed in liver, spleen, and duodenum, with feces as the main excretion route. Liver iron level and duodenal villi morphology reflect the bioavailability of the iron released from the partial transformation of γ-Fe2O3 nanoparticles in the acid gastric environment. Duodenal gene expression studies related to the absorption of iron from γ-Fe2O3 nanoparticles indicate the enhancement of a ferric over ferrous pathway supporting the role of mucins. Our findings reveal that oral administration of iron oxide nanoparticles is a safe route for drug delivery at low nanoparticle doses.

  4. Characterization of iron oxide layers using Auger electron spectroscopy

    NASA Astrophysics Data System (ADS)

    Bizjak, Milan; Zalar, Anton; Panjan, Peter; Zorko, Benjamin; Praček, Borut

    2007-02-01

    Metals can form several kinds of oxides. Iron forms wustite (FeO), magnetite (FeO + Fe 2O 3 or Fe 3O 4) and haematite (Fe 2O 3). Iron oxides, especially magnetite, are used for insulation between the lamellas of an electromotor made of electromagnetic sheet. In this work, iron oxide layers were characterized on industrial samples of electromagnetic sheet by AES depth profile analysis, and iron oxides with known chemical composition were used as reference samples, i.e. a magnetite mineral and a standard haematite reference sample. The magnetite mineral was chosen because it can be found in nature in a very pure form. The selection of reference samples was also verified on samples with an oxide layer of known composition, which were prepared by sputter deposition. The composition of the sputtered oxide layers was analysed by the weight-gain method and Rutherford backscattering without the use of standard reference materials (SRM), and the results were then compared with those obtained by AES depth profile analysis.

  5. Manganese- and iron-dependent marine methane oxidation.

    PubMed

    Beal, Emily J; House, Christopher H; Orphan, Victoria J

    2009-07-10

    Anaerobic methanotrophs help regulate Earth's climate and may have been an important part of the microbial ecosystem on the early Earth. The anaerobic oxidation of methane (AOM) is often thought of as a sulfate-dependent process, despite the fact that other electron acceptors are more energetically favorable. Here, we show that microorganisms from marine methane-seep sediment in the Eel River Basin in California are capable of using manganese (birnessite) and iron (ferrihydrite) to oxidize methane, revealing that marine AOM is coupled, either directly or indirectly, to a larger variety of oxidants than previously thought. Large amounts of manganese and iron are provided to oceans from rivers, indicating that manganese- and iron-dependent AOM have the potential to be globally important.

  6. X-Ray Photoelectron Spectroscopic Characterization of Iron Oxide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Radu, T.; Iacovita, C.; Benea, D.; Turcu, R.

    2017-05-01

    We report X-ray photoelectron spectroscopy (XPS) results on iron oxide magnetic nanoparticle (Fe3O4) synthesized using solvothermal reduction in the presence of polyethylene glycol. The magnetite obtained was employed as precursor for the synthesis of γ-Fe2O3 (by oxygen dissociation) which in turn was transformed into α-Fe2O3. We confirmed the magnetite, maghemite and hematite structure by Fourier Transformed Spectroscopy (FTIR) and X-ray diffraction (XRD). The analysis of the XPS core level and valence band (VB) photoemission spectra for all investigated samples is discussed in terms of the degree of iron oxidation. This is of fundamental importance to better understand the electronic structure of the obtained iron oxide nanoparticles in order to control and improve their quality for specific biomedical applications. Moreover, theoretical band structure calculations are performed for magnetite and the separate contributions of Fe in tetragonal and octahedral environment are shown.

  7. Virus-Templated Near-Amorphous Iron Oxide Nanotubes.

    PubMed

    Shah, Sachin N; Khan, Abid A; Espinosa, Ana; Garcia, Miguel A; Nuansing, Wiwat; Ungureanu, Mariana; Heddle, Jonathan G; Chuvilin, Andrey L; Wege, Christina; Bittner, Alexander M

    2016-06-14

    We present a simple synthesis of iron oxide nanotubes, grown under very mild conditions from a solution containing Fe(II) and Fe(III), on rod-shaped tobacco mosaic virus templates. Their well-defined shape and surface chemistry suggest that these robust bionanoparticles are a versatile platform for synthesis of small, thin mineral tubes, which was achieved efficiently. Various characterization tools were used to explore the iron oxide in detail: Electron microscopy (SEM, TEM), magnetometry (SQUID-VSM), diffraction (XRD, TEM-SAED), electron spectroscopies (EELS, EDX, XPS), and X-ray absorption (XANES with EXAFS analysis). They allowed determination of the structure, crystallinity, magnetic properties, and composition of the tubes. The protein surface of the viral templates was crucial to nucleate iron oxide, exhibiting analogies to biomineralization in natural compartments such as ferritin cages.

  8. Activation and detoxification of UICC crocidolite: the effect of conversion of oxidation state of iron on the toxicity of the fibres

    NASA Astrophysics Data System (ADS)

    Gulumian, M.; De Waard, H.; Pollak, H.

    1993-04-01

    Detoxification of crocidolite, an asbestiform riebeckite with a coating of ferric salt, converted some of the ferrous ions into ferric ions and therefore decreased the activity of the fibres to catalyse the reduction of oxygen and hydrogen peroxide. The H 2-activation of crocidolite fibres on the other hand, changed some of the ferric ions into ferrous ions and therefore increased the capacity of the fibres to catalyse these two reactions. Mössbauer spectroscopy (MS) combined with wet chemical analysis, X-ray diffraction, X-ray fluorescence, and neutron activation analysis enabled us to determine the site occupancies of iron and magnesium in UICC (Union Internationale Contre le Cancer) crocidolite and the ratio of the recoil-free fractions ƒ(Fe 2+)/ƒ(Fe 3+) = 0.86±0.07. These results and further MS studies with detoxified and activated fibres explained the effect of the two processes on the activity of iron in the fibres.

  9. Spin state switching in iron coordination compounds

    PubMed Central

    Gaspar, Ana B; Garcia, Yann

    2013-01-01

    Summary The article deals with coordination compounds of iron(II) that may exhibit thermally induced spin transition, known as spin crossover, depending on the nature of the coordinating ligand sphere. Spin transition in such compounds also occurs under pressure and irradiation with light. The spin states involved have different magnetic and optical properties suitable for their detection and characterization. Spin crossover compounds, though known for more than eight decades, have become most attractive in recent years and are extensively studied by chemists and physicists. The switching properties make such materials potential candidates for practical applications in thermal and pressure sensors as well as optical devices. The article begins with a brief description of the principle of molecular spin state switching using simple concepts of ligand field theory. Conditions to be fulfilled in order to observe spin crossover will be explained and general remarks regarding the chemical nature that is important for the occurrence of spin crossover will be made. A subsequent section describes the molecular consequences of spin crossover and the variety of physical techniques usually applied for their characterization. The effects of light irradiation (LIESST) and application of pressure are subjects of two separate sections. The major part of this account concentrates on selected spin crossover compounds of iron(II), with particular emphasis on the chemical and physical influences on the spin crossover behavior. The vast variety of compounds exhibiting this fascinating switching phenomenon encompasses mono-, oligo- and polynuclear iron(II) complexes and cages, polymeric 1D, 2D and 3D systems, nanomaterials, and polyfunctional materials that combine spin crossover with another physical or chemical property. PMID:23504535

  10. Arsenate adsorption onto iron oxide amended rice husk char.

    PubMed

    Cope, Christopher O; Webster, Damon S; Sabatini, David A

    2014-08-01

    In this study, rice husks were charred at 550 °C in a partially sealed ceramic vessel for 30minutes to create a high specific surface area (SSA) rice husk char (RHC). The RHC was then amended with iron oxides using dissolved ferric nitrate, Fe(NO3)3⋅9H2O, to provide a surface chemistry conducive to arsenic adsorption. The 550 °C iron oxide amended rice husk char's (550 IOA-RHC's) SSA was nearly 2.5 orders of magnitude higher and the arsenate adsorptive level was nearly 2 orders of magnitude higher than those reported for iron oxide amended sand, thus indicating a positive relationship between post-amendment SSA and arsenate adsorptive levels. Rice husks were then charred at temperatures ranging from 450 °C to 1050 °C to create an even higher SSA material, which might further increase arsenate adsorptive levels. The 950 °C RHC was chosen for amendment due to its high SSA and feasibility of being produced in the field. Once amended, the 950 °C iron oxide amended rice husk char (950 IOA-RHC) improved the arsenate adsorption capacity by thus confirming a positive relationship, though not a linear relationship, between post-amendment SSA and arsenic adsorptive capacity. Further study demonstrated that post-amendment mesoporous volume and mesoporous surface area appear to be better indicators of arsenic adsorptive capacity than SSA or iron content.

  11. Recovery of iron oxide from coal fly ash

    DOEpatents

    Dobbins, Michael S.; Murtha, Marlyn J.

    1983-05-31

    A high quality iron oxide concentrate, suitable as a feed for blast and electric reduction furnaces is recovered from pulverized coal fly ash. The magnetic portion of the fly ash is separated and treated with a hot strong alkali solution which dissolves most of the silica and alumina in the fly ash, leaving a solid residue and forming a precipitate which is an acid soluble salt of aluminosilicate hydrate. The residue and precipitate are then treated with a strong mineral acid to dissolve the precipitate leaving a solid residue containing at least 90 weight percent iron oxide.

  12. Electrolytic photodissociation of chemical compounds by iron oxide electrodes

    DOEpatents

    Somorjai, Gabor A.; Leygraf, Christofer H.

    1984-01-01

    Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor diode having visible light as its sole source of energy. The diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.

  13. Electrolytic photodissociation of chemical compounds by iron oxide photochemical diodes

    DOEpatents

    Somorjai, Gabor A.; Leygraf, Christofer H.

    1985-01-01

    Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor photochemical diode having visible light as its sole source of energy. The photochemical diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.

  14. Structural changes in iron-cobalt oxide nanosystems

    NASA Astrophysics Data System (ADS)

    Nishchev, K. N.; Golub'ev, M. A.; Maksimov, Yu. V.; Beglov, V. I.; Kyashkin, V. M.; Panov, A. A.

    2015-05-01

    The structure of binary iron-cobalt oxide nanosystems—precursors of bimetallic catalysts—is studied by Mössbauer spectroscopy, X-ray diffraction, and small-angle X-ray scattering. The oxide system under study represents a promising material for creating new metallic nanocatalysts for ammonia synthesis. The structural evolution in the composition range 100Fe/0Co-5Fe/95Co is found to correspond to the transition from fine-grained α-Fe2O3 to mixed iron-cobalt spinels of various compositions and degrees of dispersity.

  15. Electrolytic photodissociation of chemical compounds by iron oxide electrodes

    SciTech Connect

    Somorjai, G.A.; Leygraf, C.H.

    1984-07-17

    Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor diode having visible light as its sole source of energy. The diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.

  16. Multifunctional superparamagnetic iron oxide nanoparticles: promising tools in cancer theranostics.

    PubMed

    Santhosh, Poornima Budime; Ulrih, Nataša Poklar

    2013-08-09

    Iron-oxide nanoparticles of small dimensions that have superparamagnetic properties show immense potential to revolutionize the future of cancer theranostics, the combinatorial diagnosis and therapeutic approach towards cancer. Superparamagnetic iron-oxide nanoparticles (SPIONs) have unique magnetic properties, due to which they show excellent tumor-targeting efficiency, and this paves the way for effective personalized cancer treatment. The aim of this review is to focus on the ability of SPIONs to perform multiple roles in the field of cancer biology, such as in diagnosis, monitoring, targeting and therapy. Also, other topics are discussed, including the synthesis of SPIONs, the challenges and recent advances.

  17. Magnetic fluid hyperthermia: focus on superparamagnetic iron oxide nanoparticles.

    PubMed

    Laurent, Sophie; Dutz, Silvio; Häfeli, Urs O; Mahmoudi, Morteza

    2011-08-10

    Due to their unique magnetic properties, excellent biocompatibility as well as multi-purpose biomedical potential (e.g., applications in cancer therapy and general drug delivery), superparamagnetic iron oxide nanoparticles (SPIONs) are attracting increasing attention in both pharmaceutical and industrial communities. The precise control of the physiochemical properties of these magnetic systems is crucial for hyperthermia applications, as the induced heat is highly dependent on these properties. In this review, the limitations and recent advances in the development of superparamagnetic iron oxide nanoparticles for hyperthermia are presented.

  18. Multifunctional Iron Oxide Nanoparticles for Diagnostics, Therapy and Macromolecule Delivery

    PubMed Central

    Yen, Swee Kuan; Padmanabhan, Parasuraman; Selvan, Subramanian Tamil

    2013-01-01

    In recent years, multifunctional nanoparticles (NPs) consisting of either metal (e.g. Au), or magnetic NP (e.g. iron oxide) with other fluorescent components such as quantum dots (QDs) or organic dyes have been emerging as versatile candidate systems for cancer diagnosis, therapy, and macromolecule delivery such as micro ribonucleic acid (microRNA). This review intends to highlight the recent advances in the synthesis and application of multifunctional NPs (mainly iron oxide) in theranostics, an area used to combine therapeutics and diagnostics. The recent applications of NPs in miRNA delivery are also reviewed. PMID:24396508

  19. Relationships between oxidative stress, haematology and iron profile in anaemic and non-anaemic calves.

    PubMed

    Rajabian, Fatemeh; Mohri, Mehrdad; Heidarpour, Mohammad

    2017-09-09

    The aim of this study was to investigate the relationships between oxidative stress, haematology and iron profile in neonatal dairy calves. Serum and haemolysate malondialdehyde (MDA), serum total antioxidant capacity, thiol groups, iron, total iron binding capacity, transferrin saturation and red blood cell (RBC) parameters were assessed in two groups: anaemic calves (n=14) and non-anaemic calves (n=16). Blood samples were collected from all of the calves within 24-48 hours after birth and at 7, 14, 21 and 28 days of age. A significant decrease in serum iron amount and transferrin saturation value (P<0.05) and a significant increase in haemolysate MDA concentration (P<0.05) in the anaemic calves were observed, when compared with non-anaemic calves. Total antioxidant capacity and thiol groups showed a significant positive correlation with iron profile and RBC parameters (haematocrit and haemoglobin) in the anaemic calves at day 21 (P<0.05). On the other hand, the concentration of haemolysate MDA was inversely correlated with the value of serum total antioxidant capacity (P<0.05). The results of the present study revealed that anaemic calves showed more severe oxidative stress than non-anaemic calves. In addition, iron insufficiency may be linked to the impairment of antioxidant defence system and oxidative damage of erythrocytes in the neonatal calves. © British Veterinary Association (unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  20. Unprecedented Selective Oxidation of Styrene Derivatives using a Supported Iron Oxide Nanocatalyst in Aqueous Medium

    EPA Science Inventory

    Iron oxide nanoparticles supported on mesoporous silica-type materials have been successfully utilized in the aqueous selective oxidation of alkenes under mild conditions using hydrogen peroxide as a green oxidant. Catalysts could be easily recovered after completion of the reac...

  1. Unprecedented Selective Oxidation of Styrene Derivatives using a Supported Iron Oxide Nanocatalyst in Aqueous Medium

    EPA Science Inventory

    Iron oxide nanoparticles supported on mesoporous silica-type materials have been successfully utilized in the aqueous selective oxidation of alkenes under mild conditions using hydrogen peroxide as a green oxidant. Catalysts could be easily recovered after completion of the reac...

  2. Size-dependent magnetic properties of iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Patsula, Vitalii; Moskvin, Maksym; Dutz, Silvio; Horák, Daniel

    2016-01-01

    Uniform iron oxide nanoparticles in the size range from 10 to 24 nm and polydisperse 14 nm iron oxide particles were prepared by thermal decomposition of Fe(III) carboxylates in the presence of oleic acid and co-precipitation of Fe(II) and Fe(III) chlorides by ammonium hydroxide followed by oxidation, respectively. While the first method produced hydrophobic oleic acid coated particles, the second one formed hydrophilic, but uncoated, nanoparticles. To make the iron oxide particles water dispersible and colloidally stable, their surface was modified with poly(ethylene glycol) and sucrose, respectively. Size and size distribution of the nanoparticles was determined by transmission electron microscopy, dynamic light scattering and X-ray diffraction. Surface of the PEG-functionalized and sucrose-modified iron oxide particles was characterized by Fourier transform infrared (FT-IR) and Raman spectroscopy and thermogravimetric analysis (TGA). Magnetic properties were measured by means of vibration sample magnetometry and specific absorption rate in alternating magnetic fields was determined calorimetrically. It was found, that larger ferrimagnetic particles showed higher heating performance than smaller superparamagnetic ones. In the transition range between superparamagnetism and ferrimagnetism, samples with a broader size distribution provided higher heating power than narrow size distributed particles of comparable mean size. Here presented particles showed promising properties for a possible application in magnetic hyperthermia.

  3. Aqueous Aggregation Behavior of Engineered Superparamagnetic Iron Oxide Nanoparticles: Effects of Oxidative Surface Aging.

    PubMed

    Li, Wenlu; Lee, Seung Soo; Mittelman, Anjuliee M; Liu, Di; Wu, Jiewei; Hinton, Carl H; Abriola, Linda M; Pennell, Kurt D; Fortner, John D

    2016-12-06

    For successful aqueous-based applications, it is necessary to fundamentally understand and control nanoparticle dispersivity and stability over a range of dynamic conditions, including variable ionic strengths/types, redox chemistries, and surface ligand reactivity/degradation states (i.e., surface aging). Here, we quantitatively describe the behavior of artificially aged, oleic acid (OA) bilayer coated iron oxide nanoparticles (IONPs) under different scenarios. Hydrogen peroxide (H2O2), used here as a model oxidant under both dark and light ultraviolet (UVA) conditions, was employed to "age" materials, to varying degrees, without increasing ionic strength. Short-term stability experiments indicate that OA-IONPs, while stable in the dark, are effectively destabilized when exposed to UVA/H2O2/•OH based oxidation processes. Compared to bicarbonate, phosphate (1.0 mM) has a net stabilizing effect on OA-IONPs under oxidative conditions, which can be attributed to (surface-based) functional adsorption. Corresponding aggregation kinetics in the presence of monovalent (Na(+)) and divalent cations (Ca(2+)) show that attachment efficiencies (α) are strongly dependent on the cation concentrations/types and degree of surface aging. Taken together, our findings directly highlight the need to understand the critical role of particle surface transformation(s), via oxidative aging, among other routes, with regard to the ultimate stability and environmental fate of surface functionalized engineered nanoparticles.

  4. Iron oxides, dissolved silica, and regulation of marine phosphate concentration

    NASA Astrophysics Data System (ADS)

    Planavsky, N.; Reinhard, C.; Lyons, T.

    2008-12-01

    Phosphorous concentrations in iron oxide-rich sediments reflect orthophosphate levels in the water column from which iron oxides precipitated. Sediment P/Fe ratios are also strongly influenced by the concentrations of dissolved species that inhibit orthophosphate-to-ferrihydrite sorption, most notably silica. It may, therefore, be possible to use P/Fe ratios in iron oxide-rich sediments to estimate past dissolved P concentrations, if one considers the evolution of the silica cycle. A compilation of Fe and P data in iron oxide-rich sediments through time reveals an increase in P/Fe ratios after the Jurassic. We propose that this trend indicates evolution of the iron-oxide phosphate removal mechanism caused by decreasing levels of sorption inhibition by dissolved silica. The large difference in P/Fe ratios in Cenozoic versus older iron-oxide rich sediments can be linked with Si drawdown caused by the proliferation of siliceous plankton in the Cretaceous. There is also a late Mesozoic or Cenozoic increase in V/Fe ratios, which provides additional evidence for lower ferrihydrite anion sorption efficiency prior to diatom radiation. P/Fe ratios in iron oxide-rich sediments from the early and middle Phanerozoic are comparable to the ratios in iron formations previously presented as evidence for an early Precambrian phosphate crisis (Bjerrum and Canfield, 2002, Nature, 417:159-162). Given the compelling evidence for higher Si concentrations in the Precambrian compared to the Phanerozoic and dissolved P concentrations comparable to modern levels throughout the Phanerozoic, the presented trend of P/Fe ratios suggests dissolved P concentrations were higher in Precambrian than Phanerozoic oceans. High dissolved P levels in the Precambrian may have been linked to inhibited carbonate fluorapatite (CFA) formation as a result of persistently high levels of carbonate supersaturation. Carbonate ion substitution into CFA scales with the ambient carbonate ion activity and increases

  5. DETERMINATION OF THE RATES AND PRODUCTS OF FERROUS IRON OXIDATION IN ARSENIC-CONTAMINATED POND WATER.

    EPA Science Inventory

    Dissolved ferrous iron and arsenic in the presence of insufficient oxygenated ground water is released into a pond. When the mixing of ferrous iron and oxygenated water within the pond occurs, the ferrous iron is oxidized and precipitated as an iron oxide. Groups of experiments...

  6. Nitric oxide ameliorates the damaging effects of oxidative stress induced by iron deficiency in cyanobacterium Anabaena 7120.

    PubMed

    Kaushik, Manish Singh; Srivastava, Meenakshi; Srivastava, Alka; Singh, Anumeha; Mishra, Arun Kumar

    2016-11-01

    In cyanobacterium Anabaena 7120, iron deficiency leads to oxidative stress with unavoidable consequences. Nitric oxide reduces pigment damage and supported the growth of Anabaena 7120 in iron-deficient conditions. Elevation in nitric oxide accumulation and reduced superoxide radical production justified the role of nitric oxide in alleviating oxidative stress in iron deficiency. Increased activities of antioxidative enzymes and higher levels of ROS scavengers (ascorbate, glutathione and thiol) in iron deficiency were also observed in the presence of nitric oxide. Nitric oxide also supported the membrane integrity of Anabaena cells and reduces protein and DNA damage caused by oxidative stress induced by iron deficiency. Results suggested that nitric oxide alleviates the damaging effects of oxidative stress induced by iron deficiency in cyanobacterium Anabaena 7120.

  7. Deposition rates of oxidized iron on Mars

    NASA Technical Reports Server (NTRS)

    Burns, R. G.

    1993-01-01

    The reddened oxidized surface of Mars is indicative of temporal interactions between the Martian atmosphere and its surface. During the evolution of the Martian regolith, primary ferromagnesian silicate and sulfide minerals in basaltic rocks apparently have been oxidized to secondary ferric-bearing assemblages. To evaluate how and when such oxidized deposits were formed on Mars, information about the mechanisms and rates of chemical weathering of Fe(2+)-bearing minerals has been determined. In this paper, mechanisms and rates of deposition of ferric oxide phases on the Martian surface are discussed.

  8. Magnetic resonance imaging contrast of iron oxide nanoparticles developed for hyperthermia is dominated by iron content

    PubMed Central

    Wabler, Michele; Zhu, Wenlian; Hedayati, Mohammad; Attaluri, Anilchandra; Zhou, Haoming; Mihalic, Jana; Geyh, Alison; DeWeese, Theodore L.; Ivkov, Robert; Artemov, Dmitri

    2015-01-01

    Purpose Magnetic iron oxide nanoparticles (MNPs) are used as contrast agents for magnetic resonance imaging (MRI) and hyperthermia for cancer treatment. The relationship between MRI signal intensity and cellular iron concentration for many new formulations, particularly MNPs having magnetic properties designed for heating in hyperthermia, is lacking. In this study, we examine the correlation between MRI T2 relaxation time and iron content in cancer cells loaded with various MNP formulations. Materials and methods Human prostate carcinoma DU-145 cells were loaded with starch-coated bionised nanoferrite (BNF), iron oxide (Nanomag® D-SPIO), Feridex™, and dextran-coated Johns Hopkins University (JHU) particles at a target concentration of 50 pg Fe/cell using poly-D-lysine transfection reagent. T2-weighted MRI of serial dilutions of these labelled cells was performed at 9.4 T and iron content quantification was performed using inductively coupled plasma mass spectrometry (ICP-MS). Clonogenic assay was used to characterise cytotoxicity. Results No cytotoxicity was observed at twice the target intracellular iron concentration (~100 pg Fe/cell). ICP-MS revealed highest iron uptake efficiency with BNF and JHU particles, followed by Feridex and Nanomag-D-SPIO, respectively. Imaging data showed a linear correlation between increased intracellular iron concentration and decreased T2 times, with no apparent correlation among MNP magnetic properties. Conclusions This study demonstrates that for the range of nanoparticle concentrations internalised by cancer cells the signal intensity of T2-weighted MRI correlates closely with absolute iron concentration associated with the cells. This correlation may benefit applications for cell-based cancer imaging and therapy including nanoparticle-mediated drug delivery and hyperthermia. PMID:24773041

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

    PubMed

    Lapenna, Domenico; Ciofani, Giuliano; Obletter, Gabriele

    2017-05-01

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

  10. Synthesis, characterization, applications, and challenges of iron oxide nanoparticles

    PubMed Central

    Ali, Attarad; Zafar, Hira; Zia, Muhammad; ul Haq, Ihsan; Phull, Abdul Rehman; Ali, Joham Sarfraz; Hussain, Altaf

    2016-01-01

    Recently, iron oxide nanoparticles (NPs) have attracted much consideration due to their unique properties, such as superparamagnetism, surface-to-volume ratio, greater surface area, and easy separation methodology. Various physical, chemical, and biological methods have been adopted to synthesize magnetic NPs with suitable surface chemistry. This review summarizes the methods for the preparation of iron oxide NPs, size and morphology control, and magnetic properties with recent bioengineering, commercial, and industrial applications. Iron oxides exhibit great potential in the fields of life sciences such as biomedicine, agriculture, and environment. Nontoxic conduct and biocompatible applications of magnetic NPs can be enriched further by special surface coating with organic or inorganic molecules, including surfactants, drugs, proteins, starches, enzymes, antibodies, nucleotides, nonionic detergents, and polyelectrolytes. Magnetic NPs can also be directed to an organ, tissue, or tumor using an external magnetic field for hyperthermic treatment of patients. Keeping in mind the current interest in iron NPs, this review is designed to report recent information from synthesis to characterization, and applications of iron NPs. PMID:27578966

  11. Distribution Behavior of Phosphorus and Metallization of Iron Oxide in Carbothermic Reduction of High-Phosphorus Iron Ore

    NASA Astrophysics Data System (ADS)

    Cha, Ji-Whoe; Kim, Dong-Yuk; Jung, Sung-Mo

    2015-10-01

    Distribution behavior of phosphorus and metallization of iron ore in the carbothermic reduction of high-phosphorus iron ore were investigated. Reduction degree of the iron oxide was evaluated by quadruple mass spectrometry connected to thermogravimetric analysis. The distribution of some elements including phosphorus was examined by electron probe micro-analyzer mapping analyses. The reduction behavior of high-phosphorus iron ore was evaluated as a function of reduction temperature, C/O molar ratio, and CaO addition. High reduction temperature accelerated the reduction of both iron oxide and hydroxylapatite, and high C/O molar ratio also promotes both of them. Those were contradictory to the targets of higher reduction degree of iron oxide and of lower one of hydroxylapatite. It was confirmed that appropriate amount of CaO addition could enhance the reduction of iron oxide, and regulate the reduction of hydroxylapatite.

  12. Extending the models for iron and sulfur oxidation in the extreme Acidophile Acidithiobacillus ferrooxidans

    PubMed Central

    2009-01-01

    Background Acidithiobacillus ferrooxidans gains energy from the oxidation of ferrous iron and various reduced inorganic sulfur compounds at very acidic pH. Although an initial model for the electron pathways involved in iron oxidation has been developed, much less is known about the sulfur oxidation in this microorganism. In addition, what has been reported for both iron and sulfur oxidation has been derived from different A. ferrooxidans strains, some of which have not been phylogenetically characterized and some have been shown to be mixed cultures. It is necessary to provide models of iron and sulfur oxidation pathways within one strain of A. ferrooxidans in order to comprehend the full metabolic potential of the pangenome of the genus. Results Bioinformatic-based metabolic reconstruction supported by microarray transcript profiling and quantitative RT-PCR analysis predicts the involvement of a number of novel genes involved in iron and sulfur oxidation in A. ferrooxidans ATCC23270. These include for iron oxidation: cup (copper oxidase-like), ctaABT (heme biogenesis and insertion), nuoI and nuoK (NADH complex subunits), sdrA1 (a NADH complex accessory protein) and atpB and atpE (ATP synthetase F0 subunits). The following new genes are predicted to be involved in reduced inorganic sulfur compounds oxidation: a gene cluster (rhd, tusA, dsrE, hdrC, hdrB, hdrA, orf2, hdrC, hdrB) encoding three sulfurtransferases and a heterodisulfide reductase complex, sat potentially encoding an ATP sulfurylase and sdrA2 (an accessory NADH complex subunit). Two different regulatory components are predicted to be involved in the regulation of alternate electron transfer pathways: 1) a gene cluster (ctaRUS) that contains a predicted iron responsive regulator of the Rrf2 family that is hypothesized to regulate cytochrome aa3 oxidase biogenesis and 2) a two component sensor-regulator of the RegB-RegA family that may respond to the redox state of the quinone pool. Conclusion

  13. Facile Synthesis of Iron Oxide/Graphene Nanocomposites Using Liquid Phase Plasma Method.

    PubMed

    Lee, H; Park, Y K; Kim, S J; Kim, B J; An, K H; Kim, B H; Jung, S C

    2016-05-01

    Liquid phase plasma (LPP) method was applied, for the first time, to the impregnation of iron oxide nanoparticles onto graphene sheet. Iron oxide nanoparticles with the size of 50 nm were precipitated with uniform dispersion on the surface of graphene sheet. The amount of iron oxide nanoparticles precipitated on graphene sheets increased with increasing LPP process times. The XPS, Raman and EDX analyses showed that the iron oxide/graphene composites synthesized by the LPP process.

  14. Uptake and metabolism of iron oxide nanoparticles in brain cells.

    PubMed

    Petters, Charlotte; Irrsack, Ellen; Koch, Michael; Dringen, Ralf

    2014-09-01

    Magnetic iron oxide nanoparticles (IONPs) are used for various applications in biomedicine, for example as contrast agents in magnetic resonance imaging, for cell tracking and for anti-tumor treatment. However, IONPs are also known for their toxic effects on cells and tissues which are at least in part caused by iron-mediated radical formation and oxidative stress. The potential toxicity of IONPs is especially important concerning the use of IONPs for neurobiological applications as alterations in brain iron homeostasis are strongly connected with human neurodegenerative diseases. Since IONPs are able to enter the brain, potential adverse consequences of an exposure of brain cells to IONPs have to be considered. This article describes the pathways that allow IONPs to enter the brain and summarizes the current knowledge on the uptake, the metabolism and the toxicity of IONPs for the different types of brain cells in vitro and in vivo.

  15. From iron coordination compounds to metal oxide nanoparticles.

    PubMed

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

    2016-01-01

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

  16. From iron coordination compounds to metal oxide nanoparticles

    PubMed Central

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

    2016-01-01

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

  17. Behavior of iron aluminides in oxidizing and sulfidizing environments

    SciTech Connect

    Tortorelli, P.F.; DeVan, J.H.; DiStefano, J.R.

    1989-01-01

    To date, use of iron aluminides based on Fe/sub 3/Al (less than or equal to30 at. % Al) or FeAl (30--50 at. % Al) for structural applications has been limited by their low ductility and poor fracture toughness at room temperature and inadequate strength above 600/degree/C. However, in recent years, a renewed effort has been devoted to the development of ductile iron aluminides with increased strength, particularly in view of their good potential for use in hostile environments. While it is expected that such aluminides will be able to form oxide scales for corrosion protection in oxidizing high temperature environments, resistance to degradation in oxidizing salt or oxidizing/sulfidizing gas environments has not been adequately addressed as a function of compositional and microstructural changes. This paper reviews and extends results for iron aluminides exposed to an oxidizing/sulfidizing gas and presents the first data for corrosion of this class of materials by an aggressive oxidizing molten nitrate salt of 48.5NaNO/sub 3/--50.5KNO/sub 3/--1Na/sub 2/O/sub 2/. 14 refs., 11 figs.

  18. Oxidation resistant iron and nickel alloys for high temperature use

    NASA Technical Reports Server (NTRS)

    Hill, V. L.; Misra, S. K.; Wheaton, H. L.

    1970-01-01

    Iron-base and nickel-base alloys exhibit good oxidation resistance and improved ductility with addition of small amounts of yttrium, tantalum /or hafnium/, and thorium. They can be used in applications above the operating temperatures of the superalloys, if high strength materials are not required.

  19. New Perspectives on Biomedical Applications of Iron Oxide Nanoparticles.

    PubMed

    Magro, Massimiliano; Baratella, Davide; Bonaiuto, Emanuela; de Almeida Roger, Jessica; Vianello, Fabio

    2017-06-16

    Iron oxide nanomaterials are considered promising tools for improved therapeutic efficacy and diagnostic applications in biomedicine. Accordingly, engineered iron oxide nanomaterials are increasingly proposed in biomedicine, and the interdisciplinary researches involving physics, chemistry, biology (nanotechnology) and medicine have led to exciting developments in the last decades. The progresses of the development of magnetic nanoparticles with tailored physico-chemical and surface properties produced a variety of clinically relevant applications, spanning from magnetic resonance imaging (MRI), drug delivery, magnetic hyperthermia, to in vitro diagnostics. Notwithstanding the well-known conventional synthetic procedures and their wide use, recent advances in the synthetic methods open the door to new generations of naked iron oxide nanoparticles possessing peculiar surface chemistries, suitable for other competitive biomedical applications. New abilities to rationally manipulate iron oxides and their physical, chemical, and biological properties, allow the emersion of additional possibilities for designing novel nanomaterials for theranostic applications. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  20. Physicochemical properties of iron oxide nanoparticles that contribute to cellular ROS-dependent signaling and acellular production of hydroxyl radical.

    PubMed

    Vogel, Christoph F A; Charrier, Jessica G; Wu, Dalei; McFall, Alexander S; Li, Wen; Abid, Aamir; Kennedy, Ian M; Anastasio, Cort

    2016-01-01

    While nanoparticles (NPs) are increasingly used in a variety of consumer products and medical applications, some of these materials have potential health concerns. Macrophages are the primary responders to particles that initiate oxidative stress and inflammatory reactions. Here, we utilized six flame-synthesized, engineered iron oxide NPs with various physicochemical properties (e.g. Fe oxidation state and crystal size) to study their interactions with RAW 264.7 macrophages, their iron solubilities, and their abilities to produce hydroxyl radical in an acellular assay. Both iron solubility and hydroxyl radical production varied between NPs depending on crystalline diameter and surface area of the particles, but not on iron oxidation state. Macrophage treatment with the iron oxide NPs showed a dose-dependent increase of heme oxygenase 1 (HO-1) and NAD(P)H:quinone oxidoreductase (NQO-1). The nuclear factor (NF)-erythroid-derived 2 (E2)-related factor 2 (Nrf2) modulates the transcriptional activity of antioxidant response element (ARE)-driven genes, such as HO-1 and NQO-1. Here, we show that the iron oxide NPs activate Nrf2, leading to its increased nuclear accumulation and enhanced Nrf2 DNA-binding activity in NP-treated RAW 264.7 macrophages. Iron solubility and acellular hydroxyl radical generation depend on the physical properties of the NPs, especially crystalline diameter; however, these properties are weakly linked to the activation of cellular signaling of Nrf2 and the expression of oxidative stress markers. Overall, our work shows for the first time that iron oxide nanoparticles induce cellular marker genes of oxidative stress and that this effect is transcriptionally mediated through the Nrf2-ARE signaling pathway in macrophages.

  1. Physicochemical properties of iron oxide nanoparticles that contribute to cellular ROS-dependent signaling and acellular production of hydroxyl radical

    PubMed Central

    Vogel, Christoph F.A.; Charrier, Jessica G.; Wu, Dalei; McFall, Alexander S.; Li, Wen; Abid, Aamir; Kennedy, Ian M.; Anastasio, Cort

    2017-01-01

    While nanoparticles (NPs) are increasingly used in a variety of consumer products and medical applications, some of these materials have potential health concerns. Macrophages are the primary responders to particles that initiate oxidative stress and inflammatory reactions. Here we utilized six flame-synthesized, engineered iron oxide NPs with various physicochemical properties (e.g., Fe oxidation state and crystal size) to study their interactions with RAW 264.7 macrophages, their iron solubilities, and their abilities to produce hydroxyl radical in an acellular assay. Both iron solubility and hydroxyl radical production varied between NPs depending on crystalline diameter and surface area of the particles, but not on iron oxidation state. Macrophage treatment with the iron oxide NPs showed a dose-dependent increase of heme oxygenase 1 (HO-1) and NAD(P)H:quinone oxidoreductase (NQO-1). The nuclear factor (NF)-erythroid-derived 2 (E2)-related factor 2 (Nrf2) modulates the transcriptional activity of antioxidant response element (ARE)-driven genes such as HO-1 and NQO-1. Here, we show that the iron oxide NPs activate Nrf2, leading to its increased nuclear accumulation and enhanced Nrf2 DNA-binding activity in NP-treated RAW 264.7 macrophages. Iron solubility and acellular hydroxyl radical generation depend on the physical properties of the NPs, especially crystalline diameter; however, these properties are weakly linked to the activation of cellular signaling of Nrf2 and the expression of oxidative stress markers. Overall, our work shows for the first time that iron oxide nanoparticles induce cellular marker genes of oxidative stress and that this effect is transcriptionally mediated through the Nrf2-ARE signaling pathway in macrophages. PMID:27558512

  2. Semiconductor Oxide Interface States.

    DTIC Science & Technology

    1981-05-01

    essentially coincides. The density of state curves of the interface states based on the Terman method are shown in Fig. 7 for the three conditions: (i...terrestrial applications. A visit was made at the NASA Lewis Research Center with Dr. Brandhorst on August 31, 1979. The PI has attended DOE meetings on

  3. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Cobalt iron manganese oxide... Significant New Uses for Specific Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid... substance identified generically as cobalt iron manganese oxide, carboxylic acid-modified (PMN P-12-35) is...

  4. Molecular insights of oxidation process of iron nanoparticles: spectroscopic, magnetic, and microscopic evidence.

    PubMed

    Kumar, Naresh; Auffan, Mélanie; Gattacceca, Jérôme; Rose, Jérôme; Olivi, Luca; Borschneck, Daniel; Kvapil, Petr; Jublot, Michael; Kaifas, Delphine; Malleret, Laure; Doumenq, Pierre; Bottero, Jean-Yves

    2014-12-02

    Oxidation behavior of nano-Fe(0) particles in an anoxic environment was determined using different state-of-the-art analytical approaches, including high resolution transmission electron microscopy (HR-TEM) combined with energy filtered transmission electron microscopy (EFTEM), X-ray absorption spectroscopy (XAS), and magnetic measurements. Oxidation in controlled experiments was compared in standard double distilled (DD) water, DD water spiked with trichloroethene (TCE), and TCE contaminated site water. Using HR-TEM and EFTEM, we observed a surface oxide layer (∼3 nm) formed immediately after the particles were exposed to water. XAS analysis followed the dynamic change in total metallic iron concentration and iron oxide concentration for the experimental duration of 35 days. The metallic iron concentration in nano-Fe(0) particles exposed to water, was ∼40% after 35 days; in contrast, the samples containing TCE were reduced to ∼15% and even to nil in the case of TCE contaminated site water, suggesting that the contaminants enhance the oxidation of nano-Fe(0). Frequency dependence measurements confirmed the formation of superparamagnetic particles in the system. Overall, our results suggest that nano-Fe(0) oxidized via the Fe(0) - Fe(OH)2 - Fe3O4 - (γ-Fe2O3) route and the formation of superparamagnetic maghemite nanoparticles due to disruption of the surface oxide layer.

  5. Formation of water-soluble iron oxide nanoparticles derived from iron storage protein.

    PubMed

    Tominaga, Masato; Han, Li; Wang, Lingyan; Maye, Mathew M; Luo, Jin; Kariuki, Nancy; Zhong, Chuan-Jian

    2004-09-01

    This paper reports novel findings of an investigation of the formation of water-soluble iron oxide nanoparticles from iron-storage protein ferritin. The strategy couples thermal removal of the protein shell on a planar substrate and subsequent sonication in aqueous solution under controlled temperature. Advantages of using ferritin as a precursor include well-defined core size, core composition, water-solubility and processibility. The formation of the nanoparticles was characterized using TEM, UV-Vis and FTIR techniques. Iron oxide nanoparticles in the size range of 5-20 nm diameters were produced. In addition to thermal treatment conditions, the sonication temperature of the nanoparticles in water was found to play an important role in determining the resulting particle size. This simple and effective route has important implications to the design of composite nanoparticles for potential magnetic, catalytic, biomedical sensing and other nanotechnological applications.

  6. Iron Kinetics and Evolution of Microbial Populations in Low-pH, Ferrous Iron-Oxidizing Bioreactors.

    PubMed

    Jones, Rose M; Johnson, D Barrie

    2016-08-02

    Iron-rich, acidic wastewaters are commonplace pollutants associated with metal and coal mining. Continuous-flow bioreactors were commissioned and tested for their capacities to oxidize ferrous iron in synthetic and actual acid mine drainage waters using (initially) pure cultures of the recently described acidophilic, iron-oxidizing heterotrophic bacterium Acidithrix ferrooxidans grown in the presence of glucose and yeast extract. The bioreactors became rapidly colonized by this bacterium, which formed macroscopic streamer growths in the flowing waters. Over 97% of ferrous iron in pH 2.0-2.2 synthetic mine water was oxidized (at up to 225 mg L(-1) h(-1)) at dilution rates (D) of 0.6 h(-1). Rates of iron oxidation decreased with pH but were still significant, with influent liquors as low as pH 1.37. When fed with actual mine water, >90% of ferrous iron was oxidized at D values of 0.4 h(-1), and microbial communities within the bioreactors changed over time, with Atx. ferrooxidans becoming increasingly displaced by the autotrophic iron-oxidizing acidophiles Ferrovum myxofaciens, Acidithiobacillus ferrivorans, and Leptospirillum ferrooxidans (which were all indigenous to the mine water), although this did not have a negative impact on net ferrous-iron oxidation. The results confirmed the potential of using a heterotrophic acidophile to facilitate the rapid commissioning of iron-oxidizing bioreactors and illustrated how microbial communities within them can evolve without compromising the performances of the bioreactors.

  7. Oxidative stress, HDL functionality and effects of intravenous iron administration in women with iron deficiency anemia.

    PubMed

    Meroño, Tomás; Dauteuille, Carolane; Tetzlaff, Walter; Martín, Maximiliano; Botta, Eliana; Lhomme, Marie; Saez, María Soledad; Sorroche, Patricia; Boero, Laura; Arbelbide, Jorge; Chapman, M John; Kontush, Anatol; Brites, Fernando

    2017-04-01

    Iron deficiency anemia (IDA) affects around 20-30% of adults worldwide. An association between IDA and cardiovascular disease (CVD) has been reported. Oxidative stress, inflammation and low concentration of high-density lipoproteins (HDL) were implicated on endothelial dysfunction and CVD in IDA. We studied the effects of iron deficiency and of an intravenous iron administration on oxidative stress and HDL characteristics in IDA women. Two studies in IDA women are presented: a case-control study, including 18 patients and 18 age-matched healthy women, and a follow-up study 72hr after the administration of intravenous iron (n = 16). Lipids, malondialdehyde, cholesteryl ester transfer protein (CETP), paraoxonase-1 (PON-1) and HDL chemical composition and functionality (cholesterol efflux and antioxidative activity) were measured. Cell cholesterol efflux from iron-deficient macrophages to a reference HDL was also evaluated. IDA patients showed higher triglycerides and CETP activity and lower HDL-C than controls (all p < 0.001). HDL particles from IDA patients showed higher triglyceride content (+30%,p < 0.05) and lower antioxidative capacity (-23%,p < 0.05). Although HDL-mediated cholesterol efflux was similar between the patients and controls, iron deficiency provoked a significant reduction in macrophage cholesterol efflux (-25%,p < 0.05). Arylesterase activity of PON-1 was significantly lower in IDA patients than controls (-16%,p < 0.05). The intravenous administration of iron was associated with a decrease in malondialdehyde levels and an increase in arylesterase activity of PON-1 (-22% and +18%, respectively, p < 0.05). IDA is associated with oxidative stress and functionally deficient HDL particles. It remains to be determined if such alterations suffice to impair endothelial function in IDA. Copyright © 2016 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.

  8. Transformation of vivianite by anaerobic nitrate-reducing iron-oxidizing bacteria.

    PubMed

    Miot, J; Benzerara, K; Morin, G; Bernard, S; Beyssac, O; Larquet, E; Kappler, A; Guyot, F

    2009-06-01

    In phosphate-rich environments, vivianite (Fe(II)(3)(PO(4))(2), 8H(2)O) is an important sink for dissolved Fe(II) and is considered as a very stable mineral due to its low solubility at neutral pH. In the present study, we report the mineralogical transformation of vivianite in cultures of the nitrate-reducing iron-oxidizing bacterial strain BoFeN1 in the presence of dissolved Fe(II). Vivianite was first transformed into a greenish phase consisting mostly of an amorphous mixed valence Fe-phosphate. This precipitate became progressively orange and the final product of iron oxidation consisted of an amorphous Fe(III)-phosphate. The sub-micrometer analysis by scanning transmission X-ray microscopy of the iron redox state in samples collected at different stages of the culture indicated that iron was progressively oxidized at the contact of the bacteria and at a distance from the cells in extracellular minerals. Iron oxidation in the extracellular minerals was delayed by a few days compared with cell-associated Fe-minerals. This led to strong differences of Fe redox in between these two types of minerals and finally to local heterogeneities of redox within the sample. In the absence of dissolved Fe(II), vivianite was not significantly transformed by BoFeN1. Whereas Fe(II) oxidation at the cell contact is most probably directly catalyzed by the bacteria, vivianite transformation at a distance from the cells might result from oxidation by nitrite. In addition, processes leading to the export of Fe(III) from bacterial oxidation sites to extracellular minerals are discussed including some involving colloids observed by cryo-transmission electron microscopy in the culture medium.

  9. Simultaneous reductive dissolution of iron oxide and oxidation of iodide in ice.

    NASA Astrophysics Data System (ADS)

    Kim, Kitae; Choi, Wonyong

    2015-04-01

    Iron is an important trace element controlling the metabolism and growth of all kinds of living species. Especially, the bio-availability of iron has been regarded as the limiting factor for primary productivity in HNLC (High Nutrients Low Chlorophyll) regions including Southern ocean. The dissolution of iron oxide provides enhanced the bio-availability of iron for phytoplankton growth. The halogen chemistry in polar regions is related to various important environmental processes such as Antarctic Ozone Depletion Event(ODE), mercury depletion, oxidative processes in atmosphere, and the formation of CCN (Cloud Condensation Nuclei). In this study, we investigated the reductive dissolution of iron oxide particles to produce Fe(II)aq and simultaneous oxidation of I- (iodide) to I3- (tri-iodide) in ice phase under UV irradiation or dark condition. The reductive generation of Fe(II)aq from iron oxides and oxidation of iodide to I3- were negligible in water but significantly accelerated in frozen solution both in the presence and absence of light. The enhanced reductive generation of Fe(II)aq and oxidative formation of I3- in ice were observed regardless of the various types of iron oxides [hematite (α-Fe2O3) maghemite (γ- Fe2O3), goethite (α-FeOOH), lepidocrocite (γ-FeOOH) and, magnetite (Fe3O4)]. We explained that the enhanced redox production of Fe(II)aq and I3- in ice is contributed to the freeze concentration of iodides, protons, and dissolved oxygen in the unfrozen solution. When the concentration of both iodides and protons were raised by 10-fold each, the formation of Fe(II)aq in water under UV irradiation was approached to those in ice. The outdoor experiments were carried out under ambient solar radiation in winter season of mid-latitude (Pohang, Korea: 36°N latitude) and also confirmed that the production of Fe(II)aq via reductive dissolution of iron oxide and I3- generation via I- oxidation were enhanced in frozen solution. These results suggest that iron

  10. Iron oxide nanotubes synthesized via template-based electrodeposition

    NASA Astrophysics Data System (ADS)

    Lim, Jin-Hee; Min, Seong-Gi; Malkinski, Leszek; Wiley, John B.

    2014-04-01

    Considerable effort has been invested in the development of synthetic methods for the preparation iron oxide nanostructures for applications in nanotechnology. While a variety of structures have been reported, only a few studies have focused on iron oxide nanotubes. Here, we present details on the synthesis and characterization of iron oxide nanotubes along with a proposed mechanism for FeOOH tube formation. The FeOOH nanotubes, fabricated via a template-based electrodeposition method, are found to exhibit a unique inner-surface. Heat treatment of these tubes under oxidizing or reducing atmospheres can produce either hematite (α-Fe2O3) or magnetite (Fe3O4) structures, respectively. Hematite nanotubes are composed of small nanoparticles less than 20 nm in diameter and the magnetization curves and FC-ZFC curves show superparamagnetic properties without the Morin transition. In the case of magnetite nanotubes, which consist of slightly larger nanoparticles, magnetization curves show ferromagnetism with weak coercivity at room temperature, while FC-ZFC curves exhibit the Verwey transition at 125 K.Considerable effort has been invested in the development of synthetic methods for the preparation iron oxide nanostructures for applications in nanotechnology. While a variety of structures have been reported, only a few studies have focused on iron oxide nanotubes. Here, we present details on the synthesis and characterization of iron oxide nanotubes along with a proposed mechanism for FeOOH tube formation. The FeOOH nanotubes, fabricated via a template-based electrodeposition method, are found to exhibit a unique inner-surface. Heat treatment of these tubes under oxidizing or reducing atmospheres can produce either hematite (α-Fe2O3) or magnetite (Fe3O4) structures, respectively. Hematite nanotubes are composed of small nanoparticles less than 20 nm in diameter and the magnetization curves and FC-ZFC curves show superparamagnetic properties without the Morin transition

  11. Iron-oxide labeling of hematogenous macrophages in a model of experimental autoimmune encephalomyelitis and the contribution to signal loss in fast imaging employing steady state acquisition (FIESTA) images.

    PubMed

    Oweida, Ayman J; Dunn, Elizabeth A; Karlik, Stephen J; Dekaban, Gregory A; Foster, Paula J

    2007-07-01

    To determine the contribution of blood-derived macrophages to the signal loss observed in MR images of inflammatory lesions in experimental autoimmune encephalomyelitis (EAE). A relapsing-remitting form of EAE was induced in transgenic mice that express enhanced green fluorescent protein (EGFP) specifically in hematopoietic cells of the myelomonocytic lineage. Animals were injected with Feridex, a superparamagnetic iron oxide (SPIO) nanoparticle, 24 hours prior to in vivo MRI. MRI was performed using a 1.5T whole-body scanner; a high-performance, custom-built gradient coil insert; and a 3D steady-state free precession (SSFP) imaging pulse sequence. Comparisons were made between MR images and corresponding anti-GFP and Perl's Prussian blue (PPB)-stained brain sections. MR images revealed the presence of discrete regions of signal loss throughout the brains of EAE animals that were administered Feridex. Histological staining showed that regions of signal loss on MR images corresponded anatomically with regions of PPB- and GFP-positive cells. This experiment provides the first direct evidence that macrophages of hematogenous origin are labeled with SPIO after intravenous administration of Feridex, and contribute to the regions of signal loss detected in MR images of EAE brain. Copyright 2007 Wiley-Liss, Inc.

  12. Oxidation, carburization and/or sulfidation resistant iron aluminide alloy

    DOEpatents

    Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier S.; Hajaligol, Mohammad R.; Lilly, Jr., A. Clifton

    2003-08-19

    The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, .ltoreq.1% Cr and either .gtoreq.0.05% Zr or Zro.sub.2 stringers extending perpendicular to an exposed surface of the heating element or .gtoreq.0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Zr, .ltoreq.1% C, .ltoreq.0.1% B. .ltoreq.30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, .ltoreq.1% oxygen, .ltoreq.3% Cu, balance Fe.

  13. The Molecular Mechanism of Iron(III) Oxide Nucleation.

    PubMed

    Scheck, Johanna; Wu, Baohu; Drechsler, Markus; Rosenberg, Rose; Van Driessche, Alexander E S; Stawski, Tomasz M; Gebauer, Denis

    2016-08-18

    A molecular understanding of the formation of solid phases from solution would be beneficial for various scientific fields. However, nucleation pathways are still not fully understood, whereby the case of iron (oxyhydr)oxides poses a prime example. We show that in the prenucleation regime, thermodynamically stable solute species up to a few nanometers in size are observed, which meet the definition of prenucleation clusters. Nucleation then is not governed by a critical size, but rather by the dynamics of the clusters that are forming at the distinct nucleation stages, based on the chemistry of the linkages within the clusters. This resolves a longstanding debate in the field of iron oxide nucleation, and the results may generally apply to oxides forming via hydrolysis and condensation. The (molecular) understanding of the chemical basis of phase separation is paramount for, e.g., tailoring size, shape and structure of novel nanocrystalline materials.

  14. Discovery of the recoverable high-pressure iron oxide Fe4O5.

    PubMed

    Lavina, Barbara; Dera, Przemyslaw; Kim, Eunja; Meng, Yue; Downs, Robert T; Weck, Philippe F; Sutton, Stephen R; Zhao, Yusheng

    2011-10-18

    Phases of the iron-oxygen binary system are significant to most scientific disciplines, directly affecting planetary evolution, life, and technology. Iron oxides have unique electronic properties and strongly interact with the environment, particularly through redox reactions. The iron-oxygen phase diagram therefore has been among the most thoroughly investigated, yet it still holds striking findings. Here, we report the discovery of an iron oxide with formula Fe(4)O(5), synthesized at high pressure and temperature. The previously undescribed phase, stable from 5 to at least 30 GPa, is recoverable to ambient conditions. First-principles calculations confirm that the iron oxide here described is energetically more stable than FeO + Fe(3)O(4) at pressure greater than 10 GPa. The calculated lattice constants, equation of states, and atomic coordinates are in excellent agreement with experimental data, confirming the synthesis of Fe(4)O(5). Given the conditions of stability and its composition, Fe(4)O(5) is a plausible accessory mineral of the Earth's upper mantle. The phase has strong ferrimagnetic character comparable to magnetite. The ability to synthesize the material at accessible conditions and recover it at ambient conditions, along with its physical properties, suggests a potential interest in Fe(4)O(5) for technological applications.

  15. Cellular Precipitates Of Iron Oxide in Olivine in a Stratospheric Interplanetary Dust Particle

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1996-01-01

    The petrology of a massive olivine-sulphide interplanetary dust particle shows melting of Fe,Ni-sulphide plus complete loss of sulphur and subsequent quenching to a mixture of iron-oxides and Fe,Ni-metal. Oxidation of the fayalite component in olivine produced maghemite discs and cellular intergrowths with olivine and rare andradite-rich garnet. Cellular reactions require no long-range solid-state diffusion and are kinetically favourable during pyrometamorphic oxidation. Local melting of the cellular intergrowths resulted in three dimensional symplectic textures. Dynamic pyrometamorphism of this asteroidal particle occurred at approx. 1100 C during atmospheric entry flash (5-15 s) heating.

  16. Cellular Precipitates Of Iron Oxide in Olivine in a Stratospheric Interplanetary Dust Particle

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1996-01-01

    The petrology of a massive olivine-sulphide interplanetary dust particle shows melting of Fe,Ni-sulphide plus complete loss of sulphur and subsequent quenching to a mixture of iron-oxides and Fe,Ni-metal. Oxidation of the fayalite component in olivine produced maghemite discs and cellular intergrowths with olivine and rare andradite-rich garnet. Cellular reactions require no long-range solid-state diffusion and are kinetically favourable during pyrometamorphic oxidation. Local melting of the cellular intergrowths resulted in three dimensional symplectic textures. Dynamic pyrometamorphism of this asteroidal particle occurred at approx. 1100 C during atmospheric entry flash (5-15 s) heating.

  17. Oxide Dispersion Strengthened Iron Aluminide by CVD Coated Powders

    SciTech Connect

    Asit Biswas Andrew J. Sherman

    2006-09-25

    This I &I Category2 program developed chemical vapor deposition (CVD) of iron, aluminum and aluminum oxide coated iron powders and the availability of high temperature oxidation, corrosion and erosion resistant coating for future power generation equipment and can be used for retrofitting existing fossil-fired power plant equipment. This coating will provide enhanced life and performance of Coal-Fired Boilers components such as fire side corrosion on the outer diameter (OD) of the water wall and superheater tubing as well as on the inner diameter (ID) and OD of larger diameter headers. The program also developed a manufacturing route for readily available thermal spray powders for iron aluminide coating and fabrication of net shape component by powder metallurgy route using this CVD coated powders. This coating can also be applid on jet engine compressor blade and housing, industrial heat treating furnace fixtures, magnetic electronic parts, heating element, piping and tubing for fossil energy application and automotive application, chemical processing equipment , heat exchanger, and structural member of aircraft. The program also resulted in developing a new fabrication route of thermal spray coating and oxide dispersion strengthened (ODS) iron aluminide composites enabling more precise control over material microstructures.

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

    PubMed Central

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

    2017-01-01

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

  19. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

    SciTech Connect

    Sohn, I.; Fruehan, R.J.

    2006-04-15

    The reduction of iron oxide/carbon composite pellets with hydrogen at 900{sup o}C to 1000{sup o}C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 degrees C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H{sub 2O generated from the reduction of Fe{sub 2}O{sub 3} by H-2 was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50% reduction of the iron oxide.

  20. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

    NASA Astrophysics Data System (ADS)

    Sohn, I.; Fruehan, R. J.

    2006-04-01

    The reduction of iron oxide/carbon composite pellets with hydrogen at 900 °C to 1000 °C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 °C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H2O generated from the reduction of Fe2O3 by H2 was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50 pct reduction of the iron oxide.

  1. Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks

    PubMed Central

    Jones, J. Graham; Warner, C. G.

    1972-01-01

    Graham Jones, J., and Warner, C. G. (1972).Brit. J. industr. Med.,29, 169-177. Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks. Occupational and medical histories, smoking habits, respiratory symptoms, chest radiographs, and ventilatory capacities were studied in 14 steelworkers employed as deseamers of steel ingots for periods of up to 16 years. The men were exposed for approximately five hours of each working shift to fume concentrations ranging from 1·3 to 294·1 mg/m3 made up mainly of iron oxide with varying proportions of chromium oxide and nickel oxide. Four of the men, with 14 to 16 years' exposure, showed radiological evidence of pneumoconiosis classified as ILO categories 2 or 3. Of these, two had pulmonary function within the normal range and two had measurable loss of function, moderate in one case and mild in the other. Many observers would diagnose these cases as siderosis but the authors consider that this term should be reserved for cases exposed to pure iron compounds. The correct diagnosis is mixed-dust pneumoconiosis and the loss of pulmonary function is caused by the effects of the mixture of metallic oxides. It is probable that inhalation of pure iron oxide does not cause fibrotic pulmonary changes, whereas the inhalation of iron oxide plus certain other substances obviously does. Images PMID:5021996

  2. Iron metabolism: State of the art.

    PubMed

    Daher, R; Karim, Z

    2017-09-01

    Iron homeostasis relies on the amount of its absorption by the intestine and its release from storage sites, the macrophages. Iron homeostasis is also dependent on the amount of iron used for the erythropoiesis. Hepcidin, which is synthesized predominantly by the liver, is the main regulator of iron metabolism. Hepcidin reduces serum iron by inhibiting the iron exporter, ferroportin expressed both tissues, the intestine and the macrophages. In addition, in the enterocytes, hepcidin inhibits the iron influx by acting on the apical transporter, DMT1. A defect of hepcidin expression leading to the appearance of a parenchymal iron overload may be genetic or secondary to dyserythropoiesis. The exploration of genetic hemochromatosis has revealed the involvement of several genes, including the recently described BMP6. Non-transfusional secondary hemochromatosis is due to hepcidin repression by cytokines, in particular the erythroferone factor that is produced directly by the erythroid precursors. Iron overload is correlated with the appearance of a free form of iron called NTBI. The influx of NTBI seems to be mediated by ZIP14 transporter in the liver and by calcium channels in the cardiomyocytes. Beside the liver, hepcidin is expressed at lesser extent in several extrahepatic tissues where it plays its ancestral role of antimicrobial peptide. In the kidney, hepcidin modulates defense barriers against urinary tract infections. In the heart, hepcidin maintains tissue iron homeostasis by an autocrine regulation of ferroprotine expression on the surface of cardiomyocytes. In conclusion, hepcidin remains a promising therapeutic tool in various iron pathologies. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  3. Nitrative and oxidative modifications of enolase are associated with iron in iron-overload rats and in vitro.

    PubMed

    Lu, Naihao; Li, Xueli; Li, Jinyang; Xu, Wenjing; Li, Hailing; Gao, Zhonghong

    2011-03-01

    Iron overload is one of the most common iron-related toxicities, and liver is the major organ that is injured. Although oxidative stress is well accepted in the pathological mechanism of iron overload, nitrative modification in liver and the role of iron are relatively unknown. In this work, the nitrative and oxidative stress in liver was investigated in an iron-overload rat model. It was found that after 15 weeks of iron dextran administration, consistent with the increase of iron content in rat liver, both protein tyrosine nitration and protein oxidation were clearly elevated. By means of immunoprecipitation analysis, it was found that enolase nitration and oxidation status were significantly increased in iron-overload liver, whereas both α-enolase expression and activity were clearly decreased. The effects of different forms of iron on NaNO(2)-H(2)O(2)- and peroxynitrite (ONOO(-))-dependent enolase nitration and oxidation were further investigated in vitro to elucidate the possible role of iron in enolase dysfunction in vivo. Compared with EDTA-Fe(III), ferric citrate, and ferritin, heme (hemin and hemoglobin) showed higher efficiency in catalyzing protein nitration in both models. Besides the major contribution of free iron (Fe(2+) and Fe(3+)) to catalyze protein oxidation, Fe(2+) also directly acted as a competitive inhibitor and produced a significant decrease in enzyme activity. These results suggest that the existence of various forms of iron is an important contributing factor to the elevated nitrative/oxidative modifications and diminished activity of α-enolase in the development and progress of iron-overload-associated syndromes.

  4. The oxidation behavior of ODS iron aluminides

    SciTech Connect

    Pint, B.A.; Tortorelli, P.F.; Wright, I.G.

    1996-05-01

    Oxide-dispersed Fe-28at.%Al-2%Cr alloys were produced by a powder metallurgy technique followed by hot extrusion. A variety of stable oxides were added to the base alloy to assess the effect of these dopants on the oxidation behavior at 1200{degrees}C in air and O{sub 2}. An Al{sub 2}O{sub 3} dispersion flattened the {alpha}-Al{sub 2}O{sub 3} scale, but produced none of the other reactive element effects and had an adverse influence on the long-term oxidation behavior. A Y{sub 2}O{sub 3} dispersion improved the alumina scale adhesion relative to a Zr alloy addition at 1200{degrees} and 1300{degrees}C. However, the Y{sub 2}O{sub 3} dispersion was not as effective in improving scale adhesion in Fe{sub 3}Al as it is in FeCrAl. This inferior performance is attributed to a larger amount of interfacial void formation on ODS Fe{sub 3}Al.

  5. The global oxidation state of the upper oceanic crust

    NASA Astrophysics Data System (ADS)

    Rutter, J.; Harris, M.; Coggon, R. M.; Alt, J.; Smith-Duque, C. E.; Teagle, D. A.

    2012-12-01

    The oxidation state of the oceanic crust is an important component of the Earth system. The widespread oxidation of the crust is a major contributor to the redox state of the mantle due to the subduction of hydrothermally altered oceanic crust, which supplies 10 - 25 % of the net ferric iron flux to the global mantle Fe3+/FeTOT budget (Lécuyer and Ricard, 1999). Secondly, the degree of oxidation of the upper oceanic crust provides a measure of the biomass of microbial life sub-basement (Bach and Edwards, 2003). Thirdly, oxidation state analyses of oceanic basalt give information on the environment and relative timings of local hydrothermal alteration events. To date comprehensive measurements of Fe3+/FeTOT for the oceanic crust are lacking. Post crystallisation oxidation processes, occurring predominantly in the upper basaltic layers of the crust, elevate ratios of ferric to total iron (Fe3+/FeTOT) from mantle levels of 0.16 ± 0.01 (Cottrell and Kelley, 2011). Ferrous (Fe2+/) iron is oxidised to ferric (Fe3+/) iron during reaction with oxidised seawater, which circulates through oceanic crust for tens of millions of years following crustal formation. This study integrates published data with new analyses from six ocean crustal boreholes to categorise the global oxidation state of the upper crust. Samples range from <1 to 129 Ma, and represent basalt from medium to superfast spreading centres, depths between <100 - 2000 mbsf, and at a variety of sedimentary cover rates and thicknesses. Results show that by 1 Ma, the Fe3+/FeTOT ratio of the bulk crust is already raised to an average of 0.28 ± 0.07, implying that the oxidation state is established very early in the lifetime of the ocean crust. Post 1 Ma, Fe3+/FeTOT ratios are more variable, reflecting the effects of prolonged exposure to circulating seawater, but are on average ~0.35.

  6. Mutations and environmental factors affecting regulation of riboflavin synthesis and iron assimilation also cause oxidative stress in the yeast Pichia guilliermondii.

    PubMed

    Boretsky, Yuriy R; Protchenko, Olga V; Prokopiv, Tetiana M; Mukalov, Igor O; Fedorovych, Daria V; Sibirny, Andriy A

    2007-10-01

    Iron deficiency causes oversynthesis of riboflavin in several yeast species, known as flavinogenic yeasts. However, the mechanisms of such regulation are not known. We found that mutations causing riboflavin overproduction and iron hyperaccumulation (rib80, rib81 and hit1), as well as cobalt excess or iron deficiency all provoke oxidative stress in the Pichia guilliermondii yeast. Iron content in the cells, production both of riboflavin and malondialdehyde by P. guilliermondii wild type and hit1 mutant strains depend on a type of carbon source used in cultivation media. The data suggest that the regulation of riboflavin biosynthesis and iron assimilation in P. guilliermondii are linked with cellular oxidative state.

  7. Iron-Mediated Lysosomal Membrane Permeabilization in Ethanol-Induced Hepatic Oxidative Damage and Apoptosis: Protective Effects of Quercetin.

    PubMed

    Li, Yanyan; Chen, Man; Xu, Yanyan; Yu, Xiao; Xiong, Ting; Du, Min; Sun, Jian; Liu, Liegang; Tang, Yuhan; Yao, Ping

    2016-01-01

    Iron, in its free ferrous states, can catalyze Fenton reaction to produce OH∙, which is recognized as a crucial role in the pathogenesis of alcoholic liver diseases (ALD). As a result of continuous decomposition of iron-containing compounds, lysosomes contain a pool of redox-active iron. To investigate the important role of intralysosomal iron in alcoholic liver injury and the potential protection of quercetin, male C57BL/6J mice fed by Lieber De Carli diets containing ethanol (30% of total calories) were cotreated by quercetin or deferoxamine (DFO) for 15 weeks and ethanol-incubated mice primary hepatocytes were pretreated with FeCl3, DFO, and bafilomycin A1 at their optimal concentrations and exposure times. Chronic ethanol consumption caused an evident increase in lysosomal redox-active iron accompanying sustained oxidative damage. Iron-mediated ROS could trigger lysosomal membrane permeabilization (LMP) and subsequent mitochondria apoptosis. The hepatotoxicity was attenuated by reducing lysosomal iron while being exacerbated by escalating lysosomal iron. Quercetin substantially alleviated the alcoholic liver oxidative damage and apoptosis by decreasing lysosome iron and ameliorating iron-mediated LMP, which provided a new prospective of the use of quercetin against ALD.

  8. Iron-Mediated Lysosomal Membrane Permeabilization in Ethanol-Induced Hepatic Oxidative Damage and Apoptosis: Protective Effects of Quercetin

    PubMed Central

    Li, Yanyan; Chen, Man; Xu, Yanyan; Yu, Xiao; Xiong, Ting; Du, Min; Sun, Jian; Liu, Liegang; Tang, Yuhan; Yao, Ping

    2016-01-01

    Iron, in its free ferrous states, can catalyze Fenton reaction to produce OH∙, which is recognized as a crucial role in the pathogenesis of alcoholic liver diseases (ALD). As a result of continuous decomposition of iron-containing compounds, lysosomes contain a pool of redox-active iron. To investigate the important role of intralysosomal iron in alcoholic liver injury and the potential protection of quercetin, male C57BL/6J mice fed by Lieber De Carli diets containing ethanol (30% of total calories) were cotreated by quercetin or deferoxamine (DFO) for 15 weeks and ethanol-incubated mice primary hepatocytes were pretreated with FeCl3, DFO, and bafilomycin A1 at their optimal concentrations and exposure times. Chronic ethanol consumption caused an evident increase in lysosomal redox-active iron accompanying sustained oxidative damage. Iron-mediated ROS could trigger lysosomal membrane permeabilization (LMP) and subsequent mitochondria apoptosis. The hepatotoxicity was attenuated by reducing lysosomal iron while being exacerbated by escalating lysosomal iron. Quercetin substantially alleviated the alcoholic liver oxidative damage and apoptosis by decreasing lysosome iron and ameliorating iron-mediated LMP, which provided a new prospective of the use of quercetin against ALD. PMID:27057276

  9. Intratumoral Iron Oxide Nanoparticle Hyperthermia and Radiation Cancer Treatment.

    PubMed

    Hoopes, Pj; Strawbridge, Rr; Gibson, Uj; Zeng, Q; Pierce, Ze; Savellano, M; Tate, Ja; Ogden, Ja; Baker, I; Ivkov, R; Foreman, Ar

    2007-02-13

    The potential synergism and benefit of combined hyperthermia and radiation for cancer treatment is well established, but has yet to be optimized clinically. Specifically, the delivery of heat via external arrays /applicators or interstitial antennas has not demonstrated the spatial precision or specificity necessary to achieve appropriate a highly positive therapeutic ratio. Recently, antibody directed and possibly even non-antibody directed iron oxide nanoparticle hyperthermia has shown significant promise as a tumor treatment modality. Our studies are designed to determine the effects (safety and efficacy) of iron oxide nanoparticle hyperthermia and external beam radiation in a murine breast cancer model. MTG-B murine breast cancer cells (1 × 10(6)) were implanted subcutaneous in 7 week-old female C3H/HeJ mice and grown to a treatment size of 150 mm(3) +/- 50 mm(3). Tumors were then injected locally with iron oxide nanoparticles and heated via an alternating magnetic field (AMF) generator operated at approximately 160 kHz and 400 - 550 Oe. Tumor growth was monitored daily using standard 3-D caliper measurement technique and formula. specific Mouse tumors were heated using a cooled, 36 mm diameter square copper tube induction coil which provided optimal heating in a 1 cm wide region in the center of the coil. Double dextran coated 80 nm iron oxide nanoparticles (Triton Biosystems) were used in all studies. Intra-tumor, peri-tumor and rectal (core body) temperatures were continually measured throughout the treatment period. Preliminary in vivo nanoparticle-AMF hyperthermia (167 KHz and 400 or 550 Oe) studies demonstrated dose responsive cytotoxicity which enhanced the effects of external beam radiation. AMF associated eddy currents resulted in nonspecific temperature increases in exposed tissues which did not contain nanoparticles, however these effects were minor and not injurious to the mice. These studies also suggest that iron oxide nanoparticle hyperthermia

  10. Intratumoral iron oxide nanoparticle hyperthermia and radiation cancer treatment

    NASA Astrophysics Data System (ADS)

    Hoopes, P. J.; Strawbridge, R. R.; Gibson, U. J.; Zeng, Q.; Pierce, Z. E.; Savellano, M.; Tate, J. A.; Ogden, J. A.; Baker, I.; Ivkov, R.; Foreman, A. R.

    2007-02-01

    The potential synergism and benefit of combined hyperthermia and radiation for cancer treatment is well established, but has yet to be optimized clinically. Specifically, the delivery of heat via external arrays /applicators or interstitial antennas has not demonstrated the spatial precision or specificity necessary to achieve appropriate a highly positive therapeutic ratio. Recently, antibody directed and possibly even non-antibody directed iron oxide nanoparticle hyperthermia has shown significant promise as a tumor treatment modality. Our studies are designed to determine the effects (safety and efficacy) of iron oxide nanoparticle hyperthermia and external beam radiation in a murine breast cancer model. Methods: MTG-B murine breast cancer cells (1 x 106) were implanted subcutaneous in 7 week-old female C3H/HeJ mice and grown to a treatment size of 150 mm3 +/- 50 mm3. Tumors were then injected locally with iron oxide nanoparticles and heated via an alternating magnetic field (AMF) generator operated at approximately 160 kHz and 400 - 550 Oe. Tumor growth was monitored daily using standard 3-D caliper measurement technique and formula. specific Mouse tumors were heated using a cooled, 36 mm diameter square copper tube induction coil which provided optimal heating in a 1 cm wide region in the center of the coil. Double dextran coated 80 nm iron oxide nanoparticles (Triton Biosystems) were used in all studies. Intra-tumor, peri-tumor and rectal (core body) temperatures were continually measured throughout the treatment period. Results: Preliminary in vivo nanoparticle-AMF hyperthermia (167 KHz and 400 or 550 Oe) studies demonstrated dose responsive cytotoxicity which enhanced the effects of external beam radiation. AMF associated eddy currents resulted in nonspecific temperature increases in exposed tissues which did not contain nanoparticles, however these effects were minor and not injurious to the mice. These studies also suggest that iron oxide nanoparticle

  11. Biogenic nanosized iron oxides obtained from cultivation of iron bacteria from the genus Leptothrix.

    PubMed

    Nedkov, I; Slavov, L; Angelova, R; Blagoev, B; Kovacheva, D; Abrashev, M V; Iliev, M; Groudeva, V

    2016-10-01

    A detailed investigation of nanostructured iron oxides/(oxy)hydroxides gathered after cultivation of bacteria from the genus Leptothrix as iron (II) oxidizers is presented. A specific type of medium is selected for the cultivation of the bacteria. Results for sediment powder and bio-film on glass substrate samples from the same media are discussed. XRD, Raman spectroscopy, SEM, and TEM images and PPMS measurements are used to prove the exact composition of the biogenic products and to interpret the oxidation process. Analysis of the data collected shows that around 80 % of the iron (II) from the growth medium has been transformed into iron (III) in the form of different (oxy)hydroxides, with the rest found to be in a mixed 2,5 valence in magnetite. Our investigation shows that the bio-film sample has a phase content different from that of the powdered biomass and that lepidocrocite (γ-FeOOH) is the predominant and the initial biogenic phase in both samples. Magnetite nanoparticles are a secondary product in the bio-film, part of which possesses a defective quasi-maghemite surface layer. In the powdered biomass, the oxidation steps are not fully completed. The initial products are non-stoichiometric and due to the mixed ferric and ferrous ions present, they develop into: (i) lepidocrocite (γ-FeOOH) as a basic sediment, (ii) magnetite (Fe3O4) and (iii) goethite (α-FeOOH) in small quantities. The average size of all iron-bearing particles is found to be below 30 nm. The magnetic measurements performed show a superparamagnetic behavior of the material at room temperature.

  12. Synthesis of iron oxide/manganese oxide composite particles and their magnetic properties

    NASA Astrophysics Data System (ADS)

    Ullrich, Aladin; Hohenberger, Stefan; Özden, Ayberk; Horn, Siegfried

    2014-08-01

    We have investigated the synthesis and structural as well as magnetic properties of composite nanoparticles, including core-shell particles, consisting of iron and manganese oxides. The synthesis is based on thermal decomposition of suitable metal oleates in a high boiling solvent. Seed particles are used to avoid homogeneous nucleation and to initiate the formation of heterogeneous systems. The as-synthesized particles were characterized by energy filtered transmission electron microscopy (EFTEM) and SQUID magnetometry. The synthesized nanoparticles had diameters between 10 and 20 nm and consisted of manganese oxide and iron oxide.

  13. Enzymes of respiratory iron oxidation. Progress report, March 1990--November 1991

    SciTech Connect

    Blake, R. II

    1991-12-31

    This report focuses on the progress made in three areas of research concerned with enzymes involved in respiratory iron oxidation. The three areas are as follows: development of an improved procedure for the routine large scale culture of iron oxidizing chemolithotrophs based on the in-situ electrolysis of the soluble iron in the growth medium; to perform iron oxidation kinetic studies on whole cells using the oxygen electrode; and to identify, separate, purify, and characterize the individual cellular components.

  14. Oxidative effect of several intravenous iron complexes in the rat.

    PubMed

    Bailie, George R; Schuler, Catherine; Leggett, Robert E; Li, Hsin; Li, Hsin-Dat; Patadia, Hiten; Levin, Robert

    2013-06-01

    The objective of this study was to compare the oxidative stress induced in rat internal organs by the administration of the following clinically used intravenous (IV) iron (Fe) containing compounds: iron sucrose (IS), iron dextran (ID), ferric carboxymaltose and ferumoxytol. Groups of six adult rats received 1 mg/kg of each compound weekly for 5 doses. Seven days following the last dose, animals were euthanized and tissue samples of heart, lung, liver, and kidney were obtained, washed in warmed saline and frozen under liquid nitrogen and stored at -80 °C for analysis for nitrotyrosine (NT) and dinitro phenyl (DNP) as markers of oxidative stress. All tissues showed a similar pattern of oxidative stress. All Fe products stimulated an increase in the tissue concentration of both NT and DNP. In general, DNP was stimulated significantly less than NT except for IS. DNP was stimulated to an equal degree except for ID where NT was significantly higher than the NT concentrations in all other Fe compounds. ID produced over 10-fold the concentration of NT than any other Fe. IV Fe compounds present a risk of oxidative stress to a variety of internal organs. However, we found that IS was the least damaging and ID was the worst.

  15. Iron oxide nanotubes synthesized via template-based electrodeposition.

    PubMed

    Lim, Jin-Hee; Min, Seong-Gi; Malkinski, Leszek; Wiley, John B

    2014-05-21

    Considerable effort has been invested in the development of synthetic methods for the preparation iron oxide nanostructures for applications in nanotechnology. While a variety of structures have been reported, only a few studies have focused on iron oxide nanotubes. Here, we present details on the synthesis and characterization of iron oxide nanotubes along with a proposed mechanism for FeOOH tube formation. The FeOOH nanotubes, fabricated via a template-based electrodeposition method, are found to exhibit a unique inner-surface. Heat treatment of these tubes under oxidizing or reducing atmospheres can produce either hematite (α-Fe2O3) or magnetite (Fe3O4) structures, respectively. Hematite nanotubes are composed of small nanoparticles less than 20 nm in diameter and the magnetization curves and FC-ZFC curves show superparamagnetic properties without the Morin transition. In the case of magnetite nanotubes, which consist of slightly larger nanoparticles, magnetization curves show ferromagnetism with weak coercivity at room temperature, while FC-ZFC curves exhibit the Verwey transition at 125 K.

  16. Niobian iron oxides as heterogeneous Fenton catalysts for environmental remediation

    NASA Astrophysics Data System (ADS)

    Oliveira, Diana Q. L.; Oliveira, Luiz C. A.; Murad, Enver; Fabris, José D.; Silva, Adilson C.; de Menezes, Lucas Morais

    2010-01-01

    Heterogeneous Fenton or Fenton-like reagents consist of a mixture of an iron-containing solid matrix and a liquid medium with H2O2. The Fenton system is based on the reaction between Fe2 + and H2O2 to produce highly reactive intermediate hydroxyl radicals ( • OH), which are able to oxidize organic contaminants, whereas the Fenton-like reaction is based on the reaction between Fe3 + and H2O2. These heterogeneous systems offer several advantages over their homogeneous counterparts, such as no sludge formation, operation at near-neutral pH and the possibility of recycling the iron promoter. Some doping transition cations in the iron oxide structure are believed to enhance the catalytic efficiency for the oxidation of organic substrates in water. In this work, goethites synthesized in presence of niobium served as precursors for the preparation of magnetites (niobian magnetites) via chemical reduction with hydrogen at 400°C. These materials were used as Fenton-like catalysts. Both groups of (Nb, Fe)-oxide samples were characterized by 57Fe Mössbauer spectroscopy at 298 K. The results show that increasing niobium contents raise the catalytic potential for decomposition of methylene blue, which was, in this work, used as a model molecule for organic substrates in water.

  17. Comment on "Iron isotope constraints on the Archean and Paleoproterozoic ocean redox state".

    PubMed

    Yamaguchi, Kosei E; Ohmoto, Hiroshi

    2006-01-13

    Rouxel et al. (Reports, 18 February 2005, p. 1088) argued that changes in the iron isotopic composition of sedimentary sulfides reflect changes in the oxidation state of the atmosphere-ocean system between 2.3 and 1.8 million years ago. We show that misinterpretations of the origins of these minerals undermine their conclusions.

  18. Synthesis and properties of magnetic iron oxide/platinum nanocomposites

    NASA Astrophysics Data System (ADS)

    Serga, V.; Maiorov, M.; Kulikova, L.; Krumina, A.; Karashanova, D.

    2015-03-01

    Iron oxide/platinum nanocomposites have been synthesized by the extractive-pyrolytic method (EPM) involving gradual decomposition of iron capronate and n-trioctylammonium hexachloroplatinate initially produced by solvent extraction. The content of platinum in the composites was 1.2 wt%, 2.4 wt% and 4.8 wt%. Phase composition, morphology and magnetic properties of the produced materials were investigated. XRD analysis and magnetic measurements show that the magnetic phase (magnetite Fe3O4) dominates in a carrier sample produced by the pyrolysis of iron carboxylate, but hematite α-Fe2O3 exists there as an admixture. Referring to the TEM results, the produced composites contain ultra-disperse platinum particles on the carrier, and the mean size of these varies from 3 nm to 9 nm.

  19. Iron-mediated anaerobic oxidation of methane in brackish coastal sediments.

    PubMed

    Egger, Matthias; Rasigraf, Olivia; Sapart, Célia J; Jilbert, Tom; Jetten, Mike S M; Röckmann, Thomas; van der Veen, Carina; Bândă, Narcisa; Kartal, Boran; Ettwig, Katharina F; Slomp, Caroline P

    2015-01-06

    Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

  20. Influence of Iron Oxide Particles on the Strength of Ball-Milled Iron

    SciTech Connect

    Lesuer, D R; Syn, C K; Sherby, O D

    2005-12-07

    Detailed microstructural and mechanical property studies of ball-milled iron, in the powder and consolidated states, are reviewed and assessed. The analyses cover three and one-half orders of magnitude of grain size (from 6 nm to 20 mm) and focus on the influence of oxide particles on the strength. The study includes the early work of Koch and Yang, Kimura and Takaki and continues with the more recent work of Umemoto et al and Belyakov, Sakai et al. It is shown that the major contributors to strength are the nanooxide particles. These particles are created by adiabatic shear banding during ball-milling leading to a bimodal distribution of particles. The predicted strength from particles, {sigma}{sub p}, is given by {sigma}{sub p} = B {center_dot} (D*{sub S}){sup -1/2} where D*{sub S} is the surface-to-surface interparticle spacing, and B = 395 MPa {center_dot} {micro}m{sup -1/2}. A model is proposed that accounts for the influence of the bimodal particle size distribution on strength.

  1. Curcumin Attenuates Iron Accumulation and Oxidative Stress in the Liver and Spleen of Chronic Iron-Overloaded Rats

    PubMed Central

    Badria, Farid A.; Ibrahim, Ahmed S.; Badria, Adel F.; Elmarakby, Ahmed A.

    2015-01-01

    Objectives Iron overload is now recognized as a health problem in industrialized countries, as excessive iron is highly toxic for liver and spleen. The potential use of curcumin as an iron chelator has not been clearly identified experimentally in iron overload condition. Here, we evaluate the efficacy of curcumin to alleviate iron overload-induced hepatic and splenic abnormalities and to gain insight into the underlying mechanisms. Design and Methods Three groups of male adult rats were treated as follows: control rats, rats treated with iron in a drinking water for 2 months followed by either vehicle or curcumin treatment for 2 more months. Thereafter, we studied the effects of curcumin on iron overload-induced lipid peroxidation and anti-oxidant depletion. Results Treatment of iron-overloaded rats with curcumin resulted in marked decreases in iron accumulation within liver and spleen. Iron-overloaded rats had significant increases in malonyldialdehyde (MDA), a marker of lipid peroxidation and nitric oxide (NO) in liver and spleen when compared to control group. The effects of iron overload on lipid peroxidation and NO levels were significantly reduced by the intervention treatment with curcumin (P<0.05). Furthermore, the endogenous anti-oxidant activities/levels in liver and spleen were also significantly decreased in chronic iron overload and administration of curcumin restored the decrease in the hepatic and splenic antioxidant activities/levels. Conclusion Our study suggests that curcumin may represent a new horizon in managing iron overload-induced toxicity as well as in pathological diseases characterized by hepatic iron accumulation such as thalassemia, sickle cell anemia, and myelodysplastic syndromes possibly via iron chelation, reduced oxidative stress derived lipid peroxidation and improving the body endogenous antioxidant defense mechanism. PMID:26230491

  2. Iron atoms redistribution in oxide films of Zr-Fe, Zr-Fe-Cu alloys during corrosion in autoclave at 350°C

    NASA Astrophysics Data System (ADS)

    Filippov, V.; Bateev, A.

    2016-04-01

    The data on changes of iron atoms state in the oxide films of binary Zr-1.24 mas.%Fe and ternary Zr-1.39 mas.%Fe-0.60 mas.%Cu zirconium alloys are obtained. Alloys are subjected to corrosion tests under autoclave conditions at 350°C temperature in a steam-water environment under pressure p = 16.8 MPa. In initial specimens of the alloys the iron atoms are in the form of intermetallic compounds. In oxide films the decomposition of intermetallic compounds and formation of new compounds occurs with structural phase distortion. In the oxide films metallic the metallic iron particles α-Fe, iron oxide in the form of hematite α-Fe2O3, solid solutions of iron ions in ZrO2 are formed. The phase composition of the oxide films depends on the alloy composition and changes during the growth process of the oxide film.

  3. Low Temperature CO oxidation over Iron Oxide Nanoparticles Decorating Internal Structures of a Mesoporous Alumina

    NASA Astrophysics Data System (ADS)

    Kim, Il Hee; Seo, Hyun Ook; Park, Eun Ji; Han, Sang Wook; Kim, Young Dok

    2017-01-01

    Using a chemical vapor deposition method with regulated sample temperatures under ambient pressure conditions, we were able to fully decorate the internal structure of a mesoporous Al2O3 bead (~1 mm in particle diameter) with iron oxide nanoparticles (with a mean lateral size of less than 1 nm). The iron oxide-decorated Al2O3 showed a high CO oxidation reactivity, even at room temperature. Very little deactivation of the CO oxidation activity was observed with increasing reaction time at ~100 °C. Additionally, this catalyst showed high CO oxidation activity, even after annealing at ~900 °C under atmospheric conditions (i.e., the structure of the catalysts could be maintained under very harsh treatment conditions). We show that our catalysts have potential for application as oxidation catalysts in industrial processes due to the simplicity of their fabrication process as well as the high and stable catalytic performance.

  4. Low Temperature CO oxidation over Iron Oxide Nanoparticles Decorating Internal Structures of a Mesoporous Alumina

    PubMed Central

    Kim, Il Hee; Seo, Hyun Ook; Park, Eun Ji; Han, Sang Wook; Kim, Young Dok

    2017-01-01

    Using a chemical vapor deposition method with regulated sample temperatures under ambient pressure conditions, we were able to fully decorate the internal structure of a mesoporous Al2O3 bead (~1 mm in particle diameter) with iron oxide nanoparticles (with a mean lateral size of less than 1 nm). The iron oxide-decorated Al2O3 showed a high CO oxidation reactivity, even at room temperature. Very little deactivation of the CO oxidation activity was observed with increasing reaction time at ~100 °C. Additionally, this catalyst showed high CO oxidation activity, even after annealing at ~900 °C under atmospheric conditions (i.e., the structure of the catalysts could be maintained under very harsh treatment conditions). We show that our catalysts have potential for application as oxidation catalysts in industrial processes due to the simplicity of their fabrication process as well as the high and stable catalytic performance. PMID:28091561

  5. Multiphase equation of state for iron

    SciTech Connect

    Kerley, G I

    1993-02-01

    The PANDA code is used to build a multiphase equation of state (EOS) table for iron. Separate EOS tables were first constructed for each of the individual phases. The phase diagram and multiphase EOS were then determined from the Helmholtz free energies. The model includes four solid phases ([alpha],[gamma], [delta], and [var epsilon]) and a fluid phase (including the liquid, vapor, and supercritical regions). The model gives good agreement with experimental thermophysical data, static compression data, phase boundaries, and shock-wave measurements. Contributions from thermal electronic excitation, computed from a quantum-statistical-mechanical model, were found to be very important. This EOS covers a wide range of densities (0--1000 g/cm[sup 3]) and temperatures (0--1.2[times]10[sup 7] K). It is also applicable to RHA steel. The new EOS is used in hydrocode simulations of plate impact experiments, a nylon ball impact on steel, and the shaped charge perforation of an RHA plate. The new EOS table can be accessed through the SNL-SESAME library as material number 2150.

  6. Measurements of nitric oxide on the heme iron and -93 thiol of human hemoglobin during cycles of oxygenation and deoxygenation

    NASA Astrophysics Data System (ADS)

    Xu, Xiuli; Cho, Man; Spencer, Netanya Y.; Patel, Neil; Huang, Zhi; Shields, Howard; King, S. Bruce; Gladwin, Mark T.; Hogg, Neil; Kim-Shapiro, Daniel B.

    2003-09-01

    Nitric oxide has been proposed to be transported by hemoglobin as a third respiratory gas and to elicit vasodilation by an oxygen-linked (allosteric) mechanism. For hemoglobin to transport nitric oxide bioactivity it must capture nitric oxide as iron nitrosyl hemoglobin rather than destroy it by dioxygenation. Once bound to the heme iron, nitric oxide has been reported to migrate reversibly from the heme group of hemoglobin to the -93 cysteinyl residue, in response to an oxygen saturation-dependent conformational change, to form an S-nitrosothiol. However, such a transfer requires redox chemistry with oxidation of the nitric oxide or -93 cysteinyl residue. In this article, we examine the ability of nitric oxide to undergo this intramolecular transfer by cycling human hemoglobin between oxygenated and deoxygenated states. Under various conditions, we found no evidence for intramolecular transfer of nitric oxide from either cysteine to heme or heme to cysteine. In addition, we observed that contaminating nitrite can lead to formation of iron nitrosyl hemoglobin in deoxygenated hemoglobin preparations and a radical in oxygenated hemoglobin preparations. Using 15N-labeled nitrite, we clearly demonstrate that nitrite chemistry could explain previously reported results that suggested apparent nitric oxide cycling from heme to thiol. Consistent with our results from these experiments conducted in vitro, we found no arterial/venous gradient of iron nitrosyl hemoglobin detectable by electron paramagnetic resonance spectroscopy. Our results do not support a role for allosterically controlled intramolecular transfer of nitric oxide in hemoglobin as a function of oxygen saturation.

  7. Iron oxide and iron carbide particles produced by the polyol method

    NASA Astrophysics Data System (ADS)

    Yamada, Y.; Shimizu, R.; Kobayashi, Y.

    2016-12-01

    Iron oxide ( γ-Fe2O3) and iron carbide (Fe3C) particles were produced by the polyol method. Ferrocene, which was employed as an iron source, was decomposed in a mixture of 1,2-hexadecandiol, oleylamine, and 1-octadecene. Particles were characterized using Mössbauer spectroscopy, X-ray diffraction, and transmission electron microscopy. It was found that oleylamine acted as a capping reagent, leading to uniform-sized (12-16 nm) particles consisting of γ-Fe 2O3. On the other hand, 1-octadecene acted as a non-coordinating solvent and a carbon source, which led to particles consisting of Fe3C and α-Fe with various sizes.

  8. Iron oxide particles as a catalyst in chemical oxidation of organic contaminants

    SciTech Connect

    Gurol, M.D.; Lin, S.S.; Bhat, N.

    1995-12-31

    This research addresses the use of ozone and hydrogen peroxide in the presence of iron oxide particles which provide a catalytic surface for conversion to hydroxyl free radical. N-butylchloride (BuCl) and monochlorobenzene (MCB) were oxidized using goethite as the catalyst. The effect of varying the dosage of hydrogen peroxide or ozone, the mass and the size of the geothite particles, the mixing speed, and the gas flow rate for ozonation was investigated. The effect of water quality in terms of pH, carbonate alkalinity and initial organic concentration on reaction rates was addressed as well. Experimental observations showed that varying the stirring speed in the reactor or the size of the iron oxide particles did not have any significant effect on the oxidation rates, indicating that the rate was controlled by the intrinsic reaction rates on iron oxide surfaces. The presence of hydrogen peroxide significantly increased the removal of BuCl, and higher dosages caused considerably higher removal. Results also demonstrated a strong dependence of BuCl removal on the iron oxide dosage. MCB adsorbed strongly on goethite, but was oxidized effectively by ozone. Hydrogen peroxide decomposed rapidly in the presence of goethite at a rate directly proportional to the rate of BuCl oxidation. These results indicate that the interaction of hydrogen peroxide with goethite particles leads to the formation of hydroxyl free radical, which is responsible for oxidation of BuCl. Similarly, ozone decomposed in the presence of goethite. The oxidation efficiency for hydrogen peroxide/goethite remained unaffected when the pH and the alkalinity were varied. Furthermore, the ozone/goethite system provided mineralization as measured by the removal of the total organic carbon. Hence, both of these oxidation processes promise to be effective in oxidation of organic compounds, and may not suffer from the limitations of other radical processes.

  9. Copper Iron Conversion Coating for Solid Oxide Fuel Cell Interconnects

    NASA Astrophysics Data System (ADS)

    Grolig, Jan Gustav; Alnegren, Patrik; Froitzheim, Jan; Svensson, Jan-Erik

    2015-11-01

    A conversion coating of iron and copper was investigated with the purpose of increasing the performance of Sanergy HT as a potential SOFC interconnect material. Samples were exposed to a simulated cathode atmosphere (air, 3 % H2O) for durations of up to 1000 h at 850 °C. Their performance in terms of corrosion, chromium evaporation and electrical resistance (ASR) was monitored and compared to uncoated and cobalt-coated Sanergy HT samples. The copper iron coating had no negative effects on corrosion protection and decreased chromium evaporation by about 80%. An Area Specific Resistance (ASR) of 10 mΩcm2 was reached after 1000 h of exposure. Scanning Electron Microscopy revealed well adherent oxide layers comprised of an inner chromia layer and an outer spinel oxide layer.

  10. Dendronized iron oxide colloids for imaging the sentinel lymph node

    NASA Astrophysics Data System (ADS)

    Jouhannaud, J.; Garofalo, A.; Felder-Flesch, D.; Pourroy, G.

    2015-03-01

    Various methods have been used in medicine for more than one century to explore the lymphatic system. Radioactive colloids (RuS labelled with 99mTc) or/and Vital Blue dye are injected around the primary tumour and detected by means of nuclear probe or visual colour inspection respectively. The simultaneous clinical use of both markers (dye and radionuclide) improves the sensitivity of detection close to 100%. Superparamagnetic iron oxides (SPIOs) are currently receiving much attention as strong T2 weighted magnetic resonance imaging contrast agents that can be potentially used for preoperative localization of sentinel nodes, but also for peroperative detection of sentinel node using hand-held probes. In that context, we present the elaboration of dendronized iron oxide nanoparticles elaborated at the Institute of Physics and Chemistry of Materials of Strasbourg.

  11. Porous Iron oxide nanorods and their photothermal applications

    NASA Astrophysics Data System (ADS)

    Larsen, George; Huang, Weijie; Zhao, Yiping; Hunyadi Murph, Simona E.

    2016-09-01

    Iron oxide is a unique semiconductor material, either as a single nanoparticle, or as a component of multifunctional nanoparticles. Its desirable properties, abundance, non-toxicity, and excellent magnetic properties make it a valuable for many applications. Porous iron oxide nanorods are able to transduce light into heat through the photothermal effect. Photothermal heating arises from the energy dissipated during light absorption leading to rapid temperature rise in close proximity to the surface of the nanoparticle. The heating effect can be efficiently harnessed to drive/promote different physical phenomena. In this report, we describe the synthesis and properties of porous Fe3O4 for photothermal applications. We then demonstrate their use as photothermally enhanced and recyclable materials for environmental remediation through sorption processes.

  12. Iron aluminide alloy container for solid oxide fuel cells

    DOEpatents

    Judkins, Roddie Reagan; Singh, Prabhakar; Sikka, Vinod Kumar

    2000-01-01

    A container for fuel cells is made from an iron aluminide alloy. The container alloy preferably includes from about 13 to about 22 weight percent Al, from about 2 to about 8 weight percent Cr, from about 0.1 to about 4 weight percent M selected from Zr and Hf, from about 0.005 to about 0.5 weight percent B or from about 0.001 to about 1 weight percent C, and the balance Fe and incidental impurities. The iron aluminide container alloy is extremely resistant to corrosion and metal loss when exposed to dual reducing and oxidizing atmospheres at elevated temperatures. The alloy is particularly useful for containment vessels for solid oxide fuel cells, as a replacement for stainless steel alloys which are currently used.

  13. Exchange Bias Effects in Iron Oxide-Based Nanoparticle Systems

    SciTech Connect

    Phan, Manh-Huong; Alonso, Javier; Khurshid, Hafsa; Lampen-Kelley, Paula; Chandra, Sayan; Stojak Repa, Kristen; Nemati, Zohreh; Das, Raja; Iglesias, Óscar; Srikanth, Hariharan

    2016-11-23

    The exploration of exchange bias (EB) on the nanoscale provides a novel approach to improving the anisotropic properties of magnetic nanoparticles for prospective applications in nanospintronics and nanomedicine. However, the physical origin of EB is not fully understood. Recent advances in chemical synthesis provide a unique opportunity to explore EB in a variety of iron oxide-based nanostructures ranging from core/shell to hollow and hybrid composite nanoparticles. Experimental and atomistic Monte Carlo studies have shed light on the roles of interface and surface spins in these nanosystems. This review paper aims to provide a thorough understanding of the EB and related phenomena in iron oxide-based nanoparticle systems, knowledge of which is essential to tune the anisotropic magnetic properties of exchange-coupled nanoparticle systems for potential applications.

  14. Exchange Bias Effects in Iron Oxide-Based Nanoparticle Systems

    DOE PAGES

    Phan, Manh-Huong; Alonso, Javier; Khurshid, Hafsa; ...

    2016-11-23

    The exploration of exchange bias (EB) on the nanoscale provides a novel approach to improving the anisotropic properties of magnetic nanoparticles for prospective applications in nanospintronics and nanomedicine. However, the physical origin of EB is not fully understood. Recent advances in chemical synthesis provide a unique opportunity to explore EB in a variety of iron oxide-based nanostructures ranging from core/shell to hollow and hybrid composite nanoparticles. Experimental and atomistic Monte Carlo studies have shed light on the roles of interface and surface spins in these nanosystems. This review paper aims to provide a thorough understanding of the EB and relatedmore » phenomena in iron oxide-based nanoparticle systems, knowledge of which is essential to tune the anisotropic magnetic properties of exchange-coupled nanoparticle systems for potential applications.« less

  15. Reflection spectra and magnetochemistry of iron oxides and natural surfaces

    NASA Technical Reports Server (NTRS)

    Wasilewski, P.

    1978-01-01

    The magnetic properties and spectral characteristics of iron oxides are distinctive. Diagnostic features in reflectance spectra (0.5 to 2.4 micron) for alpha Fe2O3, gamma Fe2O3, and FeOOH include location of Fe3(+) absorption features, intensity ratios at various wavelengths, and the curve shape between 1.2 micron and 2.4 micron. The reflection spectrum of natural rock surfaces are seldom those of the bulk rock because of weathering effects. Coatings are found to be dominated by iron oxides and clay. A simple macroscopic model of rock spectra (based on concepts of stains and coatings) is considered adequate for interpretation of LANDSAT data. The magnetic properties of materials associated with specific spectral types and systematic changes in both spectra and magnetic properties are considered.

  16. Potential toxicity of superparamagnetic iron oxide nanoparticles (SPION)

    PubMed Central

    Singh, Neenu; Jenkins, Gareth J.S.; Asadi, Romisa; Doak, Shareen H.

    2010-01-01

    Superparamagnetic iron oxide nanoparticles (SPION) are being widely used for various biomedical applications, for example, magnetic resonance imaging, targeted delivery of drugs or genes, and in hyperthermia. Although, the potential benefits of SPION are considerable, there is a distinct need to identify any potential cellular damage associated with these nanoparticles. Besides focussing on cytotoxicity, the most commonly used determinant of toxicity as a result of exposure to SPION, this review also mentions the importance of studying the subtle cellular alterations in the form of DNA damage and oxidative stress. We review current studies and discuss how SPION, with or without different surface coating, may cause cellular perturbations including modulation of actin cytoskeleton, alteration in gene expression profiles, disturbance in iron homeostasis and altered cellular responses such as activation of signalling pathways and impairment of cell cycle regulation. The importance of protein-SPION interaction and various safety considerations relating to SPION exposure are also addressed. PMID:22110864

  17. Exchange Bias Effects in Iron Oxide-Based Nanoparticle Systems

    PubMed Central

    Phan, Manh-Huong; Alonso, Javier; Khurshid, Hafsa; Lampen-Kelley, Paula; Chandra, Sayan; Stojak Repa, Kristen; Nemati, Zohreh; Das, Raja; Iglesias, Óscar; Srikanth, Hariharan

    2016-01-01

    The exploration of exchange bias (EB) on the nanoscale provides a novel approach to improving the anisotropic properties of magnetic nanoparticles for prospective applications in nanospintronics and nanomedicine. However, the physical origin of EB is not fully understood. Recent advances in chemical synthesis provide a unique opportunity to explore EB in a variety of iron oxide-based nanostructures ranging from core/shell to hollow and hybrid composite nanoparticles. Experimental and atomistic Monte Carlo studies have shed light on the roles of interface and surface spins in these nanosystems. This review paper aims to provide a thorough understanding of the EB and related phenomena in iron oxide-based nanoparticle systems, knowledge of which is essential to tune the anisotropic magnetic properties of exchange-coupled nanoparticle systems for potential applications. PMID:28335349

  18. Increased endogenous DNA oxidation correlates to increased iron levels in melanocytes relative to keratinocytes.

    PubMed

    Pelle, Edward; Huang, Xi; Zhang, Qi; Pernodet, Nadine; Yarosh, Daniel B; Frenkel, Krystyna

    2014-01-01

    The endogenous oxidative state of normal human epidermal melanocytes was investigated and compared to normal human epidermal keratinocytes (NHEKs) in order to gain new insight into melanocyte biology. Previously, we showed that NHEKs contain higher levels of hydrogen peroxide (H2O2) than melanocytes and that it can migrate from NHEKs to melanocytes by passive permeation. Nevertheless, despite lower concentrations of H2O2, we now report higher levels of oxidative DNA in melanocytes as indicated by increased levels of 8-oxo-2'-deoxyguanosine (8-oxo-dG): 4.49 (±0.55 SEM) 8-oxo-dG/10(6) dG compared to 1.49 (±0.11 SEM) 8-oxo-dG/10(6) dG for NHEKs. An antioxidant biomarker, glutathione (GSH), was also lower in melanocytes (3.14 nmoles (±0.15 SEM)/cell) in comparison to NHEKs (5.98 nmoles (±0.33 SEM)/cell). Intriguingly, cellular bioavailable iron as measured in ferritin was found to be nearly fourfold higher in melanocytes than in NHEKs. Further, ferritin levels in melanocytes were also higher than in hepatocarcinoma cells, an iron-rich cell, and it indicates that higher relative iron levels may be characteristic of melanocytes. To account for the increased oxidative DNA and lower GSH and H2O2 levels that we observe, we propose that iron may contribute to higher levels of oxidation by reacting with H2O2 through a Fenton reaction leading to the generation of DNA-reactive hydroxyl radicals. In conclusion, our data support the concept of elevated oxidation and high iron levels as normal parameters of melanocytic activity. We present new evidence that may contribute to our understanding of the melanogenic process and lead to the development of new skin care products.

  19. Reducing arsenic accumulation in rice grain through iron oxide amendment.

    PubMed

    Farrow, Eric M; Wang, Jianmin; Burken, Joel G; Shi, Honglan; Yan, Wengui; Yang, John; Hua, Bin; Deng, Baolin

    2015-08-01

    Effects of soil-arsenic (As), phosphorus and iron oxide on As accumulation in rice grain were investigated. Cultivars that have significantly different sensitivity to As, straighthead-resistant Zhe 733 and straighthead-susceptible Cocodrie, were used to represent different cultivar varieties. The grain accumulation of other elements of concern, selenium (Se), molybdenum (Mo), and cadmium (Cd) was also monitored. Results demonstrated that high soil-As not only resulted in high grain-As, but could also result in high grain-Se, and Zhe 733 had significantly less grain-As than Cocodrie did. However, soil-As did not impact grain-Mo and Cd. Among all elements monitored, iron oxide amendment significantly reduced grain-As for both cultivars, while the phosphate application only reduced grain-Se for Zhe 733. Results also indicated that cultivar type significantly impacted grain accumulation of all monitored trace elements. Therefore, applying iron oxide to As-contaminated land, in addition to choosing appropriate rice cultivar, can effectively reduce the grain accumulation of As.

  20. Gentamicin coated iron oxide nanoparticles as novel antibacterial agents

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Proma; Neogi, Sudarsan

    2017-09-01

    Applications of different types of magnetic nanoparticles for biomedical purposes started a long time back. The concept of surface functionalization of the iron oxide nanoparticles with antibiotics is a novel technique which paves the path for further application of these nanoparticles by virtue of their property of superparamagnetism. In this paper, we have synthesized novel iron oxide nanoparticles surface functionalized with Gentamicin. The average size of the particles, concluded from the HR-TEM images, came to be around 14 nm and 10 nm for unmodified and modified nanoparticles, respectively. The magnetization curve M(H) obtained for these nanoparticles are typical of superparamagnetic nature and having almost zero values of coercivity and remanance. The release properties of the drug coated nanoparticles were studied; obtaining an S shaped profile, indicating the initial burst effect followed by gradual sustained release. In vitro investigations against various gram positive and gram negative strains viz Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and Bacillus subtilis indicated significant antibacterial efficiency of the drug-nanoparticle conjugate. The MIC values indicated that a small amount like 0.2 mg ml‑1 of drug capped particles induce about 98% bacterial death. The novelty of the work lies in the drug capping of the nanoparticles, which retains the superparamagnetic nature of the iron oxide nanoparticles and the medical properties of the drug simultaneously, which is found to extremely blood compatible.

  1. Modulated self-reversed magnetic hysteresis in iron oxides

    NASA Astrophysics Data System (ADS)

    Ma, Ji; Chen, Kezheng

    2017-02-01

    The steadfast rule of a ferromagnetic hysteresis loop claims its saturation positioned within the first and third quadrants, whereas its saturation positioned in the second and fourth quadrants (named as self-reversed magnetic hysteresis) is usually taken as an experimental artifact and is always intentionally ignored. In this report, a new insight in this unique hysteresis phenomenon and its modulation were discussed in depth. Different iron oxides (magnetite, maghemite and hematite) with varying dimensions were soaked in FeCl3 aqueous solution and absorbed Fe3+ cations due to their negative enough surface zeta potentials. These iron oxides@Fe3+ core-shell products exhibit well pronounced self-reversed magnetic hysteresis which concurrently have typical diamagnetic characteristics and essential ferromagnetic features. The presence of pre-magnetized Fe3+ shell and its negatively magnetic exchange coupling with post-magnetized iron-oxide core is the root cause for the observed phenomena. More strikingly, this self-reversed magnetic hysteresis can be readily modulated by changing the core size or by simply controlling Fe3+ concentration in aqueous solution. It is anticipated that this work will shed new light on the development of spintronics, magnetic recording and other magnetically-relevant fields.

  2. Modulated self-reversed magnetic hysteresis in iron oxides

    PubMed Central

    Ma, Ji; Chen, Kezheng

    2017-01-01

    The steadfast rule of a ferromagnetic hysteresis loop claims its saturation positioned within the first and third quadrants, whereas its saturation positioned in the second and fourth quadrants (named as self-reversed magnetic hysteresis) is usually taken as an experimental artifact and is always intentionally ignored. In this report, a new insight in this unique hysteresis phenomenon and its modulation were discussed in depth. Different iron oxides (magnetite, maghemite and hematite) with varying dimensions were soaked in FeCl3 aqueous solution and absorbed Fe3+ cations due to their negative enough surface zeta potentials. These iron oxides@Fe3+ core-shell products exhibit well pronounced self-reversed magnetic hysteresis which concurrently have typical diamagnetic characteristics and essential ferromagnetic features. The presence of pre-magnetized Fe3+ shell and its negatively magnetic exchange coupling with post-magnetized iron-oxide core is the root cause for the observed phenomena. More strikingly, this self-reversed magnetic hysteresis can be readily modulated by changing the core size or by simply controlling Fe3+ concentration in aqueous solution. It is anticipated that this work will shed new light on the development of spintronics, magnetic recording and other magnetically-relevant fields. PMID:28220793

  3. Modulated self-reversed magnetic hysteresis in iron oxides.

    PubMed

    Ma, Ji; Chen, Kezheng

    2017-02-21

    The steadfast rule of a ferromagnetic hysteresis loop claims its saturation positioned within the first and third quadrants, whereas its saturation positioned in the second and fourth quadrants (named as self-reversed magnetic hysteresis) is usually taken as an experimental artifact and is always intentionally ignored. In this report, a new insight in this unique hysteresis phenomenon and its modulation were discussed in depth. Different iron oxides (magnetite, maghemite and hematite) with varying dimensions were soaked in FeCl3 aqueous solution and absorbed Fe(3+) cations due to their negative enough surface zeta potentials. These iron oxides@Fe(3+) core-shell products exhibit well pronounced self-reversed magnetic hysteresis which concurrently have typical diamagnetic characteristics and essential ferromagnetic features. The presence of pre-magnetized Fe(3+) shell and its negatively magnetic exchange coupling with post-magnetized iron-oxide core is the root cause for the observed phenomena. More strikingly, this self-reversed magnetic hysteresis can be readily modulated by changing the core size or by simply controlling Fe(3+) concentration in aqueous solution. It is anticipated that this work will shed new light on the development of spintronics, magnetic recording and other magnetically-relevant fields.

  4. Iron oxide magnetic nanoparticles synthesized by atmospheric microplasmas

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Kaur, Parvin; Tan, Augustine Tuck Lee; Singh, Rajveer; Lee, Paul Choon Keat; Springham, Stuart Victor; Ramanujan, Raju V.; Rawat, R. S.

    2014-08-01

    This paper presents the synthesis of iron oxide nanoparticles using the atmospheric microplasma (AMP). The properties of iron oxide nanoparticles synthesized using AMP are compared with particles (i) formed in as-prepared solution and (ii) prepared using thermal decomposition method. Iron oxide nanoparticles prepared by all the 3 treatment methods exhibit quite soft ferromagnetic properties with coercivities less than 10 G. The AMP synthesis technique was found to be more efficient and better than thermal decomposition method due to ultra-shorter experiment time (around 2.5 min) as compared to 90 min required for thermal decomposition method. Moreover, AMP synthesized nanoparticles are better isolated and of smaller size than thermal decomposition ones. The effect of plasma discharge timings on synthesized nanoparticles has also been studied in this work. Coercivity of synthesized nanoparticles decreases with the increasing plasma discharge timings from 3 to 10 min. The nanoparticles synthesized using plasma discharge timing of 10 min exhibit the smallest coercivity of around 3 G. This suggests a high possibility of achieving super-paramagnetic nanoparticles by optimizing the plasma discharge timings of AMP.

  5. Electron uptake by iron-oxidizing phototrophic bacteria

    SciTech Connect

    Bose, A; Gardel, EJ; Vidoudez, C; Parra, EA; Girguis, PR

    2014-02-26

    Oxidation-reduction reactions underlie energy generation in nearly all life forms. Although most organisms use soluble oxidants and reductants, some microbes can access solid-phase materials as electron-acceptors or -donors via extracellular electron transfer. Many studies have focused on the reduction of solid-phase oxidants. Far less is known about electron uptake via microbial extracellular electron transfer, and almost nothing is known about the associated mechanisms. Here we show that the iron-oxidizing photoautotroph Rhodopseudomonas palustris TIE-1 accepts electrons from a poised electrode, with carbon dioxide as the sole carbon source/electron acceptor. Both electron uptake and ruBisCo form I expression are stimulated by light. Electron uptake also occurs in the dark, uncoupled from photosynthesis. Notably, the pioABC operon, which encodes a protein system essential for photoautotrophic growth by ferrous iron oxidation, influences electron uptake. These data reveal a previously unknown metabolic versatility of photoferrotrophs to use extracellular electron transfer for electron uptake.

  6. Electron uptake by iron-oxidizing phototrophic bacteria.

    PubMed

    Bose, A; Gardel, E J; Vidoudez, C; Parra, E A; Girguis, P R

    2014-02-26

    Oxidation-reduction reactions underlie energy generation in nearly all life forms. Although most organisms use soluble oxidants and reductants, some microbes can access solid-phase materials as electron-acceptors or -donors via extracellular electron transfer. Many studies have focused on the reduction of solid-phase oxidants. Far less is known about electron uptake via microbial extracellular electron transfer, and almost nothing is known about the associated mechanisms. Here we show that the iron-oxidizing photoautotroph Rhodopseudomonas palustris TIE-1 accepts electrons from a poised electrode, with carbon dioxide as the sole carbon source/electron acceptor. Both electron uptake and ruBisCo form I expression are stimulated by light. Electron uptake also occurs in the dark, uncoupled from photosynthesis. Notably, the pioABC operon, which encodes a protein system essential for photoautotrophic growth by ferrous iron oxidation, influences electron uptake. These data reveal a previously unknown metabolic versatility of photoferrotrophs to use extracellular electron transfer for electron uptake.

  7. Vessel size index measurements in a rat model of glioma: comparison of the dynamic (Gd) and steady-state (iron-oxide) susceptibility contrast MRI approaches.

    PubMed

    Pannetier, Nicolas; Lemasson, Benjamin; Christen, Thomas; Tachrount, Mohamed; Troprès, Irène; Farion, Régine; Segebarth, Christoph; Rémy, Chantal; Barbier, Emmanuel L

    2012-02-01

    Vessel size index (VSI), a parameter related to the distribution of vessel diameters, may be estimated using two MRI approaches: (i) dynamic susceptibility contrast (DSC) MRI following the injection of a bolus of Gd-chelate. This technique is routinely applied in the clinic to assess intracranial tissue perfusion in patients; (ii) steady-state susceptibility contrast with USPIO contrast agents, which is considered here as the standard method. Such agents are not available for human yet and the steady-state approach is currently limited to animal studies. The aim is to compare VSI estimates obtained with these two approaches on rats bearing C6 glioma (n = 7). In a first session, VSI was estimated from two consecutive injections of Gd-Chelate (Gd(1) and Gd(2)). In a second session (4 hours later), VSI was estimated using USPIO. Our findings indicate that both approaches yield comparable VSI estimates both in contralateral (VSI{USPIO} = 7.5 ± 2.0 µm, VSI{Gd(1)} = 6.5 ± 0.7 µm) and in brain tumour tissues (VSI{USPIO} = 19.4 ± 7.1 µm, VSI{Gd(1)} = 16.6 ± 4.5 µm). We also observed that, in the presence of BBB leakage (as it occurs typically in brain tumours), applying a preload of Gd-chelate improves the VSI estimate with the DSC approach both in contralateral (VSI{Gd(2)} = 7.1 ± 0.4 µm) and in brain tumour tissues (VSI{Gd(2)} = 18.5 ± 4.3 µm) but is not mandatory. VSI estimates do not appear to be sensitive to T(1) changes related to Gd extravasation. These results suggest that robust VSI estimates may be obtained in patients at 3 T or higher magnetic fields with the DSC approach.

  8. Oxygen fugacities determined from iron oxidation state in natural (Mg,Fe)O ferropericlase: new insights into lower mantle diamond formation

    NASA Astrophysics Data System (ADS)

    Longo, Micaela; McCammon, Catherine; Bulanova, Galina; Kaminsky, Felix; Tappert, Ralf

    2010-05-01

    Mineral inclusions in diamonds reflect the chemical composition and mineral assemblages of the two principal rock types occurring in the deep lithosphere, peridotite and eclogite. However, in the past two decades, the discovery of rare diamonds containing inclusions such as former Mg,Si-perovskite and (Mg,Fe)O ferropericlase led to the possibility that diamonds can form also at greater depths. (Mg,Fe)O ferropericlase is the most commonly found inclusion in lower mantle diamonds (more than 50% of the occurrences). Since the Fe3+ concentration in (Mg,Fe)O is sensitive to oxygen fugacity also at high pressures (Frost et al., 2004), the determination of Fe3+/Σ Fe in such inclusions provides a direct method for investigating lower mantle redox conditions during diamond formation. In the present study we explore whether variations in mantle oxygen fugacity exist as a function of chemical, physical and geographic parameters, by studying (Mg,Fe)O inclusions in lower mantle diamonds from a wide range of localities. Eighteen (Mg,Fe)O ferropericlase inclusions from lower mantle diamonds selected worldwide were measured by the flank method using the calibration previously established for synthetic ferropericlase (Longo et al., in preparation). The Fe3+/Σ Fe measured in (Mg,Fe)O inclusions of the present work (Juina, Brazil, Machado River, Brazil and Orroroo, Australia) were compared to data already available for other inclusions of larger size previously measured by Mössbauer spectroscopy (McCammon et al. 1997, 2004). Oxygen fugacity was estimated for each specimen relative to two reference buffers such as the Fe-(Mg,Fe)O buffer (reducing conditions) and the Re-ReO2 buffer (oxidizing conditions). Our results show a dependence on geographical location, and in particular, inclusions from the African province (Kankan Guinea) seem to record more reducing mantle conditions than the inclusions measured from the other provinces, which cover a larger range of fO2 conditions. It is

  9. Evidence for an oxygen evolving iron-oxo-cerium intermediate in iron-catalysed water oxidation.

    PubMed

    Codolà, Zoel; Gómez, Laura; Kleespies, Scott T; Que, Lawrence; Costas, Miquel; Lloret-Fillol, Julio

    2015-01-22

    The non-haem iron complex α-[Fe(II)(CF3SO3)2(mcp)] (mcp=(N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-1,2-cis-diaminocyclohexane) reacts with Ce(IV) to oxidize water to O2, representing an iron-based functional model for the oxygen evolving complex of photosystem II. Here we trap an intermediate, characterized by cryospray ionization high resolution mass spectrometry and resonance Raman spectroscopy, and formulated as [(mcp)Fe(IV)(O)(μ-O)Ce(IV)(NO3)3](+), the first example of a well-characterized inner-sphere complex to be formed in cerium(IV)-mediated water oxidation. The identification of this reactive Fe(IV)-O-Ce(IV) adduct may open new pathways to validate mechanistic notions of an analogous Mn(V)-O-Ca(II) unit in the oxygen evolving complex that is responsible for carrying out the key O-O bond forming step.

  10. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    SciTech Connect

    Jernigan, Glenn Geoffrey

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  11. Effects of green tea on iron accumulation and oxidative stress in livers of iron-challenged thalassemic mice.

    PubMed

    Saewong, T; Ounjaijean, S; Mundee, Y; Pattanapanyasat, K; Fucharoen, S; Porter, J B; Srichairatanakool, S

    2010-03-01

    Liver is affected by secondary iron overload in transfusions dependent b-thalassemia patients. The redox iron can generate reactive oxidants that damage biomolecules, leading to liver fibrosis and cirrhosis. Iron chelators are used to treat thalassemias to achieve negative iron balance and relieve oxidant-induced organ dysfunctions. Green tea (GT) (Camellia sinensis) catechins exhibit anti-oxidation, the inhibition of carcinogenesis, the detoxification of CYP2E1-catalyzed HepG2 cells and iron chelation. The purpose of this study was to investigate the effectiveness of GT in iron-challenged thalassemic mice. Heterozygous BKO type-thalassemia (BKO) mice (C57BL/6) experienced induced iron overload by being fed a ferrocene-supplemented diet (Fe diet) for 8 weeks, and by orally being given GT extract (300 mg/kg) and deferiprone (DFP) (50 mg/kg) for a further 8 weeks. Liver iron content (LIC) was analyzed by TPTZ colorimetric and Perl's staining techniques. Concentrations of liver reduced glutathione (GSH), collagen and malondialdehyde (MDA) were also measured. Dosages of the GT extract and DFP lowered LIC in the Fe diet-fed BKO mice effectively. The extract did not change any concentrations of liver glutathione, collagen and MDA in the BKO mice. Histochemical examination showed leukocyte infiltration in the near by hepatic portal vein and high iron accumulation in the livers of the iron-loaded BKO mice, however GT treatment lowered the elevated iron deposition. In conclusion, green tea inhibits or delays the deposition of hepatic iron in regularly iron-loaded thalassemic mice effectively. This will prevent the iron-induced generation of free radicals via Haber-Weiss and Fenton reactions, and consequently liver damage and fibrosis. Combined chelation with green tea would be investigated in beta-thalassemia patients with iron overload.

  12. Oxidation states of iron as an indicator of the techniques used to burn clays and handcraft archaeological Tupiguarani ceramics by ancient human groups in Minas Gerais, Brazil

    NASA Astrophysics Data System (ADS)

    Floresta, D. L.; Ardisson, J. D.; Fagundes, M.; Fabris, J. D.; Macedo, W. A. A.

    2014-01-01

    Ceramics of the Tupiguarani Tradition typically have in common the burning characteristics, their forms and decoration motifs. Dating such ceramic pieces with the radiocarbon method indicate that these artifacts were probably handcrafted between 1,500 and 500 years before the present. Fragments ceramic utensils were collected in the archaeological site of Beltrão, in the municipality of Corinto, state of Minas Gerais, Brazil. A fragment of about 50 mm in diameter and 15 mm thick, with a color gradation across the ceramic wall ranging from red, on one side, grayish, in the middle, and orange, on the opposite side, was selected for a more detailed examination. The fragment was transversely cut and a series of subsamples were separated from different points along the piece wall, in layer segments of ~3 mm. All subsamples were analyzed with Mössbauer spectroscopy at room temperature and 80 K. Results reveal that hematite is the magnetically ordered phase. A Fe2 + component (relative spectral area, 50 %) appears for the grayish subsample. According to these first results, the red subsample seems to be the side that had direct contact with fire used to burn the precursor clay in air. The grayish middle layer is probably due to the clay mixed with some ashes. Mössbauer data reveal that the orange layer, corresponding to the opposite side of the ceramic relatively to the direct fire, does contain about the same Fe2 + :Fe3 + ratio but much lower proportion of α-Fe2O3 than the red layer.

  13. Evaluation of iron oxide nanoparticle biocompatibility.

    PubMed

    Hanini, Amel; Schmitt, Alain; Kacem, Kamel; Chau, François; Ammar, Souad; Gavard, Julie

    2011-01-01

    Nanotechnology is an exciting field of investigation for the development of new treatments for many human diseases. However, it is necessary to assess the biocompatibility of nanoparticles in vitro and in vivo before considering clinical applications. Our characterization of polyol-produced maghemite γ-Fe(2)O(3) nanoparticles showed high structural quality. The particles showed a homogeneous spherical size around 10 nm and could form aggregates depending on the dispersion conditions. Such nanoparticles were efficiently taken up in vitro by human endothelial cells, which represent the first biological barrier to nanoparticles in vivo. However, γ-Fe(2)O(3) can cause cell death within 24 hours of exposure, most likely through oxidative stress. Further in vivo exploration suggests that although γ-Fe(2)O(3) nanoparticles are rapidly cleared through the urine, they can lead to toxicity in the liver, kidneys and lungs, while the brain and heart remain unaffected. In conclusion, γ-Fe(2)O(3) could exhibit harmful properties and therefore surface coating, cellular targeting, and local exposure should be considered before developing clinical applications.

  14. Alleviation of iron induced oxidative stress by the grape fruit flavanone naringin in vitro.

    PubMed

    Jagetia, Ganesh Chandra; Reddy, Tiyagura Koti

    2011-04-25

    Iron is an essential element that participates in several metabolic activities of cells; however, excess iron is a major cause of iron-induced oxidative stress and several human diseases. The protective effect of naringin, a grape fruit flavanone, was studied in iron overloaded isolated mouse liver mitochondria, where the isolated mitochondrial fraction was incubated with various concentrations of naringin before ferric ion loading. Iron overloading of mitochondrial fraction resulted in an increase in lipid peroxidation, protein oxidation, and DNA damage, whereas iron overload reduced the glutathione (GSH) concentration, glutathione-S-transferase (GST), glutathione peroxidase (GSHPx), catalase and superoxide dismutase (SOD) activities. Pretreatment of mitochondrial fraction with naringin inhibited iron-induced lipid peroxidation, protein oxidation, and DNA damage. Conversely, naringin supplementation arrested iron-induced depletion in the GSH contents, GSHPx, GST, SOD and catalase activities significantly. Ferric iron reduction assay revealed that naringin could not reduce ferric iron into ferrous iron indicating that it did not exhibit prooxidant activity. Iron free coordination site assay indicated that naringin was unable to occupy all the active sites of iron indicating that naringin did not completely chelate iron. Our study demonstrates that naringin was able to share the burden of endogenous oxidants by inhibiting the iron-induced depletion of all important antioxidant enzymes as well as GSH and may act as a good antioxidant.

  15. Particle interactions of polyvinylpyrrolidone-coated iron oxide particles as magnetic drug delivery agents

    NASA Astrophysics Data System (ADS)

    İşçi, Sevim; İşçi, Yavuz; Bekaroğlu, Maide Gökçe

    2017-08-01

    Iron oxide particles have been recently researched for the potential applications of targeted drug delivery due to their magnetic properties. The surfaces of the iron oxide particles must be modified to reduce the toxicity and to load the drug to the particles. Biopolymers are good surface modifiers of colloidal particles such as iron oxide particles. The degree of surface coverage of the colloidal iron oxide particles affects the stability, toxicity, magnetic properties and drug loading efficiency. In this study, the interactions of iron oxide (Fe3O4) particles and PVP were determined according to the colloidal properties. The proper concentration of PVP for the whole coverage of the iron oxide particles was found for the possible magnetic drug delivery applications by controlling the colloidal properties of the dispersions. The magnetic properties and toxicity of the fully covered bioiron oxide was also determined for possible applications.

  16. Evaluation of Characterization Techniques for Iron Pipe Corrosion Products and Iron Oxide Thin Films

    SciTech Connect

    Borch, Thomas; Camper, Anne K.; Biederman, Joel A.; Butterfield, Phillip; Gerlach, Robin; Amonette, James E.

    2008-10-01

    A common problem faced by drinking water studies is that of properly characterizing the corrosion products (CP) in iron pipescor synthetic Fe (hydr)oxides used to simulate the iron pipe used in municipal drinking-water systems. The present work compares the relative applicability of a suite of imaging and analytical techniques for the characterization of CPs and synthetic Fe oxide thin films and provide an overview of the type of data that each instrument can provide as well as their limitations to help researchers and consultants choose the best technique for a given task. Crushed CP from a water distribution system and synthetic Fe oxide thin films formed on glass surfaces were chosen as test samples for this evaluation. The CP and synthetic Fe oxide thin films were analyzed by atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive spectroscopy, time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray powder diffractometry (XRD), grazing incident diffractometry (GID), transmission electron microscopy (TEM), selected area electron diffraction, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared, Mössbauer spectroscopy, Brunauer-Emmett-Teller N2 adsorption and Fe concentration was determined by the ferrozine method. XRD and GID were found to be the most suitable techniques for identification of the mineralogical composition of CP and synthetic Fe oxide thin films, respectively. AFM and a combined ToF-SIMS-AFM approach proved excellent for roughness and depth profiling analysis of synthetic Fe oxide thin films, respectively. Corrosion products were difficult to study by AFM due to their surface roughness, while synthetic Fe oxide thin films resisted most spectroscopic methods due to their limited thickness (118 nm). XPS analysis is not recommended for mixtures of Fe (hydr)oxides due to their spectral similarities. SEM and TEM provided great detail on mineralogical morphology.

  17. Accumulation of iron oxide nanoparticles by cultured primary neurons.

    PubMed

    Petters, Charlotte; Dringen, Ralf

    2015-02-01

    Magnetic iron oxide nanoparticles (IONPs) are frequently used for biomedical applications. Although nanoparticles can enter the brain, little is known so far on the uptake of IONPs in neurons and on their neurotoxic potential. Hence, we applied dimercaptosuccinate (DMSA)-coated IONPs to cultured primary rat cerebellar granule neurons. These IONPs had average hydrodynamic diameters of around 80 nm and 120 nm when dispersed in incubation medium in the absence and the presence of 10% fetal calf serum, respectively. Acute exposure of neurons with IONPs for up to 6 h did neither alter the cell morphology nor compromise cell viability, although neurons accumulated large amounts of IONPs in a time- and concentration-dependent manner which caused delayed toxicity. For the first 30 min of incubation of neurons at 37 °C with IONPs the cellular iron content increased proportionally to the concentration of IONPs applied irrespective of the absence and the presence of serum. IONP-exposure in the absence of serum generated maximal cellular iron contents of around 3000 nmol iron/mg protein after 4 h of incubation, while the accumulation in the presence of 10% serum was slower and reached already within 1 h maximal values of around 450 nmol iron/mg protein. For both incubation conditions was the increase in cellular iron contents significantly lowered by reducing the incubation temperature to 4 °C. Application of inhibitors of endocytotic pathways did not affect neuronal IONP accumulation in the absence of serum, while inhibitors of clathrin-mediated endocytosis lowered significantly the IONP accumulation in the presence of serum. These data demonstrate that DMSA-coated IONPs are not acutely toxic to cultured neurons and that a protein corona around the particles strongly affects their interaction with neurons. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Iron isotope fractionation during photo-oxidation of aqueous ferrous iron

    NASA Astrophysics Data System (ADS)

    Staton, S.; Amskold, L.; Gordon, G.; Anbar, A.; Konhauser, K.

    2006-05-01

    The classic interpretation of banded iron formations (BIFs) presumes the presence of dissolved O2 in the surface ocean to oxidize ferrous Fe. However, at least two alternative oxidation mechanisms are possible: UV photo-oxidation; and the activity of anaerobic Fe(II)-oxidizing photosynthetic bacteria. We are investigating Fe isotope fractionation as a means of differentiating amongst these mechanisms. Photo-oxidation has been examined at pH ~ 3 and 41°C in the absence of ligands other than H2O, OH-, and Cl- using UVA (316-400 nm) and UVC (200-280 nm) light sources. In these experiments, ferrous Fe was oxidized and precipitated as ferric oxyhydroxide. We find that isotopically heavy Fe was preferentially removed from solution. The fractionation factor (α) for the overall reaction is ~ 1.0025. This value is comparable to the α between Fe2+ and Fe3+ hexaquo complexes, but larger than the effect seen during the overall process of ferrous Fe oxidation and precipitation at near-neutral pH. The magnitude of isotope fractionation is likely to change at higher pH for two reasons. First, ferric oxyhydroxide precipitation, which may impart a kinetic isotope effect, is faster at higher pH. Second, the major UV-absorbing ferrous species in the ocean is the ferrous hydroxide ion [Fe(OH)+], the concentration of which is strongly pH dependent. Photo-oxidation experiments at realistic seawater pH are under current investigation.

  19. New Insight into Microbial Iron Oxidation as Revealed by the Proteomic Profile of an Obligate Iron-Oxidizing Chemolithoautotroph

    PubMed Central

    Emerson, David; Sylvan, Jason B.; Orcutt, Beth N.; Jacobson Meyers, Myrna E.; Ramírez, Gustavo A.; Zhong, John D.; Edwards, Katrina J.

    2015-01-01

    Microaerophilic, neutrophilic, iron-oxidizing bacteria (FeOB) grow via the oxidation of reduced Fe(II) at or near neutral pH, in the presence of oxygen, making them relevant in numerous environments with elevated Fe(II) concentrations. However, the biochemical mechanisms for Fe(II) oxidation by these neutrophilic FeOB are unknown, and genetic markers for this process are unavailable. In the ocean, microaerophilic microorganisms in the genus Mariprofundus of the class Zetaproteobacteria are the only organisms known to chemolithoautotrophically oxidize Fe and concurrently biomineralize it in the form of twisted stalks of iron oxyhydroxides. The aim of this study was to identify highly expressed proteins associated with the electron transport chain of microaerophilic, neutrophilic FeOB. To this end, Mariprofundus ferrooxydans PV-1 was cultivated, and its proteins were extracted, assayed for redox activity, and analyzed via liquid chromatography-tandem mass spectrometry for identification of peptides. The results indicate that a cytochrome c4, cbb3-type cytochrome oxidase subunits, and an outer membrane cytochrome c were among the most highly expressed proteins and suggest an involvement in the process of aerobic, neutrophilic bacterial Fe oxidation. Proteins associated with alternative complex III, phosphate transport, carbon fixation, and biofilm formation were abundant, consistent with the lifestyle of Mariprofundus. PMID:26092463

  20. New Insight into Microbial Iron Oxidation as Revealed by the Proteomic Profile of an Obligate Iron-Oxidizing Chemolithoautotroph.

    PubMed

    Barco, Roman A; Emerson, David; Sylvan, Jason B; Orcutt, Beth N; Jacobson Meyers, Myrna E; Ramírez, Gustavo A; Zhong, John D; Edwards, Katrina J

    2015-09-01

    Microaerophilic, neutrophilic, iron-oxidizing bacteria (FeOB) grow via the oxidation of reduced Fe(II) at or near neutral pH, in the presence of oxygen, making them relevant in numerous environments with elevated Fe(II) concentrations. However, the biochemical mechanisms for Fe(II) oxidation by these neutrophilic FeOB are unknown, and genetic markers for this process are unavailable. In the ocean, microaerophilic microorganisms in the genus Mariprofundus of the class Zetaproteobacteria are the only organisms known to chemolithoautotrophically oxidize Fe and concurrently biomineralize it in the form of twisted stalks of iron oxyhydroxides. The aim of this study was to identify highly expressed proteins associated with the electron transport chain of microaerophilic, neutrophilic FeOB. To this end, Mariprofundus ferrooxydans PV-1 was cultivated, and its proteins were extracted, assayed for redox activity, and analyzed via liquid chromatography-tandem mass spectrometry for identification of peptides. The results indicate that a cytochrome c4, cbb3-type cytochrome oxidase subunits, and an outer membrane cytochrome c were among the most highly expressed proteins and suggest an involvement in the process of aerobic, neutrophilic bacterial Fe oxidation. Proteins associated with alternative complex III, phosphate transport, carbon fixation, and biofilm formation were abundant, consistent with the lifestyle of Mariprofundus.

  1. Comparison of the Effects of Iron Oxide, as a New Form of Iron Supplement, and Ferrous Sulfate on the Blood Levels of Iron and Total Iron-Binding Globulin in the Rabbit.

    PubMed

    Kheiri, Reyhaneh; Koohi, Mohammad Kazem; Sadeghi-Hashjin, Goudarz; Nouri, Hadiseh; Khezli, Noushin; Hassan, Mohsen Aghamohammad; Hoomani, Fatemeh; Shams, Gholamreza; Rasouli, Ali; Motaghinejad, Majid

    2017-01-01

    Iron oxide is an important biological agent that has a key role in medical processes; however, the mechanism whereby it provides iron for human and animal cells and its biological uses remains unclear. We aimed to evaluate the effects of oral iron oxide on serum iron status and compare the results with those of iron sulfate as a reference salt. Fifteen adult rabbits were divided into 3 groups of 5 each: control group, iron sulfate group, and iron oxide group. The groups received doses of 3.3, 10, and 33 mg/kg in 3 experiments. Venous blood samples were obtained just before the oral administration of iron sulfate and iron oxide (3.3 mg/kg). More blood samples were taken 3 times at the time points of 1, 6, and 12 hours after the administration of the solutions. Serum was separated for the measurement of iron (Fe) and total iron-binding globulin (TIBG) with routine methods. One week later, the same experiment was repeated with 10 mg/kg of iron sulfate and iron oxide; and 1 week later after the second experiment, again the same experiment was repeated with 33 mg/kg of iron sulfate and iron oxide. The results showed that 33 mg/kg of iron sulfate 1 hour after treatment caused a significant difference in the Fe and TIBG levels between all the groups (P=0.014 for Fe and P=0.027 for TIBG). Our data showed that the absorption of iron oxide was similar to that of ferrous sulfate and in high doses was as useful as iron supplement.

  2. Comparison of the Effects of Iron Oxide, as a New Form of Iron Supplement, and Ferrous Sulfate on the Blood Levels of Iron and Total Iron-Binding Globulin in the Rabbit

    PubMed Central

    Kheiri, Reyhaneh; Koohi, Mohammad Kazem; Sadeghi-Hashjin, Goudarz; Nouri, Hadiseh; Khezli, Noushin; Hassan, Mohsen Aghamohammad; Hoomani, Fatemeh; Shams, Gholamreza; Rasouli, Ali; Motaghinejad, Majid

    2017-01-01

    Iron oxide is an important biological agent that has a key role in medical processes; however, the mechanism whereby it provides iron for human and animal cells and its biological uses remains unclear. We aimed to evaluate the effects of oral iron oxide on serum iron status and compare the results with those of iron sulfate as a reference salt. Fifteen adult rabbits were divided into 3 groups of 5 each: control group, iron sulfate group, and iron oxide group. The groups received doses of 3.3, 10, and 33 mg/kg in 3 experiments. Venous blood samples were obtained just before the oral administration of iron sulfate and iron oxide (3.3 mg/kg). More blood samples were taken 3 times at the time points of 1, 6, and 12 hours after the administration of the solutions. Serum was separated for the measurement of iron (Fe) and total iron-binding globulin (TIBG) with routine methods. One week later, the same experiment was repeated with 10 mg/kg of iron sulfate and iron oxide; and 1 week later after the second experiment, again the same experiment was repeated with 33 mg/kg of iron sulfate and iron oxide. The results showed that 33 mg/kg of iron sulfate 1 hour after treatment caused a significant difference in the Fe and TIBG levels between all the groups (P=0.014 for Fe and P=0.027 for TIBG). Our data showed that the absorption of iron oxide was similar to that of ferrous sulfate and in high doses was as useful as iron supplement. PMID:28293054

  3. Ceruloplasmin protects injured spinal cord from iron-mediated oxidative damage.

    PubMed

    Rathore, Khizr I; Kerr, Bradley J; Redensek, Adriana; López-Vales, Rubèn; Jeong, Suh Young; Ponka, Prem; David, Samuel

    2008-11-26

    CNS injury-induced hemorrhage and tissue damage leads to excess iron, which can cause secondary degeneration. The mechanisms that handle this excess iron are not fully understood. We report that spinal cord contusion injury (SCI) in mice induces an "iron homeostatic response" that partially limits iron-catalyzed oxidative damage. We show that ceruloplasmin (Cp), a ferroxidase that oxidizes toxic ferrous iron, is important for this process. SCI in Cp-deficient mice demonstrates that Cp detoxifies and mobilizes iron and reduces secondary tissue degeneration and functional loss. Our results provide new insights into how astrocytes and macrophages handle iron after SCI. Importantly, we show that iron chelator treatment has a delayed effect in improving locomotor recovery between 3 and 6 weeks after SCI. These data reveal important aspects of the molecular control of CNS iron homeostasis after SCI and suggest that iron chelator therapy may improve functional recovery after CNS trauma and hemorrhagic stroke.

  4. Iron deficiency suppresses ileal nitric oxide synthase activity.

    PubMed

    Goldblatt, M I; Choi, S H; Swartz-Basile, D A; Nakeeb, A; Sarna, S K; Pitt, H A

    2001-01-01

    Intestinal motility disorders are more common in women of childbearing age who are prone to iron deficiency anemia. The neurotransmitters nitric oxide (NO) and acetylcholine (ACh) play a key role in ileal smooth muscle relaxation and contraction, respectively. Iron-containing heme is known to be a cofactor for nitric oxide synthase (NOS), the enzyme responsible for NO production. Therefore we tested the hypothesis that iron deficiency would downregulate ileal NOS activity without affecting the ileum's response to ACh. Twelve adult female prairie dogs were fed either an iron-supplemented (Fe+) (200 ppm) (n = 6) or an iron-deficient (Fe-) (8 ppm) (n = 6) diet for 8 weeks. Ileal circular muscle strips were harvested to measure responses to ACh and electrical field stimulation. Under nonadrenergic noncholinergic (NANC) conditions, Nomega-nitro-L-arginine (L-NNA), an NOS inhibitor, and VIP(10-28), a vasoactive intestinal peptide (VIP) inhibitor, were added prior to electrical field stimulation. NANC inhibitory responses are expressed as a percentage of optimal relaxation from EDTA. The excitatory response to ACh was similar in both groups (1.1 +/- 0.3 N/cm(2) vs. 1.5 +/- 0.3 N/cm(2), P = 0.45). The inhibitory response to electrical field stimulation under NANC conditions was greater in the Fe+ group (34.7 +/- 2.9%) compared to the Fe- group (23.9 +/- 3.2%; P<0.01). L-NNA eliminated the inhibitory response in the Fe+ group (0.02 +/- 0.02%) but not in the Fe- group (8.38 +/- 2.15%; P <0.01). VIP(10-28) led to greater relaxation in the Fe+ animals (45.8 +/- 6.6%) than in the Fe- animals (23.4 +/- 5.8%; P <0.05). Both L-NNA and VIP(10-28) had no inhibitory response (0.02 +/- 0.02%) in the Fe+ animals, whereas the Fe- animals had some residual inhibition (2.54 +/- 1.04%; P <0.05). These data suggest that ileal NANC relaxation is due to NOS and that iron deficiency results in (1) decreased NANC relaxation, (2) a compensatory relaxation due to a non-NOS, non-VIP mechanism, and

  5. Review of world literature finds iron oxides noncarcinogenic

    SciTech Connect

    Stokinger, H.E.

    1984-02-01

    Iron oxide appeared in the first list of 154 Threshold Limit Values adopted by the American Conference of Governmental Industrial Hygienists at its April 1949 annual meeting. It was set to control dust and fume at the recommended value of 15 mg/M/sup 3/, at the time, the limit for an inert or ''nuisance'' dust, and was based on studies of welders made earlier by the US Dept. of Labor and by Drinker and Nelson. By 1964, the TLV was tentatively reduced to 10 mg/M/sup 3/ after a considerable body of literature had accumulated not only on the health experience of welders, but of other occupations involving iron oxides as well. As a group, these studies indicated that 15 mg/M/sup 3/ permitted too great accumulations of iron pigmentation in the lung whose chronic retention effects were not known with certainty. Also, an occasional report of cancer of the lungs appeared particulary among British hematite miners, although these findings were immediately questioned on statistical grounds. In seeming confirmation of these early reports of cancer, an alarming number of reports of cancer of the lung and respiratory tract among welders and foundrymen began to appear by 1970, reaching a crescendo by the end of that decade. As past chairman of the TLV Committee, the author decided to examine the bases of these findings. This review is the result of this examination.

  6. Crystal structure of iron-oxide nanoparticles synthesized from ferritin

    NASA Astrophysics Data System (ADS)

    Krispin, Michael; Ullrich, Aladin; Horn, Siegfried

    2012-02-01

    We have investigated the crystal structure of nanosized iron-oxide by X-ray diffraction (XRD), extended X-ray absorption fine structure measurements at the iron K-edge as well as by transmission electron microscopy (TEM). Iron-oxide nanoparticles were produced by thermal treatment of horse spleen ferritin molecules. The structure of these particles was compared to α-Fe2O3 and γ-Fe2O3 nanopowder references. The thermal treatment of a submonolayer film of ferritin molecules results in pure γ-Fe2O3 nanoparticles, while for films above a certain thickness α-Fe2O3 and γ-Fe2O3 coexist, exhibiting two different crystallite sizes. TEM shows a characteristic particle diameter of 7 nm for γ-Fe2O3 resulting from thermal treatment of monolayers, consistent with the crystallite size of the γ-phase as obtained from XRD measurements on multi-layered samples. XRD shows the α-Fe2O3 phase to be characterized by a crystallite size of 34 nm.

  7. Mercury removal in wastewater by iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Vélez, E.; Campillo, G. E.; Morales, G.; Hincapié, C.; Osorio, J.; Arnache, O.; Uribe, J. I.; Jaramillo, F.

    2016-02-01

    Mercury is one of the persistent pollutants in wastewater; it is becoming a severe environmental and public health problem, this is why nowadays its removal is an obligation. Iron oxide nanoparticles are receiving much attention due to their properties, such as: great biocompatibility, ease of separation, high relation of surface-area to volume, surface modifiability, reusability, excellent magnetic properties and relative low cost. In this experiment, Fe3O4 and γ-Fe2O3 nanoparticles were synthesized using iron salts and NaOH as precipitation agents, and Aloe Vera as stabilizing agent; then these nanoparticles were characterized by three different measurements: first, using a Zetasizer Nano ZS for their size estimation, secondly UV-visible spectroscopy which showed the existence of resonance of plasmon at λmax∼360 nm, and lastly by Scanning Electron Microscopy (SEM) to determine nanoparticles form. The results of this characterization showed that the obtained Iron oxides nanoparticles have a narrow size distribution (∼100nm). Mercury removal of 70% approximately was confirmed by atomic absorption spectroscopy measurements.

  8. Reductive dechlorination of chlorinated solvents by zero-valent iron, iron oxide and iron sulfide minerals

    SciTech Connect

    Sivavec, T.M.; Horney, D.P.

    1996-10-01

    The degradation of chlorinated solvents by reduction at the surface of zero-valent metals and bimetallic systems has emerged as an important approach to the in-situ remediation of ground water. Reduction by iron metal was studied in batch and column systems to develop a mechanistic understanding of the reaction chemistry and to determine the factors that affect dechlorination rate and long term performance in field applications.

  9. Iron Oxidation State in Fulgurite Glass

    NASA Astrophysics Data System (ADS)

    Giuli, G.; Pratesi, G.; Paris, E.; Cibin, G.

    2016-08-01

    XAS data of both fulgurite samples are consistent with Fe being mostly divalent, similar to tektite glasses. whereas the unmolten sand enclosed in the tube fulgurite does not show any sign of reduction, Fe being mostly trivalent in the sand.

  10. Iron-oxide colloidal nanoclusters: from fundamental physical properties to diagnosis and therapy

    NASA Astrophysics Data System (ADS)

    Kostopoulou, Athanasia; Brintakis, Konstantinos; Lascialfari, Alessandro; Angelakeris, Mavroeidis; Vasilakaki, Marianna; Trohidou, Kalliopi; Douvalis, Alexios P.; Psycharakis, Stylianos; Ranella, Anthi; Manna, Liberato; Lappas, Alexandros

    2014-03-01

    Research on magnetic nanocrystals attracts wide-spread interest because of their challenging fundamental properties, but it is also driven by problems of practical importance to the society, ranging from electronics (e.g. magnetic recording) to biomedicine. In that respect, iron oxides are model functional materials as they adopt a variety of oxidation states and coordinations that facilitate their use. We show that a promising way to engineer further their technological potential in diagnosis and therapy is the assembly of primary nanocrystals into larger colloidal entities, possibly with increased structural complexity. In this context, elevated-temperature nanochemistry (c.f. based on a polyol approach) permitted us to develop size-tunable, low-cytotoxicity iron-oxide nanoclusters, entailing iso-oriented nanocrystals, with enhanced magnetization. Experimental (magnetometry, electron microscopy, Mössbauer and NMR spectroscopies) results supported by Monte Carlo simulations are reviewed to show that such assemblies of surface-functionalized iron oxide nanocrystals have a strong potential for innovation. The clusters' optimized magnetic anisotropy (including microscopic surface spin disorder) and weak ferrimagnetism at room temperature, while they do not undermine colloidal stability, endow them a profound advantage as efficient MRI contrast agents and hyperthermic mediators with important biomedical potential.

  11. Synthesis and Reactive Properties of Iron Oxide-Coated Nanoaluminum

    NASA Astrophysics Data System (ADS)

    Kaplowitz, Daniel A.; Jian, Guoqiang; Gaskell, Karen; Jacob, Rohit; Zachariah, Michael R.

    2014-04-01

    A homogeneous coating of Fe3O4 on in situ-generated nanoaluminum was accomplished by thermal decomposition of Fe(CO)5 in an aluminum aerosol stream and subsequent oxidation of iron by air bleed. X-ray photoelectron spectroscopy (XPS) investigation revealed that oxygen penetrated through this coating, and Fe3O4 facilitated the formation of an expanded aluminum oxide layer compared to an uncoated aluminum case. Closed cell combustion tests displayed a minor decrease in pressure response for the coated product, which was attributed to the increased aluminum oxide layer. The critical ignition temperature was reduced for the coated product in T-jump fine-wire combustion tests.

  12. Low-temperature formation of magnetic iron oxides

    NASA Technical Reports Server (NTRS)

    Koch, Chr. Bender; Madsen, M. B.

    1992-01-01

    Elemental analysis and magnetic measurements of the surface of Mars have indicated the presence of an iron oxide with a considerable magnetic moment. Identification of the oxide phase(s) is an important subject as this may be used to identify the process of weathering on the martian surface as well as the composition of the Mars regolith itself. Consequently, interest was in evidence of new formation of strongly magnetic phases (e.g., magnetite, maghemite, feroxyhyte) in terrestrially derived Mars sample analogs. Within the group of Mars sample analogs derived from low-temperature weathering of basalts in Arctic regions, evidence of magnetic oxides formed at the outermost weathering rind was never observed. However, in one instance where the weathering products accumulating in a crack of a basaltic stone were investigated, evidence of magnetite was found. The experimental details are presented.

  13. Low-temperature formation of magnetic iron oxides

    NASA Technical Reports Server (NTRS)

    Koch, Chr. Bender; Madsen, M. B.

    1992-01-01

    Elemental analysis and magnetic measurements of the surface of Mars have indicated the presence of an iron oxide with a considerable magnetic moment. Identification of the oxide phase(s) is an important subject as this may be used to identify the process of weathering on the martian surface as well as the composition of the Mars regolith itself. Consequently, interest was in evidence of new formation of strongly magnetic phases (e.g., magnetite, maghemite, feroxyhyte) in terrestrially derived Mars sample analogs. Within the group of Mars sample analogs derived from low-temperature weathering of basalts in Arctic regions, evidence of magnetic oxides formed at the outermost weathering rind was never observed. However, in one instance where the weathering products accumulating in a crack of a basaltic stone were investigated, evidence of magnetite was found. The experimental details are presented.

  14. Synthesis and Evaluation of Nanostructured Gold-Iron Oxide Catalysts for the Oxidative Dehydrogenation of Cyclohexane

    NASA Astrophysics Data System (ADS)

    Wu, Peng

    Shape-controlled iron oxide and gold-iron oxide catalysts with a cubic inverse spinel structure were studied in this thesis for the oxidative dehydrogenation of cyclohexane. The structure of iron oxide and gold-iron oxide catalysts has no major impact on their oxidative dehydrogenation activity. However, the product selectivity is influenced. Both cyclohexene and benzene are formed on bare iron oxide nanoshapes, while benzene is the only dehydrogenation product in the presence of gold. The selectivity of benzene over CO2 depends strongly on the stability of the iron oxide support and the gold-support interaction. The highest benzene yield has been observed on gold-iron oxide octahedra. {111}-bound nanooctahedra are highly stable in reaction conditions at 300 °C, while {100}-bound nanocubes start to sinter above 250 °C. The highest benzene yield has been observed on gold-iron oxide nanooctahedra, which are likely to have gold atoms, and few-atom gold clusters strongly-bound on their surface. Cationic gold appears to be the active site for benzene formation. An all-organic method to prepare Au-FeOx nano-catalysts is needed due to the inconvenience of the half-organic, half-inorganic synthesis process discussed above. Several methods from the literature to prepare gold-iron oxide nanocomposites completely in organic solvents were reviewed and followed. FeOx Au synthesis procedures in literatures are initially designed for a Au content of over 70%. This approach was tried here to prepare composites with a much lower Au content (2-5 atom. %). Heat treatment is required to bond Au and FeOx NPs in the organic-phase syntheses. Au-FeOx-4 was obtained as a selective catalyst for the ODH of cyclohexane. A Audelta+ peak is observed in the UV-Vis spectrum of sample Au-FeOx-4. This different Au delta+ form may be cationic Au nano-clusters interacting with the FeOx support. It has been demonstrated that cationic gold is responsible for dehydrogenation behavior. Furthermore, the

  15. Anoxic photochemical oxidation of siderite generates molecular hydrogen and iron oxides

    PubMed Central

    Kim, J. Dongun; Yee, Nathan; Nanda, Vikas; Falkowski, Paul G.

    2013-01-01

    Photochemical reactions of minerals are underappreciated processes that can make or break chemical bonds. We report the photooxidation of siderite (FeCO3) by UV radiation to produce hydrogen gas and iron oxides via a two-photon reaction. The calculated quantum yield for the reaction suggests photooxidation of siderite would have been a significant source of molecular hydrogen for the first half of Earth’s history. Further, experimental results indicate this abiotic, photochemical process may have led to the formation of iron oxides under anoxic conditions. The reaction would have continued through the Archean to at least the early phases of the Great Oxidation Event, and provided a mechanism for oxidizing the atmosphere through the loss of hydrogen to space, while simultaneously providing a key reductant for microbial metabolism. We propose that the photochemistry of Earth-abundant minerals with wide band gaps would have potentially played a critical role in shaping the biogeochemical evolution of early Earth. PMID:23733945

  16. Selective Inhibition of the Oxidation of Ferrous Iron or Sulfur in Thiobacillus ferrooxidans

    PubMed Central

    Harahuc, Lesia; Lizama, Hector M.; Suzuki, Isamu

    2000-01-01

    The oxidation of either ferrous iron or sulfur by Thiobacillus ferrooxidans was selectively inhibited or controlled by various anions, inhibitors, and osmotic pressure. Iron oxidation was more sensitive than sulfur oxidation to inhibition by chloride, phosphate, and nitrate at low concentrations (below 0.1 M) and also to inhibition by azide and cyanide. Sulfur oxidation was more sensitive than iron oxidation to the inhibitory effect of high osmotic pressure. These differences were evident not only between iron oxidation by iron-grown cells and sulfur oxidation by sulfur-grown cells but also between the iron and sulfur oxidation activities of the same iron-grown cells. Growth experiments with ferrous iron or sulfur as an oxidizable substrate confirmed the higher sensitivity of iron oxidation to inhibition by phosphate, chloride, azide, and cyanide. Sulfur oxidation was actually stimulated by 50 mM phosphate or chloride. Leaching of Fe and Zn from pyrite (FeS2) and sphalerite (ZnS) by T. ferrooxidans was differentially affected by phosphate and chloride, which inhibited the solubilization of Fe without significantly affecting the solubilization of Zn. PMID:10698768

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

    PubMed

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

    2011-11-01

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

  18. The effect of cationic polymer treatment on adhesion of iron oxide to eyelashes.

    PubMed

    Ko, S; Roh, Y H; Choo, J H; Jang, S H; Han, S H; Jang, H G

    2009-01-01

    The aim of this study was to investigate the effect of iron oxide application on improving the volume of eyelashes. Iron oxide, having a negative surface charge in its natural form, was coated with commercial cationic polymers to increase its adhesion. The iron oxides coated with different types and concentrations of these polymers were incorporated into a basic mascara formula to test their volume effects by means of the weight difference of eyelashes.The results indicated that the type and concentration of coating materials affect the surface zeta potential and particle cluster size of iron oxides. The type of cationic polymer, especially, was shown to modify both factors of iron oxide. The obtained results also suggested that the volume effect of mascara increases with a higher positive surface zeta potential and a smaller particle cluster size of the coated iron oxides.

  19. RGD-conjugated iron oxide magnetic nanoparticles for magnetic resonance imaging contrast enhancement and hyperthermia.

    PubMed

    Zheng, S W; Huang, M; Hong, R Y; Deng, S M; Cheng, L F; Gao, B; Badami, D

    2014-03-01

    The purpose of this study was to develop a specific targeting magnetic nanoparticle probe for magnetic resonance imaging and therapy in the form of local hyperthermia. Carboxymethyl dextran-coated ultrasmall superparamagnetic iron oxide nanoparticles with carboxyl groups were coupled to cyclic arginine-glycine-aspartic peptides for integrin α(v)β₃ targeting. The particle size, magnetic properties, heating effect, and stability of the arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide were measured. The arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide demonstrates excellent stability and fast magneto-temperature response. Magnetic resonance imaging signal intensity of Bcap37 cells incubated with arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide was significantly decreased compared with that incubated with plain ultrasmall superparamagnetic iron oxide. The preferential uptake of arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide by target cells was further confirmed by Prussian blue staining and confocal laser scanning microscopy.

  20. Magnetic characteristics of iron-modified oxide layers on titanium

    NASA Astrophysics Data System (ADS)

    Rudnev, V. S.; Adigamova, M. V.; Lukiyanchuk, I. V.; Tkachenko, I. A.; Morozova, V. P.; Ustinov, A. Yu.; Kharitonskii, P. V.; Frolov, A. M.

    2014-12-01

    Iron-modified TiO2 coatings on titanium exhibiting ferromagnetic properties are formed by combining plasma electrolytic oxidation (PEO) and impregnation with subsequent annealing. It is found that iron is contained in the composition of dispersed particles with sizes of 1-10 μm distributed over the surface of the coatings. It is shown that the coercive force of the coating on titanium samples is 20-70 Oe. The composition, structure, and magnetic properties of the samples with coatings prepared via direct PEO and by combining PEO and impregnation are compared. It is concluded that impregnation and annealing procedures can be used to impart ferromagnetic properties to PEO coatings with different compositions, e.g., protective coatings and coatings applied in catalysis or medicine.

  1. In Vivo Clearance and Toxicity of Monodisperse Iron Oxide Nanocrystals

    PubMed Central

    Gu, Luo; Fang, Ronnie H.; Sailor, Michael J.; Park, Ji-Ho

    2012-01-01

    Thermal decomposition of organometallic precursors have been found to generate highly crystalline iron oxide (IO) nanocrystals that display superior MR contrast and lower polydispersity than IO nanocrystals synthesized by aqueous precipitation. In the present study, the in vivo characteristics of IO nanocrystals prepared by the thermal decomposition route and then coated with a phospholipid containing a pendant poly(ethylene glycol) chain are examined. The size and surface chemistry of the IO nanocrystal influences the biodistibution, the rate of biodegradation and bioclearance, and the biodegradation products. We conclude that the in vivo fate of PEGylated monodisperse IO nanocrystals and the iron, phospholipid, and oleic acid biodegradation products may influence the cellular environments in the organs and blood that can determine their safety in the body. PMID:22646927

  2. Hydrophilic Packaging of Iron Oxide Nanoclusters for Highly Sensitive Imaging

    PubMed Central

    Smith, Cartney E.; Ernenwein, Dawn; Shkumatov, Artem; Clay, Nicholas; Lee, JuYeon; Melhem, Molly; Misra, Sanjay; Zimmerman, Steven C.; Kong, Hyunjoon

    2015-01-01

    Superparamagnetic iron oxide nanoparticles (SPIONs) are used as imaging probes to provide contrast in magnetic resonance images. Successful use of SPIONs in targeted applications greatly depends on their ability to generate contrast, even at low levels of accumulation, in the tissue of interest. In the present study, we report that SPION nanoclusters packaged to a controlled size by a hyperbranched polyglycerol (HPG) can target tissue defects and have a high relaxivity of 719 mM−1s−1, which was close to their theoretical maximal limit. The resulting nanoclusters were able to identify regions of defective vasculature in an ischemic murine hindlimb using MRI with iron doses that were 5–10 fold lower than those typically used in preclinical studies. Such high relaxivity was attributed to the molecular architecture of HPG, which mimics that of the water retentive polysaccharide, glycogen. The results of this study will be broadly useful in sensitive imaging applications. PMID:26291408

  3. Iron oxides stimulate sulfate-driven anaerobic methane oxidation in seeps.

    PubMed

    Sivan, Orit; Antler, Gilad; Turchyn, Alexandra V; Marlow, Jeffrey J; Orphan, Victoria J

    2014-10-07

    Seep sediments are dominated by intensive microbial sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Through geochemical measurements of incubation experiments with methane seep sediments collected from Hydrate Ridge, we provide insight into the role of iron oxides in sulfate-driven AOM. Seep sediments incubated with (13)C-labeled methane showed co-occurring sulfate reduction, AOM, and methanogenesis. The isotope fractionation factors for sulfur and oxygen isotopes in sulfate were about 40‰ and 22‰, respectively, reinforcing the difference between microbial sulfate reduction in methane seeps versus other sedimentary environments (for example, sulfur isotope fractionation above 60‰ in sulfate reduction coupled to organic carbon oxidation or in diffusive sedimentary sulfate-methane transition zone). The addition of hematite to these microcosm experiments resulted in significant microbial iron reduction as well as enhancing sulfate-driven AOM. The magnitude of the isotope fractionation of sulfur and oxygen isotopes in sulfate from these incubations was lowered by about 50%, indicating the involvement of iron oxides during sulfate reduction in methane seeps. The similar relative change between the oxygen versus sulfur isotopes of sulfate in all experiments (with and without hematite addition) suggests that oxidized forms of iron, naturally present in the sediment incubations, were involved in sulfate reduction, with hematite addition increasing the sulfate recycling or the activity of sulfur-cycling microorganisms by about 40%. These results highlight a role for natural iron oxides during bacterial sulfate reduction in methane seeps not only as nutrient but also as stimulator of sulfur recycling.

  4. Iron oxides stimulate sulfate-driven anaerobic methane oxidation in seeps

    PubMed Central

    Sivan, Orit; Antler, Gilad; Turchyn, Alexandra V.; Marlow, Jeffrey J.; Orphan, Victoria J.

    2014-01-01

    Seep sediments are dominated by intensive microbial sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Through geochemical measurements of incubation experiments with methane seep sediments collected from Hydrate Ridge, we provide insight into the role of iron oxides in sulfate-driven AOM. Seep sediments incubated with 13C-labeled methane showed co-occurring sulfate reduction, AOM, and methanogenesis. The isotope fractionation factors for sulfur and oxygen isotopes in sulfate were about 40‰ and 22‰, respectively, reinforcing the difference between microbial sulfate reduction in methane seeps versus other sedimentary environments (for example, sulfur isotope fractionation above 60‰ in sulfate reduction coupled to organic carbon oxidation or in diffusive sedimentary sulfate–methane transition zone). The addition of hematite to these microcosm experiments resulted in significant microbial iron reduction as well as enhancing sulfate-driven AOM. The magnitude of the isotope fractionation of sulfur and oxygen isotopes in sulfate from these incubations was lowered by about 50%, indicating the involvement of iron oxides during sulfate reduction in methane seeps. The similar relative change between the oxygen versus sulfur isotopes of sulfate in all experiments (with and without hematite addition) suggests that oxidized forms of iron, naturally present in the sediment incubations, were involved in sulfate reduction, with hematite addition increasing the sulfate recycling or the activity of sulfur-cycling microorganisms by about 40%. These results highlight a role for natural iron oxides during bacterial sulfate reduction in methane seeps not only as nutrient but also as stimulator of sulfur recycling. PMID:25246590

  5. Nitric oxide, nitrosyl iron complexes, ferritin and frataxin: a well equipped team to preserve plant iron homeostasis.

    PubMed

    Ramirez, Leonor; Simontacchi, Marcela; Murgia, Irene; Zabaleta, Eduardo; Lamattina, Lorenzo

    2011-11-01

    Iron is a key element in plant nutrition. Iron deficiency as well as iron overload results in serious metabolic disorders that affect photosynthesis, respiration and general plant fitness with direct consequences on crop production. More than 25% of the cultivable land possesses low iron availability due to high pH (calcareous soils). Plant biologists are challenged by this concern and aimed to find new avenues to ameliorate plant responses and keep iron homeostasis under control even at wide range of iron availability in various soils. For this purpose, detailed knowledge of iron uptake, transport, storage and interactions with cellular compounds will help to construct a more complete picture of its role as essential nutrient. In this review, we summarize and describe the recent findings involving four central players involved in keeping cellular iron homeostasis in plants: nitric oxide, ferritin, frataxin and nitrosyl iron complexes. We attempt to highlight the interactions among these actors in different scenarios occurring under iron deficiency or iron overload, and discuss their counteracting and/or coordinating actions leading to the control of iron homeostasis.

  6. Chitosan-Iron Oxide Coated Graphene Oxide Nanocomposite Hydrogel: A Robust and Soft Antimicrobial Biofilm.

    PubMed

    Konwar, Achyut; Kalita, Sanjeeb; Kotoky, Jibon; Chowdhury, Devasish

    2016-08-17

    We report a robust biofilm with antimicrobial properties fabricated from chitosan-iron oxide coated graphene oxide nanocomposite hydrogel. For the first time, the coprecipitation method was used for the successful synthesis of iron oxide coated graphene oxide (GIO) nanomaterial. After this, films were fabricated by the gel-casting technique aided by the self-healing ability of the chitosan hydrogel network system. Both the nanomaterial and the nanocomposite films were characterized by techniques such as scanning electron microscopy, FT-IR spectroscopy, X-ray diffraction, and vibrating sample magnetometry. Measurements of the thermodynamic stability and mechanical properties of the films indictaed a significant improvement in their thermal and mechanical properties. Moreover, the stress-strain profile indicated the tough nature of the nanocomposite hydrogel films. These improvements, therefore, indicated an effective interaction and good compatibility of the GIO nanomaterial with the chitosan hydrogel matrix. In addition, it was also possible to fabricate films with tunable surface properties such as hydrophobicity simply by varying the loading percentage of GIO nanomaterial in the hydrogel matrix. Fascinatingly, the chitosan-iron oxide coated graphene oxide nanocomposite hydrogel films displayed significant antimicrobial activities against both Gram-positive and Gram-negative bacterial strains, such as methicillin-resistant Staphylococcus aureus, Staphylococcus aureus, and Escherichia coli, and also against the opportunistic dermatophyte Candida albicans. The antimicrobial activities of the films were tested by agar diffusion assay and antimicrobial testing based on direct contact. A comparison of the antimicrobial activity of the chitosan-GIO nanocomposite hydrogel films with those of individual chitosan-graphene oxide and chitosan-iron oxide nanocomposite films demonstrated a higher antimicrobial activity for the former in both types of tests. In vitro hemolysis

  7. How Geochemistry Provides Habitability: A Case Study of Iron Oxidation

    NASA Astrophysics Data System (ADS)

    St Clair, B.; Shock, E.

    2016-12-01

    Two things have to be true for chemotrophic microbes to gain chemical energy from their environment. First, there must be a source of energy, provided by compounds in differing oxidation states that are out of thermodynamic equilibrium with one another. Second, there must be mechanistic difficulties that are keeping those compounds from reacting, preventing chemical energy from dissipating on its own. Using this energetic reference frame, geochemical habitability requires the combined presence of energy sources and kinetic barriers, which are determined by numerous variables including temperature, pH, and concentrations of reactants and products. Here we present habitable geochemical space visually as habitability diagrams. As an example, the pH and temperature ranges that can sustain life for a specific reaction can be delineated by the aforementioned kinetic and energetic boundaries, together with commonly attainable pH / temperatures of environments at Earth's surface. Other habitability diagrams can be constructed for any combination of relevant geochemical variables to better illustrate the inherently multidimensional problem. We have chosen iron oxidation reactions to illustrate this point, as kinetic and energetic boundaries can be found at conditions readily attainable in natural systems. By calculating energy availability (as affinity, A) in each system from compositional data where concentrations of all reactants and products are known, the energy boundary is defined by A=0. Evaluating the kinetic boundary means measuring the relative rates of the biotic and abiotic processes in situ, which we have done in Yellowstone hot springs, acid mine drainage in Arizona, and cold springs in the Swiss Alps. Many experiments have yielded biological rates, and all have yielded abiotic rates, which range from inconsequential to rates too rapid for biology to compete. These results encompass both sides of the kinetic boundary, defining its trajectory. When plotted in p

  8. VEGF-Iron Oxide Conjugate for Dual MR and PET Imaging of Breast Cancer Angiogenesis

    DTIC Science & Technology

    2007-09-01

    iron oxide nanoparticles conjugated with macrocyclic chelating agent DOTA for 64Cu-labeling and cyclic RGD peptide for integrin alpha (v)beta(3...Nanoparticles We have developed two types of novel superparamagentic iron oxide nanoparticles (USPIO), namely, PVP -IO and PASP-IO...Polyvinylpyrrolidone ( PVP )-coated iron oxide ( PVP -IO) nanoparticles were synthesized by a one-step thermal decomposition method (Fig. 3). The overall size of the

  9. Greenlighting Photoelectrochemical Oxidation of Water by Iron Oxide

    SciTech Connect

    Kim, Dong Wook; Riha, Shannon C.; DeMarco, Erica J.; Martinson, Alex B. F.; Farha, Omar K.; Hupp, Joseph T.

    2014-12-23

    Hematite (alpha-Fe2O3) is one of just a few candidate electrode materials that possess all of the following photocatalyst-essential properties for scalable application to water oxidation: excellent stability, earth-abundance, suitability positive valence-band-edge energy, and significant visible light absorptivity. Despite these merits, hematites modest oxygen evolution reaction kinetics and its poor efficiency in delivering photogenerated holes, especially holes generated by green photons, to the electrode/solution interface, render it ineffective as a practical water-splitting catalyst. Here we show that hole delivery and catalytic utilization can be substantially improved through Ti alloying, provided that the alloyed material is present in ultrathin-thin-film form. Notably, the effects are most pronounced for charges photogenerated by photons with energy comparable to the band gap for excitation of Fe(3d) -> Fe(3d) transitions (i.e., green photons). Additionally, at the optimum Ti substitution level the lifetimes of surface-localized holes, competent for water oxidation, are extended. Together these changes explain an overall improvement in photoelectrochemical performance, especially enhanced internal quantum efficiencies, observed upon Ti(IV) incorporation.

  10. Greenlighting photoelectrochemical oxidation of water by iron oxide.

    PubMed

    Kim, Dong Wook; Riha, Shannon C; DeMarco, Erica J; Martinson, Alex B F; Farha, Omar K; Hupp, Joseph T

    2014-12-23

    Hematite (α-Fe2O3) is one of just a few candidate electrode materials that possess all of the following photocatalyst-essential properties for scalable application to water oxidation: excellent stability, earth-abundance, suitability positive valence-band-edge energy, and significant visible light absorptivity. Despite these merits, hematite's modest oxygen evolution reaction kinetics and its poor efficiency in delivering photogenerated holes, especially holes generated by green photons, to the electrode/solution interface, render it ineffective as a practical water-splitting catalyst. Here we show that hole delivery and catalytic utilization can be substantially improved through Ti alloying, provided that the alloyed material is present in ultrathin-thin-film form. Notably, the effects are most pronounced for charges photogenerated by photons with energy comparable to the band gap for excitation of Fe(3d)→Fe(3d) transitions (i.e., green photons). Additionally, at the optimum Ti substitution level the lifetimes of surface-localized holes, competent for water oxidation, are extended. Together these changes explain an overall improvement in photoelectrochemical performance, especially enhanced internal quantum efficiencies, observed upon Ti(IV) incorporation.

  11. SURFACE COMPLEXATION OF ACTINIDES WITH IRON OXIDES: IMPLICATIONS FOR RADIONUCLIDE TRANSPORT IN NEAR-SURFACE AQUIFERS

    SciTech Connect

    J.L. Jerden Jr.; A.J. Kropf; Y. Tsai

    2005-08-25

    The surface complexation of actinides with iron oxides plays a key role in actinide transport and retardation in geosphere-biosphere systems. The development of accurate actinide transport models therefore requires a mechanistic understanding of surface complexation reactions (i.e. knowledge of chemical speciation at mineral/fluid interfaces). Iron oxides are particularly important actinide sorbents due to their pH dependent surface charges, relatively high surface areas and ubiquity in oxic and suboxic near-surface systems. In this paper we present results from field and laboratory investigations that elucidate the mechanisms involved in binding uranium and neptunium to iron oxide mineral substrates in near neutral groundwaters. The field study involved sampling and characterizing uranium-bearing groundwaters and solids from a saprolite aquifer overlying an unmined uranium deposit in the Virginia Piedmont. The groundwaters were analyzed by inductively coupled mass spectrometry and ion chromatography and the aquifer solids were analyzed by electron microprobe. The laboratory study involved a series of batch sorption tests in which U(VI) and Np(V) were reacted with goethite, hematite and magnetite in simulated groundwaters. The pH, ionic strength, aging time, and sorbent/sorbate ratios were varied in these experiments. The oxidation state and coordination environment of neptunium in solutions and sorbents from the batch tests were characterized by X-ray absorption spectroscopy (XAS) at the Advanced Photon Source, Argonne National Laboratory. Results from this work indicate that, in oxidizing near-surface aquifers, the dissolved concentration of uranium may be limited to less than 30 parts per billion due to uptake by iron oxide mineral coatings and the precipitation of sparingly soluble U(VI) phosphate minerals. Results from the batch adsorption tests showed that, in near neutral groundwaters, a significant fraction of the uranium and neptunium adsorbed as strongly

  12. Neurobehavioural Toxicity of Iron Oxide Nanoparticles in Mice.

    PubMed

    Dhakshinamoorthy, Vasanth; Manickam, Vijayprakash; Perumal, Ekambaram

    2017-08-01

    Iron oxide nanoparticles (Fe2O3-NPs) are widely used in various biomedical applications, extremely in neurotheranostics. Simultaneously, Fe2O3-NP usage is of alarming concern, as its exposure to living systems causes deleterious effects due to its redox potential. However, study on the neurobehavioural impacts of Fe2O3-NPs is very limited. In this regard, adult male mice were intraperitoneally administered with Fe2O3-NPs (25 and 50 mg/kg body weight) once a week for 4 weeks. A significant change in locomotor behaviour and spatial memory was observed in Fe2O3-NP-treated animals. Damages to blood-brain barrier permeability by Fe2O3-NPs and their accumulation in brain regions were evidenced by Evan's blue staining, iron estimation and Prussian blue staining. Elevated nitric oxide, acetylcholinesterase, lactate dehydrogenase leakage and demyelination were observed in the Fe2O3-NP-exposed brain tissues. Imbalanced levels of ROS generation and antioxidant defence mechanism (superoxide dismutase and catalase) cause damages to lipids, proteins and DNA. PARP and cleaved caspase 3 expression levels were found to be increased in the Fe2O3-NP-exposed brain regions which confirms DNA damage and apoptosis. Thus, repeated Fe2O3-NP exposure causes neurobehavioural impairments by nanoparticle accumulation, oxidative stress and apoptosis in the mouse brain.

  13. Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Iron-Natural Organic Matter Interactions.

    PubMed

    Jiang, Chao; Garg, Shikha; Waite, T David

    2015-12-15

    Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

  14. From iron oxide nanoparticles towards advanced iron-based inorganic materials designed for biomedical applications.

    PubMed

    Figuerola, Albert; Di Corato, Riccardo; Manna, Liberato; Pellegrino, Teresa

    2010-08-01

    In the last decade the progress achieved on the synthesis of inorganic nanostructures has been accompanied by the parallel exploitation of these systems in various fields, among them are biology and medicine. We provide here an overview of the iron-based inorganic nanostructured materials that have been developed and tested in these fields. We will highlight the major concepts on the preparation, physical properties and applications of such nanostructures, starting from the most investigated iron oxide nanoparticles. We will describe then the new generation of inorganic hybrid nanostructures, which are structures that integrate in each nano-object multiple inorganic nanocrystals of different materials. In our discussion we will focus on those works that have provided a sound proof of concept on the potential of the various systems as diagnostic and therapeutic agents. Copyright 2010 Elsevier Ltd. All rights reserved.

  15. Nitric Oxide Activation by Distal Redox Modulation in Tetranuclear Iron Nitrosyl Complexes

    PubMed Central

    de Ruiter, Graham; Thompson, Niklas B.; Lionetti, Davide; Agapie, Theodor

    2016-01-01

    A series of tetranuclear iron complexes displaying a site-differentiated metal center were synthesized. Three of the metal centers are coordinated to our previously reported ligand, based on a 1,3,5-triarylbenzene motif with nitrogen and oxygen donors. The fourth (apical) iron center is coordinatively unsaturated and appended to the trinuclear core through three bridging pyrazolates and an interstitial μ4-oxide moiety. Electrochemical studies of complex [LFe3(PhPz)3OFe][OTf]2 revealed three reversible redox events assigned to the FeII4/FeII3FeIII (−1.733 V), FeII3FeIII/FeII2FeIII2 (−0.727 V), and FeII2FeIII2/FeIIFeIII3 (0.018 V) redox-couples. Complexes in all redox states were isolated, and three were characterized structurally by single crystal X-ray diffraction. Combined Mössbauer spectroscopic and crystallographic studies indicate that the change in oxidation state is exclusively localized at the triiron core, without changing the oxidation state of the apical metal center. This phenomenon is assigned to differences in the coordination environment of the two metal sites in the cluster, and provides a strategy for storing electron and hole equivalents without affecting the oxidation state of the coordinatively unsaturated metal. The presence of an additional single ligand-binding site allowed for study of the effect of redox modulation on nitric oxide activation by an FeII metal center. Treatment of the clusters with nitric oxide resulted in binding of NO to the apical iron center generating a {FeNO}7 moiety. As with the NO-free precursors, three reversible redox events are observed electrochemically and are localized at the iron centers distal from the NO ligand. Altering the redox state of the triiron core resulted in significant change in the NO stretching frequency, by as much as 100 cm−1, indicative of NO activation modulated by remote metal centers. The increased activation of NO is attributed to structural changes within the clusters, in

  16. Superparamagnetic iron oxide nanoparticles: magnetic nanoplatforms as drug carriers

    PubMed Central

    Wahajuddin; Arora, Sumit

    2012-01-01

    A targeted drug delivery system is the need of the hour. Guiding magnetic iron oxide nanoparticles with the help of an external magnetic field to its target is the principle behind the development of superparamagnetic iron oxide nanoparticles (SPIONs) as novel drug delivery vehicles. SPIONs are small synthetic γ-Fe2O3 (maghemite) or Fe3O4 (magnetite) particles with a core ranging between 10 nm and 100 nm in diameter. These magnetic particles are coated with certain biocompatible polymers, such as dextran or polyethylene glycol, which provide chemical handles for the conjugation of therapeutic agents and also improve their blood distribution profile. The current research on SPIONs is opening up wide horizons for their use as diagnostic agents in magnetic resonance imaging as well as for drug delivery vehicles. Delivery of anticancer drugs by coupling with functionalized SPIONs to their targeted site is one of the most pursued areas of research in the development of cancer treatment strategies. SPIONs have also demonstrated their efficiency as nonviral gene vectors that facilitate the introduction of plasmids into the nucleus at rates multifold those of routinely available standard technologies. SPION-induced hyperthermia has also been utilized for localized killing of cancerous cells. Despite their potential biomedical application, alteration in gene expression profiles, disturbance in iron homeostasis, oxidative stress, and altered cellular responses are some SPION-related toxicological aspects which require due consideration. This review provides a comprehensive understanding of SPIONs with regard to their method of preparation, their utility as drug delivery vehicles, and some concerns which need to be resolved before they can be moved from bench top to bedside. PMID:22848170

  17. Arsenic Bioremediation by Biogenic Iron Oxides and Sulfides

    PubMed Central

    Couture, Raoul-Marie; Van Cappellen, Philippe; Corkhill, Claire L.; Charnock, John M.; Polya, David A.; Vaughan, David; Vanbroekhoven, Karolien; Lloyd, Jonathan R.

    2013-01-01

    Microcosms containing sediment from an aquifer in Cambodia with naturally elevated levels of arsenic in the associated groundwater were used to evaluate the effectiveness of microbially mediated production of iron minerals for in situ As remediation. The microcosms were first incubated without amendments for 28 days, and the release of As and other geogenic chemicals from the sediments into the aqueous phase was monitored. Nitrate or a mixture of sulfate and lactate was then added to stimulate biological Fe(II) oxidation or sulfate reduction, respectively. Without treatment, soluble As concentrations reached 3.9 ± 0.9 μM at the end of the 143-day experiment. However, in the nitrate- and sulfate-plus-lactate-amended microcosms, soluble As levels decreased to 0.01 and 0.41 ± 0.13 μM, respectively, by the end of the experiment. Analyses using a range of biogeochemical and mineralogical tools indicated that sorption onto freshly formed hydrous ferric oxide (HFO) and iron sulfide mineral phases are the likely mechanisms for As removal in the respective treatments. Incorporation of the experimental results into a one-dimensional transport-reaction model suggests that, under conditions representative of the Cambodian aquifer, the in situ precipitation of HFO would be effective in bringing groundwater into compliance with the World Health Organization (WHO) provisional guideline value for As (10 ppb or 0.13 μM), although soluble Mn release accompanying microbial Fe(II) oxidation presents a potential health concern. In contrast, production of biogenic iron sulfide minerals would not remediate the groundwater As concentration below the recommended WHO limit. PMID:23666325

  18. Nanocrystalline iron oxide aerogels as mesoporous magnetic architectures.

    PubMed

    Long, Jeffrey W; Logan, Michael S; Rhodes, Christopher P; Carpenter, Everett E; Stroud, Rhonda M; Rolison, Debra R

    2004-12-29

    We have developed crystalline nanoarchitectures of iron oxide that exhibit superparamagnetic behavior while still retaining the desirable bicontinuous pore-solid networks and monolithic nature of an aerogel. Iron oxide aerogels are initially produced in an X-ray-amorphous, high-surface-area form, by adapting recently established sol-gel methods using Fe(III) salts and epoxide-based proton scavengers. Controlled temperature/atmosphere treatments convert the as-prepared iron oxide aerogels into nanocrystalline forms with the inverse spinel structure. As a function of the bathing gas, treatment temperature, and treatment history, these nanocrystalline forms can be reversibly tuned to predominantly exhibit either Fe(3)O(4) (magnetite) or gamma-Fe(2)O(3) (maghemite) phases, as verified by electron microscopy, X-ray and electron diffraction, microprobe Raman spectroscopy, and magnetic analysis. Peak deconvolution of the Raman-active Fe-O bands yields valuable information on the local structure and vacancy content of the various aerogel forms, and facilitates the differentiation of Fe(3)O(4) and gamma-Fe(2)O(3) components, which are difficult to assign using only diffraction methods. These nanocrystalline, magnetic forms retain the inherent characteristics of aerogels, including high surface area (>140 m(2) g(-1)), through-connected porosity concentrated in the mesopore size range (2-50 nm), and nanoscale particle sizes (7-18 nm). On the basis of this synthetic and processing protocol, we produce multifunctional nanostructured materials with effective control of the pore-solid architecture, the nanocrystalline phase, and subsequent magnetic properties.

  19. Conquering the Dark Side: Colloidal Iron Oxide Nanoparticles

    PubMed Central

    Senpan, Angana; Caruthers, Shelton D.; Rhee, Ilsu; Mauro, Nicholas A.; Pan, Dipanjan; Hu, Grace; Scott, Michael J.; Fuhrhop, Ralph W.; Gaffney, Patrick J.; Wickline, Samuel A.; Lanza, Gregory M.

    2009-01-01

    Nanomedicine approaches to atherosclerotic disease will have significant impact on the practice and outcomes of cardiovascular medicine. Iron oxide nanoparticles have been extensively used for nontargeted and targeted imaging applications based upon highly sensitive T2* imaging properties, which typically result in negative contrast effects that can only be imaged 24 or more hours after systemic administration due to persistent blood pool interference. Although recent advances involving MR pulse sequences have converted these dark contrast voxels into bright ones, the marked delays in imaging from persistent magnetic background interference and prominent dipole blooming effects of the magnetic susceptibility remain barriers to overcome. We report a T1-weighted (T1w) theranostic colloidal iron oxide nanoparticle platform, CION, which is achieved by entrapping oleate-coated magnetite particles within a cross-linked phospholipid nanoemulsion. Contrary to expectations, this formulation decreased T2 effects thus allowing positive T1w contrast detection down to low nanomolar concentrations. CION, a vascular constrained nanoplatform administered in vivo permitted T1w molecular imaging 1 hour after treatment without blood pool interference, although some T2 shortening effects on blood, induced by the superparamagnetic particles persisted. Moreover, CION was shown to encapsulate antiangiogenic drugs, like fumagillin, and retained them under prolonged dissolution, suggesting significant theranostic functionality. Overall, CION is a platform technology, developed with generally recognized as safe components, that overcomes the temporal and spatial imaging challenges associated with current iron oxide nanoparticle T2 imaging agents, and which has theranostic potential in vascular diseases for detecting unstable ruptured plaque or treating atherosclerotic angiogenesis. PMID:19908850

  20. AN EFFICIENT AND ECOFRIENDLY OXIDATION OF ALKENES USING IRON NITRATE AND MOLECULAR OXYGEN

    EPA Science Inventory

    An environmentally friendly solventless oxidation of alkenes is accomplished efficiently using relatively benign iron nitrate as catalyst in the pressence of molecular oxygen under pressurized conditions.

  1. Tailoring the magnetic and pharmacokinetic properties of iron oxide magnetic particle imaging tracers

    PubMed Central

    Ferguson, Richard Mathew; Khandhar, Amit P; Arami, Hamed; Hua, Loc; Hovorka, Ondrej; Krishnan, Kannan M.

    2014-01-01

    Magnetic particle imaging (MPI) is an attractive new modality for imaging distributions of iron oxide nanoparticle tracers in vivo. With exceptional contrast, high sensitivity, and good spatial resolution, MPI shows promise for clinical imaging in angiography and oncology. Critically, MPI requires high-quality iron oxide nanoparticle tracers with tailored magnetic and surface properties to achieve its full potential. In this review, we discuss optimizing iron oxide nanoparticles’ physical, magnetic, and pharmacokinetic properties for MPI, highlighting results from our recent work in which we demonstrated tailored, biocompatible iron oxide nanoparticle tracers that provided two times better linear spatial resolution and five times better signal-to-noise ratio than Resovist. PMID:23787461

  2. Impact of Superparamagnetic Iron Oxide Nanoparticles on Vocal Fold Fibroblasts: Cell Behavior and Cellular Iron Kinetics.

    PubMed

    Pöttler, Marina; Fliedner, Anna; Schreiber, Eveline; Janko, Christina; Friedrich, Ralf Philipp; Bohr, Christopher; Döllinger, Michael; Alexiou, Christoph; Dürr, Stephan

    2017-12-01

    The voice is the most important instrument of communication. Tissue defects in the vocal fold (VF) area lead to serious reduction in quality of life, but thus far, no satisfactory VF implant exists. Therefore, we aim to establish a functional VF implant in a rabbit model by magnetic tissue engineering (MTE) using superparamagnetic iron oxide nanoparticles (SPION). Hence, iron quantification over time as well as cell behavior studies upon SPION treatment are of great importance. Rabbit VF fibroblasts (VFF) were treated with different concentrations of SPIONs (20, 40, and 80 μg/cm(2)), and iron content was examined for up to 40 days using microwave plasma-atom emission spectroscopy. The effects of SPION treatment on VFF (adhesion, spreading, and migration), which are important for the formation of 3D structures, were tested. Cellular SPION quantification revealed that there was no residual iron remaining in VFFs after 40 days. SPIONs had a dose-dependent effect on cell adhesion, with good tolerability observed up to 20 μg/cm(2). Migration and spreading were not significantly influenced by SPION treatment up to 80 μg/cm(2). To develop 3D structures, cell behavior should not be affected by SPION uptake. After 40 days, cells were free of iron as a result of metabolism or rarefication during cell division. Cell functions including adhesion, spreading, and migration were proven to be intact in a dose-dependent manner after SPION treatment, suggesting a safe usage of MTE for voice rehabilitation. Our results thus constitute a solid basis for a successful transfer of this technique into 3D constructs, in order to provide an individual and personalized human VF implant in the future.

  3. Enriched Iron(III)-Reducing Bacterial Communities are Shaped by Carbon Substrate and Iron Oxide Mineralogy.

    PubMed

    Lentini, Christopher J; Wankel, Scott D; Hansel, Colleen M

    2012-01-01

    Iron (Fe) oxides exist in a spectrum of structures in the environment, with ferrihydrite widely considered the most bioavailable phase. Yet, ferrihydrite is unstable and rapidly transforms to more crystalline Fe(III) oxides (e.g., goethite, hematite), which are poorly reduced by model dissimilatory Fe(III)-reducing microorganisms. This begs the question, what processes and microbial groups are responsible for reduction of crystalline Fe(III) oxides within sedimentary environments? Further, how do changes in Fe mineralogy shape oxide-hosted microbial populations? To address these questions, we conducted a large-scale cultivation effort using various Fe(III) oxides (ferrihydrite, goethite, hematite) and carbon substrates (glucose, lactate, acetate) along a dilution gradient to enrich for microbial populations capable of reducing Fe oxides spanning a wide range of crystallinities and reduction potentials. While carbon source was the most important variable shaping community composition within Fe(III)-reducing enrichments, both Fe oxide type and sediment dilution also had a substantial influence. For instance, with acetate as the carbon source, only ferrihydrite enrichments displayed a significant amount of Fe(III) reduction and the well-known dissimilatory metal reducer Geobacter sp. was the dominant organism enriched. In contrast, when glucose and lactate were provided, all three Fe oxides were reduced and reduction coincided with the presence of fermentative (e.g., Enterobacter spp.) and sulfate-reducing bacteria (e.g., Desulfovibrio spp.). Thus, changes in Fe oxide structure and resource availability may shift Fe(III)-reducing communities between dominantly metal-respiring to fermenting and/or sulfate-reducing organisms which are capable of reducing more recalcitrant Fe phases. These findings highlight the need for further targeted investigations into the composition and activity of speciation-directed metal-reducing populations within natural environments.

  4. Enriched Iron(III)-Reducing Bacterial Communities are Shaped by Carbon Substrate and Iron Oxide Mineralogy

    PubMed Central

    Lentini, Christopher J.; Wankel, Scott D.; Hansel, Colleen M.

    2012-01-01

    Iron (Fe) oxides exist in a spectrum of structures in the environment, with ferrihydrite widely considered the most bioavailable phase. Yet, ferrihydrite is unstable and rapidly transforms to more crystalline Fe(III) oxides (e.g., goethite, hematite), which are poorly reduced by model dissimilatory Fe(III)-reducing microorganisms. This begs the question, what processes and microbial groups are responsible for reduction of crystalline Fe(III) oxides within sedimentary environments? Further, how do changes in Fe mineralogy shape oxide-hosted microbial populations? To address these questions, we conducted a large-scale cultivation effort using various Fe(III) oxides (ferrihydrite, goethite, hematite) and carbon substrates (glucose, lactate, acetate) along a dilution gradient to enrich for microbial populations capable of reducing Fe oxides spanning a wide range of crystallinities and reduction potentials. While carbon source was the most important variable shaping community composition within Fe(III)-reducing enrichments, both Fe oxide type and sediment dilution also had a substantial influence. For instance, with acetate as the carbon source, only ferrihydrite enrichments displayed a significant amount of Fe(III) reduction and the well-known dissimilatory metal reducer Geobacter sp. was the dominant organism enriched. In contrast, when glucose and lactate were provided, all three Fe oxides were reduced and reduction coincided with the presence of fermentative (e.g., Enterobacter spp.) and sulfate-reducing bacteria (e.g., Desulfovibrio spp.). Thus, changes in Fe oxide structure and resource availability may shift Fe(III)-reducing communities between dominantly metal-respiring to fermenting and/or sulfate-reducing organisms which are capable of reducing more recalcitrant Fe phases. These findings highlight the need for further targeted investigations into the composition and activity of speciation-directed metal-reducing populations within natural environments. PMID

  5. Resistive switching in iron-oxide-filled carbon nanotubes.

    PubMed

    Cava, Carlos E; Persson, Clas; Zarbin, Aldo J G; Roman, Lucimara S

    2014-01-07

    Iron-oxide-filled carbon nanotubes exhibit an intriguing charge bipolarization behavior which allows the material to be applied in resistive memory devices. Raman analysis conducted with an electric field applied in situ shows the Kohn anomalies and a strong modification of the electronic properties related to the applied voltage intensity. In addition, the I(D)/I(G) ratio indicated the reversibility of this process. The electrical characterization indicated an electronic transport governed by two main kinds of charge hopping, one between the filling and the nanotube and the other between the nanotube shells.

  6. Iron oxide hydroxide nanoflower assisted removal of arsenic from water

    SciTech Connect

    Raul, Prasanta Kumar; Devi, Rashmi Rekha; Umlong, Iohborlang M.; Thakur, Ashim Jyoti; Banerjee, Saumen; Veer, Vijay

    2014-01-01

    Graphical abstract: Non-magnetic polycrystalline iron oxide hydroxide nanoparticle with flower like morphology is found to play as an effective adsorbent media to remove As(III) from 300 μg L{sup −1} to less than 10 μg L{sup −1} from drinking water over wide range of pH. TEM image clearly reveals that the nanoparticle looks flower like morphology with average particle size less than 20 nm. The maximum sorption capacity of the sorbent is found to be 475 μg g{sup −1} for arsenic at room temperature and the data fitted to different isotherm models indicate the heterogeneity of the adsorbent surface. The material can be regenerated up to 70% using dilute hydrochloric acid and it would be utilized for de-arsenification purposes. - Highlights: • The work includes synthesis of iron oxide hydroxide nanoflower and its applicability for the removal of arsenic from water. • The nanoparticle was characterized using modern instrumental methods like FESEM, TEM, BET, XRD, etc. • The maximum sorption capacity of the sorbent is found to be 475 μg g{sup −1} for arsenic at room temperature. • The sorption is multilayered on the heterogeneous surface of the nano adsorbent. • The mechanism of arsenic removal of IOH nanoflower follows both adsorption and ion-exchange. - Abstract: Non-magnetic polycrystalline iron oxide hydroxide nanoparticle with flower like morphology is found to play as an effective adsorbent media to remove As(III) from 300 μg L{sup −1} to less than 10 μg L{sup −1} from drinking water over wide range of pH. The nanoparticle was characterized by X-ray powder diffraction analysis (XRD), BET surface area, FTIR, FESEM and TEM images. TEM image clearly reveals flower like morphology with average particle size less than 20 nm. The nanoflower morphology is also supported by FESEM images. The maximum sorption capacity of the sorbent is found to be 475 μg g{sup −1} for arsenic and the data fitted to different isotherm models indicate the

  7. Catalytic effect of free iron ions and heme-iron on chromophore oxidation of a polyene antibiotic amphotericin B

    NASA Astrophysics Data System (ADS)

    Czernel, Grzegorz; Typek, Rafał; Klimek, Katarzyna; Czuryło, Aleksandra; Dawidowicz, Andrzej L.; Gagoś, Mariusz

    2016-05-01

    Owing to the presence of a chromophore in the amphotericin B (AmB) structure, the molecule can undergo the oxidation process. In this research, AmB chromophore oxidation was catalysed by iron ions (iron(III) chloride (FeCl3), pH 2.5) and by heme-iron (methemoglobin (HbFe(III)), and hemin (heme-Fe(III)) at pH 7.0). Additionally, we compared oxidation processes induced by the aforementioned oxidizing agents with autoxidation by dioxygen (O2) naturally occurring in a sample. The effects of the interaction of the oxidizing agents with AmB were analysed using molecular spectroscopies (electronic absorption (UV-Vis), fluorescence) and LC-MS. The use of a 1,10-phenanthroline (phen) chelator facilitated unambiguous determination of the oxidative effect of free iron(III) ions (FeIII) in an acidic solution on the AmB molecules. Also, the changes in the spectra of fluorescence emission centred at ∼470 nm indicate iron-catalysed processes of AmB chromophore oxidation. Unexpectedly, we found a similar spectroscopic effect for AmB induced by methemoglobin and hemin at pH 7.0. Methemoglobin and hemin at a concentration of 8 × 10-7 M (physiological) significantly increases the rate of the processes of AmB chromophore oxidation relative to the process of autoxidation.

  8. Reduction of Iron Oxides: A Comparison Between Biotic and Abiotic Pathways

    NASA Astrophysics Data System (ADS)

    Guyodo, Y. J.; Ona-Nguema, G.; Bonville, P.; Lagroix, F.

    2009-12-01

    The occurrence of fine particles of magnetite in soils and sediments may, under favorable climatic and environmental conditions, be the result of iron reduction in pre-existing magnetic phases. Nonetheless, the conditions and pathways leading to magnetite formation, and the connection between the amount and type of magnetite particles (size distribution, shape, etc…) and past climatic conditions remains to be elucidated. One way to address this fundamental question is to perform controlled experiments using synthetic iron bearing minerals subjected to specific physical and bio-chemical conditions. At the meeting, we will present experiments performed on synthetic maghemite (γ-Fe2O3) and lepidocrocite (γ-FeOOH) samples. In a first series of experiments, iron- reducing bacteria Shewanella putrefaciens were used to produce magnetite (Fe3O4) nanoparticles, the starting iron oxides being used as electron acceptor. In a second set of experiments, the starting iron oxides were converted to magnetite by slow heating in CO/CO2 atmosphere. Subsequently, the resulting samples were subjected to slow heating in air, in order to induce aging and oxidation of the material. In our presentation, we will show key results of our experiments, including both magnetic (low-temperature, low-field and high-field magnetic measurements, Mossbaüer spectroscopy, etc.) and non-magnetic (XRD, HRTEM, etc.) characterizations. The different series of experiments conducted on these samples shall allow us to better constrain pathways of magnetite formation and alteration in the environment, including solid-state conversion, partial or total dissolution/precipitation, and particles aggregation.

  9. The charge state of iron implanted into sapphire

    SciTech Connect

    McHargue, C.J.; Sklad, P.S.; White, C.W.; Farlow, G.C.; Perez, A.; Kornilios, N.; Marest, G.

    1987-08-01

    Several techniques (RBS, TEM, CEMS) have been used to characterize sapphire single crystals implanted with iron at room temperature to fluences of 10/sup 16/ to 10/sup 17/ ions cm/sup -2/. At low fluences the as-implanted iron is found mainly in the ferrous state. As the fluence is increased, Fe/sup 3 +/ and metallic iron clusters became dominant. There is a strong correlation between the probability of finding specific configurations of iron ions within four cation coordination shells and the relative amounts of each charge state observed. The superparamagnetic behavior of the clusters suggest that they are of the order of 2 nm in size but the large amount of irradiation-induced damage and residual stress has prevented their imaging by TEM. 13 refs., 7 figs.

  10. Role of humic substances in promoting autotrophic growth in nitrate-dependent iron-oxidizing bacteria.

    PubMed

    Kanaparthi, Dheeraj; Conrad, Ralf

    2015-05-01

    Nitrate-dependent iron oxidation was discovered in 1996 and has been reported from various environments ever since. To date, despite the widespread nature of this process, all attempts to cultivate chemolithoautotrophic nitrate-dependent iron oxidizers have been unsuccessful. The present study was focused on understanding the influence of natural chelating agents of iron, like humic substances, on the culturability, activity, and enumeration, of these microorganisms. Pure culture studies conducted with Thiobacillus denitrificans showed a constant increase in cell mass with a corresponding nitrate-dependent iron oxidation activity only when Fe(II) was provided together with humic substances, compared to no growth in control incubations without humic substances. The presence of a relatively strong chelating agent, such as EDTA, inhibited the growth of Thiobacillus denitrificans. It was concluded that complex formation between humic substances and iron was required for chemolithoautotrophic nitrate-dependent iron oxidation. Most probable number enumerations showed that numbers of chemolithoautotrophic nitrate-dependent iron-oxidizing bacteria were one to three orders of magnitude higher in the presence of humic substances compared to media without. Similar results were obtained when potential nitrate-dependent iron oxidation activity was determined in soil samples. In summary, this study showed that humic substances significantly enhanced the growth and activity of autotrophic nitrate-dependent iron-oxidizing microorganisms, probably by chelation of iron. Copyright © 2015 Elsevier GmbH. All rights reserved.

  11. Evidence for equilibrium iron isotope fractionation by nitrate-reducing iron(II)-oxidizing bacteria

    PubMed Central

    Kappler, A.; Johnson, C.M.; Crosby, H.A.; Beard, B.L.; Newman, D.K.

    2010-01-01

    Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)aq and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in 56Fe/54Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ56FeFe(OH)3 – Fe(II)aq fractionation factor of +3.0 ‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)aq and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)aq by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)aq oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)aq and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of biological and

  12. Reactions of metal ions at surfaces of hydrous iron oxide

    USGS Publications Warehouse

    Hem, J.D.

    1977-01-01

    Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10-8.00 or 10-9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn3O4 can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn4+ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10-9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems. ?? 1977.

  13. Nitric oxide activation by distal redox modulation in tetranuclear iron nitrosyl complexes.

    PubMed

    de Ruiter, Graham; Thompson, Niklas B; Lionetti, Davide; Agapie, Theodor

    2015-11-11

    A series of tetranuclear iron complexes displaying a site-differentiated metal center was synthesized. Three of the metal centers are coordinated to our previously reported ligand, based on a 1,3,5-triarylbenzene motif with nitrogen and oxygen donors. The fourth (apical) iron center is coordinatively unsaturated and appended to the trinuclear core through three bridging pyrazolates and an interstitial μ4-oxide moiety. Electrochemical studies of complex [LFe3(PhPz)3OFe][OTf]2 revealed three reversible redox events assigned to the Fe(II)4/Fe(II)3Fe(III) (-1.733 V), Fe(II)3Fe(III)/Fe(II)2Fe(III)2 (-0.727 V), and Fe(II)2Fe(III)2/Fe(II)Fe(III)3 (0.018 V) redox couples. Combined Mössbauer and crystallographic studies indicate that the change in oxidation state is exclusively localized at the triiron core, without changing the oxidation state of the apical metal center. This phenomenon is assigned to differences in the coordination environment of the two metal sites and provides a strategy for storing electron and hole equivalents without affecting the oxidation state of the coordinatively unsaturated metal. The presence of a ligand-binding site allowed the effect of redox modulation on nitric oxide activation by an Fe(II) metal center to be studied. Treatment of the clusters with nitric oxide resulted in binding of NO to the apical iron center, generating a {FeNO}(7) moiety. As with the NO-free precursors, the three reversible redox events are localized at the iron centers distal from the NO ligand. Altering the redox state of the triiron core resulted in significant change in the NO stretching frequency, by as much as 100 cm(-1). The increased activation of NO is attributed to structural changes within the clusters, in particular, those related to the interaction of the metal centers with the interstitial atom. The differences in NO activation were further shown to lead to differential reactivity, with NO disproportionation and N2O formation performed by the more

  14. Structural differences of oxidized iron-sulfur and nickel-iron cofactors in O2-tolerant and O2-sensitive hydrogenases studied by X-ray absorption spectroscopy.

    PubMed

    Sigfridsson, Kajsa G V; Leidel, Nils; Sanganas, Oliver; Chernev, Petko; Lenz, Oliver; Yoon, Ki-Seok; Nishihara, Hirofumi; Parkin, Alison; Armstrong, Fraser A; Dementin, Sébastien; Rousset, Marc; De Lacey, Antonio L; Haumann, Michael

    2015-02-01

    The class of [NiFe]-hydrogenases comprises oxygen-sensitive periplasmic (PH) and oxygen-tolerant membrane-bound (MBH) enzymes. For three PHs and four MBHs from six bacterial species, structural features of the nickel-iron active site of hydrogen turnover and of the iron-sulfur clusters functioning in electron transfer were determined using X-ray absorption spectroscopy (XAS). Fe-XAS indicated surplus oxidized iron and a lower number of ~2.7 Å Fe-Fe distances plus additional shorter and longer distances in the oxidized MBHs compared to the oxidized PHs. This supported a double-oxidized and modified proximal FeS cluster in all MBHs with an apparent trimer-plus-monomer arrangement of its four iron atoms, in agreement with crystal data showing a [4Fe3S] cluster instead of a [4Fe4S] cubane as in the PHs. Ni-XAS indicated coordination of the nickel by the thiol group sulfurs of four conserved cysteines and at least one iron-oxygen bond in both MBH and PH proteins. Structural differences of the oxidized inactive [NiFe] cofactor of MBHs in the Ni-B state compared to PHs in the Ni-A state included a ~0.05 Å longer Ni-O bond, a two times larger spread of the Ni-S bond lengths, and a ~0.1 Å shorter Ni-Fe distance. The modified proximal [4Fe3S] cluster, weaker binding of the Ni-Fe bridging oxygen species, and an altered localization of reduced oxygen species at the active site may each contribute to O2 tolerance.

  15. Morphology and phase control of iron oxide polymorph nanoparticles

    NASA Astrophysics Data System (ADS)

    Cui, Hongtao; Wang, Li; Shi, Min; Li, Yanhong

    2017-04-01

    In this work, lepidocrocite (γ-FeOOH) nanobundles were prepared by a facile NH4F assisted epoxide precipitation route. The reactions between epoxide and [Fe(H2O)6]2+ promoted the hydrolysis and condensation of [Fe(H2O)6]2+, resulting in the formation of iron oxyhydroxide. After calcination of γ-FeOOH nanobundles at 400 °C, the produced α-Fe2O3 still kept the bundle morphology. Due to the unique chemistry of epoxide, the morphology and phase of iron oxide polymorph nanoparticles (goethite, akaganeite, lepidocrocite, magnetite) were well-controlled through controlling reaction conditions such as Fe2+ concentration, NH4F additive and reaction temperature. It is particularly interesting that NH4F working as phase controlling agent is able to control the phase development of iron oxyhydroxides. This phase control effect of NH4F is attributed to the promoted reaction rate of epoxide originating from the higher electronegativity of fluoride ions than chloride ions. Based on the results in this work and our other preliminary works, it is considered that this route can be used as a general strategy for controlling the morphology and phase of transition element compounds.

  16. Macroscopic and microscopic biodistribution of intravenously administered iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Misra, Adwiteeya; Petryk, Alicia A.; Strawbridge, Rendall R.; Hoopes, P. Jack

    2015-03-01

    Iron oxide nanoparticles (IONP) are being developed for use as a cancer treatment. They have demonstrated efficacy when used either as a monotherapy or in conjunction with conventional chemotherapy and radiation. The success of IONP as a therapeutic tool depends on the delivery of a safe and controlled cytotoxic thermal dose to tumor tissue following activation with an alternating magnetic field (AMF). Prior to clinical approval, knowledge of IONP toxicity, biodistribution and physiological clearance is essential. This preliminary time-course study determines the acute toxicity and biodistribution of 110 nm dextran-coated IONP (iron) in mice, 7 days post systemic, at doses of 0.4, 0.6, and 1.0 mg Fe/ g mouse bodyweight. Acute toxicity, manifested as changes in the behavior of mice, was only observed temporarily at 1.0 mg Fe/ g mouse bodyweight, the highest dose administered. Regardless of dose, mass spectrometry and histological analysis demonstrated over 3 mg Fe/g tissue in organs within the reticuloendotheilial system (i.e. liver, spleen, and lymph nodes). Other organs (brain, heart, lungs, and kidney) had less than 0.5 mg Fe/g tissue with iron predominantly confined to the organ vasculature.

  17. Sulfur cycling in an iron oxide-dominated, dynamic marine depositional system: The Argentine continental margin

    NASA Astrophysics Data System (ADS)

    Riedinger, Natascha; Brunner, Benjamin; Krastel, Sebastian; Arnold, Gail L.; Wehrmann, Laura M.; Formolo, Michael J.; Beck, Antje; Bates, Steven M.; Henkel, Susann; Kasten, Sabine; Lyons, Timothy W.

    2017-05-01

    The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters

  18. Engineered Iron/Iron Oxide Functionalized Membranes for Selenium and Other Toxic Metal Removal from Power Plant Scrubber Water.

    PubMed

    Gui, Minghui; Papp, Joseph K; Colburn, Andrew S; Meeks, Noah D; Weaver, Benjamin; Wilf, Ilan; Bhattacharyya, Dibakar

    2015-08-15

    The remediation of toxic metals from water with high concentrations of salt has been an emerging area for membrane separation. Cost-effective nanomaterials such as iron and iron oxide nanoparticles have been widely used in reductive and oxidative degradation of toxic organics. Similar procedures can be used for redox transformations of metal species (e.g. metal oxyanions to elemental metal), and/or adsorption of species on iron oxide surface. In this study, iron-functionalized membranes were developed for reduction and adsorption of selenium from coal-fired power plant scrubber water. Iron-functionalized membranes have advantages over iron suspension as the membrane prevents particle aggregation and dissolution. Both lab-scale and full-scale membranes were prepared first by coating polyvinylidene fluoride (PVDF) membranes with polyacrylic acid (PAA), followed by ion exchange of ferrous ions and subsequent reduction to zero-valent iron nanoparticles. Water permeability of membrane decreased as the percent PAA functionalization increased, and the highest ion exchange capacity (IEC) was obtained at 20% PAA with highly pH responsive pores. Although high concentrations of sulfate and chloride in scrubber water decreased the reaction rate of selenium reduction, this was shown to be overcome by integration of nanofiltration (NF) and iron-functionalized membranes, and selenium concentration below 10 μg/L was achieved.

  19. Intracellular degradation of functionalized carbon nanotube/iron oxide hybrids is modulated by iron via Nrf2 pathway

    PubMed Central

    Elgrabli, Dan; Dachraoui, Walid; Marmier, Hélène de; Ménard-Moyon, Cécilia; Bégin, Dominique; Bégin-Colin, Sylvie; Bianco, Alberto; Alloyeau, Damien; Gazeau, Florence

    2017-01-01

    The in vivo fate and biodegradability of carbon nanotubes is still a matter of debate despite tremendous applications. In this paper we describe a molecular pathway by which macrophages degrade functionalized multi-walled carbon nanotubes (CNTs) designed for biomedical applications and containing, or not, iron oxide nanoparticles in their inner cavity. Electron microscopy and Raman spectroscopy show that intracellularly-induced structural damages appear more rapidly for iron-free CNTs in comparison to iron-loaded ones, suggesting a role of iron in the degradation mechanism. By comparing the molecular responses of macrophages derived from THP1 monocytes to both types of CNTs, we highlight a molecular mechanism regulated by Nrf2/Bach1 signaling pathways to induce CNT degradation via NOX2 complex activation and O2•−, H2O2 and OH• production. CNT exposure activates an oxidative stress-dependent production of iron via Nrf2 nuclear translocation, Ferritin H and Heme oxygenase 1 translation. Conversely, Bach1 was translocated to the nucleus of cells exposed to iron-loaded CNTs to recycle embedded iron. Our results provide new information on the role of oxidative stress, iron metabolism and Nrf2-mediated host defence for regulating CNT fate in macrophages. PMID:28120861

  20. Self-organized pattern formation in the oxidation of supported iron thin films. II. A simulation study

    NASA Astrophysics Data System (ADS)

    Ogale, Abhijit S.

    2001-07-01

    The process of oxidation of supported iron thin films is modeled by casting it into the form of an activator-inhibitor system, with precursor oxidation state as the activator, and stress produced by the large density difference between the metal and its oxide as a fast-diffusing inhibitor. An activator-substrate mechanism also coexists due to the finite availability of iron. The redistribution of iron by diffusion via vacancies also indirectly contributes to the activation process. A slow process of ripening, which minimizes surface energy, is suggested to convert the early leaflike pattern to a spiral assembly of hillocks. This model simulation yields patterns, which closely resemble the patterns observed in experiments reported by Shinde et al. [Phys. Rev. B 64, 035408 (2001)], in the accompanying Paper I.

  1. A 'degradable' poly(vinyl alcohol) iron oxide nanoparticle hydrogel.

    PubMed

    Bannerman, A Dawn; Li, Xinyi; Wan, Wankei

    2017-08-01

    Polymeric materials that contain magnetic nanoparticles are extremely useful in many applications including as multifunctional drug carriers, imaging contrast agents, or scaffold material. There is a need for biomaterials with appropriate chemical, mechanical, and magnetic properties that also have the ability to degrade or dissolve over time so they can be eliminated from the body following use. In this work, we explore the use of iron oxide nanoparticle (IONP) formation in poly(vinyl alcohol) (PVA) as a crosslinking method in conjunction with physical crosslinking achieved using low temperature thermal cycling (LTTC). PVA-IONP hydrogels were fabricated and characterized. IONPs contribute to the crosslinking of the PVA-IONP material, and their subsequent removal reduces crosslinking, and therefore stability, of the material, allowing dissolution to occur. Dissolution studies were performed on PVA-IONP hydrogels and dissolution was compared for films in solutions of varying pH, in the presence of iron chelating agents, and in simulated physiological and tumor conditions in cell culture media. Iron release, mass loss, and mechanical testing data was collected. This work demonstrates the ability of this biomaterial to 'degrade' over time, which may be very advantageous for applications such as drug delivery. This importance of this work extends to other areas such as the use of stimuli-responsive hydrogels. This manuscript explores the stability of an iron oxide nanoparticle (IONP)-containing, physically crosslinked poly(vinyl alcohol) (PVA) hydrogel. The PVA-IONP hydrogel's stability is imparted through crosslinks created through a low temperature thermal cycling process and through the IONPs. Subsequent IONP removal reduces crosslinks so material dissolution can occur, resulting in a 'degradable' and multifunctional biomaterial. PVA-IONP films were fabricated, characterized and evaluated in terms of dissolution in solutions of varying pH and in the presence of

  2. Enhancing the Performance of the Rechargeable Iron Electrode in Alkaline Batteries with Bismuth Oxide and Iron Sulfide Additives

    SciTech Connect

    Manohar, AK; Yang, CG; Malkhandi, S; Prakash, GKS; Narayanan, SR

    2013-09-07

    Iron-based alkaline rechargeable batteries have the potential of meeting the needs of large-scale electrical energy storage because of their low-cost, robustness and eco-friendliness. However, the widespread commercial deployment of iron-based batteries has been limited by the low charging efficiency and the poor discharge rate capability of the iron electrode. In this study, we have demonstrated iron electrodes containing bismuth oxide and iron sulfide with a charging efficiency of 92% and capable of being discharged at the 3C rate. Such a high value of charging efficiency combined with the ability to discharge at high rates is being reported for the first time. The bismuth oxide additive led to the in situ formation of elemental bismuth and a consequent increase in the overpotential for the hydrogen evolution reaction leading to an increase in the charging efficiency. We observed that the sulfide ions added to the electrolyte and iron sulfide added to the electrode mitigated-electrode passivation and allowed for continuous discharge at high rates. At the 3C discharge rate, a utilization of 0.2 Ah/g was achieved. The performance level of the rechargeable iron electrode demonstrated here is attractive for designing economically-viable large-scale energy storage systems based on alkaline nickel-iron and iron-air batteries. (C) 2013 The Electrochemical Society. All rights reserved.

  3. Assembly and Succession of Iron Oxide Microbial Mat Communities in Acidic Geothermal Springs.

    PubMed

    Beam, Jacob P; Bernstein, Hans C; Jay, Zackary J; Kozubal, Mark A; Jennings, Ryan deM; Tringe, Susannah G; Inskeep, William P

    2016-01-01

    Biomineralized ferric oxide microbial mats are ubiquitous features on Earth, are common in hot springs of Yellowstone National Park (YNP, WY, USA), and form due to direct interaction between microbial and physicochemical processes. The overall goal of this study was to determine the contribution of different community members to the assembly and succession of acidic high-temperature Fe(III)-oxide mat ecosystems. Spatial and temporal changes in Fe(III)-oxide accretion and the abundance of relevant community members were monitored over 70 days using sterile glass microscope slides incubated in the outflow channels of two acidic geothermal springs (pH = 3-3.5; temperature = 68-75°C) in YNP. Hydrogenobaculum spp. were the most abundant taxon identified during early successional stages (4-40 days), and have been shown to oxidize arsenite, sulfide, and hydrogen coupled to oxygen reduction. Iron-oxidizing populations of Metallosphaera yellowstonensis were detected within 4 days, and reached steady-state levels within 14-30 days, corresponding to visible Fe(III)-oxide accretion. Heterotrophic archaea colonized near 30 days, and emerged as the dominant functional guild after 70 days and in mature Fe(III)-oxide mats (1-2 cm thick). First-order rate constants of Fe(III)-oxide accretion ranged from 0.046 to 0.05 day(-1), and in situ microelectrode measurements showed that the oxidation of Fe(II) is limited by the diffusion of O2 into the Fe(III)-oxide mat. The formation of microterracettes also implicated O2 as a major variable controlling microbial growth and subsequent mat morphology. The assembly and succession of Fe(III)-oxide mat communities follows a repeatable pattern of colonization by lithoautotrophic organisms, and the subsequent growth of diverse organoheterotrophs. The unique geochemical signatures and micromorphology of extant biomineralized Fe(III)-oxide mats are also useful for understanding other Fe(II)-oxidizing systems.

  4. Assembly and Succession of Iron Oxide Microbial Mat Communities in Acidic Geothermal Springs

    SciTech Connect

    Beam, Jacob P.; Bernstein, Hans C.; Jay, Zackary J.; Kozubal, Mark A.; Jennings, Ryan deM.; Tringe, Susannah G.; Inskeep, William P.

    2016-02-15

    Biomineralized ferric oxide microbial mats are ubiquitous features on Earth, are common in hot springs of Yellowstone National Park (YNP, WY, USA), and form due to direct interaction between microbial and physicochemical processes. The overall goal of this study was to determine the contribution of different community members to the assembly and succession of acidic high-temperature Fe(III)-oxide mat ecosystems. Spatial and temporal changes in Fe(III)-oxide accretion and the abundance of relevant community members were monitored over 70 days using sterile glass microscope slides incubated in the outflow channels of two acidic geothermal springs (pH = 3-3.5; temperature = 68-75°C) in YNP. Hydrogenobaculum spp. were the most abundant taxon identified during early successional stages (4-40 days), and have been shown to oxidize arsenite, sulfide, and hydrogen coupled to oxygen reduction. Iron-oxidizing populations of Metallosphaera yellowstonensis were detected within 4 days, and reached steady-state levels within 14-30 days, corresponding to visible Fe(III)-oxide accretion. Heterotrophic archaea colonized near 30 days, and emerged as the dominant functional guild after 70 days and in mature Fe(III)-oxide mats (1-2 cm thick). First-order rate constants of Fe(III)-oxide accretion ranged from 0.046 to 0.05 day -1 , and in situ microelectrode measurements showed that the oxidation of Fe(II) is limited by the diffusion of O2 into the Fe(III)-oxide mat. The formation of microterracettes also implicated O2 as a major variable controlling microbial growth and subsequent mat morphology. The assembly and succession of Fe(III)-oxide mat communities follows a repeatable pattern of colonization by lithoautotrophic organisms, and the subsequent growth of diverse organoheterotrophs. The unique geochemical signatures and micromorphology of extant biomineralized Fe(III)-oxide mats are also useful for understanding other Fe(II)-oxidizing systems.

  5. Assembly and Succession of Iron Oxide Microbial Mat Communities in Acidic Geothermal Springs

    PubMed Central

    Beam, Jacob P.; Bernstein, Hans C.; Jay, Zackary J.; Kozubal, Mark A.; Jennings, Ryan deM.; Tringe, Susannah G.; Inskeep, William P.

    2016-01-01

    Biomineralized ferric oxide microbial mats are ubiquitous features on Earth, are common in hot springs of Yellowstone National Park (YNP, WY, USA), and form due to direct interaction between microbial and physicochemical processes. The overall goal of this study was to determine the contribution of different community members to the assembly and succession of acidic high-temperature Fe(III)-oxide mat ecosystems. Spatial and temporal changes in Fe(III)-oxide accretion and the abundance of relevant community members were monitored over 70 days using sterile glass microscope slides incubated in the outflow channels of two acidic geothermal springs (pH = 3–3.5; temperature = 68–75°C) in YNP. Hydrogenobaculum spp. were the most abundant taxon identified during early successional stages (4–40 days), and have been shown to oxidize arsenite, sulfide, and hydrogen coupled to oxygen reduction. Iron-oxidizing populations of Metallosphaera yellowstonensis were detected within 4 days, and reached steady-state levels within 14–30 days, corresponding to visible Fe(III)-oxide accretion. Heterotrophic archaea colonized near 30 days, and emerged as the dominant functional guild after 70 days and in mature Fe(III)-oxide mats (1–2 cm thick). First-order rate constants of Fe(III)-oxide accretion ranged from 0.046 to 0.05 day−1, and in situ microelectrode measurements showed that the oxidation of Fe(II) is limited by the diffusion of O2 into the Fe(III)-oxide mat. The formation of microterracettes also implicated O2 as a major variable controlling microbial growth and subsequent mat morphology. The assembly and succession of Fe(III)-oxide mat communities follows a repeatable pattern of colonization by lithoautotrophic organisms, and the subsequent growth of diverse organoheterotrophs. The unique geochemical signatures and micromorphology of extant biomineralized Fe(III)-oxide mats are also useful for understanding other Fe(II)-oxidizing systems. PMID:26913020

  6. Effects of iron oxide mineralogy on methanogenesis transpiring in soils and sediments

    NASA Astrophysics Data System (ADS)

    Gadol, H. J.; Kocar, B. D.

    2016-12-01

    Methane is an important greenhouse gas, possessing a global warming potential 30 times greater than carbon dioxide over a 100 year period. Soils and sediments, particularly within wetland environments, are dominant sources of methane to the Earth's atmosphere; however, the extent and magnitude of soil-sediment methane emissions are difficult to constrain owing to complex biogeochemical-physical controls on methanogenic activity. Methanogenesis may be inhibited in the presence of terminal electron acceptors that provide a greater free energy yield, including sulfate and iron(III)-bearing solids. Of these, Fe(III) solids (dominantly iron (hydr)oxides such as ferrihydrite, goethite, and hematite), possess a range of thermodynamic properties that impart different inhibitory effects on methanogenesis. Also, a recently proposed mechanism that predicts coupled iron reduction-methanogenesis—direct interspecies electron transfer (DIET)—may further convolute predictions of methane evolution in systems containing iron hydr(oxides). It is possible that, under energetically favorable conditions, iron reducers contribute an electron to a (semi)conductive iron oxide; this electron can then be conducted through the mineral and subsequently used by another microbe to produce methane. This research aims to explore the effect of iron chemistry and mineralogy on electron transfer between iron-reducing microbes and methanogens. A number of iron oxide minerals with varying crystallinities and conductivities were inoculated with wetland sediment. Iron and methane were monitored throughout the course of the experiments. Iron in solution was measured using inductively coupled plasma - optical emission spectroscopy (ICP-OES), while HCl-extractable iron was measured using spectrophotometric methods. Headspace methane was measured using a residual gas analyzer (RGA). According to thermodynamic predictions, enhanced methanogenic activity is observed in the presence of crystalline iron

  7. Iron and oxygen isotope fractionation during iron UV photo-oxidation: Implications for early Earth and Mars

    NASA Astrophysics Data System (ADS)

    Nie, Nicole X.; Dauphas, Nicolas; Greenwood, Richard C.

    2017-01-01

    Banded iron formations (BIFs) contain appreciable amounts of ferric iron (Fe3+). The mechanism by which ferrous iron (Fe2+) was oxidized into Fe3+ in an atmosphere that was globally anoxic is highly debated. Of the three scenarios that have been proposed to explain BIF formation, photo-oxidation by UV photons is the only one that does not involve life (the other two are oxidation by O2 produced by photosynthesis, and anoxygenic photosynthesis whereby Fe2+ is directly used as electron donor in place of water). We experimentally investigated iron and oxygen isotope fractionation imparted by iron photo-oxidation at a pH of 7.3. The iron isotope fractionation between precipitated Fe3+-bearing lepidocrocite and dissolved Fe2+ follows a Rayleigh distillation with an instantaneous 56Fe/54Fe fractionation factor of + 1.2 ‰. Such enrichment in the heavy isotopes of iron is consistent with the values measured in BIFs. We also investigated the nature of the mass-fractionation law that governs iron isotope fractionation in the photo-oxidation experiments (i.e., the slope of the δ56Fe-δ57Fe relationship). The experimental run products follow a mass-dependent law corresponding to the high-T equilibrium limit. The fact that a ∼3.8 Gyr old BIF sample (IF-G) from Isua (Greenland) falls on the same fractionation line confirms that iron photo-oxidation in the surface layers of the oceans was a viable pathway to BIF formation in the Archean, when the atmosphere was largely transparent to UV photons. Our experiments allow us to estimate the quantum yield of the photo-oxidation process (∼0.07 iron atom oxidized per photon absorbed). This yield is used to model iron oxidation on early Mars. As the photo-oxidation proceeds, the aqueous medium becomes more acidic, which slows down the reaction by changing the speciation of iron to species that are less efficient at absorbing UV-photons. Iron photo-oxidation in centimeter to meter-deep water ponds would take months to years to

  8. Iron and manganese oxide mineralization in the Pacific

    USGS Publications Warehouse

    Hein, J.R.; Koschinsky, A.; Halbach, P.; Manheim, F. T.; Bau, M.; Kang, J.-K.; Lubick, N.

    1997-01-01

    Iron, manganese, and iron-manganese deposits occur in nearly all geomorphologic and tectonic environments in the ocean basins and form by one or more of four processes: (1) hydrogenetic precipitation from cold ambient seawater, (2) precipitation from hydrothermal fluids, (3) precipitation from sediment pore waters that have been modified from bottom water compositions by diagenetic reactions in the sediment column and (4) replacement of rocks and sediment. Iron and manganese deposits occur in five forms: nodules, crusts, cements, mounds and sediment-hosted stratabound layers. Seafloor oxides show a wide range of compositions from nearly pure iron to nearly pure manganese end members. Fe/Mn ratios vary from about 24 000 (up to 58% elemental Fe) for hydrothermal seamount ironstones to about 0.001 (up to 52% Mn) for hydrothermal stratabound manganese oxides from active volcanic arcs. Hydrogenetic Fe-Mn crusts that occur on most seamounts in the ocean basins have a mean Fe/Mn ratio of 0.7 for open-ocean seamount crusts and 1.2 for continental margin seamount crusts. Fe-Mn nodules of potential economic interest from the Clarion-Clipperton Zone have a mean Fe/Mn ratio of 0.3, whereas the mean ratio for nodules from elsewhere in the Pacific is about 0.7. Crusts are enriched in Co, Ni and Pt and nodules in Cu and Ni, and both have significant concentrations of Pb, Zn, Ba, Mo, V and other elements. In contrast, hydrothermal deposits commonly contain only minor trace metal contents, although there are many exceptions, for example, with Ni contents up to 0.66%, Cr to 1.2%, and Zn to 1.4%. Chondrite-normalized REE patterns generally show a positive Ce anomaly and abundant ΣREEs for hydrogenetic and mixed hydrogenetic-diagenetic deposits, whereas the Ce anomaly is negative for hydrothermal deposits and ΣREE contents are low. However, the Ce anomaly in crusts may vary from strongly positive in East Pacific crusts to slightly negative in West Pacific crusts, which may reflect

  9. Iron release and membrane damage in erythrocytes exposed to oxidizing agents, phenylhydrazine, divicine and isouramil.

    PubMed Central

    Ferrali, M; Signorini, C; Ciccoli, L; Comporti, M

    1992-01-01

    Mouse erythrocytes were incubated with oxidizing agents, phenylhydrazine, divicine and isouramil. With all the oxidants a rapid release of iron in a desferrioxamine (DFO)-chelatable form was seen and it was accompanied by methaemoglobin formation. If the erythrocytes were depleted of GSH by a short preincubation with diethyl maleate, the release of iron was accompanied by lipid peroxidation and, subsequently, haemolysis. GSH depletion by itself did not induce iron release, methaemoglobin formation, lipid peroxidation or haemolysis. Rather, the fate of the cell in which iron is released depended on the intracellular availability of GSH. In addition, iron release was higher in depleted cells than in native ones, suggesting a role for GSH in preventing iron release when oxidative stress is imposed by the oxidants. Iron release preceded lipid peroxidation. The latter was prevented when the erythrocytes were preloaded with DFO in such a way (preincubation with 10 mM-DFO) that the intracellular concentration was equivalent to that of the released iron, but not when the intracellular DFO was lower (preincubation with 0.1 mM-DFO). Extracellular DFO did not affect lipid peroxidation and haemolysis, suggesting again that the observed events occur intracellularly (intracellular chelation of released iron). The relevance of iron release from iron complexes in the mechanisms of cellular damage induced by oxidative stress is discussed. PMID:1637315

  10. Tuning the structure and habit of iron oxide mesocrystals

    DOE PAGES

    Wetterskog, Erik; Klapper, Alice; Disch, Sabrina; ...

    2016-07-11

    A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on iron oxide nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and themore » quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6 12.6 nm) are isostructural with a body centred tetragonal (bct ) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic iron oxide nanocube mesocrystals based on nanocube edge length and magnetic field strength.« less

  11. Noble Metal-Iron Oxide Hybrid Nanomaterials: Emerging Applications.

    PubMed

    Leung, Ken Cham-Fai; Xuan, Shouhu

    2016-02-01

    This account provides an overview of current research activities that focus on the synthesis and applications of nanomaterials from noble metal (e.g., Au, Ag, Pd) and iron oxide (Fe3O4) hybrids. An introduction to the synthetic strategies that have been developed for generating M-Fe3O4 nanomaterials with different novel structures is presented. Surface functionalization and bioconjugation of these hybrid nanoparticles and nanocomposites are also reviewed. The utilization of the advantageous properties of both noble metals and iron oxide for a variety of applications, such as theranostics, gene delivery, biosensing, cell sorting, bioseparation, and catalysis, is discussed and highlighted. Finally, future trends and perspectives of these sophisticated nanocomposites are outlined. The fundamental requirements underpinning the effective preparation of M-Fex Oy hybrid nanomaterials shed light on the future development of heterogeneous catalysts, nanotheranostics, nanomedicines, and other chemical technologies. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Cerebral Blood Volume MRI with Intravascular Superparamagentic Iron Oxide Nanoparticles

    PubMed Central

    Kim, Seong-Gi; Harel, Noam; Jin, Tao; Kim, Tae; Lee, Phil; Zhao, Fuqiang

    2013-01-01

    Cerebral blood volume (CBV) is a crucial physiological indicator of tissue viability and vascular reactivity. Thus, non-invasive CBV mapping has been of great interest. For this, ultrasmall superparamagnetic iron oxide nanoparticles (USPIO) including monocrystalline iron oxide nanoparticles (MION) can be used as long half-life, intravascular susceptibility agents of CBV MRI measurements. Also, CBV-weighted fMRI with USPIO provides enhanced sensitivity, reduced large vessel contribution, and improved spatial specificity compared to conventional blood oxygenation-level dependent (BOLD) fMRI, and measures a single physiological parameter that is easily interpretable. We review physiochemical and magnetic properties as well as pharmacokinetics of USPIO in brief. We then extensively discuss quantifications of baseline CBV, vessel size index, and functional CBV change. We also provide reviews of dose-dependent sensitivity, vascular filter function, specificity, characteristics, and impulse response function of CBV fMRI. Examples of CBV fMRI specificity at the laminar and columnar resolution are provided. Finally, we briefly review application of CBV measurements to functional and pharmacological studies in animals. Overall, the use of USPIO can determine baseline CBV and its changes induced by functional activity and pharmacological interventions. PMID:23208650

  13. Evaluation of Nanodispersion of Iron Oxides Using Various Polymers

    PubMed Central

    Tanaka, Y.; Ueyama, H.; Ogata, M.; Daikoku, T.; Morimoto, M.; Kitagawa, A.; Imajo, Y.; Tahara, T.; Inkyo, M.; Yamaguchi, N.; Nagata, S.

    2014-01-01

    In order to create Fe2O3 and Fe2O3·H2O nanoparticles, various polymers were used as dispersing agents, and the resulting effects on the dispersibility and nanoparticulation of the iron oxides were evaluated. It was revealed that not only the solution viscosity but also the molecular length of the polymers and the surface tension of the particles affected the dispersibility of Fe2O3 and Fe2O3·H2O particles. Using the dispersing agents 7.5% hydroxypropylcellulose-SSL, 6.0% Pharmacoat 603, 5.0% and 6.5% Pharmacoat 904 and 7.0% Metolose SM-4, Fe2O3 nanoparticles were successfully fabricated by wet milling using Ultra Apex Mill. Fe2O3·H2O nanoparticles could also be produced using 5.0% hydroxypropylcellulose-SSL and 4.0 and 7.0% Pharmacoat 904. The index for dispersibility developed in this study appears to be an effective indicator of success in fabricating nanoparticles of iron oxides by wet milling using Ultra Apex Mill. PMID:24799739

  14. Tuning the structure and habit of iron oxide mesocrystals

    SciTech Connect

    Wetterskog, Erik; Klapper, Alice; Disch, Sabrina; Josten, Elisabeth; Hermann, Raphaël P.; Rücker, Ulrich; Brückel, Thomas; Bergström, Lennart; Salazar-Alvarez, German

    2016-07-11

    A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on iron oxide nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and the quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6 12.6 nm) are isostructural with a body centred tetragonal (bct ) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic iron oxide nanocube mesocrystals based on nanocube edge length and magnetic field strength.

  15. Photoreductive dissolution of iron oxides trapped in ice and its environmental implications.

    PubMed

    Kim, Kitae; Choi, Wonyong; Hoffmann, Michael R; Yoon, Ho-Il; Park, Byong-Kwon

    2010-06-01

    The availability of iron has been thought to be a main limiting factor for the productivity of phytoplankton and related with the uptake of atmospheric CO(2) and algal blooms in fresh and sea waters. In this work, the formation of bioavailable iron (Fe(II)(aq)) from the dissolution of iron oxide particles was investigated in the ice phase under both UV and visible light irradiation. The photoreductive dissolution of iron oxides proceeded slowly in aqueous solution (pH 3.5) but was significantly accelerated in polycrystalline ice, subsequently releasing more bioavailable ferrous iron upon thawing. The enhanced photogeneration of Fe(II)(aq) in ice was confirmed regardless of the type of iron oxides [hematite, maghemite (gamma-Fe(2)O(3)), goethite (alpha-FeOOH)] and the kind of electron donors. The ice-enhanced dissolution of iron oxides was also observed under visible light irradiation, although the dissolution rate was much slower compared with the case of UV radiation. The iron oxide particles and organic electron donors (if any) in ice are concentrated and aggregated in the liquid-like grain boundary region (freeze concentration effect) where protons are also highly concentrated (lower pH). The enhanced photodissolution of iron oxides should occur in this confined boundary region. We hypothesized that electron hopping through the interconnected grain boundaries of iron oxide particles facilitates the separation of photoinduced charge pairs. The outdoor experiments carried out under ambient solar radiation of Ny-Alesund (Svalbard, 78 degrees 55'N) also showed that the generation of dissolved Fe(II)(aq) via photoreductive dissolution is enhanced when iron oxides are trapped in ice. Our results imply that the ice(snow)-covered surfaces and ice-cloud particles containing iron-rich mineral dusts in the polar and cold environments provide a source of bioavailable iron when they thaw.

  16. Nickel aluminides and nickel-iron aluminides for use in oxidizing environments

    DOEpatents

    Liu, Chain T.

    1988-03-15

    Nickel aluminides and nickel-iron aluminides treated with hafnium or zirconium, boron and cerium to which have been added chromium to significantly improve high temperature ductility, creep resistance and oxidation properties in oxidizing environments.

  17. Oxidized Carbo-Iron causes reduced reproduction and lower tolerance of juveniles in the amphipod Hyalella azteca.

    PubMed

    Weil, Mirco; Meißner, Tobias; Springer, Armin; Bundschuh, Mirco; Hübler, Lydia; Schulz, Ralf; Duis, Karen

    2016-12-01

    For in situ remediation of groundwater contaminated by halogenated hydrocarbons Carbo-Iron(®), a composite of microscale activated carbon and nano Fe(0), was developed. Against the background of intended release of Carbo-Iron into the environment in concentrations in the g/L-range, potential ecotoxicological consequences were evaluated in the present study. The nano Fei(0) in Carbo-Iron acts as reducing agent and is oxidized in aqueous systems by chlorinated solvents, groundwater constituents (e.g. dissolved oxygen) and anaerobic corrosion. As Carbo-Iron is generally oxidized rapidly after application into the environment, the oxidized state is environmentally most relevant, and Carbo-Iron was used in its oxidized form in the ecotoxicological tests. The amphipod Hyalella azteca was selected as a surrogate test species for functionally important groundwater crustaceans. Effects of Carbo-Iron on H. azteca were determined in a 10-d acute test, a 7-d feeding activity test and a 42-d chronic test. Additionally, a 56-d life cycle test was performed with a modified design to further evaluate effects of Carbo-Iron on adult H. azteca and their offspring. The size of Carbo-Iron particles in stock and test suspensions was determined via dynamic light scattering. Potential uptake of particles into test organisms was investigated using transmission and scanning electron microscopy. At the termination of the feeding and acute toxicity test (i.e. after 7 and 10 d of exposure, respectively), Carbo-Iron had a significant effect on the weight, length and feeding rate of H. azteca at the highest test concentration of 100mg/L. While an uptake of Carbo-Iron into the gut was observed, no passage into the surrounding tissue was detected. In both chronic tests, the number of offspring was the most sensitive endpoint and significant effects were recorded at concentrations ≥50mg/L (42-d experiment) and ≥12.5mg/L (56-d experiment). Parental exposure to oxidized Carbo-Iron significantly

  18. Effect of radiation energy and intracellular iron dose on iron oxide nanoparticle enhancement of radiation cytotoxicity

    NASA Astrophysics Data System (ADS)

    Mazur, Courtney M.; Strawbridge, Rendall R.; Thompson, Ella S.; Petryk, Alicia A.; Gladstone, David J.; Hoopes, P. Jack

    2015-03-01

    Iron oxide nanoparticles (IONPs) are one of several high-Z materials currently being investigated for their ability to enhance the cytotoxic effects of therapeutic ionizing radiation. Studies with iron oxide, silver, gold, and hafnium oxide suggest radiation dose, radiation energy, cell type, and the type and level of metallic nanoparticle are all critical factors in achieving radiation enhancement in tumor cells. Using a single 4 Gy radiation dose, we compared the level of tumor cell cytotoxicity at two different intracellular iron concentrations and two different radiation energies in vitro. IONPs were added to cell culture media at concentrations of 0.25 mg Fe/mL and 1.0 mg Fe/mL and incubated with murine breast adenocarcinoma (MTG-B) cells for 72 hours. Extracellular iron was then removed and cells were irradiated at either 662 keV or 10 MV. At the 0.25 mg Fe/mL dose (4 pg Fe/cell), radiation energy did not affect the level of cytotoxicity. However with 1.0 mg Fe/mL (9 pg Fe/cell), the higher 10 MV radiation energy resulted in 50% greater cytotoxicity as compared to cells without IONPs irradiated at this energy. These results suggest IONPs may be able to significantly enhance the cytotoxic effects of radiation and improve therapeutic ratio if they can be selectively associated with cancer cells and/or tumors. Ongoing in vivo studies of IONP radiation enhancement in a murine tumor model are too immature to draw conclusions from at this time, however preliminary data suggests similar effectiveness of IONP radiation enhancement at 6 MV and 18 MV energy levels. In addition to the IONP-based radiation enhancement demonstrated here, the use of tumor-localized IONP with an externally delivered, non-toxic alternating magnetic field affords the opportunity to selectively heat and kill tumor cells. Combining IONP-based radiation sensitization and heat-based cytotoxicity provides a unique and potentially highly effective opportunity for therapeutic ratio enhancement.

  19. Effect of dietary iron and copper on performance and oxidative stability in broiler leg meat.

    PubMed

    Ruiz, J A; Pérez-Vendrell, A M; Esteve-Garcia, E

    2000-05-01

    1. An experiment was carried out to determine the effect of removal of supplemental iron and copper from broiler diets during the last 3 weeks before slaughter on broiler performance, tissue vitamin E concentrations and oxidation values in raw; cooked and stored broiler leg meat. 2. Removal of supplemental iron and copper from the diet slightly decreased food efficiency; the differences were significant only when both minerals were removed simultaneously 3. Effect of iron withdrawal on iron concentration in tissue was low. However, total copper concentration in tissue was reduced in animals deprived of iron or both minerals simultaneously. 4. Removal of dietary iron and copper did not affect vitamin E concentration in raw and cooked meat, while stored meat showed lower concentrations in animals deprived of iron and copper simultaneously. 5. The removal of iron and copper from the diet reduced oxidation values in cooked broiler leg meat as measured by the thiobarbituric acid-reacting substances method (TBARS).

  20. Clinical efficacy of two forms of intravenous iron--saccharated ferric oxide and cideferron--for iron deficiency anemia.

    PubMed

    Araki, T; Takaai, M; Miyazaki, A; Ohshima, S; Shibamiya, T; Nakamura, T; Yamamoto, K

    2012-12-01

    Over 90% of iron deficiency anemia cases are due to iron deficiency associated with depletion of stored iron or inadequate intake. Parenteral iron supplementation is an important part of the management of anemia, and some kinds of intravenous iron are used. However, few studies have evaluated the clinical efficacy of these drugs. The purpose of this study was to compare and assess the clinical efficacy of two types of intravenous iron injection, saccharated ferric oxide (SFO) and cideferron (CF). Medical records were obtained for 91 unrelated Japanese anemia patients treated with SFO (n = 37) or CF (n = 54) from May 2005 to May 2010 at Gunma University Hospital. Patients treated with blood transfusion, erythropoietin or oral iron were excluded. Hemoglobin (Hb) values measured on day 0, 7 and 14 were used to assess the efficacy of intravenous irons. A significant increase was observed in the mean Hb value by day 14 of administration in both the CF group and SFO group, and the mean Hb increase due to administration of CF for 7 days was comparable to that of SFO for 14 days. Age and sex did not affect improvement of Hb value. CF is fast acting and highly effective compared with SFO for the treatment of iron deficiency anemia. The use of CF may shorten a therapeutic period for iron deficiency anemia, and CF may be feasible for reducing the hospitalization period.

  1. Phonon density of states of iron up to 153 gigapascals.

    PubMed

    Mao, H K; Xu, J; Struzhkin, V V; Shu, J; Hemley, R J; Sturhahn, W; Hu, M Y; Alp, E E; Vocadlo, L; Alfè, D; Price, G D; Gillan, M J; Schwoerer-Böhning, M; Häusermann, D; Eng, P; Shen, G; Giefers, H; Lübbers, R; Wortmann, G

    2001-05-04

    We report phonon densities of states (DOS) of iron measured by nuclear resonant inelastic x-ray scattering to 153 gigapascals and calculated from ab initio theory. Qualitatively, they are in agreement, but the theory predicts density at higher energies. From the DOS, we derive elastic and thermodynamic parameters of iron, including shear modulus, compressional and shear velocities, heat capacity, entropy, kinetic energy, zero-point energy, and Debye temperature. In comparison to the compressional and shear velocities from the preliminary reference Earth model (PREM) seismic model, our results suggest that Earth's inner core has a mean atomic number equal to or higher than pure iron, which is consistent with an iron-nickel alloy.

  2. Potential for microbial oxidation of ferrous iron in basaltic glass.

    PubMed

    Xiong, Mai Yia; Shelobolina, Evgenya S; Roden, Eric E

    2015-05-01

    Basaltic glass (BG) is an amorphous ferrous iron [Fe(II)]-containing material present in basaltic rocks, which are abundant on rocky planets such as Earth and Mars. Previous research has suggested that Fe(II) in BG can serve as an energy source for chemolithotrophic microbial metabolism, which has important ramifications for potential past and present microbial life on Mars. However, to date there has been no direct demonstration of microbially catalyzed oxidation of Fe(II) in BG. In this study, three different culture systems were used to investigate the potential for microbial oxidation of Fe(II) in BG, including (1) the chemolithoautotrophic Fe(II)-oxidizing, nitrate-reducing "Straub culture"; (2) the mixotrophic Fe(II)-oxidizing, nitrate-reducing organism Desulfitobacterium frappieri strain G2; and (3) indigenous microorganisms from a streambed Fe seep in Wisconsin. The BG employed consisted of clay and silt-sized particles of freshly quenched lava from the TEB flow in Kilauea, Hawaii. Soluble Fe(II) or chemically reduced NAu-2 smectite (RS) were employed as positive controls to verify Fe(II) oxidation activity in the culture systems. All three systems demonstrated oxidation of soluble Fe(II) and/or structural Fe(II) in RS, whereas no oxidation of Fe(II) in BG material was observed. The inability of the Straub culture to oxidize Fe(II) in BG was particularly surprising, as this culture can oxidize other insoluble Fe(II)-bearing minerals such as biotite, magnetite, and siderite. Although the reason for the resistance of the BG toward enzymatic oxidation remains unknown, it seems possible that the absence of distinct crystal faces or edge sites in the amorphous glass renders the material resistant to such attack. These findings have implications with regard to the idea that Fe(II)-Si-rich phases in basalt rocks could provide a basis for chemolithotrophic microbial life on Mars, specifically in neutral-pH environments where acid-promoted mineral dissolution and

  3. Iron isotope fractionation during microbial dissimilatory iron oxide reduction in simulated Archaean seawater.

    PubMed

    Percak-Dennett, E M; Beard, B L; Xu, H; Konishi, H; Johnson, C M; Roden, E E

    2011-05-01

    The largest Fe isotope excursion yet measured in marine sedimentary rocks occurs in shales, carbonates, and banded iron formations of Neoarchaean and Paleoproterozoic age. The results of field and laboratory studies suggest a potential role for microbial dissimilatory iron reduction (DIR) in producing this excursion. However, most experimental studies of Fe isotope fractionation during DIR have been conducted in simple geochemical systems, using pure Fe(III) oxide substrates that are not direct analogues to phases likely to have been present in Precambrian marine environments. In this study, Fe isotope fractionation was investigated during microbial reduction of an amorphous Fe(III) oxide-silica coprecipitate in anoxic, high-silica, low-sulphate artificial Archaean seawater at 30 °C to determine if such conditions alter the extent of reduction or isotopic fractionations relative to those observed in simple systems. The Fe(III)-Si coprecipitate was highly reducible (c. 80% reduction) in the presence of excess acetate. The coprecipitate did not undergo phase conversion (e.g. to green rust, magnetite or siderite) during reduction. Iron isotope fractionations suggest that rapid and near-complete isotope exchange took place among all Fe(II) and Fe(III) components, in contrast to previous work on goethite and hematite, where exchange was limited to the outer few atom layers of the substrate. Large quantities of low-δ(56)Fe Fe(II) (aqueous and solid phase) were produced during reduction of the Fe(III)-Si coprecipitate. These findings shed new light on DIR as a mechanism for producing Fe isotope variations observed in Neoarchaean and Paleoproterozoic marine sedimentary rocks. © 2011 Blackwell Publishing Ltd.

  4. Iron oxide reduction in deep Baltic Sea sediments: the potential role of anaerobic oxidation of methane

    NASA Astrophysics Data System (ADS)

    Egger, Matthias; Slomp, Caroline P.; Dijkstra, Nikki; Sapart, Célia J.; Risgaard-Petersen, Nils; Kasten, Sabine; Riedinger, Natascha; Barker Jørgensen, Bo

    2015-04-01

    Methane is a powerful greenhouse gas and its emission from marine sediments to the atmosphere is largely controlled by anaerobic oxidation of methane (AOM). Traditionally, sulfate is considered to be the most important electron acceptor for AOM in marine sediments. However, recent studies have shown that AOM may also be coupled to the reduction of iron (Fe) oxides (Beal et al., 2009; Riedinger et al., 2014; Egger et al., 2014). In the Baltic Sea, the transition from the Ancylus freshwater phase to the Littorina brackish/marine phase (A/L-transition) ca. 9-7 ka ago (Zillén et al., 2008) resulted in the accumulation of methanogenic brackish/marine sediments overlying Fe-oxide rich lacustrine deposits. The downward diffusion of methane from the brackish/marine sediments into the lake sediments leads to an ideal diagenetic system to study a potential coupling between Fe oxide reduction and methane oxidation. Here, we use porewater and sediment geochemical data obtained at sites M0063 and M0065 during the IODP Baltic Sea Paleoenvironment Expedition 347 in 2013 to identify the potential mechanisms responsible for the apparent Fe oxide reduction in the non-sulfidic limnic sediments below the A/L transition. In this presentation, we will review the various explanations for the elevated ferrous Fe in the porewater in the lake sediments and we will specifically address the potential role of the reaction of methane with Fe-oxides. References: Beal E. J., House C. H. and Orphan V. J. (2009) Manganese- and iron-dependent marine methane oxidation. Science 325, 184-187. Egger M., Rasigraf O., Sapart C. J., Jilbert T., Jetten M. S. M., Röckmann T., van der Veen C., Banda N., Kartal B., Ettwig K. F. and Slomp C. P. (2014) Iron-mediated anaerobic oxidation of methane in brackish coastal sediments. Environ. Sci. Technol. 49, 277-283. Riedinger N., Formolo M. J., Lyons T. W., Henkel S., Beck A. and Kasten S. (2014) An inorganic geochemical argument for coupled anaerobic oxidation of

  5. Chemical characterization of iron oxide precipitates from wetlands constructed to treat polluted mine drainage

    SciTech Connect

    Fish, C.L.; Partezana, J.M.; Hedin, R.S.

    1996-12-31

    The passive treatment of abandoned mine drainage using wetlands will produce a significant amount of iron rich sludge which will require costly removal and disposal. An alternative to disposal may be the use of this iron oxide material as pigments which could defray some of these costs. In this research, iron deposits from five alkaline mine drainage wetlands were collected and a series of standard tests were run. The tests included loss on ignition, moisture, pH, acid soluble metals, oil absorption, and water soluble matter. The results of these tests were compared to those achieved using commercially available natural and synthetic iron oxides. The results indicate that iron oxides from constructed wetlands have chemical properties that are intermediate to those of natural and synthetic iron oxide products.

  6. Absorption of inorganic halides produced from Freon 12 by calcium carbonate containing iron(III) oxide

    SciTech Connect

    Imamura, Seiichiro; Matsuba, Yoichi; Yamada, Etsu; Takai, Kenji; Utani, Kazunori

    1997-09-01

    Inorganic halides produced by the catalytic decomposition of Freon 12 were fixed by calcium carbonate, which is the main component of limestone. Iron(III) oxide, which is present as a contaminant in limestone, promoted the absorption of the halides by calcium carbonate at low temperatures. The supposed action of iron(III) oxide was to first react with inorganic halides, forming iron halides, and, then, transfer them to calcium carbonate to replace carbonate ion in a catalytic way. Thus, calcium carbonate containing iron oxides (limestone) can be used as an effective absorbent for the inorganic halogens produced during the decomposition of Freons.

  7. Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity.

    PubMed

    Schneider, J J; Czap, N; Hagen, J; Engstler, J; Ensling, J; Gütlich, P; Reinoehl, U; Bertagnolli, H; Luis, F; de Jongh, L J; Wark, M; Grubert, G; Hornyak, G L; Zanoni, R

    2000-12-01

    Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. Mössbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the Mössbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From Mössbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active

  8. Oxygen vacancy promoted methane partial oxidation over iron oxide oxygen carriers in the chemical looping process.

    PubMed

    Cheng, Zhuo; Qin, Lang; Guo, Mengqing; Xu, Mingyuan; Fan, Jonathan A; Fan, Liang-Shih

    2016-11-30

    We perform ab initio DFT+U calculations and experimental studies of the partial oxidation of methane to syngas on iron oxide oxygen carriers to elucidate the role of oxygen vacancies in oxygen carrier reactivity. In particular, we explore the effect of oxygen vacancy concentration on sequential processes of methane dehydrogenation, and oxidation with lattice oxygen. We find that when CH4 adsorbs onto Fe atop sites without neighboring oxygen vacancies, it dehydrogenates with CHx radicals remaining on the same site and evolves into CO2via the complete oxidation pathway. In the presence of oxygen vacancies, on the other hand, the formed methyl (CH3) prefers to migrate onto the vacancy site while the H from CH4 dehydrogenation remains on the original Fe atop site, and evolves into CO via the partial oxidation pathway. The oxygen vacancies created in the oxidation process can be healed by lattice oxygen diffusion from the subsurface to the surface vacancy sites, and it is found that the outward diffusion of lattice oxygen atoms is more favorable than the horizontal diffusion on the same layer. Based on the proposed mechanism and energy profile, we identify the rate-limiting steps of the partial oxidation and complete oxidation pathways. Also, we find that increasing the oxygen vacancy concentration not only lowers the barriers of CH4 dehydrogenation but also the cleavage energy of Fe-C bonds. However, the barrier of the rate-limiting step cannot further decrease when the oxygen vacancy concentration reaches 2.5%. The fundamental insight into the oxygen vacancy effect on CH4 oxidation with iron oxide oxygen carriers can help guide the design and development of more efficient oxygen carriers and CLPO processes.

  9. Synthesis, Characterization and Cytotoxicity Evaluation of Nitric Oxide-Iron Oxide magnetic Nanoparticles

    NASA Astrophysics Data System (ADS)

    Haddad, P. S.; Britos, T. N.; Santos, M. C.; Seabra, A. B.; Palladino, M. V.; Justo, G. Z.

    2015-05-01

    The present work is focused on the synthesis, characterization and cytotoxic evaluation of superparamagnetic iron oxide nanoparticles (SPIONs). SPIONs have been proposed for an increasing number of biomedical applications, such as drug-delivery. To this end, toxicological studies of their potential effects in biological systems must be better evaluated. The aim of this study was to examine the in vitro cytotoxicity of thiolated (SH) and S-nitrosated (S-NO) SPIONs in cancer cell lines. SPIONs were prepared by the coprecipitation method using ferrous and ferric chlorides in aqueous solution. The nanoparticles (Fe3O4) were coated with thiol containing molecule cysteine (Cys) (molar ratio SPIONs:ligand = 1:20), leading to the formation of an aqueous dispersion of thiolated nanoparticles (SH- SPIONs). These particles were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The results obtained showed that Cys-SPIONs have a mean diameter of 14 nm at solid state and present super paramagnetic behavior at room temperature. Thiol groups on the surface of the nanoparticles were nitrosated through the addition of sodium nitrite leading to the formation of S-NOCys-SPIONs (S-nitrosated-Cys-SPIONs), which act as spontaneous nitric oxide (NO) donor). The cytotoxicity of thiolated and S-nitrosated nanoparticles was evaluated in acute T cell leukemia (Jurkat cell line) and Lewis lung carcinoma (3LL) cells. The results showed that at low concentrations thiolated (Cys) and S- nitrosated (S-NOCyst) SPIONs display low cytotoxicity in both cell types. However, at higher concentrations, Cys-SPIONs exhibited cytotoxic effects, whereas S-NOCys-SPIONs protected them, and also promoted cell proliferation.

  10. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., carboxylic acid-modified (generic). 721.10529 Section 721.10529 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid... substance identified generically as cobalt iron manganese oxide, carboxylic acid-modified (PMN P-12-35) is...

  11. Kinetic Studies of Iron Oxidation by Whole Cells of Ferrobacillus ferrooxidans

    PubMed Central

    Schnaitman, C. A.; Korczynski, M. S.; Lundgren, D. G.

    1969-01-01

    A colorimetric assay was developed for studying the kinetics of iron oxidation with whole cells of the chemoautotroph, Ferrobacillus ferrooxidans. The assay was more advantageous than the conventional method of Warburg manometry because of its simplicity, rapidity, and the small amount of cells required. The assay measured Fe3+ as a chloride complex which absorbs at 410 nm. Kinetic analysis showed the apparent Km for iron oxidation to be 5.4 × 10−3m in an unbuffered system and 2.2 × 10−3m in the presence of β-alanine-SO42− buffer. Glycine and β-alanine buffers were used in the measurement of the pH optimum for iron oxidation; the optimum ranged from 2.5 to 3.8. The effect of pH was primarily on the Vmax while the Km remained constant. Added SO42− was found to stimulate iron oxidation by increasing the Vmax of iron oxidation by whole cells, but it did not affect the Km. Results of assays of iron oxidation in systems containing various mole percentages of SO42− and Cl− indicated that Cl− did not inhibit iron oxidation but that SO42− was required. Sulfate could be partially replaced by HPO42− and HAsO42− but not by BO3−, MoO42−, NO3−, or Cl−; formate and MoO42− inhibited iron oxidation. PMID:5808080

  12. Iron-Oxide Minerals Affect Extracellular Electron-Transfer Paths of Geobacter spp

    PubMed Central

    Kato, Souichiro; Hashimoto, Kazuhito; Watanabe, Kazuya

    2013-01-01

    Some bacteria utilize (semi)conductive iron-oxide minerals as conduits for extracellular electron transfer (EET) to distant, insoluble electron acceptors. A previous study demonstrated that microbe/mineral conductive networks are constructed in soil ecosystems, in which Geobacter spp. share dominant populations. In order to examine how (semi)conductive iron-oxide minerals affect EET paths of Geobacter spp., the present study grew five representative Geobacter strains on electrodes as the sole electron acceptors in the absence or presence of (semi)conductive iron oxides. It was found that iron-oxide minerals enhanced current generation by three Geobacter strains, while no effect was observed in another strain. Geobacter sulfurreducens was the only strain that generated substantial amounts of currents both in the presence and absence of the iron oxides. Microscopic, electrochemical and transcriptomic analyses of G. sulfurreducens disclosed that this strain constructed two distinct types of EET path; in the absence of iron-oxide minerals, bacterial biofilms rich in extracellular polymeric substances were constructed, while composite networks made of mineral particles and microbial cells (without polymeric substances) were developed in the presence of iron oxides. It was also found that uncharacterized c-type cytochromes were up-regulated in the presence of iron oxides that were different from those found in conductive biofilms. These results suggest the possibility that natural (semi)conductive minerals confer energetic and ecological advantages on Geobacter, facilitating their growth and survival in the natural environment. PMID:23363619

  13. Dietary Iron Oxide Nanoparticles Delay Aging and Ameliorate Neurodegeneration in Drosophila.

    PubMed

    Zhang, Yi; Wang, Zhuyao; Li, Xiaojiao; Wang, Lu; Yin, Min; Wang, Lihua; Chen, Nan; Fan, Chunhai; Song, Haiyun

    2016-02-17

    Dietary iron oxide nanoparticles are shown to ameliorate neurodegeneration in a Drosophelia Alzheimer's disease model. Iron oxide nanoparticles can mimic catalase and can decompose reactive oxygen species (ROS). This has potential therapeutic uses for aging, metabolic disorders, and neurodegenerative diseases, in which increased production of ROS is closely implicated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Dopamine Serves as a Stable Surface Modifier for Iron Oxide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Chi, Xiaoqin; Wang, Xiaomin; Hu, Juan; Wang, Lirong; Gao, Jinhao; Zhang, Bei; Zhang, Xixiang

    2013-03-01

    Iron oxide nanoparticles are an important class of nanomaterials in a broad range of biomedical applications because of their superparamagnetism and biocompatibility. The success of biomedical applications of iron oxide nanoparticles relies on the particles' surface functionalization, which requires robust and versatile surface anchors. Here, we report on a detailed examination of the dopamine-based surface modification of iron oxide nanoparticles. We used dopamine (2-(3,4-dihydroxyphenyl)ethylamine) and L-dopa (3,4-dihydroxy-L-phenylalanine) as two surface modifiers and chose Fe2O3 hollow nanoparticles and Fe3O4 nanoparticles as two representative substrates. Optical and TEM images showed that iron oxide nanoparticles dispersed very well in water after surface modification. The analysis of the UV-Vis spectra indicated that dopamine and L-dopa are stable after being immobilized on the surface of iron oxide nanoparticles when the pH value of the environment is about 7. The magnetic properties analysis further showed that the blocking temperature of the dopamine- or L-dopa-decorated iron oxide nanoparticles hardly changed over 20 days, confirming long-term stability of these surface modified nanoparticles. Cell assay indicated that these dopamine- or L-dopa-modified iron oxide nanoparticles were biocompatible. These results confirm that dopamine serves as a stable modifier and a robust anchor to functionalize iron oxide nanoparticles in biomedical applications.

  15. Genome Sequence of the Acidophilic Iron Oxidizer Ferrimicrobium acidiphilum Strain T23T.

    PubMed

    Eisen, Sebastian; Poehlein, Anja; Johnson, D Barrie; Daniel, Rolf; Schlömann, Michael; Mühling, Martin

    2015-04-30

    Extremely acidophilic iron-oxidizing bacteria have largely been characterized for the phyla Proteobacteria and Nitrospira. Here, we report the draft genome of an iron-oxidizing and -reducing heterotrophic mesophile of the Actinobacteria, Ferrimicrobium acidiphilum, which was isolated from an abandoned pyrite mine. The genome sequence comprises 3.08 Mb.

  16. Catalytic oxidation of alkanes by iron bispidine complexes and dioxygen: oxygen activation versus autoxidation.

    PubMed

    Comba, Peter; Lee, Yong-Min; Nam, Wonwoo; Waleska, Arkadius

    2014-01-14

    Organic substrates (specifically cis-1,2-dimethylcyclohexane, DMCH) are oxidized by O2 in the presence of iron(II)-bispidine complexes. It is shown that this oxidation reaction is not based on O2 activation by the nonheme iron catalysts as in Nature but due to a radical-based initiation, followed by a radical- and ferryl-based catalytic reaction.

  17. Iron-oxide minerals affect extracellular electron-transfer paths of Geobacter spp.

    PubMed

    Kato, Souichiro; Hashimoto, Kazuhito; Watanabe, Kazuya

    2013-01-01

    Some bacteria utilize (semi)conductive iron-oxide minerals as conduits for extracellular electron transfer (EET) to distant, insoluble electron acceptors. A previous study demonstrated that microbe/mineral conductive networks are constructed in soil ecosystems, in which Geobacter spp. share dominant populations. In order to examine how (semi)conductive iron-oxide minerals affect EET paths of Geobacter spp., the present study grew five representative Geobacter strains on electrodes as the sole electron acceptors in the absence or presence of (semi)conductive iron oxides. It was found that iron-oxide minerals enhanced current generation by three Geobacter strains, while no effect was observed in another strain. Geobacter sulfurreducens was the only strain that generated substantial amounts of currents both in the presence and absence of the iron oxides. Microscopic, electrochemical and transcriptomic analyses of G. sulfurreducens disclosed that this strain constructed two distinct types of EET path; in the absence of iron-oxide minerals, bacterial biofilms rich in extracellular polymeric substances were constructed, while composite networks made of mineral particles and microbial cells (without polymeric substances) were developed in the presence of iron oxides. It was also found that uncharacterized c-type cytochromes were up-regulated in the presence of iron oxides that were different from those found in conductive biofilms. These results suggest the possibility that natural (semi)conductive minerals confer energetic and ecological advantages on Geobacter, facilitating their growth and survival in the natural environment.

  18. Enzymes of respiratory iron oxidation. Progress report, March 1990--June 1992

    SciTech Connect

    Blake, R. II

    1992-12-31

    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.

  19. Iron, Anemia, and Iron Deficiency Anemia among Young Children in the United States

    PubMed Central

    Gupta, Priya M.; Perrine, Cria G.; Mei, Zuguo; Scanlon, Kelley S.

    2016-01-01

    Iron deficiency and anemia are associated with impaired neurocognitive development and immune function in young children. Total body iron, calculated from serum ferritin and soluble transferrin receptor concentrations, and hemoglobin allow for monitoring of the iron and anemia status of children in the United States. The purpose of this analysis is to describe the prevalence of iron deficiency (ID), anemia, and iron deficiency anemia (IDA) among children 1–5 years using data from the 2007–2010 National Health and Nutrition Examination Survey (NHANES). Prevalence of ID, anemia, and IDA among children 1–5 years was 7.1% (5.5, 8.7), 3.2% (2.0, 4.3), and 1.1% (0.6, 1.7), respectively. The prevalence of both ID and anemia were higher among children 1–2 years (p < 0.05). In addition, 50% of anemic children 1–2 years were iron deficient. This analysis provides an update on the prevalence of ID, anemia, and IDA for a representative sample of US children. Our results suggest little change in these indicators over the past decade. Monitoring of ID and anemia is critical and prevention of ID in early childhood should remain a public health priority. PMID:27249004

  20. Iron Binding at Specific Sites within the Octameric HbpS Protects Streptomycetes from Iron-Mediated Oxidative Stress

    PubMed Central

    Wedderhoff, Ina; Kursula, Inari; Groves, Matthew R.; Ortiz de Orué Lucana, Darío

    2013-01-01

    The soil bacterium Streptomyces reticuli secretes the octameric protein HbpS that acts as a sensory component of the redox-signalling pathway HbpS-SenS-SenR. This system modulates a genetic response on iron- and haem-mediated oxidative stress. Moreover, HbpS alone provides this bacterium with a defence mechanism to the presence of high concentrations of iron ions and haem. While the protection against haem has been related to its haem-binding and haem-degrading activity, the interaction with iron has not been studied in detail. In this work, we biochemically analyzed the iron-binding activity of a set of generated HbpS mutant proteins and present evidence showing the involvement of one internal and two exposed D/EXXE motifs in binding of high quantities of ferrous iron, with the internal E78XXE81 displaying the tightest binding. We additionally show that HbpS is able to oxidize ferrous to ferric iron ions. Based on the crystal structure of both the wild-type and the mutant HbpS-D78XXD81, we conclude that the local arrangement of the side chains from the glutamates in E78XXE81 within the octameric assembly is a pre-requisite for interaction with iron. The data obtained led us to propose that the exposed and the internal motif build a highly specific route that is involved in the transport of high quantities of iron ions into the core of the HbpS octamer. Furthermore, physiological studies using Streptomyces transformants secreting either wild-type or HbpS mutant proteins and different redox-cycling compounds led us to conclude that the iron-sequestering activity of HbpS protects these soil bacteria from the hazardous side effects of peroxide- and iron-based oxidative stress. PMID:24013686

  1. Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

    SciTech Connect

    Zhang, Yijun; Liu, Ming; Peng, Bin; Zhou, Ziyao; Chen, Xing; Yang, Shu-Ming; Jiang, Zhuang-De; Zhang, Jie; Ren, Wei; Ye, Zuo-Guang

    2016-01-27

    Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe2O3 and superparamagnetic Fe2O3with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe2O3 in a reducing atmosphere leads to the formation of the spinel Fe3O4 phase which displays a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. Finally, the ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.

  2. Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition.

    PubMed

    Zhang, Yijun; Liu, Ming; Peng, Bin; Zhou, Ziyao; Chen, Xing; Yang, Shu-Ming; Jiang, Zhuang-De; Zhang, Jie; Ren, Wei; Ye, Zuo-Guang

    2016-01-27

    Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe2O3 and superparamagnetic Fe3O4 with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe2O3 in a reducing atmosphere leads to the formation of the spinel Fe3O4 phase which displays a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. The ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.

  3. Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

    NASA Astrophysics Data System (ADS)

    Zhang, Yijun; Liu, Ming; Peng, Bin; Zhou, Ziyao; Chen, Xing; Yang, Shu-Ming; Jiang, Zhuang-De; Zhang, Jie; Ren, Wei; Ye, Zuo-Guang

    2016-01-01

    Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe2O3 and superparamagnetic Fe3O4 with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe2O3 in a reducing atmosphere leads to the formation of the spinel Fe3O4 phase which displays a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. The ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.

  4. Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

    DOE PAGES

    Zhang, Yijun; Liu, Ming; Peng, Bin; ...

    2016-01-27

    Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe2O3 and superparamagnetic Fe2O3with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe2O3 in a reducing atmosphere leads to the formation of the spinel Fe3O4 phase which displays a distinct ferrimagnetic anisotropy and the Verwey metal-insulatormore » transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. Finally, the ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.« less

  5. Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

    PubMed Central

    Zhang, Yijun; Liu, Ming; Peng, Bin; Zhou, Ziyao; Chen, Xing; Yang, Shu-Ming; Jiang, Zhuang-De; Zhang, Jie; Ren, Wei; Ye, Zuo-Guang

    2016-01-01

    Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe2O3 and superparamagnetic Fe3O4 with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe2O3 in a reducing atmosphere leads to the formation of the spinel Fe3O4 phase which displays a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. The ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications. PMID:26813143

  6. Designed synthesis and surface engineering strategies of magnetic iron oxide nanoparticles for biomedical applications.

    PubMed

    Wu, Wei; Jiang, Chang Zhong; Roy, Vellaisamy A L

    2016-12-01

    Iron oxide nanoparticles (NPs) hold great promise for future biomedical applications because of their magnetic properties as well as other intrinsic properties such as low toxicity, colloidal stability, and surface engineering capability. Numerous related studies on iron oxide NPs have been conducted. Recent progress in nanochemistry has enabled fine control over the size, crystallinity, uniformity, and surface properties of iron oxide NPs. This review examines various synthetic approaches and surface engineering strategies for preparing naked and functional iron oxide NPs with different physicochemical properties. Growing interest in designed and surface-engineered iron oxide NPs with multifunctionalities was explored in in vitro/in vivo biomedical applications, focusing on their combined roles in bioseparation, as a biosensor, targeted-drug delivery, MR contrast agents, and magnetic fluid hyperthermia. This review outlines the limitations of extant surface engineering strategies and several developing strategies that may overcome these limitations. This study also details the promising future directions of this active research field.

  7. Porous Iron Oxide Ribbons Grown on Graphene for High-Performance Lithium Storage

    PubMed Central

    Yang, Shubin; Sun, Yi; Chen, Long; Hernandez, Yenny; Feng, Xinliang; Müllen, Klaus

    2012-01-01

    A well-designed nanostructure of transition metal oxides has been regarded as a key to solve their problems of large volume changes during lithium insertion-desertion processes which are associated with pulverization of the electrodes and rapid capacity decay. Here we report an effective approach for the fabrication of porous iron oxide ribbons by controlling the nucleation and growth of iron precursor onto the graphene surface and followed by an annealing treatment. The resultant iron oxide ribbons possess large aspect ratio, porous structure, thin feature and enhanced open-edges. These characteristics are favorable for the fast diffusion of lithium ions and electrons, and meanwhile can effectively accommodate the volume change of iron oxides during the cycling processes. As a consequence, the graphene-induced porous iron oxide ribbons exhibit a high reversible capacity and excellent cycle stability for lithium storage. PMID:22645643

  8. The concept of delayed nucleation in nanocrystal growthdemonstrated for the case of iron oxide nanodisks

    SciTech Connect

    Casula, Maria F.; Jun, Young-wook; Zaziski, David J.; Chan, EmoryM.; Corrias, Anna; Alivisatos, Paul A.

    2005-09-09

    A comprehensive study of iron oxide nanocrystal growth through non-hydrolitic, surfactant-mediated thermal reaction of iron pentacarbonyl and an oxidizer has been conducted, which includes size control, anisotropic shape evolution, and crystallographic phase transition of monodisperse iron oxide colloidal nanocrystals. The reaction was monitored by in situ UV-Vis spectroscopy taking advantage of the color change accompanying the iron oxide colloid formation allowing measurement of the induction time for nucleation. Features of the synthesis such as the size control and reproducibility are related to the occurrence of the observed delayed nucleation process. As a separate source of iron and oxygen is adopted, phase control could also be achieved by sequential injections of oxidizer.

  9. Iron(3) oxide-based nanoparticles as catalysts in advanced organic aqueous oxidation.

    PubMed

    Zelmanov, Grigory; Semiat, Raphael

    2008-01-01

    Water contaminated with dissolved organic matter is an important issue to resolve for all-purpose uses. The catalytic behavior of iron-based nanocatalysts was investigated for the treatment of contaminated water in the advanced chemical oxidation process. In this study, typical organic contaminants, such as ethylene glycol and phenol, were chosen to simulate common contaminants. It was shown that the two substances are efficiently destroyed by the Fenton-like reaction using iron(3) oxide-based nanocatalysts in the presence of hydrogen peroxide without the need for UV or visible radiation sources at room temperature. A strong effect of nanocatalyst concentration on reaction rate was shown. The kinetic reaction was found and the reaction rate coefficient k was calculated.

  10. Cadmium complexation by bacteriogenic iron oxides from a subterranean environment.

    PubMed

    Martinez, Raul E; Pedersen, Karsten; Ferris, F Grant

    2004-07-01

    This study quantifies the metal sorption characteristics of subterranean bacteriogenic iron oxides (BIOS) and their organic phases (intermixed intact and fragmented bacteria). A Cd2+ ion-selective electrode was used to generate high-resolution metal sorption data as a function of increasing pH. A multisite Langmuir model, along with a linear programming regression method (LPM), was applied to fit experimental data. This approach found two discrete Cd2+ binding sites for the BIOS with average -log10 equilibrium constants (pK(S,j)) of 1.06 +/- 0.19 and 2.24 +/- 0.28. Three discrete sites were obtained for the bacterial fraction, with pK(S,j) values of -0.05 +/- 0.12, 1.18 +/- 0.02, and 3.81 +/- 0.16. This indicated that the BIOS surface had a lower affinity for Cd2+ than that of the bacteria. pK(S,j) values for the BIOS were similar to those reported for pure iron oxide phases, while the organic fraction pK(S,j) spectrum was consistent with previous spectra for intact bacteria. Individual binding site densities of 0.04 +/- 0.01 and 0.05 +/- 0.02 and 0.29 +/- 0.05, 0.11 +/- 0.01, and 0.09 +/- 0.02 micromol/mg of BIOS corresponded to the iron oxide mixture and bacteria fraction, respectively. These values indicated high concentrations of strong affinity Cd2+ complexing groups on the bacterial surface. Comparison of total site densities of 0.08 +/- 0.02 and 0.48 +/- 0.06 micromol/mg of BIOS for the mixture and the bacterial phase, respectively, suggested a nonadditive character for the BIOS surface reactivity. This was emphasized by a higher affinity for Cd2+, as well as an increase in total site concentration observed for the bacterial phase. LPM was able to distinguish between the BIOS mixture and its organic fraction Cd2+ complexation characteristics. This approach is therefore a useful tool for the study of natural sorbent materials controlling metal partitioning in contaminated and pristine environments.

  11. Iron oxidation in Mops buffer. Effect of EDTA, hydrogen peroxide and FeCl3.

    PubMed

    Tadolini, B

    1987-01-01

    The effect of EDTA and H2O2 on iron autoxidation in Mops buffer depends on the pH of the solution. At acidic pH, EDTA caused the oxidation of a stoichiometric amount of iron. At neutral and alkaline pH, EDTA and H2O2 not only oxidizes a stoichiometric amount of iron but also causes the oxidation of the Fe2+ exceeding the concentration of these compounds. In the presence of EDTA, oxidation of Fe2+ in exceeding the concentration of these compounds has a shorter lag phase and an increased rate compared with that in the absence. The solution develops a yellow colour whose intensity is proportional to the amount of Fe2+ exceeding the concentration of these compounds in solution. When the reaction is conducted in the presence of NBT, formazan formation is greatly reduced compared to the control without EDTA and H2O2. The Fe3+-EDTA complex and Fe3+ affected iron oxidation, development of the yellow colour and NBT reduction in a similar fashion. In all these experimental conditions, iron oxidation is greatly reduced in the presence of mannitol, sorbitol and catalase. In phosphate buffer, EDTA oxidized a stoichiometric amount of iron without affecting free Fe2+ oxidation. Fe3+ has no effect on iron oxidation in this buffer.

  12. Magnetoadsorption and magnetodesorption of NO on iron oxides: Role of magnetism and surface structures of solids

    SciTech Connect

    Ozeki, Sumio; Uchiyama, Hiroyuki; Kaneko, Katsumi )

    1991-10-03

    The magnetic field effects on NO adsorption on iron oxides were observed at 303 K. Ferrimagnetic magnetite and maghemite showed magnetic field induced adsorption (magnetoadsorption); i.e., NO adsorption was promoted with an increase in external magnetic field (1-7.6 kG). Hematite (parasitic ferromagnetism) also showed magnetoadsorptivity. Antiferromagnetic iron oxyhydroxides ({alpha}-, {beta}-, and {gamma}-FeOOH) showed magnetic field induced desorption (magnetodesorption). On the other hand, an antiferromagnetic NiO and a ferrimagnetic {delta}-FeOOH exhibited magnetoadsorptivity and magnetodesorptivity, respectively. The magnetoadsorptivity of magnetites depended on the preheating conditions and that of {delta}-FeOOH was independent of its magnetism susceptibility. The results suggest that surface sites and porosity, i.e., adsorption state of NO, rather than solid magnetism would play an important role in the magnetic interactions between solid surfaces and NO molecules under a magnetic field.

  13. Iron oxide nanoparticles for magnetically assisted patterned coatings

    NASA Astrophysics Data System (ADS)

    Dodi, Gianina; Hritcu, Doina; Draganescu, Dan; Popa, Marcel I.

    2015-08-01

    Iron oxide nanoparticles able to magnetically assemble during the curing stage of a polymeric support to create micro-scale surface protuberances in a controlled manner were prepared and characterized. The bare Fe3O4 particles were obtained by two methods: co-precipitation from an aqueous solution containing Fe3+/Fe2+ ions with a molar ratio of 2:1 and partial oxidation of ferrous ions in alkaline conditions. The products were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and magnetization measurement. They were subsequently functionalized using oleic acid, sodium oleate, or non-ionic surfactant mixtures with various hydrophilic to lipophilic balance (HLB) values. Composite nanoparticle-polymer films prepared by spraying were deposited and cured by drying on glass slides under a static magnetic field in the range of 1.5-5.5 mT. Magnetic field generated surface roughness was evidenced by optical and scanning electron microscopy. The optimum hierarchical patterning was obtained with the nanoparticles produced by partial oxidation and functionalized with hydrophobic surfactants. Possible applications may include ice-phobic composite coatings.

  14. Solution voltammetry of 4 nm magnetite iron oxide nanoparticles.

    PubMed

    Roberts, Joseph J P; Westgard, John A; Cooper, Laura M; Murray, Royce W

    2014-07-30

    The voltammetry of solution-dispersed magnetite iron oxide Fe3O4 nanoparticles is described. Their currents are controlled by nanoparticle transport rates, as shown with potential step chronoamperometry and rotated disk voltammetry. In pH 2 citrate buffer with added NaClO4 electrolyte, solution cyclic voltammetry of these nanoparticles (average diameter 4.4 ± 0.9 nm, each containing ca. 30 Fe sites) displays an electrochemically irreversible oxidation with E(PEAK) at ca. +0.52 V and an irreversible reduction with E(PEAK) at ca. +0.2 V vs Ag/AgCl reference electrode. These processes are presumed to correspond to the formal potentials for one-electron oxidation of Fe(II) and reduction of Fe(III) at their different sites in the magnetite nanoparticle structure. The heterogeneous electrode reaction rates of the nanoparticles are very slow, in the 10(-5) cm/s range. The nanoparticles are additionally characterized by a variety of tools, e.g., TEM, UV/vis, and XPS spectroscopies.

  15. Processing, Microstructure, and Oxidation Behavior of Iron Foams

    NASA Astrophysics Data System (ADS)

    Park, Hyeji; Noh, Yoonsook; Choi, Hyelim; Hong, Kicheol; Kwon, Kyungjung; Choe, Heeman

    2016-09-01

    With its historically long popularity in major structural applications, the use of iron (Fe) has also recently begun to be explored as an advanced functional material. For this purpose, it is more advantageous to use Fe as a porous structure, simply because it can provide a greater surface area and a higher reaction rate. This study uses a freeze-casting method, which consists of simple and low-cost processing steps, to produce Fe foam with a mean pore size of 10 μm. We examine the influences of various parameters ( i.e., mold bottom temperature, powder content, and sintering time) on the processing of Fe foam, along with its oxidation kinetics at 823 K (550 °C) with various heat-treatment times. We confirm that Fe2O3 and Fe3O4 oxide layers are successfully formed on the surface of Fe foam. With the Fe oxide layers as an active anode material, the Fe foam can potentially be used as a three-dimensional anode current collector for an advanced lithium-ion battery.

  16. Warm dense iron equation of state from quantum molecular dynamics

    NASA Astrophysics Data System (ADS)

    Sjostrom, Travis; Crockett, Scott

    Through quantum molecular dynamics (QMD), utilizing both Kohn-Sham (orbital-based) and orbital-free density functional theory, we calculate the equation of state of warm dense iron in the density range 7-30 g/cm3 and temperatures from 1 to 100 eV. A critical examination of the iron pseudopotential is made, from which we find the previous QMD calculations of Wang et al. [Phys. Rev. E 89, 023101 (2014)] to be in error. Our results also significantly extend the ranges of density and temperature which are attempted in that prior work. We calculate the shock Hugoniot and find very good agreement with experimental results to pressures over 20 TPa. Additionally we have utilized the QMD results to generate a new SESAME tabular equation of state for fluid iron, accurate in the warm dense matter region, and also extending to much broader regions of density and temperature than can be accessed by the QMD alone.

  17. Nuclear magnetic resonance of iron and copper disease states

    SciTech Connect

    Runge, V.M.; Clanton, J.A.; Smith, F.W.; Hutchison, J.; Mallard, J.; Partain, C.L.; James, A.E. Jr.

    1983-11-01

    The tissue levels of paramagnetic ions are an important factor in the determination of T/sub 1/ values as observed by nuclear magnetic resonance (NMR) imaging. The increased levels of iron present in human disease states such as hemochromatosis lead to decreased T/sub 1/ values. The mean liver T/sub 1/ of three patients with iron storage disease was determined to be 130 msec, significantly different from the value of 154 msec, the mean for 14 normal controls. Whether NMR will be able to detect the increased copper levels in liver and brain in Wilson disease remains for further clinical trials to evaluate. NMR imaging, however, does serve as a noninvasive method for the diagnosis of states of iron overload and as a technique to follow progression of disease or response to medical therapy.

  18. Iron and carbon metabolism by a mineral-oxidizing Alicyclobacillus-like bacterium.

    PubMed

    Yahya, Adibah; Hallberg, Kevin B; Johnson, D Barrie

    2008-04-01

    A novel iron-oxidizing, moderately thermophilic, acidophilic bacterium (strain "GSM") was isolated from mineral spoil taken from a gold mine in Montana. Biomolecular analysis showed that it was most closely related to Alicyclobacillus tolerans, although the two bacteria differed in some key respects, including the absence (in strain GSM) of varpi-alicyclic fatty acids and in their chromosomal base compositions. Isolate GSM was able to grow in oxygen-free media using ferric iron as terminal electron acceptor confirming that it was a facultative anaerobe, a trait not previously described in Alicyclobacillus spp.. The acidophile used both organic and inorganic sources of energy and carbon, although growth and iron oxidation by isolate GSM was uncoupled in media that contained both fructose and ferrous iron. Fructose utilization suppressed iron oxidation, and oxidation of ferrous iron occurred only when fructose was depleted. In contrast, fructose catabolism was suppressed when bacteria were harvested while actively oxidizing iron, suggesting that both ferrous iron- and fructose-oxidation are inducible in this acidophile. Isolate GSM accelerated the oxidative dissolution of pyrite in liquid media either free of, or amended with, organic carbon, although redox potentials were significantly different in these media. The potential of this isolate for commercial mineral processing is discussed.

  19. Identification of a membrane cytochrome c from neutrophilic, iron-oxidizing Mariprofundus ferrooxydans, strain PV-1

    NASA Astrophysics Data System (ADS)

    Barco, R. A.; Zhong, J.; Ramirez, G. A.; Reese, B. K.; Edwards, K. J.

    2012-12-01

    Neutrophilic-iron oxidizing bacteria (FeOB) are a group of bacteria that can oxidize iron at -or near neutral pH, making them relevant in habitats with naturally high levels of reduced iron (i.e. Fe2+) such as hydrothermal vents. In the ocean, microorganisms in the Mariprofundus genus (zeta- Proteobacteria) are the only known organisms to chemolithoautotrophically oxidize iron. In order to identify the active bacterial oxidation<