Field-induced self-assembly of iron oxide nanoparticles investigated using small-angle neutron scattering.

PubMed

Fu, Zhendong; Xiao, Yinguo; Feoktystov, Artem; Pipich, Vitaliy; Appavou, Marie-Sousai; Su, Yixi; Feng, Erxi; Jin, Wentao; Brückel, Thomas

2016-11-03

The magnetic-field-induced assembly of magnetic nanoparticles (NPs) provides a unique and flexible strategy in the design and fabrication of functional nanostructures and devices. We have investigated the field-induced self-assembly of core-shell iron oxide NPs dispersed in toluene by means of small-angle neutron scattering (SANS). The form factor of the core-shell NPs was characterized and analyzed using SANS with polarized neutrons. Large-scale aggregates of iron oxide NPs formed above 0.02 T as indicated by very-small-angle neutron scattering measurements. A three-dimensional long-range ordered superlattice of iron oxide NPs was revealed under the application of a moderate magnetic field. The crystal structure of the superlattice has been identified to be face-centred cubic.

Synthesis and magnetic properties of cobalt-iron/cobalt-ferrite soft/hard magnetic core/shell nanowires

NASA Astrophysics Data System (ADS)

Leandro Londoño-Calderón, César; Moscoso-Londoño, Oscar; Muraca, Diego; Arzuza, Luis; Carvalho, Peterson; Pirota, Kleber Roberto; Knobel, Marcelo; Pampillo, Laura Gabriela; Martínez-García, Ricardo

2017-06-01

A straightforward method for the synthesis of CoFe2.7/CoFe2O4 core/shell nanowires is described. The proposed method starts with a conventional pulsed electrodeposition procedure on alumina nanoporous template. The obtained CoFe2.7 nanowires are released from the template and allowed to oxidize at room conditions over several weeks. The effects of partial oxidation on the structural and magnetic properties were studied by x-ray spectrometry, magnetometry, and scanning and transmission electron microscopy. The results indicate that the final nanowires are composed of 5 nm iron-cobalt alloy nanoparticles. Releasing the nanowires at room conditions promoted surface oxidation of the nanoparticles and created a CoFe2O4 shell spinel-like structure. The shell avoids internal oxidation and promotes the formation of bi-magnetic soft/hard magnetic core/shell nanowires. The magnetic properties of both the initial single-phase CoFe2.7 nanowires and the final core/shell nanowires, reveal that the changes in the properties from the array are due to the oxidation more than effects associated with released processes (disorder and agglomeration).

Synthesis and magnetic properties of cobalt-iron/cobalt-ferrite soft/hard magnetic core/shell nanowires.

PubMed

Londoño-Calderón, César Leandro; Moscoso-Londoño, Oscar; Muraca, Diego; Arzuza, Luis; Carvalho, Peterson; Pirota, Kleber Roberto; Knobel, Marcelo; Pampillo, Laura Gabriela; Martínez-García, Ricardo

2017-06-16

A straightforward method for the synthesis of CoFe 2.7 /CoFe 2 O 4 core/shell nanowires is described. The proposed method starts with a conventional pulsed electrodeposition procedure on alumina nanoporous template. The obtained CoFe 2.7 nanowires are released from the template and allowed to oxidize at room conditions over several weeks. The effects of partial oxidation on the structural and magnetic properties were studied by x-ray spectrometry, magnetometry, and scanning and transmission electron microscopy. The results indicate that the final nanowires are composed of 5 nm iron-cobalt alloy nanoparticles. Releasing the nanowires at room conditions promoted surface oxidation of the nanoparticles and created a CoFe 2 O 4 shell spinel-like structure. The shell avoids internal oxidation and promotes the formation of bi-magnetic soft/hard magnetic core/shell nanowires. The magnetic properties of both the initial single-phase CoFe 2.7 nanowires and the final core/shell nanowires, reveal that the changes in the properties from the array are due to the oxidation more than effects associated with released processes (disorder and agglomeration).

Large enhanced dielectric permittivity in polyaniline passivated core-shell nano magnetic iron oxide by plasma polymerization

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

Joy, Lija K.; Sooraj, V.; Sethulakshmi, N.

2014-03-24

Commercial samples of Magnetite with size ranging from 25–30 nm were coated with polyaniline by using radio frequency plasma polymerization to achieve a core shell structure of magnetic nanoparticle (core)–Polyaniline (shell). High resolution transmission electron microscopy images confirm the core shell architecture of polyaniline coated iron oxide. The dielectric properties of the material were studied before and after plasma treatment. The polymer coated magnetite particles exhibited a large dielectric permittivity with respect to uncoated samples. The dielectric behavior was modeled using a Maxwell–Wagner capacitor model. A plausible mechanism for the enhancement of dielectric permittivity is proposed.

Size distribution of magnetic iron oxide nanoparticles using Warren-Averbach XRD analysis

NASA Astrophysics Data System (ADS)

Mahadevan, S.; Behera, S. P.; Gnanaprakash, G.; Jayakumar, T.; Philip, J.; Rao, B. P. C.

2012-07-01

We use the Fourier transform based Warren-Averbach (WA) analysis to separate the contributions of X-ray diffraction (XRD) profile broadening due to crystallite size and microstrain for magnetic iron oxide nanoparticles. The profile shape of the column length distribution, obtained from WA analysis, is used to analyze the shape of the magnetic iron oxide nanoparticles. From the column length distribution, the crystallite size and its distribution are estimated for these nanoparticles which are compared with size distribution obtained from dynamic light scattering measurements. The crystallite size and size distribution of crystallites obtained from WA analysis are explained based on the experimental parameters employed in preparation of these magnetic iron oxide nanoparticles. The variation of volume weighted diameter (Dv, from WA analysis) with saturation magnetization (Ms) fits well to a core shell model wherein it is known that Ms=Mbulk(1-6g/Dv) with Mbulk as bulk magnetization of iron oxide and g as magnetic shell disorder thickness.

Chemical synthesis and characterization of hollow dopamine coated, pentagonal and flower shaped magnetic iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Riasat, Rabia; Kaynat, Sumbal

2018-04-01

Iron oxide nanoparticles have gained attention recently in the field of nanoscience and technology due to their unique physicochemical properties. We hereby chemically synthesized novel pentagonal flower shaped iron oxide nanoparticles by thermal decomposition of iron penta-carbonyl in a two way annealing process. Controlled oxidation by acid etching was performed for these nanoparticles. At first 13 nm core shell nanoparticles of iron oxide (Fe/Fe3O4) were synthesized at 120°C annealing temperature that act as template material. The core shell nanoparticles then converted into porous hollow core shell nanoparticles (PH Fe/ Fe3O4) in a two way annealing process of heating, first at 100°C then at 250°C and heating rate of 5°C was kept constant throughout the reaction time. X-Ray diffraction (XRD) was done for the phase confirmation of as synthesized nanoparticles. Transmission electron microscopy (TEM) and higher resolution transmission electron microscopy (HRTEM) clearly shows the flower like nanoparticles that are approx. 16 nm-18 nm in size having the 4-5 nm core of Fe and 1-2 nm of the pores in the shell while the cavity between the shell and core is about 2 nm and the shell is 4-5 nm in diameter according to the TEM micrographs. The as prepared nanoparticles were then surface functionalized by dopamine polymer to make them water dispersible. Fourier transform Infrared spectroscopy confirmed the dopamine coating on the nanoparticles and the magnetic saturation of 38 emu/g of nanoparticles was analyzed by vibrating sample magnetometer (VSM). Magnetic saturation persists in the dopamine coated nanoparticles. These nanoparticles were surface functionalized with dopamine and show dispersity in the aqueous media and can further be exploited in many nano-biotechnological applications including target specific therapeutic applications for several diseases.

Environmental and Biomedical Applications of Iron Oxide/Mesoporous Silica Core-Shell Nanocomposites

NASA Astrophysics Data System (ADS)

Egodawatte, Shani Nirasha

Mesoporous silica has shown great potential as an adsorbent for environmental contaminants and as a host for imaging and therapeutic agents. Mesoporous silica materials have a high surface area, tunable pore sizes and well defined surface properties which are governed by the surface hydroxyl groups. Surface modification of the mesoporous silica can tailor the adsorption properties for a specific metal ion or a small drug molecule by providing better sites for chelation or electrostatic interactions. Iron oxide / mesoporous silica core shell materials couple the favorable properties of both the iron oxide and mesoporous silica materials. The core-shell materials have higher adsorption properties compared to the parent material. With magnetic iron oxide nanoparticle cores, an additional magnetic property is introduced that can be used as magnetic recovery or separation. Heavy metals such as Chromium (Cr) and Arsenic (As) discharged from residential and environmental sources pose a serious threat to human health as well as groundwater pollution. In this thesis, iron oxide nanoparticles and nanofibers were coated with mesoporous silica and functionalized with (3-aminopropyl)triethoxysilane (APTES) using the post synthesis grafting method. The parent and the functionalized magnetic silica samples were characterized using powder X-ray diffraction (pXRD), thermal gravimetric analysis (TGA), Fourier Transform Infrared (FTIR) spectroscopy and nitrogen adsorption desorption isotherms for surface area and pore volumes. These materials were evaluated for Cr(III) and As(III)/As(V) adsorption from aqueous solutions in the optimum pH range for the specific metal. The aminopropyl functionalized magnetic mesoporous silica displayed the highest adsorption capacity for Cr(III) and Cu(II) of all the materials evaluated in this study. The high heavy metal adsorption capacity was attributed to a synergistic effect of iron oxide nanoparticles and amine functionalization on mesoporous silica as well as a judicious choice of pH. Modified magnetic mesoporous silica material was also found to have high adsorption capacity for high and low pH aqueous solutions of Uranium (VI). Tuning the loading and release of a small drug molecule (5-FU) onto these iron oxide/ mesoporous silica core-shell materials was also investigated. The polarity of the solvent used to load 5-FU onto the host had an impact not only on the loading but also on the release percentage of 5-FU. The synthesis of a novel core-shell material with a hematite nanofiber core and a SBA type mesoporous silica shell was also explored.

Magnetically tunable liquid dielectric with giant dielectric permittivity based on core-shell superparamagnetic iron oxide.

PubMed

Vinayasree, S; Nitha, T S; Tiwary, C S; Ajayan, P M; Joy, P A; Anantharaman, M R

2018-06-29

A liquid dielectric based on a core-shell architecture having a superparamagnetic iron oxide core and a shell of silicon dioxide was synthesized. The frequency dependence of dielectric properties was evaluated for different concentrations of iron oxide. The dependence of magnetic field on the dielectric properties was also studied. Aqueous ferrofluid exhibited a giant dielectric constant of 6.4 × 10 5 at 0.1 MHz at a concentration of 0.2 vol% and the loss tangent was 3. The large rise in dielectric constant at room temperature is modelled and explained using percolation theory and Maxwell-Wagner-Sillars type polarization. The ferrofluid is presumed to consist of nanocapacitor networks which are wired in series along the lateral direction and parallel along longitudinal direction. On the application of an external magnetic field, the chain formation and its alignment results in the variation of dielectric permittivity.

Zero-valent iron treatment of dark brown colored coffee effluent: Contributions of a core-shell structure to pollutant removals.

PubMed

Tomizawa, Mayuka; Kurosu, Shunji; Kobayashi, Maki; Kawase, Yoshinori

2016-12-01

The decolorization and total organic carbon (TOC) removal of dark brown colored coffee effluent by zero-valent iron (ZVI) have been systematically examined with solution pH of 3.0, 4.0, 6.0 and 8.0 under oxic and anoxic conditions. The optimal decolorization and TOC removal were obtained at pH 8.0 with oxic condition. The maximum efficiencies of decolorization and TOC removal were 92.6 and 60.2%, respectively. ZVI presented potential properties for pollutant removal at nearly neutral pH because of its core-shell structure in which shell or iron oxide/hydroxide layer on ZVI surface dominated the decolorization and TOC removal of coffee effluent. To elucidate the contribution of the core-shell structure to removals of color and TOC at the optimal condition, the characterization of ZVI surface by scanning electron microscopy (SEM) with an energy dispersive X-ray spectroscope (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) was conducted. It was confirmed that the core-shell structure was formed and the shell on ZVI particulate surface and the precipitates formed during the course of ZVI treatment consisted of iron oxides and hydroxides. They were significantly responsible for decolorization and TOC removal of coffee effluent via adsorption to shell on ZVI surface and inclusion into the precipitates rather than the oxidative degradation by OH radicals and the reduction by emitted electrons. The presence of dissolved oxygen (DO) enhanced the formation of the core-shell structure and as a result improved the efficiency of ZVI treatment for the removal of colored components in coffee effluents. ZVI was found to be an efficient material toward the treatment of coffee effluents. Copyright © 2016 Elsevier Ltd. All rights reserved.

High-temperature investigation on morphology, phase and size of iron/iron-oxide core–shell nanoclusters for radiation nanodetector

NASA Astrophysics Data System (ADS)

Khanal, Lokendra Raj; Williams, Thomas; Qiang, You

2018-06-01

Iron/iron-oxide (Fe–Fe3O4) core–shell nanoclusters (NCs) synthesized by a cluster deposition technique were subjected to a study of their high temperature structural and morphological behavior. Annealing effects have been investigated up to 800 °C in vacuum, oxygen and argon environments. The ~18 nm average size of the as-prepared NCs increases slowly in temperatures up to 500 °C in all three environments. The size increases abruptly in the argon environment but slowly in vacuum and oxygen when annealed at 800 °C. The x-ray diffraction (XRD) studies have shown that the iron core remains in the core–shell NCs only when they were annealed in the vacuum. A dramatic change in the surface morphology, an island like structure and/or a network like pattern, was observed at the elevated temperature. The as-prepared and annealed samples were analyzed using XRD, scanning electron microscopy and imageJ software for a close inspection of the temperature aroused properties. This work presents the temperature induced size growth mechanism, oxidation kinetics and phase transformation of the NCs accompanied by cluster aggregation, particle coalescence, and diffusion.

The effect of carboxylic acids on the oxidation of coated iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Lengyel, Attila; Tolnai, Gyula; Klencsár, Zoltán; Garg, Vijayendra Kumar; de Oliveira, Aderbal Carlos; Herojit Singh, L.; Homonnay, Zoltán; Szalay, Roland; Németh, Péter; Szabolcs, Bálint; Ristic, Mira; Music, Svetozar; Kuzmann, Ernő

2018-05-01

57Fe Mössbauer spectroscopy, XRD, and TEM were used to investigate the effect of mandelic- and salicylic acid coatings on the iron oxide nanoparticles. These two carboxylic acids have similar molecules size and stoichiometry, but different structure and acidity. Significant differences were observed between the Mössbauer spectra of samples coated with mandelic acid and salicylic acid. These results indicate that the occurrence of iron microenvironments in the mandelic- and salicylic acid-coated iron oxide nanoparticles is different. The results can be interpreted in terms of the influence of the acidity of carboxylic acids on the formation, core/shell structure, and oxidation of coated iron oxide nanocomposites.

Magnetically Recoverable Pd/Fe 3O 4 Core-Shell Nanowire Clusters with Increased Hydrogenation Activity

DOE PAGES

Watt, John; Kotula, Paul G.; Huber, Dale L.

2017-02-06

Core-shell nanostructures are promising candidates for the next generation of catalysts due to synergistic effects which can arise from having two active species in close contact, leading to increased activity. Likewise, catalysts displaying added functionality, such as a magnetic response, can increase their scientific and industrial potential. Here, we synthesize Pd/Fe 3O 4 core-shell nanowire clusters and apply them as hydrogenation catalysts for an industrially important hydrogenation reaction; the conversion of acetophenone to 1-phenylethanol. During synthesis, the palladium nanowires self-assemble into clusters which act as a high surface area framework for the growth of a magnetic iron oxide shell. Wemore » demonstrate excellent catalytic activity due to the presence of palladium while the strong magnetic properties provided by the iron oxide shell enable facile catalyst recovery.« less

Calcium hydroxide coating on highly reactive nanoscale zero-valent iron for in situ remediation application.

PubMed

Wei, Cai-Jie; Xie, Yue-Feng; Wang, Xiao-Mao; Li, Xiao-Yan

2018-05-23

Nano scale zero-valent iron (nZVI), a promising engineering technology for in situ remediation, has been greatly limited by quick self-corrosion and low mobility in porous media. Highly reactive nZVI particles produced from the borohydride reduction method were enclosed in a releasable Ca(OH) 2 layer by the chemical deposition method. The amount of Ca(OH) 2 coated on nZVI surface were well controlled by the precursor dosage. At moderate Ca(OH) 2 dosage (R Ca/TFe  = 0.25) condition, the increment of Fe 0 content for the obtained nZVI/Ca-0.25 sample was observed. The interfacial reactions between the iron oxide shell and the Ca(OH) 2 saturated environment were delicately elucidated by the X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) spectrum. And the coverage of Ca(OH) 2 shell on spherical nZVI surface was found more complete and uniform for the nZVI/Ca sample obtained from the moderate precursor dosage condition (R Ca/TFe  = 0.25). The Ca(OH) 2 shell before dissolution was demonstrated owning the anti-corrosion capability to slow down the oxidation of Fe 0 core in air, during ethanol storage and in aqueous environment. The mechanism of anti-corrosion capability for nZVI/Ca-0.25 particle was interestingly found to be attributed to the Ca(OH) 2 shell isolation and also be potentially due to the iron oxide shell phase transformation mediated by the outer Ca(OH) 2 shell. An improved trichloroethylene reduction performance was observed for nZVI/Ca-0.25 than bare nZVI. The mobility of nZVI/Ca particles in water-saturated porous media was moderately improved before shell dissolution. Copyright © 2018 Elsevier Ltd. All rights reserved.

Controllable synthesis, magnetic properties, and enhanced photocatalytic activity of spindlelike mesoporous α-Fe(2)O(3)/ZnO core-shell heterostructures.

PubMed

Wu, Wei; Zhang, Shaofeng; Xiao, Xiangheng; Zhou, Juan; Ren, Feng; Sun, Lingling; Jiang, Changzhong

2012-07-25

Mesoporous spindlelike iron oxide/ZnO core-shell heterostructures are successfully fabricated by a low-cost, surfactant-free, and environmentally friendly seed-mediate strategy with the help of postannealing treatment. The material composition and stoichiometry, as well as these magnetic and optical properties, have been examined and verified by means of high-resolution transmission electron microscopy and X-ray diffraction, the thickness of ZnO layer can be simply tailored by the concentration of zinc precursor. Considering that both α-Fe2O3 and ZnO are good photocatalytic materials, we have investigated the photodegradation performances of the core-shell heterostructures using organic dyes Rhodamin B (RhB). It is interesting to find that the as-obtained iron oxides/ZnO core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to the as-used α-Fe2O3 seeds and commercial TiO2 products (P25), mainly owing to the synergistic effect between the narrow and wide bandgap semiconductors and effective electron-hole separation at the interfaces of iron oxides/ZnO.

Engineered core-shell magnetic nanoparticle for MR dual-modal tracking and safe magnetic manipulation of ependymal cells in live rodents

NASA Astrophysics Data System (ADS)

Peng, Yung-Kang; Lui, Cathy N. P.; Chen, Yu-Wei; Chou, Shang-Wei; Chou, Pi-Tai; Yung, Ken K. L.; Edman Tsang, S. C.

2018-01-01

Tagging recognition group(s) on superparamagnetic iron oxide is known to aid localisation (imaging), stimulation and separation of biological entities using magnetic resonance imaging (MRI) and magnetic agitation/separation (MAS) techniques. Despite the wide applicability of iron oxide nanoparticles in T 2-weighted MRI and MAS, the quality of the images and safe manipulation of the exceptionally delicate neural cells in a live brain are currently the key challenges. Here, we demonstrate the engineered manganese oxide clusters-iron oxide core-shell nanoparticle as an MR dual-modal contrast agent for neural stem cells (NSCs) imaging and magnetic manipulation in live rodents. As a result, using this engineered nanoparticle and associated technologies, identification, stimulation and transportation of labelled potentially multipotent NSCs from a specific location of a live brain to another by magnetic means for self-healing therapy can therefore be made possible.

Structural characterization of encapsulated ferritin provides insight into iron storage in bacterial nanocompartments

PubMed Central

He, Didi; Hughes, Sam; Vanden-Hehir, Sally; Georgiev, Atanas; Altenbach, Kirsten; Tarrant, Emma; Mackay, C Logan; Waldron, Kevin J; Clarke, David J; Marles-Wright, Jon

2016-01-01

Ferritins are ubiquitous proteins that oxidise and store iron within a protein shell to protect cells from oxidative damage. We have characterized the structure and function of a new member of the ferritin superfamily that is sequestered within an encapsulin capsid. We show that this encapsulated ferritin (EncFtn) has two main alpha helices, which assemble in a metal dependent manner to form a ferroxidase center at a dimer interface. EncFtn adopts an open decameric structure that is topologically distinct from other ferritins. While EncFtn acts as a ferroxidase, it cannot mineralize iron. Conversely, the encapsulin shell associates with iron, but is not enzymatically active, and we demonstrate that EncFtn must be housed within the encapsulin for iron storage. This encapsulin nanocompartment is widely distributed in bacteria and archaea and represents a distinct class of iron storage system, where the oxidation and mineralization of iron are distributed between two proteins. DOI: http://dx.doi.org/10.7554/eLife.18972.001 PMID:27529188

Fabrication of iron (III) oxide doped polystyrene shells

NASA Astrophysics Data System (ADS)

Cai, Pei-Jun; Tang, Yong-Jian; Zhang, Lin; Du, Kai; Feng, Chang-Gen

2004-03-01

A type of iron (III) oxide doped plastic shell used for inertial confinement fusion experiments has been fabricated by emulsion techniques. Three different phases of solution (W1, O, and W2) are used for the fabrication process. The W1 phase is a 1 wt % of sodium lauryl sulfate in water. This W1 phase solution is mixed with a 3 wt % Fe2O3-polystyrene (PS) solution in benzene-dichloroethane (O phase) while stirring. The resulting emulsion (W1/O) is poured into a 3 wt % aqueous polyvinyl alcohol solution (W2 phase) while stirring. The resulting emulsion (W1/O/W2) is then heated to evaporate benzene and dichloroethane, and thus a solid Fe2O3-PS shell is formed. The diameter and wall thickness of the shells range from 150 to 500 μm and 5 to 15 μm, respectively. The average surface roughness of the shells is 40 nm, similar to that of the usual PS shells. .

Shape-Controlled Synthesis of Magnetic Iron Oxide@SiO₂-Au@C Particles with Core-Shell Nanostructures.

PubMed

Li, Mo; Li, Xiangcun; Qi, Xinhong; Luo, Fan; He, Gaohong

2015-05-12

The preparation of nonspherical magnetic core-shell nanostructures with uniform sizes still remains a challenge. In this study, magnetic iron oxide@SiO2-Au@C particles with different shapes, such as pseduocube, ellipsoid, and peanut, were synthesized using hematite as templates and precursors of magnetic iron oxide. The as-obtained magnetic particles demonstrated uniform sizes, shapes, and well-designed core-shell nanostructures. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) analysis showed that the Au nanoparticles (AuNPs) of ∼6 nm were uniformly distributed between the silica and carbon layers. The embedding of the metal nanocrystals into the two different layers prevented the aggregation and reduced the loss of the metal nanocrystals during recycling. Catalytic performance of the peanut-like particles kept almost unchanged without a noticeable decrease in the reduction of 4-nitrophenol (4-NP) in 8 min even after 7 cycles, indicating excellent reusability of the particles. Moreover, the catalyst could be readily recycled magnetically after each reduction by an external magnetic field.

Iron oxide shell coating on nano silicon prepared from the sand for lithium-ion battery application

NASA Astrophysics Data System (ADS)

Furquan, Mohammad; Vijayalakshmi, S.; Mitra, Sagar

2018-05-01

Elemental silicon, due to its high specific capacity (4200 mAh g-1) and non-toxicity is expected to be an attractive anode material for Li-ion battery. But its huge expansion volume (> 300 %) during charging of battery, leads to pulverization and cracking in the silicon particles and causes sudden failure of the Li-ion battery. In this work, we have designed yolk-shell type morphology of silicon, prepared from carbon coated silicon nanoparticles soaked in aqueous solution of ferric nitrate and potassium hydroxide. The soaked silicon particles were dried and finally calcined at 800 °C for 30 minutes. The product obtained is deprived of carbon and has a kind of yolk-shell morphology of nano silicon with iron oxide coating (Si@Iron oxide). This material has been tested for half-cell lithium-ion battery configuration. The discharge capacity is found to be ≈ 600 mAh g-1 at a current rate of 1.0 A g-1 for 200 cycles. It has shown a stable performance as anode for Li-ion battery application.

Boron-based nanostructures: Synthesis, functionalization, and characterization

NASA Astrophysics Data System (ADS)

Bedasso, Eyrusalam Kifyalew

Boron-based nanostructures have not been explored in detail; however, these structures have the potential to revolutionize many fields including electronics and biomedicine. The research discussed in this dissertation focuses on synthesis, functionalization, and characterization of boron-based zero-dimensional nanostructures (core/shell and nanoparticles) and one-dimensional nanostructures (nanorods). The first project investigates the synthesis and functionalization of boron-based core/shell nanoparticles. Two boron-containing core/shell nanoparticles, namely boron/iron oxide and boron/silica, were synthesized. Initially, boron nanoparticles with a diameter between 10-100 nm were prepared by decomposition of nido-decaborane (B10H14) followed by formation of a core/shell structure. The core/shell structures were prepared using the appropriate precursor, iron source and silica source, for the shell in the presence of boron nanoparticles. The formation of core/shell nanostructures was confirmed using high resolution TEM. Then, the core/shell nanoparticles underwent a surface modification. Boron/iron oxide core/shell nanoparticles were functionalized with oleic acid, citric acid, amine-terminated polyethylene glycol, folic acid, and dopamine, and boron/silica core/shell nanoparticles were modified with 3-(amino propyl) triethoxy silane, 3-(2-aminoethyleamino)propyltrimethoxysilane), citric acid, folic acid, amine-terminated polyethylene glycol, and O-(2-Carboxyethyl)polyethylene glycol. A UV-Vis and ATR-FTIR analysis established the success of surface modification. The cytotoxicity of water-soluble core/shell nanoparticles was studied in triple negative breast cancer cell line MDA-MB-231 and the result showed the compounds are not toxic. The second project highlights optimization of reaction conditions for the synthesis of boron nanorods. This synthesis, done via reduction of boron oxide with molten lithium, was studied to produce boron nanorods without any contamination and with a uniform size distribution. Various reaction parameters such as temperature, reaction time, and sonication were altered to find the optimal reaction conditions. Once these conditions were determined, boron nanorods were produced then functionalized with amine-terminated polyethylene glycol.

A Bottle-around-a-Ship Method To Generate Hollow Thin-Shelled Particles Containing Encapsulated Iron Species with Application to the Environmental Decontamination of Chlorinated Compounds.

PubMed

Su, Yang; Wang, Yingqing; Owoseni, Olasehinde; Zhang, Yueheng; Gamliel, David Pierce; Valla, Julia A; McPherson, Gary L; John, Vijay T

2018-04-25

Thin-shelled hollow silica particles are synthesized using an aerosol-based process where the concentration of a silica precursor tetraethyl orthosilicate (TEOS) determines the shell thickness. The synthesis involves a novel concept of the salt bridging of an iron salt, FeCl 3 , to a cationic surfactant, cetyltrimethylammonium bromide (CTAB), which modulates the templating effect of the surfactant on silica porosity. The salt bridging leads to a sequestration of the surfactant in the interior of the droplet with the formation of a dense silica shell around the organic material. Subsequent calcination consistently results in hollow particles with encapsulated iron oxides. Control of the TEOS levels leads to the generation of ultrathin-shelled (∼10 nm) particles which become susceptible to rupture upon exposure to ultrasound. The dense silica shell that is formed is impervious to entry of chemical species. Mesoporosity is restored to the shell through desilication and reassembly, again using CTAB as a template. The mesoporous-shelled hollow particles show good reactivity toward the reductive dichlorination of trichloroethylene (TCE), indicating access of TCE to the particle interior. The ordered mesoporous thin-shelled particles containing active iron species are viable systems for chemical reaction and catalysis.

Iron Oxide Nanoparticles: Tunable Size Synthesis and Analysis in Terms of the Core-Shell Structure and Mixed Coercive Model

NASA Astrophysics Data System (ADS)

Phong, P. T.; Oanh, V. T. K.; Lam, T. D.; Phuc, N. X.; Tung, L. D.; Thanh, Nguyen T. K.; Manh, D. H.

2017-04-01

Iron oxide nanoparticles (NPs) are currently a very active research field. To date, a comprehensive study of iron oxide NPs is still lacking not only on the size dependence of structural phases but also in the use of an appropriate model. Herein, we report on a systematic study of the structural and magnetic properties of iron oxide NPs prepared by a co-precipitation method followed by hydrothermal treatment. X-ray diffraction and transmission electron microscopy reveal that the NPs have an inverse spinel structure of iron oxide phase (Fe3O4) with average crystallite sizes ( D XRD) of 6-19 nm, while grain sizes ( D TEM) are of 7-23 nm. In addition, the larger the particle size, the closer the experimental lattice constant value is to that of the magnetite structure. Magnetic field-dependent magnetization data and analysis show that the effective anisotropy constants of the Fe3O4 NPs are about five times larger than that of their bulk counterpart. Particle size ( D) dependence of the magnetization and the non-saturating behavior observed in applied fields up to 50 kOe are discussed using the core-shell structure model. We find that with decreasing D, while the calculated thickness of the shell of disordered spins ( t ˜ 0.3 nm) remains almost unchanged, the specific surface areas S a increases significantly, thus reducing the magnetization of the NPs. We also probe the coercivity of the NPs by using the mixed coercive Kneller and Luborsky model. The calculated results indicate that the coercivity rises monotonously with the particle size, and are well matched with the experimental ones.

Activation of Persulfate by Nanosized Zero-Valent Iron (NZVI): Mechanisms and Transformation Products of NZVI.

PubMed

Kim, Cheolyong; Ahn, Jun-Young; Kim, Tae Yoo; Shin, Won Sik; Hwang, Inseong

2018-03-20

The mechanisms involved in the activation of persulfate by nanosized zero-valent iron (NZVI) were elucidated and the NZVI transformation products identified. Two distinct reaction stages, in terms of the kinetics and radical formation mechanism, were found when phenol was oxidized by the persulfate/NZVI system. In the initial stage, lasting 10 min, Fe 0 (s) was consumed rapidly and sulfate radicals were produced through activation by aqueous Fe 2+ . The second stage was governed by Fe catalyzed activation in the presence of aqueous Fe 3+ and iron (oxyhydr)oxides in the NZVI shells. The second stage was 3 orders of magnitude slower than the initial stage. An electron balance showed that the sulfate radical yield per mole of persulfate was more than two times higher in the persulfate/NZVI system than in the persulfate/Fe 2+ system. Radicals were believed to be produced more efficiently in the persulfate/NZVI system because aqueous Fe 2+ was supplied slowly, preventing sulfate radicals being scavenged by excess aqueous Fe 2+ . In the second stage, the multilayered shell conducted electrons, and magnetite in the shell provided electrons for the activation of persulfate. Iron speciation analysis (including X-ray absorption spectroscopy) results indicated that a shrinking core/growing shell model explained NZVI transformation during the persulfate/NZVI process.

In vivo magnetic resonance and fluorescence dual imaging of tumor sites by using dye-doped silica-coated iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Jang, Haeyun; Lee, Chaedong; Nam, Gi-Eun; Quan, Bo; Choi, Hyuck Jae; Yoo, Jung Sun; Piao, Yuanzhe

2016-02-01

The difficulty in delineating tumor is a major obstacle for better outcomes in cancer treatment of patients. The use of single-imaging modality is often limited by inadequate sensitivity and resolution. Here, we present the synthesis and the use of monodisperse iron oxide nanoparticles coated with fluorescent silica nano-shells for fluorescence and magnetic resonance dual imaging of tumor. The as-synthesized core-shell nanoparticles were designed to improve the accuracy of diagnosis via simultaneous tumor imaging with dual imaging modalities by a single injection of contrast agent. The iron oxide nanocrystals ( 11 nm) were coated with Rhodamine B isothiocyanate-doped silica shells via reverse microemulsion method. Then, the core-shell nanoparticles ( 54 nm) were analyzed to confirm their size distribution by transmission electron microscopy and dynamic laser scattering. Photoluminescence spectroscopy was used to characterize the fluorescent property of the dye-doped silica shell-coated nanoparticles. The cellular compatibility of the as-prepared nanoparticles was confirmed by a trypan blue dye exclusion assay and the potential as a dual-imaging contrast agent was verified by in vivo fluorescence and magnetic resonance imaging. The experimental results show that the uniform-sized core-shell nanoparticles are highly water dispersible and the cellular toxicity of the nanoparticles is negligible. In vivo fluorescence imaging demonstrates the capability of the developed nanoparticles to selectively target tumors by the enhanced permeability and retention effects and ex vivo tissue analysis was corroborated this. Through in vitro phantom test, the core/shell nanoparticles showed a T2 relaxation time comparable to Feridex® with smaller size, indicating that the as-made nanoparticles are suitable for imaging tumor. This new dual-modality-nanoparticle approach has promised for enabling more accurate tumor imaging.

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

Kaur, Maninder; Dai, Qilin; Bowden, Mark E.

Chromium (Cr) forms a solid solution with iron (Fe) lattice when doped in core-shell iron -iron oxide nanocluster (NC) and shows a mixed phase of sigma (σ) FeCr and bcc Fe. The Cr dopant affects heavily the magnetization and magnetic reversal process, and causes the hysteresis loop to shrink near the zero field axis. Dramatic transformation happens from dipolar interaction (0 at. % Cr) to strong exchange interaction (8 at. % of Cr) is confirmed from the Henkel plot and delta M plot, and is explained by a water-melon model of core-shell NC system.

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

Kaur, Maninder; McCloy, John S.; Kukkadapu, Ravi

Two sizes of iron/iron-oxide (Fe/Fe-oxide) nanoclusters (NCs) of 10 nm and 35 nm diameters were prepared using a cluster deposition technique. Both these NCs displayed XRD peaks due to body-centered cubic (bcc) Fe0 and magnetite-like phase. Mossbauer spectroscopy (MS) measurements: a) confirmed the core-shell nature of the NCs, b) the Fe-oxide shell to be nanocrystalline and partially oxidized, and c) the Fe-oxide spins are significantly canted. In addition to the bcc Fe and magnetite-like phases, a phase similar to tetragonal σ-Fe-Cr (8% Cr) was CLEARLY evident in the larger NC, based on X-ray diffraction. Origin of the tetragonallike phase inmore » the larger NC was not clear but could be due to significant distortion of the Fe0 core lattice planes; subtle peaks due to this phase were also apparent in the smaller NC. Unambiguous evidence for the presence of such a phase, however, was not clear from MS, X-ray photoelectron spectroscopy, vibrating sample magnetometry, X-ray magnetic circular dichroism, nor transmission electron microscopy. To our knowledge, this is the first report of tetragonallike phase in the Fe/Fe-oxide core-shell systems.« less

Human nitric oxide biomarker as potential NO donor in conjunction with superparamagnetic iron oxide @ gold core shell nanoparticles for cancer therapeutics.

PubMed

Singh, Nimisha; Patel, Khushbu; Sahoo, Suban K; Kumar, Rajender

2018-03-01

Nitric oxide releasing superparamagnetic (Fe 3 O 4 -Au@NTHP) nanoparticles were synthesized by conjugation of human biomarker of nitric oxide, N-nitrosothioproline with iron oxide-gold (Fe 3 O 4 -Au) core shell nanoparticles. The structure and morphology of the prepared nanoparticles were confirmed by ATR-FTIR, HR-TEM, EDAX, XPS, DLS and VSM measurements. N-nitrosothioproline is a natural molecule and nontoxic to humans. Thus, the core shell nanoparticles prepared were highly biocompatible. The prepared Fe 3 O 4 -Au@NTHP nanoparticles also provided an excellent release of nitric oxide in dark and upon light irradiation for cancer treatment. The amount of NO release was controllable with the wavelength of light and time of irradiation. The developed nanoparticles provided efficient cellular uptake and good cytotoxicity in picomolar range when tested on HeLa cancerous cells. These nanoparticles on account of their controllable NO release can also be used to release small amount of NO for killing cancerous cells without any toxic effect. Furthermore, the magnetic and photochemical properties of these nanoparticles provides dual platform for magneto therapy and phototherapy for cancer treatment. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural and Magnetic Response in Bimetallic Core/Shell Magnetic Nanoparticles

PubMed Central

Nairan, Adeela; Khan, Usman; Iqbal, Munawar; Khan, Maaz; Javed, Khalid; Riaz, Saira; Naseem, Shahzad; Han, Xiufeng

2016-01-01

Bimagnetic monodisperse CoFe2O4/Fe3O4 core/shell nanoparticles have been prepared by solution evaporation route. To demonstrate preferential coating of iron oxide onto the surface of ferrite nanoparticles X-ray diffraction (XRD), High resolution transmission electron microscope (HR-TEM) and Raman spectroscopy have been performed. XRD analysis using Rietveld refinement technique confirms single phase nanoparticles with average seed size of about 18 nm and thickness of shell is 3 nm, which corroborates with transmission electron microscopy (TEM) analysis. Low temperature magnetic hysteresis loops showed interesting behavior. We have observed large coercivity 15.8 kOe at T = 5 K, whereas maximum saturation magnetization (125 emu/g) is attained at T = 100 K for CoFe2O4/Fe3O4 core/shell nanoparticles. Saturation magnetization decreases due to structural distortions at the surface of shell below 100 K. Zero field cooled (ZFC) and Field cooled (FC) plots show that synthesized nanoparticles are ferromagnetic till room temperature and it has been noticed that core/shell sample possess high blocking temperature than Cobalt Ferrite. Results indicate that presence of iron oxide shell significantly increases magnetic parameters as compared to the simple cobalt ferrite. PMID:28335200

Bioconjugated iron oxide nanocubes: synthesis, functionalization, and vectorization.

PubMed

Wortmann, Laura; Ilyas, Shaista; Niznansky, Daniel; Valldor, Martin; Arroub, Karim; Berger, Nadja; Rahme, Kamil; Holmes, Justin; Mathur, Sanjay

2014-10-08

A facile bottom-up approach for the synthesis of inorganic/organic bioconjugated nanoprobes based on iron oxide nanocubes as the core with a nanometric silica shell is demonstrated. Surface coating and functionalization protocols developed in this work offered good control over the shell thickness (8-40 nm) and enabled biovectorization of SiO2@Fe3O4 core-shell structures by covalent attachment of folic acid (FA) as a targeting unit for cellular uptake. The successful immobilization of folic acid was investigated both quantitatively (TGA, EA, XPS) and qualitatively (AT-IR, UV-vis, ζ-potential). Additionally, the magnetic behavior of the nanocomposites was monitored after each functionalization step. Cell viability studies confirmed low cytotoxicity of FA@SiO2@Fe3O4 conjugates, which makes them promising nanoprobes for targeted internalization by cells and their imaging.

Multifunctional superparamagnetic nanoparticles for enhanced drug transport in cystic fibrosis

NASA Astrophysics Data System (ADS)

Armijo, Leisha M.; Brandt, Yekaterina I.; Rivera, Antonio C.; Cook, Nathaniel C.; Plumley, John B.; Withers, Nathan J.; Kopciuch, Michael; Smolyakov, Gennady A.; Huber, Dale L.; Smyth, Hugh D.; Osinski, Marek

2012-10-01

Iron oxide colloidal nanoparticles (ferrofluids) are investigated for application in the treatment of cystic fibrosis lung infections, the leading cause of mortality in cystic fibrosis patients. We investigate the use of iron oxide nanoparticles to increase the effectiveness of administering antibiotics through aerosol inhalation using two mechanisms: directed particle movement in the presence of an inhomogeneous static external magnetic field and magnetic hyperthermia. Magnetic hyperthermia is an effective method for decreasing the viscosity of the mucus and biofilm, thereby enhancing drug, immune cell, and antibody penetration to the affected area. Iron oxide nanoparticles of various sizes and morphologies were synthesized and tested for specific losses (heating power). Nanoparticles in the superparamagnetic to ferromagnetic size range exhibited excellent heating power. Additionally, iron oxide / zinc selenide core/shell nanoparticles were prepared, in order to enable imaging of the iron oxide nanoparticles. We also report on synthesis and characterization of MnSe/ZnSeS alloyed quantum dots.

One-pot synthesis of water soluble iron nanoparticles using rationally-designed peptides and ligand release.

PubMed

Papst, Stefanie; Cheong, Soshan; Banholzer, Moritz J; Brimble, Margaret A; Williams, David E; Tilley, Richard D

2013-05-18

Herein we report the rational design of new phosphopeptides for control of nucleation, growth and aggregation of water-soluble, superparamagnetic iron-iron oxide core-shell nanoparticles. The use of the designed peptides enables a one-pot synthesis that avoids utilizing unstable or toxic iron precursors, organic solvents, and the need for exchange of capping agent after synthesis of the NPs.

Magnetic/NIR-thermally responsive hybrid nanogels for optical temperature sensing, tumor cell imaging and triggered drug release

NASA Astrophysics Data System (ADS)

Wang, Hui; Yi, Jinhui; Mukherjee, Sumit; Banerjee, Probal; Zhou, Shuiqin

2014-10-01

The paper demonstrates a class of multifunctional core-shell hybrid nanogels with fluorescent and magnetic properties, which have been successfully developed for simultaneous optical temperature sensing, tumor cell imaging and magnetic/NIR-thermally responsive drug carriers. The as-synthesized hybrid nanogels were designed by coating bifunctional nanoparticles (BFNPs, fluorescent carbon dots embedded in the porous carbon shell and superparamagnetic iron oxide nanocrystals clustered in the core) with a thermo-responsive poly(N-isopropylacrylamide-co-acrylamide) [poly(NIPAM-AAm)]-based hydrogel as the shell. The BFNPs in hybrid nanogels not only demonstrate excellent photoluminescence (PL) and photostability due to the fluorescent carbon dots embedded in the porous carbon shell, but also has targeted drug accumulation potential and a magnetic-thermal conversion ability due to the superparamagnetic iron oxide nanocrystals clustered in the core. The thermo-responsive poly(NIPAM-AAm)-based gel shell can not only modify the physicochemical environment of the BFNPs core to manipulate the fluorescence intensity for sensing the variation of the environmental temperature, but also regulate the release rate of the loaded anticancer drug (curcumin) by varying the local temperature of environmental media. In addition, the carbon layer of BFNPs can adsorb and convert the NIR light to heat, leading to a promoted drug release under NIR irradiation and improving the therapeutic efficacy of drug-loaded hybrid nanogels. Furthermore, the superparamagnetic iron oxide nanocrystals in the core of BFNPs can trigger localized heating using an alternating magnetic field, leading to a phase change in the polymer gel to trigger the release of loaded drugs. Finally, the multifunctional hybrid nanogels can overcome cellular barriers to enter the intracellular region and light up the mouse melanoma B16F10 cells. The demonstrated hybrid nanogels would be an ideal system for the biomedical applications due to their excellent optical properties, magnetic properties, high drug loading capacity and responsive drug release behavior.The paper demonstrates a class of multifunctional core-shell hybrid nanogels with fluorescent and magnetic properties, which have been successfully developed for simultaneous optical temperature sensing, tumor cell imaging and magnetic/NIR-thermally responsive drug carriers. The as-synthesized hybrid nanogels were designed by coating bifunctional nanoparticles (BFNPs, fluorescent carbon dots embedded in the porous carbon shell and superparamagnetic iron oxide nanocrystals clustered in the core) with a thermo-responsive poly(N-isopropylacrylamide-co-acrylamide) [poly(NIPAM-AAm)]-based hydrogel as the shell. The BFNPs in hybrid nanogels not only demonstrate excellent photoluminescence (PL) and photostability due to the fluorescent carbon dots embedded in the porous carbon shell, but also has targeted drug accumulation potential and a magnetic-thermal conversion ability due to the superparamagnetic iron oxide nanocrystals clustered in the core. The thermo-responsive poly(NIPAM-AAm)-based gel shell can not only modify the physicochemical environment of the BFNPs core to manipulate the fluorescence intensity for sensing the variation of the environmental temperature, but also regulate the release rate of the loaded anticancer drug (curcumin) by varying the local temperature of environmental media. In addition, the carbon layer of BFNPs can adsorb and convert the NIR light to heat, leading to a promoted drug release under NIR irradiation and improving the therapeutic efficacy of drug-loaded hybrid nanogels. Furthermore, the superparamagnetic iron oxide nanocrystals in the core of BFNPs can trigger localized heating using an alternating magnetic field, leading to a phase change in the polymer gel to trigger the release of loaded drugs. Finally, the multifunctional hybrid nanogels can overcome cellular barriers to enter the intracellular region and light up the mouse melanoma B16F10 cells. The demonstrated hybrid nanogels would be an ideal system for the biomedical applications due to their excellent optical properties, magnetic properties, high drug loading capacity and responsive drug release behavior. Electronic supplementary information (ESI) available: Fig. S1-S12. See DOI: 10.1039/c4nr03748k

Characterization of tetraethylene glycol passivated iron nanoparticles

NASA Astrophysics Data System (ADS)

Nunes, Eloiza da Silva; Viali, Wesley Renato; da Silva, Sebastião William; Coaquira, José Antonio Huamaní; Garg, Vijayendra Kumar; de Oliveira, Aderbal Carlos; Morais, Paulo César; Jafelicci Júnior, Miguel

2014-10-01

The present study describes the synthesis and characterization of iron@iron oxide nanoparticles produced by passivation of metallic iron in tetraethylene glycol media. Structural and chemical characterizations were performed using transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mössbauer spectroscopy. Pomegranate-like core@shell nanoparticulate material in the size range of 90-120 nm was obtained. According to quantitative phase analysis using Rietveld structure refinement the synthesized iron oxide was identified as magnetite (Fe3O4) whereas the iron to magnetite mass fractions was found to be 47:53. These findings are in good agreement with the data obtained from Mössbauer and thermal gravimetric analysis (TGA). The XPS data revealed the presence of a surface organic layer with higher hydrocarbon content, possibly due to the tetraethylene glycol thermal degradation correlated with iron oxidation. The room-temperature (300 K) saturation magnetization measured for the as-synthesized iron and for the iron-iron oxide were 145 emu g-1 and 131 emu g-1, respectively. The measured saturation magnetizations are in good agreement with data obtained from TEM, XRD and Mössbauer spectroscopy.

Structural determination of Bi-doped magnetite multifunctional nanoparticles for contrast imaging.

PubMed

Laguna-Marco, M A; Piquer, C; Roca, A G; Boada, R; Andrés-Vergés, M; Veintemillas-Verdaguer, S; Serna, C J; Iadecola, A; Chaboy, J

2014-09-14

To determine with precision how Bi atoms are distributed in Bi-doped iron oxide nanoparticles their structural characterization has been carried out by X-ray absorption spectroscopy (XAS) recorded at the K edge of Fe and at the L3 edge of Bi. The inorganic nanoparticles are nominally hybrid structures integrating an iron oxide core and a bismuth oxide shell. Fe K-edge XAS indicates the formation of a structurally ordered, non-stoichiometric magnetite (Fe3-δO4) phase for all the nanoparticles. The XAS spectra show that, in the samples synthesized by precipitation in aqueous media and laser pyrolysis, the Bi atoms neither enter into the iron oxide spinel lattice nor form any other mixed Bi-Fe oxides. No modification of the local structure around the Fe atoms induced by the Bi atoms is observed at the Fe K edge. In addition, contrary to expectations, our results indicate that the Bi atoms do not form a well-defined Bi oxide structure. The XAS study at the Bi L3 edge indicates that the environment around Bi atoms is highly disordered and only a first oxygen coordination shell is observed. Indefinite [BiO6-x(OH)x] units (isolated or aggregated forming tiny amorphous clusters) bonded through hydroxyl bridges to the nanoparticle, rather than a well defined Bi2O3 shell, surround the nanoparticle. On the other hand, the XAS study indicates that, in the samples synthesized by thermal decomposition, the Bi atoms are embedded in a longer range ordered structure showing the first and second neighbors.

Functionalized magnetic iron oxide/alginate core-shell nanoparticles for targeting hyperthermia

PubMed Central

Liao, Shih-Hsiang; Liu, Chia-Hung; Bastakoti, Bishnu Prasad; Suzuki, Norihiro; Chang, Yung; Yamauchi, Yusuke; Lin, Feng-Huei; Wu, Kevin C-W

2015-01-01

Hyperthermia is one of the promising treatments for cancer therapy. However, the development of a magnetic fluid agent that can selectively target a tumor and efficiently elevate temperature while exhibiting excellent biocompatibility still remains challenging. Here a new core-shell nanostructure consisting of inorganic iron oxide (Fe3O4) nanoparticles as the core, organic alginate as the shell, and cell-targeting ligands (ie, D-galactosamine) decorated on the outer surface (denoted as Fe3O4@Alg-GA nanoparticles) was prepared using a combination of a pre-gel method and coprecipitation in aqueous solution. After treatment with an AC magnetic field, the results indicate that Fe3O4@Alg-GA nanoparticles had excellent hyperthermic efficacy in a human hepatocellular carcinoma cell line (HepG2) owing to enhanced cellular uptake, and show great potential as therapeutic agents for future in vivo drug delivery systems. PMID:26005343

Functionalized magnetic iron oxide/alginate core-shell nanoparticles for targeting hyperthermia.

PubMed

Liao, Shih-Hsiang; Liu, Chia-Hung; Bastakoti, Bishnu Prasad; Suzuki, Norihiro; Chang, Yung; Yamauchi, Yusuke; Lin, Feng-Huei; Wu, Kevin C-W

2015-01-01

Hyperthermia is one of the promising treatments for cancer therapy. However, the development of a magnetic fluid agent that can selectively target a tumor and efficiently elevate temperature while exhibiting excellent biocompatibility still remains challenging. Here a new core-shell nanostructure consisting of inorganic iron oxide (Fe3O4) nanoparticles as the core, organic alginate as the shell, and cell-targeting ligands (ie, D-galactosamine) decorated on the outer surface (denoted as Fe3O4@Alg-GA nanoparticles) was prepared using a combination of a pre-gel method and coprecipitation in aqueous solution. After treatment with an AC magnetic field, the results indicate that Fe3O4@Alg-GA nanoparticles had excellent hyperthermic efficacy in a human hepatocellular carcinoma cell line (HepG2) owing to enhanced cellular uptake, and show great potential as therapeutic agents for future in vivo drug delivery systems.

The role of interfacial metal silicates on the magnetism in FeCo/SiO 2 and Fe 49% Co 49% V 2% /SiO 2 core/shell nanoparticles

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

Desautels, R. D.; Freeland, J. W.; Rowe, M. P.

2015-05-07

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO2 and Fe49%Co49%V2%/SiO2 core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, and vanadium silicates. Magnetometry experiments havemore » shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO2-based interfacial shell.« less

Multifunctional superparamagnetic nanocrystals for imaging and targeted drug delivery to the lung

NASA Astrophysics Data System (ADS)

Armijo, Leisha M.; Brandt, Yekaterina I.; Withers, Nathan J.; Plumley, John B.; Cook, Nathaniel C.; Rivera, Antonio C.; Yadav, Surabhi; Smolyakov, Gennady A.; Monson, Todd; Huber, Dale L.; Smyth, Hugh D. C.; Osiński, Marek

2012-03-01

Iron oxide colloidal nanocrystals (ferrofluids) are investigated for application in the treatment of cystic fibrosis lung infections, the leading cause of mortality in cystic fibrosis patients. We investigate the use of iron oxide nanocrystals to increase the effectiveness of inhalation aerosol antibiotics therapy through two mechanisms: directed particle movement in the presence of a static external magnetic field and magnetic hyperthermia. Magnetic hyperthermia is an effective method for decreasing the viscosity of the mucus and biofilm thereby increasing drug, immune cell, and antibody penetration to the affected area. 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. Nanocrystals in the superparamagnetic to ferromagnetic size range exhibited excellent heating power. Additionally, iron oxide-zinc selenide core-shell nanoparticles were prepared in parallel in order to allow imaging of the iron oxide nanoparticles.

Synthesis and controllable oxidation of monodisperse cobalt-doped wüstite nanoparticles and their core-shell stability and exchange-bias stabilization.

PubMed

Chen, Chih-Jung; Chiang, Ray-Kuang; Kamali, Saeed; Wang, Sue-Lein

2015-09-14

Cobalt-doped wüstite (CWT), Co0.33Fe0.67O, nanoparticles were prepared via the thermal decomposition of CoFe2-oleate complexes in organic solvents. A controllable oxidation process was then performed to obtain Co0.33Fe0.67O/CoFe2O4 core-shell structures with different core-to-shell volume ratios and exchange bias properties. The oxidized core-shell samples with a ∼4 nm CoFe2O4 shell showed good resistance to oxygen transmission. Thus, it is inferred that the cobalt ferrite shell provides a better oxidation barrier performance than magnetite in the un-doped case. The hysteresis loops of the oxidized 19 nm samples exhibited a high exchange bias field (H(E)), an enhanced coercivity field (H(C)), and a pronounced vertical shift, thus indicating the presence of a strong exchange bias coupling effect. More importantly, the onset temperature of H(E) was found to be higher than 200 K, which suggests that cobalt doping increases the Néel temperature (T(N)) of the CWT core. In general, the results show that the homogeneous dispersion of Co in iron precursors improves the stability of the final CWT nanoparticles. Moreover, the CoFe2O4 shells formed following oxidation increase the oxidation resistance of the CWT cores and enhance their anisotropy energy.

The role of interfacial metal silicates on the magnetism in FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles

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

Desautels, R. D., E-mail: rddesautels@physics.umanitoba.ca; Toyota Research Institute of North America, Ann Arbor, Michigan 48169; Freeland, J. W.

2015-05-07

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, andmore » vanadium silicates. Magnetometry experiments have shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO{sub 2}-based interfacial shell.« less

Core-shell nanocapsules stabilized by single-component polymer and nanoparticles for magneto-chemotherapy/hyperthermia with multiple drugs.

PubMed

Hu, Shang-Hsiu; Liao, Bang-Jie; Chiang, Chin-Sheng; Chen, Po-Jung; Chen, I-Wei; Chen, San-Yuan

2012-07-17

Iron-oxide-containing double emulsion capsules carrying both hydrophilic and hydrophobic therapeutic molecules can deliver drugs and energy on demand in vivo. Magneto-chemotherapy/hyperthermia involves a burst-like release of hydrophilic doxorubicin and hydrophobic paclitaxel, remotely triggered by a high frequency magnetic field, which also releases energy via internalized iron oxide nanoparticles, all contributing to cell kill. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and characterization of hydroxyapatite-coated iron oxide particles by spray-drying technique.

PubMed

Donadel, Karina; Felisberto, Marcos D V; Laranjeira, Mauro C M

2009-06-01

Magnetic particles of iron oxide have been increasingly used in medical diagnosis by magnetic resonance imaging and in cancer therapies involving targeted drug delivery and magnetic hyperthermia. In this study we report the preparation and characterization of iron oxide particles coated with bioceramic hydroxyapatite by spray-drying. The iron oxide magnetic particles (IOMP) were coated with hydroxyapatite (HAp) by spray-drying using two IOMP/HAp ratios (0.7 and 3.2). The magnetic particles were characterized by way of scanning electronic microscopy, energy dispersive X-ray, X-ray diffraction, Fourier transformed infrared spectroscopy, flame atomic absorption spectrometry,vibrating sample magnetometry and particle size distribution (laser diffraction). The surface morphology of the coated samples is different from that of the iron oxide due to formation of hydroxyapatite coating. From an EDX analysis, it was verified that the surface of the coated magnetic particles is composed only of HAp, while the interior containsiron oxide and a few layers of HAp as expected. The results showed that spray-drying technique is an efficient and relatively inexpensive method for forming spherical particles with a core/shell structure.

Size-controlled synthesis of superparamagnetic iron oxide nanoparticles and their surface coating by gold for biomedical applications

NASA Astrophysics Data System (ADS)

Maleki, H.; Simchi, A.; Imani, M.; Costa, B. F. O.

2012-11-01

The size mono-dispersity, saturation magnetization, and surface chemistry of magnetic nanoparticles (NPs) are recognized as critical factors for efficient biomedical applications. Here, we performed modified water-in-oil inverse nano-emulsion procedure for preparation of stable colloidal superparamagnetic iron oxide NPs (SPIONs) with high saturation magnetization. To achieve mono-dispersed SPIONs, optimization process was probed on several important factors including molar ratio of iron salts [Fe3+ and Fe2+], the concentration of ammonium hydroxide as reducing agent, and molar ratio of water to surfactant. The biocompatibility of the obtained NPs, at various concentrations, was evaluated via MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay and the results showed that the NPs were non-toxic at concentrations <0.1 mg/mL. Surface functionalization was performed by conformal coating of the NPs with a thin shell of gold (˜4 nm) through chemical reduction of attached gold salts at the surface of the SPIONs. The Fe3O4 core/Au shell particles demonstrate strong plasmon resonance absorption and can be separated from solution using an external magnetic field. Experimental data from both physical and chemical determinations of the changes in particle size, surface plasmon resonance optical band, phase components, core-shell surface composition, and magnetic properties have confirmed the formation of the mono-dispersed core-shell nanostructure.

Synthesis of ligand-stabilized metal oxide nanocrystals and epitaxial core/shell nanocrystals via a lower-temperature esterification process.

PubMed

Ito, Daisuke; Yokoyama, Shun; Zaikova, Tatiana; Masuko, Keiichiro; Hutchison, James E

2014-01-28

The properties of metal oxide nanocrystals can be tuned by incorporating mixtures of matrix metal elements, adding metal ion dopants, or constructing core/shell structures. However, high-temperature conditions required to synthesize these nanocrystals make it difficult to achieve the desired compositions, doping levels, and structural control. We present a lower temperature synthesis of ligand-stabilized metal oxide nanocrystals that produces crystalline, monodisperse nanocrystals at temperatures well below the thermal decomposition point of the precursors. Slow injection (0.2 mL/min) of an oleic acid solution of the metal oleate complex into an oleyl alcohol solvent at 230 °C results in a rapid esterification reaction and the production of metal oxide nanocrystals. The approach produces high yields of crystalline, monodisperse metal oxide nanoparticles containing manganese, iron, cobalt, zinc, and indium within 20 min. Synthesis of tin-doped indium oxide (ITO) can be accomplished with good control of the tin doping levels. Finally, the method makes it possible to perform epitaxial growth of shells onto nanocrystal cores to produce core/shell nanocrystals.

Fine structural features of nanoscale zero-valent iron characterized by spherical aberration corrected scanning transmission electron microscopy (Cs-STEM).

PubMed

Liu, Airong; Zhang, Wei-xian

2014-09-21

An angstrom-resolution physical model of nanoscale zero-valent iron (nZVI) is generated with a combination of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) on the Fe L-edge. Bright-field (BF), high-angle annular dark-field (HAADF) and secondary electron (SE) imaging of nZVI acquired by a Hitachi HD-2700 STEM show near atomic resolution images and detailed morphological and structural information of nZVI. The STEM-EDS technique confirms that the fresh nZVI comprises of a metallic iron core encapsulated with a thin layer of iron oxides or oxyhydroxides. SAED patterns of the Fe core suggest the polycrystalline structure in the metallic core and amorphous nature of the oxide layer. Furthermore, Fe L-edge of EELS shows varied structural features from the innermost Fe core to the outer oxide shell. A qualitative analysis of the Fe L(2,3) edge fine structures reveals that the shell of nZVI consists of a mixed Fe(II)/Fe(III) phase close to the Fe (0) interface and a predominantly Fe(III) at the outer surface of nZVI.

Hierarchical Biosilicates by the 3-D Replication of Block Copolymer Templates in Supercritical Fluids

DTIC Science & Technology

2009-12-30

Iron Oxide Nanoparticles through Supercritical CO2 Infusion of TEOS into Ferritin Doped Block Copolymers…………………………………………………...4 4.2 Simple...which is doped with ferritin (yellow spheres). The blue PPO domains are removed during calcination as is the apoferritin shell, leaving magnetic...iron oxide particles (black) embedded in the mesoporous silica film. 5 2 TEM images of ferritin -containing samples at the specified ferritin

CD/MCD/VTVH-MCD Studies of Escherichia coli Bacterioferritin Support a Binuclear Iron Cofactor Site.

PubMed

Kwak, Yeonju; Schwartz, Jennifer K; Huang, Victor W; Boice, Emily; Kurtz, Donald M; Solomon, Edward I

2015-12-01

Ferritins and bacterioferritins (Bfrs) utilize a binuclear non-heme iron binding site to catalyze oxidation of Fe(II), leading to formation of an iron mineral core within a protein shell. Unlike ferritins, in which the diiron site binds Fe(II) as a substrate, which then autoxidizes and migrates to the mineral core, the diiron site in Bfr has a 2-His/4-carboxylate ligand set that is commonly found in diiron cofactor enzymes. Bfrs could, therefore, utilize the diiron site as a cofactor rather than for substrate iron binding. In this study, we applied circular dichroism (CD), magnetic CD (MCD), and variable-temperature, variable-field MCD (VTVH-MCD) spectroscopies to define the geometric and electronic structures of the biferrous active site in Escherichia coli Bfr. For these studies, we used an engineered M52L variant, which is known to eliminate binding of a heme cofactor but to have very minor effects on either iron oxidation or mineral core formation. We also examined an H46A/D50A/M52L Bfr variant, which additionally disrupts a previously observed mononuclear non-heme iron binding site inside the protein shell. The spectral analyses define a binuclear and an additional mononuclear ferrous site. The biferrous site shows two different five-coordinate centers. After O2 oxidation and re-reduction, only the mononuclear ferrous signal is eliminated. The retention of the biferrous but not the mononuclear ferrous site upon O2 cycling supports a mechanism in which the binuclear site acts as a cofactor for the O2 reaction, while the mononuclear site binds the substrate Fe(II) that, after its oxidation to Fe(III), migrates to the mineral core.

SANS contrast variation study of magnetoferritin structure at various iron loading

NASA Astrophysics Data System (ADS)

Melnikova, Lucia; Petrenko, Viktor I.; Avdeev, Mikhail V.; Ivankov, Oleksandr I.; Bulavin, Leonid A.; Garamus, Vasil M.; Almásy, László; Mitroova, Zuzana; Kopcansky, Peter

2015-03-01

Magnetoferritin, a synthetic derivate of iron storage protein - ferritin, has been synthesized with different iron oxide loading values. Small-angle neutron scattering experiments were applied to study the structure of magnetoferritin solutions using contrast variation method by varying the light to heavy water ratio of the solvent. Higher iron loading leads to increase of the neutron scattering length density of magnetoferritin and also to the increase of the polydispersity of complexes. The formation of the magnetic core and the variation of the protein shell structure upon iron loading are concluded.

Liquid Plasma Synthesis of Carbon Coated Iron Oxide Particles

NASA Astrophysics Data System (ADS)

Uygun, Aysegul; Hershkowitz, Noah; Eren, Esin; Uygun, Emre; Celik Cogal, Gamze; Yurdabak Karaca, Gozde; Manolache, Sorin; Sundaram, Gunasekaran; Sadak, Omer; Oksuz, Lutfi

2017-10-01

Recently, magnetic metal or metal oxide nanoparticles encapsulated in carbon are important in biomedical applications. The relevant reason to study toxicity of the magnetic nanoparticles coated by carbon is that they have great potential to contribute to cancer treatment. In this work, the synthesis of iron oxide nano-particles coated by graphitic carbon shells using pulsed plasma in liquid method. Short duration of RF plasma discharge, low electrical energy and fast quenching of the surrounding media can let to synthesize various kinds of pure nanoparticles. Corresponding author: ayseguluygun@sdu.edu.tr, lutfioksuz@sdu.edu.tr.

Tuning dipolar magnetic interactions by controlling individual silica coating of iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Rivas Rojas, P. C.; Tancredi, P.; Moscoso Londoño, O.; Knobel, M.; Socolovsky, L. M.

2018-04-01

Single and fixed size core, core-shell nanoparticles of iron oxides coated with a silica layer of tunable thickness were prepared by chemical routes, aiming to generate a frame of study of magnetic nanoparticles with controlled dipolar interactions. The batch of iron oxides nanoparticles of 4.5 nm radii, were employed as cores for all the coated samples. The latter was obtained via thermal decomposition of organic precursors, resulting on nanoparticles covered with an organic layer that was subsequently used to promote the ligand exchange in the inverse microemulsion process, employed to coat each nanoparticle with silica. The amount of precursor and times of reaction was varied to obtain different silica shell thicknesses, ranging from 0.5 nm to 19 nm. The formation of the desired structures was corroborated by TEM and SAXS measurements, the core single-phase spinel structure was confirmed by XRD, and superparamagnetic features with gradual change related to dipolar interaction effects were obtained by the study of the applied field and temperature dependence of the magnetization. To illustrate that dipolar interactions are consistently controlled, the main magnetic properties are presented and analyzed as a function of center to center minimum distance between the magnetic cores.

Magneto-optical nanoparticles for cyclic magnetomotive photoacoustic imaging

NASA Astrophysics Data System (ADS)

Arnal, Bastien; Yoon, Soon Joon; Li, Junwei; Gao, Xiaohu; O'Donnell, Matthew

2018-05-01

Photoacoustic imaging is a highly promising tool to visualize molecular events with deep tissue penetration. Like most other modalities, however, image contrast under in vivo conditions is far from optimal due to background signals from tissue. Using iron oxide-gold core-shell nanoparticles, we previously demonstrated that magnetomotive photoacoustic (mmPA) imaging can dramatically reduce the influence of background signals and produce high-contrast molecular images. Here we report two significant advances toward clinical translation of this technology. First, we introduce a new class of compact, uniform, magneto-optically coupled core-shell nanoparticle, prepared through localized copolymerization of polypyrrole (PPy) on an iron oxide nanoparticle surface. The resulting iron oxide-PPy nanoparticles solve the photo-instability and small-scale synthesis problems previously encountered by the gold coating approach, and extend the large optical absorption coefficient of the particles beyond 1000 nm in wavelength. In parallel, we have developed a new generation of mmPA imaging featuring cyclic magnetic motion and ultrasound speckle tracking, with an image capture frame rate several hundred times faster than the photoacoustic speckle tracking method demonstrated previously. These advances enable robust artifact elimination caused by physiologic motion and first application of the mmPA technology in vivo for sensitive tumor imaging.

A virus capsid-like nanocompartment that stores iron and protects bacteria from oxidative stress.

PubMed

McHugh, Colleen A; Fontana, Juan; Nemecek, Daniel; Cheng, Naiqian; Aksyuk, Anastasia A; Heymann, J Bernard; Winkler, Dennis C; Lam, Alan S; Wall, Joseph S; Steven, Alasdair C; Hoiczyk, Egbert

2014-09-01

Living cells compartmentalize materials and enzymatic reactions to increase metabolic efficiency. While eukaryotes use membrane-bound organelles, bacteria and archaea rely primarily on protein-bound nanocompartments. Encapsulins constitute a class of nanocompartments widespread in bacteria and archaea whose functions have hitherto been unclear. Here, we characterize the encapsulin nanocompartment from Myxococcus xanthus, which consists of a shell protein (EncA, 32.5 kDa) and three internal proteins (EncB, 17 kDa; EncC, 13 kDa; EncD, 11 kDa). Using cryo-electron microscopy, we determined that EncA self-assembles into an icosahedral shell 32 nm in diameter (26 nm internal diameter), built from 180 subunits with the fold first observed in bacteriophage HK97 capsid. The internal proteins, of which EncB and EncC have ferritin-like domains, attach to its inner surface. Native nanocompartments have dense iron-rich cores. Functionally, they resemble ferritins, cage-like iron storage proteins, but with a massively greater capacity (~30,000 iron atoms versus ~3,000 in ferritin). Physiological data reveal that few nanocompartments are assembled during vegetative growth, but they increase fivefold upon starvation, protecting cells from oxidative stress through iron sequestration. © 2014 The Authors.

Colloidal inorganic nanocrystals: Nucleation, growth and biological applications

NASA Astrophysics Data System (ADS)

Lynch, Jared James

Colloidal inorganic nanocrystals are a class of material whose size ranges from a few nanometers to a hundred nanometers in dimension. These nanocrystals have size dependent properties that differ significantly from the bulk material counterparts. Due to their unique physical properties colloidal inorganic nanocrystals have several promising applications in a diverse range of areas, such as biomedical diagnosis, catalysis, plasmonics, high-density data storage and solar energy conversion. This dissertation presents the study of the formation of iron oxide nanocrystals under the influence of solvent and Ar gas bubbles, the phase transfer of metal oxide nanocrystals into water using inorganic ions, and the doping of semiconductor CdS/ZnS core/shell nanocrystals with copper and silver ions. First, the formation of iron oxide nanocrystals is investigated in the presence of boiling solvent or Ar bubbles. Using a non-injection based synthesis method, the thermal decomposition of iron oleate was studied under various reaction conditions, and the role of the bubbles on the nucleation and growth of iron oxide nanocrystals was determined. Kinetics studies were used to elucidate how latent heat transfer from the bubbles allows for "active monomers" to form preferentially from exothermic reactions taking place during nucleation. General insights into colloidal inorganic nanocrystal formation are discussed. Second, a non-injection based synthesis for CdS/ZnS core/shell nanocrystals is used to make high quality semiconductor particles which are intentionally doped with Cu or Ag ions. The Ag ions effect on the optical properties of the CdS/ZnS nanocrystals is investigated. The absorption and fluorescence of the samples is measured as a function of time and temperature. Proposed mechanisms for the observations are given and thoroughly discussed. Comparisons between previous results for Cu doped CdS/ZnS nanocrystals are also made to further understand how doping of semiconductor nanocrystals can be realized. Finally, a novel phase transfer process is demonstrated using inorganic salts, such as sodium arsenite, to make water soluble metal oxide nanocrystals. The water soluble iron oxide nanocrystals are fully characterized by several complementary techniques and then used in cellular studies. The arsenite-coated iron oxide composite nanocrystals (AICN) are shown to be effective cancer therapy agents.

Templating Growth of a Pseudomorphic Lepidocrocite Microshell at the Calcite–Water Interface

DOE PAGES

Yuan, Ke; Lee, Sang Soo; Wang, Jun; ...

2018-01-05

The growth of lepidocrocite (gamma-FeOOH) has been observed through oxidation of Fe(II) on calcite (CaCO 3). Here, we seek to understand the structural relation between lepidocrocite and the calcite substrate and its growth mechanism. The formation of iron oxyhydroxide layers having distinct morphologies was observed during the dissolution of calcite in acidic Fe(II)-rich solutions. A pseudomorphic lepidocrocite shell together with multiple iron oxyhydroxide layers encapsulated within the shell was imaged by optical and transmission X-ray microscopies. The presence of a several-nanometer-thick ordered lepidocrocite film was observed by X-ray reflectivity, with the lepidocrocite (100) plane oriented parallel to the calcite (104)more » surface. Lath-shaped lepidocrocite aggregates formed during the initial precipitation, which eventually grew into clusters of parallel platy crystals. The formation of a nanometer-thick well-ordered lepidocrocite film on a pristine calcite surface appears critical for the subsequent pseudomorphic overgrowth. Detachment of the lepidocrocite film from the dissolving calcite surface yielded a free-standing pseudomorphic iron oxyhydroxide shell, suggesting weak interactions between the shell and the calcite substrate. This growth mechanism yields the potential of using carbonate minerals as templates for pseudomorphic synthesis of iron oxyhydroxides having well-defined size and morphology.« less

Biocompatible core-shell magnetic nanoparticles for cancer treatment

NASA Astrophysics Data System (ADS)

Sharma, Amit; Qiang, You; Meyer, Daniel; Souza, Ryan; Mcconnaughoy, Alan; Muldoon, Leslie; Baer, Donald

2008-04-01

Nontoxic magnetic nanoparticles (MNPs) have expanded treatment delivery options in the medical world. With a size range from 2to200nm, MNPs can be compiled with most of the small cells and tissues in the living body. Monodispersive iron-iron oxide core-shell nanoparticles were prepared by our novel cluster deposition system. This unique method of preparing core-shell MNPs gives the nanoparticles a very high magnetic moment. We tested the nontoxicity and uptake of MNPs coated with/without dextrin by incubating them with rat LX-1 small cell lung cancer cells. Since core iron enhances the heating effect [L. Baker, Q. Zeing, W. Li, and S. Sullivan, J. Appl. Phys. 99, 08H106 (2006)], the rate of oxidation of iron nanoparticles was also tested in de-ionized water at a certain time interval. Both coated and noncoated MNPs were successfully uptaken by the cells, indicating that the nanoparticles were not toxic. The stability of MNPs was verified by x-ray diffraction scan after 0, 24, 48, 96, and 204h. Due to the high magnetic moment offered by MNPs produced in our laboratory, we predict that even at low applied external alternating field, the desired temperature could be reached in cancer cells in comparison to the commercially available nanoparticles. Moreover our MNPs do not require additional transfection agent, providing a cost effective means of treatment with significantly lower dosage in the body in comparison to commercially available nanoparticles.

Design of Magnetic Gelatine/Silica Nanocomposites by Nanoemulsification: Encapsulation versus in Situ Growth of Iron Oxide Colloids

PubMed Central

Allouche, Joachim; Chanéac, Corinne; Brayner, Roberta; Boissière, Michel; Coradin, Thibaud

2014-01-01

The design of magnetic nanoparticles by incorporation of iron oxide colloids within gelatine/silica hybrid nanoparticles has been performed for the first time through a nanoemulsion route using the encapsulation of pre-formed magnetite nanocrystals and the in situ precipitation of ferrous/ferric ions. The first method leads to bi-continuous hybrid nanocomposites containing a limited amount of well-dispersed magnetite colloids. In contrast, the second approach allows the formation of gelatine-silica core-shell nanostructures incorporating larger amounts of agglomerated iron oxide colloids. Both magnetic nanocomposites exhibit similar superparamagnetic behaviors. Whereas nanocomposites obtained via an in situ approach show a strong tendency to aggregate in solution, the encapsulation route allows further surface modification of the magnetic nanocomposites, leading to quaternary gold/iron oxide/silica/gelatine nanoparticles. Hence, such a first-time rational combination of nano-emulsion, nanocrystallization and sol-gel chemistry allows the elaboration of multi-component functional nanomaterials. This constitutes a step forward in the design of more complex bio-nanoplatforms. PMID:28344239

Design of Magnetic Gelatine/Silica Nanocomposites by Nanoemulsification: Encapsulation versus in Situ Growth of Iron Oxide Colloids.

PubMed

Allouche, Joachim; Chanéac, Corinne; Brayner, Roberta; Boissière, Michel; Coradin, Thibaud

2014-07-31

The design of magnetic nanoparticles by incorporation of iron oxide colloids within gelatine/silica hybrid nanoparticles has been performed for the first time through a nanoemulsion route using the encapsulation of pre-formed magnetite nanocrystals and the in situ precipitation of ferrous/ferric ions. The first method leads to bi-continuous hybrid nanocomposites containing a limited amount of well-dispersed magnetite colloids. In contrast, the second approach allows the formation of gelatine-silica core-shell nanostructures incorporating larger amounts of agglomerated iron oxide colloids. Both magnetic nanocomposites exhibit similar superparamagnetic behaviors. Whereas nanocomposites obtained via an in situ approach show a strong tendency to aggregate in solution, the encapsulation route allows further surface modification of the magnetic nanocomposites, leading to quaternary gold/iron oxide/silica/gelatine nanoparticles. Hence, such a first-time rational combination of nano-emulsion, nanocrystallization and sol-gel chemistry allows the elaboration of multi-component functional nanomaterials. This constitutes a step forward in the design of more complex bio-nanoplatforms.

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

Exchange Bias Effects in Iron Oxide-Based Nanoparticle Systems

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

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

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

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

Comparison of magnetic properties and high-temperature phase stability of phosphate- and oleic acid-capped iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Muthukumaran, T.; Pati, S. S.; Singh, L. H.; de Oliveira, A. C.; Garg, V. K.; Philip, John

2018-03-01

We study the influence of dynamic capping of Fe3O4 nanoparticles with phosphate and oleic acid, on their structure, magnetic properties and thermal stability of magnetic nanoparticles. It is observed that the phosphate coating on iron oxide lowers the dipole-dipole interaction significantly, as compared to oleic acid capping. The Mössbauer results show that the spin canting order of oxidized shell and the mean hyperfine field values follow the order Fe0 (uncoated) > FeOA (oleic acid capped) > FP1 (phosphate capped). The uncoated Fe3O4 nanoparticle is non-stoichiometric in nature due to oxidation, whereas FP1 and FeOA are of the correct stoichiometry. Mössbauer and photoacoustic spectroscopic studies on air-annealed phosphate-coated magnetite nanoparticles confirm that the magnetic iron oxide phase is preserved up to 833 K and a complete conversion of Fe3O4 into the non-magnetic hematite phase occurs at 1173 K. The iron oxide air annealed at 833 K is found to have a shell of orthorhombic α-Fe2O3 over the magnetite core. However, in oleic acid-coated nanoparticles, the magnetic to non-magnetic phase transformation commences at 623 K and the conversion was complete at 823 K. The photoacoustic spectra of the air-annealed phosphate-coated Fe3O4 particles showed a flipping of the absorption intensity between 500-700 nm and 800-1000 nm, due to the conversion of Fe3O4 to γ-Fe2O3 at 923 and γ-Fe2O3 to α-Fe2O3 at 1173 K, respectively. The γ-Fe2O3 showed an intense absorption peak above 750 nm, whereas the α-Fe2O3 showed a peak broadening in the wavelength range of 600-700 nm, in addition to the strong peaks at a wavelength above 750 nm. This study suggests that the photoacoustic spectroscopy can distinguish clearly the three polymorphs of iron oxide i.e., Fe3O4, γ-Fe2O3 and α-Fe2O3. Our results confirm the ability of phosphate-capped iron oxide particles to retard the oxidation of Fe2+ contents during the crystal growth process.

Air-stable superparamagnetic metal nanoparticles entrapped in graphene oxide matrix

NASA Astrophysics Data System (ADS)

Tuček, Jiří; Sofer, Zdeněk; Bouša, Daniel; Pumera, Martin; Holá, Kateřina; Malá, Aneta; Poláková, Kateřina; Havrdová, Markéta; Čépe, Klára; Tomanec, Ondřej; Zbořil, Radek

2016-09-01

Superparamagnetism is a phenomenon caused by quantum effects in magnetic nanomaterials. Zero-valent metals with diameters below 5 nm have been suggested as superior alternatives to superparamagnetic metal oxides, having greater superspin magnitudes and lower levels of magnetic disorder. However, synthesis of such nanometals has been hindered by their chemical instability. Here we present a method for preparing air-stable superparamagnetic iron nanoparticles trapped between thermally reduced graphene oxide nanosheets and exhibiting ring-like or core-shell morphologies depending on iron concentration. Importantly, these hybrids show superparamagnetism at room temperature and retain it even at 5 K. The corrected saturation magnetization of 185 Am2 kg-1 is among the highest values reported for iron-based superparamagnets. The synthetic concept is generalized exploiting functional groups of graphene oxide to stabilize and entrap cobalt, nickel and gold nanoparticles, potentially opening doors for targeted delivery, magnetic separation and imaging applications.

Air-stable superparamagnetic metal nanoparticles entrapped in graphene oxide matrix.

PubMed

Tuček, Jiří; Sofer, Zdeněk; Bouša, Daniel; Pumera, Martin; Holá, Kateřina; Malá, Aneta; Poláková, Kateřina; Havrdová, Markéta; Čépe, Klára; Tomanec, Ondřej; Zbořil, Radek

2016-09-15

Superparamagnetism is a phenomenon caused by quantum effects in magnetic nanomaterials. Zero-valent metals with diameters below 5 nm have been suggested as superior alternatives to superparamagnetic metal oxides, having greater superspin magnitudes and lower levels of magnetic disorder. However, synthesis of such nanometals has been hindered by their chemical instability. Here we present a method for preparing air-stable superparamagnetic iron nanoparticles trapped between thermally reduced graphene oxide nanosheets and exhibiting ring-like or core-shell morphologies depending on iron concentration. Importantly, these hybrids show superparamagnetism at room temperature and retain it even at 5 K. The corrected saturation magnetization of 185 Am(2) kg(-1) is among the highest values reported for iron-based superparamagnets. The synthetic concept is generalized exploiting functional groups of graphene oxide to stabilize and entrap cobalt, nickel and gold nanoparticles, potentially opening doors for targeted delivery, magnetic separation and imaging applications.

Air-stable superparamagnetic metal nanoparticles entrapped in graphene oxide matrix

PubMed Central

Tuček, Jiří; Sofer, Zdeněk; Bouša, Daniel; Pumera, Martin; Holá, Kateřina; Malá, Aneta; Poláková, Kateřina; Havrdová, Markéta; Čépe, Klára; Tomanec, Ondřej; Zbořil, Radek

2016-01-01

Superparamagnetism is a phenomenon caused by quantum effects in magnetic nanomaterials. Zero-valent metals with diameters below 5 nm have been suggested as superior alternatives to superparamagnetic metal oxides, having greater superspin magnitudes and lower levels of magnetic disorder. However, synthesis of such nanometals has been hindered by their chemical instability. Here we present a method for preparing air-stable superparamagnetic iron nanoparticles trapped between thermally reduced graphene oxide nanosheets and exhibiting ring-like or core-shell morphologies depending on iron concentration. Importantly, these hybrids show superparamagnetism at room temperature and retain it even at 5 K. The corrected saturation magnetization of 185 Am2 kg–1 is among the highest values reported for iron-based superparamagnets. The synthetic concept is generalized exploiting functional groups of graphene oxide to stabilize and entrap cobalt, nickel and gold nanoparticles, potentially opening doors for targeted delivery, magnetic separation and imaging applications. PMID:27628898

Iron Polymerization and Arsenic Removal During In-Situ Iron Electrocoagulation in Synthetic Bangladeshi Groundwater

NASA Astrophysics Data System (ADS)

van Genuchten, C. M.; Pena, J.; Addy, S.; Gadgil, A.

2010-12-01

Millions of people worldwide are exposed to arsenic-contamination in groundwater drinking supplies. The majority of affected people live in rural Bangladesh. Electrocoagulation (EC) using iron electrodes is a promising arsenic removal strategy that is based on the generation of iron precipitates with a high affinity for arsenic through the electrochemical dissolution of a sacrificial iron anode. Many studies of iron hydrolysis in the presence of co-occurring ions in groundwater such as PO43-, SiO44-, and AsO43- suggest that these ions influence the polymerization and formation of iron oxide phases. However, the combined impact of these ions on precipitates generated by EC is not well understood. X-ray absorption spectroscopy (XAS) was used to examine EC precipitates generated in synthetic Bangladeshi groundwater (SBGW). The iron oxide structure and arsenic binding geometry were investigated as a function of EC operating conditions. As and Fe k-edge spectra were similar between samples regardless of the large range of current density (0.02, 1.1, 5.0, 100 mA/cm2) used during sample generation. This result suggests that current density does not play a large role in the formation EC precipitates in SBGW. Shell-by-shell fits of Fe K-edge data revealed the presence of a single Fe-Fe interatomic distance at approximately 3.06 Å. The absence of longer ranged Fe-Fe correlations suggests that EC precipitates consist of nano-scale chains (polymers) of FeO6 octahedra sharing equatorial edges. Shell-by-shell fits of As K-edge spectra show arsenic bound in primarily bidentate, binuclear corner sharing complexes. In this coordination geometry, arsenic prevents the formation of FeO6 corner-sharing linkages, which are necessary for 3-dimensional crystal growth. The individual and combined effects of other anions, such as PO43- and SiO44- present in SBGW are currently being investigated to determine the role of these ions in stunting crystal growth. The results provided by this study are useful in explaining the large adsorption capacity of EC precipitates. This study will also lead to better predictions of arsenic removal efficiency during EC and a better understanding of the long-term stability of arsenic-laden EC sludge.

Air-stable nZVI formation mediated by glutamic acid: solid-state storable material exhibiting 2D chain morphology and high reactivity in aqueous environment

NASA Astrophysics Data System (ADS)

Siskova, Karolina; Tucek, Jiri; Machala, Libor; Otyepkova, Eva; Filip, Jan; Safarova, Klara; Pechousek, Jiri; Zboril, Radek

2012-03-01

We report a new chemical approach toward air-stable nanoscale zero-valent iron (nZVI). The uniformly sized (approx. 80 nm) particles, formed by the reduction of Fe(II) salt by borohydride in the presence of glutamic acid, are coated by a thin inner shell of amorphous ferric oxide/hydroxide and a secondary shell consisting of glutamic acid. The as-prepared nanoparticles stabilized by the inorganic-organic double shell create 2D chain morphologies. They are storable for several months under ambient atmosphere without the loss of Fe(0) relative content. They show one order of magnitude higher rate constant for trichlorethene decomposition compared with the pristine particles possessing only the inorganic shell as a protective layer. This is the first example of the inorganic-organic (consisting of low-molecular weight species) double-shell stabilized nanoscale zero-valent iron material being safely transportable in solid-state, storable on long-term basis under ambient conditions, environmentally acceptable for in situ applications, and extraordinarily reactive if contacted with reducible pollutants, all in one.

Design and synthesis of magnetic nanoparticles with gold shells for single particle optical tracking

NASA Astrophysics Data System (ADS)

Lim, Jitkang

The design, synthesis, and characterization of iron oxide core, gold shell nanoparticles are studied in this thesis. Firstly, nanoparticles with 18 +/- 1.7 nm diameter iron oxide cores with ˜5 nm thick gold shells were synthesized via a new seed-mediated electroless deposition method. The nanoparticles were superparamagnetic at room temperature and could be reversibly collected by a permanent magnet. These nanoparticles displayed a sharp localized surface plasmon resonance peak at 605 nm, as predicted by scattering theory, and their large scattering cross-section allowed them to be individually resolved in darkfield optical microscopy while undergoing Brownian motion in aqueous suspension. Later, commercially available 38 +/- 3.8 nm diameter spherical iron oxide nanoparticles (from Ocean Nanotech, Inc) were employed to make core-shell particles. These particles were decorated with cationic poly(diallyldimethylammonium chloride) (PDDA) which further promotes the attachment of small gold clusters. After gold seeding, the average hydrodynamic diameter of the core-shell particles is 172 +/- 65.9 nm. The magnetophoretic motion of these particles was guided by a piece of magnetized mu-metal. Individual particle trajectories were observed by darkfield optical microscopy. The typical magnetophoretic velocity achieved was within the range of 1--10 mum/sec. Random walk analysis performed on these particles while undergoing Brownian motion confirmed that individual particles were indeed being imaged. The particle size variation within the observed sample obtained through random walk analysis was within the size distribution obtained by dynamic light scattering. When the current to the solenoid used to magnetize the mu-metal was turned off, all the collected core-shell particles were readily redispersed by diffusion back into the surrounding environment. A Peclet number analysis was performed to probe the convective motion of nanospheres and nanorods under the influence of magnetophoresis and diffusion. Under most circumstances, magnetophoretic behavior dominates diffusion for nanorods, as the magnetic field lines tend to align the magnetic moment along the rod axis. The synthesis and dispersion of fluorophore-tagged nanorods are described. Fluorescence microscopy was employed to image the nanorod motion in a magnetic field gradient. The preliminary experimental data are consistent with the Peclet number analysis. Lastly, the colloidal stability of iron oxide core, gold shell nanoparticles in high ionic strength media was investigated. Such particles are sufficiently charged to be stable against flocculation without modification in low ionic strength media, but they require surface modification to be stably dispersed in elevated ionic strength media that are appropriate for biotechnological applications. Dynamic light scattering and ultraviolet-visible spectrophotometry were used to monitor the colloidal stability of core-shell particles in pH 7.4, 150 mM ionic strength phosphate buffered saline (PBS). While uncoated particles flocculated immediately upon being introduced into PBS, core-shell particles with adsorbed layers of bovine serum albumin or the amphiphilic triblock copolymers Pluronic F127 and Pluronic F68 resist flocculation after more than five days in PBS. Adsorbed dextran allowed flocculation that was limited to the formation of small clusters, while poly(ethylene glycol) homopolymers ranging in molecular weight from 6,000 to 100,000 were ineffective steric stabilizers. The effectiveness of adsorbed Pluronic copolymers as steric stabilizers was interpreted in terms of the measured adsorbed layer thickness and extended DLVO theory predictions of the interparticle interactions.

Preparation of Metalloporphyrin-Bound Superparamagnetic Silica Particles via "Click" Reaction.

PubMed

Hollingsworth, Javoris V; Bhupathiraju, N V S Dinesh K; Sun, Jirun; Lochner, Eric; Vicente, M Graça H; Russo, Paul S

2016-01-13

A facile approach using click chemistry is demonstrated for immobilization of metalloporphyrins onto the surface of silica-coated iron oxide particles. Oleic-acid stabilized iron oxide nanocrystals were prepared by thermal decomposition of iron(III) acetylacetonate. Their crystallinity, morphology, and superparamagnetism were determined using X-ray diffraction, transmission electron microscopy, and a superconducting quantum interference device. Monodisperse core-shell particles were produced in the silica-coating of iron oxide via microemulsion synthesis. Surface modification of these particles was performed in two steps, which included the reaction of silica-coated iron oxide particles with 3-bromopropyltrichlorosilane, followed by azido-functionalization with sodium azide. Monoalkylated porphyrins were prepared using the Williamson ether synthesis of commercially available tetra(4-hydroxyphenyl) porphyrin with propargyl bromide in the presence of a base. (1)H NMR and matrix-assisted laser desorption ionization confirmed the identity of the compounds. The prepared monoalkyne porphyrins were zinc-metalated prior to their introduction to azide-functionalized, silica-coated iron oxide particles in the click reaction. X-ray photoelectron spectroscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy were used to characterize the surface chemistry after each step in the reaction. In addition, particle size was determined using dynamic light scattering and microscopy. The presented methodology is versatile and can be extended to other photoreactive systems, such as phthalocyanines and boron-dipyrromethane, which may lead to new materials for optical, photonic, and biological applications.

Magnetization of individual yeast cells by in situ formation of iron oxide on cell surfaces

NASA Astrophysics Data System (ADS)

Choi, Jinsu; Lee, Hojae; Choi, Insung S.; Yang, Sung Ho

2017-09-01

Magnetic functionalization of living cells has intensively been investigated with the aim of various bioapplications such as selective separation, targeting, and localization of the cells by using an external magnetic field. However, the magnetism has not been introduced to individual living cells through the in situ chemical reactions because of harsh conditions required for synthesis of magnetic materials. In this work, magnetic iron oxide was formed on the surface of living cells by optimizing reactions conditions to be mild sufficiently enough to sustain cell viability. Specifically, the reactive LbL strategy led to formation of magnetically responsive yeast cells with iron oxide shells. This facile and direct post-magnetization method would be a useful tool for remote manipulation of living cells with magnetic interactions, which is an important technique for the integration of cell-based circuits and the isolation of cell in microfluidic devices.

Tracking the Magnetization Evolution in γ-Fe2O3 / Metallic Fe Core-Shell Nanoparticle Variants

NASA Astrophysics Data System (ADS)

Kons, C.; Nemati, Z.; Srikanth, H.; Phan, M.-H.; Krycka, K.; Borchers, J.; Keavney, D.; Arena, D. A.

Iron-core magnetic nanoparticles (MNPs) with oxide shells exhibit varying magnetic properties due to the different ordering temperatures of the core and shell spins, as well as the coupling across the metal/oxide interface. While spin coupling across two dimensional interfaces has been well explored, less is known about three dimensional interfaces such as those presented in the MNPs. In this work, MNPs were synthesized with a bcc Fe core and γ-Fe2O3 shell and placed in an oxygen rich environment to encourage the transition from cores shell (CS) to core void shell (CVS) to hollow (H) structures. Static magnetic measurements (MvT) and AC magnetometry were performed to explore the magnetic behavior of the various synthesized structures. To further understand the nature of the spin coupling in the MNPs, TEM and conventional magnetometry as well as variable-temperature small angle neutron scattering (SANS), x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) spectroscopy were performed. Modeling of the x-ray spectra and SANS data will enable us to develop a cohesive picture of spin coupling, freezing and frustration along the three-dimensional metal / oxide interface. Supported by Department of Energy award #DE-FG02-07ER46438; NSF Award #DMR-1508249.

Synthesis of composite nanoparticles using co-precipitation of a magnetic iron-oxide shell onto core nanoparticles

NASA Astrophysics Data System (ADS)

Primc, Darinka; Belec, Blaž; Makovec, Darko

2016-03-01

Composite nanoparticles can be synthesized by coating a shell made of one material onto core nanoparticles made of another material. Here we report on a novel method for coating a magnetic iron oxide onto the surface of core nanoparticles in an aqueous suspension. The method is based on the heterogeneous nucleation of an initial product of Fe3+/Fe2+ co-precipitation on the core nanoparticles. The close control of the supersaturation of the precipitating species required for an exclusively heterogeneous nucleation and the growth of the shell were achieved by immobilizing the reactive Fe3+ ions in a nitrate complex with urea ([Fe((CO(NH2)2)6](NO3)3) and by using solid Mg(OH)2 as the precipitating reagent. The slow thermal decomposition of the complex at 60 °C homogeneously releases the reactive Fe3+ ions into the suspension of the core nanoparticles. The key stage of the process is the thermal hydrolysis of the released Fe3+ ions prior to the addition of Mg(OH)2. The thermal hydrolysis results in the formation of γ-FeOOH, exclusively at the surfaces of the core nanoparticles. After the addition of the solid hydroxide Mg(OH)2, the pH increases and at pH 5.7 the Fe2+ precipitates and reacts with the γ-FeOOH to form magnetic iron oxide with a spinel structure (spinel ferrite) at the surfaces of the core nanoparticles. The proposed low-temperature method for the synthesis of composite nanoparticles is capable of forming well-defined interfaces between the two components, important for the coupling of the different properties. The procedure is environmentally friendly, inexpensive, and appropriate for scaling up to mass production.

The B-type channel is a major route for iron entry into the ferroxidase center and central cavity of bacterioferritin

DOE PAGES

Wong, Steve G.; Grigg, Jason C.; Le Brun, Nick E.; ...

2014-12-15

Bacterioferritin is a bacterial iron storage and detoxification protein that is capable of forming a ferric oxyhydroxide mineral core within its central cavity. To do this, iron must traverse the bacterioferritin protein shell, which is expected to occur through one or more of the channels through the shell identified by structural studies. The size and negative electrostatic potential of the 24 B-type channels suggest that they could provide a route for iron into bacterioferritin. Residues at the B-type channel (Asn-34, Glu-66, Asp-132, and Asp-139) of E. coli bacterioferritin were substituted to determine if they are important for iron core formation.more » A significant decrease in the rates of initial oxidation of Fe(II) at the ferroxidase center and subsequent iron mineralization was observed for the D132F variant. The crystal structure of this variant shows that substitution of residue 132 with phenylalanine caused a steric blockage of the B-type channel and no other material structural perturbation. Here, we conclude that the B-type channel is a major route for iron entry into both the ferroxidase center and the iron storage cavity of bacterioferritin.« less

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

PubMed

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

2018-06-14

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

Deep electromagnetic sounding of the moon with Lunokhod 2 data

NASA Technical Reports Server (NTRS)

Vanyan, L. L.; Yegorov, I. V.; Faynberg, E. B.

1977-01-01

Results of electromagnetic sounding distinguished an outer high resistance shell about 200 km thick in the moon's structure. A preliminary petrological interpretation of the moon's layers indicated their origin as a consequence of differentiation of the initial peridotite material. Upon melting, 20% to 40% of the material melts and is removed to form a high resistance basaltic shell underlain by a layer of spinal peridotites enriched in divalent iron oxides and having a reduced resistance.

Anoxic and oxic removal of humic acids with Fe@Fe2O3 core-shell nanowires: a comparative study.

PubMed

Wu, Hao; Ai, Zhihui; Zhang, Lizhi

2014-04-01

In this study we comparatively investigate the removal of humic acids with Fe@Fe2O3 core-shell nanowires under anoxic and oxic conditions. The products of humic acids after reacting with Fe@Fe2O3 core-shell nanowires under anoxic and oxic conditions were carefully examined with three-dimensional excitation emission matrix fluorescence spectroscopy and gas chromatography mass spectrometry. It was found that humic acids were removed by Fe@Fe2O3 core-shell nanowires via adsorption under anoxic condition. Langmuir adsorption isotherm was applicable to describe the adsorption processes. Kinetics of humic acids adsorption onto Fe@Fe2O3 core-shell nanowires was found to follow pseudo-second-order rate equation. By contrast, the oxic removal of humic acids with Fe@Fe2O3 core-shell nanowires involved adsorption and subsequent oxidation of humic acids because Fe@Fe2O3 core-shell nanowires could activate molecular oxygen to produce reactive oxygen species to oxidize humic acids. This subsequent oxidation of humic acids could improve the oxic removal rate to 2.5 times that of anoxic removal, accompanying with about 8.4% of mineralization. This study provides a new method for humic acids removal and also sheds light on the effects of humic acids on the pollutant removal by nano zero-valent iron. Copyright © 2014 Elsevier Ltd. All rights reserved.

Can magneto-plasmonic nanohybrids efficiently combine photothermia with magnetic hyperthermia?

NASA Astrophysics Data System (ADS)

Espinosa, Ana; Bugnet, Mathieu; Radtke, Guillaume; Neveu, Sophie; Botton, Gianluigi A.; Wilhelm, Claire; Abou-Hassan, Ali

2015-11-01

Multifunctional hybrid-design nanomaterials appear to be a promising route to meet the current therapeutics needs required for efficient cancer treatment. Herein, two efficient heat nano-generators were combined into a multifunctional single nanohybrid (a multi-core iron oxide nanoparticle optimized for magnetic hyperthermia, and a gold branched shell with tunable plasmonic properties in the NIR region, for photothermal therapy) which impressively enhanced heat generation, in suspension or in vivo in tumours, opening up exciting new therapeutic perspectives.Multifunctional hybrid-design nanomaterials appear to be a promising route to meet the current therapeutics needs required for efficient cancer treatment. Herein, two efficient heat nano-generators were combined into a multifunctional single nanohybrid (a multi-core iron oxide nanoparticle optimized for magnetic hyperthermia, and a gold branched shell with tunable plasmonic properties in the NIR region, for photothermal therapy) which impressively enhanced heat generation, in suspension or in vivo in tumours, opening up exciting new therapeutic perspectives. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06168g

Human ferritin for tumor detection and therapy.

PubMed

Fan, Kelong; Gao, Lizeng; Yan, Xiyun

2013-01-01

Ferritin, a major iron storage protein found in most living organisms, is composed of a 24-subunit protein cage with a hollow interior cavity. Serum ferritin serves as a critical marker to detect total body iron status. However, recent research reveals a number of novel functions of ferritin besides iron storage; for example, a ferritin receptor, transferrin receptor 1 (TfR1), has been identified and serum ferritin levels are found to be elevated in tumors. A particular new finding is that magnetoferritin nanoparticles, biomimetically synthesized using H-chain ferritin to form a 24-subunit cage with an iron oxide core, possess intrinsic dual functionality, the protein shell specifically targeting tumors and the iron oxide core catalyzing peroxidase substrates to produce a color reaction allowing visualization of tumor tissues. Here we attempt to summarize current research on ferritin, particularly newly identified functions related to tumors, in order to address current challenges and highlight future directions. Copyright © 2013 Wiley Periodicals, Inc.

Effects of pore topology and iron oxide core on doxorubicin loading and release from mesoporous silica nanoparticles

NASA Astrophysics Data System (ADS)

Ronhovde, Cicily J.; Baer, John; Larsen, Sarah C.

2017-06-01

Mesoporous silica nanoparticles (MSNs) have a network of pores that give rise to extremely high specific surface areas, making them attractive materials for applications such as adsorption and drug delivery. The pore topology can be readily tuned to achieve a variety of structures such as the hexagonally ordered Mobil Crystalline Material 41 (MCM-41) and the disordered "wormhole" (WO) mesoporous silica (MS) structure. In this work, the effects of pore topology and iron oxide core on doxorubicin loading and release were investigated using MSNs with pore diameters of approximately 3 nm and sub-100 nm particle diameters. The nanoparticles were loaded with doxorubicin, and the drug release into phosphate-buffered saline (PBS, 10 mM, pH 7.4) at 37 °C was monitored by fluorescence spectroscopy. The release profiles were fit using the Peppas model. The results indicated diffusion-controlled release for all samples. Statistically significant differences were observed in the kinetic host-guest parameters for each sample due to the different pore topologies and the inclusion of an iron oxide core. Applying a static magnetic field to the iron oxide core WO-MS shell materials did not have a significant impact on the doxorubicin release. This is the first time that the effects of pore topology and iron oxide core have been isolated from pore diameter and particle size for these materials.

Iron Oxidation and Core Formation in Recombinant Heteropolymeric Human Ferritins.

PubMed

Mehlenbacher, Matthew; Poli, Maura; Arosio, Paolo; Santambrogio, Paolo; Levi, Sonia; Chasteen, N Dennis; Bou-Abdallah, Fadi

2017-08-01

In animals, the iron storage and detoxification protein, ferritin, is composed of two functionally and genetically distinct subunit types, H (heavy) and L (light), which co-assemble in various ratios with tissue specific distributions to form shell-like protein structures of 24 subunits within which a mineralized iron core is stored. The H-subunit possesses a ferroxidase center (FC) that catalyzes Fe(II) oxidation, whereas the L-subunit does not. To assess the role of the L-subunit in iron oxidation and core formation, two human recombinant heteropolymeric ferritins, designated H-rich and L-rich with ratios of ∼20H:4L and ∼22L:2H, respectively, were employed and compared to the human homopolymeric H-subunit ferritin (HuHF). These heteropolymeric ferritins have a composition similar to the composition of those found in hearts and brains (i.e., H-rich) and in livers and spleens (i.e., L-rich). As for HuHF, iron oxidation in H-rich ferritin was found to proceed with a 2:1 Fe(II):O 2 stoichiometry at an iron level of 2 Fe(II) atoms/H-subunit with the generation of H 2 O 2 . The H 2 O 2 reacted with additional Fe(II) in a 2:1 Fe(II):H 2 O 2 ratio, thus avoiding the production of hydroxyl radical. A μ-1,2-peroxo-diFe(III) intermediate was observed at the FC of H-rich ferritin as for HuHF. Importantly, the H-rich protein regenerated full ferroxidase activity more rapidly than HuHF did and additionally formed larger iron cores, indicating dual roles for the L-subunit in facilitating iron turnover at the FC and in mineralization of the core. The L-rich ferritin, while also facilitating iron oxidation at the FC, additionally promoted oxidation at the mineral surface once the iron binding capacity of the FC was exceeded.

Toxicity Assessment of Silica Coated Iron Oxide Nanoparticles and Biocompatibility Improvement by Surface Engineering

PubMed Central

Malvindi, Maria Ada; De Matteis, Valeria; Galeone, Antonio; Brunetti, Virgilio; Anyfantis, George C.; Athanassiou, Athanassia; Cingolani, Roberto; Pompa, Pier Paolo

2014-01-01

We have studied in vitro toxicity of iron oxide nanoparticles (NPs) coated with a thin silica shell (Fe3O4/SiO2 NPs) on A549 and HeLa cells. We compared bare and surface passivated Fe3O4/SiO2 NPs to evaluate the effects of the coating on the particle stability and toxicity. NPs cytotoxicity was investigated by cell viability, membrane integrity, mitochondrial membrane potential (MMP), reactive oxygen species (ROS) assays, and their genotoxicity by comet assay. Our results show that NPs surface passivation reduces the oxidative stress and alteration of iron homeostasis and, consequently, the overall toxicity, despite bare and passivated NPs show similar cell internalization efficiency. We found that the higher toxicity of bare NPs is due to their stronger in-situ degradation, with larger intracellular release of iron ions, as compared to surface passivated NPs. Our results indicate that surface engineering of Fe3O4/SiO2 NPs plays a key role in improving particles stability in biological environments reducing both cytotoxic and genotoxic effects. PMID:24465736

Synthesis and magnetic property of T4 virus-supported gold-coated iron ternary nanocomposite

NASA Astrophysics Data System (ADS)

Xu, Ziming; Sun, Hongjing; Gao, Faming; Hou, Li; Li, Na

2012-12-01

Herein, we present a novel method based on the use of the symmetrical T4 bacteriophage capsid as a scaffold for preparing the gold-coated iron ternary core/shell nanostructure. Results showed that the thick gold shell was obtained to effectively protect Fe core from oxidation. Magnetic measurements showed that the nanocomposites were superparamagnetic at room temperature with a blocking temperature of about 35 K. At 3 K, its coercivity of 1142.86 Oe was larger than the existing experimental values. The magnetic property of Au/T4 was also tested, demonstrating the source of the magnetic sample arising from the Fe core only. The absorption spectrum of the Fe@Au/T4 complex was measured and compared with gold/virus. Different thickness gold shells were controlled in the synthesis by tuning the Au salt addition. On the basis of results and discussion, we further speculated the general growing mechanism of the template-supported Fe@Au process.

Preparation of Fe3O4 magnetic nanoparticles coated with gallic acid for drug delivery

PubMed Central

Dorniani, Dena; Hussein, Mohd Zobir Bin; Kura, Aminu Umar; Fakurazi, Sharida; Shaari, Abdul Halim; Ahmad, Zalinah

2012-01-01

Background and methods Magnetic iron oxide nanoparticles were prepared using a sonochemical method under atmospheric conditions at a Fe2+ to Fe3+ molar ratio of 1:2. The iron oxide nanoparticles were subsequently coated with chitosan and gallic acid to produce a core-shell structure. Results X-ray diffraction demonstrated that the magnetic nanoparticles were pure Fe3O4 with a cubic inverse spinel structure. Transmission electron microscopy showed that the Fe3O4 nanoparticles were of spherical shape with a mean diameter of 11 nm, compared with 13 nm for the iron oxide-chitosan-gallic acid (FCG) nanocarriers. Conclusion The magnetic nanocarrier enhanced the thermal stability of the drug, gallic acid. Release of the active drug from the FCG nanocarrier was found to occur in a controlled manner. The gallic acid and FCG nanoparticles were not toxic in a normal human fibroblast (3T3) line, and anticancer activity was higher in HT29 than MCF7 cell lines. PMID:23166439

Iron Oxide Nanosheets and Pulse-Electrodeposited Ni-Co-S Nanoflake Arrays for High-Performance Charge Storage.

PubMed

Khani, Hadi; Wipf, David O

2017-03-01

Nanostructured nickel cobalt sulfide (Ni 4.5 Co 4.5 S 8 ) has been prepared through a single-step pulse-electrodeposition method. Iron oxide nanosheets at hollow graphite shells (Fe 3 O 4 @g-shells) were prepared from graphite-coated iron carbide/α-Fe (g-Fe 3 C/Fe) in a two-step annealing/electrochemical cycling process. Electrochemical characterization of the Ni 4.5 Co 4.5 S 8 and g-Fe 3 C/Fe materials showed that both have high specific capacities (206 mAh g -1 and 147 mAh g -1 at 1 A g -1 ) and excellent rate capabilities (∼95% and ∼83% retention at 20 A g -1 , respectively). To demonstrate the advantageous pairing of these high rate materials, a full-cell battery with supercapacitor-like power behavior was assembled with Ni 4.5 Co 4.5 S 8 and g-Fe 3 C/Fe as the positive and negative electrodes, respectively. The (Ni 4.5 Co 4.5 S 8 //g-Fe 3 C/Fe) device could be reversibly operated in a 0.0-1.6 V potential window, delivering an impressive specific energy of 89 Wh kg -1 at 1.1 kW kg -1 and a remarkable rate performance of 61 Wh kg -1 at a very high specific power of 38.5 kW kg -1 . Additionally, long-term cycling demonstrated that the asymmetric full cell assembly retained 91% of its initial specific capacity after 2500 cycles at 40 A g -1 . The performance features of this device are among the best for iron oxide/hydroxide and bimetallic sulfide based energy storage devices to date, thereby giving insight into design principles for the next generation high-energy-density devices.

Chondroitin sulfate-capped super-paramagnetic iron oxide nanoparticles as potential carriers of doxorubicin hydrochloride.

PubMed

Mallick, Neha; Anwar, Mohammed; Asfer, Mohammed; Mehdi, Syed Hassan; Rizvi, Mohammed Moshahid Alam; Panda, Amulya Kumar; Talegaonkar, Sushama; Ahmad, Farhan Jalees

2016-10-20

Chondroitin-4-sulfate (CS), a glycosaminoglycan, was used to prepare CS-capped super-paramagnetic iron oxide nanoparticles, which were further employed for loading a water-soluble chemotherapeutic agent (doxorubicin hydrochloride, DOX). CS-capped SPIONs have potential biomedical application in cancer targeting. The optimized formulation had a hydrodynamic size of 91.2±0.8nm (PDI; 0.228±0.004) and zeta potential of -49.1±1.66mV. DOX was loaded onto the formulation up to 2% (w/w) by physical interaction with CS. TEM showed nano-sized particles having a core-shell structure. XRD confirmed crystal phase of iron oxide. FT-IR conceived the interaction of iron oxide with CS as bidentate chelation and also confirmed DOX loading. Vibration sample magnetometry confirmed super-paramagnetic nature of nanoparticles, with saturation magnetization of 0.238emug(-1). In vitro release profile at pH 7.4 showed that 96.67% of DOX was released within 24h (first order kinetics). MTT assay in MCF7 cells showed significantly higher (p<0.0001) cytotoxicity for DOX in SPIONs than DOX solution (IC50 values 6.294±0.4169 and 11.316±0.1102μgmL(-1), respectively). Copyright © 2016 Elsevier Ltd. All rights reserved.

Structural evolution of Pd-doped nanoscale zero-valent iron (nZVI) in aqueous media and implications for particle aging and reactivity.

PubMed

Yan, Weile; Herzing, Andrew A; Li, Xiao-qin; Kiely, Christopher J; Zhang, Wei-xian

2010-06-01

Palladized zero-valent iron nanoparticles have been frequently employed to achieve enhanced treatment of halogenated organic compounds; however, no detailed study has been published on their structures, especially the location and distribution of palladium within the nanoparticles. In this work, the structural evolution of palladized nanoscale iron particles (Pd-nZVI, with 1.5 wt % Pd) was examined using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and X-ray energy dispersive spectroscopy (XEDS) techniques. The STEM-XEDS technique enables direct visualization of the nanoscale structural and compositional changes of the bimetallic particles. For a freshly made Pd-nZVI sample, the particles consist of a metallic iron core and a thin amorphous oxide shell, and Pd is observed to form 2-5 nm islands decorating the outer surface of the nanoparticles. Upon exposure to water, Pd-nZVI undergoes substantial morphological and structural changes. STEM-XEDS elemental maps show that Pd infiltrates through the oxide layer to the metallic iron interface, which is accompanied by oxidation and outward diffusion of the iron species. Within a 24 h period, Pd is completely buried underneath an extensive iron oxide matrix, and a fraction of the nanoparticles exhibits a hollowed-out morphology with no metallic iron remaining. The microstructural variations observed concur with the reactivity data, which shows that the aged bimetallic particles display an 80% decrease in dechlorination rate of trichloroethene (TCE) compared to that of the fresh particles. These findings shed new light on the function of palladium in hydrodechlorination reactions, nZVI aging and deactivation, and the longevity of Pd-nZVI nanoparticles for in situ remediation.

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 towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.

Significance of surface charge and shell material of superparamagnetic iron oxide nanoparticle (SPION) based core/shell nanoparticles on the composition of the protein corona.

PubMed

Sakulkhu, Usawadee; Mahmoudi, Morteza; Maurizi, Lionel; Coullerez, Geraldine; Hofmann-Amtenbrink, Margarethe; Vries, Marcel; Motazacker, Mahdi; Rezaee, Farhad; Hofmann, Heinrich

2015-02-01

As nanoparticles (NPs) are increasingly used in many applications their safety and efficient applications in nanomedicine have become concerns. Protein coronas on nanomaterials' surfaces can influence how the cell "recognizes" nanoparticles, as well as the in vitro and in vivo NPs' behaviors. The SuperParamagnetic Iron Oxide Nanoparticle (SPION) is one of the most prominent agents because of its superparamagnetic properties, which is useful for separation applications. To mimic surface properties of different types of NPs, a core-shell SPION library was prepared by coating with different surfaces: polyvinyl alcohol polymer (PVA) (positive, neutral and negative), SiO2 (positive and negative), titanium dioxide and metal gold. The SPIONs with different surfaces were incubated at a fixed serum : nanoparticle surface ratio, magnetically trapped and washed. The tightly bound proteins were quantified and identified. The surface charge has a great impact on protein adsorption, especially on PVA and silica where proteins preferred binding to the neutral and positively charged surfaces. The importance of surface material on protein adsorption was also revealed by preferential binding on TiO2 and gold coated SPION, even negatively charged. There is no correlation between the protein net charge and the nanoparticle surface charge on protein binding, nor direct correlation between the serum proteins' concentration and the proteins detected in the coronas.

Fabrication of core-shell Fe{sub 3}O{sub 4}@MIL-100(Fe) magnetic microspheres for the removal of Cr(VI) in aqueous solution

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

Yang, Qingxiang, E-mail: qxyangzz@163.com; Zhao, Qianqian; Ren, ShuangShuang

Facile regeneration of an adsorbent is very important for commercial feasibility. One typical highly porous metal-organic framework (MOF) materials based on MIL-100(Fe) and magnetic iron oxide particles (denoted as MMCs) with diameter about of 350 nm were successfully synthesized. The growth of MIL-100(Fe) shell on the surface of Fe{sub 3}O{sub 4} was utilized precursor as crystal seed via in-situ step hydrothermal reaction. It is a simple way to obtain well organized core-shell MOF composites, compared to the step-by-step method. MMCs were firstly used to uptake of Cr(VI) anions in aqueous solution. Adsorption experiments were carried out in batch sorption mode investigatingmore » with the factors of contact time (0–1000 min), pH (from 2 to 12), dose of adsorbent (4–25 mg), and initial Cr(VI) concentration (range from 10 to 100 ppm). - Graphical abstract: One typical highly porous metal-organic framework (MOF) materials based on MIL-100(Fe) and magnetic iron oxide particles (denoted as MMCs) were successfully synthesized. Utilizing Fe{sub 3}O{sub 4} precursor as crystal seed to grow MIL-100(Fe) shell by in-situ step hydrothermal reaction. It is a simple way to obtain core-shell MOF composites. MMCs could effectively uptake of Cr(VI) anions in aqueous solution. - Highlights: • Fe{sub 3}O{sub 4}@MIL-100(Fe) composites with core-shell structure were successfully prepared through a simple method. • The influence factors on Cr(VI) adsorption by Fe{sub 3}O{sub 4}@MIL-100(Fe) were investigated. • Cr(VI) can efficiently adsorbed by Fe{sub 3}O{sub 4}@MIL-100(Fe) composites from aqueous solution.« less

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

PubMed

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

2013-04-02

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

Nanotechnology and the Environment: Report of a National Nanotechnology Initiative Workshop Held in Arlington, Virginia on 8-9 May 2003

DTIC Science & Technology

2007-01-01

cover: Image shows an artist’s rendition of the core-shell structure of metal- oxide -coated palladium- doped zero-valent iron nanoparticles for catalytic...demonstrated the creation of functionalized gold nanoparticles (see figure c) without the need for many of the toxic solvents (e.g., diborane...Size-selected nanoparticle chemistry: Kinetics of soot oxidation , J. Phys. Chem. A 106, 96–103 (2002). 6. H. J. Tobias, D. E. Beving, P. J. Ziemann, H

Lysosomal degradation of the carboxydextran shell of coated superparamagnetic iron oxide nanoparticles and the fate of professional phagocytes.

PubMed

Lunov, Oleg; Syrovets, Tatiana; Röcker, Carlheinz; Tron, Kyrylo; Nienhaus, G Ulrich; Rasche, Volker; Mailänder, Volker; Landfester, Katharina; Simmet, Thomas

2010-12-01

Contrast agents based on dextran-coated superparamagnetic iron oxide nanoparticles (SPIO) are internalized by professional phagocytes such as hepatic Kupffer cells, yet their role in phagocyte biology remains largely unknown. Here we investigated the effects of the SPIO ferucarbotran on murine Kupffer cells and human macrophages. Intravenous injection of ferucarbotran into mice led to rapid accumulation of the particles in phagocytes and to long-lasting increased iron deposition in liver and kidneys. Macrophages incorporate ferucarbotran in lysosomal vesicles containing α-glucosidase, which is capable of degrading the carboxydextran shell of the ferucarbotran particles. Intravenous injection of ferucarbotran into mice followed by incorporation of the nanoparticles into Kupffer cells triggered apoptosis and the subsequent depletion of Kupffer cells. In macrophages, the proinflammatory cytokine TNF-α increased the apoptosis rate, the reactive oxygen species production and the activation of c-Jun N-terminal kinase elicited by ferucarbotran, which might be mediated by the induction of cytoplasmic phospholipase A2 by TNF-α. Notably, the nanoparticle-induced apoptosis of murine Kupffer cells could be prevented by treatment of the mice with the radical scavenger edaravone. Thus, nanosized carboxydextran-coated SPIO-based contrast agents are retained for extended time periods by liver macrophages, where they elicit delayed cell death, which can be antagonized by a therapeutic radical scavenger. Copyright © 2010 Elsevier Ltd. All rights reserved.

Human L-ferritin deficiency is characterized by idiopathic generalized seizures and atypical restless leg syndrome

PubMed Central

Cozzi, Anna; Santambrogio, Paolo; Privitera, Daniela; Broccoli, Vania; Rotundo, Luisa Ida; Garavaglia, Barbara; Benz, Rudolf; Altamura, Sandro; Goede, Jeroen S.; Muckenthaler, Martina U.

2013-01-01

The ubiquitously expressed iron storage protein ferritin plays a central role in maintaining cellular iron homeostasis. Cytosolic ferritins are composed of heavy (H) and light (L) subunits that co-assemble into a hollow spherical shell with an internal cavity where iron is stored. The ferroxidase activity of the ferritin H chain is critical to store iron in its Fe3+ oxidation state, while the L chain shows iron nucleation properties. We describe a unique case of a 23-yr-old female patient affected by a homozygous loss of function mutation in the L-ferritin gene, idiopathic generalized seizures, and atypical restless leg syndrome (RLS). We show that L chain ferritin is undetectable in primary fibroblasts from the patient, and thus ferritin consists only of H chains. Increased iron incorporation into the FtH homopolymer leads to reduced cellular iron availability, diminished levels of cytosolic catalase, SOD1 protein levels, enhanced ROS production and higher levels of oxidized proteins. Importantly, key phenotypic features observed in fibroblasts are also mirrored in reprogrammed neurons from the patient’s fibroblasts. Our results demonstrate for the first time the pathophysiological consequences of L-ferritin deficiency in a human and help to define the concept for a new disease entity hallmarked by idiopathic generalized seizure and atypical RLS. PMID:23940258

Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

NASA Technical Reports Server (NTRS)

Lowery, Thomas J., Jr.; Bunker, Jared; Zhang, Bo; Costen, Robert; Watt, Gerald D.

2004-01-01

The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

Effect of chaotropes on the kinetics of iron release from ferritin by flavin nucleotides.

PubMed

Johnson, Lindsay E; Wilkinson, Tyler; Arosio, Paolo; Melman, Artem; Bou-Abdallah, Fadi

2017-12-01

Ferritins are ubiquitous multi-subunit iron storage and detoxification proteins that play a critical role in iron homeostasis. Ferrous ions that enter the protein's shell through hydrophilic channels are rapidly oxidized at dinuclear centers on the H-subunit before transfer to the protein's cavity for storage. The mechanisms of iron loading have been extensively studied, but little is known about iron mobilization. Fe(III) reduction can occur via rapid reduction by suitable reducing agents followed by chelation of Fe(II) ions or via direct and slow Fe(III) chelation. Here, the iron release kinetics from ferritin by FMNH 2 in the presence of various chaotropic agents are studied and their in-vivo physiological significance discussed. The iron release kinetics from horse and human ferritins by FMNH 2 were monitored at 522nm where the Fe(II)-bipyridine complex absorbs. The experiments were performed in the presence of different concentrations of three chaotropic agents, urea, guanidine HCl, and triton. Under our experimental conditions, iron reductive mobilization by the non-enzymatic FMN/NAD(P)H system is limited by the concentration of FMNH 2 and is independent on the type or amount of chaotropes present. Diffusion of FMNH 2 through the ferritin pores is an unlikely mechanism for ferritin iron reduction. An iron mobilization mechanism involving rapid electron transfer through the protein shell is discussed. Caution must be exercised when interpreting the kinetics of iron mobilization from ferritin using the FMN/NAD(P)H system. The kinetics are highly dependent on the amount of dissolved oxygen and the concentration of reagents used. Copyright © 2017 Elsevier B.V. All rights reserved.

Enhanced Oxidative and Adsorptive Removal of Diclofenac in Heterogeneous Fenton-like Reaction with Sulfide Modified Nanoscale Zerovalent Iron.

PubMed

Su, Yiming; Jassby, David; Song, Shikun; Zhou, Xuefei; Zhao, Hongying; Filip, Jan; Petala, Eleni; Zhang, Yalei

2018-06-05

Sulfidation of nanoscale zerovalent iron (nZVI) has shown some fundamental improvements on reactivity and selectivity toward pollutants in dissolved-oxygen (DO)-stimulated Fenton-like reaction systems (DO/S-nZVI system). However, the pristine microstructure of sulfide-modified nanoscale zerovalent iron (S-nZVI) remains uncovered. In addition, the relationship between pollutant removal and the oxidation of the S-nZVI is largely unknown. The present study confirms that sulfidation not only imparts sulfide and sulfate groups onto the surface of the nanoparticle (both on the oxide shell and on flake-like structures) but also introduces sulfur into the Fe(0) core region. Sulfidation greatly inhibits the four-electron transfer pathway between Fe(0) and oxygen but facilitates the electron transfer from Fe(0) to surface-bound Fe(III) and consecutive single-electron transfer for the generation of H 2 O 2 and hydroxyl radical. In the DO/S-nZVI system, slight sulfidation (S/Fe molar ratio = 0.1) is able to nearly double the oxidative removal efficacy of diclofenac (DCF) (from 17.8 to 34.2%), whereas moderate degree of sulfidation (S/Fe molar ratio = 0.3) significantly enhances both oxidation and adsorption of DCF. Furthermore, on the basis of the oxidation model of S-nZVI, the DCF removal process can be divided into two steps, which are well modeled by parabolic and logarithmic law separately. This study bridges the knowledge gap between pollutant removal and the oxidation process of chemically modified iron-based nanomaterials.

Evolution of nanoscale zero-valent iron (nZVI) in water: Microscopic and spectroscopic evidence on the formation of nano- and micro-structured iron oxides.

PubMed

Liu, Airong; Liu, Jing; Han, Jinhao; Zhang, Wei-Xian

2017-01-15

Knowledge on the transformation of nanoscale zero-valent iron (nZVI) in water is essential to predict its surface chemistry including surface charge, colloidal stability and aggregation, reduction and sorption of organic contaminants, heavy metal ions and other pollutants in the environment. In this work, transmission electronic microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy are applied to study the compositional and structural evolution of nZVI under oxic and anoxic conditions. Under anoxic conditions, the core-shell structure of nZVI is well maintained even after 72h, and the corrosion products usually contain a mixture of wustite (FeO), goethite (α-FeOOH) and akaganeite (β-FeOOH). Under oxic conditions, the core-shell structure quickly collapses to flakes or acicular-shaped structures with crystalline lepidocrocite (γ-FeOOH) as the primary end product. This work provides detailed information and fills an important knowledge gap on the physicochemical characteristics and structural evolution of engineered nanomaterials in the environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Trace Uranium Partitioning in a Multiphase Nano-FeOOH System.

PubMed

McBriarty, Martin E; Soltis, Jennifer A; Kerisit, Sebastien; Qafoku, Odeta; Bowden, Mark E; Bylaska, Eric J; De Yoreo, James J; Ilton, Eugene S

2017-05-02

The characterization of trace elements in minerals using extended X-ray absorption fine structure (EXAFS) spectroscopy constitutes a first step toward understanding how impurities and contaminants interact with the host phase and the environment. However, limitations to EXAFS interpretation complicate the analysis of trace concentrations of impurities that are distributed across multiple phases in a heterogeneous system. Ab initio molecular dynamics (AIMD)-informed EXAFS analysis was employed to investigate the immobilization of trace uranium associated with nanophase iron (oxyhydr)oxides, a model system for the geochemical sequestration of radiotoxic actinides. The reductive transformation of ferrihydrite [Fe(OH) 3 ] to nanoparticulate iron oxyhydroxide minerals in the presence of uranyl (UO 2 ) 2+ (aq) resulted in the preferential incorporation of U into goethite (α-FeOOH) over lepidocrocite (γ-FeOOH), even though reaction conditions favored the formation of excess lepidocrocite. This unexpected result is supported by atomically resolved transmission electron microscopy. We demonstrate how AIMD-informed EXAFS analysis lifts the strict statistical limitations and uncertainty of traditional shell-by-shell EXAFS fitting, enabling the detailed characterization of the local bonding environment, charge compensation mechanisms, and oxidation states of polyvalent impurities in complex multiphase mineral systems.

Trace Uranium Partitioning in a Multiphase Nano-FeOOH System

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

McBriarty, Martin E.; Soltis, Jennifer A.; Kerisit, Sebastien

The characterization of trace elements in minerals using extended X-ray absorption fine structure (EXAFS) spectroscopy constitutes a first step toward understanding how impurities and contaminants interact with the host phase and the environment. However, limitations to EXAFS interpretation complicate the analysis of trace concentrations of impurities that are distributed across multiple phases in a heterogeneous system. Ab initio molecular dynamics (AIMD)-informed EXAFS analysis was employed to investigate the immobilization of trace uranium associated with nanophase iron (oxyhydr)oxides, a model system for the geochemical sequestration of radiotoxic actinides. The reductive transformation of ferrihydrite [Fe(OH)3] to nanoparticulate iron oxyhydroxide minerals in themore » presence of uranyl (UO 2) 2+(aq) resulted in the preferential incorporation of U into goethite (α-FeOOH) over lepidocrocite (γ-FeOOH), even though reaction conditions favored the formation of excess lepidocrocite. This unexpected result is supported by atomically resolved transmission electron microscopy. We demonstrate how AIMD-informed EXAFS analysis lifts the strict statistical limitations and uncertainty of traditional shell-by-shell EXAFS fitting, enabling the detailed characterization of the local bonding environment, charge compensation mechanisms, and oxidation states of polyvalent impurities in complex multiphase mineral systems.« less

Trace Uranium Partitioning in a Multiphase Nano-FeOOH System

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

McBriarty, Martin E.; Soltis, Jennifer A.; Kerisit, Sebastien

The characterization of trace elements in nanomaterials using extended X-ray absorption fine structure (EXAFS) spectroscopy constitutes a first step toward understanding how impurities or dopants affect the properties of the host phase. However, limitations to EXAFS interpretation complicate the analysis of trace concentrations of impurities that are distributed across multiple phases in a heterogeneous system. Ab initio molecular dynamics (AIMD)-informed EXAFS analysis was employed to investigate the immobilization of trace uranium associated with nanophase iron (oxyhydr)oxides, a model system for the geochemical sequestration of radiotoxic contaminants. The reductive transformation of ferrihydrite (Fe(OH)3) to nano-particulate iron oxyhydroxide minerals in the presencemore » of uranyl (UO2)2+(aq) resulted in the preferential incorporation of U into goethite (a-FeOOH) over lepidocrocite (g-FeOOH), even though reaction conditions favored the formation of excess lepidocrocite. This unexpected result is supported by atomically resolved transmission electron microscopy. Using this model system, we demonstrate how AIMD-informed EXAFS analysis lifts the strict statistical limitations of traditional shell-by-shell EXAFS modeling, enabling the detailed analysis of the local bonding environment, charge compensation mechanisms, and oxidation states of polyvalent impurities in complex multi-phase nano-systems.« less

Robust surface coating for a fast, facile fluorine-18 labeling of iron oxide nanoparticles for PET/MR dual-modality imaging

DOE PAGES

Sun, Ziyan; Cheng, Kai; Wu, Fengyu; ...

2016-10-31

Grafting a robust organic shell around inorganic nanoparticles can optimize their colloidal features to dramatically improve their physicochemical properties. Here, we have developed a polymer coating procedure for providing colloidal stability to the nanoparticles and, more importantly, for applying a fast, facile fluorine-18 labeling of iron oxide nanoparticles (IONPs) for positron emission tomography (PET)/magnetic resonance (MR) dual-modality imaging. The structure of the amphiphilic polymer is based on a backbone of polyacrylic acid, conjugated with multiple oleylamines to form a comb-like branched structure. The dense polymer shell provides high colloidal stability to the IONPs against harsh conditions such as high temperature,more » low pH value, and high ion strength. By incorporating a 1,4,7-triazacyclononane (NOTA) chelator to the comb-like amphiphilic polymer for the chelation of aluminum fluoride ions, we applied a one-step radiolabeling approach for a fast, facile radiofluorination of magnetic nanoparticles. The new strategy can significantly reduce the procedure time and radiation exposure. In conclusion, the PET/MR dual modality imaging was successfully achieved in living subjects by using 18F labeled magnetic nanoparticles.« less

Robust surface coating for a fast, facile fluorine-18 labeling of iron oxide nanoparticles for PET/MR dual-modality imaging

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

Sun, Ziyan; Cheng, Kai; Wu, Fengyu

Grafting a robust organic shell around inorganic nanoparticles can optimize their colloidal features to dramatically improve their physicochemical properties. Here, we have developed a polymer coating procedure for providing colloidal stability to the nanoparticles and, more importantly, for applying a fast, facile fluorine-18 labeling of iron oxide nanoparticles (IONPs) for positron emission tomography (PET)/magnetic resonance (MR) dual-modality imaging. The structure of the amphiphilic polymer is based on a backbone of polyacrylic acid, conjugated with multiple oleylamines to form a comb-like branched structure. The dense polymer shell provides high colloidal stability to the IONPs against harsh conditions such as high temperature,more » low pH value, and high ion strength. By incorporating a 1,4,7-triazacyclononane (NOTA) chelator to the comb-like amphiphilic polymer for the chelation of aluminum fluoride ions, we applied a one-step radiolabeling approach for a fast, facile radiofluorination of magnetic nanoparticles. The new strategy can significantly reduce the procedure time and radiation exposure. In conclusion, the PET/MR dual modality imaging was successfully achieved in living subjects by using 18F labeled magnetic nanoparticles.« less

Stability of polyelectrolyte-coated iron nanoparticles for T2-weighted magnetic resonance imaging

NASA Astrophysics Data System (ADS)

McGrath, Andrew J.; Dolan, Ciaran; Cheong, Soshan; Herman, David A. J.; Naysmith, Briar; Zong, Fangrong; Galvosas, Petrik; Farrand, Kathryn J.; Hermans, Ian F.; Brimble, Margaret; Williams, David E.; Jin, Jianyong; Tilley, Richard D.

2017-10-01

Iron nanoparticles are highly-effective magnetic nanoparticles for T2 magnetic resonance imaging (MRI). However, the stability of their magnetic properties is dependent on good protection of the iron core from oxidation in aqueous media. Here we report the synthesis of custom-synthesized phosphonate-grafted polyelectrolytes (PolyM3) of various chain lengths, for efficient coating of iron nanoparticles with a native iron oxide shell. The size of the nanoparticle-polyelectrolyte assemblies was investigated by transmission electron microscopy and dynamic light scattering, while surface attachment was confirmed by Fourier transform infrared spectroscopy. Low cytotoxicity was observed for each of the nanoparticle-polyelectrolyte ("Fe-PolyM3") assemblies, with good cell viability (>80%) remaining up to 100 μg mL-1 Fe in HeLa cells. When applied in T2-weighted MRI, corresponding T2 relaxivities (r2) of the Fe-PolyM3 assemblies were found to be dependent on the chain length of the polyelectrolyte. A significant increase in contrast was observed when polyelectrolyte chain length was increased from 6 to 65 repeating units, implying a critical chain length required for stabilization of the α-Fe nanoparticle core.

Plant Ferritin—A Source of Iron to Prevent Its Deficiency

PubMed Central

Zielińska-Dawidziak, Magdalena

2015-01-01

Iron deficiency anemia affects a significant part of the human population. Due to the unique properties of plant ferritin, food enrichment with ferritin iron seems to be a promising strategy to prevent this malnutrition problem. This protein captures huge amounts of iron ions inside the apoferritin shell and isolates them from the environment. Thus, this iron form does not induce oxidative change in food and reduces the risk of gastric problems in consumers. Bioavailability of ferritin in human and animal studies is high and the mechanism of absorption via endocytosis has been confirmed in cultured cells. Legume seeds are a traditional source of plant ferritin. However, even if the percentage of ferritin iron in these seeds is high, its concentration is not sufficient for food fortification. Thus, edible plants have been biofortified in iron for many years. Plants overexpressing ferritin may find applications in the development of bioactive food. A crucial achievement would be to develop technologies warranting stability of ferritin in food and the digestive tract. PMID:25685985

Band gap variations in ferritin-templated nanocrystals

NASA Astrophysics Data System (ADS)

Colton, John; Erickson, Stephen; Smith, Trevor; Watt, Richard

2014-03-01

Ferritin is a 12 nm diameter protein shell with an 8 nm ``cage'' inside that can be used as a template for nanoparticle formation. The native particle is an iron oxide, ferrihydrite, but can be altered or replaced. We have used optical absorption spectroscopy to study the band gap of the ferrihydrite nanoparticles as they age (and become more crystalline), and as they respond to surface interactions with ions in solution. We will also present results of particle composition variations due to incorporation of oxo-anions into the interior of the nanoparticles and substitution of iron with other metals such as cobalt and manganese.

Effect of sulfate on the transformation of corrosion scale composition and bacterial community in cast iron water distribution pipes.

PubMed

Yang, Fan; Shi, Baoyou; Bai, Yaohui; Sun, Huifang; Lytle, Darren A; Wang, Dongsheng

2014-08-01

The chemical stability of iron corrosion scales and the microbial community of biofilm in drinking water distribution system (DWDS) can have great impact on the iron corrosion and corrosion product release, which may result in "red water" issues, particularly under the situation of source water switch. In this work, experimental pipe loops were set up to investigate the effect of sulfate on the dynamical transformation characteristics of iron corrosion products and bacterial community in old cast iron distribution pipes. All the test pipes were excavated from existing DWDS with different source water supply histories, and the test water sulfate concentration was in the range of 50-350 mg/L. Pyrosequencing of 16S rRNA was used for bacterial community analysis. The results showed that iron release increased markedly and even "red water" occurred for pipes with groundwater supply history when feed water sulfate elevated abruptly. However, the iron release of pipes with only surface water supply history changed slightly without noticeable color even the feed water sulfate increased multiply. The thick-layered corrosion scales (or densely distributed tubercles) on pipes with surface water supply history possessed much higher stability due to the larger proportion of stable constituents (mainly Fe3O4) in their top shell layer; instead, the rather thin and uniform non-layered corrosion scales on pipes with groundwater supply history contained relatively higher proportion of less stable iron oxides (e.g. β-FeOOH, FeCO3 and green rust). The less stable corrosion scales tended to be more stable with sulfate increase, which was evidenced by the gradually decreased iron release and the increased stable iron oxides. Bacterial community analysis indicated that when switching to high sulfate water, iron reducing bacteria (IRB) maintained dominant for pipes with stable corrosion scales, while significant increase of sulfur oxidizing bacteria (SOB), sulfate reducing bacteria (SRB) and iron oxidizing bacteria (IOB) was observed for pipes with less stable corrosion scales. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chemical and Colloidal Stability of Carboxylated Core-Shell Magnetite Nanoparticles Designed for Biomedical Applications

PubMed Central

Szekeres, Márta; Tóth, Ildikó Y.; Illés, Erzsébet; Hajdú, Angéla; Zupkó, István; Farkas, Katalin; Oszlánczi, Gábor; Tiszlavicz, László; Tombácz, Etelka

2013-01-01

Despite the large efforts to prepare super paramagnetic iron oxide nanoparticles (MNPs) for biomedical applications, the number of FDA or EMA approved formulations is few. It is not known commonly that the approved formulations in many instances have already been withdrawn or discontinued by the producers; at present, hardly any approved formulations are produced and marketed. Literature survey reveals that there is a lack for a commonly accepted physicochemical practice in designing and qualifying formulations before they enter in vitro and in vivo biological testing. Such a standard procedure would exclude inadequate formulations from clinical trials thus improving their outcome. Here we present a straightforward route to assess eligibility of carboxylated MNPs for biomedical tests applied for a series of our core-shell products, i.e., citric acid, gallic acid, poly(acrylic acid) and poly(acrylic acid-co-maleic acid) coated MNPs. The discussion is based on physicochemical studies (carboxylate adsorption/desorption, FTIR-ATR, iron dissolution, zeta potential, particle size, coagulation kinetics and magnetization measurements) and involves in vitro and in vivo tests. Our procedure can serve as an example to construct adequate physico-chemical selection strategies for preparation of other types of core-shell nanoparticles as well. PMID:23857054

Colloidal titania-silica-iron oxide nanocomposites and the effect from silica thickness on the photocatalytic and bactericidal activities

NASA Astrophysics Data System (ADS)

Chanhom, Padtaraporn; Charoenlap, Nisanart; Tomapatanaget, Boosayarat; Insin, Numpon

2017-04-01

New types of colloidal multifunctional nanocomposites that combine superparamagnetic character and high photocatalytic activity were synthesized and investigated. The superparamagnetic nanocomposites composed of anatase titania, silica, and iron oxide nanoparticles (TSI) were synthesized using thermal decomposition method followed by microemulsion method, without calcination at high temperature. Different techniques including X-ray diffraction (XRD) and transmission electron microscope (TEM) were used to characterize and confirm the structure of the nanocomposites. These nanocomposites showed high photocatalytic activity when used in the photodegradation of methylene blue under irradiation with a black light lamp. Moreover, the nanocomposites exhibited high antibacterial properties. From our study, the nanocomposites can be useful in various applications such as removal of pollutants with readily separation from the environment using an external magnetic field. These composites could effectively photo-degrade the dye at least three cycles without regeneration. The effects of silica shell thickness on the photocatalytic activity was investigated, and the thickness of 6 nm of the silica interlayer is enough for the inhibition of electron translocation between titania and iron oxide nanoparticles and maintaining the efficiency of photocatalytic activity of titania nanoparticles.

Plasmonic and Magnetically Responsive Gold ShellMagnetic Nanorod Hybrids

DTIC Science & Technology

2017-10-10

is unlimited. 13. SUPPLEMENTARY NOTES 14. ABSTRACT In this work we demonstrated a new methodology to create asymmetric magnetic nanorods with a...Through this work, methodologies are developed to create asymmetric nanorod morphologies composed of an iron (II, III) oxide (Fe3O4) magnetic core with a...shape are preserved throughout the process. 4. Conclusions In this work we demonstrated a new methodology to create asymmetric magnetic nanorods

Synthesis, Characterization, and Preliminary Investigation of Cell Interaction of Magnetic Nanoparticles with Catechol-Containing Shells

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

Wagner, Kerstin; Seemann, Thomas; Wyrwa, Ralf

2010-12-02

Superparamagnetic iron oxide cores were synthesized by co-precipitation of Fe(II) and Fe(III) salts and subsequently stabilized by coating with different catechols (levodopa, dopamine, hydrocaffeic acid, dopamine-containing carboxymethyl dextran) known to act as high-affinity, bidentate ligands for Fe(III). The prepared stable magnetic fluids were characterized with regard to their chemical composition (content of iron and shell material, Fe(II)/Fe(III) ratio) and their physical properties (size, surface charge, magnetic parameters). The nanoparticles showed no or only slight cytotoxic effects within 1 and 4 days of incubation with 3T3 fibroblast cells. Preliminary experiments were performed to study the interaction of the prepared nanoparticles withmore » human MCF-7 breast cancer cells and leukocytes. An intense interaction of the MCF-7 cells with these particles was found whereas the leukocytes showed a lower tendency of interaction. Based on these finding, the novel magnetic nanoparticles possess the potential for use in depletion of tumor cells from peripheral blood.« less

Application of shell elements in simulation of cans ironing

NASA Astrophysics Data System (ADS)

Andrianov, A. V.; Erisov, Y. A.; Aryshensky, E. V.; Aryshensky, V. Y.

2017-01-01

In the present study, the special shell finite elements are used to simulate the drawing with high ironing ratio of aluminum beverage cans. These elements are implemented in commercial software complex PAM-STAMP 2G by means of T.T.S. normal stress option, which is used for ironing to describe well normal stress. By comparison of simulation and experimental data, it is shown that shell elements with T.T.S. option are capable to provide accurate simulation of deep drawing and ironing. The error of can thickness and height computation agrees with the engineering computation accuracy.

Magnetic properties of iron nanoparticles prepared by exploding wire technique.

PubMed

Alqudami, Abdullah; Annapoorni, S; Lamba, Subhalakshmi; Kothari, P C; Kotnala, R K

2007-06-01

Nanoparticles of iron were prepared in distilled water using very thin iron wires and sheets, by the electro-exploding wire technique. Transmission electron microscopy reveals the size of the nanoparticles to be in the range 10 to 50 nm. However, particles of different sizes can be segregated by using ultrahigh centrifuge. X-ray diffraction studies confirm the presence of the cubic phase of iron. These iron nanoparticles were found to exhibit fluorescence in the visible region in contrast to the normal bulk material. The room temperature hysteresis measurements upto a field of 1.0 tesla were performed on a suspension of iron particles in the solution as well as in the powders obtained by filtration. The hysteresis loops indicate that the particles are superparamagnetic in nature. The saturation magnetizations was approximately 60 emu/gm. As these iron particles are very sensitive to oxygen a coating of non-magnetic iron oxide tends to form around the particles giving it a core-shell structure. The core particle size is estimated theoretically from the magnetization measurements. Suspensions of iron nanoparticles in water have been proposed to be used as an effective decontaminant for ground water.

Thick-shelled, grazer-protected diatoms decouple ocean carbon and silicon cycles in the iron-limited Antarctic Circumpolar Current

PubMed Central

Assmy, Philipp; Smetacek, Victor; Montresor, Marina; Klaas, Christine; Henjes, Joachim; Strass, Volker H.; Arrieta, Jesús M.; Bathmann, Ulrich; Berg, Gry M.; Breitbarth, Eike; Cisewski, Boris; Friedrichs, Lars; Fuchs, Nike; Herndl, Gerhard J.; Jansen, Sandra; Krägefsky, Sören; Latasa, Mikel; Peeken, Ilka; Röttgers, Rüdiger; Scharek, Renate; Schüller, Susanne E.; Steigenberger, Sebastian; Webb, Adrian; Wolf-Gladrow, Dieter

2013-01-01

Diatoms of the iron-replete continental margins and North Atlantic are key exporters of organic carbon. In contrast, diatoms of the iron-limited Antarctic Circumpolar Current sequester silicon, but comparatively little carbon, in the underlying deep ocean and sediments. Because the Southern Ocean is the major hub of oceanic nutrient distribution, selective silicon sequestration there limits diatom blooms elsewhere and consequently the biotic carbon sequestration potential of the entire ocean. We investigated this paradox in an in situ iron fertilization experiment by comparing accumulation and sinking of diatom populations inside and outside the iron-fertilized patch over 5 wk. A bloom comprising various thin- and thick-shelled diatom species developed inside the patch despite the presence of large grazer populations. After the third week, most of the thinner-shelled diatom species underwent mass mortality, formed large, mucous aggregates, and sank out en masse (carbon sinkers). In contrast, thicker-shelled species, in particular Fragilariopsis kerguelensis, persisted in the surface layers, sank mainly empty shells continuously, and reduced silicate concentrations to similar levels both inside and outside the patch (silica sinkers). These patterns imply that thick-shelled, hence grazer-protected, diatom species evolved in response to heavy copepod grazing pressure in the presence of an abundant silicate supply. The ecology of these silica-sinking species decouples silicon and carbon cycles in the iron-limited Southern Ocean, whereas carbon-sinking species, when stimulated by iron fertilization, export more carbon per silicon. Our results suggest that large-scale iron fertilization of the silicate-rich Southern Ocean will not change silicon sequestration but will add carbon to the sinking silica flux. PMID:24248337

Determining the size of nanoparticles in the example of magnetic iron oxide core-shell systems

NASA Astrophysics Data System (ADS)

Jarzębski, Maciej; Kościński, Mikołaj; Białopiotrowicz, Tomasz

2017-08-01

The size of nanoparticles is one of the most important factors for their possible applications. Various techniques for the nanoparticle size characterization are available. In this paper selected techniques will be considered base on the prepared core-shell magnetite nanoparticles. Magnetite is one of the most investigated and developed magnetic material. It shows interesting magnetic properties which can be used for biomedical applications, such as drug delivery, hypothermia and also as a contrast agent. To reduce the toxic effects of Fe3O4, magnetic core was covered by dextran and gelatin. Moreover, the shell was doped by fluorescent dye for confocal microscopy investigation. The main investigation focused on the methods for particles size determination of modified magnetite nanoparticles prepared with different techniques. The size distribution were obtained by nanoparticle tracking analysis, dynamic light scattering and transmission electron microscopy. Furthermore, fluorescent correlation spectroscopy (FCS) and confocal microscopy were used to compare the results for particle size determination of core-shell systems.

Fabrication of Silica-Coated Hollow Carbon Nanospheres Encapsulating Fe3O4 Cluster for Magnetical and MR Imaging Guided NIR Light Triggering Hyperthermia and Ultrasound Imaging.

PubMed

Huang, Yun-Kai; Su, Chia-Hao; Chen, Jiu-Jeng; Chang, Chun-Ting; Tsai, Yu-Hsin; Syu, Sheng-Fu; Tseng, Tsu-Ting; Yeh, Chen-Sheng

2016-06-15

Iron oxide nanoparticles (IONPs)-carbon (C) hybrid zero-dimensional nanostructures normally can be categorized into core-shell and yolk-shell architectures. Although IONP-C is a promising theranostic nanoagent, the in vivo study has surprisingly been less described. In addition, little effort has strived toward the fabrication of yolk-shell compared to the core-shell structures. In this context, we synthesized a yolk-shell type of the silica-coated hollow carbon nanospheres encapsulating IONPs cluster, which can be dispersed in aqueous solution for systemic studies in vivo, via the preparation involving the mixed micellization, polymerization/hollowing, sol-gel (hydration-condensation), and pyrolysis processes. Through a surface modification of the polyethylenimine followed by the sol-gel process, the silica shell coating was able to escape from condensing and sintering courses resulting in aggregation, due to the annealing. Not limited to the well-known functionalities in magnetical targeting and magnetic resonance (MR) imaging for IONP-C hybrid structures, we expanded this yolk-shell NPs as a near-infrared (NIR) light-responsive echogenic nanoagent giving an enhanced ultrasound imaging. Overall, we fabricated the NIR sensitive yolk-shell IONP-C to activate ultrasound imaging and photothermal ablation under magnetically and MR imaging guided therapy.

In vitro biocompatibility study of sub-5 nm silica-coated magnetic iron oxide fluorescent nanoparticles for potential biomedical application.

PubMed

Foglia, Sabrina; Ledda, Mario; Fioretti, Daniela; Iucci, Giovanna; Papi, Massimiliano; Capellini, Giovanni; Lolli, Maria Grazia; Grimaldi, Settimio; Rinaldi, Monica; Lisi, Antonella

2017-04-19

Magnetic iron oxide nanoparticles (IONPs), for their intriguing properties, have attracted a great interest as they can be employed in many different biomedical applications. In this multidisciplinary study, we synthetized and characterized ultrafine 3 nm superparamagnetic water-dispersible nanoparticles. By a facile and inexpensive one-pot approach, nanoparticles were coated with a shell of silica and contemporarily functionalized with fluorescein isothiocyanate (FITC) dye. The obtained sub-5 nm silica-coated magnetic iron oxide fluorescent (sub-5 SIO-Fl) nanoparticles were assayed for cellular uptake, biocompatibility and cytotoxicity in a human colon cancer cellular model. By confocal microscopy analysis we demonstrated that nanoparticles as-synthesized are internalized and do not interfere with the CaCo-2 cell cytoskeletal organization nor with their cellular adhesion. We assessed that they do not exhibit cytotoxicity, providing evidence that they do not affect shape, proliferation, cellular viability, cell cycle distribution and progression. We further demonstrated at molecular level that these nanoparticles do not interfere with the expression of key differentiation markers and do not affect pro-inflammatory cytokines response in Caco-2 cells. Overall, these results showed the in vitro biocompatibility of the sub-5 SIO-Fl nanoparticles promising their safe employ for diagnostic and therapeutic biomedical applications.

SAXS analysis of single- and multi-core iron oxide magnetic nanoparticles

PubMed Central

Szczerba, Wojciech; Costo, Rocio; Morales, Maria del Puerto; Thünemann, Andreas F.

2017-01-01

This article reports on the characterization of four superparamagnetic iron oxide nanoparticles stabilized with dimercaptosuccinic acid, which are suitable candidates for reference materials for magnetic properties. Particles p1 and p2 are single-core particles, while p3 and p4 are multi-core particles. Small-angle X-ray scattering analysis reveals a lognormal type of size distribution for the iron oxide cores of the particles. Their mean radii are 6.9 nm (p1), 10.6 nm (p2), 5.5 nm (p3) and 4.1 nm (p4), with narrow relative distribution widths of 0.08, 0.13, 0.08 and 0.12. The cores are arranged as a clustered network in the form of dense mass fractals with a fractal dimension of 2.9 in the multi-core particles p3 and p4, but the cores are well separated from each other by a protecting organic shell. The radii of gyration of the mass fractals are 48 and 44 nm, and each network contains 117 and 186 primary particles, respectively. The radius distributions of the primary particle were confirmed with transmission electron microscopy. All particles contain purely maghemite, as shown by X-ray absorption fine structure spectroscopy. PMID:28381973

Preparation and characterization of magnetic core-shell iron oxide@glycyrrhizic acid nanoparticles in ethanol-water mixed solvent

NASA Astrophysics Data System (ADS)

Saeedi, Mostafa; Vahidi, Omid

2018-06-01

In this research, we used the co-precipitation method to synthesize glycyrrhizic acid coated iron oxide magnetic nanoparticles. The aim of this study is to investigate how different amounts of glycyrrhizic acid affect the structural, biological, magnetic, and hyperthermic characteristics of the synthesized magnetic nanoparticles. The synthesis was conducted under different glycyrrhizic acid concentrations in water with the presence of ethanol to generate coated nanoparticles with different amounts of coating agent. The characteristics of the synthesized nanoparticles were examined by several devices including X-ray diffractometer, transmission electron microscope, field-emission scanning electron microscope, vibrating sample magnetometer, Fourier transform infrared spectra, and thermal gravimetric analyzer. The cytotoxicity of synthesized nanoparticles was examined by MTT assay using L929 fibroblast cell line. The results indicated the enhanced biocompatibility of the coated iron oxide nanoparticles due to the presence of glycyrrhizic acid. The comparison of the coated samples shows that the samples with higher amounts of coating agent were more biocompatible. The possibility of using the synthesized magnetic nanoparticles for medical hyperthermia was examined by performing hyperthermia process on a nanofluid made up of the nanoparticles dispersed in water using a high-frequency alternating magnetic field generator and the results confirm the effectiveness of the synthesized nanoparticles in the elevation of the solutions temperature.

Passivated iodine pentoxide oxidizer for potential biocidal nanoenergetic applications.

PubMed

Feng, Jingyu; Jian, Guoqiang; Liu, Qing; Zachariah, Michael R

2013-09-25

Iodine pentoxide (I2O5), also known as diiodine pentoxide, is a strong oxidizer which has been recently proposed as an iodine-rich oxidizer in nanoenergetic formulations, whose combustion products lead to molecular iodine as a biocidal agent. However, its highly hygroscopic nature hinders its performance as a strong oxidizer and an iodine releasing agent and prevents its implementation. In this work, we developed a gas phase assisted aerosol spray pyrolysis which enables creation of iron oxide passivated I2O5. Transmission electron microscopy elemental imaging as well as temperature-jump mass spectrometry confirmed the core shell nature of the material and the fact that I2O5 could be encapsulated in pure unhydrated form. Combustion performance finds an optimal coating thickness that enables combustion performance similar to a high performing CuO based thermite.

Inorganic nanofibers with tailored placement of nanocatalysts for hydrogen production via alkaline hydrolysis of glucose.

PubMed

Hansen, Nathaniel S; Ferguson, Thomas E; Panels, Jeanne E; Park, Ah-Hyung Alissa; Joo, Yong Lak

2011-08-12

Monoaxial silica nanofibers containing iron species as well as coaxial nanofibers with a pure silica core and a silica shell containing high concentrations of iron nanocrystals were fabricated via electrospinning precursor solutions, followed by thermal treatment. Tetraethyl-orthosilicate (TEOS) and iron nitrate (Fe(NO(3))(3)) were used as the precursors for the silica and iron phases, respectively. Thermal treatments of as-spun precursor fibers were applied to generate nanocrystals of iron with various oxidation states (pure iron and hematite). Scanning electron microscopy (SEM), x-ray diffraction (XRD), and transmission electron microscopy (TEM) were used to probe the fiber morphology and crystal structures. The results indicated that the size, phase, and placement of iron nanocrystals can be tuned by varying the precursor concentration, thermal treatment conditions, and processing scheme. The resulting nanofiber/metal systems obtained via both monoaxial and coaxial electrospinning were applied as catalysts to the alkaline hydrolysis of glucose for the production of fuel gas. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and bulk weight change in a furnace with residual gas analysis (RGA) were used to evaluate the performance of the catalysts for various ratios of both Fe to Si, and catalyst to glucose, and the oxidation state of the iron nanocrystals. The product gas is composed of mostly H(2) (>96 mol%) and CH(4) with very low concentrations of CO(2) and CO. Due to the clear separation of reaction temperature for H(2) and CH(4) production, pure hydrogen can be obtained at low reaction temperatures. Our coaxial approach demonstrates that placing the iron species selectively near the fiber surface can lead to two to three fold reduction in catalytic consumption compared to the monoaxial fibers with uniform distribution of catalysts.

Development of a lauric acid/albumin hybrid iron oxide nanoparticle system with improved biocompatibility

PubMed Central

Zaloga, Jan; Janko, Christina; Nowak, Johannes; Matuszak, Jasmin; Knaup, Sabine; Eberbeck, Dietmar; Tietze, Rainer; Unterweger, Harald; Friedrich, Ralf P; Duerr, Stephan; Heimke-Brinck, Ralph; Baum, Eva; Cicha, Iwona; Dörje, Frank; Odenbach, Stefan; Lyer, Stefan; Lee, Geoffrey; Alexiou, Christoph

2014-01-01

The promising potential of superparamagnetic iron oxide nanoparticles (SPIONs) in various nanomedical applications has been frequently reported. However, although many different synthesis methods, coatings, and functionalization techniques have been described, not many core-shell SPION drug delivery systems are available for clinicians at the moment. Here, bovine serum albumin was adsorbed onto lauric acid-stabilized SPIONs. The agglomeration behavior, zeta potential, and their dependence on the synthesis conditions were characterized with dynamic light scattering. The existence and composition of the core-shell-matrix structure was investigated by transmission electron microscopy, Fourier transform infrared spectroscopy, and zeta potential measurements. We showed that the iron oxide cores form agglomerates in the range of 80 nm. Moreover, despite their remarkably low tendency to aggregate even in a complex media like whole blood, the SPIONs still maintained their magnetic properties and were well attractable with a magnet. The magnetic properties were quantified by vibrating sample magnetometry and a superconducting quantum interference device. Using flow cytometry, we further investigated the effects of the different types of nanoparticle coating on morphology, viability, and DNA integrity of Jurkat cells. We showed that by addition of bovine serum albumin, the toxicity of nanoparticles is greatly reduced. We also investigated the effect of the particles on the growth of primary human endothelial cells to further demonstrate the biocompatibility of the particles. As proof of principle, we showed that the hybrid-coated particles are able to carry payloads of up to 800 μg/mL of the cytostatic drug mitoxantrone while still staying colloidally stable. The drug-loaded system exhibited excellent therapeutic potential in vitro, exceeding that of free mitoxantrone. In conclusion, we have synthesized a biocompatible ferrofluid that shows great potential for clinical application. The synthesis is straightforward and reproducible and thus easily translatable into a good manufacturing practice environment. PMID:25364244

Anisotropic magnetic field observed at 300 K in citrate-coated iron oxide nanoparticles: effect of counterions

NASA Astrophysics Data System (ADS)

Misra, Sushil K.; Li, Lin; Mukherjee, Sudip; Ghosh, Goutam

2015-12-01

Iron oxide nanoparticles (IONPs) have been synthesized by chemical co-precipitation method and coated with three citrates, namely, tri-lithium citrate (TLC), tri-sodium citrate (TSC), or tri-potassium citrate (TKC). In these `core-shell' structures, the `core' is a cluster of average 3 IONPs which is enveloped by a `shell' of citrate molecules and counterions, and thus called `core-shell' nano-clusters (CS-NCs), of average size 20 to 22 nm. The counterions in the three CS-NCs differ in ionic radii (r_{{ion}}), in the order of Li+ < Na+ < K+. Our aim was to investigate the effect of counterions on magnetic interactions between CS-NCs in different powder samples at 300 K, using vibrating sample magnetometer and electron magnetic resonance (EMR) techniques. The hysteresis loops showed negligible coercivity field ( H c) in all samples. The saturation magnetization ( M S) was the highest for TLC-coated CS-NCs. The blocking temperature ( T B), obtained from zero-field-cooled measurements, was >300 K for TLC-coated CS-NCs and <300 K for TSC- and TKC-coated CS-NCs. The EMR linewidth (∆ B PP), measured at 300 K, was also the broadest for TLC-coated CS-NCs. At low temperatures, Δ B PP was found to increase more significantly for TSC- and TKC-coated CS-NCs than for TLC-coated CS-NCs. These results indicate a significant anisotropic field effect; arising due to thermal motion of counterions at 300 K, on the magnetic interactions in TLC-coated CS-NCs. To our knowledge, this is the first report on the effect of counterions on magnetic interactions between CS-NCs.

Core-shell iron oxide-layered double hydroxide: High electrochemical sensing performance of H2O2 biomarker in live cancer cells with plasma therapeutics.

PubMed

Asif, Muhammad; Liu, Hongwei; Aziz, Ayesha; Wang, Haitao; Wang, Zhengyun; Ajmal, Muhammad; Xiao, Fei; Liu, Hongfang

2017-11-15

In this work, we develop a new type of multifunctional core-shell nanomaterial by controllable integration of CuAl layered double hydroxides (LDHs) over the surface of iron oxides (Fe 3 O 4 ) nanospheres (NSs) to fabricate (Fe 3 O 4 @CuAl NSs) hybrid material with interior tunability of LDH phase and explore its practical application in ultrasensitive detection of emerging biomarker, i.e., H 2 O 2 as cancer diagnostic probe. In addition, atmospheric pressure plasmas (APPs) have also been used as potential therapeutic approach for cancer treatment. Due to the synergistic combination of p-type semiconductive channels of LDHs with multi-functional properties, unique morphology and abundant surface active sites, the Fe 3 O 4 @CuAl NSs modified electrode exhibited attractive electrocatalytic activity towards H 2 O 2 reduction. Under the optimized conditions, the proposed biosensor demonstrated striking electrochemical sensing performances to H 2 O 2 including linear range as broad as 8 orders of magnitude, low real detection limit of 1nM (S/N = 3), high sensitivity, good reproducibility and long-term stability. Arising from the superb efficiency, the electrochemical biosensor has been used for in vitro determination of H 2 O 2 concentrations in human urine and serum samples prior to and following the intake of coffee, and real-time monitoring of H 2 O 2 efflux from different cancer cell lines in normal state and after plasma treatment. We believe that this novel nano-platform of structurally integrated core-shell nanohybrid materials combined with APPs will enhance diagnostic as well as therapeutic window for cancer diseases. Copyright © 2017 Elsevier B.V. All rights reserved.

Magnetoferritin nanoparticles for targeting and visualizing tumour tissues

NASA Astrophysics Data System (ADS)

Fan, Kelong; Cao, Changqian; Pan, Yongxin; Lu, Di; Yang, Dongling; Feng, Jing; Song, Lina; Liang, Minmin; Yan, Xiyun

2012-07-01

Engineered nanoparticles have been used to provide diagnostic, therapeutic and prognostic information about the status of disease. Nanoparticles developed for these purposes are typically modified with targeting ligands (such as antibodies, peptides or small molecules) or contrast agents using complicated processes and expensive reagents. Moreover, this approach can lead to an excess of ligands on the nanoparticle surface, and this causes non-specific binding and aggregation of nanoparticles, which decreases detection sensitivity. Here, we show that magnetoferritin nanoparticles (M-HFn) can be used to target and visualize tumour tissues without the use of any targeting ligands or contrast agents. Iron oxide nanoparticles are encapsulated inside a recombinant human heavy-chain ferritin (HFn) protein shell, which binds to tumour cells that overexpress transferrin receptor 1 (TfR1). The iron oxide core catalyses the oxidation of peroxidase substrates in the presence of hydrogen peroxide to produce a colour reaction that is used to visualize tumour tissues. We examined 474 clinical specimens from patients with nine types of cancer and verified that these nanoparticles can distinguish cancerous cells from normal cells with a sensitivity of 98% and specificity of 95%.

General route for the assembly of functional inorganic capsules.

PubMed

Akartuna, Ilke; Tervoort, Elena; Studart, André R; Gauckler, Ludwig J

2009-11-03

Semipermeable, hollow capsules are attractive materials for the encapsulation and delivery of active agents in food processing, pharmaceutical and agricultural industries, and biomedicine. These capsules can be produced by forming a solid shell of close packed colloidal particles, typically polymeric particles, at the surface of emulsion droplets. However, current methods to prepare such capsules may involve multistep chemical procedures to tailor the surface chemistry of particles or are limited to particles that exhibit inherently the right hydrophobic-hydrophilic balance to adsorb around emulsion droplets. In this work, we describe a general and simple method to fabricate semipermeable, inorganic capsules from emulsion droplets stabilized by a wide variety of colloidal metal oxide particles. The assembly of particles at the oil-water interface is induced by the in situ hydrophobization of the particle surface through the adsorption of short amphiphilic molecules. The adsorption of particles at the interface leads to stable capsules comprising a single layer of particles in the outer shell. Such capsules can be used in the wet state or can be further processed into dry capsules. The permeability of the capsules can be modified by filling the interstices between the shell particles with polymeric or inorganic species. Functional capsules with biocompatible, bioresorbable, heat-resistant, chemical-resistant, and magnetic properties were prepared using alumina, silica, iron oxide, or tricalcium phosphate as particles in the shell.

Microwave absorption properties of the core/shell-type iron and nickel nanoparticles

NASA Astrophysics Data System (ADS)

Lu, B.; Dong, X. L.; Huang, H.; Zhang, X. F.; Zhu, X. G.; Lei, J. P.; Sun, J. P.

Iron (Fe) and nickel (Ni) nanoparticles were prepared by the DC arc-discharge method in a mixture of hydrogen and argon gases, using bulk metals as the raw materials. The microstructure of core/shell (metal/metal oxide) in nanoparticle formed after in situ passivation process. The complex electromagnetic parameters (permittivity ɛ=ɛr'+iɛr″ and permeability μ=μr'+iμr″) of the paraffin-mixed nanocomposite samples (paraffin:nanoparticles=1:1 in mass ratio) were measured in the frequency range of 2-18 GHz. The polarization mechanisms of the space charge and dipole coexist in both the Fe and Ni nanoparticles. The orientational polarization is a particular polarization for Fe nanoparticles and brings a relatively higher dielectric loss. Natural resonance is the main reason for magnetic loss and the corresponding frequencies are 11.6 and 5.2 GHz for the Fe and Ni nanoparticles, respectively. The paraffin composite with Fe nanoparticles provided excellent microwave absorption properties (reflection loss <-20 dB) in the range 6.8-16.6 GHz over the absorber thickness of 1.1-2.3 mm.

Attenuation of Mouse Melanoma by A/C Magnetic Field after Delivery of Bi-Magnetic Nanoparticles by Neural Progenitor Cells

PubMed Central

Rachakatla, Raja Shekar; Balivada, Sivasai; Seo, Gwi-Moon; Myers, Carl B; Wang, Hongwang; Samarakoon, Thilani N.; Dani, Raj; Pyle, Marla; Kroh, Franklin O.; Walker, Brandon; Leaym, Xiaoxuan; Koper, Olga B.; Chikan, Viktor; Bossmann, Stefan H.; Tamura, Masaaki; Troyer, Deryl L.

2010-01-01

Localized magnetic hyperthermia as a treatment modality for cancer has generated renewed interest, particularly if it can be targeted to the tumor site. We examined whether tumor-tropic neural progenitor cells (NPCs) could be utilized as cell delivery vehicles for achieving preferential accumulation of core/shell iron/iron oxide magnetic nanoparticles (MNPs) within a mouse model of melanoma. We developed aminosiloxane-porphyrin functionalized MNPs, evaluated cell viability and loading efficiency, and transplanted neural progenitor cells loaded with this cargo into mice with melanoma. NPCs were efficiently loaded with core/shell Fe/Fe3O4 MNPs with minimal cytotoxicity; the MNPs accumulated as aggregates in the cytosol. The NPCs loaded with MNPs could travel to subcutaneous melanomas, and after A/C (alternating current) magnetic field (AMF) exposure, the targeted delivery of MNPs by the cells resulted in a measurable regression of the tumors. The tumor attenuation was significant (p<0.05) a short time (24 hours) after the last of three AMF exposures. PMID:21058696

Size-dependent cytotoxicity and inflammatory responses of PEGylated silica-iron oxide nanocomposite size series

NASA Astrophysics Data System (ADS)

Injumpa, Wishulada; Ritprajak, Patcharee; Insin, Numpon

2017-04-01

Iron oxides nanoparticles have been utilized in biological systems and biomedical applications for many years because they are relatively safe and stable comparing to other magnetic nanomaterials. In some applications, iron oxide nanoparticles were modified with silica in order to be more stable in biological systems and able to be functionalized with various functional groups. Moreover, poly(ethylene glycol) (PEG) was one on the most used polymer to graft onto the nanoparticles in order to increase their biocompatibility, dispersibility and stability in aqueous solutions. Therefore, the nanocomposites comprising iron oxide nanoparticles, silica, and PEG could become multifunctional carriers combining superparamagnetic character, multi-functionality and high stability in biological environments. Herein, we reported the preparation of the nanocomposites and effects of their sizes on cytotoxicity and inflammatory responses. The PEGylated silica-iron oxide nanocomposites were prepared by coating of poly(poly(ethylene glycol) monomethyl ether methacrylate) (PPEGMA) on magnetic nanoparticle-silica nanocomposites via Atom Transfer Radical Polymerization (ATRP). The iron oxide nanoparticles were synthesized using a thermal decomposition method. The silica shells were then coated on iron oxides nanoparticles using reverse microemulsion and sol-gel methods. The size series of the nanocomposites with the diameter of 24.86±4.38, 45.24±5.00, 98.10±8.88 and 202.22±6.70 nm as measured using TEM were obtained. Thermogravimetric analysis (TGA) was used for the determination of % weight of PPEGMA on the nanocomposites showing the weight loss of ranging from 65% for smallest particles to 30% for largest particles. The various sizes (20, 40, 100, 200 nm) and concentrations (10, 100, 1000 μg/mL) of the nanocomposites were tested for their cytotoxicity in fibroblast and macrophage cell lines using MTT assay. The different sizes did not affect cell viability of fibroblast, albeit incubation with the highest concentration of 1000 μg/mL. Although 1000 μg/mL of all sizes of the nanocomposites decreased macrophage viability, the cytotoxicity of the nanocomposites was notably less than silica. The inflammatory response of macrophage was also observed by ELISA, and we found that the size of 20 and 40 nm, but not 100 and 200 nm, obviously stimulated IL-6 production. From this study, the preparations of multifunctional superparamagnetic nanocomposites of different sizes along with the size-dependent effects on cellular toxicity and inflammatory response were demonstrated and could be applied for designing of new drug carriers.

Hematite ``Blueberry`` Concretion Doublet and Triplets on Mars: Iron Oxide Twin Analogs From Utah

NASA Astrophysics Data System (ADS)

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

2005-12-01

Spherical concretions on Earth and Mars comprise a record of diagenetic history that may not otherwise be preserved in the more common host rock. Hematite spherules of Meridiani Planum show some joined forms of twos and threes. Joined iron oxide concretions making doublets and triplets also occur in the Jurassic Navajo Sandstone of southern Utah, and can serve as an analog to understanding why joined forms occur on Mars. The geometries of in situ Utah examples suggest two processes for creating connected forms. In one concretion growth mechanism, occasional coalescing of single forms may result from the growth of doublets or triplets in overly close proximity (typically less than 15% of a population). Joined concretions of roughly equal sizes can be aligned in a row; unequal size concretions take on the shapes of ``snowmen``, or attached ``satellites``. Where cementation is pervasive, individual concretions may grow and coalesce into a lumpy layer or cemented mass along preferential flow paths or preferential nucleation sites. In the second mechanism, nearly all (more than 75%) of the concretions form doublets that are conjoined. The occurrence of dominant twins indicates that these concretions are not coincidental as in the first mechanism. Dominant twin concretions occur regularly and evenly throughout fairly homogeneous host rock. More unusual twins show additional small twin warts suggesting duplicated nucleation and precipitation. Normally, iron oxide concretion precipitation begins when the oxide saturation reaches a precipitation threshold. Precipitation produces chemical gradients, and competition between reaction and diffusion rates determines the spacing between concretions. These factors in combination with reactant supply, competitive growth phenomena and a complex self-organizing processes may contribute to development of internal structure with varying layers of iron-depleted zones to resistant iron-cemented shells. The pervasive nature of sandstone coloration and iron concretion formation throughout much of the Navajo Sandstone indicates a favorable environment for iron mobilization and precipitation. However, the spectrum of sedimentologic, hydrologic, chemical, and nucleation parameters involved in producing the varying concretion forms shows the potential diagenetic subtleties that may be involved to precipitate similar joined concretion forms on Mars.

On the interplay of shell structure with low- and high-frequency mechanics of multifunctional magnetic microbubbles.

PubMed

Poehlmann, Melanie; Grishenkov, Dmitry; Kothapalli, Satya V V N; Härmark, Johan; Hebert, Hans; Philipp, Alexandra; Hoeller, Roland; Seuss, Maximilian; Kuttner, Christian; Margheritelli, Silvia; Paradossi, Gaio; Fery, Andreas

2014-01-07

Polymer-shelled magnetic microbubbles have great potential as hybrid contrast agents for ultrasound and magnetic resonance imaging. In this work, we studied US/MRI contrast agents based on air-filled poly(vinyl alcohol)-shelled microbubbles combined with superparamagnetic iron oxide nanoparticles (SPIONs). The SPIONs are integrated either physically or chemically into the polymeric shell of the microbubbles (MBs). As a result, two different designs of a hybrid contrast agent are obtained. With the physical approach, SPIONs are embedded inside the polymeric shell and with the chemical approach SPIONs are covalently linked to the shell surface. The structural design of hybrid probes is important, because it strongly determines the contrast agent's response in the considered imaging methods. In particular, we were interested how structural differences affect the shell's mechanical properties, which play a key role for the MBs' US imaging performance. Therefore, we thoroughly characterized the MBs' geometric features and investigated low-frequency mechanics by using atomic force microscopy (AFM) and high-frequency mechanics by using acoustic tests. Thus, we were able to quantify the impact of the used SPIONs integration method on the shell's elastic modulus, shear modulus and shear viscosity. In summary, the suggested approach contributes to an improved understanding of structure-property relations in US-active hybrid contrast agents and thus provides the basis for their sustainable development and optimization.

History of bioavailable lead and iron in the Greater North Sea and Iceland during the last millennium - a bivalve sclerochronological reconstruction.

PubMed

Holland, Hilmar A; Schöne, Bernd R; Marali, Soraya; Jochum, Klaus P

2014-10-15

We present the first annually resolved record of biologically available Pb and Fe in the Greater North Sea and Iceland during 1040-2004 AD based on shells of the long-lived marine bivalve Arctica islandica. The iron content in pre-industrial shells from the North Sea largely remained below the detection limit. Only since 1830, shell Fe levels rose gradually reflecting the combined effect of increased terrestrial runoff of iron-bearing sediments and eutrophication. Although the lead gasoline peak of the 20th century was well recorded by the shells, bivalves that lived during the medieval heyday of metallurgy showed four-fold higher shell Pb levels than modern specimens. Presumably, pre-industrial bivalves were offered larger proportions of resuspended (Pb-enriched) organics, whereas modern specimens receive fresh increased amounts of (Pb-depleted) phytoplankton. As expected, metal loads in the shells from Iceland were much lower. Our study confirms that bivalve shells provide a powerful tool for retrospective environmental biomonitoring. Copyright © 2014 Elsevier Ltd. All rights reserved.

Diblock-copolymer-mediated self-assembly of protein-stabilized iron oxide nanoparticle clusters for magnetic resonance imaging.

PubMed

Tähkä, Sari; Laiho, Ari; Kostiainen, Mauri A

2014-03-03

Superparamagnetic iron oxide nanoparticles (SPIONs) can be used as efficient transverse relaxivity (T2 ) contrast agents in magnetic resonance imaging (MRI). Organizing small (D<10 nm) SPIONs into large assemblies can considerably enhance their relaxivity. However, this assembly process is difficult to control and can easily result in unwanted aggregation and precipitation, which might further lead to lower contrast agent performance. Herein, we present highly stable protein-polymer double-stabilized SPIONs for improving contrast in MRI. We used a cationic-neutral double hydrophilic poly(N-methyl-2-vinyl pyridinium iodide-block-poly(ethylene oxide) diblock copolymer (P2QVP-b-PEO) to mediate the self-assembly of protein-cage-encapsulated iron oxide (γ-Fe2 O3 ) nanoparticles (magnetoferritin) into stable PEO-coated clusters. This approach relies on electrostatic interactions between the cationic N-methyl-2-vinylpyridinium iodide block and magnetoferritin protein cage surface (pI≈4.5) to form a dense core, whereas the neutral ethylene oxide block provides a stabilizing biocompatible shell. Formation of the complexes was studied in aqueous solvent medium with dynamic light scattering (DLS) and cryogenic transmission electron microcopy (cryo-TEM). DLS results indicated that the hydrodynamic diameter (Dh ) of the clusters is approximately 200 nm, and cryo-TEM showed that the clusters have an anisotropic stringlike morphology. MRI studies showed that in the clusters the longitudinal relaxivity (r1 ) is decreased and the transverse relaxivity (r2 ) is increased relative to free magnetoferritin (MF), thus indicating that clusters can provide considerable contrast enhancement. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Can magneto-plasmonic nanohybrids efficiently combine photothermia with magnetic hyperthermia?

PubMed

Espinosa, Ana; Bugnet, Mathieu; Radtke, Guillaume; Neveu, Sophie; Botton, Gianluigi A; Wilhelm, Claire; Abou-Hassan, Ali

2015-12-07

Multifunctional hybrid-design nanomaterials appear to be a promising route to meet the current therapeutics needs required for efficient cancer treatment. Herein, two efficient heat nano-generators were combined into a multifunctional single nanohybrid (a multi-core iron oxide nanoparticle optimized for magnetic hyperthermia, and a gold branched shell with tunable plasmonic properties in the NIR region, for photothermal therapy) which impressively enhanced heat generation, in suspension or in vivo in tumours, opening up exciting new therapeutic perspectives.

Synthesis, Characterization and Reactivity of Nanostructured Zero-Valent Iron Particles for Degradation of Azo Dyes

NASA Astrophysics Data System (ADS)

Mikhailov, Ivan; Levina, Vera; Leybo, Denis; Masov, Vsevolod; Tagirov, Marat; Kuznetsov, Denis

Nanostructured zero-valent iron (NSZVI) particles were synthesized by the method of ferric ion reduction with sodium borohydride with subsequent drying and passivation at room temperature in technical grade nitrogen. The obtained sample was characterized by means of X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and dynamic light scattering studies. The prepared NSZVI particles represent 100-200nm aggregates, which consist of 20-30nm iron nanoparticles in zero-valent oxidation state covered by thin oxide shell. The reactivity of the NSZVI sample, as the removal efficiency of refractory azo dyes, was investigated in this study. Two azo dye compounds, namely, orange G and methyl orange, are commonly detected in waste water of textile production. Experimental variables such as NSZVI dosage, initial dye concentration and solution pH were investigated. The kinetic rates of degradation of both dyes by NSZVI increased with the decrease of solution pH from 10 to 3 and with the increase of NSZVI dosage, but decreased with the increase of initial dye concentration. The removal efficiencies achieved for both orange G and methyl orange were higher than 90% after 80min of treatment.

Macrophage membrane-coated iron oxide nanoparticles for enhanced photothermal tumor therapy

NASA Astrophysics Data System (ADS)

Meng, Qian-Fang; Rao, Lang; Zan, Minghui; Chen, Ming; Yu, Guang-Tao; Wei, Xiaoyun; Wu, Zhuhao; Sun, Yue; Guo, Shi-Shang; Zhao, Xing-Zhong; Wang, Fu-Bing; Liu, Wei

2018-04-01

Nanotechnology possesses the potential to revolutionize the diagnosis and treatment of tumors. The ideal nanoparticles used for in vivo cancer therapy should have long blood circulation times and active cancer targeting. Additionally, they should be harmless and invisible to the immune system. Here, we developed a biomimetic nanoplatform with the above properties for cancer therapy. Macrophage membranes were reconstructed into vesicles and then coated onto magnetic iron oxide nanoparticles (Fe3O4 NPs). Inherited from the Fe3O4 core and the macrophage membrane shell, the resulting Fe3O4@MM NPs exhibited good biocompatibility, immune evasion, cancer targeting and light-to-heat conversion capabilities. Due to the favorable in vitro and in vivo properties, biomimetic Fe3O4@MM NPs were further used for highly effective photothermal therapy of breast cancer in nude mice. Surface modification of synthetic nanomaterials with biomimetic cell membranes exemplifies a novel strategy for designing an ideal nanoplatform for translational medicine.

Exceptionally strong, stiff and hard hybrid material based on an elastomer and isotropically shaped ceramic nanoparticles.

PubMed

Georgopanos, Prokopios; Schneider, Gerold A; Dreyer, Axel; Handge, Ulrich A; Filiz, Volkan; Feld, Artur; Yilmaz, Ezgi D; Krekeler, Tobias; Ritter, Martin; Weller, Horst; Abetz, Volker

2017-08-04

In this work the fabrication of hard, stiff and strong nanocomposites based on polybutadiene and iron oxide nanoparticles is presented. The nanocomposites are fabricated via a general concept for mechanically superior nanocomposites not based on the brick and mortar structure, thus on globular nanoparticles with nanosized organic shells. For the fabrication of the composites oleic acid functionalized iron oxide nanoparticles are decorated via ligand exchange with an α,ω-polybutadiene dicarboxylic acid. The functionalized particles were processed at 145 °C. Since polybutadiene contains double bonds the nanocomposites obtained a crosslinked structure which was enhanced by the presence of oxygen or sulfur. It was found that the crosslinking and filler percolation yields high elastic moduli of approximately 12-20 GPa and hardness of 15-18 GPa, although the polymer volume fraction is up to 40%. We attribute our results to a catalytically enhanced crosslinking reaction of the polymer chains induced by oxygen or sulfur and to the microstructure of the nanocomposite.

Viruslike Nanoparticles with Maghemite Cores Allow for Enhanced MRI Contrast Agents

DOE PAGES

Malyutin, Andrey G.; Easterday, Rosemary; Lozovyy, Yaroslav; ...

2014-12-15

Here, for the first time, we demonstrate formation of virus-like nanoparticles (VNPs) utilizing gold-coated iron oxide nanoparticles as cores and capsidprotein of brome mosaic virus (BMV) or hepatitis B virus (HBV) as shells. Further, utilizing cryo-electron microscopy and single particle methods, we are able to show that the BMV coat on VNPs assembles into a structure very close to that of a native virion. This is a consequence of an optimal iron oxide NP size (~11 nm) fitting the virus cavity and an ultrathin gold layer on the maghemite cores, which allows for utilization of SH-(CH 2) 11-(CH 2-CH 2-O)more » 4-OCH 2-COOH as capping molecules to provide sufficient stability, charge density, and small form factor. MRI studies show unique relaxivity ratios that diminish only slightly with gold coating. In conclusion, a virus protein coating of a magnetic core mimicking the wild-type virus makes these VNPs a versatile platform for biomedical applications.« less

A comprehensive literatures update of clinical researches of superparamagnetic resonance iron oxide nanoparticles for magnetic resonance imaging

PubMed Central

Idée, Jean-Marc

2017-01-01

This paper aims to update the clinical researches using superparamagnetic iron oxide (SPIO) nanoparticles as magnetic resonance imaging (MRI) contrast agent published during the past five years. PubMed database was used for literature search, and the search terms were (SPIO OR superparamagnetic iron oxide OR Resovist OR Ferumoxytol OR Ferumoxtran-10) AND (MRI OR magnetic resonance imaging). The literature search results show clinical research on SPIO remains robust, particularly fuelled by the approval of ferumoxytol for intravenously administration. SPIOs have been tested on MR angiography, sentinel lymph node detection, lymph node metastasis evaluation; inflammation evaluation; blood volume measurement; as well as liver imaging. Two experimental SPIOs with unique potentials are also discussed in this review. A curcumin-conjugated SPIO can penetrate brain blood barrier (BBB) and bind to amyloid plaques in Alzheime’s disease transgenic mice brain, and thereafter detectable by MRI. Another SPIO was fabricated with a core of Fe3O4 nanoparticle and a shell coating of concentrated hydrophilic polymer brushes and are almost not taken by peripheral macrophages as well as by mononuclear phagocytes and reticuloendothelial system (RES) due to the suppression of non-specific protein binding caused by their stealthy ‘‘brush-afforded’’ structure. This SPIO may offer potentials for the applications such as drug targeting and tissue or organ imaging other than liver and lymph nodes. PMID:28275562

The use of the core-shell structure of zero-valent iron nanoparticles (NZVI) for long-term removal of sulphide in sludge during anaerobic digestion.

PubMed

Su, Lianghu; Zhen, Guangyin; Zhang, Longjiang; Zhao, Youcai; Niu, Dongjie; Chai, Xiaoli

2015-12-01

A core-shell structure results in zero-valent iron nanoparticles (NZVI) with manifold functional properties. In this study, the long-term effects of NZVI on hydrogen sulphide removal in an anaerobic sludge digester were investigated. Within 20 days, the average hydrogen sulphide content in the biogas was successfully reduced from 300 (or 3620 of sulphate-rich sludge) mg Nm(-3) to 6.1 (121), 0.9 (3.3) and 0.5 (1.3) mg Nm(-3) in the presence of 0.05, 0.10 and 0.20% (wt) NZVI, respectively. Methane yield was enhanced at the low NZVI dose (0.05-0.10%) but decreased at the elevated dose (0.20%). Methane production and volatile solid degradation analyses implied that doses of 0.5-0.10% NZVI could accelerate sludge stabilization during anaerobic digestion. The phosphorus fractionation profile suggested that methane production could be inhibited at the elevated NZVI dose, partly due to the limited availability of soluble phosphorus due to the immobilization of bioavailable-P through the formation of vivianite. An analysis of the reducible inorganic sulphur species revealed that the elimination of hydrogen sulphide occurred via the reaction between hydrogen sulphide and the oxide shell of NZVI, which mainly formed FeS and some FeS2 and S(0).

Magnetic and fluorescent glycopolymer hybrid nanoparticles for intranuclear optical imaging.

PubMed

Pfaff, André; Schallon, Anja; Ruhland, Thomas M; Majewski, Alexander P; Schmalz, Holger; Freitag, Ruth; Müller, Axel H E

2011-10-10

The synthesis of galactose-displaying core-shell nanospheres exhibiting both fluorescent and magnetic properties by grafting a glycocopolymer consisting of 6-O-methacryloylgalactopyranose (MAGal) and 4-(pyrenyl)butyl methacrylate (PyMA) onto magnetic silica particles via thiol-ene chemistry is reported. Magnetization measurements indicated that neither the encapsulation of the iron oxide particles into silica nor the grafting of the glycocopolymer chains had a significant influence on the superparamagnetic properties. This not only simplifies the purification of the particles but may facilitate the use of the particles in applications such as hyperthermia or magnetic resonance imaging (MRI). Furthermore, the hydrophilic glycopolymer shell provided solubility of the particles in aqueous medium and enabled the uptake of the particles into the cytoplasm and nucleus of lung cancer cells via carbohydrate-lectin recognition effects.

Iron release from corroded iron pipes in drinking water distribution systems: effect of dissolved oxygen.

PubMed

Sarin, P; Snoeyink, V L; Bebee, J; Jim, K K; Beckett, M A; Kriven, W M; Clement, J A

2004-03-01

Iron release from corroded iron pipes is the principal cause of "colored water" problems in drinking water distribution systems. The corrosion scales present in corroded iron pipes restrict the flow of water, and can also deteriorate the water quality. This research was focused on understanding the effect of dissolved oxygen (DO), a key water quality parameter, on iron release from the old corroded iron pipes. Corrosion scales from 70-year-old galvanized iron pipe were characterized as porous deposits of Fe(III) phases (goethite (alpha-FeOOH), magnetite (Fe(3)O(4)), and maghemite (alpha-Fe(2)O(3))) with a shell-like, dense layer near the top of the scales. High concentrations of readily soluble Fe(II) content was present inside the scales. Iron release from these corroded pipes was investigated for both flow and stagnant water conditions. Our studies confirmed that iron was released to bulk water primarily in the ferrous form. When DO was present in water, higher amounts of iron release was observed during stagnation in comparison to flowing water conditions. Additionally, it was found that increasing the DO concentration in water during stagnation reduced the amount of iron release. Our studies substantiate that increasing the concentration of oxidants in water and maintaining flowing conditions can reduce the amount of iron release from corroded iron pipes. Based on our studies, it is proposed that iron is released from corroded iron pipes by dissolution of corrosion scales, and that the microstructure and composition of corrosion scales are important parameters that can influence the amount of iron released from such systems.

Fe2 PO5 -Encapsulated Reverse Energetic ZnO/Fe2 O3 Heterojunction Nanowire for Enhanced Photoelectrochemical Oxidation of Water.

PubMed

Qin, Dong-Dong; He, Cai-Hua; Li, Yang; Trammel, Antonio C; Gu, Jing; Chen, Jing; Yan, Yong; Shan, Duo-Liang; Wang, Qiu-Hong; Quan, Jing-Jing; Tao, Chun-Lan; Lu, Xiao-Quan

2017-07-10

Zinc oxide is regarded as a promising candidate for application in photoelectrochemical water oxidation due to its higher electron mobility. However, its instability under alkaline conditions limits its application in a practical setting. Herein, we demonstrate an easily achieved wet-chemical route to chemically stabilize ZnO nanowires (NWs) by protecting them with a thin layer Fe 2 O 3 shell. This shell, in which the thickness can be tuned by varying reaction times, forms an intact interface with ZnO NWs, thus protecting ZnO from corrosion in a basic solution. The reverse energetic heterojunction nanowires are subsequently activated by introducing an amorphous iron phosphate, which substantially suppressed surface recombination as a passivation layer and improved photoelectrochemical performance as a potential catalyst. Compared with pure ZnO NWs (0.4 mA cm -2 ), a maximal photocurrent of 1.0 mA cm -2 is achieved with ZnO/Fe 2 O 3 core-shell NWs and 2.3 mA cm -2 was achieved for the PH 3 -treated NWs at 1.23 V versus RHE. The PH 3 low-temperature treatment creates a dual function, passivation and catalyst layer (Fe 2 PO 5 ), examined by X-ray photoelectron spectroscopy, TEM, photoelectrochemical characterization, and impedance measurements. Such a nano-composition design offers great promise to improve the overall performance of the photoanode material. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mössbauer spectroscopy and the understanding of the role of iron in neurodegeneration

NASA Astrophysics Data System (ADS)

Friedman, A.; Galazka-Friedman, J.

2017-11-01

The possible role of iron in neurodegeneration may be related to the oxidative stress, triggered by Fenton reaction. In this reaction hydroxyl free radical production is generated by divalent iron. Motor symptoms of Parkinson's disease depend on the destruction of substantia nigra (SN). As the substantive questions were: 1/ what is the concentration of iron in the samples, 2/ what is the proportion of divalent vs. trivalent iron in the samples, and 3/ what is the iron-binding compound, it seemed appropriate to use Mössbauer spectroscopy to answer those questions. We found no difference in the concentration of total iron between PD and control, with the ratio of iron in PD vs. control being 1.00 ± 0.13. The divalent iron could not exceed 5% of the total iron. The main iron-binding compound in SN, both in PD and control is ferritin. Our further studies of ferritin in parkinsonian SN demonstrated a decrease, compared to control, of L-ferritin involved in the storage of iron within ferritin. This could allow an efflux of iron from the ferritin shell and an increase of non-ferritin iron in PD SN, which was confirmed by us. Mössbauer studies in Alzheimer showed slightly higher concentration of iron in hippocampal cortex with significantly higher concentrations of L and H ferritins compared to control. In atypical parkinsonism, progressive supranuclear palsy, higher concentration of iron was found in globus pallidus and SN compared to control. Mössbauer spectroscopy may play crucial role in further studies of human neurodegeneration.

Distribution of iron oxide core-titanium dioxide shell nanoparticles in VX2 tumor bearing rabbits introduced by two different delivery modalities

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

Refaat, Tamer; West, Derek; El Achy, Samar

This work compares intravenous (IV) versus fluoroscopy-guided transarterial intra-catheter (IC) delivery of iron oxide core-titanium dioxide shell nanoparticles (NPs) in vivo in VX2 model of liver cancer in rabbits. NPs coated with glucose and decorated with a peptide sequence from cortactin were administered to animals with developed VX2 liver cancer. Two hours after NPs delivery tumors, normal liver, kidney, lung and spleen tissues were harvested and used for a series on histological and elemental analysis tests. Quantification of NPs in tissues was done both by bulk inductively coupled plasma mass spectrometry (ICP-MS) analysis and by hard X-ray fluorescence microscopy. Bothmore » IV and IC NPs injection are feasible modalities for delivering NPs to VX2 liver tumors with comparable tumor accumulation. It is possible that this is an outcome of the fact that VX2 tumors are highly vascularized and hemorrhagic, and therefore enhanced permeability and retention (EPR) plays the most significant role in accumulation of nanoparticles in tumor tissue. It is, however, interesting to note that IV delivery led to increased sequestration of NPs by spleen and normal liver tissue, while IC delivery lead to more NP positive Kupffer cells. Furthermore, this difference is most likely a direct outcome of blood flow dynamics. Armed with this knowledge about nanoparticle delivery, we plan to test them as radiosensitizers in the future.« less

Distribution of iron oxide core-titanium dioxide shell nanoparticles in VX2 tumor bearing rabbits introduced by two different delivery modalities

DOE PAGES

Refaat, Tamer; West, Derek; El Achy, Samar; ...

2016-08-03

This work compares intravenous (IV) versus fluoroscopy-guided transarterial intra-catheter (IC) delivery of iron oxide core-titanium dioxide shell nanoparticles (NPs) in vivo in VX2 model of liver cancer in rabbits. NPs coated with glucose and decorated with a peptide sequence from cortactin were administered to animals with developed VX2 liver cancer. Two hours after NPs delivery tumors, normal liver, kidney, lung and spleen tissues were harvested and used for a series on histological and elemental analysis tests. Quantification of NPs in tissues was done both by bulk inductively coupled plasma mass spectrometry (ICP-MS) analysis and by hard X-ray fluorescence microscopy. Bothmore » IV and IC NPs injection are feasible modalities for delivering NPs to VX2 liver tumors with comparable tumor accumulation. It is possible that this is an outcome of the fact that VX2 tumors are highly vascularized and hemorrhagic, and therefore enhanced permeability and retention (EPR) plays the most significant role in accumulation of nanoparticles in tumor tissue. It is, however, interesting to note that IV delivery led to increased sequestration of NPs by spleen and normal liver tissue, while IC delivery lead to more NP positive Kupffer cells. Furthermore, this difference is most likely a direct outcome of blood flow dynamics. Armed with this knowledge about nanoparticle delivery, we plan to test them as radiosensitizers in the future.« less

Facile Preparation of Drug-Loaded Tristearin Encapsulated Superparamagnetic Iron Oxide Nanoparticles Using Coaxial Electrospray Processing.

PubMed

Rasekh, Manoochehr; Ahmad, Zeeshan; Cross, Richard; Hernández-Gil, Javier; Wilton-Ely, James D E T; Miller, Philip W

2017-06-05

Naturally occurring polymers are promising biocompatible materials that have many applications for emerging therapies, drug delivery systems, and diagnostic agents. The handling and processing of such materials still constitutes a major challenge, which can limit the full exploitation of their properties. This study explores an ambient environment processing technique: coaxial electrospray (CO-ES) to encapsulate genistein (an isoflavonoid and model drug), superparamagnetic iron oxide nanoparticles (SPIONs, 10-15 nm), and a fluorophore (BODIPY) into a layered (triglyceride tristearin shell) particulate system, with a view to constructing a theranostic agent. Mode mapping of CO-ES led to an optimized atomization engineering window for stable jetting, leading to encapsulation of SPIONs within particles of diameter 0.65-1.2 μm and drug encapsulation efficiencies of around 92%. Electron microscopy was used to image the encapsulated SPIONs and confirm core-shell triglyceride encapsulation in addition to further physicochemical characterization (AFM, FTIR, DSC, and TGA). Cell viability assays (MTT, HeLa cells) were used to determine optimal SPION loaded particles (∼1 mg/mL), while in vitro release profile experiments (PBS, pH = 7.4) demonstrate a triphasic release profile. Further cell studies confirmed cell uptake and internalization at selected time points (t = 1, 2, and 4 h). The results suggest potential for using the CO-ES technique as an efficient way to encapsulate SPIONs together with sensitive drugs for the development of multimodal particles that have potential application for combined imaging and therapy.

Surface plasmon resonance enhanced light absorption and wavelength tuneable in gold-coated iron oxide spherical nanoparticle

NASA Astrophysics Data System (ADS)

Dasri, Thananchai; Chingsungnoen, Artit

2018-06-01

Surface plasmon in nano-sized particles, such as gold, silver, copper and their composites, has recently attracted a great deal of attention due to its possible uses in many applications, especially in life sciences. It is desirable for application devices with a tenability of surface plasmon wavelength and optical properties enhancement. This article presents enhanced optical light absorption and tunable wavelength in gold-coated magnetite (Fe3O4@Au core-shell) nanoparticles embedded in water using the theoretical method of discrete dipole approximation (DDA). The absorption spectra in the wavelengths from 350 to 900 nm were found to be the spectra obtained from Fe3O4@Au core-shell nanoparticles, and when compared with pure Fe3O4 nanoparticles, the surface plasmon resonance can be enhanced and tuned over the entire visible spectrum (viz. 350-800 nm) of the electromagnetic spectrum by varying the Au shell thickness (2-5 nm). Similarly, the Faraday rotation spectra can also be obtained.

Surface functionalized magnetic nanoparticles for cancer therapy applications

NASA Astrophysics Data System (ADS)

Wydra, Robert John

Despite recent advances, cancer remains the second leading cause of deaths in the United States. Magnetic nanoparticles have found various applications in cancer research as drug delivery platforms, enhanced contrast agents for improved diagnostic imaging, and the delivery of thermal energy as standalone therapy. Iron oxide nanoparticles absorb the energy from an alternating magnetic field and convert it into heat through Brownian and Neel relaxations. To better utilize magnetic nanoparticles for cancer therapy, surface functionalization is essential for such factors as decreasing cytotoxicity of healthy tissue, extending circulation time, specific targeting of cancer cells, and manage the controlled delivery of therapeutics. In the first study, iron oxide nanoparticles were coated with a poly(ethylene glycol) (PEG) based polymer shell. The PEG coating was selected to prevent protein adsorption and thus improve circulation time and minimize host response to the nanoparticles. Thermal therapy application feasibility was demonstrated in vitro with a thermoablation study on lung carcinoma cells. Building on the thermal therapy demonstration with iron oxide nanoparticles, the second area of work focused on intracellular delivery. Nanoparticles can be appropriately tailored to enter the cell and deliver energy on the nanoscale eliminating individual cancer cells. The underlying mechanism of action is still under study, and we were interested in determining the role of reactive oxygen species (ROS) catalytically generated from the surface of iron oxide nanoparticles in this measured cytotoxicity. When exposed to an AMF, the nanoscale heating effects are capable of enhancing the Fenton-like generation of ROS determined through a methylene blue degradation assay. To deliver this enhanced ROS effect to cells, monosaccharide coated nanoparticles were developed and successfully internalized by colon cancer cell lines. Upon AMF exposure, there was a measured increase in cellular ROS and apoptosis that was attributed to lysosomal disruption since the surface functionalization selected inhibited the Fenton-like surface chemistry. To overcome this surface inhibition, a biodegradable poly(beta-amino ester) (PBAE) polymer coating was synthesized to deliver bare iron oxide to intracellular components. Delivering enhanced ROS to cancer cells is a promising new route of therapy that deserves future studies.

Intra- and interparticle magnetism of cobalt-doped iron-oxide nanoparticles encapsulated in a synthetic ferritin cage

NASA Astrophysics Data System (ADS)

Skoropata, E.; Desautels, R. D.; Falvo, E.; Ceci, P.; Kasyutich, O.; Freeland, J. W.; van Lierop, J.

2014-11-01

We present an in-depth examination of the composition and magnetism of cobalt (Co2 +)-doped iron-oxide nanoparticles encapsulated in Pyrococcus furiosus ferritin shells. We show that the Co2 + dopant ions were incorporated into the γ -Fe2O3/Fe3O4 core, with small paramagnetic-like clusters likely residing on the surface of the nanoparticle that were observed for all cobalt-doped samples. In addition, element-specific characterization using Mössbauer spectroscopy and polarized x-ray absorption indicated that Co2 + was incorporated exclusively into the octahedral B sites of the spinel-oxide nanoparticle. Comparable superparamagnetic blocking temperatures, coercivities, and effective anisotropies were obtained for 7%, 10%, and 12% cobalt-doped nanoparticles, and were only slightly reduced for 3% cobalt, indicating a strong effect of cobalt incorporation, with a lesser effect of cobalt content. Due to the regular particle size and separation that result from the use of the ferritin cage, a comparison of the effects of interparticle interactions on the disordered assembly of nanoparticles was also obtained that indicated significantly different behaviors between undoped and cobalt-doped nanoparticles.

Planetary ecology; Proceedings of the Sixth International Symposium on Environmental Biogeochemistry, Santa Fe, NM, October 10-14, 1983

NASA Technical Reports Server (NTRS)

Caldwell, D. E. (Editor); Brierley, J. A. (Editor); Brierley, C. L. (Editor)

1985-01-01

Topics presented include biological evolution and planetary chemistry; C-1 compounds; transport, deposition, and weathering; sulfur transformations; ground water; transformation processes for nitrogen oxides; and soils. Papers are presented on immunological studies on the organic matrix of recent and fossil invertebrate shells; biogenic gases in sediments deposited since Miocene times on the Walvis Ridge, South Atlantic Ocean; aspects of the biogeochemistry of Big Soda Lake, NV; mesophilic manganese-oxidizing bacteria from hydrothermal discharge areas at 21 deg North on the East Pacific Rise; and autotrophic growth and iron oxidation and inhibition kinetics of Leptospirillum ferrooxidans. Consideration is also given to thermophilic archaebacteria occurring in submarine hydrothermal areas; fate of sulfate in a soft-water, acidic lake; geochemical conditions in the ground water environment; microbial transformations as sources and sinks for nitrogen oxides; and the biogeochemistry of soil phosphorus.

Reduced molybenum-oxide-based core-shell hybrids: "blue" electrons are delocalized on the shell.

PubMed

Todea, Ana Maria; Szakács, Julia; Konar, Sanjit; Bögge, Hartmut; Crans, Debbie C; Glaser, Thorsten; Rousselière, Hélène; Thouvenot, René; Gouzerh, Pierre; Müller, Achim

2011-06-06

The present study refers to a variety of reduced metal-oxide core-shell hybrids, which are unique with regard to their electronic structure, their geometry, and their formation. They contain spherical {Mo72Fe30} Keplerate-type shells encapsulating Keggin-type polyoxomolybdates based on very weak interactions. Studies on the encapsulation of molybdosilicate as well as on the earlier reported molybdophosphate, coupled with the use of several physical methods for the characterization led to unprecedented results (see title). Upon standing in air at room temperature, acidified aqueous solutions obtained by dissolving sodium molybdate, iron(II) chloride, acetic acid, and molybdosilicic acid led to the precipitation of monoclinic greenish crystals (1). A rhombohedral variant (2) has also been observed. Upon drying at room temperature, compound 3 with a layer structure was obtained from 1 in a solid-state reaction based on cross-linking of the shells. The compounds 1, 2, and 3 have been characterized by a combination of methods including single-crystal X-ray crystallography, magnetic studies, as well as IR, Mössbauer, (resonance) Raman, and electronic absorption spectroscopy. In connection with detailed studies of the guest-free two-electron-reduced {Mo72Fe30}-type Keplerate (4) and of the previously reported molybdophosphate-based hybrids (including 31P NMR spectroscopy results), it is unambiguously proved that 1, 2, and 3 contain non-reduced Keggin ion cores and reduced {Mo72Fe30}-type shells. The results are discussed in terms of redox considerations (the shell as well as the core can be reduced) including those related to the reduction of "molybdates" by FeII being of interdisciplinary including catalytic interest (the MoVI/MoV and FeIII/FeII couples have very close redox potentials!), while also referring to the special formation of the hybrids based on chemical Darwinism.

X-ray spectra of Hercules X-1. 1: Iron line fluorescence from a subrelativistic shell

NASA Technical Reports Server (NTRS)

Pravdo, S. H.; Becker, R. H.; Boldt, E. A.; Holt, S. S.; Serlemitsos, P. J.; Swank, J. H.

1977-01-01

The X-ray spectrum of Hercules X-1 was observed in the energy range 2-24 keV from August 29 to September 3, 1975. A broad iron line feature is observed in the normal high state spectrum. The line equivalent width is given along with its full-width-half-maximum energy. Iron line fluorescence from an opaque, cool shell of material at the Alfven surface provides the necessary luminosity in this feature. The line energy width can be due to Doppler broadening if the shell is forced to corotate with the pulsar at a radius 800 million cm. Implications of this model regarding physical conditions near Her X-1 are discussed.

Production and characterization of functional recombinant hybrid heteropolymers of camel hepcidin and human ferritin H and L chains.

PubMed

Boumaiza, Mohamed; Carmona, Fernando; Poli, Maura; Asperti, Michela; Gianoncelli, Alessandra; Bertuzzi, Michela; Ruzzenenti, Paola; Arosio, Paolo; Marzouki, Mohamed Nejib

2017-02-01

Hepcidin is a liver-synthesized hormone that plays a central role in the regulation of systemic iron homeostasis. To produce a new tool for its functional properties the cDNA coding for camel hepcidin-25 was cloned at the 5'end of human FTH sequence into the pASK-IBA43plus vector for expression in Escherichia coli The recombinant fusion hepcidin-ferritin-H subunit was isolated as an insoluble iron-containing protein. When alone it did not refold in a 24-mer ferritin molecule, but it did when renatured together with H- or L-ferritin chains. We obtained stable ferritin shells exposing about 4 hepcidin peptides per 24-mer shell. The molecules were then reduced and re-oxidized in a controlled manner to allow the formation of the proper hepcidin disulfide bridges. The functionality of the exposed hepcidin was confirmed by its ability to specifically bind the mouse macrophage cell line J774 that express ferroportin and to promote ferroportin degradation. This chimeric protein may be useful for studying the hepcidin-ferroportin interaction in cells and also as drug-delivery agent. © Crown copyright 2016.

Nitrogen activation of carbon-encapsulated zero-valent iron nanoparticles and influence of the activation temperature on heavy metals removal

NASA Astrophysics Data System (ADS)

Bonaiti, Stefania; Calderon, Blanca; Collina, Elena; Lasagni, Marina; Mezzanotte, Valeria; Aracil, Ignacio; Fullana, Andrés

2017-05-01

Nanoparticles of zero-valent iron (nZVI) represent a promising agent for environmental remediation. This is due to their core-shell structure which presents the characteristics of both metallic and oxidised iron, leading to sorption and reductive precipitation of metal ions. Nevertheless, nZVI application presents some limitations regarding their rapid oxidation and aggregation in the media which leads to the delivery of the ions after some hours (the “aging effect”). To address these issues, modifications of nZVI structure and synthesis methods have been developed in the last years. The aging problem was solved by using nZVI encapsulated inside carbon spheres (CE-nZVI), synthetized through Hydrothermal Carbonization (HTC). Results showed high heavy metals removal percentage. Furthermore, CE-nZVI were activated with nitrogen in order to increase the metallic iron content. The aim of this study was to test CE-nZVI post-treated with nitrogen at different temperatures in heavy metals removal, demonstrating that the influence of the temperature was negligible in nanoparticles removal efficiency.

Photoreduction and incorporation of iron into ferritins.

PubMed Central

Laulhère, J P; Labouré, A M; Briat, J F

1990-01-01

Pea seed ferritin is able to incorporate ferrous iron into the mineral core. Fe2+ may be formed by reduction of exogenous Fe3+ with ascorbate or by photoreduction by ferritin and by ferric citrate. In our experimental conditions the bulk of the photoreduction is carried out by ferritin, which is able to photoreduce its endogenous iron. Citrate does not enhance the photoreduction capacity of ferritin, and exogenous ferric citrate improves the yield of the reaction by about 30%. The mineral core of the ferritin is shown to photoreduce actively, and the protein shell does not participate directly in the photoreduction. Low light intensities and low concentration of reducing agents do not allow a release of iron from ferritins, but induce a 'redox mill' of photoreduction and simultaneous ferroxidase-mediated incorporation. High ascorbate concentrations induce the release of ferritin iron. These reactions are accompanied by the correlated occurrence of damage caused by radicals arising from Fenton reactions, leading to specific cleavages in the 28 kDa phytoferritin subunit. This damage caused by radicals occurs during the oxidative incorporation into the mineral core and is prevented by o-phenanthroline or by keeping the samples in the dark. Images Fig. 1. Fig. 2. Fig. 3. Fig. 5. PMID:2375759

Efficient one-pot sonochemical synthesis of thickness-controlled silica-coated superparamagnetic iron oxide (Fe3O4/SiO2) nanospheres

NASA Astrophysics Data System (ADS)

Abbas, Mohamed; Abdel-Hamed, M. O.; Chen, Jiangang

2017-12-01

A facile and eco-friendly efficient sonochemical approach was designed for the synthesis of highly crystalline Fe3O4 and Fe3O4/SiO2 core/shell nanospheres in single reaction. The generated physical properties (shock waves, microjets, and turbulent flows) from ultrasonication as a consequence of the collapse of microbubbles and polyvinylpyrrolidone (PVP) as a chemical linker were found to play a crucial role in the successful formation of the core/shell NPs within short time than the previously reported methods. Transmission electron microscopy revealed that a uniform SiO2 shell is successfully coated over Fe3O4 nanospheres, and the thickness of the silica shell could be easily controlled in the range from 5 to 15 nm by adjusting the reaction parameters. X-ray diffraction data were employed to confirm the formation of highly crystalline and pure phase of a cubic inverse spinel structure for magnetite (Fe3O4) nanospheres. The magnetic properties of the as-synthesized Fe3O4 and Fe3O4/SiO2 core/shell nanospheres were measured at room temperature using vibrating sample magnetometer, and the results demonstrated a high magnetic moment values with superparamagnetic properties.

Bifunctional catalyst of graphite-encapsulated iron compound nanoparticle for magnetic carbon nanotubes growth by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Saraswati, Teguh Endah; Prasiwi, Oktaviana Dewi Indah; Masykur, Abu; Anwar, Miftahul

2017-01-01

The carbon nanotube has widely taken great attractive in carbon nanomaterial research and application. One of its preparation methods is catalytic chemical vapor deposition (CCVD) using catalyst i.e. iron, nickel, etc. Generally, except the catalyst, carbon source gasses as the precursor are still required. Here, we report the use of the bifunctional material of Fe3O4/C which has an incorporated core/shell structures of carbon-encapsulated iron compound nanoparticles. The bifunctional catalyst was prepared by submerged arc discharge that simply performed using carbon and carbon/iron oxide electrodes in ethanol 50%. The prepared material was then used as a catalyst in thermal chemical vapor deposition at 800°C flown with ethanol vapor as the primer carbon source in a low-pressure condition. This catalyst might play a dual role as a catalyst and secondary carbon source for growing carbon nanotubes at the time. The synthesized products were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. The successful formation of carbon nanotubes was assigned by the shifted X-ray diffracted peak of carbon C(002), the iron oxides of Fe3O4 and γ-Fe2O3, and the other peaks which were highly considered to the other carbon allotropes with sp2 hybridization structures. The other assignment was studied by electron microscopy which successfully observed the presence of single-wall carbon nanotubes. In addition, the as-prepared carbon nanotubes have a magnetic property which was induced by the remaining of metal catalyst inside the CNT.

D, L-Sulforaphane Loaded Fe3O4@ Gold Core Shell Nanoparticles: A Potential Sulforaphane Delivery System.

PubMed

Kheiri Manjili, Hamidreza; Ma'mani, Leila; Tavaddod, Sharareh; Mashhadikhan, Maedeh; Shafiee, Abbas; Naderi-Manesh, Hossein

2016-01-01

A novel design of gold-coated iron oxide nanoparticles was fabricated as a potential delivery system to improve the efficiency and stability of d, l-sulforaphane as an anticancer drug. To this purpose, the surface of gold-coated iron oxide nanoparticles was modified for sulforaphane delivery via furnishing its surface with thiolated polyethylene glycol-folic acid and thiolated polyethylene glycol-FITC. The synthesized nanoparticles were characterized by different techniques such as FTIR, energy dispersive X-ray spectroscopy, UV-visible spectroscopy, scanning and transmission electron microscopy. The average diameters of the synthesized nanoparticles before and after sulforaphane loading were obtained ∼ 33 nm and ∼ 38 nm, respectively, when ∼ 2.8 mmol/g of sulforaphane was loaded. The result of cell viability assay which was confirmed by apoptosis assay on the human breast cancer cells (MCF-7 line) as a model of in vitro-cancerous cells, proved that the bare nanoparticles showed little inherent cytotoxicity, whereas the sulforaphane-loaded nanoparticles were cytotoxic. The expression rate of the anti-apoptotic genes (bcl-2 and bcl-xL), and the pro-apoptotic genes (bax and bak) were quantified, and it was found that the expression rate of bcl-2 and bcl-xL genes significantly were decreased when MCF-7 cells were incubated by sulforaphane-loaded nanoparticles. The sulforaphane-loaded into the designed gold-coated iron oxide nanoparticles, acceptably induced apoptosis in MCF-7 cells.

Biomolecular crystals for material applications and a mechanistic study of an iron oxide nanoparticle synthesis

NASA Astrophysics Data System (ADS)

Falkner, Joshua Charles

The three projects within this work address the difficulties of controlling biomolecular crystal formats (i.e. size and shape), producing 3-D ordered composite materials from biomolecular crystal templates, and understanding the mechanism of a practical iron oxide synthesis. The unifying thread consistent throughout these three topics is the development of methods to manipulate nanomaterials using a bottom-up approach. Biomolecular crystals are nanometer to millimeter sized crystals that have well ordered mesoporous solvent channels. The overall physical dimensions of these crystals are highly dependent on crystallization conditions. The controlled growth of micro- and nanoprotein crystals was studied to provide new pathways for creating smaller crystalline protein materials. This method produced tetragonal hen egg-white lysozyme crystals (250--100,000 nm) with near monodisperse size distributions (<15%). With this degree of control, existing protein crystal applications such as drug delivery and analytical sensors can reach their full potential. Applications for larger crystals with inherently ubiquitous pore structures could extend to materials used for membranes or templates. In this work, the porous structure of larger cowpea mosaic virus crystals was used to template metal nanoparticle growth within the body centered cubic crystalline network. The final composite material was found to have long range ordering of palladium and platinum nonocrystal aggregates (10nm) with symmetry consistent to the virus template. Nanoparticle synthesis itself is an immense field of study with an array of diverse applications. The final piece of this work investigates the mechanism behind a previously developed iron oxide synthesis to gain more understanding and direction to future synthesis strategies. The particle growth mechanism was found to proceed by the formation of a solvated iron(III)oleate complex followed by a reduction of iron (III) to iron (II). This unstable iron(II) nucleates to form a wustite (FeO) core which serves as an epitaxial surface for the magnetite (Fe3O4) shell growth. This method produces spherical particles (6-60nm) with relative size distributions of less than 15%.

Facile fabrication of well-defined hydrogel beads with magnetic nanocomposite shells.

PubMed

Liu, Hongxia; Wang, Chaoyang; Gao, Quanxing; Chen, Jianxin; Ren, Biye; Liu, Xinxing; Tong, Zhen

2009-07-06

Well-defined magnetic nanocomposite beads with alginate gel cores and shells of iron oxide (gamma-Fe(2)O(3)) nanoparticles were prepared by self-assembly of colloidal particles at liquid-liquid interfaces and subsequent in situ gelation. Fe(2)O(3) nanoparticles could spontaneously adsorb onto the water droplet surfaces to stabilize water-in-hexane emulsions. Water droplets containing sodium alginate were in situ gelled by calcium cations, which were released from calcium-ethylenediamine tetraacetic acid (Ca-EDTA) chelate by decreasing pH value through slow hydrolysis of d-glucono-delta-lactone (GDL). The resulting hybrid beads with a core-shell structure were easily collected by removing hexane. This facile and high efficient fabrication had a 100% yield and could be carried out at room temperature. Insulin microcrystal was encapsulated into the hybrid beads by dispersing them in the aqueous solution of alginate sodium in the fabrication process. The sustained release could be obtained due to the dual barriers of the hydrogel core and the close-packed inorganic shell. The release curves were nicely fitted by the Weibull equation and the release followed Fickian diffusion. The hybrid beads may find applications as delivery vehicles for biomolecules, drugs, cosmetics, food supplements and living cells.

Iron Oxide and Gold Based Magneto-Plasmonic Nanostructures for Medical Applications: A Review

PubMed Central

Mammeri, Fayna; Ammar, Souad

2018-01-01

Iron oxide and gold-based magneto-plasmonic nanostructures exhibit remarkable optical and superparamagnetic properties originating from their two different components. As a consequence, they have improved and broadened the application potential of nanomaterials in medicine. They can be used as multifunctional nanoprobes for magneto-plasmonic heating as well as for magnetic and optical imaging. They can also be used for magnetically assisted optical biosensing, to detect extreme traces of targeted bioanalytes. This review introduces the previous work on magneto-plasmonic hetero-nanostructures including: (i) their synthesis from simple “one-step” to complex “multi-step” routes, including seed-mediated and non-seed-mediated methods; and (ii) the characterization of their multifunctional features, with a special emphasis on the relationships between their synthesis conditions, their structures and their properties. It also focuses on the most important progress made with regard to their use in nanomedicine, keeping in mind the same aim, the correlation between their morphology—namely spherical and non-spherical, core-satellite and core-shell, and the desired applications. PMID:29518969

Self-assembled iron oxide nanoparticle multilayer: x-ray and polarized neutron reflectivity.

PubMed

Mishra, D; Benitez, M J; Petracic, O; Badini Confalonieri, G A; Szary, P; Brüssing, F; Theis-Bröhl, K; Devishvili, A; Vorobiev, A; Konovalov, O; Paulus, M; Sternemann, C; Toperverg, B P; Zabel, H

2012-02-10

We have investigated the structure and magnetism of self-assembled, 20 nm diameter iron oxide nanoparticles covered by an oleic acid shell for scrutinizing their structural and magnetic correlations. The nanoparticles were spin-coated on an Si substrate as a single monolayer and as a stack of 5 ML forming a multilayer. X-ray scattering (reflectivity and grazing incidence small-angle scattering) confirms high in-plane hexagonal correlation and a good layering property of the nanoparticles. Using polarized neutron reflectivity we have also determined the long range magnetic correlations parallel and perpendicular to the layers in addition to the structural ones. In a field of 5 kOe we determine a magnetization value of about 80% of the saturation value. At remanence the global magnetization is close to zero. However, polarized neutron reflectivity reveals the existence of regions in which magnetic moments of nanoparticles are well aligned, while losing order over longer distances. These findings confirm that in the nanoparticle assembly the magnetic dipole-dipole interaction is rather strong, dominating the collective magnetic properties at room temperature.

Iron translocation into and out of Listeria innocua Dps and size distribution of the protein-enclosed nanomineral are modulated by the electrostatic gradient at the 3-fold "ferritin-like" pores.

PubMed

Bellapadrona, Giuliano; Stefanini, Simonetta; Zamparelli, Carlotta; Theil, Elizabeth C; Chiancone, Emilia

2009-07-10

Elucidating pore function at the 3-fold channels of 12-subunit, microbial Dps proteins is important in understanding their role in the management of iron/hydrogen peroxide. The Dps pores are called "ferritin-like" because of the structural resemblance to the 3-fold channels of 24-subunit ferritins used for iron entry and exit to and from the protein cage. In ferritins, negatively charged residues lining the pores generate a negative electrostatic gradient that guides iron ions toward the ferroxidase centers for catalysis with oxidant and destined for the mineralization cavity. To establish whether the set of three aspartate residues that line the pores in Listeria innocua Dps act in a similar fashion, D121N, D126N, D130N, and D121N/D126N/D130N proteins were produced; kinetics of iron uptake/release and the size distribution of the iron mineral in the protein cavity were compared. The results, discussed in the framework of crystal growth in a confined space, indicate that iron uses the hydrophilic 3-fold pores to traverse the protein shell. For the first time, the strength of the electrostatic potential is observed to modulate kinetic cooperativity in the iron uptake/release processes and accordingly the size distribution of the microcrystalline iron minerals in the Dps protein population.

Field-emission property of self-purification SiC/SiOx coaxial nanowires synthesized via direct microwave irradiation using iron-containing catalyst

NASA Astrophysics Data System (ADS)

Zhou, Qing; Yu, Yongzhi; Huang, Shan; Meng, Jiang; Wang, Jigang

2017-07-01

SiC/SiOx coaxial nanowires were rapidly synthesized via direct microwave irradiation in low vacuum atmosphere. During the preparation process, only graphite, silicon, silicon dioxide powders were used as raw materials and iron-containing substance was employed as catalyst. Comprehensive characterizations were employed to investigate the microstructure of the products. The results showed that a great quantity of coaxial nanowires with uniform sizes and high aspect ratio had been successfully achieved. The coaxial nanowires consist of a silicon oxide (SiOx) shell and a β-phase silicon carbide (β-SiC) core that exhibited in special tube brush like. In additional, nearly all the products were achieved in the statement of pure SiC/SiOx coaxial nanowires without the existence of metallic catalyst, indicating that the self-removal of iron (Fe) catalyst should be occurred during the synthesis process. Photoluminescence (PL) spectral analysis result indicated that such novel SiC/SiOx coaxial nanowires exhibited significant blue-shift. Besides, the measurement results of field-emission (FE) demonstrated that the SiC/SiOx coaxial nanowires had ultralow turn-on field and threshold field with values of 0.2 and 2.1 V/μm, respectively. The hetero-junction structure formed between SiOx shell and SiC core, lots of emission sites, as well as clear tips of the nanowires were applied to explain the excellent FE properties.[Figure not available: see fulltext.

Theoretical studies of massive stars. II - Evolution of a 15 solar-mass star from carbon shell burning to iron core collapse

NASA Technical Reports Server (NTRS)

Sparks, W. M.; Endal, A. S.

1980-01-01

The evolution of a Population I star of 15 solar masses is described from the carbon shell burning stage to the formation and collapse of an iron core. An unusual aspect of the evolution is that neon ignition occurs off-center and neon burning propagates inward by a series of shell flashes. The extent of the core burning is generally smaller than the Chandrasekhar mass, so that most of the nuclear energy generation occurs in shell sources. Because of degeneracy and the influence of rapid convective mixing, these shell sources are unstable and the core goes through large excursions in temperature and density. The small core also causes the shell sources to converge into a narrow mass region slightly above the Chandrasekhar mass. Thus, the final nucleosynthesis yields are generally small, with silicon being most strongly enhanced with respect to solar system abundances.

First-Principles Fe L 2,3 -Edge and O K-Edge XANES and XMCD Spectra for Iron Oxides

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

Sassi, Michel; Pearce, Carolyn I.; Bagus, Paul S.

X-ray absorption near-edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) spectroscopies are tools in widespread use for providing detailed local atomic structure, oxidation state, and magnetic structure information for materials and organometallic complexes. The analysis of these spectra for transition-metal L-edges is routinely performed on the basis of ligand-field multiplet theory because one- and two-particle mean-field ab initio methods typically cannot describe the multiplet structure. Here we show that multireference configuration interaction (MRCI) calculations can satisfactorily reproduce measured XANES spectra for a range of complex iron oxide materials including hematite and magnetite. MRCI Fe L2,3-edge XANES and XMCD spectramore » of Fe(II)O6, Fe(III)O6, and Fe(III)O4 in magnetite are found to be in very good qualitative agreement with experiment and multiplet calculations. Point-charge embedding and small distortions of the first-shell oxygen ligands have only small effects. Oxygen K-edge XANES/XMCD spectra for magnetite investigated by a real-space Green’s function approach complete the very good qualitative agreement with experiment. Material-specific differences in local coordination and site symmetry are well reproduced, making the approach useful for assigning spectral features to specific oxidation states and coordination environments.« less

Synthesis of core-shell iron nanoparticles via a new (novel) approach

NASA Astrophysics Data System (ADS)

Chaudhary, Rakesh P.; Koymen, Ali R.

2014-03-01

Carbon-encapsulated iron (Fe) nanoparticles were synthesized by a newly developed method in toluene. Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM) of the as prepared sample reveal that core-shell nanostructures have been formed with Fe as core and graphitic carbon as shell. Fe nanoparticles with diameter 11nm to 102 nm are encapsulated by 6-8 nm thick graphitic carbon layers. There was no iron carbide formation observed between the Fe core and the graphitic shell. The Fe nanoparticles have body centered cubic (bcc) crystal structure. The magnetic hysteresis loop of the as synthesized powder at room temperature showed a saturation magnetization of 9 Am2 kg-1. After thermal treatment crystalline order of the samples improved and hence saturation magnetization increased to 24 Am2kg-1. We foresee that the carbon-encapsulated Fe nanoparticles are biologically friendly and could have potential applications in Magnetic Resonance Imaging (MRI) and Photothermal cancer therapy.

Dielectronic Recombination In Active Galactic Nuclei

NASA Technical Reports Server (NTRS)

Lukic, D. V.; Schnell, M.; Savin, D. W.; Altun, Z.; Badnell, N.; Brandau, C.; Schmidt, E. W.; Mueller, A.; Schippers, S.; Sprenger, F.;

One-dimensional arrangement of nanoparticles utilizing the V-groove and cage shaped proteins

NASA Astrophysics Data System (ADS)

Ban, Takahiko; Uenuma, Mutsunori; Migita, Shinji; Okamoto, Naofumi; Ishikawa, Yasuaki; Uraoka, Yukiharu; Yamashita, Ichiro; Yamamoto, Shin-ichi

2017-06-01

The one-dimensional arrangement of nanoparticles (NPs) was performed using a V-groove and ferritins as spherical shell proteins. The V-groove was synthesized by lithography and anisotropic etching of a Si substrate. Ferritin has an outer diameter of 12 nm and an inner diameter of 6 nm, and various inorganic substances can be formed into the cavity. In this study, iron oxide, cobalt oxide, and indium oxide cores were used. The surface potential of ferritin can be changed by genetic modification. Particularly, by using Fer8-K98E, NPs could be arranged one-dimensionally onto the bottom of the V-groove. In addition, we succeeded in selectively forming a one-dimensional array of one layer, two layers, and three layers by changing the protein concentration. This experiment is expected to be applicable to various one-dimensional devices.

Solution and solid state NMR approaches to draw iron pathways in the ferritin nanocage.

PubMed

Lalli, Daniela; Turano, Paola

2013-11-19

Ferritins are intracellular proteins that can store thousands of iron(III) ions as a solid mineral. These structures autoassemble from four-helix bundle subunits to form a hollow sphere and are a prototypical example of protein nanocages. The protein acts as a reservoir, encapsulating iron as ferric oxide in its central cavity in a nontoxic and bioavailable form. Scientists have long known the structural details of the protein shell, owing to very high resolution X-ray structures of the apoform. However, the atomic level mechanism governing the multistep biomineralization process remained largely elusive. Through analysis of the chemical behavior of ferritin mutants, chemists have found the role of some residues in key reaction steps. Using Mössbauer and XAS, they have identified some di-iron intermediates of the catalytic reaction trapped by rapid freeze quench. However, structural information about the iron interaction sites remains scarce. The entire process is governed by a number of specific, but weak, interactions between the protein shell and the iron species moving across the cage. While this situation may constitute a major problem for crystallography, NMR spectroscopy represents an optimal tool to detect and characterize transient species involving soluble proteins. Regardless, NMR analysis of the 480 kDa ferritin represents a real challenge. Our interest in ferritin chemistry inspired us to use an original combination of solution and solid state approaches. While the highly symmetric structure of the homo-24-mer frog ferritin greatly simplifies the spectra, the large protein size hinders the efficient coherence transfer in solution, thus preventing the sequence specific assignments. In contrast, extensive (13)C-spin diffusion makes the solution (13)C-(13)C NOESY experiment our gold standard to monitor protein side chains both in the apoprotein alone and in its interaction with paramagnetic iron species, inducing line broadening on the resonances of nearby residues. We could retrieve the structural information embedded in the (13)C-(13)C NOESY due to a partial sequence specific assignment of protein backbone and side chains we obtained from solid state MAS NMR of ferritin microcrystals. We used the 59 assigned amino acids (∼33% of the total) as probes to locate paramagnetic ferric species in the protein cage. Through this approach, we could identify ferric dimers at the ferroxidase site and on their pathway towards the nanocage. Comparison with existing data on bacterioferritins and bacterial ferritins, as well as with eukaryotic ferritins loaded with various nonfunctional divalent ions, allowed us to reinterpret the available information. The resulting picture of the ferroxidase site is slightly different with various ferritins but is designed to provide multiple and generally weak iron ligands. The latter assist binding of two incoming iron(II) ions in two proximal positions to facilitate coupling with oxygen. Subsequent oxidation is accompanied by a decrease in the metal-metal distance (consistent with XAS/Mössbauer) and in the number of protein residues involved in metal coordination, facilitating the release of products as di-iron clusters under the effect of new incoming iron(II) ions.

Preparation and characterization of polymer-coated core-shell structured magnetic microbeads

NASA Astrophysics Data System (ADS)

Liu, Z. L.; Ding, Z. H.; Yao, K. L.; Tao, J.; Du, G. H.; Lu, Q. H.; Wang, X.; Gong, F. L.; Chen, X.

2003-09-01

Composite microbeads consisting of polymer-coated iron oxide nanoparticles are prepared by the microemulsion polymerization of styrene, divinyl benzene and methacrylic acid in the presence of emulsifiers. Fourier transform infrared spectrometer analysis indicates the presence of -COOH groups and Fe 3O 4 of the microbeads. The amount of -COOH groups localized on the surface, which is about 0.15 mmol/g, is determined by conductometric titration. Transmission electron microscope picture reveals that the microbeads have a core-shell structure. The dissolving experiments of microbeads in hydrochloric acid and toluene further identify the core-shell structure. Optical microscope indicates that the magnetic microbeads have uniform and spherical forms with the size of 1-5 μm. Magnetic sensitivity measurement indicates that the microbeads can be used conveniently. Magnetic property measurement shows very little residual magnetization and coercivity, which are below 0.5 emu/g and around 15 Oe, respectively. The magnetic properties are greatly related to the particle sizes. The thermal gravity analysis result shows the improvement of thermal stability. The experiment of immobilized antibody indicates that the functional groups on the surface are appropriate.

Tuning the magnetism of ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Viñas, S. Liébana; Simeonidis, K.; Li, Z.-A.; Ma, Z.; Myrovali, E.; Makridis, A.; Sakellari, D.; Angelakeris, M.; Wiedwald, U.; Spasova, M.; Farle, M.

2016-10-01

The importance of magnetic interactions within an individual nanoparticle or between adjacent ones is crucial not only for the macroscopic collective magnetic behavior but for the AC magnetic heating efficiency as well. On this concept, single-(MFe2O4 where M=Fe, Co, Mn) and core-shell ferrite nanoparticles consisting of a magnetically softer (MnFe2O4) or magnetically harder (CoFe2O4) core and a magnetite (Fe3O4) shell with an overall size in the 10 nm range were synthesized and studied for their magnetic particle hyperthermia efficiency. Magnetic measurements indicate that the coating of the hard magnetic phase (CoFe2O4) by Fe3O4 provides a significant enhancement of hysteresis losses over the corresponding single-phase counterpart response, and thus results in a multiplication of the magnetic hyperthermia efficiency opening a novel pathway for high-performance, magnetic hyperthermia agents. At the same time, the existence of a biocompatible Fe3O4 outer shell, toxicologically renders these systems similar to iron-oxide ones with significantly milder side-effects.

Complement proteins bind to nanoparticle protein corona and undergo dynamic exchange in vivo

NASA Astrophysics Data System (ADS)

Chen, Fangfang; Wang, Guankui; Griffin, James I.; Brenneman, Barbara; Banda, Nirmal K.; Holers, V. Michael; Backos, Donald S.; Wu, Linping; Moghimi, Seyed Moein; Simberg, Dmitri

2017-05-01

When nanoparticles are intravenously injected into the body, complement proteins deposit on the surface of nanoparticles in a process called opsonization. These proteins prime the particle for removal by immune cells and may contribute toward infusion-related adverse effects such as allergic responses. The ways complement proteins assemble on nanoparticles have remained unclear. Here, we show that dextran-coated superparamagnetic iron oxide core-shell nanoworms incubated in human serum and plasma are rapidly opsonized with the third complement component (C3) via the alternative pathway. Serum and plasma proteins bound to the nanoworms are mostly intercalated into the nanoworm shell. We show that C3 covalently binds to these absorbed proteins rather than the dextran shell and the protein-bound C3 undergoes dynamic exchange in vitro. Surface-bound proteins accelerate the assembly of the complement components of the alternative pathway on the nanoworm surface. When nanoworms pre-coated with human plasma were injected into mice, C3 and other adsorbed proteins undergo rapid loss. Our results provide important insight into dynamics of protein adsorption and complement opsonization of nanomedicines.

Rate of Iron Transfer Through the Horse Spleen Ferritin Shell Determined by the Rate of Formation of Prussian Blue and Fe-desferrioxamine Within the Ferritin Cavity

NASA Technical Reports Server (NTRS)

Zhang, Bo; Watt, Richard K.; Galvez, Natividad; Dominquez-Vera, Jose M.; Watt, Gerald D.

2005-01-01

Iron (2+ and 3+) is believed to transfer through the three-fold channels in the ferritin shell during iron deposition and release in animal ferritins. However, the rate of iron transit in and out through these channels has not been reported. The recent synthesis of [Fe(CN)(sub 6)](3-), Prussian Blue (PB) and desferrioxamine (DES) all trapped within the horse spleen ferritin (HoSF) interior makes these measurements feasible. We report the rate of Fe(2+) penetrating into the ferritin interior by adding external Fe(2+) to [Fe(CN)(sub 6)](3-) encapsulated in the HoSF interior and measuring the rate of formation of the resulting encapsulated PB. The rate at which Fe(2+) reacts with [Fe(CN)(sub 6)](3-) in the HoSF interior is much slower than the formation of free PB in solution and is proceeded by a lag period. We assume this lag period and the difference in rate represent the transfer of Fe(2+) through the HoSF protein shell. The calculated diffusion coefficient, D approx. 5.8 x 10(exp -20) square meters per second corresponds to the measured lag time of 10-20 s before PB forms within the HoSF interior. The activation energy for Fe(2+) transfer from the outside solution through the protein shell was determined to be 52.9 kJ/mol by conducting the reactions at 10 to approximately 40 C. The reaction of Fe(3+) with encapsulated [Fe(CN)6](4-) also readily forms PB in the HoSF interior, but the rate is faster than the corresponding Fe(2+) reaction. The rate for Fe(3+) transfer through the ferritin shell was confirmed by measuring the rate of the formation of Fe-DES inside HoSF and an activation energy of 58.4 kJ/mol was determined. An attempt was made to determine the rate of iron (2+ and 3+) transit out from the ferritin interior by adding excess bipyridine or DES to PB trapped within the HoSF interior. However, the reactions are slow and occur at almost identical rates for free and HoSF-encapsulated PB, indicating that the transfer of iron from the interior through the protein shell is faster than the rate-limiting step of PB dissociation. The method described in this work presents a novel way of determining the rate of transfer of iron and possibly other small molecules through the ferritin shell.

Hybrid Magnetic Core-Shell Nanophotocatalysts for Environmental Applications

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

Gaulden, Patrick; Murph, Simona Hunyadi

2016-07-29

This research study describes a facile sol-gel method to creating hybrid iron (III) oxide/silica/titania nanomaterials decorated with gold nanoparticles for use in environmental applications. The multi-functional composition of the nanomaterials allows for photocatalyzed reactions to occur in both the visible and the UV range. The morphologies, elemental composition, and surface charge of the nanoparticles were determined by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and Phase Analysis Light Scattering (PALS), respectively. The photocatalytic activity of the synthesized hybrid nanoparticles for breaking down a model analyte, methyl orange (MO), was then evaluated using UV-Vis Spectroscopy. The efficiency of themore » photocatalyst under UV light irradiation was measured and compared to other well-studied nanophotocatalysts, namely titanium oxide and iron oxide nanoparticles. The concentration dependence of both the photocatalyst and the analyte was also investigated. By utilizing the known UV-active properties of TiO 2, the magnetic properties of Fe 2O 3, the optical properties of gold in the visible range of the spectrum, and the high stability of silica, a novel, highly efficient photocatalyst that is active on a broad range of the spectrum (UV-Vis) can be created to destroy organic pollutants in wastewater streams.« less

Plasma-assisted synthesis and study of structural and magnetic properties of Fe/C core shell

NASA Astrophysics Data System (ADS)

Shinde, K. P.; Ranot, M.; Choi, C. J.; Kim, H. S.; Chung, K. C.

2017-07-01

Pure and carbon-encapsulated iron nanoparticles with an average diameter of 25 nm were synthesized by using the DC plasma arc discharge method. Fe core nanoparticles were encapsulated with carbon layer, which is acting as protection layer against both oxidation and chemical reaction. The morphology and the Fe/C core/shell structure of the nanoparticles were studied by using field emission scanning electron microscopy and transmission electron microscopy. The x-ray diffraction study showed that the α-Fe phase exists with γ-Fe as an impurity. The studied samples have been interrelated with the variation of saturation magnetization, remanent magnetization and coercive field with the amount of carbon coating. The pure α-Fe sample shows saturation magnetization = 172 emu/g, and coercive field = 150 Oe, on the other hand few layer carbon coated α-Fe sample shows saturation magnetization =169 emu/g with higher coercive field 398 Oe.

Formation, Phase, and Elemental Composition of Micro- and Nano-Dimensional Particles of the Fe-Ti System

NASA Astrophysics Data System (ADS)

Dresvyannikov, A. F.; Kolpakov, M. E.

2018-05-01

X-ray fluorescence, X-ray phase analysis, and transmission Mössbauer and NGR spectrometry are used to study the formation, phase, and elemental composition of Fe-Ti particles. The interaction between Fe(III) ions and dispersed titanium in an aqueous solution containing chloride ions and HF is studied. It is shown that the resulting Fe-Ti samples are a set of core-shell microparticles with titanium cores coated with micro- and nanosized α-Fe nucleation centers with the thinness outer layer of iron(III) oxide characterized by a developed surface.

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.

Energetic electron processes fluorescence effects for structured nanoparticles X-ray analysis and nuclear medicine applications

NASA Astrophysics Data System (ADS)

Taborda, A.; Desbrée, A.; Carvalho, A.; Chaves, P. C.; Reis, M. A.

2016-08-01

Superparamagnetic iron oxide (SPIO) nanoparticles are widely used as contrast agents for nuclear magnetic resonance imaging (MRI), and can be modified for improved imaging or to become tissue-specific or even protein-specific. The knowledge of their detailed elemental composition characterisation and potential use in nuclear medicine applications, is, therefore, an important issue. X-ray fluorescence techniques such as particle induced X-ray emission (PIXE) or X-ray fluorescence spectrometry (XRF), can be used for elemental characterisation even in problematic situations where very little sample volume is available. Still, the fluorescence coefficient of Fe is such that, during the decay of the inner-shell ionised atomic structure, keV Auger electrons are produced in excess to X-rays. Since cross-sections for ionisation induced by keV electrons, for low atomic number atoms, are of the order of 103 barn, care should be taken to account for possible fluorescence effects caused by Auger electrons, which may lead to the wrong quantification of elements having atomic number lower than the atomic number of Fe. Furthermore, the same electron processes will occur in iron oxide nanoparticles containing 57Co, which may be used for nuclear medicine therapy purposes. In the present work, simple approximation algorithms are proposed for the quantitative description of radiative and non-radiative processes associated with Auger electrons cascades. The effects on analytical processes and nuclear medicine applications are quantified for the case of iron oxide nanoparticles, by calculating both electron fluorescence emissions and energy deposition on cell tissues where the nanoparticles may be embedded.

Disorders of metal metabolism

PubMed Central

Ferreira, Carlos R.; Gahl, William A.

2017-01-01

Trace elements are chemical elements needed in minute amounts for normal physiology. Some of the physiologically relevant trace elements include iodine, copper, iron, manganese, zinc, selenium, cobalt and molybdenum. Of these, some are metals, and in particular, transition metals. The different electron shells of an atom carry different energy levels, with those closest to the nucleus being lowest in energy. The number of electrons in the outermost shell determines the reactivity of such an atom. The electron shells are divided in sub-shells, and in particular the third shell has s, p and d sub-shells. Transition metals are strictly defined as elements whose atom has an incomplete d sub-shell. This incomplete d sub-shell makes them prone to chemical reactions, particularly redox reactions. Transition metals of biologic importance include copper, iron, manganese, cobalt and molybdenum. Zinc is not a transition metal, since it has a complete d sub-shell. Selenium, on the other hand, is strictly speaking a nonmetal, although given its chemical properties between those of metals and nonmetals, it is sometimes considered a metalloid. In this review, we summarize the current knowledge on the inborn errors of metal and metalloid metabolism. PMID:29354481

Model compounds of iron gall inks - a Mössbauer study

NASA Astrophysics Data System (ADS)

Lerf, A.; Wagner, F. E.

2016-12-01

Ferrogallic inks were used for at least two millennia before they became obsolete in the 20th century. The chemistry of such inks is, however, still largely unclear. Today it is of particular interest for the conservation of old manuscripts. 57Fe Mössbauer spectra of the ink on historical documents showed the presence of Fe(II) oxalate and of Fe(III) sites presumably representing iron oxihydroxides. To obtain more information on the behaviour of ink on paper we have performed Mössbauer studies at 300 and 4.2 K on iron gall inks prepared from FeSO4ṡ7H2O and tannin. These inks were either written on paper or isolated as a precipitate by centrifugation. In the dried precipitate there is still a strong contribution of the FeSO4ṡ7H2O which is absent in the same ink written on paper, for which a broad ferrous component with a quadrupole splitting (QS) of about 2.5 mm/s was found. The dominant Fe(III) site present in all inks on paper with QS ≈ 0.82 mm/s is not Fe(III) gallate and different from the precipitates. We propose that nanoparticulate oxidic clusters or molecular composites covered by a shell of polymerized oxidation products of the phenols are formed on the paper.

49 CFR 230.26 - Tensile strength of shell plates.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 49 Transportation 4 2011-10-01 2011-10-01 false Tensile strength of shell plates. 230.26 Section... Appurtenances Strength of Materials § 230.26 Tensile strength of shell plates. When the tensile strength of steel or wrought-iron shell plates is not known, it shall be taken at 50,000 psi for steel and 45,000...

49 CFR 230.26 - Tensile strength of shell plates.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Tensile strength of shell plates. 230.26 Section... Appurtenances Strength of Materials § 230.26 Tensile strength of shell plates. When the tensile strength of steel or wrought-iron shell plates is not known, it shall be taken at 50,000 psi for steel and 45,000...

Synthesis of fly ash based core-shell composites for use as functional pigment in paints

NASA Astrophysics Data System (ADS)

Sharma, Richa; Tiwari, Sangeeta

2016-04-01

Fly ash is a combustion residue, mainly composed of silica, alumina and iron oxides. It is produced by the power industries in very large amounts and usually disposed in landfills, which have represented an environmental problem in recent years1. The need to generate a market for fly ash consumption is the main reason why alternative applications have been studied. It has been applied as an additive in construction materials like cement and pavements2. The present work describes the synthesis of Flyash-Titania core-shell particles by precipitation technique using Titanium tetra isopropoxide (TTIP) which can be used for variety of applications such as NIR reflecting materials for cool coatings, Photocatalysis etc. In this work, Fly ash is used in core and Nano -TiO2 is coated as shell on it. Surfactants are used to improve the adhesion of Nano Titania shell on fly ash core. Effect on adhesion of TiO2 on Fly ash is studied by using different types of surfactant. The preparation of core shells was carried out in absence of surfactant as well as using anionic and non-ionic surfactants. The percentage of surfactant was varied to study the effect of amount of surfactant on the uniformity and size of particles in the shell using Kubelka-Munk transformed reflectance spectra. The morphology of core shell structures was studied using SEM technique. Use of anionic surfactant results in more uniform coating with reduced particle size of the shell material. The composite particles prepared by using anionic surfactant are having good pigment properties and also shows good reflectance in Near Infrared region and hence can be used as a pigment in cool coatings.

Preparation of Multifunctional Fe@Au Core-Shell Nanoparticles with Surface Grafting as a Potential Treatment for Magnetic Hyperthermia.

PubMed

Chung, Ren-Jei; Shih, Hui-Ting

2014-01-24

Iron core gold shell nanoparticles grafted with Methotrexate (MTX) and indocyanine green (ICG) were synthesized for the first time in this study, and preliminarily evaluated for their potential in magnetic hyperthermia treatment. The core-shell Fe@Au nanoparticles were prepared via the microemulsion process and then grafted with MTX and ICG using hydrolyzed poly(styrene-alt-maleic acid) (PSMA) to obtain core-shell Fe@Au-PSMA-ICG/MTX nanoparticles. MTX is an anti-cancer therapeutic, and ICG is a fluorescent dye. XRD, TEM, FTIR and UV-Vis spectrometry were performed to characterize the nanoparticles. The data indicated that the average size of the nanoparticles was 6.4 ± 09 nm and that the Au coating protected the Fe core from oxidation. MTX and ICG were successfully grafted onto the surface of the nanoparticles. Under exposure to high frequency induction waves, the superparamagnetic nanoparticles elevated the temperature of a solution in a few minutes, which suggested the potential for an application in magnetic hyperthermia treatment. The in vitro studies verified that the nanoparticles were biocompatible; nonetheless, the Fe@Au-PSMA-ICG/MTX nanoparticles killed cancer cells (Hep-G2) via the magnetic hyperthermia mechanism and the release of MTX.

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.

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

PubMed

Lapenna, Domenico; Ciofani, Giuliano; Obletter, Gabriele

2017-05-01

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

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.

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

Magnetic resonance imaging of reconstructed ferritin as an iron-induced pathological model system

NASA Astrophysics Data System (ADS)

Balejcikova, Lucia; Strbak, Oliver; Baciak, Ladislav; Kovac, Jozef; Masarova, Marta; Krafcik, Andrej; Frollo, Ivan; Dobrota, Dusan; Kopcansky, Peter

2017-04-01

Iron, an essential element of the human body, is a significant risk factor, particularly in the case of its concentration increasing above the specific limit. Therefore, iron is stored in the non-toxic form of the globular protein, ferritin, consisting of an apoferritin shell and iron core. Numerous studies confirmed the disruption of homeostasis and accumulation of iron in patients with various diseases (e.g. cancer, cardiovascular or neurological conditions), which is closely related to ferritin metabolism. Such iron imbalance enables the use of magnetic resonance imaging (MRI) as a sensitive technique for the detection of iron-based aggregates through changes in the relaxation times, followed by the change in the inherent image contrast. For our in vitrostudy, modified ferritins with different iron loadings were prepared by chemical reconstruction of the iron core in an apoferritin shell as pathological model systems. The magnetic properties of samples were studied using SQUID magnetometry, while the size distribution was detected via dynamic light scattering. We have shown that MRI could represent the most advantageous method for distinguishing native ferritin from reconstructed ferritin which, after future standardisation, could then be suitable for the diagnostics of diseases associated with iron accumulation.

The velocity and composition of supernova ejecta

NASA Technical Reports Server (NTRS)

Colgate, S. A.

1971-01-01

In case of the Gum nebula, a pulsar - a presumed neutron star - is believed to be a relic of the supernova explosion. Regardless of the mechanism of the explosion, the velocity distribution and composition of the ejected matter will be roughly the same. The reimploding mass fraction is presumed to be neutron rich. The final composition is thought to be roughly 1/3 iron and 2/3 silicon, with many small fractions of elements from helium to iron. The termination of helium shell burning occurs because the shell is expanded and cooled by radiation stress. The mass fraction of the helium burning shell was calculated.

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.

Different storage conditions influence biocompatibility and physicochemical properties of iron oxide nanoparticles.

PubMed

Zaloga, Jan; Janko, Christina; Agarwal, Rohit; Nowak, Johannes; Müller, Robert; Boccaccini, Aldo R; Lee, Geoffrey; Odenbach, Stefan; Lyer, Stefan; Alexiou, Christoph

2015-04-24

Superparamagnetic iron oxide nanoparticles (SPIONs) have attracted increasing attention in many biomedical fields. In magnetic drug targeting SPIONs are injected into a tumour supplying artery and accumulated inside the tumour with a magnet. The effectiveness of this therapy is thus dependent on magnetic properties, stability and biocompatibility of the particles. A good knowledge of the effect of storage conditions on those parameters is of utmost importance for the translation of the therapy concept into the clinic and for reproducibility in preclinical studies. Here, core shell SPIONs with a hybrid coating consisting of lauric acid and albumin were stored at different temperatures from 4 to 45 °C over twelve weeks and periodically tested for their physicochemical properties over time. Surprisingly, even at the highest storage temperature we did not observe denaturation of the protein or colloidal instability. However, the saturation magnetisation decreased by maximally 28.8% with clear correlation to time and storage temperature. Furthermore, the biocompatibility was clearly affected, as cellular uptake of the SPIONs into human T-lymphoma cells was crucially dependent on the storage conditions. Taken together, the results show that the particle properties undergo significant changes over time depending on the way they are stored.

Hollow spiny shell of porous Ni-Mn oxides: A facile synthesis route and their application as electrode in supercapacitors

NASA Astrophysics Data System (ADS)

Wan, Houzhao; Lv, Lin; Peng, Lu; Ruan, Yunjun; Liu, Jia; Ji, Xiao; Miao, Ling; Jiang, Jianjun

2015-07-01

Hollow spiny shell Ni-Mn precursors composed of one-dimensional nanoneedles were synthesized via a simple hydrothermal method without any template. The hollow Spiny shell Ni-Mn oxides are obtained under thermal treatment at different temperatures. The BET surface areas of Ni-Mn oxides reach up to 112 and 133 m2 g-1 when calcination temperatures occur at 300 and 400 °C, respectively. The electrochemical performances of as-synthesized hollow spiny shell Ni-Mn oxides gradually die down with annealing temperatures increasing. The porous hollow spiny shell Ni-Mn oxide obtained at 300 °C delivers a maximum capacitance of 1140 F g-1 at a high current density of 1 A g-1 after 1000th cycles and the specific capacitance of Ni-Mn oxide will increase with cycling times increasing. So, porous hollow spiny shell Ni-Mn oxide obtained at low annealing temperature can form a competitive electrode material for supercapacitors.

Design of Super-Paramagnetic Core-Shell Nanoparticles for Enhanced Performance of Inverted Polymer Solar Cells.

PubMed

Jaramillo, Johny; Boudouris, Bryan W; Barrero, César A; Jaramillo, Franklin

2015-11-18

Controlling the nature and transfer of excited states in organic photovoltaic (OPV) devices is of critical concern due to the fact that exciton transport and separation can dictate the final performance of the system. One effective method to accomplish improved charge separation in organic electronic materials is to control the spin state of the photogenerated charge-carrying species. To this end, nanoparticles with unique iron oxide (Fe3O4) cores and zinc oxide (ZnO) shells were synthesized in a controlled manner. Then, the structural and magnetic properties of these core-shell nanoparticles (Fe3O4@ZnO) were tuned to ensure superior performance when they were incorporated into the active layers of OPV devices. Specifically, small loadings of the core-shell nanoparticles were blended with the previously well-characterized OPV active layer of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Upon addition of the core-shell nanoparticles, the performance of the OPV devices was increased up to 25% relative to P3HT-PCBM active layer devices that contained no nanoparticles; this increase was a direct result of an increase in the short-circuit current densities of the devices. Furthermore, it was demonstrated that the increase in photocurrent was not due to enhanced absorption of the active layer due to the presence of the Fe3O4@ZnO core-shell nanoparticles. In fact, this increase in device performance occurred because of the presence of the superparamagnetic Fe3O4 in the core of the nanoparticles as incorporation of ZnO only nanoparticles did not alter the device performance. Importantly, however, the ZnO shell of the nanoparticles mitigated the negative optical effect of Fe3O4, which have been observed previously. This allowed the core-shell nanoparticles to outperform bare Fe3O4 nanoparticles when the single-layer nanoparticles were incorporated into the active layer of OPV devices. As such, the new materials described here present a tangible pathway toward the development of enhanced design schemes for inorganic nanoparticles such that magnetic and energy control pathways can be tailored for flexible electronic applications.

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.

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

Review of the Evidence from Epidemiology, Toxicology, and Lung Bioavailability on the Carcinogenicity of Inhaled Iron Oxide Particulates.

PubMed

Pease, Camilla; Rücker, Thomas; Birk, Thomas

2016-03-21

Since the iron-age and throughout the industrial age, humans have been exposed to iron oxides. Here, we review the evidence from epidemiology, toxicology, and lung bioavailability as to whether iron oxides are likely to act as human lung carcinogens. Current evidence suggests that observed lung tumors in rats result from a generic particle overload effect and local inflammation that is rat-specific under the dosing conditions of intratracheal instillation. This mode of action therefore, is not relevant to human exposure. However, there are emerging differences seen in vitro, in cell uptake and cell bioavailability between "bulk" iron oxides and "nano" iron oxides. "Bulk" particulates, as defined here, are those where greater than 70% are >100 nm in diameter. Similarly, "nano" iron oxides are defined in this context as particulates where the majority, usually >95% for pure engineered forms of primary particulates (not agglomerates), fall in the range 1-100 nm in diameter. From the weight of scientific evidence, "bulk" iron oxides are not genotoxic/mutagenic. Recent evidence for "nano" iron oxide is conflicting regarding genotoxic potential, albeit genotoxicity was not observed in an in vivo acute oral dose study, and "nano" iron oxides are considered safe and are being investigated for biomedical uses; there is no specific in vivo genotoxicity study on "nano" iron oxides via inhalation. Some evidence is available that suggests, hypothetically due to the larger surface area of "nano" iron oxide particulates, that toxicity could be exerted via the generation of reactive oxygen species (ROS) in the cell. However, the potential for ROS generation as a basis for explaining rodent tumorigenicity is only apparent if free iron from intracellular "nano" scale iron oxide becomes bioavailable at significant levels inside the cell. This would not be expected from "bulk" iron oxide particulates. Furthermore, human epidemiological evidence from a number of studies suggests that iron oxide is not a human carcinogen, and therefore, based upon the complete weight of evidence, we conclude that "bulk" iron oxides are not human carcinogens.

Construction of Matryoshka-type structures from supercharged protein nanocages.

PubMed

Beck, Tobias; Tetter, Stephan; Künzle, Matthias; Hilvert, Donald

2015-01-12

Designing nanoscaled hierarchical structures with increasing levels of complexity is challenging. Here we show that electrostatic interactions between two complementarily supercharged protein nanocages can be effectively utilized to create nested Matryoshka-type structures. Cage-within-cage complexes containing spatially ordered iron oxide nanoparticles spontaneously self-assemble upon mixing positively supercharged ferritin compartments with AaLS-13, a larger shell-forming protein with a negatively supercharged lumen. Exploiting engineered Coulombic interactions and protein dynamics in this way opens up new avenues for creating hierarchically organized supramolecular assemblies for application as delivery vehicles, reaction chambers, and artificial organelles. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of magnetic nanoparticles and overcoatings for biological applications including a sensor device

NASA Astrophysics Data System (ADS)

Grancharov, Stephanie G.

I. A general introduction to the field of nanomaterials is presented, highlighting their special attributes and characteristics. Nanoparticles in general are discussed with respect to their structure, form and properties. Magnetic particles in particular are highlighted, especially the iron oxides. The importance and interest of integrating these materials with biological media is discussed, with emphasis on transferring particles from one medium to another, and subsequent modification of surfaces with different types of materials. II. A general route to making magnetic iron oxide nanoparticles is explained, both as maghemite and magnetite, including properties of the particles and characterization. A novel method of producing magnetite particles without a ligand is then presented, with subsequent characterization and properties described. III. Attempts to coat iron oxide nanoparticles with a view to creating biofunctional magnetic nanoparticles are presented, using a gold overcoating method. Methods of synthesis and characterization are examined, with unique problems to core-shell structures analyzed. IV. Solubility of nanoparticles in both aqueous and organic media is discussed and examined. The subsequent functionalization of the surface of maghemite and magnetite nanoparticles with a variety of biomaterials including block copolypeptides, phospholipids and carboxydextran is then presented. These methods are integral to the use of magnetic nanoparticles in biological applications, and therefore their properties are examined once tailored with these molecules. V. A new type of magnetic nanoparticle sensor-type device is described. This device integrates bio-and DNA-functionalized nanoparticles with conjugate functionalized silicon dioxide surfaces. These techniques to pattern particles to a surface are then incorporated into a device with a magnetic tunnel junction, which measures magnetoresistance in the presence of an external magnetic field. This configuration thereby introduces a new way to detect magnetic nanoparticles via their magnetic properties after conjugation via biological entities.

Properties and biomedical applications of magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Regmi, Rajesh Kumar

Magnetic nanoparticles have a number of unique properties, making them promising agents for applications in medicine including magnetically targeted drug delivery, magnetic hyperthermia, magnetic resonance imaging, and radiation therapy. They are biocompatible and can also be coated with biocompatible surfactants, which may be further functionalized with optically and therapeutically active molecules. These nanoparticles can be manipulated with non-invasive external magnetic field to produce heat, target specific site, and monitor their distribution in vivo. Within this framework, we have investigated a number of biomedical applications of these nanoparticles. We synthesized a thermosensitive microgel with iron oxide adsorbed on its surface. An alternating magnetic field applied to these nanocomposites heated the system and triggered the release of an anticancer drug mitoxantrone. We also parameterized the chain length dependence of drug release from dextran coated iron oxide nanoparticles, finding that both the release rate and equilibrium release fraction depend on the molecular mass of the surfactant. Finally, we also localized dextran coated iron oxide nanoparticles labeled with tat peptide to the cell nucleus, which permits this system to be used for a variety of biomedical applications. Beyond investigating magnetic nanoparticles for biomedical applications, we also studied their magnetohydrodynamic and dielectric properties in solution. Magnetohydrodynamic properties of ferrofluid can be controlled by appropriate selection of surfactant and deielctric measurement showed magnetodielectric coupling in this system. We also established that some complex low temperature spin structures are suppressed in Mn3O4 nanoparticles, which has important implications for nanomagnetic devices. Furthermore, we explored exchange bias effects in Ni-NiO core-shell nanoparticles. Finally, we also performed extensive magnetic studies in nickel metalhydride (NiMH) batteries to determine the size of Ni clusters, which plays important role on catalyzing the electrochemical reaction and powering Ni-MH batteries.

Roles of nuclear weak rates on the evolution of degenerate cores in stars

NASA Astrophysics Data System (ADS)

Suzuki, Toshio; Tsunodaa, Naofumi; Tsunoda, Yuhsuke; Shimizu, Noritaka; Otsuka, Takaharu

2018-01-01

Electron-capture and β-decay rates in stellar environments are evaluated with the use of new shell-model Hamiltonians for sd-shell and pf-shell nuclei as well as for nuclei belonging to the island of inversion. Important role of the nuclear weak rates on the final evolution of stellar degenerate cores is presented. The weak interaction rates for sd-shell nuclei are calculated to study nuclear Urca processes in O-Ne-Mg cores of stars with 8-10 M⊙ (solar mass) and their effects on the final fate of the stars. Nucleosynthesis of iron-group elements in Type Ia supernova explosions are studied with the weak rates for pf-shell nuclei. The problem of the neutron-rich iron-group isotope over-production compared to the solar abundances is shown to be nearly solved with the use of the new rates and explosion model of slow defraglation with delayed detonation. Evaluation of the weak rates is extended to the island of inversion and the region of neutron-rich nuclei near 78Ni, where two major shells contribute to their configurations.

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.

Improved open-circuit voltage in polymer/oxide-nanoarray hybrid solar cells by formation of homogeneous metal oxide core/shell structures.

PubMed

Wu, Fan; Cui, Qi; Qiu, Zeliang; Liu, Changwen; Zhang, Hui; Shen, Wei; Wang, Mingtai

2013-04-24

Incorporation of vertically aligned nanorod/nanowire arrays of metal oxide (oxide-NAs) with a polymer can produce efficient hybrid solar cells with an ideal bulk-heterojunction architecture. However, polymer/oxide-NAs solar cells still suffer from a rather low (normally, < 0.4 V) open-circuit voltage (Voc). Here we demonstrate, for the first time, a novel strategy to improve the Voc in polymer/oxide-NAs solar cells by formation of homogeneous core/shell structures and reveal the intrinsic principles involved therein. A feasible hydrothermal-solvothermal combined method is developed for preparing homogeneous core/shell nanoarrays of metal oxides with a single-crystalline nanorod as core and the aggregation layer of corresponding metal oxide quantum dots (QDs) as shell, and the shell thickness (L) is easily controlled by the solvothermal reaction time for growing QDs on the nanorod. The core/shell formation dramatically improves the device Voc up to ca. 0.7-0.8 V depending on L. Based on steady-state and dynamic measurements, as well as modeling by space-charge-limited current method, it is found that the improved Voc originates from the up-shifted conduction band edge in the core by the interfacial dipole field resulting from the decreased mobility difference between photogenerated electrons and holes after the shell growth, which increases the energy difference between the quasi-Fermi levels of photogenerated electrons in the core and holes in the polymer for a higher Voc. Our results indicate that increasing Voc by the core/shell strategy seems not to be dependent on the kinds of metal oxides.

Analysis of magnetite crystals and inclusion bodies inside magnetotactic bacteria from different environmental locations

NASA Astrophysics Data System (ADS)

Oestreicher, Z.; Lower, B.; Lower, S.; Bazylinski, D. A.

2011-12-01

Biomineralization occurs throughout the living world; a few common examples include iron oxide in chiton teeth, calcium carbonate in mollusk shells, calcium phosphate in animal bones and teeth, silica in diatom shells, and magnetite crystals inside the cells of magnetotactic bacteria. Biologically controlled mineralization is characterized by biominerals that have species-specific properties such as: preferential crystallographic orientation, consistent particle size, highly ordered spatial locations, and well-defined composition and structure. It is well known that magnetotactic bacteria synthesize crystals of magnetite inside of their cells, but how they mineralize the magnetite is poorly understood. Magnetosomes have a species-specific morphology that is due to specific proteins involved in the mineralization process. In addition to magnetite crystals, magnetotactic bacteria also produce inclusion bodies or granules that contain different elements, such as phosphorus, calcium, and sulfur. In this study we used the transmission electron microscope to analyze the structure of magnetite crystals and inclusion bodies from different species of magnetotactic bacteria in order to determine the composition of the inclusion bodies and to ascertain whether or not the magnetite crystals contain elements other than iron and oxygen. Using energy dispersive spectroscopy we found that different bacteria from different environments possess inclusion bodies that contain different elements such as phosphorus, calcium, barium, magnesium, and sulfur. These differences may reflect the conditions of the environment in which the bacteria inhabit.

Developing Test Apparatus and Measurements of AC Loss of High Temperature Superconductors

DTIC Science & Technology

2012-11-01

temperature of the coil is not raised significantly. The second system, a larger machine, designed with a long term prospective to serve a test bed for...four sample chambers inside the vacuum gap, LN2 – cooled sample holder (currently only one is in use), the laminated back iron, and the outer shell...machine. accommodate a variety of different small coils and linear tapes. This assembly is surrounded by the laminated back iron and the outer shell

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

Lu, S; Chourey, Karuna; REICHE, M

Metaproteomics combined with total nucleic acid-based methods aided in deciphering the roles of microorganisms in the formation and transformation of iron-rich macroscopic aggregates (iron snow) formed in the redoxcline of an acidic lignite mine lake. Iron snow had high total bacterial 16S rRNA gene copies, with 2 x 109 copies g (dry wt)-1 in the acidic (pH 3.5) central lake basin and 4 x 1010 copies g (dry wt)-1 in the less acidic (pH 5.5) northern lake basin. Active microbial communities in the central basin were dominated by Alphaproteobacteria (36.6%) and Actinobacteria (21.4%), and by Betaproteobacteria (36.2%) in the northernmore » basin. Microbial Fe-cycling appeared to be the dominant metabolism in the schwertmannite-rich iron snow, because cloning and qPCR assigned up to 61% of active bacteria as Fe-cycling bacteria (FeB). Metaproteomics revealed 70 unique proteins from central basin iron snow and 283 unique proteins from 43 genera from northern basin. Protein identification provided a glimpse into in situ processes, such as primary production, motility, metabolism of acidophilic FeB, and survival strategies of neutrophilic FeB. Expression of carboxysome shell proteins and RubisCO indicated active CO2 fixation by Fe(II) oxidizers. Flagellar proteins from heterotrophs indicated their activity to reach and attach surfaces. Gas vesicle proteins related to CO2-fixing Chlorobium suggested that microbes could influence iron snow sinking. We suggest that iron snow formed by autotrophs in the redoxcline acts as a microbial parachute, since it is colonized by motile heterotrophs during sinking which start to dissolve schwertmannite.« less

Redox Transformations of Iron at Extremely Low pH: Fundamental and Applied Aspects.

PubMed

Johnson, D Barrie; Kanao, Tadayoshi; Hedrich, Sabrina

2012-01-01

Many different species of acidophilic prokaryotes, widely distributed within the domains Bacteria and Archaea, can catalyze the dissimilatory oxidation of ferrous iron or reduction of ferric iron, or can do both. Microbially mediated cycling of iron in extremely acidic environments (pH < 3) is strongly influenced by the enhanced chemical stability of ferrous iron and far greater solubility of ferric iron under such conditions. Cycling of iron has been demonstrated in vitro using both pure and mixed cultures of acidophiles, and there is considerable evidence that active cycling of iron occurs in acid mine drainage streams, pit lakes, and iron-rich acidic rivers, such as the Rio Tinto. Measurements of specific rates of iron oxidation and reduction by acidophilic microorganisms show that different species vary in their capacities for iron oxido-reduction, and that this is influenced by the electron donor provided and growth conditions used. These measurements, and comparison with corresponding data for oxidation of reduced sulfur compounds, also help explain why ferrous iron is usually used preferentially as an electron donor by acidophiles that can oxidize both iron and sulfur, even though the energy yield from oxidizing iron is much smaller than that available from sulfur oxidation. Iron-oxidizing acidophiles have been used in biomining (a technology that harness their abilities to accelerate the oxidative dissolution of sulfidic minerals and thereby facilitate the extraction of precious and base metals) for several decades. More recently they have also been used to simultaneously remediate iron-contaminated surface and ground waters and produce a useful mineral by-product (schwertmannite). Bioprocessing of oxidized mineral ores using acidophiles that catalyze the reductive dissolution of ferric iron minerals such as goethite has also recently been demonstrated, and new biomining technologies based on this approach are being developed.

Redox Transformations of Iron at Extremely Low pH: Fundamental and Applied Aspects

PubMed Central

Johnson, D. Barrie; Kanao, Tadayoshi; Hedrich, Sabrina

2012-01-01

Many different species of acidophilic prokaryotes, widely distributed within the domains Bacteria and Archaea, can catalyze the dissimilatory oxidation of ferrous iron or reduction of ferric iron, or can do both. Microbially mediated cycling of iron in extremely acidic environments (pH < 3) is strongly influenced by the enhanced chemical stability of ferrous iron and far greater solubility of ferric iron under such conditions. Cycling of iron has been demonstrated in vitro using both pure and mixed cultures of acidophiles, and there is considerable evidence that active cycling of iron occurs in acid mine drainage streams, pit lakes, and iron-rich acidic rivers, such as the Rio Tinto. Measurements of specific rates of iron oxidation and reduction by acidophilic microorganisms show that different species vary in their capacities for iron oxido-reduction, and that this is influenced by the electron donor provided and growth conditions used. These measurements, and comparison with corresponding data for oxidation of reduced sulfur compounds, also help explain why ferrous iron is usually used preferentially as an electron donor by acidophiles that can oxidize both iron and sulfur, even though the energy yield from oxidizing iron is much smaller than that available from sulfur oxidation. Iron-oxidizing acidophiles have been used in biomining (a technology that harness their abilities to accelerate the oxidative dissolution of sulfidic minerals and thereby facilitate the extraction of precious and base metals) for several decades. More recently they have also been used to simultaneously remediate iron-contaminated surface and ground waters and produce a useful mineral by-product (schwertmannite). Bioprocessing of oxidized mineral ores using acidophiles that catalyze the reductive dissolution of ferric iron minerals such as goethite has also recently been demonstrated, and new biomining technologies based on this approach are being developed. PMID:22438853

Effects of iron content in Ni-Cr-xFe alloys and immersion time on the oxide films formed in a simulated PWR water environment

NASA Astrophysics Data System (ADS)

Ru, Xiangkun; Lu, Zhanpeng; Chen, Junjie; Han, Guangdong; Zhang, Jinlong; Hu, Pengfei; Liang, Xue

2017-12-01

The iron content in Ni-Cr-xFe (x = 0-9 at.%) alloys strongly affected the properties of oxide films after 978 h of immersion in the simulated PWR primary water environment at 310 °C. Increasing the iron content in the alloys increased the amount of iron-bearing polyhedral spinel oxide particles in the outer oxide layer and increased the local oxidation penetrations into the alloy matrix from the chromium-rich inner oxide layer. The effects of iron content in the alloys on the oxide film properties after 500 h of immersion were less significant than those after 978 h. Iron content increased, and chromium content decreased, in the outer oxide layer with increasing iron content in the alloys. Increasing the immersion time facilitated the formation of the local oxidation penetrations along the matrix/film interface and the nickel-bearing spinel oxides in the outer oxide layer.

Highly magneto-responsive multilayer microcapsules for controlled release of insulin.

PubMed

Zheng, Chunli; Ding, Yafei; Liu, Xiaoqing; Wu, Yunkai; Ge, Liang

2014-11-20

In this study, magneto-responsive polyelectrolyte multilayer microcapsules were successfully prepared by the formation of shell with biocompatible iron oxide nanoparticles (Fe₃O₄ NPs) and polyallylamine hydrochloride (PAH) by layer-by-layer (LbL) self-assembly technique. The self-assembled microcapsules were characterized by SEM, TEM and zeta-potential analyzer. According to the pH sensitivity of the microcapsule membrane permeability, insulin was encapsulated, with the encapsulation efficiency of 92.08±5.57%. The in vitro release behavior in an external alternating magnetic field indicated that once the magnetic field was applied, the drug release was greatly accelerated. In addition, according to the observed pulse release upon cyclic on-off operations of magnetic field, it could be assumed that the magneto-responsive microcapsules had an excellent "switching on" effect, which might be attributed to the rearrangement of shell structure caused by magnetic nanoparticles twisting and polyelectrolyte chains shaking, hence the increase of microcapsule membrane permeability and the enhancement of insulin release. Copyright © 2014 Elsevier B.V. All rights reserved.

Methanol oxidation reaction on core-shell structured Ruthenium-Palladium nanoparticles: Relationship between structure and electrochemical behavior

NASA Astrophysics Data System (ADS)

Kübler, Markus; Jurzinsky, Tilman; Ziegenbalg, Dirk; Cremers, Carsten

2018-01-01

In this work the relationship between structural composition and electrochemical characteristics of Palladium(Pd)-Ruthenium(Ru) nanoparticles during alkaline methanol oxidation reaction is investigated. The comparative study of a standard alloyed and a precisely Ru-core-Pd-shell structured catalyst allows for a distinct investigation of the electronic effect and the bifunctional mechanism. Core-shell catalysts benefit from a strong electronic effect and an efficient Pd utilization. It is found that core-shell nanoparticles are highly active towards methanol oxidation reaction for potentials ≥0.6 V, whereas alloyed catalysts show higher current outputs in the lower potential range. However, differential electrochemical mass spectrometry (DEMS) experiments reveal that the methanol oxidation reaction on core-shell structured catalysts proceeds via the incomplete oxidation pathway yielding formaldehyde, formic acid or methyl formate. Contrary, the alloyed catalyst benefits from the Ru atoms at its surface. Those are found to be responsible for high methanol oxidation activity at lower potentials as well as for complete oxidation of CH3OH to CO2 via the bifunctional mechanism. Based on these findings a new Ru-core-Pd-shell-Ru-terrace catalyst was synthesized, which combines the advantages of the core-shell structure and the alloy. This novel catalyst shows high methanol electrooxidation activity as well as excellent selectivity for the complete oxidation pathway.

Tropical forest soil microbial communities couple iron and carbon biogeochemistry

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

Dubinsky, E.A.; Silver, W.L.; Firestone, M.K.

2009-10-15

We report that iron-reducing bacteria are primary mediators of anaerobic carbon oxidation in upland tropical soils spanning a rainfall gradient (3500 - 5000 mm yr-1) in northeast Puerto Rico. The abundant rainfall and high net primary productivity of these tropical forests provide optimal soil habitat for iron-reducing and iron-oxidizing bacteria. Spatially and temporally dynamic redox conditions make iron-transforming microbial communities central to the belowground carbon cycle in these wet tropical forests. The exceedingly high abundance of iron-reducing bacteria (up to 1.2 x 10{sup 9} cells per gram soil) indicated that they possess extensive metabolic capacity to catalyze the reduction ofmore » iron minerals. In soils from the higher rainfall sites, measured rates of ferric iron reduction could account for up to 44 % of organic carbon oxidation. Iron reducers appeared to compete with methanogens when labile carbon availability was limited. We found large numbers of bacteria that oxidize reduced iron at sites with high rates of iron reduction and large numbers of iron-reducers. the coexistence of large populations of ironreducing and iron-oxidizing bacteria is evidence for rapid iron cycling between its reduced and oxidized states, and suggests that mutualistic interactions among these bacteria ultimately fuel organic carbon oxidation and inhibit CH4 production in these upland tropical forests.« less

Use of Walnut Shell Powder to Inhibit Expression of Fe2+-Oxidizing Genes of Acidithiobacillus Ferrooxidans

PubMed Central

Li, Yuhui; Liu, Yehao; Tan, Huifang; Zhang, Yifeng; Yue, Mei

2016-01-01

Acidithiobacillus ferrooxidans is a Gram-negative bacterium that obtains energy by oxidizing Fe2+ or reduced sulfur compounds. This bacterium contributes to the formation of acid mine drainage (AMD). This study determined whether walnut shell powder inhibits the growth of A. ferrooxidans. First, the effects of walnut shell powder on Fe2+ oxidization and H+ production were evaluated. Second, the chemical constituents of walnut shell were isolated to determine the active ingredient(s). Third, the expression of Fe2+-oxidizing genes and rus operon genes was investigated using real-time polymerase chain reaction. Finally, growth curves were plotted, and a bioleaching experiment was performed to confirm the active ingredient(s) in walnut shells. The results indicated that both walnut shell powder and the phenolic fraction exert high inhibitory effects on Fe2+ oxidation and H+ production by A. ferrooxidans cultured in standard 9K medium. The phenolic components exert their inhibitory effects by down-regulating the expression of Fe2+-oxidizing genes and rus operon genes, which significantly decreased the growth of A. ferrooxidans. This study revealed walnut shell powder to be a promising substance for controlling AMD. PMID:27144574

Synthesis and characterization of fluorinated magnetic core-shell nanoparticles for inhibition of insulin amyloid fibril formation

NASA Astrophysics Data System (ADS)

Skaat, Hadas; Belfort, Georges; Margel, Shlomo

2009-06-01

Maghemite (γ-Fe2O3) magnetic nanoparticles of 15.0 ± 2.1 nm are formed by nucleation followed by controlled growth of maghemite thin films on gelatin-iron oxide nuclei. Uniform magnetic γ-Fe2O3/poly (2,2,3,3,4,4,4-heptafluorobutyl acrylate) (γ-Fe2O3/PHFBA) core-shell nanoparticles are prepared by emulsion polymerization of the fluorinated monomer 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) in the presence of the maghemite nanoparticles. The kinetics of the insulin fibrillation process in the absence and in the presence of the γ-Fe2O3/PHFBA core-shell nanoparticles are elucidated. A significant direct slow transition from α-helix to β-sheets during insulin fibril formation is observed in the presence of the γ-Fe2O3/PHFBA nanoparticles. This is in contradiction to our previous manuscript, which illustrated that the γ-Fe2O3 core nanoparticles do not affect the kinetics of the formation of the insulin fibrils, and to other previous publications that describe acceleration of the fibrillation process by using various types of nanoparticles. These core-shell nanoparticles may therefore be also useful for the inhibition of conformational changes of other amyloidogenic proteins that lead to neurodegenerative diseases such as Alzheimer's, Parkinson's, Huntington's, mad cow and prion diseases.

Hollow nanoparticle cathode materials for sodium electrochemical cells and batteries

DOEpatents

Shevchenko, Elena; Rajh, Tijana; Johnson, Christopher S.; Koo, Bonil

2016-07-12

A cathode comprises, in its discharged state, a layer of hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles disposed between two layers of carbon nanotubes, and preferably including a metallic current collector in contact with one of the layers of carbon nanotubes. Individual particles of the hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles comprise a crystalline shell of .gamma.-Fe.sub.2O.sub.3 including cation vacancies within the crystal structure of the shell (i.e., iron vacancies of anywhere between 3% to 90%, and preferably 44 to 77% of available octahedral iron sites). Sodium ions are intercalated within at least some of the cation vacancies within the crystalline shell of the hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles.

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

PubMed

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

2011-11-01

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

SYNTHESIS AND APPLICATIONS OF Fe3O4/SiO2 CORE-SHELL MATERIALS.

PubMed

Sonmez, Maria; Georgescu, Mihai; Alexandrescu, Laurentia; Gurau, Dana; Ficai, Anton; Ficai, Denisa; Andronescu, Ecaterina

2015-01-01

Multifunctional nanoparticles based on magnetite/silica core-shell, consisting of iron oxides coated with silica matrix doped with fluorescent components such as organic dyes (fluorescein isothiocyanate - FITC, Rhodamine 6G) or quantum dots, have drawn remarkable attention in the last years. Due to the bi-functionality of these types of nanoparticles (simultaneously having magnetic and fluorescent properties), they are successfully used in highly efficient human stem cell labeling, magnetic carrier for photodynamic therapy, drug delivery, hyperthermia and other biomedical applications. Another application of core-shell-based nanoparticles, in which the silica is functionalized with aminosilanes, is for immobilization and separation of various biological entities such as proteins, antibodies, enzymes etc. as well as in environmental applications, as adsorbents for heavy metal ions. In vitro tests on human cancerous cells, such as A549 (human lung carcinoma), breast, human cervical cancer, THP-1 (human acute monocytic leukaemia) etc. , were conducted to assess the potential cytotoxic effects that may occur upon contact of nanoparticles with cancerous tissue. Results show that core-shell nanoparticles doped with cytostatics (cisplatin, doxorubicin, etc.), are easily adsorbed by affected tissue and in some cases lead to an inhibition of cell proliferation and induce cell death by apoptosis. The goal of this review is to summarize the advances in the field of core-shell materials, particularly those based on magnetite/silica with applicability in medicine and environmental protection. This paper briefly describes synthesis methods of silica-coated magnetite nanoparticles (Stöber method and microemulsion), the method of encapsulating functional groups based on aminosilanes in silica shell, as well as applications in medicine of these types of simple or modified nanoparticles for cancer therapy, MRI, biomarker immobilization, drug delivery, biocatalysis etc., and in environmental applications (removal of heavy metal ions and catalysis).

Protein Nanoscaffolds for Delivering Toxic Inorganic Cargo to Cancer Cells

NASA Astrophysics Data System (ADS)

Cioloboc, Daniela

Targeted delivery of anticancer drugs or prodrugs to tumors can minimize systemic toxicity and side effects. This study develops platforms for targeted delivery of two potentially less systemically toxic prodrugs by exploiting the native and/or bioinorganic properties of two ferritins, both of which function naturally as iron storage proteins. Two delivery approaches were investigated. The first system was designed to serve as either an enhancement or alternative to traditional photodynamic therapy by generating hydroxyl radical in addition to singlet oxygen as the toxic reactive oxygen species. This system used Escherichia coli bacterioferritin (Bfr) loaded with 2,500 irons and multiple zinc-porphyrin (ZnP) photosensitizers. Ferrous iron was released by photoreduction of ferric iron stored within the Bfr protein shell. Hydroxyl radicals were generated via the Fenton reaction between hydrogen peroxide and the released ferrous iron. The outer surface of the Bfr protein shell was coated with peptides that specifically bind to a receptor known to be overexpressed in many tumor cells and tumor vasculature. The iron-loaded peptide-ZnP-Bfr was endocytosed by melanoma cells, where it showed photo-triggered release of iron and light-dependent cytotoxicity. The second system, built around human heavy chain ferritin (HFn), was loaded with arsenate as a less toxic "prodrug" and designed to release arsenic in its toxic, therapeutically effective reduced form, arsenic trioxide (ATO). The Hfn shell was coated with peptides targeting receptors that are hyperexpressed in triple negative breast cancers. The arsenate/iron-loaded-Hfn was endocytosed by a breast cancer cell line and showed cytotoxicity equivalent to that of free ATO on an arsenic basis, whereas the "empty" or iron-only loaded Hfn showed no cytotoxicity. Although HFn has previously been used to deliver organic drugs and imaging agents, these new results demonstrate that both Bfr and HFn can be manipulated to function as 'Trojan horse' nanocarriers for inorganic drugs.

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.

Nanostructured core-shell electrode materials for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Jiang, Long-bo; Yuan, Xing-zhong; Liang, Jie; Zhang, Jin; Wang, Hou; Zeng, Guang-ming

2016-11-01

Core-shell nanostructure represents a unique system for applications in electrochemical energy storage devices. Owing to the unique characteristics featuring high power delivery and long-term cycling stability, electrochemical capacitors (ECs) have emerged as one of the most attractive electrochemical storage systems since they can complement or even replace batteries in the energy storage field, especially when high power delivery or uptake is needed. This review aims to summarize recent progress on core-shell nanostructures for advanced supercapacitor applications in view of their hierarchical architecture which not only create the desired hierarchical porous channels, but also possess higher electrical conductivity and better structural mechanical stability. The core-shell nanostructures include carbon/carbon, carbon/metal oxide, carbon/conducting polymer, metal oxide/metal oxide, metal oxide/conducting polymer, conducting polymer/conducting polymer, and even more complex ternary core-shell nanoparticles. The preparation strategies, electrochemical performances, and structural stabilities of core-shell materials for ECs are summarized. The relationship between core-shell nanostructure and electrochemical performance is discussed in detail. In addition, the challenges and new trends in core-shell nanomaterials development have also been proposed.

Influence of Shell Thickness on the Colloidal Stability of Magnetic Core-Shell Particle Suspensions

PubMed Central

Neville, Frances; Moreno-Atanasio, Roberto

2018-01-01

We present a Discrete Element study of the behavior of magnetic core-shell particles in which the properties of the core and the shell are explicitly defined. Particle cores were considered to be made of pure iron and thus possessed ferromagnetic properties, while particle shells were considered to be made of silica. Core sizes ranged between 0.5 and 4.0 μm with the actual particle size of the core-shell particles in the range between 0.6 and 21 μm. The magnetic cores were considered to have a magnetization of one tenth of the saturation magnetization of iron. This study aimed to understand how the thickness of the shell hinders the formation of particle chains. Chain formation was studied with different shell thicknesses and particle sizes in the presence and absence of an electrical double layer force in order to investigate the effect of surface charge density on the magnetic core-shell particle interactions. For core sizes of 0.5 and 4.0 μm the relative shell thicknesses needed to hinder the aggregation process were approximately 0.4 and 0.6 respectively, indicating that larger core sizes are detrimental to be used in applications in which no flocculation is needed. In addition, the presence of an electrical double layer, for values of surface charge density of less than 20 mC/m2, could stop the contact between particles without hindering their vertical alignment. Only when the shell thickness was considerably larger, was the electrical double layer able to contribute to the full disruption of the magnetic flocculation process. PMID:29922646

Influence of Shell Thickness on the Colloidal Stability of Magnetic Core-Shell Particle Suspensions.

PubMed

Neville, Frances; Moreno-Atanasio, Roberto

2018-01-01

We present a Discrete Element study of the behavior of magnetic core-shell particles in which the properties of the core and the shell are explicitly defined. Particle cores were considered to be made of pure iron and thus possessed ferromagnetic properties, while particle shells were considered to be made of silica. Core sizes ranged between 0.5 and 4.0 μm with the actual particle size of the core-shell particles in the range between 0.6 and 21 μm. The magnetic cores were considered to have a magnetization of one tenth of the saturation magnetization of iron. This study aimed to understand how the thickness of the shell hinders the formation of particle chains. Chain formation was studied with different shell thicknesses and particle sizes in the presence and absence of an electrical double layer force in order to investigate the effect of surface charge density on the magnetic core-shell particle interactions. For core sizes of 0.5 and 4.0 μm the relative shell thicknesses needed to hinder the aggregation process were approximately 0.4 and 0.6 respectively, indicating that larger core sizes are detrimental to be used in applications in which no flocculation is needed. In addition, the presence of an electrical double layer, for values of surface charge density of less than 20 mC/m 2 , could stop the contact between particles without hindering their vertical alignment. Only when the shell thickness was considerably larger, was the electrical double layer able to contribute to the full disruption of the magnetic flocculation process.

Whey Peptide-Iron Complexes Increase the Oxidative Stability of Oil-in-Water Emulsions in Comparison to Iron Salts.

PubMed

Caetano-Silva, Maria Elisa; Barros Mariutti, Lilian Regina; Bragagnolo, Neura; Bertoldo-Pacheco, Maria Teresa; Netto, Flavia Maria

2018-02-28

Food fortification with iron may favor lipid oxidation in both food matrices and the human body. This study aimed at evaluating the effect of peptide-iron complexation on lipid oxidation catalyzed by iron, using oil-in-water (O/W) emulsions as a model system. The extent of lipid oxidation of emulsions containing iron salts (FeSO 4 or FeCl 2 ) or iron complexes (peptide-iron complexes or ferrous bisglycinate) was evaluated during 7 days, measured as primary (peroxide value) and secondary products (TBARS and volatile compounds). Both salts catalyzed lipid oxidation, leading to peroxide values 2.6- to 4.6-fold higher than the values found for the peptide-iron complexes. The addition of the peptide-iron complexes resulted in the formation of lower amounts of secondary volatiles of lipid oxidation (up to 78-fold) than those of iron salts, possibly due to the antioxidant activity of the peptides and their capacity to keep iron apart from the lipid phase, since the iron atom is coordinated and takes part in a stable structure. The peptide-iron complexes showed potential to reduce the undesirable sensory changes in food products and to decrease the side effects related to free iron and the lipid damage of cell membranes in the organism, due to the lower reactivity of iron in the complexed form.

Convection-enhanced delivery and in vivo imaging of polymeric nanoparticles for the treatment of malignant glioma.

PubMed

Bernal, Giovanna M; LaRiviere, Michael J; Mansour, Nassir; Pytel, Peter; Cahill, Kirk E; Voce, David J; Kang, Shijun; Spretz, Ruben; Welp, Ulrich; Noriega, Sandra E; Nunez, Luis; Larsen, Gustavo F; Weichselbaum, Ralph R; Yamini, Bakhtiar

2014-01-01

A major obstacle to the management of malignant glioma is the inability to effectively deliver therapeutic agent to the tumor. In this study, we describe a polymeric nanoparticle vector that not only delivers viable therapeutic, but can also be tracked in vivo using MRI. Nanoparticles, produced by a non-emulsion technique, were fabricated to carry iron oxide within the shell and the chemotherapeutic agent, temozolomide (TMZ), as the payload. Nanoparticle properties were characterized and subsequently their endocytosis-mediated uptake by glioma cells was demonstrated. Convection-enhanced delivery (CED) can disperse nanoparticles through the rodent brain and their distribution is accurately visualized by MRI. Infusion of nanoparticles does not result in observable animal toxicity relative to control. CED of TMZ-bearing nanoparticles prolongs the survival of animals with intracranial xenografts compared to control. In conclusion, the described nanoparticle vector represents a unique multifunctional platform that can be used for image-guided treatment of malignant glioma. GBM remains one of the most notoriously treatment-unresponsive cancer types. In this study, a multifunctional nanoparticle-based temozolomide delivery system was demonstrated to possess enhanced treatment efficacy in a rodent xenograft GBM model, with the added benefit of MRI-based tracking via the incorporation of iron oxide as a T2* contrast material in the nanoparticles. © 2014.

Hematite Core Nanoparticles with Carbon Shell: Potential for Environmentally Friendly Production from Iron Mining Sludge

NASA Astrophysics Data System (ADS)

Stević, Dragana; Mihajlović, Dijana; Kukobat, Radovan; Hattori, Yoshiyuki; Sagisaka, Kento; Kaneko, Katsumi; Atlagić, Suzana Gotovac

2016-08-01

Hematite nanoparticles with amorphous, yet relatively uniform carbon shell, were produced based exclusively on the waste sludge from the iron mine as the raw material. The procedure for acid digestion-based purification of the sludge with the full recovery of acid vapors and the remaining non-toxic rubble is described. Synthesis of the hematite nanoparticles was performed by the arrested precipitation method with cationic surfactant. The particles were thoroughly characterized and the potential of their economical production for the battery industry is indicated.

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.

Fabrication and characterization of iron oxide dextran composite layers

NASA Astrophysics Data System (ADS)

Iconaru, S. L.; Predoi, S. A.; Beuran, M.; Ciobanu, C. S.; Trusca, R.; Ghita, R.; Negoi, I.; Teleanu, G.; Turculet, S. C.; Matei, M.; Badea, Monica; Prodan, A. M.

2018-02-01

Super paramagnetic iron oxide nanoparticles such as maghemite have been shown to exhibit antimicrobial properties [1-5]. Moreover, the iron oxide nanoparticles have been proposed as a potential magnetically controllable antimicrobial agent which could be directed to a specific infection [3-5]. The present research has focused on studies of the surface and structure of iron oxide dextran (D-IO) composite layers surface and structure. These composite layers were deposited on Si substrates. The structure of iron oxide dextran composite layers was investigated by X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) while the surface morphology was evaluated by Scanning Electron Microscopy (SEM). The structural characterizations of the iron oxide dextran composite layers revealed the basic constituents of both iron and dextran structure. Furthermore, the in vitro evaluation of the antifungal effect of the complex layers, which have been shown revealed to be active against C. albicans cells at distinct intervals of time, is exhibited. Our research came to confirm the fungicidal effect of iron oxide dextran composite layers. Also, our results suggest that iron oxide dextran surface may be used for medical treatment of biofilm associated Candida infections.

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-Fe 2 O 3 , Fe 3 O 4 , 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.

Preparation and evaluation of poly(2-hydroxyethyl aspartamide)-hexadecylamine-iron oxide for MR imaging of lymph nodes

PubMed Central

2014-01-01

The purpose of this study was to synthesize biocompatible poly(2-hydroxyethyl aspartamide)–C16-iron oxide (PHEA-C16-iron oxide) nanoparticles and to evaluate their efficacy as a contrast agent for magnetic resonance imaging of lymph nodes. The PHEA-C16-iron oxide nanoparticles were synthesized by coprecipitation method. The core size of the PHEA-C16-iron oxide nanoparticles was about 5 to 7 nm, and the overall size of the nanoparticles was around 20, 60, and 150 nm in aqueous solution. The size of the nanoparticles was controlled by the amount of C16. The 3.0-T MRI signal intensity of a rabbit lymph node was effectively reduced after intravenous administration of PHEA-C16-iron oxide with the size of 20 nm. The in vitro and in vivo toxicity tests revealed the high biocompatibility of PHEA-C16-iron oxide nanoparticles. Therefore, PHEA-C16-iron oxide nanoparticles with 20-nm size can be potentially useful as T2-weighted MR imaging contrast agents for the detection of lymph nodes. PMID:24438671

Nanoparticulate NaA zeolite composites for MRI: Effect of iron oxide content on image contrast

NASA Astrophysics Data System (ADS)

Gharehaghaji, Nahideh; Divband, Baharak; Zareei, Loghman

2018-06-01

In the current study, Fe3O4/NaA nanocomposites with various amounts of Fe3O4 (3.4, 6.8 & 10.2 wt%) were synthesized and characterized to study the effect of nano iron oxide content on the magnetic resonance (MR) image contrast. The cell viability of the nanocomposites was investigated by MTT assay method. T2 values as well as r2 relaxivities were determined with a 1.5 T MRI scanner. The results of the MTT assay confirmed the nanocomposites cytocompatibility up to 6.8% of the iron oxide content. Although the magnetization saturations and susceptibility values of the nanocomposites were increased as a function of the iron oxide content, their relaxivity was decreased from 921.78 mM-1 s-1 for the nanocomposite with the lowest iron oxide content to 380.16 mM-1 s-1 for the highest one. Therefore, Fe3O4/NaA nanocomposite with 3.4% iron oxide content led to the best MR image contrast. Nano iron oxide content and dispersion in the nanocomposites structure have important role in the nanocomposite r2 relaxivity and the MR image contrast. Aggregation of the iron oxide nanoparticles is a limiting factor in using of the high iron oxide content nanocomposites.

Sensing the quantum behaviour of magnetic nanoparticles by electron magnetic resonance.

PubMed

Fittipaldi, M; Mercatelli, R; Sottini, S; Ceci, P; Falvo, E; Gatteschi, D

2016-02-07

We have investigated Magnetic Nanoparticles (MNPs) of spinel type iron oxide (of approximately 8 nm) mineralized in the internal cavity of the bioreactor ferritin nanocage. In particular, we have used Electron Magnetic Resonance, EMR, spectroscopy and taken advantage of the capacity of the protein shells to control the size of the MNPs. EMR measurements in perpendicular and parallel configurations have been recorded at various temperatures. A model based on the giant spin is used to interpret the experimental results. The analysis indicates that the observed quantum behaviour has to be ascribed to the whole MNP and that the thermal population of excited spin states has a strong influence in the EMR behaviour of MNPs.

High temperature coatings for gas turbines

DOEpatents

Zheng, Xiaoci Maggie

2003-10-21

Coating for high temperature gas turbine components that include a MCrAlX phase, and an aluminum-rich phase, significantly increase oxidation and cracking resistance of the components, thereby increasing their useful life and reducing operating costs. The aluminum-rich phase includes aluminum at a higher concentration than aluminum concentration in the MCrAlX alloy, and an aluminum diffusion-retarding composition, which may include cobalt, nickel, yttrium, zirconium, niobium, molybdenum, rhodium, cadmium, indium, cerium, iron, chromium, tantalum, silicon, boron, carbon, titanium, tungsten, rhenium, platinum, and combinations thereof, and particularly nickel and/or rhenium. The aluminum-rich phase may be derived from a particulate aluminum composite that has a core comprising aluminum and a shell comprising the aluminum diffusion-retarding composition.

77 FR 32986 - Notice of Inventory Completion: The University of Alabama Museums, Tuscaloosa, AL

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-04

... than 2,032 glass beads, 1 lot of more than 17 shell beads, 1 unidentified bead, 1 gun lock, 1 gun butt plate, 1 gun stock, 2 gun barrels, 1 brass ramrod support, 8 musket balls, 2 iron buckles, 1 iron handle... fragments, 1 unidentified bead, 2 glass beads, 1 gun flint, 1 iron knife blade, 1 iron nail, 1 musket ball...

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 complete. Oxidation by O2 in acidic conditions would be slower. Iron photo-oxidation is thus likely responsible for the formation of jarosite-hematite deposits on Mars, provided that shallow standing water bodies could persist for extended periods of time. The oxygen isotopic composition of lepidocrocite precipitated from the photo-oxidation experiment was measured and it is related to the composition of water by mass-dependent fractionation. The precipitate-fluid 18O/16O isotope fractionation of ∼ + 6 ‰ is consistent with previous determinations of oxygen equilibrium fraction factors between iron oxyhydroxides and water.

Single and multi-layered core-shell structures based on ZnO nanorods obtained by aerosol assisted chemical vapor deposition

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

Sáenz-Trevizo, A.; Amézaga-Madrid, P.; Pizá-Ruiz, P.

2015-07-15

Core–shell nanorod structures were prepared by a sequential synthesis using an aerosol assisted chemical vapor deposition technique. Several samples consisting of ZnO nanorods were initially grown over TiO{sub 2} film-coated borosilicate glass substrates, following the synthesis conditions reported elsewhere. Later on, a uniform layer consisting of individual Al, Ni, Ti or Fe oxides was grown onto ZnO nanorod samples forming the so-called single MO{sub x}/ZnO nanorod core–shell structures, where MO{sub x} was the metal oxide shell. Additionally, a three-layer core–shell sample was developed by growing Fe, Ti and Fe oxides alternately, onto the ZnO nanorods. The microstructure of the core–shellmore » materials was characterized by grazing incidence X-ray diffraction, scanning and transmission electron microscopy. Energy dispersive X-ray spectroscopy was employed to corroborate the formation of different metal oxides. X-ray diffraction outcomes for single core–shell structures showed solely the presence of ZnO as wurtzite and TiO{sub 2} as anatase. For the multi-layered shell sample, the existence of Fe{sub 2}O{sub 3} as hematite was also detected. Morphological observations suggested the existence of an outer material grown onto the nanorods and further microstructural analysis by HR-STEM confirmed the development of core–shell structures in all cases. These studies also showed that the individual Al, Fe, Ni and Ti oxide layers are amorphous; an observation that matched with X-ray diffraction analysis where no apparent extra oxides were detected. For the multi-layered sample, the development of a shell consisting of three different oxide layers onto the nanorods was found. Overall results showed that no alteration in the primary ZnO core was produced during the growth of the shells, indicating that the deposition technique used herein was and it is suitable for the synthesis of homogeneous and complex nanomaterials high in quality and purity. In addition, materials absorptance determined from the total transmittance and reflectance spectra revealed a broader absorption interval including visible light, indicating potential uses of these nanostructures on solar energy appliances. - Graphical abstract: Display Omitted - Highlights: • Uniform ZnO nanorods (core)–metal oxide (shell) were obtained sequentially by AACVD. • Shells were structured of homogeneous single or multi-layered non-mixed metal oxides. • ZnO nanorod core was preserved during the shell synthesis. • Optical absorptance revealed visible interval absorption for FeO{sub x} shell samples. • Materials can be suitable for photocatalytic or photovoltaic applications.« less

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...

49 CFR 192.145 - Valves.

Code of Federal Regulations, 2010 CFR

2010-10-01

..., bonnet, cover, and/or end flange) components made of ductile iron may be used at pressures exceeding 80... having shell components made of ductile iron may be used at pressures up to 80 percent of the pressure... pressure does not exceed 1,000 p.s.i. (7 Mpa) gage; and (2) Welding is not used on any ductile iron...

Antioxidants Mediate Both Iron Homeostasis and Oxidative Stress.

PubMed

Imam, Mustapha Umar; Zhang, Shenshen; Ma, Jifei; Wang, Hao; Wang, Fudi

2017-06-28

Oxidative stress is a common denominator in the pathogenesis of many chronic diseases. Therefore, antioxidants are often used to protect cells and tissues and reverse oxidative damage. It is well known that iron metabolism underlies the dynamic interplay between oxidative stress and antioxidants in many pathophysiological processes. Both iron deficiency and iron overload can affect redox state, and these conditions can be restored to physiological conditions using iron supplementation and iron chelation, respectively. Similarly, the addition of antioxidants to these treatment regimens has been suggested as a viable therapeutic approach for attenuating tissue damage induced by oxidative stress. Notably, many bioactive plant-derived compounds have been shown to regulate both iron metabolism and redox state, possibly through interactive mechanisms. This review summarizes our current understanding of these mechanisms and discusses compelling preclinical evidence that bioactive plant-derived compounds can be both safe and effective for managing both iron deficiency and iron overload conditions.

Antioxidants Mediate Both Iron Homeostasis and Oxidative Stress

PubMed Central

Zhang, Shenshen; Ma, Jifei; Wang, Hao; Wang, Fudi

2017-01-01

Oxidative stress is a common denominator in the pathogenesis of many chronic diseases. Therefore, antioxidants are often used to protect cells and tissues and reverse oxidative damage. It is well known that iron metabolism underlies the dynamic interplay between oxidative stress and antioxidants in many pathophysiological processes. Both iron deficiency and iron overload can affect redox state, and these conditions can be restored to physiological conditions using iron supplementation and iron chelation, respectively. Similarly, the addition of antioxidants to these treatment regimens has been suggested as a viable therapeutic approach for attenuating tissue damage induced by oxidative stress. Notably, many bioactive plant-derived compounds have been shown to regulate both iron metabolism and redox state, possibly through interactive mechanisms. This review summarizes our current understanding of these mechanisms and discusses compelling preclinical evidence that bioactive plant-derived compounds can be both safe and effective for managing both iron deficiency and iron overload conditions. PMID:28657578

A Silica-Supported Iron Oxide Catalyst Capable of Activating Hydrogen Peroxide at Neutral pH Values

PubMed Central

Pham, Anh Le-Tuan; Lee, Changha; Doyle, Fiona M.; Sedlak, David L.

2009-01-01

Iron oxides catalyze the conversion of hydrogen peroxide (H2O2) into oxidants capable of transforming recalcitrant contaminants. Unfortunately, the process is relatively inefficient at circumneutral pH values due to competing reactions that decompose H2O2 without producing oxidants. Silica- and alumina-containing iron oxides prepared by sol-gel processing of aqueous solutions containing Fe(ClO4)3, AlCl3 and tetraethyl orthosilicate efficiently catalyzed the decomposition of H2O2 into oxidants capable of transforming phenol at circumneutral pH values. Relative to hematite, goethite and amorphous FeOOH, the silica-iron oxide catalyst exhibited a stoichiometric efficiency, defined as the number of moles of phenol transformed per mole of H2O2 consumed, that was 10 to 40 times higher than that of the iron oxides. The silica-alumina-iron oxide catalyst had a stoichiometric efficiency that was 50 to 80 times higher than that of the iron oxides. The significant enhancement in oxidant production is attributable to the interaction of Fe with Al and Si in the mixed oxides, which alters the surface redox processes, favoring the production of strong oxidants during H2O2 decomposition. PMID:19943668

Microbial diversity and iron oxidation at Okuoku-hachikurou Onsen, a Japanese hot spring analog of Precambrian iron formations.

PubMed

Ward, L M; Idei, A; Terajima, S; Kakegawa, T; Fischer, W W; McGlynn, S E

2017-11-01

Banded iron formations (BIFs) are rock deposits common in the Archean and Paleoproterozoic (and regionally Neoproterozoic) sedimentary successions. Multiple hypotheses for their deposition exist, principally invoking the precipitation of iron via the metabolic activities of oxygenic, photoferrotrophic, and/or aerobic iron-oxidizing bacteria. Some isolated environments support chemistry and mineralogy analogous to processes involved in BIF deposition, and their study can aid in untangling the factors that lead to iron precipitation. One such process analog system occurs at Okuoku-hachikurou (OHK) Onsen in Akita Prefecture, Japan. OHK is an iron- and CO 2 -rich, circumneutral hot spring that produces a range of precipitated mineral textures containing fine laminae of aragonite and iron oxides that resemble BIF fabrics. Here, we have performed 16S rRNA gene amplicon sequencing of microbial communities across the range of microenvironments in OHK to describe the microbial diversity present and to gain insight into the cycling of iron, oxygen, and carbon in this ecosystem. These analyses suggest that productivity at OHK is based on aerobic iron-oxidizing Gallionellaceae. In contrast to other BIF analog sites, Cyanobacteria, anoxygenic phototrophs, and iron-reducing micro-organisms are present at only low abundances. These observations support a hypothesis where low growth yields and the high stoichiometry of iron oxidized per carbon fixed by aerobic iron-oxidizing chemoautotrophs like Gallionellaceae result in accumulation of iron oxide phases without stoichiometric buildup of organic matter. This system supports little dissimilatory iron reduction, further setting OHK apart from other process analog sites where iron oxidation is primarily driven by phototrophic organisms. This positions OHK as a study area where the controls on primary productivity in iron-rich environments can be further elucidated. When compared with geological data, the metabolisms and mineralogy at OHK are most similar to specific BIF occurrences deposited after the Great Oxygenation Event, and generally discordant with those that accumulated before it. © 2017 John Wiley & Sons Ltd.

Temperature-responsive magnetite/PEO-PPO-PEO block copolymer nanoparticles for controlled drug targeting delivery.

PubMed

Chen, Shu; Li, Ying; Guo, Chen; Wang, Jing; Ma, Junhe; Liang, Xiangfeng; Yang, Liang-Rong; Liu, Hui-Zhou

2007-12-04

In this study, temperature-responsive magnetite/polymer nanoparticles were developed from iron oxide nanoparticles and poly(ethyleneimine)-modified poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer. The particles were characterized by TEM, XRD, DLS, VSM, FTIR, and TGA. A typical product has an approximately 20 nm magnetite core and an approximately 40 nm hydrodynamic diameter with a narrow size distribution and is superparamagnetic with large saturation magnetization (51.34 emu/g) at room temperature. The most attractive feature of the nanoparticles is their temperature-responsive volume-transition property. DLS results indicated that their average hydrodynamic diameter underwent a sharp decrease from 45 to 25 nm while evaluating the temperature from 20 to 35 degrees C. The temperature-dependent evolution of the C-O stretching band in the FTIR spectra of the aqueous nanoparticles solution revealed that thermo-induced self-assembly of the immobilized block copolymers occurred on the magnetite solid surfaces, which is accompanied by a conformational change from a fully extended state to a highly coiled state of the copolymer. Consequently, the copolymer shell could act as a temperature-controlled "gate" for the transit of guest substance. The uptake and release of both hydrophobic and hydrophilic model drugs were well controlled by switching the transient opening and closing of the polymer shell at different temperatures. A sustained release of about 3 days was achieved in simulated human body conditions. In primary mouse experiments, drug-entrapped magnetic nanoparticles showed good biocompatibility and effective therapy for spinal cord damage. Such intelligent magnetic nanoparticles are attractive candidates for widespread biomedical applications, particularly in controlled drug-targeting delivery.

Doxorubicin loaded dual pH- and thermo-responsive magnetic nanocarrier for combined magnetic hyperthermia and targeted controlled drug delivery applications

NASA Astrophysics Data System (ADS)

Hervault, Aziliz; Dunn, Alexander E.; Lim, May; Boyer, Cyrille; Mott, Derrick; Maenosono, Shinya; Thanh, Nguyen T. K.

2016-06-01

Magnetic nanocarriers have attracted increasing attention for multimodal cancer therapy due to the possibility to deliver heat and drugs locally. The present study reports the development of magnetic nanocomposites (MNCs) made of an iron oxide core and a pH- and thermo-responsive polymer shell, that can be used as both hyperthermic agent and drug carrier. The conjugation of anticancer drug doxorubicin (DOX) to the pH- and thermo-responsive MNCs via acid-cleavable imine linker provides advanced features for the targeted delivery of DOX molecules via the combination of magnetic targeting, and dual pH- and thermo-responsive behaviour which offers spatial and temporal control over the release of DOX. The iron oxide cores exhibit a superparamagnetic behaviour with a saturation magnetization around 70 emu g-1. The MNCs contained 8.1 wt% of polymer and exhibit good heating properties in an alternating magnetic field. The drug release experiments confirmed that only a small amount of DOX was released at room temperature and physiological pH, while the highest drug release of 85.2% was obtained after 48 h at acidic tumour pH under hyperthermia conditions (50 °C). The drug release kinetic followed Korsmeyer-Peppas model and displayed Fickian diffusion mechanism. From the results obtained it can be concluded that this smart magnetic nanocarrier is promising for applications in multi-modal cancer therapy, to target and efficiently deliver heat and drug specifically to the tumour.Magnetic nanocarriers have attracted increasing attention for multimodal cancer therapy due to the possibility to deliver heat and drugs locally. The present study reports the development of magnetic nanocomposites (MNCs) made of an iron oxide core and a pH- and thermo-responsive polymer shell, that can be used as both hyperthermic agent and drug carrier. The conjugation of anticancer drug doxorubicin (DOX) to the pH- and thermo-responsive MNCs via acid-cleavable imine linker provides advanced features for the targeted delivery of DOX molecules via the combination of magnetic targeting, and dual pH- and thermo-responsive behaviour which offers spatial and temporal control over the release of DOX. The iron oxide cores exhibit a superparamagnetic behaviour with a saturation magnetization around 70 emu g-1. The MNCs contained 8.1 wt% of polymer and exhibit good heating properties in an alternating magnetic field. The drug release experiments confirmed that only a small amount of DOX was released at room temperature and physiological pH, while the highest drug release of 85.2% was obtained after 48 h at acidic tumour pH under hyperthermia conditions (50 °C). The drug release kinetic followed Korsmeyer-Peppas model and displayed Fickian diffusion mechanism. From the results obtained it can be concluded that this smart magnetic nanocarrier is promising for applications in multi-modal cancer therapy, to target and efficiently deliver heat and drug specifically to the tumour. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07773g

Next generation ultrasound platforms for theranostics.

PubMed

Oddo, Letizia; Cerroni, Barbara; Domenici, Fabio; Bedini, Angelico; Bordi, Federico; Chiessi, Ester; Gerbes, Stefan; Paradossi, Gaio

2017-04-01

Microbubbles are a well-established contrast agent which improves diagnostic ultrasound imaging. During the last decade research has focused on expanding their use to include molecular imaging, targeted therapy and imaging modalities other than ultrasound. However, bioadhesion of targeted microbubbles under physiological flow conditions is still difficult to achieve, the main challenge being connected to the poor stability of lipid microbubbles in the body's circulation system. In this article, we investigate the use of polymeric microbubbles based on a poly (vinyl alcohol) shell as an alternative to lipid microbubbles. In particular, we report on the development of microbubble shell modification, using mild reaction conditions, with the aim of designing a multifunctional platform to enable diagnosis and therapy. Superparamagnetic iron oxide nanoparticles and a near infrared fluorescent probe, indocyanine green, are coupled to the bubbles surface in order to support magnetic resonance and fluorescence imaging. Furthermore, anchoring cyclic arginyl-glycyl-aspartic acid (RGD) peptide, and cyclodextrin molecules, allows targeting and drug loading, respectively. Last but not least, shell topography is provided by atomic force microscopy. These applications and features, together with the high echogenicity of poly (vinyl alcohol) microbubbles, may offer a more stable alternative to lipid microbubbles for the development of a multimodal theranostic platform. Copyright © 2016 Elsevier Inc. All rights reserved.

Iron and manganese oxides modified maize straw to remove tylosin from aqueous solutions.

PubMed

Yin, Yongyuan; Guo, Xuetao; Peng, Dan

2018-08-01

Maize straw modified by iron and manganese oxides was synthesized via a simple and environmentally friendly method. Three maize straw materials, the original maize straw, maize straw modified by manganese oxides and maize straw modified by iron and manganese oxides, were detected by SEM, BET, XPS, XRD and FTIR. The results showed that maize straw was successfully modified and maize straw modified by iron and manganese oxides has a larger surface area than MS. According to the experimental data, the sorption trend could conform to the pseudo-second-order kinetic model well, and the sorption ability of tylosin on sorbents followed the order of original maize straw < maize straw modified by manganese oxides < maize straw modified by iron and manganese oxides. The study indicated that manganese oxides and iron-manganese oxides could significantly enhance the sorption capacity of original maize straw. The sorption isotherm data of tylosin on original maize straw fit a linear model well, while Freundlich models were more suitable for maize straw modified by manganese oxides and maize straw modified by iron and manganese oxides. The pH, ionic strength and temperature can affect the sorption process. The sorption mechanisms of tylosin on iron and manganese oxides modified maize straw were attribute to the surface complexes, electrostatic interactions, H bonding and hydrophobic interactions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Treatment of antimony mine drainage: challenges and opportunities with special emphasis on mineral adsorption and sulfate reducing bacteria.

PubMed

Li, Yongchao; Hu, Xiaoxian; Ren, Bozhi

2016-01-01

The present article summarizes antimony mine distribution, antimony mine drainage generation and environmental impacts, and critically analyses the remediation approach with special emphasis on iron oxidizing bacteria and sulfate reducing bacteria. Most recent research focuses on readily available low-cost adsorbents, such as minerals, wastes, and biosorbents. It is found that iron oxides prepared by chemical methods present superior adsorption ability for Sb(III) and Sb(V). However, this process is more costly and iron oxide activity can be inhibited by plenty of sulfate in antimony mine drainage. In the presence of sulfate reducing bacteria, sulfate can be reduced to sulfide and form Sb(2)S(3) precipitates. However, dissolved oxygen and lack of nutrient source in antimony mine drainage inhibit sulfate reducing bacteria activity. Biogenetic iron oxide minerals from iron corrosion by iron-oxidizing bacteria may prove promising for antimony adsorption, while the micro-environment generated from iron corrosion by iron oxidizing bacteria may provide better growth conditions for symbiotic sulfate reducing bacteria. Finally, based on biogenetic iron oxide adsorption and sulfate reducing bacteria followed by precipitation, the paper suggests an alternative treatment for antimony mine drainage that deserves exploration.

Magnetic interaction reversal in watermelon nanostructured Cr-doped Fe nanoclusters

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

Kaur, Maninder; Dai, Qilin; Bowden, Mark

2013-01-01

Cr-doped core-shell Fe/Fe-oxide nanoclusters (NCs) were synthesized at varied atomic percentages of Cr from 0 at. % to 8 at. %. The low concentrations of Cr (<10 at. %) were selected in order to inhibit the complete conversion of the Fe-oxide shell to Cr2O3 and the Fe core to FeCr alloy. The magnetic interaction in Fe/Fe-oxide NCs (rv25 nm) can be controlled by antiferromagnetic Cr-dopant. We report the origin of r-FeCr phase at very low Cr concentration (2 at. %) unlike in previous studies, and the interaction reversal from dipolar to exchange interaction in watermelon-like Cr-doped core-shell NCs. The giantmore » magnetoresistance (GMR) effect,1,2 where an antiferromagnetic (AFM) exchange coupling exists between two ferromagnetic (FM) layers separated by a certain type of magnetic or non-magnetic spacer,3 has significant potential for application in the magnetic recording industry. Soon after the discovery of the GMR, the magnetic properties of multilayer systems (FeCr) became a subject of intensive study. The application of bulk iron-chromium (Fe-Cr) alloys has been of great interest, as these alloys exhibit favorable prop- erties including corrosion resistance, high strength, hardness, low oxidation rate, and strength retention at elevated temper- ature. However, the structural and magnetic properties of Cr-doped Fe nanoclusters (NCs) have not been investigated in-depth. Of all NCs, Fe-based clusters have unique magnetic properties as well as favorable catalytic characteristics in reactivity, selectivity, and durability.4 The incorporation of dopant of varied type and concentration in Fe can modify its chemical ordering, thereby optimizing its electrical, optical, and magnetic properties and opening up many new applications. The substitution of an Fe atom (1.24 A°) by a Cr atom (1.25 A° ) can easily modify the magnetic properties, since (i) the curie temperature (Tc ) of Fe is 1043 K, while Cr is an itinerant AFM with a bulk Neel temperature TN =311 K, and (ii) Fe and Cr share the same crystal structure (bcc) with only 0.5% difference between their lattice constants.« less

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.

Neonatal iron supplementation potentiates oxidative stress, energetic dysfunction and neurodegeneration in the R6/2 mouse model of Huntington's disease

PubMed Central

Berggren, Kiersten L.; Chen, Jianfang; Fox, Julia; Miller, Jonathan; Dodds, Lindsay; Dugas, Bryan; Vargas, Liset; Lothian, Amber; McAllum, Erin; Volitakis, Irene; Roberts, Blaine; Bush, Ashley I.; Fox, Jonathan H.

2015-01-01

Huntington’s disease (HD) is a progressive neurodegenerative disorder caused by a CAG repeat expansion that encodes a polyglutamine tract in huntingtin (htt) protein. Dysregulation of brain iron homeostasis, oxidative stress and neurodegeneration are consistent features of the HD phenotype. Therefore, environmental factors that exacerbate oxidative stress and iron dysregulation may potentiate HD. Iron supplementation in the human population is common during infant and adult-life stages. In this study, iron supplementation in neonatal HD mice resulted in deterioration of spontaneous motor running activity, elevated levels of brain lactate and oxidized glutathione consistent with increased energetic dysfunction and oxidative stress, and increased striatal and motor cortical neuronal atrophy, collectively demonstrating potentiation of the disease phenotype. Oxidative stress, energetic, and anatomic markers of degeneration were not affected in wild-type littermate iron-supplemented mice. Further, there was no effect of elevated iron intake on disease outcomes in adult HD mice. We have demonstrated an interaction between the mutant huntingtin gene and iron supplementation in neonatal HD mice. Findings indicate that elevated neonatal iron intake potentiates mouse HD and promotes oxidative stress and energetic dysfunction in brain. Neonatal-infant dietary iron intake level may be an environmental modifier of human HD. PMID:25703232

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.

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

The detection of HBV DNA with gold-coated iron oxide nanoparticle gene probes

NASA Astrophysics Data System (ADS)

Xi, Dong; Luo, XiaoPing; Lu, QiangHua; Yao, KaiLun; Liu, ZuLi; Ning, Qin

2008-03-01

Gold-coated iron oxide nanoparticle Hepatitis B virus (HBV) DNA probes were prepared, and their application for HBV DNA measurement was studied. Gold-coated iron oxide nanoparticles were prepared by the citrate reduction of tetra-chloroauric acid in the presence of iron oxide nanoparticles which were added as seeds. With a fluorescence-based method, the maximal surface coverage of hexaethiol 30-mer oligonucleotides and the maximal percentage of hybridization strands on gold-coated iron oxide nanoparticles were (120 ± 8) oligonucleotides per nanoparticle, and (14 ± 2%), respectively, which were comparable with those of (132 ± 10) and (22 ± 3%) in Au nanoparticle groups. Large network aggregates were formed when gold-coated iron oxide nanoparticle HBV DNA gene probe was applied to detect HBV DNA molecules as evidenced by transmission electron microscopy and the high specificity was verified by blot hybridization. Our results further suggested that detecting DNA with iron oxide nanoparticles and magnetic separator was feasible and might be an alternative effective method.

Petrographic and Isotopic Evidence for Siderite Precursors to Iron Oxide Cements

NASA Astrophysics Data System (ADS)

Loope, D.

2015-12-01

The origin of iron oxide mineralization in the Navajo Sandstone on the Colorado Plateau is important because of the different forms of distinct self-organization exhibited by these systems, the potential importance of the cements as geochronometers, and their use as analogs for similar mineralization on other planets. We consider this mineralization to be the product of microbially mediated oxidation of siderite in evolving groundwater systems. Iron oxide grain coatings were dissolved and the iron precipitated as siderite during a reducing phase of diagenesis. Upon invasion by oxidizing waters, iron-oxidizing bacteria colonized the redox interface between siderite-cemented and porous sandstone. Precipitation of iron oxide at this interface generated acid that facilitated further siderite dissolution. One difficulty in testing this hypothesis is that siderite is destroyed by the cm-scale transport of iron during oxidation. There are two lines of evidence that support the presence of a siderite precursor in these systems. 1)Rhombic grains that we interpret to be iron oxide pseudomorphs after siderite occur where in-situ oxidation rather than dissolution of the siderite precursor has occurred. 2) The δ56Fe values of these iron oxide cements are typically negative. We have measured the δ56Fe value of Navajo Sandstone to be 0.2‰; a value in good agreement with previous workers (Chan et al., 2006; Busigny and Dauphas, 2007). Bleaching of the sandstones apparently results in near complete removal of Fe with little change in the δ56Fe values of the bulk sandstone. The δ56Fe values of iron oxide cements have a median value of -0.8‰; similar to the value we obtained from ferroan carbonate (-0.86‰). Iron oxide from samples that comprise largely rhombic grains has similar δ56Fe values (-0.5‰) to those obtained from cements produced by siderite dissolution and subsequent oxidation (-0.4‰). Our interpretation is that siderite precipitated from an aqueous solution in which the δ56Fe value was <0.2‰ yielding siderite with δ56Fe values that ranged upward from -1.4‰. Invasion of the Navajo by oxidizing waters resulted in microbially mediated oxidation of the siderite concretions. The strongly negative values of the Fe oxides result from the near-quantitative oxidation of the siderite in a closed system.

Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

PubMed

Chancharoenrith, Sittikorn; Kamonsatikul, Choavarit; Namkajorn, Montree; Kiatisevi, Supavadee; Somsook, Ekasith

2015-03-06

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE. Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis and characterization of dextran-coated iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Predescu, Andra Mihaela; Matei, Ecaterina; Berbecaru, Andrei Constantin; Pantilimon, Cristian; Drăgan, Claudia; Vidu, Ruxandra; Predescu, Cristian; Kuncser, Victor

2018-03-01

Synthesis and characterization of iron oxide nanoparticles coated with a large molar weight dextran for environmental applications are reported. The first experiments involved the synthesis of iron oxide nanoparticles which were coated with dextran at different concentrations. The synthesis was performed by a co-precipitation technique, while the coating of iron oxide nanoparticles was carried out in solution. The obtained nanoparticles were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction spectrometry, Fourier transform infrared spectroscopy and superconducting quantum interference device magnetometry. The results demonstrated a successful coating of iron oxide nanoparticles with large molar weight dextran, of which agglomeration tendency depended on the amount of dextran in the coating solution. SEM and TEM observations have shown that the iron oxide nanoparticles are of about 7 nm in size.

Method for producing iron-based catalysts

DOEpatents

Farcasiu, Malvina; Kaufman, Phillip B.; Diehl, J. Rodney; Kathrein, Hendrik

1999-01-01

A method for preparing an acid catalyst having a long shelf-life is provided comprising doping crystalline iron oxides with lattice-compatible metals and heating the now-doped oxide with halogen compounds at elevated temperatures. The invention also provides for a catalyst comprising an iron oxide particle having a predetermined lattice structure, one or more metal dopants for said iron oxide, said dopants having an ionic radius compatible with said lattice structure; and a halogen bound with the iron and the metal dopants on the surface of the particle.

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2013 CFR

2013-04-01

... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing practice...

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2012 CFR

2012-04-01

... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing practice...

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2014 CFR

2014-04-01

... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing practice...

Spatially resolved variations in reflectivity across iron oxide thin films

NASA Astrophysics Data System (ADS)

Kelley, Chris S.; Thompson, Sarah M.; Gilks, Daniel; Sizeland, James; Lari, Leonardo; Lazarov, Vlado K.; Matsuzaki, Kosuke; LeFrançois, Stéphane; Cinque, Gianfelice; Dumas, Paul

2017-11-01

The spin polarising properties of the iron oxide magnetite (Fe3O4) make it attractive for use in spintronic devices, but its sensitivity to compositional and structural variations make it challenging to prepare reliably. Infrared microspectroscopy and modelling are used to determine the spatial variation in the chemical composition of three thin films of iron oxide; one prepared by pulsed laser deposition (PLD), one by molecular beam epitaxy (MBE) deposition of iron whilst simultaneously flowing oxygen into the chamber and one by flowing oxygen only once deposition is complete. The technique is easily able to distinguish between films which contain metallic iron and different iron oxide phases as well as spatial variations in composition across the films. The film grown by post-oxidising iron is spatially uniform but not fully oxidised, the film grown by simultaneously oxidising iron showed spatial variation in oxide composition while the film grown by PLD was spatially uniform magnetite.

Synthesis, characterization and application of iron (II, III) oxide (Fe3O4) magnetic nanoparticles in mimic of wound healing model

NASA Astrophysics Data System (ADS)

Konyala, Divya

The research study focused on synthesis, characterization and applications of Fe3O4 core-shelled magnetic nanomaterials. This Fe3O4 magnetic nanomaterials will be prepared by using cost effective and convenient wet-chemistry method and will encapsulated using aqueous extracts of medicinal natural products. Three natural products namely Symplocos racemosa, Picrorhiza kurroa and Butea monosperma used to encapsulate Fe3O 4 MNMs due to their scope to reduce the risk of cancer, improves health, increase energy and enhance the immunity. These three medicinal natural products are synthesize by using water as a solvents to derive its active constituents, which will further used to functionalize the magnetic nanomaterials. The magnetic nanoparticles characterization studies performed using X-ray powder diffraction, Scanning electron microscope, Transmission electron microscope, Ultraviolet-visible spectroscopy, Fourier Transform Infrared spectroscopy (FT-IR) and Magnetic property. Fe3O4 magnetic nanomaterials biological activity was tested on Gram-negative bacteria (Escherichia coli). The results pointed out that, due to the adequate coating of Fe 3O4 (Iron Oxide) core by the medicinal chemical constituents from the natural products, the absorption of Fe3O4 magnetic nanomaterials was not detected in the UV-VIS Spectroscopy. TEM images showed that Fe3O4 coated with natural product extract in core-shelled structure, and the size of the particle ranges from 6 nm to 10 nm. Fourier Transform Infrared spectroscopy (FT-IR) was performed to determine the nature of chemicals present in natural extracts and functionalized Fe3O 4 magnetic nanomaterials. The model of wound healing mimic and antibacterial activity performed on gram-negative (Escherichia coli), indicating steady increasing cell growth after adding Fe3O4 MNMs. It was also found that MNMs synthesized at high temperatures shows less wound healing activity, when compared to MNMs prepared at room temperature due to formation of clusters at high temperatures.

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2012 CFR

2012-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2014 CFR

2014-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2013 CFR

2013-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

Carbonaceous fuel combustion with improved desulfurization

DOEpatents

Yang, Ralph T.; Shen, Ming-shing

1980-01-01

Lime utilization for sulfurous oxides adsorption 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. The iron oxide present in the spent limestone is found to catalyze the regeneration rate of the spent limestone in a reducing environment. Thus both the calcium and iron components may be recycled.

Modeling X-Ray Photoionized Plasmas: Ion Storage Ring Measurements of Low Temperature Dielectronic Recombination Rate Coefficients for L-Shell Iron

NASA Technical Reports Server (NTRS)

Savin, D. W.; Badnell, N. R.; Bartsch, T.; Brandau, C.; Chen, M. H.; Grieser, M.; Gwinner, G.; Hoffknecht, A.; Kahn, S. M.; Linkemann, J.

2000-01-01

Iron L-shell ions (Fe XVII to Fe XXIV) play an important role in determining the line emission and thermal and ionization structures of photoionized gases. Existing uncertainties in the theoretical low temperature dielectronic recombination (DR) rate coefficients for these ions significantly affects our ability to model and interpret observations of photoionized plasmas. To help address this issue, we have initiated a laboratory program to produce reliable low temperature DR rates. Here, we present some of our recent results and discuss some of their astrophysical implications.

Influence of Fe(2+)-catalysed iron oxide recrystallization on metal cycling.

PubMed

Latta, Drew E; Gorski, Christopher A; Scherer, Michelle M

2012-12-01

Recent work has indicated that iron (oxyhydr-)oxides are capable of structurally incorporating and releasing metals and nutrients as a result of Fe2+-induced iron oxide recrystallization. In the present paper, we briefly review the current literature examining the mechanisms by which iron oxides recrystallize and summarize how recrystallization affects metal incorporation and release. We also provide new experimental evidence for the Fe2+-induced release of structural manganese from manganese-doped goethite. Currently, the exact mechanism(s) for Fe2+-induced recrystallization remain elusive, although they are likely to be both oxide-and metal-dependent. We conclude by discussing some future research directions for Fe2+-catalysed iron oxide recrystallization.

Cancer Cells with Irons in the Fire

PubMed Central

Bystrom, Laura M.; Rivella, Stefano

2014-01-01

Iron is essential for the growth and proliferation of cells, as well as for many biological processes that are important for the maintenance and survival of the human body. However, excess iron is associated with the development of cancer and other pathological conditions, due in part to the pro-oxidative nature of iron and its damaging effects on DNA. Current studies suggest that iron depletion may be beneficial for patients that have diseases associated with iron overload or other iron metabolism disorders that may increase the risk for cancer. On the other hand, studies suggest that cancer cells are more vulnerable to the effects of iron depletion and oxidative stress in comparison to normal cells. Therefore, cancer patients might benefit from treatments that alter both iron metabolism and oxidative stress. This review highlights the pro-oxidant effects of iron, the relationship between iron and cancer development, the vulnerabilities of iron-dependent cancer phenotype, and how these characteristics may be exploited to prevent or treat cancer. PMID:24835768

Cu(II) removal by Anoxybacillus flavithermus-iron oxide composites during the addition of Fe(II)aq

NASA Astrophysics Data System (ADS)

Franzblau, Rachel E.; Daughney, Christopher J.; Swedlund, Peter J.; Weisener, Christopher G.; Moreau, Magali; Johannessen, Bernt; Harmer, Sarah L.

2016-01-01

There is currently poor understanding of metal removal by composites of bacteria and iron oxide minerals, even though they commonly co-occur and are among the most important sorbents in near-surface fluid-rock environments. This study evaluated Cu removal by composites of Anoxybacillus flavithermus and iron oxide over time during the addition, oxidation, and hydrolysis of Fe(II)aq and precipitation of the mineral, in comparison to Cu removal in the two single-sorbent end-member systems. In the absence of iron oxide, Cu removal by A. flavithermus was well described by a previously published surface complexation model, after inclusion of additional reactions describing aqueous complexation by exudate ligands released by the bacteria. In the absence of bacterial cells, Cu removal by iron oxide synthesized in the presence of the bacterial exudate ligands demonstrated the formation of ternary surface complexes. Removal of Cu by the A. flavithermus-iron oxide composites was ca. 20% greater than the prediction based on assumption of additivity in the two end-member systems. This non-additive behavior was attributed to (1) progressive physical blockage of bacterial surface sites by the iron oxide particles, (2) physical blockage of adsorption sites as a result of self-aggregation of the iron oxide particles, and (3) the reduction of Cu(II) to Cu(I) at the bacterial cell surface, as demonstrated by X-ray absorption spectroscopy. The extent of reduction of Cu(II) to Cu(I) was proportional to the concentration of solid phase Fe(II), suggesting that iron oxidation and copper reduction are linked. This study has shown that Cu removal by bacteria-iron oxide composites is greatly affected by redox processes such as Cu(II) reduction on the cell surface both by other bacterial surface ligands and the oxidation of sorbed Fe(II), as well as Fe(II) redox interactions, and aging effects of the mineral (i.e. surface site masking).

Iron Isotope Systematics

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

Dauphas, Nicolas; John, Seth G.; Rouxel, Olivier

Iron is a ubiquitous element with a rich (i.e., complex) chemical behavior. It possesses three oxidation states, metallic iron (Fe0), ferrous iron (Fe2+) and ferric iron (Fe3+). The distribution of these oxidation states is markedly stratified in the Earth.

Respiratory interactions of soil bacteria with (semi)conductive iron-oxide minerals.

PubMed

Kato, Souichiro; Nakamura, Ryuhei; Kai, Fumiyoshi; Watanabe, Kazuya; Hashimoto, Kazuhito

2010-12-01

Pure-culture studies have shown that dissimilatory metal-reducing bacteria are able to utilize iron-oxide nanoparticles as electron conduits for reducing distant terminal acceptors; however, the ecological relevance of such energy metabolism is poorly understood. Here, soil microbial communities were grown in electrochemical cells with acetate as the electron donor and electrodes (poised at 0.2 V versus Ag/AgCl) as the electron acceptors in the presence and absence of iron-oxide nanoparticles, and respiratory current generation and community structures were analysed. Irrespective of the iron-oxide species (hematite, magnetite or ferrihydrite), the supplementation with iron-oxide minerals resulted in large increases (over 30-fold) in current, while only a moderate increase (∼10-fold) was observed in the presence of soluble ferric/ferrous irons. During the current generation, insulative ferrihydrite was transformed into semiconductive goethite. Clone-library analyses of 16S rRNA gene fragments PCR-amplified from the soil microbial communities revealed that iron-oxide supplementation facilitated the occurrence of Geobacter species affiliated with subsurface clades 1 and 2. We suggest that subsurface-clade Geobacter species preferentially thrive in soil by utilizing (semi)conductive iron oxides for their respiration. © 2010 Society for Applied Microbiology and Blackwell Publishing Ltd.

Nanoscale Au-In alloy-oxide core-shell particles as electrocatalysts for efficient hydroquinone detection

DOE PAGES

Sutter, E.; Tong, X.; Medina-Plaza, C.; ...

2015-10-09

The presence of hydroquinone (HQ), a phenol ubiquitous in nature and widely used in industry, needs to be monitored because of its toxicity to the environment. Here we demonstrate efficient detection of HQ using simple, fast, and noninvasive electrochemical measurements on indium tin oxide (ITO) electrodes modified with nanoparticles comprising bimetallic Au–In cores and mixed Au–In oxide shells. Whereas bare ITO electrodes show very low activity for the detection of HQ, their modification with Au–In core–shell nanoparticles induces a pronounced shift of the oxidation peak to lower potentials, i.e., facilitated oxidation. The response of the different electrodes was correlated withmore » the initial composition of the bimetallic nanoparticle cores, which in turn determined the amount of Au and In stabilized on the surface of the amorphous Au–In oxide shells available for the electrochemical reaction. While adding core–shell nanostructures with different compositions of the alloy core facilitates the electrocatalytic (reduction-) oxidation of HQ, the activity is highest for particles with AuIn cores (i.e., a Au:In ratio of 1). This optimal system is found to follow a single pathway, the two-electron oxidation of the quinone–hydroquinone couple, which gives rise to high oxidation peaks and is most effective in facilitating the electrode-to-analyte charge transfer and thus detection. The limits of detection (LOD) decreased when increasing the amount of Au exposed on the surface of the amorphous Au–In oxide shells. As a result the LODs were in the range of 10 –5 – 10 –6 M and were lower than those obtained using bulk Au.« less

Magnetic Characterization of Iron Oxide Nanoparticles for Biomedical Applications.

PubMed

Maldonado-Camargo, Lorena; Unni, Mythreyi; Rinaldi, Carlos

2017-01-01

Iron oxide nanoparticles are of interest in a wide range of biomedical applications due to their response to applied magnetic fields and their unique magnetic properties. Magnetization measurements in constant and time-varying magnetic field are often carried out to quantify key properties of iron oxide nanoparticles. This chapter describes the importance of thorough magnetic characterization of iron oxide nanoparticles intended for use in biomedical applications. A basic introduction to relevant magnetic properties of iron oxide nanoparticles is given, followed by protocols and conditions used for measurement of magnetic properties, along with examples of data obtained from each measurement, and methods of data analysis.

Steel refining with an electrochemical cell

DOEpatents

Blander, M.; Cook, G.M.

1988-05-17

Apparatus is described for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contact with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight oxygen and not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom. 2 figs.

Steel refining with an electrochemical cell

DOEpatents

Blander, M.; Cook, G.M.

1985-05-21

Disclosed is an apparatus for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contact with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom.

Steel refining with an electrochemical cell

DOEpatents

Blander, Milton; Cook, Glenn M.

1988-01-01

Apparatus for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contact with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight oxygen and not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom.

Refractory lining for electrochemical cell

DOEpatents

Blander, Milton; Cook, Glenn M.

1987-01-01

Apparatus for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contcat with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight oxygen and not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom.

Incorporating Geochemical And Microbial Kinetics In Reactive Transport Models For Generation Of Acid Rock Drainage

NASA Astrophysics Data System (ADS)

Andre, B. J.; Rajaram, H.; Silverstein, J.

2010-12-01

Acid mine drainage, AMD, results from the oxidation of metal sulfide minerals (e.g. pyrite), producing ferrous iron and sulfuric acid. Acidophilic autotrophic bacteria such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans obtain energy by oxidizing ferrous iron back to ferric iron, using oxygen as the electron acceptor. Most existing models of AMD do not account for microbial kinetics or iron geochemistry rigorously. Instead they assume that oxygen limitation controls pyrite oxidation and thus focus on oxygen transport. These models have been successfully used for simulating conditions where oxygen availability is a limiting factor (e.g. source prevention by capping), but have not been shown to effectively model acid generation and effluent chemistry under a wider range of conditions. The key reactions, oxidation of pyrite and oxidation of ferrous iron, are both slow kinetic processes. Despite being extensively studied for the last thirty years, there is still not a consensus in the literature about the basic mechanisms, limiting factors or rate expressions for microbially enhanced oxidation of metal sulfides. An indirect leaching mechanism (chemical oxidation of pyrite by ferric iron to produce ferrous iron, with regeneration of ferric iron by microbial oxidation of ferrous iron) is used as the foundation of a conceptual model for microbially enhanced oxidation of pyrite. Using literature data, a rate expression for microbial consumption of ferrous iron is developed that accounts for oxygen, ferrous iron and pH limitation. Reaction rate expressions for oxidation of pyrite and chemical oxidation of ferrous iron are selected from the literature. A completely mixed stirred tank reactor (CSTR) model is implemented coupling the kinetic rate expressions, speciation calculations and flow. The model simulates generation of AMD and effluent chemistry that qualitatively agrees with column reactor and single rock experiments. A one dimensional reaction diffusion model at the scale of a single rock is developed incorporating the proposed kinetic rate expressions. Simulations of initiation, washout and AMD flows are discussed to gain a better understanding of the role of porosity, effective diffusivity and reactive surface area in generating AMD. Simulations indicate that flow boundary conditions control generation of acid rock drainage as porosity increases.

Synthesis of superparamagnetic silica-coated magnetite nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

Kaur, Navjot; Chudasama, Bhupendra

2015-05-01

Multifunctional superparamagnetic iron oxide nanoparticles (SPIONs) coated with silica are widely researched for biomedical applications such as magnetic resonance imaging, tissue repair, cell separation, hyperthermia, drug delivery, etc. In this article synthesis of magnetite (Fe3O4) nanoparticles and their coating with SiO2 is reported. Fe3O4 nanoparticles were synthesized by chemical co-precipitation and it was coated with silica by hydrolysis and condensation of tetraethylorthosilicate. XRD, FTIR, TEM and VSM techniques were used to characterize bare and coated nanoparticles. Results indicated that the average size of SPIONS was 8.4 nm. X-ray diffraction patterns of silica coated SPIONS were identical to that of SPIONS confirming the inner spinal structure of SPIONS. FTIR results confirmed the binding of silica with the magnetite and the formation of the silica shell around the magnetite core. Magnetic properties of SPIONS and silica coated SPIONS are determined by VSM. They are superparamagnetic. The major conclusion drawn from this study is that the synthesis route yields stable, non-aggregated magnetite-silica core-shell nanostructures with tailored morphology and excellent magnetic properties.

Oxidative degradation stability and hydrogen sulfide removal performance of dual-ligand iron chelate of Fe-EDTA/CA.

PubMed

Miao, Xinmei; Ma, Yiwen; Chen, Zezhi; Gong, Huijuan

2017-09-05

Catalytic oxidation desulfurization using chelated iron catalyst is an effective method to remove H 2 S from various gas streams including biogas. However, the ligand of ethylenediaminetetraacetic acid (EDTA), which is usually adopted to prepare chelated iron catalyst, is liable to be oxidative degraded, and leads to the loss of desulfurization performance. In order to improve the degradation stability of the iron chelate, a series of iron chelates composed of two ligands including citric acid (CA) and EDTA were prepared and the oxidative degradation stability as well as desulfurization performance of these chelated iron catalysts were studied. Results show that the iron chelate of Fe-CA is more stable than Fe-EDTA, while for the desulfurization performance, the situation is converse. For the dual-ligand iron chelates of Fe-EDTA/CA, with the increase of mol ratio of CA to EDTA in the iron chelate solution, the oxidative degradation stability increased while the desulfurization performance decreased. The results of this work showed that Fe-EDTA/CA with a mol ratio of CA:EDTA = 1:1 presents a relative high oxidative degradation stability and an acceptable desulfurization performance with over 90% of H 2 S removal efficiency.

Oxidative stress-induced iron signaling is responsible for peroxide-dependent oxidation of dichlorodihydrofluorescein in endothelial cells: role of transferrin receptor-dependent iron uptake in apoptosis.

PubMed

Tampo, Yoshiko; Kotamraju, Srigiridhar; Chitambar, Christopher R; Kalivendi, Shasi V; Keszler, Agnes; Joseph, Joy; Kalyanaraman, B

2003-01-10

Dichlorodihydrofluorescein (DCFH) is one of the most frequently used probes for detecting intracellular oxidative stress. In this study, we report that H2O2-dependent intracellular oxidation of DCFH to a green fluorescent product, 2',7'-dichlorofluorescein (DCF), required the uptake of extracellular iron transported through a transferrin receptor (TfR) in endothelial cells. H2O2-induced DCF fluorescence was inhibited by the monoclonal IgA-class anti-TfR antibody (42/6) that blocked TfR endocytosis and the iron uptake. H2O2-mediated inactivation of cytosolic aconitase was responsible for activation of iron regulatory protein-1 and increased expression of TfR, resulting in an increased iron uptake into endothelial cells. H2O2-mediated caspase-3 proteolytic activation was inhibited by anti-TfR antibody. Similar results were obtained in the presence of a lipid hydroperoxide. We conclude that hydroperoxide-induced DCFH oxidation and endothelial cell apoptosis required the uptake of extracellular iron by the TfR-dependent iron transport mechanism and that the peroxide-induced iron signaling, in general, has broader implications in oxidative vascular biology.

Oxidative stability of a heme iron-fortified bakery product: Effectiveness of ascorbyl palmitate and co-spray-drying of heme iron with calcium caseinate.

PubMed

Alemán, Mercedes; Bou, Ricard; Tres, Alba; Polo, Javier; Codony, Rafael; Guardiola, Francesc

2016-04-01

Fortification of food products with iron is a common strategy to prevent or overcome iron deficiency. However, any form of iron is a pro-oxidant and its addition will cause off-flavours and reduce a product's shelf life. A highly bioavailable heme iron ingredient was selected to fortify a chocolate cream used to fill sandwich-type cookies. Two different strategies were assessed for avoiding the heme iron catalytic effect on lipid oxidation: ascorbyl palmitate addition and co-spray-drying of heme iron with calcium caseinate. Oxidation development and sensory acceptability were monitored in the cookies over one-year of storage at room temperature in the dark. The addition of ascorbyl palmitate provided protection against oxidation and loss of tocopherols and tocotrienols during the preparation of cookies. In general, ascorbyl palmitate, either alone or in combination with the co-spray-dried heme iron, prevented primary oxidation and hexanal formation during storage. The combination of both strategies resulted in cookies that were acceptable from a sensory point of view after 1year of storage. Copyright © 2015 Elsevier Ltd. All rights reserved.

Colour and toxic characteristics of metakaolinite–hematite pigment for integrally coloured concrete, prepared from iron oxide recovered from a water treatment plant of an abandoned coal mine

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

Sadasivam, Sivachidambaram, E-mail: sadasivams@cardiff.ac.uk; Thomas, Hywel Rhys

A metakaolinite-hematite (KH) red pigment was prepared using an ocherous iron oxide sludge recovered from a water treatment plant of an abandoned coal mine. The KH pigment was prepared by heating the kaolinite and the iron oxide sludge at kaolinite's dehydroxylation temperature. Both the raw sludge and the KH specimen were characterised for their colour properties and toxic characteristics. The KH specimen could serve as a pigment for integrally coloured concrete and offers a potential use for the large volumes of the iron oxide sludge collected from mine water treatment plants. - Graphical abstract: A kaolinite based red pigment wasmore » prepared using an ocherous iron oxide sludge recovered from an abandoned coal mine water treatment plant. Display Omitted - Highlights: • A red pigment was prepared by heating a kaolinite and an iron oxide sludge. • The iron oxide and the pigment were characterised for their colour properties. • The red pigment can be a potential element for integrally coloured concrete.« less

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

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.

Magnetic iron oxides in the cementation technology of the boron-containing radioactive waste

NASA Astrophysics Data System (ADS)

Fedotov, M. A.; Gorbunova, O. A.; Fedorova, O. V.; Folmanis, G. E.; Kovalenko, L. V.

2015-04-01

Two ways of synthesis of non-detachable dispersed particles of magnetic materials useful for the boron-containing waste cementation process regulation were developed. Powder XRD showed that the method of carbothermic recovery of nanoscale iron hydroxide allows obtaining a mixture of iron oxides with content of the magnetic phase up to 70%. Method of low-temperature hydrogen reduction of the raw materials allows obtaining various compositions of a-iron and iron oxides with the possibility to change the size of the final particles in a wide range. The possibility of using composites of magnetic iron oxides and metal oxide compositions instead of ferromagnetic rods with VEP of boron-containing liquid radioactive waste in the fluidized field was studied. It was shown that the use of fine and nano particles of the iron oxides in the pre-treatment of the boron-containing LRW increases the strength of the final compounds and accelerates the cement setting compounds from 13 to 5-9 days.

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

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

Hansen, Stephanie B.; Harding, Eric C.; Knapp, Patrick F.

The burning core of an inertial confinement fusion (ICF) plasma produces bright x-rays at stagnation that can directly diagnose core conditions essential for comparison to simulations and understanding fusion yields. These x-rays also backlight the surrounding shell of warm, dense matter, whose properties are critical to understanding the efficacy of the inertial confinement and global morphology. In this work, we show that the absorption and fluorescence spectra of mid-Z impurities or dopants in the warm dense shell can reveal the optical depth, temperature, and density of the shell and help constrain models of warm, dense matter. This is illustrated bymore » the example of a high-resolution spectrum collected from an ICF plasma with a beryllium shell containing native iron impurities. Lastly, analysis of the iron K-edge provides model-independent diagnostics of the shell density (2.3 × 10 24 e/cm 3) and temperature (10 eV), while a 12-eV red shift in Kβ and 5-eV blue shift in the K-edge discriminate among models of warm dense matter: Both shifts are well described by a self-consistent field model based on density functional theory but are not fully consistent with isolated-atom models using ad-hoc density effects.« less

Fluorescence and absorption spectroscopy for warm dense matter studies and ICF plasma diagnostics

NASA Astrophysics Data System (ADS)

Hansen, S. B.; Harding, E. C.; Knapp, P. F.; Gomez, M. R.; Nagayama, T.; Bailey, J. E.

2018-05-01

The burning core of an inertial confinement fusion (ICF) plasma produces bright x-rays at stagnation that can directly diagnose core conditions essential for comparison to simulations and understanding fusion yields. These x-rays also backlight the surrounding shell of warm, dense matter, whose properties are critical to understanding the efficacy of the inertial confinement and global morphology. We show that the absorption and fluorescence spectra of mid-Z impurities or dopants in the warm dense shell can reveal the optical depth, temperature, and density of the shell and help constrain models of warm, dense matter. This is illustrated by the example of a high-resolution spectrum collected from an ICF plasma with a beryllium shell containing native iron impurities. Analysis of the iron K-edge provides model-independent diagnostics of the shell density (2.3 × 1024 e/cm3) and temperature (10 eV), while a 12-eV red shift in Kβ and 5-eV blue shift in the K-edge discriminate among models of warm dense matter: Both shifts are well described by a self-consistent field model based on density functional theory but are not fully consistent with isolated-atom models using ad-hoc density effects.

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.

Isolation of microorganisms involved in reduction of crystalline iron(III) oxides in natural environments

PubMed Central

Hori, Tomoyuki; Aoyagi, Tomo; Itoh, Hideomi; Narihiro, Takashi; Oikawa, Azusa; Suzuki, Kiyofumi; Ogata, Atsushi; Friedrich, Michael W.; Conrad, Ralf; Kamagata, Yoichi

2015-01-01

Reduction of crystalline Fe(III) oxides is one of the most important electron sinks for organic compound oxidation in natural environments. Yet the limited number of isolates makes it difficult to understand the physiology and ecological impact of the microorganisms involved. Here, two-stage cultivation was implemented to selectively enrich and isolate crystalline iron(III) oxide reducing microorganisms in soils and sediments. Firstly, iron reducers were enriched and other untargeted eutrophs were depleted by 2-years successive culture on a crystalline ferric iron oxide (i.e., goethite, lepidocrocite, hematite, or magnetite) as electron acceptor. Fifty-eight out of 136 incubation conditions allowed the continued existence of microorganisms as confirmed by PCR amplification. High-throughput Illumina sequencing and clone library analysis based on 16S rRNA genes revealed that the enrichment cultures on each of the ferric iron oxides contained bacteria belonging to the Deltaproteobacteria (mainly Geobacteraceae), followed by Firmicutes and Chloroflexi, which also comprised most of the operational taxonomic units (OTUs) identified. Venn diagrams indicated that the core OTUs enriched with all of the iron oxides were dominant in the Geobacteraceae while each type of iron oxides supplemented selectively enriched specific OTUs in the other phylogenetic groups. Secondly, 38 enrichment cultures including novel microorganisms were transferred to soluble-iron(III) containing media in order to stimulate the proliferation of the enriched iron reducers. Through extinction dilution-culture and single colony isolation, six strains within the Deltaproteobacteria were finally obtained; five strains belonged to the genus Geobacter and one strain to Pelobacter. The 16S rRNA genes of these isolates were 94.8–98.1% identical in sequence to cultured relatives. All the isolates were able to grow on acetate and ferric iron but their physiological characteristics differed considerably in terms of growth rate. Thus, the novel strategy allowed to enrich and isolate novel iron(III) reducers that were able to thrive by reducing crystalline ferric iron oxides. PMID:25999927

Water oxidation catalysis with nonheme iron complexes under acidic and basic conditions: homogeneous or heterogeneous?

PubMed

Hong, Dachao; Mandal, Sukanta; Yamada, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Llobet, Antoni; Fukuzumi, Shunichi

2013-08-19

Thermal water oxidation by cerium(IV) ammonium nitrate (CAN) was catalyzed by nonheme iron complexes, such as Fe(BQEN)(OTf)2 (1) and Fe(BQCN)(OTf)2 (2) (BQEN = N,N'-dimethyl-N,N'-bis(8-quinolyl)ethane-1,2-diamine, BQCN = N,N'-dimethyl-N,N'-bis(8-quinolyl)cyclohexanediamine, OTf = CF3SO3(-)) in a nonbuffered aqueous solution; turnover numbers of 80 ± 10 and 20 ± 5 were obtained in the O2 evolution reaction by 1 and 2, respectively. The ligand dissociation of the iron complexes was observed under acidic conditions, and the dissociated ligands were oxidized by CAN to yield CO2. We also observed that 1 was converted to an iron(IV)-oxo complex during the water oxidation in competition with the ligand oxidation. In addition, oxygen exchange between the iron(IV)-oxo complex and H2(18)O was found to occur at a much faster rate than the oxygen evolution. These results indicate that the iron complexes act as the true homogeneous catalyst for water oxidation by CAN at low pHs. In contrast, light-driven water oxidation using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer and S2O8(2-) as a sacrificial electron acceptor was catalyzed by iron hydroxide nanoparticles derived from the iron complexes under basic conditions as the result of the ligand dissociation. In a buffer solution (initial pH 9.0) formation of the iron hydroxide nanoparticles with a size of around 100 nm at the end of the reaction was monitored by dynamic light scattering (DLS) in situ and characterized by X-ray photoelectron spectra (XPS) and transmission electron microscope (TEM) measurements. We thus conclude that the water oxidation by CAN was catalyzed by short-lived homogeneous iron complexes under acidic conditions, whereas iron hydroxide nanoparticles derived from iron complexes act as a heterogeneous catalyst in the light-driven water oxidation reaction under basic conditions.

Isolation of microorganisms involved in reduction of crystalline iron(III) oxides in natural environments.

PubMed

Hori, Tomoyuki; Aoyagi, Tomo; Itoh, Hideomi; Narihiro, Takashi; Oikawa, Azusa; Suzuki, Kiyofumi; Ogata, Atsushi; Friedrich, Michael W; Conrad, Ralf; Kamagata, Yoichi

2015-01-01

Reduction of crystalline Fe(III) oxides is one of the most important electron sinks for organic compound oxidation in natural environments. Yet the limited number of isolates makes it difficult to understand the physiology and ecological impact of the microorganisms involved. Here, two-stage cultivation was implemented to selectively enrich and isolate crystalline iron(III) oxide reducing microorganisms in soils and sediments. Firstly, iron reducers were enriched and other untargeted eutrophs were depleted by 2-years successive culture on a crystalline ferric iron oxide (i.e., goethite, lepidocrocite, hematite, or magnetite) as electron acceptor. Fifty-eight out of 136 incubation conditions allowed the continued existence of microorganisms as confirmed by PCR amplification. High-throughput Illumina sequencing and clone library analysis based on 16S rRNA genes revealed that the enrichment cultures on each of the ferric iron oxides contained bacteria belonging to the Deltaproteobacteria (mainly Geobacteraceae), followed by Firmicutes and Chloroflexi, which also comprised most of the operational taxonomic units (OTUs) identified. Venn diagrams indicated that the core OTUs enriched with all of the iron oxides were dominant in the Geobacteraceae while each type of iron oxides supplemented selectively enriched specific OTUs in the other phylogenetic groups. Secondly, 38 enrichment cultures including novel microorganisms were transferred to soluble-iron(III) containing media in order to stimulate the proliferation of the enriched iron reducers. Through extinction dilution-culture and single colony isolation, six strains within the Deltaproteobacteria were finally obtained; five strains belonged to the genus Geobacter and one strain to Pelobacter. The 16S rRNA genes of these isolates were 94.8-98.1% identical in sequence to cultured relatives. All the isolates were able to grow on acetate and ferric iron but their physiological characteristics differed considerably in terms of growth rate. Thus, the novel strategy allowed to enrich and isolate novel iron(III) reducers that were able to thrive by reducing crystalline ferric iron oxides.

Pilot scale application of nanosized iron oxides as electron acceptors for bioremediation

NASA Astrophysics Data System (ADS)

Bosch, Julian; Fritzsche, Andreas; Frank-Fahle, Beatrice; Lüders, Tilmann; Höss, Sebastian; Eisenmann, Heinrich; Held, Thomas; Totsche, Kai U.; Meckenstock, Rainer U.

2014-05-01

Microbial reduction of ferric iron is a major biogeochemical process in groundwater aquifer ecosystems and often associated with the degradation of organic contaminants, as bacteria couple iron reduction to the oxidation reduced carbon like e.g. BTEX. Yet in general the low bioavailability of natural iron oxides limits microbial reduction rates. However, nanosized iron oxides have an unequally enhanced bioavailability and reactivity compared to their respective bulk, macro-sized, and more crystalline materials. At the same time, nanosized iron oxides can be produced in stable colloidal suspensions, permitting efficient injections into contaminated aquifers. We examined the reactivity of nanosized synthetic colloidal iron oxides in microbial iron reduction. Application of colloidal nanoparticles led to a strong and sustainable enhancement of microbial reaction rates in batch experiments and sediment columns. Toluene oxidation was increased five-fold as compared to bulk, non-colloidal ferrihydrite as electron acceptor. Furthermore, we developed a unique approach for custom-tailoring the subsurface mobility of these particles after being injected into a contaminant plume. In a field pilot application, we injected 18 m3 of an iron oxide nanoparticle solution into a BTEX contaminated aquifer with a maximum excess pressure as low as 0.2 bar. The applied suspension showed a superior subsurface mobility, creating a reactive zone of 4 m height (corresponding to the height of the confined aquifer) and 6 m in diameter. Subsequent monitoring of BTEX, microbial BTEX degradation metabolites, ferrous iron generation, stable isotopes fractionation, microbial populations, and methanogenesis demonstrated the strong impact of our approach. Mathematic processed X-ray diffractograms and FTIR spectra provided a semi-quantitatively estimate of the long-term fate of the iron oxide colloids in the aquifer. Potential environmental risks of the injection itself were monitored with ecotoxicological investigations. Our data suggest that the injection of ferric iron nanoparticles as electron acceptors into contaminated aquifers for the enhancement of microbial contaminant degradation might develop into a novel bioremediation strategy.

Measurement of L-shell transitions in M-shell ions in the laboratory and identification in stellar coronae

DOE PAGES

Lepson, J. K.; Beiersdorfer, P.; Hell, N.; ...

2017-04-04

Based on laboratory data from the Lawrence Livermore EBIT-I electron beam ion trap and calculations using the relativistic multi-reference Møller-Plesset (MRMP) perturbation theory approach, we identify L-shell transitions of M-shell iron ions in emission spectra of the nearby stars Capella and Procyon. In conclusion, these lines are weaker than the well known, prominent lines from Fe XVII. However, they need to be taken into account when modeling the spectra, especially of cool stars.

Effect of calcium oxide on the efficiency of ferrous ion oxidation and total iron precipitation during ferrous ion oxidation in simulated acid mine drainage treatment with inoculation of Acidithiobacillus ferrooxidans.

PubMed

Liu, Fenwu; Zhou, Jun; Jin, Tongjun; Zhang, Shasha; Liu, Lanlan

2016-01-01

Calcium oxide was added into ferrous ion oxidation system in the presence of Acidithiobacillus ferrooxidans at concentrations of 0-4.00 g/L. The pH, ferrous ion oxidation efficiency, total iron precipitation efficiency, and phase of the solid minerals harvested from different treatments were investigated during the ferrous ion oxidation process. In control check (CK) system, pH of the solution decreased from 2.81 to 2.25 when ferrous ions achieved complete oxidation after 72 h of Acidithiobacillus ferrooxidans incubation without the addition of calcium oxide, and total iron precipitation efficiency reached 20.2%. Efficiency of ferrous ion oxidation and total iron precipitation was significantly improved when the amount of calcium oxide added was ≤1.33 g/L, and the minerals harvested from systems were mainly a mixture of jarosite and schwertmannite. For example, the ferrous ion oxidation efficiency reached 100% at 60 h and total iron precipitation efficiency was increased to 32.1% at 72 h when 1.33 g/L of calcium oxide was added. However, ferrous ion oxidation and total iron precipitation for jarosite and schwertmannite formation were inhibited if the amount of calcium oxide added was above 2.67 g/L, and large amounts of calcium sulfate dihydrate were generated in systems.

pH sensitive core-shell magnetic nanoparticles for targeted drug delivery in cancer therapy.

PubMed

Lungu, Iulia Ioana; Rădulescu, Marius; Mogoşanu, George Dan; Grumezescu, Alexandru Mihai

2016-01-01

In the last decade, nanobiotechnology has evolved rapidly with an extensive impact on biomedical area. In order to improve bioavailability and minimize adverse effects, drug delivery systems based on magnetic nanocomposites are under development mainly for cancer imaging and antitumor therapy. In this regard, pH sensitive core-shell magnetic nanoparticles (NPs) with accurate controlled size and shape are synthesized by various modern methods, such as homogeneous precipitation, coprecipitation, microemulsion or polyol approaches, high temperature and hydrothermal reactions, sol-gel reactions, aerosol÷vapor processes and sonolysis. Due to their unique combined physico-chemical and biological properties (such as higher dispensability, chemical and thermal stability, biocompatibility), pH responsive core-shell magnetic NPs are widely investigated for controlled release of cytostatic drugs into the tumor site by means of pH change: magnetite@silicon dioxide (Fe3O4@SiO2), Fe3O4@titanium dioxide (TiO2), β-thiopropionate-polyethylene glycol (PEG)-modified Fe3O4@mSiO2, Fe3O4 NPs core coated with SiO2 with an imidazole group modified PEG-polypeptide (mPEG-poly-L-Asparagine), polyacrylic acid (PAA) and folic acid (FA) coating of the iron oxide NP core, methoxy polyethylene glycol-block-polymethacrylic acid-block-polyglycerol monomethacrylate (MPEG-b-PMAA-b-PGMA) attached by a PGMA block to a Fe3O4 core, PEG-modified polyamidoamine (PAMAM) dendrimer shell with Fe3O4 core and mesoporous silica coated on Fe3O4, mostly coated with an anticancer drug. This review paper highlights the modern research directions currently employed to demonstrate the utility of the pH responsive core-shell magnetic NPs in diagnosis and treatment of oncological diseases.

Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia

NASA Astrophysics Data System (ADS)

Glassell, M.; Robles, J.; Das, R.; Phan, M. H.; Srikanth, H.

Iron oxide nanoparticles especially Fe3O4, γ-Fe2O3 have been extensively studied for magnetic hyperthermia because of their tunable magnetic properties and stable suspension in superparamagnetic regime. However, their relatively low heating capacity hindered practical application. Recently, a large improvement in heating efficiency has been reported in exchange-coupled nanoparticles with exchange coupling between soft and hard magnetic phases. Here, we systematically studied the effect of core and shell size on the heating efficiency of the Fe3O4/CoFe2O4 core/shell nanoparticles. The nanoparticles were synthesized using thermal decomposition of organometallic precursors. Transmission electron microscopy (TEM) showed formation of spherical shaped Fe3O4 and Fe3O-/CoFe2O4 nanoparticles. Magnetic measurements showed high magnetization (≅70 emu/g) and superparamagnetic behavior for the nanoparticles at room temperature. Magnetic hyperthermia results showed a large increase in specific absorption rate (SAR) for 8nm Fe3O4/CoFe2O4 compared to Fe3O4 nanoparticles of the same size. The heating efficiency of the Fe3O4/CoFe2O4 with 1 nm CoFe2O4 (shell) increased from 207 to 220 W/g (for 800 Oe) with increase in core size from 6 to 8 nm. The heating efficiency of the Fe3O4/CoFe2O4 with 2 nm CoFe2O4 (shell) and core size of 8 nm increased from 220 to 460 W/g (for 800 Oe). These exchange-coupled Fe3O4/CoFe2O4 core/shell nanoparticles can be a good candidate for advanced hyperthermia application.

Porous Core-Shell Nanostructures for Catalytic Applications

NASA Astrophysics Data System (ADS)

Ewers, Trevor David

Porous core-shell nanostructures have recently received much attention for their enhanced thermal stability. They show great potential in the field of catalysis, as reactant gases can diffuse in and out of the porous shell while the core particle is protected from sintering, a process in which particles coalesce to form larger particles. Sintering is a large problem in industry and is the primary cause of irreversible deactivation. Despite the obvious advantages of high thermal stability, porous core-shell nanoparticles can be developed to have additional interactive properties from the combination of the core and shell together, rather than just the core particle alone. This dissertation focuses on developing new porous core-shell systems in which both the core and shell take part in catalysis. Two types of systems are explored; (1) yolk-shell nanostructures with reducible oxide shells formed using the Kirkendall effect and (2) ceramic-based porous oxide shells formed using sol-gel chemistry. Of the Kirkendall-based systems, Au FexOy and Cu CoO were synthesized and studied for catalytic applications. Additionally, ZnO was explored as a potential shelling material. Sol-gel work focused on optimizing synthetic methods to allow for coating of small gold particles, which remains a challenge today. Mixed metal oxides were explored as a shelling material to make dual catalysts in which the product of a reaction on the core particle becomes a reactant within the shell.

Hydrothermal oxidation in the Biwabik Iron Formation, MN, USA

NASA Astrophysics Data System (ADS)

Losh, Steven; Rague, Ryan

2018-02-01

Precambrian iron formations throughout the world, notably in Australia, Brazil, and South Africa, show evidence of hypogene (≥ 110 °C, mostly > 250 °C) oxidation, alteration, and silica dissolution as a result of tectonic or magmatic activity. Although hydrothermal oxidation has been proposed for the prototype Lake Superior-type iron formation, the Biwabik Iron Formation in Minnesota (USA), it has not been documented there. By examining oxidized and unoxidized Biwabik Iron Formation in three mines, including material from high-angle faults that are associated with oxidation, we document an early hypogene oxidation event ( 175 °C) involving medium-salinity aqueous fluids (8.4 ± 4.9 wt% NaCl equiv) that infiltrated iron formation along high-angle faults. At the Hibbing Taconite Mine, hydrothermal fluids oxidized iron carbonates and silicates near faults, producing goethite ± quartz. In contrast with much of the oxidized iron ores on the Mesabi Range, silica was not removed but rather recrystallized during this event, perhaps lying in a rock-dominated system at low cumulative fluid flux. During the hydrothermal oxidation event in the Hibbing Taconite deposit, quartz-filled microfractures and irregular inclusions commonly formed in coarse variably oxidized magnetite, currently the ore mineral: these inclusions degrade the ore by introducing excess silica in magnetic concentrate. Hydrothermal oxidation at Hibbing Taconite Mine is overprinted by later, relatively minor supergene oxidation both along faults and near the surface, which locally dissolved quartz. At the Fayal Reserve Mine, widespread silicate and carbonate gangue dissolution and iron oxidation was followed by precipitation of pyrite, Mn-siderite, apatite, and other minerals in void spaces, which prevented post-oxidation compaction and significant volume loss in the sampled rocks. Although definitive temperature data for this assemblage are needed, the weight of evidence indicates that this mineralization is hypogene. The association of oxidation with epithermal conditions constrains the oxidation and subsequent mineralization to have taken place during the Precambrian, the only time when these rocks would have experienced the necessary temperatures. The mineralization at Fayal Reserve shows little supergene overprint: pyrite is largely unoxidized. Hydrothermal oxidation in both mines was likely produced by basinal fluids that were expelled during the 1.83-1.87 Ga Penokean Orogeny, and mixing with meteoric fluids along faults, although a 1.1 Ga rift-related fluid flow event is also possible. Later supergene overprinting of the iron formation was minor.

The Iron-Dependent Regulation of the Candida albicans Oxidative Stress Response by the CCAAT-Binding Factor

PubMed Central

Chakravarti, Ananya; Camp, Kyle; McNabb, David S.

2017-01-01

Candida albicans is the most frequently encountered fungal pathogen in humans, capable of causing mucocutaneous and systemic infections in immunocompromised individuals. C. albicans virulence is influenced by multiple factors. Importantly, iron acquisition and avoidance of the immune oxidative burst are two critical barriers for survival in the host. Prior studies using whole genome microarray expression data indicated that the CCAAT-binding factor is involved in the regulation of iron uptake/utilization and the oxidative stress response. This study examines directly the role of the CCAAT-binding factor in regulating the expression of oxidative stress genes in response to iron availability. The CCAAT-binding factor is a heterooligomeric transcription factor previously shown to regulate genes involved in respiration and iron uptake/utilization in C. albicans. Since these pathways directly influence the level of free radicals, it seemed plausible the CCAAT-binding factor regulates genes necessary for the oxidative stress response. In this study, we show the CCAAT-binding factor is involved in regulating some oxidative stress genes in response to iron availability, including CAT1, SOD4, GRX5, and TRX1. We also show that CAT1 expression and catalase activity correlate with the survival of C. albicans to oxidative stress, providing a connection between iron obtainability and the oxidative stress response. We further explore the role of the various CCAAT-binding factor subunits in the formation of distinct protein complexes that modulate the transcription of CAT1 in response to iron. We find that Hap31 and Hap32 can compensate for each other in the formation of an active transcriptional complex; however, they play distinct roles in the oxidative stress response during iron limitation. Moreover, Hap43 was found to be solely responsible for the repression observed under iron deprivation. PMID:28122000

Concerted Motions Networking Pores and Distant Ferroxidase Centers Enable Bacterioferritin Function and Iron Traffic£ξ

PubMed Central

Yao, Huili; Rui, Huan; Kumar, Ritesh; Eshelman, Kate; Lovell, Scott; Battaile, Kevin P.; Im, Wonpil; Rivera, Mario

2015-01-01

X-ray crystallography, molecular dynamics (MD) simulations and biochemistry were utilized to investigate the effect of introducing hydrophobic interactions in the 4-fold (N148L and Q151L) and B-pores (D34F) of Pseudomonas aeruginosa bacterioferritin B (BfrB) on BfrB function. The structures show only local structural perturbations and confirm the anticipated hydrophobic interactions. Surprisingly, structures obtained after soaking crystals in Fe2+-containing crystallization solution revealed that although iron loads into the ferroxidase centers of the mutants, the side chains of ferroxidase ligands E51 and H130 do not reorganize to bind the iron ions, as is seen in the wt BfrB structures. Similar experiments with a double mutant (C89S/K96C) prepared to introduce changes outside the pores show competent ferroxidase centers that function akin to those in wt BfrB. MD simulations comparing wt BfrB with the D34F and N148L mutants show that the mutants exhibit significantly reduced flexibility, and reveal a network of concerted motions linking ferroxidase centers and 4-fold and B-pores, which are important for imparting ferroxidase centers in BfrB with the required flexibility to function efficiently. In agreement, the efficiency of Fe2+ oxidation and uptake of the 4-fold and B-pore mutants in solution is significantly compromised relative to wt or C89S/K96C BfrB. Finally, our structures show a large number of previously unknown iron binding sites in the interior cavity and B-pores of BfrB, which reveal in unprecedented detail conduits followed by iron and phosphate ions across the BfrB shell, as well as paths in the interior cavity that may facilitate nucleation of the iron phosphate mineral. PMID:25640193

Long-period seismology on Europa: 1. Physically consistent interior models

NASA Astrophysics Data System (ADS)

Cammarano, F.; Lekic, V.; Manga, M.; Panning, M.; Romanowicz, B.

2006-12-01

In order to examine the potential of seismology to determine the interior structure and properties of Europa, it is essential to calculate seismic velocities and attenuation for the range of plausible interiors. We calculate a range of models for the physical structure of Europa, as constrained by the satellite's composition, mass, and moment of inertia. We assume a water-ice shell, a pyrolitic or a chondritic mantle, and a core composed of pure iron or iron plus 20 weight percent of sulfur. We consider two extreme mantle thermal states: hot and cold. Given a temperature and composition, we determine density, seismic velocities, and attenuation using thermodynamical models. While anelastic effects will be negligible in a cold mantle and the brittle part of the ice shell, strong dispersion and dissipation are expected in a hot convective mantle and the bulk of the ice shell. There is a strong relationship between different thermal structures and compositions. The ``hot'' mantle may maintain temperatures consistent with a liquid core made of iron plus light elements. For the ``cold scenarios,'' the possibility of a solid iron core cannot be excluded, and it may even be favored. The depths of the ocean and core-mantle boundary are determined with high precision, 10 km and 40 km, respectively, once we assume a composition and thermal structure. Furthermore, the depth of the ocean is relatively insensitive (4 km) to the core composition used.

Electronic coupling in iron oxide-modified TiO2 leads to a reduced band gap and charge separation for visible light active photocatalysis.

PubMed

Nolan, Michael

2011-10-28

In recent experiments Tada et al. have shown that TiO(2) surfaces modified with iron oxide display visible light photocatalytic activity. This paper presents first principles simulations of iron oxide clusters adsorbed at the rutile TiO(2) (110) surface to elucidate the origin of the visible light photocatalytic activity of iron oxide modified TiO(2). Small iron oxide clusters adsorb at rutile (110) surface and their presence shifts the valence band so that the band gap of the composite is narrowed towards the visible, thus confirming the origin of the visible light activity of this composite material. The presence of iron oxide at the TiO(2) surface leads to charge separation, which is the origin of enhanced photocatalytic efficiency, consistent with experimental photoluminesence and photocurrent data. Surface modification of a metal oxide is thus an interesting route in the development of visible light photocatalytic materials. This journal is © the Owner Societies 2011

Comparison of Iron and Tungsten Based Oxygen Carriers for Hydrogen Production Using Chemical Looping Reforming

NASA Astrophysics Data System (ADS)

Khan, M. N.; Shamim, T.

2017-08-01

Hydrogen production by using a three reactor chemical looping reforming (TRCLR) technology is an innovative and attractive process. Fossil fuels such as methane are the feedstocks used. This process is similar to a conventional steam-methane reforming but occurs in three steps utilizing an oxygen carrier. As the oxygen carrier plays an important role, its selection should be done carefully. In this study, two oxygen carrier materials of base metal iron (Fe) and tungsten (W) are analysed using a thermodynamic model of a three reactor chemical looping reforming plant in Aspen plus. The results indicate that iron oxide has moderate oxygen carrying capacity and is cheaper since it is abundantly available. In terms of hydrogen production efficiency, tungsten oxide gives 4% better efficiency than iron oxide. While in terms of electrical power efficiency, iron oxide gives 4.6% better results than tungsten oxide. Overall, a TRCLR system with iron oxide is 2.6% more efficient and is cost effective than the TRCLR system with tungsten oxide.

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

Molecular design of cage iron(II) and cobalt(II,III) complexes with a second fluorine-enriched superhydrophobic shell.

PubMed

Belov, Alexander S; Zelinskii, Genrikh E; Varzatskii, Oleg A; Belaya, Irina G; Vologzhanina, Anna V; Dolganov, Alexander V; Novikov, Valentin V; Voloshin, Yan Z

2015-02-28

Pentafluorophenylboron-capped iron and cobalt(II) hexachloroclathrochelate precursors were obtained by the one-pot template condensation of dichloroglyoxime with pentafluorophenylboronic acid on iron and cobalt(II) ions under vigorous reaction conditions in trifluoroacetic acid media. These reactive precursors easily undergo nucleophilic substitution with (per)fluoroarylthiolate anions, giving (per)fluoroarylsulfide macrobicyclic complexes with encapsulated iron and cobalt(II) ions; nucleophilic substitution of the cobalt(II) hexachloroclathrochelate precursor with a pentafluorophenylsulfide anion gave the target hexasulfide monoclathrochelate and the mixed-valence Co(III)Co(II)Co(III) bis-clathrochelate as a side product. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, (57)Fe Mössbauer (for the X-rayed iron complexes), (1)H, (11)B, (13)C and (19)F NMR spectroscopies and by X-ray diffraction; their redox and electrocatalytic behaviors were studied using cyclic voltammetry and gas chromatography. As can be seen from the single-crystal X-ray diffraction data, the second superhydrophobic shell of such caged metal ions is formed by fluorine atoms of both the apical and ribbed (per)fluoroaryl peripheral groups. The main bond distances and chelate N=C-C=N angles in their molecules are similar, but rotational elongation (contraction) along the molecular C3-pseudoaxes, accompanied by changes in the geometry of the corresponding MN6-coordination polyhedra from a trigonal prism to a trigonal antiprism, allowed encapsulating Fe(2+), Co(2+) and Co(3+) ions. The nature of an encapsulated metal ion and its oxidation state affect the M-N bond lengths, and, for cobalt(ii) clathrochelate with an electronic configuration d(7) the Jahn-Teller structural effect is observed as an alternation of the Co-N distances. Pentafluorophenylboron-capped hexachloroclathrochelate precursors, giving stable catalytically active metal(I)-containing intermediates due to the electron-withdrawing effect of their six ribbed chlorine substituents, were found to show moderate electrocatalytic activity in a 2H(+)/H2 hydrogen-forming reaction. In the case of their ribbed-functionalized sulfide derivatives, the strong electron-withdrawing (per)fluoroaryl groups do not stabilize the reduced electrocatalytically active metal(i)-containing species as their mesomeric effect is absent or substantially decreased by steric hindrances between them.

Development of Sediment Quality Values for Puget Sound. Volume 1.

DTIC Science & Technology

1986-09-01

62 cadmium CHROMIUM,63 chromium COPPER ,64 copper IRON ,65 iron LEAD ,66 lead MANGANES ,67 manganese NICKEL ,68 nickel SELENIUM,69 selenium SILVER ,70...BERYLLIU beryllium 67. CADMIUM cadmium 68. CHROMIUM chromium 69. COPPER copper 70. IRON iron 71. LEAD lead 72. MANGANES manganese 73. NICKEL nickel 74...they can also be strongly influenced by iron and manganese oxide and hydrous oxide surfaces (these phases can scavenge metals under oxidizing

The anticancer properties of iron core–gold shell nanoparticles in colorectal cancer cells

PubMed Central

Wu, Ya-Na; Wu, Ping-Ching; Yang, Li-Xing; Ratinac, Kyle R; Thordarson, Pall; Jahn, Kristina A; Chen, Dong-Hwang; Shieh, Dar-Bin; Braet, Filip

2013-01-01

Previously, iron core–gold shell nanoparticles (Fe@Au) have been shown to possess cancer-preferential cytotoxicity in oral and colorectal cancer (CRC) cells. However, CRC cell lines are less sensitive to Fe@Au treatment when compared with oral cancer cell lines. In this research, Fe@Au are found to decrease the cell viability of CRC cell lines, including Caco-2, HT-29, and SW480, through growth inhibition rather than the induction of cell death. The cytotoxicity induced by Fe@Au in CRC cells uses different subcellular pathways to the mitochondria-mediated autophagy found in Fe@Au-treated oral cancer cells, OECM1. Interestingly, the Caco-2 cell line shows a similar response to OECM1 cells and is thus more sensitive to Fe@Au treatment than the other CRC cell lines studied. We have investigated the underlying cell resistance mechanisms of Fe@Au-treated CRC cells. The resistance of CRC cells to Fe@Au does not result from the total amount of Fe@Au internalized. Instead, the different amounts of Fe and Au internalized appear to determine the different response to treatment with Fe-only nanoparticles in Fe@Au-resistant CRC cells compared with the Fe@Au-sensitive OECM1 cells. The only moderately cytotoxic effect of Fe@Au nanoparticles on CRC cells, when compared to the highly sensitive OECM1 cells, appears to arise from the CRC cells’ relative insensitivity to Fe, as is demonstrated by our Fe-only treatments. This is a surprising outcome, given that Fe has thus far been considered to be the “active” component of Fe@Au nanoparticles. Instead, we have found that the Au coatings, previously considered only as a passivating coating to protect the Fe cores from oxidation, significantly enhance the cytotoxicity of Fe@Au in certain CRC cells. Therefore, we conclude that both the Fe and Au in these core–shell nanoparticles are essential for the anticancer properties observed in CRC cells. PMID:24039416

Synthesis and detection the oxidization of Co cores of Co@SiO2 core-shell nanoparticles by in situ XRD and EXAFS.

PubMed

Zhang, Kunhao; Zhao, Ziyan; Wu, Zhonghua; Zhou, Ying

2015-01-01

In this paper, the Co@SiO2 core-shell nanoparticles were prepared by the sol-gel method. The oxidization of Co core nanoparticles was studied by the synchrotron radiation-based techniques including in situ X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) up to 800°C in air and N2 protection conditions, respectively. It was found that the oxidization of Co cores is undergoing three steps regardless of being in air or in N2 protection condition. In the first step ranging from room temperature to 200°C, the Co cores were dominated by Co(0) state as well as small amount of Co(2+) ions. When temperature was above 300°C, the interface between Co cores and SiO2 shells was gradually oxidized into Co(2+), and the CoO layer was observed. As the temperature increasing to 800°C, the Co cores were oxidized to Co3O4 or Co3O4/CoO. Nevertheless, the oxidization kinetics of Co cores is different for the Co@SiO2 in air and N2 gas conditions. Generally, the O2 in the air could get through the SiO2 shells easily onto the Co core surface and induce the oxidization of the Co cores due to the mesoporous nature of the SiO2 shells. However, in N2 gas condition, the O atoms can only be from the SiO2 shells, so the diffusion effect of O atoms in the interface between Co core and SiO2 shell plays a key role.

Implications of room temperature oxidation on crystal structure and exchange bias effect in Co/CoO nanoparticles

DOE PAGES

Feygenson, Mikhail; Formo, Eric V.; Freeman, Katherine; ...

2015-11-02

In this study, we describe how the exchange bias effect in Co/CoO nanoparticles depends on the size focusing and temperature treatment of precursor Co nanoparticles before oxidation at ambient conditions. By appealing to magnetization, microscopy, neutron and synchrotron x-ray measurements we found that as-synthesized Co nanoparticles readily oxidize in air only after 20 days. The highest exchange bias field of 814 Oe is observed at T = 2K. When the same nanoparticles are centrifuged and annealed at 70 °C in vacuum prior to oxidation, the exchange bias field is increased to 2570 Oe. Annealing of Co nanoparticles in vacuum improvesmore » their crystallinity and prevents complete oxidation, so that Co-core/CoO-shell structure is preserved even after 120 days. The crystal structure of CoO shell in both samples is different from its bulk counterpart. Implications of such distorted CoO shells on exchange bias are discussed. Coating of Co nanoparticles with amorphous silica shell makes them resistant to oxidation, but ultimately modifies the crystal structure of both Co core and SiO 2 shell.« less

Ferric Oxide Mediated Formation of PCDD/Fs from 2-Monochlorophenol

PubMed Central

Nganai, Shadrack; Lomnicki, Slawo; Dellinger, Barry

2012-01-01

The copper oxide, surface-mediated formation of polychlorinated dibenzop-dioxins and dibenzofurans (PCDD/F) from precursors such as chlorinated phenols is considered to be a major source of PCDD/F emissions from combustion sources. In spite of being present at 2–50x higher concentrations than copper oxide, virtually no studies of the iron oxide-mediated formation of PCDD/F have been reported in the literature. We have performed packed bed, flow reactor studies of the reaction of 50 ppm gas phase 2-monochlorophenol (2-MCP) over a surface of 5% iron oxide on silica over a temperature range of 200–500 °C. Dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), 4,6-dichlorodibenzofuran (4,6-DCDF), and dibenzofuran (DF) were formed in maximum yields of 0.1, 0.2, 0.3, and 0.4 %, respectively. The yield of PCDD/F over iron oxide peaked at temperatures 50–100 °C higher in temperature than over copper oxide. The maximum yields of DD, 1-MCDD and 4,6-DCDF were 2x and 5x higher over iron oxide, respectively, than over copper oxide, while DF was not observed at all for copper oxide. The resulting PCDD/PCDF ratio was 0.39 versus 1.2 observed for iron oxide and copper oxide, respectively, which is in agreement with PCDD to PCDF ratios in full-scale combustors that are typically ≪1. The combination of 2–50x higher concentrations of iron oxide than copper oxide in most full-scale combustors and 2.5x higher yields of PCDD/F observed in the laboratory, suggest that iron oxide may contribute as much as 5–125x more than copper oxide to the emissions of PCDD/F from full-scale combustors. PMID:19238966

Yolk@Shell Nanoarchitectures with Bimetallic Nanocores-Synthesis and Electrocatalytic Applications.

PubMed

Guiet, Amandine; Unmüssig, Tobias; Göbel, Caren; Vainio, Ulla; Wollgarten, Markus; Driess, Matthias; Schlaad, Helmut; Polte, Jörg; Fischer, Anna

2016-10-10

In the present paper, we demonstrate a versatile approach for the one-pot synthesis of metal oxide yolk@shell nanostructures filled with bimetallic nanocores. This novel approach is based on the principles of hydrophobic nanoreactor soft-templating and is exemplified for the synthesis of various AgAu NP @tin-rich ITO (AgAu@ITO TR ) yolk@shell nanomaterials. Hydrophobic nanoreactor soft-templating thereby takes advantage of polystyrene-block-poly(4-vinylpiridine) inverse micelles as two-compartment nanoreactor template, in which the core and the shell of the micelles serve as metal and metal oxide precursor reservoir, respectively. The composition, size and number of AuAg bimetallic nanoparticles incorporated within the ITO TR yolk@shell can easily be tuned. The conductivity of the ITO TR shell and the bimetallic composition of the AuAg nanoparticles, the as-synthesized AuAg NP @ITO TR yolk@shell materials could be used as efficient electrocatalysts for electrochemical glucose oxidation with improved onset potential when compared to their gold counterpart.

Ultrafast Recombination Dynamics in Dye-Sensitized SnO2/TiO2 Core/Shell Films.

PubMed

Gish, Melissa K; Lapides, Alexander M; Brennaman, M Kyle; Templeton, Joseph L; Meyer, Thomas J; Papanikolas, John M

2016-12-15

Interfacial dynamics are investigated in SnO 2 /TiO 2 core/shell films derivatized with a Ru(II)-polypyridyl chromophore ([Ru II (bpy) 2 (4,4'-(PO 3 H 2 ) 2 bpy)] 2+ , RuP) using transient absorption methods. Electron injection from the chromophore into the TiO 2 shell occurs within a few picoseconds after photoexcitation. Loss of the oxidized dye through recombination occurs across time scales spanning 10 orders of magnitude. The majority (60%) of charge recombination events occur shortly after injection (τ = 220 ps), while a small fraction (≤20%) of the oxidized chromophores persists for milliseconds. The lifetime of long-lived charge-separated states (CSS) depends exponentially on shell thickness, suggesting that the injected electrons reside in the SnO 2 core and must tunnel through the TiO 2 shell to recombine with oxidized dyes. While the core/shell architecture extends the lifetime in a small fraction of the CSS, making water oxidation possible, the subnanosecond recombination process has profound implications for the overall efficiencies of dye-sensitized photoelectrosynthesis cells (DSPECs).

Oxidation driven ZnS Core-ZnO shell photocatalysts under controlled oxygen atmosphere for improved photocatalytic solar water splitting

NASA Astrophysics Data System (ADS)

Bak, Daegil; Kim, Jung Hyeun

2018-06-01

Zinc type photocatalysts attract great attentions in solar hydrogen production due to their easy availability and benign environmental characteristics. Spherical ZnS particles are synthesized with a facile hydrothermal method, and they are further used as core materials to introduce ZnO shell layer surrounding the core part by partial oxidation under controlled oxygen contents. The resulting ZnS core-ZnO shell photocatalysts represent the heterostructural type II band alignment. The existence of oxide layer also influences on proton adsorption power with an aid of strong base cites derived from highly electronegative oxygen atoms in ZnO shell layer. Photocatalytic water splitting reaction is performed to evaluate catalyst efficiency under standard one sun condition, and the highest hydrogen evolution rate (1665 μmolg-1h-1) is achieved from the sample oxidized at 16.2 kPa oxygen pressure. This highest hydrogen production rate is achieved in cooperation with increased light absorption and promoted charge separations. Photoluminescence analysis reveals that the improved visible light response is obtained after thermal oxidation process due to the oxygen vacancy states in the ZnO shell layer. Therefore, overall photocatalytic efficiency in solar hydrogen production is enhanced by improved charge separations, crystallinity, and visible light responses from the ZnS core-ZnO shell structures induced by thermal oxidation.

DLVO and XDLVO calculations for bacteriophage MS2 adhesion to iron oxide particles.

PubMed

Park, Jeong-Ann; Kim, Song-Bae

2015-10-01

In this study, batch experiments were performed to examine the adhesion of bacteriophage MS2 to three iron oxide particles (IOP1, IOP2 and IOP3) with different particle properties. The characteristics of MS2 and iron oxides were analyzed using various techniques to construct the classical DLVO and XDLVO potential energy profiles between MS2 and iron oxides. X-ray diffractometry peaks indicated that IOP1 was mainly composed of maghemite (γ-Fe2O3), but also contained some goethite (α-FeOOH). IOP2 was composed of hematite (α-Fe2O3) and IOP3 was composed of iron (Fe), magnetite (Fe3O4) and iron oxide (FeO). Transmission electron microscope images showed that the primary particle size of IOP1 (γ-Fe2O3) was 12.3±4.1nm. IOP2 and IOP3 had primary particle sizes of 167±35nm and 484±192nm, respectively. A surface angle analyzer demonstrated that water contact angles of IOP1, IOP2, IOP3 and MS2 were 44.83, 64.00, 34.33 and 33.00°, respectively. A vibrating sample magnetometer showed that the magnetic saturations of IOP1, IOP2 and IOP3 were 176.87, 17.02 and 946.85kA/m, respectively. Surface potentials measured in artificial ground water (AGW; 0.075mM CaCl2, 0.082mM MgCl2, 0.051mM KCl, and 1.5mM NaHCO3; pH7.6) indicated that iron oxides and MS2 were negatively charged in AGW (IOP1=-0.0185V; IOP2=-0.0194V; IOP3=-0.0301V; MS2=-0.0245V). Batch experiments demonstrated that MS2 adhesion to iron oxides was favorable in the order of IOP1>IOP2>IOP3. This tendency was well predicted by the classical DLVO model. In the DLVO calculations, both the sphere-plate and sphere-sphere geometries predicted the same trend of MS2 adhesion to iron oxides. Additionally, noticeable differences were not found between the DLVO and XDLVO interaction energy profiles, indicating that hydrophobic interactions did not play a major role; electrostatic interactions, however, did influence MS2 adhesion to iron oxides. Furthermore, the aggregation of iron oxides was investigated with a modified XDLVO model. This model included magnetic interactions between the particles in order to predict the aggregation of iron oxides. Even though iron oxide particle aggregation could occur under experimental conditions, the DLVO model results using primary particle size were more suitable for the interactions between MS2 and the iron oxides because of fast sorption of MS2 onto the surfaces of iron oxides. Copyright © 2015 Elsevier B.V. All rights reserved.

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.

PubMed

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-11-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder.

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments

PubMed Central

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-01-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration—a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder. PMID:25871933

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.

Chronic Iron Limitation Confers Transient Resistance to Oxidative Stress in Marine Diatoms1

PubMed Central

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

2016-01-01

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. PMID:27503604

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.

Tucum-Do-Cerrado (Bactris setosa Mart.) Consumption Modulates Iron Homeostasis and Prevents Iron-Induced Oxidative Stress in the Rat Liver

PubMed Central

Fustinoni-Reis, Adriana M.; Arruda, Sandra F.; Dourado, Lívia P. S.; da Cunha, Marcela S. B.; Siqueira, Egle M. A.

2016-01-01

This study investigated the effect of tucum-do-cerrado consumption in the oxidative status of iron-supplemented rats. Four groups of rats were treated: Control (AIN-93G), Tuc (AIN-93G added of tucum-do-cerrado), Fe (AIN-93G iron-enriched), or TucFe (AIN-93G with tucum-do-cerrado and iron-enriched) diet, for 30 days. Iron-enriched diet increased serum, liver, spleen, and intestine iron levels; transferrin saturation; liver lipid oxidation; mRNA levels of hepatic Hamp and Bmp6, and Nrf2 in the intestine. Tucum-do-cerrado consumption reduced spleen lipid and protein oxidation; mRNA levels of hepatic Hamp and Ftl, and increased serum antioxidant capacity and hepatic mRNA levels of Bmp6, Hmox1, Nqo1, and Nrf2. TucFe diet consumption abrogated the liver Hamp iron-induced up-regulation, prevented intestinal iron accumulation; hepatic lipid peroxidation; splenic protein damage, and the increase of catalase, glutathione reductase, and glutathione peroxidase activity in some tissues. These results suggest that tucum-do-cerrado protects tissues against oxidative damage, by reducing iron availability in liver and consequently inhibiting liver Hamp expression. PMID:26901220

Application of Iron Oxide as a pH-dependent Indicator for Improving the Nutritional Quality

PubMed Central

2016-01-01

Acid food indicators can be used as pH indicators for evaluating the quality and freshness of fermented products during the full course of distribution. Iron oxide particles are hardly suspended in water, but partially or completely agglomerated. The agglomeration degree of the iron oxide particles depends on the pH. The pH-dependent particle agglomeration or dispersion can be useful for monitoring the acidity of food. The zeta potential of iron oxide showed a decreasing trend as the pH increased from 2 to 8, while the point of zero charge (PZC) was observed around at pH 6.0-7.0. These results suggested that the size of the iron oxide particles was affected by the change in pH levels. As a result, the particle sizes of iron oxide were smaller at lower pH than at neutral pH. In addition, agglomeration of the iron oxide particles increased as the pH increased from 2 to 7. In the time-dependent aggregation test, the average particle size was 730.4 nm and 1,340.3 nm at pH 2 and 7, respectively. These properties of iron oxide particles can be used to develop an ideal acid indicator for food pH and to monitor food quality, besides a colorant or nutrient for nutrition enhancement and sensory promotion in food industry. PMID:27482521

Oxidation Induced Doping of Nanoparticles Revealed by in Situ X-ray Absorption Studies.

PubMed

Kwon, Soon Gu; Chattopadhyay, Soma; Koo, Bonil; Dos Santos Claro, Paula Cecilia; Shibata, Tomohiro; Requejo, Félix G; Giovanetti, Lisandro J; Liu, Yuzi; Johnson, Christopher; Prakapenka, Vitali; Lee, Byeongdu; Shevchenko, Elena V

2016-06-08

Doping is a well-known approach to modulate the electronic and optical properties of nanoparticles (NPs). However, doping at nanoscale is still very challenging, and the reasons for that are not well understood. We studied the formation and doping process of iron and iron oxide NPs in real time by in situ synchrotron X-ray absorption spectroscopy. Our study revealed that the mass flow of the iron triggered by oxidation is responsible for the internalization of the dopant (molybdenum) adsorbed at the surface of the host iron NPs. The oxidation induced doping allows controlling the doping levels by varying the amount of dopant precursor. Our in situ studies also revealed that the dopant precursor substantially changes the reaction kinetics of formation of iron and iron oxide NPs. Thus, in the presence of dopant precursor we observed significantly faster decomposition rate of iron precursors and substantially higher stability of iron NPs against oxidation. The same doping mechanism and higher stability of host metal NPs against oxidation was observed for cobalt-based systems. Since the internalization of the adsorbed dopant at the surface of the host NPs is driven by the mass transport of the host, this mechanism can be potentially applied to introduce dopants into different oxidized forms of metal and metal alloy NPs providing the extra degree of compositional control in material design.

Increasing Stability and Activity of Core-Shell Catalysts by Preferential Segregation of Oxide on Edges and Vertexes: Oxygen Reduction on Ti-Au@Pt/C

DOE PAGES

Hu, J.; Wu, L.; Kuttiyiel, K.; ...

2016-06-30

We describe a new class of core-shell nanoparticle catalysts having edges and vertexes covered by refractory metal oxide that preferentially segregates onto these catalyst sites. The monolayer shell is deposited on the oxidefree core atoms. The oxide on edges and vertexes induces high catalyst’s stability and activity. The catalyst and synthesis are exemplified by fabrication of Au nanoparticles doped by Ti atoms that segregate as oxide onto low–coordination sites of edges and vertexes. Pt monolayer shell deposited on Au sites has the mass and specific activities for the oxygen reduction reaction about 13 and 5 times higher than those ofmore » commercial Pt/C catalysts. The durability tests show no activity loss after 10000 potential cycles from 0.6 to 1.0V. The superior activity and durability of the Ti-Au@Pt catalyst originate from protective Ti oxide located at the most dissolution-prone edge and vertex sites, and Au-supported active and stable Pt shell.« less

Responses of Saccharomyces cerevisiae Strains from Different Origins to Elevated Iron Concentrations

PubMed Central

Martínez-Garay, Carlos Andrés; de Llanos, Rosa; Romero, Antonia María; Martínez-Pastor, María Teresa

2016-01-01

Iron is an essential micronutrient for all eukaryotic organisms. However, the low solubility of ferric iron has tremendously increased the prevalence of iron deficiency anemia, especially in women and children, with dramatic consequences. Baker's yeast Saccharomyces cerevisiae is used as a model eukaryotic organism, a fermentative microorganism, and a feed supplement. In this report, we explore the genetic diversity of 123 wild and domestic strains of S. cerevisiae isolated from different geographical origins and sources to characterize how yeast cells respond to elevated iron concentrations in the environment. By using two different forms of iron, we selected and characterized both iron-sensitive and iron-resistant yeast strains. We observed that when the iron concentration in the medium increases, iron-sensitive strains accumulate iron more rapidly than iron-resistant isolates. We observed that, consistent with excess iron leading to oxidative stress, the redox state of iron-sensitive strains was more oxidized than that of iron-resistant strains. Growth assays in the presence of different oxidative reagents ruled out that this phenotype was due to alterations in the general oxidative stress protection machinery. It was noteworthy that iron-resistant strains were more sensitive to iron deficiency conditions than iron-sensitive strains, which suggests that adaptation to either high or low iron is detrimental for the opposite condition. An initial gene expression analysis suggested that alterations in iron homeostasis genes could contribute to the different responses of distant iron-sensitive and iron-resistant yeast strains to elevated environmental iron levels. PMID:26773083

Role of clay minerals in the transportation of iron

USGS Publications Warehouse

Carroll, D.

1958-01-01

The clay minerals have iron associated with them in several ways: 1. (1) as an essential constituent 2. (2) as a minor constituent within the crystal lattice where it is in isomorphous substitution and 3. (3) as iron oxide on the surface of the mineral platelets. Nontronite, "hydromica," some chlorites, vermiculite, glauconite and chamosite contain iron as an essential constituent. Kaolinite and halloysite have no site within the lattice for iron, but in certain environments iron oxide (goethite or hematite) is intimately associated as a coating on the micelles. Analyses of clay minerals show that the content of Fe2O3 varies: 29 per cent (nontronite), 7??3 per cent (griffithite), 4.5 per cent ("hydromica"), 5.5 per cent (chlorite), 4 per cent (vermiculite) and 18 per cent (glauconite). The FeO content is: 40 per cent (chamosite), 7.8 per cent (griffithite), 1-2 per cent ("hydromica"), 3 per cent (glauconite) and 2 per cent (chlorite). The iron associated with the clay minerals remains stable in the environment in which the minerals occur, but if either pH or Eh or both are changed the iron may be affected. Change of environment will cause: 1. (1) removal of iron by reduction of Fe3+ to Fe2+; 2. (2) ion-exchange reactions; 3. (3) instability of the crystal lattice. Experiments using bacterial activity to produce reducing conditions with kaolinite and halloysite coated with iron oxides and with nontronite in which ferric iron is in the octahedral position within the lattice showed that ferric oxide is removed at Eh +0??215 in fresh water and at Eh +0.098 in sea water. Hematite, goethite, and indefinite iron oxides were removed at different rates. Red ferric oxides were changed to black indefinite noncrystalline ferrous sulphide at Eh -0.020 but reverted to ferric oxide under oxidizing conditions. Nontronite turned bright green under reducing conditions and some of the ferrous iron remained within the lattice on a return to oxidizing conditions. Bacterial activity seems to be necessary for maintaining reducing conditions in the environments studied. ?? 1958.

The effect of oxide shell thickness on the structural, electronic, and optical properties of Si-SiO{sub 2} core-shell nano-crystals: A (time dependent)density functional theory study

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

Nazemi, Sanaz, E-mail: s.nazemi@ut.ac.ir, E-mail: pourfath@ut.ac.ir; Soleimani, Ebrahim Asl; Pourfath, Mahdi, E-mail: s.nazemi@ut.ac.ir, E-mail: pourfath@ut.ac.ir

2016-04-14

Due to their tunable properties, silicon nano-crystals (NC) are currently being investigated. Quantum confinement can generally be employed for size-dependent band-gap tuning at dimensions smaller than the Bohr radius (∼5 nm for silicon). At the nano-meter scale, however, increased surface-to-volume ratio makes the surface effects dominant. Specifically, in Si-SiO{sub 2} core-shell semiconductor NCs the interfacial transition layer causes peculiar electronic and optical properties, because of the co-existence of intermediate oxidation states of silicon (Si{sup n+}, n = 0–4). Due to the presence of the many factors involved, a comprehensive understanding of the optical properties of these NCs has not yet been achieved. Inmore » this work, Si-SiO{sub 2} NCs with a diameter of 1.1 nm and covered by amorphous oxide shells with thicknesses between 2.5 and 4.75 Å are comprehensively studied, employing density functional theory calculations. It is shown that with increased oxide shell thickness, the low-energy part of the optical transition spectrum of the NC is red shifted and attenuated. Moreover, the absorption coefficient is increased in the high-energy part of the spectrum which corresponds to SiO{sub 2} transitions. Structural examinations indicate a larger compressive stress on the central silicon cluster with a thicker oxide shell. Examination of the local density of states reveals the migration of frontier molecular orbitals from the oxide shell into the silicon core with the increase of silica shell thickness. The optical and electrical properties are explained through the analysis of the density of states and the spatial distribution of silicon sub-oxide species.« less

Influence of iron solubility and charged surface-active compounds on lipid oxidation in fatty acid ethyl esters containing association colloids.

PubMed

Homma, Rika; Johnson, David R; McClements, D Julian; Decker, Eric A

2016-05-15

The impact of iron compounds with different solubilities on lipid oxidation was studied in the presence and absence of association colloids. Iron (III) sulfate only accelerated lipid oxidation in the presence of association colloids while iron (III) oleate accelerated oxidation in the presence and absence of association colloids. Further, iron (III) oxide retarded lipid oxidation both with and without association colloids. The impact of charged association colloids on lipid oxidation in ethyl oleate was also investigated. Association colloids consisting of the anionic surface-active compound dodecyl sulphosuccinate sodium salt (AOT), cationic surface-active compound hexadecyltrimethylammonium bromide (CTAB), and nonionic surface-active compound 4-(1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol (Triton X-100) retarded, promoted, and had no effect on lipid oxidation rates, respectively. These results indicate that the polarity of metal compounds and the charge of association colloids play a big role in lipid oxidation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of atmospheric processes on the solubility and composition of iron in Saharan dust

DOE PAGES

Longo, Amelia F.; Feng, Yan; Lai, Barry; ...

2016-06-10

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

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

PubMed

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

2016-07-05

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

Synthesis of AG@AgCl Core-Shell Structure Nanowires and Its Photocatalytic Oxidation of Arsenic (III) Under Visible Light.

PubMed

Qin, Yanyan; Cui, Yanping; Tian, Zhen; Wu, Yangling; Li, Yilian

2017-12-01

Ag@AgCl core-shell nanowires were synthesized by oxidation of Ag nanowires with moderate FeCl 3 , which exhibited excellent photocatalytic activity for As(III) oxidation under visible light. It was proved that the photocatalytic oxidation efficiency was significantly dependent on the mole ratio of Ag:AgCl. The oxidation rate of As(III) over Ag@AgCl core-shell nanowires first increased with the decrease of Ag 0 percentage, up until the optimized synthesis mole ratio of Ag nanowires:FeCl 3 was 2.32:2.20, with 0.023 mg L -1  min -1 As(III) oxidation rate; subsequently, the oxidation rate dropped with the further decrease of Ag 0 percentage. Effects of the pH, ionic strength, and concentration of humic acid on Ag@AgCl photocatalytic ability were also studied. Trapping experiments using radical scavengers confirmed that h + and ·O 2 - acted as the main active species during the visible-light-driven photocatalytic process for As(III) oxidation. The recycling experiments validated that Ag@AgCl core-shell nanowires were a kind of efficient and stable photocatalyst for As(III) oxidation under visible-light irradiation.

Ultrafast recombination dynamics in dye-sensitized SnO 2/TiO 2 core/shell films

DOE PAGES

Gish, Melissa K.; Lapides, Alexander M.; Brennaman, M. Kyle; ...

2016-12-02

In dye-sensitized photoelectrosynthesis cells (DSPECs), molecular chromophores and catalysts are integrated on a semiconductor surface to perform water oxidation or CO 2 reduction after a series of light-induced electron transfer events. Unfortunately, recombination of the charge separated state (CSS) is competitive with productive catalysis. To overcome this major obstacle, implementation of photoanodic core/shell films within these devices improve electrochemical behavior and slow recombination through the introduction of an energetic barrier between the semiconductor core and oxidized species on the surface. In this study, interfacial dynamics are investigated in SnO 2/TiO 2 core/shell films derivatized with a Ru(II)-polypyridyl chromophore ([RuII(bpy)2(4,4'-(PO 3Hmore » 2) 2bpy)] 2+, RuP) using transient absorption methods. Electron injection from the chromophore into the TiO 2 shell occurs within a few picoseconds after photoexcitation. Loss of the oxidized dye through recombination occurs across time scales spanning 10 orders of magnitude. The majority (60%) of charge recombination events occur shortly after injection (τ = 220 ps), while a small fraction (≤20%) of the oxidized chromophores persists for milliseconds. The lifetime of long-lived CSS depends exponentially on shell thickness, suggesting that the injected electrons reside in the SnO 2 core and must tunnel through the TiO 2 shell to recombine with oxidized dyes. While the core/shell architecture extends the lifetime in a small fraction of the CSS, making water oxidation possible, the subnanosecond recombination process has profound implications for the overall efficiencies of DSPECs.« less

Reactive Iron and Iron-Reducing Bacteria in Louisiana Continental Shelf Sediments

EPA Science Inventory

The Mississippi and Atchafalaya Rivers release sediments containing 15 x 106 t of iron onto the Louisiana continental shelf (LCS) each year. Iron oxides reaching the seafloor may be utilized as electron acceptors by iron-reducing bacteria for organic matter oxidation or become r...

The microstructure and magnetic properties of Cu/CuO/Ni core/multi-shell nanowire arrays

NASA Astrophysics Data System (ADS)

Yang, Feng; Shi, Jie; Zhang, Xiaofeng; Hao, Shijie; Liu, Yinong; Feng, Chun; Cui, Lishan

2018-04-01

Multifunctional metal/oxide/metal core/multi-shell nanowire arrays were prepared mostly by physical or chemical vapor deposition. In our study, the Cu/CuO/Ni core/multi-shell nanowire arrays were prepared by AAO template-electrodeposition and oxidation processes. The Cu/Ni core/shell nanowire arrays were prepared by AAO template-electrodeposition method. The microstructure and chemical compositions of the core/multi-shell nanowires and core/shell nanowires have been characterized using transmission electron microscopy with HADDF-STEM and X-ray diffraction. Magnetization measurements revealed that the Cu/CuO/Ni and Cu/Ni nanowire arrays have high coercivity and remanence ratio.

29. DEPENDABLE FORDATHSHELL CORE MACHINES IN THE GREY IRON FOUNDRY ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

29. DEPENDABLE FORDATH-SHELL CORE MACHINES IN THE GREY IRON FOUNDRY INJECTS SAND INTO A CLOSED CORE BOX. SOME OF THE UNITS HEAT THE CORE BOX TO FIX THE RESINS AS THE CORE REMAINS IN THE BOX, OTHERS MERELY SHAPED THE CORE SAND REQUIRING BAKING OF THE CORES TO HARDEN THEM. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

Methyltrimethoxysilane (MTMS)-based silica-iron oxide superhydrophobic nanocomposites.

PubMed

Nadargi, Digambar; Gurav, Jyoti; Marioni, Miguel A; Romer, Sara; Matam, Santhosh; Koebel, Matthias M

2015-12-01

We report a facile synthesis of superhydrophobic silica-iron oxide nanocomposites via a co-precursor sol-gel process. The choice of the silica precursor (Methyltrimethoxysilane, MTMS) in combination with iron nitrate altered the pore structure dramatically. The influence of iron oxide doping on the structural properties of pristine MTMS aerogel is discussed. Copyright © 2015 Elsevier Inc. All rights reserved.

Method and apparatus for capturing carbon dioxide during combustion of carbon containing fuel

DOEpatents

Axelbaum, Richard L.; Kumfer, Benjamin M.; Xia, Fei; Gopan, Akshay; Dhungel, Bhupesh

2018-04-10

A boiler system having a series of boilers. Each boiler includes a shell having an upstream end, a downstream end, and a hollow interior. The boilers also have an oxidizer inlet entering the hollow interior adjacent the upstream end of the shell and a fuel nozzle positioned adjacent the upstream end of the shell for introducing fuel into the hollow interior of the shell. Each boiler includes a flue duct connected to the shell adjacent the downstream end for transporting flue gas from the hollow interior. Oxygen is delivered to the oxidizer inlet of the first boiler in the series. Flue gas from the immediately preceding boiler in the series is delivered through the oxidizer inlet of each boiler subsequent to the first boiler in the series.

Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

USGS Publications Warehouse

Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

2009-01-01

Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

Importance of a martian hematite site for astrobiology

NASA Technical Reports Server (NTRS)

Allen, C. C.; Westall, F.; Schelble, R. T.

2001-01-01

Defining locations where conditions may have been favorable for life is a key objective for the exploration of Mars. Of prime importance are sites where conditions may have been favorable for the preservation of evidence of prebiotic or biotic processes. Areas displaying significant concentrations of the mineral hematite (alpha-Fe2O3), recently identified by thermal emission spectrometry, may have significance in the search for evidence of extraterrestrial life. Since iron oxides can form as aqueous mineral precipitates, the potential exists to preserve microscopic evidence of life in iron oxide-depositing ecosystems. Terrestrial hematite deposits proposed as possible analogs for hematite deposits on Mars include massive (banded) iron formations, iron oxide hydrothermal deposits, iron-rich laterites and ferricrete soils, and rock varnish. We report the potential for long-term preservation of microfossils by iron oxide mineralization in specimens of the approximately 2,100-Ma banded iron deposit of the Gunflint Formation, Canada. Scanning and analytical electron microscopy reveals micrometer-scale rods, spheres, and filaments consisting predominantly of iron and oxygen with minor carbon. We interpret these objects as microbial cells permineralized by an iron oxide, presumably hematite. The confirmation of ancient martian microbial life in hematite deposits will require the return of samples to terrestrial laboratories. A hematite-rich deposit composed of aqueous iron oxide precipitates may thus prove to be a prime site for future sample return.

Synthesis of iron oxides nanoparticles with very high saturation magnetization form TEA-Fe(III) complex via electrochemical deposition for supercapacitor applications

NASA Astrophysics Data System (ADS)

Elrouby, Mahmoud; Abdel-Mawgoud, A. M.; El-Rahman, Rehab Abd

2017-11-01

This work is devoted to the synthesis of magnetic iron oxides nanoparticles with very high saturation magnetization to be qualified for supercapacitor applications using, a simple electrodeposition technique. It is found that the electrochemical reduction process depends on concentration, temperature, deposition potential and the scan rate of potential. The nature of electrodeposition process has been characterized via voltammetric and chronoamperometric techniques. The morphology of the electrodeposits has been investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure and phase content of these investigated electrodeposits have been examined and calculated. The obtained iron oxides show a high saturation magnetization (Ms) of about 229 emu g-1. The data exhibited a relation between Ms of electrodeposited iron oxide and specific capacitance. This relation exhibits that the highest Ms value of electrodeposited iron oxides gives also highest specific capacitance of about 725 Fg-1. Moreover, the electrodeposited iron oxides exhibit a very good stability. The new characteristics of the electro synthesized iron oxides at our optimized conditions, strongly qualify them as a valuable material for high-performance supercapacitor applications.

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.

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.

Comparative study on the uptake and bioimpact of metal nanoparticles released into environment

NASA Astrophysics Data System (ADS)

Andries, Maria; Pricop, Daniela; Grigoras, Marian; Lupu, Nicoleta; Sacarescu, Liviu; Creanga, Dorina; Iacomi, Felicia

2015-12-01

Metallic particles of very small size are ubiquitously released in the air, water and soil from various natural and artificial sources - the last ones with enhanced extent since nanotechnology development accelerated exponentially. In this study we focused on the impact of metal nanoparticles in vegetal species of agroindustrial interest namely the maize (Zea mais L.). Laboratory simulation of environmental pollution was carried out by using engineered nanoparticles of two types: iron oxides with magnetic properties and gold nanoparticles supplied in the form of dilutes stable suspensions in the culture medium of maize seedlings. Magnetic nanoparticle (MNPs) preparation was performed by applying chemical route from iron ferric and ferrous precursor salts in alkali reaction medium at relatively high temperature (over 80 °C). Gold nanoparticles (GNPs) synthesis was accomplished from auric hydrochloride acid in alkali reaction medium in similar temperature conditions. In both types of metallic nanoparticles citrate ions were used as coating shell with role of suspension stabilization. Plantlet response was assessed at the level of assimilatory pigment contents in green tissue of seedlings in early ontogenetic stages.

Oil shale powders and their interactions with ciprofloxacin, ofloxacin, and oxytetracycline antibiotics.

PubMed

Gouza, Asmae; Saoiabi, Sanaa; El Karbane, Miloud; Masse, Sylvie; Laurent, Guillaume; Rami, Ahmed; Saoiabi, Ahmed; Laghzizil, Abdelaziz; Coradin, Thibaud

2017-11-01

The interaction of oil shale, as a widespread sedimentary rock, with common antibiotics ofloxacine, oxytetracycline, and ciprofloxacine was studied. The selected Moroccan deposit and its thermally treated forms were fully characterized from a chemical and structural point of view, indicating the prevalence of quartz as a mineral component together with aluminum- and iron-rich phase that are converted into Al-doped iron oxide phases upon heating. The presence of 4 wt% organics was also detected, which was removed at 550 °C without significant loss of specific surface area. The pseudo-second-order kinetic model and Langmuir equation were found the most adequate to reproduce the kinetics and isothermal sorption experiments. These analyses enlighten the contribution of the organic matter on antibiotic retention as well as the key role of hydrophobic interactions on the molecule-mineral surface interactions. Our results emphasize the possible contribution of raw oil shale in the accumulation of antibiotics in soils and suggest that thermally treated oil shell powders can constitute cheap mineral sorbents for environmental cleaning.

Fe(0) Nanomotors in Ton Quantities (10(20) Units) for Environmental Remediation.

PubMed

Teo, Wei Zhe; Zboril, Radek; Medrik, Ivo; Pumera, Martin

2016-03-24

Despite demonstrating potential for environmental remediation and biomedical applications, the practical environmental applications of autonomous self-propelled micro-/nanorobots have been limited by the inability to fabricate these devices in large (kilograms/tons) quantities. In view of the demand for large-scale environmental remediation by micro-/nanomotors, which are easily synthesized and powered by nontoxic fuel, we have developed bubble-propelled Fe(0) Janus nanomotors by a facile thermally induced solid-state procedure and investigated their potential as decontamination agents of pollutants. These Fe(0) Janus nanomotors, stabilized by an ultrathin iron oxide shell, were fuelled by their decomposition in citric acid, leading to the asymmetric bubble propulsion. The degradation of azo-dyes was dramatically increased in the presence of moving self-propelled Fe(0) nanomotors, which acted as reducing agents. Such enhanced pollutant decomposition triggered by biocompatible Fe(0) (nanoscale zero-valent iron motors), which can be handled in the air and fabricated in ton quantities for low cost, will revolutionize the way that environmental remediation is carried out. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic carbon nanostructures: microwave energy-assisted pyrolysis vs. conventional pyrolysis.

PubMed

Zhu, Jiahua; Pallavkar, Sameer; Chen, Minjiao; Yerra, Narendranath; Luo, Zhiping; Colorado, Henry A; Lin, Hongfei; Haldolaarachchige, Neel; Khasanov, Airat; Ho, Thomas C; Young, David P; Wei, Suying; Guo, Zhanhu

2013-01-11

Magnetic carbon nanostructures from microwave assisted- and conventional-pyrolysis processes are compared. Unlike graphitized carbon shells from conventional heating, different carbon shell morphologies including nanotubes, nanoflakes and amorphous carbon were observed. Crystalline iron and cementite were observed in the magnetic core, different from a single cementite phase from the conventional process.

Drug-loaded gold/iron/gold plasmonic nanoparticles for magnetic targeted chemo-photothermal treatment of rheumatoid arthritis.

PubMed

Kim, Hyung Joon; Lee, Sun-Mi; Park, Kyu-Hyung; Mun, Chin Hee; Park, Yong-Beom; Yoo, Kyung-Hwa

2015-08-01

We have developed methotrexate (MTX)-loaded poly(lactic-co-glycolic acid, PLGA) gold (Au)/iron (Fe)/gold (Au) half-shell nanoparticles conjugated with arginine-glycine-aspartic acid (RGD), which can be applied for magnetic targeted chemo-photothermal treatment, and in vivo multimodal imaging of rheumatoid arthritis (RA). Upon near-infrared (NIR) irradiation, local heat is generated at the inflammation region due to the NIR resonance of Au half-shells and MTX release from PLGA nanoparticles is accelerated. The Fe half-shell layer embedded between the Au half-shell layers enables in vivo T2-magnetic resonance (MR) imaging in addition to NIR absorbance imaging. Furthermore, the delivery of the nanoparticles to the inflammation region in collagen-induced arthritic (CIA) mice, and their retention can be enhanced under external magnetic field. When combined with consecutive NIR irradiation and external magnetic field application, these nanoparticles provide enhanced therapeutic effects with an MTX dosages of only 0.05% dosage compared to free MTX therapy for the treatment of RA. Copyright © 2015 Elsevier Ltd. All rights reserved.

Retinal iron homeostasis in health and disease

PubMed Central

Song, Delu; Dunaief, Joshua L.

2013-01-01

Iron is essential for life, but excess iron can be toxic. As a potent free radical creator, iron generates hydroxyl radicals leading to significant oxidative stress. Since iron is not excreted from the body, it accumulates with age in tissues, including the retina, predisposing to age-related oxidative insult. Both hereditary and acquired retinal diseases are associated with increased iron levels. For example, retinal degenerations have been found in hereditary iron overload disorders, like aceruloplasminemia, Friedreich's ataxia, and pantothenate kinase-associated neurodegeneration. Similarly, mice with targeted mutation of the iron exporter ceruloplasmin and its homolog hephaestin showed age-related retinal iron accumulation and retinal degeneration with features resembling human age-related macular degeneration (AMD). Post mortem AMD eyes have increased levels of iron in retina compared to age-matched healthy donors. Iron accumulation in AMD is likely to result, in part, from inflammation, hypoxia, and oxidative stress, all of which can cause iron dysregulation. Fortunately, it has been demonstrated by in vitro and in vivo studies that iron in the retinal pigment epithelium (RPE) and retina is chelatable. Iron chelation protects photoreceptors and retinal pigment epithelial cells (RPE) in a variety of mouse models. This has therapeutic potential for diminishing iron-induced oxidative damage to prevent or treat AMD. PMID:23825457

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...

Volume-labeled nanoparticles and methods of preparation

DOEpatents

Wang, Wei; Gu, Baohua; Retterer, Scott T; Doktycz, Mitchel J

2015-04-21

Compositions comprising nanosized objects (i.e., nanoparticles) in which at least one observable marker, such as a radioisotope or fluorophore, is incorporated within the nanosized object. The nanosized objects include, for example, metal or semi-metal oxide (e.g., silica), quantum dot, noble metal, magnetic metal oxide, organic polymer, metal salt, and core-shell nanoparticles, wherein the label is incorporated within the nanoparticle or selectively in a metal oxide shell of a core-shell nanoparticle. Methods of preparing the volume-labeled nanoparticles are also described.

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 sequences all represented novel culturable iron oxidizers most closely related to Gallionella spp. Based on their nucleotide sequences four groups could be identified, which were comparable to the DGGE banding pattern obtained before with the gradient tubes enrichments. The above mentioned nested PCR-DGGE method was used to study the distribution and community composition of Gallionella-like iron-oxidizing bacteria under the influence of plants species, soil depth, as well as season. Soil samples from Appels, Belgium, an intertidal, freshwater marsh known to hold intensive iron cycling, were taken from 5 different vegetation types in April, July and October 2007. Soil cores were sliced at 1-cm intervals and subjected to chemical and molecular analyses. The DGGE patterns showed that the community of iron-oxidizing bacteria differed with vegetation type, and sediment depth. Samples taken in autumn held lower diversity in Gallionella-related iron oxidizers than those sampled in spring and summer.

Identification of a Unique Fe-S Cluster Binding Site in a Glycyl-Radical Type Microcompartment Shell Protein

PubMed Central

Thompson, Michael C.; Wheatley, Nicole M.; Jorda, Julien; Sawaya, Michael R.; Gidaniyan, Soheil D.; Ahmed, Hoda; Yang, Zhongyu; McCarty, Krystal N.; Whitelegge, Julian P.; Yeates, Todd O.

2014-01-01

Recently, progress has been made toward understanding the functional diversity of bacterial microcompartment (MCP) systems, which serve as protein-based metabolic organelles in diverse microbes. New types of MCPs have been identified, including the glycyl-radical propanediol (Grp) MCP. Within these elaborate protein complexes, BMC-domain shell proteins assemble to form a polyhedral barrier that encapsulates the enzymatic contents of the MCP. Interestingly, the Grp MCP contains a number of shell proteins with unusual sequence features. GrpU is one such shell protein, whose amino acid sequence is particularly divergent from other members of the BMC-domain superfamily of proteins that effectively defines all MCPs. Expression, purification, and subsequent characterization of the protein showed, unexpectedly, that it binds an iron-sulfur cluster. We determined X-ray crystal structures of two GrpU orthologs, providing the first structural insight into the homohexameric BMC-domain shell proteins of the Grp system. The X-ray structures of GrpU, both obtained in the apo form, combined with spectroscopic analyses and computational modeling, show that the metal cluster resides in the central pore of the BMC shell protein at a position of broken 6-fold symmetry. The result is a structurally polymorphic iron-sulfur cluster binding site that appears to be unique among metalloproteins studied to date. PMID:25102080

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

Longo, Amelia F.; Feng, Yan; Lai, Barry

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

A general strategy toward graphitized carbon coating on iron oxides as advanced anodes for lithium-ion batteries.

PubMed

Ding, Chunyan; Zhou, Weiwei; Wang, Bin; Li, Xin; Wang, Dong; Zhang, Yong; Wen, Guangwu

2017-08-25

Integration of carbon materials with benign iron oxides is blazing a trail in constructing high-performance anodes for lithium-ion batteries (LIBs). In this paper, a unique general, simple, and controllable strategy is developed toward in situ uniform coating of iron oxide nanostructures with graphitized carbon (GrC) layers. The basic synthetic procedure only involves a simple dip-coating process for the loading of Ni-containing seeds and a subsequent Ni-catalyzed chemical vapor deposition (CVD) process for the growth of GrC layers. More importantly, the CVD treatment is conducted at a quite low temperature (450 °C) and with extremely facile liquid carbon sources consisting of ethylene glycol (EG) and ethanol (EA). The GrC content of the resulting hybrids can be controllably regulated by altering the amount of carbon sources. The electrochemical results reveal remarkable performance enhancements of iron oxide@GrC hybrids compared with pristine iron oxides in terms of high specific capacity, excellent rate and cycling performance. This can be attributed to the network-like GrC coating, which can improve not only the electronic conductivity but also the structural integrity of iron oxides. Moreover, the lithium storage performance of samples with different GrC contents is measured, manifesting that optimized electrochemical property can be achieved with appropriate carbon content. Additionally, the superiority of GrC coating is demonstrated by the advanced performance of iron oxide@GrC compared with its corresponding counterpart, i.e., iron oxides with amorphous carbon (AmC) coating. All these results indicate the as-proposed protocol of GrC coating may pave the way for iron oxides to be promising anodes for LIBs.

Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex

DOE PAGES

Hong, Seungwoo; Lu, Xiaoyan; Lee, Yong -Min; ...

2017-09-29

Here, a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [Fe V(NTs)(TAML)] – (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [Fe V(NTs)(TAML +•)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML +•). 2 is a competent oxidant in C–H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.

Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation

PubMed Central

2017-01-01

Area-selective atomic layer deposition (ALD) is envisioned to play a key role in next-generation semiconductor processing and can also provide new opportunities in the field of catalysis. In this work, we developed an approach for the area-selective deposition of metal oxides on noble metals. Using O2 gas as co-reactant, area-selective ALD has been achieved by relying on the catalytic dissociation of the oxygen molecules on the noble metal surface, while no deposition takes place on inert surfaces that do not dissociate oxygen (i.e., SiO2, Al2O3, Au). The process is demonstrated for selective deposition of iron oxide and nickel oxide on platinum and iridium substrates. Characterization by in situ spectroscopic ellipsometry, transmission electron microscopy, scanning Auger electron spectroscopy, and X-ray photoelectron spectroscopy confirms a very high degree of selectivity, with a constant ALD growth rate on the catalytic metal substrates and no deposition on inert substrates, even after 300 ALD cycles. We demonstrate the area-selective ALD approach on planar and patterned substrates and use it to prepare Pt/Fe2O3 core/shell nanoparticles. Finally, the approach is proposed to be extendable beyond the materials presented here, specifically to other metal oxide ALD processes for which the precursor requires a strong oxidizing agent for growth. PMID:29503508

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 iron for metabolism. It is anticipated that integrated and complex regulatory networks sensing different environmental signals, such as the energy source and/or the redox state of the cell as well as the oxygen availability, are involved. © 2011 Society for Applied Microbiology and Blackwell Publishing Ltd.

Single step, phase controlled, large scale synthesis of ferrimagnetic iron oxide polymorph nanoparticles by thermal plasma route and their rheological properties

NASA Astrophysics Data System (ADS)

Raut, Suyog A.; Mutadak, Pallavi R.; Kumar, Shiv; Kanhe, Nilesh S.; Huprikar, Sameer; Pol, Harshawardhan V.; Phase, Deodatta M.; Bhoraskar, Sudha V.; Mathe, Vikas L.

2018-03-01

In this paper we report single step large scale synthesis of highly crystalline iron oxide nanoparticles viz. magnetite (Fe3O4) and maghemite (γ-Fe2O3) via gas phase condensation process, where micron sized iron metal powder was used as a precursor. Selective phases of iron oxide were obtained by variation of gas flow rate of oxygen and hence partial pressure of oxygen inside the plasma reactor. Most of the particles were found to possesses average crystallite size of about 20-30 nm. The DC magnetization curves recorded indicate almost super-paramagnetic nature of the iron oxide magnetic nanoparticles. Further, iron oxide nanoparticles were analyzed using Raman spectroscopy, X-ray photoelectron spectroscopy and Mossbauer spectroscopy. In order to explore the feasibility of these nanoparticles for magnetic damper application, rheological studies have been carried out and compared with commercially available Carbonyl Iron (CI) particles. The nanoparticles obtained by thermal plasma route show improved dispersion which is useful for rheological applications.

Structural characterization, antibacterial and catalytic effect of iron oxide nanoparticles synthesised using the leaf extract of Cynometra ramiflora

NASA Astrophysics Data System (ADS)

Groiss, Silvia; Selvaraj, Raja; Varadavenkatesan, Thivaharan; Vinayagam, Ramesh

2017-01-01

In the present investigation, the leaf extract of Cynometra ramiflora was used to synthesize iron oxide nanoparticles. Within minutes of adding iron sulphate to the leaf extract, iron oxide nanoparticles were formed and thus, the method is very simple and fast. UV-VIS spectra showed the strong absorption band in the visible region. SEM images showed discrete spherical shaped particles and EDS spectra confirmed the iron and oxygen presence. The XRD results depicted the crystalline structure of iron oxide nanoparticles. FT-IR spectra portrayed the existence of functional groups of phytochemicals which are probably involved in the formation and stabilization of nanoparticles. The iron oxide nanoparticles exhibited effective inhibition against E. coli and S. epidermidis which may find its applications in the antibacterial drug development. Furthermore, the catalytic activity of the nanoparticles as Fenton-like catalyst was successfully investigated for the degradation of Rhodamine-B dye. This outcome could play a prominent role in the wastewater treatment.

Recent progress in magnetic iron oxide-semiconductor composite nanomaterials as promising photocatalysts

NASA Astrophysics Data System (ADS)

Wu, Wei; Changzhong Jiang, Affc; Roy, Vellaisamy A. L.

2014-11-01

Photocatalytic degradation of toxic organic pollutants is a challenging tasks in ecological and environmental protection. Recent research shows that the magnetic iron oxide-semiconductor composite photocatalytic system can effectively break through the bottleneck of single-component semiconductor oxides with low activity under visible light and the challenging recycling of the photocatalyst from the final products. With high reactivity in visible light, magnetic iron oxide-semiconductors can be exploited as an important magnetic recovery photocatalyst (MRP) with a bright future. On this regard, various composite structures, the charge-transfer mechanism and outstanding properties of magnetic iron oxide-semiconductor composite nanomaterials are sketched. The latest synthesis methods and recent progress in the photocatalytic applications of magnetic iron oxide-semiconductor composite nanomaterials are reviewed. The problems and challenges still need to be resolved and development strategies are discussed.

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

Aortic iron overload with oxidative stress and inflammation in human and murine abdominal aortic aneurysm.

PubMed

Sawada, Hisashi; Hao, Hiroyuki; Naito, Yoshiro; Oboshi, Makiko; Hirotani, Shinichi; Mitsuno, Masataka; Miyamoto, Yuji; Hirota, Seiichi; Masuyama, Tohru

2015-06-01

Although iron is an essential element for maintaining physiological function, excess iron leads to tissue damage caused by oxidative stress and inflammation. Oxidative stress and inflammation play critical roles for the development of abdominal aortic aneurysm (AAA). However, it has not been investigated whether iron plays a role in AAA formation through oxidative stress and inflammation. We, therefore, examined whether iron is involved in the pathophysiology of AAA formation using human AAA walls and murine AAA models. Human aortic walls were collected from 53 patients who underwent cardiovascular surgery (non-AAA=34; AAA=19). Murine AAA was induced by infusion of angiotensin II to apolipoprotein E knockout mice. Iron was accumulated in human and murine AAA walls compared with non-AAA walls. Immunohistochemistry showed that both 8-hydroxy-2'-deoxyguanosine and CD68-positive areas were increased in AAA walls compared with non-AAA walls. The extent of iron accumulated area positively correlated with that of 8-hydroxy-2'-deoxyguanosine expression area and macrophage infiltration area in human and murine AAA walls. We next investigated the effects of dietary iron restriction on AAA formation in mice. Iron restriction reduced the incidence of AAA formation with attenuation of oxidative stress and inflammation. Aortic expression of transferrin receptor 1, intracellular iron transport protein, was increased in human and murine AAA walls, and transferrin receptor 1-positive area was similar to areas where iron accumulated and F4/80 were positive. Iron is involved in the pathophysiology of AAA formation with oxidative stress and inflammation. Dietary iron restriction could be a new therapeutic strategy for AAA progression. © 2015 American Heart Association, Inc.

Molecular Structures of Al/Si and Fe/Si Coprecipitates and the Implication for Selenite Removal

PubMed Central

Chan, Ya-Ting; Kuan, Wen-Hui; Tzou, Yu-Min; Chen, Tsan-Yao; Liu, Yu-Ting; Wang, Ming-Kuang; Teah, Heng-Yi

2016-01-01

Aluminum and iron oxides have been often used in the coagulation processes during water purification due to their unique surface properties toward anions. In the presence of silica, the coprecipitation of Al/Si or Fe/Si might decrease the efficiency of wastewater purification and reuse. In this study, surface properties and molecular structures of Al/Si and Fe/Si coprecipitates were characterized using spectroscopic techniques. Also, the selenite removal efficiency of Al/Si and Fe/Si coprecipitates in relation to their surface and structural properties was investigated. While dissolved silicate increased with increasing pH from Fe/Si coprecipitates, less than 7% of silicate was discernible from Al/Si samples over the range from acidic to alkaline conditions. Our spectroscopic results showed that the associations between Al and Si were relatively stronger than that between Fe and Si in coprecipitates. In Al/Si coprecipitates, core-shell structures were developed with AlO6/AlO4 domains as the shells and Si frameworks polymerized from the SiO2 as the cores. However, Si framework remained relatively unchanged upon coprecipitation with Fe hydroxides in Fe/Si samples. The Si core with Al shell structure of Al/Si coprecipitates shielded the negative charges from SiO2 and thereby resulted in a higher adsorption capacity of selenite than Fe/Si coprecipitates. PMID:27095071

A method for recovery of iron, titanium, and vanadium from vanadium-bearing titanomagnetite

NASA Astrophysics Data System (ADS)

Zhang, Yi-min; Wang, Li-na; Chen, De-sheng; Wang, Wei-jing; Liu, Ya-hui; Zhao, Hong-xin; Qi, Tao

2018-02-01

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures: low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

Effect of oxidative stress induced by intracranial iron overload on central pain after spinal cord injury.

PubMed

Meng, Fan Xing; Hou, Jing Ming; Sun, Tian Sheng

2017-02-08

Central pain (CP) is a common clinical problem in patients with spinal cord injury (SCI). Recent studies found the pathogenesis of CP was related to the remodeling of the brain. We investigate the roles of iron overload and subsequent oxidative stress in the remodeling of the brain after SCI. We established a rat model of central pain after SCI. Rats were divided randomly into four groups: SCI, sham operation, SCI plus deferoxamine (DFX) intervention, and SCI plus nitric oxide synthase (NOS) inhibitor treatment. Pain behavior was observed and thermal pain threshold was measured regularly, and brain levels of iron, transferrin receptor 1 (TfR1), ferritin (Fn), and lactoferrin (Lf), were detected in the different groups 12 weeks after establishment of the model. Rats demonstrated self-biting behavior after SCI. Furthermore, the latent period of thermal pain was reduced and iron levels in the hind limb sensory area, hippocampus, and thalamus increased after SCI. Iron-regulatory protein (IRP) 1 levels increased in the hind limb sensory area, while Fn levels decreased. TfR1 mRNA levels were also increased and oxidative stress was activated. Oxidative stress could be inhibited by ferric iron chelators and NOS inhibitors. SCI may cause intracranial iron overload through the NOS-iron-responsive element/IRP pathway, resulting in central pain mediated by the oxidative stress response. Iron chelators and oxidative stress inhibitors can effectively relieve SCI-associated central pain.

Iron Opacity Platform Performance Characterization at the National Ignition Facility

NASA Astrophysics Data System (ADS)

Opachich, Y. P.; Ross, P. W.; Heeter, R. F.; Barrios, M. A.; Liedahl, D. A.; May, M. J.; Schneider, M. B.; Craxton, R. S.; Garcia, E. M.; McKenty, P. W.; Zhang, R.; Weaver, J. L.; Flippo, K. A.; Kline, J. L.; Perry, T. S.; Los Alamos National Laboratory Collaboration; Naval Research Laboratory Collaboration; University of Rochester LaboratoryLaser Energetics Collaboration; Lawrence Livermore National Lab Collaboration; National Security Technologies, LLC Collaboration

2016-10-01

A high temperature opacity platform has been fielded at the National Ignition Facility (NIF). The platform will be used to study opacity in iron at a temperature of 160 eV. The platform uses a 6 mm diameter hohlraum driven by 128 laser beams with 530 kJ of energy in a 3 ns pulse to heat an iron sample. Absorption spectra of the heated sample are generated with a broadband pulsed X-ray backlighter produced by imploding a vacuum-filled CH shell. The shell is 2 mm in diameter and 20 microns thick, driven by 64 beams with 250 kJ in a 2.5 ns pulse. The hohlraum and backlighter performance have both been investigated recently and will be discussed in this presentation. This work was performed by National Security Technologies, LLC, under Contract No. DE-AC52-06NA25946 with the U.S. Department of Energy. DOE/NV/25946-2892.

A general route towards well-defined magneto- or fluorescent-plasmonic nanohybrids

NASA Astrophysics Data System (ADS)

Schmidtke, Christian; Kloust, Hauke; Bastús, Neus G.; Merkl, Jan-Philip; Tran, Huong; Flessau, Sandra; Feld, Artur; Schotten, Theo; Weller, Horst

2013-11-01

Herein, we present a general route towards defined nanohybrids, comprised of a fluorescent quantum dot (QD) or superparamagnetic iron oxide (Fe2O3) nanocrystal core and a tuneable corona of plasmonic gold or silver nanoparticles (NPs), adhered by a cross-linked poly(isoprene)-b-poly(ethylene glycol) diblock copolymer (PI-b-PEG) matrix. To this end, the PEG-terminus of the amphiphilic polymer was acylated with lipoic acid (LA), which, as is known, forms quasi-covalent Au-thiol- or Ag-thiol-bonds. Surprisingly, by variation of the ratio of the different NPs, inverse core/satellite structures bearing QDs or Fe2O3 around a metallic NP core were obtained. Furthermore, gold NPs or even closed gold shells were grown by in situ reductive deposition of Au3+ ions on Fe2O3 NP seeds. Finally, in order to demonstrate the scope of the method, ternary nanohybrids, composed of QDs, Fe2O3 and Au NPs, were accomplished. All magneto-plasmonic and fluorescent-plasmonic materials were thoroughly characterized by absorption and emission spectroscopy, TEM and TEM-EDX. Antibody conjugation to these novel nanohybrids proved their practical utility in a prototype immunoassay.Herein, we present a general route towards defined nanohybrids, comprised of a fluorescent quantum dot (QD) or superparamagnetic iron oxide (Fe2O3) nanocrystal core and a tuneable corona of plasmonic gold or silver nanoparticles (NPs), adhered by a cross-linked poly(isoprene)-b-poly(ethylene glycol) diblock copolymer (PI-b-PEG) matrix. To this end, the PEG-terminus of the amphiphilic polymer was acylated with lipoic acid (LA), which, as is known, forms quasi-covalent Au-thiol- or Ag-thiol-bonds. Surprisingly, by variation of the ratio of the different NPs, inverse core/satellite structures bearing QDs or Fe2O3 around a metallic NP core were obtained. Furthermore, gold NPs or even closed gold shells were grown by in situ reductive deposition of Au3+ ions on Fe2O3 NP seeds. Finally, in order to demonstrate the scope of the method, ternary nanohybrids, composed of QDs, Fe2O3 and Au NPs, were accomplished. All magneto-plasmonic and fluorescent-plasmonic materials were thoroughly characterized by absorption and emission spectroscopy, TEM and TEM-EDX. Antibody conjugation to these novel nanohybrids proved their practical utility in a prototype immunoassay. Electronic supplementary information (ESI) available: NMR spectra, magnetic purification, BrCN coupling of 2,2'-dithiobis(ethylamine), Au domain growth on OH- and COOH-functionalized iron oxide NPs, Ag/QD core/satellite hybrids and dot-blot analysis of Ms mAb to ovalbumin conjugated hybrids. See DOI: 10.1039/c3nr04155g

A modular continuous flow reactor system for the selective bio-oxidation of iron and precipitation of schwertmannite from mine-impacted waters.

PubMed

Hedrich, Sabrina; Johnson, D Barrie

2012-02-01

A novel modular bioremediation system which facilitates the selective removal of soluble iron from extremely acidic (pH ∼2) metal-rich wastewaters by ferrous iron oxidation and selective precipitation of the ferric iron produced is described. In the first of the three modules, rapid ferrous iron oxidation was mediated by the recently-characterized iron-oxidizing autotrophic acidophile, "Ferrovum myxofaciens", which grew as long "streamers" within the reactor. Over 90% of the iron present in influent test liquors containing 280mg/L iron was oxidized at a dilution rate of 0.41h(-1), in a proton-consuming reaction. The ferric iron-rich solutions produced were pumped into a second reactor where controlled addition of sodium hydroxide caused the water pH to increase to 3.5 and ferric iron to precipitate as the mineral schwertmannite. Addition of a flocculating agent promoted rapid aggregation and settling of the fine-grain schwertmannite particles. A third passive module (a packed-bed bioreactor, also inoculated with "Fv. myxofaciens") acted as a polishing reactor, lowering soluble iron concentrations in the processed water to <1mg/L. The system was highly effective in selectively removing iron from a synthetic acidic (pH 2.1) mine water that contained soluble aluminum, copper, manganese and zinc in addition to iron. Schwertmannite was again produced, with little or no co-precipitation of other metals. Copyright © 2011 Elsevier Ltd. All rights reserved.

Transmission electron microscopy and ab initio calculations to relate interfacial intermixing and the magnetism of core/shell nanoparticles

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

Chi, C.-C.; Hsiao, C.-H.; Ouyang, Chuenhou, E-mail: houyang@mx.nthu.edu.tw

2015-05-07

Significant efforts towards understanding bi-magnetic core-shell nanoparticles are underway currently as they provide a pathway towards properties unavailable with single-phased systems. Recently, we have demonstrated that the magnetism of γ-Fe2O3/CoO core-shell nanoparticles, in particular, at high temperatures, originates essentially from an interfacial doped iron-oxide layer that is formed by the migration of Co{sup 2+} from the CoO shell into the surface layers of the γ-Fe2O3 core [Skoropata et al., Phys. Rev. B 89, 024410 (2014)]. To examine directly the nature of the intermixed layer, we have used high-resolution transmission electron microscopy (HRTEM) and first-principles calculations to examine the impact ofmore » the core-shell intermixing at the atomic level. By analyzing the HRTEM images and energy dispersive spectra, the level and nature of intermixing was confirmed, mainly as doping of Co into the octahedral site vacancies of γ-Fe2O3. The average Co doping depths for different processing temperatures (150 °C and 235 °C) were 0.56 nm and 0.78 nm (determined to within 5% through simulation), respectively, establishing that the amount of core-shell intermixing can be altered purposefully with an appropriate change in synthesis conditions. Through first-principles calculations, we find that the intermixing phase of γ-Fe2O3 with Co doping is ferromagnetic, with even higher magnetization as compared to that of pure γ-Fe2O3. In addition, we show that Co doping into different octahedral sites can cause different magnetizations. This was reflected in a change in overall nanoparticle magnetization, where we observed a 25% reduction in magnetization for the 235 °C versus the 150 °C sample, despite a thicker intermixed layer.« less

The nanophase iron mineral(s) in Mars soil

NASA Technical Reports Server (NTRS)

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

1993-01-01

A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.

Nanoscale oxidation and complex oxide growth on single crystal iron surfaces and external electric field effects.

PubMed

Jeon, Byoungseon; Van Overmeere, Quentin; van Duin, Adri C T; Ramanathan, Shriram

2013-02-14

Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.

Oxidative Injury and Iron Redistribution Are Pathological Hallmarks of Marmoset Experimental Autoimmune Encephalomyelitis.

PubMed

Dunham, Jordon; Bauer, Jan; Campbell, Graham R; Mahad, Don J; van Driel, Nikki; van der Pol, Susanne M A; 't Hart, Bert A; Lassmann, Hans; Laman, Jon D; van Horssen, Jack; Kap, Yolanda S

2017-06-01

Oxidative damage and iron redistribution are associated with the pathogenesis and progression of multiple sclerosis (MS), but these aspects are not entirely replicated in rodent experimental autoimmune encephalomyelitis (EAE) models. Here, we report that oxidative burst and injury as well as redistribution of iron are hallmarks of the MS-like pathology in the EAE model in the common marmoset. Active lesions in the marmoset EAE brain display increased expression of nicotinamide adenine dinucleotide phosphate (NADPH) oxidase (p22phox, p47phox, and gp91phox) and inducible nitric oxide synthase immunoreactivity within lesions with active inflammation and demyelination, coinciding with enhanced expression of mitochondrial heat-shock protein 70 and superoxide dismutase 1 and 2. The EAE lesion-associated liberation of iron (due to loss of iron-containing myelin) was associated with altered expression of the iron metabolic markers FtH1, lactoferrin, hephaestin, and ceruloplasmin. The enhanced expression of oxidative damage markers in inflammatory lesions indicates that the enhanced antioxidant enzyme expression could not counteract reactive oxygen and nitrogen species-induced cellular damage, as is also observed in MS brains. This study demonstrates that oxidative injury and aberrant iron distribution are prominent pathological hallmarks of marmoset EAE thus making this model suitable for therapeutic intervention studies aimed at reducing oxidative stress and associated iron dysmetabolism. © 2017 American Association of Neuropathologists, Inc. All rights reserved.

Phenolic Wastewater Treatment Alternatives.

DTIC Science & Technology

1980-06-01

15 Potassium Permanganate ................ 19 Iron (VI) Ferrate ..................... 22 Catalytic Oxidation ..................... 22...carbon dioxide, potassium hydroxide, and manganese dioxide which were readily handled by the existing system. d. Iron (VI) Ferrate Ferrate is iron in...the following systems/processes: Granular Activated Carbon (GAC) adsorption, ozone oxidation, hydrogen peroxide oxidation, potassium permanganate

Prediction of iron oxide contents using diffuse reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Marques, José, Jr.; Arantes Camargo, Livia

2015-04-01

Determining soil iron oxides using conventional analysis is relatively unfeasible when large areas are mapped, with the aim of characterizing spatial variability. Diffuse reflectance spectroscopy (DRS) is rapid, less expensive, non-destructive and sometimes more accurate than conventional analysis. Furthermore, this technique allows the simultaneous characterization of many soil attributes with agronomic and environmental relevance. This study aims to assess the DRS capability to predict iron oxides content -hematite and goethite - , characterizing their spatial variability in soils of Brazil. Soil samples collected from an 800-hectare area were scanned in the visible and near-infrared spectral range. Moreover, chemometric calibration was obtained through partial least-squares regression (PLSR). Then, spatial distribution maps of the attributes were constructed using predicted values from calibrated models through geostatistical methods. The studied area presented soils with varied contents of iron oxides as examples for the Oxisols and Entisols. In the spectra of each soil is observed that the reflectance decreases with the content of iron oxides present in the soil. In soils with a high content of iron oxides can be observed more pronounced concavities between 380 and 1100 nm which are characteristic of the presence of these oxides. In soils with higher reflectance it were observed concavity characteristics due to the presence of kaolinite, in agreement with the low iron contents of those soils. The best accuracy of prediction models [residual prediction deviation (RPD) = 1.7] was obtained for goethite within the visible region (380-800 nm), and for hematite (RPD = 2.0) within the visible near infrared (380-2300 nm). The maps of goethite and hematite predicted showed the spatial distribution pattern similar to the maps of clay and iron extracted by dithionite-citrate-bicarbonate, being consistent with the iron oxide contents of soils present in the study area. These results confirm the value of DRS in the mapping of iron oxides in large areas at detailed scale.

Fluorescence and absorption spectroscopy for warm dense matter studies and ICF plasma diagnostics

DOE PAGES

Hansen, Stephanie B.; Harding, Eric C.; Knapp, Patrick F.; ...

2018-03-07

The burning core of an inertial confinement fusion (ICF) plasma produces bright x-rays at stagnation that can directly diagnose core conditions essential for comparison to simulations and understanding fusion yields. These x-rays also backlight the surrounding shell of warm, dense matter, whose properties are critical to understanding the efficacy of the inertial confinement and global morphology. In this work, we show that the absorption and fluorescence spectra of mid-Z impurities or dopants in the warm dense shell can reveal the optical depth, temperature, and density of the shell and help constrain models of warm, dense matter. This is illustrated bymore » the example of a high-resolution spectrum collected from an ICF plasma with a beryllium shell containing native iron impurities. Lastly, analysis of the iron K-edge provides model-independent diagnostics of the shell density (2.3 × 10 24 e/cm 3) and temperature (10 eV), while a 12-eV red shift in Kβ and 5-eV blue shift in the K-edge discriminate among models of warm dense matter: Both shifts are well described by a self-consistent field model based on density functional theory but are not fully consistent with isolated-atom models using ad-hoc density effects.« less

Modulation of the antioxidative response of Spartina densiflora against iron exposure.

PubMed

Martínez Domínguez, David; Torronteras Santiago, Rafael; Córdoba García, Francisco

2009-06-01

Spartina densiflora, an invader cordgrass living in polluted salt marshes of the Odiel estuary (SW Spain), was collected and cultured under controlled laboratory conditions. After acclimation to non-polluted soils for 28 days, both metabolites and enzymes activities used as indicators of oxidative stress were reduced significantly. Then, plants were exposed to 500 and 1000 ppm Fe-ethylenediamine-N,N'-2-hydroxyphenyl acetic acid (EDDHA) for 28 days. Our data demonstrate that iron content in leaves was enhanced by iron exposure. This iron increase caused an enhancement in the concentration of H2O2, hydroperoxides and lipid peroxidation, and a decrease in chlorophyll levels. Thus, iron exposure led to oxidative stress conditions. However, oxidative indicators stabilised after first 2 weeks of exposure, although the highest iron levels in leaves were reached at the end of treatments. Iron exposure induced an enhancement of catalase, ascorbate peroxidase and guaiacol peroxidase activities, together with an increase in total and oxidised ascorbate. This response may be defensive against oxidative stress and thus help to explain why cell oxidative damages were stabilised. Thus, by using a sensitive long-time protocol, iron-dependent oxidative damages may be controlled and even reverted successfully by the activation of the antioxidative defences of S. densiflora. This efficient antioxidative system, rapidly modulated in response to excess iron and other environmental stressors, may account for S. densiflora's successful adaptation to stress conditions in its habitat.

Impact of iron and vitamin C-containing supplements on preterm human milk: in vitro.

PubMed

Friel, James K; Diehl-Jones, William L; Suh, Miyoung; Tsopmo, Apollinaire; Shirwadkar, Vaibhav P

2007-05-15

Stress due to reactive oxygen species (ROS) may lead to neonatal diseases, such as necrotizing enterocolitis and respiratory distress. Enteral supplements for premature infants (PREM) added to human milk (HM) to increase nutrient content may induce lipid oxidation due to free radical formation via Fenton chemistry. We hypothesized that ferrous iron and vitamin C-containing supplements added to HM in vitro cause oxidation of milk fats, affect intracellular redox balance, and induce DNA damage. Lipid peroxidation in HM was measured by FOX-2 and TBARS assays; fatty acid composition of supplemented HM was measured by gas chromatography. Two cell culture bioassays were used for assessing either intracellular oxidative stress or DNA damage: the former involved Caco-2BBe cells, a secondary differentiated cell line, and the latter utilized FHS-74 Int cells, a primary fetal small intestinal culture. Lipid oxidation products of HM increased after the addition of iron alone, iron and vitamin C, or iron and a vitamin C-containing supplement (Trivisol, TVS). A reduced content of mono and polyunsaturated fatty acids in HM was also observed. Iron, not iron+vitamin C, but iron+TVS induced significant intracellular oxidative stress in FHS-74 Int cells. In contrast, iron, either alone or in combination with TVS or vitamin C, increased DNA damage in Caco-2BBE cells. Iron supplementation may increase oxidative stress in PREM infants and should be given separately from vitamin C-containing supplements.

Isolation of iron bacteria from terrestrial and aquatic environments

NASA Astrophysics Data System (ADS)

Schmidt, Bertram; Szewzyk, Ulrich

2010-05-01

Bacteria, which are capable of iron oxidation or at least iron deposition are widely distributed in environments where zones of dissolved ferrous iron and oxygen gradients are overlapping [1]. They take part in the biological cycling of iron and influence other cycles of elements for example carbon [2]. Manganese can be used for similar metabolic purposes as iron, because it can be biologically oxidized by chemolithotrophs or can be reduced by respirating bacteria as well [3, 4]. Bacterial activity is responsible for the accumulation of ferric iron compounds in their surroundings. The formation of bog ore is a well known example for a soil horizon, with an extreme enrichment of biogenic ferric iron [5]. We focused on the isolation of neutrophilic iron bacteria and bacteria capable of manganese oxidation. We used samples from Tierra del Fuego (Argentina) the National Park "Unteres Odertal" (Germany) and Berlin ground water wells. Microscopic examination of the samples revealed a considerable diversity of iron encrusted structures of bacterial origin. Most of these morphologic types are already well known. The taxonomic classification of many of these organisms is based on morphologic features and is not reliable compared to recent methods of molecular biology. That is mainly due to the fact, that most of these bacteria are hardly culturable or do not show their characteristic morphologic features under culture conditions. We established a collection of more than 300 iron depositing strains. Phylogenetic analyses showed that we have many yet uncultured strains in pure culture. We obtained many isolates which form distinct branches within long known iron bacteria groups like the Sphaerotilus-Leptothrix cluster. But some of the strains belong to groups, which have not yet been associated with iron oxidation activity. The strains deposit high amounts of oxidized iron and manganese compounds under laboratory conditions. However it is unclear if these precipitations are due to biological oxidation or biological deposition of chemically oxidized iron. We examined the morphologic characteristics of selected isolates under near-natural conditions to assign them to morphologic structures which occur in native samples. Our aim for the future is to describe several strains. References: [1] Weber, K. A. ; Achenbach, L. A. ; Coates, J. D. : Microorganisms pumping iron: anaerobic microbial iron oxidation and reduction. In: Nature Reviews Microbiology 4 (2006) 752-764 [2] Van Capellen, P. ; Wang Y. : Cycling of iron and manganese in surface sediments: a general theory for the coupled transport and reaction of carbon, oxygen, nitrogen, sulfur, iron and manganese. In: American Journal of Science 296 (1996) 197-243 [3] Tebo, B. M. ; Bargar, J. R. ; Clement, B. G. ; Dick, G. J. ; Murray, K. J. ; Parker, D. Verity R. ; Webb, S. M. : Biogenic manganese oxides: properties and mechanisms of formation. In: Annual Reviews Earth Planet Science 32 (2004) 287-328 [4] Erlich, H. L. : Manganese oxide reduction as a form of anaerobic respiration. In: Geomicrobiology Journal 5 (1987) 423-431 [5] Ghiorse W. C. : Biology of iron- and manganese-depositing bacteria. In: Annual Reviews 38 (1984) 515-550

Transport properties of Sb doped Si nanowires

NASA Astrophysics Data System (ADS)

Nukala, Prathyusha; Sapkota, Gopal; Gali, Pradeep; Usha, Philipose

2011-10-01

n-type Si nanowires were synthesized at ambient pressure using SiCl4 as Si source and Sb source as the dopant. Sb doping of 3-4 wt % was achieved through a post growth diffusion technique. The nanowires were found to have an amorphous oxide shell that developed post-growth; the thickness of the shell is estimated to be about 3-4 nm. The composition of the amorphous shell covering the crystalline Si core was determined by Raman spectroscopy, with evidence that the shell was an amorphous oxide layer. Optical characterization of the as-grown nanowires showed green emission, attributed to the presence of the oxide shell covering the Si nanowire core. Etching of the oxide shell was found to decrease the intensity of this green emission. A single undoped Si nanowire contacted in an FET type configuration was found to be p-type with channel mobility of 20 cm^2V-1S-1. Sb doped Si nanowires exhibited n-type behavior, compensating for the holes in the undoped nanowire. The doped nanowires had carrier mobility and concentration of 160 cm^2V-1S-1 and 9.6 x 10^18cm-3 respectively.

Arsenic mobilization and immobilization in paddy soils

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

Enhancing oxidative stability in heated oils using core/shell structures of collagen and α-tocopherol complex.

PubMed

Gim, Seo Yeong; Hong, Seungmi; Kim, Jisu; Kwon, YongJun; Kim, Mi-Ja; Kim, GeunHyung; Lee, JaeHwan

2017-11-15

In this study, collagen mesh structure was prepared by carrying α-tocopherol in the form of core/shell complex. Antioxidant properties of α-tocopherol loaded carriers were tested in moisture added bulk oils at 140°C. From one gram of collagen core/shell complex, 138mg α-tocopherol was released in medium chain triacylglycerol (MCT). α-Tocopherol was substantially protected against heat treatment when α-tocopherol was complexed in collagen core/shell. Oxidative stability in bulk oil was significantly enhanced by added collagen mesh structure or collagen core/shell complex with α-tocopherol compared to that in control bulk oils (p<0.05), although no significant difference was observed between oils containing collagen mesh structure and collagen core/shell with α-tocopherol (p>0.05). Results of DPPH loss in methanol demonstrated that collagen core/shell with α-tocopherol had significantly (p<0.05) higher antioxidant properties than collagen mesh structure up to a certain period. Therefore, collagen core/shell complex is a promising way to enhance the stability of α-tocopherol and oxidative stability in oil-rich foods prepared at high temperature. Copyright © 2017 Elsevier Ltd. All rights reserved.

Novel chiral core-shell silica microspheres with trans-(1R,2R)-diaminocyclohexane bridged in the mesoporous shell: synthesis, characterization and application in high performance liquid chromatography.

PubMed

Wu, Xiabing; You, Linjun; Di, Bin; Hao, Weiqiang; Su, Mengxiang; Gu, Yu; Shen, Lingling

2013-07-19

Novel chiral core-shell silica microspheres with trans-(1R,2R)-diaminocyclohexane (DACH) moiety bridged in the mesoporous shell were synthesized using layer-by-layer method. The chiral mesoporous shell around the nonporous silica core was formed by the co-condensation of N,N'-bis-[(triethoxysilyl)propyl]-trans-(1R,2R)-bis-(ureido)-cyclohexane (DACH-BS) and tetraethoxysilane (TEOS) using octadecyltrimethylammonium chloride (C18TMACl) and triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (P123) as the templates. The functionalized core-shell silica microspheres were characterized and tested as chiral stationary phases for high performance liquid chromatography (HPLC). R/S-1,1'-bi-2,2'-naphthol, R/S-6,6'-dibromo-1,1'-bi-2-naphthol and R/S-1,1'-bi-2,2'-phenanthrol were enantioseparated rapidly on the column packed with the DACH core-shell silica particles. Moreover, the column packed with core-shell particles exhibited better performance than the column packed with the DACH functionalized periodic mesoporous organosilicas. Copyright © 2013 Elsevier B.V. All rights reserved.

Bmp6 Regulates Retinal Iron Homeostasis and Has Altered Expression in Age-Related Macular Degeneration

PubMed Central

Hadziahmetovic, Majda; Song, Ying; Wolkow, Natalie; Iacovelli, Jared; Kautz, Leon; Roth, Marie-Paule; Dunaief, Joshua L.

2011-01-01

Iron-induced oxidative stress causes hereditary macular degeneration in patients with aceruloplasminemia. Similarly, retinal iron accumulation in age-related macular degeneration (AMD) may exacerbate the disease. The cause of retinal iron accumulation in AMD is poorly understood. Given that bone morphogenetic protein 6 (Bmp6) is a major regulator of systemic iron, we examined the role of Bmp6 in retinal iron regulation and in AMD pathogenesis. Bmp6 was detected in the retinal pigment epithelium (RPE), a major site of pathology in AMD. In cultured RPE cells, Bmp6 was down-regulated by oxidative stress and up-regulated by iron. Intraocular Bmp6 protein injection in mice up-regulated retinal hepcidin, an iron regulatory hormone, and altered retinal labile iron levels. Bmp6−/− mice had age-dependent retinal iron accumulation and degeneration. Postmortem RPE from patients with early AMD exhibited decreased Bmp6 levels. Because oxidative stress is associated with AMD pathogenesis and down-regulates Bmp6 in cultured RPE cells, the diminished Bmp6 levels observed in RPE cells in early AMD may contribute to iron build-up in AMD. This may in turn propagate a vicious cycle of oxidative stress and iron accumulation, exacerbating AMD and other diseases with hereditary or acquired iron excess. PMID:21703414

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 and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

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 and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

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 and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

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 and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

21 CFR 73.2250 - 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. 73.2250 Section 73.2250 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally...

21 CFR 73.2250 - 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. 73.2250 Section 73.2250 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally...

46 CFR 56.50-95 - Overboard discharges and shell connections.

Code of Federal Regulations, 2011 CFR

2011-10-01

..., or ductile cast iron specification listed in Table 56.60-1(a). Lead or other heat sensitive materials... flooding. Brittle materials such as cast iron shall not be used in such service. Where nonmetallic... inch, except that the use of suitable corrosion-resistant material of lesser thickness will be given...

46 CFR 56.50-95 - Overboard discharges and shell connections.

Code of Federal Regulations, 2010 CFR

2010-10-01

..., or ductile cast iron specification listed in Table 56.60-1(a). Lead or other heat sensitive materials... flooding. Brittle materials such as cast iron shall not be used in such service. Where nonmetallic... inch, except that the use of suitable corrosion-resistant material of lesser thickness will be given...

Impact of Microcystis aeruginosa Exudate on the Formation and Reactivity of Iron Oxide Particles Following Fe(II) and Fe(III) Addition.

PubMed

Garg, Shikha; Wang, Kai; Waite, T David

2017-05-16

Impact of the organic exudate secreted by a toxic strain of Microcystis aeruginosa on the formation, aggregation, and reactivity of iron oxides that are formed on addition of Fe(II) and Fe(III) salts to a solution of the exudate is investigated in this study. The exudate has a stabilizing effect on the particles formed with decreased aggregation rate and increased critical coagulant concentration required for diffusion-limited aggregation to occur. These results suggest that the presence of algal exudates from Microcystis aeruginosa may significantly influence particle aggregation both in natural water bodies where Fe(II) oxidation results in oxide formation and in water treatment where Fe(III) salts are commonly added to aid particle growth and contaminant capture. The exudate also affects the reactivity of iron oxide particles formed with exudate coated particles undergoing faster dissolution than bare iron oxide particles. This has implications to iron availability, especially where algae procure iron via dissolution of iron oxide particles as a result of either reaction with reducing moieties, light-mediated ligand to metal charge transfer and/or reaction with siderophores. The increased reactivity of exudate coated particles is attributed, for the most part, to the smaller size of these particles, higher surface area and increased accessibility of surface sites.

Terrestrial Fe-oxide Concretions and Mars Blueberries: Comparisons of Similar Advective and Diffusive Chemical Infiltration Reaction Mechanisms

NASA Astrophysics Data System (ADS)

Park, A. J.; Chan, M. A.

2006-12-01

Abundant iron oxide concretions occurring in Navajo Sandstone of southern Utah and those discovered at Meridiani Planum, Mars share many common observable physical traits such as their spheriodal shapes, occurrence, and distribution patterns in sediments. Terrestrial concretions are products of interaction between oxygen-rich aquifer water and basin-derived reducing (iron-rich) water. Water-rock interaction simulations show that diffusion of oxygen and iron supplied by slow-moving water is a reasonable mechanism for producing observed concretion patterns. In short, southern Utah iron oxide concretions are results of Liesegang-type diffusive infiltration reactions in sediments. We propose that the formation of blueberry hematite concretions in Mars sediments followed a similar diagenetic mechanism where iron was derived from the alteration of volcanic substrate and oxygen was provided by the early Martian atmosphere. Although the terrestrial analog differs in the original host rock composition, both the terrestrial and Mars iron-oxide precipitation mechanisms utilize iron and oxygen interactions in sedimentary host rock with diffusive infiltration of solutes from two opposite sources. For the terrestrial model, slow advection of iron-rich water is an important factor that allowed pervasive and in places massive precipitation of iron-oxide concretions. In Mars, evaporative flux of water at the top of the sediment column may have produced a slow advective mass-transfer mechanism that provided a steady source and the right quantity of iron. The similarities of the terrestrial and Martian systems are demonstrated using a water-rock interaction simulator Sym.8, initially in one-dimensional systems. Boundary conditions such as oxygen content of water, partial pressure of oxygen, and supply rate of iron were varied. The results demonstrate the importance of slow advection of water and diffusive processes for producing diagenetic iron oxide concretions.

Interaction of fluorescent sensor with superparamagnetic iron oxide nanoparticles.

PubMed

Karunakaran, Chockalingam; Jayabharathi, Jayaraman; Sathishkumar, Ramalingam; Jayamoorthy, Karunamoorthy

2013-06-01

To sense superparamagnetic iron oxides (Fe2O3 and Fe3O4) nanocrystals a sensitive bioactive phenanthroimidazole based fluorescent molecule, 2-(4-fluorophenyl)-1-phenyl-1H-phenanthro [9,10-d] imidazole has been designed and synthesized. Electronic spectral studies show that phenanthroimidazole is bound to the surface of iron oxide semiconductors. Fluorescent enhancement has been explained on the basis of photo-induced electron transfer (PET) mechanism and apparent binding constants have been deduced. Binding of phenanthroimidazole with iron oxide nanoparticles lowers the HOMO and LUMO energy levels of phenanthroimidazole molecule. Chemical affinity between the nitrogen atom of the phenanthroimidazole and Fe(2+) and Fe(3+) ions on the surface of the nano-oxide may result in strong binding of the phenanthroimidazole derivative with the nanoparticles. The electron injection from the photoexcited phenanthroimidazole to the iron oxides conduction band explains the enhanced fluorescence. Copyright © 2013 Elsevier B.V. All rights reserved.

Magnetite-hematite transformation: correlation between natural and synthetic features

NASA Astrophysics Data System (ADS)

Barbosa, Paola F.; Lagoeiro, Leonardo; Scholz, Ricardo; Graça, Leonardo M.; Mohallem, Nelcy

2015-06-01

The iron-oxide system can be used as a marker of oxidized and reduced conditions in closed systems. However, natural rocks with iron oxide minerals also exhibit such reactions, although the natural system is typically open. To understand the behaviour of this natural system, some similarities were investigated, in terms of crystallographic textures, between the microstructures of two systems: natural open system and synthetic closed system of iron oxide phase transformation. Particular cases of phase transformation in iron oxide minerals, described as natural reactions of magnetite to hematite and synthetic reactions of hematite to magnetite, were chosen. It is observed, in both scenarios, that the transformation obeys the topotaxial and epitaxial relationship, which are well described for the iron oxide system. However, in natural open systems, the precipitation of a new phase during the in situ transformation modifies the microstructures and must be taken into account as an important factor to describe them.

Ferroxidase-Mediated Iron Oxide Biomineralization: Novel Pathways to Multifunctional Nanoparticles.

PubMed

Zeth, Kornelius; Hoiczyk, Egbert; Okuda, Mitsuhiro

2016-02-01

Iron oxide biomineralization occurs in all living organisms and typically involves protein compartments ranging from 5 to 100nm in size. The smallest iron-oxo particles are formed inside dodecameric Dps protein cages, while the structurally related ferritin compartments consist of twice as many identical protein subunits. The largest known compartments are encapsulins, icosahedra made of up to 180 protein subunits that harbor additional ferritin-like proteins in their interior. The formation of iron-oxo particles in all these compartments requires a series of steps including recruitment of iron, translocation, oxidation, nucleation, and storage, that are mediated by ferroxidase centers. Thus, compartmentalized iron oxide biomineralization yields uniform nanoparticles strictly determined by the sizes of the compartments, allowing customization for highly diverse nanotechnological applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

Gene identification and substrate regulation provide insights into sulfur accumulation during bioleaching with the psychrotolerant acidophile Acidithiobacillus ferrivorans.

PubMed

Liljeqvist, Maria; Rzhepishevska, Olena I; Dopson, Mark

2013-02-01

The psychrotolerant acidophile Acidithiobacillus ferrivorans has been identified from cold environments and has been shown to use ferrous iron and inorganic sulfur compounds as its energy sources. A bioinformatic evaluation presented in this study suggested that Acidithiobacillus ferrivorans utilized a ferrous iron oxidation pathway similar to that of the related species Acidithiobacillus ferrooxidans. However, the inorganic sulfur oxidation pathway was less clear, since the Acidithiobacillus ferrivorans genome contained genes from both Acidithiobacillus ferrooxidans and Acidithiobacillus caldus encoding enzymes whose assigned functions are redundant. Transcriptional analysis revealed that the petA1 and petB1 genes (implicated in ferrous iron oxidation) were downregulated upon growth on the inorganic sulfur compound tetrathionate but were on average 10.5-fold upregulated in the presence of ferrous iron. In contrast, expression of cyoB1 (involved in inorganic sulfur compound oxidation) was decreased 6.6-fold upon growth on ferrous iron alone. Competition assays between ferrous iron and tetrathionate with Acidithiobacillus ferrivorans SS3 precultured on chalcopyrite mineral showed a preference for ferrous iron oxidation over tetrathionate oxidation. Also, pure and mixed cultures of psychrotolerant acidophiles were utilized for the bioleaching of metal sulfide minerals in stirred tank reactors at 5 and 25°C in order to investigate the fate of ferrous iron and inorganic sulfur compounds. Solid sulfur accumulated in bioleaching cultures growing on a chalcopyrite concentrate. Sulfur accumulation halted mineral solubilization, but sulfur was oxidized after metal release had ceased. The data indicated that ferrous iron was preferentially oxidized during growth on chalcopyrite, a finding with important implications for biomining in cold environments.

Gene Identification and Substrate Regulation Provide Insights into Sulfur Accumulation during Bioleaching with the Psychrotolerant Acidophile Acidithiobacillus ferrivorans

PubMed Central

Liljeqvist, Maria; Rzhepishevska, Olena I.

2013-01-01

The psychrotolerant acidophile Acidithiobacillus ferrivorans has been identified from cold environments and has been shown to use ferrous iron and inorganic sulfur compounds as its energy sources. A bioinformatic evaluation presented in this study suggested that Acidithiobacillus ferrivorans utilized a ferrous iron oxidation pathway similar to that of the related species Acidithiobacillus ferrooxidans. However, the inorganic sulfur oxidation pathway was less clear, since the Acidithiobacillus ferrivorans genome contained genes from both Acidithiobacillus ferrooxidans and Acidithiobacillus caldus encoding enzymes whose assigned functions are redundant. Transcriptional analysis revealed that the petA1 and petB1 genes (implicated in ferrous iron oxidation) were downregulated upon growth on the inorganic sulfur compound tetrathionate but were on average 10.5-fold upregulated in the presence of ferrous iron. In contrast, expression of cyoB1 (involved in inorganic sulfur compound oxidation) was decreased 6.6-fold upon growth on ferrous iron alone. Competition assays between ferrous iron and tetrathionate with Acidithiobacillus ferrivorans SS3 precultured on chalcopyrite mineral showed a preference for ferrous iron oxidation over tetrathionate oxidation. Also, pure and mixed cultures of psychrotolerant acidophiles were utilized for the bioleaching of metal sulfide minerals in stirred tank reactors at 5 and 25°C in order to investigate the fate of ferrous iron and inorganic sulfur compounds. Solid sulfur accumulated in bioleaching cultures growing on a chalcopyrite concentrate. Sulfur accumulation halted mineral solubilization, but sulfur was oxidized after metal release had ceased. The data indicated that ferrous iron was preferentially oxidized during growth on chalcopyrite, a finding with important implications for biomining in cold environments. PMID:23183980

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

Gold and gold-iron oxide magnetic glyconanoparticles: synthesis, characterization and magnetic properties.

PubMed

de la Fuente, Jesús M; Alcántara, David; Eaton, Peter; Crespo, Patricia; Rojas, Teresa C; Fernandez, Asunción; Hernando, Antonio; Penadés, Soledad

2006-07-06

The preparation, characterization and the magnetic properties of gold and gold-iron oxide glyconanoparticles (GNPs) are described. Glyconanoparticles were prepared in a single step procedure in the presence of aqueous solution of thiol functionalized neoglycoconjugates and either gold salts or both gold and iron salts. Neoglycoconjugates of lactose and maltose disaccharides with different linkers were used. Iron-free gold or gold-iron oxide GNPs with controlled gold-iron ratios were obtained. The average core-size diameters are in the range of 1.5-2.5 nm. The GNPs are fully characterized by (1)H NMR spectrometry, transmission electron microscopy (TEM), and UV-vis and X-ray absorption (XAS) spectroscopies. Inductive plasma-atomic emission spectrometry (ICP) and elemental analysis gave the average number of neoglycoconjugates per cluster. The magnetic properties were measured in a SQUID magnetometer. The most remarkable results was the observation of a permanent magnetism up to room temperature in the iron-free gold GNPs, that was not present in the corresponding gold-iron oxide GNPs.

Toward a Mechanistic Understanding of Anaerobic Nitrate-Dependent Iron Oxidation: Balancing Electron Uptake and Detoxification

PubMed Central

Carlson, Hans K.; Clark, Iain C.; Melnyk, Ryan A.; Coates, John D.

2011-01-01

The anaerobic oxidation of Fe(II) by subsurface microorganisms is an important part of biogeochemical cycling in the environment, but the biochemical mechanisms used to couple iron oxidation to nitrate respiration are not well understood. Based on our own work and the evidence available in the literature, we propose a mechanistic model for anaerobic nitrate-dependent iron oxidation. We suggest that anaerobic iron-oxidizing microorganisms likely exist along a continuum including: (1) bacteria that inadvertently oxidize Fe(II) by abiotic or biotic reactions with enzymes or chemical intermediates in their metabolic pathways (e.g., denitrification) and suffer from toxicity or energetic penalty, (2) Fe(II) tolerant bacteria that gain little or no growth benefit from iron oxidation but can manage the toxic reactions, and (3) bacteria that efficiently accept electrons from Fe(II) to gain a growth advantage while preventing or mitigating the toxic reactions. Predictions of the proposed model are highlighted and experimental approaches are discussed. PMID:22363331

Evaluation of the effect of sulfate, alkalinity and disinfector on iron release of iron pipe and iron corrosion scale characteristics under water quality changing condition using response surface methodology

NASA Astrophysics Data System (ADS)

Yang, Fan; Shi, Baoyou; Zhang, Weiyu; Guo, Jianbo; Wu, Nana; Liu, Xinyuan

2018-02-01

The response surface methodology (RSM), particularly Box-Behnken design model, was used in this study to evaluate the sulfate, alkalinity and free chlorine on iron release of pipe with groundwater supply history and its iron corrosion scale characteristics under water quality changing experiment. The RSM results together with response surface contour plots indicated that the iron release of pipe section reactors was positively related with Larson Ratio and free chlorine. The thin Corrosion scales with groundwater supply history upon collection site contained Fe3O4 (18%), α-FeOOH (64%), FeCO3 (9%), β-FeOOH (8%) and γ-FeOOH (5%), besides their averaged amorphous iron oxide content was 13.6%. After the RSM water quality changing experiment, Fe3O4, amorphous iron oxide and intermediate iron products (FeCO3, Green Rust (GR)) content on scale of Cl2Rs increased, while their α-FeOOH contents decreased and β-FeOOH disappeared. The high iron released Cl2Rs receiving higher LR water (1.40-2.04) contained highest FeCO3 (20%) and amorphous iron oxide (42%), while the low iron release Cl2Rs receiving lower LR water (0.52-0.73) had higher GR(6.5%) and the amorphous iron oxide (23.7%). In high LR water (>0.73), the thin and non-protective corrosion scale containing higher amorphous iron oxide, Fe(II) derived from new produced Fe3O4 or FeCO3 or GR was easy for oxidants and sulfate ions penetration, and had higher iron release. However the same unstable corrosion scale didn’t have much iron release in low LR water (≤0.73). RSM experiment indicated that iron release of these unstable corrosion scales had close relationship with water quality (Larson Ratio and disinfectant). Optimizing the water quality of new source water and using reasonable water purification measures can help to eliminate the red water case.

Arsenic Mobilization Influenced By Iron Reduction And Sulfidogenesis Under Dynamic Flow

NASA Astrophysics Data System (ADS)

Kocar, B. D.; Stewart, B. D.; Herbel, M.; Fendorf, S.

2004-12-01

Sulfidogenesis and iron reduction are ubiquitous processes that occur in a variety of anoxic subsurface and surface environments, which profoundly impact the cycling of arsenic. Of the iron (hydr)oxides, ferrihydrite possesses one of the highest capacities to retain arsenic, and is globally distributed within soils and sediments. Upon dissimilatory iron reduction, ferrihydrite may transform to lower surface area minerals, such as goethite and magnetite, which decreases arsenic retention, thus enhancing its transport. Here we examine how arsenic retained on ferrihydrite is mobilized under dynamic flow in the presence of Sulfurosprillum barnesii strain SES-3, a bacteria capable of reducing both As(V) and Fe(III). Ferrihydrite coated sands, loaded with 150 mg kg-1 As(V), were inoculated with S. barnesii, packed into a column and reacted with a synthetic groundwater solution. Within several days after initiation of flow, the concentration of arsenic in the column effluent increased dramatically coincident with the mineralogical transformation of ferrihydrite and As(V) reduction to As(III). Following the initial pulse of arsenic, effluent concentration then declined to less than 10 μ M. Thus, arsenic release into the aqueous phase is contingent upon the incongruent reduction of As(V) and Fe(III) as mediated by biological activity. Reaction of abiotically or biotically generated dissolved sulfide with iron (hydr)oxides may have a dramatic influence on the fate of arsenic within surface and subsurface environments. Accordingly, we examined the reaction of dissolved bisulfide and iron (hydr)oxide complexed with arsenic in both batch and column systems. Low ratios of sulfide to iron in batch reaction systems result in the formation of elemental sulfur and concomitant arsenic release from the iron (hydr)oxide surface. High sulfide to iron ratios, in contrast, appear to favor the formation of iron and arsenic sulfides. Our findings demonstrate that iron (hydr)oxides may quench reactions between sulfide and constituents sorbed to iron (hydr)oxide surfaces, forming elemental sulfur as opposed to sulfide-arsenic complexes. In addition, reductive transformation of iron (hydr)oxide by dissolved sulfide may release sorbed constituents. Hence, moderate to low concentrations of dissolved sulfide in association with iron (hydr)oxides may inhibit sequestration of important contaminants that are attenuated by Fe(III) and/or S(-II) bearing phases.

Iron oxide nanoparticles supported on ultradispersed diamond powders: Effect of the preparation procedure

NASA Astrophysics Data System (ADS)

Dimitrov, Momtchil; Ivanova, Ljubomira; Paneva, Daniela; Tsoncheva, Tanya; Stavrev, Stavry; Mitov, Ivan; Minchev, Christo

2009-01-01

The state of the iron oxide nanoparticles, supported on ultradispersed diamond (UDD) powders is studied by X-ray diffraction, nitrogen physisorption, temperature-programmed reduction, FTIR and Mössbauer spectroscopy. Methanol decomposition to hydrogen and CO is used as a catalytic test. The peculiarities of the iron oxide species strongly depend on the detonation procedure used for the UDD powders preparation as well as on the iron modification procedure.

In-situ determination of the oxidation state of iron in Fe-bearing silicate melts

NASA Astrophysics Data System (ADS)

Courtial, P.; Wilke, M.; Potuzak, M.; Dingwell, D. B.

2005-12-01

Terrestrial lavas commonly contain up to 10 wt% of iron. Furthermore, rocks returned from the Moon indicate lunar lava containing up to 25 wt% of iron and planetary scientists estimated that the martian mantle has about 18 wt% of iron. An experimental challenge in dealing with Fe-bearing silicate melts is that the oxidation state, controlling the proportions of ferric and ferrous iron, is a function of composition, oxygen fugacity and temperature and may vary significantly. Further complications concerning iron originate from its potential to be either four-, six- or even five-fold coordinated in both valence states. Therefore, the oxidation state of iron was determined in air for various Fe-bearing silicate melts. Investigated samples were Na-disilicate (NS), one atmosphere anorthite-diopside eutectic (AD) and haplogranitic (HPG8) melts containing up to 20, 20 and 10 wt% of iron, respectively. XANES spectra at the Fe K-edge were collected for all the melts at beamline A1, HASYLAB, Hamburg, using a Si(111) 4-crystal monochromator. Spectra were collected for temperatures up to 1573 K using a Pt-Rh loop as heating device. The Fe oxidation state was determined from the centroid position of the pre-edge feature using the calibration of Wilke et al. (2004). XANES results suggest that oxidation state of iron does not change within error for NS melts with addition of Fe, while AD and HPG8 melts become more oxidised with increasing iron content. Furthermore, NS melts are well more oxidised than AD and HPG8 melts that exhibit relatively similar oxidation states for identical iron contents. The oxidation state of iron for NS melts appears to be slightly temperature-dependent within the temperature range investigated (1073-1573 K). However, this trend is stronger for AD and HPG8 melts. Assuming that glass reflects a picture of the homogeneous equilibria of the melt, the present in-situ Fe-oxidation states determined for these melts were compared to those obtained on quenched glasses from different temperatures, when possible, using wet-chemical analysis (i.e., K-dichromate potentiometry). Both datasets agree reasonably well (within 10 %). References: Wilke et al. (2004) Chemical Geology, 213, 71-87.

Recovery of iron oxides from acid mine drainage and their application as adsorbent or catalyst.

PubMed

Flores, Rubia Gomes; Andersen, Silvia Layara Floriani; Maia, Leonardo Kenji Komay; José, Humberto Jorge; Moreira, Regina de Fatima Peralta Muniz

2012-11-30

Iron oxide particles recovered from acid mine drainage represent a potential low-cost feedstock to replace reagent-grade chemicals in the production of goethite, ferrihydrite or magnetite with relatively high purity. Also, the properties of iron oxides recovered from acid mine drainage mean that they can be exploited as catalysts and/or adsorbents to remove azo dyes from aqueous solutions. The main aim of this study was to recover iron oxides with relatively high purity from acid mine drainage to act as a catalyst in the oxidation of dye through a Fenton-like mechanism or as an adsorbent to remove dyes from an aqueous solution. Iron oxides (goethite) were recovered from acid mine drainage through a sequential precipitation method. Thermal treatment at temperatures higher than 300 °C produces hematite through a decrease in the BET area and an increase in the point of zero charge. In the absence of hydrogen peroxide, the solids adsorbed the textile dye Procion Red H-E7B according to the Langmuir model, and the maximum amount adsorbed decreased as the temperature of the thermal treatment increased. The decomposition kinetics of hydrogen peroxide is dependent on the H(2)O(2) concentration and iron oxides dosage, but the second-order rate constant normalized to the BET surface area is similar to that for different iron oxides tested in this and others studies. These results indicate that acid mine drainage could be used as a source material for the production of iron oxide catalysts/adsorbents, with comparable quality to those produced using analytical-grade reagents. Copyright © 2012 Elsevier Ltd. All rights reserved.

Photoluminescence emission from GaAs nanodisks in GaAs/AlGaAs nanopillar arrays fabricated by neutral beam etching

NASA Astrophysics Data System (ADS)

Ohori, Daisuke; Fukuyama, Atsuhiko; Sakai, Kentaro; Higo, Akio; Thomas, Cedric; Samukawa, Seiji; Ikari, Tetsuo

2017-05-01

GaAs quantum nanodisks (QNDs) in nanopillar (NP) arrays are considered to be an attractive candidate for photonic device applications. We report a damageless fabrication technique that can be used to produce large-area lattice-matched GaAs/AlGaAs heterostructure NP arrays through the use of a bio-template and neutral beam etching. We have successfully realized GaAs QNDs in NPs owing to nanoscale iron oxide masks included in poly(ethylene glycol)-decorated ferritin protein shells. We observed for first time the photoluminescence emission from as-etched GaAs QNDs and confirmed quantum confinement by quantum mechanical calculation. Our methodology is vital for high-efficiency pillar-based optoelectronic devices such as NP laser diodes.

Process for the synthesis of iron powder

DOEpatents

Not Available

1982-03-06

A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder.

Process for the synthesis of iron powder

DOEpatents

Welbon, William W.

1983-01-01

A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder.

Effect of bicarbonate on iron-mediated oxidation of low-density lipoprotein

NASA Astrophysics Data System (ADS)

Arai, Hirofumi; Berlett, Barbara S.; Chock, P. Boon; Stadtman, Earl R.

2005-07-01

Oxidation of low-density lipoprotein (LDL) may play an important role in atherosclerosis. We studied the effects of bicarbonate/CO2 and phosphate buffer systems on metal ion-catalyzed oxidation of LDL to malondialdehyde (MDA) and to protein carbonyl and MetO derivatives. Our results revealed that LDL oxidation in mixtures containing free iron or heme derivatives was much greater in bicarbonate/CO2 compared with phosphate buffer. However, when copper was substituted for iron in these mixtures, the rate of LDL oxidation in both buffers was similar. Iron-catalyzed oxidation of LDL was highly sensitive to inhibition by phosphate. Presence of 0.3-0.5 mM phosphate, characteristic of human serum, led to 30-40% inhibition of LDL oxidation in bicarbonate/CO2 buffer. Iron-catalyzed oxidation of LDL to MDA in phosphate buffer was inhibited by increasing concentrations of albumin (10-200 μM), whereas MDA formation in bicarbonate/CO2 buffer was stimulated by 10-50 μM albumin but inhibited by higher concentrations. However, albumin stimulated the oxidation of LDL proteins to carbonyl derivatives at all concentrations examined in both buffers. Conversion of LDL to MDA in bicarbonate/CO2 buffer was greatly stimulated by ADP, ATP, and EDTA but only when EDTA was added at a concentration equal to that of iron. At higher than stoichiometric concentrations, EDTA prevented oxidation of LDL. Results of these studies suggest that interactions between bicarbonate and iron or heme derivatives leads to complexes with redox potentials that favor the generation of reactive oxygen species and/or to the generation of highly reactive CO2 anion or bicarbonate radical that facilitates LDL oxidation. Freely available online through the PNAS open access option.Abbreviations: LDL, low-density lipoprotein; MDA, malondialdehyde; MetO, methionine sulfoxide.

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2012 CFR

2012-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2013 CFR

2013-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2014 CFR

2014-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

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 Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

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 Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

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 Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

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 Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

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 Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

Preparation and characterization of iron oxide magnetic nanoparticles functionalized by nisin.

PubMed

Gruskiene, Ruta; Krivorotova, Tatjana; Staneviciene, Ramune; Ratautas, Dalius; Serviene, Elena; Sereikaite, Jolanta

2018-05-08

Nisin is a known bacteriocin approved as a food additive for food preservation. It exhibits a wide spectrum antimicrobial activity against Gram-positive bacteria. Iron oxide magnetic nanoparticles were synthesized and characterized by X-ray diffraction method. A main part of iron oxide nanoparticles was found to be maghemite though a small quantity of magnetite could also be present. Magnetic nanoparticles were stabilized by citric, ascorbic, gallic or glucuronic acid coating. Stable iron oxide magnetic nanoparticles were functionalized by nisin using a simple and low cost adsorption method. Nisin loading was confirmed by FT-IR spectra, thermogravimetric analysis, dynamic light scattering and atomic force microscopy methods. Nisin-loaded iron oxide magnetic nanoparticles were stable at least six weeks as judged by the measurements of zeta-potential and hydrodynamic diameter. The antimicrobial activity of nisin-loaded iron oxide magnetic nanoparticles was demonstrated toward Gram-positive bacteria. Functionalized nanoparticles could therefore find the application as antimicrobials in innovative and emerging technologies based on the magnetic field. Copyright © 2018 Elsevier B.V. All rights reserved.

An image processing approach for investigation on transport of iron oxide nanoparticles (FE3O4) stabilized with poly acrylic acid in two-dimensional porous media

NASA Astrophysics Data System (ADS)

Golzar, M.; Azhdary Moghaddam, M.; Saghravani, S. F.; Dahrazma, B.

2018-04-01

Iron oxide nanoparticles were stabilized using poly acrylic acid (PAA) to yield stabilized slurry of Iron oxide nanoparticles. A two-dimensional physical model filled by glass beads was used to study the fate and transport of the iron oxide nanoparticles stabilized with PAA in porous media under saturated, steady-state flow conditions. Transport data for a nonreactive tracer, slurry of iron oxide nanoparticles stabilized with PAA were collected under similar flow conditions. The results show that low concentration slurry of iron oxide nanoparticles stabilized with PAA can be transported like a tracer without significant retardation. The image processing technique was employed to measure the tracer/nanoparticle concentration inside the 2-D model filled with glass beads. The groundwater flow model, Visual MODFLOW, was used to model the observed transport patterns through MT3DMS module. Finally, it was demonstrated that the numerical model MODFLOW can be used to predict the fate and transport characteristics of nanoparticles stabilized with PAA in groundwater aquifers.

Effect of Organic Substances on the Efficiency of Fe(Ii) to Fe(Iii) Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process

NASA Astrophysics Data System (ADS)

Krupińska, Izabela

2017-09-01

One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3). The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D). It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot]), efficiency of Fe(II) to Fe(III) oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII) when used as an oxidizing agent. The application of potassium manganate (VII) for oxidation of Fe(II) ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.

Ultrastructural study of iron oxide precipitates: implications for the search for biosignatures in the Meridiani hematite concretions, Mars.

PubMed

Souza-Egipsy, Virginia; Ormö, Jens; Beitler Bowen, Brenda; Chan, Marjorie A; Komatsu, Goro

2006-08-01

Two terrestrial environments that have been proposed as analogs for the iron oxide precipitation in the Meridiani Planum region of Mars include the Rio Tinto precipitates and southern Utah marble concretions. Samples of two typical Utah iron oxide concretions and iron oxide precipitates in contact with biofilms from Rio Tinto have been studied to determine whether evidence could be found for biomediation in the precipitation process and to identify likely locations for fossil microorganisms. Scanning electron microscopy, energy dispersive X-ray, and gas chromatography-mass spectrometry (GC-MS) were used to search for biosignatures in the Utah marbles. The precipitation of iron oxides resembles known biosignatures, though organic compounds could not be confirmed with GC-MS analysis. In contrast, textural variations induced by biological activity are abundant in the modern Rio Tinto samples. Although no compelling evidence of direct or indirect biomediation was found in the Utah marbles, the ultrastructure of the iron oxide cement in the concretion suggests an inward growth during concretion precipitation from an initially spherical redox front. No indication for growth from a physical nucleus was found.

Microbial Communities Associated with Biogenic Iron Oxide Mineralization in Circumneutral pH Environments

NASA Astrophysics Data System (ADS)

Chan, C. S.; Banfield, J. F.

2002-12-01

Lithotrophic growth on iron is a metabolism that has been found in a variety of neutral pH environments and is likely important in sustaining life in microaerophilic solutions, especially those low in organics. The composition of the microbial communities, especially the organisms that are responsible for iron oxidation, and carbon and nitrogen fixation, are not known, yet the ability to recognize these contributions is vital to our understanding of iron cycling in natural environments. Our approach has been to study the microbial community structure, mineralogy, and geochemistry of ~20 cm thick, 100's meters long, fluffy iron oxide-encrusted biological mats growing in the Piquette Mine tunnel, and to compare the results to those from geochemically similar environments. In situ measurements (Hydrolab) and geochemical characterization of bulk water samples and peepers (dialysis sampling vials) indicate that the environment is microaerobic, with micromolar levels of iron, high carbonate and sulfate, and typical groundwater nitrate and nitrite concentrations. 16S rDNA clone libraries show that the microbial mat and water contain communities with considerable diversity within the Bacterial domain, a large proportion of Nitrospira and Betaproteobacteria, and no Archaea. Because clone library data are not necessarily indicative of actual abundance, fluorescence in-situ hybridization (FISH) was performed on water, mat, and sediment samples from the Piquette mine and two circumneutral iron- and carbonate-rich springs in the Oregon Cascade Range. Domain- and phylum-level probes were chosen based on the clone library results (Nitrospira, Beta- and Gammaproteobacteria, Acidobacteria, Actinobacteria, Chloroflexi, and Planctomyces). FISH data reveal spatial associations between specific microbial groups and mineralized structures. The organisms responsible for making the mineralized sheaths that compose the bulk of the iron oxide mat are Betaproteobacteria (probably Leptothrix spp.). However, only a small proportion of the cells in the mat reside within the sheaths. Most are located on or around the sheaths, which provide a physical framework for the community. Preliminary results from FISH experiments on the iron-rich spring samples show some similarities, including an abundance of Betaproteobacteria. Enrichment and isolation experiments are being performed to identify the iron-oxidizing organisms. Iron-oxidizers have been enriched from all sites. In some cultures it has been difficult to isolate the iron-oxidizing organisms from a non-iron-oxidizing heterotroph, possibly indicating co-dependence. Knowledge of the microbial community structure and the metabolic activities of key members will enable us to better understand the processes and chemical conditions which generate iron oxide deposits found in the geologic record on Earth and possibly extraterrestrial habitats.

Poly(vinylpyrrolidone) coated iron nanoparticles in polar aprotic solvent.

PubMed

Ban, Zhihui; Cushing, Brian L; O'Connor, Charles J

2008-04-01

Poly(vinylpyrrolidone) (PVP) coated iron nanoparticles which show well-defined core-shell structures have been successfully synthesized in a polar aprotic solvent. In this approach, PVP was employed not as capping agent, but as coating polymer directly applied to the metallic (iron) core nanoparticles. The morphologies, structures, compositions and magnetic properties of the products were investigated by transmission electron microscopy (TEM), X-ray powder diffraction (XRD), energy dispersive X-ray spectroscopy (EDXS), SQUID magnetometry and FTIR spectroscopy.

The Possible Emergence of Life and Differentiation of a Shallow Biosphere on Irradiated Icy Worlds: The Example of Europa

NASA Astrophysics Data System (ADS)

Russell, Michael J.; Murray, Alison E.; Hand, Kevin P.

2017-12-01

Irradiated ice-covered ocean worlds with rocky mafic mantles may provide the conditions needed to drive the emergence and maintenance of life. Alkaline hydrothermal springs - relieving the geophysical, thermal, and chemical disequilibria between oceans and tidally stressed crusts - could generate inorganic barriers to the otherwise uncontrolled and kinetically disfavored oxidation of hydrothermal hydrogen and methane. Ionic gradients imposed across these inorganic barriers, comprising iron oxyhydroxides and sulfides, could drive the hydrogenation of carbon dioxide and the oxidation of methane through thermodynamically favorable metabolic pathways leading to early life-forms. In such chemostatic environments, fuels may eventually outweigh oxidants. Ice-covered oceans are primarily heated from below, creating convection that could transport putative microbial cells and cellular cooperatives upward to congregate beneath an ice shell, potentially giving rise to a highly focused shallow biosphere. It is here where electron acceptors, ultimately derived from the irradiated surface, could be delivered to such life-forms through exchange with the icy surface. Such zones would act as "electron disposal units" for the biosphere, and occupants might be transferred toward the surface by buoyant diapirs and even entrained into plumes.

Study of manganese binding to the ferroxidase centre of human H-type ferritin.

PubMed

Ardini, Matteo; Howes, Barry D; Fiorillo, Annarita; Falvo, Elisabetta; Sottini, Silvia; Rovai, Donella; Lantieri, Marco; Ilari, Andrea; Gatteschi, Dante; Spina, Gabriele; Chiancone, Emilia; Stefanini, Simonetta; Fittipaldi, Maria

2018-05-01

Ferritins are ubiquitous and conserved proteins endowed with enzymatic ferroxidase activity, that oxidize Fe(II) ions at the dimetal ferroxidase centre to form a mineralized Fe(III) oxide core deposited within the apo-protein shell. Herein, the in vitro formation of a heterodimetal cofactor constituted by Fe and Mn ions has been investigated in human H ferritin (hHFt). Namely, Mn and Fe binding at the hHFt ferroxidase centre and its effects on Fe(II) oxidation have been investigated by UV-Vis ferroxidation kinetics, fluorimetric titrations, multifrequency EPR, and preliminary Mössbauer spectroscopy. Our results show that in hHFt, both Fe(II) and Mn(II) bind the ferroxidase centre forming a Fe-Mn cofactor. Moreover, molecular oxygen seems to favour Mn(II) binding and increases the ferroxidation activity of the Mn-loaded protein. The data suggest that Mn influences the Fe binding and the efficiency of the ferroxidation reaction. The higher efficiency of the Mn-Fe heterometallic centre may have a physiological relevance in specific cell types (i.e. glia cells), where the concentration of Mn is the same order of magnitude as iron. Copyright © 2018 Elsevier Inc. All rights reserved.

Degradation of trichloroethylene (TCE) by nanoscale zero-valent iron (nZVI) immobilized in alginate bead.

PubMed

Kim, Hojeong; Hong, Hye-Jin; Jung, Juri; Kim, Seong-Hye; Yang, Ji-Won

2010-04-15

Nowadays, many researchers have studied the environmental application of the nanoscale zero-valent iron (nZVI) and several field applications for the groundwater remediation have been reported. Still, there are many concerns on the fate and transport of the nZVI and the corresponding risks. To avoid such concerns, it was investigated to immobilize nZVI in a support and then it was applied to degrade trichloroethylene (TCE). The nZVI and palladium-doped nZVI (Fe(0)- and Fe/Pd-alginate) were immobilized in the alginate bead where ferric and barium ions are used as the cross-linking cations of the bead. According to TEM (transmission electron microscopy), the size of the immobilized ZVI was as small as a few nanometers. From the surface analysis of the Fe/Pd-alginate, it is found that the immobilized nZVI has the core-shell structure. The core is composed of single crystal Fe(0), while most of irons on the surface are oxidized to Fe(3+). When 50 g/L of Fe/Pd-alginate (3.7 g Fe/L) was introduced to the aqueous solution, >99.8% of TCE was removed and the release of metal from the support was <3% of the loaded iron. The removal of TCE by Fe/Pd-alginate followed pseudo-first-order kinetics. The observed pseudo-first-order reaction constant (k(obs)) of Fe/Pd-alginate was 6.11 h(-1) and the mass normalized rate constant (k(m)) was 1.6 L h(-1) g(-1). The k(m) is the same order of magnitude with that of iron nanoparticles. In conclusion, it is considered that Fe/Pd-alginate can be used efficiently in the treatment of chlorinated solvent. 2009 Elsevier B.V. All rights reserved.

Synthesis of phase-pure and monodisperse iron oxide nanoparticles by thermal decomposition

NASA Astrophysics Data System (ADS)

Hufschmid, Ryan; Arami, Hamed; Ferguson, R. Matthew; Gonzales, Marcela; Teeman, Eric; Brush, Lucien N.; Browning, Nigel D.; Krishnan, Kannan M.

2015-06-01

Superparamagnetic iron oxide nanoparticles (SPIONs) are used for a wide range of biomedical applications requiring precise control over their physical and magnetic properties, which are dependent on their size and crystallographic phase. Here we present a comprehensive template for the design and synthesis of iron oxide nanoparticles with control over size, size distribution, phase, and resulting magnetic properties. We investigate critical parameters for synthesis of monodisperse SPIONs by organic thermal decomposition. Three different, commonly used, iron containing precursors (iron oleate, iron pentacarbonyl, and iron oxyhydroxide) are evaluated under a variety of synthetic conditions. We compare the suitability of these three kinetically controlled synthesis protocols, which have in common the use of iron oleate as a starting precursor or reaction intermediate, for producing nanoparticles with specific size and magnetic properties. Monodisperse particles were produced over a tunable range of sizes from approximately 2-30 nm. Reaction parameters such as precursor concentration, addition of surfactant, temperature, ramp rate, and time were adjusted to kinetically control size and size-distribution, phase, and magnetic properties. In particular, large quantities of excess surfactant (up to 25 : 1 molar ratio) alter reaction kinetics and result in larger particles with uniform size; however, there is often a trade-off between large particles and a narrow size distribution. Iron oxide phase, in addition to nanoparticle size and shape, is critical for establishing magnetic properties such as differential susceptibility (dm/dH) and anisotropy. As an example, we show the importance of obtaining the required size and iron oxide phase for application to Magnetic Particle Imaging (MPI), and describe how phase purity can be controlled. These results provide much of the information necessary to determine which iron oxide synthesis protocol is best suited to a particular application.

The role of the iron catalyst in the toxicity of multi-walled carbon nanotubes (MWCNTs).

PubMed

Visalli, Giuseppa; Facciolà, Alessio; Iannazzo, Daniela; Piperno, Anna; Pistone, Alessandro; Di Pietro, Angela

2017-09-01

This study aimed to investigate the role of iron, used as a catalyst, in the biological response to pristine and functionalized multi-walled carbon nanotubes (p/fMWCNTs) with an iron content of 2.5-2.8%. Preliminarily, we assessed the pro-oxidant activity of MWCNTs-associated iron by an abiotic test. To evaluate iron bioavailability, we measured intracellular redox-active iron in A549 cells exposed to both MWCNT suspensions and to the cell medium preconditioned by MWCNTs, in order to assess the iron dissolution rate under physiological conditions. Moreover, in exposed cells, we detected ROS levels, 8-oxo-dG and mitochondrial function. The results clearly highlighted that MWCNTs- associated iron was not redox-active and that iron leakage did not occur under physiological conditions, including the oxidative burst of specialized cells. Despite this, in MWCNTs exposed cells, higher level of intracellular redox-active iron was measured in comparison to control and a significant time-dependent ROS increase was observed (P<0.01). Higher levels of 8-oxo-dG, a marker of oxidative DNA damage, and decreased mitochondrial function, confirmed the oxidative stress induced by MWCNTs. Based on the results we believe that oxidative damage could be attributable to the release of endogenous redox-active iron. This was due to the damage of acidic vacuolar compartment caused by endocytosis-mediated MWCNT internalization. Copyright © 2017 Elsevier GmbH. All rights reserved.

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.

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

PubMed

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

2016-11-15

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

The Global Redox Responding RegB/RegA Signal Transduction System Regulates the Genes Involved in Ferrous Iron and Inorganic Sulfur Compound Oxidation of the Acidophilic Acidithiobacillus ferrooxidans.

PubMed

Moinier, Danielle; Byrne, Deborah; Amouric, Agnès; Bonnefoy, Violaine

2017-01-01

The chemical attack of ore by ferric iron and/or sulfuric acid releases valuable metals. The products of these reactions are recycled by iron and sulfur oxidizing microorganisms. These acidophilic chemolithotrophic prokaryotes, among which Acidithiobacillus ferrooxidans , grow at the expense of the energy released from the oxidation of ferrous iron and/or inorganic sulfur compounds (ISCs). In At. ferrooxidans , it has been shown that the expression of the genes encoding the proteins involved in these respiratory pathways is dependent on the electron donor and that the genes involved in iron oxidation are expressed before those responsible for ISCs oxidation when both iron and sulfur are present. Since the redox potential increases during iron oxidation but remains stable during sulfur oxidation, we have put forward the hypothesis that the global redox responding two components system RegB/RegA is involved in this regulation. To understand the mechanism of this system and its role in the regulation of the aerobic respiratory pathways in At. ferrooxidans , the binding of different forms of RegA (DNA binding domain, wild-type, unphosphorylated and phosphorylated-like forms of RegA) on the regulatory region of different genes/operons involved in ferrous iron and ISC oxidation has been analyzed. We have shown that the four RegA forms are able to bind specifically the upstream region of these genes. Interestingly, the phosphorylation of RegA did not change its affinity for its cognate DNA. The transcriptional start site of these genes/operons has been determined. In most cases, the RegA binding site(s) was (were) located upstream from the -35 (or -24) box suggesting that RegA does not interfere with the RNA polymerase binding. Based on the results presented in this report, the role of the RegB/RegA system in the regulation of the ferrous iron and ISC oxidation pathways in At. ferrooxidans is discussed.

Iron(II) Initiation of Lipid and Protein Oxidation in Pork: The Role of Oxymyoglobin.

PubMed

Zhou, Feibai; Jongberg, Sisse; Zhao, Mouming; Sun, Weizheng; Skibsted, Leif H

2016-06-08

Iron(II), added as FeSO4·7H2O, was found to increase the rate of oxygen depletion as detected electrochemically in a pork homogenate from Longissimus dorsi through an initial increase in metmyoglobin formation from oxymyoglobin and followed by formation of primary and secondary lipid oxidation products and protein oxidation as detected as thiol depletion in myofibrillar proteins. Without added iron(II), under the same conditions at 37 °C, oxygen consumption corresponded solely to the slow oxymyoglobin autoxidation. Long-lived myofibrillar protein radicals as detected by ESR spectroscopy in the presence of iron(II) were formed subsequently to oxymyoglobin oxidation, and their level was increased by lipid oxidation when oxygen was completely depleted. Similarly, the time profile for formation of lipid peroxide indicated that oxymyoglobin oxidation initiates both protein oxidation and lipid oxidation.

Synthesis and cytotoxicity assessment of superparamagnetic iron-gold core-shell nanoparticles coated with polyglycerol.

PubMed

Jafari, T; Simchi, A; Khakpash, N

2010-05-01

Core-shell iron-gold (Fe@Au) nanoparticles were synthesized by a facile reverse micelle procedure and the effect of water to surfactant molar ratio (w) on the size, size distribution and magnetic properties of the nanoparticles was studied. MTT assay was utilized to evaluate the cell toxicity of the nanoparticles. To functionalize the particles for MRI imaging and targeted drug delivery, the particles were coated by polyglycerol through capping with thiol followed by polymerization of glycidol. The characteristics of the particles were examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), UV-visible spectroscopy, and Fourier transform infrared spectroscopy (FT-IR). It was found that the size and size distribution of the nanoparticles increase by increasing the water to surfactant molar ratio (w). The particles were spherical in shape with a thin layer of gold. Complementary growth of the gold shell on the iron core was noticed. Meanwhile, two types of agglomeration including magnetic beads and magnetic colloidal nanocrystals clusters were observed dependent on the w-value. The magnetic measurement studies revealed the superparamagnetic behavior of the nanoparticles. MTT assay result indicated the synthesized nanoparticles are nontoxic that will be useful for biomedical applications. Copyright 2010 Elsevier Inc. All rights reserved.

Thermogravimetric analysis of the interaction of ferromagnetic metal atom and multiwalled carbon nanotubes.

PubMed

Rawat, Naveen; Gudyaka, Russel; Kumar, Mohit; Joshi, Bharat; Santhanam, Kalathur S V

2008-04-01

This paper describes the thermal oxidative behavior of atomized iron or atomized cobalt in the presence of multiwalled carbon nanotubes (MWCNT). The thermogravimetric analysis shows the atomized iron thermal oxidation starts at about 500 degrees C that is absent when the atomized iron is sintered with multiwalled carbon naonotubes. The thermal oxidation of iron in the sintered samples requires the collapse of the multiwalled carbon nanotubes. A similar behavior is observed with atomized cobalt when its oxidation requires the collapse of the nanotubes. This thermal oxidative shift is interpreted as due to the atomized iron or atomized cobalt atom experiencing extensive overlap and confinement effect with multiwalled carbon nanotubes causing a spin transfer. This confinement effect is suggested to produce a transformation of iron from the outermost electronic distribution of 3d64s2 to an effective configuration of 3d84s0 and for cobalt 3d74s2 to 3d94s0 producing spintronics effect.

Multicopper oxidase-1 is a ferroxidase essential for iron homeostasis in Drosophila melanogaster

PubMed Central

Lang, Minglin; Braun, Caroline L.; Kanost, Michael R.; Gorman, Maureen J.

2012-01-01

Multicopper ferroxidases catalyze the oxidation of ferrous iron to ferric iron. In yeast and algae, they participate in cellular uptake of iron; in mammals, they facilitate cellular efflux. The mechanisms of iron metabolism in insects are still poorly understood, and insect multicopper ferroxidases have not been identified. In this paper, we present evidence that Drosophila melanogaster multicopper oxidase-1 (MCO1) is a functional ferroxidase. We identified candidate iron-binding residues in the MCO1 sequence and found that purified recombinant MCO1 oxidizes ferrous iron. An association between MCO1 function and iron homeostasis was confirmed by two observations: RNAi-mediated knockdown of MCO1 resulted in decreased iron accumulation in midguts and whole insects, and weak knockdown increased the longevity of flies fed a toxic concentration of iron. Strong knockdown of MCO1 resulted in pupal lethality, indicating that MCO1 is an essential gene. Immunohistochemistry experiments demonstrated that MCO1 is located on the basal surfaces of the digestive system and Malpighian tubules. We propose that MCO1 oxidizes ferrous iron in the hemolymph and that the resulting ferric iron is bound by transferrin or melanotransferrin, leading to iron storage, iron withholding from pathogens, regulation of oxidative stress, and/or epithelial maturation. These proposed functions are distinct from those of other known ferroxidases. Given that MCO1 orthologues are present in all insect genomes analyzed to date, this discovery is an important step toward understanding iron metabolism in insects. PMID:22847425

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.

Unravelling the cross-talk between iron starvation and oxidative stress responses highlights the key role of PerR (alr0957) in peroxide signalling in the cyanobacterium Nostoc PCC 7120.

PubMed

Yingping, Fan; Lemeille, Sylvain; Talla, Emmanuel; Janicki, Annick; Denis, Yann; Zhang, Cheng-Cai; Latifi, Amel

2014-10-01

The cyanobacterial phylum includes oxygenic photosynthetic prokaryotes of a wide variety of morphologies, metabolisms and ecologies. Their adaptation to their various ecological niches is mainly achieved by sophisticated regulatory mechanisms and depends on a fine cross-talk between them. We assessed the global transcriptomic response of the filamentous cyanobacterium Nostoc PCC 7120 to iron starvation and oxidative stress. More than 20% of the differentially expressed genes in response to iron stress were also responsive to oxidative stress. These transcripts include antioxidant proteins-encoding genes that confirms that iron depletion leads to reactive oxygen accumulation. The activity of the Fe-superoxide dismutase was not significantly decreased under iron starvation, indicating that the oxidative stress generated under iron deficiency is not a consequence of (SOD) deficiency. The transcriptional data indicate that the adaptation of Nostoc to iron-depleted conditions displays important differences with what has been shown in unicellular cyanobacteria. While the FurA protein that regulates the response to iron deprivation has been well characterized in Nostoc, the regulators in charge of the oxidative stress response are unknown. Our study indicates that the alr0957 (perR) gene encodes the master regulator of the peroxide stress. PerR is a peroxide-sensor repressor that senses peroxide by metal-catalysed oxidation.

Iron cycling at corroding carbon steel surfaces.

PubMed

Lee, Jason S; McBeth, Joyce M; Ray, Richard I; Little, Brenda J; Emerson, David

2013-01-01

Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media.

Iron cycling at corroding carbon steel surfaces

PubMed Central

Lee, Jason S.; McBeth, Joyce M.; Ray, Richard I.; Little, Brenda J.; Emerson, David

2013-01-01

Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with three culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media. PMID:24093730

Fluoride-induced iron overload contributes to hepatic oxidative damage in mouse and the protective role of Grape seed proanthocyanidin extract.

PubMed

Niu, Qiang; He, Ping; Xu, Shangzhi; Ma, Ruling; Ding, Yusong; Mu, Lati; Li, Shugang

2018-01-01

Emerging evidence has demonstrated that iron overload plays an important role in oxidative stress in the liver. This study aimed to explore whether fluoride-induced hepatic oxidative stress is associated with iron overload and whether grape seed proanthocyanidin extract (GSPE) alleviates oxidative stress by reducing iron overload. Forty Kunming male mice were randomly divided into 4 groups and treated for 5 weeks with distilled water (control), sodium fluoride (NaF) (100 mg/L), GSPE (400 mg/kg bw), or NaF (100 mg/L) + GSPE (400 mg/kg bw). Mice exposed to NaF showed typical poisoning changes of morphology, increased aspartate aminotransferase and alanine aminotransferase activities in the liver. NaF treatment also increased MDA accumulation, decreased GSH-Px, SOD and T-AOC levels in liver, indicative of oxidative stress. Intriguingly, all these detrimental effects were alleviated by GSPE. Further study revealed that NaF induced disorders of iron metabolism, as manifested by elevated iron level with increased hepcidin but decreased ferroportin expression, which contributed to hepatic oxidative stress. Importantly, the iron dysregulation induced by NaF could be normalized by GSPE. Collectively, these data provide a novel insight into mechanisms underlying fluorosis and highlight the potential of GSPE as a naturally occurring prophylactic treatment for fluoride-induced hepatotoxicity associated with iron overload.

Microbial Iron Cycling in Acidic Geothermal Springs of Yellowstone National Park: Integrating Molecular Surveys, Geochemical Processes, and Isolation of Novel Fe-Active Microorganisms

PubMed Central

Kozubal, Mark A.; Macur, Richard E.; Jay, Zackary J.; Beam, Jacob P.; Malfatti, Stephanie A.; Tringe, Susannah G.; Kocar, Benjamin D.; Borch, Thomas; Inskeep, William P.

2012-01-01

Geochemical, molecular, and physiological analyses of microbial isolates were combined to study the geomicrobiology of acidic iron oxide mats in Yellowstone National Park. Nineteen sampling locations from 11 geothermal springs were studied ranging in temperature from 53 to 88°C and pH 2.4 to 3.6. All iron oxide mats exhibited high diversity of crenarchaeal sequences from the Sulfolobales, Thermoproteales, and Desulfurococcales. The predominant Sulfolobales sequences were highly similar to Metallosphaera yellowstonensis str. MK1, previously isolated from one of these sites. Other groups of archaea were consistently associated with different types of iron oxide mats, including undescribed members of the phyla Thaumarchaeota and Euryarchaeota. Bacterial sequences were dominated by relatives of Hydrogenobaculum spp. above 65–70°C, but increased in diversity below 60°C. Cultivation of relevant iron-oxidizing and iron-reducing microbial isolates included Sulfolobus str. MK3, Sulfobacillus str. MK2, Acidicaldus str. MK6, and a new candidate genus in the Sulfolobales referred to as Sulfolobales str. MK5. Strains MK3 and MK5 are capable of oxidizing ferrous iron autotrophically, while strain MK2 oxidizes iron mixotrophically. Similar rates of iron oxidation were measured for M. yellowstonensis str. MK1 and Sulfolobales str. MK5. Biomineralized phases of ferric iron varied among cultures and field sites, and included ferric oxyhydroxides, K-jarosite, goethite, hematite, and scorodite depending on geochemical conditions. Strains MK5 and MK6 are capable of reducing ferric iron under anaerobic conditions with complex carbon sources. The combination of geochemical and molecular data as well as physiological observations of isolates suggests that the community structure of acidic Fe mats is linked with Fe cycling across temperatures ranging from 53 to 88°C. PMID:22470372

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

PubMed

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

2014-04-01

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

The Effect of Citric Acid on the Oxidation of Organic Contaminants by Fenton's Reagent

NASA Astrophysics Data System (ADS)

Seol, Y.; Javandel, I.; Lee, G.

2003-12-01

Combined with acids and iron catalysts, hydrogen peroxide (H2O2) as Fenton's reagent is proven to be effective in oxidizing halogenated volatile organic compounds (VOCs). The Fenton's reagent, traditionally used for waste water treatment technique, has been applied to the remediation of contaminated soil systems and numerous investigators have found intrinsic iron salts are effective source of iron catalyst for the reaction. Citric acid, which is naturally occurring nutrients to microorganisms and less destructive to soil chemical properties, is selected for an acidifying agent to create acidic soil condition. However, citric acid has been considered as a reaction inhibitant because it sequesters ferric iron from Fenton's catalytic cycle by forming strong chelates with iron. This paper presents the feasibility of using citric acid as an acidifying agent of soil matrix for the Fenton-like oxidation. Series of batch tests were performed to test disappearance of VOCs in various aqueous systems with two acidifying agents (citric acid or sulfuric acid) and three iron sources (iron sulfate, water soluble soil iron, or soil matrix). Batch results show that soluble iron is essential for near complete disappearance of VOCs and that citric acid performs similarly to sulfuric acid at low H2O2 dosage (< 1 wt%). The test soil provided water-soluble soil iron but also contained scavengers of the oxidizing agents, resulting in limited removals of VOCs. Column tests confirmed the results of the batch tests, suggesting citric acid is also as effective as sulfuric acid in providing acidic environment for the Fenton-like oxidation. The batch experiments also reveal that higher doses of H2O2 lower the degree of VOC removals in citric acid systems. Potential explanations for this declining include that excessive presence of H2O2 expedites the oxidation of ferrous to ferric iron, which then forms a strong complex with citrate, leading to the sequestration of the iron from the Fenton's reaction cycle. Consequently, additional supply of ferrous iron would be required for continuing oxidation of VOCs, as well as slow injection of H2O2. Detailed mechanistic study would be needed for factual understanding.

Additional oxidative stress reroutes the global response of Aspergillus fumigatus to iron depletion.

PubMed

Kurucz, Vivien; Krüger, Thomas; Antal, Károly; Dietl, Anna-Maria; Haas, Hubertus; Pócsi, István; Kniemeyer, Olaf; Emri, Tamás

2018-05-10

Aspergillus fumigatus has to cope with a combination of several stress types while colonizing the human body. A functional interplay between these different stress responses can increase the chances of survival for this opportunistic human pathogen during the invasion of its host. In this study, we shed light on how the H 2 O 2 -induced oxidative stress response depends on the iron available to this filamentous fungus, using transcriptomic analysis, proteomic profiles, and growth assays. The applied H 2 O 2 treatment, which induced only a negligible stress response in iron-replete cultures, deleteriously affected the fungus under iron deprivation. The majority of stress-induced changes in gene and protein expression was not predictable from data coming from individual stress exposure and was only characteristic for the combination of oxidative stress plus iron deprivation. Our experimental data suggest that the physiological effects of combined stresses and the survival of the fungus highly depend on fragile balances between economization of iron and production of essential iron-containing proteins. One observed strategy was the overproduction of iron-independent antioxidant proteins to combat oxidative stress during iron deprivation, e.g. the upregulation of superoxide dismutase Sod1, the thioredoxin reductase Trr1, and the thioredoxin orthologue Afu5g11320. On the other hand, oxidative stress induction overruled iron deprivation-mediated repression of several genes. In agreement with the gene expression data, growth studies underlined that in A. fumigatus iron deprivation aggravates oxidative stress susceptibility. Our data demonstrate that studying stress responses under separate single stress conditions is not sufficient to understand how A. fumigatus adapts in a complex and hostile habitat like the human body. The combinatorial stress of iron depletion and hydrogen peroxide caused clear non-additive effects upon the stress response of A. fumigatus. Our data further supported the view that the ability of A. fumigatus to cause diseases in humans strongly depends on its fitness attributes and less on specific virulence factors. In summary, A. fumigatus is able to mount and coordinate complex and efficient responses to combined stresses like iron deprivation plus H 2 O 2 -induced oxidative stress, which are exploited by immune cells to kill fungal pathogens.

Iron supplementation at high altitudes induces inflammation and oxidative injury to lung tissues in rats

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

Salama, Samir A., E-mail: salama.3@buckeyemail.osu.edu; Department of Biochemistry, Faculty of Pharmacy, Al-Azhar University, Cairo 11751; Department of Pharmacology and GTMR Unit, College of Clinical Pharmacy, Taif University, Al-Haweiah, Taif 21974

2014-01-01

Exposure to high altitudes is associated with hypoxia and increased vulnerability to oxidative stress. Polycythemia (increased number of circulating erythrocytes) develops to compensate the high altitude associated hypoxia. Iron supplementation is, thus, recommended to meet the demand for the physiological polycythemia. Iron is a major player in redox reactions and may exacerbate the high altitudes-associated oxidative stress. The aim of this study was to explore the potential iron-induced oxidative lung tissue injury in rats at high altitudes (6000 ft above the sea level). Iron supplementation (2 mg elemental iron/kg, once daily for 15 days) induced histopathological changes to lung tissuesmore » that include severe congestion, dilatation of the blood vessels, emphysema in the air alveoli, and peribronchial inflammatory cell infiltration. The levels of pro-inflammatory cytokines (IL-1β, IL-6, and TNF-α), lipid peroxidation product and protein carbonyl content in lung tissues were significantly elevated. Moreover, the levels of reduced glutathione and total antioxidant capacity were significantly reduced. Co-administration of trolox, a water soluble vitamin E analog (25 mg/kg, once daily for the last 7 days of iron supplementation), alleviated the lung histological impairments, significantly decreased the pro-inflammatory cytokines, and restored the oxidative stress markers. Together, our findings indicate that iron supplementation at high altitudes induces lung tissue injury in rats. This injury could be mediated through excessive production of reactive oxygen species and induction of inflammatory responses. The study highlights the tissue injury induced by iron supplementation at high altitudes and suggests the co-administration of antioxidants such as trolox as protective measures. - Highlights: • Iron supplementation at high altitudes induced lung histological changes in rats. • Iron induced oxidative stress in lung tissues of rats at high altitudes. • Iron increased the levels of IL-1β, IL-6 and TNF-α in lung tissues at high altitudes. • Trolox alleviated the iron-induced histological and biochemical changes to the lungs.« less

Process for the synthesis of iron powder

DOEpatents

Welbon, W.W.

1983-11-08

A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder. 2 figs.

Iron-mediated redox modulation in neural plasticity

PubMed Central

Muñoz, Pablo

2012-01-01

The role of iron in brain physiology has focused on the neuropathological, effects due to iron-induced oxidative stress. However, our recent work has established a physiological relationship between the iron-mediated oxidative modification and normal neuronal function. Our results obtained from hippocampal neurons, suggest that iron-generated reactive species oxygen (ROS) are involved in calcium signaling initiated by stimulation of NMDA receptors. This signal is amplified by ryanodine receptors (RyR), a redox- sensitive calcium channel, allowing the phosphorylation and nuclear translocation of ERK1/2. Furthermore, using electrophysiological approaches, we showed that iron is required for basal synaptic transmission and full expression of long-term potentiation, a type of synaptic plasticity. Our data combined suggest that the oxidative effect of iron is critical to activate processes that are downstream of NMDAR activation. Finally, due to the high reactivity of DNA with iron-generated ROS, we hypothesize an additional function of iron in gene regulation. PMID:22808323

Efficient Low-pH Iron Removal by a Microbial Iron Oxide Mound Ecosystem at Scalp Level Run.

PubMed

Grettenberger, Christen L; Pearce, Alexandra R; Bibby, Kyle J; Jones, Daniel S; Burgos, William D; Macalady, Jennifer L

2017-04-01

Acid mine drainage (AMD) is a major environmental problem affecting tens of thousands of kilometers of waterways worldwide. Passive bioremediation of AMD relies on microbial communities to oxidize and remove iron from the system; however, iron oxidation rates in AMD environments are highly variable among sites. At Scalp Level Run (Cambria County, PA), first-order iron oxidation rates are 10 times greater than at other coal-associated iron mounds in the Appalachians. We examined the bacterial community at Scalp Level Run to determine whether a unique community is responsible for the rapid iron oxidation rate. Despite strong geochemical gradients, including a >10-fold change in the concentration of ferrous iron from 57.3 mg/liter at the emergence to 2.5 mg/liter at the base of the coal tailings pile, the bacterial community composition was nearly constant with distance from the spring outflow. Scalp Level Run contains many of the same taxa present in other AMD sites, but the community is dominated by two strains of Ferrovum myxofaciens , a species that is associated with high rates of Fe(II) oxidation in laboratory studies. IMPORTANCE Acid mine drainage pollutes more than 19,300 km of rivers and streams and 72,000 ha of lakes worldwide. Remediation is frequently ineffective and costly, upwards of $100 billion globally and nearly $5 billion in Pennsylvania alone. Microbial Fe(II) oxidation is more efficient than abiotic Fe(II) oxidation at low pH (P. C. Singer and W. Stumm, Science 167:1121-1123, 1970, https://doi.org/10.1126/science.167.3921.1121). Therefore, AMD bioremediation could harness microbial Fe(II) oxidation to fuel more-cost-effective treatments. Advances will require a deeper understanding of the ecology of Fe(II)-oxidizing microbial communities and the factors that control their distribution and rates of Fe(II) oxidation. We investigated bacterial communities that inhabit an AMD site with rapid Fe(II) oxidation and found that they were dominated by two operational taxonomic units (OTUs) of Ferrovum myxofaciens , a taxon associated with high laboratory rates of iron oxidation. This research represents a step forward in identifying taxa that can be used to enhance cost-effective AMD bioremediation. Copyright © 2017 American Society for Microbiology.

Electron-capture Rates for pf-shell Nuclei in Stellar Environments and Nucleosynthesis

NASA Astrophysics Data System (ADS)

Suzuki, Toshio; Honma, Michio; Mori, Kanji; Famiano, Michael A.; Kajino, Toshitaka; Hidakai, Jun; Otsuka, Takaharu

Gamow-Teller strengths in pf-shell nuclei obtained by a new shell-model Hamltonian, GXPF1J, are used to evaluate electron-capture rates in pf-shell nuclei at stellar environments. The nuclear weak rates with GXPF1J, which are generally smaller than previous evaluations for proton-rich nuclei, are applied to nucleosynthesis in type Ia supernova explosions. The updated rates are found to lead to less production of neutron-rich nuclei such as 58Ni and 54Cr, thus toward a solution of the problem of over-production of neutron-rich isotopes of iron-group nuclei compared to the solar abundance.

Morphology of the ferritin iron core by aberration corrected scanning transmission electron microscopy

NASA Astrophysics Data System (ADS)

Jian, Nan; Dowle, Miriam; Horniblow, Richard D.; Tselepis, Chris; Palmer, Richard E.

2016-11-01

As the major iron storage protein, ferritin stores and releases iron for maintaining the balance of iron in fauna, flora, and bacteria. We present an investigation of the morphology and iron loading of ferritin (from equine spleen) using aberration-corrected high angle annular dark field scanning transmission electron microscopy. Atom counting method, with size selected Au clusters as mass standards, was employed to determine the number of iron atoms in the nanoparticle core of each ferritin protein. Quantitative analysis shows that the nuclearity of iron atoms in the mineral core varies from a few hundred iron atoms to around 5000 atoms. Moreover, a relationship between the iron loading and iron core morphology is established, in which mineral core nucleates from a single nanoparticle, then grows along the protein shell before finally forming either a solid or hollow core structure.

Aluminum and Fenton reaction: how can the reaction be modulated by speciation? A computational study using citrate as a test case.

PubMed

Mujika, Jon I; Dalla Torre, Gabriele; Lopez, Xabier

2018-06-13

The pro-oxidant ability of aluminum is behind many of the potential toxic effects of this exogenous element in the human organism. Although the overall process is still far from being understood at the molecular level, the well known ability of aluminum to promote the Fenton reaction is mediated through the formation of stable aluminum-superoxide radical complexes. However, the properties of metal complexes are highly influenced by the speciation of the metal. In this paper, we investigate the effect that speciation could have on the pro-oxidant activity of aluminum. We choose citrate as a test case, because it is the main low-molecular-mass chelator of aluminum in blood serum, forming very stable aluminum-citrate complexes. The influence of citrate in the interaction of aluminum with the superoxide radical is investigated, determining how the formation of aluminum-citrate complexes affects the promotion of the Fenton reaction. The results indicate that citrate increases the stability of the aluminum-superoxide complexes through the formation of ternary compounds, and that the Fenton reaction is even more favorable when aluminum is chelated to citrate. Nevertheless, our results demonstrate that overall, citrate may prevent the pro-oxidant activity of aluminum: on one hand, in an excess of citrate, the formation of 1 : 2 aluminum-citrate complexes is expected. On the other hand, the chelation of iron by citrate makes the reduction of iron thermodynamically unfavorable. In summary, the results suggest that citrate can have both a promotion and protective role, depending on subtle factors, such as initial concentration, non-equilibrium behavior and the exchange rate of ligands in the first shell of the metals.

Surface coating with Ca(OH)2 for improvement of the transport of nanoscale zero-valent iron (nZVI) in porous media.

PubMed

Wei, Cai-jie; Li, Xiao-yan

2013-01-01

A novel thermal deposition method was developed to coat Ca(OH)2 on the surface of nanoscale zero-valent iron (nZVI). The nZVI particles with the Ca(OH)2 coating layer, nZVI/Ca(OH)2, had a clear core-shell structure based on the transmission electron microscopy observations, and the Ca(OH)2 shell was identified as an amorphous phase. The Ca(OH)2 coating shell would not only function as an effective protection layer for nZVI but also improve the mobility of nZVI in porous media for its use in environmental decontamination. A 10% Ca/Fe mass ratio was found to result in a proper thickness of the Ca(OH)2 shell on the nZVI surface. Based on the filtration tests in sand columns, the Ca(OH)2-based surface coating could greatly improve the mobility and transport of nZVI particles in porous media. In addition, batch experiments were conducted to evaluate the reactivity of Ca(OH)2-coated nZVI particles for the reduction of Cr(VI) and its removal from water.

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

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2011 CFR

2011-04-01

... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... food. (2) Synthetic iron oxide may be safely used for the coloring of dog and cat foods in an amount... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... food. (2) Synthetic iron oxide may be safely used for the coloring of dog and cat foods in an amount... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

Origin of the magnetic transition at 100 K in ɛ-Fe2O3 nanoparticles studied by x-ray absorption fine structure spectroscopy

NASA Astrophysics Data System (ADS)

López-Sánchez, J.; Muñoz-Noval, A.; Castellano, C.; Serrano, A.; del Campo, A.; Cabero, M.; Varela, M.; Abuín, M.; de la Figuera, J.; Marco, J. F.; Castro, G. R.; Rodríguez de la Fuente, O.; Carmona, N.

2017-12-01

The current study unveils the structural origin of the magnetic transition of the ɛ-Fe2O3 polymorph from an incommensurate magnetic order to a collinear ferrimagnetic state at low temperature. The high crystallinity of the samples and the absence of other iron oxide polymorphs have allowed us to carry out temperature-dependent x-ray absorption fine structure spectroscopy experiments out. The deformation of the structure is followed by the Debye-Waller factor for each selected Fe-O and Fe-Fe sub-shell. For nanoparticle sizes between 7 and 15 nm, the structural distortions between the Fete and Fe-D1oc sites are localized in a temperature range before the magnetic transition starts. On the contrary, the inherent interaction between the other sub-shells (named Fe-O1,2 and Fe-Fe1) provokes cooperative magneto-structural changes in the same temperature range. This means that the Fete with Fe-D1oc polyhedron interaction seems to be uncoupled with temperature dealing with these nanoparticle sizes wherein the structural distortions are likely moderate due to surface effects.

Synthesis of superparamagnetic silica-coated magnetite nanoparticles for biomedical applications

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

Kaur, Navjot, E-mail: navjot.dhindsa2989@gmail.com; Chudasama, Bhupendra, E-mail: bnchudasama@gmail.com

Multifunctional superparamagnetic iron oxide nanoparticles (SPIONs) coated with silica are widely researched for biomedical applications such as magnetic resonance imaging, tissue repair, cell separation, hyperthermia, drug delivery, etc. In this article synthesis of magnetite (Fe{sub 3}O{sub 4}) nanoparticles and their coating with SiO{sub 2} is reported. Fe{sub 3}O{sub 4} nanoparticles were synthesized by chemical co-precipitation and it was coated with silica by hydrolysis and condensation of tetraethylorthosilicate. XRD, FTIR, TEM and VSM techniques were used to characterize bare and coated nanoparticles. Results indicated that the average size of SPIONS was 8.4 nm. X-ray diffraction patterns of silica coated SPIONS were identicalmore » to that of SPIONS confirming the inner spinal structure of SPIONS. FTIR results confirmed the binding of silica with the magnetite and the formation of the silica shell around the magnetite core. Magnetic properties of SPIONS and silica coated SPIONS are determined by VSM. They are superparamagnetic. The major conclusion drawn from this study is that the synthesis route yields stable, non-aggregated magnetite-silica core-shell nanostructures with tailored morphology and excellent magnetic properties.« less

Application of sequential extraction analysis to Pb(II) recovery by zerovalent iron-based particles.

PubMed

Zhu, Neng-Min; Xu, Yan-Sheng; Dai, Lichun; Zhang, Yun-Fei; Hu, Guo-Quan

2018-06-05

Zerovalent iron (ZVI) is an environmental-friendly reactive reagent for recovering heavy metals. However, the detailed recovery mechanism remains unclear due to a lack of quantitative analysis of recovery products. Herein, microscale ZVI, nanoscale ZVI and Ni/Fe nanoparticles were used to recover Pb(II) in aqueous solution and a sequential extraction procedure (SEP) was applied to determine the formed lead species quantitatively. At high initial Pb(II) concentration (500 mg L -1 ), more than 99.5% of Pb(II) was immobilized by Ni/Fe and n-ZVI, whereas m-ZVI caused inferior recovery efficiency (<25%). XRD and XPS results revealed that Pb(II) was reduced to Pb 0 prior to the formation of metal hydroxides as the external shell of ZVI. SEP results showed that the fraction bound to carbonates (PbO), fraction bound to iron oxides and exchangeable fraction were the main lead species conducted by Ni/Fe, n-ZVI and m-ZVI, respectively. Consequently, (co-)precipitation and specific adsorption dominated Pb(II) recovery by Ni/Fe and n-ZVI, whereas m-ZVI conducted Pb(II) recovery mainly via weak adsorption. The reactivity of ZVI toward Pb(II) followed the increasing order of m-ZVI < n-ZVI ≤ Ni/Fe. The detailed mechanisms of Pb(II) recovery conducted by different ZVI were proposed. Copyright © 2018 Elsevier B.V. All rights reserved.

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...

Spectroscopic investigation and direct comparison of the reactivities of iron pyridyl oxidation catalysts

NASA Astrophysics Data System (ADS)

Song, Yang; Mayes, Howard G.; Queensen, Matthew J.; Bauer, Eike B.; Dupureur, Cynthia M.

2017-03-01

The growing interest in green chemistry has fueled attention to the development and characterization of effective iron complex oxidation catalysts. A number of iron complexes are known to catalyze the oxidation of organic substrates utilizing peroxides as the oxidant. Their development is complicated by a lack of direct comparison of the reactivities of the iron complexes. To begin to correlate reactivity with structural elements, we compare the reactivities of a series of iron pyridyl complexes toward a single dye substrate, malachite green (MG), for which colorless oxidation products are established. Complexes with tetradentate, nitrogen-based ligands with cis open coordination sites were found to be the most reactive. While some complexes reflect sensitivity to different peroxides, others are similarly reactive with either H2O2 or tBuOOH, which suggests some mechanistic distinctions. [Fe(S,S-PDP)(CH3CN)2](SbF6)2 and [Fe(OTf)2(tpa)] transition under the oxidative reaction conditions to a single intermediate at a rate that exceeds dye degradation (PDP = bis(pyridin-2-ylmethyl) bipyrrolidine; tpa = tris(2-pyridylmethyl)amine). For the less reactive [Fe(OTf)2(dpa)] (dpa = dipicolylamine), this reaction occurs on a timescale similar to that of MG oxidation. Thus, the spectroscopic method presented herein provides information about the efficiency and mechanism of iron catalyzed oxidation reactions as well as about potential oxidative catalyst decomposition and chemical changes of the catalyst before or during the oxidation reaction.

Resistance to High-Temperature Oxidation and Wear of Various Ferrous Alloys Used in Rolling Mills

NASA Astrophysics Data System (ADS)

Delaunois, Fabienne; Stanciu, Victor Ioan; Sinnaeve, Mario

2018-03-01

Various materials are commonly used to manufacture work rolls for hot rolling mills, such as ICDP (Indefinite Chill Double Pour) cast irons, high-chromium white cast irons, and high speed steels (HSS). Various chemical compositions and microstructures are studied in order to optimize the in-use behavior of those grades of rolls. In this paper, six grades of ferrous alloys (an ICDP cast iron; an ICDP cast iron enriched in vanadium, niobium, and molybdenum; a HSS; a graphitic HSS; a high-chromium white cast iron (Hi-Cr); and a niobium-molybdenum-doped high-chromium white cast iron) were investigated. High-temperature oxidation tests with gravimetric means at 575 °C in water vapor atmosphere and sliding wear tests were carried out. The oxidation kinetics was followed during oxidation test. The microstructure was observed by optical and scanning electron microscopies. The oxides formed on the surface of the samples were analyzed by XRD and EDS. The thickness of the oxide scales and the mass gain were measured after oxidation test. The results showed that the behavior of all the grades differed. The oxide scale of HSS and HSS-G grades was fine and their friction coefficient was low. The weight gain after oxidation test of HSS was high. Hi-Cr and M-Hi-Cr grades presented highly porous oxide layer and an important increase of the friction coefficient during wear test. ICDP and M-ICDP had intermediate behavior.

Investigation of Redox Metal Oxides for Carbonaceous Fuel Conversion and CO2 Capture

NASA Astrophysics Data System (ADS)

Galinsky, Nathan Lee

The chemical looping combustion (CLC) process uses metal oxides, also referred to as oxygen carriers, in a redox scheme for conversion of carbonaceous fuels into a concentrated stream of CO2 and steam while also producing heat and electricity. The unique redox scheme of CLC allows CO2 capture with minimal energy penalty. The CLC process performance greatly depends on the oxygen carrier that is chosen. To date, more than 1000 oxygen carriers have been developed for chemical-looping processes using metal oxides containing first-row transition metals. Oxygen carriers are typically mixed with an inert ceramic support to improve their overall mechanical stability and recyclability. This study focuses on design of (i) iron oxide oxygen carriers for conversion of gaseous carbonaceous fuels and (ii) development of perovskite CaMnO 3-d with improved stability and redox properties for conversion of solid fuels. Iron oxide is cheap and environmentally benign. However, it suffers from low activity with carbonaceous fuels due partially to the low ionic conductivity of iron oxides. In order to address the low activity of iron-oxide-based oxygen carriers, support addition has been shown to lower the energy barrier of oxygen anion transport within the oxygen carrier. This work adds a mixed-ionic-and-electronic-conductor (MIEC) support to iron oxide to help facilitate O2- transport inside the lattice of iron oxide. The MIEC-supported iron oxide is compared to commonly used supports including TiO2 and Al2O 3 and the pure ionic conductor support yttria-stabilized zirconia (YSZ) for conversion of different carbonaceous fuels and hydrogen. Results show that the MIEC-supported iron oxide exhibits up to 70 times higher activity than non-MIEC-supported iron oxides for methane conversion. The MIEC supported iron oxide also shows good recyclability with only minor agglomeration and carbon formation observed. The effect of support-iron oxide synergies is further investigated to understand other physical and chemical properties that lead to highly active and recyclable oxygen carriers. Perovskite and fluorite-structured MIEC supports are tested for conversion of methane. The perovskite supported iron oxides exhibit higher activity and stability resulting from the high mixed conductivity of the support. Fluorite-structured CeO2 oxygen carriers deactivated by 75% after 10 redox cycles. This deactivation was attributed to agglomeration of iron oxide. The agglomeration was determined to occur due to Fe x+ transport during the oxidation step leading to high content of Fe on the surface of the oxygen carrier. Besides the MIEC supports, inert MgAl2O4 supported iron oxide is observed to activate in methane. The activation is attributed to carbon formation causing physical degradation of the oxygen carrier and leading to higher surface area and porosity. To achieve high activity with solid fuels, chemical looping with oxygen uncoupling (CLOU) is commonly used. This process uses oxygen carriers with high PO2 that allows the oxygen carrier to release a portion of their lattice oxygen as gaseous oxygen. In turn, the gaseous oxygen can react with solid fuel particles at a higher rate than the lattice oxygen. CaMnO 3 perovskite oxygen carriers offer high potential for CLOU. However, pure CaMnO3 suffers from long-term recyclability and sulfur poisoning. Addition of A-site (Ba and Sr) and B-site (Fe, Ni, Co, Al, and V) dopants are used to improve the performance of the base CaMnO3 oxygen carrier. Sr (A-site) and Fe (B-site) exhibit high compatibility with the base perovskite structure. Both dopants observe oxygen uncoupling properties up to 200°C below that of pure CaMnO3. Additionally, the doped structures also exhibit higher stability at high temperatures (>1000°C) and during redox cycles. The doped oxygen carriers also demonstrate significantly improved activity for coal char conversion.

Iron oxide nanoparticles stabilized with dendritic polyglycerols as selective MRI contrast agents

NASA Astrophysics Data System (ADS)

Nordmeyer, Daniel; Stumpf, Patrick; Gröger, Dominic; Hofmann, Andreas; Enders, Sven; Riese, Sebastian B.; Dernedde, Jens; Taupitz, Matthias; Rauch, Ursula; Haag, Rainer; Rühl, Eckart; Graf, Christina

2014-07-01

Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 +/- 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI.Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 +/- 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI. Electronic supplementary information (ESI) available: A detailed description of the synthesis of the ligands as well as the preparation and functionalization of the iron oxide nanoparticles including their physico-chemical characterization are presented. Further, details of the cell experiments and the SPR experiments are given. Two representative movies are provided showing leukocyte rolling on the ligand coated surface of the flow chamber. See DOI: 10.1039/c3nr04793h

Complex Resonance Absorption Structure in the X-Ray Spectrum of IRAS 13349+2438

NASA Technical Reports Server (NTRS)

Sako, M.; Kahn, S. M.; Behar, E.; Kaastra, J. S.; Brinkman, A. C.; Boller, Th.; Puchnarewicz, E. M.; Starling, R.; Liedahl, D. A.; Clavel, J.

2000-01-01

The luminous infrared-loud quasar IRAS 13349+2438 was observed with the XMM - Newton Observatory as part of the Performance Verification program. The spectrum obtained by the Reflection Grating Spectrometer (RGS) exhibits broad (FWHM - 1400 km/s) absorption lines from highly ionized elements including hydrogen- and helium-like carbon, nitrogen, oxygen, and neon, and several iron L - shell ions (Fe XVII - XX). Also shown in the spectrum is the first astrophysical detection of a broad absorption feature around lambda = 16 - 17 A identified as an unresolved transition array (UTA) of 2p - 3d inner-shell absorption by iron M-shell ions in a much cooler medium; a feature that might be misidentified as an O VII edge when observed with moderate resolution spectrometers. No absorption edges are clearly detected in the spectrum. We demonstrate that the RGS spectrum of IRAS 13349+2438 exhibits absorption lines from two distinct regions, one of which is tentatively associated with the medium that produces the optical/UV reddening.

Bidirectional Photoswitching via Alternating NIR and UV Irradiation on a Core-Shell UCNP-SCO Nanosphere.

PubMed

Luo, Yang-Hui; Wang, Jing-Wen; Wang, Wen; He, Xiao-Tong; Hong, Dan-Li; Chen, Chen; Xu, Tao; Shao, Qiyue; Sun, Bai-Wang

2018-05-16

Bidirectional photoswitching of molecular materials under ambient condition is of significant importance. Herein, we present for the first time that a core-shell UCNP-SCO nanosphere (UCNP = upconversion nanophosphor, SCO = spin crossover), which was composed of a UCNP core (NaYF 4 : 20 mol % Yb 3+ , 1 mol % Er 3+ ) and an SCO iron(II) shell ([Fe(H 2 Bpz) 2 (bipy-COOH)], H 2 Bpz = dihydrobis(1-pyrazolyl)borate, bipy-COOH = 4,4'-dicarboxy-2,2'-bipyridine), can be reversibly photoswitched between the high-spin and low-spin states at room temperature in the solid state, via alternating irradiation with near-infrared (λ = 980 nm) and ultraviolet (λ = 310 nm) light. What's more, this reversible spin-state switching was accompanied by a variation of fluorescent spectrum and dielectric constants. The strategy here, that is, integrating the SCO iron(II) complex into a UCNP-SCO nanosphere for molecular photoswitching, may open a new area in the development of photocontrolled molecular devices.

Exploring Iron Silicate Precursors of Ancient Iron Formations through Rock Record, Laboratory and Field Analogue Investigations

NASA Astrophysics Data System (ADS)

Johnson, J. E.; Rasmussen, B.; Muhling, J.; Benzerara, K.; Jezequel, D.; Cosmidis, J.; Templeton, A. S.

2016-12-01

In direct contrast to today's oceans, iron-rich chemical precipitates dominate the deep marine sedimentary record > 2.3 billion years ago. The deposition of these minerals resulted in massive iron formations and indicate that the ocean was previously ferruginous and largely anoxic. To precipitate and concentrate iron in the sediments, many hypotheses have centered on the oxidation of soluble Fe(II) to solid Fe(III)-oxyhydroxides; these ideas have stimulated extensive research using iron-oxidizing bacteria to produce Fe(III)-oxides and trace metal sorption experiments on Fe(III)-oxides, leading to inferences of trace metal availability and implications for enzymatic and microbial evolution as well as pO2 levels and seawater chemistry. However, recent discoveries of disseminated iron-silicate nanoparticles in early-silicifying chert indicate that iron-silicates may have instead been the primary precipitates from these Archean ferruginous oceans (Rasmussen et al, 2015). Considering the significant paradigm shift this discovery implies for interpretations of Archean elemental cycling, redox state and potential microbial metabolisms, we investigated these iron-silicate inclusions and their implications for ancient seawater chemistry in a multi-faceted approach using spectroscopic- and diffraction-based techniques. The crystal structure, Fe oxidation state and Fe coordination environment of iron-silicate nanoparticles have been interrogated using microscale X-ray absorption spectroscopy, TEM and nanoscale scanning transmission X-ray microscopy. To further explore the chemical and potential biological controls on iron-silicate formation, we have also performed laboratory experiments to mimic Archean seawater and precipitate iron-bearing silicate minerals under abiotic conditions and in the presence of iron-oxidizing bacteria. In a complementary study, sediments from a natural Archean analogue system were sampled to determine if iron-silicate minerals form in Mexican crater lakes that are variably iron- and silica-rich. As we continue to probe the mechanism of Fe(II/III)-silicate formation, we can constrain the activity of silica, pH, and pO2 on early Earth and describe any potential influence of microbial activity on the precipitation of these phases.

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.

The effect of Mg dopants on magnetic and structural properties of iron oxide and zinc ferrite thin films

NASA Astrophysics Data System (ADS)

Saritaş, Sevda; Ceviz Sakar, Betul; Kundakci, Mutlu; Yildirim, Muhammet

2018-06-01

Iron oxide thin films have been obtained significant interest as a material that put forwards applications in photovoltaics, gas sensors, biosensors, optoelectronic and especially in spintronics. Iron oxide is one of the considerable interest due to its chemical and thermal stability. Metallic ion dopant influenced superexchange interactions and thus changed the structural, electrical and magnetic properties of the thin film. Mg dopped zinc ferrite (Mg:ZnxFe3-xO4) crystal was used to avoid the damage of Fe3O4 (magnetite) crystal instead of Zn2+ in this study. Because the radius of the Mg2+ ion in the A-site (tetrahedral) is almost equal to that of the replaced Fe3+ ion. Inverse-spinel structure in which oxygen ions (O2-) are arranged to form a face-centered cubic (FCC) lattice where there are two kinds of sublattices, namely, A-site and B-site (octahedral) interstitial sites and in which the super exchange interactions occur. In this study, to increase the saturation of magnetization (Ms) value for iron oxide, inverse-spinal ferrite materials have been prepared, in which the iron oxide was doped by multifarious divalent metallic elements including Zn and Mg. Triple and quaternary; iron oxide and zinc ferrite thin films with Mg metal dopants were grown by using Spray Pyrolysis (SP) technique. The structural, electrical and magnetic properties of Mg dopped iron oxide (Fe2O3) and zinc ferrite (ZnxFe3-xO4) thin films have been investigated. Vibrating Sample Magnetometer (VSM) technique was used to study for the magnetic properties. As a result, we can say that Mg dopped iron oxide thin film has huge diamagnetic and of Mg dopped zinc ferrite thin film has paramagnetic property at bigger magnetic field.

Laboratory Investigation of Complex Conductivity and Magnetic Susceptibility on Natural Iron Oxide Coated Sand

NASA Astrophysics Data System (ADS)

Wang, C.; Slater, L. D.; Day-Lewis, F. D.; Briggs, M. A.

2017-12-01

Redox reactions occurring at the oxic/anoxic interface where groundwater discharges to surface water commonly result in iron oxide deposition that coats sediment grains. With relatively large total surface area, these iron oxide coated sediments serve as a sink for sorption of dissolved contaminants, although this sink may be temporary if redox conditions fluctuate with varied flow conditions. Characterization of the distribution of iron oxides in streambed sediments could provide valuable understanding of biogeochemical reactions and the ability of a natural system to sorb contaminants. Towards developing a field methodology, we conducted laboratory spectral induced polarization (SIP) and magnetic susceptibility (MS) measurements on natural iron oxide coated sand (Fe-sand) with grain sizes ranging from 0.3 to 2.0 mm in order to assess the sensitivity of these measurements to iron oxides in sediments. The Fe-sand was also sorted by sieving into various grain sizes to study the impact of grain size on the polarization mechanisms. The unsorted Fe-sand saturated with 0.01 S/m NaCl solution exhibited a distinct phase response ( > 4 mrad) in the frequency range from 0.001 to 100 Hz whereas regular silica sand was characterized by a phase response less than 1 mrad under the same conditions. The presence of iron oxide substantially increased MS (3.08×10-3 SI) over that of regular sand ( < 10-5 SI). An increase of both phase peak and relaxation time was found with increasing grain size of the sorted Fe-sand. Laboratory results demonstrated that SIP and MS may be well suited to mapping the distribution of iron oxides in streambed sediments associated with anoxic groundwater discharge.

Laser Flash Photolysis Generation of High-Valent Transition Metal-Oxo Species: Insights from Kinetic Studies in Real Time

PubMed Central

Zhang, Rui; Newcomb, Martin

2010-01-01

Conspectus High-valent transition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time-scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 × 103 M−1 s−1 for a corrole-iron(V)-oxo species and 1.6 × 106 M−1 s−1 for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions. PMID:18278877

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time.

PubMed

Zhang, Rui; Newcomb, Martin

2008-03-01

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species and 1.6 x 10(6) M(-1) s(-1) for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions.

Novel electrochemical-enzymatic model which quantifies the effect of the solution Eh on the kinetics of ferrous iron oxidation with Acidithiobacillus ferrooxidans.

PubMed

Meruane, G; Salhe, C; Wiertz, J; Vargas, T

2002-11-05

The influence of solution Eh on the rate of ferrous iron oxidation by Acidithiobacillus ferrooxidans is characterized. The experimental approach was based on the use of a two-chamber bioelectrochemical cell, which can determine the ferrous iron oxidation rate at controlled potential. Results enabled the formulation of a novel kinetic model, which incorporates the effect of solution Eh in an explicit form but still integrates the effect of ferrous iron concentration and ferric inhibition. The results showed that at Eh values below 650 mV (standard hydrogen electrode, SHE) the bacterial oxidative activity is mainly dependent on ferrous iron concentration. At Eh values between 650 and 820 mV (SHE) the oxidation rate is mainly controlled by ferric inhibition. Over 820 mV (SHE) the bacterial oxidative activity is strongly inhibited by the Eh increase, being completely inhibited at Eh = 840 mV (SHE). Copyright 2002 Wiley Periodicals, Inc. Biotechnol Bioeng 80: 280-288, 2002.

Reactive iron transport in an acidic mountain stream in Summit County, Colorado: A hydrologic perspective

USGS Publications Warehouse

McKnight, Diane M.; Bencala, K.E.

1989-01-01

A pH perturbation experiment was conducted in an acidic, metal-enriched, mountain stream to identify relative rates of chemical and hydrologic processes as they influence iron transport. During the experiment the pH was lowered from 4.2 to 3.2 for three hours by injection of sulfuric acid. Amorphous iron oxides are abundant on the streambed, and dissolution and photoreduction reactions resulted in a rapid increase in the dissolved iron concentration. The increase occurred simultaneously with the decrease in pH. Ferrous iron was the major aqueous iron species. The changes in the iron concentration during the experiment indicate that variation exists in the solubility properties of the hydrous iron oxides on the streambed with dissolution of at least two compartments of hydrous iron oxides contributing to the iron pulse. Spatial variations of the hydrologic properties along the stream were quantified by simulating the transport of a coinjected tracer, lithium. A simulation of iron transport, as a conservative solute, indicated that hydrologie transport had a significant role in determining downstream changes in the iron pulse. The rapidity of the changes in iron concentration indicates that a model based on dynamic equilibrium may be adequate for simulating iron transport in acid streams. A major challenge for predictive solute transport models of geochemical processes may be due to substantial spatial and seasonal variations in chemical properties of the reactive hydrous oxides in such streams, and in the physical and hydrologic properties of the stream. ?? 1989.

Oxygen in the Martian atmosphere: Regulation of PO2 by the deposition of iron formations on Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1992-01-01

During Earth's early history, and prior to the evolution of its present day oxygenated atmosphere, extensive iron rich siliceous sedimentary rocks were deposited, consisting of alternating layers of silica (chert) and iron oxide minerals (hematite and magnetite). The banding in iron formations recorded changes of atmosphere-hydrosphere interactions near sea level in the ancient ocean, which induced the oxidation of dissolved ferrous iron, precipitation of insoluble ferric oxides and silica, and regulation of oxygen in Earth's early atmosphere. Similarities between the Archean Earth and the composition of the present day atmosphere on Mars, together with the pervasive presence of ferric oxides in the Martian regolith suggest that iron formation might also have been deposited on Mars and influenced the oxygen content of the Martian atmosphere. Such a possibility is discussed here with a view to assessing whether the oxygen content of the Martian atmosphere has been regulated by the chemical precipitation of iron formations on Mars.

Facile transformation of FeO/Fe3O4 core-shell nanocubes to Fe3O4 via magnetic stimulation

NASA Astrophysics Data System (ADS)

Lak, Aidin; Niculaes, Dina; Anyfantis, George C.; Bertoni, Giovanni; Barthel, Markus J.; Marras, Sergio; Cassani, Marco; Nitti, Simone; Athanassiou, Athanassia; Giannini, Cinzia; Pellegrino, Teresa

2016-09-01

Here, we propose the use of magnetic hyperthermia as a means to trigger the oxidation of Fe1-xO/Fe3-δO4 core-shell nanocubes to Fe3-δO4 phase. As a first relevant consequence, the specific absorption rate (SAR) of the initial core-shell nanocubes doubles after exposure to 25 cycles of alternating magnetic field stimulation. The improved SAR value was attributed to a gradual transformation of the Fe1-xO core to Fe3-δO4, as evidenced by structural analysis including high resolution electron microscopy and Rietveld analysis of X-ray diffraction patterns. The magnetically oxidized nanocubes, having large and coherent Fe3-δO4 domains, reveal high saturation magnetization and behave superparamagnetically at room temperature. In comparison, the treatment of the same starting core-shell nanocubes by commonly used thermal annealing process renders a transformation to γ-Fe2O3. In contrast to other thermal annealing processes, the method here presented has the advantage of promoting the oxidation at a macroscopic temperature below 37 °C. Using this soft oxidation process, we demonstrate that biotin-functionalized core-shell nanocubes can undergo a mild self-oxidation transformation without losing their functional molecular binding activity.

Tuning of shell thickness of solid lipid particles impacts the chemical stability of encapsulated ω-3 fish oil.

PubMed

Salminen, Hanna; Helgason, Thrandur; Kristinsson, Bjarki; Kristbergsson, Kristberg; Weiss, Jochen

2017-03-15

This study demonstrates that tuning the shell thickness of lipid particles can modulate their oxidative stability. We hypothesized that a thick crystallized shell around the incorporated fish oil would improve the oxidative stability due to the reduced diffusion of prooxidants and oxygen. We prepared solid lipid nanoparticles (5%w/w lipid phase, 1.5%w/w surfactant, pH 7) by using different ratios of tristearin as carrier lipid and ω-3 fish oil as incorporated liquid lipid stabilized by high- or low-melting lecithin. The physical, polymorphic and oxidative stability of the lipid particles was assessed. The high-melting lecithin was the key in inducing the formation of a solidified tristearin shell around the lipid particles by interfacial heterogeneous nucleation. Lipid particles containing a higher ratio of tristearin showed a better oxidative stability. The results revealed that a crystallized tristearin layer above 10nm was required to inhibit oxidation of the incorporated fish oil. This cut-off was shown for lipid particles containing 50-60% fish oil. This research gives important insights into understanding the relation between the thickness of the crystallized shell around the lipid particles and their chemical stability. Copyright © 2016 Elsevier Inc. All rights reserved.

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.