Metal substitution in the active site of nitrogenase MFe(7)S(9) (M = Mo(4+), V(3+), Fe(3+)).

Science.gov (United States)

Lovell, Timothy; Torres, Rhonda A; Han, Wen-Ge; Liu, Tiqing; Case, David A; Noodleman, Louis

2002-11-04

The unifying view that molybdenum is the essential component in nitrogenase has changed over the past few years with the discovery of a vanadium-containing nitrogenase and an iron-only nitrogenase. The principal question that has arisen for the alternative nitrogenases concerns the structures of their corresponding cofactors and their metal-ion valence assignments and whether there are significant differences with that of the more widely known molybdenum-iron cofactor (FeMoco). Spin-polarized broken-symmetry (BS) density functional theory (DFT) calculations are used to assess which of the two possible metal-ion valence assignments (4Fe(2+)4Fe(3+) or 6Fe(2+)2Fe(3+)) for the iron-only cofactor (FeFeco) best represents the resting state. For the 6Fe(2+)2Fe(3+) oxidation state, the spin coupling pattern for several spin state alignments compatible with S = 0 were generated and assessed by energy criteria. The most likely BS spin state is composed of a 4Fe cluster with spin S(a) = (7)/(2) antiferromagnetically coupled to a 4Fe' cluster with spin S(b) = (7)/(2). This state has the lowest DFT energy for the isolated FeFeco cluster and displays calculated Mössbauer isomer shifts consistent with experiment. Although the S = 0 resting state of FeFeco has recently been proposed to have metal-ion valencies of 4Fe(2+)4Fe(3+) (derived from experimental Mössbauer isomer shifts), our isomer shift calculations for the 4Fe(2+)4Fe(3+) oxidation state are in poorer agreement with experiment. Using the Mo(4+)6Fe(2+)Fe(3+) oxidation level of the cofactor as a starting point, the structural consequences of replacement of molybdenum (Mo(4+)) with vanadium (V(3+)) or iron (Fe(3+)) in the cofactor have been investigated. The size of the cofactor cluster shows a dependency on the nature of the heterometal and increases in the order FeMoco < FeVco < FeFeco.

Orphan Spins in the S=5/2 Antiferromagnet CaFe_{2}O_{4}.

Science.gov (United States)

Stock, C; Rodriguez, E E; Lee, N; Demmel, F; Fouquet, P; Laver, M; Niedermayer, Ch; Su, Y; Nemkovski, K; Green, M A; Rodriguez-Rivera, J A; Kim, J W; Zhang, L; Cheong, S-W

2017-12-22

CaFe_{2}O_{4} is an anisotropic S=5/2 antiferromagnet with two competing A (↑↑↓↓) and B (↑↓↑↓) magnetic order parameters separated by static antiphase boundaries at low temperatures. Neutron diffraction and bulk susceptibility measurements, show that the spins near these boundaries are weakly correlated and a carry an uncompensated ferromagnetic moment that can be tuned with a magnetic field. Spectroscopic measurements find these spins are bound with excitation energies less than the bulk magnetic spin waves and resemble the spectra from isolated spin clusters. Localized bound orphaned spins separate the two competing magnetic order parameters in CaFe_{2}O_{4}.

Orphan Spins in the S =5/2 Antiferromagnet CaFe2O4

Science.gov (United States)

Stock, C.; Rodriguez, E. E.; Lee, N.; Demmel, F.; Fouquet, P.; Laver, M.; Niedermayer, Ch.; Su, Y.; Nemkovski, K.; Green, M. A.; Rodriguez-Rivera, J. A.; Kim, J. W.; Zhang, L.; Cheong, S.-W.

2017-12-01

CaFe2O4 is an anisotropic S =5/2 antiferromagnet with two competing A (↑↑↓↓) and B (↑↓↑↓) magnetic order parameters separated by static antiphase boundaries at low temperatures. Neutron diffraction and bulk susceptibility measurements, show that the spins near these boundaries are weakly correlated and a carry an uncompensated ferromagnetic moment that can be tuned with a magnetic field. Spectroscopic measurements find these spins are bound with excitation energies less than the bulk magnetic spin waves and resemble the spectra from isolated spin clusters. Localized bound orphaned spins separate the two competing magnetic order parameters in CaFe2 O4 .

A Model Study on the Possible Effects of an External Electrical Field on Enzymes Having Dinuclear Iron Cluster [2Fe-2S

Directory of Open Access Journals (Sweden)

Lemi Türker

2012-01-01

Full Text Available Hydrogenases which catalyze the H2 ↔ 2H+ + 2e− reaction are metalloenzymes that can be divided into two classes, the NiFe and Fe enzymes, on the basis of their metal content. Iron-sulfur clusters [2Fe-2S] and [4Fe-4S] are common in ironhydrogenases. In the present model study, [2Fe-2S] cluster has been considered to visualize the effect of external electric field on various quantum chemical properties of it. In the model, all the cysteinyl residues are in the amide form. The PM3 type semiempirical calculations have been performed for the geometry optimization of the model structure in the absence and presence of the external field. Then, single point DFT calculations (B3LYP/6-31+G(d have been carried out. Depending on the direction of the field, the chemical reactivity of the model enzyme varies which suggests that an external electric field could, under proper conditions, improve the enzymatic hydrogen production.

Role of protein-glutathione contacts in defining glutaredoxin-3 [2Fe-2S] cluster chirality, ligand exchange and transfer chemistry.

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Sen, Sambuddha; Cowan, J A

2017-10-01

Monothiol glutaredoxins (Grx) serve as intermediate cluster carriers in iron-sulfur cluster trafficking. The [2Fe-2S]-bound holo forms of Grx proteins display cysteinyl coordination from exogenous glutathione (GSH), in addition to contact from protein-derived Cys. Herein, we report mechanistic studies that investigate the role of exogenous glutathione in defining cluster chirality, ligand exchange, and the cluster transfer chemistry of Saccharomyces cerevisiae Grx3. Systematic perturbations were introduced to the glutathione-binding site by substitution of conserved charged amino acids that form crucial electrostatic contacts with the glutathione molecule. Native Grx3 could also be reconstituted in the absence of glutathione, with either DTT, BME or free L-cysteine as the source of the exogenous Fe-S ligand contact, while retaining full functional reactivity. The delivery of the [2Fe-2S] cluster to Grx3 from cluster donor proteins such as Isa, Nfu, and a [2Fe-2S](GS) 4 complex, revealed that electrostatic contacts are of key importance for positioning the exogenous glutathione that in turn influences the chiral environment of the cluster. All Grx3 derivatives were reconstituted by standard chemical reconstitution protocols and found to transfer cluster to apo ferredoxin 1 (Fdx1) at rates comparable to native protein, even when using DTT, BME or free L-cysteine as a thiol source in place of GSH during reconstitution. Kinetic analysis of cluster transfer from holo derivatives to apo Fdx1 has led to a mechanistic model for cluster transfer chemistry of native holo Grx3, and identification of the likely rate-limiting step for the reaction.

Homoleptic diphosphacyclobutadiene complexes [M(η(4)-P2C2R2)2]x- (M = Fe, Co; x = 0, 1).

Science.gov (United States)

Wolf, Robert; Ehlers, Andreas W; Khusniyarov, Marat M; Hartl, František; de Bruin, Bas; Long, Gary J; Grandjean, Fernande; Schappacher, Falko M; Pöttgen, Rainer; Slootweg, J Chris; Lutz, Martin; Spek, Anthony L; Lammertsma, Koop

2010-12-27

The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands are reported. Compounds [K([18]crown-6)(thf)(2)][Fe(η(4)-P(2)C(2)tBu(2))(2)] (K1), [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)tBu(2))(2)] (K2), and [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)Ad(2))(2)] (K3, Ad = adamantyl) were obtained from reactions of [K([18]crown-6)(thf)(2)][M(η(4)-C(14)H(10))(2)] (M = Fe, Co) with tBuC[triple bond]P (1, 2), or with AdC[triple bond]P (3). Neutral sandwiches [M(η(4)-P(2)C(2)tBu(2))(2)] (4: M = Fe 5: M = Co) were obtained by oxidizing 1 and 2 with [Cp(2)Fe]PF(6). Cyclic voltammetry and spectro-electrochemistry indicate that the two [M(η(4)-P(2)C(2)tBu(2))(2)](-)/[M(η(4)-P(2)C(2)tBu(2))(2)] moieties can be reversibly interconverted by one electron oxidation and reduction, respectively. Complexes 1-5 were characterized by multinuclear NMR, EPR (1 and 5), UV/Vis, and Mössbauer spectroscopies (1 and 4), mass spectrometry (4 and 5), and microanalysis (1-3). The molecular structures of 1-5 were determined by using X-ray crystallography. Essentially D(2d)-symmetric structures were found for all five complexes, which show the two 1,3-diphosphacyclobutadiene rings in a staggered orientation. Density functional theory calculations revealed the importance of covalent metal-ligand π bonding in 1-5. Possible oxidation state assignments for the metal ions are discussed.

Protonation/reduction dynamics at the [4Fe-4S] cluster of the hydrogen-forming cofactor in [FeFe]-hydrogenases.

Science.gov (United States)

Senger, Moritz; Mebs, Stefan; Duan, Jifu; Shulenina, Olga; Laun, Konstantin; Kertess, Leonie; Wittkamp, Florian; Apfel, Ulf-Peter; Happe, Thomas; Winkler, Martin; Haumann, Michael; Stripp, Sven T

2018-01-31

The [FeFe]-hydrogenases of bacteria and algae are the most efficient hydrogen conversion catalysts in nature. Their active-site cofactor (H-cluster) comprises a [4Fe-4S] cluster linked to a unique diiron site that binds three carbon monoxide (CO) and two cyanide (CN - ) ligands. Understanding microbial hydrogen conversion requires elucidation of the interplay of proton and electron transfer events at the H-cluster. We performed real-time spectroscopy on [FeFe]-hydrogenase protein films under controlled variation of atmospheric gas composition, sample pH, and reductant concentration. Attenuated total reflection Fourier-transform infrared spectroscopy was used to monitor shifts of the CO/CN - vibrational bands in response to redox and protonation changes. Three different [FeFe]-hydrogenases and several protein and cofactor variants were compared, including element and isotopic exchange studies. A protonated equivalent (HoxH) of the oxidized state (Hox) was found, which preferentially accumulated at acidic pH and under reducing conditions. We show that the one-electron reduced state Hred' represents an intrinsically protonated species. Interestingly, the formation of HoxH and Hred' was independent of the established proton pathway to the diiron site. Quantum chemical calculations of the respective CO/CN - infrared band patterns favored a cysteine ligand of the [4Fe-4S] cluster as the protonation site in HoxH and Hred'. We propose that proton-coupled electron transfer facilitates reduction of the [4Fe-4S] cluster and prevents premature formation of a hydride at the catalytic diiron site. Our findings imply that protonation events both at the [4Fe-4S] cluster and at the diiron site of the H-cluster are important in the hydrogen conversion reaction of [FeFe]-hydrogenases.

4-Demethylwyosine Synthase from Pyrococcus abyssi Is a Radical-S-adenosyl-l-methionine Enzyme with an Additional [4Fe-4S]+2 Cluster That Interacts with the Pyruvate Co-substrate*

Science.gov (United States)

Perche-Letuvée, Phanélie; Kathirvelu, Velavan; Berggren, Gustav; Clemancey, Martin; Latour, Jean-Marc; Maurel, Vincent; Douki, Thierry; Armengaud, Jean; Mulliez, Etienne; Fontecave, Marc; Garcia-Serres, Ricardo; Gambarelli, Serge; Atta, Mohamed

2012-01-01

Wybutosine and its derivatives are found in position 37 of tRNA encoding Phe in eukaryotes and archaea. They are believed to play a key role in the decoding function of the ribosome. The second step in the biosynthesis of wybutosine is catalyzed by TYW1 protein, which is a member of the well established class of metalloenzymes called “Radical-SAM.” These enzymes use a [4Fe-4S] cluster, chelated by three cysteines in a CX3CX2C motif, and S-adenosyl-l-methionine (SAM) to generate a 5′-deoxyadenosyl radical that initiates various chemically challenging reactions. Sequence analysis of TYW1 proteins revealed, in the N-terminal half of the enzyme beside the Radical-SAM cysteine triad, an additional highly conserved cysteine motif. In this study we show by combining analytical and spectroscopic methods including UV-visible absorption, Mössbauer, EPR, and HYSCORE spectroscopies that these additional cysteines are involved in the coordination of a second [4Fe-4S] cluster displaying a free coordination site that interacts with pyruvate, the second substrate of the reaction. The presence of two distinct iron-sulfur clusters on TYW1 is reminiscent of MiaB, another tRNA-modifying metalloenzyme whose active form was shown to bind two iron-sulfur clusters. A possible role for the second [4Fe-4S] cluster in the enzyme activity is discussed. PMID:23043105

Fe-S Cluster Biogenesis in Isolated Mammalian Mitochondria

Science.gov (United States)

Pandey, Alok; Pain, Jayashree; Ghosh, Arnab K.; Dancis, Andrew; Pain, Debkumar

2015-01-01

Iron-sulfur (Fe-S) clusters are essential cofactors, and mitochondria contain several Fe-S proteins, including the [4Fe-4S] protein aconitase and the [2Fe-2S] protein ferredoxin. Fe-S cluster assembly of these proteins occurs within mitochondria. Although considerable data exist for yeast mitochondria, this biosynthetic process has never been directly demonstrated in mammalian mitochondria. Using [35S]cysteine as the source of sulfur, here we show that mitochondria isolated from Cath.A-derived cells, a murine neuronal cell line, can synthesize and insert new Fe-35S clusters into aconitase and ferredoxins. The process requires GTP, NADH, ATP, and iron, and hydrolysis of both GTP and ATP is necessary. Importantly, we have identified the 35S-labeled persulfide on the NFS1 cysteine desulfurase as a genuine intermediate en route to Fe-S cluster synthesis. In physiological settings, the persulfide sulfur is released from NFS1 and transferred to a scaffold protein, where it combines with iron to form an Fe-S cluster intermediate. We found that the release of persulfide sulfur from NFS1 requires iron, showing that the use of iron and sulfur for the synthesis of Fe-S cluster intermediates is a highly coordinated process. The release of persulfide sulfur also requires GTP and NADH, probably mediated by a GTPase and a reductase, respectively. ATP, a cofactor for a multifunctional Hsp70 chaperone, is not required at this step. The experimental system described here may help to define the biochemical basis of diseases that are associated with impaired Fe-S cluster biogenesis in mitochondria, such as Friedreich ataxia. PMID:25398879

Cs[FeSe{sub 2}], Cs{sub 3}[FeSe{sub 2}]{sub 2}, and Cs{sub 7}[Fe{sub 4}Se{sub 8}]. Missing links of known chalcogenido ferrate series

Energy Technology Data Exchange (ETDEWEB)

Stueble, Pirmin; Roehr, Caroline [Institut fuer Anorganische und Analytische Chemie, Universitaet Freiburg (Germany)

2017-11-17

The three cesium selenido ferrate title compounds with an Se:Fe ratio of 2:1 were synthesized from stoichiometric samples reacting elemental Cs either (A) with Fe and Se in a double-crucible setup (Cs[FeSe{sub 2}], Cs{sub 3}[FeSe{sub 2}]{sub 2}) or (B) with previously prepared FeSe{sub 2} (Cs{sub 3}[FeSe{sub 2}]{sub 2}, Cs{sub 7}[Fe{sub 4}S{sub 8}]) (T{sub max} = 800-1000 C). The pure Fe{sup III} ferrate Cs[FeSe{sub 2}] crystallizes in the Tl[FeSe{sub 2}] type [monoclinic, space group C2/m, a = 1392.95(10), b = 564.43(3), c = 737.44(6) pm, β = 119.163(5) , Z = 4, R{sub 1} = 0.0550]. It is thus not isotypic to all other alkali ferrates(III) A[FeS{sub 2}] and A[FeSe{sub 2}] containing chains of edge-sharing tetrahedra, but crystallizes in a t2 subgroup of the Immm structure of Cs[FeS{sub 2}]. The mixed-valent chain compound Cs{sub 3}[FeSe{sub 2}]{sub 2} is isotypic to its sulfido analogue [orthorhombic, space group Pnma, a = 777.88(6), b = 1151.02(6), c = 1341.61(7) pm, Z = 4, R{sub 1} = 0.0470]. In contrast to the isopunctal Na{sub 3}[FeSe{sub 2}]{sub 2} type K/Rb compounds the chains are only slightly corrugated. The monoclinic, likewise mixed-valent Fe{sup II/III} selenido ferrate Cs{sub 7}[Fe{sub 4}Se{sub 8}] [monoclinic, space group C2/c, a = 1953.79(10), b = 879.71(5), c = 1717.03(10) pm, β = 117.890(2) , Z = 4, R{sub 1} = 0.0816] is isostructural both to the cesium sulfido and tellurido compound. The structure contains oligomeric moieties of four edge sharing [FeSe{sub 4}] tetrahedra forming slightly distorted tetrahedral clusters [Fe{sub 4}Se{sub 8}]{sup 7-}, which are surrounded by a cube of 26 Cs cations. Based on a structure map, the crystal chemistry of the three title compounds is discussed together with all chain/cluster ferrates of the general series A{sub 1+x}[Fe{sup III}{sub 1-x}Fe{sup II}{sub x}Q{sub 2}] (x = 0-1; A = Na, K, Rb, Cs; Q = S, Se, Te). (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Heterometal cubane-type MFe(3)S(4) clusters (M = Mo, V) trigonally symmetrized with hydrotris(pyrazolyl)borate(1-) and tris(pyrazolyl)methanesulfonate(1-) capping ligands.

Science.gov (United States)

Fomitchev, Dmitry V; McLauchlan, Craig C; Holm, R H

2002-02-25

A series of heterometal cubane-type clusters containing [VFe(3)S(4)](2+) and [MoFe(3)S(4)](3+,2+) cores has been prepared. Ligand substitution of [(DMF)(3)VFe(3)S(4)Cl(3)](-) affords [(Tpms)VFe(3)S(4)L(3)](2)(-) (L = Cl(-) (8), EtS(-) (9), p-MeC(6)H(4)S(-), p-MeC(6)H(4)O(-)). A new procedure for the preparation of molybdenum single cubanes is introduced by the reaction of recently reported [(Tp)MoS(S(4))](-) with FeCl(2)/NaSEt to afford [(Tp)MoFe(3)S(4)Cl(3)](-) (1, 75% yield). This procedure is more efficient that the existing multistep synthesis of single cubanes, which generally affords clusters of mirror symmetry. Also prepared were [(Tp)MoFe(3)S(4)L(3)](-) (L = EtS(-) (2), p-MeC(6)H(4)S(-)). Reduction of 1 with borohydride gives [(Tp)MoFe(3)S(4)Cl(3)](2-) (5, 67%). Owing to the nature of the heterometal ligand, all clusters have idealized trigonal symmetry, reflected in their (1)H NMR spectra. Trigonal structures are demonstrated by crystallography of (Bu(4)N)[1,2], (Bu(4)N)(2)[5] x MeCN, and (Me(4)N)(2)[8,9]. The availability of 1 and 5 allows the first comparison of structures and (57)Fe isomer shifts of [MoFe(3)S(4)](3+,2+) in a constant ligand environment. Small increases in most bond distances indicate that an antibonding electron is added in the reduction of 1. Collective synthetic and electrochemical results from this and other studies demonstrate the existence of the series of oxidation states [VFe(3)S(4)](3+,2+,1+) and [MoFe(3)S(4)](4+,3+,2+) whose relative stabilities within a given series are strongly ligand dependent. Isomer shifts indicate that the reduction of 1 largely affects the Fe(3) subcluster and are consistent with the formal descriptions [MoFe(3+)(2)Fe(2+)S(4)](3+) (1) and [MoFe(3+)Fe(2+)(2)S(4)](2+) (5). Reaction of 1 with excess Li(2)S in acetonitrile affords the double cubane [[(Tp)MoFe(3)S(4)Cl(2)](2)(mu(2)(-)S)](2)(-), whose sulfide-bridged structure is supported by two sequential reductions separated by 290 mV, in analogy with

Ab Initio Electronic Structure Calculation of [4Fe-3S] Cluster of Hydrogenase as Dihydrogen Dissociation/Production Catalyst

Science.gov (United States)

Kim, Jaehyun; Kang, Jiyoung; Nishigami, Hiroshi; Kino, Hiori; Tateno, Masaru

2018-03-01

Hydrogenases catalyze both the dissociation and production of dihydrogen (H2). Most hydrogenases are inactivated rapidly and reactivated slowly (in vitro), in the presence of dioxygen (O2) and H2, respectively. However, membrane-bound [NiFe] hydrogenases (MBHs) sustain their activity even together with O2, which is termed "O2 tolerance". In previous experimental analyses, an MBH was shown to include a hydroxyl ion (OH-) bound to an Fe of the super-oxidized [4Fe-3S]5+ cluster in the proximity of the [NiFe] catalytic cluster. In this study, the functional role of the OH- in the O2 tolerance was investigated by ab initio electronic structure calculation of the [4Fe-3S] proximal cluster. The analysis revealed that the OH- significantly altered the electronic structure, thereby inducing the delocalization of the lowest unoccupied molecular orbital (LUMO) toward the [NiFe] catalytic cluster, which may intermediate the electron transfer between the catalytic and proximal clusters. This can promote the O2-tolerant catalytic cycle in the hydrogenase reaction.

Nitrosylation of Nitric-Oxide-Sensing Regulatory Proteins Containing [4Fe-4S] Clusters Gives Rise to Multiple Iron-Nitrosyl Complexes

Energy Technology Data Exchange (ETDEWEB)

Serrano, Pauline N. [Department of Chemistry, University of California, Davis CA 95616 USA; Wang, Hongxin [Department of Chemistry, University of California, Davis CA 95616 USA; Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley CA 94720 USA; Crack, Jason C. [Centre for Molecular and Structural Biochemistry, School of Chemistry, University of East Anglia, Norwich Research Park Norwich NR4 7TJ UK; Prior, Christopher [Centre for Molecular and Structural Biochemistry, School of Chemistry, University of East Anglia, Norwich Research Park Norwich NR4 7TJ UK; Hutchings, Matthew I. [School of Biological Sciences, University of East Anglia, Norwich NR4 7TJ UK; Thomson, Andrew J. [Centre for Molecular and Structural Biochemistry, School of Chemistry, University of East Anglia, Norwich Research Park Norwich NR4 7TJ UK; Kamali, Saeed [University of Tennessee Space Institute, Tullahome TN 37388-9700 USA; Yoda, Yoshitaka [Research and Utilization Division, SPring-8/JASRI, 1-1-1 Kouto, Sayo Hyogo 679-5198 Japan; Zhao, Jiyong [Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Hu, Michael Y. [Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Alp, Ercan E. [Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Oganesyan, Vasily S. [Centre for Molecular and Structural Biochemistry, School of Chemistry, University of East Anglia, Norwich Research Park Norwich NR4 7TJ UK; Le Brun, Nick E. [Centre for Molecular and Structural Biochemistry, School of Chemistry, University of East Anglia, Norwich Research Park Norwich NR4 7TJ UK; Cramer, Stephen P. [Department of Chemistry, University of California, Davis CA 95616 USA; Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley CA 94720 USA

2016-10-25

The reaction of protein-bound iron–sulfur (Fe-S) clusters with nitric oxide (NO) plays key roles in NO-mediated toxicity and signaling. Elucidation of the mechanism of the reaction of NO with DNA regulatory proteins that contain Fe-S clusters has been hampered by a lack of information about the nature of the iron-nitrosyl products formed. Herein, we report nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) calculations that identify NO reaction products in WhiD and NsrR, regulatory proteins that use a [4Fe-4S] cluster to sense NO. This work reveals that nitrosylation yields multiple products structurally related to Roussin's Red Ester (RRE, [Fe₂(NO)₄(Cys)₂]) and Roussin's Black Salt (RBS, [Fe₄(NO)₇S₃]. In the latter case, the absence of ³²S/³⁴S shifts in the Fe-S region of the NRVS spectra suggest that a new species, Roussin's Black Ester (RBE), may be formed, in which one or more of the sulfide ligands is replaced by Cys thiolates.

Fe4 cluster and a buckled macrocycle complex from the reduction of [(dmgBF2)2Fe(L)2] (L = MeCN, (t)Bu(i)NC).

Science.gov (United States)

Rose, Michael J; Winkler, Jay R; Gray, Harry B

2012-02-20

We report the syntheses, X-ray structures, and reductive electrochemistry of the Fe(II) complexes [(dmgBF(2))(2)Fe(MeCN)(2)] (1; dmg = dimethylglyoxime, MeCN = acetonitrile) and [(dmgBF(2))Fe((t)Bu(i)NC)(2)] (2; (t)Bu(i)NC = tert-butylisocyanide). The reaction of 1 with Na/Hg amalgam led to isolation and the X-ray structure of [(dmgBF(2))(2)Fe(glyIm)] (3; glyIm = glyimine), wherein the (dmgBF(2))(2) macrocyclic frame is bent to accommodate the binding of a bidentate apical ligand. We also report the X-ray structure of a rare mixed-valence Fe(4) cluster with supporting dmg-type ligands. In the structure of [(dmg(2)BF(2))(3)Fe(3)((1)/(2)dmg)(3)Fe(O)(6)] (4), the (dmgBF(2))(2) macrocycle has been cleaved, eliminating BF(2) groups. Density functional theory calculations and electron paramagnetic resonance data are in accordance with a central Fe(III) ion surrounded by three formally Fe(II)dmg(2)BF(2) units.

The s-process enrichment of the globular clusters M4 and M22

Energy Technology Data Exchange (ETDEWEB)

Shingles, Luke J.; Karakas, Amanda I.; Fishlock, Cherie K.; Yong, David; Da Costa, Gary S.; Marino, Anna F. [Research School of Astronomy and Astrophysics, Australian National University, Canberra, ACT 2611 (Australia); Hirschi, Raphael, E-mail: luke.shingles@anu.edu.au [Institute for the Physics and Mathematics of the Universe (WPI), University of Tokyo, 5-1-5 Kashiwanoha, 277-8583 Kashiwa (Japan)

2014-11-01

We investigate the enrichment in elements produced by the slow neutron-capture process (s-process) in the globular clusters M4 (NGC 6121) and M22 (NGC 6656). Stars in M4 have homogeneous abundances of Fe and neutron-capture elements, but the entire cluster is enhanced in s-process elements (Sr, Y, Ba, Pb) relative to other clusters with a similar metallicity. In M22, two stellar groups exhibit different abundances of Fe and s-process elements. By subtracting the mean abundances of s-poor from s-rich stars, we derive s-process residuals or empirical s-process distributions for M4 and M22. We find that the s-process distribution in M22 is more weighted toward the heavy s-peak (Ba, La, Ce) and Pb than M4, which has been enriched mostly with light s-peak elements (Sr, Y, Zr). We construct simple chemical evolution models using yields from massive star models that include rotation, which dramatically increases s-process production at low metallicity. We show that our massive star models with rotation rates of up to 50% of the critical (break-up) velocity and changes to the preferred {sup 17}O(α, γ){sup 21}Ne rate produce insufficient heavy s-elements and Pb to match the empirical distributions. For models that incorporate asymptotic giant branch yields, we find that intermediate-mass yields (with a {sup 22}Ne neutron source) alone do not reproduce the light-to-heavy s-element ratios for M4 and M22, and that a small contribution from models with a {sup 13}C pocket is required. With our assumption that {sup 13}C pockets form for initial masses below a transition range between 3.0 and 3.5 M {sub ☉}, we match the light-to-heavy s-element ratio in the s-process residual of M22 and predict a minimum enrichment timescale of between 240 and 360 Myr. Our predicted value is consistent with the 300 Myr upper limit age difference between the two groups derived from isochrone fitting.

Na7 [Fe2S6 ] , Na2 [FeS2 ] and Na2 [FeSe2 ] : New 'reduced' sodium chalcogenido ferrates

Science.gov (United States)

Stüble, Pirmin; Peschke, Simon; Johrendt, Dirk; Röhr, Caroline

2018-02-01

Three new 'reduced' FeII containing sodium chalcogenido ferrates were obtained applying a reductive synthetic route. The mixed-valent sulfido ferrate Na7 [Fe2S6 ] , which forms bar-shaped crystals with metallic greenish luster, was synthesized in pure phase from natural pyrite and elemental sodium at a maximum temperature of 800 °C. Its centrosymmetric triclinic structure (SG P 1 bar , a = 764.15(2), b = 1153.70(2), c = 1272.58(3) pm, α = 62.3325 (7) , β = 72.8345 (8) , γ = 84.6394 (8) ° , Z = 3, R1 = 0.0185) exhibits two crystallographically different [Fe2S6 ] 7 - dimers of edge-sharing [FeS4 ] tetrahedra, with somewhat larger Fe-S distances than in the fully oxidized FeIII dimers of e.g. Na6 [Fe2III S6 ] . In contrast to the localized AFM ordered pure di-ferrates(III), the Curie-Weiss behavior of the magnetic susceptibility proves the rarely observed valence-delocalized S = 9/2 state of the mixed-valent FeIII /FeII dimer. The nearly spin-only value of the magnetic moment combined with the chemical bonding not generally differing from that in pure ferrates(II) and (III), provides a striking argument, that the reduction of the local Fe spin moments observed in all condensed sulfido ferrate moieties is connected with the AFM spin ordering. The two isotypic ferrates(II) Na2 [FeS2 ] and Na2 [FeSe2 ] with chain-like structural units (SG Ibam, a = 643.54(8)/ 660.81(1), b = 1140.2(2)/1190.30(2) c = 562.90(6)/585.59(1) pm, Z = 4, R1 = 0.0372/0.0466) crystallize in the K2 [ZnO2 ] -type structure. Although representing merely further members of the common series of chalcogenido metallates(II) Na2 [MIIQ2 ] , these two new phases, together with Na6 [FeS4 ] and Li2 [FeS2 ] , are the only examples of pure FeII alkali chalcogenido ferrates. The new compounds allow for a general comparison of di- and chain ferrates(II) and (III) and mixed-valent analogs concerning the electronic and magnetic properties (including Heisenberg super-exchange and double-exchange interactions

Mössbauer spectroscopy and DFT calculations on all protonation states of the 2Fe-2S cluster of the Rieske protein

Science.gov (United States)

Müller, C. S.; Auerbach, H.; Stegmaier, K.; Wolny, J. A.; Schünemann, V.; Pierik, A. J.

2017-11-01

The Thermus thermophilus Rieske protein ( TtRP) contains a 2Fe-2S cluster with one iron (Fe-Cys) coordinated by four sulfur atoms (2xS2- and 2xCys) and one iron (Fe-His) by two sulfur and two nitrogen atoms (2xS2-, His134 and His154). Here, the protein is investigated at three pH values (6.0, 8.5 and 10.5) in order to elucidate the protonation states of the His-ligands. Examination of the effect of protonation on the electronic structure of the cluster via Mössbauer spectroscopy gives a deeper understanding of the coupling of electron transfer to the protonation state of the His-ligands. Two components (1 referring to Fe-Cys and 2 to Fe-His) with parameters typical for a diamagnetic [2Fe-2S]2+ cluster are detected. The Mössbauer parameters and the protonation state clearly correlate: while δ remains almost pH-independent with δ 1 (pH6.0) = 0.23 (± 0.01) mms- 1 and δ 1 (pH10.5) = 0.24 (± 0.01) mms- 1 for Fe-Cys, it decreases for Fe-His from δ 2 (pH6.0) = 0.34 (± 0.01) mms- 1 to δ 2 (pH10.5) = 0.28 (± 0.01) mms- 1. Δ E Q changes from Δ E Q1 (pH6.0) = 0.57 (± 0.01) mms- 1 to Δ E Q1 (pH10.5) = 0.45 (± 0.01) mms- 1 and from Δ E Q2 (pH6.0) = 1.05 (± 0.01) mms- 1 to Δ E Q2 (pH10.5) = 0.71 (± 0.01) mms- 1. Density functional theory (DFT)-calculations based on the crystal structure (pdb 1NYK) (Hunsicker-Wang et al. Biochemistry 42, 7303, 2003) have been performed for the Rieske-cluster with different His-ligand protonation states, reproducing the experimentally observed trend.

Molecular [(Fe3)–(Fe3)] and [(Fe4)–(Fe4)] coordination cluster pairs as single or composite arrays.

Science.gov (United States)

Sañudo, E Carolina; Uber, Jorge Salinas; Pons Balagué, Alba; Roubeau, Olivier; Aromí, Guillem

2012-08-06

The synthesis of molecular cluster pairs is a challenge for coordination chemists due to the potential applications of these species in molecular spintronics or quantum computing. The ligand H(4)L, 1,3-bis-(3-oxo-3-(2-hydroxyphenyl)-propionyl)-2-methoxybenzene, has been successfully used to obtain a series of such complexes using the basic Fe(III) trinuclear carboxylates as starting materials. Synthetic control has allowed the isolation of the two molecular cluster pairs that form the composite [Fe(4)O(2)(PhCO(2))(6)(H(2)L)(pz)](2)[Fe(3)O(PhCO(2))(5)(py)(H(2)L)](2) (1). The dimers of trinuclear units, [Fe(3)O(PhCO(2))(5)(H(2)O)(H(2)L)](2) (2) and [Fe(3)O(o-MePhCO(2))(5)(H(2)L)(py)](2) (3), and the dimers of tetranuclear units, [Fe(4)O(2)(PhCO(2))(6)(H(2)L)(pz)](2) (4) and [Fe(4)O(2)(o-MePhCO(2))(6)(H(2)L)(pz)](2) (5), are presented here. The magnetic properties of the reported aggregates show that they are pairs of semi-independent clusters weakly interacting magnetically as required for two-qubit quantum gates.

Fe-S cluster coordination of the chromokinesin KIF4A alters its sub-cellular localization during mitosis.

Science.gov (United States)

Ben-Shimon, Lilach; Paul, Viktoria D; David-Kadoch, Galit; Volpe, Marina; Stümpfig, Martin; Bill, Eckhard; Mühlenhoff, Ulrich; Lill, Roland; Ben-Aroya, Shay

2018-05-30

Fe-S clusters act as co-factors of proteins with diverse functions, e.g. in DNA repair. Down-regulation of the cytosolic iron-sulfur protein assembly (CIA) machinery promotes genomic instability by the inactivation of multiple DNA repair pathways. Furthermore, CIA deficiencies are associated with so far unexplained mitotic defects. Here, we show that CIA2B and MMS19, constituents of the CIA targeting complex involved in facilitating Fe-S cluster insertion into cytosolic and nuclear target proteins, co-localize with components of the mitotic machinery. Down-regulation of CIA2B and MMS19 impairs the mitotic cycle. We identify the chromokinesin KIF4A as a mitotic component involved in these effects. KIF4A binds a Fe-S cluster in vitro through its conserved cysteine-rich domain. We demonstrate in vivo that this domain is required for the mitosis-related KIF4A localization and for the mitotic defects associated with KIF4A knockout. KIF4A is the first identified mitotic component carrying such a post-translational modification. These findings suggest that the lack of Fe-S clusters in KIF4A upon down-regulation of the CIA targeting complex contributes to the mitotic defects. © 2018. Published by The Company of Biologists Ltd.

Spectroscopic properties of Fe2+ ions at tetragonal sites-Crystal field effects and microscopic modeling of spin Hamiltonian parameters for Fe2+ (S=2) ions in K2FeF4 and K2ZnF4

International Nuclear Information System (INIS)

Rudowicz, C.; Piwowarska, D.

2011-01-01

Magnetic and spectroscopic properties of the planar antiferromagnet K 2 FeF 4 are determined by the Fe 2+ ions at tetragonal sites. The two-dimensional easy-plane anisotropy exhibited by K 2 FeF 4 is due to the zero field splitting (ZFS) terms arising from the orbital singlet ground state of Fe 2+ ions with the spin S=2. To provide insight into the single-ion magnetic anisotropy of K 2 FeF 4 , the crystal field theory and the microscopic spin Hamiltonian (MSH) approach based on the tensor method is adopted. Survey of available experimental data on the crystal field energy levels and free-ion parameters for Fe 2+ ions in K 2 FeF 4 and related compounds is carried out to provide input for microscopic modeling of the ZFS parameters and the Zeeman electronic ones. The ZFS parameters are expressed in the extended Stevens notation and include contributions up to the fourth-order using as perturbation the spin-orbit and electronic spin-spin couplings within the tetragonal crystal field states of the ground 5 D multiplet. Modeling of the ZFS parameters and the Zeeman electronic ones is carried out. Variation of these parameters is studied taking into account reasonable ranges of the microscopic ones, i.e. the spin-orbit and spin-spin coupling constants, and the energy level splittings, suitable for Fe 2+ ions in K 2 FeF 4 and Fe 2+ :K 2 ZnF 4 . Conversions between the ZFS parameters in the extended Stevens notation and the conventional ones are considered to enable comparison with the data of others. Comparative analysis of the MSH formulas derived earlier and our more complete ones indicates the importance of terms omitted earlier as well as the fourth-order ZFS parameters and the spin-spin coupling related contributions. The results may be useful also for Fe 2+ ions at axial symmetry sites in related systems, i.e. Fe:K 2 MnF 4 , Rb 2 Co 1-x Fe x F 4 , Fe 2+ :Rb 2 CrCl 4 , and Fe 2+ :Rb 2 ZnCl 4 . - Highlights: → Truncated zero field splitting (ZFS) terms for Fe 2+ in K

Radiative rates for E1, E2, M1 and M2 transitions in Fe X

International Nuclear Information System (INIS)

Aggarwal, K.M.; Keenan, F.P.

2004-01-01

Energies of the 54 levels belonging to the (1s 2 2s 2 2p 6 ) 3s 2 3p 5 , 3s3p 6 , 3s 2 3p 4 3d and 3s3p 5 3d configurations of Fe X have been calculated using the GRASP code of Dyall and colleagues (1989). Additionally, radiative rates, oscillator strengths, and line strengths are calculated for all electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2), and magnetic quadrupole (M2) transitions among these levels. Comparisons are made with results available in the literature, and the accuracy of the data is assessed. Our energy levels are estimated to be accurate to better than 3%, whereas results for other parameters are probably accurate to better than 20% . Additionally, the agreement between measured and calculated lifetimes is better than 10%. (authors)

Spinel FeCo2S4 nanoflower arrays grown on Ni foam as novel binder-free electrodes for long-cycle-life supercapacitors

Science.gov (United States)

Deng, Cuifen; Yang, Lishan; Yang, Chunming; Shen, Ping; Zhao, Liping; Wang, Zhiyu; Wang, Chunhui; Li, Junhua; Qian, Dong

2018-01-01

Spinel FeCo2S4 nanoflower arrays grown on Ni foam (FeCo2S4@Ni) have been successfully fabricated via a facile hydrothermal sulfurization of the corresponding FeCo2O4 precursor. The results of X-ray diffraction and X-ray photoelectron spectroscopy characterizations affirm that partial Co2+/Co3+ ions in Co3S4 have been substituted by Fe2+/Fe3+ ions to form FeCo2S4. The obtained FeCo2S4@Ni exhibits an ultrahigh specific capacitance (1644.07 mF cm-2 at 50 mA cm-2) and a supreme cycling stability (∼100% after 10,000 cycles at 50 mA cm-2) as binder-free electrodes for supercapacitors. The cycling stability of the fabricated product is the highest among the documented ternary metallic sulfides so far. The excellent supercapacitive performance of FeCo2S4@Ni emanates from the unique architectures of Fe2Co2S4 nanoflower arrays constituted by ultrathin nanoflakes, three-dimensional porous and conductive Ni foam, and solid skeleton of Ni foam for robust connections to the Fe2Co2S4.

Facile polyol synthesis of CoFe2O4 nanosphere clusters and investigation of their electrochemical behavior in different aqueous electrolytes

Science.gov (United States)

Malaie, K.; Ganjali, M. R.; Alizadeh, T.; Norouzi, P.

2018-04-01

CoFe2O4 nanosphere clusters (CFNCs) with good crystallinity were synthesized through a facile polyol process without using any surfactant or template. FESEM images show cobalt ferrite clusters with a diameter of 200-400 nm with nanospheres grown on the surface. The electrochemical behavior of the CFNCs was investigated in different electrolytes of KOH, K2SO4, and Na2SO3 in the negative potential window of - 0.3 to - 1.3 V for possible application in supercapacitor electrodes. CFNCs exhibited best performance in KOH electrolyte with a specific capacitance of 151 F g-1 in 5 mV s-1 and a cycling stability of 87% over 1000 voltammetric cycles. These studies indicate the potential application of the as-obtained CFNCs as negative electrodes in alkaline supercapacitors.

Bacillus cereus Fnr binds a [4Fe-4S] cluster and forms a ternary complex with ResD and PlcR

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Esbelin Julia

2012-06-01

Full Text Available Abstract Background Bacillus cereus is a facultative anaerobe that causes diarrheal disease in humans. Diarrheal syndrome may result from the secretion of various virulence factors including hemolysin BL and nonhemolytic enterotoxin Nhe. Expression of genes encoding Hbl and Nhe is regulated by the two redox systems, ResDE and Fnr, and the virulence regulator PlcR. B. cereus Fnr is a member of the Crp/Fnr family of iron-sulfur (Fe-S proteins. Only its apo-form has so far been studied. A major goal in deciphering the Fnr-dependent regulation of enterotoxin genes is thus to obtain and characterize holoFnr. Results Fnr has been subjected to in vitro Fe-S cluster reconstitution under anoxic conditions. UV-visible and EPR spectroscopic analyses together with the chemical estimation of the iron content indicated that Fnr binds one [4Fe-4S]2+ cluster per monomer. Atmospheric O2 causes disassembly of the Fe-S cluster, which exhibited a half-life of 15 min in air. Holo- and apoFnr have similar affinities for the nhe and hbl promoter regions, while holoFnr has a higher affinity for fnr promoter region than apoFnr. Both the apo- and holo-form of Fnr interact with ResD and PlcR to form a ternary complex. Conclusions Overall, this work shows that incorporation of the [4Fe-4S]2+ cluster is not required for DNA binding of Fnr to promoter regions of hbl and nhe enterotoxin genes or for the formation of a ternary complex with ResD and PlcR. This points to some new unusual properties of Fnr that may have physiological relevance in the redox regulation of enterotoxin gene regulation.

Characterisation of the antiferromagnetic transition of Cu2FeSnS4, the synthetic analogue of stannite

Science.gov (United States)

Caneschi, A.; Cipriani, C.; di Benedetto, F.; Sessoli, R.

2003-04-01

Magnetisation measurements between 260 and 1.9K were performed on the synthetic analogue of stannite, Cu_2FeSnS_4, tetragonal Ioverline{4}2m. Fe(II) ions, in the high spin S=2 configuration for tetrahedral coordination, are responsible for the high temperature paramagnetism. In agreement with Bernardini et al. (2000), an antiferromagnetic transition was observed, lowering temperature below 8K. Refined measurements evidenced a T_N=6.1K for the Néel temperature. In spite of a small difference, observed in the behaviour between the zero-field cooled and the field cooled curves, which suggests the possible presence of a spin-glass phase, the AC measurements did not provide evidence of dependence of the magnetic susceptibility on frequency, as expected in spin-glass systems. On the basis of the experimental data, in agreement with the existent literature (Fries et al., 1997), a collinear antiferromagnetic structure should be preferred. The Fe ions, in fact, are distributed in two sublattices obtained by magnetic differentiation of the symmetry equivalent (0,0,0) and (frac{1}{2}frac{1}{2}frac{1}{2}) Fe positions (wyckoff: 2a). The low value for the Nèel temperature, as compared e.g. to the room-temperature antiferromagnet chalcopyrite (CuFeS_2), very close in composition and structure to stannite, is to be related to the increased distance between the Fe ions (˜6.6Å). This weak interaction is not detected in natural samples, where diamagnetic Zn(II) replace paramagnetic Fe(II), thus increasing the mean Fe-Fe distance. Fries, T., Shapira, Y., Palacio, F., Moròn, M.C., McIntyre, G.J., Kershaw, R., Wold, A. and McNiff, E.J. Jr. (1997): Mangetic ordering of the antiferromagnet Cu_2MnSnS_4 from magnetisation and neutron-scattering measurements. Phys. Rev. B, 6(9), 5424-5431 Bernardini, G.P., Borrini, D., Caneschi, A. Di Benedetto, F., Gatteschi, D., Ristori, S. and Romanelli, M. (2000): EPR and SQUID magnetometry study of Cu_2FeSnS_4 (stannite) and Cu_2ZnSnS_4 (kesterite

Synthesis of novel spherical Fe_3O_4@Ni_3S_2 composite as improved anode material for rechargeable nickel-iron batteries

International Nuclear Information System (INIS)

Li, Jing; Guo, Litan; Shangguan, Enbo; Yue, Mingzhu; Xu, Min; Wang, Dong; Chang, Zhaorong; Li, Quanmin

2017-01-01

Highlights: • Fe_3O_4@Ni_3S_2 microspheres are fabricated through a facile method for the first time. • Fe_3O_4@Ni_3S_2 is firstly proposed as alkaline anode materials for Ni/Fe batteries. • Fe_3O_4@Ni_3S_2 shows enhanced high-rate capability and improved cycle stability. • Ni_3S_2 can suppress the passivation and hydrogen evolution behavior of the iron anode. - Abstract: Fe_3O_4@Ni_3S_2 microspheres as a novel alkaline anode material have been successfully fabricated through a four-step process for the first time. In this composite, Ni_3S_2 nanoparticles are coated tightly on the surface of Fe_3O_4 microspheres. Compared with the pure Fe_3O_4 and Fe_3O_4@NiO microspheres, the proposed Fe_3O_4@Ni_3S_2 delivers a significantly improved high-rate performance and enhanced cycling stability. At a high discharge rate of 1200 mA g"−"1, the specific capacity of the Fe_3O_4@Ni_3S_2 is ∼481.2 mAh g"−"1 in comparison with ∼83.7 mAh g"−"1 for the pure Fe_3O_4. After 100 cycles at 120 mA g"−"1, the Fe_3O_4@Ni_3S_2 can achieve a capacity retention of 95.1%, while the value for the pure Fe_3O_4 electrode is only 52.5%. The favorable electrochemical performance of the Fe_3O_4@Ni_3S_2 is mainly attributed to the beneficial impact of Ni_3S_2. The Ni_3S_2 layer as a useful additive is significantly conducive to lessening the formation of Fe(OH)_2 passivation layer, enhancing the electronic conductivity, improving the reaction reversibility and suppressing the hydrogen evolution reaction of the alkaline iron anode. Owing to its outstanding electrochemical properties, we believe that the novel Fe_3O_4@Ni_3S_2 composite is potentially a promising candidate for anode material of alkaline iron-based batteries.

Magnetic Fe2MO4 (M:Fe, Mn) activated carbons: Fabrication, characterization and heterogeneous Fenton oxidation of methyl orange

International Nuclear Information System (INIS)

Nguyen, Thi Dung; Phan, Ngoc Hoa; Do, Manh Huy; Ngo, Kim Tham

2011-01-01

We present a simple and efficient method for the fabrication of magnetic Fe 2 MO 4 (M:Fe and Mn) activated carbons (Fe 2 MO 4 /AC-H, M:Fe and Mn) by impregnating the activated carbon with simultaneous magnetic precursor and carbon modifying agent followed by calcination. The obtained samples were characterized by nitrogen adsorption isotherms, X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM), and the catalytic activity in heterogeneous Fenton oxidation of methyl orange (MO) was evaluated. The resulting Fe 2 MnO 4 /AC-H showed higher catalytic activity in the methyl orange oxidation than Fe 3 O 4 /AC-H. The effect of operational parameters (pH, catalyst loading H 2 O 2 dosage and initial MO concentration) on degradation performance of the oxidation process was investigated. Stability and reusability of selected catalyst were also tested.

Small-volume potentiometric titrations: EPR investigations of Fe-S cluster N2 in mitochondrial complex I.

Science.gov (United States)

Wright, John J; Salvadori, Enrico; Bridges, Hannah R; Hirst, Judy; Roessler, Maxie M

2016-09-01

EPR-based potentiometric titrations are a well-established method for determining the reduction potentials of cofactors in large and complex proteins with at least one EPR-active state. However, such titrations require large amounts of protein. Here, we report a new method that requires an order of magnitude less protein than previously described methods, and that provides EPR samples suitable for measurements at both X- and Q-band microwave frequencies. We demonstrate our method by determining the reduction potential of the terminal [4Fe-4S] cluster (N2) in the intramolecular electron-transfer relay in mammalian respiratory complex I. The value determined by our method, E m7 =-158mV, is precise, reproducible, and consistent with previously reported values. Our small-volume potentiometric titration method will facilitate detailed investigations of EPR-active centres in non-abundant and refractory proteins that can only be prepared in small quantities. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Phase relations in the systems M2MoO4-Cr2(MoO4)3-Zr(MoO4)2 (M=Li, Na, or Rb)

International Nuclear Information System (INIS)

Bazarov, B.G.; Chimitova, O.D.; Bazarova, Ts.T.; Arkhincheeva, S.I.; Bazarova, Zh.G.

2008-01-01

Phase equilibria in the systems M 2 MoO 4 -Cr 2 (MoO 4 ) 3 -Zr(MoO 4 ) 2 (M=Li, Na, or Rb) were investigated by X-ray powder diffraction analysis, DTA, and IR spectroscopy. The subsolidus structure of the phase diagrams of the systems under study was established. Two phases are formed in the Rb 2 MoO 4 -Cr 2 (MoO 4 ) 3 -Zr(MoO 4 ) 2 system with the molar ratios of the starting components equal to 5:1:1 (S 2 ) and 1:1:1 (S 1 ). Proceeding from isostructural character of Rb 5 FeHf(MoO 4 ) 6 and S 2 , the unit cell parameters are determined for S 2 [ru

Electronic and magnetic properties of organic conductors (DMET) sub 2 MBr sub 4 (M=Fe, Ga)

CERN Document Server

Enomoto, K; Enoki, T; Yamaura, J I

2003-01-01

(DMET) sub 2 MBr sub 4 (M=Fe, Ga) are isostructural organic conductors whose crystal structure consists of an alternate stacking of quasi one-dimensional chain-based donor layers and anion square lattices. The resistivity, ESR, magnetic susceptibility, magnetization, and magnetoresistance of these salts were investigated in order to clarify the correlation between the electronic structure and the magnetism. The electronic structures of both salts are metallic down to T sub M sub I - 40 K, below which a Mott insulating state is stabilized, accompanied by an SDW transition at T sub S sub D sub W - 25 K. The FeBr sub 4 salt with Fe sup 3 sup + (S=5/2) localized spins undergoes an antiferromagnetic transition at T sub N = 3.7 K. In the FeBr sub 4 salt, the magnetization curves, which show field-direction-dependent anomalies in addition to a spin-flop transition, are demonstrated to have a participation of donor pi-electron spins in the magnetization processes. The field dependence of the magnetoresistances below ...

Impact of mutations on the midpoint potential of the [4Fe-4S]+1,+2 cluster and on catalytic activity in electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO).

Science.gov (United States)

Usselman, Robert J; Fielding, Alistair J; Frerman, Frank E; Watmough, Nicholas J; Eaton, Gareth R; Eaton, Sandra S

2008-01-08

Electron-transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is an iron-sulfur flavoprotein that accepts electrons from electron-transfer flavoprotein (ETF) and reduces ubiquinone from the Q-pool. ETF-QO contains a single [4Fe-4S]2+,1+ cluster and one equivalent of FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. Mutations were introduced by site-directed mutagenesis of amino acids in the vicinity of the iron-sulfur cluster of Rhodobacter sphaeroides ETF-QO. Y501 and T525 are equivalent to Y533 and T558 in the porcine ETF-QO. In the porcine protein, these residues are within hydrogen-bonding distance of the Sgamma of the cysteine ligands to the iron-sulfur cluster. Y501F, T525A, and Y501F/T525A substitutions were made to determine the effects on midpoint potential, activity, and EPR spectral properties of the cluster. The integrity of the mutated proteins was confirmed by optical spectra, EPR g-values, and spin-lattice relaxation rates, and the cluster to flavin point-dipole distance was determined by relaxation enhancement. Potentiometric titrations were monitored by changes in the CW EPR signals of the cluster and semiquinone. Single mutations decreased the midpoint potentials of the iron-sulfur cluster from +37 mV for wild type to -60 mV for Y501F and T525A and to -128 mV for Y501F/T525A. Lowering the midpoint potential resulted in a decrease in steady-state ubiquinone reductase activity and in ETF semiquinone disproportionation. The decrease in activity demonstrates that reduction of the iron-sulfur cluster is required for activity. There was no detectable effect of the mutations on the flavin midpoint potentials.

Electrical properties of FeGa2S4

International Nuclear Information System (INIS)

Niftiev, N.N.; Alidzhanov, M.A.; Tagiev, O.B.; Mamedov, F.M.

2004-01-01

Temperature dependence of the electrical conductivity and current-voltage characteristics (CVCs) of FeGa 2 S 4 crystals have been studied. It has been shown that the current in the nonlinear range of CVCs is caused by the field effect. The activation energy of carriers and the trap concentrations have been determined

Development of novel exchange spring magnet by employing nanocomposites of CoFe_2O_4 and CoFe_2

International Nuclear Information System (INIS)

Safi, Rohollah; Ghasemi, Ali; Shoja-Razavi, Reza; Tavoosi, Majid

2016-01-01

CoFe_2O_4−CoFe2 hard–soft nanocomposites were prepared via reduction of the cobalt ferrite CoFe_2O_4 in hydrogen atmosphere at different temperature. The structure and the room temperature magnetization of the samples were characterized by X-ray diffraction, field emission scanning electron microscope (FESEM) and vibrating sample magnetometer (VSM). It was found that the saturation magnetization of the nanocomposite powders increases by reduction temperature while their coercivity decreases. The highest M_r/M_s ratio of 0.52 was obtained for sample reduced at 550 °C. Single smooth hysteresis loops of nanocomposites show that these nanocomposites behave as the single-phase materials. This result indicates the presence of exchange coupling between two different hard and soft phases. - Highlights: • CoFe_2O_4–CoFe_2 was successfully synthesized by reduction diffusion process. • Two phases are effectively exchange coupled in nanocomposite. • Single smooth hysteresis loop was developed in nanocomposites.

Magnetocapacidad en nanopartículas de Fe3O4 y NiFe2O4

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Mira, J.

2010-02-01

Full Text Available We have synthesized NiFe2O4 (φ∼ 6 nm and Fe3O4 (φ∼ 30 nm magnetic nanoparticles by solvothermal synthesis; furthermore the Fe3O4 nanoparticles have been coated with a SiO2 shell of approximately 5 nm of thickness by the Stöber method. In the study of the dielectric properties as a function of the frequency, temperature and applied magnetic field, we observe a magnetocapacitive behavior (MC at room temperature and under a moderate magnetic field (H=0.5T, that is specially important in the case of the Fe3O4, nanoparticles (MC≈ 6%. On the other hand, the NiFe2O4 and Fe3O4@SiO2 samples present smaller magnetocapacitive effects: MC≈ 2% y MC≈ 1%, respectively. These MC values, that are higher than those reported in the literature for other related magnetic nanoparticles, corroborate the theoretical model proposed by Catalán in which the combination of Maxwell-Wagner effects and magnetoresistance promote the appearance of stronger magnetocapacitive effects.Hemos preparado nanopartículas magnéticas de NiFe2O4 (φ∼ 6 nm y Fe3O4 (φ∼ 30 nm mediante el método de síntesis solvotermal; además estas últimas han sido recubiertas con una capa de SiO2 de unos 5 nm de espesor mediante el método de Stöber. Al estudiar el comportamiento dieléctrico en función de la frecuencia, temperatura y campo magnético aplicado, observamos un comportamiento magnetocapacitivo (MC a temperatura ambiente y bajo un campo magnético moderado (H= 0.5 T que es especialmente importante en el caso de las nanopartículas de Fe3O4 (MC≈ 6%. Por su parte las muestras de NiFe2O4 y Fe3O4@SiO2 presentan efectos magnetocapacitivos menores: MC≈ 2% y MC≈ 1%, respectivamente. Estos valores de MC, que son considerablemente superiores a los descritos hasta el momento para otras nanopartículas magnéticas, corroboran la predicción teórica de Catalán de que la combinación de efecto Maxwell-Wagner con efectos magnetorresitivos potencian la aparición de fen

Pentacarbonyl-1κ2C,2κ3C-[(diphenylphosphoryldiphenylphosphane-1κP]-μ-ethane-1,2-dithiolato-1:2κ4S,S′:S,S′-diiron(I(Fe—Fe

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Xu-Feng Liu

2011-11-01

Full Text Available The dinuclear title compound, [Fe2(C2H4S2(C24H20OP2(CO5] or (μ-SCH2CH2S-μFe2(CO5[Ph2PP(OPh2], contains a butterfly-shaped Fe2S2 core in which the Fe...Fe separation is 2.5275 (6 Å. One of the Fe atoms is also coordinated to three carbonyl ligands and the other to two carbonyl ligands and one phosphane ligand [Ph2PP(OPh2]. Both Fe-atom geometries could be described as grossly distorted octahedral and the Ph2PP(OPh2 ligand lies trans to the Fe...Fe link.

Spin structures of S = 5/2 antiferromagnetic triangular lattices: AAg{sub 2}M[VO{sub 4}]{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Moeller, Angela; Amuneke, Ngozi E.; Tapp, Joshua [Department of Chemistry and TcSUH, University of Houston (United States); Cruz, Clarina R. de la [Quantum Condensed Matter Division, ORNL, Oak Ridge (United States)

2015-07-01

The AAg{sub 2}M[VO{sub 4}]{sub 2} compounds present a unique series for studying structure-property relationships. The size of the A cation (Ba{sup 2+}, K{sup +}, Rb{sup +}, or Ag{sup +}) controls (i) the inter-layer distances between the magnetic triangular lattices (M, here Mn{sup 2+} or Fe{sup 3+}) and (ii) the distortion of the non-magnetic vanadate units. The crystal and magnetic structures were refined from neutron diffraction data under applied fields (ORNL, HB2A) and reveal the complex magnetic phase diagrams of frustrated S=5/2 triangular lattices with axial and XY-anisotropy, respectively.

Quaternary (FeIn{sub 2}S{sub 4}){sub x}(MnIn{sub 2}S{sub 4}){sub 1-x} alloys and photosensitive structures on their basis

Energy Technology Data Exchange (ETDEWEB)

Bodnar, I. V. [Belarusian State University of Informatics and Radioelectronics (Belarus); Rud, V. Yu., E-mail: rudvas.spb@gmail.com [St. Petersburg State Polytechnical University (Russian Federation); Rud, Yu. V. [Russian Academy of Sciences, Ioffe Physical Technical Institute (Russian Federation); Lozhkin, D. V. [Belarusian State University of Informatics and Radioelectronics (Belarus)

2011-07-15

Using directional crystallization of the melt of the (FeIn{sub 2}S{sub 4}){sub x}(MnIn{sub 2}S{sub 4}){sub 1-x} alloy, homogeneous crystals of a similar atomic composition are grown over the entire range of compositions 1 {>=} x {>=} 0. It is established that the crystals of the continuous series of quaternary alloys in the range x = 0-1 crystallize in the spinel structure and lattice parameter a linearly depends on x. It is established that it is possible to obtain In(Al)/(FeIn{sub 2}S{sub 4}){sub x}(MnIn{sub 2}S{sub 4}){sub 1-x} photosensitive structures. Room-temperature spectra of relative quantum efficiency of photoconversion of the In(Al)/(FeIn{sub 2}S{sub 4}){sub x}(MnIn{sub 2}S{sub 4}){sub 1-x} structures fabricated for the first time are obtained. From the analysis of these spectra, activation energies of direct and indirect band-to-band transitions for the crystals of the (FeIn{sub 2}S{sub 4}){sub x}(MnIn{sub 2}S{sub 4}){sub 1-x} alloys are determined and the dependence of these parameters on the composition of the position-disordered phases of mentioned alloys is discussed. It is concluded that the crystals of the (FeIn{sub 2}S{sub 4}){sub x}(MnIn{sub 2}S{sub 4}){sub 1-x} alloys can be used in broadband photoconverters of optical radiation.

Ground and excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters: Insight into the electronic structure of the [Fe(H2O)6]2+ – [Fe(H2O)6]3+ complex

Energy Technology Data Exchange (ETDEWEB)

Miliordos, Evangelos; Xantheas, Sotiris S.

2015-04-14

We report the ground and low lying electronically excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters using multi-configuration electronic structure theory. In particular, we have constructed the Potential Energy Curves (PECs) with respect to the iron-oxygen distance when removing all water ligands at the same time from the cluster minima and established their correlation to the long range dissociation channels. Due to the fact that both the second and third ionization potentials of iron are larger than the one for water, the ground state products asymptotically correlate with dissociation channels that are repulsive in nature at large separations as they contain at least one H2O+ fragment and a positive metal center. The most stable equilibrium structures emanate – via intersections and/or avoided crossings – from the channels consisting of the lowest electronic states of Fe2+(5D; 3d6) or Fe3+(6S; 3d5) and six neutral water molecules. Upon hydration, the ground state of Fe2+(H2O)6 is a triply (5Tg) degenerate one with the doubly (5Eg) degenerate state lying slightly higher in energy. Similarly, Fe3+(H2O)6 has a ground state of 6Ag symmetry under Th symmetry. We furthermore examine a multitude of electronically excited states of many possible spin multiplicities, and report the optimized geometries for several selected states. The PECs for those cases are characterized by a high density of states. Focusing on the ground and the first few excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters, we studied their mutual interaction in the gas phase. We obtained the optimal geometries of the Fe2+(H2O)6 – Fe3+(H2O)6 gas phase complex for different Fe–Fe distances. For distances shorter than 6.0 Å, the water molecules in the respective first solvation shells located between the two metal centers were found to interact via weak hydrogen bonds. We examined a total of ten electronic states for this complex, including those corresponding to the

Pressure-induced phase transition in KxFe2-yS2

International Nuclear Information System (INIS)

Tsuchiya, Yuu; Ikeda, Shugo; Kobayashi, Hisao; Zhang, Xiao-Wei; Kishimoto, Shunji; Kikegawa, Takumi; Hirao, Naohisa; Kawaguchi, Saori I.; Ohishi, Yasuo

2017-01-01

The structural and electronic properties of high-quality K 0.66(6) Fe 1.75(10) S 2 single crystals have been investigated by angle-resolved X-ray diffraction and 57 Fe nuclear forward scattering using synchrotron radiation under pressure at room temperature. The samples exhibit phase separation into antiferromagnetic ordered K 2 Fe 4 S 5 and nonmagnetic K x Fe 2 S 2 phases. It was found that a pressure-induced phase transition occurs at p c = 5.9(4) GPa with simultaneous suppression of the antiferromagnetic and Fe vacancy orders. >From the results of 57 Fe nuclear forward scattering, the refined magnetic hyperfine field remains unchanged with pressure below p c , suggesting that the Néel temperature does not decrease with pressure up to p c . Above p c , all Fe atoms in K 0.66 Fe 1.75 S 2 are in the same nonmagnetic state. A discontinuous increase in the center shift was observed at p c , reflecting a change in the Fe electronic state in K 0.66 Fe 1.75 S 2 . (author)

First principles prediction of the magnetic properties of Fe-X6 (X = S, C, N, O, F) doped monolayer MoS2

KAUST Repository

Feng, Nan; Mi, Wenbo; Cheng, Yingchun; Guo, Zaibing; Schwingenschlö gl, Udo; Bai, Haili

2014-01-01

Using first-principles calculations, we have investigated the electronic structure and magnetic properties of Fe-X 6 clusters (X = S, C, N, O, and F) incorporated in 4 4 monolayer MoS 2, where a Mo atom is substituted by Fe and its nearest S atoms are substituted by C, N, O, and F. Single Fe and Fe-F 6 substituions make the system display half-metallic properties, Fe-C 6 and Fe-N 6 substitutions lead to a spin gapless semiconducting behavior, and Fe-O 6 doped monolayer MoS 2 is semiconducting. Magnetic moments of 1.93, 1.45, 3.18, 2.08, and 2.21...? B are obtained for X = S, C, N, O, and F, respectively. The different electronic and magnetic characters originate from hybridization between the X and Fe/Mo atoms. Our results suggest that cluster doping can be an efficient strategy for exploring two-dimensional diluted magnetic semiconductors.

First principles prediction of the magnetic properties of Fe-X6 (X = S, C, N, O, F) doped monolayer MoS2

KAUST Repository

Feng, Nan

2014-02-05

Using first-principles calculations, we have investigated the electronic structure and magnetic properties of Fe-X 6 clusters (X = S, C, N, O, and F) incorporated in 4 4 monolayer MoS 2, where a Mo atom is substituted by Fe and its nearest S atoms are substituted by C, N, O, and F. Single Fe and Fe-F 6 substituions make the system display half-metallic properties, Fe-C 6 and Fe-N 6 substitutions lead to a spin gapless semiconducting behavior, and Fe-O 6 doped monolayer MoS 2 is semiconducting. Magnetic moments of 1.93, 1.45, 3.18, 2.08, and 2.21...? B are obtained for X = S, C, N, O, and F, respectively. The different electronic and magnetic characters originate from hybridization between the X and Fe/Mo atoms. Our results suggest that cluster doping can be an efficient strategy for exploring two-dimensional diluted magnetic semiconductors.

Impact of Mutations on the Midpoint Potential of the [4Fe-4S]+1,+2 Cluster and on Catalytic Activity in Electron Transfer Flavoprotein-ubiquinone Oxidoreductase (ETF-QO)†

Science.gov (United States)

Usselman, Robert J.; Fielding, Alistair J.; Frerman, Frank E.; Watmough, Nicholas J.; Eaton, Gareth R.; Eaton, Sandra S.

2011-01-01

Electron transfer flavoprotein - ubiquinone oxidoreductase (ETF-QO) is an iron-sulfur flavoprotein that accepts electrons from electron-transfer flavoprotein (ETF) and reduces ubiquinone from the Q-pool. ETF-QO contains a single [4Fe-4S]2+,1+ cluster and one equivalent of FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. Mutations were introduced by site-directed mutagenesis of amino acids in the vicinity of the iron-sulfur cluster of Rhodobacter sphaeroides ETF-QO. Y501 and T525 are equivalent to Y533 and T558 in the porcine ETF-QO. In the porcine protein, these residues are within hydrogen bonding distance of the Sγ of the cysteine ligands to the iron-sulfur cluster. Y501F, T525A, and Y501F/T525A substitutions were made to determine the effects on midpoint potential, activity, and EPR spectral properties of the cluster. The integrity of the mutated proteins was confirmed by optical spectra, EPR g-values, and spin-lattice relaxation rates, and the cluster to flavin point-dipole distance was determined by relaxation enhancement. Potentiometric titrations were monitored by changes in the CW EPR signals of the cluster and semiquinone. Single mutations decreased the mid-point potentials of the iron-sulfur cluster from +37 mV for wild type to −60 mV for Y501F and T525A and to −128 mV for Y501F/T525A. Lowering the midpoint potential resulted in a decrease in steady-state ubiquinone reductase activity and in ETF semiquinone disproportionation. The decrease in activity demonstrates that reduction of the iron-sulfur cluster is required for activity. There was no detectable effect of the mutations on the flavin midpoint potentials. PMID:18069858

K2 and M4: A Unique Opportunity to Unlock the Mysteries of Globular Clusters

Science.gov (United States)

Kuehn, Charles A.; Stello, Dennis; Campbell, Simon; Drury, Jason; de Silva, Gayandhi; Maclean, Ben; Bedding, Timothy R.; Huber, Daniel

2016-01-01

One of the most exciting opportunities presented by K2 is the ability to study variable stars in globular clusters (GCs). The K2 observations allow us to perform ensemble asteroseismology of a population that is much older than that in the open clusters in the original Kepler field. This should help us answer long-standing questions concerning mass loss on the red giant branch and the spread in masses along the horizontal branch. By combining the asteroseismic data with chemical tagging of sub-populations from spectroscopy, we hope to better constrain stellar evolution models and potentially shed some light on the formation history of GCs. The very crowded nature of stars in GCs poses a challenge, however, due to Kepler's large pixels. M4, observed during K2's campaign 2, presents an excellent opportunity to study GCs with a combination of K2 and ground-based data. M4 is one of the two nearest GCs and thus should appear less crowded and brighter; in fact M4 is likely the only GC whose horizontal branch stars, other than RR Lyraes, will be accessible with K2. We discuss our method of obtaining photometry for the stars in M4 and present sample lightcurves for different classes of oscillating stars in the cluster. We also discuss efforts to use ground-based observations to increase the utility of the K2 dataset.

High-efficiency Thin-film Fe₂SiS₄ and Fe₂GeS₄-based Solar Cells Prepared from Low-Cost Solution Precursors. Final Report

Energy Technology Data Exchange (ETDEWEB)

Radu, Daniela Rodica [Delaware State Univ., Dover, DE (United States); Univ. of Delaware, Newark, DE (United States); Liu, Mimi [Delaware State Univ., Dover, DE (United States); Hwang, Po-yu [Delaware State Univ., Dover, DE (United States); Berg, Dominik [Rowan Univ., Glassboro, NJ (United States); Dobson, Kevin [Univ. of Delaware, Newark, DE (United States). Inst. of Energy Conversion (IEC)

2017-12-28

The project aimed to provide solar energy education to students from underrepresented groups and to develop a novel, nano-scale approach, in utilizing Fe₂SiS₄ and Fe₂GeS₄ materials as precursors to the absorber layer in photovoltaic thin-film devices. The objectives of the project were as follows: 1. Develop and implement one solar-related course at Delaware State University and train two graduate students in solar research. 2. Fabricate and characterize high-efficiency (larger than 7%) Fe₂SiS₄ and Fe₂GeS₄-based solar devices. The project has been successful in both the educational components, implementing the solar course at DSU as well as in developing multiple routes to prepare the Fe₂GeS₄ with high purity and in large quantities. The project did not meet the efficiency objective, however, a functional solar device was demonstrated.

Synthesis and characterization of sulfur-voided cubanes. Structural analogues for the MoFe(3)S(3) subunit in the nitrogenase cofactor.

Science.gov (United States)

Coucouvanis, Dimitri; Han, Jaehong; Moon, Namdoo

2002-01-16

A new class of Mo/Fe/S clusters with the MoFe(3)S(3) core has been synthesized in attempts to model the FeMo-cofactor in nitrogenase. These clusters are obtained in reactions of the (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (I), (n)Pr (II)] clusters with CO. The new clusters include those preliminarily reported: (Cl(4)-cat)MoFe(3)S(3)(PEt(3))(2)(CO)(6) (III), (Cl(4)-cat)(O)MoFe(3)S(3)(PEt(3))(3)(CO)(5) (IV), (Cl(4)-cat)(Pyr)MoFe(3)S(3)(PEt(3))(2)(CO)(6) (VI), and (Cl(4)-cat)(Pyr)MoFe(3)S(3)(P(n)Pr(3))(3)(CO)(4) (VIII). In addition the new (Cl(4)-cat)(O)MoFe(3)S(3)(P(n)Pr(3))(3)(CO)(5) cluster (IVa), the (Cl(4)-cat)(O)MoFe(3)S(3)(PEt(3))(2)(CO)(6)cluster (V), the (Cl(4)-cat)(O)MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (Va), the (Cl(4)-cat)(Pyr)MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (VIa), and the (Cl(4)-cat)(P(n)Pr(3))MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (VII) also are reported. Clusters III-VIII have been structurally and spectroscopically characterized. EPR, zero-field (57)Fe-Mössbauer spectroscopic characterizations, and magnetic susceptibility measurements have been used for a tentative assignment of the electronic and oxidation states of the MoFe(3)S(3) sulfur-voided cuboidal clusters. A structural comparison of the clusters with the MoFe(3)S(3) subunit of the FeMo-cofactor has led to the suggestion that the storage of reducing equivalents into M-M bonds, and their use in the reduction of substrates, may occur with the FeMo-cofactor, which also appears to have M-M bonding. On the basis of this argument, a possible N(2)-binding and reduction mechanism on the FeMoco-cofactor is proposed.

Magnetism by interfacial hybridization and p-type doping of MoS(2) in Fe(4)N/MoS(2) superlattices: a first-principles study.

Science.gov (United States)

Feng, Nan; Mi, Wenbo; Cheng, Yingchun; Guo, Zaibing; Schwingenschlögl, Udo; Bai, Haili

2014-03-26

Magnetic and electronic properties of Fe4N(111)/MoS2(√3 × √3) superlattices are investigated by first-principles calculations, considering two models: (I) Fe(I)Fe(II)-S and (II) N-S interfaces, each with six stacking configurations. In model I, strong interfacial hybridization between Fe(I)/Fe(II) and S results in magnetism of monolayer MoS2, with a magnetic moment of 0.33 μB for Mo located on top of Fe(I). For model II, no magnetism is induced due to weak N-S interfacial bonding, and the semiconducting nature of monolayer MoS2 is preserved. Charge transfer between MoS2 and N results in p-type MoS2 with Schottky barrier heights of 0.5-0.6 eV. Our results demonstrate that the interfacial geometry and hybridization can be used to tune the magnetism and doping in Fe4N(111)/MoS2(√3 × √3) superlattices.

Homoleptic Diphosphacyclobutadiene Complexes [M(η4-P2C2R2)2]x- (M=Fe, Co; x=0, 1)

NARCIS (Netherlands)

Wolf, Robert; Ehlers, A.W.; Khusniyarov, M.M.; Hartl, F.; de Bruin, B.; Long, G.J.; Grandjean, F.; Schappacher, F.M.; Pöttgen, R.; Slootweg, J.C.; Lutz, M.; Spek, A.L.; Lammertsma, K.

2011-01-01

The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands are reported. Compounds [K([18]crown-6)ACHTUNGTRENUNG(thf)2][Fe(η4- P2C2tBu2)2] (K1), [K([18]crown-6)- ACHTUNGTRENUNG(thf)2][Co(h4-P2C2tBu2)2] (K2), and

Homoleptic Diphosphacyclobutadiene Complexes [M(η(4)-P2C2R2)(2]x- (M = Fe, Co; x=0, 1)

NARCIS (Netherlands)

Wolf, R.; Ehlers, A.W.; Khusniyarov, M.M.; Hartl, F.; de Bruin, B.; Long, G.J.; Grandjean, F.; Schappacher, F.M.; Pöttgen, R.; Slootweg, J.C.; Lutz, M.; Spek, A.L.; Lammertsma, K.

2010-01-01

The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands are reported. Compounds [K([18]crown-6)(thf)(2)[Fe(η(4)-P(2)C(2)tBu(2))(2)] (K1), [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)tBu(2))(2)] (K2), and

Electronic and magnetic properties of organic conductors (DMET)2MBr4 (M=Fe, Ga)

International Nuclear Information System (INIS)

Enomoto, Kengo; Miyazaki, Akira; Enoki, Toshiaki; Yamaura, Jun-ichi

2003-01-01

(DMET) 2 MBr 4 (M=Fe, Ga) are isostructural organic conductors whose crystal structure consists of an alternate stacking of quasi one-dimensional chain-based donor layers and anion square lattices. The resistivity, ESR, magnetic susceptibility, magnetization, and magnetoresistance of these salts were investigated in order to clarify the correlation between the electronic structure and the magnetism. The electronic structures of both salts are metallic down to T MI - 40 K, below which a Mott insulating state is stabilized, accompanied by an SDW transition at T SDW - 25 K. The FeBr 4 salt with Fe 3+ (S=5/2) localized spins undergoes an antiferromagnetic transition at T N = 3.7 K. In the FeBr 4 salt, the magnetization curves, which show field-direction-dependent anomalies in addition to a spin-flop transition, are demonstrated to have a participation of donor π-electron spins in the magnetization processes. The field dependence of the magnetoresistances below T N tracks faithfully that of the magnetization, where the donor π-electrons and Fe 3+ d-electrons are responsible for the former and the latter, respectively. This clearly demonstrates the presence of the π-d interaction that plays an important role in the interplay between electron transport and magnetism. (author)

Polaronic transport and thermoelectricity in Fe1 -xCoxSb2S4 (x =0 , 0.1, and 0.2)

Science.gov (United States)

Liu, Yu; Kang, Chang-Jong; Stavitski, Eli; Du, Qianheng; Attenkofer, Klaus; Kotliar, G.; Petrovic, C.

2018-04-01

We report a study of Co-doped berthierite Fe1 -xCoxSb2S4 (x =0 , 0.1, and 0.2). The alloy series of Fe1 -xCoxSb2S4 crystallize in an orthorhombic structure with the Pnma space group, similar to FeSb2, and show semiconducting behavior. The large discrepancy between activation energy for conductivity, Eρ (146 ˜270 meV ), and thermopower, ES (47 ˜108 meV ), indicates the polaronic transport mechanism. Bulk magnetization and heat-capacity measurements of pure FeSb2S4 (x =0 ) exhibit a broad antiferromagnetic transition (TN=46 K ) followed by an additional weak transition (T*=50 K ). Transition temperatures (TN and T*) slightly decrease with increasing Co content x . This is also reflected in the thermal conductivity measurement, indicating strong spin-lattice coupling. Fe1 -xCoxSb2S4 shows relatively high value of thermopower (up to ˜624 μ V K-1 at 300 K) and thermal conductivity much lower when compared to FeSb2, a feature desired for potential applications based on FeSb2 materials.

Magnetic Fe{sub 2}MO{sub 4} (M:Fe, Mn) activated carbons: Fabrication, characterization and heterogeneous Fenton oxidation of methyl orange

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Thi Dung [Institute of Chemical Technology, Vietnamese Academy of Science and Technology, 01 Mac Dinh Chi, District 1, Ho Chi Minh (Viet Nam); Phan, Ngoc Hoa [Department of Chemical Technology, Hochiminh University of Technology, 268 Ly Thuong Kiet, District 10, Ho Chi Minh (Viet Nam); Do, Manh Huy, E-mail: huydoma@vast-hcm.ac.vn [Institute of Chemical Technology, Vietnamese Academy of Science and Technology, 01 Mac Dinh Chi, District 1, Ho Chi Minh (Viet Nam); Ngo, Kim Tham [Institute of Chemical Technology, Vietnamese Academy of Science and Technology, 01 Mac Dinh Chi, District 1, Ho Chi Minh (Viet Nam); College of science, Can Tho University, 3/2, Can Tho (Viet Nam)

2011-01-30

We present a simple and efficient method for the fabrication of magnetic Fe{sub 2}MO{sub 4} (M:Fe and Mn) activated carbons (Fe{sub 2}MO{sub 4}/AC-H, M:Fe and Mn) by impregnating the activated carbon with simultaneous magnetic precursor and carbon modifying agent followed by calcination. The obtained samples were characterized by nitrogen adsorption isotherms, X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM), and the catalytic activity in heterogeneous Fenton oxidation of methyl orange (MO) was evaluated. The resulting Fe{sub 2}MnO{sub 4}/AC-H showed higher catalytic activity in the methyl orange oxidation than Fe{sub 3}O{sub 4}/AC-H. The effect of operational parameters (pH, catalyst loading H{sub 2}O{sub 2} dosage and initial MO concentration) on degradation performance of the oxidation process was investigated. Stability and reusability of selected catalyst were also tested.

Magnetic properties of M0.3Fe2.7O4 (M = Fe, Zn and Mn) ferrites nanoparticles

Science.gov (United States)

Modaresi, Nahid; Afzalzadeh, Reza; Aslibeiki, Bagher; Kameli, Parviz

2018-06-01

In the present article a comparative study on the structural and magnetic properties of nano-sized M0.3Fe0.7Fe2O4 (M = Fe, Zn and Mn) ferrites have been reported. The X-ray diffraction (XRD) patterns show that the crystallite size depends on the cation distribution. The Rietveld refinement of XRD patterns using MAUD software determines the distribution of cations and unit cell dimensions. The magnetic measurements show that the maximum and minimum value of saturation magnetization is obtained for Zn and Mn doped samples, respectively. The peak temperature of AC magnetic susceptibility of Zn and Fe doped samples below 300 K shows the superparamagnetic behavior in these samples at room temperature. the AC susceptibility results confirm the presence of strong interactions between the nanoparticles which leads to a superspin glass state in the samples at low temperatures.

1s2p resonant inelastic x-ray scattering in a-Fe2O3

NARCIS (Netherlands)

Caliebe, W.A.; Kao, C.-C.; Hastings, J.B.; Taguchi, M.; Kotani, A.; Uozumi, T.; Groot, F.M.F. de

1998-01-01

We report experimental and theoretical results on the Fe K edge x-ray absorption spectrum and 1s2p resonant inelastic x-ray scattering (RIXS) spectra in a-Fe2O3 . The results are interpreted using an FeO6^9- cluster model with intra-atomic multiplet coupling and interatomic covalency

Study on Formation Mechanism of Fayalite (Fe2SiO4) by Solid State Reaction in Sintering Process

Science.gov (United States)

Wang, Zhongbing; Peng, Bing; Zhang, Lifeng; Zhao, Zongwen; Liu, Degang; Peng, Ning; Wang, Dawei; He, Yinghe; Liang, Yanjie; Liu, Hui

2018-04-01

The sintering behaviors among SiO2, FeS and Fe3O4 were detected to reveal the formation mechanism of Fe2SiO4. The results indicated that the formation mechanism is divided into five steps: (1) migration of O2- induced by S2- under a reducing atmosphere; (2) formation of Fe3O4- β ; (3) migration of Fe(II) into a ferrite cluster structure to gain oxygen and form Fe3- x O4; (4) Fe(II) invaded the silicon atomic position and released Si(IV); and (5) formation of the stable structure of Fe2SiO4 through chemical diffusion between cations of Fe(II) and Si(IV). These findings can provide theoretical support for controlling the process of the recovery of valuable metals in copper slag through the combined roasting modification-magnetic separation process.

Synthesis and Characterization of Mixed Chalcogen Triangular Complexes with New Mo-3(mu(3)-S)(mu(2)-Se-2)(3)(4+) and M-3(mu(3)-S)mu(2)-Se)(3)(4+) (M = Mo, W) Cluster Cores

DEFF Research Database (Denmark)

Gushchin, Artem; Ooi, Bee Lean; Harris, Pernille

2009-01-01

In our pursuit of mixed chalcogen-bridged cluster complexes, solids of the compositions Mo3SSe6Br4 and W3SSe6Br4 were prepared using high-temperature synthesis from the elements. Treatment of Mo3SSe6Br4 with Bu4NBr in a vibration mill yielded (Bu4N)(3)([Mo-3(mu(3)-S)(mu(2)-Se-2)(3)Br-6]Br} (I). Its......), was isolated and its structure determined using X-ray crystallography. W3SSe6Br4 upon reaction with H3PO2 gave a mixture of all of the [W3SxSe4-x(H2O)(9)](4+) species. After repeated chromatography, crystals of {[W-3(mu(3)-S)(mu(2)-Se)(3)(H2O)(7)Cl--(2)](2)CB[6]}Cl-4 center dot 12H(2)O (IV) were crystallized...

Site-directed mutagenesis of Azotobacter vinelandii ferredoxin I: [Fe-S] cluster-driven protein rearrangement

International Nuclear Information System (INIS)

Martin, A.E.; Burgess, B.K.; Stout, C.D.; Cash, V.L.; Dean, D.R.; Jensen, G.M.; Stephens, P.J.

1990-01-01

Azotobacter vinelandii ferredoxin I is a small protein that contains one [4Fe-4S] cluster and one [3Fe-4S] cluster. Recently the x-ray crystal structure has been redetermined and the fdxA gene, which encodes the protein, has been cloned and sequenced. Here the authors report the site-directed mutation of Cys-20, which is a ligand of the [4Fe-4S] cluster in the native protein, to alanine and the characterization of the protein product by x-ray crystallographic and spectroscopic methods. The data show that the mutant protein again contains one [4Fe-4S] cluster and one [3Fe-4S] cluster. The new [4Fe-4S] cluster obtains its fourth ligand from Cys-24, a free cysteine in the native structure. The formation of this [4Fe-4S] cluster drives rearrangement of the protein structure

Pressure-dependent ground states and fermiology in β- ( BDA-TTP ) 2 M Cl4 ( M=Fe,Ga )

Science.gov (United States)

Choi, E. S.; Graf, D.; Brooks, J. S.; Yamada, J.; Akutsu, H.; Kikuchi, K.; Tokumoto, M.

2004-07-01

We have investigated pressure- and magnetic-field-dependent electrical transport properties in the charge transfer salts β-(BDA-TTP)2MCl4(M=Fe,Ga) , both of which show a metal-insulator (MI) transition around 120K at ambient pressure. The zero field temperature-pressure phase diagrams of the two compounds are quite similar; the MI transition temperature decreases with pressure, and superconductivity is observed in both the magnetic and non-magnetic compounds above ˜4.5kbar . Likewise, Shubnikov-de Haas effect measurements show nearly identical Fermi surfaces. These similarities suggest that the magnetic interaction J between the conduction electrons and the magnetic moments in β-(BDA-TTP)2FeCl4 is small. Nevertheless, magnetoresistance measurements show remarkable differences and reveal that magnetic interactions with the conduction electrons are still effective in M=Fe compounds.

Sodium intercalation in the phosphosulfate cathode NaFe2(PO4)(SO4)2

Science.gov (United States)

Ben Yahia, Hamdi; Essehli, Rachid; Amin, Ruhul; Boulahya, Khalid; Okumura, Toyoki; Belharouak, Ilias

2018-04-01

The compound NaFe2(PO4)(SO4)2 is successfully synthesized via a solid state reaction route and its crystal structure is determined using powder X-ray diffraction data. NaFe2(PO4)(SO4)2 phase is also characterized by cyclic voltammetry, galvanostatic cycling and electrochemical impedance spectroscopy. NaFe2(PO4)(SO4)2 crystallizes with the well-known NASICON-type structure. SAED and HRTEM experiments confirm the structural model, and no ordering between the PO4-3 and SO4-2 polyanions is detected. The electrochemical tests indicate that NaFe2(PO4)(SO4)2 is a 3 V sodium intercalating cathode. The electrical conductivity is relatively low (2.2 × 10-6 Scm-1 at 200 °C) and the obtained activation energy is ∼0.60eV. The GITT experiments indicate that the diffusivity values are in the range of 10-11-10-12 cm2/s within the measured sodium concentrations.

μ(4)-Orthothio-carbonato-tetra-kis-[tri-carbonyl-iron(I)](2 Fe-Fe).

Science.gov (United States)

Shi, Yao-Cheng; Cheng, Huan-Ren; Yuan, Li-Min; Li, Qian-Kun

2011-11-01

The fused bis-butterfly-shaped title compound, [Fe(4)(CS(4))(CO)(12)], possesses an orthothio-carbonate (CS(4) (4-)) ligand that acts as a bridge between two Fe(2)(CO)(6) units. A short intra-molecular S⋯S contact [2.6984 (8) and 2.6977 (8) Å] occurs in each S(2)Fe(2)(CO)(6) fragment.

Al/Fe isomorphic substitution versus Fe{sub 2}O{sub 3} clusters formation in Fe-doped aluminosilicate nanotubes (imogolite)

Energy Technology Data Exchange (ETDEWEB)

Shafia, Ehsan [Politecnico di Torino, Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico (Italy); Esposito, Serena [Università degli Studi di Cassino e del Lazio Meridionale, Department of Civil and Mechanical Engineering (Italy); Manzoli, Maela; Chiesa, Mario [Università di Torino, Dipartimento di Chimica and Centro Interdipartimentale NIS (Italy); Tiberto, Paola [Electromagnetism, I.N.Ri.M. (Italy); Barrera, Gabriele [Università di Torino, Dipartimento di Chimica and Centro Interdipartimentale NIS (Italy); Menard, Gabriel [Harvard University, Department of Chemistry and Chemical Biology (United States); Allia, Paolo, E-mail: paolo.allia@polito.it [Politecnico di Torino, Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico (Italy); Freyria, Francesca S. [Massachusetts Institute of Technology, Department of Chemistry (United States); Garrone, Edoardo; Bonelli, Barbara, E-mail: barbara.bonelli@polito.it [Politecnico di Torino, Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico (Italy)

2015-08-15

Textural, magnetic and spectroscopic properties are reported of Fe-doped aluminosilicate nanotubes (NTs) of the imogolite type, IMO, with nominal composition (OH){sub 3}Al{sub 2−x}Fe{sub x}O{sub 3}SiOH (x = 0, 0.025, 0.050). Samples were obtained by either direct synthesis (Fe-0.025-IMO, Fe-0.050-IMO) or post-synthesis loading (Fe-L-IMO). The Fe content was either 1.4 wt% (both Fe-0.050-IMO and Fe-L-IMO) or 0.7 wt% (Fe-0.025-IMO). Textural properties were characterized by High-Resolution Transmission Electron Microscopy, X-ray diffraction and N{sub 2} adsorption/desorption isotherms at 77 K. The presence of different iron species was studied by magnetic moment measurements and three spectroscopies: Mössbauer, UV–Vis and electron paramagnetic resonance, respectively. Fe{sup 3+}/Al{sup 3+} isomorphic substitution (IS) at octahedral sites at the external surface of NTs is the main process occurring by direct synthesis at low Fe loadings, giving rise to the formation of isolated high-spin Fe{sup 3+} sites. Higher loadings give rise, besides IS, to the formation of Fe{sub 2}O{sub 3} clusters. IS occurs up to a limit of Al/Fe atomic ratio of ca. 60 (corresponding to x = 0.032). A fraction of the magnetism related to NCs is pinned by the surface anisotropy; also, clusters are magnetically interacting with each other. Post-synthesis loading leads to a system rather close to that obtained by direct synthesis, involving both IS and cluster formations. Slightly larger clusters than with direct synthesis samples, however, are formed. The occurrence of IS indicates a facile cleavage/sealing of Al–O–Al bonds: this opens the possibility to exchange Al{sup 3+} ions in pre-formed IMO NTs, a much simpler procedure compared with direct synthesis.

Magnetism by interfacial hybridization and p-type doping of MoS2 in Fe4N/MoS2 superlattices: A first-principles study

KAUST Repository

Feng, Nan

2014-03-26

Magnetic and electronic properties of Fe4N(111)/MoS 2(√3 × √3) superlattices are investigated by first-principles calculations, considering two models: (I) FeIFe II-S and (II) N-S interfaces, each with six stacking configurations. In model I, strong interfacial hybridization between FeI/Fe II and S results in magnetism of monolayer MoS2, with a magnetic moment of 0.33 μB for Mo located on top of Fe I. For model II, no magnetism is induced due to weak N-S interfacial bonding, and the semiconducting nature of monolayer MoS2 is preserved. Charge transfer between MoS2 and N results in p-type MoS2 with Schottky barrier heights of 0.5-0.6 eV. Our results demonstrate that the interfacial geometry and hybridization can be used to tune the magnetism and doping in Fe4N(111)/MoS2(√3 × √3) superlattices. © 2014 American Chemical Society.

Magnetism by interfacial hybridization and p-type doping of MoS2 in Fe4N/MoS2 superlattices: A first-principles study

KAUST Repository

Feng, Nan; Mi, Wenbo; Cheng, Yingchun; Guo, Zaibing; Schwingenschlö gl, Udo; Bai, Haili

2014-01-01

Magnetic and electronic properties of Fe4N(111)/MoS 2(√3 × √3) superlattices are investigated by first-principles calculations, considering two models: (I) FeIFe II-S and (II) N-S interfaces, each with six stacking configurations. In model I, strong interfacial hybridization between FeI/Fe II and S results in magnetism of monolayer MoS2, with a magnetic moment of 0.33 μB for Mo located on top of Fe I. For model II, no magnetism is induced due to weak N-S interfacial bonding, and the semiconducting nature of monolayer MoS2 is preserved. Charge transfer between MoS2 and N results in p-type MoS2 with Schottky barrier heights of 0.5-0.6 eV. Our results demonstrate that the interfacial geometry and hybridization can be used to tune the magnetism and doping in Fe4N(111)/MoS2(√3 × √3) superlattices. © 2014 American Chemical Society.

STAR CLUSTERS IN M31. II. OLD CLUSTER METALLICITIES AND AGES FROM HECTOSPEC DATA

International Nuclear Information System (INIS)

Caldwell, Nelson; Schiavon, Ricardo; Morrison, Heather; Harding, Paul; Rose, James A.

2011-01-01

We present new high signal-to-noise spectroscopic data on the M31 globular cluster (GC) system, obtained with the Hectospec multifiber spectrograph on the 6.5 m MMT. More than 300 clusters have been observed at a resolution of 5 A and with a median S/N of 75 per A, providing velocities with a median uncertainty of 6 km s -1 . The primary focus of this paper is the determination of mean cluster metallicities, ages, and reddenings. Metallicities were estimated using a calibration of Lick indices with [Fe/H] provided by Galactic GCs. These match well the metallicities of 24 M31 clusters determined from Hubble Space Telescope color-magnitude diagrams, the differences having an rms of 0.2 dex. The metallicity distribution is not generally bimodal, in strong distinction with the bimodal Galactic globular distribution. Rather, the M31 distribution shows a broad peak, centered at [Fe/H] = -1, possibly with minor peaks at [Fe/H] = -1.4, -0.7, and -0.2, suggesting that the cluster systems of M31 and the Milky Way had different formation histories. Ages for clusters with [Fe/H] > - 1 were determined using the automatic stellar population analysis program EZ A ges. We find no evidence for massive clusters in M31 with intermediate ages, those between 2 and 6 Gyr. Moreover, we find that the mean ages of the old GCs are remarkably constant over about a decade in metallicity (-0.95∼< [Fe/H] ∼<0.0).

{sup 57}Fe Mössbauer spectroscopic studies of single-crystalline K{sub x}Fe{sub 2-y}S{sub 2} and K{sub x}Fe{sub 2-y}Se{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Tsuchiya, Yuu, E-mail: tsuchiya.yuu1990@gmail.com; Ikeda, Shugo; Kobayashi, Hisao [University of Hyogo (Japan)

2016-12-15

We have investigated the physical properties of single-crystalline K{sub x}Fe{sub 2-y}S{sub 2} and K{sub x}Fe{sub 2-y}Se{sub 2} samples using {sup 57}Fe Mössbauer spectroscopy. The observed {sup 57}Fe Mössbauer spectra were reconstructed using a major antiferromagnetic ordered K{sub 2}Fe{sub 4}Se{sub 5} phase and a minor paramagnetic phase down to 5 K, despite being superconducting below 32.2 K in K{sub x}Fe{sub 2-y}Se{sub 2}. The analysis of {sup 57}Fe Mössbauer spectrum for K{sub x}Fe{sub 2-y}S{sub 2} at 290 K confirms the presence of a major antiferromagnetic ordered K{sub 2}Fe{sub 4}S{sub 5} phase and a minor paramagnetic phase in the K{sub x}Fe{sub 2-y}S{sub 2} single crystal. The derived hyperfine interaction parameters of the paramagnetic phase in K{sub x}Fe{sub 2-y}S{sub 2} suggest that the microstructure of this phase in K{sub x}Fe{sub 2-y}S{sub 2} is similar to that of the superconducting phase in K{sub x}Fe{sub 2-y}Se{sub 2} although the K{sub x}Fe{sub 2-y}S{sub 2} single crystals exhibit no superconductivity down to 5 K.

Photocatalytic degradation of Acephate, Omethoate, and Methyl parathion by Fe_3O_4@SiO_2@mTiO_2 nanomicrospheres

International Nuclear Information System (INIS)

Zheng, Lingling; Pi, Fuwei; Wang, Yifan; Xu, Hui; Zhang, Yinzhi; Sun, Xiulan

2016-01-01

Highlights: • An efficient photocatalyst Fe_3O_4@SiO_2@mTiO_2 with high magnetic response and large specific surface area was synthesized. • Photocatalytic efficiency of Fe_3O_4@SiO_2@mTiO_2 on Acephate, Omethoate, and Methyl Parathion was higher than TiO_2 P-25. • Possible photocatalytic degradation mechanisms for the Acephate, Omethoate, and Methyl Parathion were proposed. - Abstract: A novel magnetic mesoporous nanomicrospheres Fe_3O_4@SiO_2@mTiO_2 were synthetized and characterized by a series of techniques including FE-TEM, EDS, FE-SEM, PXRD, XPS, BET, TGA as well as VSM, and subsequently tested as a photocatalyst for the degradation of Acephate, Omethoate, and Methyl parathion under UV irradiation. The well-designed nanomicrospheres exhibit a pure and highly crystalline anatase TiO_2 layer, large specific surface area, and high-magnetic-response. Photocatalytic degradation of the three organophosphorus pesticides (OPPs) and the formation intermediates were identified using HPLC, TOC-V_c_p_n, IC, pH meter and GC–MS. Acephate, Omethoate, and Methyl parathion disappeared after 45 min, 45 min, and 80 min UV illumination, respectively. At the end of the treatment, the total organic carbon (TOC) of the OPPs was reduced 80–85%. The main mineralization products were SO_4"2"−, NO_3"− and PO_4"3"− and Omethoate additionally formed NO_2"−. Based on the results, we proposed the photocatalytic degradation pathways for Acephate, Omethoate, and Methyl parathion.

Spectroscopic and magnetic properties of Fe2+ (3d6; S = 2) ions in Fe(NH4)2(SO4)2·6H2O - Modeling zero-field splitting and Zeeman electronic parameters by microscopic spin Hamiltonian approach

Science.gov (United States)

Zając, Magdalena; Rudowicz, Czesław; Ohta, Hitoshi; Sakurai, Takahiro

2018-03-01

Utilizing the package MSH/VBA, based on the microscopic spin Hamiltonian (MSH) approach, spectroscopic and magnetic properties of Fe2+ (3d6; S = 2) ions at (nearly) orthorhombic sites in Fe(NH4)2(SO4)2·6H2O (FASH) are modeled. The zero-field splitting (ZFS) parameters and the Zeeman electronic (Ze) factors are predicted for wide ranges of values of the microscopic parameters, i.e. the spin-orbit (λ), spin-spin (ρ) coupling constants, and the crystal-field (ligand-field) energy levels (Δi) within the 5D multiplet. This enables to consider the dependence of the ZFS parameters bkq (in the Stevens notation), or the conventional ones (e.g., D and E), and the Zeeman factors gi on λ, ρ, and Δi. By matching the theoretical SH parameters and the experimental ones measured by electron magnetic resonance (EMR), the values of λ, ρ, and Δi best describing Fe2+ ions in FASH are determined. The novel aspect is prediction of the fourth-rank ZFS parameters and the ρ(spin-spin)-related contributions, not considered in previous studies. The higher-order contributions to the second- and fourth-rank ZFSPs are found significant. The MSH predictions provide guidance for high-magnetic field and high-frequency EMR (HMF-EMR) measurements and enable assessment of suitability of FASH for application as high-pressure probes for HMF-EMR studies. The method employed here and the present results may be also useful for other structurally related Fe2+ (S = 2) systems.

The iron uptake repressor Fep1 in the fission yeast binds Fe-S cluster through conserved cysteines

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyo-Jin; Lee, Kang-Lok; Kim, Kyoung-Dong; Roe, Jung-Hye, E-mail: jhroe@snu.ac.kr

2016-09-09

Iron homeostasis is tightly regulated since iron is an essential but toxic element in the cell. The GATA-type transcription factor Fep1 and its orthologs contribute to iron homeostasis in many fungi by repressing genes for iron uptake when intracellular iron is high. Even though the function and interaction partners of Fep1 have been elucidated extensively In Schizosaccharomyces pombe, the mechanism behind iron-sensing by Fep1 remains elusive. It has been reported that Fep1 interacts with Fe-S-containing monothiol glutaredoxin Grx4 and Grx4-Fra2 complex. In this study, we demonstrate that Fep1 also binds iron, in the form of Fe-S cluster. Spectroscopic and biochemical analyses of as isolated and reconstituted Fep1 suggest that the dimeric Fep1 binds Fe-S clusters. The mutation study revealed that the cluster-binding depended on the conserved cysteines located between the two zinc fingers in the DNA binding domain. EPR analyses revealed [Fe-S]-specific peaks indicative of mixed presence of [2Fe-2S], [3Fe-4S], or [4Fe-4S]. The finding that Fep1 is an Fe-S protein fits nicely with the model that the Fe-S-trafficking Grx4 senses intracellular iron environment and modulates the activity of Fep1. - Highlights: • Fep1, a prototype fungal iron uptake regulator, was isolated stably from Schizosaccharomyces pombe. • Fep1 exhibits UV–visible absorption spectrum, characteristic of [Fe-S] proteins. • The iron and sulfide contents in purified or reconstituted Fep1 also support [Fe-S]. • The conserved cysteines are critical for [Fe-S]-binding. • EPR spectra at 5 K and 123 K suggest a mixed population of [Fe-S].

ZnFe2O4 Containing Nanoparticles: Synthesis and Magnetic Properties

Directory of Open Access Journals (Sweden)

Zālīte Ilmārs

2017-05-01

Full Text Available Solid solutions of Co1−xZnxFe2O4 and Ni1−xZnxFe2O4 (0 < x < 1 nanoparticles were synthesized by sol-gel self-propagating combustion method. The obtained single cubic phase product has a specific surface area 25 m2∙g−1 to 33 m2∙g−1 and crystallite size 25 nm to 40 nm. Lattice parameters change linearly from 8.371 A (CoFe2O4 and 8.337 A (NiFe2O4 to 8.431 A (ZnFe2O4. The saturation magnetization (Ms changes non-linearly from 60.8 emu∙g−1 (CoFe2O4, respectively, from 35.6 emu∙g−1 (NiFe2O4 to 3.3 emu∙g−1 (ZnFe2O4 reaching maximal value 76.1 emu∙g−1 for Co0.8Zn0.2Fe2O4 and 64.9 emu∙g−1 – for Ni0.6Zn0.4Fe2O4.

Unusual electronic features and reactivity of the dipyridylazaallyl ligand: characterizations of (smif)2M [M = Fe, Co, Co+, Ni; smif = {(2-py)CH}2N] and [(TMS)2NFe]2(smif)2.

Science.gov (United States)

Frazier, Brenda A; Wolczanski, Peter T; Lobkovsky, Emil B; Cundari, Thomas R

2009-03-18

Application of the dipyridylazaallyl ligand (2-py)CHNCH(2-py) (smif) to a series of first-row transition metals afforded (smif)(2)M(n) [n = 0, M = Fe (1), Co (2), Ni (3); n = +1, M = Co (2+)] and {(TMS)(2)NFe}(2)(smif)(2) (4(2)) via metathetical procedures. The Mossbauer spectrum of 1 (S = 0) and TDDFT calculations, including a UV-vis spectral simulation, reveal it to be a covalent, strong-field system with Delta(o) estimated as approximately 18,000 cm(-1) and B approximately 470 cm(-1). (smif)(2)Co (2) has S = 1/2 according to SQUID data at 10 K. DFT calculations suggest that the odd electron is localized in a smif pi* orbital, i.e., smif is redox-active. EPR-silent (smif)(2)Ni (3) has S = 1 (SQUID), and calculations show that the unpaired spins reside in the d(z(2)) and d(x(2))(-y(2)) orbitals. X-ray structural parameters suggest that low-spin d(6) 1 and 2+ are relatively symmetric D(2d) species, but 2 and 3 manifest a distortion in which one smif is canted in the plane perpendicular to the other. (smif)FeN(TMS)(2) (4) is principally monomeric in solution, but reversibly dimerizes (K(eq) approximately 10(-4) M(-1)) via C-C bond formation in the azaallyl backbone to crystallize as {(TMS)(2)NFe}(2)(smif)(2) (4(2)). The azaallyl compounds possess extraordinary UV-vis absorptivities (epsilon approximately 18,000-52,000) at 580 +/- 15 nm and 406(25) nm that have been identified as intraligand bands with C(nb) --> smif pi* character.

Cysteine as a ligand platform in the biosynthesis of the FeFe hydrogenase H cluster.

Science.gov (United States)

Suess, Daniel L M; Bürstel, Ingmar; De La Paz, Liliana; Kuchenreuther, Jon M; Pham, Cindy C; Cramer, Stephen P; Swartz, James R; Britt, R David

2015-09-15

Hydrogenases catalyze the redox interconversion of protons and H2, an important reaction for a number of metabolic processes and for solar fuel production. In FeFe hydrogenases, catalysis occurs at the H cluster, a metallocofactor comprising a [4Fe-4S]H subcluster coupled to a [2Fe]H subcluster bound by CO, CN(-), and azadithiolate ligands. The [2Fe]H subcluster is assembled by the maturases HydE, HydF, and HydG. HydG is a member of the radical S-adenosyl-L-methionine family of enzymes that transforms Fe and L-tyrosine into an [Fe(CO)2(CN)] synthon that is incorporated into the H cluster. Although it is thought that the site of synthon formation in HydG is the "dangler" Fe of a [5Fe] cluster, many mechanistic aspects of this chemistry remain unresolved including the full ligand set of the synthon, how the dangler Fe initially binds to HydG, and how the synthon is released at the end of the reaction. To address these questions, we herein show that L-cysteine (Cys) binds the auxiliary [4Fe-4S] cluster of HydG and further chelates the dangler Fe. We also demonstrate that a [4Fe-4S]aux[CN] species is generated during HydG catalysis, a process that entails the loss of Cys and the [Fe(CO)2(CN)] fragment; on this basis, we suggest that Cys likely completes the coordination sphere of the synthon. Thus, through spectroscopic analysis of HydG before and after the synthon is formed, we conclude that Cys serves as the ligand platform on which the synthon is built and plays a role in both Fe(2+) binding and synthon release.

The magnetization reversal in CoFe{sub 2}O{sub 4}/CoFe{sub 2} granular systems

Energy Technology Data Exchange (ETDEWEB)

Jin, J.; Sun, X.; Wang, M.; Ding, Z.L.; Ma, Y.Q., E-mail: yqma@ahu.edu.cn [Anhui University, Anhui Key Laboratory of Information Materials and Devices, School of Physics and Materials Science (China)

2016-12-15

The temperature-dependent field cooling (FC) and zero-field cooling (ZFC) magnetizations, i.e., M{sub FC} and M{sub ZFC}, measured under different magnetic fields from 500 Oe to 20 kOe have been investigated on two exchange–spring CoFe{sub 2}O{sub 4}/CoFe{sub 2} composites with different relative content of CoFe{sub 2}. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at a field-dependent irreversible temperature T{sub irr}. For the sample with less CoFe{sub 2}, the curves of −d(M{sub FC} − M{sub ZFC})/dT versus temperature T exhibit a broad peak at an intermediate temperature T{sub 2} below T{sub irr}, and the moments are suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the −d(M{sub FC} − M{sub ZFC})/dT curves of the sample with more CoFe{sub 2}, besides a broad peat at an intermediate temperature T{sub 2}, a rapid rise around the low temperature T{sub 1}~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T{sub 2} and T{sub irr} towards a lower temperature, and the shift of T{sub 2} is attributable to the moment reversal of CoFe{sub 2}O{sub 4}.

Isochrones for old (>5 Gyr) stars and stellar populations. I. Models for –2.4 ≤ [Fe/H] ≤+0.6, 0.25 ≤ Y ≤ 0.33, and –0.4 ≤ [α/Fe] ≤+0.4

Energy Technology Data Exchange (ETDEWEB)

VandenBerg, Don A. [Department of Physics and Astronomy, University of Victoria, P.O. Box 1700 STN CSC, Victoria, B.C., V8W 2Y2 (Canada); Bergbusch, Peter A. [Department of Physics, University of Regina, Regina, Saskatchewan, S4S 0A2 (Canada); Ferguson, Jason W. [Department of Physics, Wichita State University, Wichita, KS 67260-0032 (United States); Edvardsson, Bengt, E-mail: vandenbe@uvic.ca, E-mail: pbergbusch@accesscomm.ca, E-mail: Jason.Ferguson@wichita.edu, E-mail: Bengt.Edvardsson@physics.uu.se [Theoretical Astrophysics, Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala (Sweden)

2014-10-10

Canonical grids of stellar evolutionary sequences have been computed for the helium mass-fraction abundances Y = 0.25, 0.29, and 0.33, and for iron abundances that vary from –2.4 to +0.4 (in 0.2 dex increments) when [α/Fe] =+0.4, or for the ranges –2.0 ≤ [Fe/H] ≤+0.6, –1.8 ≤ [Fe/H] ≤+0.6 when [α/Fe] =0.0 and –0.4, respectively. The grids, which consist of tracks for masses from 0.12 M{sub ⊙} to 1.1-1.5 M{sub ⊙} (depending on the metallicity) are based on up-to-date physics, including the gravitational settling of helium (but not metals diffusion). Interpolation software is provided to generate isochrones for arbitrary ages between ≈5 and 15 Gyr and any values of Y, [α/Fe], and [Fe/H] within the aformentioned ranges. Comparisons of isochrones with published color-magnitude diagrams (CMDs) for the open clusters M67 ([Fe/H] ≈0.0) and NGC 6791 ([Fe/H] ≈0.3) and for four of the metal-poor globular clusters (47 Tuc, M3, M5, and M92) indicate that the models for the observed metallicities do a reasonably good job of reproducing the locations and slopes of the cluster main sequences and giant branches. The same conclusion is reached from a consideration of plots of nearby subdwarfs that have accurate Hipparcos parallaxes and metallicities in the range –2.0 ≲ [Fe/H] ≲ –1.0 on various CMDs and on the (log T {sub eff}, M{sub V} ) diagram. A relatively hot temperature scale similar to that derived in recent calibrations of the infrared flux method is favored by both the isochrones and the adopted color transformations, which are based on the latest MARCS model atmospheres.

CO-Bridged H-Cluster Intermediates in the Catalytic Mechanism of [FeFe]-Hydrogenase CaI.

Science.gov (United States)

Ratzloff, Michael W; Artz, Jacob H; Mulder, David W; Collins, Reuben T; Furtak, Thomas E; King, Paul W

2018-06-20

The [FeFe]-hydrogenases ([FeFe] H 2 ases) catalyze reversible H 2 activation at the H-cluster, which is composed of a [4Fe-4S] H subsite linked by a cysteine thiolate to a bridged, organometallic [2Fe-2S] ([2Fe] H ) subsite. Profoundly different geometric models of the H-cluster redox states that orchestrate the electron/proton transfer steps of H 2 bond activation have been proposed. We have examined this question in the [FeFe] H 2 ase I from Clostridium acetobutylicum (CaI) by Fourier-transform infrared (FTIR) spectroscopy with temperature annealing and H/D isotope exchange to identify the relevant redox states and define catalytic transitions. One-electron reduction of H ox led to formation of H red H + ([4Fe-4S] H 2+ -Fe I -Fe I ) and H red ' ([4Fe-4S] H 1+ -Fe II -Fe I ), with both states characterized by low frequency μ-CO IR modes consistent with a fully bridged [2Fe] H . Similar μ-CO IR modes were also identified for H red H + of the [FeFe] H 2 ase from Chlamydomonas reinhardtii (CrHydA1). The CaI proton-transfer variant C298S showed enrichment of an H/D isotope-sensitive μ-CO mode, a component of the hydride bound H-cluster IR signal, H hyd . Equilibrating CaI with increasing amounts of NaDT, and probed at cryogenic temperatures, showed H red H + was converted to H hyd . Over an increasing temperature range from 10 to 260 K catalytic turnover led to loss of H hyd and appearance of H ox , consistent with enzymatic turnover and H 2 formation. The results show for CaI that the μ-CO of [2Fe] H remains bridging for all of the "H red " states and that H red H + is on pathway to H hyd and H 2 evolution in the catalytic mechanism. These results provide a blueprint for designing small molecule catalytic analogs.

Investigation of glutathione-derived electrostatic and hydrogen-bonding interactions and their role in defining Grx5 [2Fe-2S] cluster optical spectra and transfer chemistry.

Science.gov (United States)

Sen, Sambuddha; Bonfio, Claudia; Mansy, Sheref S; Cowan, J A

2018-03-01

Human glutaredoxin 5 (Grx5) is one of the core components of the Isc (iron-sulfur cluster) assembly and trafficking machinery, and serves as an intermediary cluster carrier, putatively delivering cluster from the Isu scaffold protein to target proteins. The tripeptide glutathione is intimately involved in this role, providing cysteinyl coordination to the iron center of the Grx5-bound [2Fe-2S] cluster. Grx5 has a well-defined glutathione-binding pocket with protein amino acid residues providing many ionic and hydrogen binding contacts to the bound glutathione. In this report, we investigated the importance of these interactions in cluster chirality and exchange reactivity by systematically perturbing the crucial contacts by use of natural and non-natural amino acid substitutions to disrupt the binding contacts from both the protein and glutathione. Native Grx5 could be reconstituted with all of the glutathione analogs used, as well as other thiol ligands, such as DTT or L-cysteine, by in vitro chemical reconstitution, and the holo proteins were found to transfer [2Fe-2S] cluster to apo ferredoxin 1 at comparable rates. However, the circular dichroism spectra of these derivatives displayed prominent differences that reflect perturbations in local cluster chirality. These studies provided a detailed molecular understanding of glutathione-protein interactions in holo Grx5 that define both cluster spectroscopy and exchange chemistry.

FeS2-doped MoS2 nanoflower with the dominant 1T-MoS2 phase as an excellent electrocatalyst for high-performance hydrogen evolution

International Nuclear Information System (INIS)

Zhao, Xue; Ma, Xiao; Lu, Qingqing; Li, Qun; Han, Ce; Xing, Zhicai; Yang, Xiurong

2017-01-01

Well-established methods to improve the hydrogen evolution reaction (HER) performances include, but are not limited to, tailoring the morphology and electronic structure of transition metal dichalcogenides (TMDs), and doping of earth abundant chemicals such as iron pyrite FeS 2 into existing TMDs. In this work, MoS 2 nanoflowers with the majority being octahedral MoS 2 (1T-MoS 2 ) and doped with FeS 2 were prepared and applied to HER. The as-prepared catalysts were characterized by X-ray absorption fine structure at the K-edge of Mo, S, and Fe to probe the local electronic structures. The resulting nanomaterial was identified to be FeS 2 doped MoS 2 nanoflower (denoted as Fe-MoS 2 NF) with 66% 1T-MoS 2 which was the metallic phase and could drastically boost the HER properties. The Fe-MoS 2 NF exhibited high HER performance with a Tafel slope of 82 mV dec −1 and it needs 136 mV to achieve a current density of 10 mA cm −2 . The synthesis of Fe-MoS 2 NF with refined morphology and active electronic structure is expected to open a new era for improving the catalytic activity and stability of MoS 2 .

Chemical and electrochemical lithium insertion into ternary transition metal sulfides MMo[sub 2]S[sub 4] (M: V, Cr, Fe)

Energy Technology Data Exchange (ETDEWEB)

Maffi, S.; Peraldo Bicelli, L. (Milan Polytechnic (Italy). Dept. of Applied Physical Chemistry CNR, Milan (Italy). Research Centre on Electrode Processes); Barriga, C.; Lavela, P.; Morales, J.; Tirado, J.L. (Cordoba Univ. (Spain). Dept. de Quimica Inorganica e Ingenieria Quimica)

1992-08-01

The effects of lithium insertion in MMo[sub 2]S[sub 4] (M: V, Cr, Fe) have been studied by means of chemical and electrochemical insertion methods. The reaction has a topotactic character and a higher degree of lithium insertion was found for the compound FeMo[sub 2]S[sub 4] which has a greater unit cell volume. For this compound the changes in lattice parameters with lithium content are also more pronounced. The voltage composition curves show a smooth voltage decrease with a quasi-plateau located at around 1.3 V. For discharge at lithium content higher than 0.8, the voltage decreases quickly followed by an extended plateau below 1 V, a region where electrolyte decomposition may occur. The X-ray powder diffraction patterns of the electrochemical lithiated compounds show that the original monoclinic structure is maintained up to 0.8 e[sup -] per mole, buth with a significant change in the intensity of the peaks, indicative of an alteration of cation distribution for this degree of insertion. For high lithium content, such disorder promotes the collapse of the structure, resulting in the loss of long-range order of the material. (orig.).

Design and syntheses of hybrid metal-organic materials based on K3[M(C2O4)3]·3H2O [M(III)=Fe, Al, Cr] metallotectons

Science.gov (United States)

Sun, Yayong; Zong, Yingxia; Ma, Haoran; Zhang, Ao; Liu, Kang; Wang, Debao; Wang, Wenqiang; Wang, Lei

2016-05-01

By using K3[M(C2O4)3]·3H2O [M(III)=Fe, Al, Cr] (C2O42-=oxalate) metallotectons as the starting material, we have synthesized eight novel complexes with formulas [{Fe(C2O4)2(H2O)2}2]·(H-L1)2·H2O 1, [Fe(C2O4)Cl2]·(H2-L2)0.5·(L2)0.5·H2O 2, [{Fe(C2O4)1.5Cl2}2]·(H-L3)43, [Fe2(C2O4)Cl8]·(H2-L4)2·2H2O 4, K[Al(C2O4)3]·(H2-L5)·2H2O 5, K[Al(C2O4)3]·(H-L6)2·2H2O 6, K[Cr(C2O4)3]·2H2O 7, Na[Fe(C2O4)3]·(H-L6)2·2H2O 8 (with L1=4-dimethylaminopyridine, L2=2,3,5,6-tetramethylpyrazine, L3=2-aminobenzimidazole, L4=1,4-bis-(1H-imidazol-1-yl)benzene, L5=1,4-bis((2-methylimidazol-1-yl)methyl)benzene, L6=2-methylbenzimidazole). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra and thermogravimetric analyses. Compound 3 is a 2D H-bonded supramolecular architecture. Others are 3D supramolecular structures. Compound 1 shows a [Fe(C2O4)2(H2O)2]- unit and 3D antionic H-bonded framework. Compound 2 features a [Fe(C2O4)Cl2]- anion and 1D iron-oxalate-iron chain. Compound 3 features a [Fe2(C2O4)3Cl4]4- unit. Compound 4 features distinct [Fe2(C2O4)Cl8]4- units, which are mutual linked by water molecules to generated a 2D H-bonded network. Compound 5 features infinite ladder-like chains constructed by [Al(C2O4)3]3- units and K+ cations. The 1D chains are further extended into 3D antionic H-bonded framework through O-H···O H-bonds. Compounds 6-8 show 2D [KAl(C2O4)3]2- layer, [KCr(C2O4)3]2- layer and [NaFe(C2O4)3]2- layer, respectively.

Structural and magnetic properties of Ni0.8M0.2Fe2O4 (M = Cu, Co) nano-crystalline ferrites

Science.gov (United States)

Vijaya Babu, K.; Satyanarayana, G.; Sailaja, B.; Santosh Kumar, G. V.; Jalaiah, K.; Ravi, M.

2018-06-01

Nano-crystalline nickel ferrites are interesting materials due to their large physical and magnetic properties. In the present work, two kinds of spinel ferrites Ni0.8M0.2Fe2O4 (M = Cu, Co) are synthesized by using sol-gel auto-combustion method and the results are compared with NiFe2O4. The structural properties of synthesized ferrites are determined by using X-ray powder diffraction; scanning electron microscope and Fourier transform infrared spectroscopy. The cation distribution obtained from X-ray diffraction show that cobalt/copper occupies only tetrahedral site in spinel lattice. The lattice constant increases with the substitution of cobalt/copper. The structural parameters like bond lengths, tetrahedral and octahedral edges have been varied with the substitution. The microstructural study is carried out by using SEM technique and the average grain size is increased with nickel ferrite. The initial permeability (μi) is improving with the substitution. The observed g-value from ESR is approximately equal to standard value.

Development of novel exchange spring magnet by employing nanocomposites of CoFe{sub 2}O{sub 4} and CoFe{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Safi, Rohollah; Ghasemi, Ali, E-mail: ali13912001@yahoo.com; Shoja-Razavi, Reza; Tavoosi, Majid

2016-12-01

CoFe{sub 2}O{sub 4}−CoFe2 hard–soft nanocomposites were prepared via reduction of the cobalt ferrite CoFe{sub 2}O{sub 4} in hydrogen atmosphere at different temperature. The structure and the room temperature magnetization of the samples were characterized by X-ray diffraction, field emission scanning electron microscope (FESEM) and vibrating sample magnetometer (VSM). It was found that the saturation magnetization of the nanocomposite powders increases by reduction temperature while their coercivity decreases. The highest M{sub r}/M{sub s} ratio of 0.52 was obtained for sample reduced at 550 °C. Single smooth hysteresis loops of nanocomposites show that these nanocomposites behave as the single-phase materials. This result indicates the presence of exchange coupling between two different hard and soft phases. - Highlights: • CoFe{sub 2}O{sub 4}–CoFe{sub 2} was successfully synthesized by reduction diffusion process. • Two phases are effectively exchange coupled in nanocomposite. • Single smooth hysteresis loop was developed in nanocomposites.

Decacarbonyl[μ4-(ethane-1,2-diyldinitrilotetrakis(methanethiolato]bis(triphenylphosphanetetrairon(2 Fe—Fe

Directory of Open Access Journals (Sweden)

Wei-Ming Gao

2012-02-01

Full Text Available In the title compound, [Fe4(C6H12N2S4(C18H15P2(CO10], the unit cell contains one molecule, which exhibits a crystallographically imposed center of symmetry. The independent Fe2S2 fragment [Fe—Fe = 2.527 (1 Å] is in a butterfly conformation, and each Fe atom displays a pseudo-square-pyramidal coordination geometry. The phosphane group occupies an apical position [Fe—P = 2.2670 (14 Å]. In the crystal, weak intermolecular C—H...O hydrogen bonds link the molecules into chains along [110].

Disappearance of superconductivity in the solid solution between (Ca4Al2O6)(Fe2As2) and (Ca4Al2O6)(Fe2P2) superconductors.

Science.gov (United States)

Shirage, Parasharam M; Kihou, Kunihiro; Lee, Chul-Ho; Takeshita, Nao; Eisaki, Hiroshi; Iyo, Akira

2012-09-19

The effect of alloying the two perovskite-type iron-based superconductors (Ca(4)Al(2)O(6))(Fe(2)As(2)) and (Ca(4)Al(2)O(6))(Fe(2)P(2)) was examined. While the two stoichiometric compounds possess relatively high T(c)'s of 28 and 17 K, respectively, their solid solutions of the form (Ca(4)Al(2)O(6))(Fe(2)(As(1-x)P(x))(2)) do not show superconductivity over a wide range from x = 0.50 to 0.95. The resultant phase diagram is thus completely different from those of other typical iron-based superconductors such as BaFe(2)(As,P)(2) and LaFe(As,P)O, in which superconductivity shows up when P is substituted for As in the non-superconducting "parent" compounds. Notably, the solid solutions in the non-superconducting range exhibit resistivity anomalies at temperatures of 50-100 K. The behavior is reminiscent of the resistivity kink commonly observed in various non-superconducting parent compounds that signals the onset of antiferromagnetic/orthorhombic long-range order. The similarity suggests that the suppression of the superconductivity in the present case also has a magnetic and/or structural origin.

Lithium insertion into Fe 2(SO 4) 3 frameworks

Science.gov (United States)

Manthiram, A.; Goodenough, J. B.

1989-05-01

The two polymorphs of Fe 2(SO 4) 3 consist of framework structures built up of tetrahedra sharing corners with octahedra and vice versa. One is rhombohedral, the other is monoclinic. Two moles of lithium insert rapidly into both structures at room temperature. However, lithium insertion into the rhombohedral phase is topotactic without any change of symmetry of the framework, whereas the monoclinic modification is converted to an orthorombic Li 2Fe 2(SO 4) 3 phase via a displacement transition; the existence of a two-phase region between Fe 2(SO 4) 3 and Li 2Fe 2(SO 4) 3 results in a flat OCV of 3.6 V versus lithium, which is 600 mV higher than is found for Li xFFe 2(WO 4) 3 or Li xFe 2(MoO 4) 3. This difference is discussed in terms of the influence of the counter cation on the solid-state Fe {3+}/{2+} redox couple.

Crystallochemical features of solid solutions based on Ga/sub 2/3/Cr/sub 2/S/sub 4/

Energy Technology Data Exchange (ETDEWEB)

Titov, V.V.; Kesler, Ya.A.; Gordeev, I.V.; Stupnikov, V.A.

1988-04-01

Ga/sub 2/3/Cr/sub 2/S/sub 4/ shows a rare type of phase transition where increases in temperature and pressure produce the disordered modification. A source of disordering can be isomorphous substitution in the tetrahedral sublattice. The authors therefore made and examined solid solutions of Ga/sub (2/3-2x/3)/M/sub x/(Cr/sub 2/)S/sub 4/ type, where M = Fe, Co, Ni, Cu. Specimens containing Fe and show a quasi-continuous solid-solution series, where the Fe system obeys Vegard's rule. Specimens containing nickel show a narrow ordering range. The most interesting results have been obtained for specimens containing copper. Cu/sub x/Ga/sub 2/3(1-x)/Cr/sub 2/S/sub 4/ specimens show a transition from a structure ordered on the tetrahedral positions, symmetry F/anti/43m, to the normal-spinel structure, Fd3m.

Nanotextured Spikes of α-Fe2O3/NiFe2O4 Composite for Efficient Photoelectrochemical Oxidation of Water.

Science.gov (United States)

Hussain, Shabeeb; Tavakoli, Mohammad Mahdi; Waleed, Aashir; Virk, Umar Siddique; Yang, Shihe; Waseem, Amir; Fan, Zhiyong; Nadeem, Muhammad Arif

2018-03-27

We demonstrate for the first time the application of p-NiFe 2 O 4 /n-Fe 2 O 3 composite thin films as anode materials for light-assisted electrolysis of water. The p-NiFe 2 O 4 /n-Fe 2 O 3 composite thin films were deposited on planar fluorinated tin oxide (FTO)-coated glass as well as on 3D array of nanospike (NSP) substrates. The effect of substrate (planar FTO and 3D-NSP) and percentage change of each component (i.e., NiFe 2 O 4 and Fe 2 O 3 ) of composite was studied on photoelectrochemical (PEC) water oxidation reaction. This work also includes the performance comparison of p-NiFe 2 O 4 /n-Fe 2 O 3 composite (planar and NSP) devices with pure hematite for PEC water oxidation. Overall, the nanostructured p-NiFe 2 O 4 /n-Fe 2 O 3 device with equal molar 1:1 ratio of NiFe 2 O 4 and Fe 2 O 3 was found to be highly efficient for PEC water oxidation as compared with pure hematite, 1:2 and 1:3 molar ratios of composite. The photocurrent density of 1:1 composite thin film on planar substrate was equal to 1.07 mA/cm 2 at 1.23 V RHE , which was 1.7 times higher current density as compared with pure hematite device (0.63 mA/cm 2 at 1.23 V RHE ). The performance of p-NiFe 2 O 4 /n-Fe 2 O 3 composites in PEC water oxidation was further enhanced by their deposition over 3D-NSP substrate. The highest photocurrent density of 2.1 mA/cm 2 at 1.23 V RHE was obtained for the 1:1 molar ratio p-NiFe 2 O 4 /n-Fe 2 O 3 composite on NSP (NF1-NSP), which was 3.3 times more photocurrent density than pure hematite. The measured applied bias photon-to-current efficiency (ABPE) value of NF1-NSP (0.206%) was found to be 1.87 times higher than that of NF1-P (0.11%) and 4.7 times higher than that of pure hematite deposited on FTO-coated glass (0.044%). The higher PEC water oxidation activity of p-NiFe 2 O 4 /n-Fe 2 O 3 composite thin film as compared with pure hematite is attributed to the Z-path scheme and better separation of electrons and holes. The increased surface area and greater light

Positron annihilation study of the CoFe2O4 ferrofluid

International Nuclear Information System (INIS)

Zhao Baogang; Ma Zhongping; Liu Cunye; Li Jian; Lin Yueqiang

2000-01-01

The CoFe 2 O 4 ferro fluid was studied by positron annihilation technique. The experimental results showed that there were three kinds of life-time state τ 1 = 151.0 ps, τ 2 = 457.9 ps and τ 3 = 2325.6 ps in the positron annihilation spectrum. It indicated that there were a large number of vacancy and vacancy cluster in the surface layer of the CoFe 2 O 4 nanoparticles

NMR of proteins (4Fe-4S): structural properties and intramolecular electron transfer; RMN de proteines (4Fe-4S): proprietes structurales et transfert electronique intramoleculaire

Energy Technology Data Exchange (ETDEWEB)

Huber, J G

1996-10-17

NMR started to be applied to Fe-S proteins in the seventies. Its use has recently been enlarged as the problems arising from the paramagnetic polymetallic clusters ware overcome. Applications to [4Fe-4S] are presented herein. The information derived thereof deepens the understanding of the redox properties of these proteins which play a central role in the metabolism of bacterial cells. The secondary structure elements and the overall folding of Chromatium vinosum ferredoxin (Cv Fd) in solution have been established by NMR. The unique features of this sequence have been shown to fold as an {alpha} helix at the C-terminus and as a loop between two cysteines ligand of one cluster: these two parts localize in close proximity from one another. The interaction between nuclear and electronic spins is a source of additional structural information for (4Fe-AS] proteins. The conformation of the cysteine-ligands, as revealed by the Fe-(S{sub {gamma}}-C{sub {beta}}-H{sub {beta}})Cys dihedral angles, is related to the chemical shifts of the signals associated with the protons of these residues. The longitudinal relaxation times of the protons depend on their distance to the cluster. A quantitative relationship has been established and used to show that the solution structure of the high-potential ferredoxin from Cv differs significantly from the crystal structure around Phe-48. Both parameters (chemical shifts and longitudinal relaxation times) give also insight into the electronic and magnetic properties of the [4Fe-4S] clusters. The rate of intramolecular electron transfer between the two [4FE-4S] clusters of ferredoxins has been measured by NMR. It is far slower in the case of Cv Fd than for shorter ferredoxins. The difference may be associated with changes in the magnetic and/or electronic properties of one cluster. The strong paramagnetism of the [4Fe-4S] clusters, which originally limited the applicability of NMR to proteins containing these cofactors, has been proven

Cluster model calculation for X-ray magnetic circular dichroism at rare-earth (R) L sub 2 sub , sub 3 absorption edges in R sub 2 Fe sub 1 sub 4 B

CERN Document Server

Asakura, K; Harada, I; Ogasawara, H; Fukui, K; Kotani, A

2002-01-01

X-ray magnetic circular dichroism (MCD) at the L sub 2 sub , sub 3 absorption edges for the entire series of rare-earth (RE) elements in R sub 2 Fe sub 1 sub 4 B (R=RE) is studied based on a cluster model including 10 RE and 16 Fe atoms. The cluster model takes into account band effects of RE 5d states, to which the electric dipole transition occurs from the core 2p states, as well as spin polarization of the 5d states due to the interatomic hybridization with the spin polarized Fe 3d states. We also take into account spin and orbital polarization of the 5d states due to the 5d-4f intra-atomic exchange interaction, and the 2p to 4f quadrupole transition. The calculated results are in satisfactory agreement with experimental ones, suggesting that the cluster model calculation provides a new method to calculate quantitatively MCD spectra of RE systems with complicated atomic arrangements. (author)

Out-of-equilibrium nanocrystalline R1-s(Fe,M)5+2s alloys (R=Sm,Pr; M=Co,Si,Ga)

International Nuclear Information System (INIS)

Bessais, L.; Djega-Mariadassou, C.

2005-01-01

The out-of-equilibrium hexagonal P6/mmm R 1-s (Fe,M) 5+2s (R=Sm,Pr and M=Co, Si or Ga) intermetallics are obtained by controlled nanocrystallization. A model is presented to explain the structure of the hexagonal phases, which stoichiometry is consistent with Sm(Fe,M) 9 and R(Fe,Ti,Co) 10 . The Curie temperatures increase versus Ga, Si, Co content. The analysis of the Moessbauer spectra leads to monotonous variation of the hyperfine parameters. The refinement of the Moessbauer spectra was performed on the basis of the correlation between Wigner-Seitz cell volumes obtained from X-ray diffraction results and isomer shifts. The abundance of each magnetic site was calculated by the multinomial distribution law. For a given substituting Co, Si, Ga content, the sequence for the isomer shift in the hexagonal cell is 2e>3g>6l. With increasing M content, the isomer shift of the 3g site remains quasi-constant. Those approaches lead to the location of Si, Ga, Co in 3g site, Ti in 6l site. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Magnetic and catalytic properties of inverse spinel CuFe{sub 2}O{sub 4} nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Anandan, S., E-mail: sanand@nitt.edu [Nanomaterials and Solar Energy Conversion Lab, Department of Chemistry, National Institute of Technology, Trichy 620 015 (India); Department of Environmental Engineering and Science, Feng Chia University, Taichung 407, Taiwan (China); Selvamani, T.; Prasad, G. Guru [Nanomaterials and Solar Energy Conversion Lab, Department of Chemistry, National Institute of Technology, Trichy 620 015 (India); Asiri, A.M. [The Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21413 (Saudi Arabia); Wu, J.J., E-mail: jjwu@fcu.edu.tw [Department of Environmental Engineering and Science, Feng Chia University, Taichung 407, Taiwan (China)

2017-06-15

Highlights: • Copper ferrite (CuFe{sub 2}O{sub 4}) nanoparticles were synthesized via citrate-nitrate combustion method. • Spectroscopic information’s have found that CuFe{sub 2}O{sub 4} nanoparticles as an inverse spinel structure. • Magnetic study exhibits CuFe{sub 2}O{sub 4} nanoparticles have ferromagnetic behavior. • CuFe{sub 2}O{sub 4} nanoparticles employed for photocatalytic decolourisation of methylene blue under visible light irradiation. - Abstract: In this research, inverse spinel copper ferrite nanoparticles (CuFe{sub 2}O{sub 4} NPs) were synthesized via citrate-nitrate combustion method. The crystal structure, particle size, morphology and magnetic studies were investigated using various instrumental tools to illustrate the formation of the inverse spinel structure. Mossbauer spectrometry identified Fe is located both in the tetrahedral and octahedral site in the ratio (40:60) and the observed magnetic parameters values such as saturation magnetization (M{sub s} = 20.62 emu g{sup −1}), remnant magnetization (M{sub r} = 11.66 emu g{sup −1}) and coercivity (H{sub c} = 63.1 mTesla) revealed that the synthesized CuFe{sub 2}O{sub 4} NPs have a typical ferromagnetic behaviour. Also tested CuFe{sub 2}O{sub 4} nanoparticles as a photocatalyst for the decolourisation of methylene blue (MB) in the presence of peroxydisulphate as the oxidant.

Synthesis and characterization of Sr2Ir1−xMxO4 (M=Ti, Fe, Co) solid solutions

International Nuclear Information System (INIS)

Gatimu, Alvin J.; Berthelot, Romain; Muir, Sean; Sleight, Arthur W.; Subramanian, M.A.

2012-01-01

The effects of Ti, Fe and Co substitutions for Ir on the structure and on the physical properties of Sr 2 IrO 4 are investigated. A complete solid solution Sr 2 Ir 1−x Ti x O 4 is obtained while both Fe and Co doping are relatively limited. In each case however, the c-axis cell parameter and the initial IrO 6 octahedra tilting decreases with substitution. Doping with Ti, Fe and Co results in a decrease of the magnetic susceptibility and in an increase in the paramagnetic effective moment for Co and Fe doped samples and a suppression of the weak ferromagnetic ordering observed for Sr 2 IrO 4 . - Graphical abstract: Solid solutions of Sr 2 Ir 1−x M x O 4 (M=Ti, Fe, Co) have been synthesized and characterized by powder X-ray diffraction, magnetism and electrical measurements. Changes in the a parameter and decreases in both the c-axis cell parameters and the initial IrO 6 octahedra tilting are found to be correlated. Highlights: ► Solid Solutions of Sr 2 Ir 1−x M x O 4 (M=Ti, Fe, Co) are synthesized. ► The Sr 2 Ir 1−x Ti x O 4 solid solution is complete while those of Fe and Co are relatively limited. ► The change in a cell parameter with substitution is much less than that of the c parameter. ► Decreased tilting and the smaller size of the M cation contrastingly affect the a parameter. ► Doping results in a suppression of the weak ferromagnetic ordering in Sr 2 IrO 4 .

Synthesis and characterization of Sr{sub 2}Ir{sub 1-x}M{sub x}O{sub 4} (M=Ti, Fe, Co) solid solutions

Energy Technology Data Exchange (ETDEWEB)

Gatimu, Alvin J.; Berthelot, Romain; Muir, Sean; Sleight, Arthur W. [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States); Subramanian, M.A., E-mail: mas.subramanian@oregonstate.edu [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States)

2012-06-15

The effects of Ti, Fe and Co substitutions for Ir on the structure and on the physical properties of Sr{sub 2}IrO{sub 4} are investigated. A complete solid solution Sr{sub 2}Ir{sub 1-x}Ti{sub x}O{sub 4} is obtained while both Fe and Co doping are relatively limited. In each case however, the c-axis cell parameter and the initial IrO{sub 6} octahedra tilting decreases with substitution. Doping with Ti, Fe and Co results in a decrease of the magnetic susceptibility and in an increase in the paramagnetic effective moment for Co and Fe doped samples and a suppression of the weak ferromagnetic ordering observed for Sr{sub 2}IrO{sub 4}. - Graphical abstract: Solid solutions of Sr{sub 2}Ir{sub 1-x}M{sub x}O{sub 4} (M=Ti, Fe, Co) have been synthesized and characterized by powder X-ray diffraction, magnetism and electrical measurements. Changes in the a parameter and decreases in both the c-axis cell parameters and the initial IrO{sub 6} octahedra tilting are found to be correlated. Highlights: Black-Right-Pointing-Pointer Solid Solutions of Sr{sub 2}Ir{sub 1-x}M{sub x}O{sub 4} (M=Ti, Fe, Co) are synthesized. Black-Right-Pointing-Pointer The Sr{sub 2}Ir{sub 1-x}Ti{sub x}O{sub 4} solid solution is complete while those of Fe and Co are relatively limited. Black-Right-Pointing-Pointer The change in a cell parameter with substitution is much less than that of the c parameter. Black-Right-Pointing-Pointer Decreased tilting and the smaller size of the M cation contrastingly affect the a parameter. Black-Right-Pointing-Pointer Doping results in a suppression of the weak ferromagnetic ordering in Sr{sub 2}IrO{sub 4}.

Dopant driven tunability of dielectric relaxation in MxCo(1-x)Fe2O4 (M: Zn2+, Mn2+, Ni2+) nano-ferrites

Science.gov (United States)

Datt, Gopal; Abhyankar, A. C.

2017-07-01

Nano-ferrites with tunable dielectric and magnetic properties are highly desirable in modern electronics industries. This work reports the effect of ferromagnetic (Ni), anti-ferromagnetic (Mn), and non-magnetic (Zn) substitution on cobalt-ferrites' dielectric and magnetic properties. The Rietveld analysis of XRD data and the Raman spectroscopic study reveals that all the samples are crystallized in the Fd-3m space group. The T2g Raman mode was observed to split into branches, which is due to the presence of different cations (with different vibrational frequencies) at crystallographic A and B-sites. The magnetization study shows that the MnCoFe2O4 sample has the highest saturation magnetization of 87 emu/g, which is attributed to the presence of Mn2+ cations at the B-site with a magnetic moment of 5 μB. The dielectric permittivity of these nanoparticles (NPs) obeys the modified Debye model, which is further supported by Cole-Cole plots. The dielectric constant of MnCoFe2O4 ferrite is found to be one order higher than that of the other two ferrites. The increased bond length of the Mn2+-O2- bond along with the enhanced d-d electron transition between Mn 2 +/Co 2 +⇋Fe 3 + cations at the B-site are found to be the main contributing factors for the enhanced dielectric constant of MnCoFe2O4 ferrite. We find evidence of variable-range hopping of localized polarons in these ferrite NPs. The activation energy, hopping range, and density of states N (" separators="|EF ), of these polarons were calculated using Motts' 1/4th law. The estimated activation energies of these polarons at 300 K were found to be 288 meV, 426 meV, and 410 meV, respectively, for the MnCoFe2O4, NiCoFe2O4, and ZnCoFe2O4 ferrite NPs, while the hopping range of these polarons were found to be 27.14 Å, 11.66 Å, and 8.17 Å, respectively. Observation of a low dielectric loss of ˜0.04, in the frequency range of 0.1-1 MHz, in these NPs makes them potential candidates for energy harvesting devices in

Structural and magnetic properties of CoFe{sub 2}O{sub 4}/NiFe{sub 2}O{sub 4} core/shell nanocomposite prepared by the hydrothermal method

Energy Technology Data Exchange (ETDEWEB)

Sattar, A.A. [Department of Physics, Faculty of Science, Ain Shams University, 11566 Abbasia, Cairo (Egypt); EL-Sayed, H.M., E-mail: h_m_elsaid@hotmail.com [Department of Physics, Faculty of Science, Ain Shams University, 11566 Abbasia, Cairo (Egypt); ALsuqia, Ibrahim [Department of Physics, Faculty of Education and Applied Science, Hajjah University, Alshahli, Hajjah (Yemen)

2015-12-01

CoFe{sub 2}O{sub 4}/NiFe{sub 2}O{sub 4} core/shell magnetic nanocomposite was synthesized by using hydrothermal method.The analysis of XRD indicated the coexistence of CoFe{sub 2}O{sub 4}, NiFe{sub 2}O{sub 4}as core/shell composite. The core/shell structure of the composite sample has been confirmed by HR-TEM images, EDX and FT-IR measurements. The size of obtained core/shell nanoparticles was 17 nm in core diameter and about 3 nm in shell thickness. The magnetization measurements showed that both the coercive field and the saturation magnetization of the resulting core/shell nanocomposite were slightly decreased compared to those of the CoFe{sub 2}O{sub 4} core but the thermal stability is of the magnetization parameter was enhanced. Furthermore, superparamagnetic phase is established at temperatures higher than the room temperature. The results were discussed in terms of the surface pinning and the magnetic interaction at the interface between the core and shell. - Highlights: • CoFe{sub 2}O{sub 4}/NiFe{sub 2}O{sub 4} core/shell could be prepared by hydrothermal method. • The structural analysis proved the formation of NiFe{sub 2}O{sub 4} shell with thickness 3 nm. • The thermal stability of M{sub s} and H{sub c} is enhanced due to the presence of NiFe{sub 2}O{sub 4} as a shell. • Super paramagnetic transition is confirmed and the effective magnetic anisotropy was calculated.

Magnetic MoS2 pizzas and sandwiches with Mnn (n = 1-4) cluster toppings and fillings: A first-principles investigation

Science.gov (United States)

Zhang, Meng; Huang, Zhongjia; Wang, Xiao; Zhang, Hongyu; Li, Taohai; Wu, Zhaolong; Luo, Youhua; Cao, Wei

2016-01-01

The inorganic layered crystal (ILC) MoS2 in low dimensions is considered as one of the most promising and efficient semiconductors. To enable the magnetism and keep intrinsic crystal structures, we carried out a first-principles study of the magnetic and semiconductive monolayer MoS2 adsorbed with the Mnn (n = 1-4) clusters, and bilayer MoS2 intercalated with the same clusters. Geometric optimizations of the Mnn@MoS2 systems show the complexes prefer to have Mnn@MoS2(M) pizza and Mnn@MoS2(B) sandwich forms in the mono- and bi-layered cases, respectively. Introductions of the clusters will enhance complex stabilities, while bonds and charge transfers are found between external Mn clusters and the S atoms in the hosts. The pizzas have medium magnetic moments of 3, 6, 9, 4 μB and sandwiches of 3, 2, 3, 2 μB following the manganese numbers. The pizzas and sandwiches are semiconductors, but with narrower bandgaps compared to their corresponding pristine hosts. Direct bandgaps were found in the Mnn@MoS2(M) (n = 1,4) pizzas, and excitingly in the Mn1@MoS2(B) sandwich. Combining functional clusters to the layered hosts, the present work shows a novel material manipulation strategy to boost semiconductive ILCs applications in magnetics.

High pressure structural investigation on alluaudites Na{sub 2}Fe{sub 3}(PO{sub 4}){sub 3}-Na{sub 2}FeMn{sub 2}(PO{sub 4}){sub 3} system

Energy Technology Data Exchange (ETDEWEB)

Gao, Jing [Key Laboratory of Orogenic Belts and Crustal Evolution, MOE, School of Earth and Space Sciences, Peking University, Beijing 100871 (China); Huang, Weifeng [College of Engineering, Peking University, Beijing 100871 (China); Qin, Shan [Key Laboratory of Orogenic Belts and Crustal Evolution, MOE, School of Earth and Space Sciences, Peking University, Beijing 100871 (China); Wu, Xiang, E-mail: wuxiang@cug.edu.cn [State key laboratory of geological processes and mineral resources, China University of Geosciences, Wuhan 430074 (China)

2017-03-15

Alluaudites are promising electrochemical materials benefited from the open structure. Structural variations of alluaudites Na{sub 2}M{sub 3}(PO{sub 4}){sub 3} (M{sub 3}=Fe{sub 3}, Fe{sub 2}Mn and FeMn{sub 2}) system have been studied by synchrotron radiation X-ray diffraction combined with diamond anvil cell technique up to ~10 GPa at room temperature. No phase transition is observed. The excellent structural stability is mainly due to the flexible framework plus strong covalent P-O bond. Mn{sup 2+} instead of Fe can be described as Na{sup +}+2Fe{sup 2+}→Mn{sup 2+}+Fe{sup 3+}+□ where □ represents a lattice vacancy. The replacement of Fe with larger Mn{sup 2+} is equivalent to applying negative chemical pressure to the material. And it causes a more compressible b-axis, lattice expansion, structural compressibility and intensifies the core/electron-electron interactions of Fe. External pressure effect produces anisotropic lattice shrinkage. Structural considerations related to these variations and promising application prospects are discussed. - Graphical abstract: Figure 1 The crystal structure of alluaudites Na{sub 2}M{sub 3}(PO{sub 4}){sub 3} (M{sub 3}=Fe{sub 3}, Fe{sub 2}Mn and FeMn{sub 2}) projected along the c-axis. Alluaudites adopt a flexible framework plus strong covalent P-O bond, which contribute to excellent structural stability up to ~10 GPa. Mn{sup 2+} instead of Fe can be described as Na{sup ++}2Fe{sup 2+}→Mn{sup 2+}+Fe{sup 3+}+□ where □ represents a lattice vacancy, and it is equivalent to applying negative chemical pressure to the host. The substitution causes a more compressible b-axis, lattice expansion, structural compressibility and intensifies the core/electron-electron interactions of Fe.

Effect of mitochondrial complex I inhibition on Fe-S cluster protein activity

Energy Technology Data Exchange (ETDEWEB)

Mena, Natalia P. [Department of Biology, Faculty of Sciences, Universidad de Chile, Las Palmeras 3425, Santiago (Chile); Millennium Institute of Cell Dynamics and Biotechnology, Santiago (Chile); Bulteau, Anne Laure [UPMC Univ Paris 06, UMRS 975 - UMR 7725, Centre de Recherche en Neurosciences, ICM, Therapeutique Experimentale de la Neurodegenerescence, Hopital de la Salpetriere, F-75005 Paris (France); Inserm, U 975, Centre de Recherche en Neurosciences, ICM, Therapeutique Experimentale de la Neurodegenerescence, Hopital de la Salpetriere, F-75005 Paris (France); CNRS, UMR 7225, Centre de Recherche en Neurosciences, ICM, Therapeutique Experimentale de la Neurodegenerescence, Hopital de la Salpetriere, F-75005 Paris (France); ICM, Therapeutique Experimentale de la Neurodegenerescence, Hopital de la Salpetriere, Paris 75013 (France); Salazar, Julio [Millennium Institute of Cell Dynamics and Biotechnology, Santiago (Chile); Hirsch, Etienne C. [UPMC Univ Paris 06, UMRS 975 - UMR 7725, Centre de Recherche en Neurosciences, ICM, Therapeutique Experimentale de la Neurodegenerescence, Hopital de la Salpetriere, F-75005 Paris (France); Inserm, U 975, Centre de Recherche en Neurosciences, ICM, Therapeutique Experimentale de la Neurodegenerescence, Hopital de la Salpetriere, F-75005 Paris (France); CNRS, UMR 7225, Centre de Recherche en Neurosciences, ICM, Therapeutique Experimentale de la Neurodegenerescence, Hopital de la Salpetriere, F-75005 Paris (France); ICM, Therapeutique Experimentale de la Neurodegenerescence, Hopital de la Salpetriere, Paris 75013 (France); Nunez, Marco T., E-mail: mnunez@uchile.cl [Department of Biology, Faculty of Sciences, Universidad de Chile, Las Palmeras 3425, Santiago (Chile); Millennium Institute of Cell Dynamics and Biotechnology, Santiago (Chile)

2011-06-03

Highlights: {yields} Mitochondrial complex I inhibition resulted in decreased activity of Fe-S containing enzymes mitochondrial aconitase and cytoplasmic aconitase and xanthine oxidase. {yields} Complex I inhibition resulted in the loss of Fe-S clusters in cytoplasmic aconitase and of glutamine phosphoribosyl pyrophosphate amidotransferase. {yields} Consistent with loss of cytoplasmic aconitase activity, an increase in iron regulatory protein 1 activity was found. {yields} Complex I inhibition resulted in an increase in the labile cytoplasmic iron pool. -- Abstract: Iron-sulfur (Fe-S) clusters are small inorganic cofactors formed by tetrahedral coordination of iron atoms with sulfur groups. Present in numerous proteins, these clusters are involved in key biological processes such as electron transfer, metabolic and regulatory processes, DNA synthesis and repair and protein structure stabilization. Fe-S clusters are synthesized mainly in the mitochondrion, where they are directly incorporated into mitochondrial Fe-S cluster-containing proteins or exported for cytoplasmic and nuclear cluster-protein assembly. In this study, we tested the hypothesis that inhibition of mitochondrial complex I by rotenone decreases Fe-S cluster synthesis and cluster content and activity of Fe-S cluster-containing enzymes. Inhibition of complex I resulted in decreased activity of three Fe-S cluster-containing enzymes: mitochondrial and cytosolic aconitases and xanthine oxidase. In addition, the Fe-S cluster content of glutamine phosphoribosyl pyrophosphate amidotransferase and mitochondrial aconitase was dramatically decreased. The reduction in cytosolic aconitase activity was associated with an increase in iron regulatory protein (IRP) mRNA binding activity and with an increase in the cytoplasmic labile iron pool. Since IRP activity post-transcriptionally regulates the expression of iron import proteins, Fe-S cluster inhibition may result in a false iron deficiency signal. Given that

Effect of mitochondrial complex I inhibition on Fe-S cluster protein activity

International Nuclear Information System (INIS)

Mena, Natalia P.; Bulteau, Anne Laure; Salazar, Julio; Hirsch, Etienne C.; Nunez, Marco T.

2011-01-01

Highlights: → Mitochondrial complex I inhibition resulted in decreased activity of Fe-S containing enzymes mitochondrial aconitase and cytoplasmic aconitase and xanthine oxidase. → Complex I inhibition resulted in the loss of Fe-S clusters in cytoplasmic aconitase and of glutamine phosphoribosyl pyrophosphate amidotransferase. → Consistent with loss of cytoplasmic aconitase activity, an increase in iron regulatory protein 1 activity was found. → Complex I inhibition resulted in an increase in the labile cytoplasmic iron pool. -- Abstract: Iron-sulfur (Fe-S) clusters are small inorganic cofactors formed by tetrahedral coordination of iron atoms with sulfur groups. Present in numerous proteins, these clusters are involved in key biological processes such as electron transfer, metabolic and regulatory processes, DNA synthesis and repair and protein structure stabilization. Fe-S clusters are synthesized mainly in the mitochondrion, where they are directly incorporated into mitochondrial Fe-S cluster-containing proteins or exported for cytoplasmic and nuclear cluster-protein assembly. In this study, we tested the hypothesis that inhibition of mitochondrial complex I by rotenone decreases Fe-S cluster synthesis and cluster content and activity of Fe-S cluster-containing enzymes. Inhibition of complex I resulted in decreased activity of three Fe-S cluster-containing enzymes: mitochondrial and cytosolic aconitases and xanthine oxidase. In addition, the Fe-S cluster content of glutamine phosphoribosyl pyrophosphate amidotransferase and mitochondrial aconitase was dramatically decreased. The reduction in cytosolic aconitase activity was associated with an increase in iron regulatory protein (IRP) mRNA binding activity and with an increase in the cytoplasmic labile iron pool. Since IRP activity post-transcriptionally regulates the expression of iron import proteins, Fe-S cluster inhibition may result in a false iron deficiency signal. Given that inhibition of complex

Investigation into the dehydration of selenate doped Na2M(SO4)2·2H2O (M = Mn, Fe, Co and Ni): Stabilisation of the high Na content alluaudite phases Na3M1.5(SO4)3-1.5x(SeO4)1.5x (M = Mn, Co and Ni) through selenate incorporation

Science.gov (United States)

Driscoll, L. L.; Kendrick, E.; Knight, K. S.; Wright, A. J.; Slater, P. R.

2018-02-01

In this paper we report an investigation into the phases formed on dehydration of Na2M(SO4)2-x(SeO4)x·2H2O (0 ≤ x ≤ 1; M = Mn, Fe, Co and Ni). For the Fe series, all attempts to dehydrate the samples doped with selenate resulted in amorphous products, and it is suspected that a side redox reaction involving the Fe and selenate may be occurring leading to phase decomposition and hence the lack of a crystalline product on dehydration. For M = Mn, Co, Ni, the structure observed was shown to depend upon the transition metal cation and level of selenate doping. An alluaudite phase, Na3M1.5(SO4)3-1.5x(SeO4)1.5x, was observed for the selenate doped compositions, with this phase forming as a single phase for x ≥ 0.5 M = Co, and x = 1.0 M = Ni. For M = Mn, the alluaudite structure is obtained across the series, albeit with small impurities for lower selenate content samples. Although the alluaudite-type phases Na2+2y(Mn/Co)2-y(SO4)3 have recently been reported [1,2], doping with selenate appears to increase the maximum sodium content within the structure. Moreover, the selenate doped Ni based samples reported here are the first examples of a Ni sulfate/selenate containing system exhibiting the alluaudite structure.

2D parallel interpenetration of [M2(bpp)4X4] [M, Fe(II)/Co(II); bpp, 4,4'-trimethylenedipyridine; X, SCN-, SeCN- and N3-] complexes: Pseudohalide-dependent conformation of bpp

International Nuclear Information System (INIS)

Manna, Subal Chandra; Jana, Atish Dipankar; Rosair, Georgina M.; Drew, Michael G.B.; Mostafa, Golam; Ray Chaudhuri, Nirmalendu

2008-01-01

Three coordination complexes of Co(II)/Fe(II) with 4,4'-trimethylenedipyridine (bpp) and pseudohalides (SCN - , SeCN - and N 3 - ) have been synthesized. The complexes have been characterized by X-ray single crystal structure determination. They are isomorphous having 2D layers in which two independent wavy nets display parallel interwoven structures. Pseudohalide binds metal centers through N terminal and occupies the trans axial positions of the octahedral metal coordination environment. Pseudohalide remains pendant on both sides of the polymeric layer and help the stacking through hydrogen bonding. The conformation of bpp in the interpenetrated nets is observed to be dependent on the choice of pseudohalide. - Graphical abstract: Complexes of [M 2 (bpp) 4 X 4 ] [M, Fe(II)/Co(II); bpp, 4,4'-trimethylenedipyridine; X, SCN - , SeCN - and N3 - ] have been synthesized. The structural analysis reveals undulated 2D network with (4,4) net topology adopting two different conformations of bpp alternately. Two such networks undergo parallel interpenetration. Pseudohalides are observed to help in stacking the interpenetrated nets through hydrogen bonding

Structural, optical and magnetic studies of CuFe2O4, MgFe2O4 and ZnFe2O4 nanoparticles prepared by hydrothermal/solvothermal method

Science.gov (United States)

Kurian, Jessyamma; Mathew, M. Jacob

2018-04-01

In this paper we report the structural, optical and magnetic studies of three spinel ferrites namely CuFe2O4, MgFe2O4 and ZnFe2O4 prepared in an autoclave under the same physical conditions but with two different liquid medium and different surfactant. We use water as the medium and trisodium citrate as the surfactant for one method (Hydrothermal method) and ethylene glycol as the medium and poly ethylene glycol as the surfactant for the second method (solvothermal method). The phase identification and structural characterization are done using XRD and morphological studies are carried out by TEM. Cubical and porous spherical morphologies are obtained for hydrothermal and solvothermal process respectively without any impurity phase. The optical studies are carried out using FTIR and UV-Vis reflectance spectra. In order to elucidate the nonlinear optical behaviour of the prepared nanomaterial, open aperture z-scan technique is used. From the fitted z-scan curves nonlinear absorption coefficient and the saturation intensity are determined. The magnetic characterization of the samples is performed at room temperature using vibrating sample magnetometer measurements. The M-H curves obtained are fitted using theoretical equation and the different components of magnetization are determined. Nanoparticles with high saturation magnetization are obtained for MgFe2O4 and ZnFe2O4 prepared under solvothermal reaction. The magnetic hyperfine parameters and the cation distribution of the prepared materials are determined using room temperature Mössbauer spectroscopy. The fitted spectra reveal the difference in the magnetic hyperfine parameters owing to the change in size and morphology.

Phase transformations, ionic conductivity and dipole ordering of NASICON-like double phosphates Na3M2(PO4)3 (M-Sc,Fe,Cr)

International Nuclear Information System (INIS)

Kalinin, V.B.

1990-01-01

Experimental data obtained using ceramic samples of Na 3 M 2 (PO 4 ) 3 and solid solutions on their basis have been analyzed and generalized. It is shown that isostoichiometry of Na 3 M 2 (PO 4 ) 3 compounds and different types of dipole ordering in their α-phases stimulate investigations of subsolidus regions in the systems Na 3 Sc 2 (PO 4 ) 3 -Na 3 Fe 2 (PO 4 ) 3 , Na 3 Sc 2 (PO 4 ) 3 -Na 3 Cr 2 (PO 4 ) 3 , Na 3 Fe 2 (PO 4 ) 3 -Na 3 Cr 2 (PO 4 ) 3 .It proved possible to detect changes of the properties in case of ferroelectric-antiferroelectric, antiferroelectric-antiferroelectric transitions

Electrospun ZnFe{sub 2}O{sub 4}-based nanofiber composites with enhanced supercapacitive properties

Energy Technology Data Exchange (ETDEWEB)

Agyemang, Frank Ofori; Kim, Hern, E-mail: hernkim@mju.ac.kr

2016-09-15

Highlights: • Electrospun ZnFe{sub 2}O{sub 4}-based nanofibers were successfully fabricated. • The electrochemical properties of ZnFe{sub 2}O{sub 4} were enhanced by addition of ZnO and Fe{sub 2}O{sub 3.} • A specific capacitance of 590 F g{sup −1} was achieved from a CV curve at a scan rate of 5 mV s{sup −1.} • The electrode materials poses excellent cycling stability even after 3000 cycles. - Abstract: Herein, we are reporting a facile method to synthesis ZnFe{sub 2}O{sub 4}-based nanofibers (ZnFe{sub 2}O{sub 4}, ZnO–ZnFe{sub 2}O{sub 4} and Fe{sub 2}O{sub 3}–ZnFe{sub 2}O{sub 4}) via the electrospinning technique using zinc acetonate and ferric acetonate as the metal oxide precursor and polyvinyl pyrrolidone (PVP) as the polymer. The as-prepared electrospun nanofiber composites were calcined at 500 °C to obtain crystalline porous nanofibers. The effect of different compositions on the morphology of each sample as well as their electrochemical properties when employed as electrode materials was studied. The results show that the as-prepared electrodes exhibited excellent performance with their specific capacitances calculated from the CV curves as 590, 490 and 450 F g{sup −1} for Fe{sub 2}O{sub 3}–ZnFe{sub 2}O{sub 4}, ZnO–ZnFe{sub 2}O{sub 4} and ZnFe{sub 2}O{sub 4} respectively at a scan rate of 5 mV s{sup −1}. Excellent stability of the electrodes was also observed even after 3000 cycles. The results obtained suggest these electrode materials might be promising candidates for supercapacitor application.

Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties

International Nuclear Information System (INIS)

Lin, Qisheng; Taufour, Valentin; Zhang, Yuemei; Wood, Max; Drtina, Thomas; Bud’ko, Sergey L.; Canfield, Paul C.; Miller, Gordon J.

2015-01-01

Single crystals of Nd 4 FeOS 6 were grown from an Fe–S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd 4 MnOSe 6 -type structure (P6 3 mc, a=9.2693(1) Å, c=6.6650(1)Å, V=495.94(1) Å 3 , Z=2), featuring parallel chains of face-sharing [FeS 6×1/2 ] 4− trigonal antiprisms and interlinked [Nd 4 OS 3 ] 4+ cubane-like clusters. Oxygen atoms were found to be trapped by Nd 4 clusters in the [Nd 4 OS 3 ] 4 + chains. Structural differences among Nd 4 MnOSe 6 -type Nd 4 FeOS 6 and the related La 3 CuSiS 7 − and Pr 8 CoGa 3 -type structures have been described. Magnetic susceptibility measurements on Nd 4 FeOS 6 suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions. - Graphical abstract: Trapping of oxygen in Nd 4 tetrahedral clusters results in the formation of the Nd 4 MnOSe 6 -type Nd 4 FeOS 6 , in contrast to the La 3 CuSiS 7 -type oxygen-free Nd 4 FeS 7 and related Pr 8 CoGa 3 -type structures. Complex magnetic frustration inhibits magnetic ordering at low temperature. - Highlights: • Single crystals of Nd 4 FeOS 6 were grown using self-flux method. • Oxygen was found trapped by Nd 4 tetrahedral clusters. • Comparison with two closely related structural types were discussed. • Magnetic measurements revealed antiferromagnetic (AFM) interaction. • VASP calculations confirmed strong magnetic frustration in AFM model

Examination of the magnetic hyperthermia and other magnetic properties of CoFe2O4@MgFe2O4 nanoparticles using external field Mössbauer spectroscopy

Science.gov (United States)

Park, Jeongho; Choi, Hyunkyung; Kim, Sam Jin; Kim, Chul Sung

2018-05-01

CoFe2O4@MgFe2O4 core/shell nanoparticles were synthesized by high temperature thermal decomposition with seed-mediated growth. The crystal structure and magnetic properties of the nanoparticles were investigated using X-ray diffractometry (XRD), vibrating sample magnetometry (VSM), and Mössbauer spectrometry. The magnetic hyperthermia properties were investigated using a MagneTherm device. Analysis of the XRD patterns showed that CoFe2O4@MgFe2O4 had a cubic spinel crystal structure with space group Fd-3m and a lattice constant (a0) of 8.3686 Å. The size and morphology of the CoFe2O4@MgFe2O4 nanoparticles were confirmed by HR-TEM. The VSM measurements showed that the saturation magnetization (MS) of CoFe2O4@MgFe2O4 was 77.9 emu/g. The self-heating temperature of CoFe2O4@MgFe2O4 was 37.8 °C at 112 kHz and 250 Oe. The CoFe2O4@MgFe2O4 core/shell nanoparticles showed the largest saturation magnetization value, while their magnetic hyperthermia properties were between those of the CoFe2O4 and MgFe2O4 nanoparticles. In order to investigate the hyperfine interactions of CoFe2O4, MgFe2O4, and CoFe2O4@MgFe2O4, we performed Mössbauer spectrometry at various temperatures. In addition, Mössbauer spectrometry of CoFe2O4@MgFe2O4 was performed at 4.2 K with applied fields of 0-4.5 T, and the results were analyzed with sextets for the tetrahedral A-site and sextets for the octahedral B-site.

Reduction under hydrogen of ferrite MFe{sub 2}O{sub 4} (M: Fe, Co, Ni) nanoparticles obtained by hydrolysis in polyol medium: A novel route to elaborate CoFe{sub 2}, Fe and Ni{sub 3}Fe nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Ballot, N.; Schoenstein, F.; Mercone, S.; Chauveau, T.; Brinza, O. [Laboratoire des Sciences des Procedes et des Materiaux, CNRS, LSPM - UPR 3407, Universite Paris 13, PRES Sorbonne-Paris-Cite, 99 Avenue J.-B. Clement, 93430 Villetaneuse (France); Jouini, N., E-mail: jouini@univ-paris13.fr [Laboratoire des Sciences des Procedes et des Materiaux, CNRS, LSPM - UPR 3407, Universite Paris 13, PRES Sorbonne-Paris-Cite, 99 Avenue J.-B. Clement, 93430 Villetaneuse (France)

2012-09-25

Highlights: Black-Right-Pointing-Pointer Spinels nano-particles MFe{sub 2}O{sub 4} (M: Co, Fe or Ni) are obtained by hydrolysis in polyol medium. Black-Right-Pointing-Pointer Gentle reduction under hydrogen flow of spinel nano-particles yields metal and alloy nanoparticles. Black-Right-Pointing-Pointer TEM and X-ray analysis show that CoFe{sub 2}, Fe and Ni{sub 3}Fe nano-particles are monocrystalline particles with size less than 160 nm. Black-Right-Pointing-Pointer Iron with size of 150 nm presents ferromagnetic behavior. Black-Right-Pointing-Pointer CoFe{sub 2} alloy with size of 55 nm could be considered as a superparamagnetic material. - Abstract: A novel method to process metal and various alloy particles of nanometric size is described. The first step consists in the elaboration of MFe{sub 2}O{sub 4} (M: Fe, Ni or Co) spinel nanoparticles in polyol medium via hydrolysis and the second one in gently reducing these latter under hydrogen at 300 Degree-Sign C. X-ray diffraction analysis shows that pure Fe and CoFe{sub 2} alloy are well obtained by reducing Fe{sub 3}O{sub 4} and CoFe{sub 2}O{sub 4}, respectively. This is not the case when we try to reduce NiFe{sub 2}O{sub 4}. A mixture of Fe and Ni{sub 3}Fe is observed. TEM analysis reveals that the size of metal particles stays within the range of a few tenths of nm up to 150 nm, while the precursors (MFe{sub 2}O{sub 4}) never exceed 5 nm. Our results show that the formation of metal particles occurs via two main steps: (i) reduction of the spinel oxide nanoparticles into metal ones and (ii) aggregation of the latter, leading to larger metal nanoparticles. Magnetic measurements indicate that the as-obtained metallic materials have good magnetic properties mainly affected by the sizes of the nanoparticles and the purity of the reduced phases.

Fe-S Clusters Emerging as Targets of Therapeutic Drugs

Directory of Open Access Journals (Sweden)

Laurence Vernis

2017-01-01

Full Text Available Fe-S centers exhibit strong electronic plasticity, which is of importance for insuring fine redox tuning of protein biological properties. In accordance, Fe-S clusters are also highly sensitive to oxidation and can be very easily altered in vivo by different drugs, either directly or indirectly due to catabolic by-products, such as nitric oxide species (NOS or reactive oxygen species (ROS. In case of metal ions, Fe-S cluster alteration might be the result of metal liganding to the coordinating sulfur atoms, as suggested for copper. Several drugs presented through this review are either capable of direct interaction with Fe-S clusters or of secondary Fe-S clusters alteration following ROS or NOS production. Reactions leading to Fe-S cluster disruption are also reported. Due to the recent interest and progress in Fe-S biology, it is very likely that an increasing number of drugs already used in clinics will emerge as molecules interfering with Fe-S centers in the near future. Targeting Fe-S centers could also become a promising strategy for drug development.

Synthesis and electrochemical characterization of LiCo_1_/_3Fe_2_/_3PO_4/C composite using nano CoFe_2O_4 as precursor

International Nuclear Information System (INIS)

Wu, Kaipeng; Hu, Guorong; Du, Ke; Peng, Zhongdong; Cao, Yanbing

2015-01-01

LiCo_1_/_3Fe_2_/_3PO_4/C composite was synthesized by a solid state method with CoFe_2O_4 as the precursor and glucose as the carbon source. The composite consists of homogeneous Co–Fe distributed LiCo_1_/_3Fe_2_/_3PO_4 with its particles covered by nano-carbon layers, which could prevent the growth of the particles as well as form a fast path for electronic transmission during charging and discharging process. It shows excellent electrochemical performance as the cathode for lithium-ion batteries, which delivers discharge capacities of 154.6, 152.9, 135.4, 122.3, 105.2 and 91.3 mAh g"−"1 at 0.05, 0.1, 0.5, 1, 2 and 5 C, respectively, and retains 94.6% of its initial discharge capacity after 30 cycles at 5 C. - Highlights: • Nano CoFe_2O_4 was prepared by a co-precipitation method. • LiCo_1_/_3Fe_2_/_3PO_4/C composite was synthesized using nano CoFe_2O_4 as a precursor. • Homogeneous Co–Fe distributed LiCo_1_/_3Fe_2_/_3PO_4 is obtained. • LiCo_1_/_3Fe_2_/_3PO_4/C composite exhibits a quite good electrochemical performance.

Crystal structures and magnetic properties of iron (III)-based phosphates: Na4NiFe(PO4)3 and Na2Ni2Fe(PO4)3

International Nuclear Information System (INIS)

Essehli, Rachid; Bali, Brahim El; Benmokhtar, Said; Bouziane, Khalid; Manoun, Bouchaib; Abdalslam, Mouner Ahmed; Ehrenberg, Helmut

2011-01-01

Graphical abstract: A perspective view of the Na 2 Ni 2 Fe(PO 4 ) 3 structure along the [0 0 1] direction. Both compounds seem to exibit antiferromagnetic interactions between magnetic entities at low temperature. Display Omitted Research highlights: → Nasicon and Alluaudite compounds, Iron(III)-based phosphates, Crystal structures of Na 4 NiFe(PO 4 ) 3 and Na 2 Ni 2 Fe(PO 4 ) 3 . → Magnetism behaviours of Na 4 NiFe(PO 4 ) 3 and Na 2 Ni 2 Fe(PO 4 ) 3 . → Antiferromagnetism interactions. → Mossbauer spectroscopy. - Abstract: Crystal structures from two new phosphates Na 4 NiFe(PO 4 ) 3 (I) and Na 2 Ni 2 Fe(PO 4 ) 3 (II) have been determined by single crystal X-ray diffraction analysis. Compound (I) crystallizes in a rhombohedral system (S. G: R-3c, Z = 6, a = 8.7350(9) A, c = 21.643(4) A, R 1 = 0.041, wR 2 =0.120). Compound (II) crystallizes in a monoclinic system (S. G: C2/c, Z = 4, a = 11.729(7) A, b = 12.433(5) A, c = 6.431(2) A, β = 113.66(4) o , R 1 = 0.043, wR 2 =0.111). The three-dimensional structure of (I) is closely related to the Nasicon structural type, consisting of corner sharing [(Ni/Fe)O 6 ] octahedra and [PO 4 ] tetrahedra forming [NiFe(PO 4 ) 3 ] 4+ units which align in chains along the c-axis. The Na + cations fill up trigonal antiprismatic sites within these chains. The crystal structure of (II) belongs to the alluaudite type. Its open framework results from [Ni 2 O 10 ] units of edge-sharing [NiO 6 ] octahedra, which alternate with [FeO 6 ] octahedra that form infinite chains. Coordination of these chains yields two distinct tunnels in which site Na + . The magnetization data of compound (I) reveal antiferromagnetic (AFM) interactions by the onset of deviations from a Curie-Weiss behaviour at low temperature as confirmed by Moessbauer measurements performed at 4.2 K. The corresponding temperature dependence of the reciprocal susceptibility χ -1 follows a typical Curie-Weiss behaviour for T > 105 K. A canted AFM state is proposed for

Investigation on pseudosymmetry, twinning and disorder in crystal structure determinations: Ba(H2O)M2III[PO3(OH)]4 (M=Fe, V) as examples

International Nuclear Information System (INIS)

Sun Wei; Huang Yaxi; Pan Yuanming; Mi Jinxiao

2012-01-01

Twinning commonly occurs in monoclinic crystals with dimensionally similar a and c axes and results in pseudo-orthorhombic symmetries with overlapping diffractions. For example, twinning in the new synthetic compound Ba(H 2 O)Fe 2 [PO 3 (OH)] 4 , which varies in space group from P2 1 to P2 1 /c with approximately equal a and c axial lengths, gives rise to a pseudosymmetry of C222 1 . Similarly, the related compound Ba(H 2 O)V 2 [PO 3 (OH)] 4 is commonly twinned and varies in space groups as well, arising from ordered to disordered distributions of the barium cations and water molecules in the cavities. Moreover, analyses of these and other twinned structures show that the small average standard uncertainty of bond distances is a sensitive criterion for structure determinations, especially for those involving crystal twinning as well as order–disorder. A proper structure determination leads to small standard uncertainties of the atomic displacement parameters, which further result in the small standard uncertainties of bond distances. - Graphical abstract: Ba(H 2 O)M 2 III [PO 3 (OH)] 4 (M=Fe, V) varies in space group from P2 1 to P2 1 /c, arising from ordered to disordered distributions of Ba 2+ and H 2 O in the cavities. Highlights: ► Twinning commonly occurs in monoclinic crystals with a≈c. ► Overlapping diffractions from twin domains hamper with the determination of real space groups. ► Conventional criteria for evaluating the real space groups are not effective in this case. ► Small standard uncertainty of bond distances is proposed as a sensitive criterion. ► Using this criterion we determined the order–disorder structures of Ba(H 2 O)M 2 III [PO 3 (OH)] 4 (M=Fe, V) from twinned crystals.

Synthesis of MoS2-reduced graphene oxide/Fe3O4 nanocomposite for enhanced electromagnetic interference shielding effectiveness

Science.gov (United States)

Prasad, Jagdees; Singh, Ashwani Kumar; Shah, Jyoti; Kotnala, R. K.; Singh, Kedar

2018-05-01

This article presents a facile two step hydrothermal process for the synthesis of MoS2-reduced graphene oxide/Fe3O4 (MoS2-rGO/Fe3O4) nanocomposite and its application as an excellent electromagnetic interference shielding material. Characterization tools like; scanning electron microscope, transmission electron microscope, x-ray diffraction, and Raman spectroscopy were used to confirm the formation of nanocomposite and found that spherical Fe3O4 nanoparticles are well dispersed over MoS2-rGO composite with average particle size ∼25–30 nm was confirmed by TEM. Structural characterization done by XRD was found inconsistent with the known lattice parameter of MoS2 nanosheet, reduced graphene oxide and Fe3O4 nanoparticles. Electromagnetic shielding effectiveness of MoS2-rGO/Fe3O4 nanocomposite was evaluated and found to be an excellent EMI shielding material in X-band range (8.0–12.0 GHz). MoS2-rGO composite shows poor shielding capacity (SET ∼ 3.81 dB) in entire range as compared to MoS2-rGO/Fe3O4 nanocomposite (SET ∼ 8.27 dB). It is due to interfacial polarization in the presence of EM field. The result indicates that MoS2-rGO/Fe3O4 nanocomposite provide a new stage for the next generation in high-performance EM wave absorption and EMI shielding effectiveness.

Effect of Water Content on Properties of Homogeneous [bmim]Fe(IIICl4–H2O Mixtures and Their Application in Oxidative Absorption of H2S

Directory of Open Access Journals (Sweden)

Jianhong Wang

2018-01-01

Full Text Available The potential of 1-butyl-3-methylimidazolium tetrachloroferrate ([bmim]Fe(IIICl4 for replacing an iron(III chelate catalytic solution in the catalytic oxidation of H2S is attributed to its no side reaction and no degradation of the chelating agent. The catalytic oxidation product of water in non-aqueous [bmim]Fe(IIICl4 possibly has an influence on the oxidative absorption of H2S. Water and hydrophobic [bmim]Fe(IIICl4 mixtures at water volume percents from 40% to 70% formed separate phases after srirring, without affecting the oxidative absorption of hydrogen sulfide. Then, studies on the properties of homogeneous [bmim]Fe(IIICl4–H2O mixtures at water volume percents in the range of 5.88–30% and above 80% reveal that these mixtures are both Brønsted and Lewis acids at vol % (H2O ≤ 30%, and only Lewis acids at vol % (H2O ≥ 80%. Raman spectra showed that [bmim]Fe(IIICl4 was the dominating species at vol % (H2O ≤ 30%, in contrast, [bmim]Fe(IIICl4 decomposed into FeCl3·2H2O and [bmim]Cl at vol % (H2O ≥ 80%. Further research on oxidative absorption of H2S by homogeneous [bmim]Fe(IIICl4–H2O mixtures demonstrated that [bmim]Fe(IIICl4 was reduced by H2S to [bmim]Fe(IICl4H and FeCl3·2H2O was reduced to FeCl2, at the same time, H2S was oxidized to S8. In addition, the decrease in acidity caused by increasing the water content increased the weight percent of absorbed H2S, and decreased volatile HCl emissions. However, it is difficult to prevent the suspended S8 generated at vol % (H2O ≥ 80% from the formation of sulfur blockage. Therefore, oxidative absorption of H2S by [bmim]Fe(IIICl4–H2O mixtures is feasible at vol % (H2O < 80% without sulfur blockage.

Structural features of layered iron pnictide oxides (Fe{sub 2}As{sub 2})(Sr{sub 4}M{sub 2}O{sub 6})

Energy Technology Data Exchange (ETDEWEB)

Ogino, H., E-mail: tuogino@mail.ecc.u-tokyo.ac.j [Department of Applied Chemistry, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); JST-TRIP, Sanban-cho, Chiyoda-ku, Tokyo 102-0075 (Japan); Sato, S.; Matsumura, Y.; Kawaguchi, N.; Ushiyama, K. [Department of Applied Chemistry, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); JST-TRIP, Sanban-cho, Chiyoda-ku, Tokyo 102-0075 (Japan); Katsura, Y. [Magnetic Materials Laboratory, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198 (Japan); Horii, S. [JST-TRIP, Sanban-cho, Chiyoda-ku, Tokyo 102-0075 (Japan); Kochi University of Technology, Kami, Kochi 782-8502 (Japan); Kishio, K.; Shimoyama, J. [Department of Applied Chemistry, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); JST-TRIP, Sanban-cho, Chiyoda-ku, Tokyo 102-0075 (Japan)

2010-12-15

Structural features of newly found perovskite-based iron pnictide oxide system have been studied. Compared to REFePnO system, perovskite-based system tend to have smaller Pn-Fe-Pn angle and higher pnictogen height owing to low electronegativity of alkaline earth metal and small repulsive force between pnictogen and oxigen atoms. As-Fe-As angles of (Fe{sub 2}As{sub 2})(Sr{sub 4}Cr{sub 2}O{sub 6}), (Fe{sub 2}As{sub 2})(Sr{sub 4}V{sub 2}O{sub 6}) and (Fe{sub 2}Pn{sub 2})(Sr{sub 4}MgTiO{sub 6}) are close to ideal tetrahedron and those pnictogen heights of about 1.40 A are close to NdFeAsO with optimized carrier concentration. These structural features of this system may lead to realization of high-T{sub c} superconductivity in this system.

NiFe2O4 nanoparticles decorated activated carbon nanocomposite ...

Indian Academy of Sciences (India)

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Figure S4. Standard deviation plot and DPV response of blank voltammogram on NiFe2O4-. AC/GCE……..5 ... plot (µA µM-1). m= 0.47 µA µM-1. Sm is defined as. Sm = Sbl + kσbl. (3). Where k is a number illustrating the confidence level of the detection, usually 3 and σbl is the standard deviation of the blank (0.063 µA).

The role of reduced graphene oxide on the electrochemical activity of MFe2O4 (M = Fe, Co, Ni and Zn) nanohybrids

Science.gov (United States)

Suresh, Shravan; Prakash, Anand; Bahadur, D.

2018-02-01

In this work, a comparative study of electrochemical performance of reduced graphene oxide-ferrites (RGO-MFe2O4, M = Fe, Co, Ni, and Zn) nanohybrids synthesized by hydrothermal method was done. The structural morphology and investigation of other physical properties of nanohybrids confirm the cubic spinel phase of the MFe2O4, reduction of graphene oxide and the distribution of ferrite nanoparticles (NPs) on RGO nanosheets. The role of RGO on the electrochemical behavior of nanohybrids was understood by quantifying the charge storage capacitance and charging-discharging behavior in a 0.1 M Na2SO4 electrolyte. The specific capacitance values of pristine Fe3O4, CoFe2O4, NiFe2O4, and ZnFe2O4 are 128, 117, 15.2 and 9.1 F g-1 respectively whereas specific capacitance of RGO-Fe3O4, RGO-CoFe2O4, RGO-NiFe2O4 and RGO-ZnFe2O4 are 233, 200, 25 and 66.8 F g-1 respectively. Our investigation suggests that apart from specific surface area of nanohybrids other factors such as structural morphology determine interaction between nanohybrids and electrolyte ions which play critical role in elevating the performance of electrodes.

{μ-2-[4-(1,3-Benzothiazol-2-ylphenyl]-2-azapropane-1,3-dithiolato-κ4S,S′:S,S′}bis[tricarbonyliron(I

Directory of Open Access Journals (Sweden)

Da-yong Jiang

2012-03-01

Full Text Available The title compound, [Fe2(C15H12N2S3(CO6], was prepared as an azadithiolatodiiron model for the active site of [FeFe]-hydrogenase. The Fe2S2 core adopts a butterfly shape, with each metal having a pseudo square-pyramidal geometry. The N-substituted azadithiolate is μ2-κ4S,S′:S,S′-coordinated to the Fe(CO3 moieties to form two fused six-membered rings with different conformations. The sum of the C—N—C angles around the N atom [356.85 (15°] indicates a flattening of the trigonal–pyramidal geometry about the N atom and an increase in the degree of sp2-hybridization.

Effect of surface Fe2O3 clusters on the photocatalytic activity of TiO2 for phenol degradation in water

International Nuclear Information System (INIS)

Sun, Qiong; Leng, Wenhua; Li, Zhen; Xu, Yiming

2012-01-01

Graphical abstract: Surface modified TiO 2 with iron oxide clusters through adsorption and decomposition of a large Fe(III) complex shows an enhanced activity for phenol degradation in water under UV light. But it was only observed with the clusters in a small size and at very low coverage on anatase. Highlights: ► Iron oxide clusters are made by decomposition of a large Fe(III) complex on TiO 2 . ► The modified anatase shows an enhanced activity for phenol photodegradation. ► The composite catalyst is very stable during four repeated experiments. - Abstract: Surface modification of TiO 2 with Fe 2 O 3 clusters was made through chemisorption of ferric phthalocyaninetetracarboxylate onto TiO 2 , followed by sintering in air to remove organic moiety. Solid characterization with electron paramagnetic resonance spectroscopy and other techniques showed that ferric oxides were highly dispersed on TiO 2 as a noncrystallized cluster, while TiO 2 phases remained unchanged. For phenol degradation in aerated aqueous suspension, only the sample containing less than 0.3 at.% Fe was more active than bare TiO 2 under UV light, whereas no activity was found under visible light. As anatase thermally transferred into rutile, the Fe-containing catalyst became less active than bare TiO 2 , mainly ascribed to the increased size of Fe 2 O 3 clusters. In the presence of H 2 O 2 , all Fe-containing catalysts were more active than bare TiO 2 . Moreover, similar trend in activity among different catalysts was also observed with the formation of hydroxyl radicals, and with the generation of photocurrent measured under N 2 with Fe/TiO 2 electrode. Present work clearly shows that only Fe 2 O 3 clusters in a small size and at low coverage on TiO 2 are beneficial to the photocatalytic reaction, while excess iron oxide is detrimental. Possible mechanism is discussed in the text.

A Novel Ternary CoFe2O4/CuO/CoFe2O4 as a Giant Magnetoresistance Sensor

Directory of Open Access Journals (Sweden)

Ramli

2016-12-01

Full Text Available This paper reports the results of a study relating to the synthesis of a novel ternary CoFe2O4/CuO/CoFe2O4 thin film as a giant magnetoresistance (GMR sensor. The CoFe2O4/CuO/CoFe2O4 thin film was prepared onto silicon substrate via DC magnetron sputtering with the targets facing each other. X-ray diffraction was used to determine the structure of the thin film and a 4-point method was used to measure the MR ratio. The GMR ratio is highly dependent on the ferrimagnetic (CoFe2O4 and nonmagnetic (CuO layer thickness. The maximum GMR ratio at room temperature obtained in the CoFe2O4/CuO/CoFe2O4 thin film was 70% when the CoFe2O4 and the CuO layer had a thickness of 62.5 nm and 14.4 nm respectively.

Dense Fe cluster-assembled films by energetic cluster deposition

International Nuclear Information System (INIS)

Peng, D.L.; Yamada, H.; Hihara, T.; Uchida, T.; Sumiyama, K.

2004-01-01

High-density Fe cluster-assembled films were produced at room temperature by an energetic cluster deposition. Though cluster-assemblies are usually sooty and porous, the present Fe cluster-assembled films are lustrous and dense, revealing a soft magnetic behavior. Size-monodispersed Fe clusters with the mean cluster size d=9 nm were synthesized using a plasma-gas-condensation technique. Ionized clusters are accelerated electrically and deposited onto the substrate together with neutral clusters from the same cluster source. Packing fraction and saturation magnetic flux density increase rapidly and magnetic coercivity decreases remarkably with increasing acceleration voltage. The Fe cluster-assembled film obtained at the acceleration voltage of -20 kV has a packing fraction of 0.86±0.03, saturation magnetic flux density of 1.78±0.05 Wb/m 2 , and coercivity value smaller than 80 A/m. The resistivity at room temperature is ten times larger than that of bulk Fe metal

Synthesis and properties MFe2O4 (M = Fe, Co) nanoparticles and core-shell structures

Science.gov (United States)

Yelenich, O. V.; Solopan, S. O.; Greneche, J. M.; Belous, A. G.

2015-08-01

Individual Fe3-xO4 and CoFe2O4 nanoparticles, as well as Fe3-xO4/CoFe2O4 core/shell structures were synthesized by the method of co-precipitation from diethylene glycol solutions. Core/shell structure were synthesized with CoFe2O4-shell thickness of 1.0, 2.5 and 3.5 nm. X-ray diffraction patterns of individual nanoparticles and core/shell are similar and indicate that all synthesized samples have a cubic spinel structure. Compares Mössbauer studies of CoFe2O4, Fe3-xO4 nanoparticles indicate superparamagnetic properties at 300 K. It was shown that individual magnetite nanoparticles are transformed into maghemite through oxidation during the synthesis procedure, wherein the smallest nanoparticles are completely oxidized while a magnetite core does occur in the case of the largest nanoparticles. The Mössbauer spectra of core/shell nanoparticles with increasing CoFe2O4-shell thickness show a gradual decrease in the relative intensity of the quadrupole doublet and significant decrease of the mean isomer shift value at both RT and 77 K indicating a decrease of the superparamagnetic relaxation phenomena. Specific loss power for the prepared ferrofluids was experimentally calculated and it was determined that under influence of ac-magnetic field magnetic fluid based on individual CoFe2O4 and Fe3-xO4 particles are characterized by very low heating temperature, when magnetic fluids based on core/shell nanoparticles demonstrate higher heating effect.

Monothiol glutaredoxin Grx5 interacts with Fe-S scaffold proteins Isa1 and Isa2 and supports Fe-S assembly and DNA integrity in mitochondria of fission yeast

International Nuclear Information System (INIS)

Kim, Kyoung-Dong; Chung, Woo-Hyun; Kim, Hyo-Jin; Lee, Kyung-Chang; Roe, Jung-Hye

2010-01-01

Mitochondrial monothiol glutaredoxins that bind Fe-S cluster are known to participate in Fe-S cluster assembly. However, their precise role has not been well understood. Among three monothiol glutaredoxins (Grx3, 4, and 5) in Schizosaccharomyces pombe only Grx5 resides in mitochondria. The Δgrx5 mutant requires cysteine on minimal media, and does not grow on non-fermentable carbon source such as glycerol. We found that the mutant is low in the activity of Fe-S enzymes in mitochondria as well as in the cytoplasm. Screening of multi-copy suppressor of growth defects of the mutant identified isa1 + gene encoding a putative A-type Fe-S scaffold, in addition to mas5 + and hsc1 + genes encoding putative chaperones for Fe-S assembly process. Examination of other scaffold and chaperone genes revealed that isa2 + , but not isu1 + and ssc1 + , complemented the growth phenotype of Δgrx5 mutant as isa1 + did, partly through restoration of Fe-S enzyme activities. The mutant also showed a significant decrease in the amount of mitochondrial DNA. We demonstrated that Grx5 interacts in vivo with Isa1 and Isa2 proteins in mitochondria by observing bimolecular fluorescence complementation. These results indicate that Grx5 plays a central role in Fe-S assembly process through interaction with A-type Fe-S scaffold proteins Isa1 and Isa2, each of which is an essential protein in S. pombe, and supports mitochondrial genome integrity as well as Fe-S assembly.

Mild hydrothermal synthesis, crystal structure, spectroscopic and magnetic properties of the [MxIIM2.5-xIII(H2O)2(HPIIIO3)y(PVO4)2-yF] [M=Fe, x=2.08, y=1.58; M=Co, Ni, x=2.5, y=2] compounds

International Nuclear Information System (INIS)

Orive, Joseba; Mesa, Jose L.; Legarra, Estibaliz; Plazaola, Fernando; Arriortua, Maria I.; Rojo, Teofilo

2009-01-01

The [M x II M 2.5-x III (H 2 O) 2 (HP III O 3 ) y (P V O 4 ) 2-y F] [M=Fe (1), x=2.08, y=1.58; M=Co (2), x=2.5, y=2; Ni (3), x=2.5, y=2] compounds have been synthesized using mild hydrothermal conditions at 170 deg. C during five days. Single-crystals of (1) and (2), and polycrystalline sample of (3) were obtained. These isostructural compounds crystallize in the orthorhombic system, space group Aba2, with a=9.9598(2), b=18.8149(4) and c=8.5751(2) A for (1), a=9.9142(7), b=18.570(1) and c=8.4920(5) A for (2) and a=9.8038(2), b=18.2453(2) and c=8.4106(1) A for (3), with Z=8 in the three phases. An X-ray diffraction study reveals that the crystal structure is composed of a three-dimensional skeleton formed by [MO 5 F] and [MO 4 F 2 ] (M=Fe, Co and Ni) octahedra and [HPO 3 ] tetrahedra, partially substituted by [PO 4 ] tetrahedra in phase (1). The IR spectra show the vibrational modes of the water molecules and those of the (HPO 3 ) 2- tetrahedral oxoanions. The thermal study indicates that the limit of thermal stability of these phases is 195 deg. C for (1) and 315 deg. C for (2) and (3). The electronic absorption spectroscopy shows the characteristic bands of the Fe(II), Co(II) and Ni(II) high-spin cations in slightly distorted octahedral geometry. Magnetic measurements indicate the existence of global antiferromagnetic interactions between the metallic centers with a ferromagnetic transition in the three compounds at 28, 14 and 21 K for (1), (2) and (3), respectively. Compound (1) exhibits a hysteresis loop with remnant magnetization and coercive field values of 0.72 emu/mol and 880 Oe, respectively. - Abstract: Polyhedral view of the crystal structure of the [M x II M 2.5-x III (H 2 O) 2 (HP III O 3 ) y (P IV O 4 ) 2-y F] [M=Fe, x=2.08, y=1.58; M=Co, Ni, x=2.5, y=2] compounds showing the sheets along the [001] direction.

Separated CoFe{sub 2}O{sub 4}/CoFe nanoparticles by the SiO{sub x} matrix: revealing the intrinsic origin for the small remanence magnetization

Energy Technology Data Exchange (ETDEWEB)

Geng, B. Q.; Ma, Y. Q., E-mail: yqma@ahu.edu.cn; Xu, Y. F.; Xu, S. T.; Sun, X.; Zheng, G. H.; Dai, Z. X. [Anhui University, Anhui Key Laboratory of Information Materials and Devices, School of Physics and Materials Science (China)

2015-07-15

In order to clarify the intrinsic reason for the smaller remanence (M{sub r})-to-saturation (M{sub s}) magnetization ratio M{sub r}/M{sub s} than that expected by the Stoner–Wohlfarth model in CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanoparticles in the previous report, we first prepared well-dispersed CoFe{sub 2}O{sub 4} nanoparticles, and then they were diluted in the SiO{sub 2} matrix followed by reduction in H{sub 2} as far as possible to exclude or reduce disadvantageous variables (such as the growth and aggregation of particles and the exchange coupling between soft magnetic particles in the process of reducing) affecting magnetic properties. Such an idea has not been taken into account before to our knowledge. The analyses on the magnetic results indicate that the CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanoparticles herein reported are a pure dipolar system, in which the coercivity (H{sub c}) and M{sub r}/M{sub s} ratio are very sensitive to the anisotropy and the strength of dipolar interaction. These results signify that it is important to maintain the CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanoparticles with higher anisotropy and weaker dipolar interaction for improving M{sub r}/M{sub s} and H{sub c}. This suggestion was further confirmed by our another result wherein an M{sub r}/M{sub s} value of 0.64 was obtained even though no exchange coupling was observed in the CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanoparticles, and further work is in process. Graphical abstract: Numerous efforts have devoted to improve the values of M{sub s} and M{sub r}/M{sub s} by compositing hard CoFe{sub 2}O{sub 4} (CFO) ferrite with soft CoFe{sub 2} (CF) alloy, which unfortunately give the low M{sub r}/M{sub s} value (<0.5) even in presence of the exchange coupling. Key issues involve the preparation of CFO/CF composite. Previously the preparation of CFO/CF undergoes the synthesis of CFO and the subsequent reducing in the H{sub 2} ambient, as shown in Figure (a), while in this work well dispersed CFO

Effective S =2 antiferromagnetic spin chain in the salt (o -MePy-V)FeCl4

Science.gov (United States)

Iwasaki, Y.; Kida, T.; Hagiwara, M.; Kawakami, T.; Hosokoshi, Y.; Tamekuni, Y.; Yamaguchi, H.

2018-02-01

We present a model compound for the S =2 antiferromagnetic (AF) spin chain composed of the salt (o -MePy-V ) FeCl4 . Ab initio molecular-orbital calculations indicate the formation of a partially stacked two-dimensional (2D) spin model comprising five types of exchange interactions between S =1 /2 and S =5 /2 spins, which locate on verdazyl radical and Fe ion, respectively. The magnetic properties of the synthesized crystals indicate that the dominant interaction between the S =1 /2 and S =5 /2 spins stabilizes an S =2 spin in the low-temperature region, and an effective S =2 AF chain is formed for T ≪10 K and H chain. At higher fields above quantitatively 4 T, the magnetization curve assumes two-thirds of the full saturation value for fields between 4 and 20 T, and approaches saturation at ˜40 T. The spin model in the high-field region can be considered as a quasi-2D S =1 /2 honeycomb lattice under an effective internal field caused by the fully polarized S =5 /2 spin.

NMR of proteins (4Fe-4S): structural properties and intramolecular electron transfer

International Nuclear Information System (INIS)

Huber, J.G.

1996-01-01

NMR started to be applied to Fe-S proteins in the seventies. Its use has recently been enlarged as the problems arising from the paramagnetic polymetallic clusters ware overcome. Applications to [4Fe-4S] are presented herein. The information derived thereof deepens the understanding of the redox properties of these proteins which play a central role in the metabolism of bacterial cells. The secondary structure elements and the overall folding of Chromatium vinosum ferredoxin (Cv Fd) in solution have been established by NMR. The unique features of this sequence have been shown to fold as an α helix at the C-terminus and as a loop between two cysteines ligand of one cluster: these two parts localize in close proximity from one another. The interaction between nuclear and electronic spins is a source of additional structural information for (4Fe-AS] proteins. The conformation of the cysteine-ligands, as revealed by the Fe-(S γ -C β -H β )Cys dihedral angles, is related to the chemical shifts of the signals associated with the protons of these residues. The longitudinal relaxation times of the protons depend on their distance to the cluster. A quantitative relationship has been established and used to show that the solution structure of the high-potential ferredoxin from Cv differs significantly from the crystal structure around Phe-48. Both parameters (chemical shifts and longitudinal relaxation times) give also insight into the electronic and magnetic properties of the [4Fe-4S] clusters. The rate of intramolecular electron transfer between the two [4FE-4S] clusters of ferredoxins has been measured by NMR. It is far slower in the case of Cv Fd than for shorter ferredoxins. The difference may be associated with changes in the magnetic and/or electronic properties of one cluster. The strong paramagnetism of the [4Fe-4S] clusters, which originally limited the applicability of NMR to proteins containing these cofactors, has been proven instrumental in affording new

Design and syntheses of hybrid metal–organic materials based on K{sub 3}[M(C{sub 2}O{sub 4}){sub 3}]·3H{sub 2}O [M(III)=Fe, Al, Cr] metallotectons

Energy Technology Data Exchange (ETDEWEB)

Sun, Yayong; Zong, Yingxia; Ma, Haoran; Zhang, Ao; Liu, Kang; Wang, Debao, E-mail: dbwang@qust.edu.cn; Wang, Wenqiang; Wang, Lei, E-mail: inorchemwl@126.com

2016-05-15

By using K{sub 3}[M(C{sub 2}O{sub 4}){sub 3}]·3H{sub 2}O [M(III)=Fe, Al, Cr] (C{sub 2}O{sub 4}{sup 2−}=oxalate) metallotectons as the starting material, we have synthesized eight novel complexes with formulas [{Fe(C_2O_4)_2(H_2O)_2}{sub 2}]·(H–L{sub 1}){sub 2}·H{sub 2}O 1, [Fe(C{sub 2}O{sub 4})Cl{sub 2}]·(H{sub 2}–L{sub 2}){sub 0.5}·(L{sub 2}){sub 0.5}·H{sub 2}O 2, [{Fe(C_2O_4)_1_._5Cl_2}{sub 2}]·(H–L{sub 3}){sub 4}3, [Fe{sub 2}(C{sub 2}O{sub 4})Cl{sub 8}]·(H{sub 2}–L{sub 4}){sub 2}·2H{sub 2}O 4, K[Al(C{sub 2}O{sub 4}){sub 3}]·(H{sub 2}–L{sub 5})·2H{sub 2}O 5, K[Al(C{sub 2}O{sub 4}){sub 3}]·(H–L{sub 6}){sub 2}·2H{sub 2}O 6, K[Cr(C{sub 2}O{sub 4}){sub 3}]·2H{sub 2}O 7, Na[Fe(C{sub 2}O{sub 4}){sub 3}]·(H–L{sub 6}){sub 2}·2H{sub 2}O 8 (with L{sub 1}=4-dimethylaminopyridine, L{sub 2}=2,3,5,6-tetramethylpyrazine, L{sub 3}=2-aminobenzimidazole, L{sub 4}=1,4-bis-(1H-imidazol-1-yl)benzene, L{sub 5}=1,4-bis((2-methylimidazol-1-yl)methyl)benzene, L{sub 6}=2-methylbenzimidazole). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra and thermogravimetric analyses. Compound 3 is a 2D H-bonded supramolecular architecture. Others are 3D supramolecular structures. Compound 1 shows a [Fe(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2}]{sup −} unit and 3D antionic H-bonded framework. Compound 2 features a [Fe(C{sub 2}O{sub 4})Cl{sub 2}]{sup -} anion and 1D iron-oxalate-iron chain. Compound 3 features a [Fe{sub 2}(C{sub 2}O{sub 4}){sub 3}Cl{sub 4}]{sup 4−} unit. Compound 4 features distinct [Fe{sub 2}(C{sub 2}O{sub 4})Cl{sub 8}]{sup 4−} units, which are mutual linked by water molecules to generated a 2D H-bonded network. Compound 5 features infinite ladder-like chains constructed by [Al(C{sub 2}O{sub 4}){sub 3}]{sup 3−} units and K{sup +} cations. The 1D chains are further extended into 3D antionic H-bonded framework through O–H···O H-bonds. Compounds 6–8 show 2D [KAl(C{sub 2}O

Optimization of α-Fe{sub 2}O{sub 3}@Fe{sub 3}O{sub 4} incorporated N-TiO{sub 2} as super effective photocatalysts under visible light irradiation

Energy Technology Data Exchange (ETDEWEB)

Mohamed, Mohamed Mokhtar, E-mail: mohmok2000@yahoo.com [Benha University, Faculty of Science, Chemistry Department, Benha (Egypt); Bayoumy, W.A. [Benha University, Faculty of Science, Chemistry Department, Benha (Egypt); Goher, M.E. [National Institute of Oceanography & Fisheries, Environmental Chemistry, Cairo (Egypt); Abdo, M.H., E-mail: mh_omr@yahoo.com [National Institute of Oceanography & Fisheries, Environmental Chemistry, Cairo (Egypt); Mansour El-Ashkar, T.Y. [National Institute of Oceanography & Fisheries, Environmental Chemistry, Cairo (Egypt)

2017-08-01

Highlights: • The α-Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} doped n-TiO{sub 2} was synthesized via deposition-self assembly technique. • The photocatalyst 1%α-Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4}/n-TiO{sub 2} show a remarkable performance while MB degradation. • The strong interaction between α-Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} and n-TiO{sub 2} plays an important role. • It exhibits a unique textural, optical and charge transfer properties. - Abstract: Well dispersed α-Fe{sub 2}O{sub 3}@Fe{sub 3}O{sub 4} nanoparticles (7 nm) supported on mesoporous nitrogen doped titanium dioxide (N-TiO{sub 2}) are synthesized by deposition self-assembly route and their performances as photocatalysts toward methylene blue (MB) degradation are evaluated. The results illustrate that the spherical yolk-shell structure of α-Fe{sub 2}O{sub 3}@Fe{sub 3}O{sub 4}@N-TiO{sub 2} at the loading of 1%; of excellent S{sub BET} (187 m{sup 2} g{sup −1}) and pore volume (0.50 cm{sup 3} g{sup −1}), achieved high photocatalytic performance for the MB degradation (20 ppm, λ > 420 nm, lamp power = 160 W) under visible light illumination (k = 0.059 min{sup −1}). The influence of the interface formation between α-Fe{sub 2}O{sub 3}@Fe{sub 3}O{sub 4} and n-TiO{sub 2} affects severely the charges separation efficiency and enhances the electron transfer to keep on the existence of Fe{sup 3+}/Fe{sup 2+} moieties; those take significant role in the reaction mechanism. The existence of the latter junction is affirmed via XRD, TEM-SAED, Raman and FTIR techniques whereas, the photogenerated charges, their separation together with their transport and recombination rates are depicted via photoluminescence, electrical conductivity, incident photon to current efficiency (IPCE), cyclic voltammetry (CV) and impedance (EIS) measurements. The catalyst loading, zero point charge, pH variation, total organic carbon (TOC%) and the effect of lamps power are thoroughly investigated. The 1%α-Fe{sub 2}O{sub 3

Synthesis, structure and magnetic properties of CoFe_2O_4 nanomaterial by coprecipitation method

International Nuclear Information System (INIS)

Nguyen Anh Tien; Hoang Thi Tuyet

2015-01-01

CoFe_2O_4 spinel nanomaterial has been synthesized by coprecipitation method through the hydrolysis of Co(II) and Fe(III) cations in boiling water. The results of DTA/TGA/DrTGA, XRD, TEM methods showed that CoFe_2O_4 crystals formed after a calcination at 700 °C exhibited structure of cubic with the particles size of 30-50 nm, H_c = 1526.89 Oe, M_s = 41.703 emu/g, M_r = 19.545 emu/g. (author)

Spin Crossover in Fe(II)-M(II) Cyanoheterobimetallic Frameworks (M = Ni, Pd, Pt) with 2-Substituted Pyrazines.

Science.gov (United States)

Kucheriv, Olesia I; Shylin, Sergii I; Ksenofontov, Vadim; Dechert, Sebastian; Haukka, Matti; Fritsky, Igor O; Gural'skiy, Il'ya A

2016-05-16

Discovery of spin-crossover (SCO) behavior in the family of Fe(II)-based Hofmann clathrates has led to a "new rush" in the field of bistable molecular materials. To date this class of SCO complexes is represented by several dozens of individual compounds, and areas of their potential application steadily increase. Starting from Fe(2+), square planar tetracyanometalates M(II)(CN)4(2-) (M(II) = Ni, Pd, Pt) and 2-substituted pyrazines Xpz (X = Cl, Me, I) as coligands we obtained a series of nine new Hofmann clathrate-like coordination frameworks. X-ray diffraction reveals that in these complexes Fe(II) ion has a pseudo-octahedral coordination environment supported by four μ4-tetracyanometallates forming its equatorial coordination environment. Depending on the nature of X and M, axial positions are occupied by two 2X-pyrazines (X = Cl and M(II) = Ni (1), Pd (2), Pt (3); X = Me and M(II) = Ni (4), Pd (5)) or one 2X-pyrazine and one water molecule (X = I and M(II) = Ni (7), Pd (8), Pt (9)), or, alternatively, two distinct Fe(II) positions with either two pyrazines or two water molecules (X = Me and M(II) = Pt (6)) are observed. Temperature behavior of magnetic susceptibility indicates that all compounds bearing FeN6 units (1-6) display cooperative spin transition, while Fe(II) ions in N5O or N4O2 surrounding are high spin (HS). Structural changes in the nearest Fe(II) environment upon low-spin (LS) to HS transition, which include ca. 10% Fe-N distance increase, lead to the cell expansion. Mössbauer spectroscopy is used to characterize the spin state of all HS, LS, and intermediate phases of 1-9 (see abstract figure). Effects of a pyrazine substituent and M(II) nature on the hyperfine parameters in both spin states are established.

A point mutation in the [2Fe–2S] cluster binding region of the NAF-1 protein (H114C) dramatically hinders the cluster donor properties

Energy Technology Data Exchange (ETDEWEB)

Tamir, Sagi; Eisenberg-Domovich, Yael [The Hebrew University of Jerusalem, Edmond J. Safra Campus at Givat Ram, Jerusalem 91904 (Israel); Conlan, Andrea R.; Stofleth, Jason T.; Lipper, Colin H.; Paddock, Mark L. [University of California at San Diego, La Jolla, CA 92093 (United States); Mittler, Ron [University of North Texas, Denton, TX 76203 (United States); Jennings, Patricia A. [University of California at San Diego, La Jolla, CA 92093 (United States); Livnah, Oded, E-mail: oded.livnah@huji.ac.il; Nechushtai, Rachel, E-mail: oded.livnah@huji.ac.il [The Hebrew University of Jerusalem, Edmond J. Safra Campus at Givat Ram, Jerusalem 91904 (Israel)

2014-06-01

NAF-1 has been shown to be related with human health and disease, is upregulated in epithelial breast cancer and suppression of its expression significantly suppresses tumor growth. It is shown that replacement of the single His ligand with Cys resulted in dramatic changes to the properties of its 2Fe-2S clusters without any global crystal structural changes. NAF-1 is an important [2Fe–2S] NEET protein associated with human health and disease. A mis-splicing mutation in NAF-1 results in Wolfram Syndrome type 2, a lethal childhood disease. Upregulation of NAF-1 is found in epithelial breast cancer cells, and suppression of NAF-1 expression by knockdown significantly suppresses tumor growth. Key to NAF-1 function is the NEET fold with its [2Fe–2S] cluster. In this work, the high-resolution structure of native NAF-1 was determined to 1.65 Å resolution (R factor = 13.5%) together with that of a mutant in which the single His ligand of its [2Fe–2S] cluster, His114, was replaced by Cys. The NAF-1 H114C mutant structure was determined to 1.58 Å resolution (R factor = 16.0%). All structural differences were localized to the cluster binding site. Compared with native NAF-1, the [2Fe–2S] clusters of the H114C mutant were found to (i) be 25-fold more stable, (ii) have a redox potential that is 300 mV more negative and (iii) have their cluster donation/transfer function abolished. Because no global structural differences were found between the mutant and the native (wild-type) NAF-1 proteins, yet significant functional differences exist between them, the NAF-1 H114C mutant is an excellent tool to decipher the underlying biological importance of the [2Fe–2S] cluster of NAF-1 in vivo.

A point mutation in the [2Fe–2S] cluster binding region of the NAF-1 protein (H114C) dramatically hinders the cluster donor properties

International Nuclear Information System (INIS)

Tamir, Sagi; Eisenberg-Domovich, Yael; Conlan, Andrea R.; Stofleth, Jason T.; Lipper, Colin H.; Paddock, Mark L.; Mittler, Ron; Jennings, Patricia A.; Livnah, Oded; Nechushtai, Rachel

2014-01-01

NAF-1 has been shown to be related with human health and disease, is upregulated in epithelial breast cancer and suppression of its expression significantly suppresses tumor growth. It is shown that replacement of the single His ligand with Cys resulted in dramatic changes to the properties of its 2Fe-2S clusters without any global crystal structural changes. NAF-1 is an important [2Fe–2S] NEET protein associated with human health and disease. A mis-splicing mutation in NAF-1 results in Wolfram Syndrome type 2, a lethal childhood disease. Upregulation of NAF-1 is found in epithelial breast cancer cells, and suppression of NAF-1 expression by knockdown significantly suppresses tumor growth. Key to NAF-1 function is the NEET fold with its [2Fe–2S] cluster. In this work, the high-resolution structure of native NAF-1 was determined to 1.65 Å resolution (R factor = 13.5%) together with that of a mutant in which the single His ligand of its [2Fe–2S] cluster, His114, was replaced by Cys. The NAF-1 H114C mutant structure was determined to 1.58 Å resolution (R factor = 16.0%). All structural differences were localized to the cluster binding site. Compared with native NAF-1, the [2Fe–2S] clusters of the H114C mutant were found to (i) be 25-fold more stable, (ii) have a redox potential that is 300 mV more negative and (iii) have their cluster donation/transfer function abolished. Because no global structural differences were found between the mutant and the native (wild-type) NAF-1 proteins, yet significant functional differences exist between them, the NAF-1 H114C mutant is an excellent tool to decipher the underlying biological importance of the [2Fe–2S] cluster of NAF-1 in vivo

Antimicrobial activity study of a μ3-oxo bridged [Fe3O(PhCO2)6(MeOH)3](NO3)(MeOH)2] cluster

Science.gov (United States)

Pathak, Sayantan; Jana, Barun; Mandal, Manab; Mandal, Vivekananda; Ghorai, Tanmay K.

2017-11-01

Synthesis, characterization and antimicrobial activity of a tri-nuclear μ3-Oxobridged Fe(III) cluster [Fe3O(PhCO2)6(MeOH)3](NO3)(MeOH)2(1) is reported. Cluster 1 is synthesized in a single pot reaction among Fe(NO3)3·9H2O, C6H5COOH, NaN3 (1:4:1) in MeOH. Single crystal X-ray diffraction studies of the isolated crystals show that it is μ3-Oxo bridged trimeric assembly of three Fe atoms via bridging benzoate anions. Furthermore, BVS calculations show that all three Fe atoms in complex 1 are in +3 oxidation state and are surrounded by benzoate anions and methanol in octahedral environment. The oxidation state of iron is also confirmed from the cyclic voltamogram. FT-IR spectroscopy and CHN analysis of the isolated crystals further supports the functional group attached to the periphery of the complex. The nanomolecular size of complex 1 is 1.29 nm. The antimicrobial efficiency studies of the complex 1 show significant inhibition of the growth of the organisms, viz. B. cereus MTCC 1272, S. epidermidis MTCC 3086 and S. typhimurium MTCC 98 and produced 23 ± 1.93 mm, 16 ± 1.77 mm and 12 ± 2.42 mm inhibition zones respectively. However, it shows zero inhibition to the strain of E. coli MTCC 723.

Facile synthesis, dielectric properties and electrocatalytic activities of PMMA-NiFe2O4 nanocomposite

International Nuclear Information System (INIS)

Maji, Pranabi; Choudhary, Ram Bilash

2017-01-01

The paper deals with the dielectric and catalytic properties of poly (methyl methacrylate)-nikel ferrite (PMMA-NiFe 2 O 4 ) nanocomposite. The nanocomposite was prepared by using a general and facile synthesis strategy. Fourier transform infrared (FTIR) and X-ray diffraction (XRD) spectra confirmed the formation of PMMA-NiFe 2 O 4 nanocomposite. Field effect scanning electron microscopic (FESEM) and transmission electron microscopic (TEM) images revealed that NiFe 2 O 4 nanoparticles were uniformly distributed and were tightly adhered with PMMA matrix owing to surface modification with 3-methacryloyloxy propyl trimethoxy silane (KH-570). Thermal stability was enhanced by incorporation of NiFe 2 O 4 nanofillers. The nanocomposite showed high dielectric constant and low dielectric loss. The achieved dielectric and thermal property inferred the potential application of this material in energy storage and embedded electronics devices. Further, the as prepared nanocomposite also offered a remarkable electrochemical performance towards hydrogen peroxide (H 2 O 2 ) sensing. - Highlights: • PMMA-NiFe 2 O 4 nanocomposite was synthesized via free radical polymerization. • The nanocomposite exhibited high value of dielectric constant (51) and tanδ (0.3). • Thermal stability of the PMMA matrix was improved by the incorporation of NiFe 2 O 4. • The H 2 O 2 detection limit was estimated 44 μM when signal to noise (S/N) ration was 3. • The electrochemical sensitivity of H 2 O 2 was calculated 0.6727 μA mM -1 .

The WAGGS project - I. The WiFeS Atlas of Galactic Globular cluster Spectra

Science.gov (United States)

Usher, Christopher; Pastorello, Nicola; Bellstedt, Sabine; Alabi, Adebusola; Cerulo, Pierluigi; Chevalier, Leonie; Fraser-McKelvie, Amelia; Penny, Samantha; Foster, Caroline; McDermid, Richard M.; Schiavon, Ricardo P.; Villaume, Alexa

2017-07-01

We present the WiFeS Atlas of Galactic Globular cluster Spectra, a library of integrated spectra of Milky Way and Local Group globular clusters. We used the WiFeS integral field spectrograph on the Australian National University 2.3 m telescope to observe the central regions of 64 Milky Way globular clusters and 22 globular clusters hosted by the Milky Way's low-mass satellite galaxies. The spectra have wider wavelength coverage (3300-9050 Å) and higher spectral resolution (R = 6800) than existing spectral libraries of Milky Way globular clusters. By including Large and Small Magellanic Cloud star clusters, we extend the coverage of parameter space of existing libraries towards young and intermediate ages. While testing stellar population synthesis models and analysis techniques is the main aim of this library, the observations may also further our understanding of the stellar populations of Local Group globular clusters and make possible the direct comparison of extragalactic globular cluster integrated light observations with well-understood globular clusters in the Milky Way. The integrated spectra are publicly available via the project website.

Synthesis, characterization of spinels NiFe_2O_4 e CoFe_2O_4 and evaluation of performance in the trans esterification and esterification of cottonseed oil

International Nuclear Information System (INIS)

Dantas, J.; Silva, A.S.A.; Costa, A.C.F.M.; Freitas, N.L.

2012-01-01

The present study aimed synthesizes by combustion reaction and characterization of the spinel CoFe_2O_4 and NiFe_2O_4, and evaluation in the esterification and transesterification reaction of cottonseed oil for biodiesel. The samples were characterized by XRD, nitrogen adsorption/desorption (BET), SEM and transesterification e esterification reaction of the cottonseed oil for biodiesel. The results show that the synthesis was effective in achievement the CoFe_2O_4 and NiFe_2O_4 with surface area 23.75 and 18.18 m"2g"1. The results for esterification indicated that CoFe_2O_4 conversion 16.8 and 38.6%, however for transesterification reaction was observed that NiFe_2O_4 conversion 8.6 and 16.8% for ethanol and methanol, respectively. (author)

CoFe2O4-SiO2 Composites: Preparation and Magnetodielectric Properties

Directory of Open Access Journals (Sweden)

T. Ramesh

2016-01-01

Full Text Available Cobalt ferrite (CoFe2O4 and silica (SiO2 nanopowders have been prepared by the microwave hydrothermal (M-H method using metal nitrates as precursors of CoFe2O4 and tetraethyl orthosilicate as a precursor of SiO2. The synthesized powders were characterized by XRD and FESEM. The (100-x (CoFe2O4 + xSiO2 (where x = 0%, 10%, 20%, and 30% composites with different weight percentages have been prepared using ball mill method. The composite samples were sintered at 800°C/60 min using the microwave sintering method and then their structural and morphological studies were investigated using X-ray diffraction (XRD, Fourier transformation infrared (FTIR spectra, and scanning electron microscopy (SEM, respectively. The effect of SiO2 content on the magnetic and electrical properties of CoFe2O4/SiO2 nanocomposites has been studied via the magnetic hysteresis loops, complex permeability, permittivity spectra, and DC resistivity measurements. The synthesized nanocomposites with adjustable grain sizes and controllable magnetic properties make the applicability of cobalt ferrite even more versatile.

Exchange coupling behavior in bimagnetic CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite

Energy Technology Data Exchange (ETDEWEB)

Leite, G.C.P. [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Chagas, E.F., E-mail: efchagas@fisica.ufmt.br [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Pereira, R.; Prado, R.J. [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Terezo, A.J. [Departamento de Quimica, Universidade Federal do Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Alzamora, M.; Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Fisicas, Rua Xavier Sigaud 150 Urca, Rio de Janeiro (Brazil)

2012-09-15

In this work we report a study of the magnetic behavior of ferrimagnetic oxide CoFe{sub 2}O{sub 4} and ferrimagnetic oxide/ferromagnetic metal CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite. The latter compound is a good system to study hard ferrimagnet/soft ferromagnet exchange coupled. Two steps were followed to synthesize the bimagnetic CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite: (i) first, preparation of CoFe{sub 2}O{sub 4} nanoparticles using a simple hydrothermal method, and (ii) second, reduction reaction of cobalt ferrite nanoparticles using activated charcoal in inert atmosphere and high temperature. The phase structures, particle sizes, morphology, and magnetic properties of CoFe{sub 2}O{sub 4} nanoparticles were investigated by X-Ray diffraction (XRD), Mossbauer spectroscopy (MS), transmission electron microscopy (TEM), and vibrating sample magnetometer (VSM) with applied field up to 3.0 kOe at room temperature and 50 K. The mean diameter of CoFe{sub 2}O{sub 4} particles is about 16 nm. Mossbauer spectra revealed two sites for Fe{sup 3+}. One site is related to Fe in an octahedral coordination and the other one to the Fe{sup 3+} in a tetrahedral coordination, as expected for a spinel crystal structure of CoFe{sub 2}O{sub 4}. TEM measurements of nanocomposite showed the formation of a thin shell of CoFe{sub 2} on the cobalt ferrite and indicate that the nanoparticles increase to about 100 nm. The magnetization of the nanocomposite showed a hysteresis loop that is characteristic of exchange coupled systems. A maximum energy product (BH){sub max} of 1.22 MGOe was achieved at room temperature for CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposites, which is about 115% higher than the value obtained for CoFe{sub 2}O{sub 4} precursor. The exchange coupling interaction and the enhancement of product (BH){sub max} in nanocomposite CoFe{sub 2}O{sub 4}/CoFe{sub 2} are discussed. - Highlights: Black-Right-Pointing-Pointer CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite

Photocatalytic degradation of Acephate, Omethoate, and Methyl parathion by Fe{sub 3}O{sub 4}@SiO{sub 2}@mTiO{sub 2} nanomicrospheres

Energy Technology Data Exchange (ETDEWEB)

Zheng, Lingling, E-mail: zllyslngj@126.com [State Key Laboratory of Food Science and Technology, School of Food Science of Jiangnan University, School of Food Science Synergetic Innovation Center of Food Safety and Quality Control, Wuxi, Jiangsu 214122 (China); Pi, Fuwei; Wang, Yifan [State Key Laboratory of Food Science and Technology, School of Food Science of Jiangnan University, School of Food Science Synergetic Innovation Center of Food Safety and Quality Control, Wuxi, Jiangsu 214122 (China); Xu, Hui [Key Laboratory of Healthy & Intelligent Kitchen System Integration, Ningbo, Zhejiang 315336 (China); Zhang, Yinzhi [State Key Laboratory of Food Science and Technology, School of Food Science of Jiangnan University, School of Food Science Synergetic Innovation Center of Food Safety and Quality Control, Wuxi, Jiangsu 214122 (China); Sun, Xiulan, E-mail: sxlzzz@jiangnan.edu.cn [State Key Laboratory of Food Science and Technology, School of Food Science of Jiangnan University, School of Food Science Synergetic Innovation Center of Food Safety and Quality Control, Wuxi, Jiangsu 214122 (China)

2016-09-05

Highlights: • An efficient photocatalyst Fe{sub 3}O{sub 4}@SiO{sub 2}@mTiO{sub 2} with high magnetic response and large specific surface area was synthesized. • Photocatalytic efficiency of Fe{sub 3}O{sub 4}@SiO{sub 2}@mTiO{sub 2} on Acephate, Omethoate, and Methyl Parathion was higher than TiO{sub 2} P-25. • Possible photocatalytic degradation mechanisms for the Acephate, Omethoate, and Methyl Parathion were proposed. - Abstract: A novel magnetic mesoporous nanomicrospheres Fe{sub 3}O{sub 4}@SiO{sub 2}@mTiO{sub 2} were synthetized and characterized by a series of techniques including FE-TEM, EDS, FE-SEM, PXRD, XPS, BET, TGA as well as VSM, and subsequently tested as a photocatalyst for the degradation of Acephate, Omethoate, and Methyl parathion under UV irradiation. The well-designed nanomicrospheres exhibit a pure and highly crystalline anatase TiO{sub 2} layer, large specific surface area, and high-magnetic-response. Photocatalytic degradation of the three organophosphorus pesticides (OPPs) and the formation intermediates were identified using HPLC, TOC-V{sub cpn}, IC, pH meter and GC–MS. Acephate, Omethoate, and Methyl parathion disappeared after 45 min, 45 min, and 80 min UV illumination, respectively. At the end of the treatment, the total organic carbon (TOC) of the OPPs was reduced 80–85%. The main mineralization products were SO{sub 4}{sup 2−}, NO{sub 3}{sup −} and PO{sub 4}{sup 3−} and Omethoate additionally formed NO{sub 2}{sup −}. Based on the results, we proposed the photocatalytic degradation pathways for Acephate, Omethoate, and Methyl parathion.

A feasibility study on SnO2/NiFe2O4 nanocomposites as anodes for Li ion batteries

International Nuclear Information System (INIS)

Balaji, S.; Vasuki, R.; Mutharasu, D.

2013-01-01

Highlights: ► The morphological analysis performed has shown the existence of nanocomposite. ► Sp. capacity after 50 cycles of pure NiFe 2 O 4 , 5 and 10 wt.% SnO 2 are 450, 750 and 780 mA h/g. ► The results are higher than the theoretical capacity of graphite (374 mA h/g). ► The capacity retention is also found to increase with SnO 2 addition in the NiFe 2 O 4 . ► Charge and discharge capacities of LiMn 2 O 4 vs. 10 wt.% SnO 2 /NiFe 2 O 4 are 232 and 138 mA h/g. -- Abstract: The SnO 2 /NiFe 2 O 4 nanocomposite samples with varying concentration of SnO 2 such as 5 wt.% and 10 wt.% were synthesized via urea assisted combustion synthesis. The kinetics of the combustion reactions were studied using thermo gravimetry analysis and from which the compound formation temperature of all the samples were observed to be below 400 °C. From the morphological analysis the grain size of NiFe 2 O 4 , 5 wt.% SnO 2 /NiFe 2 O 4 and 10 wt.% SnO 2 /NiFe 2 O 4 samples were observed to be around 1.7, 2.3 and 3.5 μm. The chrono potentiometry analyses of the samples were performed against lithium metal electrode. The capacity retention was found to be higher for composite with 10 wt.% SnO 2 . The discharge capacity of 10 wt.% SnO 2 sample with respect to Li metal and LiMn 2 O 4 electrode was observed to be around 980 mA h/g and 138 mA h/g respectively

Synthesis and characterization of Cr doped CoFe2O4

Science.gov (United States)

Verma, Kavita; Patel, K. R.; Ram, Sahi; Barbar, S. K.

2016-05-01

Polycrystalline samples of pure and Cr-doped cobalt ferrite (CoFe2O4 and CoCrFeO4) were prepared by solid state reaction route method. X-ray diffraction pattern infers that both the samples are in single phase with Fd3m space group. Slight reduction in the lattice parameter of CoCrFeO4 has been observed as compared to CoFe2O4. The dielectric dispersion has been explained on the basis of Fe2+ ↔ Fe3+ hopping mechanism. The polarizations at lower frequencies are mainly attributed to electronic exchange between Fe2+ ↔ Fe3+ ions on the octahedral site in the ferrite lattice. In the present system a part from n-type charge carrier (Fe3+/Fe2+), the presence of (Co3+/Co2+) ions give rise to p-type charge carrier. Therefore in addition to n-type charge carrier, the local displacement of p-type charge carrier in direction of external electric field also contributes to net polarization. However, the dielectric constant and loss tangent of CoCrFeO4 are found to be lower than CoFe2O4 and is attributed to the availability of ferrous ion. CoCrFeO4 have less amount of ferrous ion available for polarization as compared to that of CoFe2O4. The impedance spectra reveal a grain interior contribution to the conduction process.

Neutron transitions within the S=10 ground multiplet of a Fe8 magnetic cluster

Science.gov (United States)

Carretta, S.; Liviotti, E.; Amoretti, G.; Caciuffo, R.; Caneschi, A.; Gatteschi, D.

2002-02-01

Inelastic neutron scattering has been used to determine the anisotropic spin Hamiltonian that splits the S=10 ground multiplet of the cluster (tacn)6Fe8O2(OH)12Br4.3(ClO4)3.76H2O (Fe8PCl), where (tacn) is the organic ligand 1,4,7-triazacyclononane. This single-molecule magnet,which is obtained from the well known Fe8Br cluster, by partial replacement of the bromide ions by perchlorate anions, presents a larger transverse anisotropy than the parent compound, the E/D ratio being 0.22 instead of 0.16. This is in agreement with the relaxation measurements in the pure quantum tunneling regime. The details of the neutron spectra detected at three different temperatures (2, 10, and 15 K) allowed us to determine the spin Hamiltonian parameters up to fourth order and to identify the main source of the transition linewidth broadening with the occupational disorder of the bromide and perchlorate ions, rather than with the random internal dipolar field distribution.

New Insights into Mn1−xZnxFe2O4 via Fabricating Magnetic Photocatalyst Material BiVO4/Mn1−xZnxFe2O4

Directory of Open Access Journals (Sweden)

Taiping Xie

2018-02-01

Full Text Available BiVO4/Mn1−xZnxFe2O4 was prepared by the impregnation roasting method. XRD (X-ray Diffractometer tests showed that the prepared BiVO4 is monoclinic crystal, and the introduction of Mn1−xZnxFe2O4 does not change the crystal structure of BiVO4. The introduction of a soft-magnetic material, Mn1−xZnxFe2O4, was beneficial to the composite photocatalyst’s separation from the liquid solution using an extra magnet after use. UV-vis spectra analysis indicated that Mn1−xZnxFe2O4 enhanced the absorption intensity of visible light for BiVO4. EIS (electrochemical impedance spectroscopy investigation revealed that the introduction of Mn1−xZnxFe2O4 enhanced the conductivity of BiVO4, further decreasing its electron transfer impedance. The photocatalytic efficiency of BiVO4/Mn1−xZnxFe2O4 was higher than that of pure BiVO4. In other words, Mn1−xZnxFe2O4 could enhance the photocatalytic reaction rate.

Fe2O3/Reduced Graphene Oxide/Fe3O4 Composite in Situ Grown on Fe Foil for High-Performance Supercapacitors.

Science.gov (United States)

Zhao, Chongjun; Shao, Xiaoxiao; Zhang, Yuxiao; Qian, Xiuzhen

2016-11-09

A Fe 2 O 3 /reduced graphene oxide (RGO)/Fe 3 O 4 nanocomposite in situ grown on Fe foil was synthesized via a simple one-step hydrothermal growth process, where the iron foil served as support, reductant of graphene oxide, Fe source of Fe 3 O 4 , and also the current collector of the electrode. When it directly acted as the electrode of a supercapacitor, as-synthesized Fe 2 O 3 /RGO/Fe 3 O 4 @Fe exhibited excellent electrochemical performance with a high capability of 337.5 mF/cm 2 at 20 mA/cm 2 and a superior cyclability with 2.3% capacity loss from the 600th to the 2000th cycle.

Electronic and magnetic properties of 3d-metal trioxides superhalogen cluster-doped monolayer MoS2: A first-principles study

International Nuclear Information System (INIS)

Li, Dan; Niu, Yuan; Zhao, Hongmin; Liang, Chunjun; He, Zhiqun

2014-01-01

Utilizing first-principle calculations, the structural, electronic, and magnetic properties of monolayer MoS 2 doped with 3d transition-metal (TM) atoms and 3d-metal trioxides (TMO 3 ) superhalogen clusters are investigated. 3d-metal TMO 3 superhalogen cluster-doped monolayers MoS 2 almost have negative formation energies except CoO 3 and NiO 3 doped monolayer MoS 2 , which are much lower than those of 3d TM-doped structures. 3d-metal TMO 3 superhalogen clusters are more easily embedded in monolayer MoS 2 than 3d-metal atoms. MnO 3 , FeO 3 , CoO 3 , and NiO 3 incorporated into monolayer MoS 2 are magnetic, and the total magnetic moments are approximately 1.0, 2.0, 3.0, and 4.0 μB per supercell, respectively. MnO 3 and FeO 3 incorporated into monolayer MoS 2 become semiconductors, whereas CoO 3 and NiO 3 incorporated into monolayer MoS 2 become half-metallic. Our studies demonstrate that the half-metallic ferromagnetic nature of 3d-metal TMO 3 superhalogen clusters-doped monolayer MoS 2 has a great potential for MoS 2 -based spintronic device applications. -- Highlights: •TMO 3 superhalogen clusters incorporated into monolayer MoS 2 were investigated. •TMO 3 doped structures have much lower formation energies than TM doped structures. •TMO 3 cluster-doped MoS 2 are thermodynamically favored. •Significant charge transfers between O atoms and Mo atoms in TMO 3 doped structures. •MnO 3 , FeO 3 , CoO 3 , and NiO 3 incorporated into monolayer MoS 2 are magnetic.

Mutation of the His ligand in mitoNEET stabilizes the 2Fe–2S cluster despite conformational heterogeneity in the ligand environment

Energy Technology Data Exchange (ETDEWEB)

Conlan, Andrea R.; Paddock, Mark L.; Homer, Christina [University of California at San Diego, La Jolla, CA 92093 (United States); Axelrod, Herbert L.; Cohen, Aina E. [Stanford Synchrotron Radiation Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025 (United States); Abresch, Edward C.; Zuris, John A. [University of California at San Diego, La Jolla, CA 92093 (United States); Nechushtai, Rachel [Hebrew University of Jerusalem, Edmond J. Safra Campus, Givat Ram, Jerusalem 91904 (Israel); Jennings, Patricia A., E-mail: pajennin@ucsd.edu [University of California at San Diego, La Jolla, CA 92093 (United States)

2011-06-01

The spectroscopic and stability properties and X-ray crystal structure of the H87C mutant of the 2Fe–2S ligand mitoNEET are reported. Strikingly, the single point mutation leads to changes in its absorbance and CD spectra and an increase of around sixfold in the stability of the 2Fe–2S clusters over the pH range 5–7. However, the crystal structure of the H87C mutant displays heterogeneity in a few key residues, including the introduced cysteine ligand. Nonetheless, the cluster is highly stabilized from release. MitoNEET is the only identified Fe–S protein localized to the outer mitochondrial membrane and a 1.5 Å resolution X-ray analysis has revealed a unique structure [Paddock et al. (2007 ▶), Proc. Natl Acad. Sci. USA, 104, 14342–14347]. The 2Fe–2S cluster is bound with a 3Cys–1His coordination which defines a new class of 2Fe–2S proteins. The hallmark feature of this class is the single noncysteine ligand His87, which when replaced by Cys decreases the redox potential (E{sub m}) by ∼300 mV and increases the stability of the cluster by around sixfold. Unexpectedly, the pH dependence of the lifetime of the 2Fe–2S cluster remains the same as in the wild-type protein. Here, the crystal structure of H87C mitoNEET was determined to 1.7 Å resolution (R factor = 18%) to investigate the structural basis of the changes in the properties of the 2Fe–2S cluster. In comparison to the wild type, structural changes are localized to the immediate vicinity of the cluster-binding region. Despite the increased stability, Cys87 displays two distinct conformations, with distances of 2.3 and 3.2 Å between the S{sup γ} and the outer Fe of the 2Fe–2S cluster. In addition, Lys55 exhibits multiple conformations in the H87C mutant protein. The structure and distinct characteristics of the H87C mutant provide a framework for further studies investigating the effects of mutation on the properties of the 2Fe–2S cluster in this new class of proteins.

Thermodynamic properties of the solid solutions CuCr/sub 2/S/sub 4/ in Cu/sub 1///sub 2/M/sub 1///sub 2/Cr/sub 2/S/sub 4/ (M=Ga, In)

Energy Technology Data Exchange (ETDEWEB)

Titov, V.V.; Gordeev, I.V.; Kesler, Y.A.; Shchelkotunov, V.A.; Tret' yakov, Y.D.

1985-09-01

Using an adiabatic calorimeter and a quartz dilatometer, the temperature dependences of the heat capacity for the solid solutions CuCr/sub 2/S/sub 4/ in Cu/sub 1///sub 2/M/sub 1///sub 2/Cr/sub 2/S/sub 4/ (M - Ga, In) were determined, the different components of the heat capacity were evaluated, and the thermodynamic parameters of the magnetic transformation were calculated.

Evaluation of Antioxidant and Cytotoxicity Activities of Copper Ferrite (CuFe2O4 and Zinc Ferrite (ZnFe2O4 Nanoparticles Synthesized by Sol-Gel Self-Combustion Method

Directory of Open Access Journals (Sweden)

Samikannu Kanagesan

2016-08-01

Full Text Available Spinel copper ferrite (CuFe2O4 and zinc ferrite (ZnFe2O4 nanoparticles were synthesized using a sol-gel self-combustion technique. The structural, functional, morphological and magnetic properties of the samples were investigated by Fourier transform infrared spectroscopy (FTIR, X-ray diffraction (XRD, Transmission electron microscopy (TEM and vibrating sample magnetometry (VSM. XRD patterns conform to the copper ferrite and zinc ferrite formation, and the average particle sizes were calculated by using a transmission electron microscope, the measured particle sizes being 56 nm for CuFe2O4 and 68 nm for ZnFe2O4. Both spinel ferrite nanoparticles exhibit ferromagnetic behavior with saturation magnetization of 31 emug−1 for copper ferrite (50.63 Am2/Kg and 28.8 Am2/Kg for zinc ferrite. Both synthesized ferrite nanoparticles were equally effective in scavenging 2,2-diphenyl-1-picrylhydrazyl hydrate (DPPH free radicals. ZnFe2O4 and CuFe2O4 nanoparticles showed 30.57% ± 1.0% and 28.69% ± 1.14% scavenging activity at 125 µg/mL concentrations. In vitro cytotoxicity study revealed higher concentrations (>125 µg/mL of ZnFe2O4 and CuFe2O4 with increased toxicity against MCF-7 cells, but were found to be non-toxic at lower concentrations suggesting their biocompatibility.

Profound Interfacial Effects in CoFe2O4/Fe3O4 and Fe3O4/CoFe2O4 Core/Shell Nanoparticles

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Polishchuk, Dmytro; Nedelko, Natalia; Solopan, Sergii; Ślawska-Waniewska, Anna; Zamorskyi, Vladyslav; Tovstolytkin, Alexandr; Belous, Anatolii

2018-03-01

Two sets of core/shell magnetic nanoparticles, CoFe2O4/Fe3O4 and Fe3O4/CoFe2O4, with a fixed diameter of the core ( 4.1 and 6.3 nm for the former and latter sets, respectively) and thickness of shells up to 2.5 nm were synthesized from metal chlorides in a diethylene glycol solution. The nanoparticles were characterized by X-ray diffraction, transmission electron microscopy, and magnetic measurements. The analysis of the results of magnetic measurements shows that coating of magnetic nanoparticles with the shells results in two simultaneous effects: first, it modifies the parameters of the core-shell interface, and second, it makes the particles acquire combined features of the core and the shell. The first effect becomes especially prominent when the parameters of core and shell strongly differ from each other. The results obtained are useful for optimizing and tailoring the parameters of core/shell spinel ferrite magnetic nanoparticles for their use in various technological and biomedical applications.

Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia

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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.

Vibrational properties of stannite and kesterite type compounds: Raman scattering analysis of Cu2(Fe,Zn)SnS4

International Nuclear Information System (INIS)

Fontané, X.; Izquierdo-Roca, V.; Saucedo, E.; Schorr, S.; Yukhymchuk, V.O.; Valakh, M.Ya.; Pérez-Rodríguez, A.; Morante, J.R.

2012-01-01

Highlights: ► Analysis of main and weaker Raman peaks from Cu 2 FeZnS 4 and Cu 2 ZnSnS 4 compounds. ► Identification of a cation disorder induced Raman peak in Cu 2 ZnSnS 4 . ► Analysis of spectral features of main Raman peaks from Cu 2 (Fe,Zn)SnS 4 . - Abstract: This work reports the analysis of the vibrational properties of stannite–kesterite Cu 2 (Fe,Zn)SnS 4 compounds that has been performed by Raman scattering measurements. The detailed analysis of the experimental spectra has allowed determining the frequency and symmetry assignment of the main and weaker peaks from both stannite Cu 2 FeSnS 4 (CFTS) and kesterite Cu 2 ZnSnS 4 (CZTS) phases. The measurements performed in the kesterite CZTS samples have also revealed the presence of local inhomogeneities that are characterised by an additional peak in the spectra at about 331 cm −1 . This peak has been related to the presence in these local regions of a high degree of disorder in the cation sublattice, in agreement with previous neutron diffraction analysis in similar samples. Finally, the spectra from the solid solution alloys show a one-mode behaviour of the main A/A 1 peak with the chemical composition.

Defining the Architecture of the Core Machinery for the Assembly of Fe-S Clusters in Human Mitochondria.

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Gakh, Oleksandr; Ranatunga, Wasantha; Galeano, Belinda K; Smith, Douglas S; Thompson, James R; Isaya, Grazia

2017-01-01

Although Fe-S clusters may assemble spontaneously from elemental iron and sulfur in protein-free systems, the potential toxicity of free Fe 2+ , Fe 3+ , and S 2- ions in aerobic environments underscores the requirement for specialized proteins to oversee the safe assembly of Fe-S clusters in living cells. Prokaryotes first developed multiprotein systems for Fe-S cluster assembly, from which mitochondria later derived their own system and became the main Fe-S cluster suppliers for eukaryotic cells. Early studies in yeast and human mitochondria indicated that Fe-S cluster assembly in eukaryotes is centered around highly conserved Fe-S proteins (human ISCU) that serve as scaffolds upon which new Fe-S clusters are assembled from (i) elemental sulfur, provided by a pyridoxal phosphate-dependent cysteine desulfurase (human NFS1) and its stabilizing-binding partner (human ISD11), and (ii) elemental iron, provided by an iron-binding protein of the frataxin family (human FXN). Further studies revealed that all of these proteins could form stable complexes that could reach molecular masses of megadaltons. However, the protein-protein interaction surfaces, catalytic mechanisms, and overall architecture of these macromolecular machines remained undefined for quite some time. The delay was due to difficulties inherent in reconstituting these very large multiprotein complexes in vitro or isolating them from cells in sufficient quantities to enable biochemical and structural studies. Here, we describe approaches we developed to reconstitute the human Fe-S cluster assembly machinery in Escherichia coli and to define its remarkable architecture. © 2017 Elsevier Inc. All rights reserved.

Dilute Magnetic Semiconductor Cu2FeSnS4 Nanocrystals with a Novel Zincblende Structure

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Xiaolu Liang

2012-01-01

Full Text Available Diluted magnetic semiconductor Cu2FeSnS4 nanocrystals with a novel zincblende structure have been successfully synthesized by a hot-injection approach. Cu+, Fe2+, and Sn4+ ions occupy the same position in the zincblende unit cell, and their occupancy possibilities are 1/2, 1/4, and 1/4, respectively. The nanocrystals were characterized by means of X-ray diffraction (XRD, transmission electron microscopy (TEM, selected area electron diffraction (SAED, energy-dispersive spectroscopy (EDS, and UV-vis-NIR absorption spectroscopy. The nanocrystals have an average size of 7.5 nm and a band gap of 1.1 eV and show a weak ferromagnetic behavior at low temperature.

Magnetic and electrical properties of (FeIn2S4)1−x(CuIn5S8)x solid solutions

International Nuclear Information System (INIS)

Trukhanov, S.V.; Bodnar, I.V.; Zhafar, M.A.

2015-01-01

In this study, single crystals of FeIn 2 S 4 and CuIn 5 S 8 compounds, and (FeIn 2 S 4 ) 1−x (CuIn 5 S 8 ) x solid solutions were grown using the Bridgman method. The magnetic and electrical properties of the samples obtained were investigated at temperatures of 5–300 K and in a magnetic field range of 0–14 T. It was established that all of the solid solutions were paramagnets down to low temperatures of ~10 K. It was shown that the ground state of the magnetic phase of the samples was a spin glass state, where the freezing temperature increased monotonically with the increase in the concentration of Fe 2+ cations. All of the samples exhibited semiconductor characteristics in terms of electrical resistivity. The concentration-dependent critical magnetic temperatures, magnetic moment, and activation energy were plotted, which are probably explained by the magnetic state formation of the (FeIn 2 S 4 ) 1−x (CuIn 5 S 8 ) x solid solution single crystals based on the empirical Goodenough–Kanamori rules

Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation.

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Pesavento, Russell P; Berlinguette, Curtis P; Holm, R H

2007-01-22

Recent work has shown that cyanide ligation increases the redox potentials of Fe(4)S(4) clusters, enabling the isolation of [Fe(4)S(4)(CN)4]4-, the first synthetic Fe(4)S(4) cluster obtained in the all-ferrous oxidation state (Scott, T. A.; Berlinguette, C. P.; Holm, R. H.; Zhou, H.-C. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 9741). The generality of reduced cluster stabilization has been examined with MoFe(3)S(4) clusters. Reaction of single-cubane [(Tp)MoFe(3)S(4)(PEt(3))3]1+ and edge-bridged double-cubane [(Tp)2Mo(2)Fe(6)S(8)(PEt(3))4] with cyanide in acetonitrile affords [(Tp)MoFe(3)S(4)(CN)3]2- (2) and [(Tp)2Mo(2)Fe(6)S(8)(CN)4]4- (5), respectively. Reduction of 2 with KC(14)H(10) yields [(Tp)MoFe(3)S(4)(CN)3]3- (3). Clusters were isolated in approximately 70-90% yields as Et(4)N+ or Bu(4)N+ salts; clusters 3 and 5 contain all-ferrous cores, and 3 is the first [MoFe(3)S(4)]1+ cluster isolated in substance. The structures of 2 and 3 are very similar; the volume of the reduced cluster core is slightly larger (2.5%), a usual effect upon reduction of cubane-type Fe(4)S(4) and MFe(3)S(4) clusters. Redox potentials and 57Fe isomer shifts of [(Tp)MoFe(3)S(4)L3]2-,3- and [(Tp)2Mo(2)Fe(6)S(8)L(4)]4-,3- clusters with L = CN-, PhS-, halide, and PEt3 are compared. Clusters with pi-donor ligands (L = halide, PhS) exhibit larger isomer shifts and lower (more negative) redox potentials, while pi-acceptor ligands (L = CN, PEt3) induce smaller isomer shifts and higher (less-negative) redox potentials. When the potentials of 3/2 and [(Tp)MoFe(3)S(4)(SPh)3]3-/2- are compared, cyanide stabilizes 3 by 270 mV versus the reduced thiolate cluster, commensurate with the 310 mV stabilization of [Fe(4)S(4)(CN)4]4- versus [Fe(4)S(4)(SPh)4]4- where four ligands differ. These results demonstrate the efficacy of cyanide stabilization of lower cluster oxidation states. (Tp = hydrotris(pyrazolyl)borate(1-)).

Selective detection of Fe2+ by combination of CePO4:Tb3+ nanocrystal-H2O2 hybrid system with synchronous fluorescence scan technique.

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Chen, Hongqi; Ren, Jicun

2012-04-21

A new method for quenching kinetic discrimination of Fe(2+) and Fe(3+), and sensitive detection of trace amount of Fe(2+) was developed by using synchronous fluorescence scan technique. The principle of this assay is based on the quenching kinetic discrimination of Fe(2+) and Fe(3+) in CePO(4):Tb(3+) nanocrytals-H(2)O(2) hybrid system and the Fenton reaction between Fe(2+) and H(2)O(2). Stable, water-soluble and well-dispersible CePO(4):Tb(3+) nanocrystals were synthesized in aqueous solutions, and characterized by transmission electron microscopy (TEM) and electron diffraction spectroscopy (EDS). We found that both Fe(2+) and Fe(3+) could quench the synchronous fluorescence of CePO(4):Tb(3+) nanocrytals-H(2)O(2) system, but their quenching kinetics velocities were quite different. In the presence of Fe(3+), the synchronous fluorescent intensity was unchanged after only one minute, but in the presence of Fe(2+), the synchronous fluorescent intensity decreased slowly until 28 min later. The Fenton reaction between Fe(2+) and H(2)O(2) resulted in hydroxyl radicals which effectively quenched the synchronous fluorescence of the CePO(4):Tb(3+) nanocrystals due to the oxidation of Ce(3+) into Ce(4+) by hydroxyl radicals. Under optimum conditions, the linear range for Fe(2+) is 3 nM-2 μM, and the limit of detection is 2.0 nM. The method was used to analyze water samples.

X-ray spectra, chemical bonding, and electron structure of ScM2Si2 (M = Fe, Co, Ni)

International Nuclear Information System (INIS)

Shcherba, I.D.; Kotur, B.Ya.

1990-01-01

In a study of the interaction of the components in the ternary systems Sc-M-Si (where M is a 3d transition metal) it was established that there are compounds of the empirical formula ScM 2 Si 2 (M = Fe, Co, Ni). They crystallize in two structural types, HfFe 2 Si 2 (the compound ScFe 2 Si 2 ) and CeGa 2 Al 2 (ScCo 2 Si 2 and ScNi 2 Si 2 ) (ref. 1), leading to different coordination environment of the atoms in the structures of the compounds. With the aim of investigating the electron structure and the type ofin these compounds, they authors made a systematic x-ray spectral investigation with simultaneous analysis of the crystal structures of ScM 2 Si 2

Stabilization of Reduced Molybdenum-Iron-Sulfur Single and Double Cubane Clusters by Cyanide Ligation

Science.gov (United States)

Pesavento, Russell P.; Berlinguette, Curtis P.; Holm, R. H.

2008-01-01

Recent work has shown that cyanide ligation increases the redox potentials of Fe4S4 clusters, enabling the isolation of [Fe4S4(CN)4]4−, the first synthetic Fe4S4 cluster obtained in the all-ferrous oxidation state (Scott, T. A.; Berlinguette, C. P.; Holm, R. H.; Zhou, H.-C., Proc. Natl. Acad. Sci. USA 2005, 102, 9741). The generality of reduced cluster stabilization has been examined with MoFe3S4 clusters. Reaction of single cubane [(Tp)MoFe3S4(PEt3)3]1+ and edge-bridged double cubane [(Tp)2Mo2Fe6S8(PEt3)4] with cyanide in acetonitrile affords [(Tp)MoFe3S4(CN)3]2− (2) and [(Tp)2Mo2Fe6S8(CN)4]4− (5), respectively. Reduction of 2 with KC14H10 yields [(Tp)MoFe3S4(CN)3]3− (3). Clusters were isolated in ca. 70–90% yields as Et4N+ or Bu4N+ salts; Clusters 3 and 5 contain all-ferrous cores; 3 is the first [MoFe3S4]1+ cluster isolated in substance. The structures of 2 and 3 are very similar; the volume of the reduced cluster core is slightly larger (2.5%), a usual effect upon reduction of cubane-type Fe4S4 and MFe3S4 clusters. Redox potentials and 57Fe isomer shifts of [(Tp)MoFe3S4L3]2−,3 and [(Tp)2Mo2Fe6S8L4]4−,3− clusters with L = CN, PhS, halide, and PEt3 are compared. Clusters with π-donor ligands (L = halide, PhS) exhibit larger isomer shifts and lower (more negative) redox potentials while π-acceptor ligands (L = CN, PEt3) induce smaller isomer shifts and higher (less negative) redox potentials. When potentials of 3/2 and [(Tp)MoFe3S4(SPh)3]3−/2− are compared, cyanide stabilizes 3 by 270 mV vs. the reduced thiolate cluster, commensurate with the 310 mV stabilization of [Fe4S4(CN)4]4− vs. [Fe4S4(SPh)4]4− where four ligands differ. These results demonstrate the efficacy of cyanide stabilization of lower cluster oxidation states. (Tp = hydrotris(pyrazolyl)borate(1−)). PMID:17279830

First principles calculations of the electronic structure and magnetic properties of Y(Fe,M)9.2 and Y(Fe,M)9.2C (M= Si, Ga, Zr)

Science.gov (United States)

Tian, Guang; Zha, Liang; Yang, Wenyun; Qiao, Guanyi; Wang, Changsheng; Yang, Yingchang; Yang, Jinbo

2018-06-01

The preferential site substitution of the Fe by Si, Ga and Zr in the Y(Fe,M)9.2 and Y(Fe,M)9.2C compounds, and the doping effects on the magnetic properties have been studied by the first-principles calculations. It is found that the doping of the Si or Zr can improve the thermodynamic stability of the 1:9 phase, while the substitution of the Fe by Ga makes it unstable. Si atom tends to enter the 3g crystal site and Zr prefers to occupy the 2e site when Y(Fe,M)9.2 and their carbides are synthesized. Although the substitution of the Fe by Si and Zr will reduce the total magnetic moments of the YFe9.2 and their carbides, the volumetric and the d-band narrowing effects caused by the doping can still modify the electron density distributions of the Fe near the Fermi level, improving the magnetic ordering temperature of the non-carbonated compound YFe9.2. The calculated magnetic ordering temperatures of Y(Fe,M)9.2C decrease with the increasing content of the doping elements M due to the stronger hybridization of the d bands in the carbides. For the rare-earth(RE) iron based intermetallics REFe9.2 with the TbCu7-type structure, it is suggested that Zr is able to stabilize the phase and enhance the magnetic ordering temperature, indicating the possible further application in the field of permanent magnets, which has not been reported before.

Solitary Magnons in the S =5/2 Antiferromagnet CaFe2O4

Science.gov (United States)

Stock, C.; Rodriguez, E. E.; Lee, N.; Green, M. A.; Demmel, F.; Ewings, R. A.; Fouquet, P.; Laver, M.; Niedermayer, Ch.; Su, Y.; Nemkovski, K.; Rodriguez-Rivera, J. A.; Cheong, S.-W.

2016-07-01

CaFe2O4 is a S =5/2 anisotropic antiferromagnet based upon zig-zag chains having two competing magnetic structures, denoted as the A (↑↑↓↓) and B (↑↓↑↓) phases, which differ by the c -axis stacking of ferromagnetic stripes. We apply neutron scattering to demonstrate that the competing A and B phase order parameters result in magnetic antiphase boundaries along c which freeze on the time scale of ˜1 ns at the onset of magnetic order at 200 K. Using high resolution neutron spectroscopy, we find quantized spin wave levels and measure 9 such excitations localized in regions ˜1 - 2 c -axis lattice constants in size. We discuss these in the context of solitary magnons predicted to exist in anisotropic systems. The magnetic anisotropy affords both competing A +B orders as well as localization of spin excitations in a classical magnet.

Hierarchical Fe_3O_4@MoS_2/Ag_3PO_4 magnetic nanocomposites: Enhanced and stable photocatalytic performance for water purification under visible light irradiation

International Nuclear Information System (INIS)

Guo, Na; Li, Haiyan; Xu, Xingjian; Yu, Hongwen

2016-01-01

Highlights: • The FM/A-6% possesses a large specific surface area: 76.56 m"2/g. • The FM/A-6% displays high photocatalytic stability. • The FM/A-6% can be collected easily from the water by magnetic field. - Abstract: Novel hierarchical Fe_3O_4@MoS_2/Ag_3PO_4 magnetic nanophotocatalyst with remarkable photocatalytic capability were prepared by simply depositing the Ag_3PO_4 onto the surface of crumpled Fe_3O_4@MoS_2 nanosphere. The nanocomposites were characterized by XRD, TEM, HRTEM, XPS, BET, and UV–vis DRS. The outcome of the photocatalytic experiments demonstrated that Fe_3O_4@MoS_2/Ag_3PO_4 with 6 wt% content of Ag_3PO_4 (FM/A-6%) showed the highest photocatalytic activity upon the degradation Congo red (CR) and Rhodamine B (RhB) under both visible light and simulated sunlight irradiation. In addition, FM/A-6% possessed larger specific surface area (76.56 m"2/g) and excellent optical property. The possible Z-scheme charge carriers transfer mechanism for the enhanced photocatalytic properties of the FM/A-6% was also discussed. The Z-scheme charge carriers transfer mechanism established between MoS_2 and Ag_3PO_4 facilitate the charge separation efficiency. Moreover, FM/A-6% can be separated and collected easily by external magnetic field and maintain high activity after five times photoreaction cycles. Given the remarkable photocatalytic performance and high stability of FM/A-6% nanocomposite, it is looking forward to exhibit great potential for applications in water purification.

Comparison of FeS, FeS + S and solid superacid catalytic properties for coal hydro-liquefaction

Energy Technology Data Exchange (ETDEWEB)

Zhicai Wang; Hengfu Shui; Dexiang Zhang; Jinsheng Gao [East China University of Science and Technology, Shanghai (China). College of Resource and Environment Engineering

2007-03-15

Catalyst plays an important role in direct coal liquefaction. This paper focuses on the catalytic behavior of a novel SO{sub 4}{sup 2-}/ZrO{sub 2} superacid catalyst in coal hydro-liquefaction. A series of hydro-liquefaction experiments were conducted under mild conditions - 400{sup o}C, 30 min and H{sub 2} initial pressure 4 MPa in a batch autoclave with a volume of 100 ml. The catalytic property of SO{sub 4}{sup 2-}/ZrO{sub 2} was compared with FeS and FeS + S by Shenhua coal. The liquefaction products catalyzed by different catalysts were analyzed by FTIR spectrum, {sup 1}H NMR spectrum and element analysis. In addition, the SO{sub 4}{sup 2-}/ZrO{sub 2} solid superacid was characterized. The results indicated that the SO{sub 4}{sup 2-}/ZrO{sub 2} solid superacid shows outstanding catalytic property for direct liquefaction of coal and gives the highest coal conversion and gas + oil yield compared to other two catalysts. The THF conversion and the extraction yield of CS{sub 2}/NMP mixed solvent of liquefied coal catalyzed with SO{sub 4}{sup 2-}/ZrO{sub 2} are 76.3%, daf and 81.2%, daf respectively, and the yield of gas + oil is 62.5%, daf under the condition used in this study. The pyrolysis of coal macromolecular clusters can be promoted by catalysts such as FeS, FeS + S and SO{sub 4}{sup 2-}/ZrO{sub 2}. There may be only the pyrolysis of volatile matter and the relaxation of the structure of coal macromolecular clusters in non-catalytic liquefaction at 400{sup o}C. Added sulfur in FeS can improve the catalytic activity of hydrogenation. SO{sub 4}{sup 2-}/ZrO{sub 2} is a notable catalyst in the study of coal direct liquefaction because it shows excellent catalytic activities for the pyrolysis and the hydrogenation. In addition, it has been found that the C-O bond is the most stable group in coal liquefaction reaction except for the covalent bond between carbon and carbon. 34 refs., 6 figs., 6 tabs.

Liquid-Solid-Solution Assembly of CoFe2O4/Graphene Nanocomposite as a High-Performance Lithium-Ion Battery Anode

International Nuclear Information System (INIS)

Zhu, Yanfang; Lv, Xingbin; Zhang, Lili; Guo, Xiaodong; Liu, Daijun; Chen, Jianjun; Ji, Junyi

2016-01-01

Graphical abstract: CoFe 2 O 4 /rGO composites are fabricated via a liquid-solid-solution assemble strategy with a well controlled CoFe 2 O 4 size, the composite exhibits a high rate performance for lithium ion batteries anode. - Highlights: • Crumpled CoFe 2 O 4 @graphene composite with uniform CoFe 2 O 4 nanoparticles intimately anchored on graphene sheets was fabricated. • The novel fabrication strategy: liquid-solid-solution strategy where the CoFe 2 O 4 are nucleation and controlled growth at the oil/water interface. • High reversible specific capacity of 1102 mAh g −1 after 100 cycles and high rate capability of 410 mAh g −1 within 230 s charging. - Abstract: CoFe 2 O 4 /graphene composites were fabricated via a novel one-pot liquid-solid-solution (LSS) hydrothermal process. Through ions electrostatic adsorption onto graphene sheets and oil microemulsion encapsulation, CoFe 2 O 4 nanoparticles can be uniformly anchored on crumpled graphene sheets without aggregation, and the size distribution of CoFe 2 O 4 particles can be controlled by the microemulsion shell in the range of 50–100 nm. With the synergistic effect between CoFe 2 O 4 and graphene, the CoFe 2 O 4 /graphene hybrid exhibits a high reversible specific capacity of 1102 mAh g −1 at 0.2 A g −1 after 100 cycles, and a good cycling stability as well. Moreover, the composite has good rate capability. The specific capacity can reach a high value of 410 mAh g −1 even under a high current density of 6.4 A g −1 (corresponds to a charge time of ∼230 s), indicating its promising application as an anode material for lithium ion batteries.