The Molecular Bases of the Dual Regulation of Bacterial Iron Sulfur Cluster Biogenesis by CyaY and IscX

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Salvatore Adinolfi

2018-02-01

Full Text Available IscX (or YfhJ is a protein of unknown function which takes part in the iron-sulfur cluster assembly machinery, a highly specialized and essential metabolic pathway. IscX binds to iron with low affinity and interacts with IscS, the desulfurase central to cluster assembly. Previous studies have suggested a competition between IscX and CyaY, the bacterial ortholog of frataxin, for the same binding surface of IscS. This competition could suggest a link between the two proteins with a functional significance. Using a hybrid approach based on nuclear magnetic resonance, small angle scattering and biochemical methods, we show here that IscX is a modulator of the inhibitory properties of CyaY: by competing for the same site on IscS, the presence of IscX rescues the rates of enzymatic cluster formation which are inhibited by CyaY. The effect is stronger at low iron concentrations, whereas it becomes negligible at high iron concentrations. These results strongly suggest the mechanism of the dual regulation of iron sulfur cluster assembly under the control of iron as the effector.

Synthetic modeling chemistry of iron-sulfur clusters in nitric oxide signaling.

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Fitzpatrick, Jessica; Kim, Eunsuk

2015-08-18

Nitric oxide (NO) is an important signaling molecule that is involved in many physiological and pathological functions. Iron-sulfur proteins are one of the main reaction targets for NO, and the [Fe-S] clusters within these proteins are converted to various iron nitrosyl species upon reaction with NO, of which dinitrosyl iron complexes (DNICs) are the most prevalent. Much progress has been made in identifying the origin of cellular DNIC generation. However, it is not well-understood which other products besides DNICs may form during [Fe-S] cluster degradation nor what effects DNICs and other degradation products can have once they are generated in cells. Even more elusive is an understanding of the manner by which cells cope with unwanted [Fe-S] modifications by NO. This Account describes our synthetic modeling efforts to identify cluster degradation products derived from the [2Fe-2S]/NO reaction in order to establish their chemical reactivity and repair chemistry. Our intent is to use the chemical knowledge that we generate to provide insight into the unknown biological consequences of cluster modification. Our recent advances in three different areas are described. First, new reaction conditions that lead to the formation of previously unrecognized products during the reaction of [Fe-S] clusters with NO are identified. Hydrogen sulfide (H2S), a gaseous signaling molecule, can be generated from the reaction between [2Fe-2S] clusters and NO in the presence of acid or formal H• (e(-)/H(+)) donors. In the presence of acid, a mononitrosyl iron complex (MNIC) can be produced as the major iron-containing product. Second, cysteine analogues can efficiently convert MNICs back to [2Fe-2S] clusters without the need for any other reagents. This reaction is possible for cysteine analogues because of their ability to labilize NO from MNICs and their capacity to undergo C-S bond cleavage, providing the necessary sulfide for [2Fe-2S] cluster formation. Lastly, unique dioxygen

Photoelectron Spectroscopy and Density Functional Theory Studies of Iron Sulfur (FeS)m- (m = 2-8) Cluster Anions: Coexisting Multiple Spin States.

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Yin, Shi; Bernstein, Elliot R

2017-10-05

Iron sulfur cluster anions (FeS) m - (m = 2-8) are studied by photoelectron spectroscopy (PES) at 3.492 eV (355 nm) and 4.661 eV (266 nm) photon energies, and by density functional theory (DFT) calculations. The most probable structures and ground state spin multiplicities for (FeS) m - (m = 2-8) clusters are tentatively assigned through a comparison of their theoretical and experiment first vertical detachment energy (VDE) values. Many spin states lie within 0.5 eV of the ground spin state for the larger (FeS) m - (m ≥ 4) clusters. Theoretical VDEs of these low lying spin states are in good agreement with the experimental VDE values. Therefore, multiple spin states of each of these iron sulfur cluster anions probably coexist under the current experimental conditions. Such available multiple spin states must be considered when evaluating the properties and behavior of these iron sulfur clusters in real chemical and biological systems. The experimental first VDEs of (FeS) m - (m = 1-8) clusters are observed to change with the cluster size (number m). The first VDE trends noted can be related to the different properties of the highest singly occupied molecular orbitals (NBO, HSOMOs) of each cluster anion. The changing nature of the NBO/HSOMO of these (FeS) m - (m = 1-8) clusters from a p orbital on S, to a d orbital on Fe, and to an Fe-Fe bonding orbital is probably responsible for the observed increasing trend for their first VDEs with respect to m.

Analysis of NFU-1 metallocofactor binding-site substitutions-impacts on iron-sulfur cluster coordination and protein structure and function.

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Wesley, Nathaniel A; Wachnowsky, Christine; Fidai, Insiya; Cowan, J A

2017-11-01

Iron-sulfur (Fe/S) clusters are ancient prosthetic groups found in numerous metalloproteins and are conserved across all kingdoms of life due to their diverse, yet essential functional roles. Genetic mutations to a specific subset of mitochondrial Fe/S cluster delivery proteins are broadly categorized as disease-related under multiple mitochondrial dysfunction syndrome (MMDS), with symptoms indicative of a general failure of the metabolic system. Multiple mitochondrial dysfunction syndrome 1 (MMDS1) arises as a result of the missense mutation in NFU1, an Fe/S cluster scaffold protein, which substitutes a glycine near the Fe/S cluster-binding pocket to a cysteine (p.Gly208Cys). This substitution has been shown to promote protein dimerization such that cluster delivery to NFU1 is blocked, preventing downstream cluster trafficking. However, the possibility of this additional cysteine, located adjacent to the cluster-binding site, serving as an Fe/S cluster ligand has not yet been explored. To fully understand the consequences of this Gly208Cys replacement, complementary substitutions at the Fe/S cluster-binding pocket for native and Gly208Cys NFU1 were made, along with six other variants. Herein, we report the results of an investigation on the effect of these substitutions on both cluster coordination and NFU1 structure and function. The data suggest that the G208C substitution does not contribute to cluster binding. Rather, replacement of the glycine at position 208 changes the oligomerization state as a result of global structural alterations that result in the downstream effects manifest as MMDS1, but does not perturb the coordination chemistry of the Fe-S cluster. © 2017 Federation of European Biochemical Societies.

EPR spectroscopy of complex biological iron-sulfur systems.

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Hagen, Wilfred R

2018-02-21

From the very first discovery of biological iron-sulfur clusters with EPR, the spectroscopy has been used to study not only purified proteins but also complex systems such as respiratory complexes, membrane particles and, later, whole cells. In recent times, the emphasis of iron-sulfur biochemistry has moved from characterization of individual proteins to the systems biology of iron-sulfur biosynthesis, regulation, degradation, and implications for human health. Although this move would suggest a blossoming of System-EPR as a specific, non-invasive monitor of Fe/S (dys)homeostasis in whole cells, a review of the literature reveals limited success possibly due to technical difficulties in adherence to EPR spectroscopic and biochemical standards. In an attempt to boost application of System-EPR the required boundary conditions and their practical applications are explicitly and comprehensively formulated.

Deficiency of the iron-sulfur clusters of mitochondrial reduced nicotinamide-adenine dinucleotide-ubiquinone oxidoreductase (complex I) in an infant with congenital lactic acidosis.

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Moreadith, R W; Batshaw, M L; Ohnishi, T; Kerr, D; Knox, B; Jackson, D; Hruban, R; Olson, J; Reynafarje, B; Lehninger, A L

1984-09-01

We report the case of an infant with hypoglycemia, progressive lactic acidosis, an increased serum lactate/pyruvate ratio, and elevated plasma alanine, who had a moderate to profound decrease in the ability of mitochondria from four organs to oxidize pyruvate, malate plus glutamate, citrate, and other NAD+-linked respiratory substrates. The capacity to oxidize the flavin adenine dinucleotide-linked substrate, succinate, was normal. The most pronounced deficiency was in skeletal muscle, the least in kidney mitochondria. Enzymatic assays on isolated mitochondria ruled out defects in complexes II, III, and IV of the respiratory chain. Further studies showed that the defect was localized in the inner membrane mitochondrial NADH-ubiquinone oxidoreductase (complex I). When ferricyanide was used as an artificial electron acceptor, complex I activity was normal, indicating that electrons from NADH could reduce the flavin mononucleotide cofactor. However, electron paramagnetic resonance spectroscopy performed on liver submitochondrial particles showed an almost total loss of the iron-sulfur clusters characteristic of complex I, whereas normal signals were noted for other mitochondrial iron-sulfur clusters. This infant is presented as the first reported case of congenital lactic acidosis caused by a deficiency of the iron-sulfur clusters of complex I of the mitochondrial electron transport chain.

Fe-S Cluster Biogenesis in Isolated Mammalian Mitochondria

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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

Unifying principles in homodimeric type I photosynthetic reaction centers: properties of PscB and the FA, FB and FX iron-sulfur clusters in green sulfur bacteria.

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Jagannathan, Bharat; Golbeck, John H

2008-12-01

The photosynthetic reaction center from the green sulfur bacterium Chlorobium tepidum (CbRC) was solubilized from membranes using Triton X-100 and isolated by sucrose density ultra-centrifugation. The CbRC complexes were subsequently treated with 0.5 M NaCl and ultrafiltered over a 100 kDa cutoff membrane. The resulting CbRC cores did not exhibit the low-temperature EPR resonances from FA- and FB- and were unable to reduce NADP+. SDS-PAGE and mass spectrometric analysis showed that the PscB subunit, which harbors the FA and FB clusters, had become dissociated, and was now present in the filtrate. Attempts to rebind PscB onto CbRC cores were unsuccessful. Mössbauer spectroscopy showed that recombinant PscB contains a heterogeneous mixture of [4Fe-4S]2+,1+ and other types of Fe/S clusters tentatively identified as [2Fe-2S]2+,1+ clusters and rubredoxin-like Fe3+,2+ centers, and that the [4Fe-4S]2+,1+ clusters which were present were degraded at high ionic strength. Quantitative analysis confirmed that the amount of iron and sulfide in the recombinant protein was sub-stoichiometric. A heme-staining assay indicated that cytochrome c551 remained firmly attached to the CbRC cores. Low-temperature EPR spectroscopy of photoaccumulated CbRC complexes and CbRC cores showed resonances between g=5.4 and 4.4 assigned to a S=3/2 ground spin state [4Fe-4S]1+ cluster and at g=1.77 assigned to a S=1/2 ground spin state [4Fe-4S]1+ cluster, both from FX-. These results unify the properties of the acceptor side of the Type I homodimeric reaction centers found in green sulfur bacteria and heliobacteria: in both, the FA and FB iron-sulfur clusters are present on a salt-dissociable subunit, and FX is present as an interpolypeptide [4Fe-4S]2+,1+ cluster with a significant population in a S=3/2 ground spin state.

Structure of the nucleotide-binding domain of a dipeptide ABC transporter reveals a novel iron-sulfur cluster-binding domain.

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Li, Xiaolu; Zhuo, Wei; Yu, Jie; Ge, Jingpeng; Gu, Jinke; Feng, Yue; Yang, Maojun; Wang, Linfang; Wang, Na

2013-02-01

Dipeptide permease (Dpp), which belongs to an ABC transport system, imports peptides consisting of two or three L-amino acids from the matrix to the cytoplasm in microbes. Previous studies have indicated that haem competes with dipeptides to bind DppA in vitro and in vivo and that the Dpp system can also translocate haem. Here, the crystal structure of DppD, the nucleotide-binding domain (NBD) of the ABC-type dipeptide/oligopeptide/nickel-transport system from Thermoanaerobacter tengcongensis, bound with ATP, Mg(2+) and a [4Fe-4S] iron-sulfur cluster is reported. The N-terminal domain of DppD shares a similar structural fold with the NBDs of other ABC transporters. Interestingly, the C-terminal domain of DppD contains a [4Fe-4S] cluster. The UV-visible absorbance spectrum of DppD was consistent with the presence of a [4Fe-4S] cluster. A search with DALI revealed that the [4Fe-4S] cluster-binding domain is a novel structural fold. Structural analysis and comparisons with other ABC transporters revealed that this iron-sulfur cluster may act as a mediator in substrate (dipeptide or haem) binding by electron transfer and may regulate the transport process in Dpp ABC transport systems. The crystal structure provides a basis for understanding the properties of ABC transporters and will be helpful in investigating the functions of NBDs in the regulation of ABC transporter activity.

1H NMR of High-Potential Iron-Sulfur Protein from the Purple Non-Sulfur Bacterium Rhodoferax fermentans

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Ciurli, Stefano; Cremonini, Mauro Andrea; Kofod, Pauli

1996-01-01

residues bound to the [4Fe-4S]3+/2+ cluster have been performed using one-dimensional NOE and exchange spectroscopy experiments. 1H-NMR hyperfine shifts and relaxation rates of cluster-bound Cys β-CH2 protons indicate that in the [4Fe-4S]3+ cluster one iron ion can be formally described as Fe(III), while......Oxidized and reduced forms of high-potential iron-sulfur protein (HiPIP) from the purple non-sulfur photosynthetic bacterium Rhodoferux fermentans have been characterized using 1H-NMR spectroscopy. Pairwise and sequence-specific assignments of hyperfine-shifted 1H-NMR signals to protons of cysteine...... longitudinal relaxation rates of Cys β-CH2 protons in HiPIPs from six different sources as a function of the Fe-S-Cβ-Cα dihedral angle, indicate that the major contribution is due to a dipolar metal-centered mechanism, with a non-negligeable contribution from a ligand-centered dipolar mechanism which involves...

The crystal structure of TrxA(CACA): Insights into the formation of a [2Fe-2S] iron-sulfur cluster in an Escherichia coli thioredoxin mutant.

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Collet, Jean-Francois; Peisach, Daniel; Bardwell, James C A; Xu, Zhaohui

2005-07-01

Escherichia coli thioredoxin is a small monomeric protein that reduces disulfide bonds in cytoplasmic proteins. Two cysteine residues present in a conserved CGPC motif are essential for this activity. Recently, we identified mutations of this motif that changed thioredoxin into a homodimer bridged by a [2Fe-2S] iron-sulfur cluster. When exported to the periplasm, these thioredoxin mutants could restore disulfide bond formation in strains lacking the entire periplasmic oxidative pathway. Essential for the assembly of the iron-sulfur was an additional cysteine that replaced the proline at position three of the CGPC motif. We solved the crystalline structure at 2.3 Angstroms for one of these variants, TrxA(CACA). The mutant protein crystallized as a dimer in which the iron-sulfur cluster is replaced by two intermolecular disulfide bonds. The catalytic site, which forms the dimer interface, crystallized in two different conformations. In one of them, the replacement of the CGPC motif by CACA has a dramatic effect on the structure and causes the unraveling of an extended alpha-helix. In both conformations, the second cysteine residue of the CACA motif is surface-exposed, which contrasts with wildtype thioredoxin where the second cysteine of the CXXC motif is buried. This exposure of a pair of vicinal cysteine residues apparently allows thioredoxin to acquire an iron-sulfur cofactor at its active site, and thus a new activity and mechanism of action.

The crystal structure of TrxA(CACA): Insights into the formation of a [2Fe-2S] iron-sulfur cluster in an Escherichia coli thioredoxin mutant

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Collet, Jean-Francois; Peisach, Daniel; Bardwell, James C.A.; Xu, Zhaohui [Michigan

2010-07-13

Escherichia coli thioredoxin is a small monomeric protein that reduces disulfide bonds in cytoplasmic proteins. Two cysteine residues present in a conserved CGPC motif are essential for this activity. Recently, we identified mutations of this motif that changed thioredoxin into a homodimer bridged by a [2Fe-2S] iron-sulfur cluster. When exported to the periplasm, these thioredoxin mutants could restore disulfide bond formation in strains lacking the entire periplasmic oxidative pathway. Essential for the assembly of the iron-sulfur was an additional cysteine that replaced the proline at position three of the CGPC motif. We solved the crystalline structure at 2.3 {angstrom} for one of these variants, TrxA(CACA). The mutant protein crystallized as a dimer in which the iron-sulfur cluster is replaced by two intermolecular disulfide bonds. The catalytic site, which forms the dimer interface, crystallized in two different conformations. In one of them, the replacement of the CGPC motif by CACA has a dramatic effect on the structure and causes the unraveling of an extended {alpha}-helix. In both conformations, the second cysteine residue of the CACA motif is surface-exposed, which contrasts with wildtype thioredoxin where the second cysteine of the CXXC motif is buried. This exposure of a pair of vicinal cysteine residues apparently allows thioredoxin to acquire an iron-sulfur cofactor at its active site, and thus a new activity and mechanism of action.

Interactions of iron-bound frataxin with ISCU and ferredoxin on the cysteine desulfurase complex leading to Fe-S cluster assembly.

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Cai, Kai; Frederick, Ronnie O; Tonelli, Marco; Markley, John L

2018-06-01

Frataxin (FXN) is involved in mitochondrial iron‑sulfur (Fe-S) cluster biogenesis and serves to accelerate Fe-S cluster formation. FXN deficiency is associated with Friedreich ataxia, a neurodegenerative disease. We have used a combination of isothermal titration calorimetry and multinuclear NMR spectroscopy to investigate interactions among the components of the biological machine that carries out the assembly of iron‑sulfur clusters in human mitochondria. Our results show that FXN tightly binds a single Fe 2+ but not Fe 3+ . While FXN (with or without bound Fe 2+ ) does not bind the scaffold protein ISCU directly, the two proteins interact mutually when each is bound to the cysteine desulfurase complex ([NFS1] 2 :[ISD11] 2 :[Acp] 2 ), abbreviated as (NIA) 2 , where "N" represents the cysteine desulfurase (NFS1), "I" represents the accessory protein (ISD11), and "A" represents acyl carrier protein (Acp). FXN binds (NIA) 2 weakly in the absence of ISCU but more strongly in its presence. Fe 2+ -FXN binds to the (NIA) 2 -ISCU 2 complex without release of iron. However, upon the addition of both l-cysteine and a reductant (either reduced FDX2 or DTT), Fe 2+ is released from FXN as consistent with Fe 2+ -FXN being the proximal source of iron for Fe-S cluster assembly. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Sulfur Removal by Adding Iron During the Digestion Process of High-sulfur Bauxite

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Zhanwei, Liu; Hengwei, Yan; Wenhui, Ma; Keqiang, Xie; Dunyong, Li; Licong, Zheng; Pengfei, Li

2018-04-01

This paper proposes a novel approach to sulfur removal by adding iron during the digestion process. Iron can react with high-valence sulfur (S2O3 2-, SO3 2-, SO4 2-) to generate S2- at digestion temperature, and then S2- enter red mud in the form of Na3FeS3 to be removed. As iron dosage increases, high-valence sulfur concentration decreases, but the concentration of S2- increases; sulfur digestion rate decreases while sulfur content in red mud markedly increases; the alumina digestion rate, conversely, remains fairly stable. So sulfur can be removed completely by adding iron in digestion process, which provide a theoretical basis for the effective removal of sulfur in alumina production process.

Sulfur-binding in recent environments: II. Speciation of sulfur and iron and implications for the occurrence of organo-sulfur compounds

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Hartgers, Walter A.; Lòpez, Jordi F.; Sinninghe Damsté, Jaap S.; Reiss, Christine; Maxwell, James R.; Grimalt, Joan O.

1997-11-01

Speciation of iron and sulfur species was determined for two recent sediments (La Trinitat and Lake Cisó) which were deposited in environments with a high biological productivity and sulfate-reducing activity. In sediments from calcite ponds of La Trinitat an excess of reactive iron species (iron monosulfides, iron hydroxides) results in a depletion of reactive sulfur which is accompanied by a virtual absence of organo-sulfur compounds, both in low (LMW) and high molecular-weight (HMW) fractions. Small amounts of phytanyl and highly branched isoprenoid (HBI) thiophenes in the extract demonstrate that these molecules exhibit a higher reactivity towards reduced sulfur species as compared to detrital iron. Euxinic sediments from Lake Cisó are characterised by an excess of reduced sulfur species which can rapidly trap reactive iron. High concentrations of H 2S results in the formation of organo-sulfur compounds which were encountered in both LMW and HMW fractions. The major part of the organic sulfur is bound to the carbohydrate portion of woody tissues, whose presence was revealed by a specific alkylthiophene distribution in the flash pyrolysate and by Li/EtNH 2 desulfurisation of the kerogen which resulted in the solubilisation of the sulfur-enriched hemicellulose fraction. Relatively high amounts of sulfurised C 25 HBI compounds in the sediment extract of Lake Cisó reflect the incorporation of sulfur into algal derived organic matter upon early diagenesis. The combined approach of the speciation of iron and sulfur species and the molecular analysis of sedimentary fractions demonstrates that abiotic sulfur binding to organic matter occurs at the earliest stages of diagenesis under specific depositional conditions (anoxic, stratified water column) in which an excess of reduced sulfur species relative to the amount of reactive iron is a controlling factor.

A missed Fe-S cluster handoff causes a metabolic shakeup.

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Berteau, Olivier

2018-05-25

The general framework of pathways by which iron-sulfur (Fe-S) clusters are assembled in cells is well-known, but the cellular consequences of disruptions to that framework are not fully understood. Crooks et al. report a novel cellular system that creates an acute Fe-S cluster deficiency, using mutants of ISCU, the main scaffold protein for Fe-S cluster assembly. Surprisingly, the resultant metabolic reprogramming leads to the accumulation of lipid droplets, a situation encountered in many poorly understood pathological conditions, highlighting unanticipated links between Fe-S assembly machinery and human disease. © 2018 Berteau.

Iron Sulfur and Molybdenum Cofactor Enzymes Regulate the Drosophila Life Cycle by Controlling Cell Metabolism

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Marelja, Zvonimir; Leimkühler, Silke; Missirlis, Fanis

2018-01-01

Iron sulfur (Fe-S) clusters and the molybdenum cofactor (Moco) are present at enzyme sites, where the active metal facilitates electron transfer. Such enzyme systems are soluble in the mitochondrial matrix, cytosol and nucleus, or embedded in the inner mitochondrial membrane, but virtually absent from the cell secretory pathway. They are of ancient evolutionary origin supporting respiration, DNA replication, transcription, translation, the biosynthesis of steroids, heme, catabolism of purines, hydroxylation of xenobiotics, and cellular sulfur metabolism. Here, Fe-S cluster and Moco biosynthesis in Drosophila melanogaster is reviewed and the multiple biochemical and physiological functions of known Fe-S and Moco enzymes are described. We show that RNA interference of Mocs3 disrupts Moco biosynthesis and the circadian clock. Fe-S-dependent mitochondrial respiration is discussed in the context of germ line and somatic development, stem cell differentiation and aging. The subcellular compartmentalization of the Fe-S and Moco assembly machinery components and their connections to iron sensing mechanisms and intermediary metabolism are emphasized. A biochemically active Fe-S core complex of heterologously expressed fly Nfs1, Isd11, IscU, and human frataxin is presented. Based on the recent demonstration that copper displaces the Fe-S cluster of yeast and human ferredoxin, an explanation for why high dietary copper leads to cytoplasmic iron deficiency in flies is proposed. Another proposal that exosomes contribute to the transport of xanthine dehydrogenase from peripheral tissues to the eye pigment cells is put forward, where the Vps16a subunit of the HOPS complex may have a specialized role in concentrating this enzyme within pigment granules. Finally, we formulate a hypothesis that (i) mitochondrial superoxide mobilizes iron from the Fe-S clusters in aconitase and succinate dehydrogenase; (ii) increased iron transiently displaces manganese on superoxide dismutase, which

Iron Sulfur and Molybdenum Cofactor Enzymes Regulate the Drosophila Life Cycle by Controlling Cell Metabolism

Directory of Open Access Journals (Sweden)

Zvonimir Marelja

2018-02-01

Full Text Available Iron sulfur (Fe-S clusters and the molybdenum cofactor (Moco are present at enzyme sites, where the active metal facilitates electron transfer. Such enzyme systems are soluble in the mitochondrial matrix, cytosol and nucleus, or embedded in the inner mitochondrial membrane, but virtually absent from the cell secretory pathway. They are of ancient evolutionary origin supporting respiration, DNA replication, transcription, translation, the biosynthesis of steroids, heme, catabolism of purines, hydroxylation of xenobiotics, and cellular sulfur metabolism. Here, Fe-S cluster and Moco biosynthesis in Drosophila melanogaster is reviewed and the multiple biochemical and physiological functions of known Fe-S and Moco enzymes are described. We show that RNA interference of Mocs3 disrupts Moco biosynthesis and the circadian clock. Fe-S-dependent mitochondrial respiration is discussed in the context of germ line and somatic development, stem cell differentiation and aging. The subcellular compartmentalization of the Fe-S and Moco assembly machinery components and their connections to iron sensing mechanisms and intermediary metabolism are emphasized. A biochemically active Fe-S core complex of heterologously expressed fly Nfs1, Isd11, IscU, and human frataxin is presented. Based on the recent demonstration that copper displaces the Fe-S cluster of yeast and human ferredoxin, an explanation for why high dietary copper leads to cytoplasmic iron deficiency in flies is proposed. Another proposal that exosomes contribute to the transport of xanthine dehydrogenase from peripheral tissues to the eye pigment cells is put forward, where the Vps16a subunit of the HOPS complex may have a specialized role in concentrating this enzyme within pigment granules. Finally, we formulate a hypothesis that (i mitochondrial superoxide mobilizes iron from the Fe-S clusters in aconitase and succinate dehydrogenase; (ii increased iron transiently displaces manganese on superoxide

Characterization and uranium bioleaching performance of mixed iron- and sulfur-oxidizers versus iron-oxidizers

International Nuclear Information System (INIS)

Qian Li; Jing Sun; Dexin Ding; Qingliang Wang; Wenge Shi; Eming Hu; Xiaoyu Jiang; University of South China, Hengyang; Xingxing Wang

2017-01-01

In order to develop and apply mixed iron- and sulfur-oxidizers in uranium bioleaching, the characteristics of a mixed iron- and sulfur-oxidizing consortium (Consortium ISO) were comparatively investigated versus an iron-oxidizing consortium (Consortium IO). The results showed, the Consortium ISO exerted stronger oxidative ability and acid-producing ability than Consortium IO did. The synergy of sulfur-oxidizers and iron-oxidizers could change the structure and properties of the passivation substance, and work positively for eliminating the accumulation of passivation substance. In the bioleaching process, the uranium bioleaching experiments showed the recovery percentage of uranium reached 99.5% with Consortium ISO, 6.3% more than that of Consortium IO. (author)

The iron-sulfur cluster assembly network component NARFL is a key element in the cellular defense against oxidative stress.

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Corbin, Monique V; Rockx, Davy A P; Oostra, Anneke B; Joenje, Hans; Dorsman, Josephine C

2015-12-01

Aim of this study was to explore cellular changes associated with increased resistance to atmospheric oxygen using high-resolution DNA and RNA profiling combined with functional studies. Two independently selected oxygen-resistant substrains of HeLa cells (capable of proliferating at >80% O2, i.e. hyperoxia) were compared with their parental cells (adapted to growth at 20% O2, but unable to grow at >80% O2). A striking consistent alteration found to be associated with the oxygen-resistant state appeared to be an amplified and overexpressed region on chromosome 16p13.3 harboring 21 genes. The driver gene of this amplification was identified by functional studies as NARFL, which encodes a component of the cytosolic iron-sulfur cluster assembly system. In line with this result we found the cytosolic c-aconitase activity as well as the nuclear protein RTEL1, both Fe-S dependent proteins, to be protected by NARFL overexpression under hyperoxia. In addition, we observed a protective effect of NARFL against hyperoxia-induced loss of sister-chromatid cohesion. NARFL thus appeared to be a key factor in the cellular defense against hyperoxia-induced oxidative stress in human cells. Our findings suggest that new insight into age-related degenerative processes may come from studies that specifically address the involvement of iron-sulfur proteins. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Altered sterol metabolism in budding yeast affects mitochondrial iron-sulfur (Fe-S) cluster synthesis.

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Ward, Diane M; Chen, Opal S; Li, Liangtao; Kaplan, Jerry; Bhuiyan, Shah Alam; Natarajan, Selvamuthu K; Bard, Martin; Cox, James E

2018-05-17

Ergosterol synthesis is essential for cellular growth and viability of the budding yeast Saccharomyces cerevisiae, and intracellular sterol distribution and homeostasis are therefore highly regulated in this species. Erg25 is an iron-containing C4-methyl sterol oxidase that contributes to the conversion of 4,4-dimethylzymosterol to zymosterol, a precursor of ergosterol. The ERG29 gene encodes an endoplasmic reticulum (ER)-associated protein, and here we identified a role for Erg29 in the methyl sterol oxidase step of ergosterol synthesis. ERG29 deletion resulted in lethality in respiring cells, but respiration-incompetent (Rho- or Rho0) cells survived, suggesting that Erg29 loss leads to accumulation of oxidized sterol metabolites that affect cell viability. Down-regulation of ERG29 expression in Δerg29 cells indeed led to accumulation of methyl sterol metabolites, resulting in increased mitochondrial oxidants and a decreased ability of mitochondria to synthesize iron-sulfur (Fe-S) clusters due to reduced levels of Yfh1, the mammalian frataxin homolog, which is involved in mitochondrial Fe metabolism. Using a high-copy genomic library, we identified suppressor genes that permitted growth of Δerg29 cells on respiratory substrates, and these included genes encoding the mitochondrial proteins Yfh1, Mmt1, Mmt2, and Pet20, which reversed all phenotypes associated with loss of ERG29. Of note, loss of Erg25 also resulted in accumulation of methyl sterol metabolites and also increased mitochondrial oxidants and degradation of Yfh1. We propose that accumulation of toxic intermediates of the methyl sterol oxidase reaction increase mitochondrial oxidants, which affect Yfh1 protein stability. These results indicate an interaction between sterols generated by ER proteins and mitochondrial iron metabolism. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

The Rieske Iron-Sulfur Protein: Import and Assembly into the Cytochrome bc 1 Complex of Yeast Mitochondria

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Conte, Laura; Zara, Vincenzo

2011-01-01

The Rieske iron-sulfur protein, one of the catalytic subunits of the cytochrome bc 1 complex, is involved in electron transfer at the level of the inner membrane of yeast mitochondria. The Rieske iron-sulfur protein is encoded by nuclear DNA and, after being synthesized in the cytosol, is imported into mitochondria with the help of a cleavable N-terminal presequence. The imported protein, besides incorporating the 2Fe-2S cluster, also interacts with other catalytic and non-catalytic subunits of the cytochrome bc 1 complex, thereby assembling into the mature and functional respiratory complex. In this paper, we summarize the most recent findings on the import and assembly of the Rieske iron-sulfur protein into Saccharomyces cerevisiae mitochondria, also discussing a possible role of this protein both in the dimerization of the cytochrome bc 1 complex and in the interaction of this homodimer with other complexes of the mitochondrial respiratory chain. PMID:21716720

The Rieske Iron-Sulfur Protein: Import and Assembly into the Cytochrome bc(1) Complex of Yeast Mitochondria.

Science.gov (United States)

Conte, Laura; Zara, Vincenzo

2011-01-01

The Rieske iron-sulfur protein, one of the catalytic subunits of the cytochrome bc(1) complex, is involved in electron transfer at the level of the inner membrane of yeast mitochondria. The Rieske iron-sulfur protein is encoded by nuclear DNA and, after being synthesized in the cytosol, is imported into mitochondria with the help of a cleavable N-terminal presequence. The imported protein, besides incorporating the 2Fe-2S cluster, also interacts with other catalytic and non-catalytic subunits of the cytochrome bc(1) complex, thereby assembling into the mature and functional respiratory complex. In this paper, we summarize the most recent findings on the import and assembly of the Rieske iron-sulfur protein into Saccharomyces cerevisiae mitochondria, also discussing a possible role of this protein both in the dimerization of the cytochrome bc(1) complex and in the interaction of this homodimer with other complexes of the mitochondrial respiratory chain.

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

Science.gov (United States)

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

2015-11-01

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

The Iron-Sulfur Cluster of Electron Transfer Flavoprotein-ubiquinone Oxidoreductase (ETF-QO) is the Electron Acceptor for Electron Transfer Flavoprotein†

Science.gov (United States)

Swanson, Michael A.; Usselman, Robert J.; Frerman, Frank E.; Eaton, Gareth R.; Eaton, Sandra S.

2011-01-01

Electron-transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) accepts electrons from electron-transfer flavoprotein (ETF) and reduces ubiquinone from the ubiquinone-pool. It contains one [4Fe-4S]2+,1+ and one FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. In the porcine protein, threonine 367 is hydrogen bonded to N1 and O2 of the flavin ring of the FAD. The analogous site in Rhodobacter sphaeroides ETF-QO is asparagine 338. Mutations N338T and N338A were introduced into the R. sphaeroides protein by site-directed mutagenesis to determine the impact of hydrogen bonding at this site on redox potentials and activity. The mutations did not alter the optical spectra, EPR g-values, spin-lattice relaxation rates, or the [4Fe-4S]2+,1+ to FAD point-dipole interspin distances. The mutations had no impact on the reduction potential for the iron-sulfur cluster, which was monitored by changes in the continuous wave EPR signals of the [4Fe-4S]+ at 15 K. For the FAD semiquinone, significantly different potentials were obtained by monitoring the titration at 100 or 293 K. Based on spectra at 293 K the N338T mutation shifted the first and second midpoint potentials for the FAD from +47 mV and −30 mV for wild type to −11 mV and −19 mV, respectively. The N338A mutation decreased the potentials to −37 mV and −49 mV. Lowering the midpoint potentials resulted in a decrease in the quinone reductase activity and negligible impact on disproportionation of ETF1e− catalyzed by ETF-QO. These observations indicate that the FAD is involved in electron transfer to ubiquinone, but not in electron transfer from ETF to ETF-QO. Therefore the iron-sulfur cluster is the immediate acceptor from ETF. PMID:18672901

Modulation of intestinal sulfur assimilation metabolism regulates iron homeostasis

Science.gov (United States)

Hudson, Benjamin H.; Hale, Andrew T.; Irving, Ryan P.; Li, Shenglan; York, John D.

2018-01-01

Sulfur assimilation is an evolutionarily conserved pathway that plays an essential role in cellular and metabolic processes, including sulfation, amino acid biosynthesis, and organismal development. We report that loss of a key enzymatic component of the pathway, bisphosphate 3′-nucleotidase (Bpnt1), in mice, both whole animal and intestine-specific, leads to iron-deficiency anemia. Analysis of mutant enterocytes demonstrates that modulation of their substrate 3′-phosphoadenosine 5′-phosphate (PAP) influences levels of key iron homeostasis factors involved in dietary iron reduction, import and transport, that in part mimic those reported for the loss of hypoxic-induced transcription factor, HIF-2α. Our studies define a genetic basis for iron-deficiency anemia, a molecular approach for rescuing loss of nucleotidase function, and an unanticipated link between nucleotide hydrolysis in the sulfur assimilation pathway and iron homeostasis. PMID:29507250

Decoupling of Neoarchean sulfur sources recorded in Algoma-type banded iron formation

Science.gov (United States)

Diekrup, David; Hannington, Mark D.; Strauss, Harald; Ginley, Stephen J.

2018-05-01

Neoarchean Algoma-type banded iron formations (BIFs) are widely viewed as direct chemical precipitates from proximal volcanic-hydrothermal vents. However, a systematic multiple sulfur isotope study of oxide-facies BIF from a type locality in the ca. 2.74 Ga Temagami greenstone belt reveals mainly bacterial turnover of atmospheric elemental sulfur in the host basin rather than deposition of hydrothermally cycled seawater sulfate or sulfur from direct volcanic input. Trace amounts of chromium reducible sulfur that were extracted for quadruple sulfur isotope (32S-33S-34S-36S) analysis record the previously known mass-independent fractionation of volcanic SO2 in the Archean atmosphere (S-MIF) and biological sulfur cycling but only minor contributions from juvenile sulfur, despite the proximity of volcanic sources. We show that the dominant bacterial metabolisms were iron reduction and sulfur disproportionation, and not sulfate reduction, consistent with limited availability of organic matter and the abundant ferric iron deposited as Fe(OH)3. That sulfur contained in the BIF was not a direct volcanic-hydrothermal input, as expected, changes the view of an important archive of the Neoarchean sulfur cycle in which the available sulfur pools were strongly decoupled and only species produced photochemically under anoxic atmospheric conditions were deposited in the BIF-forming environment.

Electron-induced chemistry in microhydrated sulfuric acid clusters

Science.gov (United States)

Lengyel, Jozef; Pysanenko, Andriy; Fárník, Michal

2017-11-01

We investigate the mixed sulfuric acid-water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT) calculations. The microhydration of (H2SO4)m(H2O)n clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4)m(H2O)nHSO4- and (H2O)nH2SO4-. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4- ṡ ṡ ṡ H3O+) formation in the neutral H2SO4(H2O)n clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO4)2(H2O)n this process starts as early as n ≥ 2 water molecules. The (H2SO4)m(H2O)nHSO4- clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4- ṡ ṡ ṡ H3O+) ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2O)nH2SO4- cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid-water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid-water aerosols are discussed.

Effect of sulfur and iron fertilizers on yield, yield components and ...

African Journals Online (AJOL)

Jane

2011-06-13

Jun 13, 2011 ... per plant. Interaction between water stress and combination of iron and sulfur fertilizers had significant .... Results of analysis of variance (ANOVA) of water stress (W), sulfur (B) and iron (C), and their interaction with gain yield, yield components and ... the soil structure and it increased the usefulness of other.

Sulfur-Modified Zero-Valent Iron for Remediation Applications at DOE Sites - 13600

Energy Technology Data Exchange (ETDEWEB)

Fogwell, Thomas W. [Fogwell Consulting, P.O. Box 20221, Piedmont, CA 94620 (United States); Santina, Pete [SMI-PS, Inc., 2073 Prado Vista, Lincoln, CA 95648 (United States)

2013-07-01

Many DOE remediation sites have chemicals of concern that are compounds in higher oxidation states, which make them both more mobile and more toxic. The chemical reduction of these compounds both prevents the migration of these chemicals and in some cases reduces the toxicity. It has also been shown that zero-valent iron is a very effective substance to use in reducing oxygenated compounds in various treatment processes. These have included the treatment of halogenated hydrocarbons in the form volatile organic compounds used as solvents and pesticides. Zero-valent iron has also been used to reduce various oxidized metals such as chromium, arsenic, and mercury in order to immobilize them, decrease their toxicity, and prevent further transport. In addition, it has been used to immobilize or break down other non-metallic species such as selenium compounds and nitrates. Of particular interest at several DOE remediation sites is the fact that zero-valent iron is very effective in immobilizing several radioactive metals which are mobile in their oxidized states. These include both technetium and uranium. The main difficulty in using zero-valent iron has been its tendency to become inactive after relatively short periods of time. While it is advantageous to have the zero-valent iron particles as porous as possible in order to provide maximum surface area for reactions to take place, these pores can become clogged when the iron is oxidized. This is due to the fact that ferric oxide has a greater volume for a given mass than metallic iron. When the surfaces of the iron particles oxidize to ferric oxide, the pores become narrower and will eventually shut. In order to minimize the degradation of the chemical activity of the iron due to this process, a modification of zero-valent iron has been developed which prevents or slows this process, which decreases its effectiveness. It is called sulfur-modified iron, and it has been produced in high purity for applications in

Photoactive thin film semiconducting iron pyrite prepared by sulfurization of iron oxides

Energy Technology Data Exchange (ETDEWEB)

Smestad, G.; Ennaoui, A.; Fiechter, S.; Tributsch, H.; Hofmann, W.K.; Birkholz, M. (Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Solare Energetik Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Materialforschung); Kautek, W. (Bundesanstalt fuer Materialforschung und -pruefung, Berlin (Germany, F.R.))

1990-03-01

Photoactive iron pyrite (FeS{sub 2}) thin film layers have been synthesized by a simple method involving the reaction of Fe{sub 3}O{sub 4} or Fe{sub 2}O{sub 3} with elemental sulfur. The films were formed on a variety of different substrate materials by converting or sulfurizing iron oxide layers. The subsequent sulfur treatment of the oxide layers consisted of exposure of the films to gaseous sulfur in open or closed ampules at 350degC for 0.5-2 h. The morphology, composition and photoactivity of the films produced were checked using X-ray diffraction, X-ray photoelectron spectroscopy (ESCA), optical absorption, steady state and transient photoconductivity. The best films showed good crystallinity and purity with concurrent photoconductivity and photoelectrochemical response. The ability of this technique to produce photoactive material can be explained by interpretation of the Gibbs ternary phase diagram for the Fe-O-S system, and may be related to the production of photoactive pyrite in nature. A discussion is made as to the future improvement of the solar cell response by proper optimization of geometric and configurational properties. (orig.).

Research field development ou iron-sulfur proteins by the Moessbauer spectroscopy and EPR

International Nuclear Information System (INIS)

Arsenio, T.P.; Taft, C.A.

1984-01-01

A research line on iron sulfides (chemical and structurally seemed with the iron-sulfur proteins), implanted and developed at CBPF-Brazil, using the same theoretical and experimental models used in the development of the research field on iron-sulfur proteins is reported. The techniques used are Moessbauer spectroscopy and EPR. (L.C.) [pt

Monomeric Yeast Frataxin is an Iron-Binding Protein

International Nuclear Information System (INIS)

Cook, J.; Bencze, K.; Jankovic, A.; Crater, A.; Busch, C.; Bradley, P.; Stemmler, A.; Spaller, M.; Stemmler, T.

2006-01-01

Friedreich's ataxia, an autosomal cardio- and neurodegenerative disorder that affects 1 in 50 000 humans, is caused by decreased levels of the protein frataxin. Although frataxin is nuclear-encoded, it is targeted to the mitochondrial matrix and necessary for proper regulation of cellular iron homeostasis. Frataxin is required for the cellular production of both heme and iron-sulfur (Fe-S) clusters. Monomeric frataxin binds with high affinity to ferrochelatase, the enzyme involved in iron insertion into porphyrin during heme production. Monomeric frataxin also binds to Isu, the scaffold protein required for assembly of Fe-S cluster intermediates. These processes (heme and Fe-S cluster assembly) share requirements for iron, suggesting that monomeric frataxin might function as the common iron donor. To provide a molecular basis to better understand frataxin's function, we have characterized the binding properties and metal-site structure of ferrous iron bound to monomeric yeast frataxin. Yeast frataxin is stable as an iron-loaded monomer, and the protein can bind two ferrous iron atoms with micromolar binding affinity. Frataxin amino acids affected by the presence of iron are localized within conserved acidic patches located on the surfaces of both helix-1 and strand-1. Under anaerobic conditions, bound metal is stable in the high-spin ferrous state. The metal-ligand coordination geometry of both metal-binding sites is consistent with a six-coordinate iron-(oxygen/nitrogen) based ligand geometry, surely constructed in part from carboxylate and possibly imidazole side chains coming from residues within these conserved acidic patches on the protein. On the basis of our results, we have developed a model for how we believe yeast frataxin interacts with iron

Electron-induced chemistry in microhydrated sulfuric acid clusters

Directory of Open Access Journals (Sweden)

J. Lengyel

2017-11-01

Full Text Available We investigate the mixed sulfuric acid–water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT calculations. The microhydration of (H2SO4m(H2On clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4m(H2OnHSO4− and (H2OnH2SO4−. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4−  ⋅  ⋅  ⋅  H3O+ formation in the neutral H2SO4(H2On clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO42(H2On this process starts as early as n ≥ 2 water molecules. The (H2SO4m(H2OnHSO4− clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4−  ⋅  ⋅  ⋅  H3O+ ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2OnH2SO4− cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid–water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid–water aerosols are discussed.

Atomic Iron Catalysis of Polysulfide Conversion in Lithium-Sulfur Batteries.

Science.gov (United States)

Liu, Zhenzhen; Zhou, Lei; Ge, Qi; Chen, Renjie; Ni, Mei; Utetiwabo, Wellars; Zhang, Xiaoling; Yang, Wen

2018-06-13

Lithium-sulfur batteries have been regarded as promising candidates for energy storage because of their high energy density and low cost. It is a main challenge to develop long-term cycling stability battery. Here, a catalytic strategy is presented to accelerate reversible transformation of sulfur and its discharge products in lithium-sulfur batteries. This is achieved with single-atomic iron active sites in porous nitrogen-doped carbon, prepared by polymerizing and carbonizing diphenylamine in the presence of iron phthalocyanine and a hard template. The Fe-PNC/S composite electrode exhibited a high discharge capacity (427 mAh g -1 ) at a 0.1 C rate after 300 cycles with the Columbic efficiency of above 95.6%. Besides, the electrode delivers much higher capacity of 557.4 mAh g -1 at 0.5 C over 300 cycles. Importantly, the Fe-PCN/S has a smaller phase nucleation overpotential of polysulfides than nitrogen-doped carbon alone for the formation of nanoscale of Li 2 S as revealed by ex situ SEM, which enhance lithium-ion diffusion in Li 2 S, and therefore a high rate performance and remarkable cycle life of Li-sulfur batteries were achieved. Our strategy paves a new way for polysulfide conversion with atomic iron catalysis to exploit high-performance lithium-sulfur batteries.

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Directory of Open Access Journals (Sweden)

Natascha Riedinger

2017-05-01

Full Text Available The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates (SRR. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT. Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydroxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron

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

Science.gov (United States)

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.

Transfer of sulfur from IscS to IscU during Fe/S cluster assembly.

Science.gov (United States)

Urbina, H D; Silberg, J J; Hoff, K G; Vickery, L E

2001-11-30

The cysteine desulfurase enzymes NifS and IscS provide sulfur for the biosynthesis of Fe/S proteins. NifU and IscU have been proposed to serve as template or scaffold proteins in the initial Fe/S cluster assembly events, but the mechanism of sulfur transfer from NifS or IscS to NifU or IscU has not been elucidated. We have employed [(35)S]cysteine radiotracer studies to monitor sulfur transfer between IscS and IscU from Escherichia coli and have used direct binding measurements to investigate interactions between the proteins. IscS catalyzed transfer of (35)S from [(35)S]cysteine to IscU in the absence of additional thiol reagents, suggesting that transfer can occur directly and without involvement of an intermediate carrier. Surface plasmon resonance studies and isothermal titration calorimetry measurements further revealed that IscU binds to IscS with high affinity (K(d) approximately 2 microm) in support of a direct transfer mechanism. Transfer was inhibited by treatment of IscU with iodoacetamide, and (35)S was released by reducing reagents, suggesting that transfer of persulfide sulfur occurs to cysteinyl groups of IscU. A deletion mutant of IscS lacking C-terminal residues 376-413 (IscSDelta376-413) displayed cysteine desulfurase activity similar to the full-length protein but exhibited lower binding affinity for IscU, decreased ability to transfer (35)S to IscU, and reduced activity in assays of Fe/S cluster assembly on IscU. The findings with IscSDelta376-413 provide additional support for a mechanism of sulfur transfer involving a direct interaction between IscS and IscU and suggest that the C-terminal region of IscS may be important for binding IscU.

Isolation, Characterization, and Functional Role of the High-Potential Iron-Sulfur Protein (HiPIP) from Rhodoferax fermentans

DEFF Research Database (Denmark)

Hochkoeppler, A.; Kofod, P.; Ferro, G.

1995-01-01

A new high-potential iron-sulfur protein (HiPIP) has been isolated and purified to homogeneity from the soluble fraction obtained from light-grown cells of the facultative photoheterotrophic bacterium Rhodoferax fermentans. The new protein was identified as a HiPIP by virtue of its molecular...... other sources and, in particular, the iron content is consistent with the presence of one [Fe4S4] cubane cluster per molecule. The isoelectric pH values of the two redox forms are consistent with a basic protein. Kinetic studies of HiPIP oxidation, performed by monitoring the absorbance changes induced...

Effect of Iron Oxides (Ordinary and Nano and Municipal Solid Waste Compost (MSWC Coated Sulfur on Wheat (Triticum aestivum L. Plant Iron Concentration and Growth

Directory of Open Access Journals (Sweden)

S Mazaherinia

2011-02-01

Full Text Available Abstract A greenhouse study was conducted to compare the effects of ordinary iron oxide (0.02-0.06 mm and nano iron oxide (25-250 nm and five levels of both iron oxides (0, 0.05, 0.1, 0.5, and 1.0 %w/w and two levels of sulfurous granular compost (MSW (0 and 2% w/w on plant height, spike length, grain weight per spike, total plant dry matter weight and thousands grain weight of wheat. The experimental factors were combined in factorial arrangement in a completely randomized design with 3 replications. Results showed that nano iron oxide was superior over ordinary iron oxide in all parameters studied. Fe concentration, spike length, plant height, grain weight per spike, total plant dry weight and thousands grain weight showed increasing trend per increase in both of iron oxides levels. Also, all parameters studied in sulfurous granular compost (MSW treatment were superior over granular compost without sulfurous (MSW. This increase in all parameters were significantly higher when urban solid waste compost coated with sulfur coupled with nano iron oxide compared to urban sulfurous granular compost (MSW along with ordinary iron oxide. Keywords: Sulfurous granular compost (MSW, Nano and ordinary iron oxides, Wheat

Genomic and Evolutionary Perspectives on Sulfur Metabolism in Green Sulfur Bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Bryant, Donald A.

2008-01-01

Green sulfur bacteria (GSB) are anaerobic photoautotrophs that oxidize sulfide, elemental sulfur, thiosulfate, ferrous iron, and hydrogen for growth. We present here an analysis of the distribution and evolution of enzymes involved in oxidation of sulfur compounds in GSB based on genome sequence......, in combination with phylogenetic analyses, suggests that the Dsr system in GSB could be a recent acquisition, which was obtained by lateral gene transfer in part from sulfideoxidizing bacteria and in part from sulfate-reducing bacteria. All thiosulfate-utilizing GSB strains have an identical sox gene cluster...

Insights into the iron and sulfur energetic metabolism of Acidithiobacillus ferrooxidans by microarray transcriptome profiling

Energy Technology Data Exchange (ETDEWEB)

R. Quatrini; C. Appia-Ayme; Y. Denis; J. Ratouchniak; F. Veloso; J. Valdes; C. Lefimil; S. Silver; F. Roberto; O. Orellana; F. Denizot; E. Jedlicki; D. Holmes; V. Bonnefoy

2006-09-01

Acidithiobacillus ferrooxidans is a well known acidophilic, chemolithoautotrophic, Gram negative, bacterium involved in bioleaching and acid mine drainage. In aerobic conditions, it gains energy mainly from the oxidation of ferrous iron and/or reduced sulfur compounds present in ores. After initial oxidation of the substrate, electrons from ferrous iron or sulfur enter respiratory chains and are transported through several redox proteins to oxygen. However, the oxidation of ferrous iron and reduced sulfur compounds has also to provide electrons for the reduction of NAD(P) that is subsequently required for many metabolic processes including CO2 fixation. To help to unravel the enzymatic pathways and the electron transfer chains involved in these processes, a genome-wide microarray transcript profiling analysis was carried out. Oligonucleotides corresponding to approximately 3000 genes of the A. ferrooxidans type strain ATCC23270 were spotted onto glass-slides and hybridized with cDNA retrotranscribed from RNA extracted from ferrous iron and sulfur grown cells. The genes which are preferentially transcribed in ferrous iron conditions and those preferentially transcribed in sulfur conditions were analyzed. The expression of a substantial number of these genes has been validated by real-time PCR, Northern blot hybridization and/or immunodetection analysis. Our results support and extend certain models of iron and sulfur oxidation and highlight previous observations regarding the possible presence of alternate electron pathways. Our findings also suggest ways in which iron and sulfur oxidation may be co-ordinately regulated. An accompanying paper (Appia-Ayme et al.) describes results pertaining to other metabolic functions.

The addition zirconium effect on the solubility and activity of sulfur in liquid iron

International Nuclear Information System (INIS)

Burylev, B.P.; Mojsov, L.P.

1994-01-01

Critical analysis of reference data on thermodynamic properties of zirconium sulfides is conducted for evaluation of zirconium desulfonation ability in liquid steel. Sulfur solubility dependence on zirconium concentration in liquid iron is presented. Curves of sulfur solubility in liquid iron in the presence of other elements, including titanium, manganese, vanadium and chromium are presented for comparison. It is shown that equilibrium concentration of sulfur is much lower than standard sulfur concentrations in steel, therefore zirconium appears to be the best desulfonator among the metals considered

Amine reactivity with charged sulfuric acid clusters

Directory of Open Access Journals (Sweden)

B. R. Bzdek

2011-08-01

Full Text Available The distribution of charged species produced by electrospray of an ammonium sulfate solution in both positive and negative polarities is examined using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS. Positively-charged ammonium bisulfate cluster composition differs significantly from negatively-charged cluster composition. For positively-charged clusters all sulfuric acid is neutralized to bisulfate, whereas for negatively-charged clusters the degree of sulfuric acid neutralization is cluster size-dependent. With increasing cluster size (and, therefore, a decreasing role of charge, both positively- and negatively-charged cluster compositions converge toward ammonium bisulfate. The reactivity of negatively-charged sulfuric acid-ammonia clusters with dimethylamine and ammonia is also investigated by FTICR-MS. Two series of negatively-charged clusters are investigated: [(HSO₄(H₂SO_4x]⁻ and [(NH_4x(HSO_4x+1(H₂SO₄₃]⁻. Dimethylamine substitution for ammonia in [(NH_{4 x}(HSO_{4 x+1}(H₂SO₄₃]⁻ clusters is nearly collision-limited, and subsequent addition of dimethylamine to neutralize H₂SO₄ to bisulfate is within one order of magnitude of the substitution rate. Dimethylamine addition to [(HSO₄ (H₂SO_{4 x}]⁻ clusters is either not observed or very slow. The results of this study indicate that amine chemistry will be evident and important only in large ambient negative ions (>m/z 400, whereas amine chemistry may be evident in small ambient positive ions. Addition of ammonia to unneutralized clusters occurs at a rate that is ~2–3 orders of magnitude slower than incorporation of dimethylamine either by substitution or addition

Iron-induced changes in the proteome of Trichomonas vaginalis hydrogenosomes.

Directory of Open Access Journals (Sweden)

Neritza Campo Beltrán

Full Text Available Iron plays a crucial role in metabolism as a key component of catalytic and redox cofactors, such as heme or iron-sulfur clusters in enzymes and electron-transporting or regulatory proteins. Limitation of iron availability by the host is also one of the mechanisms involved in immunity. Pathogens must regulate their protein expression according to the iron concentration in their environment and optimize their metabolic pathways in cases of limitation through the availability of respective cofactors. Trichomonas vaginalis, a sexually transmitted pathogen of humans, requires high iron levels for optimal growth. It is an anaerobe that possesses hydrogenosomes, mitochondrion-related organelles that harbor pathways of energy metabolism and iron-sulfur cluster assembly. We analyzed the proteomes of hydrogenosomes obtained from cells cultivated under iron-rich and iron-deficient conditions employing two-dimensional peptide separation combining IEF and nano-HPLC with quantitative MALDI-MS/MS. We identified 179 proteins, of which 58 were differentially expressed. Iron deficiency led to the upregulation of proteins involved in iron-sulfur cluster assembly and the downregulation of enzymes involved in carbohydrate metabolism. Interestingly, iron affected the expression of only some of multiple protein paralogues, whereas the expression of others was iron independent. This finding indicates a stringent regulation of differentially expressed multiple gene copies in response to changes in the availability of exogenous iron.

Genomic Insights into the Sulfur Metabolism of Phototrophic Green Sulfur Bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Bryant, Donald A.

2008-01-01

Green sulfur bacteria (GSB) utilize various combinations of sulfide, elemental sulfur, thiosulfate, ferrous iron, and hydrogen for anaerobic photoautotrophic growth. Genome sequence data is currently available for 12 strains of GSB. We present here a genome-based survey of the distribution...... and phylogenies of genes involved in oxidation of sulfur compounds in these strains. Sulfide:quinone reductase, encoded by sqr, is the only known sulfur-oxidizing enzyme found in all strains. All sulfide-utilizing strains contain the dissimilatory sulfite reductase dsrABCEFHLNMKJOPT genes, which appear...... to be involved in elemental sulfur utilization. All thiosulfate-utilizing strains have an identical sox gene cluster (soxJXYZAKBW). The soxCD genes found in certain other thiosulfate-utilizing organisms like Paracoccus pantotrophus are absent from GSB. Genes encoding flavocytochrome c (fccAB), adenosine-5...

Effects of sulfur in flooded paddy soils: Implications for iron chemistry and arsenic mobilization

Science.gov (United States)

Avancha, S.; Boye, K.

2013-12-01

In the Mekong delta in Cambodia, naturally occurring arsenic (amplified by erosion in the Himalaya Mountains) in paddy soils is mobilized during the seasonal flooding. As a consequence, rice grown on the flooded soils may take up arsenic and expose people eating the rice to this carcinogenic substance. Iron and sulfur both interact strongly with arsenic in paddy soils: iron oxides are strong adsorbents for arsenic in oxic conditions, and sulfur (in the form of sulfide) is a strong adsorbent under anoxic conditions. In the process of reductive dissolution of iron oxides, arsenic, which had been adsorbed to the iron oxides, is released. Therefore, higher levels of reduced iron (ferrous iron) will likely correlate with higher levels of mobilized arsenic. However, the mobilized arsenic may then co-precipitate with or adsorb to iron sulfides, which form under sulfate-reducing conditions and with the aid of certain microbes already present in the soil. In a batch experiment, we investigated how these processes correlate and which has the greatest influence on arsenic mobilization and potential plant availability. The experiment was designed to measure the effects of various sources of sulfur (dried rice straw, charred rice straw, and gypsum) on the iron and arsenic release in an arsenic-contaminated paddy soil from Cambodia under flooded conditions. The two types of rice straw were designed to introduce the same amount of organic sulfur (7.7 μg/g of soil), but different levels of available carbon, since carbon stimulates microbial activity in the soil. In comparison, two different levels of gypsum (calcium sulfate) were used, 7.7 and 34.65 μg/g of soil, to test the effect of directly available inorganic sulfate without carbon addition. The soil was flooded with a buffer solution at pH 7.07 in airtight serum vials and kept as a slurry on a shaker at 25 °C. We measured pH, alkalinity, ferrous iron, ferric iron, sulfide, sulfate, total iron, sulfur, and arsenic in the

Mitochondrial iron-sulfur cluster biogenesis from molecular understanding to clinical disease

Science.gov (United States)

Alfadhel, Majid; Nashabat, Marwan; Ali, Qais Abu; Hundallah, Khalid

2017-01-01

Iron–sulfur clusters (ISCs) are known to play a major role in various protein functions. Located in the mitochondria, cytosol, endoplasmic reticulum and nucleus, they contribute to various core cellular functions. Until recently, only a few human diseases related to mitochondrial ISC biogenesis defects have been described. Such diseases include Friedreich ataxia, combined oxidative phosphorylation deficiency 19, infantile complex II/III deficiency defect, hereditary myopathy with lactic acidosis and mitochondrial muscle myopathy, lipoic acid biosynthesis defects, multiple mitochondrial dysfunctions syndromes and non ketotic hyperglycinemia due to glutaredoxin 5 gene defect. Disorders of mitochondrial import, export and translation, including sideroblastic anemia with ataxia, EVEN-PLUS syndrome and mitochondrial complex I deficiency due to nucleotide-binding protein-like protein gene defect, have also been implicated in ISC biogenesis defects. With advances in next generation sequencing technologies, more disorders related to ISC biogenesis defects are expected to be elucidated. In this article, we aim to shed the light on mitochondrial ISC biogenesis, related proteins and their function, pathophysiology, clinical phenotypes of related disorders, diagnostic approach, and future implications. PMID:28064324

Disease: H00898 [KEGG MEDICUS

Lifescience Database Archive (English)

Full Text Available ice mutation in the iron-sulfur cluster scaffold protein ISCU causes myopathy with exercise intolerance. ... JOURNAL ... Am J Hum Genet 82:652-60 (2008) DOI:10.1016/j.ajhg.2007.12.012

Genetic/metabolic effect of iron metabolism and rare anemias

Directory of Open Access Journals (Sweden)

Clara Camaschella

2013-03-01

Full Text Available Advances in iron metabolism have allowed a novel classification of iron disorders and to identify previously unknown diseases. These disorders include genetic iron overload (hemochromatosis and inherited iron-related anemias, in some cases accompanied by iron overload. Rare inherited anemias may affect the hepcidin pathway, iron absorption, transport, utilization and recycling. Among the genetic iron-related anemias the most common form is likely the iron-refractory iron-deficiency anemia (IRIDA, due to mutations of the hepcidin inhibitor TMPRSS6 encoding the serine protease matriptase-2. IRIDA is characterized by hepcidin up-regulation, decrease iron absorption and macrophage recycling and by microcytic- hypochromic anemia, unresponsive to oral iron. High serum hepcidin levels may suggest the diagnosis, which requires demonstrating the causal TMPRSS6 mutations by gene sequencing. Other rare microcytic hypochromic anemias associated with defects of iron transport-uptake are the rare hypotransferrinemia, and DMT1 and STEAP3 mutations. The degree of anemia is variable and accompanied by secondary iron overload even in the absence of blood transfusions. This is due to the iron-deficient or expanded erythropoiesis that inhibits hepcidin transcription, increases iron absorption, through the erythroid regulator, as in untransfused beta-thalassemia. Sideroblastic anemias are due to decreased mitochondrial iron utilization for heme or sulfur cluster synthesis. Their diagnosis requires demonstrating ringed sideroblasts by Perl’s staining of the bone marrow smears. The commonest X-linked form is due to deltaamino- levulinic-synthase-2-acid (ALAS2 mutations. The recessive, more severe form, affects SLC25A38, which encodes a potential mitochondrial importer of glycine, an amino acid essential for ALA synthesis and thus results in heme deficiency. Two disorders affect iron/sulfur cluster biogenesis: deficiency of the ATP-binding cassette B7 (ABCB7 causes X

2010 IRON-SULFUR ENZYMES GORDON RESEARCH CONFERENCE, JUNE 6-11, 2010

Energy Technology Data Exchange (ETDEWEB)

Nancy Ryan Gray

2010-06-11

Iron-sulfur (FeS) centers are essential for biology and inspirational in chemistry. These protein cofactors are broadly defined as active sites in which Fe is coordinated by S-donor ligands, often in combination with extra non-protein components, for example, additional metal atoms such as Mo and Ni, and soft ligands such as CN{sup -} and CO. Iron-sulfur centers are inherently air sensitive: they are found in essentially all organisms and it is possible that they were integral components of the earliest forms of life, well before oxygen (O{sub 2}) appeared. Proteins containing FeS cofactors perform a variety of biological functions ranging across electron transfer, acid-base catalysis, and sensing where they are agents for cell regulation through transcription (DNA) or translation (RNA). They are redox catalysts for radical-based reactions and the activation of H{sub 2}, N{sub 2} and CO{sub 2}, processes that offer scientific and economic challenges for industry. Iron-sulfur centers provide the focus for fundamental investigations of chemical bonding, spectroscopy and paramagnetism, and their functions have numerous implications for health and medicine and applications for technology, including renewable energy. The 2010 Iron-Sulfur Enzymes GRC will bring together researchers from different disciplines for in-depth discussions and presentations of the latest developments. There will be sessions on structural and functional analogues of FeS centers, advances in physical methods, roles of FeS centers in energy and technology, catalysis (including radical-based rearrangements and the activation of nitrogen, hydrogen and carbon), long-range electron transfer, FeS centers in health and disease, cellular regulation, cofactor assembly, their relevance in industry, and experiments and hypotheses relating to the origins of life.

Assembling Fe/S-clusters and modifying tRNAs: ancient co-factors meet ancient adaptors.

Science.gov (United States)

Alfonzo, Juan D; Lukeš, Julius

2011-06-01

Trypanosoma brucei undergoes two clearly distinct develomental stages: in the insect vector (procyclic stage) the cells generate the bulk of their energy through respiration, whereas in the bloodstream of the mammalian host (bloodstream stage) they grow mostly glycolytically. Several mitochondrial respiratory proteins require iron-sulfur clusters for activity, and their activation coincides with developmental changes. Likewise some tRNA modification enzymes either require iron-sulfur clusters or use components of the iron-sulfur cluster assembly pathway for activity. These enzymes affect the anticodon loop of various tRNAs and can impact protein synthesis. Herein, the possibility of these pathways being integrated and exploited by T. brucei to carefully coordinate energy demands to translational rates in response to enviromental changes is examined.

2008 GRC Iron Sulfur Enzymes-Conference to be held June 8-13, 2008

Energy Technology Data Exchange (ETDEWEB)

Cramer, Stephen [Univ. of California, Davis, CA (United States); Gray, Nancy Ryan [Gordon Research Conferences, West Kingston, RI (United States)

2009-01-01

Iron-sulfur proteins are among the most common and ancient enzymes and electron-transfer agents in nature. They play key roles in photosynthesis, respiration, and the metabolism of small molecules such as H2, CO, and N2. The Iron Sulfur Enzyme Gordon Research Conference evolved from an earlier GRC on Nitrogen Fixation that began in 1994. The scope of the current meeting has broadened to include all enzymes or metalloproteins in which Fe-S bonds play a key role. This year's meeting will focus on the biosynthesis of Fe-S clusters, as well as the structure and mechanism of key Fe-S enzymes such as hydrogenase, nitrogenase and its homologues, radical SAM enzymes, and aconitase-related enzymes. Recent progress on the role of Fe-S enzymes in health, disease, DNA/RNA-processing, and alternative bio-energy systems will also be highlighted. This conference will assemble a broad, diverse, and international group of biologists and chemists who are investigating fundamental issues related to Fe-S enzymes, on atomic, molecular, organism, and environmental scales. The topics to be addressed will include: Biosynthesis & Genomics of Fe-S Enzymes; Fundamental Fe-S Chemistry; Hydrogen and Fe-S Enzymes; Nitrogenase & Homologous Fe-S Enzymes; Fe-S Enzymes in Health & Disease; Radical SAM and Aconitase-Related Fe-S Enzymes; Fe-S Enzymes and Synthetic Analogues in BioEnergy; and Fe-S Enzymes in Geochemistry and the Origin of Life.

Identification of vital and dispensable sulfur utilization factors in the Plasmodium apicoplast

NARCIS (Netherlands)

Haussig, J.M.; Matuschewski, K.; Kooij, T.W.A.

2014-01-01

Iron-sulfur [Fe-S] clusters are ubiquitous and critical cofactors in diverse biochemical processes. They are assembled by distinct [Fe-S] cluster biosynthesis pathways, typically in organelles of endosymbiotic origin. Apicomplexan parasites, including Plasmodium, the causative agent of malaria,

Regulation of human Nfu activity in Fe-S cluster delivery-characterization of the interaction between Nfu and the HSPA9/Hsc20 chaperone complex.

Science.gov (United States)

Wachnowsky, Christine; Liu, Yushi; Yoon, Taejin; Cowan, J A

2018-01-01

Iron-sulfur cluster biogenesis is a complex, but highly regulated process that involves de novo cluster formation from iron and sulfide ions on a scaffold protein, and subsequent delivery to final targets via a series of Fe-S cluster-binding carrier proteins. The process of cluster release from the scaffold/carrier for transfer to the target proteins may be mediated by a dedicated Fe-S cluster chaperone system. In human cells, the chaperones include heat shock protein HSPA9 and the J-type chaperone Hsc20. While the role of chaperones has been somewhat clarified in yeast and bacterial systems, many questions remain over their functional roles in cluster delivery and interactions with a variety of human Fe-S cluster proteins. One such protein, Nfu, has recently been recognized as a potential interaction partner of the chaperone complex. Herein, we examined the ability of human Nfu to function as a carrier by interacting with the human chaperone complex. Human Nfu is shown to bind to both chaperone proteins with binding affinities similar to those observed for IscU binding to the homologous HSPA9 and Hsc20, while Nfu can also stimulate the ATPase activity of HSPA9. Additionally, the chaperone complex was able to promote Nfu function by enhancing the second-order rate constants for Fe-S cluster transfer to target proteins and providing directionality in cluster transfer from Nfu by eliminating promiscuous transfer reactions. Together, these data support a hypothesis in which Nfu can serve as an alternative carrier protein for chaperone-mediated cluster release and delivery in Fe-S cluster biogenesis and trafficking. © 2017 Federation of European Biochemical Societies.

The role of iron-sulfides on cycling of organic carbon in the St Lawrence River system: Evidence of sulfur-promoted carbon sequestration?

Science.gov (United States)

Balind, K.; Barber, A.; Gélinas, Y.

2017-12-01

The biogeochemical cycle of sulfur is intimately linked with that of carbon, as well as with that of iron through the formation of iron-sulfur complexes. Iron-sulfide minerals such as mackinawite (FeS) and greigite (Fe3S4) form below the oxic/anoxic redox boundary in marine and lacustrine sediments and soils. Reactive iron species, abundant in surface sediments, can undergo reductive dissolution leading to the formation of soluble Fe(II) which can then precipitate in the form of iron sulfur species. While sedimentary iron-oxides have been thoroughly explored in terms of their ability to sorb and sequester organic carbon (OC) (Lalonde et al.; 2012), the role of FeS in the long-term preservation of OC remains undefined. In this study, we present depth profiles for carbon, iron, and sulfur in the aqueous-phase, along with data from sequential extractions of sulfur speciation in the solid-phase collected from sediment cores from the St Lawrence River and estuarine system, demonstrating the transition from fresh to saltwater sediments. Additionally, we present synthetic iron sulfur sorption experiments using both model and natural organic molecules in order to assess the importance of FeS in sedimentary carbon storage.

Sulfur and iron accumulation in three marine-archaeological shipwrecks in the Baltic Sea: The Ghost, the Crown and the Sword

Science.gov (United States)

Fors, Yvonne; Grudd, Håkan; Rindby, Anders; Jalilehvand, Farideh; Sandström, Magnus; Cato, Ingemar; Bornmalm, Lennart

2014-02-01

Sulfur and iron concentrations in wood from three 17th century shipwrecks in the Baltic Sea, the Ghost wreck, the Crown and the Sword, were obtained by X-ray fluorescence (XRF) scanning. In near anaerobic environments symbiotic microorganisms degrade waterlogged wood, reduce sulfate and promote accumulation of low-valent sulfur compounds, as previously found for the famous wrecks of the Vasa and Mary Rose. Sulfur K-edge X-ray absorption near-edge structure (XANES) analyses of Ghost wreck wood show that organic thiols and disulfides dominate, together with elemental sulfur probably generated by sulfur-oxidizing Beggiatoa bacteria. Iron sulfides were not detected, consistent with the relatively low iron concentration in the wood. In a museum climate with high atmospheric humidity oxidation processes, especially of iron sulfides formed in the presence of corroding iron, may induce post-conservation wood degradation. Subject to more general confirmation by further analyses no severe conservation concerns are expected for the Ghost wreck wood.

Toward High-Performance Lithium-Sulfur Batteries: Upcycling of LDPE Plastic into Sulfonated Carbon Scaffold via Microwave-Promoted Sulfonation.

Science.gov (United States)

Kim, Patrick J; Fontecha, Harif D; Kim, Kyungho; Pol, Vilas G

2018-05-02

Lithium-sulfur batteries were intensively explored during the last few decades as next-generation batteries owing to their high energy density (2600 Wh kg -1 ) and effective cost benefit. However, systemic challenges, mainly associated with polysulfide shuttling effect and low Coulombic efficiency, plague the practical utilization of sulfur cathode electrodes in the battery market. To address the aforementioned issues, many approaches have been investigated by tailoring the surface characteristics and porosities of carbon scaffold. In this study, we first present an effective strategy of preparing porous sulfonated carbon (PSC) from low-density polyethylene (LDPE) plastic via microwave-promoted sulfonation. Microwave process not only boosts the sulfonation reaction of LDPE but also induces huge amounts of pores within the sulfonated LDPE plastic. When a PSC layer was utilized as an interlayer in lithium-sulfur batteries, the sulfur cathode delivered an improved capacity of 776 mAh g -1 at 0.5C and an excellent cycle retention of 79% over 200 cycles. These are mainly attributed to two materialistic benefits of PSC: (a) porous structure with high surface area and (b) negatively charged conductive scaffold. These two characteristics not only facilitate the improved electrochemical kinetics but also effectively block the diffusion of polysulfides via Coulomb interaction.

Neutron-capture gamma-ray analysis of coal for sulfur, iron, silicon and moisture

International Nuclear Information System (INIS)

Fay, D.A.

1979-05-01

Samples of coal weighing approximately 200 grams placed in a collimated beam of neutrons from the thermal column of the Ames Laboratory Research Reactor produced capture gamma-rays which could be used for the simultaneous determination of sulfur and iron. Spectra from NaI(Tl) and Ge(Li) detectors were used and interferences were located by examining spectra of the major elemental components of coal. In determining sulfur, iron is a potential source of interference when gamma-ray spectra are collected with a NaI(Tl) detector. Corrections for iron interference were made by use of a higher energy iron peak. The possibility of determining silicon in coal was investigated but this element determination was unsuccessful since capture gamma-ray spectrometry lacked the necessary sensitivity for silicon. A linear relation was found between the area of the hydrogen capture peak at 2.23 MeV and the amount of water added to coal

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

Science.gov (United States)

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

2016-05-12

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

The impact of particle size, relative humidity, and sulfur dioxide on iron solubility in simulated atmospheric marine aerosols.

Science.gov (United States)

Cartledge, Benton T; Marcotte, Aurelie R; Herckes, Pierre; Anbar, Ariel D; Majestic, Brian J

2015-06-16

Iron is a limiting nutrient in about half of the world's oceans, and its most significant source is atmospheric deposition. To understand the pathways of iron solubilization during atmospheric transport, we exposed size segregated simulated marine aerosols to 5 ppm sulfur dioxide at arid (23 ± 1% relative humidity, RH) and marine (98 ± 1% RH) conditions. Relative iron solubility increased as the particle size decreased for goethite and hematite, while for magnetite, the relative solubility was similar for all of the fine size fractions (2.5-0.25 μm) investigated but higher than the coarse size fraction (10-2.5 μm). Goethite and hematite showed increased solubility at arid RH, but no difference (p > 0.05) was observed between the two humidity levels for magnetite. There was no correlation between iron solubility and exposure to SO2 in any mineral for any size fraction. X-ray absorption near edge structure (XANES) measurements showed no change in iron speciation [Fe(II) and Fe(III)] in any minerals following SO2 exposure. SEM-EDS measurements of SO2-exposed goethite revealed small amounts of sulfur uptake on the samples; however, the incorporated sulfur did not affect iron solubility. Our results show that although sulfur is incorporated into particles via gas-phase processes, changes in iron solubility also depend on other species in the aerosol.

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile

Science.gov (United States)

Zopfi, Jakob; Böttcher, Michael E.; Jørgensen, Bo Barker

2008-02-01

The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S 0 was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H 2S. At the shelf stations, on the other hand, pyrite was significantly depleted in 34S relative to its potential precursors FeS and S 0. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ 34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the

Iron and zinc partitioning between coexisting stannite and sphalerite: a possible indicator of temperature and sulfur fugacity

Science.gov (United States)

Shimizu, M.; Shikazono, N.

1985-10-01

Stannite and sphalerite coexisting with iron sulfides (pyrite and/or pyrrhotite) from Japanese ore deposits associated with tin mineralization were analyzed. Based on the iron and zinc partitioning between stannite and sphalerite, the formation temperature and sulfur fugacity for this mineral assemblage were estimated. A good correlation between stannite-sphalerite temperatures and filling temperatures of fluid inclusions and sulfur isotope temperatures was obtained. This good correlation suggests that the stannite-sphalerite pair is a useful indicator of temperature and sulfur fugacity. It is deduced that the formation temperatures are not different for skarn-type, polymetallic vein-type and Sn-W vein-type deposits, whereas the sulfur fugacities are different; sulfur fugacities increase from the skarn-type through the Sn-W vein-type to the polymetallic vein-type deposits.

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

A cascade of iron-containing proteins governs the genetic iron starvation response to promote iron uptake and inhibit iron storage in fission yeast.

Directory of Open Access Journals (Sweden)

Javier Encinar del Dedo

2015-03-01

Full Text Available Iron is an essential cofactor, but it is also toxic at high levels. In Schizosaccharomyces pombe, the sensor glutaredoxin Grx4 guides the activity of the repressors Php4 and Fep1 to mediate a complex transcriptional response to iron deprivation: activation of Php4 and inactivation of Fep1 leads to inhibition of iron usage/storage, and to promotion of iron import, respectively. However, the molecular events ruling the activity of this double-branched pathway remained elusive. We show here that Grx4 incorporates a glutathione-containing iron-sulfur cluster, alone or forming a heterodimer with the BolA-like protein Fra2. Our genetic study demonstrates that Grx4-Fra2, but not Fep1 nor Php4, participates not only in iron starvation signaling but also in iron-related aerobic metabolism. Iron-containing Grx4 binds and inactivates the Php4 repressor; upon iron deprivation, the cluster in Grx4 is probably disassembled, the proteins dissociate, and Php4 accumulates at the nucleus and represses iron consumption genes. Fep1 is also an iron-containing protein, and the tightly bound iron is required for transcriptional repression. Our data suggest that the cluster-containing Grx4-Fra2 heterodimer constitutively binds to Fep1, and upon iron deprivation the disassembly of the iron cluster between Grx4 and Fra2 promotes reverse metal transfer from Fep1 to Grx4-Fra2, and de-repression of iron-import genes. Our genetic and biochemical study demonstrates that the glutaredoxin Grx4 independently governs the Php4 and Fep1 repressors through metal transfer. Whereas iron loss from Grx4 seems to be sufficient to release Php4 and allow its nuclear accumulation, total or partial disassembly of the Grx4-Fra2 cluster actively participates in iron-containing Fep1 activation by sequestering its iron and decreasing its interaction with promoters.

The E. coli monothiol glutaredoxin GrxD forms homodimeric and heterodimeric FeS cluster containing complexes.

Science.gov (United States)

Yeung, N; Gold, B; Liu, N L; Prathapam, R; Sterling, H J; Willams, E R; Butland, G

2011-10-18

Monothiol glutaredoxins (mono-Grx) represent a highly evolutionarily conserved class of proteins present in organisms ranging from prokaryotes to humans. Mono-Grxs have been implicated in iron sulfur (FeS) cluster biosynthesis as potential scaffold proteins and in iron homeostasis via an FeS-containing complex with Fra2p (homologue of E. coli BolA) in yeast and are linked to signal transduction in mammalian systems. However, the function of the mono-Grx in prokaryotes and the nature of an interaction with BolA-like proteins have not been established. Recent genome-wide screens for E. coli genetic interactions reported the synthetic lethality (combination of mutations leading to cell death; mutation of only one of these genes does not) of a grxD mutation when combined with strains defective in FeS cluster biosynthesis (isc operon) functions [Butland, G., et al. (2008) Nature Methods 5, 789-795]. These data connected the only E. coli mono-Grx, GrxD to a potential role in FeS cluster biosynthesis. We investigated GrxD to uncover the molecular basis of this synthetic lethality and observed that GrxD can form FeS-bound homodimeric and BolA containing heterodimeric complexes. These complexes display substantially different spectroscopic and functional properties, including the ability to act as scaffold proteins for intact FeS cluster transfer to the model [2Fe-2S] acceptor protein E. coli apo-ferredoxin (Fdx), with the homodimer being significantly more efficient. In this work, we functionally dissect the potential cellular roles of GrxD as a component of both homodimeric and heterodimeric complexes to ultimately uncover if either of these complexes performs functions linked to FeS cluster biosynthesis. © 2011 American Chemical Society

Characterization of magnetic Ni clusters on graphene scaffold after high vacuum annealing

Energy Technology Data Exchange (ETDEWEB)

Zhang, Zhenjun, E-mail: zzhang1@albany.edu; Matsubayashi, Akitomo, E-mail: norwegianwood.1984@gmail.com; Grisafe, Benjamin, E-mail: bgrisafe@albany.edu; Lee, Ji Ung, E-mail: jlee1@albany.edu; Lloyd, James R., E-mail: JLloyd@sunycnse.com

2016-02-15

Magnetic Ni nanoclusters were synthesized by electron beam deposition utilizing CVD graphene as a scaffold. The subsequent clusters were subjected to high vacuum (5−8 x10{sup −7} torr) annealing between 300 and 600 °C. The chemical stability, optical and morphological changes were characterized by X-ray photoemission microscopy, Raman spectroscopy, atomic force microscopy and magnetic measurement. Under ambient exposure, nickel nanoparticles were observed to be oxidized quickly, forming antiferromagnetic nickel oxide. Here, we report that the majority of the oxidized nickel is in non-stoichiometric form and can be reduced under high vacuum at temperature as low as 300 °C. Importantly, the resulting annealed clusters were relatively stable and no further oxidation was detectable after three weeks of air exposure at room temperature. - Highlights: • Random oriented nickel clusters were assembled on monolayer graphene scaffold. • Nickel oxide shell was effectively reduced at moderate temperature. • Coercivity of nickel clusters are greatly improved after high vacuum annealing.

Formation of a homocitrate-free iron-molybdenum cluster on NifEN: implications for the role of homocitrate in nitrogenase assembly.

Science.gov (United States)

Fay, Aaron Wolfe; Blank, Michael Aaron; Yoshizawa, Janice Mariko; Lee, Chi Chung; Wiig, Jared Andrew; Hu, Yilin; Hodgson, Keith Owen; Hedman, Britt; Ribbe, Markus Walter

2010-03-28

Molybdenum (Mo)-dependent nitrogenase is a complex metalloprotein that catalyzes the biological reduction of dinitrogen (N(2)) to ammonia (NH(3)) at the molybdenum-iron cofactor (FeMoco) site of its molybdenum-iron (MoFe) protein component. Here we report the formation of a homocitrate-free, iron-molybdenum ("FeMo") cluster on the biosynthetic scaffold of FeMoco, NifEN. Such a NifEN-associated "FeMo" cluster exhibits EPR features similar to those of the NifEN-associated, fully-complemented "FeMoco", which originate from the presence of Mo in both cluster species; however, "FeMo" cluster and "FeMoco" display different temperature-dependent changes in the line shape and the signal intensity of their respective EPR features, which reflect the impact of homocitrate on the redox properties of these clusters. XAS/EXAFS analysis reveals that the Mo centers in both "FeMo" cluster and "FeMoco" are present in a similar coordination environment, although Mo in "FeMo" cluster is more loosely coordinated as compared to that in "FeMoco" with respect to the Mo-O distances in the cluster, likely due to the absence of homocitrate that normally serves as an additional ligand for the Mo in the cluster. Subsequent biochemical investigation of the "FeMo" cluster not only facilitates the determination of the sequence of events in the mobilization of Mo and homocitrate during FeMoco maturation, but also permits the examination of the role of homocitrate in the transfer of FeMoco between NifEN and MoFe protein. Combined outcome of these studies establishes a platform for future structural analysis of the interactions between NifEN and MoFe protein, which will provide useful insights into the mechanism of cluster transfer between the two proteins.

Scaffold Architecture Controls Insulinoma Clustering, Viability, and Insulin Production

Science.gov (United States)

Blackstone, Britani N.; Palmer, Andre F.; Rilo, Horacio R.

2014-01-01

Recently, in vitro diagnostic tools have shifted focus toward personalized medicine by incorporating patient cells into traditional test beds. These cell-based platforms commonly utilize two-dimensional substrates that lack the ability to support three-dimensional cell structures seen in vivo. As monolayer cell cultures have previously been shown to function differently than cells in vivo, the results of such in vitro tests may not accurately reflect cell response in vivo. It is therefore of interest to determine the relationships between substrate architecture, cell structure, and cell function in 3D cell-based platforms. To investigate the effect of substrate architecture on insulinoma organization and function, insulinomas were seeded onto 2D gelatin substrates and 3D fibrous gelatin scaffolds with three distinct fiber diameters and fiber densities. Cell viability and clustering was assessed at culture days 3, 5, and 7 with baseline insulin secretion and glucose-stimulated insulin production measured at day 7. Small, closely spaced gelatin fibers promoted the formation of large, rounded insulinoma clusters, whereas monolayer organization and large fibers prevented cell clustering and reduced glucose-stimulated insulin production. Taken together, these data show that scaffold properties can be used to control the organization and function of insulin-producing cells and may be useful as a 3D test bed for diabetes drug development. PMID:24410263

Cytosolic iron chaperones: Proteins delivering iron cofactors in the cytosol of mammalian cells.

Science.gov (United States)

Philpott, Caroline C; Ryu, Moon-Suhn; Frey, Avery; Patel, Sarju

2017-08-04

Eukaryotic cells contain hundreds of metalloproteins that are supported by intracellular systems coordinating the uptake and distribution of metal cofactors. Iron cofactors include heme, iron-sulfur clusters, and simple iron ions. Poly(rC)-binding proteins are multifunctional adaptors that serve as iron ion chaperones in the cytosolic/nuclear compartment, binding iron at import and delivering it to enzymes, for storage (ferritin) and export (ferroportin). Ferritin iron is mobilized by autophagy through the cargo receptor, nuclear co-activator 4. The monothiol glutaredoxin Glrx3 and BolA2 function as a [2Fe-2S] chaperone complex. These proteins form a core system of cytosolic iron cofactor chaperones in mammalian cells. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Hsc66 substrate specificity is directed toward a discrete region of the iron-sulfur cluster template protein IscU.

Science.gov (United States)

Hoff, Kevin G; Ta, Dennis T; Tapley, Tim L; Silberg, Jonathan J; Vickery, Larry E

2002-07-26

Hsc66 and Hsc20 comprise a specialized chaperone system important for the assembly of iron-sulfur clusters in Escherchia coli. Only a single substrate, the Fe/S template protein IscU, has been identified for the Hsc66/Hsc20 system, but the mechanism by which Hsc66 selectively binds IscU is unknown. We have investigated Hsc66 substrate specificity using phage display and a peptide array of IscU. Screening of a heptameric peptide phage display library revealed that Hsc66 prefers peptides with a centrally located Pro-Pro motif. Using a cellulose-bound peptide array of IscU we determined that Hsc66 interacts specifically with a region (residues 99-103, LPPVK) that is invariant among all IscU family members. A synthetic peptide (ELPPVKIHC) corresponding to IscU residues 98-106 behaves in a similar manner to native IscU, stimulating the ATPase activity of Hsc66 with similar affinity as IscU, preventing Hsc66 suppression of bovine rhodanese aggregation, and interacting with the peptide-binding domain of Hsc66. Unlike native IscU, however, the synthetic peptide is not bound by Hsc20 and does not synergistically stimulate Hsc66 ATPase activity with Hsc20. Our results indicate that Hsc66 and Hsc20 recognize distinct regions of IscU and further suggest that Hsc66 will not bind LPPVK motifs with high affinity in vivo unless they are in the context of native IscU and can be directed to Hsc66 by Hsc20.

Prevention of formation of acid drainage from high-sulfur coal refuse by inhibition of iron- and sulfur-oxidizing microorganisms. II. Inhibition in run of mine refuse under simulated field conditions

Energy Technology Data Exchange (ETDEWEB)

Dugan, P.R.

1987-01-01

The combination of sodium lauryl sulfate and benzoic acid effectively inhibits iron- and sulfur-oxidizing bacteria in coal refuse and prevents the conversion of iron pyrite to sulfate, ferric iron, and sulfuric acid, thereby significantly reducing the formation of acidic drainage from coal refuse. The inhibitors were effective in a concentration of 1.1. mg/kg refuse, and data indicate that the SLS was in excess of the concentration required. The treatment was compatible with the use of lime for neutralization of acid present prior to inhibition of its formation.

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.

Three-Dimensional Scaffold Chip with Thermosensitive Coating for Capture and Reversible Release of Individual and Cluster of Circulating Tumor Cells.

Science.gov (United States)

Cheng, Shi-Bo; Xie, Min; Chen, Yan; Xiong, Jun; Liu, Ya; Chen, Zhen; Guo, Shan; Shu, Ying; Wang, Ming; Yuan, Bi-Feng; Dong, Wei-Guo; Huang, Wei-Hua

2017-08-01

Tumor metastasis is attributed to circulating tumor cells (CTC) or CTC clusters. Many strategies have hitherto been designed to isolate CTCs, but there are few methods that can capture and gently release CTC clusters as efficient as single CTCs. Herein, we developed a three-dimensional (3D) scaffold chip with thermosensitive coating for high-efficiency capture and release of individual and cluster CTCs. The 3D scaffold chip successfully combines the specific recognition and physically obstructed effect of 3D scaffold structure to significantly improve cell clusters capture efficiency. Thermosensitive gelatin hydrogel uniformly coated on the scaffold dissolves at 37 °C quickly, and the captured cells are gently released from chip with high viability. Notably, this platform was applied to isolate CTCs from cancer patients' blood samples. This allows global DNA and RNA methylation analysis of collected single CTC and CTC clusters, indicating the great potential of this platform in cancer diagnosis and downstream analysis at the molecular level.

Iron Sulfur Proteins and their Synthetic Analogues: Structure ...

Indian Academy of Sciences (India)

... and functions at a molecular level through model system~ are described. .... analysis of this structure and the tri-iron cluster was corrected as having a non planar Fe3S4 .... couple has potentials of -300 m V difference from the corresponding ...

Unraveling the atomic structure of ultrafine iron clusters

KAUST Repository

Wang, Hongtao; Li, Kun; Yao, Yingbang; Wang, Qingxiao; Cheng, Yingchun; Schwingenschlö gl, Udo; Zhang, Xixiang; Yang, Wei

2012-01-01

Unraveling the atomic structures of ultrafine iron clusters is critical to understanding their size-dependent catalytic effects and electronic properties. Here, we describe the stable close-packed structure of ultrafine Fe clusters for the first

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.

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

Anodic Dissolution of Spheroidal Graphite Cast Iron with Different Pearlite Areas in Sulfuric Acid Solutions

Directory of Open Access Journals (Sweden)

Yoshikazu Miyata

2013-01-01

Full Text Available The rate equation of anodic dissolution reaction of spheroidal graphite cast iron in sulfuric acid solutions at 298 K has been studied. The cast irons have different areas of pearlite. The anodic Tafel slope of 0.043 V decade−1 and the reaction order with respect to the hydroxyl ion activity of 1 are obtained by the linear potential sweep technique. The anodic current density does not depend on the area of pearlite. There is no difference in the anodic dissolution reaction mechanisms between pure iron and spheroidal graphite cast iron. The anodic current density of the cast iron is higher than that of the pure iron.

One-Step Extraction of Antimony in Low Temperature from Stibnite Concentrate Using Iron Oxide as Sulfur-Fixing Agent

Directory of Open Access Journals (Sweden)

Yun Li

2016-07-01

Full Text Available A new process for one-step extraction of antimony in low temperature from stibnite concentrate by reductive sulfur-fixation smelting in sodium molten salt, using iron oxide as sulfur-fixing agent, was presented. The influences of molten salt addition and composition, ferric oxide dosage, smelting temperature and duration on extraction efficiency of antimony were investigated in details, respectively. The optimum conditions were determined as follows: 1.0 time stoichiometric requirement (α of mixed sodium salt (αsalt = 1.0, WNaCl:Wsalt = 40%, αFe2O3 = 1.0, Wcoke:Wstibnite = 40%, where W represents weight, smelting at 850 °C (1123 K for 60 min. Under the optimum conditions, the direct recovery rate of antimony can reach 91.48%, and crude antimony with a purity of 96.00% has been achieved. 95.31% of sulfur is fixed in form of FeS in the presence of iron oxide. Meanwhile, precious metals contained in stibnite concentrate are enriched and recovered comprehensively in crude antimony. In comparison to traditional antimony pyrometallurgical process, the smelting temperature of present process is reduced from 1150–1200 °C (1423–1473 K to 850–900 °C (1123–1173 K. Sulfur obtained in stibnite is fixed in FeS which avoids SO2 emission owing to the sulfur-fixing agent. Sodium salt can be regenerated and recycled in smelting system when the molten slag is operated to filter solid residue. The solid residue is subjected to mineral dressing operation to obtain iron sulfide concentrate which can be sold directly or roasted to regenerate into iron oxide.

Oxygen, hydrogen, sulfur, and carbon isotopes in the Pea Ridge magnetite-apatite deposit, southeast Missouri, and sulfur isotope comparisons to other iron deposits in the region

Science.gov (United States)

Johnson, Craig A.; Day, Warren C.; Rye, Robert O.

2016-01-01

Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ18O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ18O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes.Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ34S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition

Identification of the iron-sulfur center of spinach ferredoxin-nitrite reductase as a tetranuclear center, and preliminary EPR studies of mechanism.

Science.gov (United States)

Lancaster, J R; Vega, J M; Kamin, H; Orme-Johnson, N R; Orme-Johnson, W H; Krueger, R J; Siegel, L M

1979-02-25

EPR spectroscopic and chemical analyses of spinach nitrite reductase show that the enzyme contains one reducible iron-sulfur center, and one site for binding either cyanide or nitrite, per siroheme. The heme is nearly all in the high spin ferric state in the enzyme as isolated. The extinction coefficient of the enzyme has been revised to E386 = 7.6 X 10(4) cm-1 (M heme)-1. The iron-sulfur center is reduced with difficulty by agents such as reduced methyl viologen (equilibrated with 1 atm of H2 at pH 7.7 in the presence of hydrogenase) or dithionite. Complexation of the enzyme with CO (a known ligand for nitrite reductase heme) markedly increases the reducibility of the iron-sulfur center. New chemical analyses and reinterpretation of previous data show that the enzyme contains 6 mol of iron and 4 mol of acid-labile S2-/mol of siroheme. The EPR spectrum of reduced nitrite reductase in 80% dimethyl sulfoxide establishes clearly that the enzyme contains a tetranuclear iron-sulfur (Fe4S4) center. The ferriheme and Fe4S4 centers are reduced at similar rates (k = 3 to 4 s-1) by dithionite. The dithionite-reduced Fe4S4 center is rapidly (k = 100 s-1) reoxidized by nitrite. These results indicate a role for the Fe4S4 center in catalysis.

Effect of iron and chromium on the graphitization behaviour of sulfur-containing carbon

International Nuclear Information System (INIS)

Tyumentsev, V.A.; Belenkov, E.A.; Saunina, S.I.; Podkopaev, S.A.; Shvejkin, G.P.

1998-01-01

Process of transition of carbonaceous material, containing structurally incorporated sulfur, into graphite and impact of iron and chromium additions are studied. It is established that carbonaceous material, containing more than 1.5 mass % S and also 1.5 mass % Cr 2 O 3 is heterogeneous after thermal treatment at 1300-1600 deg C. It consists of large and sufficiency complete areas of coherent scattering having graphite structure and ultra-dispersed matrix. The number of graphite crystals formed in the presence of dispersed iron within this temperature range, decreases by two times [ru

Mutations in iron-sulfur cluster proteins that improve xylose utilization

Science.gov (United States)

Froehlich, Allan; Henningsen, Brooks; Covalla, Sean; Zelle, Rintze M.

2018-03-20

There is provided an engineered host cells comprising (a) one or more mutations in one or more endogenous genes encoding a protein associated with iron metabolism; and (b) at least one gene encoding a polypeptide having xylose isomerase activity, and methods of their use thereof.

Sulfur metabolism in phototrophic sulfur bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Dahl, Christiane

2008-01-01

Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB......). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms...... in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative...

Iron solubility related to particle sulfur content in source emission and ambient fine particles.

Science.gov (United States)

Oakes, M; Ingall, E D; Lai, B; Shafer, M M; Hays, M D; Liu, Z G; Russell, A G; Weber, R J

2012-06-19

The chemical factors influencing iron solubility (soluble iron/total iron) were investigated in source emission (e.g., biomass burning, coal fly ash, mineral dust, and mobile exhaust) and ambient (Atlanta, GA) fine particles (PM2.5). Chemical properties (speciation and mixing state) of iron-containing particles were characterized using X-ray absorption near edge structure (XANES) spectroscopy and micro-X-ray fluorescence measurements. Bulk iron solubility (soluble iron/total iron) of the samples was quantified by leaching experiments. Major differences were observed in iron solubility in source emission samples, ranging from low solubility (iron solubility did not correspond to silicon content or Fe(II) content. However, source emission and ambient samples with high iron solubility corresponded to the sulfur content observed in single particles. A similar correspondence between bulk iron solubility and bulk sulfate content in a series of Atlanta PM2.5 fine particle samples (N = 358) further supported this trend. In addition, results of linear combination fitting experiments show the presence of iron sulfates in several high iron solubility source emission and ambient PM2.5 samples. These results suggest that the sulfate content (related to the presence of iron sulfates and/or acid-processing mechanisms by H(2)SO(4)) of iron-containing particles is an important proxy for iron solubility.

Magnetic Properties of Iron Clusters in Silver

Energy Technology Data Exchange (ETDEWEB)

Elzain, M., E-mail: elzain@squ.edu.om; Al Rawas, A.; Yousif, A.; Gismelseed, A.; Rais, A.; Al-Omari, I.; Bouziane, K. [College of Science, Department of Physics (Oman); Widatallah, H. [Khartoum University, Department of Physics, Faculty of Science (Sudan)

2004-12-15

The discrete variational method is used to study the effect of interactions of iron impurities on the magnetic moments, hyperfine fields and isomer shifts at iron sites in silver. We study small clusters of iron atoms as they grow to form FCC phase that is coherent with the silver lattice. The effects of the lattice relaxation and the ferromagnetic and antiferromagnetic couplings are also considered. When Fe atoms congregate around a central Fe atom in an FCC arrangement under ferromagnetic coupling, the local magnetic moment and the contact charge density at the central atom hardly change as the cluster builds up, whereas the hyperfine field increases asymptotically as the number of Fe nearest neighbors increases. Introduction of antiferromagnetic coupling has minor effect on the local magnetic moments and isomer shifts, however it produces large reduction in the hyperfine field. The lattice relaxation of the surrounding Fe atoms towards a BCC phase around a central Fe atom leads to reduction in the magnetic moment accompanied by increase in the magnetic hyperfine field.

Evolution of Fe/S cluster biogenesis in the anaerobic parasite Blastocystis

Czech Academy of Sciences Publication Activity Database

Tsaousis, A.D.; de Choudens, S. O.; Gentekaki, E.; Long, Shaojun; Gaston, D.; Stechmann, A.; Vinella, D.; Py, B.; Fontecave, M.; Barras, F.; Lukeš, Julius; Roger, A. J.

2012-01-01

Roč. 109, č. 26 (2012), s. 10426-10431 ISSN 0027-8424 R&D Projects: GA ČR GA204/09/1667; GA ČR(CZ) GAP305/11/2179 Institutional support: RVO:60077344 Keywords : iron/sulfur cluster biosynthesis * lateral gene transfer * parasite evolution * sulfur-mobilization machinery * oxygen stress adaptation Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 9.737, year: 2012

Degradation and in vitro cell–material interaction studies on hydroxyapatite-coated biodegradable porous iron for hard tissue scaffolds

Directory of Open Access Journals (Sweden)

Nurizzati Mohd Daud

2014-10-01

Full Text Available This paper describes degradation and cell–material interaction studies on hydroxyapatite (HA-coated biodegradable porous iron proposed for hard tissue scaffolds. Porous iron scaffolds are expected to serve as an ideal platform for bone regeneration. To couple their inherent mechanical strength, pure HA and HA/poly(ε-caprolactone (HA/PCL were coated onto porous iron using dip coating technique. The HA/PCL mixture was prepared to provide a more stable and flexible coating than HA alone. Degradation of the samples was evaluated by weight loss and potentiodynamic polarisation. Human skin fibroblast (HSF and human mesenchymal stem cells (hMSC were put in contact with the samples and their interaction was observed. Results showed that coated samples degraded ∼10 times slower (0.002 mm/year for HA/PCL-Fe, 0.003 mm/year for HA-Fe than the uncoated ones (0.031 mm/year, indicating an inhibition effect of the coating on degradation. Both HSF and hMSC maintained high viability when in contact with the coated samples (100–110% control for hMSC during 2–5 days of incubation, indicating the effect of HA in enhancing cytocompatibility of the surface. This study provided early evidence of the potential translation of biodegradable porous iron scaffolds for clinical use in orthopedic surgery. However, further studies including in vitro and in vivo tests are necessary.

Penentuan Efisiensi Penyerapan Sulfur Oleh Sponge Iron Vessel (61-201-DA) Unit Desulfurizer Pada Ammonia Plant-II PT. Pupuk Iskandar Muda-Lhokseumawe

OpenAIRE

Ricky Hidayat

2009-01-01

Telah dilakukan pengamatan data life time sponge iron pada sponge iron vessel 61-201-DA charge 10. Dari pengamatan data dapat dhitung efisiensi penyerapan sulfur oleh sponge iron vessel 61-201-DA sebesar 232,6% dengan life time selama 144 hari. 09E02841

Characterization of Glutaredoxin Fe-S Cluster-Binding Interactions Using Circular Dichroism Spectroscopy.

Science.gov (United States)

Albetel, Angela-Nadia; Outten, Caryn E

2018-01-01

Monothiol glutaredoxins (Grxs) with a conserved Cys-Gly-Phe-Ser (CGFS) active site are iron-sulfur (Fe-S) cluster-binding proteins that interact with a variety of partner proteins and perform crucial roles in iron metabolism including Fe-S cluster transfer, Fe-S cluster repair, and iron signaling. Various analytical and spectroscopic methods are currently being used to monitor and characterize glutaredoxin Fe-S cluster-dependent interactions at the molecular level. The electronic, magnetic, and vibrational properties of the protein-bound Fe-S cluster provide a convenient handle to probe the structure, function, and coordination chemistry of Grx complexes. However, some limitations arise from sample preparation requirements, complexity of individual techniques, or the necessity for combining multiple methods in order to achieve a complete investigation. In this chapter, we focus on the use of UV-visible circular dichroism spectroscopy as a fast and simple initial approach for investigating glutaredoxin Fe-S cluster-dependent interactions. © 2018 Elsevier Inc. All rights reserved.

A Facile Bottom-Up Approach to Construct Hybrid Flexible Cathode Scaffold for High-Performance Lithium-Sulfur Batteries.

Science.gov (United States)

Ghosh, Arnab; Manjunatha, Revanasiddappa; Kumar, Rajat; Mitra, Sagar

2016-12-14

Lithium-sulfur batteries mostly suffer from the low utilization of sulfur, poor cycle life, and low rate performances. The prime factors that affect the performance are enormous volume change of the electrode, soluble intermediate product formation, poor electronic and ionic conductivity of S, and end discharge products (i.e., Li 2 S 2 and Li 2 S). The attractive way to mitigate these challenges underlying in the fabrication of a sulfur nanocomposite electrode consisting of different nanoparticles with distinct properties of lithium storage capability, mechanical reinforcement, and ionic as well as electronic conductivity leading to a mechanically robust and mixed conductive (ionic and electronic conductive) sulfur electrode. Herein, we report a novel bottom-up approach to synthesize a unique freestanding, flexible cathode scaffold made of porous reduced graphene oxide, nanosized sulfur, and Mn 3 O 4 nanoparticles, and all are three-dimensionally interconnected to each other by hybrid polyaniline/sodium alginate (PANI-SA) matrix to serve individual purposes. A capacity of 1098 mAh g -1 is achieved against lithium after 200 cycles at a current rate of 2 A g -1 with 97.6% of initial capacity at a same current rate, suggesting the extreme stability and cycling performance of such electrode. Interestingly, with the higher current density of 5 A g -1 , the composite electrode exhibited an initial capacity of 1015 mA h g -1 and retained 71% of the original capacity after 500 cycles. The in situ Raman study confirms the polysulfide absorption capability of Mn 3 O 4 . This work provides a new strategy to design a mechanically robust, mixed conductive nanocomposite electrode for high-performance lithium-sulfur batteries and a strategy that can be used to develop flexible large power storage devices.

Effective sulfur and energy recovery from hydrogen sulfide through incorporating an air-cathode fuel cell into chelated-iron process.

Science.gov (United States)

Sun, Min; Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi

2013-12-15

The chelated-iron process is among the most promising techniques for the hydrogen sulfide (H2S) removal due to its double advantage of waste minimization and resource recovery. However, this technology has encountered the problem of chelate degradation which made it difficult to ensure reliable and economical operation. This work aims to develop a novel fuel-cell-assisted chelated-iron process which employs an air-cathode fuel cell for the catalyst regeneration. By using such a process, sulfur and electricity were effectively recovered from H2S and the problem of chelate degradation was well controlled. Experiment on a synthetic sulfide solution showed the fuel-cell-assisted chelated-iron process could maintain high sulfur recovery efficiencies generally above 90.0%. The EDTA was preferable to NTA as the chelating agent for electricity generation, given the Coulombic efficiencies (CEs) of 17.8 ± 0.5% to 75.1 ± 0.5% for the EDTA-chelated process versus 9.6 ± 0.8% to 51.1 ± 2.7% for the NTA-chelated process in the pH range of 4.0-10.0. The Fe (III)/S(2-) ratio exhibited notable influence on the electricity generation, with the CEs improved by more than 25% as the Fe (III)/S(2-) molar ratio increased from 2.5:1 to 3.5:1. Application of this novel process in treating a H2S-containing biogas stream achieved 99% of H2S removal efficiency, 78% of sulfur recovery efficiency, and 78.6% of energy recovery efficiency, suggesting the fuel-cell-assisted chelated-iron process was effective to remove the H2S from gas streams with favorable sulfur and energy recovery efficiencies. Copyright © 2013 Elsevier B.V. All rights reserved.

Atomistic studies of nucleation of He clusters and bubbles in bcc iron

International Nuclear Information System (INIS)

Yang, L.; Deng, H.Q.; Gao, F.; Heinisch, H.L.; Kurtz, R.J.; Hu, S.Y.; Li, Y.L.; Zu, X.T.

2013-01-01

Atomistic simulations of the nucleation of He clusters and bubbles in bcc iron at 800 K have been carried out using the newly developed Fe–Fe interatomic potential, along with Ackland potential for the Fe–Fe interactions. Microstructure changes were analyzed in detail. We found that a He cluster with four He atoms is able to push out an iron interstitial from the cluster, creating a Frenkel pair. Small He clusters and self-interstitial atom (SIA) can migrate in the matrix, but He-vacancy (He-V) clusters are immobile. Most SIAs form clusters, and only the dislocation loops with a Burgers vector of b = 1/2 appear in the simulations. SIA clusters (or loops) are attached to He-V clusters for He implantation up to 1372 appm, while the He-V cluster–loop complexes with more than one He-V cluster are formed at the He concentration of 2057 appm and larger

Controlled expression of nif and isc iron-sulfur protein maturation components reveals target specificity and limited functional replacement between the two systems.

Science.gov (United States)

Dos Santos, Patricia C; Johnson, Deborah C; Ragle, Brook E; Unciuleac, Mihaela-Carmen; Dean, Dennis R

2007-04-01

The nitrogen-fixing organism Azotobacter vinelandii contains at least two systems that catalyze formation of [Fe-S] clusters. One of these systems is encoded by nif genes, whose products supply [Fe-S] clusters required for maturation of nitrogenase. The other system is encoded by isc genes, whose products are required for maturation of [Fe-S] proteins that participate in general metabolic processes. The two systems are similar in that they include an enzyme for the mobilization of sulfur (NifS or IscS) and an assembly scaffold (NifU or IscU) upon which [Fe-S] clusters are formed. Normal cellular levels of the Nif system, which supplies [Fe-S] clusters for the maturation of nitrogenase, cannot also supply [Fe-S] clusters for the maturation of other cellular [Fe-S] proteins. Conversely, when produced at the normal physiological levels, the Isc system cannot supply [Fe-S] clusters for the maturation of nitrogenase. In the present work we found that such target specificity for IscU can be overcome by elevated production of NifU. We also found that NifU, when expressed at normal levels, is able to partially replace the function of IscU if cells are cultured under low-oxygen-availability conditions. In contrast to the situation with IscU, we could not establish conditions in which the function of IscS could be replaced by NifS. We also found that elevated expression of the Isc components, as a result of deletion of the regulatory iscR gene, improved the capacity for nitrogen-fixing growth of strains deficient in either NifU or NifS.

Water clustering on nanostructured iron oxide films

DEFF Research Database (Denmark)

Merte, Lindsay Richard; Bechstein, Ralf; Peng, G.

2014-01-01

, but it is not well-understood how these hydroxyl groups and their distribution on a surface affect the molecular-scale structure at the interface. Here we report a study of water clustering on a moire-structured iron oxide thin film with a controlled density of hydroxyl groups. While large amorphous monolayer...... islands form on the bare film, the hydroxylated iron oxide film acts as a hydrophilic nanotemplate, causing the formation of a regular array of ice-like hexameric nanoclusters. The formation of this ordered phase is localized at the nanometre scale; with increasing water coverage, ordered and amorphous...

Danburite decomposition by sulfuric acid

International Nuclear Information System (INIS)

Mirsaidov, U.; Mamatov, E.D.; Ashurov, N.A.

2011-01-01

Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by sulfuric acid. The process of decomposition of danburite concentrate by sulfuric acid was studied. The chemical nature of decomposition process of boron containing ore was determined. The influence of temperature on the rate of extraction of boron and iron oxides was defined. The dependence of decomposition of boron and iron oxides on process duration, dosage of H 2 SO 4 , acid concentration and size of danburite particles was determined. The kinetics of danburite decomposition by sulfuric acid was studied as well. The apparent activation energy of the process of danburite decomposition by sulfuric acid was calculated. The flowsheet of danburite processing by sulfuric acid was elaborated.

Oxidation state of sulfur, iron and tin at the surface of float glasses

International Nuclear Information System (INIS)

Lagarde, P; Flank, A-M; Jupille, J; Montigaud, H

2009-01-01

Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO 3 ), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 μm 2 ) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

Oxidation state of sulfur, iron and tin at the surface of float glasses

Energy Technology Data Exchange (ETDEWEB)

Lagarde, P; Flank, A-M [Synchrotron SOLEIL, l' Orme des Merisiers, BP 48 91192 Gif/Yvette cedex (France); Jupille, J [IMPMC, Universite P. and M. Curie, Campus de Boucicaut, 140 rue de Lourmel 75015 Paris (France); Montigaud, H [Saint-Gobain Recherche 39, quai Lucien Lefranc, BP 135 93303 Aubervilliers Cedex (France)

2009-11-15

Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO{sub 3}), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 {mu}m{sup 2}) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

Study of the sulfur mechanism on the formation of coke deposition on iron surfaces; Etude des mecanismes d'action du soufre sur le cokage catalytique du fer

Energy Technology Data Exchange (ETDEWEB)

Bonnet, F.

2001-12-01

The formation of coke deposition which occurs in a range of temperature 500 deg C-650 deg C is a major problem in many chemical and petrochemical processes where hydrocarbons or other strongly carburizing atmospheres are involved. To reduce the rate of coke deposition, sulfur can be added in the gas phase. The topic of this work is to study the sulfur mechanism on the formation of coke deposition on iron surfaces. Firstly, we study the mechanism of graphitic filament formation on reduced and oxidised iron surfaces. A new mechanism of catalytic particle formation is proposed when the surface is initially oxidised. This mechanism is based on thermodynamic, kinetic and structural considerations. The results show that oxide/carbide transitions are involved in the transformation of the oxide layer in catalytic particles. Although the different iron oxides are precursors for the formation of catalytic particles, wustite (FeO) has a better reactivity than magnetite (Fe{sub 3}O{sub 4}) and hematite (Fe{sub 2}O{sub 3}). Sulfur acts on different steps of the coke formation, preventing phase transformations (carburation, graphitization) which occur during the formation of catalytic particles. Sulfur activity required to prevent these transformations changes with the temperature, the chemical state of iron (reduced or oxidised) and the carbon activity in the gas phase. Sulfur/ethylene co-adsorption studies were performed on mono-crystal of iron (110). The results show that sulfur can prevent adsorption and decomposition of this hydrocarbon on metallic surface (Fe) and on magnetite (Fe{sub 3}O{sub 4}). Then, sulfur prevents the reaction leading to the carburation and graphitization of the surface. (author)

Determination of sulfur isotopic composition for the study of iron sulfides origin, biotic or abiotic, in anoxic corrosion

International Nuclear Information System (INIS)

Grousset, Sophie

2016-01-01

The first goal of this project was to develop a methodology based on the study of the sulfur isotopic composition enabling the determination of iron sulfides origin, biotic or abiotic, within the corrosion products layers (CPL). Then, the aim was to apply this methodology to real corrosion systems in order to determine the mechanisms of iron sulfides formation. Sulfur isotopic analyses methodologies, adapted to micrometric iron sulfides layers observed in real corrosion systems, were developed in nanoSIMS and ToF-SIMS. The study of iron sulfides formed in anoxic carbonated medium with or without sulphate-reducing bacteria validated the use of these methods for the determination of iron sulfides origin. The application of these methods coupled with the precise characterization of irons sulfides formed in the real corrosion systems show two kind of corrosion pattern. In pattern 1, the iron sulfides are localized in the external part of the CPL. They result from the Fe 2+ migration from the metal surface to areas rich in biotic S 2- . In this pattern, corrosion rates are lower than 20 μm/year for laboratory systems, and lower than 5 μm/year for archaeological objects. In pattern 2, the large presence of conductive phases in the CPL results in the delocalization of electrons, and so a disequilibrium of the charges at the metal's surface. That leads to the migration of biotic S 2- in the CPL till the metal where they precipitate in iron sulphides. This pattern shows high corrosion rates (∼100 μm/an) that might be resulting from the accumulation of bio-corrosion and chloride corrosion mechanisms. (author) [fr

submitter On the composition of ammonia–sulfuric-acid ion clusters during aerosol particle formation

CERN Document Server

Schobesberger, S; Bianchi, F; Rondo, L; Duplissy, J; Kürten, A; Ortega, I K; Metzger, A; Schnitzhofer, R; Almeida, J; Amorim, A; Dommen, J; Dunne, E M; Ehn, M; Gagné, S; Ickes, L; Junninen, H; Hansel, A; Kerminen, V -M; Kirkby, J; Kupc, A; Laaksonen, A; Lehtipalo, K; Mathot, S; Onnela, A; Petäjä, T; Riccobono, F; Santos, F D; Sipilä, M; Tomé, A; Tsagkogeorgas, G; Viisanen, Y; Wagner, P E; Wimmer, D; Curtius, J; Donahue, N M; Baltensperger, U; Kulmala, M; Worsnop, D R

2015-01-01

The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia $(NH_3)$ and sulfuric acid $(H-2SO_4)$. Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small $NH_3–H_2SO_4$ clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from 10. Positively charged clusters grew on average by Δm/Δn = 1.05 and were only observed at sufficiently high $[NH_3]$ / $[H_2SO_4]$. The $H_2SO_4$ molecules of these clusters are partially neutralized by $NH_3$, in close resemblance...

Interaction between sulfur and lead in toxicity, iron plaque formation and lead accumulation in rice plant.

Science.gov (United States)

Yang, Junxing; Liu, Zhiyan; Wan, Xiaoming; Zheng, Guodi; Yang, Jun; Zhang, Hanzhi; Guo, Lin; Wang, Xuedong; Zhou, Xiaoyong; Guo, Qingjun; Xu, Ruixiang; Zhou, Guangdong; Peters, Marc; Zhu, Guangxu; Wei, Rongfei; Tian, Liyan; Han, Xiaokun

2016-06-01

Human activities have resulted in lead and sulfur accumulation in paddy soils in parts of southern China. A combined soil-sand pot experiment was conducted to investigate the influence of S supply on iron plaque formation and Pb accumulation in rice (Oryza sativa L.) under two Pb levels (0 and 600 mg kg(-1)), combined with four S concentrations (0, 30, 60, and 120 mg kg(-1)). Results showed that S supply significantly decreased Pb accumulation in straw and grains of rice. This result may be attributed to the enhancement of Fe plaque formation, decrease of Pb availability in soil, and increase of reduced glutathione (GSH) in rice leaves. Moderate S supply (30 mg kg(-1)) significantly increased Fe plaque formation on the root surface and in the rhizosphere, whereas excessive S supply (60 and 120 mg kg(-1)) significantly decreased the amounts of iron plaque on the root surface. Sulfur supply significantly enhanced the GSH contents in leaves of rice plants under Pb treatment. With excessive S application, the rice root acted as a more effective barrier to Pb accumulation compared with iron plaque. Excessive S supply may result in a higher monosulfide toxicity and decreased iron plaque formation on the root surface during flooded conditions. However, excessive S supply could effectively decrease Pb availability in soils and reduce Pb accumulation in rice plants. Copyright © 2016 Elsevier Inc. All rights reserved.

Unraveling the atomic structure of ultrafine iron clusters

KAUST Repository

Wang, Hongtao

2012-12-18

Unraveling the atomic structures of ultrafine iron clusters is critical to understanding their size-dependent catalytic effects and electronic properties. Here, we describe the stable close-packed structure of ultrafine Fe clusters for the first time, thanks to the superior properties of graphene, including the monolayer thickness, chemical inertness, mechanical strength, electrical and thermal conductivity. These clusters prefer to take regular planar shapes with morphology changes by local atomic shuffling, as suggested by the early hypothesis of solid-solid transformation. Our observations differ from observations from earlier experimental study and theoretical model, such as icosahedron, decahedron or cuboctahedron. No interaction was observed between Fe atoms or clusters and pristine graphene. However, preferential carving, as observed by other research groups, can be realized only when Fe clusters are embedded in graphene. The techniques introduced here will be of use in investigations of other clusters or even single atoms or molecules.

Electronic, magnetic structure and water splitting reactivity of the iron-sulfur dimers and their hexacarbonyl complexes: A density functional study

Energy Technology Data Exchange (ETDEWEB)

Uzunova, Ellie L., E-mail: ellie@svr.igic.bas.bg [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia 1113 (Bulgaria); Mikosch, Hans [Institute for Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/E164-EC, 1060 Vienna (Austria)

2014-07-28

The iron sulfide dimers (FeS){sub 2} and their persulfide isomers with S–S bonds are studied with the B3LYP density functional as bare clusters and as hexacarbonyls. The disulfides are more stable than the persulfides as bare clusters and the persulfide ground state lies at 3.2 eV above the global minimum, while in the hexacarbonyl complexes this order is reversed: persulfides are more stable, but the energy gap between disulfides and persulfides becomes much smaller and the activation barrier for the transition persulfide → disulfide is 1.11 eV. Carbonylation also favors a non-planar Fe{sub 2}S{sub 2} ring for both the disulfides and the persulfides and high electron density in the Fe{sub 2}S{sub 2} core is induced. The diamagnetic ordering is preferred in the hexacarbonyls, unlike the bare clusters. The hexacarbonyls possess low-lying triplet excited states. In the persulfide, the lowest singlet-to-triplet state excitation occurs by electron transition from the iron centers to an orbital located predominantly at S{sub 2} via metal-to-ligand charge transfer. In the disulfide this excitation corresponds to ligand-to-metal charge transfer from the sulfur atoms to an orbital located at the iron centers and the Fe–Fe bond. Water splitting occurs on the hexacarbonyls, but not on the bare clusters. The singlet and triplet state reaction paths were examined and activation barriers were determined: 50 kJ mol{sup −1} for HO–H bond dissociation and 210 kJ mol{sup −1} for hydrogen evolution from the intermediate sulfoxyl-hydroxyl complexes Fe{sub 2}S(OH)(SH)(CO){sub 6} formed. The lowest singlet-singlet excitations in the hexacarbonyls, the water adsorption complexes and in the reaction intermediates, formed prior to dihydrogen release, fall in the visible light region. The energy barrier of 210 kJ mol{sup −1} for the release of one hydrogen molecule corresponds to one visible photon of 570 nm. The dissociation of a second water molecule, followed by H{sub 2

The Global Redox Responding RegB/RegA Signal Transduction System Regulates the Genes Involved in Ferrous Iron and Inorganic Sulfur Compound Oxidation of the Acidophilic Acidithiobacillus ferrooxidans

Directory of Open Access Journals (Sweden)

Danielle Moinier

2017-07-01

Full Text Available The chemical attack of ore by ferric iron and/or sulfuric acid releases valuable metals. The products of these reactions are recycled by iron and sulfur oxidizing microorganisms. These acidophilic chemolithotrophic prokaryotes, among which Acidithiobacillus ferrooxidans, grow at the expense of the energy released from the oxidation of ferrous iron and/or inorganic sulfur compounds (ISCs. In At. ferrooxidans, it has been shown that the expression of the genes encoding the proteins involved in these respiratory pathways is dependent on the electron donor and that the genes involved in iron oxidation are expressed before those responsible for ISCs oxidation when both iron and sulfur are present. Since the redox potential increases during iron oxidation but remains stable during sulfur oxidation, we have put forward the hypothesis that the global redox responding two components system RegB/RegA is involved in this regulation. To understand the mechanism of this system and its role in the regulation of the aerobic respiratory pathways in At. ferrooxidans, the binding of different forms of RegA (DNA binding domain, wild-type, unphosphorylated and phosphorylated-like forms of RegA on the regulatory region of different genes/operons involved in ferrous iron and ISC oxidation has been analyzed. We have shown that the four RegA forms are able to bind specifically the upstream region of these genes. Interestingly, the phosphorylation of RegA did not change its affinity for its cognate DNA. The transcriptional start site of these genes/operons has been determined. In most cases, the RegA binding site(s was (were located upstream from the −35 (or −24 box suggesting that RegA does not interfere with the RNA polymerase binding. Based on the results presented in this report, the role of the RegB/RegA system in the regulation of the ferrous iron and ISC oxidation pathways in At. ferrooxidans is discussed.

The Global Redox Responding RegB/RegA Signal Transduction System Regulates the Genes Involved in Ferrous Iron and Inorganic Sulfur Compound Oxidation of the Acidophilic Acidithiobacillus ferrooxidans

Science.gov (United States)

Moinier, Danielle; Byrne, Deborah; Amouric, Agnès; Bonnefoy, Violaine

2017-01-01

The chemical attack of ore by ferric iron and/or sulfuric acid releases valuable metals. The products of these reactions are recycled by iron and sulfur oxidizing microorganisms. These acidophilic chemolithotrophic prokaryotes, among which Acidithiobacillus ferrooxidans, grow at the expense of the energy released from the oxidation of ferrous iron and/or inorganic sulfur compounds (ISCs). In At. ferrooxidans, it has been shown that the expression of the genes encoding the proteins involved in these respiratory pathways is dependent on the electron donor and that the genes involved in iron oxidation are expressed before those responsible for ISCs oxidation when both iron and sulfur are present. Since the redox potential increases during iron oxidation but remains stable during sulfur oxidation, we have put forward the hypothesis that the global redox responding two components system RegB/RegA is involved in this regulation. To understand the mechanism of this system and its role in the regulation of the aerobic respiratory pathways in At. ferrooxidans, the binding of different forms of RegA (DNA binding domain, wild-type, unphosphorylated and phosphorylated-like forms of RegA) on the regulatory region of different genes/operons involved in ferrous iron and ISC oxidation has been analyzed. We have shown that the four RegA forms are able to bind specifically the upstream region of these genes. Interestingly, the phosphorylation of RegA did not change its affinity for its cognate DNA. The transcriptional start site of these genes/operons has been determined. In most cases, the RegA binding site(s) was (were) located upstream from the −35 (or −24) box suggesting that RegA does not interfere with the RNA polymerase binding. Based on the results presented in this report, the role of the RegB/RegA system in the regulation of the ferrous iron and ISC oxidation pathways in At. ferrooxidans is discussed. PMID:28747899

Microbial communities from different subsystems in biological heap leaching system play different roles in iron and sulfur metabolisms.

Science.gov (United States)

Xiao, Yunhua; Liu, Xueduan; Ma, Liyuan; Liang, Yili; Niu, Jiaojiao; Gu, Yabing; Zhang, Xian; Hao, Xiaodong; Dong, Weiling; She, Siyuan; Yin, Huaqun

2016-08-01

The microbial communities are important for minerals decomposition in biological heap leaching system. However, the differentiation and relationship of composition and function of microbial communities between leaching heap (LH) and leaching solution (LS) are still unclear. In this study, 16S rRNA gene sequencing was used to assess the microbial communities from the two subsystems in ZiJinShan copper mine (Fujian province, China). Results of PCoA and dissimilarity test showed that microbial communities in LH samples were significantly different from those in LS samples. The dominant genera of LH was Acidithiobacillus (57.2 ∼ 87.9 %), while Leptospirillum (48.6 ∼ 73.7 %) was predominant in LS. Environmental parameters (especially pH) were the major factors to influence the composition and structure of microbial community by analysis of Mantel tests. Results of functional test showed that microbial communities in LH utilized sodium thiosulfate more quickly and utilized ferrous sulfate more slowly than those in LS, which further indicated that the most sulfur-oxidizing processes of bioleaching took place in LH and the most iron-oxidizing processes were in LS. Further study found that microbial communities in LH had stronger pyrite leaching ability, and iron extraction efficiency was significantly positively correlated with Acidithiobacillus (dominated in LH), which suggested that higher abundance ratio of sulfur-oxidizing microbes might in favor of minerals decomposition. Finally, a conceptual model was designed through the above results to better exhibit the sulfur and iron metabolism in bioleaching systems.

The function and properties of the iron-sulfur center in spinach ferredoxin: Thioredoxin reductase: A new biological role for iron-sulfur clusters

Energy Technology Data Exchange (ETDEWEB)

Staples, C.R.; Ameyibor, E.; Fu, Weiguang; Johnson, M.K. [Univ. of Georgia, Athens, GA (United States)] [and others

1996-09-03

Thioredoxin reduction in chloroplasts in catalyzed by a unique class of disulfide reductases which use a [2Fe-2S]{sup 2+/+} ferredoxin as the electron donor and contain an Fe-S cluster as the sole prosthetic group in addition to the active-site disulfide. The nature, properties, and function of the Fe-S cluster in spinach ferredoxin: thioredoxin reductase (FTR) have been investigated by the combination of UV/visible absorption, variable-temperature magnetic circular dichroism (MCD), EPR, and resonance Raman (RR) spectroscopies. 66 refs., 5 figs., 1 tab.

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.

Regulation of the HscA ATPase reaction cycle by the co-chaperone HscB and the iron-sulfur cluster assembly protein IscU.

Science.gov (United States)

Silberg, Jonathan J; Tapley, Tim L; Hoff, Kevin G; Vickery, Larry E

2004-12-24

The ATPase activity of HscA, a specialized hsp70 molecular chaperone from Escherichia coli, is regulated by the iron-sulfur cluster assembly protein IscU and the J-type co-chaperone HscB. IscU behaves as a substrate for HscA, and HscB enhances the binding of IscU to HscA. To better understand the mechanism by which HscB and IscU regulate HscA, we examined binding of HscB to the different conformational states of HscA and the effects of HscB and IscU on the kinetics of the individual steps of the HscA ATPase reaction cycle. Affinity sensor studies revealed that whereas IscU binds both ADP (R-state) and ATP (T-state) HscA complexes, HscB interacts only with an ATP-bound state. Studies of ATPase activity under single-turnover and rapid mixing conditions showed that both IscU and HscB interact with the low peptide affinity T-state of HscA (HscA++.ATP) and that both modestly accelerate (3-10-fold) the rate-determining steps in the HscA reaction cycle, k(hyd) and k(T-->R). When present together, IscU and HscB synergistically stimulate both k(hyd) (approximately = 500-fold) and k(T-->R) (approximately = 60-fold), leading to enhanced formation of the HscA.ADP-IscU complex (substrate capture). Following ADP/ATP exchange, IscU also stimulates k(R-->T) (approximately = 50-fold) and thereby accelerates the rate at which the low peptide affinity HscA++.ATP T-state is regenerated. Because HscA nucleotide exchange is fast, the overall rate of the chaperone cycle in vivo will be determined by the availability of the IscU-HscB substrate-co-chaperone complex.

Sulfur Nanoparticles Synthesis and Characterization from H2S Gas, Using Novel Biodegradable Iron Chelates in W/O Microemulsion

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Harle Arti

2008-01-01

Full Text Available AbstractSulfur nanoparticles were synthesized from hazardous H2S gas using novel biodegradable iron chelates in w/o microemulsion system. Fe3+–malic acid chelate (0.05 M aqueous solution was studied in w/o microemulsion containing cyclohexane, Triton X-100 andn-hexanol as oil phase, surfactant, co-surfactant, respectively, for catalytic oxidation of H2S gas at ambient conditions of temperature, pressure, and neutral pH. The structural features of sulfur nanoparticles have been characterized by X-ray diffraction (XRD, transmission electron microscope (TEM, energy dispersive spectroscopy (EDS, diffused reflectance infra-red Fourier transform technique, and BET surface area measurements. XRD analysis indicates the presence of α-sulfur. TEM analysis shows that the morphology of sulfur nanoparticles synthesized in w/o microemulsion system is nearly uniform in size (average particle size 10 nm and narrow particle size distribution (in range of 5–15 nm as compared to that in aqueous surfactant systems. The EDS analysis indicated high purity of sulfur (>99%. Moreover, sulfur nanoparticles synthesized in w/o microemulsion system exhibit higher antimicrobial activity (against bacteria, yeast, and fungi than that of colloidal sulfur.

Microbial siderophore-based iron assimilation and therapeutic applications.

Science.gov (United States)

Li, Kunhua; Chen, Wei-Hung; Bruner, Steven D

2016-06-01

Siderophores are structurally diverse, complex natural products that bind metals with extraordinary specificity and affinity. The acquisition of iron is critical for the survival and virulence of many pathogenic microbes and diverse strategies have evolved to synthesize, import and utilize iron. There has been a substantial increase of known siderophore scaffolds isolated and characterized in the past decade and the corresponding biosynthetic gene clusters have provided insight into the varied pathways involved in siderophore biosynthesis, delivery and utilization. Additionally, therapeutic applications of siderophores and related compounds are actively being developed. The study of biosynthetic pathways to natural siderophores augments the understanding of the complex mechanisms of bacterial iron acquisition, and enables a complimentary approach to address virulence through the interruption of siderophore biosynthesis or utilization by targeting the key enzymes to the siderophore pathways.

Proteomic analysis of iron acquisition, metabolic and regulatory responses of Yersinia pestis to iron starvation

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Fleischmann Robert D

2010-01-01

Full Text Available Abstract Background The Gram-negative bacterium Yersinia pestis is the causative agent of the bubonic plague. Efficient iron acquisition systems are critical to the ability of Y. pestis to infect, spread and grow in mammalian hosts, because iron is sequestered and is considered part of the innate host immune defence against invading pathogens. We used a proteomic approach to determine expression changes of iron uptake systems and intracellular consequences of iron deficiency in the Y. pestis strain KIM6+ at two physiologically relevant temperatures (26°C and 37°C. Results Differential protein display was performed for three Y. pestis subcellular fractions. Five characterized Y. pestis iron/siderophore acquisition systems (Ybt, Yfe, Yfu, Yiu and Hmu and a putative iron/chelate outer membrane receptor (Y0850 were increased in abundance in iron-starved cells. The iron-sulfur (Fe-S cluster assembly system Suf, adapted to oxidative stress and iron starvation in E. coli, was also more abundant, suggesting functional activity of Suf in Y. pestis under iron-limiting conditions. Metabolic and reactive oxygen-deactivating enzymes dependent on Fe-S clusters or other iron cofactors were decreased in abundance in iron-depleted cells. This data was consistent with lower activities of aconitase and catalase in iron-starved vs. iron-rich cells. In contrast, pyruvate oxidase B which metabolizes pyruvate via electron transfer to ubiquinone-8 for direct utilization in the respiratory chain was strongly increased in abundance and activity in iron-depleted cells. Conclusions Many protein abundance differences were indicative of the important regulatory role of the ferric uptake regulator Fur. Iron deficiency seems to result in a coordinated shift from iron-utilizing to iron-independent biochemical pathways in the cytoplasm of Y. pestis. With growth temperature as an additional variable in proteomic comparisons of the Y. pestis fractions (26°C and 37°C, there was

Carbon/Sulfur Composite Cathodes for Flexible Lithium/Sulfur Batteries: Status and Prospects

International Nuclear Information System (INIS)

Zhao, Yan; Zhang, Yongguang; Bakenova, Zagipa; Bakenov, Zhumabay

2015-01-01

High specific energy and low cost flexible lithium/sulfur batteries have attracted significant attention as a promising power source to enable future flexible and wearable electronic devices. Here, we review recent progress in the development of free-standing sulfur composite cathodes, with special emphasis on electrode material selectivity and battery structural design. The mini-review is organized based on the dimensionality of different scaffold materials, namely one-dimensional carbon nanotube (CNT), two-dimensional graphene, and three-dimensional CNT/graphene composite, respectively. Finally, the opportunities and perspectives of the future research directions are discussed.

ErpA, an iron sulfur (Fe S) protein of the A-type essential for respiratory metabolism in E.coli.

NARCIS (Netherlands)

Loiseau, L.; Gerez, C.; Bekker, M.; Ollagnier-de Choudens, S.; Py, B.; Sanakis, Y.; Teixeira De Mattos, M.J.; Fontecave, M.; Barras, F.

2007-01-01

Understanding the biogenesis of iron-sulfur (Fe-S) proteins is relevant to many fields, including bioenergetics, gene regulation, and cancer research. Several multiprotein complexes assisting Fe-S assembly have been identified in both prokaryotes and eukaryotes. Here, we identify in Escherichia coli

Unravelling atmospheric photolysis and ocean redox chemistry from Paleoarchean pyrite : a multiple sulfur and iron stable isotope study

NARCIS (Netherlands)

Galić, A.

2015-01-01

This thesis brought together four individual studies on the geochemistry of three recently obtained drill cores from the Barberton Greenstone Belt, South Africa. These data were used to provide a synthesis of the iron and sulfur cycles in the Paleoarchean, with a particular focus on the nature and

How Escherichia coli and Saccharomyces cerevisiae build Fe/S proteins.

Science.gov (United States)

Barras, Frédéric; Loiseau, Laurent; Py, Béatrice

2005-01-01

Owing to the versatile electronic properties of iron and sulfur, iron sulfur (Fe/S) clusters are perfectly suited for sensing changes in environmental conditions and regulating protein properties accordingly. Fe/S proteins have been recruited in a wide array of diverse biological processes, including electron transfer chains, metabolic pathways and gene regulatory circuits. Chemistry has revealed the great diversity of Fe/S clusters occurring in proteins. The question now is to understand how iron and sulfur come together to form Fe/S clusters and how these clusters are subsequently inserted into apoproteins. Iron, sulfide and reducing conditions were found to be sufficient for successful maturation of many apoproteins in vitro, opening the possibility that insertion might be a spontaneous event. However, as in many other biological pathways such as protein folding, genetic analyses revealed that Fe/S cluster biogenesis and insertion depend in vivo upon auxiliary proteins. This was brought to light by studies on Azotobacter vinelandii nitrogenase, which, in particular, led to the concept of scaffold proteins, the role of which would be to allow transient assembly of Fe/S cluster. These studies paved the way toward the identification of the ISC and SUF systems, subjects of the present review that allow Fe/S cluster assembly into apoproteins of most organisms. Despite the recent discovery of the SUF and ISC systems, remarkable progress has been made in our understanding of their molecular composition and biochemical mechanisms. Such a rapid increase in our knowledge arose from a convergent interest from researchers engaged in unrelated fields and whose complementary expertise covered most experimental approaches used in biology. Also, the high conservation of ISC and SUF systems throughout a wide array of organisms helped cross-feeding between studies. The ISC system is conserved in eubacteria and most eukaryotes, while the SUF system arises in eubacteria, archaea

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.

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

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

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-)).

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

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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.

Heterotrophic Bioleaching of Sulfur, Iron, and Silicon Impurities from Coal by Fusarium oxysporum FE and Exophiala spinifera FM with Growing and Resting Cells.

Science.gov (United States)

Etemadzadeh, Shekoofeh Sadat; Emtiazi, Giti; Etemadifar, Zahra

2016-06-01

Coal is the most abundant fossil fuel containing sulfur and other elements which promote environmental pollution after burning. Also the silicon impurities make the transportation of coal expensive. In this research, two isolated fungi from oil contaminated soil with accessory number KF554100 (Fusarium oxysporum FE) and KC925672 (Exophiala spinifera FM) were used for heterotrophic biological leaching of coal. The leaching were detected by FTIR, CHNS, XRF analyzer and compared with iron and sulfate released in the supernatant. The results showed that E. spinifera FM produced more acidic metabolites in growing cells, promoting the iron and sulfate ions removal while resting cells of F. oxysporum FE enhanced the removal of aromatic sulfur. XRF analysis showed that the resting cells of E. spinifera FM proceeded maximum leaching for iron and silicon (48.8, 43.2 %, respectively). CHNS analysis demonstrated that 34.21 % of sulfur leaching was due to the activities of resting cells of F. oxysporum FE. Also F. oxysporum FE removed organic sulfur more than E. spinifera FM in both growing and resting cells. FTIR data showed that both fungi had the ability to remove pyrite and quartz from coal. These data indicated that inoculations of these fungi to the coal are cheap and impurity removals were faster than autotrophic bacteria. Also due to the removal of dibenzothiophene, pyrite, and quartz, we speculated that they are excellent candidates for bioleaching of coal, oil, and gas.

Manganese doped-iron oxide nanoparticle clusters and their potential as agents for magnetic resonance imaging and hyperthermia

KAUST Repository

Casula, Maria F.

2016-06-10

A simple, one pot method to synthesize water-dispersible Mn doped iron oxide colloidal clusters constructed of nanoparticles arranged into secondary flower-like structures was developed. This method allows the successful incorporation and homogeneous distribution of Mn within the nanoparticle iron oxide clusters. The formed clusters retain the desired morphological and structural features observed for pure iron oxide clusters, but possess intrinsic magnetic properties that arise from Mn doping. They show distinct performance as imaging contrast agents and excellent characteristics as heating mediators in magnetic fluid hyperthermia. It is expected that the outcomes of this study will open up new avenues for the exploitation of doped magnetic nanoparticle assemblies in biomedicine. © the Owner Societies 2016.

Manganese doped-iron oxide nanoparticle clusters and their potential as agents for magnetic resonance imaging and hyperthermia

KAUST Repository

Casula, Maria F.; Conca, Erika; Bakaimi, Ioanna; Sathya, Ayyappan; Materia, Maria Elena; Casu, Alberto; Falqui, Andrea; Sogne, Elisa; Pellegrino, Teresa; Kanaras, Antonios G.

2016-01-01

A simple, one pot method to synthesize water-dispersible Mn doped iron oxide colloidal clusters constructed of nanoparticles arranged into secondary flower-like structures was developed. This method allows the successful incorporation and homogeneous distribution of Mn within the nanoparticle iron oxide clusters. The formed clusters retain the desired morphological and structural features observed for pure iron oxide clusters, but possess intrinsic magnetic properties that arise from Mn doping. They show distinct performance as imaging contrast agents and excellent characteristics as heating mediators in magnetic fluid hyperthermia. It is expected that the outcomes of this study will open up new avenues for the exploitation of doped magnetic nanoparticle assemblies in biomedicine. © the Owner Societies 2016.

Mechanisms of iron sensing and regulation in the yeast Saccharomyces cerevisiae.

Science.gov (United States)

Martínez-Pastor, María Teresa; Perea-García, Ana; Puig, Sergi

2017-04-01

Iron is a redox active element that functions as an essential cofactor in multiple metabolic pathways, including respiration, DNA synthesis and translation. While indispensable for eukaryotic life, excess iron can lead to oxidative damage of macromolecules. Therefore, living organisms have developed sophisticated strategies to optimally regulate iron acquisition, storage and utilization in response to fluctuations in environmental iron bioavailability. In the yeast Saccharomyces cerevisiae, transcription factors Aft1/Aft2 and Yap5 regulate iron metabolism in response to low and high iron levels, respectively. In addition to producing and assembling iron cofactors, mitochondrial iron-sulfur (Fe/S) cluster biogenesis has emerged as a central player in iron sensing. A mitochondrial signal derived from Fe/S synthesis is exported and converted into an Fe/S cluster that interacts directly with Aft1/Aft2 and Yap5 proteins to regulate their transcriptional function. Various conserved proteins, such as ABC mitochondrial transporter Atm1 and, for Aft1/Aft2, monothiol glutaredoxins Grx3 and Grx4 are implicated in this iron-signaling pathway. The analysis of a wide range of S. cerevisiae strains of different geographical origins and sources has shown that yeast strains adapted to high iron display growth defects under iron-deficient conditions, and highlighted connections that exist in the response to both opposite conditions. Changes in iron accumulation and gene expression profiles suggest differences in the regulation of iron homeostasis genes.

Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

Science.gov (United States)

Clay, David T.; Lynn, Scott

1976-10-19

A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

Iron oxide nanoparticle layer templated by polydopamine spheres: a novel scaffold toward hollow-mesoporous magnetic nanoreactors.

Science.gov (United States)

Huang, Liang; Ao, Lijiao; Xie, Xiaobin; Gao, Guanhui; Foda, Mohamed F; Su, Wu

2015-01-14

Superparamagnetic iron oxide nanoparticle layers with high packing density and controlled thickness were in situ deposited on metal-affinity organic templates (polydopamine spheres), via one-pot thermal decomposition. The as synthesized hybrid structure served as a facile nano-scaffold toward hollow-mesoporous magnetic carriers, through surfactant-assisted silica encapsulation and its subsequent calcination. Confined but accessible gold nanoparticles were successfully incorporated into these carriers to form a recyclable catalyst, showing quick magnetic response and a large surface area (642.5 m(2) g(-1)). Current nano-reactors exhibit excellent catalytic performance and high stability in reduction of 4-nitrophenol, together with convenient magnetic separability and good reusability. The integration of compact iron oxide nanoparticle layers with programmable polydopamine templates paves the way to fabricate magnetic-response hollow structures, with high permeability and multi-functionality.

Identification of vital and dispensable sulfur utilization factors in the Plasmodium apicoplast.

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Joana M Haussig

Full Text Available Iron-sulfur [Fe-S] clusters are ubiquitous and critical cofactors in diverse biochemical processes. They are assembled by distinct [Fe-S] cluster biosynthesis pathways, typically in organelles of endosymbiotic origin. Apicomplexan parasites, including Plasmodium, the causative agent of malaria, harbor two separate [Fe-S] cluster biosynthesis pathways in the their mitochondrion and apicoplast. In this study, we systematically targeted the five nuclear-encoded sulfur utilization factors (SUF of the apicoplast [Fe-S] cluster biosynthesis pathway by experimental genetics in the murine malaria model parasite Plasmodium berghei. We show that four SUFs, namely SUFC, D, E, and S are refractory to targeted gene deletion, validating them as potential targets for antimalarial drug development. We achieved targeted deletion of SUFA, which encodes a potential [Fe-S] transfer protein, indicative of a dispensable role during asexual blood stage growth in vivo. Furthermore, no abnormalities were observed during Plasmodium life cycle progression in the insect and mammalian hosts. Fusion of a fluorescent tag to the endogenous P. berghei SUFs demonstrated that all loci were accessible to genetic modification and that all five tagged SUFs localize to the apicoplast. Together, our experimental genetics analysis identifies the key components of the SUF [Fe-S] cluster biosynthesis pathway in the apicoplast of a malarial parasite and shows that absence of SUFC, D, E, or S is incompatible with Plasmodium blood infection in vivo.

Sulfur dioxide leaching of spent zinc-carbon-battery scrap

Energy Technology Data Exchange (ETDEWEB)

Avraamides, J.; Senanayake, G.; Clegg, R. [A.J. Parker Cooperative Research Centre for Hydrometallurgy, Murdoch University, Perth, WA 6150 (Australia)

2006-09-22

Zinc-carbon batteries, which contain around 20% zinc, 35% manganese oxides and 10% steel, are currently disposed after use as land fill or reprocessed to recover metals or oxides. Crushed material is subjected to magnetic separation followed by hydrometallurgical treatment of the non-magnetic material to recover zinc metal and manganese oxides. The leaching with 2M sulfuric acid in the presence of hydrogen peroxide recovers 93% Zn and 82% Mn at 25{sup o}C. Alkaline leaching with 6M NaOH recovers 80% zinc. The present study shows that over 90% zinc and manganese can be leached in 20-30min at 30{sup o}C using 0.1-1.0M sulfuric acid in the presence of sulfur dioxide. The iron extraction is sensitive to both acid concentration and sulfur dioxide flow rate. The effect of reagent concentration and particle size on the extraction of zinc, manganese and iron are reported. It is shown that the iron and manganese leaching follow a shrinking core kinetic model due to the formation of insoluble metal salts/oxides on the solid surface. This is supported by (i) the decrease in iron and manganese extraction from synthetic Fe(III)-Mn(IV)-Zn(II) oxide mixtures with increase in acid concentration from 1M to 2M, and (ii) the low iron dissolution and re-precipitation of dissolved manganese and zinc during prolonged leaching of battery scrap with low sulfur dioxide. (author)

Comparative study of reactions between µ-nitrido- or µ-oxo-bridged iron tetrasulfophthalocyanines and sulfur-containing reductants

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Dereven’kov Ilia A.

2013-01-01

Full Text Available A comparative study of reactivity of μ-nitrido- and μ-oxo-dimers of iron tetrasulfophthalocyanine has been performed in aqueous solutions of various acidity. The substantially higher stability of nitrido-bridged structure under both strongly acidic and strongly alkaline environments was demonstrated. Reactions of the complexes with sulfur-containing reductants (sodium dithionite, thiourea dioxide, sodium hydroxymethanesulfinate, L-cysteine has been studied. Differences in reduction processes were explained.

Iron and Sulfur Species and Sulfur Isotopic Compositions of Authigenic Pyrite in Gas Hydrate-Bearing Sediments from Hydrate Ridge, Cascadia Margin (ODP Leg 204): A Proposal of Conceptual Models to Indicate the Non-Steady State Depositional and Diagenetic Processes

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Liu, C.; Jiang, S. Y.; Su, X.

2017-12-01

Two accretionary sediment sequences from Sites 1245 and 1252 recovered during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge, Cascadia Margin were investigated to explore the non-steady state depositional and diagenetic history. Five iron species and three sulfur species were chemically extracted, and their concentrations and the sulfur isotopic compositions of pyrite were determined. After the mineral recognitions of these species and detailed comparative analyses, the aerobic history of bottom seawater has been determined. The formation of pyrite is thought to be controlled by the limited production of hydrogen sulfide relative to the supply of reactive iron. Also, the intrusion of oxygen by bioturbation would oxidize the reduced sulfur species and further suppress pyritization. To explain the geochemical relationship between pyrite and siderite and the sulfur isotope characteristics of pyrite, we propose seven conceptual models based on the variations in depositional rate and methane flux, and the models succeed in explaining the geochemical results and are validated by the observed non-steady state events. These models may contribute to the reconstruction of the non-steady state processes in other research areas in the future.

Spectroscopic and functional characterization of iron-sulfur cluster-bound forms of Azotobacter vinelandii (Nif)IscA.

Science.gov (United States)

Mapolelo, Daphne T; Zhang, Bo; Naik, Sunil G; Huynh, Boi Hanh; Johnson, Michael K

2012-10-16

The mechanism of [4Fe-4S] cluster assembly on A-type Fe-S cluster assembly proteins, in general, and the specific role of (Nif)IscA in the maturation of nitrogen fixation proteins are currently unknown. To address these questions, in vitro spectroscopic studies (UV-visible absorption/CD, resonance Raman and Mössbauer) have been used to investigate the mechanism of [4Fe-4S] cluster assembly on Azotobacter vinelandii(Nif)IscA, and the ability of (Nif)IscA to accept clusters from NifU and to donate clusters to the apo form of the nitrogenase Fe-protein. The results show that (Nif)IscA can rapidly and reversibly cycle between forms containing one [2Fe-2S](2+) and one [4Fe-4S](2+) cluster per homodimer via DTT-induced two-electron reductive coupling of two [2Fe-2S](2+) clusters and O(2)-induced [4Fe-4S](2+) oxidative cleavage. This unique type of cluster interconversion in response to cellular redox status and oxygen levels is likely to be important for the specific role of A-type proteins in the maturation of [4Fe-4S] cluster-containing proteins under aerobic growth or oxidative stress conditions. Only the [4Fe-4S](2+)-(Nif)IscA was competent for rapid activation of apo-nitrogenase Fe protein under anaerobic conditions. Apo-(Nif)IscA was shown to accept clusters from [4Fe-4S] cluster-bound NifU via rapid intact cluster transfer, indicating a potential role as a cluster carrier for delivery of clusters assembled on NifU. Overall the results support the proposal that A-type proteins can function as carrier proteins for clusters assembled on U-type proteins and suggest that they are likely to supply [2Fe-2S] clusters rather than [4Fe-4S] for the maturation of [4Fe-4S] cluster-containing proteins under aerobic or oxidative stress growth conditions.

Redox Behavior of the S-Adenosylmethionine (SAM)-Binding Fe-S Cluster in Methylthiotransferase RimO, toward Understanding Dual SAM Activity.

Science.gov (United States)

Molle, Thibaut; Moreau, Yohann; Clemancey, Martin; Forouhar, Farhad; Ravanat, Jean-Luc; Duraffourg, Nicolas; Fourmond, Vincent; Latour, Jean-Marc; Gambarelli, Serge; Mulliez, Etienne; Atta, Mohamed

2016-10-18

RimO, a radical-S-adenosylmethionine (SAM) enzyme, catalyzes the specific C 3 methylthiolation of the D89 residue in the ribosomal S 12 protein. Two intact iron-sulfur clusters and two SAM cofactors both are required for catalysis. By using electron paramagnetic resonance, Mössbauer spectroscopies, and site-directed mutagenesis, we show how two SAM molecules sequentially bind to the unique iron site of the radical-SAM cluster for two distinct chemical reactions in RimO. Our data establish that the two SAM molecules bind the radical-SAM cluster to the unique iron site, and spectroscopic evidence obtained under strongly reducing conditions supports a mechanism in which the first molecule of SAM causes the reoxidation of the reduced radical-SAM cluster, impeding reductive cleavage of SAM to occur and allowing SAM to methylate a HS - ligand bound to the additional cluster. Furthermore, by using density functional theory-based methods, we provide a description of the reaction mechanism that predicts the attack of the carbon radical substrate on the methylthio group attached to the additional [4Fe-4S] cluster.

[Nitrogen oxide is involved in the regulation of the Fe-S cluster assembly in proteins and the formation of biofilms by Escherichia coli cells].

Science.gov (United States)

Vasil'eva, S V; Streltsova, D A; Starostina, I A; Sanina, N A

2013-01-01

The functions of nitrogen oxide (NO) in the regulation of the reversible processes of Fe-S cluster assembly in proteins and the formation of Escherichia coli biofilms have been investigated. S-nitrosoglutathione (GSNO) and crystalline nitrosyl complexes of iron with sulfur-containing aliphatic ligands cisaconite (CisA) and penaconite have been used as NO donors for the first time. Wild-type E. coli cells of the strain MC4100, mutants deltaiscA and deltasufA, and the double paralog mutant deltaiscA/sufA with deletions in the alternative pathways of Fe2+ supply for cluster assembly (all derived from the above-named strain) were used in this study. Plankton growth of bacterial cultures, the mass of mature biofilms, and the expression of the SoxRS[2Fe-2S] regulon have been investigated and shown to depend on strain genotype, the process of Fe-S cluster assembly in iron-sulfur proteins, NO donor structure, and the presence of Fe2+ chelator ferene in the incubation medium. The antibiotic ciprofloxacine (CF) was used as an inhibitor of E. coli biofilm formation in the positive control. NO donors regulating Fe-S cluster assembly in E. coli have been shown to control plankton growth of the cultures and the process of mature biofilm formation; toxic doses of NO caused a dramatic (3- to 4-fold) stimulation of cell entry into biofilms as a response to nitrosative stress; NO donors CisA and GSNO in physiological concentrations suppressed the formation of mature biofilms, and the activity of these compounds was comparable to that of CE Regulation of both Fe-S cluster assembly in iron-sulfur proteins and biofilm formation by NO is indicative of the connection between these processes in E. coli.

Method of distillation of sulfurous bituminous shales

Energy Technology Data Exchange (ETDEWEB)

Hallback, A J.S.; Bergh, S V

1918-04-22

A method of distillation of sulfur-containing bituminous shales is characterized by passing the hot sulfur-containing and oil-containing gases and vapors formed during the distillation through burned shale containing iron oxide, so that when these gases and vapors are thereafter cooled they will be, as far as possible, free from sulfur compounds. The patent contains six more claims.

Biochemistry of the normal dura mater of the human brain determination of water, sodium, potassium, calcium, phosphorus, magnesium, copper, iron, sulfur and nitrogen contents

Directory of Open Access Journals (Sweden)

Horacio M. Canelas

1969-06-01

Full Text Available The concentrations of water, sodium, potassium, calcium, phosphorus, magnesium, copper, iron, sulfur, and nitrogen were determined in samples of apparently normal dura mater removed from 18 subjects recently dead by craniocerebral trauma. The average concentrations expressed in dry weight were: water 79.55 g/100 g ± 2.52; sodium 1.63 mequiv/100 g ±0.27; potassium 3.68 mequiv/100 g ± 0.66; calcium 119.84 mg/100 g ± 107.40; phosphorus 68.2 mg/100 g ± 34.5; magnesium 0.61 mequiv/100 g ± 0.37; copper 249.8 /xg/100 g ± 109.4; iron 0.82 mg/100 g ± 0.28; sulfur 490.7 mg/100 g ± 22.5; nitrogen 3.33 g/100 g ± 0.17.

Magnetite Crisis in Miniature: Vanadium, Sulfur, and Iron Valence State Measurements in Melt Inclusions from Nyamuragira Volcano (D.R. Congo, Africa)

Science.gov (United States)

Head, E.; Lanzirotti, A.; Sutton, S.; Newville, M.

2017-12-01

Sulfur (S), vanadium (V), and iron (Fe) K-edge micro-X-ray absorption near edge structure (micro-XANES) spectroscopy of melt inclusions (MI) from Nyamuragira volcano (D.R. Congo, Africa) shows that diffusive loss of H from olivine-hosted melt inclusions may lead to crystallization of submicron magnetite and sulfide crystallites that are imperceptible petrographically or via electron microscopy. Micro-XANES was used to constrain the evolution of oxygen fugacity (fO2) and sulfur speciation for MI preserved in Nyamuragira tephra (1986 and 2006) and lava (1938 and 1948). The S, V, and Fe valence state oxybarometry for 1938, 1948, and 2006 MI are all consistent with equilibration at FMQ-1, and sulfur in MI from these three eruptions are sulfide-dominated (water loss in olivine-hosted MIs.

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].

Investigation on the Effect of Sulfur and Titanium on the Microstructure of Lamellar Graphite Iron

DEFF Research Database (Denmark)

Moumeni, Elham; Stefanescu, Doru Michael; Tiedje, Niels Skat

2013-01-01

The goal of this work was to identify the inclusions in lamellar graphite cast iron in an effort to explain the nucleation of the phases of interest. Four samples of approximately the same carbon equivalent but different levels of sulfur and titanium were studied. The Ti/S ratios were from 0...... of complex Al, Ca, Mg oxide. An increased titanium level of 0.35 pct produced superfine interdendritic graphite (~10 μm) at low (0.012 wt pct) as well as at high-S contents. Ti also caused increased segregation in the microstructure of the analyzed irons and larger eutectic grains (cells). TiC did not appear...... to be a nucleation site for the primary austenite as it was found mostly at the periphery of the secondary arms of the austenite, in the last region to solidify. The effect of titanium in refining the graphite and increasing the austenite fraction can be explained through the widening of the liquidus...

Gene Identification and Substrate Regulation Provide Insights into Sulfur Accumulation during Bioleaching with the Psychrotolerant Acidophile Acidithiobacillus ferrivorans

Science.gov (United States)

Liljeqvist, Maria; Rzhepishevska, Olena I.

2013-01-01

The psychrotolerant acidophile Acidithiobacillus ferrivorans has been identified from cold environments and has been shown to use ferrous iron and inorganic sulfur compounds as its energy sources. A bioinformatic evaluation presented in this study suggested that Acidithiobacillus ferrivorans utilized a ferrous iron oxidation pathway similar to that of the related species Acidithiobacillus ferrooxidans. However, the inorganic sulfur oxidation pathway was less clear, since the Acidithiobacillus ferrivorans genome contained genes from both Acidithiobacillus ferrooxidans and Acidithiobacillus caldus encoding enzymes whose assigned functions are redundant. Transcriptional analysis revealed that the petA1 and petB1 genes (implicated in ferrous iron oxidation) were downregulated upon growth on the inorganic sulfur compound tetrathionate but were on average 10.5-fold upregulated in the presence of ferrous iron. In contrast, expression of cyoB1 (involved in inorganic sulfur compound oxidation) was decreased 6.6-fold upon growth on ferrous iron alone. Competition assays between ferrous iron and tetrathionate with Acidithiobacillus ferrivorans SS3 precultured on chalcopyrite mineral showed a preference for ferrous iron oxidation over tetrathionate oxidation. Also, pure and mixed cultures of psychrotolerant acidophiles were utilized for the bioleaching of metal sulfide minerals in stirred tank reactors at 5 and 25°C in order to investigate the fate of ferrous iron and inorganic sulfur compounds. Solid sulfur accumulated in bioleaching cultures growing on a chalcopyrite concentrate. Sulfur accumulation halted mineral solubilization, but sulfur was oxidized after metal release had ceased. The data indicated that ferrous iron was preferentially oxidized during growth on chalcopyrite, a finding with important implications for biomining in cold environments. PMID:23183980

STAR-TO-STAR IRON ABUNDANCE VARIATIONS IN RED GIANT BRANCH STARS IN THE GALACTIC GLOBULAR CLUSTER NGC 3201

International Nuclear Information System (INIS)

Simmerer, Jennifer; Ivans, Inese I.; Filler, Dan; Francois, Patrick; Charbonnel, Corinne; Monier, Richard; James, Gaël

2013-01-01

We present the metallicity as traced by the abundance of iron in the retrograde globular cluster NGC 3201, measured from high-resolution, high signal-to-noise spectra of 24 red giant branch stars. A spectroscopic analysis reveals a spread in [Fe/H] in the cluster stars at least as large as 0.4 dex. Star-to-star metallicity variations are supported both through photometry and through a detailed examination of spectra. We find no correlation between iron abundance and distance from the cluster core, as might be inferred from recent photometric studies. NGC 3201 is the lowest mass halo cluster to date to contain stars with significantly different [Fe/H] values.

Star-to-star Iron Abundance Variations in Red Giant Branch Stars in the Galactic Globular Cluster NGC 3201

Science.gov (United States)

Simmerer, Jennifer; Ivans, Inese I.; Filler, Dan; Francois, Patrick; Charbonnel, Corinne; Monier, Richard; James, Gaël

2013-02-01

We present the metallicity as traced by the abundance of iron in the retrograde globular cluster NGC 3201, measured from high-resolution, high signal-to-noise spectra of 24 red giant branch stars. A spectroscopic analysis reveals a spread in [Fe/H] in the cluster stars at least as large as 0.4 dex. Star-to-star metallicity variations are supported both through photometry and through a detailed examination of spectra. We find no correlation between iron abundance and distance from the cluster core, as might be inferred from recent photometric studies. NGC 3201 is the lowest mass halo cluster to date to contain stars with significantly different [Fe/H] values.

Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

Directory of Open Access Journals (Sweden)

J. N. Crowley

2012-01-01

Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

Assembling Fe/S-clusters and modifying tRNAs: ancient co-factors meet ancient adaptors

Czech Academy of Sciences Publication Activity Database

Alfonzo, J. D.; Lukeš, Julius

2011-01-01

Roč. 27, č. 6 (2011), 234-237 ISSN 1471-4922 R&D Projects: GA MŠk LC07032; GA MŠk 2B06129; GA ČR GA204/09/1667 Institutional research plan: CEZ:AV0Z60220518 Keywords : IRON-SULFUR CLUSTERS * TRYPANOSOMA-BRUCEI * MITOCHONDRIAL * PROTEIN * FRATAXIN * BIOSYNTHESIS * SYNTHETASES * BIOGENESIS * THIOLATION * ANTICODON Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 5.144, year: 2011

Early diagenesis in the sediments of the Congo deep-sea fan dominated by massive terrigenous deposits: Part II - Iron-sulfur coupling

Science.gov (United States)

Taillefert, Martial; Beckler, Jordon S.; Cathalot, Cécile; Michalopoulos, Panagiotis; Corvaisier, Rudolph; Kiriazis, Nicole; Caprais, Jean-Claude; Pastor, Lucie; Rabouille, Christophe

2017-08-01

Deep-sea fans are well known depot centers for organic carbon that should promote sulfate reduction. At the same time, the high rates of deposition of unconsolidated metal oxides from terrigenous origin may also promote metal-reducing microbial activity. To investigate the eventual coupling between the iron and sulfur cycles in these environments, shallow sediment cores (Congo River deep-sea fan ( 5000 m) were profiled using a combination of geochemical methods. Interestingly, metal reduction dominated suboxic carbon remineralization processes in most of these sediments, while dissolved sulfide was absent. In some 'hotspot' patches, however, sulfate reduction produced large sulfide concentrations which supported chemosynthetic-based benthic megafauna. These environments were characterized by sharp geochemical boundaries compared to the iron-rich background environment, suggesting that FeS precipitation efficiently titrated iron and sulfide from the pore waters. A companion study demonstrated that methanogenesis was active in the deep sediment layers of these patchy ecosystems, suggesting that sulfate reduction was promoted by alternative anaerobic processes. These highly reduced habitats could be fueled by discrete, excess inputs of highly labile natural organic matter from Congo River turbidites or by exhumation of buried sulfide during channel flank erosion and slumping. Sulfidic conditions may be maintained by the mineralization of decomposition products from local benthic macrofauna or bacterial symbionts or by the production of more crystalline Fe(III) oxide phases that are less thermodynamically favorable than sulfate reduction in these bioturbated sediments. Overall, the iron and sulfur biogeochemical cycling in this environment is unique and much more similar to a coastal ecosystem than a deep-sea environment.

Interaction of the iron–sulfur cluster assembly protein IscU with the Hsc66/Hsc20 molecular chaperone system of Escherichia coli

Science.gov (United States)

Hoff, Kevin G.; Silberg, Jonathan J.; Vickery, Larry E.

2000-01-01

The iscU gene in bacteria is located in a gene cluster encoding proteins implicated in iron–sulfur cluster assembly and an hsc70-type (heat shock cognate) molecular chaperone system, iscSUA-hscBA. To investigate possible interactions between these systems, we have overproduced and purified the IscU protein from Escherichia coli and have studied its interactions with the hscA and hscB gene products Hsc66 and Hsc20. IscU and its iron–sulfur complex (IscU–Fe/S) stimulated the basal steady-state ATPase activity of Hsc66 weakly in the absence of Hsc20 but, in the presence of Hsc20, increased the ATPase activity up to 480-fold. Hsc20 also decreased the apparent Km for IscU stimulation of Hsc66 ATPase activity, and surface plasmon resonance studies revealed that Hsc20 enhances binding of IscU to Hsc66. Surface plasmon resonance and isothermal titration calorimetry further showed that IscU and Hsc20 form a complex, and Hsc20 may thereby aid in the targeting of IscU to Hsc66. These results establish a direct and specific role for the Hsc66/Hsc20 chaperone system in functioning with isc gene components for the assembly of iron–sulfur cluster proteins. PMID:10869428

Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle

Science.gov (United States)

Wirick, S.; Flynn, G. J.; Keller, L. P.; Sanford, S. A.; Zolensky, M. E.; Messenger, Nakamura K.; Jacobsen, C.

2008-01-01

Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

The life sulfuric: microbial ecology of sulfur cycling in marine sediments.

Science.gov (United States)

Wasmund, Kenneth; Mußmann, Marc; Loy, Alexander

2017-08-01

Almost the entire seafloor is covered with sediments that can be more than 10 000 m thick and represent a vast microbial ecosystem that is a major component of Earth's element and energy cycles. Notably, a significant proportion of microbial life in marine sediments can exploit energy conserved during transformations of sulfur compounds among different redox states. Sulfur cycling, which is primarily driven by sulfate reduction, is tightly interwoven with other important element cycles (carbon, nitrogen, iron, manganese) and therefore has profound implications for both cellular- and ecosystem-level processes. Sulfur-transforming microorganisms have evolved diverse genetic, metabolic, and in some cases, peculiar phenotypic features to fill an array of ecological niches in marine sediments. Here, we review recent and selected findings on the microbial guilds that are involved in the transformation of different sulfur compounds in marine sediments and emphasise how these are interlinked and have a major influence on ecology and biogeochemistry in the seafloor. Extraordinary discoveries have increased our knowledge on microbial sulfur cycling, mainly in sulfate-rich surface sediments, yet many questions remain regarding how sulfur redox processes may sustain the deep-subsurface biosphere and the impact of organic sulfur compounds on the marine sulfur cycle. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Saline-water bioleaching of chalcopyrite with thermophilic, iron(II)- and sulfur-oxidizing microorganisms.

Science.gov (United States)

Watling, Helen R; Collinson, David M; Corbett, Melissa K; Shiers, Denis W; Kaksonen, Anna H; Watkin, Elizabeth L J

2016-09-01

The application of thermoacidophiles for chalcopyrite (CuFeS2) bioleaching in hot, acidic, saline solution was investigated as a possible process route for rapid Cu extraction. The study comprised a discussion of protective mechanisms employed for the survival and/or adaptation of thermoacidophiles to osmotic stress, a compilation of chloride tolerances for three genera of thermoacidophiles applied in bioleaching and an experimental study of the activities of three species in a saline bioleaching system. The data showed that the oxidation rates of iron(II) and reduced inorganic sulfur compounds (tetrathionate) were reduced in the presence of chloride levels well below chloride concentrations in seawater, limiting the applicability of these microorganisms in the bioleaching of CuFeS2 in saline water. Copyright © 2016. Published by Elsevier Masson SAS.

Removal of sulfur from process streams

International Nuclear Information System (INIS)

Brignac, D.G.

1984-01-01

A process wherein water is added to a non-reactive gas stream, preferably a hydrogen or hydrogen-containing gas stream, sufficient to raise the water level thereof to from about 0.2 percent to about 50 percent, based on the total volume of the process gas stream, and the said moist gas stream is contacted, at elevated temperature, with a particulate mass of a sulfur-bearing metal alumina spinel characterized by the formula MAl 2 O 4 , wherein M is chromium, iron, cobalt, nickel, copper, cadmium, mercury, or zinc to desorb sulfur thereon. In the sulfur sorption cycle, due to the simultaneous adsorption of water and sulfur, the useful life of the metal alumina spinel for sulfur adsorption can be extended, and the sorbent made more easily regenerable after contact with a sulfur-bearing gas stream, notably sulfur-bearing wet hydrogen or wet hydrogen-rich gas streams

Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Chen, Renjie, E-mail: kx210@cam.ac.uk, E-mail: chenrj@bit.edu.cn; Zhao, Teng [Beijing Key Laboratory of Environmental Science and Engineering, School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081 (China); Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS (United Kingdom); Tian, Tian; Fairen-Jimenez, David [Department of Chemical Engineering and Biotechnology, University of Cambridge, Pembroke Street, Cambridge CB2 3RA (United Kingdom); Cao, Shuai; Coxon, Paul R.; Xi, Kai, E-mail: kx210@cam.ac.uk, E-mail: chenrj@bit.edu.cn; Vasant Kumar, R.; Cheetham, Anthony K. [Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS (United Kingdom)

2014-12-01

A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/C{sub ZIF8-D}) composite for use in a cathode for a lithium sulfur (Li-S) battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8), a typical zinc-containing metal organic framework (MOF), which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/C{sub ZIF8-D}) composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/C{sub ZIF8-D} sample, Li-S batteries with the GS-S/C{sub ZIF8-D} composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

Directory of Open Access Journals (Sweden)

Renjie Chen

2014-12-01

Full Text Available A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/CZIF8-D composite for use in a cathode for a lithium sulfur (Li-S battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8, a typical zinc-containing metal organic framework (MOF, which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/CZIF8-D composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/CZIF8-D sample, Li-S batteries with the GS-S/CZIF8-D composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

Unanticipated coordination of tris buffer to the Radical SAM cluster of the RimO methylthiotransferase.

Science.gov (United States)

Molle, Thibaut; Clémancey, Martin; Latour, Jean-Marc; Kathirvelu, Velavan; Sicoli, Giuseppe; Forouhar, Farhad; Mulliez, Etienne; Gambarelli, Serge; Atta, Mohamed

2016-07-01

Radical SAM enzymes generally contain a [4Fe-4S](2+/1+) (RS cluster) cluster bound to the protein via the three cysteines of a canonical motif CxxxCxxC. The non-cysteinyl iron is used to coordinate SAM via its amino-carboxylate moiety. The coordination-induced proximity between the cluster acting as an electron donor and the adenosyl-sulfonium bond of SAM allows for the homolytic cleavage of the latter leading to the formation of the reactive 5'-deoxyadenosyl radical used for substrate activation. Most of the structures of Radical SAM enzymes have been obtained in the presence of SAM, and therefore, little is known about the situation when SAM is not present. In this report, we show that RimO, a methylthiotransferase belonging to the radical SAM superfamily, binds a Tris molecule in the absence of SAM leading to specific spectroscopic signatures both in Mössbauer and pulsed EPR spectroscopies. These data provide a cautionary note for researchers who work with coordinative unsaturated iron sulfur clusters.

Expression of Critical Sulfur- and Iron-Oxidation Genes and the Community Dynamics During Bioleaching of Chalcopyrite Concentrate by Moderate Thermophiles.

Science.gov (United States)

Zhou, Dan; Peng, Tangjian; Zhou, Hongbo; Liu, Xueduan; Gu, Guohua; Chen, Miao; Qiu, Guanzhou; Zeng, Weimin

2015-07-01

Sulfate adenylyltransferase gene and 4Fe-4S ferredoxin gene are the key genes related to sulfur and iron oxidations during bioleaching system, respectively. In order to better understand the bioleaching and microorganism synergistic mechanism in chalcopyrite bioleaching by mixed culture of moderate thermophiles, expressions of the two energy metabolism genes and community dynamics of free and attached microorganisms were investigated. Specific primers were designed for real-time quantitative PCR to study the expression of these genes. Real-time PCR results showed that sulfate adenylyltransferase gene was more highly expressed in Sulfobacillus thermosulfidooxidans than that in Acidithiobacillus caldus, and expression of 4Fe-4S ferredoxin gene was higher in Ferroplasma thermophilum than that in S. thermosulfidooxidans and Leptospirillum ferriphilum. The results indicated that in the bioleaching system of chalcopyrite concentrate, sulfur and iron oxidations were mainly performed by S. thermosulfidooxidans and F. thermophilum, respectively. The community dynamics results revealed that S. thermosulfidooxidans took up the largest proportion during the whole period, followed by F. thermophilum, A. caldus, and L. ferriphilum. The CCA analysis showed that 4Fe-4S ferredoxin gene expression was mainly affected (positively correlated) by high pH and elevated concentration of ferrous ion, while no factor was observed to prominently influence the expression of sulfate adenylyltransferase gene.

Bacterial Disproportionation of Elemental Sulfur Coupled to Chemical Reduction of Iron or Manganese

Science.gov (United States)

Thamdrup, Bo; Finster, Kai; Hansen, Jens Würgler; Bak, Friedhelm

1993-01-01

A new chemolithotrophic bacterial metabolism was discovered in anaerobic marine enrichment cultures. Cultures in defined medium with elemental sulfur (S0) and amorphous ferric hydroxide (FeOOH) as sole substrates showed intense formation of sulfate. Furthermore, precipitation of ferrous sulfide and pyrite was observed. The transformations were accompanied by growth of slightly curved, rod-shaped bacteria. The quantification of the products revealed that S0 was microbially disproportionated to sulfate and sulfide, as follows: 4S0 + 4H2O → SO42- + 3H2S + 2H+. Subsequent chemical reactions between the formed sulfide and the added FeOOH led to the observed precipitation of iron sulfides. Sulfate and iron sulfides were also produced when FeOOH was replaced by FeCO3. Further enrichment with manganese oxide, MnO2, instead of FeOOH yielded stable cultures which formed sulfate during concomitant reduction of MnO2 to Mn2+. Growth of small rod-shaped bacteria was observed. When incubated without MnO2, the culture did not grow but produced small amounts of SO42- and H2S at a ratio of 1:3, indicating again a disproportionation of S0. The observed microbial disproportionation of S0 only proceeds significantly in the presence of sulfide-scavenging agents such as iron and manganese compounds. The population density of bacteria capable of S0 disproportionation in the presence of FeOOH or MnO2 was high, > 104 cm-3 in coastal sediments. The metabolism offers an explanation for recent observations of anaerobic sulfide oxidation to sulfate in anoxic sediments. PMID:16348835

Chinese mitten crab (Eriocheir sinensis) iron-sulphur cluster assembly protein 2 (EsIscA2) is differentially regulated after immune and oxidative stress challenges.

Science.gov (United States)

Zhang, Peng; Liu, Yu; Wang, Min; Dong, Miren; Liu, Zhaoqun; Jia, Zhihao; Wang, Weilin; Zhang, Anguo; Wang, Lingling; Song, Linsheng

2018-07-01

Iron-sulphur clusters (ISCs), one of the oldest and most versatile cofactors of proteins, are involved in catalysis reactions, electron transport reactions, regulation processes as well as sensing of ambient conditions. Iron-sulphur cluster assembly protein (IscA) is a scaffold protein member of ISC formation system, which plays a significant role in the assembly and maturation process of ISC proteins. In the present study, the cDNA sequence of iron-sulphur cluster assembly protein 2 (designated as EsIscA2) was cloned from Eriocheir sinensis. The open reading frame (ORF) of EsIscA2 was of 507 bp, encoding a peptide of 168 amino acids with a typically conserved Fe-S domain. A tetrameric form was predicated by the SWISS-MODEL prediction algorithm, and three conserved cysteine residues (Cys-93, Cys-158, Cys-160) from each IscA monomer were predicted to form a 'cysteine pocket'. The deduced amino acid sequence of EsIscA2 shared over 50% similarity with that of other IscAs. EsIscA2 was clustered with IscA2 proteins from invertebrates and vertebrates, indicating that the protein was highly conservative in the evolution. rEsIscA2 exhibited a high iron binding affinity in the concentration ranging from 2 to 200 μM. EsIscA2 transcripts were detected in all the tested tissues including gonad, hemocytes, gill, muscle, heart, hepatopancreas and eyestalk, and EsIscA2 protein was detected in the mitochondria of hemocytes. The highest mRNA expression level of EsIscA2 was detected in muscle and hepatopancreas, which was about 34.66-fold (p < 0.05) and 27.07-fold (p < 0.05) of that in hemocytes, respectively. After Aeromonas hydrophila and lipopolysaccharide (LPS) stimulations, the mRNA expression of EsIscA2 in hemocytes was down-regulated and reached the lowest level at 24 h (0.31-fold, p < 0.05) and 48 h (0.29-fold, p < 0.05) compared to control group, respectively. And the expression of EsIscA2 mRNA in hepatopancreas was repressed from 6 h to 48 h post

Soilaluminum, iron, and phosphorus dynamics in response to long-term experimental nitrogen and sulfur additions at the Bear Brook Watershed in Maine, USA

Science.gov (United States)

Jessica Sherman; Ivan J. Fernandez; Stephen A. Norton; Tsutomu Ohno; Lindsey E. Rustad

2006-01-01

Atmospheric deposition of nitrogen (N) and sulfur (S) containing compounds affects soil chemistry in forested ecosystems through (1) acidification and the depletion of base cations, (2) metal mobilization, particularly aluminum (Al), and iron (Fe), (3) phosphorus (P) mobilization, and (4) N accumulation. The Bear BrookWatershed in Maine (BBWM) is a long-term paired...

Magnetism of iron, cobalt and nickel clusters studied in molecular beams

International Nuclear Information System (INIS)

Billas, I.

1995-01-01

The magnetic properties of iron, cobalt and nickel clusters in a molecular beam have been studied in a magnetic Stern-Gerlach deflection experiment. The molecular beam apparatus consists of a laser vaporization cluster source with high intensity and stability and a high-resolution time-of-flight mass spectrometer for the deflection measurements. Several novel experimental features have been developed in this work, like a nozzle which can be heated up to 1000 K and a chopper to measure the dwell times of the clusters in the source and their corresponding velocities. These new developments have allowed the measurement and the control of the temperature of the free clusters. The Stern-Gerlach deflection experiments have been performed on Fe, Co and Ni clusters in the mass range from 20 to 700 atoms. All clusters show single-sided deflection toward increasing field. This observation indicates that a spin relaxation process occurs within the isolated clusters. The participation of both the cluster rotational and vibrational degrees of freedom to the spin relaxation has been experimentally demonstrated. The cluster magnetization has been determined as a function of applied magnetic field B and as a function of dwell times of the clusters in the source before the supersonic expansion into vacuum. Superparamagnetic behavior has been observed when the cluster rotational speed is much larger than the Larmor frequency of the cluster magnetic moment μ in the field B. In particular, for μB<< kT, the cluster magnetization depends on B/T. For lower rotational speeds, reduced values of the magnetization have been observed. The magnetic moments of the superparamagnetic Fe, Co and Ni clusters have been measured as a) a function of cluster size N at low temperature and b) as a function of cluster temperature T for various size ranges. (author) figs., tabs., refs

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

Science.gov (United States)

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

2014-03-03

Superparamagnetic iron oxide nanoparticles (SPIONs) can be used as efficient transverse relaxivity (T2 ) contrast agents in magnetic resonance imaging (MRI). Organizing small (Doxide) diblock copolymer (P2QVP-b-PEO) to mediate the self-assembly of protein-cage-encapsulated iron oxide (γ-Fe2 O3 ) nanoparticles (magnetoferritin) into stable PEO-coated clusters. This approach relies on electrostatic interactions between the cationic N-methyl-2-vinylpyridinium iodide block and magnetoferritin protein cage surface (pI≈4.5) to form a dense core, whereas the neutral ethylene oxide block provides a stabilizing biocompatible shell. Formation of the complexes was studied in aqueous solvent medium with dynamic light scattering (DLS) and cryogenic transmission electron microcopy (cryo-TEM). DLS results indicated that the hydrodynamic diameter (Dh ) of the clusters is approximately 200 nm, and cryo-TEM showed that the clusters have an anisotropic stringlike morphology. MRI studies showed that in the clusters the longitudinal relaxivity (r1 ) is decreased and the transverse relaxivity (r2 ) is increased relative to free magnetoferritin (MF), thus indicating that clusters can provide considerable contrast enhancement. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel acidophilic, thermophilic iron and sulfur-oxidizing archaeon isolated from a hot spring of tengchong, yunnan, China

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Jiannan Ding

2011-06-01

Full Text Available A novel thermoacidophilic iron and sulfur-oxidizing archaeon, strain YN25, was isolated from an in situ enriched acid hot spring sample collected in Yunnan, China. Cells were irregular cocci, about 0.9-1.02 µm×1.0-1.31 µm in the medium containing elemental sulfur and 1.5-2.22 µm×1.8-2.54 µm in ferrous sulfate medium. The ranges of growth and pH were 50-85 (optimum 65 and pH 1.0-6.0 (optimum 1.5-2.5. The acidophile was able to grow heterotrophically on several organic substrates, including various monosaccharides, alcohols and amino acids, though the growth on single substrate required yeast extract as growth factor. Growth occurred under aerobic conditions or via anaerobic respiration using elemental sulfur as terminal electron acceptor. Results of morphology, physiology, fatty acid analysis and analysis based on 16S rRNA gene sequence indicated that the strain YN25 should be grouped in the species Acidianus manzaensis. Bioleaching experiments indicated that this strain had excellent leaching capacity, with a copper yielding ratio up to 79.16% in 24 d. The type strain YN25 was deposited in China Center for Type Culture Collection (=CCTCCZNDX0050.

Effects of applied strain on nanoscale self-interstitial cluster formation in BCC iron

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Gao, Ning; Setyawan, Wahyu; Kurtz, Richard J.; Wang, Zhiguang

2017-09-01

The effect of applied strains on the configurational evolution of self-interstitial clusters in BCC iron (Fe) is explored with atomistic simulations. A novel cluster configuration is discovered at low temperatures (family of 〈 hkl 〉 loops is calculated as a function of strain. The results show that loop anisotropy is governed by the angle between the stress direction and the orientation of the 〈 111 〉 crowdions in the loop, and directly linked to the stress induced preferred nucleation of self-interstitial atoms.

Improved R2* liver iron concentration assessment using a novel fuzzy c-mean clustering scheme

International Nuclear Information System (INIS)

Saiviroonporn, Pairash; Viprakasit, Vip; Krittayaphong, Rungroj

2015-01-01

In thalassemia patients, R2* liver iron concentration (LIC) measurement is a common clinical tool for assessing iron overload and for determining necessary chelator dose and evaluating its efficacy. Despite the importance of accurate LIC measurement, existing methods suffer from LIC variability, especially at the severe iron overload range due to inclusion of vessel parts in LIC calculation. In this study, we build upon previous Fuzzy C-Mean (FCM) clustering work to formulate a scheme with superior performance in segmenting vessel pixels from the parenchyma. Our method (MIX-FCM) combines our novel 2D-FCM with the existing 1D-FCM algorithm. This study further assessed possible optimal clustering parameters (OP scheme) and proposed a semi-automatic (SA) scheme for routine clinical application. Segmentation of liver parenchyma and vessels was performed on T2* images and their LIC maps in 196 studies from 147 thalassemia major patients. We used manual segmentation as the reference. 1D-FCM clustering was performed on the acquired image alone and 2D-FCM used both the acquired image and its LIC data. To execute the MIX-FCM method, the best outcome (OP-MIX-FCM) was selected from the aforementioned methods and was compared to the SA-MIX-FCM scheme. We used the percent value of the normalized interquartile range (nIQR) to its median to evaluate the variability of all methods. 2D-FCM clustering is more effective than 1D-FCM clustering at the severe overload range only, but inferior for other ranges (where 1D-FCM provides suitable results). This complementary performance between the two methods allows MIX-FCM to improve results for all ranges. OP-MIX-FCM clustering error was 2.1 ± 2.3 %, compared with 10.3 ± 9.9 % and 7.0 ± 11.9 % from 1D- and 2D-FCM clustering, respectively. SA-MIX-FCM result was comparable to OP-MIX-FCM result, with both schemes showing ability to decrease overall nIQR by approximately 30 %. Our proposed 2D-FCM algorithm is not as superior to 1D-FCM as

Estimation of sulfur in coal by fast neutron activation

International Nuclear Information System (INIS)

Das, G.C.; Bhattacharyya, P.K.

1995-01-01

A simple method is described for estimation of sulfur in coal using fast neutron activation of sulfur, i.e. 32 S(n,p) 32 P and subsequent measurement of 32 P β-activity (1.72 MeV) by a Geiger-Mueller counter. Since the sulfur content of Indian coal ranges from 0.25 to 3%, simulated samples of coal containing sulfur in the range from 0.25 to 3% and common impurities like oxides of aluminium, calcium, iron and silicon have been used to establish the method. (author). 6 refs., 2 figs., 1 tab

Sulfur and Iron Cycling in a Coastal Sediment - Radiotracer Studies and Seasonal Dynamics

DEFF Research Database (Denmark)

MOESLUND, L.; THAMDRUP, B.; JØRGENSEN, BB

1994-01-01

The seasonal variation in sulfate reduction and the dynamics of sulfur and iron geochemistry were studied throughout a year in sediment of Aarhus Bay, Denmark. A radiotracer method for measuring sulfate reduction rates was applied with incubation times down to 15 min and a depth resolution down...... to 2 mm in the oxidized surface layer of the sediment. The radiotracer data were analyzed by a mathematical model which showed that, due to partial, rapid reoxidation of radioactive sulfide during incubation, the actual reduction rates in this layer were probably underestimated 5-fold. In the deeper......, sulfidic zone, measured rates appeared to be correct. Sulfate reduction followed the seasonal variation in temperature with maximum activity at 1-2 cm depth in late summer. In spite of its rapid production, free H2S was detectable in the porewater only below the depth of free Fe2+ at 6-7 cm throughout...

Identification of localized redox states in plant-type two-iron ferrodoxins using the nuclear Overhauser effect

International Nuclear Information System (INIS)

Dugad, L.B.; La Mar, G.N.; Banci, L.; Bertini, I.

1990-01-01

The homonuclear Overhauser effect (NOE), in conjunction with nonselective spin-lattice relaxation measurements, has been employed to assign the contact-shifted resonances for the reduced form of two typical plant-type two-iron ferrodoxins from the algae Spirulina platensis and Porphyra umbilicalis. These results demonstrate that the NOE should have broad general applicability for the assignments and electronic structural elucidation of diverse subclasses of paramagnetic iron-sulfur cluster proteins. NOE connectivities were detected only among sets of resonances exhibiting characteristically different deviations from Curie behavior, providing strong support for the applicability of the spin Hamiltonian formulation for the NMR properties of the antiferromagnetically coupled iron clusters. The geminal β-methylene protons for the two cysteines bound to the iron(II) center were clearly identified, as well as the C α H and one C β H for each of the cysteines bound to the iron(III). The identification of the iron bound to cysteines 41 and 46 as the iron(II) in the reduced protein was effected on the basis of dipolar contacts between the bound cysteines. Resolved labile proton contact-shifted resonances are attributed to hydrogen bonding to the iron(III) center, and it is concluded that the contact-shifted resonances for the more numerous hydrogen bonds to the iron(II) center are not resolved from the diamagnetic envelope. The identification of the iron closer to the protein surface as the more reducible one is consistent with predictions based on a larger number of hydrogen bonds to this center

Investigating the provenance of iron artifacts of the Royal Iron Factory of Sao Joao de Ipanema by hierarchical cluster analysis of EDS microanalyses of slag inclusions

Energy Technology Data Exchange (ETDEWEB)

Mamani-Calcina, Elmer Antonio; Landgraf, Fernando Jose Gomes; Azevedo, Cesar Roberto de Farias, E-mail: c.azevedo@usp.br [Universidade de Sao Paulo (USP), Sao Paulo, SP (Brazil). Escola Politecnica. Departmento de Engenharia Metalurgica e de Materiais

2017-01-15

Microstructural characterization techniques, including EDX (Energy Dispersive X-ray Analysis) microanalyses, were used to investigate the slag inclusions in the microstructure of ferrous artifacts of the Royal Iron Factory of Sao Joao de Ipanema (first steel plant of Brazil, XIX century), the D. Pedro II Bridge (located in Bahia, assembled in XIX century and produced in Scotland) and the archaeological sites of Sao Miguel de Missoes (Rio Grande do Sul, Brazil, production site of iron artifacts, the XVIII century) and Afonso Sardinha (Sao Paulo, Brazil production site of iron artifacts, XVI century). The microanalyses results of the main micro constituents of the microstructure of the slag inclusions were investigated by hierarchical cluster analysis and the dendrogram with the microanalyses results of the wüstite phase (using as critical variables the contents of MnO, MgO, Al{sub 2}O{sub 3}, V{sub 2}O{sub 5} and TiO{sub 2}) allowed the identification of four clusters, which successfully represented the samples of the four investigated sites (Ipanema, Sardinha, Missoes and Bahia). Finally, the comparatively low volumetric fraction of slag inclusions in the samples of Ipanema (∼1%) suggested the existence of technological expertise at the iron making processing in the Royal Iron Factory of Sao Joao de Ipanema. (author)

Sulfur isotopes in coal constrain the evolution of the Phanerozoic sulfur cycle

DEFF Research Database (Denmark)

Canfield, Donald Eugene

2013-01-01

Sulfate is the second most abundant anion (behind chloride) in modern seawater, and its cycling is intimately coupled to the cycling of organic matter and oxygen at the Earth’s surface. For example, the reduction of sulfide by microbes oxidizes vast amounts of organic carbon and the subsequent......, these compositions do not deviate substantially from the modern surface-water input to the oceans. When applied to mass balance models, these results support previous interpretations of sulfur cycle operation and counter recent suggestions that sulfate has been a minor player in sulfur cycling through...... reaction of sulfide with iron produces pyrite whose burial in sediments is an important oxygen source to the atmosphere. The concentrations of seawater sulfate and the operation of sulfur cycle have experienced dynamic changes through Earth’s history, and our understanding of this history is based mainly...

Atomically precise arrays of fluorescent silver clusters: a modular approach for metal cluster photonics on DNA nanostructures.

Science.gov (United States)

Copp, Stacy M; Schultz, Danielle E; Swasey, Steven; Gwinn, Elisabeth G

2015-03-24

The remarkable precision that DNA scaffolds provide for arraying nanoscale optical elements enables optical phenomena that arise from interactions of metal nanoparticles, dye molecules, and quantum dots placed at nanoscale separations. However, control of ensemble optical properties has been limited by the difficulty of achieving uniform particle sizes and shapes. Ligand-stabilized metal clusters offer a route to atomically precise arrays that combine desirable attributes of both metals and molecules. Exploiting the unique advantages of the cluster regime requires techniques to realize controlled nanoscale placement of select cluster structures. Here we show that atomically monodisperse arrays of fluorescent, DNA-stabilized silver clusters can be realized on a prototypical scaffold, a DNA nanotube, with attachment sites separated by <10 nm. Cluster attachment is mediated by designed DNA linkers that enable isolation of specific clusters prior to assembly on nanotubes and preserve cluster structure and spectral purity after assembly. The modularity of this approach generalizes to silver clusters of diverse sizes and DNA scaffolds of many types. Thus, these silver cluster nano-optical elements, which themselves have colors selected by their particular DNA templating oligomer, bring unique dimensions of control and flexibility to the rapidly expanding field of nano-optics.

Sulfur isotope evidence for the contemporary formation of pyrite in a coastal acid sulfate soil

International Nuclear Information System (INIS)

Bush, R.T.; Sullivan, L.A.; Prince, K.; White, I.

2000-01-01

The sulfur isotopic composition of pyrite (FeS 2 ), greigite (Fe 3 S 4 ) and pore-water sulfate was determined for a typical coastal acid sulfate soil (ASS). Greigite occurs only in the partially oxidised upper-most pyrite sediments as blackish clusters within vertical fissures and other macro-pores. The concentration of pyrite was an order of magnitude greater than greigite in this layer, continuing through the underlying reduced estuarine sediments. δ 34 S of pyrite (0.45 per mil) associated with greigite accumulations were distinctly different to the bulk average for pyrite (-3.7 per mil), but similar to greigite (0.9 per mil). Greigite is meta-stable under reducing conditions, readily transforming to pyrite. The transformation of iron monosulfides (including greigite) to pyrite is a sulfur-isotope conservative process and therefore, these observations indicate that pyrite is forming from greigite at the oxic/anoxic boundary

The design of 3D scaffold for tissue engineering using automated scaffold design algorithm.

Science.gov (United States)

Mahmoud, Shahenda; Eldeib, Ayman; Samy, Sherif

2015-06-01

Several progresses have been introduced in the field of bone regenerative medicine. A new term tissue engineering (TE) was created. In TE, a highly porous artificial extracellular matrix or scaffold is required to accommodate cells and guide their growth in three dimensions. The design of scaffolds with desirable internal and external structure represents a challenge for TE. In this paper, we introduce a new method known as automated scaffold design (ASD) for designing a 3D scaffold with a minimum mismatches for its geometrical parameters. The method makes use of k-means clustering algorithm to separate the different tissues and hence decodes the defected bone portions. The segmented portions of different slices are registered to construct the 3D volume for the data. It also uses an isosurface rendering technique for 3D visualization of the scaffold and bones. It provides the ability to visualize the transplanted as well as the normal bone portions. The proposed system proves good performance in both the segmentation results and visualizations aspects.

Structural studies of the Enterococcus faecalis SufU [Fe-S] cluster protein

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Frazzon Jeverson

2009-02-01

Full Text Available Abstract Background Iron-sulfur clusters are ubiquitous and evolutionarily ancient inorganic prosthetic groups, the biosynthesis of which depends on complex protein machineries. Three distinct assembly systems involved in the maturation of cellular Fe-S proteins have been determined, designated the NIF, ISC and SUF systems. Although well described in several organisms, these machineries are poorly understood in Gram-positive bacteria. Within the Firmicutes phylum, the Enterococcus spp. genus have recently assumed importance in clinical microbiology being considered as emerging pathogens for humans, wherein Enterococcus faecalis represents the major species associated with nosocomial infections. The aim of this study was to carry out a phylogenetic analysis in Enterococcus faecalis V583 and a structural and conformational characterisation of it SufU protein. Results BLAST searches of the Enterococcus genome revealed a series of genes with sequence similarity to the Escherichia coli SUF machinery of [Fe-S] cluster biosynthesis, namely sufB, sufC, sufD and SufS. In addition, the E. coli IscU ortholog SufU was found to be the scaffold protein of Enterococcus spp., containing all features considered essential for its biological activity, including conserved amino acid residues involved in substrate and/or co-factor binding (Cys50,76,138 and Asp52 and, phylogenetic analyses showed a close relationship with orthologues from other Gram-positive bacteria. Molecular dynamics for structural determinations and molecular modeling using E. faecalis SufU primary sequence protein over the PDB:1su0 crystallographic model from Streptococcus pyogenes were carried out with a subsequent 50 ns molecular dynamic trajectory. This presented a stable model, showing secondary structure modifications near the active site and conserved cysteine residues. Molecular modeling using Haemophilus influenzae IscU primary sequence over the PDB:1su0 crystal followed by a MD

Sulfur metabolism in the extreme acidophile Acidithiobacillus caldus

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Stefanie eMangold

2011-02-01

Full Text Available Given the challenges to life at low pH, an analysis of inorganic sulfur compound oxidation was initiated in the chemolithoautotrophic extremophile Acidithiobacillus caldus. A. caldus is able to metabolize elemental sulfur and a broad range of inorganic sulfur compounds. It has been implicated in the production of environmentally damaging acidic solutions as well as participating in industrial bioleaching operations where it forms part of microbial consortia used for the recovery of metal ions. Based upon the recently published A. caldus type strain genome sequence, a bioinformatic reconstruction of elemental sulfur and inorganic sulfur compound metabolism predicted genes included: sulfide quinone reductase (sqr, tetrathionate hydrolase (tth, two sox gene clusters potentially involved in thiosulfate oxidation (soxABXYZ, sulfur oxygenase reductase (sor, and various electron transport components. RNA transcript profiles by semi-quantitative reverse transcription PCR suggested up-regulation of sox genes in the presence of tetrathionate. Extensive gel based proteomic comparisons of total soluble and membrane enriched protein fractions during growth on elemental sulfur and tetrathionate identified differential protein levels from the two Sox clusters as well as several chaperone and stress proteins up-regulated in the presence of elemental sulfur. Proteomics results also suggested the involvement of heterodisulfide reductase (HdrABC in A. caldus inorganic sulfur compound metabolism. A putative new function of Hdr in acidophiles is discussed. Additional proteomic analysis evaluated protein expression differences between cells grown attached to solid, elemental sulfur versus planktonic cells. This study has provided insights into sulfur metabolism of this acidophilic chemolithotroph and gene expression during attachment to solid elemental sulfur.

Isolation and characterization of ferrous- and sulfur-oxidizing bacteria from Tengchong solfataric region, China.

Science.gov (United States)

Jiang, Chengying; Liu, Ying; Liu, Yanyang; Guo, Xu; Liu, Shuang-Jiang

2009-01-01

Microbial oxidation and reduction of iron and sulfur are important parts of biogeochemical cycles in acidic environments such as geothermal solfataric regions. Species of Acidithiobacillus and Leptospirillum are the common ferrous-iron and sulfur oxidizers from such environments. This study focused on the Tengchong sofataric region, located in Yunnan Province, Southwest China. Based on cultivation, 9 strains that grow on ferrous-iron and sulfuric compounds were obtained. Analysis of 16S rRNA genes of the 9 strains indicated that they were affiliated to Acidithiobacillus, Alicyclobacillus, Sulfobacillus, Leptospirillum and Acidiphilium. Physiological and phylogenetic studies indicated that two strains (TC-34 and TC-71) might represent two novel members of Alicyclobacillus. Strain TC-34 and TC-71 showed 94.8%-97.1% 16S rRNA gene identities to other species of Alicyclobacillus. Different from the previously described Alicyclobacillus species, strains TC-34 and TC-71 were mesophilic and their cellular fatty acids do not contain omega-cyclic fatty acids. Strain TC-71 was obligately dependent on ferrous-iron for growth. It was concluded that the ferrous-iron oxidizers were diversified and Alicyclobacillus species were proposed to take part in biochemical geocycling of iron in the Tengchong solfataric region.

A laboratory study to evaluate the possibility of sulphur and phosphorous removal from iron ore concentrate by leaching

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Pour Hassan Rezvani

2016-01-01

Full Text Available Iron ore concentrates with high grade sulfur cause several problems in the steel making process, and hence affect the concentrate price. Environmental issues such as sulfur dioxide emission during the concentrate pelletizing process and effect on the steel quality are other issues. The current study was focused on removal of sulfur from the iron ore concentrate by using the chemical leaching technique. The magnetite iron ore concentrate was chosen for this purpose. The results obtained showed that more than 90% of the total sulfur content was removed from the iron ore concentrate by chemical leaching. Effects of several parameters such as temperature, particle size and use of organic solvent on sulfur removal were investigated by a series of experiments. After optimizing the experimental conditions, it was demonstrated that with addition of sulfur, phosphorus, another important impurity was also removed from the iron ore concentrate. In addition, one of the major advantages of our proposed method was transformation of mineral pyrites to useful by-products such as elemental sulfur.

Effects of applied strain on nanoscale self-interstitial cluster formation in BCC iron

Energy Technology Data Exchange (ETDEWEB)

Gao, Ning; Setyawan, Wahyu; Kurtz, Richard J.; Wang, Zhiguang

2017-09-01

The effect of applied strains on the configurational evolution of self-interstitial clusters in BCC iron (Fe) is explored with atomistic simulations. A novel cluster configuration is discovered at low temperatures (<600 K), which consists of <110> dumbbells and <111> crowdions in a specific configuration, resulting in an immobile defect. The stability and diffusion of this cluster at higher temperatures is explored. In addition, an anisotropy distribution factor of a particular [hkl] interstitial loop within the family of loops is calculated as a function of strain. The results show that loop anisotropy is governed by the angle between the stress direction and the orientation of the <111> crowdions in the loop, and directly linked to the stress induced preferred nucleation of self-interstitial atoms.

Microarray and bioinformatic analyses suggest models for carbon metabolism in the autotroph Acidithiobacillus ferrooxidans

Energy Technology Data Exchange (ETDEWEB)

C. Appia-ayme; R. Quatrini; Y. Denis; F. Denizot; S. Silver; F. Roberto; F. Veloso; J. Valdes; J. P. Cardenas; M. Esparza; O. Orellana; E. Jedlicki; V. Bonnefoy; D. Holmes

2006-09-01

Acidithiobacillus ferrooxidans is a chemolithoautotrophic bacterium that uses iron or sulfur as an energy and electron source. Bioinformatic analysis was used to identify putative genes and potential metabolic pathways involved in CO2 fixation, 2P-glycolate detoxification, carboxysome formation and glycogen utilization in At. ferrooxidans. Microarray transcript profiling was carried out to compare the relative expression of the predicted genes of these pathways when the microorganism was grown in the presence of iron versus sulfur. Several gene expression patterns were confirmed by real-time PCR. Genes for each of the above predicted pathways were found to be organized into discrete clusters. Clusters exhibited differential gene expression depending on the presence of iron or sulfur in the medium. Concordance of gene expression within each cluster, suggested that they are operons Most notably, clusters of genes predicted to be involved in CO2 fixation, carboxysome formation, 2P-glycolate detoxification and glycogen biosynthesis were up-regulated in sulfur medium, whereas genes involved in glycogen utilization were preferentially expressed in iron medium. These results can be explained in terms of models of gene regulation that suggest how A. ferrooxidans can adjust its central carbon management to respond to changing environmental conditions.

In vivo fluorescent detection of Fe-S clusters coordinated by human GRX2.

Science.gov (United States)

Hoff, Kevin G; Culler, Stephanie J; Nguyen, Peter Q; McGuire, Ryan M; Silberg, Jonathan J; Smolke, Christina D

2009-12-24

A major challenge to studying Fe-S cluster biosynthesis in higher eukaryotes is the lack of simple tools for imaging metallocluster binding to proteins. We describe the first fluorescent approach for in vivo detection of 2Fe2S clusters that is based upon the complementation of Venus fluorescent protein fragments via human glutaredoxin 2 (GRX2) coordination of a 2Fe2S cluster. We show that Escherichia coli and mammalian cells expressing Venus fragments fused to GRX2 exhibit greater fluorescence than cells expressing fragments fused to a C37A mutant that cannot coordinate a metallocluster. In addition, we find that maximal fluorescence in the cytosol of mammalian cells requires the iron-sulfur cluster assembly proteins ISCU and NFS1. These findings provide evidence that glutaredoxins can dimerize within mammalian cells through coordination of a 2Fe2S cluster as observed with purified recombinant proteins. Copyright 2009 Elsevier Ltd. All rights reserved.

Chemistry and the iron - only hydrogenase

International Nuclear Information System (INIS)

Tard, C.; Razavet, M.; Liu, X.; Ibrahim, S.; Pickett, Ch.

2005-01-01

Complete text of publication follows: Chemistry related to the hydrogenases is developing very rapidly and providing some informative insights into how the biological systems might function. Although still very much at a blue skies stage, there is some prospect for the design of artificial assemblies, materials and devices with technological application for hydrogen production/uptake provided robust system can be designed with low over potentials for hydrogen/proton interconversion (1). The iron-only hydrogenase possesses a peculiar di-iron unit coordinated by CO and CN, ligands which are normally associated with poisoning biological function. This sub-site unit is attached to a [4Fe4S] cubane center to form the catalytic site of the hydrogenase which is known as the 'H-cluster'. The synthesis of artificial sub-sites will first be described together with how their structures, spectroscopy and reactivity provides some key insights into the natural system viz. unprecedented bridging carbonyl and Fe(I) motifs in biology (2-4). How we have approached putting together the entire iron-sulfur framework of the H-cluster will then be described together with its electron-transfer and electrocatalytic properties (4). Finally, I will describe some early work on how we are beginning to incorporate structural motifs of the active-site into conducting polymer matrices, how they function as (albeit poor) electrocatalysts for hydrogen evolution, and where we see the way ahead. (1)The Chemistry and the Hydrogenases. D.J. Evans and C.J. Pickett, Chem. Soc. Rev., 32, 268-275, 2003; (2)Electron-Transfer at a Di-thiolate-Bridged Di-Iron Assembly; Electrocatalytic Hydrogen Evolution. S.J. Borg, T. Behrsing and S.P. Best, M. Ravazet, X. Liu and C.J. Pickett, J Amer. Chem. Soc., 2004, 126, 509-533; (3) Dissecting the intimate mechanism of cyanation of [Fe2S3] complexes related to the active site of all-iron hydrogenases by DFT analysis of energetics, transition states, intermediates and

Synthesis and Application of Iron Oxide/Silica Gel Nanocomposite for Removal of Sulfur Dyes from Aqueous Solutions

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Naser Tavassoli

2017-03-01

Full Text Available Background & Aims of the Study: water pollution by synthetic organic dyes is mainly regarded as environmental and ecological critical issues worldwide. In this research, magnetite iron oxide/silica gel nanocomposite (termed as Fe3O4/SG was synthesized chemically and then used as an effective adsorbent for removal of sulfur dyes from aqueous solution. Materials and Methods: The various parameters such as pH, sorbent dosage, initial dye concentration, contact time and dye solution temperature were investigated in a batch system. The equilibrium data were analyzed by Langmuir and Freundlich isotherm models. Results: The experimental data fit well with pseudo-second-order kinetic model (R2≥0.998 and conformed better to Langmuir isotherm model (R2≥0.997. The maximum adsorption capacity for Fe3O4/SG obtained from the Langmuir model was 11.1mg/g. Evaluation of thermodynamic parameters proved that the adsorption process was normally feasible, spontaneous and exothermic. Conclusion: It can be concluded that the Fe3O4/SG can be considered as a cost-effective and an environmental friendly adsorbent for efficient removal of sulfur dyes from aqueous solutions.

Hydrometallurgical process for recovering iron sulfate and zinc sulfate from baghouse dust

Science.gov (United States)

Zaromb, Solomon; Lawson, Daniel B.

1994-01-01

A process for recovering zinc/rich and iron-rich fractions from the baghouse dust that is generated in various metallurgical operations, especially in steel-making and other iron-making plants, comprises the steps of leaching the dust by hot concentrated sulfuric acid so as to generate dissolved zinc sulfate and a precipitate of iron sulfate, separating the precipitate from the acid by filtration and washing with a volatile liquid, such as methanol or acetone, and collecting the filtered acid and the washings into a filtrate fraction. The volatile liquid may be recovered distillation, and the zinc may be removed from the filtrate by alternative methods, one of which involves addition of a sufficient amount of water to precipitate hydrated zinc sulfate at 10.degree. C., separation of the precipitate from sulfuric acid by filtration, and evaporation of water to regenerate concentrated sulfuric acid. The recovery of iron may also be effected in alternative ways, one of which involves roasting the ferric sulfate to yield ferric oxide and sulfur trioxide, which can be reconverted to concentrated sulfuric acid by hydration. The overall process should not generate any significant waste stream.

Neutral molecular cluster formation of sulfuric acid–dimethylamine observed in real time under atmospheric conditions

CERN Document Server

Kürten, Andreas; Simon, Mario; Sipilä, Mikko; Sarnela, Nina; Junninen, Heikki; Adamov, Alexey; Almeida, João; Amorim, Antonio; Bianchi, Federico; Breitenlechner, Martin; Dommen, Josef; Donahue, Neil M; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Hutterli, Manuel; Kangasluoma, Juha; Kirkby, Jasper; Laaksonen, Ari; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Praplan, Arnaud P; Riccobono, Francesco; Rissanen, Matti P; Rondo, Linda; Schobesberger, Siegfried; Seinfeld, John H; Steiner, Gerhard; Tomé, António; Tröstl, Jasmin; Winkler, Paul M; Williamson, Christina; Wimmer, Daniela; Ye, Penglin; Baltensperger, Urs; Carslaw, Kenneth S; Kulmala, Markku; Worsnop, Douglas R; Curtius, Joachim

2014-01-01

For atmospheric sulfuric acid (SA) concentrations the presence of dimethylamine (DMA) at mixing ratios of several parts per trillion by volume can explain observed boundary layer new particle formation rates. However, the concentration and molecular composition of the neutral (uncharged) clusters have not been reported so far due to the lack of suitable instrumentation. Here we report on experiments from the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research revealing the formation of neutral particles containing up to 14 SA and 16 DMA molecules, corresponding to a mobility diameter of about 2 nm, under atmospherically relevant conditions. These measurements bridge the gap between the molecular and particle perspectives of nucleation, revealing the fundamental processes involved in particle formation and growth. The neutral clusters are found to form at or close to the kinetic limit where particle formation is limited only by the collision rate of SA molecules. Even tho...

Iron-niobium-aluminum alloy having high-temperature corrosion resistance

Science.gov (United States)

Hsu, Huey S.

1988-04-14

An alloy for use in high temperature sulfur and oxygen containing environments, having aluminum for oxygen resistance, niobium for sulfur resistance and the balance iron, is discussed. 4 figs., 2 tabs.

Heme metabolism as an integral part of iron homeostasis

Directory of Open Access Journals (Sweden)

Paweł Lipiński

2014-01-01

Full Text Available Heme, a ferrous iron protoporphyrin IX complex, is employed as a prosthetic group in a number of diverse heme proteins that participate in important cellular and systemic physiological processes. Provision of an adequate amount of iron for heme biosynthesis is one of the elemental hallmarks of intracellular iron homeostasis. In the cell the bioavailability of iron for the two main iron biological pathways – heme synthesis and the biogenesis of iron-sulfur clusters ([Fe-S] – is mainly regulated by the IRP/IRE posttranscriptional system. The biogenesis of [Fe-S] centers is crucial for heme synthesis because these co-factors determine the activity of IRP1 and that of ferrochelatase, an enzyme responsible for the insertion of an iron into protoporphyrin IX to produce heme. On the other hand, delivery of iron for heme and hemoglobin synthesis in erythroblasts, precursors of erythrocytes in bone marrow, is an indispensable element of body iron homeostasis. This process relies on the recovery of iron from senescent red blood cells through the enzymatic degradation of heme molecules and recycling of iron to the circulation. Molecular coordination of these processes involves the activity of heme oxygenase 1, IRP1 and IRP2 as well as the functioning of the hepcidin-ferroportin regulatory axis. Recent studies show in mammals the existence of an expanded system of proteins involved in the transport of intact heme molecules at the cellular and systemic levels. The biological role of this system is of particular importance when the concentration of free heme reaches a toxic level in the body (intravascular hemolysis as well as locally in cells having intensive heme metabolism such as erythroblasts and macrophages.

[Heme metabolism as an integral part of iron homeostasis].

Science.gov (United States)

Lipiński, Paweł; Starzyński, Rafał R; Styś, Agnieszka; Gajowiak, Anna; Staroń, Robert

2014-01-02

Heme, a ferrous iron protoporphyrin IX complex, is employed as a prosthetic group in a number of diverse heme proteins that participate in important cellular and systemic physiological processes. Provision of an adequate amount of iron for heme biosynthesis is one of the elemental hallmarks of intracellular iron homeostasis. In the cell the bioavailability of iron for the two main iron biological pathways--heme synthesis and the biogenesis of iron-sulfur clusters ([Fe-S])--is mainly regulated by the IRP/IRE posttranscriptional system. The biogenesis of [Fe-S] centers is crucial for heme synthesis because these co-factors determine the activity of IRP1 and that of ferrochelatase, an enzyme responsible for the insertion of an iron into protoporphyrin IX to produce heme. On the other hand, delivery of iron for heme and hemoglobin synthesis in erythroblasts, precursors of erythrocytes in bone marrow, is an indispensable element of body iron homeostasis. This process relies on the recovery of iron from senescent red blood cells through the enzymatic degradation of heme molecules and recycling of iron to the circulation. Molecular coordination of these processes involves the activity of heme oxygenase 1, IRP1 and IRP2 as well as the functioning of the hepcidin-ferroportin regulatory axis. Recent studies show in mammals the existence of an expanded system of proteins involved in the transport of intact heme molecules at the cellular and systemic levels. The biological role of this system is of particular importance when the concentration of free heme reaches a toxic level in the body (intravascular hemolysis) as well as locally in cells having intensive heme metabolism such as erythroblasts and macrophages.

Experimental Investigation of Sulfuric Acid Condensation and Corrosion Rate in Motored Bukh DV24 Diesel Engine

DEFF Research Database (Denmark)

Kjemtrup, Lars; Cordtz, Rasmus Faurskov; Meyer, Martin

2017-01-01

The work conducted in this paper presents a novel experimental setup to study sulfuric acid cold corrosion of cylinder liners in large two-stroke marine diesel engines. The process is simulated in a motored light duty BUKH DV24 diesel engine where the charge air contain known amounts of H2SO4 and H......2O vapor. Liner corrosion is measured as iron accumulation in the lubeoil. Similarly sulfuric acid condensation is assessed by measuring the accumulation of sulfur in the lube oil. To clarify the corrosive effect of sulfuric acid the lube oil utilized for experiments is a sulfur free neutral oil...... without alkaline additives (Chevron Neutral Oil 600R). Iron and sulfur accumulation in the lube oil is analyzed withan Energy Dispersive X-Ray Fluorescence (ED-XRF) apparatus. Three test cases with different H2SO4 concentrations are run. Results reveal good agreement between sulfuric acid injection flow...

Photoelectron spectroscopy and density functional theory studies of (FeS)mH- (m = 2-4) cluster anions: effects of the single hydrogen.

Science.gov (United States)

Yin, Shi; Bernstein, Elliot R

2017-12-20

Single hydrogen containing iron hydrosulfide cluster anions (FeS) m H - (m = 2-4) are studied by photoelectron spectroscopy (PES) at 3.492 eV (355 nm) and 4.661 eV (266 nm) photon energies, and by Density Functional Theory (DFT) calculations. The structural properties, relative energies of different spin states and isomers, and the first calculated vertical detachment energies (VDEs) of different spin states for these (FeS) m H - (m = 2-4) cluster anions are investigated at various reasonable theory levels. Two types of structural isomers are found for these (FeS) m H - (m = 2-4) clusters: (1) the single hydrogen atom bonds to a sulfur site (SH-type); and (2) the single hydrogen atom bonds to an iron site (FeH-type). Experimental and theoretical results suggest such available different SH- and FeH-type structural isomers should be considered when evaluating the properties and behavior of these single hydrogen containing iron sulfide clusters in real chemical and biological systems. Compared to their related, respective pure iron sulfur (FeS) m - clusters, the first VDE trend of the diverse type (FeS) m H 0,1 - (m = 1-4) clusters can be understood through (1) the different electron distribution properties of their highest singly occupied molecular orbital employing natural bond orbital analysis (NBO/HSOMO), and (2) the partial charge distribution on the NBO/HSOMO localized sites of each cluster anion. Generally, the properties of the NBO/HSOMOs play the principal role with regard to the physical and chemical properties of all the anions. The change of cluster VDE from low to high is associated with the change in nature of their NBO/HSOMO from a dipole bound and valence electron mixed character, to a valence p orbital on S, to a valence d orbital on Fe, and to a valence p orbital on Fe or an Fe-Fe delocalized valence bonding orbital. For clusters having the same properties for NBO/HSOMOs, the partial charge distributions at the NBO/HSOMO localized sites additionally

Plasmon waveguide resonance spectroscopic evidence for differential binding of oxidized and reduced rhodobacter capsulatus cytochrome c(2) to the cytochrome bc(1) complex mediated by the conformation of the rieske iron-sulfur protein

International Nuclear Information System (INIS)

Devanathan, S.; Salamon, Z.; Tollin, G.; Fitch, J.C.; Meyer, T.E.; Berry, E.A.; Cusanovich, M.A.

2007-01-01

The dissociation constants for the binding of Rhodobacter capsulatus cytochrome c2 and its K93P mutant to the cytochrome bc1 complex embedded in a phospholipid bilayer were measured by plasmon waveguide resonance spectroscopy in the presence and absence of the inhibitor stigmatellin. The reduced form of cytochrome c2 strongly binds to reduced cytochrome bc1 (Kd = 0.02 M) but binds much more weakly to the oxidized form (Kd = 3.1 M). In contrast, oxidized cytochrome c2 binds to oxidized cytochrome bc1 in a biphasic fashion with Kd values of 0.11 and 0.58 M. Such a biphasic interaction is consistent with binding to two separate sites or conformations of oxidized cytochrome c2 and/or cytochrome bc1. However, in the presence of stigmatellin, we find that oxidized cytochrome c2 binds to oxidized cytochrome bc1 in a monophasic fashion with high affinity (Kd = 0.06 M) and reduced cytochrome c2 binds less strongly (Kd = 0.11 M) but ∼30-fold more tightly than in the absence of stigmatellin. Structural studies with cytochrome bc1, with and without the inhibitor stigmatellin, have led to the proposal that the Rieske protein is mobile, moving between the cytochrome b and cytochrome c1 components during turnover. In one conformation, the Rieske protein binds near the heme of cytochrome c1, while the cytochrome c2 binding site is also near the cytochrome c1 heme but on the opposite side from the Rieske site, where cytochrome c2 cannot directly interact with Rieske. However, the inhibitor, stigmatellin, freezes the Rieske protein iron-sulfur cluster in a conformation proximal to cytochrome b and distal to cytochrome c1. We conclude from this that the dual conformation of the Rieske protein is primarily responsible for biphasic binding of oxidized cytochrome c2 to cytochrome c1. This optimizes turnover by maximizing binding of the substrate, oxidized cytochrome c2, when the iron-sulfur cluster is proximal to cytochrome b and minimizing binding of the product, reduced cytochrome c

Stabilization of sulfuric acid dimers by ammonia, methylamine, dimethylamine, and trimethylamine

Science.gov (United States)

Jen, Coty N.; McMurry, Peter H.; Hanson, David R.

2014-06-01

This study experimentally explores how ammonia (NH3), methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA) affect the chemical formation mechanisms of electrically neutral clusters that contain two sulfuric acid molecules (dimers). Dimers may also contain undetectable compounds, such as water or bases, that evaporate upon ionization and sampling. Measurements were conducted using a glass flow reactor which contained a steady flow of humidified nitrogen with sulfuric acid concentrations of 107 to 109 cm-3. A known molar flow rate of a basic gas was injected into the flow reactor. The University of Minnesota Cluster Chemical Ionization Mass Spectrometer was used to measure the resulting sulfuric acid vapor and cluster concentrations. It was found that, for a given concentration of sulfuric acid vapor, the dimer concentration increases with increasing concentration of the basic gas, eventually reaching a plateau. The base concentrations at which the dimer concentrations saturate suggest NH3 heuristic models for cluster formation by acid-base reactions are developed to interpret the data. The models provide ranges of evaporation rate constants that are consistent with observations and leads to an analytic expression for nucleation rates that is consistent with atmospheric observations.

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

Measurements of the gas temperature and iron abundance distribution in the Coma Cluster

International Nuclear Information System (INIS)

Hughes, J.P.; Gorenstein, P.; Fabricant, D.

1988-01-01

The medium energy X-ray detectors onboard the EXOSAT Observatory have been used to determine the gas temperature at several positions in the Coma Cluster of galaxies. Evidence is found at greater than 95 percent confidence for a higher temperature in the center of the cluster than in a position approximately 45 arcmin off-center. No difference in iron abundance is observed between the center and off-center regions and the equilibrium model for the distribution of elements in the Coma Cluster of Abramopoulos, Chanan, and Ku can be rejected with greater than 99.5 percent confidence, in favor of a model with more uniform composition. A phenomenological model is presented of the Coma Cluster, which is consistent with the data presented here, as well as the imaging data from the Einstein Observatory and the Tenma X-ray spectrum. The model has a central isothermal region of temperature about 9 keV extending to about 25 arcmin (about 1 Mpc). Beyond this radius the temperature falls as a polytrope with index about 1.6. 36 references

Observations concerning the quinol oxidation site of the cytochrome bc{sub 1} complex

Energy Technology Data Exchange (ETDEWEB)

Berry, Edward A.; Huang, Li-Shar

2003-09-07

A direct hydrogen bond between ubiquinone/quinol bound at the QO site and a cluster-ligand histidine of the iron-sulfur protein (ISP) is described as a major determining factor explaining much experimental data on position of the ISP ectodomain, EPR lineshape and midpoint potential of the iron-sulfur cluster, and the mechanism of the bifurcated electron transfer from ubiquinol to the high and low potential chains of the bc1 complex.

Role of sulfate reduction in long term accumulation of organic and inorganic sulfur in lake sediments

International Nuclear Information System (INIS)

Rudd, J.W.M.; Kelly, C.A.; Furutani, A.

1986-01-01

Sulfate reduction and the accumulation of reduced sulfur in epilimnetic sediments were studied in lakes in southern Norway, the Adirondack Mountains, and at the Experimental Lakes Area (ELA) of northwestern Ontario. In all of the lakes, sulfate reduction produced substantial quantities of pyrite and organic sulfur compounds. In 9-month in situ experiments at ELA using 35 S, there was a large loss (55%) with time of the S initially reduced and deposited in the sediments and a preferential loss of inorganic S compounds which led to a predominance of organic 35 S accumulation in the sediments. An intensive study of long term accumulation of sulfur in the epilimnetic sediments of four Adirondack lakes also showed that the most important long term end product of sulfate reduction was organic S and that sulfate reduction was the major source of S to the sediments. Because of high concentrations of iron in all of the sediments samples and because of the long term storage of sulfur in sediments, mostly as organic S, iron did not limit iron sulfide accumulation in these sediments. Iron limitation is unlikely to occur except in unusual circumstances. This study indicates that formation of organic S in epilimnetic sediments is primarily responsible for H + consumption via sulfate reduction in acidified lakes

Neuronal Networks on Nanocellulose Scaffolds.

Science.gov (United States)

Jonsson, Malin; Brackmann, Christian; Puchades, Maja; Brattås, Karoline; Ewing, Andrew; Gatenholm, Paul; Enejder, Annika

2015-11-01

Proliferation, integration, and neurite extension of PC12 cells, a widely used culture model for cholinergic neurons, were studied in nanocellulose scaffolds biosynthesized by Gluconacetobacter xylinus to allow a three-dimensional (3D) extension of neurites better mimicking neuronal networks in tissue. The interaction with control scaffolds was compared with cationized nanocellulose (trimethyl ammonium betahydroxy propyl [TMAHP] cellulose) to investigate the impact of surface charges on the cell interaction mechanisms. Furthermore, coatings with extracellular matrix proteins (collagen, fibronectin, and laminin) were investigated to determine the importance of integrin-mediated cell attachment. Cell proliferation was evaluated by a cellular proliferation assay, while cell integration and neurite propagation were studied by simultaneous label-free Coherent anti-Stokes Raman Scattering and second harmonic generation microscopy, providing 3D images of PC12 cells and arrangement of nanocellulose fibrils, respectively. Cell attachment and proliferation were enhanced by TMAHP modification, but not by protein coating. Protein coating instead promoted active interaction between the cells and the scaffold, hence lateral cell migration and integration. Irrespective of surface modification, deepest cell integration measured was one to two cell layers, whereas neurites have a capacity to integrate deeper than the cell bodies in the scaffold due to their fine dimensions and amoeba-like migration pattern. Neurites with lengths of >50 μm were observed, successfully connecting individual cells and cell clusters. In conclusion, TMAHP-modified nanocellulose scaffolds promote initial cellular scaffold adhesion, which combined with additional cell-scaffold treatments enables further formation of 3D neuronal networks.

Selective Sulfidation of Lead Smelter Slag with Sulfur

Science.gov (United States)

Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Qin, Wenqing

2016-02-01

The selective sulfidation of lead smelter slag with sulfur was studied. The effects of temperature, sulfur dosage, carbon, and Na salts additions were investigated based on thermodynamic calculation. The results indicated that more than 96 pct of zinc in the slag could be converted into sulfides. Increasing temperature, sulfur dosage, or Na salts dosage was conducive to the sulfidation of the zinc oxides in the slag. High temperature and excess Na salts would result in the more consumption of carbon and sulfur. Carbon addition not only promoted the selective sulfidation but reduced the sulfur dosage and eliminated the generation of SO2. Iron oxides had a buffering role on the sulfur efficient utilization. The transformation of sphalerite to wurtzite was feasible under reducing condition at high temperature, especially above 1273 K (1000 °C). The growth of ZnS particles largely depended upon the roasting temperature. They were significantly increased when the temperature was above 1273 K (1000 °C), which was attributed to the formation of a liquid phase.

Studying disorders of vertebrate iron and heme metabolism using zebrafish.

Science.gov (United States)

van der Vorm, Lisa N; Paw, Barry H

2017-01-01

Iron is a crucial component of heme- and iron-sulfur clusters, involved in vital cellular functions such as oxygen transport, DNA synthesis, and respiration. Both excess and insufficient levels of iron and heme-precursors cause human disease, such as iron-deficiency anemia, hemochromatosis, and porphyrias. Hence, their levels must be tightly regulated, requiring a complex network of transporters and feedback mechanisms. The use of zebrafish to study these pathways and the underlying genetics offers many advantages, among others their optical transparency, ex-vivo development and high genetic and physiological conservations. This chapter first reviews well-established methods, such as large-scale mutagenesis screens that have led to the initial identification of a series of iron and heme transporters and the generation of a variety of mutant lines. Other widely used techniques are based on injection of RNA, including complementary morpholino knockdown and gene overexpression. In addition, we highlight several recently developed approaches, most notably endonuclease-based gene knockouts such as TALENs or the CRISPR/Cas9 system that have been used to study how loss of function can induce human disease phenocopies in zebrafish. Rescue by chemical complementation with iron-based compounds or small molecules can subsequently be used to confirm causality of the genetic defect for the observed phenotype. All together, zebrafish have proven to be - and will continue to serve as an ideal model to advance our understanding of the pathogenesis of human iron and heme-related diseases and to develop novel therapies to treat these conditions. Copyright © 2017 Elsevier Inc. All rights reserved.

Molecular clusters of 3D and lower magnetic dimensionality

International Nuclear Information System (INIS)

Papaefthymiou, G.C

1991-01-01

Controlled polymerization of iron leads to the synthesis of molecular clusters of ever-increasing size, tending to extended structures. Polymerization of oxo-bridged octahedrally coordinated iron leads to clusters with 3D magnetic interactions between iron ions, while sulfide- and selenide-bridged tetrahedrally coordinated iron ions produce clusters of lower magnetic dimensionality. In this paper the magnetic properties of the resulting large molecular clusters with N ≥ 17 (where N = the number of iron ions in the cluster) are investigated for the presence of collective magnetic correlations associated with the solid state

Mass-selected iron-cobalt alloy clusters. Correlation of magnetic and structural properties; Massenselektierte Eisen-Kobalt-Legierungscluster. Korrelation magnetischer und struktureller Eigenschaften

Energy Technology Data Exchange (ETDEWEB)

Bulut, Furkan

2008-10-13

In this work, I present results concerning structural and magnetic properties of massselected iron-cobalt alloy clusters with diameters between 5 and 15 nm. I have studied the structure of FeCo alloy clusters with high resolution transmission electron microscopy (HRTEM) and scanning tunneling microscopy (STM). I have also investigated the crystalline structure of pure iron and pure cobalt clusters with HRTEM to ensure a reliable determination of the lattice parameter for the alloy clusters. The FeCo nanoparticles have a truncated dodecahedral shape with a CsCl-structure. The clusters were produced with a continuously working arc cluster ion source and subsequently mass-selected with an electrostatic quadrupole deflector. The composition of the alloy clusters was checked with energy dispersive x-ray spectroscopy (EDX). The lateral size distribution was investigated by TEM and the height of the deposited FeCo clusters on the (110) surface of tungsten was determined by STM. Comparing the results I have observed that the supported clusters were flattened due to the high surface energy of W(110). The decrease in height of the mass-selected supported clusters amounts to about 1 nm. Furthermore, element specific magnetic studies performed by means of X-ray magnetic circular dichroism (XMCD) have shown that magnetic moments of Fe{sub 50}Co{sub 50} alloy clusters are in good agreement with the theoretically expected values in the bulk. I have also examined the behavior of the alloy clusters at elevated temperatures. The clusters exhibit an anisotropic melting on the W(110) surface. (orig.)

Isolation and characterization of the small subunit of the uptake hydrogenase from the cyanobacterium Nostoc punctiforme.

Science.gov (United States)

Raleiras, Patrícia; Kellers, Petra; Lindblad, Peter; Styring, Stenbjörn; Magnuson, Ann

2013-06-21

In nitrogen-fixing cyanobacteria, hydrogen evolution is associated with hydrogenases and nitrogenase, making these enzymes interesting targets for genetic engineering aimed at increased hydrogen production. Nostoc punctiforme ATCC 29133 is a filamentous cyanobacterium that expresses the uptake hydrogenase HupSL in heterocysts under nitrogen-fixing conditions. Little is known about the structural and biophysical properties of HupSL. The small subunit, HupS, has been postulated to contain three iron-sulfur clusters, but the details regarding their nature have been unclear due to unusual cluster binding motifs in the amino acid sequence. We now report the cloning and heterologous expression of Nostoc punctiforme HupS as a fusion protein, f-HupS. We have characterized the anaerobically purified protein by UV-visible and EPR spectroscopies. Our results show that f-HupS contains three iron-sulfur clusters. UV-visible absorption of f-HupS has bands ∼340 and 420 nm, typical for iron-sulfur clusters. The EPR spectrum of the oxidized f-HupS shows a narrow g = 2.023 resonance, characteristic of a low-spin (S = ½) [3Fe-4S] cluster. The reduced f-HupS presents complex EPR spectra with overlapping resonances centered on g = 1.94, g = 1.91, and g = 1.88, typical of low-spin (S = ½) [4Fe-4S] clusters. Analysis of the spectroscopic data allowed us to distinguish between two species attributable to two distinct [4Fe-4S] clusters, in addition to the [3Fe-4S] cluster. This indicates that f-HupS binds [4Fe-4S] clusters despite the presence of unusual coordinating amino acids. Furthermore, our expression and purification of what seems to be an intact HupS protein allows future studies on the significance of ligand nature on redox properties of the iron-sulfur clusters of HupS.

The crystal structure of TrxA(CACA): Insights into the formation of a [2Fe-2S] iron–sulfur cluster in an Escherichia coli thioredoxin mutant

Science.gov (United States)

Collet, Jean-Francois; Peisach, Daniel; Bardwell, James C.A.; Xu, Zhaohui

2005-01-01

Escherichia coli thioredoxin is a small monomeric protein that reduces disulfide bonds in cytoplasmic proteins. Two cysteine residues present in a conserved CGPC motif are essential for this activity. Recently, we identified mutations of this motif that changed thioredoxin into a homodimer bridged by a [2Fe-2S] iron–sulfur cluster. When exported to the periplasm, these thioredoxin mutants could restore disulfide bond formation in strains lacking the entire periplasmic oxidative pathway. Essential for the assembly of the iron–sulfur was an additional cysteine that replaced the proline at position three of the CGPC motif. We solved the crystalline structure at 2.3 Å for one of these variants, TrxA(CACA). The mutant protein crystallized as a dimer in which the iron–sulfur cluster is replaced by two intermolecular disulfide bonds. The catalytic site, which forms the dimer interface, crystallized in two different conformations. In one of them, the replacement of the CGPC motif by CACA has a dramatic effect on the structure and causes the unraveling of an extended α-helix. In both conformations, the second cysteine residue of the CACA motif is surface-exposed, which contrasts with wildtype thioredoxin where the second cysteine of the CXXC motif is buried. This exposure of a pair of vicinal cysteine residues apparently allows thioredoxin to acquire an iron–sulfur cofactor at its active site, and thus a new activity and mechanism of action. PMID:15987909

Iron and sulfur geochemistry in semi-arid mangrove soils (Ceará, Brazil) in relation to seasonal changes and shrimp farming effluents.

Science.gov (United States)

Nóbrega, G N; Ferreira, T O; Romero, R E; Marques, A G B; Otero, X L

2013-09-01

Iron and sulfur are key elements in the biogeochemistry of estuarine soils, in which Fe and sulfate reduction (SR) pathways are important for organic matter decomposition. In the semi-arid coast of NE Brazil, mangroves are characterized by large seasonal variations in weather and the presence of numerous shrimp farms. The objective was to determine the impacts of shrimp farm effluents on iron and sulfur geochemistry in mangrove soils under the semi-arid climate of NE Brazil. A seasonal study was made of two mangrove forest soils (SF, a mangrove forest that directly receives wastewater from shrimp ponds and CS, a control site). Pyrite Fe, oxyhydroxides Fe, acid volatile sulfide, degree of pyritization (DOP), pH, Eh, total organic carbon (TOC) and total S were determined. There was a clear decrease in pyritic Fe and DOP in the SF soils, which may be related to the anaerobic oxidation of pyrite coupled with nitrate reduction, or to the dominance of denitrification over SR. Lower TOC contents in the SF site suggest that below ground decomposition increased in response to eutrophication. The seasonal variations led to important changes in the semi-arid mangrove soils. During the dry period, both soils experienced oxidizing conditions with remarkable loss of reduced and oxidized forms of Fe, which may have important environmental implications as Fe is biolimiting for marine primary production. The data show that both factors (seasonal weather variations and shrimp effluents) play important roles in the geochemical processes that occur in these soils and, thus, may affect their functioning and maintenance.

HYBRID SULFUR RECOVERY PROCESS FOR NATURAL GAS UPGRADING

International Nuclear Information System (INIS)

Girish Srinivas; Steven C. Gebhard; David W. DeBerry

2001-01-01

This first quarter report of 2001 describes progress on a project funded by the U.S. Department of Energy (DOE) to test a hybrid sulfur recovery process for natural gas upgrading. The process concept represents a low cost option for direct treatment of natural gas streams to remove H(sub 2)S in quantities equivalent to 0.2-25 metric tons (LT) of sulfur per day. This process is projected to have lower capital and operating costs than the competing technologies, amine/aqueous iron liquid redox and amine/Claus/tail gas treating, and have a smaller plant footprint, making it well suited to both on-shore and offshore applications. CrystaSulf(trademark) (service mark of Gas Research Institute) is a new nonaqueous sulfur recovery process that removes hydrogen sulfide (H(sub 2)S) from gas streams and converts it into elemental sulfur. CrystaSulf features high sulfur recovery similar to aqueous-iron liquid redox sulfur recovery processes, but differs from the aqueous processes in that CrystaSulf controls the location where elemental sulfur particles are formed. In the hybrid process, approximately 1/3 of the total H(sub 2)S in the natural gas is first oxidized to SO(sub 2) at low temperatures over a heterogeneous catalyst. Low temperature oxidation is done so that the H(sub 2)S can be oxidized in the presence of methane and other hydrocarbons without oxidation of the hydrocarbons. The project involves the development of a catalyst using laboratory/bench-scale catalyst testing, and then demonstration of the catalyst at CrystaTech's pilot plant in west Texas. During this reporting periods new catalyst formulations were tested. The experiments showed that the newest catalyst has slightly better performance, but catalyst TDA No.2 is still superior overall for use with the hybrid CrystaSulf process due to lower costs. Plans for catalyst pelletization and continued testing are described

THERMODYNAMICS AND CHARGING OF INTERSTELLAR IRON NANOPARTICLES

Energy Technology Data Exchange (ETDEWEB)

Hensley, Brandon S. [Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109 (United States); Draine, B. T., E-mail: brandon.s.hensley@jpl.nasa.gov [Department of Astrophysical Sciences, Princeton University, Princeton, NJ 08544 (United States)

2017-01-10

Interstellar iron in the form of metallic iron nanoparticles may constitute a component of the interstellar dust. We compute the stability of iron nanoparticles to sublimation in the interstellar radiation field, finding that iron clusters can persist down to a radius of ≃4.5 Å, and perhaps smaller. We employ laboratory data on small iron clusters to compute the photoelectric yields as a function of grain size and the resulting grain charge distribution in various interstellar environments, finding that iron nanoparticles can acquire negative charges, particularly in regions with high gas temperatures and ionization fractions. If ≳10% of the interstellar iron is in the form of ultrasmall iron clusters, the photoelectric heating rate from dust may be increased by up to tens of percent relative to dust models with only carbonaceous and silicate grains.

Microbial iron management mechanisms in extremely acidic environments: comparative genomics evidence for diversity and versatility

Directory of Open Access Journals (Sweden)

Nieto Pamela A

2008-11-01

uptake systems could reflect their obligatory occupation of extremely low pH environments where high concentrations of soluble iron may always be available and were oxidized sulfur species might not compromise iron speciation dynamics. Presence of bacterioferritin in the Acidithiobacilli, polyphosphate accumulation functions and variants of FieF-like diffusion facilitators in both Acidithiobacilli and Leptospirilla, indicate that they may remove or store iron under conditions of variable availability. In addition, the Fe(II-oxidizing capacity of both A. ferrooxidans and Leptospirilla could itself be a way to evade iron stress imposed by readily available Fe(II ions at low pH. Fur regulatory sites have been predicted for a number of gene clusters including iron related and non-iron related functions in both the Acidithiobacilli and Leptospirilla, laying the foundation for the future discovery of iron regulated and iron-phosphate coordinated regulatory control circuits. Conclusion In silico analyses of the genomes of acidophilic bacteria are beginning to tease apart the mechanisms that mediate iron uptake and homeostasis in low pH environments. Initial models pinpoint significant differences in abundance and diversity of iron management mechanisms between Leptospirilla and Acidithiobacilli, and begin to reveal how these two groups respond to iron cycling and iron fluctuations in naturally acidic environments and in industrial operations. Niche partitions and ecological successions between acidophilic microorganisms may be partially explained by these observed differences. Models derived from these analyses pave the way for improved hypothesis testing and well directed experimental investigation. In addition, aspects of these models should challenge investigators to evaluate alternative iron management strategies in non-acidophilic model organisms.

Using self-consistent Gibbs free energy surfaces to calculate size distributions of neutral and charged clusters for the sulfuric acid-water binary system

Science.gov (United States)

Smith, J. A.; Froyd, K. D.; Toon, O. B.

2012-12-01

We construct tables of reaction enthalpies and entropies for the association reactions involving sulfuric acid vapor, water vapor, and the bisulfate ion. These tables are created from experimental measurements and quantum chemical calculations for molecular clusters and a classical thermodynamic model for larger clusters. These initial tables are not thermodynamically consistent. For example, the Gibbs free energy of associating a cluster consisting of one acid molecule and two water molecules depends on the order in which the cluster was assembled: add two waters and then the acid or add an acid and a water and then the second water. We adjust the values within the tables using the method of Lagrange multipliers to minimize the adjustments and produce self-consistent Gibbs free energy surfaces for the neutral clusters and the charged clusters. With the self-consistent Gibbs free energy surfaces, we calculate size distributions of neutral and charged clusters for a variety of atmospheric conditions. Depending on the conditions, nucleation can be dominated by growth along the neutral channel or growth along the ion channel followed by ion-ion recombination.

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

Science.gov (United States)

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

1999-05-03

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

Energetics of formation and migration of self-interstitials and self-interstitial clusters in α-iron

International Nuclear Information System (INIS)

Wirth, B.D.; Odette, G.R.; California Univ., Santa Barbara, CA; Maroudas, D.; Lucas, G.E.; California Univ., Santa Barbara, CA

1997-01-01

Energetic primary recoil atoms from fast neutron irradiation generate both isolated point defects and clusters of vacancies and interstitials. Self-interstitial mobility as well as defect cluster stability and mobility play key roles in the subsequent fate of defects and, hence, in the overall microstructural evolution under irradiation. Self-interstitials and two, three and four-member self-interstitial clusters are highly mobile at low temperatures as observed in molecular-dynamics simulations and high mobility probably also extends to larger clusters. In this study, the morphology, energetics and mobility of self-interstitials and small self-interstitial clusters in α-iron are studied by molecular-statics and molecular-dynamics simulations using a Finnis-Sinclair many-body interatomic potential. Self-interstitial migration is found to be a two-step process consisting of a rotation out of the split-dumbbell configuration into the split-dumbbell configuration and translational jumps through the crowdion configuration before returning to the dumbbell configuration. Self-interstitial clusters of type split-interstitials assembled on adjacent {110} planes migrate along directions in an amoeba-like fashion by sequential local dissociation and re-association processes. (orig.)

The Application of Stable Isotopes for Assessing the Hydrological, Sulfur, and Iron Balances of Acidic Mining Lake ML 111 (Lusatia, Germany) as a Basis for Biotechnological Remediation

International Nuclear Information System (INIS)

Knoeller, K.; Strauch, G.

2002-01-01

Stable isotope (δ 18 O-H 2 O, δ 2 H-H 2 O δ 34 S-SO 4 2- ) and hydrochemical data (SO 4 2- , Fe-concentrations) have been used to estimate the annual groundwater inflow and outflow of mining lake ML 111 and to calculate the total amount of dissolved sulfate and iron that is carried into the lake by groundwater. The hydrological balance suggests an annual groundwater inflow of 23 700 m 3 and an annual groundwater outflow of 15 700 m 3 . The calculation of the sulfur and iron balances yielded an annual sulfate input of 37 800 kg and an annual iron input of 7000 kg with the groundwater inflow. Furthermore it was shown that significant fluxes of these elements go into the lake sediments which results in continuous release of acidity in the lake water

Effect of sulfur addition and heat treatment on electrical conductivity of barium vanadate glasses containing iron

Energy Technology Data Exchange (ETDEWEB)

Hassaan, M.Y., E-mail: myhassaan@yahoo.com [Al-Azhar University, Faculty of Science, Physics Department, 11884 Cairo (Egypt); Ebrahim, F.M.; Mostafa, A.G. [Al-Azhar University, Faculty of Science, Physics Department, 11884 Cairo (Egypt); El-Desoky, M.M., E-mail: mmdesoky@gmail.com [Suez Canal University, Faculty of Science, Physics Department, Suez (Egypt)

2011-09-15

Highlights: {yields} Selected glasses of V{sub 2}O{sub 5}-BaO-5Fe{sub 2}O{sub 3} system have been transformed into nanomaterials by annealing at temperature close to crystallization temperature (T{sub c}) for 1 h. {yields} Glass ceramic nanocrystals are important because of their physical properties which are not obtainable in other classes of materials. {yields} Crystal and grain sizes are the most significant structural parameters in electronic nanocrystalline glassy phases. {yields} These phases have very high electrical conductivity, hence glass-ceramic nanocrystals are expected to be used, for example, as a gas sensor. - Abstract: Six glass samples with a composition of 75V{sub 2}O{sub 5} + 10BaO + 15Fe{sub 2}O{sub 3} mol%, with 0, 10, 15, 20, and 25 wt% of sulfur were prepared by using a quenching method. The samples were measured by XRD, DSC, TEM, Moessbauer spectrometry and D.C. conductivity. The prepared samples were heat treated at temperature close to their crystallization temperatures for 1 h, and then the previous measurements were repeated. The results showed that the treatment process caused the formation of V{sub 2}O{sub 5} and FeVO{sub 4} nanocrystals with size of 17-25 nm dispersed in the glass matrix. The addition of sulfur reduced only the vanadium ions to V{sup 4+}, while it was found that iron ions were Fe{sup 3+} only. D.C. conduction enhanced due to the small polaron or electron hopping from V{sup 4+} to V{sup 5+} ions. The heat treated samples exhibit much higher conductivity and much lower activation energy than the as-prepared glasses. The heat treated samples showed decreased thermal stability with the addition of sulfur. This considerable enhancement of electrical conductivity after nanocrystallization referred to the formation of extensive and dense network of electronic conduction paths which are situated between V{sub 2}O{sub 5} nanocrystals and their surfaces.

Embroidered polymer-collagen hybrid scaffold variants for ligament tissue engineering.

Science.gov (United States)

Hoyer, M; Drechsel, N; Meyer, M; Meier, C; Hinüber, C; Breier, A; Hahner, J; Heinrich, G; Rentsch, C; Garbe, L-A; Ertel, W; Schulze-Tanzil, G; Lohan, A

2014-10-01

Embroidery techniques and patterns used for scaffold production allow the adaption of biomechanical scaffold properties. The integration of collagen into embroidered polylactide-co-caprolactone [P(LA-CL)] and polydioxanone (PDS) scaffolds could stimulate neo-tissue formation by anterior cruciate ligament (ACL) cells. Therefore, the aim of this study was to test embroidered P(LA-CL) and PDS scaffolds as hybrid scaffolds in combination with collagen hydrogel, sponge or foam for ligament tissue engineering. ACL cells were cultured on embroidered P(LA-CL) and PDS scaffolds without or with collagen supplementation. Cell adherence, vitality, morphology and ECM synthesis were analyzed. Irrespective of thread size, ACL cells seeded on P(LA-CL) scaffolds without collagen adhered and spread over the threads, whereas the cells formed clusters on PDS and larger areas remained cell-free. Using the collagen hydrogel, the scaffold colonization was limited by the gel instability. The collagen sponge layers integrated into the scaffolds were hardly penetrated by the cells. Collagen foams increased scaffold colonization in P(LA-CL) but did not facilitate direct cell-thread contacts in the PDS scaffolds. The results suggest embroidered P(LA-CL) scaffolds as a more promising basis for tissue engineering an ACL substitute than PDS due to superior cell attachment. Supplementation with a collagen foam presents a promising functionalization strategy. Copyright © 2014 Elsevier B.V. All rights reserved.

Redox transformations of iron at extremely low pH: fundamental and applied aspects

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D. Barrie eJohnson

2012-03-01

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

The role of ammonia in sulfuric acid ion induced nucleation

Directory of Open Access Journals (Sweden)

I. K. Ortega

2008-06-01

Full Text Available We have developed a new multi-step strategy for quantum chemical calculations on atmospherically relevant cluster structures that makes calculation for large clusters affordable with a good accuracy-to-computational effort ratio. We have applied this strategy to evaluate the relevance of ternary ion induced nucleation; we have also performed calculations for neutral ternary nucleation for comparison. The results for neutral ternary nucleation agree with previous results, and confirm the important role of ammonia in enhancing the growth of sulfuric acid clusters. On the other hand, we have found that ammonia does not enhance the growth of ionic sulfuric acid clusters. The results also confirm that ion-induced nucleation is a barrierless process at high altitudes, but at ground level there exists a barrier due to the presence of a local minimum on the free energy surface.

Hunger for iron: the alternative siderophore iron scavenging systems in highly virulent Yersinia.

Directory of Open Access Journals (Sweden)

Alexander eRakin

2012-11-01

Full Text Available Low molecular weight siderophores are used by many living organisms to scavenge scarcely available ferric iron. Presence of at least a single siderophore-based iron acquisition system is usually acknowledged as a virulence-associated trait and a prerequisite to become an efficient and successful pathogen. Currently it is assumed that yersiniabactin (Ybt is the solely functional endogenous siderophore iron uptake system in highly virulent Yersinia (Yersinia pestis, Y. pseudotuberculosis and Y. enterocolitica biotype 1B. Genes responsible for biosynthesis, transport and regulation of the yersiniabactin (ybt production are clustered on a mobile genetic element, the High Pathogenicity Island (HPI that is responsible for broad dissemination of the ybt genes in Enterobacteriaceae. However, the ybt gene cluster is absent from nearly half of Y. pseudotuberculosis O3 isolates and epidemic Y. pseudotuberculosis O1 isolates responsible for the Far East Scarlet-like Fever. Several potential siderophore-mediated iron uptake gene clusters are documented in Yersinia genomes, however neither of them have been proven to be functional. It has been suggested that at least two siderophores alternative to Ybt may operate in the highly virulent Yersinia pestis / Y. pseudotuberculosis group, and are referred to as pseudochelin (Pch and yersiniachelin (Ych. Furthermore, most sporadic Y. pseudotuberculosis O1 strains possess gene clusters encoding all three iron scavenging systems. Thus, the Ybt system appears not to be the sole endogenous siderophore iron uptake system in the highly virulent yersiniae and may be efficiently substituted and / or supplemented by alternative iron scavenging systems.

The effect of diluting ruthenium by iron in RuxSey catalyst for oxygen reduction

International Nuclear Information System (INIS)

Delacote, Cyril; Lewera, Adam; Pisarek, Marcin; Kulesza, Pawel J.; Zelenay, Piotr; Alonso-Vante, Nicolas

2010-01-01

This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru x Se y . The catalysts were obtained by thermal decomposition of Ru 3 (CO) 12 and Fe(CO) 5 in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

Sulfur Earth

Science.gov (United States)

de Jong, B. H.

2007-12-01

Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

Research on the development strategy of Pingdingshan iron and steel industry cluster with Wugang Company as the core

Directory of Open Access Journals (Sweden)

Wang Shuai

2017-01-01

Full Text Available Arouse the great potential of the industrial clusters will play a significant role in promoting the development of local WuGang company. The article takes the Pingdingshan City as the research object, who is a typical resource-based city and develops on the basis of the local resources of coal and iron ore, the core enterprise WuGang Company is a large state-owned enterprise based on the wide and thick steel plate production. Many problems also exit in the cluster innovation, company network construction, company cooperation. The article is from the perspective of steel industry cluster and cluster innovation. Firstly, the article introduces the correlation theory about the steel industry cluster and the basic development information of Pingdingshan steel industry cluster, and promotes the research purpose and meaning.The article will give the analysis to the problems from the Pingdingshan steel industry cluster and develop the reform proposals and development strategy according to the actual situation.

Experimental studies on the electronic structure of pyrite FeS2 films prepared by thermally sulfurizing iron films

International Nuclear Information System (INIS)

Zhang Hui; Wang Baoyi; Zhang Rengang; Zhang Zhe; Wei Long; Qian Haijie; Su Run; Kui Rexi

2006-01-01

Pyrite FeS 2 films have been prepared by thermally sulfurizing iron films deposited by magnetron sputtering. The electronic structures were studies by X-ray absorption near edge structure and X-ray photoemission spectrum. The results show that an S 3p valence band with relatively higher intensity compared to the calculation exists in 2-10 eV range and a high density below the Fermi level of Fe 3d states were detected. A second gap of 2.8 eV in the unoccupied density of states was found above the conduction band which was 2.4 eV by experimentally calculation. The difference between t 2g and e g which were formed in an octahedral crystal field was computed to be 2.1 eV. (authors)

Parameters Influencing Sulfur Speciation in Environmental Samples Using Sulfur K-Edge X-Ray Absorption Near-Edge Structure

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Siwatt Pongpiachan

2012-01-01

Full Text Available This paper aims to enhance the credibility of applying the sulfur K-edge XANES spectroscopy as an innovative “fingerprint” for characterizing environmental samples. The sensitivities of sulfur K-edge XANES spectra of ten sulfur compound standards detected by two different detectors, namely, Lytle detector (LyD and Germanium detector (GeD, were studied and compared. Further investigation on “self-absorption” effect revealed that the maximum sensitivities of sulfur K-edge XANES spectra were achieved when diluting sulfur compound standards with boron nitride (BN at the mixing ratio of 0.1%. The “particle-size” effect on sulfur K-edge XANES spectrum sensitivities was examined by comparing signal-to-noise ratios of total suspended particles (TSP and particulate matter of less than 10 millionths of a meter (PM10 collected at three major cities of Thailand. The analytical results have demonstrated that the signal-to-noise ratios of sulfur K-edge XANES spectra were positively correlated with sulfate content in aerosols and negatively connected with particle sizes. The combination of hierarchical cluster analysis (HCA and principal component analysis (PCA has proved that sulfur K-edge XANES spectrum can be used to characterize German terrestrial soils and Andaman coastal sediments. In addition, this study highlighted the capability of sulfur K-edge XANES spectra as an innovative “fingerprint” to distinguish tsunami backwash deposits (TBD from typical marine sediments (TMS.

On the structure and reactivity of small iron clusters with benzene, [Fe{sub n}–C{sub 6}H{sub 6}]{sup 0,+,−}, n ⩽ 7: A theoretical study

Energy Technology Data Exchange (ETDEWEB)

Valencia, Israel, E-mail: israelv@unam.mx

2016-09-12

Highlights: • Optimized structures of iron clusters capped with one benzene molecule. • Adsorption of benzene molecules quenches the magnetic moment of Fe clusters. • Adsorption of benzene on iron clusters leads to activation of non IR active vibrations of benzene. • Adsorption of benzene in small Fe{sub n} clusters is explained by the charge transfer model. • Relation between Fe{sub n}–benzene electron affinity and reactivity is observed. - Abstract: The structural, energetic, electronic, vibrational, and magnetic properties of iron–benzene clusters, Fe{sub n}–C{sub 6}H{sub 6}, n ⩽ 7, were calculated using an all-electron density functional theory, DFT, with the generalized gradient approximation and the 6−311++G(2d,2p) basis set. A proposal regarding the mechanism of the adsorption of benzene on iron clusters related to the charge transfer model is described. A direct relation between the calculated electron affinity, EA, of the Fe{sub n}–C{sub 6}H{sub 6} clusters and their reactivity were also determined.

CH3SH adsorption properties and mechanism of deodorant filter made of iron hydroxide on porous iron frame; Tetsu takotaisei dasshu filter no methyl mercaptan jokyo seino to jokyo kiko

Energy Technology Data Exchange (ETDEWEB)

Noda, T. [Nippon Steel Corp., Tokyo (Japan)

1998-05-10

It is suggested that methyl mercaptan is decomposed to methyl sulfide and hydrogen by reaction with the a-iron hydroxide, and then the methyl sulfide combines with sulfur crystal and the hydrogen changes into water by the chemical reaction with the {alpha}-iron hydroxide. A deodorant filter was made by treating porous metallic iron with an aqueous solution of L-ascorbic acid, iron (II) sulfate and calcium hydroxide aqueous solution to deposit the iron ascorbate and the {alpha}-iron hydroxide on it. Then the deodorant filter was exposed to the hydrogen sulfide to yield the sulfur crystals on the surface of the deodorant filter. The methyl mercaptan removal capacity of the deodorant filter was studied with repetition of removal tests. Results show that the methyl mercaptan removal capacity of the deodorant filter is a little smaller than that of conventional granular activated carbon. 6 refs., 6 figs., 3 tabs.

Electron Spectroscopy Studies of Iron, Iron Sulfides and Supported Iron Surfaces: Chemisorption of Simple Gases.

Science.gov (United States)

Lee, Yiu Chung

EELS was used to investigate the chemisorption of oxygen and carbon on iron. The EELS spectra of oxidized iron show characteristic features with strong enhancement of the interband transitions involving the Fe 3d band (4.6 and 7.5 eV) and moderate enhancement of the M(,2,3) transition doublet (54.4 and 58.2 eV). The changes in the electron energy loss structures with an overlayer of graphitic or carbidic carbon were investigated. The adsorption and growth of iron on Ni(100) has been studied using the combined techniques of LEED and EELS. Initially iron grows by a layer-by-layer mechanism for the first few layers. High iron coverages result in the observation of complex LEED patterns with satellites around the main (1 x 1) diffraction sports. This is due to the formation of b.c.c. Fe(110) crystallites arranged in domains with different orientations. EELS studies show the presence of three stages in the growth of iron on Ni(100): low-coverage, film-like and bulk-like. Auger and EELS were used to study the iron sulfide (FeS(,2), Fe(,7)S(,8) and FeS) surfaces. A characteristic M(,2,3) VV Auger doublet with a separation of 5.0 eV was observed on the sulfides. An assignment of the electron energy loss peaks was made based on the energy dependence of the loss peaks and previous photoemission results. The effect of argon ion bombardment was studied. Peaks with strong iron and sulfur character were observed. Heating the damaged sulfides results in reconstruction of the sulfide surfaces. The reactions of the sulfides with simple gases, such as H(,2), CO, CH(,4), C(,2)H(,4), NH(,3) and O(,2) were also studied. Using XPS, the chemisorption of SO(,2) on CaO(100) has been studied. The chemical state of sulfur has been identified as that of sulfate. The kinetics of SO(,2) chemisorption on CaO are discussed. The binding states of Fe and Na on CaO were determined to be Fe('2+) and Na('+) respectively. At low Fe or Na coverages (< 0.5 ML), there is a large increase in the rate of

Isotope effects of sulfur in chemical reactions

International Nuclear Information System (INIS)

Mikolajczuk, A.

1999-01-01

Sulfur is an important component of organic matter because it forms compounds with many elements. Due to high chemical activity of sulfur, it takes part in biological and geological processes in which isotope effects are occurring. It has been shown during last years research of isotope effects that we have take into account not only mass difference but also many other physical properties of nuclides e.g. even or odd number of neutrons in nuclei, shape and distribution of charge, turn of nuclear spin etc. The factor remains that new theoretical ideas have been formed on the base of data, being obtained in fractionation processes of heavy element isotope, particularly uranium. Now it is being well known that effects unconnected with vibration energy have also caused an effect on fractionation of considerably lighter elements like iron and magnesium. The important question is, if these effects would come to light during the separation of sulfur isotopes. Sulfur have three even isotopes M = (32, 34, 36) and one odd M 33). This problem is still open. (author)

Mechanisms and evolution of oxidative sulfur metabolism in green sulfur bacteria

DEFF Research Database (Denmark)

Gregersen, Lea Haarup; Bryant, Donald A.; Frigaard, Niels-Ulrik

2011-01-01

Green sulfur bacteria (GSB) constitute a closely related group of photoautotrophic and thiotrophic bacteria with limited phenotypic variation. They typically oxidize sulfide and thiosulfate to sulfate with sulfur globules as an intermediate. Based on genome sequence information from 15 strains...... product is further oxidized to sulfite by the dissimilatory sulfite reductase (DSR) system. This system consists of components horizontally acquired partly from sulfide-oxidizing and partly from sulfate-reducing bacteria. Depending on the strain, the sulfite is probably oxidized to sulfate by one of two...... in sulfate formation in other bacteria has been replaced by the DSR system in GSB. Sequence analyses suggested that the conserved soxJXYZAKBW gene cluster was horizontally acquired by Chlorobium phaeovibrioides DSM 265 from the Chlorobaculum lineage and that this acquisition was mediated by a mobile genetic...

The interplay between iron accumulation, mitochondrial dysfunction and inflammation during the execution step of neurodegenerative disorders

Directory of Open Access Journals (Sweden)

Pamela J. Urrutia

2014-03-01

Full Text Available A growing set of observations points to mitochondrial dysfunction, iron accumulation, oxidative damage and chronic inflammation as common pathognomonic signs of a number of neurodegenerative diseases that includes Alzheimer's disease, Huntington disease, amyotrophic lateral sclerosis, Friedrich’s ataxia and Parkinson’s disease. Particularly relevant for neurodegenerative processes is the relationship between mitochondria and iron. The mitochondrion upholds the synthesis of iron-sulfur clusters and heme, the most abundant iron-containing prosthetic groups in a large variety of proteins, so a fraction of incoming iron must go through this organelle before reaching its final destination. In turn, the mitochondrial respiratory chain is the source of reactive oxygen species (ROS derived from leaks in the electron transport chain. The co-existence of both iron and ROS in the secluded space of the mitochondrion makes this organelle particularly prone to hydroxyl radical-mediated damage. In addition, a connection between the loss of iron homeostasis and inflammation is starting to emerge; thus, inflammatory cytokines like TNF-alpha and IL-6 induce the synthesis of the divalent metal transporter 1 and promote iron accumulation in neurons and microglia. Here, we review the recent literature on mitochondrial iron homeostasis and the role of inflammation on mitochondria dysfunction and iron accumulation on the neurodegenerative process that lead to cell death in Parkinson’s disease. We also put forward the hypothesis that mitochondrial dysfunction, iron accumulation and inflammation are part of a synergistic self-feeding cycle that ends in apoptotic cell death, once the antioxidant cellular defense systems are finally overwhelmed.

Spectroscopic and functional characterization of iron-bound forms of Azotobacter vinelandii (Nif)IscA.

Science.gov (United States)

Mapolelo, Daphne T; Zhang, Bo; Naik, Sunil G; Huynh, Boi Hanh; Johnson, Michael K

2012-10-16

The ability of Azotobacter vinelandii(Nif)IscA to bind Fe has been investigated to assess the role of Fe-bound forms in NIF-specific Fe-S cluster biogenesis. (Nif)IscA is shown to bind one Fe(III) or one Fe(II) per homodimer and the spectroscopic and redox properties of both the Fe(III)- and Fe(II)-bound forms have been characterized using the UV-visible absorption, circular dichroism, and variable-temperature magnetic circular dichroism, electron paramagnetic resonance, Mössbauer and resonance Raman spectroscopies. The results reveal a rhombic intermediate-spin (S = 3/2) Fe(III) center (E/D = 0.33, D = 3.5 ± 1.5 cm(-1)) that is most likely 5-coordinate with two or three cysteinate ligands and a rhombic high spin (S = 2) Fe(II) center (E/D = 0.28, D = 7.6 cm(-1)) with properties similar to reduced rubredoxins or rubredoxin variants with three cysteinate and one or two oxygenic ligands. Iron-bound (Nif)IscA undergoes reversible redox cycling between the Fe(III)/Fe(II) forms with a midpoint potential of +36 ± 15 mV at pH 7.8 (versus NHE). l-Cysteine is effective in mediating release of free Fe(II) from both the Fe(II)- and Fe(III)-bound forms of (Nif)IscA. Fe(III)-bound (Nif)IscA was also shown to be a competent iron source for in vitro NifS-mediated [2Fe-2S] cluster assembly on the N-terminal domain of NifU, but the reaction occurs via cysteine-mediated release of free Fe(II) rather than direct iron transfer. The proposed roles of A-type proteins in storing Fe under aerobic growth conditions and serving as iron donors for cluster assembly on U-type scaffold proteins or maturation of biological [4Fe-4S] centers are discussed in light of these results.

Disproportionation of elemental sulfur by haloalkaliphilic bacteria from soda lakes.

Science.gov (United States)

Poser, Alexander; Lohmayer, Regina; Vogt, Carsten; Knoeller, Kay; Planer-Friedrich, Britta; Sorokin, Dimitry; Richnow, Hans-H; Finster, Kai

2013-11-01

Microbial disproportionation of elemental sulfur to sulfide and sulfate is a poorly characterized part of the anoxic sulfur cycle. So far, only a few bacterial strains have been described that can couple this reaction to cell growth. Continuous removal of the produced sulfide, for instance by oxidation and/or precipitation with metal ions such as iron, is essential to keep the reaction exergonic. Hitherto, the process has exclusively been reported for neutrophilic anaerobic bacteria. Here, we report for the first time disproportionation of elemental sulfur by three pure cultures of haloalkaliphilic bacteria isolated from soda lakes: the Deltaproteobacteria Desulfurivibrio alkaliphilus and Desulfurivibrio sp. AMeS2, and a member of the Clostridia, Dethiobacter alkaliphilus. All cultures grew in saline media at pH 10 by sulfur disproportionation in the absence of metals as sulfide scavengers. Our data indicate that polysulfides are the dominant sulfur species under highly alkaline conditions and that they might be disproportionated. Furthermore, we report the first organism (Dt. alkaliphilus) from the class Clostridia that is able to grow by sulfur disproportionation.

A Regulatory Circuit Composed of a Transcription Factor, IscR, and a Regulatory RNA, RyhB, Controls Fe-S Cluster Delivery

Directory of Open Access Journals (Sweden)

Pierre Mandin

2016-09-01

Full Text Available Fe-S clusters are cofactors conserved through all domains of life. Once assembled by dedicated ISC and/or SUF scaffolds, Fe-S clusters are conveyed to their apo-targets via A-type carrier proteins (ATCs. Escherichia coli possesses four such ATCs. ErpA is the only ATC essential under aerobiosis. Recent studies reported a possible regulation of the erpA mRNA by the small RNA (sRNA RyhB, which controls the expression of many genes under iron starvation. Surprisingly, erpA has not been identified in recent transcriptomic analysis of the iron starvation response, thus bringing into question the actual physiological significance of the putative regulation of erpA by RyhB. Using an sRNA library, we show that among 26 sRNAs, only RyhB represses the expression of an erpA-lacZ translational fusion. We further demonstrate that this repression occurs during iron starvation. Using mutational analysis, we show that RyhB base pairs to the erpA mRNA, inducing its disappearance. In addition, IscR, the master regulator of Fe-S homeostasis, represses expression of erpA at the transcriptional level when iron is abundant, but depleting iron from the medium alleviates this repression. The conjunction of transcriptional derepression by IscR and posttranscriptional repression by RyhB under Fe-limiting conditions is best described as an incoherent regulatory circuit. This double regulation allows full expression of erpA at iron concentrations for which Fe-S biogenesis switches from the ISC to the SUF system. We further provide evidence that this regulatory circuit coordinates ATC usage to iron availability.

Identification and Analysis of a Novel Gene Cluster Involves in Fe2+ Oxidation in Acidithiobacillus ferrooxidans ATCC 23270, a Typical Biomining Acidophile.

Science.gov (United States)

Ai, Chenbing; Liang, Yuting; Miao, Bo; Chen, Miao; Zeng, Weimin; Qiu, Guanzhou

2018-07-01

Iron-oxidizing Acidithiobacillus spp. are applied worldwide in biomining industry to extract metals from sulfide minerals. They derive energy for survival through Fe 2+ oxidation and generate Fe 3+ for the dissolution of sulfide minerals. However, molecular mechanisms of their iron oxidation still remain elusive. A novel two-cytochrome-encoding gene cluster (named tce gene cluster) encoding a high-molecular-weight cytochrome c (AFE_1428) and a c 4 -type cytochrome c 552 (AFE_1429) in A. ferrooxidans ATCC 23270 was first identified in this study. Bioinformatic analysis together with transcriptional study showed that AFE_1428 and AFE_1429 were the corresponding paralog of Cyc2 (AFE_3153) and Cyc1 (AFE_3152) which were encoded by the extensively studied rus operon and had been proven involving in ferrous iron oxidation. Both AFE_1428 and AFE_1429 contained signal peptide and the classic heme-binding motif(s) as their corresponding paralog. The modeled structure of AFE_1429 showed high resemblance to Cyc1. AFE_1428 and AFE_1429 were preferentially transcribed as their corresponding paralogs in the presence of ferrous iron as sole energy source as compared with sulfur. The tce gene cluster is highly conserved in the genomes of four phylogenetic-related A. ferrooxidans strains that were originally isolated from different sites separated with huge geographical distance, which further implies the importance of this gene cluster. Collectively, AFE_1428 and AFE_1429 involve in Fe 2+ oxidation like their corresponding paralog by integrating with the metalloproteins encoded by rus operon. This study provides novel insights into the Fe 2+ oxidation mechanism in Fe 2+ -oxidizing A. ferrooxidans ssp.

Nanoengineered Carbon Scaffolds for Hydrogen Storage

Energy Technology Data Exchange (ETDEWEB)

Leonard, A. D.; Hudson, J. L.; Fan, H.; Booker, R.; Simpson, L. J.; O' Neill, K. J.; Parilla, P. A.; Heben, M. J.; Pasquali, M.; Kittrell, C.; Tour, J. M.

2009-01-01

Single-walled carbon nanotube (SWCNT) fibers were engineered to become a scaffold for the storage of hydrogen. Carbon nanotube fibers were swollen in oleum (fuming sulfuric acid), and organic spacer groups were covalently linked between the nanotubes using diazonium functionalization chemistry to provide 3-dimensional (3-D) frameworks for the adsorption of hydrogen molecules. These 3-D nanoengineered fibers physisorb twice as much hydrogen per unit surface area as do typical macroporous carbon materials. These fiber-based systems can have high density, and combined with the outstanding thermal conductivity of carbon nanotubes, this points a way toward solving the volumetric and heat-transfer constraints that limit some other hydrogen-storage supports.

Culture of hESC-derived pancreatic progenitors in alginate-based scaffolds.

Science.gov (United States)

Formo, Kjetil; Cho, Candy H-H; Vallier, Ludovic; Strand, Berit L

2015-12-01

The effect of alginate-based scaffolds with added basement membrane proteins on the in vitro development of hESC-derived pancreatic progenitors was investigated. Cell clusters were encapsulated in scaffolds containing the basement membrane proteins collagen IV, laminin, fibronectin, or extracellular matrix-derived peptides, and maintained in culture for up to 46 days. The cells remained viable throughout the experiment with no signs of central necrosis. Whereas nonencapsulated cells aggregated into larger clusters, some of which showed signs of morphological changes and tissue organization, the alginate matrix stabilized the cluster size and displayed more homogeneous cell morphologies, allowing culture for long periods of time. For all conditions tested, a stable or declining expression of insulin and PDX1 and an increase in glucagon and somatostatin over time indicated a progressive reduction in beta cell-related gene expression. Alginate scaffolds can provide a chemically defined, xeno-free and easily scalable alternative for culture of pancreatic progenitors. Although no increase in insulin and PDX1 gene expression after alginate-immobilized cell culture was seen in this study, further optimization of the matrix physicochemical and biological properties and of the medium composition may still be a relevant strategy to promote the stabilization or maturation of stem cell-derived beta cells. © 2015 Wiley Periodicals, Inc.

Magnetic properties of free alkali and transition metal clusters

International Nuclear Information System (INIS)

Heer, W. de; Milani, P.; Chatelain, A.

1991-01-01

The Stern-Gerlach deflections of small alkali clusters (N<6) and iron clusters (10< N<500) show that the paramagnetic alkali clusters always have a nondeflecting component, while the iron clusters always deflect in the high field direction. Both of these effects appear to be related to spin relaxation however in the case of alkali clusters it is shown that they are in fact caused by avoided level crossing in the Zeeman diagram. For alkali clusters the relatively weak couplings cause reduced magnetic moments where levels cross. For iron clusters however the total spin is strongly coupled to the molecular framework. Consequently this coupling is responsible for avoided level crossing which ultimately cause the total energy of the cluster to decrease with increasing magnetic field so that the iron clusters will deflect in one direction when introduced in an inhomogeneous magnetic field. Experiment and theory are discussed for both cases. (orig.)

Distribution of sulfur and pyrite in coal seams from Kutai Basin (East Kalimantan, Indonesia): Implications for paleoenvironmental conditions

Energy Technology Data Exchange (ETDEWEB)

Widodo, Sri [Department of Mining Engineering, Moslem University of Indonesia, Jln. Urip Sumoharjo, Makassar (Indonesia); Oschmann, Wolfgang [Institute of Geosciece, J.W. Goethe-University, Altenhoeferallee 1, D-60438 Frankfurt a.M. (Germany); Bechtel, Achim; Sachsenhofer, Reinhard F. [Department of Applied Geoscience and Geophysics, University of Leoben, Peter-Tunner-Str.5, A-8700 Leoben (Austria); Anggayana, Komang [Department of Mining Engineering, Bandung Institute of Technology, Jln. Ganesa 10, I-40132 Bandung (Indonesia); Puettmann, Wilhelm [Institute of Atmospheric and Environmental Sciences, Dapartment of Analytical Enviromental Chemistry, J.W. Goethe-University, Altenhoeferallee 1, D-60438 Frankfurt a.M. (Germany)

2010-03-01

Thirteen Miocene coal samples from three active open pit and underground coal mines in the Kutai Basin (East Kalimantan, Indonesia) were collected. According to our microscopical and geochemical investigations, coal samples from Sebulu and Centra Busang coal mines yield high sulfur and pyrite contents as compared to the Embalut coal mine. The latter being characterized by very low sulfur (< 1%) and pyrite contents. The ash, mineral, total sulfur, iron (Fe) and pyrite contents of most of the coal samples from the Sebulu and Centra Busang coal mines are high and positively related in these samples. Low contents of ash, mineral, total sulfur, iron (Fe) and pyrite have been found only in sample TNT-32 from Centra Busang coal mine. Pyrite was the only sulfur form that we could recognize under reflected light microscope (oil immersion). Pyrite occurred in the coal as framboidal, euhedral, massive, anhedral and epigenetic pyrite in cleats/fractures. High concentration of pyrite argues for the availability of iron (Fe) in the coal samples. Most coal samples from the Embalut coal mine show lower sulfur (< 1 wt.%) and pyrite contents as found within Centra Busang and Sebulu coals. One exception is the coal sample KTD-38 from Embalut mine with total sulfur content of 1.41 wt.%. The rich ash, mineral, sulfur and pyrite contents of coals in the Kutai Basin (especially Centra Busang and Sebulu coals) can be related to the volcanic activity (Nyaan volcanic) during Tertiary whereby aeolian material was transported to the mire during or after the peatification process. Moreover, the adjacent early Tertiary deep marine sediment, mafic igneous rocks and melange in the center of Kalimantan Island might have provided mineral to the coal by uplift and erosion. The inorganic matter in the mire might also originate from the ground and surface water from the highland of central Kalimantan. (author)

Biogeochemistry of an iron-rich hypersaline microbial mat (Camargue, France).

Science.gov (United States)

Wieland, A; Zopfi, J; Benthien, M; Kühl, M

2005-01-01

In situ microsensor measurements were combined with biogeochemical methods to determine oxygen, sulfur, and carbon cycling in microbial mats growing in a solar saltern (Salin-de-Giraud, France). Sulfate reduction rates closely followed the daily temperature changes and were highest during the day at 25 degrees C and lowest during the night at 11 degrees C, most probably fueled by direct substrate interactions between cyanobacteria and sulfate-reducing bacteria. Sulfate reduction was the major mineralization process during the night and the contribution of aerobic respiration to nighttime DIC production decreased. This decrease of aerobic respiration led to an increasing contribution of sulfide (and iron) oxidation to nighttime O2 consumption. A peak of elemental sulfur in a layer of high sulfate reduction at low sulfide concentration underneath the oxic zone indicated anoxygenic photosynthesis and/or sulfide oxidation by iron, which strongly contributed to sulfide consumption. We found a significant internal carbon cycling in the mat, and sulfate reduction directly supplied DIC for photosynthesis. The mats were characterized by a high iron content of 56 micromol Fe cm(-3), and iron cycling strongly controlled the sulfur cycle in the mat. This included sulfide precipitation resulting in high FeS contents with depth, and reactions of iron oxides with sulfide, especially after sunset, leading to a pronounced gap between oxygen and sulfide gradients and an unusual persistence of a pH peak in the uppermost mat layer until midnight.

New Parameterizations for Neutral and Ion-Induced Sulfuric Acid-Water Particle Formation in Nucleation and Kinetic Regimes

Science.gov (United States)

Määttänen, Anni; Merikanto, Joonas; Henschel, Henning; Duplissy, Jonathan; Makkonen, Risto; Ortega, Ismael K.; Vehkamäki, Hanna

2018-01-01

We have developed new parameterizations of electrically neutral homogeneous and ion-induced sulfuric acid-water particle formation for large ranges of environmental conditions, based on an improved model that has been validated against a particle formation rate data set produced by Cosmics Leaving OUtdoor Droplets (CLOUD) experiments at European Organization for Nuclear Research (CERN). The model uses a thermodynamically consistent version of the Classical Nucleation Theory normalized using quantum chemical data. Unlike the earlier parameterizations for H2SO4-H2O nucleation, the model is applicable to extreme dry conditions where the one-component sulfuric acid limit is approached. Parameterizations are presented for the critical cluster sulfuric acid mole fraction, the critical cluster radius, the total number of molecules in the critical cluster, and the particle formation rate. If the critical cluster contains only one sulfuric acid molecule, a simple formula for kinetic particle formation can be used: this threshold has also been parameterized. The parameterization for electrically neutral particle formation is valid for the following ranges: temperatures 165-400 K, sulfuric acid concentrations 104-1013 cm-3, and relative humidities 0.001-100%. The ion-induced particle formation parameterization is valid for temperatures 195-400 K, sulfuric acid concentrations 104-1016 cm-3, and relative humidities 10-5-100%. The new parameterizations are thus applicable for the full range of conditions in the Earth's atmosphere relevant for binary sulfuric acid-water particle formation, including both tropospheric and stratospheric conditions. They are also suitable for describing particle formation in the atmosphere of Venus.

Overexpression of Drosophila frataxin triggers cell death in an iron-dependent manner.

Science.gov (United States)

Edenharter, Oliver; Clement, Janik; Schneuwly, Stephan; Navarro, Juan A

2017-12-01

Friedreich ataxia (FRDA) is the most important autosomal recessive ataxia in the Caucasian population. FRDA patients display severe neurological and cardiac symptoms that reflect a strong cellular and axonal degeneration. FRDA is caused by a loss of function of the mitochondrial protein frataxin which impairs the biosynthesis of iron-sulfur clusters and in turn the catalytic activity of several enzymes in the Krebs cycle and the respiratory chain leading to a diminished energy production. Although FRDA is due to frataxin depletion, overexpression might also be very helpful to better understand cellular functions of frataxin. In this work, we have increased frataxin expression in neurons to elucidate specific roles that frataxin might play in these tissues. Using molecular, biochemical, histological and behavioral methods, we report that frataxin overexpression is sufficient to increase oxidative phosphorylation, modify mitochondrial morphology, alter iron homeostasis and trigger oxidative stress-dependent cell death. Interestingly, genetic manipulation of mitochondrial iron metabolism by silencing mitoferrin successfully improves cell survival under oxidative-attack conditions, although enhancing antioxidant defenses or mitochondrial fusion failed to ameliorate frataxin overexpression phenotypes. This result suggests that cell degeneration is directly related to enhanced incorporation of iron into the mitochondria. Drosophila frataxin overexpression might also provide an alternative approach to identify processes that are important in FRDA such as changes in mitochondrial morphology and oxidative stress induced cell death.

Magnetic and Moessbauer-spectroscopic studies of iron-clusters in zeolites. [Reduction of ferrous ions

Energy Technology Data Exchange (ETDEWEB)

Schmidt, F; Gunsser, W; Knappwost, A [Hamburg Univ. (F.R. Germany). Inst. fuer Physikalische Chemie

1975-12-01

Iron clusters have been prepared within zeolite holes by reduction of zeolites containing ferrous ions. The diameter of these particles must therefore be smaller that 13 A. They are superparamagnetic and their Moessbauer spectra show no HFS, even at 4K. The temperature dependence of the magnetic susceptibility of the unreduced zeolites obeys a Curie-Weiss law with p/sub eff/ = 4.45 ..mu..B and THETA = 105K. The Weiss curves of the reduced samples lie distinctly below those of the bulk material.

Iron-sulfide crystals in probe deposits

DEFF Research Database (Denmark)

Laursen, Karin; Frandsen, Flemming

1998-01-01

Iron-sulfides were observed in deposits collected on a probe inserted at the top of the furnace of a coal-fired power station in Denmark. The chemical composition of the iron-sulfides is equivalent to pyrrhotite (FeS). The pyrrhotites are present as crystals and, based on the shape of the crystals......: (1) impact of low viscous droplets of iron sulfide; and (2) sulfur diffusion. Previous research on the influence of pyrite on slagging focused on the decomposition of pyrite into pyrrhotite and especially on the oxidation stage of this product during impact on the heat transfer surfaces...

Treatment of air pollution control residues with iron rich waste sulfuric acid: does it work for antimony (Sb)?

Science.gov (United States)

Okkenhaug, Gudny; Breedveld, Gijs D; Kirkeng, Terje; Lægreid, Marit; Mæhlum, Trond; Mulder, Jan

2013-03-15

Antimony (Sb) in air pollution control (APC) residues from municipal solid waste incineration has gained increased focus due to strict Sb leaching limits set by the EU landfill directive. Here we study the chemical speciation and solubility of Sb at the APC treatment facility NOAH Langøya (Norway), where iron (Fe)-rich sulfuric acid (∼3.6M, 2.3% Fe(II)), a waste product from the industrial extraction of ilmenite, is used for neutralization. Antimony in water extracts of untreated APC residues occurred exclusively as pentavalent antimonate, even at low pH and Eh values. The Sb solubility increased substantially at pH<10, possibly due to the dissolution of ettringite (at alkaline pH) or calcium (Ca)-antimonate. Treated APC residues, stored anoxically in the laboratory, simulating the conditions at the NOAH Langøya landfill, gave rise to decreasing concentrations of Sb in porewater, occurring exclusively as Sb(V). Concentrations of Sb decreased from 87-918μgL(-1) (day 3) to 18-69μgL(-1) (day 600). We hypothesize that an initial sorption of Sb to Fe(II)-Fe(III) hydroxides (green rust) and eventually precipitation of Ca- and Fe-antimonates (tripuhyite; FeSbO4) occurred. We conclude that Fe-rich, sulfuric acid waste is efficient to immobilize Sb in APC residues from waste incineration. Copyright © 2013 Elsevier B.V. All rights reserved.

A new biocompatible delivery scaffold containing heparin and bone morphogenetic protein 2

Directory of Open Access Journals (Sweden)

Thanyaphoo Suphannee

2016-09-01

Full Text Available Silicon-substituted calcium phosphate (Si-CaP was developed in our laboratory as a biomaterial for delivery in bone tissue engineering. It was fabricated as a 3D-construct of scaffolds using chitosan-trisodium polyphosphate (TPP cross-linked networks. In this study, heparin was covalently bonded to the residual -NH2 groups of chitosan on the scaffold applying carbodiimide chemistry. Bonded heparin was not leached away from scaffold surfaces upon vigorous washing or extended storage. Recombinant human bone morphogenetic protein 2 (rhBMP-2 was bound to conjugated scaffolds by ionic interactions between the negatively charged SO42- clusters of heparin and positively charged amino acids of rhBMP-2. The resulting scaffolds were inspected for bone regenerative capacity by subcutaneous implanting in rats. Histological observation and mineralization assay were performed after 4 weeks of implantation. Results from both in vitro and in vivo experiments suggest the potential of the developed scaffolds for bone tissue engineering applications in the future.

Resistivity recovery simulations of electron-irradiated iron: Kinetic Monte Carlo versus cluster dynamics

International Nuclear Information System (INIS)

Dalla Torre, J.; Fu, C.-C.; Willaime, F.; Barbu, A.; Bocquet, J.-L.

2006-01-01

The isochronal resistivity recovery in high purity α-iron irradiated by electrons was successfully reproduced by a multiscale modelling approach. The stability and mobility of small self-defect clusters determined by ab initio methods were used as input data for an event based Kinetic Monte Carlo (KMC) model, used to explore the defect population evolution during the annealing and to extract the resistivity recovery peaks. In this paper, we investigate the possibility of using an efficient mesoscale model, the Cluster Dynamics (CD), instead of KMC in this approach. The comparison between the two methods for various CD initial conditions shows the importance of spatial correlations between defects, which are neglected in the CD model. However, using appropriate initial conditions, e.g. starting from the concentration of Frenkel pairs after the uncorrelated stage I E , the CD model captures the main characteristics of subsequent defect population evolution, and it can therefore be used for fast and semi-quantitative investigations

Effect of gamma irradiation and sulfur dioxide treatment on storability of some grape varieties (Vitis Vinifera L.) in Syria

International Nuclear Information System (INIS)

Al-Bachir, M.

1997-12-01

The feasibility of using gamma irradiation and sulfur dioxide to control post-harvest diseases and to extend shelf life of table grapes in cold storage (1-2 C deg) was studied using two local varieties of grapes (Baladi and Helwani). The experiment was conducted for two years (1995 and 1996). In the first year, the clusters of both varieties were subjected to one of the following treatments: Irradiation with 0, 0.5, 1.0 and 1.5 kGy of gamma rays, sulfur dioxide (3 g Na 2 S 2 O 5 / 5 Kg clusters) or combination of both 1.0 KGy of gamma irradiation and sulfur dioxide. In the second year, two additional doses were applied: 0.1 and 0.25 KGy for Helwani and 2.0 and 2.5 KGy for Baladi. Clusters of both var. were treated with combined treatments (1.5 KGy and sulfur dioxide for Baladi) and (0.5 KGy and sulfur dioxide for Helwani). Treated and untreated clusters were kept in cold storage (temperature, 1 to 2 C deg). Weight loss, spoilage and total loss were evaluated every two and four weeks of storage for Baladi and Helwani, respectively. With the exception of Helwani var. produced in the first year and treated with sulfur dioxide, the results indicated that separate application of sulfur dioxide and gamma radiation reduced the rotting induced by (B. cinerea) and improved the storability of both varieties. Gamma irradiation in combination with sulfur dioxide preserved the two varieties of table grapes. (author)

SAXS and stability studies of iron-induced oligomers of bacterial frataxin CyaY.

Directory of Open Access Journals (Sweden)

Mostafa Fekry

Full Text Available Frataxin is a highly conserved protein found in both prokaryotes and eukaryotes. It is involved in several central functions in cells, which include iron delivery to biochemical processes, such as heme synthesis, assembly of iron-sulfur clusters (ISC, storage of surplus iron in conditions of iron overload, and repair of ISC in aconitase. Frataxin from different organisms has been shown to undergo iron-dependent oligomerization. At least two different classes of oligomers, with different modes of oligomer packing and stabilization, have been identified. Here, we continue our efforts to explore the factors that control the oligomerization of frataxin from different organisms, and focus on E. coli frataxin CyaY. Using small-angle X-ray scattering (SAXS, we show that higher iron-to-protein ratios lead to larger oligomeric species, and that oligomerization proceeds in a linear fashion as a results of iron oxidation. Native mass spectrometry and online size-exclusion chromatography combined with SAXS show that a dimer is the most common form of CyaY in the presence of iron at atmospheric conditions. Modeling of the dimer using the SAXS data confirms the earlier proposed head-to-tail packing arrangement of monomers. This packing mode brings several conserved acidic residues into close proximity to each other, creating an environment for metal ion binding and possibly even mineralization. Together with negative-stain electron microscopy, the experiments also show that trimers, tetramers, pentamers, and presumably higher-order oligomers may exist in solution. Nano-differential scanning fluorimetry shows that the oligomers have limited stability and may easily dissociate at elevated temperatures. The factors affecting the possible oligomerization mode are discussed.

Molecular interaction of pinic acid with sulfuric acid

DEFF Research Database (Denmark)

Elm, Jonas; Kurtén, Theo; Bilde, Merete

2014-01-01

We investigate the molecular interactions between the semivolatile α-pinene oxidation product pinic acid and sulfuric acid using computational methods. The stepwise Gibbs free energies of formation have been calculated utilizing the M06-2X functional, and the stability of the clusters is evaluated...... cluster. The involvement of more than one pinic acid molecule in a single cluster is observed to lead to the formation of favorable (pinic acid)2(H2SO4) and (pinic acid)2(H2SO4)2 clusters. The identified most favorable growth paths starting from a single pinic acid molecule lead to closed structures...

Theoretical investigation of existence of meta-stability in iron and cobalt clusters

Science.gov (United States)

Berry, Habte Dulla; Zhang, Qinfang; Wang, Baolin

2018-03-01

Nowadays considerable attention has been given for researches on magnetic properties of transition metal clusters (specifically FeN and CoN). This is because these clusters offer big hopes for the possibility of presenting significant magnetic anisotropy energy which is critical for technological applications. This study intends to find out the causes for the existence of the two states (ground and meta-stable) in Iron and Cobalt clusters. The study also explains the role of valence electrons for the existence of magnetism in the two states by using the concept of ionization potential, electron dipole polarizabilities, chemical hardness and softness of the clusters. Assuming that, when all itinerant electrons are at s-level and also at the d-level (ns = n andns → 0.) the ground state and meta-stable state energies with distinct energy minima are (Egs = l / 2 n +εc n - 2μB hn andEms =εd n - gμB hn) respectively. The findings also showed that polarizability of small cluster of the specified elements are increased compared with the bulk value, which means that there is an effective increase in the cluster radius due to the spilling out of the electronic charge. Furthermore, it is obvious that 4s electrons are more delocalized than the 3d electrons so that they spill out more than the 3d electrons. This leads to the conclusion that 4s electrons are primarily responsible for the enhanced polarizabilities and for shell structure effects. This indicates that polarizability at the meta-stable state is less than that of the ground state i.e. the meta-stable state loses its s electron. Therefore the two minima represent a ground state of configuration 3 d↑5 3 d↓ 2 + δ 4s 2 - δ with energy Egs and meta-stable state of configuration 3 d↑5 3 d↓ 3 + δ 4s 1 - δ with energy Ems for Co clusters and a ground state configuration 3 d↑5 3 d↓ 1 + δ 4s 2 - δ with energy Egs an meta-stable state of configuration 3 d↑5 3 d↓ 2 + δ 4s 1 - δ with energy Ems for

Biomimetic nanoclay scaffolds for bone tissue engineering

Science.gov (United States)

Ambre, Avinash Harishchandra

Tissue engineering offers a significant potential alternative to conventional methods for rectifying tissue defects by evoking natural regeneration process via interactions between cells and 3D porous scaffolds. Imparting adequate mechanical properties to biodegradable scaffolds for bone tissue engineering is an important challenge and extends from molecular to macroscale. This work focuses on the use of sodium montmorillonite (Na-MMT) to design polymer composite scaffolds having enhanced mechanical properties along with multiple interdependent properties. Materials design beginning at the molecular level was used in which Na-MMT clay was modified with three different unnatural amino acids and further characterized using Fourier Transform Infrared (FTIR) spectroscopy, X-ray diffraction (XRD). Based on improved bicompatibility with human osteoblasts (bone cells) and intermediate increase in d-spacing of MMT clay (shown by XRD), 5-aminovaleric acid modified clay was further used to prepare biopolymer (chitosan-polygalacturonic acid complex) scaffolds. Osteoblast proliferation in biopolymer scaffolds containing 5-aminovaleric acid modified clay was similar to biopolymer scaffolds containing hydroxyapatite (HAP). A novel process based on biomineralization in bone was designed to prepare 5-aminovaleric acid modified clay capable of imparting multiple properties to the scaffolds. Bone-like apatite was mineralized in modified clay and a novel nanoclay-HAP hybrid (in situ HAPclay) was obtained. FTIR spectroscopy indicated a molecular level organic-inorganic association between the intercalated 5-aminovaleric acid and mineralized HAP. Osteoblasts formed clusters on biopolymer composite films prepared with different weight percent compositions of in situ HAPclay. Human MSCs formed mineralized nodules on composite films and mineralized extracellular matrix (ECM) in composite scaffolds without the use of osteogenic supplements. Polycaprolactone (PCL), a synthetic polymer, was

HYBRID SULFUR RECOVERY PROCESS FOR NATURAL GAS UPGRADING

International Nuclear Information System (INIS)

Girish Srinivas; Steven C. Gebhard; David W. DeBerry

2002-01-01

This first quarter report of 2002 describes progress on a project funded by the U.S. Department of Energy (DOE) to test a hybrid sulfur recovery process for natural gas upgrading. The process concept represents a low cost option for direct treatment of natural gas streams to remove H(sub 2)S in quantities equivalent to 0.2-25 metric tons (LT) of sulfur per day. This process is projected to have lower capital and operating costs than the competing technologies, amine/aqueous iron liquid redox and amine/Claus/tail gas treating, and have a smaller plant footprint, making it well suited to both on-shore and offshore applications. CrystaSulf(sup SM) (service mark of CrystaTech, Inc.) is a new nonaqueous sulfur recovery process that removes hydrogen sulfide (H(sub 2)S) from gas streams and converts it into elemental sulfur. CrystaSulf features high sulfur recovery similar to aqueous-iron liquid redox sulfur recovery processes, but differs from the aqueous processes in that CrystaSulf controls the location where elemental sulfur particles are formed. In the hybrid process, approximately 1/3 of the total H(sub 2)S in the natural gas is first oxidized to SO(sub 2) at low temperatures over a heterogeneous catalyst. Low temperature oxidation is done so that the H(sub 2)S can be oxidized in the presence of methane and other hydrocarbons without oxidation of the hydrocarbons. The project involves the development of a catalyst using laboratory/bench-scale catalyst testing, and then demonstration of the catalyst at CrystaTech's pilot plant in west Texas. In a previous reporting period tests were done to determine the effect of hydrocarbons such as n-hexane on catalyst performance with and without H(sub 2)S present. The experiments showed that hexane oxidation is suppressed when H(sub 2)S is present. Hexane represents the most reactive of the C1 to C6 series of alkanes. Since hexane exhibits low reactivity under H(sub 2)S oxidation conditions, and more importantly, does not change

Process for iron separation from an organic solution containing uranium

International Nuclear Information System (INIS)

Textoris, A.; Lyaudet, G.; Bathelier, A.

1987-01-01

Iron is separated from an organic solution of U and Fe in a phosphine oxide and an acid organic phosphorus compound by reaction on oxalic acid or a mixture of sulfuric and phosphoric acid or phosphoric acid. Uranium stays in the initial organic solution and iron is transferred to the aqueous phase [fr

pH-induced conformational change of IscU at low pH correlates with protonation/deprotonation of two conserved histidine residues.

Science.gov (United States)

Dai, Ziqi; Kim, Jin Hae; Tonelli, Marco; Ali, Ibrahim K; Markley, John L

2014-08-19

IscU, the scaffold protein for the major iron-sulfur cluster biosynthesis pathway in microorganisms and mitochondria (ISC pathway), plays important roles in the formation of [2Fe-2S] and [4Fe-4S] clusters and their delivery to acceptor apo-proteins. Our laboratory has shown that IscU populates two distinct, functionally relevant conformational states, a more structured state (S) and a more dynamic state (D), that differ by cis/trans isomerizations about two peptidyl-prolyl peptide bonds [Kim, J. H., Tonelli, M., and Markley, J. L. (2012) Proc. Natl. Acad. Sci. U.S.A., 109, 454-459. Dai Z., Tonelli, M., and Markley, J. L. (2012) Biochemistry, 51, 9595-9602. Cai, K., Frederick, R. O., Kim, J. H., Reinen, N. M., Tonelli, M., and Markley, J. L. (2013) J. Biol. Chem., 288, 28755-28770]. Here, we report our findings on the pH dependence of the D ⇄ S equilibrium for Escherichia coli IscU in which the D-state is stabilized at low and high pH values. We show that the lower limb of the pH dependence curve results from differences in the pKa values of two conserved histidine residues (His10 and His105) in the two states. The net proton affinity of His10 is about 50 times higher and that of His105 is 13 times higher in the D-state than in the S-state. The origin of the high limb of the D ⇄ S pH dependence remains to be determined. These results show that changes in proton inventory need to be taken into account in the steps in iron-sulfur cluster assembly and transfer that involve transitions of IscU between its S- and D-states.

Influence of iron impurities on defected graphene

Energy Technology Data Exchange (ETDEWEB)

Faccio, Ricardo; Pardo, Helena [Centro NanoMat, Cryssmat-Lab, DETEMA, Polo Tecnológico de Pando, Facultad de Química, Universidad de la República, Cno. Saravia s/n, CP 91000 Pando (Uruguay); Centro Interdisciplinario en Nanotecnología, Química y Física de Materiales, Espacio Interdisciplinario, Universidad de la República, Montevideo (Uruguay); Araújo-Moreira, Fernando M. [Materials and Devices Group, Department of Physics, Universidade Federal de São Carlos, SP 13565-905 (Brazil); Mombrú, Alvaro W., E-mail: amombru@fq.edu.uy [Centro NanoMat, Cryssmat-Lab, DETEMA, Polo Tecnológico de Pando, Facultad de Química, Universidad de la República, Cno. Saravia s/n, CP 91000 Pando (Uruguay); Centro Interdisciplinario en Nanotecnología, Química y Física de Materiales, Espacio Interdisciplinario, Universidad de la República, Montevideo (Uruguay)

2015-03-01

Highlights: • The interaction among a multivacancy graphene system and iron impurities is studied. • The studied iron impurities were single atom and tetrahedral and octahedral clusters. • DFT calculations using the VASP code were performed. • The embedding of Fe affects the structure and electronic behavior in the graphene. • Half metal or semimetal behavior can be obtained, depending on the Fe impurities. - Abstract: The aim of this work is to study the interaction of selected iron cluster impurities and a multivacancy graphene system, in terms of the structural distortion that the impurities cause as well as their magnetic response. While originally, the interaction has been limited to vacancies and isolated metallic atoms, in this case, we consider small iron clusters. This study was undertaken using Density Functional Theory (DFT) calculations. The influence of the iron impurities in the electronic structure of the vacant graphene system is discussed. The main conclusion of this work is that the presence of iron impurities acts lowering the magnetic signal due to the occurrence of spin pairing between carbon and iron, instead of enhancing the possible intrinsic carbon magnetism.

Influence of iron impurities on defected graphene

International Nuclear Information System (INIS)

Faccio, Ricardo; Pardo, Helena; Araújo-Moreira, Fernando M.; Mombrú, Alvaro W.

2015-01-01

Highlights: • The interaction among a multivacancy graphene system and iron impurities is studied. • The studied iron impurities were single atom and tetrahedral and octahedral clusters. • DFT calculations using the VASP code were performed. • The embedding of Fe affects the structure and electronic behavior in the graphene. • Half metal or semimetal behavior can be obtained, depending on the Fe impurities. - Abstract: The aim of this work is to study the interaction of selected iron cluster impurities and a multivacancy graphene system, in terms of the structural distortion that the impurities cause as well as their magnetic response. While originally, the interaction has been limited to vacancies and isolated metallic atoms, in this case, we consider small iron clusters. This study was undertaken using Density Functional Theory (DFT) calculations. The influence of the iron impurities in the electronic structure of the vacant graphene system is discussed. The main conclusion of this work is that the presence of iron impurities acts lowering the magnetic signal due to the occurrence of spin pairing between carbon and iron, instead of enhancing the possible intrinsic carbon magnetism

The effect of diluting ruthenium by iron in Ru{sub x}Se{sub y} catalyst for oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Delacote, Cyril [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France); CEISAM, CNRS, University of Nantes, F-44322 Nantes Cedex 3 (France); Lewera, Adam [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Pisarek, Marcin [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw (Poland); Kulesza, Pawel J. [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Zelenay, Piotr [Materials Physics and Applications, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Alonso-Vante, Nicolas, E-mail: nicolas.alonso.vante@univ-poitiers.f [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France)

2010-11-01

This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru{sub x}Se{sub y}. The catalysts were obtained by thermal decomposition of Ru{sub 3}(CO){sub 12} and Fe(CO){sub 5} in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

Bone tissue engineering scaffolding: computer-aided scaffolding techniques.

Science.gov (United States)

Thavornyutikarn, Boonlom; Chantarapanich, Nattapon; Sitthiseripratip, Kriskrai; Thouas, George A; Chen, Qizhi

Tissue engineering is essentially a technique for imitating nature. Natural tissues consist of three components: cells, signalling systems (e.g. growth factors) and extracellular matrix (ECM). The ECM forms a scaffold for its cells. Hence, the engineered tissue construct is an artificial scaffold populated with living cells and signalling molecules. A huge effort has been invested in bone tissue engineering, in which a highly porous scaffold plays a critical role in guiding bone and vascular tissue growth and regeneration in three dimensions. In the last two decades, numerous scaffolding techniques have been developed to fabricate highly interconnective, porous scaffolds for bone tissue engineering applications. This review provides an update on the progress of foaming technology of biomaterials, with a special attention being focused on computer-aided manufacturing (Andrade et al. 2002) techniques. This article starts with a brief introduction of tissue engineering (Bone tissue engineering and scaffolds) and scaffolding materials (Biomaterials used in bone tissue engineering). After a brief reviews on conventional scaffolding techniques (Conventional scaffolding techniques), a number of CAM techniques are reviewed in great detail. For each technique, the structure and mechanical integrity of fabricated scaffolds are discussed in detail. Finally, the advantaged and disadvantage of these techniques are compared (Comparison of scaffolding techniques) and summarised (Summary).

Transformation of Reactive Iron Minerals in a Permeable Reactive Barrier (Biowall) Used to Treat TCE in Groundwater

Science.gov (United States)

Abstract: Iron and sulfur reducing conditions are generally created in permeable reactive barrier (PRB) systems constructed for groundwater treatment, which usually leads to formation of iron sulfide phases. Iron sulfides have been shown to play an important role in degrading ch...

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.

Hybrid Carbon-Based Scaffolds for Applications in Soft Tissue Reconstruction

Science.gov (United States)

Lafdi, Khalid; Joseph, Robert M.; Tsonis, Panagiotis A.

2012-01-01

Current biomedical scaffolds utilized in surgery to repair soft tissues commonly fail to meet the optimal combination of biomechanical and tissue regenerative properties. Carbon is a scaffold alternative that potentially optimizes the balance between mechanical strength, durability, and function as a cell and biologics delivery vehicle that is necessary to restore tissue function while promoting tissue repair. The goals of this study were to investigate the feasibility of fabricating hybrid fibrous carbon scaffolds modified with biopolymer, polycaprolactone and to analyze their mechanical properties and ability to support cell growth and proliferation. Environmental scanning electron microscopy, micro-computed tomography, and cell adhesion and cell proliferation studies were utilized to test scaffold suitability as a cell delivery vehicle. Mechanical properties were tested to examine load failure and elastic modulus. Results were compared to an acellular dermal matrix scaffold control (GraftJacket® [GJ] Matrix), selected for its common use in surgery for the repair of soft tissues. Results indicated that carbon scaffolds exhibited similar mechanical maximums and capacity to support fibroblast adhesion and proliferation in comparison with GJ. Fibroblast adhesion and proliferation was collinear with carbon fiber orientation in regions of sparsely distributed fibers and occurred in clusters in regions of higher fiber density and low porosity. Overall, fibroblast adhesion and proliferation was greatest in lower porosity carbon scaffolds with highly aligned fibers. Stepwise multivariate regression showed that the variability in maximum load of carbon scaffolds and controls were dependent on unique and separate sets of parameters. These finding suggested that there were significant differences in the functional implications of scaffold design and material properties between carbon and dermis derived scaffolds that affect scaffold utility as a tissue replacement

The transformation of inorganic sulfur compounds and the assimilation of organic and inorganic carbon by the sulfur disproportionating bacterium Desulfocapsa sulfoexigens.

Science.gov (United States)

Frederiksen, Trine-Maria; Finster, Kai

2004-02-01

The physiology of the sulfur disproportionator Desulfocapsa sulfoexigens was investigated in batch cultures and in a pH-regulated continuously flushed fermentor system. It was shown that a sulphide scavanger in the form of ferric iron was not obligatory and that the control of pH allowed production of more biomass than was possible in carbonate buffered but unregulated batch cultures. Small amounts of sulphite were produced during disproportionation of elemental sulfur and thiosulphate. In addition, it was shown that in the presence of hydrogen, a respiratory type of process is favored before the disproportionation of sulphite, thiosulphate and elemental sulfur. Sulphate reduction was not observed. D. sulfoexigens assimilated inorganic carbon even in the presence of organic carbon sources. Inorganic carbon assimilation was probably catalyzed by the reverse CO-dehydrogenase pathway, which was supported by the constitutive expression of the gene encoding CO-dehydrogenase in cultures grown in the presence of acetate and by the high carbon fractionation values that are indicative of this pathway.

Blockage of mitochondrial calcium uniporter prevents iron accumulation in a model of experimental subarachnoid hemorrhage

Energy Technology Data Exchange (ETDEWEB)

Yan, Huiying [Department of Neurosurgery, Jinling Hospital, School of Medicine, Nanjing University, 305 East Zhongshan Road, Nanjing 210002, Jiangsu Province (China); Hao, Shuangying; Sun, Xiaoyan [Jiangsu Key Laboratory for Molecular Medicine, Medical School of Nanjing University, 22 Hankou Road, Nanjing 210093, Jiangsu Province (China); Zhang, Dingding; Gao, Xin; Yu, Zhuang [Department of Neurosurgery, Jinling Hospital, School of Medicine, Nanjing University, 305 East Zhongshan Road, Nanjing 210002, Jiangsu Province (China); Li, Kuanyu, E-mail: likuanyu@nju.edu.cn [Jiangsu Key Laboratory for Molecular Medicine, Medical School of Nanjing University, 22 Hankou Road, Nanjing 210093, Jiangsu Province (China); Hang, Chun-Hua, E-mail: hang_neurosurgery@163.com [Department of Neurosurgery, Jinling Hospital, School of Medicine, Nanjing University, 305 East Zhongshan Road, Nanjing 210002, Jiangsu Province (China)

2015-01-24

Highlights: • Iron accumulation was involved in the acute phase following SAH. • Blockage of MCU could attenuate cellular iron accumulation following SAH. • Blockage of MCU could decrease ROS generation and improve cell energy supply following SAH. • Blockage of MCU could alleviate apoptosis and brain injury following SAH. - Abstract: Previous studies have shown that iron accumulation is involved in the pathogenesis of brain injury following subarachnoid hemorrhage (SAH) and chelation of iron reduced mortality and oxidative DNA damage. We previously reported that blockage of mitochondrial calcium uniporter (MCU) provided benefit in the early brain injury after experimental SAH. This study was undertaken to identify whether blockage of MCU could ameliorate iron accumulation-associated brain injury following SAH. Therefore, we used two reagents ruthenium red (RR) and spermine (Sper) to inhibit MCU. Sprague–Dawley (SD) rats were randomly divided into four groups including sham, SAH, SAH + RR, and SAH + Sper. Biochemical analysis and histological assays were performed. The results confirmed the iron accumulation in temporal lobe after SAH. Interestingly, blockage of MCU dramatically reduced the iron accumulation in this area. The mechanism was revealed that inhibition of MCU reversed the down-regulation of iron regulatory protein (IRP) 1/2 and increase of ferritin. Iron–sulfur cluster dependent-aconitase activity was partially conserved when MCU was blocked. In consistence with this and previous report, ROS levels were notably reduced and ATP supply was rescued; levels of cleaved caspase-3 dropped; and integrity of neurons in temporal lobe was protected. Taken together, our results indicated that blockage of MCU could alleviate iron accumulation and the associated injury following SAH. These findings suggest that the alteration of calcium and iron homeostasis be coupled and MCU be considered to be a therapeutic target for patients suffering from SAH.

Heavy metal extraction from PCB wastewater treatment sludge by sulfuric acid

International Nuclear Information System (INIS)

Kuan, Yu-Chung; Lee, I-Hsien; Chern, Jia-Ming

2010-01-01

Heavy metals contaminated wastewater sludge is classified as hazardous solid waste and needs to be properly treated to prevent releasing heavy metals to the environment. In this study, the wastewater treatment sludge from a printed circuit board manufacturing plant was treated in a batch reactor by sulfuric acid to remove the contained heavy metals. The effects of sulfuric acid concentration and solid to liquid ratio on the heavy metal removal efficiencies were investigated. The experimental results showed that the total and individual heavy metal removal efficiencies increased with increasing sulfuric acid concentration, but decreased with increasing solid to liquid ratio. A mathematical model was developed to predict the residual sludge weights at varying sulfuric concentrations and solid to liquid ratios. The trivalent heavy metal ions, iron and chromium were more difficult to be removed than the divalent ions, copper, zinc, nickel, and cadmium. For 5 g/L solid to liquid ratio, more than 99.9% of heavy metals can be removed from the sludge by treating with 0.5 M sulfuric acid in 2 h.

In-situ synthesis of magnetic iron-oxide nanoparticle-nanofibre composites using electrospinning

International Nuclear Information System (INIS)

Burke, Luke; Mortimer, Chris J.; Curtis, Daniel J.; Lewis, Aled R.; Williams, Rhodri; Hawkins, Karl; Maffeis, Thierry G.G.; Wright, Chris J.

2017-01-01

We demonstrate a facile, one-step process to form polymer scaffolds composed of magnetic iron oxide nanoparticles (MNPs) contained within electrospun nano- and micro-fibres of two biocompatible polymers, Poly(ethylene oxide) (PEO) and Poly(vinyl pyrrolidone) (PVP). This was achieved with both needle and free-surface electrospinning systems demonstrating the scalability of the composite fibre manufacture; a 228 fold increase in fibre fabrication was observed for the free-surface system. In all cases the nanoparticle-nanofibre composite scaffolds displayed morphological properties as good as or better than those previously described and fabricated using complex multi-stage techniques. Fibres produced had an average diameter (Needle-spun: 125 ± 18 nm (PEO) and 1.58 ± 0.28 μm (PVP); Free-surface electrospun: 155 ± 31 nm (PEO)) similar to that reported previously, were smooth with no bead defects. Nanoparticle-nanofibre composites were characterised using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS) (Nanoparticle average diameter ranging from 8 ± 3 nm to 27 ± 5 nm), XRD (Phase of iron oxide nanoparticles identified as magnetite) and nuclear magnetic resonance relaxation measurements (NMR) (T1/T2: 32.44 for PEO fibres containing MNPs) were used to verify the magnetic behaviour of MNPs. This study represents a significant step forward for production rates of magnetic nanoparticle-nanofibre composite scaffolds by the electrospinning technique. - Graphical abstract: We present a novel facile, one-step process for the in-situ synthesis of magnetic iron oxide nanoparticle-nanofibre composites using both needle and free-surface electrospinning. This is a significant step forward for production rates of magnetic nanoparticle-nanofibre scaffolds both in terms of fibre and nanoparticle production. - Highlights: • We present a novel process for the in-situ synthesis of magnetic iron oxide nanoparticle

In-situ synthesis of magnetic iron-oxide nanoparticle-nanofibre composites using electrospinning

Energy Technology Data Exchange (ETDEWEB)

Burke, Luke; Mortimer, Chris J. [Biomaterials, Biofouling and Biofilms Engineering Laboratory (B3EL), Systems and Process Engineering Centre, College of Engineering, Swansea University, Fabian Way, Swansea SA1 8EN (United Kingdom); Systems and Process Engineering Centre, College of Engineering, Swansea University, Fabian Way, Swansea SA1 8EN (United Kingdom); Curtis, Daniel J.; Lewis, Aled R.; Williams, Rhodri [Systems and Process Engineering Centre, College of Engineering, Swansea University, Fabian Way, Swansea SA1 8EN (United Kingdom); Hawkins, Karl [Centre for NanoHealth (CNH), Swansea University, Singleton Park, Swansea SA2 8PP (United Kingdom); Maffeis, Thierry G.G. [Systems and Process Engineering Centre, College of Engineering, Swansea University, Fabian Way, Swansea SA1 8EN (United Kingdom); Wright, Chris J., E-mail: c.wright@swansea.ac.uk [Biomaterials, Biofouling and Biofilms Engineering Laboratory (B3EL), Systems and Process Engineering Centre, College of Engineering, Swansea University, Fabian Way, Swansea SA1 8EN (United Kingdom); Systems and Process Engineering Centre, College of Engineering, Swansea University, Fabian Way, Swansea SA1 8EN (United Kingdom); Centre for NanoHealth (CNH), Swansea University, Singleton Park, Swansea SA2 8PP (United Kingdom)

2017-01-01

We demonstrate a facile, one-step process to form polymer scaffolds composed of magnetic iron oxide nanoparticles (MNPs) contained within electrospun nano- and micro-fibres of two biocompatible polymers, Poly(ethylene oxide) (PEO) and Poly(vinyl pyrrolidone) (PVP). This was achieved with both needle and free-surface electrospinning systems demonstrating the scalability of the composite fibre manufacture; a 228 fold increase in fibre fabrication was observed for the free-surface system. In all cases the nanoparticle-nanofibre composite scaffolds displayed morphological properties as good as or better than those previously described and fabricated using complex multi-stage techniques. Fibres produced had an average diameter (Needle-spun: 125 ± 18 nm (PEO) and 1.58 ± 0.28 μm (PVP); Free-surface electrospun: 155 ± 31 nm (PEO)) similar to that reported previously, were smooth with no bead defects. Nanoparticle-nanofibre composites were characterised using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS) (Nanoparticle average diameter ranging from 8 ± 3 nm to 27 ± 5 nm), XRD (Phase of iron oxide nanoparticles identified as magnetite) and nuclear magnetic resonance relaxation measurements (NMR) (T1/T2: 32.44 for PEO fibres containing MNPs) were used to verify the magnetic behaviour of MNPs. This study represents a significant step forward for production rates of magnetic nanoparticle-nanofibre composite scaffolds by the electrospinning technique. - Graphical abstract: We present a novel facile, one-step process for the in-situ synthesis of magnetic iron oxide nanoparticle-nanofibre composites using both needle and free-surface electrospinning. This is a significant step forward for production rates of magnetic nanoparticle-nanofibre scaffolds both in terms of fibre and nanoparticle production. - Highlights: • We present a novel process for the in-situ synthesis of magnetic iron oxide nanoparticle

Investigation of rare earths sorption from sulfuric- and hydrochloric media

International Nuclear Information System (INIS)

Nikonov, V.N.; Mikhlin, E.B.; Norina, T.M.; Afonina, T.A.

1978-01-01

A rate of equilibrium attainment has been studied during REE sorption from sulfuric and hydrochloric acid solutions and pulps. It has been shown that equilibrium upon sorption from hydrochloric acid solutions is attained faster than from sulfuric acid solutions. Equilibrium upon sorption from pulps is attained considerably slower than upon sorption from solutions. In all cases REM of cerium subgroup are sorbed better. An effect has been studied of the medium acidity on sorbability of REM and elements of iron and calcium impurities. It has been established that sorbability of these elements decreases with increasing acid concentration. Selectivity of REM sorption from sulfuric acid solutions decreases with a rise in H 2 SO 4 concentration in the solution. For hydrochloric acid solutions it remains constant in a wide range of HCl concentrations. Sorption leaching of REM from concentrates and cakes of sulfuric and hydrochloric acids in the presence of KU-2 leads to high technical and economic indexes: extraction with respect to the total amount of REM and yttrium into a commercial product is 76-86% for sulfuric acid solutions and 81-90% for hydrochloric solutions

Rieske iron-sulfur protein of the cytochrome bc(1) complex: a potential target for fungicide discovery.

Science.gov (United States)

Yang, Wen-Chao; Li, Hui; Wang, Fu; Zhu, Xiao-Lei; Yang, Guang-Fu

2012-07-23

The cytochrome bc(1) complex (complex III, cyt bc(1)) is an essential component of cellular respiration. Cyt bc(1) has three core subunits that are required for its catalytic activity: cytochrome b, cytochrome c(1), and the Rieske iron-sulfur protein (ISP). Although most fungicides inhibit this enzyme by binding to the cytochrome b subunit, resistance to these fungicides has developed rapidly due to their widespread application. Resistance is mainly associated with mutations in cytochrome b, the only subunit encoded by mitochondrial DNA. Recently, the flexibility and motion of the ISP and its essential role in electron transfer have received intense attention; this leads us to propose a new classification of cyt bc(1) inhibitors (three types of Q(o) inhibitors) that mobilize, restrict, or fix the rotation of the ISP. Importantly, the strengths of the ISP-inhibitor interactions correlate with inhibitor activity and the development of resistance to Q(o) inhibitors, thereby offering clues for designing novel cyt bc(1) inhibitors with high potency and a low risk of resistance. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of an M-Cluster-Substituted Nitrogenase VFe Protein.

Science.gov (United States)

Rebelein, Johannes G; Lee, Chi Chung; Newcomb, Megan; Hu, Yilin; Ribbe, Markus W

2018-03-13

The Mo- and V-nitrogenases are two homologous members of the nitrogenase family that are distinguished mainly by the presence of different heterometals (Mo or V) at their respective cofactor sites (M- or V-cluster). However, the V-nitrogenase is ~600-fold more active than its Mo counterpart in reducing CO to hydrocarbons at ambient conditions. Here, we expressed an M-cluster-containing, hybrid V-nitrogenase in Azotobacter vinelandii and compared it to its native, V-cluster-containing counterpart in order to assess the impact of protein scaffold and cofactor species on the differential reactivities of Mo- and V-nitrogenases toward CO. Housed in the VFe protein component of V-nitrogenase, the M-cluster displayed electron paramagnetic resonance (EPR) features similar to those of the V-cluster and demonstrated an ~100-fold increase in hydrocarbon formation activity from CO reduction, suggesting a significant impact of protein environment on the overall CO-reducing activity of nitrogenase. On the other hand, the M-cluster was still ~6-fold less active than the V-cluster in the same protein scaffold, and it retained its inability to form detectable amounts of methane from CO reduction, illustrating a fine-tuning effect of the cofactor properties on this nitrogenase-catalyzed reaction. Together, these results provided important insights into the two major determinants for the enzymatic activity of CO reduction while establishing a useful framework for further elucidation of the essential catalytic elements for the CO reactivity of nitrogenase. IMPORTANCE This is the first report on the in vivo generation and in vitro characterization of an M-cluster-containing V-nitrogenase hybrid. The "normalization" of the protein scaffold to that of the V-nitrogenase permits a direct comparison between the cofactor species of the Mo- and V-nitrogenases (M- and V-clusters) in CO reduction, whereas the discrepancy between the protein scaffolds of the Mo- and V-nitrogenases (MoFe and VFe

The enigmatic SAR202 cluster up close: shedding light on a globally distributed dark ocean lineage involved in sulfur cycling.

Science.gov (United States)

Mehrshad, Maliheh; Rodriguez-Valera, Francisco; Amoozegar, Mohammad Ali; López-García, Purificación; Ghai, Rohit

2018-03-01

The dark ocean microbiota represents the unknown majority in the global ocean waters. The SAR202 cluster belonging to the phylum Chloroflexi was the first microbial lineage discovered to specifically inhabit the aphotic realm, where they are abundant and globally distributed. The absence of SAR202 cultured representatives is a significant bottleneck towards understanding their metabolic capacities and role in the marine environment. In this work, we use a combination of metagenome-assembled genomes from deep-sea datasets and publicly available single-cell genomes to construct a genomic perspective of SAR202 phylogeny, metabolism and biogeography. Our results suggest that SAR202 cluster members are medium sized, free-living cells with a heterotrophic lifestyle, broadly divided into two distinct clades. We present the first evidence of vertical stratification of these microbes along the meso- and bathypelagic ocean layers. Remarkably, two distinct species of SAR202 cluster are highly abundant in nearly all deep bathypelagic metagenomic datasets available so far. SAR202 members metabolize multiple organosulfur compounds, many appear to be sulfite-oxidizers and are predicted to play a major role in sulfur turnover in the dark water column. This concomitantly suggests an unsuspected availability of these nutrient sources to allow for the high abundance of these microbes in the deep sea.

Uranium,Radium and Iron Absorption from Liquid Waste Uranium Ore Processing by Zeolite

International Nuclear Information System (INIS)

Wismawati, T; Sorot sudiro, A; Herjati, T

1998-01-01

The aim of this work is to determine zeolites sorption capacity and the distribution coefficient of uranium, radium, and iron in zeolite-liquid waste system. Mineralogical composition of zeolite used in the experiment has been determine by examining the thin sections of zeolite grains under a microscope. Zeolite has ben activated by the dilute sulfuric acid or sodium hydroxide solution. The results show that the use of 0.25 N sodium hydroxide solution could be optimizing the zeolite for uranium and iron ions sorption and that of 0.1 N sulfuric acid solution is for radium sorption. The re-activation process has been carried out in three hours. Under such a condition, the sorption efficiency of zeolite to those ions have been known to be 45.85% for uranium, 96.63 % for iron and 87.80 % for radium. The distribution coefficients of uranium, radium and iron ion in zeolite-liquid waste system have been calculated 0.85, 7.02, and 28.65 ml/g respectively

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

Energy Technology Data Exchange (ETDEWEB)

Kohnert, Aaron A.; Wirth, Brian D. [University of Tennessee, Knoxville, Tennessee 37996-2300 (United States)

2015-04-21

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

Control of the interparticle spacing in superparamagnetic iron oxide nanoparticle clusters by surface ligand engineering

Science.gov (United States)

Dan, Wang; Bingbing, Lin; Taipeng, Shen; Jun, Wu; Fuhua, Hao; Chunchao, Xia; Qiyong, Gong; Huiru, Tang; Bin, Song; Hua, Ai

2016-07-01

Polymer-mediated self-assembly of superparamagnetic iron oxide (SPIO) nanoparticles allows modulation of the structure of SPIO nanocrystal cluster and their magnetic properties. In this study, dopamine-functionalized polyesters (DA-polyester) were used to directly control the magnetic nanoparticle spacing and its effect on magnetic resonance relaxation properties of these clusters was investigated. Monodisperse SPIO nanocrystals with different surface coating materials (poly(ɛ-caprolactone), poly(lactic acid)) of different molecular weights containing dopamine (DA) structure (DA-PCL2k, DA-PCL1k, DA-PLA1k)) were prepared via ligand exchange reaction, and these nanocrystals were encapsulated inside amphiphilic polymer micelles to modulate the SPIO nanocrystal interparticle spacing. Small-angle x-ray scattering (SAXS) was applied to quantify the interparticle spacing of SPIO clusters. The results demonstrated that the tailored magnetic nanoparticle clusters featured controllable interparticle spacing providing directly by the different surface coating of SPIO nanocrystals. Systematic modulation of SPIO nanocrystal interparticle spacing can regulate the saturation magnetization (M s) and T 2 relaxation of the aggregation, and lead to increased magnetic resonance (MR) relaxation properties with decreased interparticle spacing. Project supported by the National Key Basic Research Program of China (Grant No. 2013CB933903), the National Key Technology R&D Program of China (Grant No. 2012BAI23B08), and the National Natural Science Foundation of China (Grant Nos. 20974065, 51173117, and 50830107).

Iron/iron oxide core-shell nanoclusters for biomedical applications

International Nuclear Information System (INIS)

Qiang You; Antony, Jiji; Sharma, Amit; Nutting, Joseph; Sikes, Daniel; Meyer, Daniel

2006-01-01

Biocompatible magnetic nanoparticles have been found promising in several biomedical applications for tagging, imaging, sensing and separation in recent years. Most magnetic particles or beads currently used in biomedical applications are based on ferromagnetic iron oxides with very low specific magnetic moments of about 20-30 emu/g. Here we report a new approach to synthesize monodispersed core-shell nanostructured clusters with high specific magnetic moments above 200 emu/g. Iron nanoclusters with monodispersive size of diameters from 2 nm to 100 nm are produced by our newly developed nanocluster source and go to a deposition chamber, where a chemical reaction starts, and the nanoclusters are coated with iron oxides. HRTEM Images show the coatings are very uniform and stable. The core-shell nanoclusters are superparamagnetic at room temperature for sizes less than 15 nm, and then become ferromagnetic when the cluster size increases. The specific magnetic moment of core-shell nanoclusters is size dependent, and increases rapidly from about 80 emu/g at the cluster size of around 3 nm to over 200 emu/g up to the size of 100 nm. The use of high magnetic moment nanoclusters for biomedical applications could dramatically enhance the contrast for MRI, reduce the concentration of magnetic particle needs for cell separation, or make drug delivery possible with much lower magnetic field gradients

Three-dimensional iron sulfide-carbon interlocked graphene composites for high-performance sodium-ion storage

DEFF Research Database (Denmark)

Huang, Wei; Sun, Hongyu; Shangguan, Huihui

2018-01-01

Three-dimensional (3D) carbon-wrapped iron sulfide interlocked graphene (Fe7S8@C-G) composites for high-performance sodium-ion storage are designed and produced through electrostatic interactions and subsequent sulfurization. The iron-based metal–organic frameworks (MOFs, MIL-88-Fe) interact with...

Sulfur in serpentinized oceanic peridotites: Serpentinization processes and microbial sulfate reduction

Science.gov (United States)

Alt, J.C.; Shanks, Wayne C.

1998-01-01

The mineralogy, contents, and isotopic compositions of sulfur in oceanic serpentinites reflect variations in temperatures and fluid fluxes. Serpentinization of serpentinization of Iberian Margin peridotites occurred at low temperatures (???20??-200??C) and high water/rock ratios. Complete serpentinization and consumption of ferrous iron allowed evolution to higher fO2. Microbial reduction of seawater sulfate resulted in addition of low-??34S sulfide (-15 to -43???) and formation of higher-sulfur assemblages that include valleriite and pyrite. The high SO4/total S ratio of Hess Deep serpentinites (0.89) results in an increase of total sulfur and high ??34S of total sulfur (mean ??? 8???). In contrast, Iberian Margin serpentinites gained large amounts of 34S-poor sulfide (mean total S = 3800 ppm), and the high sulfide/total S ratio (0.61) results in a net decrease in ??34S of total sulfur (mean ??? -5???). Thus serpentinization is a net sink for seawater sulfur, but the amount fixed and its isotopic composition vary significantly. Serpentinization may result in uptake of 0.4-14 ?? 1012 g S yr-1 from the oceans, comparable to isotopic exchange in mafic rocks of seafloor hydrothermal systems and approaching global fluxes of riverine sulfate input and sedimentary sulfide output.

Biogeochemical conversion of sulfur species in saline lakes of Steppe Altai

Science.gov (United States)

Borzenko, Svetlana V.; Kolpakova, Marina N.; Shvartsev, Stepan L.; Isupov, Vitaly P.

2017-08-01

The aim of the present research is to identify the main mechanisms of sulfur behavior in saline lakes in the course of time and followed transformations in their chemical composition. The influence of water on chemical composition of biochemical processes involved in decomposition of organic matter was determined by the study of behavior of reduced forms of sulfur in lakes. The determination of reduced forms of sulfur was carried out by successive transfer of each form of sulfur to hydrogen sulfide followed by photometric measurements. The other chemical components were determined by standard methods (atomic absorption, potentiometric method, titration method and others). The salt lakes of the Altai steppe were studied in summer season 2013-2015. Analysis of the chemical composition of the saline lakes of Altai Krai has shown that carbonate-, hydrocarbonate- and chloride ions dominate among anions; sodium is main cation; sulfates are found in subordinate amounts. Reduced forms of sulfur occur everywhere: hydrogen and hydrosulfide sulfur S2- prevail in the bottom sediments; its derivative—elemental S0—prevails in the lakes water. The second important species in water of soda lakes is hydrosulfide sulfur S2-, and in chloride lakes is thiosulfate sulfur S2O3 2- . The lag in the accumulation of sulfates in soda lakes in comparison to chloride lakes can be explained by their bacterial reduction, followed by the formation and deposition of iron sulfides in sediments. In chloride lakes gypsum is a predominantly barrier for sulfates.

Insight into acid-base nucleation experiments by comparison of the chemical composition of positive, negative, and neutral clusters.

Science.gov (United States)

Bianchi, Federico; Praplan, Arnaud P; Sarnela, Nina; Dommen, Josef; Kürten, Andreas; Ortega, Ismael K; Schobesberger, Siegfried; Junninen, Heikki; Simon, Mario; Tröstl, Jasmin; Jokinen, Tuija; Sipilä, Mikko; Adamov, Alexey; Amorim, Antonio; Almeida, Joao; Breitenlechner, Martin; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Kangasluoma, Juha; Keskinen, Helmi; Kim, Jaeseok; Kirkby, Jasper; Laaksonen, Ari; Lawler, Michael J; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Riccobono, Francesco; Rissanen, Matti P; Rondo, Linda; Tomé, António; Virtanen, Annele; Viisanen, Yrjö; Williamson, Christina; Wimmer, Daniela; Winkler, Paul M; Ye, Penglin; Curtius, Joachim; Kulmala, Markku; Worsnop, Douglas R; Donahue, Neil M; Baltensperger, Urs

2014-12-02

We investigated the nucleation of sulfuric acid together with two bases (ammonia and dimethylamine), at the CLOUD chamber at CERN. The chemical composition of positive, negative, and neutral clusters was studied using three Atmospheric Pressure interface-Time Of Flight (APi-TOF) mass spectrometers: two were operated in positive and negative mode to detect the chamber ions, while the third was equipped with a nitrate ion chemical ionization source allowing detection of neutral clusters. Taking into account the possible fragmentation that can happen during the charging of the ions or within the first stage of the mass spectrometer, the cluster formation proceeded via essentially one-to-one acid-base addition for all of the clusters, independent of the type of the base. For the positive clusters, the charge is carried by one excess protonated base, while for the negative clusters it is carried by a deprotonated acid; the same is true for the neutral clusters after these have been ionized. During the experiments involving sulfuric acid and dimethylamine, it was possible to study the appearance time for all the clusters (positive, negative, and neutral). It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge. The growth rate is then probably limited by the arrival rate of sulfuric acid or cluster-cluster collision.

Excessive sulfur supply reduces cadmium accumulation in brown rice (Oryza sativa L.)

International Nuclear Information System (INIS)

Fan Jianling; Hu Zhengyi; Ziadi, Noura; Xia Xu; Wu Congyanghui

2010-01-01

Human activities have resulted in cadmium (Cd) and sulfur (S) accumulation in paddy soils in parts of southern China. A combined soil-sand pot experiment was conducted to investigate the influence of excessive S supply on iron plaque formation and Cd accumulation in rice plants, using two Cd levels (0, 1.5 mg kg -1 ) combined with three S concentrations (0, 60, 120 mg kg -1 ). The results showed that excessive S supply significantly decreased Cd accumulation in brown rice due to the decrease of Cd availability and the increase of glutathione in rice leaves. But excessive S supply obviously increased Cd accumulation in roots due to the decrease of iron plaque formation on the root surface of rice. Therefore, excessive S supply may result in loss of rice yield, but it could effectively reduce Cd accumulation in brown rice exposed to Cd contaminated soils. - Excessive sulfur reduces cadmium accumulation in brown rice.

A new approach to fabrication of Cs/BG/CNT nanocomposite scaffold towards bone tissue engineering and evaluation of its properties

Energy Technology Data Exchange (ETDEWEB)

Shokri, S. [Department of Nanotechnology Engineering, Faculty of Advanced Sciences and Technologies, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of); Movahedi, B., E-mail: b.movahedi@ast.ui.ac.ir [Department of Nanotechnology Engineering, Faculty of Advanced Sciences and Technologies, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of); Rafieinia, M. [Biosensor Research Center, Department of Advanced Medical Technology, Isfahan University of Medical Sciences, Isfahan, 64716 (Iran, Islamic Republic of); Salehi, H. [Department of Anatomical Sciences, Isfahan University of Medical Sciences, Isfahan, 64716 (Iran, Islamic Republic of)

2015-12-01

Graphical abstract: - Highlights: • Nanocomposite scaffold was produced using a novel technique. • Bioactive glass, carbon nanotube and chitosan were used for fabrication of nanocomposite scaffold. • The compressive strength of the scaffold was near to the cancellous bone. • Biodegradability of the scaffolds in PBS shows the slow destruction. - Abstract: In the present study, bioactive glass (BG), carbon nanotube (CNT), and chitosan (Cs) were used with different ratios for the fabrication of nanocomposite scaffold for bone tissue engineering. BG was synthesized by sol–gel process and CNT was functionalized by immersing in sulfuric acid as well as nitric acid. Nanocomposite scaffold was produced using a novel technique, hot press, and salt leaching process and cross-linked by Hexamethylene diisocyanate (HDI). The optimum porosity of the scaffold with respect to the ratio of salt and precursor was kept around 70%. Mechanical properties of the scaffolds were increased by the addition of CNT and hence, the compressive strength of them with 4 wt% CNT was increased up to 5.95 ± 0.5 MPa. The nanocomposite scaffolds were characterized by FT-IR, SEM, XRD, and electrochemical analysis. Furthermore, scaffolds were immersed in PBS for evaluating the biodegradability, water absorption, and CNT release. The results indicated that water absorption of the scaffolds was increased by adding CNT to the scaffold. The amount of released CNT after 30 days was measured within 6 × 10{sup −4} and 1 × 10{sup −3} mg/ml. Attachment and proliferation of MG63 osteoblast cell line on Cs/BG/CNT scaffolds were investigated by MTT assay indicating no toxicity for this nanocomposite scaffolds. According to the results of the experiments, the nanocomposite scaffold with modified composition (Cs/BG/CNT, 80:20:2 wt%) was the best one in matters of mechanical, chemical, and cellular properties and also the most appropriate for trabecular bone tissue.

Surface modification of beta-tricalcium phosphate scaffolds with topological nanoapatite coatings

International Nuclear Information System (INIS)

Zhang Faming; Chang Jiang; Lu Jianxi; Ning Congqin

2008-01-01

A biomimetic process was developed to create a modulable surface topography of nanocrystalline apatite on pure beta-tricalcium phosphate (β-TCP) scaffolds. The scaffolds were immersed in a newly revised simulated body fluid (R n -SBF) to produce nanocrystalline apatite. The obtained surfaces were investigated using scanning electric microscopy, energy dispersion spectrum, Fourier transform infrared spectroscopy, X-ray diffraction, and transmission electric microscopy. Nanoparticulates apatite were produced on the surface of the scaffolds for 1 day's soaking; increasing soaking to 3 days led to the formation of a surface covered by needle-like apatite nanocrystals; and a surface coating of needle-like apatite clusters was created after two weeks' soaking in the R n -SBF without bicarbonate ion concentrations. The increase of bicarbonate ion concentrations progressively in the R n -SBF provided a surface entirely coated with a nanostructured thick layer of apatite. These apatite nanostructures were low-crystalline bone-like apatite. The mechanisms for the apatite formation and transition of surface topographies were also discussed. Therefore, a variety of surface topography of nanoapatite coatings on the β-TCP scaffolds can be obtained using this method, which may enhance cell adhesion to the scaffolds for bone tissue engineering applications

Trichomonas vaginalis Repair of Iron Centres Proteins: The Different Role of Two Paralogs.

Science.gov (United States)

Nobre, Lígia S; Meloni, Dionigia; Teixeira, Miguel; Viscogliosi, Eric; Saraiva, Lígia M

2016-06-01

Trichomonas vaginalis, the causative parasite of one of the most prevalent sexually transmitted diseases is, so far, the only protozoan encoding two putative Repair of Iron Centres (RIC) proteins. Homologs of these proteins have been shown to protect bacteria from the chemical stress imposed by mammalian immunity. In this work, the biochemical and functional characterisation of the T. vaginalis RICs revealed that the two proteins have different properties. Expression of ric1 is induced by nitrosative stress but not by hydrogen peroxide, while ric2 transcription remained unaltered under similar conditions. T. vaginalis RIC1 contains a di-iron centre, but RIC2 apparently does not. Only RIC1 resembles bacterial RICs on spectroscopic profiling and repairing ability of oxidatively-damaged iron-sulfur clusters. Unexpectedly, RIC2 was found to bind DNA plasmid and T. vaginalis genomic DNA, a function proposed to be related with its leucine zipper domain. The two proteins also differ in their cellular localization: RIC1 is expressed in the cytoplasm only, and RIC2 occurs both in the nucleus and cytoplasm. Therefore, we concluded that the two RIC paralogs have different roles in T. vaginalis, with RIC2 showing an unprecedented DNA binding ability when compared with all other until now studied RICs. Copyright © 2016 Elsevier GmbH. All rights reserved.

Sulfuric acid dissolution of the Chashma-Sang deposit's green clays

International Nuclear Information System (INIS)

Mirzoev, D.Kh.; Boboev, Kh.E.; Pulatov, M.S.; Mirsaidov, U.M.

2005-01-01

Present article is presenting the results of the roentgen phase, thermodynamic and physical-chemical investigations of the green clays of the Chashma-Sang deposit of the Republic of Tajikistan. It is presented mineralogical and chemical composition of the mineral raw materials. Kinetic of decomposition of the oxides of aluminum and iron on temperature, time and concentration of the sulfuric acid has been investigated

Hybrid scaffold bearing polymer-siloxane Schiff base linkage for bone tissue engineering

Energy Technology Data Exchange (ETDEWEB)

Nair, Bindu P., E-mail: bindumelekkuttu@gmail.com; Gangadharan, Dhanya; Mohan, Neethu; Sumathi, Babitha; Nair, Prabha D., E-mail: pdnair49@gmail.com

2015-07-01

Scaffolds that can provide the requisite biological cues for the fast regeneration of bone are highly relevant to the advances in tissue engineering and regenerative medicine. In the present article, we report the fabrication of a chitosan–gelatin–siloxane scaffold bearing interpolymer-siloxane Schiff base linkage, through a single-step dialdehyde cross-linking and freeze-drying method using 3-aminopropyltriethoxysilane as the siloxane precursor. Swelling of the scaffolds in phosphate buffered saline indicates enhancement with increase in siloxane concentration, whereas compressive moduli of the wet scaffolds reveal inverse dependence, owing to the presence of siloxane, rich in silanol groups. It is suggested that through the strategy of dialdehyde cross-linking, a limiting siloxane loading of 20 wt.% into a chitosan-gelatin matrix should be considered ideal for bone tissue engineering, because the scaffold made with 30 wt.% siloxane loading degrades by 48 wt.%, in 21 days. The hybrid scaffolds bearing Schiff base linkage between the polymer and siloxane, unlike the stable linkages in earlier reports, are expected to give a faster release of siloxanes and enhancement in osteogenesis. This is verified by the in vitro evaluation of the hybrid scaffolds using rabbit adipose mesenchymal stem cells, which revealed osteogenic cell-clusters on a polymer-siloxane scaffold, enhanced alkaline phosphatase activity and the expression of bone-specific genes, whereas the control scaffold without siloxane supported more of cell-proliferation than differentiation. A siloxane concentration dependent enhancement in osteogenic differentiation is also observed. - Highlights: • A hybrid scaffold bearing interpolymer-siloxane Schiff base linkage • A limiting siloxane loading of 20 wt.% into chitosan–gelatin matrix • A siloxane concentration dependent enhancement in osteogenic differentiation.

Iron minerals formed by dissimilatory iron-and sulfur reducing bacteria studied by Moessbauer spectrometry

International Nuclear Information System (INIS)

Chistyakova, N. I.; Rusakov, V. S.; Nazarova, K. A.; Koksharov, Yu. A.; Zavarzina, D. G.; Greneche, J.-M.

2008-01-01

Zero-field and in-field Moessbauer investigations and electron paramagnetic resonance (EPR) measurements to follow the kinetics of the iron mineral formation by thermophilic dissimilatory anaerobic Fe(III)-reducing bacteria (strain Z-0001) and anaerobic alkaliphilic bacteria (strain Z-0531) were carried out.

Clustering of amines and hydrazines in atmospheric nucleation

Science.gov (United States)

Li, Siyang; Qu, Kun; Zhao, Hailiang; Ding, Lei; Du, Lin

2016-06-01

It has been proved that the presence of amines in the atmosphere can enhance aerosol formation. Hydrazine (HD) and its substituted derivatives, monomethylhydrazine (MMH) and unsymmetrical dimethylhydrazine (UDMH), which are organic derivatives of amine and ammonia, are common trace atmospheric species that may contribute to the growth of nucleation clusters. The structures of the hydrazine and amine clusters containing one or two common nucleation molecules (ammonia, water, methanol and sulfuric acid) have been optimized using density functional theory (DFT) methods. The clusters growth mechanism has been explored from the thermochemistry by calculating the Gibbs free energies of adding an ammonia, water, methanol or sulfuric acid molecule step by step at room temperature, respectively. The results show that hydrazine and its derivatives could enhance heteromolecular homogeneous nucleation in the earth's atmosphere.

Arsenic Removal from Water Using Various Adsorbents: Magnetic Ion Exchange Resins, Hydrous Ion Oxide Particles, Granular Ferric Hydroxide, Activated Alumina, Sulfur Modified Iron, and Iron Oxide-Coated Microsand

KAUST Repository

Sinha, Shahnawaz

2011-09-30

The equilibrium and kinetic adsorption of arsenic on six different adsorbents were investigated with one synthetic and four natural types (two surface and two ground) of water. The adsorbents tested included magnetic ion exchange resins (MIEX), hydrous ion oxide particles (HIOPs), granular ferric hydroxide (GFH), activated alumina (AA), sulfur modified iron (SMI), and iron oxide-coated mic - rosand (IOC-M), which have different physicochemical properties (shape, charge, surface area, size, and metal content). The results showed that adsorption equilibriums were achieved within a contact period of 20 min. The optimal doses of adsorbents determined for a given equilibrium concentration of C eq = 10 μg/L were 500 mg/L for AA and GFH, 520–1,300 mg/L for MIEX, 1,200 mg/L for HIOPs, 2,500 mg/L for SMI, and 7,500 mg/L for IOC-M at a contact time of 60 min. At these optimal doses, the rate constants of the adsorbents were 3.9, 2.6, 2.5, 1.9, 1.8, and 1.6 1/hr for HIOPs, AA, GFH, MIEX, SMI, and IOC-M, respectively. The presence of silicate significantly reduced the arsenic removal efficiency of HIOPs, AA, and GFH, presumably due to the decrease in chemical binding affinity of arsenic in the presence of silicate. Additional experiments with natural types of water showed that, with the exception of IOC-M, the adsorbents had lower adsorption capacities in ground water than with surface and deionized water, in which the adsorption capacities decreased by approximately 60–95 % .

Synthesis and photochemical properties of a novel iron-sulfur-nitrosyl cluster derivatized with the pendant chromophore protoporphyrin IX.

Science.gov (United States)

Conrado, Christa L; Wecksler, Stephen; Egler, Christian; Magde, Douglas; Ford, Peter C

2004-09-06

The novel Roussin red-salt ester (PPIX-RSE) with a pendant porphyrin chromophore was prepared and investigated as a precursor for the photochemical generation of nitric oxide. PPIX-RSE has the general formula Fe(2)(NO)(4)[(mu-S,mu-S')P] (where (S,S')P is the bis(2-thiolatoethyl) diester of protoporphyrin IX. The photoexcitation of PPIX-RSE with 436- or 546-nm light in an aerated chloroform solution led to the photodecomposition of the cluster with the respective quantum yields (5.2 +/- 0.7) x 10(-4) and (2.5 +/- 0.5 x 10(-4)) and the concomitant release of NO. PPIX-RSE is a significantly more effective NO generator at longer wavelength excitation than are other Fe(2)(mu-SR)(2)(NO)(4) esters for which R is a simple alkyl group such as CH(3)CH(2)- because of the much higher absorptivity of the pendant PPIX chromophore at these wavelengths and a modestly higher quantum yield. Fluorescence intensity and lifetime data indicate that the photoexcited porphyrin of PPIX-RSE is largely quenched by the energy transfer to the Fe(2)S(2)(NO)(4) cluster's core. However, a small fraction of this emission is not quenched, and it is proposed that PPIX-RSE may exist in solution as two conformers.

Extending the Compositional Range of Nanocasting in the Oxozirconium Cluster-Based Metal–Organic Framework NU-1000—A Comparative Structural Analysis

Energy Technology Data Exchange (ETDEWEB)

Zhao, Wenyang [Department; Wang, Zhao [Department; Malonzo, Camille D. [Department; Webber, Thomas E. [Department; Platero-Prats, Ana E. [X-ray; Sotomayor, Francisco [Quantachrome Instruments, 1900 Corporate; Vermeulen, Nicolaas A. [Department; Wang, Timothy C. [Department; Hupp, Joseph T. [Department; Farha, Omar K. [Department; Department; Penn, R. Lee [Department; Chapman, Karena W. [X-ray; Thommes, Matthias [Quantachrome Instruments, 1900 Corporate; Stein, Andreas [Department

2018-02-08

The process of nanocasting in metal-organic frameworks (MOFs) is a versatile approach to modify these porous materials by introducing supporting scaffolds. The nanocast scaffolds can stabilize metal-oxo clusters in MOFs at high temperatures and modulate their chemical environments. Here we demonstrate a range of nanocasting approaches in the MOF NU-1000, which contains hexanuclear oxozirconium clusters (denoted as Zr6 clusters) that are suitable for modification with other metals. We developed methods for introducing SiO2, TiO2, polymeric, and carbon scaffolds into the NU-1000 structure. The responses of NU-1000 towards different scaffold precursors were studied, including the effects on morphology, precursor distribution, and porosity after nanocasting. Upon removal of organic linkers in the MOF by calcination/pyrolysis at 500 °C or above, the Zr6 clusters remained accessible and maintained their Lewis acidity in SiO2 nanocast samples, whereas additional treatment was necessary for Zr6 clusters to become accessible in carbon nanocast samples. Aggregation of Zr6 clusters was largely prevented with SiO2 or carbon scaffolds even after thermal treatment at 500 °C or above. In the case of titania nanocasting, NU- 1000 crystals underwent a pseudomorphic transformation, in which Zr6 clusters reacted with titania to form small oxaggregates of a Zr/Ti mixed oxide with a local structure resembling that of ZrTi2O6. The ability to maintain high densities of discrete Lewis acidic Zr6 clusters on SiO2 or carbon supports at high temperatures provides a starting point for designing new thermally stable catalysts.

Sulfur flows and biosolids processing: Using Material Flux Analysis (MFA) principles at wastewater treatment plants.

Science.gov (United States)

Fisher, R M; Alvarez-Gaitan, J P; Stuetz, R M; Moore, S J

2017-08-01

High flows of sulfur through wastewater treatment plants (WWTPs) may cause noxious gaseous emissions, corrosion of infrastructure, inhibit wastewater microbial communities, or contribute to acid rain if the biosolids or biogas is combusted. Yet, sulfur is an important agricultural nutrient and the direct application of biosolids to soils enables its beneficial re-use. Flows of sulfur throughout the biosolids processing of six WWTPs were investigated to identify how they were affected by biosolids processing configurations. The process of tracking sulfur flows through the sites also identified limitations in data availability and quality, highlighting future requirements for tracking substance flows. One site was investigated in more detail showing sulfur speciation throughout the plant and tracking sulfur flows in odour control systems in order to quantify outflows to air, land and ocean sinks. While the majority of sulfur from WWTPs is removed as sulfate in the secondary effluent, the sulfur content of biosolids is valuable as it can be directly returned to soils to combat the potential sulfur deficiencies. Biosolids processing configurations, which focus on maximising solids recovery, through high efficiency separation techniques in primary sedimentation tanks, thickeners and dewatering centrifuges retain more sulfur in the biosolids. However, variations in sulfur loads and concentrations entering the WWTPs affect sulfur recovery in the biosolids, suggesting industrial emitters, and chemical dosing of iron salts are responsible for differences in recovery between sites. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulphur-binding in recent environments. II. Speciation of sulphur and iron and implications for the occurrence of organo-sulphur compounds

NARCIS (Netherlands)

Sinninghe Damsté, J.S.; Hartgers, W.A.; Lopez, J.F.; Reiss, C.; Maxwell, J.R.; Grimalt, J.O.

1997-01-01

Speciation of iron and sulfur species was determined for two recent sediments (La Trinitat and Lake Cisó) which were deposited in environments with a high biological productivity and sulfate-reducing activity. In sediments from calcite ponds of La Trinitat an excess of reactive iron species (iron

Citrate Defines a Regulatory Link Between Energy Metabolism and the Liver Hormone Hepcidin

OpenAIRE

Ladeira Courelas da Silva, Ana Rita

2017-01-01

Iron plays a critical role as an oxygen carrier in hemoglobin as well as a constituent of iron-sulfur clusters. Increasing evidence suggests that mechanisms maintaining iron homeostasis cross-talk to intermediary metabolism. The liver hormone hepcidin is the key regulator of systemic iron metabolism. Hepcidin transcriptional control is linked to the nutrient-sensing mTOR pathway, proliferative signals, gluconeogenic responses during starvation and hormones that modulate energy metabolism. The...

Sulfur solubility of liquid and solid Fe-Cr alloys. A thermodynamic analysis

Energy Technology Data Exchange (ETDEWEB)

Waldner, Peter [Leoben Univ. (Austria). Dept. of General, Analytical and Physical Chemistry

2015-04-15

Gibbs energy modeling for sulfur solving liquid and solid iron-chromium phases with body- and face-centered cubic structure has been carried out using a substitutional approach. Experimental data available from the literature on sulfur potentials in the temperature range 1 525 to 1 755 C for the liquid metallic phase and 1 000 to 1 300 C for the solid alloys have been taken into consideration. Recent thermodynamic evaluations of the Fe-S and Cr-S binary subsystems served as basis for the presented work. The obtained models allow a satisfactory reproduction of the majority of the sulfur potential data as well as the prediction of an isothermal partial section at 1 300 C. Consistent embedding of the optimized Gibbs energies within a recent thermodynamic modeling of the complete Cr-Fe-S system is achieved.

Analyzing the anodic reactions for iron surface with a porous Al2O3 cluster with the scanning vibrating electrode

Science.gov (United States)

Eliyan, Faysal Fayez

2017-09-01

The Scanning Vibrating Electrode Technique (SVET) was used to analyze the anodic reactions inside and around a porous Al2O3 cluster embedded onto an iron foil. The tests were carried out at -0.7 V vs. Saturated Calomel Electrode, in naturally aerated solutions of 0.1, 0.2, 0.35, and 0.5 M bicarbonate concentration. During 10 h of testing, the SVET showed evidence for a formation of a passive film in and around the cluster, in the scanning area shown in the graphical abstract. In the dilute 0.1 and 0.2 M solutions, the passive films formed slower than those in 0.35 and 0.5 M solutions. In the SVET maps, the passive films showed that they could suppress dissolution to currents comparable to those of slower dissolution under the porous Al2O3 cluster.

A Regulatory Circuit Composed of a Transcription Factor, IscR, and a Regulatory RNA, RyhB, Controls Fe-S Cluster Delivery.

Science.gov (United States)

Mandin, Pierre; Chareyre, Sylvia; Barras, Frédéric

2016-09-20

Fe-S clusters are cofactors conserved through all domains of life. Once assembled by dedicated ISC and/or SUF scaffolds, Fe-S clusters are conveyed to their apo-targets via A-type carrier proteins (ATCs). Escherichia coli possesses four such ATCs. ErpA is the only ATC essential under aerobiosis. Recent studies reported a possible regulation of the erpA mRNA by the small RNA (sRNA) RyhB, which controls the expression of many genes under iron starvation. Surprisingly, erpA has not been identified in recent transcriptomic analysis of the iron starvation response, thus bringing into question the actual physiological significance of the putative regulation of erpA by RyhB. Using an sRNA library, we show that among 26 sRNAs, only RyhB represses the expression of an erpA-lacZ translational fusion. We further demonstrate that this repression occurs during iron starvation. Using mutational analysis, we show that RyhB base pairs to the erpA mRNA, inducing its disappearance. In addition, IscR, the master regulator of Fe-S homeostasis, represses expression of erpA at the transcriptional level when iron is abundant, but depleting iron from the medium alleviates this repression. The conjunction of transcriptional derepression by IscR and posttranscriptional repression by RyhB under Fe-limiting conditions is best described as an incoherent regulatory circuit. This double regulation allows full expression of erpA at iron concentrations for which Fe-S biogenesis switches from the ISC to the SUF system. We further provide evidence that this regulatory circuit coordinates ATC usage to iron availability. Regulatory small RNAs (sRNAs) have emerged as major actors in the control of gene expression in the last few decades. Relatively little is known about how these regulators interact with classical transcription factors to coordinate genetic responses. We show here how an sRNA, RyhB, and a transcription factor, IscR, regulate expression of an essential gene, erpA, in the bacterium E

TLR-activated repression of Fe-S cluster biogenesis drives a metabolic shift and alters histone and tubulin acetylation.

Science.gov (United States)

Tong, Wing-Hang; Maio, Nunziata; Zhang, De-Liang; Palmieri, Erika M; Ollivierre, Hayden; Ghosh, Manik C; McVicar, Daniel W; Rouault, Tracey A

2018-05-22

Given the essential roles of iron-sulfur (Fe-S) cofactors in mediating electron transfer in the mitochondrial respiratory chain and supporting heme biosynthesis, mitochondrial dysfunction is a common feature in a growing list of human Fe-S cluster biogenesis disorders, including Friedreich ataxia and GLRX5-related sideroblastic anemia. Here, our studies showed that restriction of Fe-S cluster biogenesis not only compromised mitochondrial oxidative metabolism but also resulted in decreased overall histone acetylation and increased H3K9me3 levels in the nucleus and increased acetylation of α-tubulin in the cytosol by decreasing the lipoylation of the pyruvate dehydrogenase complex, decreasing levels of succinate dehydrogenase and the histone acetyltransferase ELP3, and increasing levels of the tubulin acetyltransferase MEC17. Previous studies have shown that the metabolic shift in Toll-like receptor (TLR)-activated myeloid cells involves rapid activation of glycolysis and subsequent mitochondrial respiratory failure due to nitric oxide (NO)-mediated damage to Fe-S proteins. Our studies indicated that TLR activation also actively suppresses many components of the Fe-S cluster biogenesis machinery, which exacerbates NO-mediated damage to Fe-S proteins by interfering with cluster recovery. These results reveal new regulatory pathways and novel roles of the Fe-S cluster biogenesis machinery in modifying the epigenome and acetylome and provide new insights into the etiology of Fe-S cluster biogenesis disorders.

The performance of oil-fired boilers: The influence of fuel sulfur on emissions and appliance integrity

International Nuclear Information System (INIS)

Lee, S.W.

1997-01-01

ASHRAE research project RP-757 examined the impact of distillate fuel sulfur content on the energy and emission performance of oil-fired boilers. The project involved construction of a combustion test rig housed in a constant-temperature test room; installation of a 102.5 kW (350,000 Btu/h) capacity, steel hot water boiler equipped with a special test section to simulate boiler heat exchanger surfaces; introduction of continuous emission analyzers and data-acquisition/control systems; and preparation of specific test fuel oils in the 0.01% to 1.2% sulfur range. The combustion experiments provided comprehensive data including flue gas composition, total deposit weight on test heat exchanger surfaces, pH, sulfite and sulfate in the flue gas condensate and soluble deposits, and iron and sulfur in soluble and insoluble deposits. Controlled combustion experiments using the experimental boiler and fuels have provided the following observations for a systematic increase of boiler fuel sulfur: the flue gas SO 2 increased linearly; the acidity and concentrations of sulfite and sulfate in flue gas condensate and the soluble deposits increased; total surface deposits, which are made up of the soluble and insoluble portions, increased linearly; higher amounts of soluble iron sulfates formed with apparent increased corrosion potential of metal surfaces; and the boiler efficiency remained unchanged during the short-term combustion experiments

Iron and its complexes in silicon

Science.gov (United States)

Istratov, A. A.; Hieslmair, H.; Weber, E. R.

This article is the first in a series of two reviews on the properties of iron in silicon. It offers a comprehensive of the current state of understanding of fundamental physical properties of iron and its complexes in silicon. The first section of this review discusses the position of iron in the silicon lattice and the electrical properties of interstitial iron. Updated expressions for the solubility and the diffusivity of iron in silicon are presented, and possible explanations for conflicting experimental data obtained by different groups are discussed. The second section of the article considers the electrical and the structural properties of complexes of interstitial iron with shallow acceptors (boron, aluminum, indium, gallium, and thallium), shallow donors (phosphorus and arsenic) and other impurities (gold, silver, platinum, palladium, zinc, sulfur, oxygen, carbon, and hydrogen). Special attention is paid to the kinetics of iron pairing with shallow acceptors, the dissociation of these pairs, and the metastability of iron-acceptor pairs. The parameters of iron-related defects in silicon are summarized in tables that include more than 30 complexes of iron as detected by electron paramagnetic resonance (EPR) and almost 20 energy levels in the band gap associated with iron. The data presented in this review illustrate the enormous complexing activity of iron, which is attributed to the partial or complete (depending on the temperature and the conductivity type) ionization of iron as well as the high diffusivity of iron in silicon. It is shown that studies of iron in silicon require exceptional cleanliness of experimental facilities and highly reproducible diffusion and temperature ramping (quenching) procedures. Properties of iron that are not yet completely understood and need further research are outlined.

Carbon Solubility in Silicon-Iron-Bearing Metals during Core Formation on Mercury

Science.gov (United States)

Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Ross, D. Kent; Rapp, Jennifer F.; Danielson, Lisa R.; Keller, Lindsay P.; Righter, Kevin

2016-01-01

Recent results obtained from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft showed the surface of Mercury has high S abundances (approximately 4 wt%) and low Iron(II) Oxide abundances (less than 2 wt%). Based on these extreme values, the oxygen fugacity of Mercury's surface materials was estimated to be approximately 3 to 7 log(sub 10) units below the IW buffer (Delta IW-3 to Delta IW-7). This highly reducing nature of the planet has resulted in a large core and relatively thin mantle, extending to only approximately 420 km depth (corresponding to a core-mantle boundary pressure of approximately 4-7 GPa) within the planet. Furthermore, MESSENGER results have suggested the presence of carbon on the surface of the planet. Previous experimental results from have also suggested the possibility of a primary floatation crust on Mercury composed of graphite, produced after a global magma ocean event. With these exotic conditions of this compositional end-member planet, it begs the question, what is the core composition of Mercury? Although no definitive conclusion has been reached, previous studies have made advances towards answering this question. Riner et al. and Chen et al. looked at iron sulfide systems and implemented various crystallization and layered core scenarios to try and determine the composition and structure of Mercury's core. Malavergne et al. examined core crystallization scenarios in the presence of sulfur and silicon. Hauck et al. used the most recent geophysical constraints from the MESSENGER spacecraft to model the internal structure of Mercury, including the core, in a iron-sulfur-silicon system. More recently, Chabot et al. conducted a series of metal-silicate partitioning experiments in a iron-sulfur-silicon system. These results showed the core of Mercury has the potential to contain more than 15 wt% silicon. However, with the newest results from MESSENGER's low altitude campaign, carbon is another

Iron and manganese in anaerobic respiration: environmental significance, physiology, and regulation

Science.gov (United States)

Nealson, K. H.; Saffarini, D.

1994-01-01

Dissimilatory iron and/or manganese reduction is known to occur in several organisms, including anaerobic sulfur-reducing organisms such as Geobacter metallireducens or Desulfuromonas acetoxidans, and facultative aerobes such as Shewanella putrefaciens. These bacteria couple both carbon oxidation and growth to the reduction of these metals, and inhibitor and competition experiments suggest that Mn(IV) and Fe(III) are efficient electron acceptors similar to nitrate in redox abilities and capable of out-competing electron acceptors of lower potential, such as sulfate (sulfate reduction) or CO2 (methanogenesis). Field studies of iron and/or manganese reduction suggest that organisms with such metabolic abilities play important roles in coupling the oxidation of organic carbon to metal reduction under anaerobic conditions. Because both iron and manganese oxides are solids or colloids, they tend to settle downward in aquatic environments, providing a physical mechanism for the movement of oxidizing potential into anoxic zones. The resulting biogeochemical metal cycles have a strong impact on many other elements including carbon, sulfur, phosphorous, and trace metals.

Super-paramagnetic responsive silk fibroin/chitosan/magnetite scaffolds with tunable pore structures for bone tissue engineering applications

Energy Technology Data Exchange (ETDEWEB)

Aliramaji, Shamsa; Zamanian, Ali, E-mail: a-zamanian@merc.ac.ir; Mozafari, Masoud

2017-01-01

Tissue engineering is a promising approach in repairing damaged tissues. During the last few years, magnetic nanoparticles have been of great interest in this field of study due to their controlled responsive characteristics in specific external magnetic fields. In this study, after synthesizing iron oxide (magnetite) nanoparticles through a reverse coprecipitation method, silk fibroin/chitosan-based magnetic scaffolds were prepared using different amounts of magnetite nanoparticles (0, 0.5, 1 and 2%) by freeze-casting method. The physicochemical activity of the scaffolds was monitored in phosphate-buffered saline (PBS) solution to determine the biodegradation and swelling behaviors. The stability of the magnetite nanoparticles in the fabricated scaffolds was determined by atomic absorption spectroscopy (AAS). Moreover, the cellular activity of the magnetic scaffolds was examined under a static magnetic field. The results showed that the lamellar structured scaffolds having MNPs in the walls could not affect the final structure and deteriorate the biological characteristics of the scaffolds, while the ability of magnetic responsivity was added to the scaffolds. This study warrants further pre-clinical and clinical evaluations. - Highlights: • Based on TEM micrograph and Rietveld refinement the particle size of MNPs was approximately 12 nm. • The water absorption of silk scaffolds increases by the addition of chitosan content. • Addition of 0.5 wt% MNPs led to decrease in scaffolds degradation and number of living cells. • By increasing the MNPs from 0.5 to 1 and 2, the degradation rate and living cells increased. • In scaffolds with 2 wt% MNPs cell attachment is slightly better than those of 0.5 wt%.

Growth of Thiobacillus ferrooxidans on elemental sulfur

International Nuclear Information System (INIS)

Espejo, R.T.; Romero, P.

1987-01-01

Growth kinetics of Thiobacillus ferrooxidans in batch cultures, containing prills of elementary sulfur as the sole energy source, were studied by measuring the incorporation of radioactive phosphorus in free and adsorbed bacteria. The data obtained indicate an initial exponential growth of the attached bacteria until saturation of the susceptible surface was reached, followed by a linear release of free bacteria due to successive replication of a constant number of adsorbed bacteria. These adsorbed bacteria could continue replication provided the colonized prills were transferred to fresh medium each time the stationary phase was reached. The bacteria released from the prills were unable to multiply, and in the medium employed they lost viability with a half-live of 3.5 days. The spreading of the progeny on the surface was followed by staining the bacteria on the prills with crystal violet; this spreading was not uniform but seemed to proceed through distortions present in the surface. The specific growth rate of T. ferrooxidans ATCC 19859 was about 0.5 day -1 , both before and after saturation of the sulfur surface. The growth of adsorbed and free bacteria in medium containing both ferrous iron and elementary sulfur indicated that T. ferrooxidans can simultaneously utilize both energy sources

Nano/macro porous bioactive glass scaffold

Science.gov (United States)

Wang, Shaojie

Bioactive glass (BG) and ceramics have been widely studied and developed as implants to replace hard tissues of the musculo-skeletal system, such as bones and teeth. Recently, instead of using bulk materials, which usually do not degrade rapidly enough and may remain in the human body for a long time, the idea of bioscaffold for tissue regeneration has generated much interest. An ideal bioscaffold is a porous material that would not only provide a three-dimensional structure for the regeneration of natural tissue, but also degrade gradually and, eventually be replaced by the natural tissue completely. Among various material choices the nano-macro dual porous BG appears as the most promising candidate for bioscaffold applications. Here macropores facilitate tissue growth while nanopores control degradation and enhance cell response. The surface area, which controls the degradation of scaffold can also be tuned by changing the nanopore size. However, fabrication of such 3D structure with desirable nano and macro pores has remained challenging. In this dissertation, sol-gel process combined with spinodal decomposition or polymer sponge replication method has been developed to fabricate the nano-macro porous BG scaffolds. Macropores up to 100microm are created by freezing polymer induced spinodal structure through sol-gel transition, while larger macropores (>200um) of predetermined size are obtained by the polymer sponge replication technique. The size of nanopores, which are inherent to the sol-gel method of glass fabrication, has been tailored using several approaches: Before gel point, small nanopores are generated using acid catalyst that leads to weakly-branched polymer-like network. On the other hand, larger nanopores are created with the base-catalyzed gel with highly-branched cluster-like structure. After the gel point, the nanostructure can be further modified by manipulating the sintering temperature and/or the ammonia concentration used in the solvent

The role of sulfur-oxidizing bacteria Thiobacillus thiooxidans in pyrite weathering

International Nuclear Information System (INIS)

Sasaki, K.; Tsunekawa, M.; Ohtsuka, T.; Konno, H.

1998-01-01

The paper investigates the role of the sulfur-oxidizing bacteria Thiobacillus thiooxidans in pyrite weathering in order to clarify the effects of the bacteria on the dissolution behavior of pyrite and the formation of secondary minerals using Raman spectroscopy and powder X-ray diffraction (XRD) in addition to solution analysis. It was found that T. thiooxidans, when present with the iron-oxidizing bacteria Thiobacillus ferrooxidans, enhanced the dissolution of Fe and S species for pyrite, whereas T. thiooxidans alone did not oxidize pyrite. Enhancement of the consumption of elemental sulfur and regeneration of Fe(II) ions were also observed with T. thiooxidans together with T. ferrooxidans, while this did not occur with T. ferrooxidans alone

Purification and characterization of acetylene hydratase of Pelobacter acetylenicus, a tungsten iron-sulfur protein.

Science.gov (United States)

Rosner, B M; Schink, B

1995-10-01

Acetylene hydratase of the mesophilic fermenting bacterium Pelobacter acetylenicus catalyzes the hydration of acetylene to acetaldehyde. Growth of P. acetylenicus with acetylene and specific acetylene hydratase activity depended on tungstate or, to a lower degree, molybdate supply in the medium. The specific enzyme activity in cell extract was highest after growth in the presence of tungstate. Enzyme activity was stable even after prolonged storage of the cell extract or of the purified protein under air. However, enzyme activity could be measured only in the presence of a strong reducing agent such as titanium(III) citrate or dithionite. The enzyme was purified 240-fold by ammonium sulfate precipitation, anion-exchange chromatography, size exclusion chromatography, and a second anion-exchange chromatography step, with a yield of 36%. The protein was a monomer with an apparent molecular mass of 73 kDa, as determined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The isoelectric point was at pH 4.2. Per mol of enzyme, 4.8 mol of iron, 3.9 mol of acid-labile sulfur, and 0.4 mol of tungsten, but no molybdenum, were detected. The Km for acetylene as assayed in a coupled photometric test with yeast alcohol dehydrogenase and NADH was 14 microM, and the Vmax was 69 mumol.min-1.mg of protein-1. The optimum temperature for activity was 50 degrees C, and the apparent pH optimum was 6.0 to 6.5. The N-terminal amino acid sequence gave no indication of resemblance to any enzyme protein described so far.

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.

Efficacy of iron-supplement bars to reduce anemia in urban Indian women: a cluster-randomized controlled trial.

Science.gov (United States)

Mehta, Rajvi; Platt, Alyssa C; Sun, Xizi; Desai, Mukesh; Clements, Dennis; Turner, Elizabeth L

2017-03-01

Background: India's high prevalence of iron-deficiency anemia has largely been attributed to the local diet consisting of nonheme iron, which has lower absorption than that of heme iron. Objective: We assessed the efficacy of the consumption of iron-supplement bars in raising hemoglobin concentrations and hematocrit percentages in anemic (hemoglobin concentration Indian women of reproductive age. Design: The Let's be Well Red study was a 90-d, pair-matched, cluster-randomized controlled trial. A total of 361 nonpregnant women (age 18-35 y) were recruited from 10 sites within Mumbai and Navi Mumbai, India. All participants received anemia education and a complete blood count (CBC). Random assignment of anemic participants to intervention and control arms occurred within 5 matched site-pairs. Intervention participants received 1 iron-supplement bar (containing 14 mg Fe)/d for 90 d, whereas control subjects received nothing. CBC tests were given at days 15, 45, and 90. Primary outcomes were 90-d changes from baseline in hemoglobin concentrations and hematocrit percentages. Linear mixed models and generalized estimating equations were used to model continuous and binary outcomes, respectively. Results: Of 179 anemic participants, 136 (76.0%) completed all follow-up assessments (65 intervention and 71 control participants). Baseline characteristics were comparable by arm. Mean hemoglobin and hematocrit increases after 90 d were greater for intervention than for control participants [1.4 g/dL (95% CI: 1.3, 1.6 g/dL) and 2.7% (95% CI: 2.2%, 3.2%), respectively]. The anemia prevalence at 90 d was lower for intervention (29.2%) than for control participants (98.6%) (OR: 0.007; 95% CI: 0.001, 0.04). Conclusions: The daily consumption of an iron-supplement bar leads to increased hemoglobin concentrations and hematocrit percentages and to a lower anemia prevalence in the target population with no reported side effects. This intervention is an attractive option to combat anemia

Rational Design of a Water-Storable Hierarchical Architecture Decorated with Amorphous Barium Oxide and Nickel Nanoparticles as a Solid Oxide Fuel Cell Anode with Excellent Sulfur Tolerance.

Science.gov (United States)

Song, Yufei; Wang, Wei; Ge, Lei; Xu, Xiaomin; Zhang, Zhenbao; Julião, Paulo Sérgio Barros; Zhou, Wei; Shao, Zongping

2017-11-01

Solid oxide fuel cells (SOFCs), which can directly convert chemical energy stored in fuels into electric power, represent a useful technology for a more sustainable future. They are particularly attractive given that they can be easily integrated into the currently available fossil fuel infrastructure to realize an ideal clean energy system. However, the widespread use of the SOFC technology is hindered by sulfur poisoning at the anode caused by the sulfur impurities in fossil fuels. Therefore, improving the sulfur tolerance of the anode is critical for developing SOFCs for use with fossil fuels. Herein, a novel, highly active, sulfur-tolerant anode for intermediate-temperature SOFCs is prepared via a facile impregnation and limited reaction protocol. During synthesis, Ni nanoparticles, water-storable BaZr 0.4 Ce 0.4 Y 0.2 O 3- δ (BZCY) perovskite, and amorphous BaO are formed in situ and deposited on the surface of a Sm 0.2 Ce 0.8 O 1.9 (SDC) scaffold. More specifically, a porous SDC scaffold is impregnated with a well-designed proton-conducting perovskite oxide liquid precursor with the nominal composition of Ba(Zr 0.4 Ce 0.4 Y 0.2 ) 0.8 Ni 0.2 O 3- δ (BZCYN), calcined and reduced in hydrogen. The as-synthesized hierarchical architecture exhibits high H 2 electro-oxidation activity, excellent operational stability, superior sulfur tolerance, and good thermal cyclability. This work demonstrates the potential of combining nanocatalysts and water-storable materials in advanced electrocatalysts for SOFCs.

Graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

Science.gov (United States)

Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuiliang; Li, Xiaolin

2014-06-17

Rechargeable lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter less than 50 nm..

Identification of a multi-protein reductive dehalogenase complex in Dehalococcoides mccartyi strain CBDB1 suggests a protein-dependent respiratory electron transport chain obviating quinone involvement

DEFF Research Database (Denmark)

Kublik, Anja; Deobald, Darja; Hartwig, Stefanie

2016-01-01

electrophoresis (BN-PAGE), gel filtration and ultrafiltration an active dehalogenating protein complex with a molecular mass of 250–270 kDa was identified. The active subunit of reductive dehalogenase (RdhA) colocalised with a complex iron-sulfur molybdoenzyme (CISM) subunit (CbdbA195) and an iron-sulfur cluster...... of the dehalogenating complex prior to membrane solubilisation. Taken together, the identification of the respiratory dehalogenase protein complex and the absence of indications for quinone participation in the respiration suggest a quinone-independent protein-based respiratory electron transfer chain in D. mccartyi....

Sulfur degassing due to contact metamorphism during flood basalt eruptions

Science.gov (United States)

Yallup, Christine; Edmonds, Marie; Turchyn, Alexandra V.

2013-11-01

We present a study aimed at quantifying the potential for generating sulfur-rich gas emissions from the devolatilization of sediments accompanying sill emplacement during flood basalt eruptions. The potential contribution of sulfur-rich gases from sediments might augment substantially the magma-derived sulfur gases and hence impact regional and global climate. We demonstrate, from a detailed outcrop-scale study, that sulfur and total organic carbon have been devolatilized from shales immediately surrounding a 3-m thick dolerite sill on the Isle of Skye, Scotland. Localized partial melting occurred within a few centimetres of the contact in the shale, generating melt-filled cracks. Pyrite decomposed on heating within 80 cm of the contact, generating sulfur-rich gases (a mixture of H2S and SO2) and pyrrhotite. The pyrrhotite shows 32S enrichment, due to loss of 34S-enriched SO2. Further decomposition and oxidation of pyrrhotite resulted in hematite and/or magnetite within a few cm of the contact. Iron sulfates were produced during retrogressive cooling and oxidation within 20 cm of the contact. Decarbonation of the sediments due to heating is also observed, particularly along the upper contact of the sill, where increasing δ13C is consistent with loss of methane gas. The geochemical and mineralogical features observed in the shales are consistent with a short-lived intrusion, emplaced in desulfurization, as well as decarbonation, of shales adjacent to an igneous intrusion. The liberated fluids, rich in sulfur and carbon, are likely to be focused along regions of low pore fluid pressure along the margins of the sill. The sulfur gases liberated from the sediments would have augmented the sulfur dioxide (and hydrogen sulfide) yield of the eruption substantially, had they reached the surface. This enhancement of the magmatic sulfur budget has important implications for the climate impact of large flood basalt eruptions that erupt through thick, volatile-rich sedimentary

Catalytic dehydrogenation of alcohol over solid-state molybdenum sulfide clusters with an octahedral metal framework

Energy Technology Data Exchange (ETDEWEB)

Kamiguchi, Satoshi, E-mail: kamigu@riken.jp [Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Organometallic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Okumura, Kazu [School of Advanced Engineering, Kogakuin University, Nakano-machi, Hachioji City, Tokyo 192-0015 (Japan); Nagashima, Sayoko; Chihara, Teiji [Graduate School of Science and Engineering, Saitama University, Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan)

2015-12-15

Graphical abstract: - Highlights: • Solid-state molybdenum sulfide clusters catalyzed the dehydrogenation of alcohol. • The dehydrogenation proceeded without the addition of any oxidants. • The catalytic activity developed when the cluster was activated at 300–500 °C in H{sub 2}. • The Lewis-acidic molybdenum atom and basic sulfur ligand were catalytically active. • The clusters function as bifunctional acid–base catalysts. - Abstract: Solid-state molybdenum sulfide clusters with an octahedral metal framework, the superconducting Chevrel phases, are applied to catalysis. A copper salt of a nonstoichiometric sulfur-deficient cluster, Cu{sub x}Mo{sub 6}S{sub 8–δ} (x = 2.94 and δ ≈ 0.3), is stored in air for more than 90 days. When the oxygenated cluster is thermally activated in a hydrogen stream above 300 °C, catalytic activity for the dehydrogenation of primary alcohols to aldehydes and secondary alcohols to ketones develops. The addition of pyridine or benzoic acid decreases the dehydrogenation activity, indicating that both a Lewis-acidic coordinatively unsaturated molybdenum atom and a basic sulfur ligand synergistically act as the catalytic active sites.

Transformation of Nitrate and Toluene in Groundwater by Sulfur Modified Iron(SMI-III)

Science.gov (United States)

Lee, W.; Park, S.; Lim, J.; Hong, U.; Kwon, S.; Kim, Y.

2009-12-01

In Korea, nitrate and benzene, toluene, ethylbenzene, and xylene isomers (BTEX) are frequently detected together as ground water contaminants. Therefore, a system simultaneously treating both nitrate (inorganic compound) and BTEX (organic compounds) is required to utilize groundwater as a water resource. In this study, we investigated the efficiency of Sulfur Modified Iron (SMI-III) in treating both nitrate and BTEX contaminated groundwater. Based on XRD (X-Ray Diffraction) analysis, the SMI-III is mainly composed of Fe3O4, S, and Fe. A series of column tests were conducted at three different empty bed contact times (EBCTs) for each compound. During the experiments, removal efficiency for both nitrate and toluene were linearly correlated with EBCT, suggesting that SMI-III have an ability to transform both nitrate and toluene. The concentration of SO42- and oxidation/reduction potential (ORP) were also measured. After exposed to nitrate contaminated groundwater, the composition of SMI-III was changed to Fe2O3, Fe3O4, Fe, and Fe0.95S1.05. The trends of effluent sulfate concentrations were inversely correlated with effluent nitrate concentrations, while the trends of ORP values, having the minimum values of -480 mV, were highly correlated with effluent nitrate concentrations. XRD analysis before and after exposed to nitrate contaminated groundwater, sulfate production, and nitrite detection as a reductive transformation by-product of nitrate suggest that nitrate is reductively transformed by SMI-III. Interestingly, in the toluene experiments, the trends of ORP values were inversely correlated with effluent toluene concentrations, suggesting that probably degrade through oxidation reaction. Consequently, nitrate and toluene probably degrade through reduction and oxidation reaction, respectively and SMI-III could serve as both electron donor and acceptor.

Catalase as a sulfide-sulfur oxido-reductase: An ancient (and modern?) regulator of reactive sulfur species (RSS).

Science.gov (United States)

Olson, Kenneth R; Gao, Yan; DeLeon, Eric R; Arif, Maaz; Arif, Faihaan; Arora, Nitin; Straub, Karl D

2017-08-01

Catalase is well-known as an antioxidant dismutating H 2 O 2 to O 2 and H 2 O. However, catalases evolved when metabolism was largely sulfur-based, long before O 2 and reactive oxygen species (ROS) became abundant, suggesting catalase metabolizes reactive sulfide species (RSS). Here we examine catalase metabolism of H 2 S n , the sulfur analog of H 2 O 2 , hydrogen sulfide (H 2 S) and other sulfur-bearing molecules using H 2 S-specific amperometric electrodes and fluorophores to measure polysulfides (H 2 S n ; SSP4) and ROS (dichlorofluorescein, DCF). Catalase eliminated H 2 S n , but did not anaerobically generate H 2 S, the expected product of dismutation. Instead, catalase concentration- and oxygen-dependently metabolized H 2 S and in so doing acted as a sulfide oxidase with a P 50 of 20mmHg. H 2 O 2 had little effect on catalase-mediated H 2 S metabolism but in the presence of the catalase inhibitor, sodium azide (Az), H 2 O 2 rapidly and efficiently expedited H 2 S metabolism in both normoxia and hypoxia suggesting H 2 O 2 is an effective electron acceptor in this reaction. Unexpectedly, catalase concentration-dependently generated H 2 S from dithiothreitol (DTT) in both normoxia and hypoxia, concomitantly oxidizing H 2 S in the presence of O 2 . H 2 S production from DTT was inhibited by carbon monoxide and augmented by NADPH suggesting that catalase heme-iron is the catalytic site and that NADPH provides reducing equivalents. Catalase also generated H 2 S from garlic oil, diallyltrisulfide, thioredoxin and sulfur dioxide, but not from sulfite, metabisulfite, carbonyl sulfide, cysteine, cystine, glutathione or oxidized glutathione. Oxidase activity was also present in catalase from Aspergillus niger. These results show that catalase can act as either a sulfide oxidase or sulfur reductase and they suggest that these activities likely played a prominent role in sulfur metabolism during evolution and may continue do so in modern cells as well. This also appears

Isolation and characterization of a sulfur-oxidizing chemolithotroph growing on crude oil under anaerobic conditions.

Science.gov (United States)

Kodama, Yumiko; Watanabe, Kazuya

2003-01-01

Molecular approaches have shown that a group of bacteria (called cluster 1 bacteria) affiliated with the epsilon subclass of the class Proteobacteria constituted major populations in underground crude-oil storage cavities. In order to unveil their physiology and ecological niche, this study isolated bacterial strains (exemplified by strain YK-1) affiliated with the cluster 1 bacteria from an oil storage cavity at Kuji in Iwate, Japan. 16S rRNA gene sequence analysis indicated that its closest relative was Thiomicrospira denitrificans (90% identity). Growth experiments under anaerobic conditions showed that strain YK-1 was a sulfur-oxidizing obligate chemolithotroph utilizing sulfide, elemental sulfur, thiosulfate, and hydrogen as electron donors and nitrate as an electron acceptor. Oxygen also supported its growth only under microaerobic conditions. Strain YK-1 could not grow on nitrite, and nitrite was the final product of nitrate reduction. Neither sugars, organic acids (including acetate), nor hydrocarbons could serve as carbon and energy sources. A typical stoichiometry of its energy metabolism followed an equation: S(2-) + 4NO(3)(-) --> SO(4)(2-) + 4NO(2)(-) (Delta G(0) = -534 kJ mol(-1)). In a difference from other anaerobic sulfur-oxidizing bacteria, this bacterium was sensitive to NaCl; growth in medium containing more than 1% NaCl was negligible. When YK-1 was grown anaerobically in a sulfur-depleted inorganic medium overlaid with crude oil, sulfate was produced, corresponding to its growth. On the contrary, YK-1 could not utilize crude oil as a carbon source. These results suggest that the cluster 1 bacteria yielded energy for growth in oil storage cavities by oxidizing petroleum sulfur compounds. Based on its physiology, ecological interactions with other members of the groundwater community are discussed.

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central Chile

DEFF Research Database (Denmark)

Zopfi, Jakob; Michael E., Böttcher; Jørgensen, Bo Barker

2008-01-01

suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition...... of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the bottom water composition due to intracellular isotope exchange reactions during microbial sulfur transformations....

OSO 8 X-ray spectra of clusters of galaxies. I - Observations of twenty clusters: Physical correlations

Science.gov (United States)

Mushotzky, R. F.; Serlemitsos, P. J.; Boldt, E. A.; Holt, S. S.; Smith, B. W.

1978-01-01

OSO 8 X-ray spectra from 2 to 20 keV have been analyzed for 26 clusters of galaxies. For 20 clusters temperatures, emission integrals, iron abundances, and low-energy absorption measurements are presented. The data give, in general, better fits to thermal bremsstrahlung than to power-law models. Eight clusters have positive iron emission-line detections at the 90% confidence level, and all 20 cluster spectra are consistent with Fe/H = 0.000014 by number with the possible exception of Virgo. Thus it is confirmed that X-ray emission in this energy band is predominantly thermal radiation from hot intracluster gas rather than inverse Compton radiation. Physical correlations between X-ray spectral parameters and other cluster properties are examined. It is found that (1) the X-ray temperature is approximately proportional to the square of the velocity dispersion of the galaxies; (2) the emission integral is a strong function of the X-ray temperature; (3) the X-ray temperature and emission integral are better correlated with cluster central-galaxy density than with richness; and (4) the fraction of galaxies which are spirals is correlated with the observed ram pressure in the cluster core.

Overexpression of the yeast frataxin homolog (Yfh1): contrasting effects on iron-sulfur cluster assembly, heme synthesis and resistance to oxidative stress

DEFF Research Database (Denmark)

Seguin, Alexandra; Bayot, Aurélien; Dancis, Andrew

2009-01-01

of 2muYFH1 cells compared to wild-type cells. To our knowledge, this work is the first description where major frataxin-related phenotypes ([Fe-S] cluster assembly and heme synthesis) can be split in vivo, suggesting that frataxin has independent roles in both processes, and that the optimal conditions......Friedreich's ataxia is generally associated with defects in [Fe-S] cluster assembly/stability and heme synthesis and strong susceptibility to oxidative stress. We used the yeast (Saccharomyces cerevisiae) model of Friedreich's ataxia to study the physiological consequences of modulating...... for these independent roles are different....

Microbial Oxidation of Iron Sulfides in Anaerobic Environments

DEFF Research Database (Denmark)

Vaclavkova, Sarka

Abstract (shortened): Iron sulfides (FeSx), representing 0.04-10 % of Danish dry soil weight, oxidize in a presence of oxygen, releasing sulfuric acid and free iron. Environmental impact of FeSx oxidation is commonly seen on agricultural sites cultivated by drainage as acid sulfate soil formation....... MISON was found to count for about 1/3 of the net NO3- reduction in MISON active environments, despite the presence of alternative electron donor, organic carbon. The rate of MISON was found to be dependent on the available reactive surface area of FeSx and on the microorganism involved. The findings...

Microbial transformations of nitrogen, sulfur and iron dictate vegetation composition in wetlands: a review

Directory of Open Access Journals (Sweden)

Leon P.M. Lamers

2012-04-01

Full Text Available The majority of studies on rhizospheric interactions between microbial communities and vegetation focus on pathogens, mycorrhizal symbiosis, and/or carbon transformations. Although the biogeochemical transformations of nitrogen (N, sulfur (S and iron (Fe have profound effects on plants, these effects have received far less attention. Firstly, all three elements are plant nutrients, and microbial activity significantly changes their mobility and availability. Secondly, microbial oxidation with oxygen supplied by radial oxygen loss (ROL from roots in wetlands causes acidification, while reduction using alternative electron acceptors leads to generation of alkalinity, affecting pH in the rhizosphere and hence plant composition. Thirdly, reduced species of all three elements may become phytotoxic. In addition, Fe cycling is tightly linked to that of S and phosphorus (P. As water level fluctuations are very common in wetlands, rapid changes in the availability of oxygen and alternative terminal electron acceptors will result in strong changes in the prevalent microbial redox reactions, with significant effects on plant growth. Depending on geological and hydrological settings, these interacting microbial transformations change the conditions and resource availability for plants, which are strong drivers of vegetation development and composition by changing relative competitive strengths. Conversely, microbial composition is strongly driven by vegetation composition. Therefore, the combination of micro- and macroecological knowledge is essential to understand the biogeochemical and biological key factors driving heterogeneity and total (i.e., micro-macro community composition at different spatial and temporal scales. As N and S inputs have drastically increased due to anthropogenic forcing and Fe inputs have decreased at a global scale, this combined approach has become even more urgent.

Genome-Wide Search for Genes Required for Bifidobacterial Growth under Iron-Limitation

Science.gov (United States)

Lanigan, Noreen; Bottacini, Francesca; Casey, Pat G.; O'Connell Motherway, Mary; van Sinderen, Douwe

2017-01-01

Bacteria evolved over millennia in the presence of the vital micronutrient iron. Iron is involved in numerous processes within the cell and is essential for nearly all living organisms. The importance of iron to the survival of bacteria is obvious from the large variety of mechanisms by which iron may be acquired from the environment. Random mutagenesis and global gene expression profiling led to the identification of a number of genes, which are essential for Bifidobacterium breve UCC2003 survival under iron-restrictive conditions. These genes encode, among others, Fe-S cluster-associated proteins, a possible ferric iron reductase, a number of cell wall-associated proteins, and various DNA replication and repair proteins. In addition, our study identified several presumed iron uptake systems which were shown to be essential for B. breve UCC2003 growth under conditions of either ferric and/or ferrous iron chelation. Of these, two gene clusters encoding putative iron-uptake systems, bfeUO and sifABCDE, were further characterised, indicating that sifABCDE is involved in ferrous iron transport, while the bfeUO-encoded transport system imports both ferrous and ferric iron. Transcription studies showed that bfeUO and sifABCDE constitute two separate transcriptional units that are induced upon dipyridyl-mediated iron limitation. In the anaerobic gastrointestinal environment ferrous iron is presumed to be of most relevance, though a mutation in the sifABCDE cluster does not affect B. breve UCC2003's ability to colonise the gut of a murine model. PMID:28620359

Genome-Wide Search for Genes Required for Bifidobacterial Growth under Iron-Limitation

Directory of Open Access Journals (Sweden)

Noreen Lanigan

2017-05-01

Full Text Available Bacteria evolved over millennia in the presence of the vital micronutrient iron. Iron is involved in numerous processes within the cell and is essential for nearly all living organisms. The importance of iron to the survival of bacteria is obvious from the large variety of mechanisms by which iron may be acquired from the environment. Random mutagenesis and global gene expression profiling led to the identification of a number of genes, which are essential for Bifidobacterium breve UCC2003 survival under iron-restrictive conditions. These genes encode, among others, Fe-S cluster-associated proteins, a possible ferric iron reductase, a number of cell wall-associated proteins, and various DNA replication and repair proteins. In addition, our study identified several presumed iron uptake systems which were shown to be essential for B. breve UCC2003 growth under conditions of either ferric and/or ferrous iron chelation. Of these, two gene clusters encoding putative iron-uptake systems, bfeUO and sifABCDE, were further characterised, indicating that sifABCDE is involved in ferrous iron transport, while the bfeUO-encoded transport system imports both ferrous and ferric iron. Transcription studies showed that bfeUO and sifABCDE constitute two separate transcriptional units that are induced upon dipyridyl-mediated iron limitation. In the anaerobic gastrointestinal environment ferrous iron is presumed to be of most relevance, though a mutation in the sifABCDE cluster does not affect B. breve UCC2003's ability to colonise the gut of a murine model.

Amelioration of Adverse Effects of Salt Stress on Maize (Zea Mays L.) Cultivars by Exogenous Application of Sulfur at Seedling Stage

International Nuclear Information System (INIS)

Riffat, A.; Ahmad, M. S. A.

2016-01-01

Sulfur is an important plant nutrient involved in seed germination and seedling establishment. It also plays an important role in response of plants to tolerate abiotic stresses such as salinity. A study was conducted to assess the role of sulfur on salinity tolerance of maize (Zea mays L.) at seed germination stage. Six varieties (Sadaf, MMRI, Pearl Basic, Agaitti 2003, Saiwal 2002 and Pak Afgoi 2003) and two hybrids (Yusafwala Hybrid and Hybrid 1898) of maize were used to assess the modulation of salt stress by exogenously applied sulfur. Three NaCl (25, 50 and 75 mM) and five potassium sulfate (20, 40, 60, 80 and 100 mM) levels were applied to plants as sand amendment at sowing time along with a control. The experiment was laid down in a Completely Randomized Design (CRD) with three replicates. The data for various germination attributes were recorded. The results revealed that sulfur application significantly modulated all germination parameters i-e. germination percentage germination index, coefficient of velocity of emergence, mean emergence time, vigour index, germination energy, germination speed, mean daily germination and germination value and thus reduced the toxic effect of salinity. It was found that sulfur at 60 and 80 mM had more pronounced effect in enhancing seed germination. Application of sulfur at 60 to 80 mM improved all germination parameters and reduced time needed for 50 percent seed to germinate. The phylogenetic tree constructed by NTSysPC clearly clustered all genotypes the two distinct clusters. The tolerant cluster mainly contained 4 varieties (Sadaf, MMRI, Pearl Basic and Agati 2003) while the sensitive cluster included two varieties (Sahiwal 2002, Pak Afgoi 2003) and two hybrids (Hybrid 1898 and Yusaf wala hybrid). Based on the distance matrixes generated by software, Agati 2003 proved to be the most tolerant genotype. In comparison, a maize variety (Pak Afgoi-2003) and a Hybrid-1898 showed the least improvement by exogenously applied

Shared Sulfur Mobilization Routes for tRNA Thiolation and Molybdenum Cofactor Biosynthesis in Prokaryotes and Eukaryotes

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Silke Leimkühler

2017-01-01

Full Text Available Modifications of transfer RNA (tRNA have been shown to play critical roles in the biogenesis, metabolism, structural stability and function of RNA molecules, and the specific modifications of nucleobases with sulfur atoms in tRNA are present in pro- and eukaryotes. Here, especially the thiomodifications xm5s2U at the wobble position 34 in tRNAs for Lys, Gln and Glu, were suggested to have an important role during the translation process by ensuring accurate deciphering of the genetic code and by stabilization of the tRNA structure. The trafficking and delivery of sulfur nucleosides is a complex process carried out by sulfur relay systems involving numerous proteins, which not only deliver sulfur to the specific tRNAs but also to other sulfur-containing molecules including iron–sulfur clusters, thiamin, biotin, lipoic acid and molybdopterin (MPT. Among the biosynthesis of these sulfur-containing molecules, the biosynthesis of the molybdenum cofactor (Moco and the synthesis of thio-modified tRNAs in particular show a surprising link by sharing protein components for sulfur mobilization in pro- and eukaryotes.

Method of removing oxides of sulfur and oxides of nitrogen from exhaust gases

Science.gov (United States)

Walker, Richard J.

1986-01-01

A continuous method is presented for removing both oxides of sulfur and oxides of nitrogen from combustion or exhaust gases with the regeneration of the absorbent. Exhaust gas is cleaned of particulates and HCl by a water scrub prior to contact with a liquid absorbent that includes an aqueous solution of bisulfite and sulfite ions along with a metal chelate, such as, an iron or zinc aminopolycarboxylic acid. Following contact with the combustion gases the spent absorbent is subjected to electrodialysis to transfer bisulfite ions into a sulfuric acid solution while splitting water with hydroxide and hydrogen ion migration to equalize electrical charge. The electrodialysis stack includes alternate layers of anion selective and bipolar membranes. Oxides of nitrogen are removed from the liquid absorbent by air stripping at an elevated temperature and the regenerated liquid absorbent is returned to contact with exhaust gases for removal of sulfur oxides and nitrogen oxides.

Bacterial disproportionation of elemental sulfur coupled to chemical reduction of iron or manganese

DEFF Research Database (Denmark)

Thamdrup, Bo; Finster, Kai; Hansen, Jens Würgler

1993-01-01

A new chemolithotrophic bacterial metabolism was discovered in anaerobic marine enrichment cultures. Cultures in defined medium with elemental sulfur (S) and amorphous ferric hydroxide (FeOOH) as sole substrates showed intense formation of sulfate. Furthermore, precipitation of ferrous sulfide an...

Iron(III) species formed during iron(II) oxidation and iron-core formation in bacterioferritin of Escherichia coli

International Nuclear Information System (INIS)

Hawkins, C.; Treffry, A.; Mackey, J.; Williams, J.M.; Andrews, S.C.; Guest, J.R.; Harrison, P.M.

1996-01-01

This paper describes a preliminary investigation of the mechanisms of Fe(II) oxidation and storage of Fe(III) in the bacterioferritin of Escherichia coli (EcBFR). Using Moessbauer spectroscopy to examine the initial oxidation of iron by EcBFR it is confirmed that this ferritin exhibits 'ferroxidase' activity and is shown that dimeric and monomeric iron species are produced as intermediates. The characteristics of ferroxidase activity in EcBFR is compare d with those of human H-chain ferritin (HuHF) and discuss the different Moessbauer parameters of their dimeric iron with reference to the structures of their di-metal sites. In addition, it is presented preliminary findings suggesting that after an initial 'burst', the rate of oxidation is greatly reduced, possibly due to blockage of the ferroxidase centre by bound iron. A new component, not found in HuHF and probably representing a small cluster of Fe(III) atoms, is reported

Multifunctional fluorescent iron quantum clusters for non-invasive radiofrequency ablationof cancer cells.

Science.gov (United States)

Jose, Akhila; Surendran, Mrudula; Fazal, Sajid; Prasanth, Bindhu-Paul; Menon, Deepthy

2018-05-01

This work reports the potential of iron quantum clusters (FeQCs) as a hyperthermia agent for cancer, by testing its in-vitro response to shortwave (MHz range), radiofrequency (RF) waves non-invasively. Stable, fluorescent FeQCs of size ∼1 nm prepared by facile aqueous chemistry from endogenous protein haemoglobin were found to give a high thermal response, with a ΔT ∼50 °C at concentrationsas low as165 μg/mL. The as-prepared nanoclusters purified by lyophilization as well as dialysis showed a concentration, power and time-dependent RF response, with the lyophilized FeQCs exhibiting pronounced heating effects. FeQCs were found to be cytocompatible to NIH-3T3 fibroblast and 4T1 cancer cells treated at concentrations upto 1000 μg/mL for 24 h. Upon incubation with FeQCs and exposure to RF waves, significant cancer cell death was observed which proves its therapeutic ability. The fluorescent ability of the clusters could additionally be utilized for imaging cancer cells upon excitation at ∼450 nm. Further, to demonstrate the feasibility of imparting additional functionality such as drug/biomolecule/dye loading to FeQCs, they were self assembled with cationic polymers to form nanoparticles. Self assembly did not alter the RF heating potential of FeQCs and additionally enhanced its fluorescence. The multifunctional fluorescent FeQCs therefore show good promise as a novel therapeutic agent for RF hyperthermia and drug loading. Copyright © 2018 Elsevier B.V. All rights reserved.

Mitochondrial Iron Transport and Homeostasis in Plants

Directory of Open Access Journals (Sweden)

Anshika eJain

2013-09-01

Full Text Available Iron (Fe is an essential nutrient for plants and although the mechanisms controlling iron uptake from the soil are relatively well understood, comparatively little is known about subcellular trafficking of iron in plant cells. Mitochondria represent a significant iron sink within cells, as iron is required for the proper functioning of respiratory chain protein complexes. Mitochondria are a site of Fe-S cluster synthesis, and possibly heme synthesis as well. Here we review recent insights into the molecular mechanisms controlling mitochondrial iron transport and homeostasis. We focus on the recent identification of a mitochondrial iron uptake transporter in rice and a possible role for metalloreductases in iron uptake by mitochondria. In addition, we highlight recent advances in mitochondrial iron homeostasis with an emphasis on the roles of frataxin and ferritin in iron trafficking and storage within mitochondria.

Influence of Diet, Menstruation and Genetic Factors on Iron Status: A Cross-Sectional Study in Spanish Women of Childbearing Age

Directory of Open Access Journals (Sweden)

Ruth Blanco-Rojo

2014-03-01

Full Text Available The aim of this study was to investigate the combined influence of diet, menstruation and genetic factors on iron status in Spanish menstruating women (n = 142. Dietary intake was assessed by a 72-h detailed dietary report and menstrual blood loss by a questionnaire, to determine a Menstrual Blood Loss Coefficient (MBLC. Five selected SNPs were genotyped: rs3811647, rs1799852 (Tf gene; rs1375515 (CACNA2D3 gene; and rs1800562 and rs1799945 (HFE gene, mutations C282Y and H63D, respectively. Iron biomarkers were determined and cluster analysis was performed. Differences among clusters in dietary intake, menstrual blood loss parameters and genotype frequencies distribution were studied. A categorical regression was performed to identify factors associated with cluster belonging. Three clusters were identified: women with poor iron status close to developing iron deficiency anemia (Cluster 1, n = 26; women with mild iron deficiency (Cluster 2, n = 59 and women with normal iron status (Cluster 3, n = 57. Three independent factors, red meat consumption, MBLC and mutation C282Y, were included in the model that better explained cluster belonging (R2 = 0.142, p < 0.001. In conclusion, the combination of high red meat consumption, low menstrual blood loss and the HFE C282Y mutation may protect from iron deficiency in women of childbearing age. These findings could be useful to implement adequate strategies to prevent iron deficiency anemia.

Influence of diet, menstruation and genetic factors on iron status: a cross-sectional study in Spanish women of childbearing age.

Science.gov (United States)

Blanco-Rojo, Ruth; Toxqui, Laura; López-Parra, Ana M; Baeza-Richer, Carlos; Pérez-Granados, Ana M; Arroyo-Pardo, Eduardo; Vaquero, M Pilar

2014-03-06

The aim of this study was to investigate the combined influence of diet, menstruation and genetic factors on iron status in Spanish menstruating women (n = 142). Dietary intake was assessed by a 72-h detailed dietary report and menstrual blood loss by a questionnaire, to determine a Menstrual Blood Loss Coefficient (MBLC). Five selected SNPs were genotyped: rs3811647, rs1799852 (Tf gene); rs1375515 (CACNA2D3 gene); and rs1800562 and rs1799945 (HFE gene, mutations C282Y and H63D, respectively). Iron biomarkers were determined and cluster analysis was performed. Differences among clusters in dietary intake, menstrual blood loss parameters and genotype frequencies distribution were studied. A categorical regression was performed to identify factors associated with cluster belonging. Three clusters were identified: women with poor iron status close to developing iron deficiency anemia (Cluster 1, n = 26); women with mild iron deficiency (Cluster 2, n = 59) and women with normal iron status (Cluster 3, n = 57). Three independent factors, red meat consumption, MBLC and mutation C282Y, were included in the model that better explained cluster belonging (R2 = 0.142, p < 0.001). In conclusion, the combination of high red meat consumption, low menstrual blood loss and the HFE C282Y mutation may protect from iron deficiency in women of childbearing age. These findings could be useful to implement adequate strategies to prevent iron deficiency anemia.

Production of ferrous sulfate from residue from the iron mining

International Nuclear Information System (INIS)

Cardoso, K.A; Riella, H.G.; Abreu, E.F.; Carvalho, E.F. Urano de; Durazzo, M.

2012-01-01

This paper was developed from a residue obtained by processing iron ore exploited by the mining company Samarco S/A. The residue was characterized and the analyses showed that it contains about 70% of the mineral hematite (Fe 2 O 3 ) and also that some economically important products could be produced. One is the ferrous sulfate that can be used in pharmaceuticals and also that can be used in the treatment of iron deficiency anemia. The iron, in addition to is importance for the industrial production of steel and parts in general, also has great biological importance in all living beings. In order to produce ferrous sulfate from the byproduct in question, it was developed a obtaining route using metallic iron as hematite reductor and sulfuric acid to form the salt. (author)

CO dissociation on magnetic Fen clusters

KAUST Repository

Jedidi, Abdesslem

2014-01-01

This work theoretically investigates the CO dissociation on Fen nanoparticles, for n in the range of 1-65, focusing on size dependence in the context of the initial step of the Fischer-Tropsch reaction. CO adsorbs molecularly through its C-end on a triangular facet of the nanoparticle. Dissociation becomes easier when the cluster size increases. Then, the C atom is bonded to a square facet that is generated as a result of the adsorption if it does not yet exist in the bare cluster, while the O atom is adsorbed on a triangular facet. In the most stable situation, the two adsorbed atoms remain close together, both having in common one shared first-neighbor iron atom. There is a partial spin quenching of the neighboring Fe atoms, which become more positively charged than the other Fe atoms. The shared surface iron atom resembles a metal-cation from a complex. Despite the small size of the iron cluster considered, fluctuations due to specific configurations do not influence properties for n > 25 and global trends seem significant.

Systematic Prediction of Scaffold Proteins Reveals New Design Principles in Scaffold-Mediated Signal Transduction

Science.gov (United States)

Hu, Jianfei; Neiswinger, Johnathan; Zhang, Jin; Zhu, Heng; Qian, Jiang

2015-01-01

Scaffold proteins play a crucial role in facilitating signal transduction in eukaryotes by bringing together multiple signaling components. In this study, we performed a systematic analysis of scaffold proteins in signal transduction by integrating protein-protein interaction and kinase-substrate relationship networks. We predicted 212 scaffold proteins that are involved in 605 distinct signaling pathways. The computational prediction was validated using a protein microarray-based approach. The predicted scaffold proteins showed several interesting characteristics, as we expected from the functionality of scaffold proteins. We found that the scaffold proteins are likely to interact with each other, which is consistent with previous finding that scaffold proteins tend to form homodimers and heterodimers. Interestingly, a single scaffold protein can be involved in multiple signaling pathways by interacting with other scaffold protein partners. Furthermore, we propose two possible regulatory mechanisms by which the activity of scaffold proteins is coordinated with their associated pathways through phosphorylation process. PMID:26393507

Magnetic micro-manipulations to probe the local physical properties of porous scaffolds and to confine stem cells.

Science.gov (United States)

Robert, Damien; Fayol, Delphine; Le Visage, Catherine; Frasca, Guillaume; Brulé, Séverine; Ménager, Christine; Gazeau, Florence; Letourneur, Didier; Wilhelm, Claire

2010-03-01

The in vitro generation of engineered tissue constructs involves the seeding of cells into porous scaffolds. Ongoing challenges are to design scaffolds to meet biochemical and mechanical requirements and to optimize cell seeding in the constructs. In this context, we have developed a simple method based on a magnetic tweezer set-up to manipulate, probe, and position magnetic objects inside a porous scaffold. The magnetic force acting on magnetic objects of various sizes serves as a control parameter to retrieve the local viscosity of the scaffolds internal channels as well as the stiffness of the scaffolds pores. Labeling of human stem cells with iron oxide magnetic nanoparticles makes it possible to perform the same type of measurement with cells as probes and evaluate their own microenvironment. For 18 microm diameter magnetic beads or magnetically labeled stem cells of similar diameter, the viscosity was equivalently equal to 20 mPa s in average. This apparent viscosity was then found to increase with the magnetic probes sizes. The stiffness probed with 100 microm magnetic beads was found in the 50 Pa range, and was lowered by a factor 5 when probed with cells aggregates. The magnetic forces were also successfully applied to the stem cells to enhance the cell seeding process and impose a well defined spatial organization into the scaffold. (c) 2009 Elsevier Ltd. All rights reserved.

Biologically produced sulfur

NARCIS (Netherlands)

Kleinjan, W.E.; Keizer, de A.; Janssen, A.J.H.

2003-01-01

Sulfur compound oxidizing bacteria produce sulfur as an intermediate in the oxidation of hydrogen sulfide to sulfate. Sulfur produced by these microorganisms can be stored in sulfur globules, located either inside or outside the cell. Excreted sulfur globules are colloidal particles which are

The Origin of Sulfur Tolerance in Supported Platinum Catalysts: The Relationship between Structural and Catalytic Properties in Acidic and Alkaline Pt/LTL.

NARCIS (Netherlands)

Koningsberger, D.C.; Miller, J.T.

1996-01-01

The reactivity, structure, and sulfur tolerance is compared for platinum supported on acidic and alkaline LTL zeolite. In the absence of sulfur, EXAFS spectroscopy indicates that small metallic platinum particles of approximately 6 to 14 atoms/cluster are present. The TOF for neopentane

Influence of sulfur on the accumulation of mercury in rice plant (Oryza sativa L.) growing in mercury contaminated soils.

Science.gov (United States)

Li, Yunyun; Zhao, Jiating; Guo, Jingxia; Liu, Mengjiao; Xu, Qinlei; Li, Hong; Li, Yu-Feng; Zheng, Lei; Zhang, Zhiyong; Gao, Yuxi

2017-09-01

Sulfur (S) is an essential element for plant growth and its biogeochemical cycling is strongly linked to the species of heavy metals in soil. In this work, the effects of S (sulfate and elemental sulfur) treatment on the accumulation, distribution and chemical forms of Hg in rice growing in Hg contaminated soil were investigated. It was found that S could promote the formation of iron plaque on the root surface and decrease total mercury (T-Hg) and methylmercury (MeHg) accumulation in rice grains, straw, and roots. Hg in the root was dominated in the form of RS-Hg-SR. Sulfate treatment increased the percentage of RS-Hg-SR to T-Hg in the rice root and changed the Hg species in soil. The dominant Hg species (70%) in soil was organic substance bound fractions. Sulfur treatment decreased Hg motility in the rhizosphere soils by promoting the conversion of RS-Hg-SR to HgS. This study is significant since it suggests that low dose sulfur treatment in Hg-containing water irrigated soil can decrease both T-Hg and MeHg accumulation in rice via inactivating Hg in the soil and promoting the formation of iron plaque in rice root, which may reduce health risk for people consuming those crops. Copyright © 2017. Published by Elsevier Ltd.

WiseScaffolder: an algorithm for the semi-automatic scaffolding of Next Generation Sequencing data.

Science.gov (United States)

Farrant, Gregory K; Hoebeke, Mark; Partensky, Frédéric; Andres, Gwendoline; Corre, Erwan; Garczarek, Laurence

2015-09-03

The sequencing depth provided by high-throughput sequencing technologies has allowed a rise in the number of de novo sequenced genomes that could potentially be closed without further sequencing. However, genome scaffolding and closure require costly human supervision that often results in genomes being published as drafts. A number of automatic scaffolders were recently released, which improved the global quality of genomes published in the last few years. Yet, none of them reach the efficiency of manual scaffolding. Here, we present an innovative semi-automatic scaffolder that additionally helps with chimerae resolution and generates valuable contig maps and outputs for manual improvement of the automatic scaffolding. This software was tested on the newly sequenced marine cyanobacterium Synechococcus sp. WH8103 as well as two reference datasets used in previous studies, Rhodobacter sphaeroides and Homo sapiens chromosome 14 (http://gage.cbcb.umd.edu/). The quality of resulting scaffolds was compared to that of three other stand-alone scaffolders: SSPACE, SOPRA and SCARPA. For all three model organisms, WiseScaffolder produced better results than other scaffolders in terms of contiguity statistics (number of genome fragments, N50, LG50, etc.) and, in the case of WH8103, the reliability of the scaffolds was confirmed by whole genome alignment against a closely related reference genome. We also propose an efficient computer-assisted strategy for manual improvement of the scaffolding, using outputs generated by WiseScaffolder, as well as for genome finishing that in our hands led to the circularization of the WH8103 genome. Altogether, WiseScaffolder proved more efficient than three other scaffolders for both prokaryotic and eukaryotic genomes and is thus likely applicable to most genome projects. The scaffolding pipeline described here should be of particular interest to biologists wishing to take advantage of the high added value of complete genomes.

Effects of aerobic-anaerobic transient conditions on sulfur and metal cycles in sewer biofilms

NARCIS (Netherlands)

Nielsen, A.; Lens, P.N.L.; Vollertsen, J.; Hvitved-Jacobsen, Th.

2005-01-01

Interactions between sulfur and metals were studied in aerobic and anaerobic biofilms grown on domestic waste water at 15°C. The dominant metals in the waste water were iron, zinc and copper, which were present in average concentrations of 0.5mg/l, 0.6mg/l and 0.1m/l, respectively. Copper and zinc

Effect of sulfur content in a sulfur-activated carbon composite on the electrochemical properties of a lithium/sulfur battery

Energy Technology Data Exchange (ETDEWEB)

Park, Jin-Woo; Kim, Changhyeon; Ryu, Ho-Suk; Cho, Gyu-Bong; Cho, Kwon-Koo; Kim, Ki-Won [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Ahn, Jou-Hyeon [Department of Chemical & Biological Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Wang, Guoxiu [School of Chemistry and Forensic Science, University of Technology Sydney, Sydney, NSW 2007 (Australia); Ahn, Jae-Pyeung [Advanced Analysis Center, Research Planning & Coordination Division, KIST, Seoul (Korea, Republic of); Ahn, Hyo-Jun, E-mail: ahj@gnu.ac.kr [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of)

2015-09-15

Highlights: • The content of sulfur in activated carbon was controlled by solution process. • The sulfur electrode with low sulfur content shows the best performance. • The Li/S battery has capacity of 1360 mAh/g at 1 C and 702 mAh/g at 10 C. - Abstract: The content of sulfur in sulfur/activated carbon composite is controlled from 32.37 wt.% to 55.33 wt.% by a one-step solution-based process. When the sulfur content is limited to 41.21 wt.%, it can be loaded into the pores of an activated carbon matrix in a highly dispersed state. On the contrary, when the sulfur content is 55.33 wt.%, crystalline sulfur can be detected on the surface of the activated carbon matrix. The best electrochemical performance can be obtained for a sulfur electrode with the lowest sulfur content. The sulfur/activated carbon composite with 32.37 wt.% sulfur afforded the highest first discharge capacity of 1360 mAh g{sup −1} at 1 C rate and a large reversible capacity of 702 mAh g{sup −1} at 10 C (16.75 A/g)

Proteomic Insights into Sulfur Metabolism in the Hydrogen-Producing Hyperthermophilic Archaeon Thermococcus onnurineus NA1

Directory of Open Access Journals (Sweden)

Yoon-Jung Moon

2015-04-01

Full Text Available The hyperthermophilic archaeon Thermococcus onnurineus NA1 has been shown to produce H2 when using CO, formate, or starch as a growth substrate. This strain can also utilize elemental sulfur as a terminal electron acceptor for heterotrophic growth. To gain insight into sulfur metabolism, the proteome of T. onnurineus NA1 cells grown under sulfur culture conditions was quantified and compared with those grown under H2-evolving substrate culture conditions. Using label-free nano-UPLC-MSE-based comparative proteomic analysis, approximately 38.4% of the total identified proteome (589 proteins was found to be significantly up-regulated (≥1.5-fold under sulfur culture conditions. Many of these proteins were functionally associated with carbon fixation, Fe–S cluster biogenesis, ATP synthesis, sulfur reduction, protein glycosylation, protein translocation, and formate oxidation. Based on the abundances of the identified proteins in this and other genomic studies, the pathways associated with reductive sulfur metabolism, H2-metabolism, and oxidative stress defense were proposed. The results also revealed markedly lower expression levels of enzymes involved in the sulfur assimilation pathway, as well as cysteine desulfurase, under sulfur culture condition. The present results provide the first global atlas of proteome changes triggered by sulfur, and may facilitate an understanding of how hyperthermophilic archaea adapt to sulfur-rich, extreme environments.

Proteomic Insights into Sulfur Metabolism in the Hydrogen-Producing Hyperthermophilic Archaeon Thermococcus onnurineus NA1

Science.gov (United States)

Moon, Yoon-Jung; Kwon, Joseph; Yun, Sung-Ho; Lim, Hye Li; Kim, Jonghyun; Kim, Soo Jung; Kang, Sung Gyun; Lee, Jung-Hyun; Kim, Seung Il; Chung, Young-Ho

2015-01-01

The hyperthermophilic archaeon Thermococcus onnurineus NA1 has been shown to produce H2 when using CO, formate, or starch as a growth substrate. This strain can also utilize elemental sulfur as a terminal electron acceptor for heterotrophic growth. To gain insight into sulfur metabolism, the proteome of T. onnurineus NA1 cells grown under sulfur culture conditions was quantified and compared with those grown under H2-evolving substrate culture conditions. Using label-free nano-UPLC-MSE-based comparative proteomic analysis, approximately 38.4% of the total identified proteome (589 proteins) was found to be significantly up-regulated (≥1.5-fold) under sulfur culture conditions. Many of these proteins were functionally associated with carbon fixation, Fe–S cluster biogenesis, ATP synthesis, sulfur reduction, protein glycosylation, protein translocation, and formate oxidation. Based on the abundances of the identified proteins in this and other genomic studies, the pathways associated with reductive sulfur metabolism, H2-metabolism, and oxidative stress defense were proposed. The results also revealed markedly lower expression levels of enzymes involved in the sulfur assimilation pathway, as well as cysteine desulfurase, under sulfur culture condition. The present results provide the first global atlas of proteome changes triggered by sulfur, and may facilitate an understanding of how hyperthermophilic archaea adapt to sulfur-rich, extreme environments. PMID:25915030

Selective catalytic reduction of sulfur dioxide to elemental sulfur. Final report

Energy Technology Data Exchange (ETDEWEB)

Liu, W.; Flytzani-Stephanopoulos, M.; Sarofim, A.F.

1995-06-01

This project has investigated new metal oxide catalysts for the single stage selective reduction of SO{sub 2} to elemental sulfur by a reductant, such as CO. Significant progress in catalyst development has been made during the course of the project. We have found that fluorite oxides, CeO{sub 2} and ZrO{sub 2}, and rare earth zirconates such as Gd{sub 2}Zr{sub 2}O{sub 7} are active and stable catalysts for reduction Of SO{sub 2} by CO. More than 95% sulfur yield was achieved at reaction temperatures about 450{degrees}C or higher with the feed gas of stoichiometric composition. Reaction of SO{sub 2} and CO over these catalysts demonstrated a strong correlation of catalytic activity with the catalyst oxygen mobility. Furthermore, the catalytic activity and resistance to H{sub 2}O and CO{sub 2} poisoning of these catalysts were significantly enhanced by adding small amounts of transition metals, such as Co, Ni, Co, etc. The resulting transition metal-fluorite oxide composite catalyst has superior activity and stability, and shows promise in long use for the development of a greatly simplified single-step sulfur recovery process to treat variable and dilute SO{sub 2} concentration gas streams. Among various active composite catalyst systems the Cu-CeO{sub 2} system has been extensively studied. XRD, XPS, and STEM analyses of the used Cu-CeO{sub 2} catalyst found that the fluorite crystal structure of ceria was stable at the present reaction conditions, small amounts of copper was dispersed and stabilized on the ceria matrix, and excess copper oxide particles formed copper sulfide crystals of little contribution to catalytic activity. A working catalyst consisted of partially sulfated cerium oxide surface and partially sulfided copper clusters. The overall reaction kinetics were approximately represented by a first order equation.

Composition and oxidation state of sulfur in atmospheric particulate matter

Directory of Open Access Journals (Sweden)

A. F. Longo

2016-10-01

Full Text Available The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS and X-ray fluorescence (XRF microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

Magnetic and Structural Properties of Electrodeposited Iron on Copper and Silver

International Nuclear Information System (INIS)

Koempe, K.; Kuehl, E.; Nagorny, K.

2002-01-01

Electrodeposition of iron on copper or silver leads to the formation of bcc-iron or amorphous iron. Thermal annealing usually results in soluted iron (also γ-iron and clusters) in copper. On silver the insolubility of iron never causes the formation of bcc-iron. Instead on copper as well as on silver fcc-iron states are formed, especially at relatively low temperatures with short times of annealing. Moessbauer spectroscopy accompanied by X-ray diffraction (XRD) and vibrating sample magnetometry (VSM) are applied for characterisation of the iron states.

Stable isotope phenotyping via cluster analysis of NanoSIMS data as a method for characterizing distinct microbial ecophysiologies and sulfur-cycling in the environment

Directory of Open Access Journals (Sweden)

Katherine S Dawson

2016-05-01

Full Text Available Stable isotope probing (SIP is a valuable tool for gaining insights into ecophysiology and biogeochemical cycling of environmental microbial communities by tracking isotopically labeled compounds into cellular macromolecules as well as into byproducts of respiration. SIP, in conjunction with nanoscale secondary ion mass spectrometry (NanoSIMS, allows for the visualization of isotope incorporation at the single cell level. In this manner, both active cells within a diverse population as well as heterogeneity in metabolism within a homogeneous population can be observed. The ecophysiological implications of these single cell stable isotope measurements are often limited to the taxonomic resolution of paired fluorescence in situ hybridization (FISH microscopy. Here we introduce a taxonomy-independent method using multi-isotope SIP and NanoSIMS for identifying and grouping phenotypically similar microbial cells by their chemical and isotopic fingerprint. This method was applied to SIP experiments in a sulfur-cycling biofilm collected from sulfidic intertidal vents amended with 13C-acetate, 15N-ammonium, and 33S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope (13C/12C, 15N/14N, and 33S/32S and elemental ratio (C/CN and S/CN profiles, our analysis partitioned ~2200 cellular regions of interest (ROIs into 5 distinct groups. These isotope phenotype groupings are reflective of the variation in labeled substrate uptake by cells in a multispecies metabolic network dominated by Gamma- and Deltaproteobacteria. Populations independently grouped by isotope phenotype were subsequently compared with paired FISH data, demonstrating a single coherent deltaproteobacterial cluster and multiple gammaproteobacterial groups, highlighting the distinct ecophysiologies of spatially-associated microbes within the sulfur-cycling biofilm from White Point Beach, CA.

Adventures in Scaffold Morphing: Discovery of Fused Ring Heterocyclic Checkpoint Kinase 1 (CHK1) Inhibitors.

Science.gov (United States)

Yang, Bin; Vasbinder, Melissa M; Hird, Alexander W; Su, Qibin; Wang, Haixia; Yu, Yan; Toader, Dorin; Lyne, Paul D; Read, Jon A; Breed, Jason; Ioannidis, Stephanos; Deng, Chun; Grondine, Michael; DeGrace, Nancy; Whitston, David; Brassil, Patrick; Janetka, James W

2018-02-08

Checkpoint kinase 1 (CHK1) inhibitors are potential cancer therapeutics that can be utilized for enhancing the efficacy of DNA damaging agents. Multiple small molecule CHK1 inhibitors from different chemical scaffolds have been developed and evaluated in clinical trials in combination with chemotherapeutics and radiation treatment. Scaffold morphing of thiophene carboxamide ureas (TCUs), such as AZD7762 (1) and a related series of triazoloquinolines (TZQs), led to the identification of fused-ring bicyclic CHK1 inhibitors, 7-carboxamide thienopyridines (7-CTPs), and 7-carboxamide indoles. X-ray crystal structures reveal a key intramolecular noncovalent sulfur-oxygen interaction in aligning the hinge-binding carboxamide group to the thienopyridine core in a coplanar fashion. An intramolecular hydrogen bond to an indole NH was also effective in locking the carboxamide in the preferred bound conformation to CHK1. Optimization on the 7-CTP series resulted in the identification of lead compound 44, which displayed respectable drug-like properties and good in vitro and in vivo potency.

Magnetically triggered clustering of biotinylated iron oxide nanoparticles in the presence of streptavidinylated enzymes

International Nuclear Information System (INIS)

Hodenius, Michael; De Cuyper, Marcel; Hieronymus, Thomas; Zenke, Martin; Becker, Christiane; Elling, Lothar; Bornemann, Jörg; Wong, John E; Richtering, Walter; Himmelreich, Uwe

2012-01-01

This work deals with the production and characterization of water-compatible, iron oxide based nanoparticles covered with functional poly(ethylene glycol) (PEG)–biotin surface groups (SPIO–PEG–biotin). Synthesis of the functionalized colloids occurred by incubating the oleate coated particles used as precursor magnetic fluid with anionic liposomes containing 14 mol% of a phospholipid–PEG–biotin conjugate. The latter was prepared by coupling dimyristoylphosphatidylethanolamine (DC 14:0 PE) to activated α-biotinylamido-ω –N-hydroxy-succinimidcarbonyl–PEG (NHS–PEG–biotin). Physical characterization of the oleate and PEG–biotin iron oxide nanocolloids revealed that they appear as colloidal stable clusters with a hydrodynamic diameter of 160 nm and zeta potentials of − 39 mV (oleate coated particles) and − 14 mV (PEG–biotin covered particles), respectively, as measured by light scattering techniques. Superconducting quantum interference device (SQUID) measurements revealed specific saturation magnetizations of 62–73 emu g −1 Fe 3 O 4 and no hysteresis was observed at 300 K. MR relaxometry at 3 T revealed very high r 2 relaxivities and moderately high r 1 values. Thus, both nanocolloids can be classified as small, superparamagnetic, negative MR contrast agents. The capacity to functionalize the particles was illustrated by binding streptavidin alkaline phosphatase (SAP). It was found, however, that these complexes become highly aggregated after capturing them on the magnetic filter device during high-gradient magnetophoresis, thereby reducing the accessibility of the SAP. (paper)

bcl::Cluster : A method for clustering biological molecules coupled with visualization in the Pymol Molecular Graphics System.

Science.gov (United States)

Alexander, Nathan; Woetzel, Nils; Meiler, Jens

2011-02-01

Clustering algorithms are used as data analysis tools in a wide variety of applications in Biology. Clustering has become especially important in protein structure prediction and virtual high throughput screening methods. In protein structure prediction, clustering is used to structure the conformational space of thousands of protein models. In virtual high throughput screening, databases with millions of drug-like molecules are organized by structural similarity, e.g. common scaffolds. The tree-like dendrogram structure obtained from hierarchical clustering can provide a qualitative overview of the results, which is important for focusing detailed analysis. However, in practice it is difficult to relate specific components of the dendrogram directly back to the objects of which it is comprised and to display all desired information within the two dimensions of the dendrogram. The current work presents a hierarchical agglomerative clustering method termed bcl::Cluster. bcl::Cluster utilizes the Pymol Molecular Graphics System to graphically depict dendrograms in three dimensions. This allows simultaneous display of relevant biological molecules as well as additional information about the clusters and the members comprising them.

Sulfur-Kβ /sub emission studies on sulfur-bearing heterocycles

International Nuclear Information System (INIS)

Phillips, D.R.; Andermann, G.G.; Fujiwara, F.

1986-01-01

Sulfur-K/β /sub x-ray fluorescence spectroscopy (XFS) has been used to study the electronic structure and bonding in sulfur-bearing heterocycles. XFS not only has the capability of experimentally measuring valence electron energies in molecular species, but can also provide intensity data which can help define the nature of the molecular orbitals defined by the electrons. This report discusses the feasibility of using XFS as an analytical tool for the determination of total and specific sulfur heterocycle content in samples. A variety of compounds were studied. These include thiophene, thiophene derivatives, tetranydrothiophene, several more complex saturated and unsaturated sulfur heterocycles, and heterocycles containing both sulfur and nitrogen. The sulfur-K/β /sub spectra were obtained using a double crystal spectrometer which provided an instrumental resolution of about 0.7 eV

Effect of low-dose versus higher-dose antenatal iron supplementation on child health outcomes at 36 months of age in Viet Nam: longitudinal follow-up of a cluster randomised controlled trial.

Science.gov (United States)

Hanieh, Sarah; Ha, Tran T; Simpson, Julie A; Braat, Sabine; Thuy, Tran T; Tran, Thach D; King, Janet; Tuan, Tran; Fisher, Jane; Biggs, Beverley-Ann

2017-01-01

Intermittent iron-folic acid supplementation (IFA) is currently recommended for pregnant women in populations where anaemia prevalence among pregnant women is Viet Nam among children of 36 months of age, born to women previously enrolled in a cluster randomised controlled trial of antenatal micronutrient supplementation (daily IFA (60 mg elemental iron) vs twice-weekly IFA (60 mg elemental iron) vs twice-weekly multiple micronutrient (MMN) supplementation (60 mg elemental iron)). Primary outcomes were height-for-age z-scores (HAZ), according to WHO growth standards and cognitive composite scores (Bayley Scales of Infant and Toddler Development, third edition) at 36 months of age. A total of 1017 children born to mothers enrolled in the cluster randomised trial were assessed at 36 months of age. Adjusted mean differences (MDs) in HAZ were -0.14 (95% CI -0.28 to -0.01) and -0.15 (95% CI -0.29 to -0.01) in children born to mothers who received twice-weekly IFA or MMN compared with those who received daily IFA. Children born to mothers who received twice-weekly MMN had lower composite motor scores compared with those who received daily IFA (MD -2.07, 95% CI -4.11 to -0.03). There were no differences in composite cognitive scores in the twice-weekly compared with daily regimens. Low-dose antenatal IFA supplementation (120 mg elemental iron per week) resulted in lower HAZ and motor composite scores in children compared with higher-dose antenatal IFA supplementation (420 mg elemental iron per week). This highlights the importance of adequate iron stores during pregnancy and the need for careful monitoring when lower-dose antenatal iron regimens are used. Australia New Zealand Clinical Trials Registry: 12610000944033.

Expression and Characterisation of Recombinant Rhodocyclus tenuis High Potential Iron-Sulphur Protein

DEFF Research Database (Denmark)

Caspersen, Michael Bjerg; Bennet, K.; Christensen, Hans Erik Mølager

2000-01-01

The high potential iron-sulfur protein (HiPIP) from Rhodocyclus tenuis strain 2761 has been overproduced in Escherichia coli from its structural gene, purified to apparent homogeneity, and then characterized by an array of methods. UV-visible spectra of the reduced and oxidized recombinant protein...

Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

CERN Document Server

Schobesberger, Siegfried; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

2013-01-01

Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molec...

Graphene-wrapped sulfur nanospheres with ultra-high sulfur loading for high energy density lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Ya; Guo, Jinxin; Zhang, Jun, E-mail: zhangjun@zjnu.cn; Su, Qingmei; Du, Gaohui, E-mail: gaohuidu@zjnu.edu.cn

2015-01-01

Graphical abstract: - Highlights: • A graphene-wrapped sulfur nanospheres composite with 91 wt% S is prepared. • It shows highly improved electrochemical performance as cathode for Li–S cell. • The PVP coating and conductive graphene minimize polysulfides dissolution. • The flexible coatings with void space accommodate the volume expansion of sulfur. - Abstract: Lithium–sulfur (Li–S) battery with high theoretical energy density is one of the most promising energy storage systems for electric vehicles and intermittent renewable energy. However, due to the poor conductivity of the active material, considerable weight of the electrode is occupied by the conductive additives. Here we report a graphene-wrapped sulfur nanospheres composite (S-nanosphere@G) with sulfur content up to 91 wt% as the high energy density cathode material for Li–S battery. The sulfur nanospheres with diameter of 400–500 nm are synthesized through a solution-based approach with the existence of polyvinylpyrrolidone (PVP). Then the sulfur nanospheres are uniformly wrapped by conductive graphene sheets through the electrostatic interaction between graphene oxide and PVP, followed by reducing of graphene oxide with hydrazine. The design of graphene wrapped sulfur nanoarchitecture provides flexible conductive graphene coating with void space to accommodate the volume expansion of sulfur and to minimize polysulfide dissolution. As a result, the S-nanosphere@G nanocomposite with 91 wt% sulfur shows a reversible initial capacity of 970 mA h g{sup −1} and an average columbic efficiency > 96% over 100 cycles at a rate of 0.2 C. Taking the total mass of electrode into account, the S-nanosphere@G composite is a promising cathode material for high energy density Li–S batteries.

Multiple-heteroatom-containing sulfur compounds in a high sulfur coal

International Nuclear Information System (INIS)

Winans, R.E.; Neill, P.H.

1990-01-01

Flash vacuum pyrolysis of a high sulfur coal has been combined with high resolution mass spectrometry yielding information on aromatic sulfur compounds containing an additional heteroatom. Sulfur emission from coal utilization is a critical problem and in order to devise efficient methods for removing organic sulfur, it is important to know what types of molecules contain sulfur. A high sulfur Illinois No. 6 bituminous coal (Argonne Premium Coal Sample No. 3) was pyrolyzed on a platinum grid using a quartz probe inserted into a modified all glass heated inlet system and the products characterized by high resolution mass spectrometry (HRMS). A significant number of products were observed which contained both sulfur and an additional heteroatom. In some cases two additional heteroatoms were observed. These results are compared to those found in coal extracts and liquefaction products

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

Science.gov (United States)

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.

Osteoinduction and proliferation of bone-marrow stromal cells in three-dimensional poly (ε-caprolactone)/ hydroxyapatite/collagen scaffolds.

Science.gov (United States)

Wang, Ting; Yang, Xiaoyan; Qi, Xin; Jiang, Chaoyin

2015-05-08

Osteoinduction and proliferation of bone-marrow stromal cells (BMSCs) in three-dimensional (3D) poly(ε-caprolactone) (PCL) scaffolds have not been studied throughly and are technically challenging. This study aimed to optimize nanocomposites of 3D PCL scaffolds to provide superior adhesion, proliferation and differentiation environment for BMSCs in this scenario. BMSCs were isolated and cultured in a novel 3D tissue culture poly(ε-caprolactone) (PCL) scaffold coated with poly-lysine, hydroxyapatite (HAp), collagen and HAp/collagen. Cell morphology was observed and BMSC biomarkers for osteogenesis, osteoblast differentiation and activation were analyzed. Scanning Electron Microscope (SEM) micrographs showed that coating materials were uniformly deposited on the surface of PCL scaffolds and BMSCs grew and aggregated to form clusters during 3D culture. Both mRNA and protein levels of the key players of osteogenesis and osteoblast differentiation and activation, including runt-related transcription factor 2 (Runx2), alkaline phosphates (ALP), osterix, osteocalcin, and RANKL, were significantly higher in BMSCs seeded in PCL scaffolds coated with HAp or HAp/collagen than those seeded in uncoated PCL scaffolds, whereas the expression levels were not significantly different in collagen or poly-lysine coated PCL scaffolds. In addition, poly-lysine, collagen, HAp/collagen, and HAp coated PCL scaffolds had significantly more viable cells than uncoated PCL scaffolds, especially scaffolds with HAp/collagen and collagen-alone coatings. That BMSCs in HAp or HAp/collagen PCL scaffolds had remarkably higher ALP activities than those in collagen-coated alone or uncoated PCL scaffolds indicating higher osteogenic differentiation levels of BMSCs in HAp or HAp/collagen PCL scaffolds. Moreover, morphological changes of BMSCs after four-week of 3D culture confirmed that BMSCs successfully differentiated into osteoblast with spread-out phenotype in HAp/collagen coated PCL scaffolds

Polysulfide coordination clusters of the lanthanides

Energy Technology Data Exchange (ETDEWEB)

Ma, Ying-Zhao; Bestgen, Sebastian; Gamer, Michael T.; Roesky, Peter W. [Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Karlsruhe (Germany); Konchenko, Sergey N. [Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Karlsruhe (Germany); Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk (Russian Federation); Novosibirsk State University (Russian Federation)

2017-10-16

The reaction of [(DippForm){sub 2}Ln(thf){sub 2}] with an excess of elemental sulfur in toluene resulted in the formation of the trinuclear polysulfide coordination clusters [(DippForm){sub 3}Ln{sub 3}S{sub 12}] (Ln=Sm, Yb; DippForm=N,N'-bis(2,6-diisopropylphenyl)formamidinate). These are the first f element coordination clusters (Ln{sub n}S{sub x}) with a larger polysulfide unit (n and x>2). The formation of the coordination clusters can be rationalized by the reductive cleavage of S{sub 8} with divalent lanthanides. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Insight into the loading temperature of sulfur on sulfur/carbon cathode in lithium-sulfur batteries

International Nuclear Information System (INIS)

Ye, Huan; Yin, Ya-Xia; Guo, Yu-Guo

2015-01-01

Highlights: • A cost-effective chemical activation method to prepare porous carbon nanospheres. • Carbon nanospheres with bimodal microporous structure show high specific area and large micropore volume. • The S/C composite cathodes with in-situformed S−C bond exhibit high sulfur activity with a reversible capacity of 1000 mA h g −1 . • S−C bond enables well confinement on sulfur and polysulfides. - Abstract: Lithium–sulfur batteries are highly desired because of their characteristics such as high energy density. However, the applications of Li-S batteries are limited because they exist dissolution of polysulfides into electrolytes. This study reports the preparation of sulfur cathodes by using bimodal microporous (0.5 nm and 0.8 nm to 2.0 nm) carbon spheres with high specific area (1992 m 2 g −1 ) and large micropore volume (1.2 g cm −1 ), as well as the encapsulation of polysulfides via formation of carbon–sulfur bonds in a sealed vacuum glass tube at high temperature. Given that sulfur and polysulfides are well confined by the S−C bond, the shuttle effect is effectively suppressed. The prepared S/C cathodes with a sulfur loading of up to 75% demonstrate high sulfur activity with reversible capacity of 1000 mA h g −1 at the current density of 0.1 A g −1 and good cycling stability (667 mA h g −1 after 100 cycles).

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

Directory of Open Access Journals (Sweden)

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.

Improved method for minimizing sulfur loss in analysis of particulate organic sulfur.

Science.gov (United States)

Park, Ki-Tae; Lee, Kitack; Shin, Kyoungsoon; Jeong, Hae Jin; Kim, Kwang Young

2014-02-04

The global sulfur cycle depends primarily on the metabolism of marine microorganisms, which release sulfur gas into the atmosphere and thus affect the redistribution of sulfur globally as well as the earth's climate system. To better quantify sulfur release from the ocean, analysis of the production and distribution of organic sulfur in the ocean is necessary. This report describes a wet-based method for accurate analysis of particulate organic sulfur (POS) in the marine environment. The proposed method overcomes the considerable loss of sulfur (up to 80%) that occurs during analysis using conventional methods involving drying. Use of the wet-based POS extraction procedure in conjunction with a sensitive sulfur analyzer enabled accurate measurements of cellular POS. Data obtained using this method will enable accurate assessment of how rapidly sulfur can transfer among pools. Such information will improve understanding of the role of POS in the oceanic sulfur cycle.

First-principles investigation of the electronic and Li-ion diffusion properties of LiFePO4 by sulfur surface modification

International Nuclear Information System (INIS)

Xu, Guigui; Zhong, Kehua; Zhang, Jian-Min; Huang, Zhigao

2014-01-01

We present a first-principles calculation for the electronic and Li-ion diffusion properties of the LiFePO 4 (010) surface modified by sulfur. The calculated formation energy indicates that the sulfur adsorption on the (010) surface of the LiFePO 4 is energetically favored. Sulfur is found to form Fe-S bond with iron. A much narrower band gap (0.67 eV) of the sulfur surface-modified LiFePO 4 [S-LiFePO 4 (010)] is obtained, indicating the better electronic conductive properties. By the nudged elastic band method, our calculations show that the activation energy of Li ions diffusion along the one-dimensional channel on the surface can be effectively reduced by sulfur surface modification. In addition, the surface diffusion coefficient of S-LiFePO 4 (010) is estimated to be about 10 −11 (cm 2 /s) at room temperature, which implies that sulfur modification will give rise to a higher Li ion carrier mobility and enhanced electrochemical performance

Iron Fortified Complementary Foods Containing a Mixture of Sodium Iron EDTA with Either Ferrous Fumarate or Ferric Pyrophosphate Reduce Iron Deficiency Anemia in 12- to 36-Month-Old Children in a Malaria Endemic Setting: A Secondary Analysis of a Cluster-Randomized Controlled Trial.

Science.gov (United States)

Glinz, Dominik; Wegmüller, Rita; Ouattara, Mamadou; Diakité, Victorine G; Aaron, Grant J; Hofer, Lorenz; Zimmermann, Michael B; Adiossan, Lukas G; Utzinger, Jürg; N'Goran, Eliézer K; Hurrell, Richard F

2017-07-14

Iron deficiency anemia (IDA) is a major public health problem in sub-Saharan Africa. The efficacy of iron fortification against IDA is uncertain in malaria-endemic settings. The objective of this study was to evaluate the efficacy of a complementary food (CF) fortified with sodium iron EDTA (NaFeEDTA) plus either ferrous fumarate (FeFum) or ferric pyrophosphate (FePP) to combat IDA in preschool-age children in a highly malaria endemic region. This is a secondary analysis of a nine-month cluster-randomized controlled trial conducted in south-central Côte d'Ivoire. 378 children aged 12-36 months were randomly assigned to no food intervention ( n = 125; control group), CF fortified with 2 mg NaFeEDTA plus 3.8 mg FeFum for six days/week ( n = 126; FeFum group), and CF fortified with 2 mg NaFeEDTA and 3.8 mg FePP for six days/week ( n = 127; FePP group). The outcome measures were hemoglobin (Hb), plasma ferritin (PF), iron deficiency (PF anemia (Hb iron deficiency with or without anemia ( p = 0.068). IDA prevalence sharply decreased in the FeFum (32.8% to 1.2%, p anemia. These data indicate that, despite the high endemicity of malaria and elevated inflammation biomarkers (C-reactive protein or α-1-acid-glycoprotein), IDA was markedly reduced by provision of iron fortified CF to preschool-age children for 9 months, with no significant differences between a combination of NaFeEDTA with FeFum or NaFeEDTA with FePP. However, there was no overall effect on anemia, suggesting most of the anemia in this setting is not due to ID. This trial is registered at clinicaltrials.gov (NCT01634945).

Expression of Genes Involved in Iron and Sulfur Respiration in a Novel Thermophilic Crenarchaeon Isolated from Acid-Sulfate-Chloride Geothermal Systems

Science.gov (United States)

Kozubal, M.; Macur, R.; Inskeep, W. P.

2007-12-01

Acidic geothermal springs within Yellowstone National Park (YNP) provide an excellent opportunity to study microbial populations and their relationship with geochemical processes such as redox cycling and biomineralization of iron. Fourteen acid-sulfate-chloride (ASC) and acid-sulfate (AS) geothermal springs located in (YNP) have been extensively characterized for aqueous chemistry, solid phase mineral deposition and microbial diversity and distribution. The oxidation of Fe(II) with oxygen as an electron acceptor is exergonic under these conditions, consequently, Fe(II) may be an important electron donor driving primary production in ASC and AS habitats, and products of biomineralization (e.g. Fe[III]-oxides of varying crystallinity and structure, as well as jarosite in some cases) are common in the outflow channels of these environments. Recently, we isolated a novel Metallosphaera-like microorganism (Metallosphaera strain MK1) from an ASC spring in Norris Geyser Basin, YNP. Clone libraries (16S rRNA gene) from multiple sites suggest that microorganisms closely related to strain MK1 (between 98-100 percent similarity) dominate many spring locations between 55-80 C. The in situ abiotic oxidation rate of Fe(II) has been shown to be very slow in these systems and Metallosphaera strain MK1 has been directly implicated in biotic Fe(II) oxidation. Metallosphaera strain MK1 has been submitted for full genome sequencing and is yielding gene sequences related to the terminal oxidases SOXABC and SOXM super-complex. In addition, sequences from a recently characterized terminal oxidase FOX complex involved in Fe(II) and pyrite oxidation from Sulfolobus metallicus have been found in Metallosphaera strain MK1. A protein complex analogous to Metallosphaera sedula has been identified in strain MK1 and this complex has also been expressed in cells grown on pyrite and Fe(II). Other sequences identified in Metallosphaera strain MK1 that are involved in respiration are the TQO

Magnetic resonance imaging tracking of human adipose derived stromal cells within three-dimensional scaffolds for bone tissue engineering

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C Lalande

2011-04-01

Full Text Available For bone tissue engineering, human Adipose Derived Stem Cells (hADSCs are proposed to be associated with a scaffold for promoting bone regeneration. After implantation, cellularised scaffolds require a non-invasive method for monitoring their fate in vivo. The purpose of this study was to use Magnetic Resonance Imaging (MRI-based tracking of these cells, labelled with magnetic agents for in vivo longitudinal assessment. hADSCs were isolated from adipose tissue and labelled with USPIO-rhodamine (Ultrasmall SuperParamagnetic Iron Oxide. USPIO internalisation, absence of toxicity towards hADSCs, and osteogenic differentiation of the labelled cells were evaluated in standard culture conditions. Labelled cells were then seeded within a 3D porous polysaccharide-based scaffold and imaged in vitro using fluorescence microscopy and MRI. Cellularised scaffolds were implanted subcutaneously in nude mice and MRI analyses were performed from 1 to 28 d after implantation. In vitro, no effect of USPIO labelling on cell viability and osteogenic differentiation was found. USPIO were efficiently internalised by hADSCs and generated a high T2* contrast. In vivo MRI revealed that hADSCs remain detectable until 28 d after implantation and could migrate from the scaffold and colonise the area around it. These data suggested that this scaffold might behave as a cell carrier capable of both holding a cell fraction and delivering cells to the site of implantation. In addition, the present findings evidenced that MRI is a reliable technique to validate cell-seeding procedures in 3D porous scaffolds, and to assess the fate of hADSCs transplanted in vivo.

Sulfur isotope studies of biogenic sulfur emissions at Wallops Island, Virginia

International Nuclear Information System (INIS)

Hitchcock, D.R.; Black, M.S.; Herbst, R.P.

1978-03-01

This research attempted to determine whether it is possible to measure the stable sulfur isotope distributions of atmospheric particulate and gaseous sulphur, and to use this information together with measurements of the ambient levels of sulfur gases and particulate sulfate and sodium in testing certain hypotheses. Sulfur dioxide and particulate sulfur samples were collected at a coastal marine location and their delta (34)S values were determined. These data were used together with sodium concentrations to determine the presence of biogenic sulfur and the identity of the biological processes producing it. Excess (non-seasalt) sulfate levels ranged from 2 to 26 micrograms/cu m and SO2 from 1 to 9 ppb. Analyses of air mass origins and lead concentrations indicated that some anthropogenic contaminants were present on all days, but the isotope data revealed that most of the atmospheric sulfur originated locally from the metabolism of bacterial sulfate reducers on all days, and that the atmospheric reactions leading to the production of sulfate from this biogenic sulfur source are extremely rapid. Delta 34 S values of atmospheric sulfur dioxide correlated well with those of excess sulfate, and implied little or no sulfur isotope fractionation during the oxidation of sulfur gases to sulfate

Studies of structure change of iron sulfates and its catalysis; Ryusantetsukei shokubai no kozo henka to sono shokubai sayo

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Ogata, E.; Horie, K. [The University of Tokyo, Tokyo (Japan). Faculty of Engineering; Nishijima, A. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

1996-10-28

Since a huge amount of coal containing inorganic ash is treated for the commercial hydroliquefaction process, cheap catalysts widely distributing on the earth with large reserves are desired rather than expensive catalysts. This paper describes the effects of addition of sulfur on the catalysis of iron sulfates during the hydroconversion of 1-methylnaphthalene (1-MN). Reactions of 1-MN were conducted at the same charging amount of iron in the reaction system. Sulfur was directly added in the reaction system using ferrous sulfate (FeSO4) as precursor. Consequently, it was found that FeSO4 provides lower but similar catalytic activity to the synthetic pyrite catalyst prepared through the complex processes with the precise control. Thus, it was revealed that high performance pyrrhotite (Fe(1-x)S) catalyst can be prepared for the hydrogenation of aromatic-rings by adding solid sulfur into the reaction system using commercial reagent, FeSO4 as a precursor of the catalyst. 9 figs.

Sulfate- and Sulfur-Reducing Bacteria as Terrestrial Analogs for Microbial Life on Jupiter's Satellite Io

Science.gov (United States)

Pikuta, Elena V.; Hoover, Richard B.; Six, N. Frank (Technical Monitor)

2001-01-01

Observations from the Voyager and Galileo spacecraft have revealed Jupiter's moon Io to be the most volcanically active body of our Solar System. The Galileo Near Infrared Imaging Spectrometer (NIMS) detected extensive deposits of sulfur compounds, elemental sulfur and SO2 frost on the surface of Io. There are extreme temperature variations on Io's surface, ranging from -130 C to over 2000 C at the Pillan Patera volcanic vent. The active volcanoes, fumaroles, calderas, and lava lakes and vast sulfur deposits on this frozen moon indicate that analogs of sulfur- and sulfate-reducing bacteria might inhabit Io. Hence Io may have great significance to Astrobiology. Earth's life forms that depend on sulfur respiration are members of two domains: Bacteria and Archaea. Two basic links of the biogeochemical sulfur cycle of Earth have been studied: 1) the sulfur oxidizing process (occurring at aerobic conditions) and 2) the process of sulfur-reduction to hydrogen sulfide (anaerobic conditions). Sulfate-reducing bacteria (StRB) and sulfur-reducing bacteria (SrRB) are responsible for anaerobic reducing processes. At the present time the systematics of StRB include over 112 species distributed into 35 genera of Bacteria and Archaea. Moderately thermophilic and mesophilic SrRB belong to the Bacteria. The hyperthermophilic SrRB predominately belong to the domain Archaea and are included in the genera: Pyrodictium, Thermoproteus, Pyrobaculum, Thermophilum, Desulfurococcus, and Thermodiscus. The StRB and SrRB use a wide spectrum of substrates as electron donors for lithotrophic and heterotrophic type nutrition. The electron acceptors for the StRB include: sulfate, thiosulfate, sulfite, sulfur, arsenate, dithionite, tetrathionate, sulfur monoxide, iron, nitrite, selenite, fumarate, oxygen, carbon dioxide, and chlorine-containing phenol compounds. The Sulfate- and Sulfur-reducing bacteria are widely distributed in anaerobic ecosystems, including extreme environments like hot springs

Sulfur-Containing Agrochemicals.

Science.gov (United States)

Devendar, Ponnam; Yang, Guang-Fu

2017-10-09

Modern agricultural chemistry has to support farmers by providing innovative agrochemicals. In this context, the introduction of sulfur atoms into an active ingredient is still an important tool in modulating the properties of new crop-protection compounds. More than 30% of today's agrochemicals contain at least one sulfur atom, mainly in fungicides, herbicides and insecticides. A number of recently developed sulfur-containing agrochemical candidates represent a novel class of chemical compounds with new modes of action, so we intend to highlight the emerging interest in commercially active sulfur-containing compounds. This chapter gives a comprehensive overview of selected leading sulfur-containing pesticidal chemical families namely: sulfonylureas, sulfonamides, sulfur-containing heterocyclics, thioureas, sulfides, sulfones, sulfoxides and sulfoximines. Also, the most suitable large-scale synthetic methods of the recently launched or provisionally approved sulfur-containing agrochemicals from respective chemical families have been highlighted.

Importance of different physiological groups of iron reducing microorganisms in an acidic mining lake remediation experiment.

Science.gov (United States)

Porsch, Katharina; Meier, Jutta; Kleinsteuber, Sabine; Wendt-Potthoff, Katrin

2009-05-01

Iron- and sulfate-reducing microorganisms play an important role for alkalinity-generating processes in mining lakes with low pH. In the acidic mining lake 111 in Lusatia, Germany, a passive in situ remediation method was tested in a large scale experiment, in which microbial iron and sulfate reduction are stimulated by addition of Carbokalk (a mixture of the nonsugar compounds of sugar beets and lime) and straw. The treated surface sediment consisted of three layers of different pH and geochemical composition. The top layer was acidic and rich in Fe(III), the second and third layer both showed moderately acidic to circum-neutral pH values, but only the second was rich in organics, strongly reduced and sulfidic. Aim of the study was to elucidate the relative importance of neutrophilic heterotrophic, acidophilic heterotrophic, and acidophilic autotrophic iron-reducing microorganisms in each of the three layers. In order to distinguish between them, the effect of their respective characteristic electron donors acetate, glucose, and elemental sulfur on potential iron reduction rates was investigated. Limitation of iron reduction by the availability of Fe(III) was revealed by the addition of Fe(OH)(3). The three groups of iron-reducing microorganisms were quantified by most probable number (MPN) technique and their community composition was analyzed by cloning and sequencing of 16S rRNA genes. In the acidic surface layer, none of the three electron donors stimulated iron reduction; acetate even had an inhibiting effect. In agreement with this, no decrease of the added electron donors was observed. Iron reduction rates were low in comparison to the other layers. Iron reduction in layers 2 and 3 was enhanced by glucose and acetate, accompanied by a decrease of these electron donors. Addition of elemental sulfur did not enhance iron reduction in either layer. Layer 2 exhibited the highest iron reduction rate (4.08 mmol dm(-3) d(-1)) and the highest cell numbers in MPN

Infrared Multiple Photon Dissociation Spectroscopy Of Metal Cluster-Adducts

Science.gov (United States)

Cox, D. M.; Kaldor, A.; Zakin, M. R.

1987-01-01

Recent development of the laser vaporization technique combined with mass-selective detection has made possible new studies of the fundamental chemical and physical properties of unsupported transition metal clusters as a function of the number of constituent atoms. A variety of experimental techniques have been developed in our laboratory to measure ionization threshold energies, magnetic moments, and gas phase reactivity of clusters. However, studies have so far been unable to determine the cluster structure or the chemical state of chemisorbed species on gas phase clusters. The application of infrared multiple photon dissociation IRMPD to obtain the IR absorption properties of metal cluster-adsorbate species in a molecular beam is described here. Specifically using a high power, pulsed CO2 laser as the infrared source, the IRMPD spectrum for methanol chemisorbed on small iron clusters is measured as a function of the number of both iron atoms and methanols in the complex for different methanol isotopes. Both the feasibility and potential utility of IRMPD for characterizing metal cluster-adsorbate interactions are demonstrated. The method is generally applicable to any cluster or cluster-adsorbate system dependent only upon the availability of appropriate high power infrared sources.

Radiation Induced Precipitation in Iron

International Nuclear Information System (INIS)

Solly, B.

1964-02-01

Foils of iron have been neutron-irradiated in the Swedish re- search reactor R2 to integrated doses in the range 10 17 - 10 19 nvt (> 1 MeV) and examined by transmission electron microscopy. Features have been observed having diffraction contrast similar to that of the prismatic dislocation loops formed in f.c.c. metals by the collapse of point-defect clusters. The features have been shown to be due to precipitation of impurities at radiation damage centres in the iron matrix

A Chemical Composition Survey of the Iron-complex Globular Cluster NGC 6273 (M19)

Energy Technology Data Exchange (ETDEWEB)

Johnson, Christian I.; Caldwell, Nelson [Harvard–Smithsonian Center for Astrophysics, 60 Garden Street, MS-15, Cambridge, MA 02138 (United States); Rich, R. Michael [Department of Physics and Astronomy, UCLA, 430 Portola Plaza, Box 951547, Los Angeles, CA 90095-1547 (United States); Mateo, Mario [Department of Astronomy, University of Michigan, Ann Arbor, MI 48109 (United States); Bailey, John I. III [Leiden Observatory, Leiden University, P.O. Box 9513, 2300RA Leiden (Netherlands); Clarkson, William I. [Department of Natural Sciences, University of Michigan–Dearborn, 4901 Evergreen Road, Dearborn, MI 48128 (United States); Olszewski, Edward W. [Steward Observatory, The University of Arizona, 933 N. Cherry Avenue, Tucson, AZ 85721 (United States); Walker, Matthew G., E-mail: cjohnson@cfa.harvard.edu, E-mail: ncaldwell@cfa.harvard.edu, E-mail: rmr@astro.ucla.edu, E-mail: mmateo@umich.edu, E-mail: baileyji@strw.leidenuniv.nl, E-mail: wiclarks@umich.edu, E-mail: eolszewski@as.arizona.edu, E-mail: mgwalker@andrew.cmu.edu [McWilliams Center for Cosmology, Department of Physics, Carnegie Mellon University, 5000 Forbes Avenue, Pittsburgh, PA 15213 (United States)

2017-02-20

Recent observations have shown that a growing number of the most massive Galactic globular clusters contain multiple populations of stars with different [Fe/H] and neutron-capture element abundances. NGC 6273 has only recently been recognized as a member of this “iron-complex” cluster class, and we provide here a chemical and kinematic analysis of >300 red giant branch and asymptotic giant branch member stars using high-resolution spectra obtained with the Magellan –M2FS and VLT–FLAMES instruments. Multiple lines of evidence indicate that NGC 6273 possesses an intrinsic metallicity spread that ranges from about [Fe/H] = −2 to −1 dex, and may include at least three populations with different [Fe/H] values. The three populations identified here contain separate first (Na/Al-poor) and second (Na/Al-rich) generation stars, but a Mg–Al anti-correlation may only be present in stars with [Fe/H] ≳ −1.65. The strong correlation between [La/Eu] and [Fe/H] suggests that the s-process must have dominated the heavy element enrichment at higher metallicities. A small group of stars with low [ α /Fe] is identified and may have been accreted from a former surrounding field star population. The cluster’s large abundance variations are coupled with a complex, extended, and multimodal blue horizontal branch (HB). The HB morphology and chemical abundances suggest that NGC 6273 may have an origin that is similar to ω Cen and M54.

Iron-Coupled Anaerobic Oxidation of Methane Performed by a Mixed Bacterial-Archaeal Community Based on Poorly Reactive Minerals.

Science.gov (United States)