Linkage of iron elution and dissolved oxygen consumption with removal of organic pollutants by nanoscale zero-valent iron: Effects of pH on iron dissolution and formation of iron oxide/hydroxide layer.

PubMed

Fujioka, Nanae; Suzuki, Moe; Kurosu, Shunji; Kawase, Yoshinori

2016-02-01

The iron elution and dissolved oxygen (DO) consumption in organic pollutant removal by nanoscale zero-valent iron (nZVI) was examined in the range of solution pH from 3.0 to 9.0. Their behaviors were linked with the removal of organic pollutant through the dissolution of iron and the formation of iron oxide/hydroxide layer affected strongly by solution pH and DO. As an example of organic pollutants, azo-dye Orange II was chosen in this study. The chemical composition analyses before and after reaction confirmed the corrosion of nZVI into ions, the formation of iron oxide/hydroxide layer on nZVI surface and the adsorption of the pollutant and its intermediates. The complete decolorization of Orange II with nZVI was accomplished very quickly. On the other hand, the total organic carbon (TOC) removal was considerably slow and the maximum TOC removal was around 40% obtained at pH 9.0. The reductive cleavage of azo-bond by emitted electrons more readily took place as compared with the cleavage of aromatic rings of Orange II leading to the degradation to smaller molecules and subsequently the mineralization. A reaction kinetic model based on the Langmuir-Hinshelwood/Eley-Rideal approach was developed to elucidate mechanisms for organic pollutant removal controlled by the formation of iron oxide/hydroxide layer, the progress of which could be characterized by considering the dynamic concentration changes in Fe(2+) and DO. The dynamic profiles of Orange II removal linked with Fe(2+) and DO could be reasonably simulated in the range of pH from 3.0 to 9.0. Copyright © 2015 Elsevier Ltd. All rights reserved.

Role of iron overload-induced macrophage apoptosis in the pathogenesis of peritoneal endometriosis.

PubMed

Pirdel, Leila; Pirdel, Manijeh

2014-06-01

This article presents an overview of the involvement of iron overload-induced nitric oxide (NO) overproduction in apoptosis of peritoneal macrophages of women with endometriosis. We have postulated that the peritoneal iron overload originated from retrograde menstruation or bleeding lesions in the ectopic endometrium, which may contribute to the development of endometriosis by a wide range of mechanisms, including oxidative damage and chronic inflammation. Excessive NO production may also be associated with impaired clearance of endometrial cells by macrophages, which promotes cell growth in the peritoneal cavity. Therefore, further research of the mechanisms and consequences of macrophage apoptosis in endometriosis helps discover novel therapeutic strategies that are designed to prevent progression of endometriosis. © 2014 Society for Reproduction and Fertility.

Intersections of pathways involving biotin and iron relative to therapeutic mechanisms for progressive multiple sclerosis.

PubMed

Heidker, Rebecca M; Emerson, Mitchell R; LeVine, Steven M

2016-12-01

While there are a variety of therapies for relapsing remitting multiple sclerosis (MS), there is a lack of treatments for progressive MS. An early study indicated that high dose biotin therapy has beneficial effects in approximately 12-15% of patients with progressive MS. The mechanisms behind the putative improvements seen with biotin therapy are not well understood, but have been postulated to include: 1) improving mitochondrial function which is impaired in MS, 2) increasing synthesis of lipids and cholesterol to facilitate remyelination, and 3) affecting gene expression. We suggest one reason that a greater percentage of patients with MS didn't respond to biotin therapy is the inaccessibility or lack of other nutrients, such as iron. In addition to biotin, iron (or heme) is necessary for energy production, biosynthesis of cholesterol and lipids, and for some protective mechanisms. Both biotin and iron are required for myelination during development, and by inference, remyelination. However, iron can also play a role in the pathology of MS. Increased deposition of iron can occur in some CNS structures possibly promoting oxidative damage while low iron levels can occur in other areas. Thus, the potential, detrimental effects of iron need to be considered together with the need for iron to support metabolic demands associated with repair and/or protective processes. We propose the optimal utilization of iron may be necessary to maximize the beneficial effects of biotin. This review will examine the interactions between biotin and iron in pathways that may have therapeutic or pathogenic implications for MS.

Zim17/Tim15 links mitochondrial iron-sulfur cluster biosynthesis to nuclear genome stability.

PubMed

Díaz de la Loza, María Del Carmen; Gallardo, Mercedes; García-Rubio, María Luisa; Izquierdo, Alicia; Herrero, Enrique; Aguilera, Andrés; Wellinger, Ralf Erik

2011-08-01

Genomic instability is related to a wide-range of human diseases. Here, we show that mitochondrial iron-sulfur cluster biosynthesis is important for the maintenance of nuclear genome stability in Saccharomyces cerevisiae. Cells lacking the mitochondrial chaperone Zim17 (Tim15/Hep1), a component of the iron-sulfur biosynthesis machinery, have limited respiration activity, mimic the metabolic response to iron starvation and suffer a dramatic increase in nuclear genome recombination. Increased oxidative damage or deficient DNA repair do not account for the observed genomic hyperrecombination. Impaired cell-cycle progression and genetic interactions of ZIM17 with components of the RFC-like complex involved in mitotic checkpoints indicate that replicative stress causes hyperrecombination in zim17Δ mutants. Furthermore, nuclear accumulation of pre-ribosomal particles in zim17Δ mutants reinforces the importance of iron-sulfur clusters in normal ribosome biosynthesis. We propose that compromised ribosome biosynthesis and cell-cycle progression are interconnected, together contributing to replicative stress and nuclear genome instability in zim17Δ mutants.

Surface Behavior of Iron Sulfide Ore during Grinding with Alumina Media

NASA Astrophysics Data System (ADS)

Martín, Reyes P.; Elia, Palácios B.; Patiño, Francisco C.; Escudero, Ramiro G.; Mizraim, Uriel Flores G.; Reyes, Iván A. D.; Palazuelos, Laura Angeles

This research was conducted to study the oxidation and surface modification of pyrite in an inert mill and alumina grinding media at different pH values. The extent and progress of the oxidation function of milling time, by measuring some physicochemical variables, zeta potential (ZP), infrared analysis and monitoring. The results indicate pyrite oxidation during grinding, releasing iron and sulfur ions to the solution increasing its concentration with the initial pH and the milling time, the ORP and DO decrease the grinding time, on the other hand presents negative values ZP pH of 9, 11 and 12, whereas at pH 5, 7 and 13, the ZP is positive, FTIR generally detect the presence of free sulfate ion molecule 1084 cm-1, goethite with the absorption band at about 794 cm-1, also occurs in a band assigned to 470 cm-1 lepidocrocite oxy iron hydroxide γ- FeOOH, nucleated species or formed during milling.

Iron in Multiple Sclerosis and Its Noninvasive Imaging with Quantitative Susceptibility Mapping

PubMed Central

Stüber, Carsten; Pitt, David; Wang, Yi

2016-01-01

Iron is considered to play a key role in the development and progression of Multiple Sclerosis (MS). In particular, iron that accumulates in myeloid cells after the blood-brain barrier (BBB) seals may contribute to chronic inflammation, oxidative stress and eventually neurodegeneration. Magnetic resonance imaging (MRI) is a well-established tool for the non-invasive study of MS. In recent years, an advanced MRI method, quantitative susceptibility mapping (QSM), has made it possible to study brain iron through in vivo imaging. Moreover, immunohistochemical investigations have helped defining the lesional and cellular distribution of iron in MS brain tissue. Imaging studies in MS patients and of brain tissue combined with histological studies have provided important insights into the role of iron in inflammation and neurodegeneration in MS. PMID:26784172

Iron and neurodegeneration in the multiple sclerosis brain

PubMed Central

Hametner, Simon; Wimmer, Isabella; Haider, Lukas; Pfeifenbring, Sabine; Brück, Wolfgang; Lassmann, Hans

2013-01-01

Objective Iron may contribute to the pathogenesis and progression of multiple sclerosis (MS) due to its accumulation in the human brain with age. Our study focused on nonheme iron distribution and the expression of the iron-related proteins ferritin, hephaestin, and ceruloplasmin in relation to oxidative damage in the brain tissue of 33 MS and 30 control cases. Methods We performed (1) whole-genome microarrays including 4 MS and 3 control cases to analyze the expression of iron-related genes, (2) nonheme iron histochemistry, (3) immunohistochemistry for proteins of iron metabolism, and (4) quantitative analysis by digital densitometry and cell counting in regions representing different stages of lesion maturation. Results We found an age-related increase of iron in the white matter of controls as well as in patients with short disease duration. In chronic MS, however, there was a significant decrease of iron in the normal-appearing white matter (NAWM) corresponding with disease duration, when corrected for age. This decrease of iron in oligodendrocytes and myelin was associated with an upregulation of iron-exporting ferroxidases. In active MS lesions, iron was apparently released from dying oligodendrocytes, resulting in extracellular accumulation of iron and uptake into microglia and macrophages. Iron-containing microglia showed signs of cell degeneration. At lesion edges and within centers of lesions, iron accumulated in astrocytes and axons. Interpretation Iron decreases in the NAWM of MS patients with increasing disease duration. Cellular degeneration in MS lesions leads to waves of iron liberation, which may propagate neurodegeneration together with inflammatory oxidative burst. PMID:23868451

Impact of thermal oxidation on chemical composition and magnetic properties of iron nanoparticles

NASA Astrophysics Data System (ADS)

Krajewski, Marcin; Brzozka, Katarzyna; Tokarczyk, Mateusz; Kowalski, Grzegorz; Lewinska, Sabina; Slawska-Waniewska, Anna; Lin, Wei Syuan; Lin, Hong Ming

2018-07-01

The main objective of this work is to study the influence of thermal oxidation on the chemical composition and magnetic properties of iron nanoparticles which were manufactured in a simple chemical reduction of Fe3+ ions coming from iron salt with sodium borohydride. The annealing processing was performed in an argon atmosphere containing the traces of oxygen to avoid spontaneous oxidation of iron at temperatures ranging from 200 °C to 800 °C. The chemical composition and magnetic properties of as-prepared and thermally-treated nanoparticles were determined by means of X-ray diffractometry, Raman spectroscopy, Mössbauer spectroscopy and vibrating sample magnetometry. Due to the magnetic interactions, the investigated iron nanoparticles tended to create the dense aggregates which were difficult to split even at low temperatures. This caused that there was no empty space between them, which led to their partial sintering at elevated temperatures. These features hindered their precise morphological observations using the electron microscopy techniques. The obtained results show that the annealing process up to 800 °C resulted in a progressive change in the chemical composition of as-prepared iron nanoparticles which was associated with their oxidation. As a consequence, their magnetic properties also depended on the annealing temperature. For instance, considering the values of saturation magnetization, its highest value was recorded for the as-prepared nanoparticles at 1 T and it equals 149 emu/g, while the saturation point for nanoparticles treated at 600 °C and higher temperatures was not reached even at the magnetic field of about 5 T. Moreover, a significant enhancement of coercivity was observed for the iron nanoparticles annealed over 600 °C.

Status of neurocognitive and oxidative stress conditions in iron-steel workers.

PubMed

Malekirad, Ali Akbar; Mirabdollahi, Mansuoreh; Pilehvarian, Ali Asghar; Nassajpour, Ali Reza; Abdollahi, Mohammad

2015-07-01

The aim of this study was to determine oxidative stress status as well as ferrous (Fe) and Copper (Cu) levels in blood, neurocognitive impairment, and clinical markers in iron-steel workers. A comparative cross-sectional analysis was performed in 50 iron-steel workers who have been in contact with Fe and Cu in comparison with a control group containing 50 healthy subjects in the same age group and sex. Blood levels of lipid peroxidation, total antioxidant capacity, Fe, and Cu along with neurocognitive impairment were measured in workers and controls. Clinical examination was accomplished to record any abnormal sign or symptoms. Comparing with controls, the workers showed higher blood levels of lipid peroxidation and Cu and also a lower total antioxidant capacity. There was a positive correlation between work history and interstitial lung disease that strengths the presumption to progress to chronic obstructive lung disease in future. The results indicate that exposure to a combination of Fe and Cu in iron-steel workers induces oxidative stress. Especially, in the present case, toxic effect of Cu has been more than positive effects of Fe, but the combined exposure resulted in no such critical toxicity. © The Author(s) 2013.

Recent research progress on iron- and manganese-based positive electrode materials for rechargeable sodium batteries

PubMed Central

Yabuuchi, Naoaki; Komaba, Shinichi

2014-01-01

Large-scale high-energy batteries with electrode materials made from the Earth-abundant elements are needed to achieve sustainable energy development. On the basis of material abundance, rechargeable sodium batteries with iron- and manganese-based positive electrode materials are the ideal candidates for large-scale batteries. In this review, iron- and manganese-based electrode materials, oxides, phosphates, fluorides, etc, as positive electrodes for rechargeable sodium batteries are reviewed. Iron and manganese compounds with sodium ions provide high structural flexibility. Two layered polymorphs, O3- and P2-type layered structures, show different electrode performance in Na cells related to the different phase transition and sodium migration processes on sodium extraction/insertion. Similar to layered oxides, iron/manganese phosphates and pyrophosphates also provide the different framework structures, which are used as sodium insertion host materials. Electrode performance and reaction mechanisms of the iron- and manganese-based electrode materials in Na cells are described and the similarities and differences with lithium counterparts are also discussed. Together with these results, the possibility of the high-energy battery system with electrode materials made from only Earth-abundant elements is reviewed. PMID:27877694

Recent research progress on iron- and manganese-based positive electrode materials for rechargeable sodium batteries.

PubMed

Yabuuchi, Naoaki; Komaba, Shinichi

2014-08-01

Large-scale high-energy batteries with electrode materials made from the Earth-abundant elements are needed to achieve sustainable energy development. On the basis of material abundance, rechargeable sodium batteries with iron- and manganese-based positive electrode materials are the ideal candidates for large-scale batteries. In this review, iron- and manganese-based electrode materials, oxides, phosphates, fluorides, etc, as positive electrodes for rechargeable sodium batteries are reviewed. Iron and manganese compounds with sodium ions provide high structural flexibility. Two layered polymorphs, O3- and P2-type layered structures, show different electrode performance in Na cells related to the different phase transition and sodium migration processes on sodium extraction/insertion. Similar to layered oxides, iron/manganese phosphates and pyrophosphates also provide the different framework structures, which are used as sodium insertion host materials. Electrode performance and reaction mechanisms of the iron- and manganese-based electrode materials in Na cells are described and the similarities and differences with lithium counterparts are also discussed. Together with these results, the possibility of the high-energy battery system with electrode materials made from only Earth-abundant elements is reviewed.

Iron Accumulates in Huntington’s Disease Neurons: Protection by Deferoxamine

PubMed Central

Chen, Jianfang; Lai, Barry; Zhang, Zhaojie; Duce, James A.; Lam, Linh Q.; Volitakis, Irene; Bush, Ashley I.; Hersch, Steven

2013-01-01

Huntington’s disease (HD) is a progressive neurodegenerative disorder caused by a polyglutamine-encoding CAG expansion in the huntingtin gene. Iron accumulates in the brains of HD patients and mouse disease models. However, the cellular and subcellular sites of iron accumulation, as well as significance to disease progression are not well understood. We used independent approaches to investigate the location of brain iron accumulation. In R6/2 HD mouse brain, synchotron x-ray fluorescence analysis revealed iron accumulation as discrete puncta in the perinuclear cytoplasm of striatal neurons. Further, perfusion Turnbull’s staining for ferrous iron (II) combined with transmission electron microscope ultra-structural analysis revealed increased staining in membrane bound peri-nuclear vesicles in R6/2 HD striatal neurons. Analysis of iron homeostatic proteins in R6/2 HD mice revealed decreased levels of the iron response proteins (IRPs 1 and 2) and accordingly decreased expression of iron uptake transferrin receptor (TfR) and increased levels of neuronal iron export protein ferroportin (FPN). Finally, we show that intra-ventricular delivery of the iron chelator deferoxamine results in an improvement of the motor phenotype in R6/2 HD mice. Our data supports accumulation of redox-active ferrous iron in the endocytic / lysosomal compartment in mouse HD neurons. Expression changes of IRPs, TfR and FPN are consistent with a compensatory response to an increased intra-neuronal labile iron pool leading to increased susceptibility to iron-associated oxidative stress. These findings, together with protection by deferoxamine, support a potentiating role of neuronal iron accumulation in HD. PMID:24146952

Oxidative stress and damage in liver, but not in brain, of Fischer 344 rats subjected to dietary iron supplementation with lipid-soluble [(3,5,5-trimethylhexanoyl)ferrocene].

PubMed

Lykkesfeldt, Jens; Morgan, Evan; Christen, Stephan; Skovgaard, Lene Theil; Moos, Torben

2007-01-01

Accumulation of iron probably predisposes the aging brain to progressive neuronal loss. We examined various markers of oxidative stress and damage in the brain and liver of 3- and 24-month-old rats following supplementation with the lipophilic iron derivative [(3,5,5-trimethylhexanoyl)ferrocene] (TMHF), which is capable of crossing the blood-brain barrier. At both ages, iron concentration increased markedly in the liver but failed to increase in the brain. In the liver of TMHF-treated young rats, levels of alpha- and gamma-tocopherols and glutathione (GSH) were also higher. In contrast, the brain displayed unaltered levels of the tocopherols and GSH. Malondialdehyde (MDA) level was also higher in the cerebrospinal fluid (CSF) and the liver but not in the brain. In old rats, the absence of an increase in iron concentration in the brain was reflected by unaltered concentrations of GSH, tocopherols, and MDA as compared to that in untreated rats. In the aging liver, concentrations of GSH and MDA increased with TMHF treatment. Morphological studies revealed unaltered levels of iron, ferritin, heme oxygenase-1 (HO-1), nitrotyrosine (NT), or MDA in the brains of both young and old rats treated with TMHF. In contrast, TMHF treatment increased the level of HO-1 in Kupffer cells, NT in hepatic endothelial cells, and MDA and ferritin in hepatocytes. Although these results demonstrated an increase in the biochemical markers of oxidative stress and damage in response to increasing concentrations of iron in the liver, they also demonstrated that the brain is well protected against dietary iron overload by using iron in a lipid-soluble formulation.

Disrupted iron homeostasis causes dopaminergic neurodegeneration in mice

PubMed Central

Matak, Pavle; Matak, Andrija; Moustafa, Sarah; Aryal, Dipendra K.; Benner, Eric J.; Wetsel, William; Andrews, Nancy C.

2016-01-01

Disrupted brain iron homeostasis is a common feature of neurodegenerative disease. To begin to understand how neuronal iron handling might be involved, we focused on dopaminergic neurons and asked how inactivation of transport proteins affected iron homeostasis in vivo in mice. Loss of the cellular iron exporter, ferroportin, had no apparent consequences. However, loss of transferrin receptor 1, involved in iron uptake, caused neuronal iron deficiency, age-progressive degeneration of a subset of dopaminergic neurons, and motor deficits. There was gradual depletion of dopaminergic projections in the striatum followed by death of dopaminergic neurons in the substantia nigra. Damaged mitochondria accumulated, and gene expression signatures indicated attempted axonal regeneration, a metabolic switch to glycolysis, oxidative stress, and the unfolded protein response. We demonstrate that loss of transferrin receptor 1, but not loss of ferroportin, can cause neurodegeneration in a subset of dopaminergic neurons in mice. PMID:26929359

Detox{sup SM} wet oxidation system studies for engineering scale up

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

Robertson, D.T.; Moslander, J.E.; Zigmond, J.A.

1995-12-31

Catalyzed wet oxidation utilizing iron(III) has been shown to have promise for treating many hazardous and mixed wastes. The reaction occurs at the surface of contact between an aqueous iron(III) solution and organic material. Studies with liquid- and vapor-phase organic waste surrogates have established reaction kinetics and the limits of reaction rate based on organic concentration and iron(III) diffusion. Continuing engineering studies have concentrated on reaction vessel agitator and solids feed configurations, an improved bench scale reflux condenser and reflux condenser calculations, sparging of organic compounds from the process condensate water, filtration of solids from the process solution, and flammabilitymore » limits for volatile organic compounds in the headspace of the reaction vessel under the reaction conditions. Detailed engineering design and fabrication of a demonstration unit for treatment of mixed waste is in progress.« less

Is the iron regulatory hormone hepcidin a risk factor for alcoholic liver disease?

PubMed Central

Harrison-Findik, Duygu Dee

2009-01-01

Despite heavy consumption over a long period of time, only a small number of alcoholics develop alcoholic liver disease. This alludes to the possibility that other factors, besides alcohol, may be involved in the progression of the disease. Over the years, many such factors have indeed been identified, including iron. Despite being crucial for various important biological processes, iron can also be harmful due to its ability to catalyze Fenton chemistry. Alcohol and iron have been shown to interact synergistically to cause liver injury. Iron-mediated cell signaling has been reported to be involved in the pathogenesis of experimental alcoholic liver disease. Hepcidin is an iron-regulatory hormone synthesized by the liver, which plays a pivotal role in iron homeostasis. Both acute and chronic alcohol exposure suppress hepcidin expression in the liver. The sera of patients with alcoholic liver disease, particularly those exhibiting higher serum iron indices, have also been reported to display reduced prohepcidin levels. Alcohol-mediated oxidative stress is involved in the inhibition of hepcidin promoter activity and transcription in the liver. This in turn leads to an increase in intestinal iron transport and liver iron storage. Hepcidin is expressed primarily in hepatocytes. It is noteworthy that both hepatocytes and Kupffer cells are involved in the progression of alcoholic liver disease. However, the activation of Kupffer cells and TNF-α signaling has been reported not to be involved in the down-regulation of hepcidin expression by alcohol in the liver. Alcohol acts within the parenchymal cells of the liver to suppress the synthesis of hepcidin. Due to its crucial role in the regulation of body iron stores, hepcidin may act as a secondary risk factor in the progression of alcoholic liver disease. The clarification of the mechanisms by which alcohol disrupts iron homeostasis will allow for further understanding of the pathogenesis of alcoholic liver disease. PMID:19291818

Abnormal iron metabolism and oxidative stress in mice expressing a mutant form of the ferritin light polypeptide gene

PubMed Central

Barbeito, Ana G.; Garringer, Holly J.; Baraibar, Martin A.; Gao, Xiaoying; Arredondo, Miguel; Núñez, Marco T.; Smith, Mark A.; Ghetti, Bernardino; Vidal, Ruben

2009-01-01

Insertional mutations in exon 4 of the ferritin light chain (FTL) gene are associated with hereditary ferritinopathy (HF) or neuroferritinopathy, an autosomal dominant neurodegenerative disease characterized by progressive impairment of motor and cognitive functions. To determine the pathogenic mechanisms by which mutations in FTL lead to neurodegeneration, we investigated iron metabolism and markers of oxidative stress in the brain of transgenic (Tg) mice that express the mutant human FTL498-499InsTC cDNA. Compared with wild-type mice, brain extracts from Tg (FTL-Tg) mice showed an increase in the cytoplasmic levels of both FTL and ferritin heavy chain polypeptides, a decrease in the protein and mRNA levels of transferrin receptor-1, and a significant increase in iron levels. Transgenic mice also showed the presence of markers for lipid peroxidation, protein carbonyls, and nitrone–protein adducts in the brain. However, gene expression analysis of iron management proteins in the liver of Tg mice indicates that the FTL-Tg mouse liver is iron deficient. Our data suggest that disruption of iron metabolism in the brain has a primary role in the process of neurodegeneration in HF and that the pathogenesis of HF is likely to result from a combination of reduction in iron storage function and enhanced toxicity associated with iron-induced ferritin aggregates in the brain. PMID:19519778

Iron-Induced Damage in Cardiomyopathy: Oxidative-Dependent and Independent Mechanisms

PubMed Central

Gammella, Elena; Recalcati, Stefania; Rybinska, Ilona; Buratti, Paolo; Cairo, Gaetano

2015-01-01

The high incidence of cardiomyopathy in patients with hemosiderosis, particularly in transfusional iron overload, strongly indicates that iron accumulation in the heart plays a major role in the process leading to heart failure. In this context, iron-mediated generation of noxious reactive oxygen species is believed to be the most important pathogenetic mechanism determining cardiomyocyte damage, the initiating event of a pathologic progression involving apoptosis, fibrosis, and ultimately cardiac dysfunction. However, recent findings suggest that additional mechanisms involving subcellular organelles and inflammatory mediators are important factors in the development of this disease. Moreover, excess iron can amplify the cardiotoxic effect of other agents or events. Finally, subcellular misdistribution of iron within cardiomyocytes may represent an additional pathway leading to cardiac injury. Recent advances in imaging techniques and chelators development remarkably improved cardiac iron overload detection and treatment, respectively. However, increased understanding of the pathogenic mechanisms of iron overload cardiomyopathy is needed to pave the way for the development of improved therapeutic strategies. PMID:25878762

The yeast metacaspase is implicated in oxidative stress response in frataxin-deficient cells.

PubMed

Lefevre, Sophie; Sliwa, Dominika; Auchère, Françoise; Brossas, Caroline; Ruckenstuhl, Christoph; Boggetto, Nicole; Lesuisse, Emmanuel; Madeo, Frank; Camadro, Jean-Michel; Santos, Renata

2012-01-20

Friedreich ataxia is the most common recessive neurodegenerative disease and is caused by reduced expression of mitochondrial frataxin. Frataxin depletion causes impairment in iron-sulfur cluster and heme biosynthesis, disruption of iron homeostasis and hypersensitivity to oxidants. Currently no pharmacological treatment blocks disease progression, although antioxidant therapies proved to benefit patients. We show that sensitivity of yeast frataxin-deficient cells to hydrogen peroxide is partially mediated by the metacaspase. Metacaspase deletion in frataxin-deficient cells results in recovery of antioxidant capacity and heme synthesis. In addition, our results suggest that metacaspase is associated with mitochondrial respiration, intracellular redox control and genomic stability. Copyright © 2011 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

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

Brown, Kyle E.; Division of Gastroenterology-Hepatology, University of Iowa Roy J. and Lucille A. Carver College of Medicine; Program in Free Radical and Radiation Biology, University of Iowa Roy J. and Lucille A. Carver College of Medicine, Iowa City, IA

Introduction:: Oxidative stress can trigger a cellular stress response characterized by induction of antioxidants, acute phase reactants (APRs) and heat shock proteins (HSPs), which are presumed to play a role in limiting tissue damage. In rodents, hepatic iron overload causes oxidative stress that results in upregulation of antioxidant defenses with minimal progressive liver injury. The aim of this study was to determine whether iron overload modulates expression of other stress-responsive proteins such as APRs and HSPs that may confer protection against iron-induced damage in rodent liver. Methods:: Male rats received repeated injections of iron dextran or dextran alone over amore » 6-month period. Hepatic transcript levels for a panel of APRs and HSPs were quantitated by real-time PCR and protein expression was evaluated by Western blot and immunohistochemistry. Results:: Hepatic iron concentrations were increased > 50-fold in the iron-loaded rats compared to controls. Iron loading resulted in striking increases in mRNAs for Hsp32 (heme oxygenase-1; 12-fold increase vs. controls) and metallothionein-1 and -2 (both increased {approx} 6-fold). Transcripts for {alpha}1-acid glycoprotein, the major rat APR, were increased {approx} 3-fold, while expression of other classical APRs was unaltered. Surprisingly, although mRNA levels for the HSPs were not altered by iron, the abundance of Hsp25, Hsp70 and Hsp90 proteins was uniformly reduced in the iron-loaded livers, as were levels of NAD(P)H:quinone oxidoreductase 1, an Hsp70 client protein. Conclusions:: Chronic iron administration elicits a unique pattern of stress protein expression. These alterations may modulate hepatic responses to iron overload, as well as other injury processes.« less

Method for preparing hydrous iron oxide gels and spherules

DOEpatents

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

2003-07-29

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

Epoetin beta pegol alleviates oxidative stress and exacerbation of renal damage from iron deposition, thereby delaying CKD progression in progressive glomerulonephritis rats.

PubMed

Hirata, Michinori; Tashiro, Yoshihito; Aizawa, Ken; Kawasaki, Ryohei; Shimonaka, Yasushi; Endo, Koichi

2015-12-01

The increased deposition of iron in the kidneys that occurs with glomerulopathy hinders the functional and structural recovery of the tubules and promotes progression of chronic kidney disease (CKD). Here, we evaluated whether epoetin beta pegol (continuous erythropoietin receptor activator: CERA), which has a long half-life in blood and strongly suppresses hepcidin-25, exerts renoprotection in a rat model of chronic progressive glomerulonephritis (cGN). cGN rats showed elevated urinary total protein excretion (uTP) and plasma urea nitrogen (UN) from day 14 after the induction of kidney disease (day 0) and finally declined into end-stage kidney disease (ESKD), showing reduced creatinine clearance with glomerulosclerosis, tubular dilation, and tubulointerstitial fibrosis. A single dose of CERA given on day 1, but not on day 16, alleviated increasing uTP and UN, thereby delaying ESKD. In the initial disease phase, CERA significantly suppressed urinary 8-OHdG and liver-type fatty acid-binding protein (L-FABP), a tubular damage marker. CERA also inhibited elevated plasma hepcidin-25 levels and alleviated subsequent iron accumulation in kidneys in association with elevated urinary iron excretion and resulted in alleviation of growth of Ki67-positive tubular and glomerular cells. In addition, at day 28 when the exacerbation of uTP occurs, a significant correlation was observed between iron deposition in the kidney and urinary L-FABP. In our study, CERA mitigated increasing kidney damage, thereby delaying CKD progression in this glomerulonephritis rat model. Alleviation by CERA of the exacerbation of kidney damage could be attributable to mitigation of tubular damage that might occur with lowered iron deposition in tubules. © 2015 Chugai Pharmaceutical Co., Ltd. Physiological Reports published by Wiley Periodicals, Inc. on behalf of the American Physiological Society and The Physiological Society.

ENVIRONMENTAL CONDITIONS, MICROBIAL POPULATIONS, AND THE ROLE OF ATTACHMENT IN OXIDATIVE DISSOLUTION OF PYRITE AT IRON MT. (R826189)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Inhibition of bacterial oxidation of ferrous iron by lead nitrate in sulfate-rich systems

USGS Publications Warehouse

Wang, Hongmei; Gong, Linfeng; Cravotta,, Charles A.; Yang, Xiaofen; Tuovinen, Olli H.; Dong, Hailiang; Fu, Xiang

2013-01-01

Inhibition of bacterial oxidation of ferrous iron (Fe(II)) by Pb(NO3)2 was investigated with a mixed culture of Acidithiobacillus ferrooxidans. The culture was incubated at 30 °C in ferrous-sulfate medium amended with 0–24.2 mM Pb(II) added as Pb(NO3)2. Anglesite (PbSO4) precipitated immediately upon Pb addition and was the only solid phase detected in the abiotic controls. Both anglesite and jarosite (KFe3(SO4)2(OH)6) were detected in inoculated cultures. Precipitation of anglesite maintained dissolved Pb concentrations at 16.9–17.6 μM regardless of the concentrations of Pb(NO3)2 added. Fe(II) oxidation was suppressed by 24.2 mM Pb(NO3)2 addition even when anglesite was removed before inoculation. Experiments with 0–48 mM KNO3 demonstrated that bacterial Fe(II) oxidation decreased as nitrate concentration increased. Therefore, inhibition of Fe(II) oxidation at 24.2 mM Pb(NO3)2 addition resulted from nitrate toxicity instead of Pb addition. Geochemical modeling that considered the initial precipitation of anglesite to equilibrium followed by progressive oxidation of Fe(II) and the precipitation of jarosite and an amorphous iron hydroxide phase, without allowing plumbojarosite to precipitate were consistent with the experimental time-series data on Fe(II) oxidation under biotic conditions. Anglesite precipitation in mine tailings and other sulfate-rich systems maintains dissolved Pb concentrations below the toxicity threshold of A. ferrooxidans.

GADOLINIUM(Gd)-BASED and Ion Oxide Nanoparticle Contrast Agents for Pre-Clinical and Clinical Magnetic Resonance Imaging (mri) Research

NASA Astrophysics Data System (ADS)

Ng, Thian C.

2012-06-01

It is known that one strength of MRI is its excellent soft tissue discrimination. It naturally provides sufficient contrast between the structural differences of normal and pathological tissues, their spatial extent and progression. However, to further extend its applications and enhance even more contrast for clinical studies, various Gadolinium (Gd)-based contrast agents have been developed for different organs (brain strokes, cancer, cardio-MRI, etc). These Gd-based contrast agents are paramagnetic compounds that have strong T1-effect for enhancing the contrast between tissue types. Gd-contrast can also enhance magnetic resonance angiography (CE-MRA) for studying stenosis and for measuring perfusion, vascular susceptibility, interstitial space, etc. Another class of contrast agents makes use of ferrite iron oxide nanoparticles (including Superparamagnetic Ion Oxide (SPIO) and Ultrasmall Superparamagnetic Iron Oxide (USPIO)). These nanoparticles have superior magnetic susceptibility effect and produce a drop in signal, namely in T2*-weighted images, useful for the determination of lymph nodes metastases, angiogenesis and arteriosclerosis plaques.

Optimizing therapy for iron overload in the myelodysplastic syndromes: recent developments.

PubMed

Leitch, Heather A

2011-01-22

The myelodysplastic syndromes (MDS) are characterized by cytopenias and risk of progression to acute myeloid leukaemia (AML). Most MDS patients eventually require transfusion of red blood cells for anaemia, placing them at risk of transfusional iron overload. In β-thalassaemia major, transfusional iron overload leads to organ dysfunction and death; however, with iron chelation therapy, organ function is improved, and survival improved to near normal and correlated with the degree of compliance with chelation. In lower-risk MDS, several nonrandomized studies suggest an adverse effect of iron overload on survival and that lowering iron with chelation may minimize this impact. Emerging data indicate that chelation may improve organ function, particularly hepatic function, and a minority of patients may have improvement in cell counts and decreased transfusion requirements. While guidelines for MDS generally recommend chelation in selected lower-risk patients, data from nonrandomized trials suggest iron overload may impact adversely on the outcome of higher-risk MDS and stem cell transplantation (SCT). This effect may be due to increased transplant-related mortality, infection and AML progression, and preliminary data suggest that lowering iron may be beneficial in this patient group. Other areas of active and future investigation include optimizing the monitoring of iron overload using imaging such as T2* MRI and measures of labile iron and oxidative stress; correlating new methods of measuring iron to clinical outcomes; clarifying the contribution of different cellular and extracellular iron pools to iron toxicity; optimizing chelation by using agents that access the appropriate iron pools to minimize the relevant clinical consequences in individual patients; and incorporating measures of quality of life and co-morbidities into clinical trials of chelation in MDS. It should be noted that chelation is costly and potentially toxic, and in MDS should be initiated after weighing potential risks and benefits for each patient until more definitive data are available. In this review, data on the impact of iron overload in MDS and SCT are discussed; for example, several noncontrolled studies show inferior survival in patients with iron overload in these clinical settings, including an increase in transplant-related mortality and infection risk. Possible mechanisms of iron toxicity include oxidative stress, which can damage cellular components, and the documented impact of lowering iron on organ function with measures such as iron chelation therapy includes an improvement in elevated liver transaminases. Lowering iron also appears to improve survival in both lower-risk MDS and SCT in nonrandomized studies. Selected aspects of iron metabolism, transport, storage and distribution that may be amenable to future intervention and improved removal of iron from important cellular sites are discussed, as are attempts to quantify quality of life and the importance of co-morbidities in measures to treat MDS, including chelation therapy.

Tubular iron deposition and iron handling proteins in human healthy kidney and chronic kidney disease.

PubMed

Raaij, Sanne van; Swelm, Rachel van; Bouman, Karlijn; Cliteur, Maaike; Heuvel, Marius van den; Pertijs, Jeanne; Patel, Dominic; Bass, Paul; Goor, Harry van; Unwin, Robert; Srai, Surjit Kaila; Swinkels, Dorine

2018-06-19

Iron is suggested to play a detrimental role in the progression of chronic kidney disease (CKD). The kidney recycles iron back into the circulation. However, the localization of proteins relevant for physiological tubular iron handling and their potential role in CKD remain unclear. We examined associations between iron deposition, expression of iron handling proteins and tubular injury in kidney biopsies from CKD patients and healthy controls using immunohistochemistry. Iron was deposited in proximal (PT) and distal tubules (DT) in 33% of CKD biopsies, predominantly in pathologies with glomerular dysfunction, but absent in controls. In healthy kidney, PT contained proteins required for iron recycling including putative iron importers ZIP8, ZIP14, DMT1, iron storage proteins L- and H-ferritin and iron exporter ferroportin, while DT only contained ZIP8, ZIP14, and DMT1. In CKD, iron deposition associated with increased intensity of iron importers (ZIP14, ZIP8), storage proteins (L-, H-ferritin), and/or decreased ferroportin abundance. This demonstrates that tubular iron accumulation may result from increased iron uptake and/or inadequate iron export. Iron deposition associated with oxidative injury as indicated by heme oxygenase-1 abundance. In conclusion, iron deposition is relatively common in CKD, and may result from altered molecular iron handling and may contribute to renal injury.

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

PubMed

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

2016-11-01

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

Oxidative Damage in Parkinson’s Disease

DTIC Science & Technology

2005-01-01

inhibitors of MMPs, TIMP-1 and TIMP-2 in postmortem brain tissue of progressive supranuclear palsy . J Neurol Sci 2004; 218:39-45. Martinat C, Shendelman S...inhibitors of MMPs, TIMP-1 and TIMP-2 in postmortem brain tissue of progressive supranuclear palsy . J Neurol Sci 2004; 218:39-45. Martinat C...excess can have serious neurologi- effects at the higher dosages needed to overcome the In Viva Iron Chelation Prevents MPTP Toxicity 905 A 0 20 in

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

PubMed

Lapenna, Domenico; Ciofani, Giuliano; Obletter, Gabriele

2017-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Selective Inhibition of the Oxidation of Ferrous Iron or Sulfur in Thiobacillus ferrooxidans

PubMed Central

Harahuc, Lesia; Lizama, Hector M.; Suzuki, Isamu

2000-01-01

The oxidation of either ferrous iron or sulfur by Thiobacillus ferrooxidans was selectively inhibited or controlled by various anions, inhibitors, and osmotic pressure. Iron oxidation was more sensitive than sulfur oxidation to inhibition by chloride, phosphate, and nitrate at low concentrations (below 0.1 M) and also to inhibition by azide and cyanide. Sulfur oxidation was more sensitive than iron oxidation to the inhibitory effect of high osmotic pressure. These differences were evident not only between iron oxidation by iron-grown cells and sulfur oxidation by sulfur-grown cells but also between the iron and sulfur oxidation activities of the same iron-grown cells. Growth experiments with ferrous iron or sulfur as an oxidizable substrate confirmed the higher sensitivity of iron oxidation to inhibition by phosphate, chloride, azide, and cyanide. Sulfur oxidation was actually stimulated by 50 mM phosphate or chloride. Leaching of Fe and Zn from pyrite (FeS2) and sphalerite (ZnS) by T. ferrooxidans was differentially affected by phosphate and chloride, which inhibited the solubilization of Fe without significantly affecting the solubilization of Zn. PMID:10698768

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

PubMed

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

2015-01-06

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

Molecular Beam Epitaxial Growth of Iron Nitrides on Zinc-Blende Gallium Nitride(001)

NASA Astrophysics Data System (ADS)

Pak, Jeongihm; Lin, Wenzhi; Chinchore, Abhijit; Wang, Kangkang; Smith, Arthur R.

2008-03-01

Iron nitrides are attractive materials for their high magnetic moments, corrosion, and oxidation resistance. We present the successful epitaxial growth of iron nitride on zinc-blende gallium nitride (c-GaN) in order to develop a novel magnetic transition metal nitride/semiconductor system. First, GaN is grown on magnesium oxide (MgO) substrates having (001) orientation using rf N2-plasma molecular beam epitaxy. Then we grow FeN at substrate temperature of ˜ 210 ^oC up to a thickness of ˜ 10.5 nm. In-situ reflection high-energy electron diffraction (RHEED) is used to monitor the surface during growth. Initial results suggest that the epitaxial relationship is FeN[001] || GaN[001] and FeN[100] || GaN[100]. Work in progress is to investigate the surface using in-situ scanning tunneling microscopy (STM) to reveal the surface structure at atomic scale, as well as to explore more Fe-rich magnetic phases.

The role of oxidative stress in the metabolic syndrome.

PubMed

Whaley-Connell, Adam; McCullough, Peter A; Sowers, James R

2011-01-01

Loss of reduction-oxidation (redox) homeostasis and generation of excess free oxygen radicals play an important role in the pathogenesis of diabetes, hypertension, and consequent cardiovascular disease. Reactive oxygen species are integral in routine in physiologic mechanisms. However, loss of redox homeostasis contributes to proinflammatory and profibrotic pathways that promote impairments in insulin metabolic signaling, reduced endothelial-mediated vasorelaxation, and associated cardiovascular and renal structural and functional abnormalities. Redox control of metabolic function is a dynamic process with reversible pro- and anti-free radical processes. Labile iron is necessary for the catalysis of superoxide anion, hydrogen peroxide, and the generation of the damaging hydroxyl radical. Acute hypoxia and cellular damage in cardiovascular tissue liberate larger amounts of cytosolic and extracellular iron that is poorly liganded; thus, large increases in the generation of oxygen free radicals are possible, causing tissue damage. The understanding of iron and the imbalance of redox homeostasis within the vasculature is integral in hypertension and progression of metabolic dysregulation that contributes to insulin resistance, endothelial dysfunction, and cardiovascular and kidney disease.

Synthesis of nanostructured iron oxides dispersed in carbon materials and in situ XRD study of the changes caused by thermal treatment

NASA Astrophysics Data System (ADS)

Gonçalves, Gustavo R.; Schettino, Miguel A.; Morigaki, Milton K.; Nunes, Evaristo; Cunha, Alfredo G.; Emmerich, Francisco G.; Passamani, Edson C.; Baggio-Saitovitch, Elisa; Freitas, Jair C. C.

2015-07-01

Carbon-based magnetic nanocomposites are of large interest for applications in catalysis, magnetic separation, water cleaning, and magnetic resonance imaging, among others. This work describes the synthesis of nanocomposites consisting of iron oxides dispersed into a char (obtained from the carbonization at 700 °C of a lignocellulosic precursor) and the study of the thermal transformations occurring in these materials as a consequence of heat treatments. The materials were prepared by impregnation of the char with iron nitrate in the presence of ammonium hydroxide in aqueous suspension. X-ray diffraction experiments performed using synchrotron radiation and Mössbauer spectroscopy showed that the as-prepared material was composed of amorphous Fe3+ oxides. Scanning electron microscopy images combined with energy-dispersive X-ray spectrometry indicated a homogeneous dispersion of iron oxides and of silica particles (naturally present in the lignocellulosic precursor) throughout the char. X-ray diffractograms recorded in situ during the heat treatment of the as-prepared material showed the presence of small hematite crystallites (average size 22 nm) starting from ca. 300 °C. Further heating caused a progressive growth of the hematite crystallites up to ca. 500 °C, when the conversion to magnetite (Fe3O4) started to take place. At higher temperatures, wüstite (Fe1-xO) was detected as an intermediate phase and austenitic iron (γ-Fe) became the dominant phase at temperatures from 900 °C. A steep weight loss was observed in the TG curve accompanying this last reduction stage; upon cooling, γ-Fe was converted into α-Fe (ferrite), which was the dominant phase at room temperature in this heat-treated sample.

COPPER, CHROMIUM, AND ARSENIC ADSORPTION AND EQUILIBRIUM MODELING IN AN IRON-OXIDE-COATED SAND, BACKGROUND ELECTROLYTE SYSTEM. (R825689C024)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Recent progress on magnetic iron oxide nanoparticles: synthesis, surface functional strategies and biomedical applications

PubMed Central

Wu, Wei; Wu, Zhaohui; Yu, Taekyung; Jiang, Changzhong; Kim, Woo-Sik

2015-01-01

This review focuses on the recent development and various strategies in the preparation, microstructure, and magnetic properties of bare and surface functionalized iron oxide nanoparticles (IONPs); their corresponding biological application was also discussed. In order to implement the practical in vivo or in vitro applications, the IONPs must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of IONPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The new functionalized strategies, problems and major challenges, along with the current directions for the synthesis, surface functionalization and bioapplication of IONPs, are considered. Finally, some future trends and the prospects in these research areas are also discussed. PMID:27877761

Engineering design and test plan for demonstrating DETOX treatment of mixed wastes

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

Goldblatt, S.; Dhooge, P.

1995-03-01

DETOX is a cocatalyzed wet oxidation process in which the catalysts are a relatively great concentration of iron ions (typically as iron(III) chloride) in the presence of small amounts of platinum and ruthenium ions. Organic compounds are oxidized completely to carbon dioxide, water, and (if chlorinated) hydrogen chloride. The process has shown promise as a non-thermal alternative to incineration for treatment and/or volume reduction of hazardous, radioactive, and mixed wastes. Design and fabrication of a demonstration unit capable of destroying 25. Kg/hr of organic material is now in progress. This paper describes the Title 2 design of the demonstration unit,more » and the planned demonstration effort at Savannah River Site (SRS) and Weldon Spring Site Remedial Action Project (WSSRAP).« less

The formation of magnetite in the early Archean oceans

NASA Astrophysics Data System (ADS)

Li, Yi-Liang; Konhauser, Kurt O.; Zhai, Mingguo

2017-05-01

Banded iron formations (BIFs) are iron- and silica-rich chemical sedimentary rocks that were deposited throughout much of the Precambrian. The biological oxidation of dissolved Fe(II) led to the precipitation of a ferric oxyhydroxide phase, such as ferrihydrite, in the marine photic zone. Upon burial, ferrihydrite was either transformed into hematite through dehydration or it was reduced to magnetite via biological or abiological Fe(III) reduction coupled to the oxidation of buried microbial biomass. However, it has always been intriguing as to why the oldest BIFs are characteristically magnetite-rich, while BIFs formed after the Neoarchean are dominated by hematite. Here, we propose that some magnetite in early Archean BIF could have precipitated directly from seawater through the reaction of settling ferrihydrite and hot, Fe(II)-rich hydrothermal fluids that existed in the deeper waters. We conducted experiments that showed the reaction of Fe(II) with biogenic ferric iron mats under strict anoxic conditions lead to the formation of a metastable green rust phase that within hours transformed into magnetite. Our model further posits that with the progressive cooling and oxidation of the Earth's oceans, the above reaction shuts off, and magnetite was subsequently restricted to reactions associated with diagenesis and metamorphism.

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

PubMed

Sayed, Farheen N; Polshettiwar, Vivek

2015-05-05

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

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

PubMed Central

Sayed, Farheen N.; Polshettiwar, Vivek

2015-01-01

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

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

PubMed

Pease, Camilla; Rücker, Thomas; Birk, Thomas

2016-03-21

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

Inhibition of bacterial oxidation of ferrous iron by lead nitrate in sulfate-rich systems.

PubMed

Wang, Hongmei; Gong, Linfeng; Cravotta, Charles A; Yang, Xiaofen; Tuovinen, Olli H; Dong, Hailiang; Fu, Xiang

2013-01-15

Inhibition of bacterial oxidation of ferrous iron (Fe(II)) by Pb(NO(3))(2) was investigated with a mixed culture of Acidithiobacillus ferrooxidans. The culture was incubated at 30 °C in ferrous-sulfate medium amended with 0-24.2 mM Pb(II) added as Pb(NO(3))(2). Anglesite (PbSO(4)) precipitated immediately upon Pb addition and was the only solid phase detected in the abiotic controls. Both anglesite and jarosite (KFe(3)(SO(4))(2)(OH)(6)) were detected in inoculated cultures. Precipitation of anglesite maintained dissolved Pb concentrations at 16.9-17.6 μM regardless of the concentrations of Pb(NO(3))(2) added. Fe(II) oxidation was suppressed by 24.2 mM Pb(NO(3))(2) addition even when anglesite was removed before inoculation. Experiments with 0-48 mM KNO(3) demonstrated that bacterial Fe(II) oxidation decreased as nitrate concentration increased. Therefore, inhibition of Fe(II) oxidation at 24.2 mM Pb(NO(3))(2) addition resulted from nitrate toxicity instead of Pb addition. Geochemical modeling that considered the initial precipitation of anglesite to equilibrium followed by progressive oxidation of Fe(II) and the precipitation of jarosite and an amorphous iron hydroxide phase, without allowing plumbojarosite to precipitate were consistent with the experimental time-series data on Fe(II) oxidation under biotic conditions. Anglesite precipitation in mine tailings and other sulfate-rich systems maintains dissolved Pb concentrations below the toxicity threshold of A. ferrooxidans. Copyright © 2012 Elsevier B.V. All rights reserved.

Toxicokinetics and biodistribution of dextran stabilized iron oxide nanoparticles in rats

NASA Astrophysics Data System (ADS)

Easo, S. L.; Neelima, R.; Mohanan, P. V.

2015-07-01

Dextran stabilized iron oxide nanoparticles (DIONPs) synthesized and characterized for hyperthermia application were tested for toxicokinetics and biodistribution in order to analyze the prospect of safety and biocompatibility of these particles for advanced use. Rats were administered a single dose of DIONPs at a concentration of 10 mg kg-1 by intravenous injection with a post-exposure period of 1, 7, 14 and 28 days. Liver, spleen, kidney, blood, urine and feces were examined for iron content by inductively coupled plasma atomic emission spectroscopy. At 24 h, greater amounts of nanoparticles were deposited in liver and spleen. Maximum absorption of iron in blood occurred at day 7 and excess iron appeared to be eliminated by liver, seemingly via biliary excretion. Serum hematology and biochemistry analysis revealed an overall lack of systemic toxicity due to metabolism of DIONPs. Additionally, pathological changes associated with repeated exposure to DIONPs with a post exposure period of 28 days were also assessed. Although no significant pathological alterations were seen in spleen or kidney, slight morphological deviations from normal were observed in liver. Further progression in the analysis of biological response towards DIONPs will be determined in long-term studies in the presence of an alternating magnetic field in the context of hyperthermia application.

[Recent research progress on the biomining bacteria of Acidithiobacillus caldus--a review].

PubMed

Pang, Xin; Chen, Dandan; Lin, Jianqun; Liu, Xiangmei; Lin, Jianqiang; Yan, Wangming

2009-11-01

Acidithiobacillus caldus (A. caldus) is one of the predominant biomining bacteria, which shows application prospect in biological metallurgy. It can enhance the biomining efficiency together with iron oxidation bacteria in mixed biomining system. Based on the published papers and our study on this bacterium, we described the research progress on it from four aspects, including the biomining mechanism, arsenic-resistant mechanism, genome study and genetic reconstruction. Furthermore, we discussed the prospects of research on A. caldus.

Experimental oral iron administration: Histological investigations and expressions of iron handling proteins in rat retina with aging.

PubMed

Kumar, Pankaj; Nag, Tapas Chandra; Jha, Kumar Abhiram; Dey, Sanjay Kumar; Kathpalia, Poorti; Maurya, Meenakshi; Gupta, Chandan Lal; Bhatia, Jagriti; Roy, Tara Sankar; Wadhwa, Shashi

2017-12-01

Iron is implicated in age-related macular degeneration (AMD). The aim of this study was to see if long-term, experimental iron administration with aging modifies retinal and choroidal structures and expressions of iron handling proteins, to understand some aspects of iron homeostasis. Male Wistar rats were fed with ferrous sulphate heptahydrate (500mg/kg body weight/week, oral; elemental iron availability: 20%) from 2 months of age onward until they were 19.5 month-old. At 8, 14 and 20 months of age, they were sacrificed and serum and retinal iron levels were detected by HPLC. Oxidative stress was analyzed by TBARS method. The retinas were examined for cell death (TUNEL), histology (electron microscopy) and the expressions of transferrin, transferrin receptor-1 [TFR-1], H- and L-ferritin. In control animals, at any age, there was no difference in the serum and retinal iron levels, but the latter increased significantly in 14- and 20 month-old iron-fed rats, indicating that retinal iron accumulation proceeds with progression of aging (>14 months). The serum and retinal TBARS levels increased significantly with progression of aging in experimental but not in control rats. There was significant damage to choriocapillaris, accumulation of phagosomes in retinal pigment epithelium and increased incidence of TUNEL+ cells in outer nuclear layer and vacuolation in inner nuclear layer (INL) of 20 month-aged experimental rats, compared to those in age-matched controls. Vacuolations in INL could indicate a long-term effect of iron accumulation in the inner retina. These events paralleled the increased expression of ferritins and transferrin and a decrease in the expression of TFR-1 in iron-fed rats with aging, thereby maintaining iron homeostasis in the retina. As some of these changes mimic with those happening in eyes with AMD, this model can be utilized to understand iron-induced pathophysiological changes in AMD. Copyright © 2017 Elsevier B.V. All rights reserved.

Catalytic iron oxide for lime regeneration in carbonaceous fuel combustion

DOEpatents

Shen, Ming-Shing; Yang, Ralph T.

1980-01-01

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

Iron metabolism: current facts and future directions

PubMed Central

Tandara, Leida; Salamunic, Ilza

2012-01-01

Iron metabolism has been intensively examined over the last decade and there are many new players in this field which are worth to be introduced. Since its discovery many studies confirmed role of liver hormone hepcidin as key regulator of iron metabolism and pointed out liver as the central organ of system iron homeostasis. Liver cells receive multiple signals related to iron balance and respond by transcriptional regulation of hepcidin expression. This liver hormone is negative regulator of iron metabolism that represses iron efflux from macrophages, hepatocytes and enterocytes by its binding to iron export protein ferroportin. Ferroportin degradation leads to cellular iron retention and decreased iron availability. At level of a cell IRE/IRP (iron responsive elements/iron responsive proteins) system allows tight regulation of iron assimilation that prevents an excess of free intracellular iron which could lead to oxidative stress and damage of DNA, proteins and lipid membranes by ROS (reactive oxygen species). At the same time IRE/IRP system provides sufficient iron in order to meet the metabolic needs. Recently a significant progress in understanding of iron metabolism has been made and new molecular participants have been characterized. Article gives an overview of the current understanding of iron metabolism: absorption, distribution, cellular uptake, release, and storage. We also discuss mechanisms underlying systemic and cellular iron regulation with emphasis on central regulatory hormone hepcidin. PMID:23092063

The role of halide ions on the electrochemical behaviour of iron in alkali solutions

NASA Astrophysics Data System (ADS)

Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

2008-02-01

Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

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

PubMed

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

2012-01-01

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

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

PubMed Central

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

2012-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Tropical forest soil microbial communities couple iron and carbon biogeochemistry

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

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

2009-10-15

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

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

NASA Astrophysics Data System (ADS)

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

2005-12-01

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

Imaging of oxidation-specific epitopes with targeted nanoparticles to detect high-risk atherosclerotic lesions: Progress and future directions

PubMed Central

Briley-Saebo, Karen; Yeang, Calvin; Witztum, Joseph L.; Tsimikas, Sotirios

2014-01-01

Oxidation-specific epitopes (OSE) within developing atherosclerotic lesions are key antigens that drive innate and adaptive immune responses in atherosclerosis, leading to chronic inflammation. Oxidized phospholipids and malondialdehyde-lysine epitopes are well-characterized OSE present in human atherosclerotic lesions, particularly in pathologically defined vulnerable plaques. Using murine and human OSE-specific antibodies as targeting agents, we have developed radionuclide and magnetic resonance based nanoparticles, containing gadolinium, manganese or lipid-coated ultrasmall superparamagnetic iron oxide, to noninvasively image OSE within experimental atherosclerotic lesions. These methods quantitate plaque burden, allow detection of lesion progression and regression, plaque stabilization, and accumulation of OSE within macrophage-rich areas of the artery wall, suggesting they detect the most active lesions. Future studies will focus on using “natural” antibodies, lipopeptides and mimotopes for imaging applications. These approaches should enhance the clinical translation of this technique to image, monitor, evaluate efficacy of novel therapeutic agents and guide optimal therapy of high-risk atherosclerotic lesions. PMID:25297940

Upregulation of transferrin receptor-1 induces cholangiocarcinoma progression via induction of labile iron pool.

PubMed

Jamnongkan, Wassana; Thanan, Raynoo; Techasen, Anchalee; Namwat, Nisana; Loilome, Watcharin; Intarawichian, Piyapharom; Titapun, Attapol; Yongvanit, Puangrat

2017-07-01

Labile iron pool is a cellular source of ions available for Fenton reactions resulting in oxidative stress. Living organisms avoid an excess of free irons by a tight control of iron homeostasis. We investigated the altered expression of iron regulatory proteins and iron discrimination in the development of liver fluke-associated cholangiocarcinoma. Additionally, the levels of labile iron pool and the functions of transferrin receptor-1 on cholangiocarcinoma development were also identified. Iron deposition was determined using the Prussian blue staining method in human cholangiocarcinoma tissues. We investigated the alteration of iron regulatory proteins including transferrin, transferrin receptor-1, ferritin, ferroportin, hepcidin, and divalent metal transporter-1 in cholangiocarcinoma tissues using immunohistochemistry. The clinicopathological data of cholangiocarcinoma patients and the expressions of proteins were analyzed. Moreover, the level of intracellular labile iron pool in cholangiocarcinoma cell lines was identified by the RhoNox-1 staining method. We further demonstrated transferrin receptor-1 functions on cell proliferation and migration upon small interfering RNA for human transferrin receptor 1 transfection. Results show that Iron was strongly stained in tumor tissues, whereas negative staining was observed in normal bile ducts of healthy donors. Interestingly, high iron accumulation was significantly correlated with poor prognosis of cholangiocarcinoma patients. The expressions of iron regulatory proteins in human cholangiocarcinoma tissues and normal liver from cadaveric donors revealed that transferrin receptor-1 expression was increased in the cancer cells of cholangiocarcinoma tissues when compared with the adjacent normal bile ducts and was significantly correlated with cholangiocarcinoma metastasis. Labile iron pool level and transferrin receptor-1 expression were significantly increased in KKU-214 and KKU-213 when compared with cholangiocyte cells (MMNK1). Additionally, the suppression of transferrin receptor-1 expression significantly decreased intracellular labile iron pool, cholangiocarcinoma migration, and cell proliferation when compared with control media and control small interfering RNA. In Conclusion, high expression of transferrin receptor-1 resulting in iron uptake contributes to increase in the labile iron pool which plays roles in cholangiocarcinoma progression with aggressive clinical outcomes.

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

PubMed

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

2011-11-01

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

Chemistry and mineralogy of pyrite-enriched sediments at a passive margin sulfide brine seep: abyssal Gulf of Mexico

USGS Publications Warehouse

Commeau, R.F.; Paull, C.K.; Commeau, J.A.; Poppe, L.J.

1987-01-01

Pyrite is rapidly accumulating at the contact between the Cretaceous limestones of the Florida Platform and the hemipelagic sediments of the abyssal Gulf of Mexico. Sediments sampled with the submersible "Alvin" in 3266 m of water are associated with a dense community of organisms that depend on chemosynthetic primary production as a food source. Analysis of the chemistry, mineralogy, and textural composition of these sediments indicate that iron sulfide mineralization is occurring at the seafloor within an anoxic micro-habitat sustained by the advection of hydrogen sulfide-charged saline brines from the adjacent platform. The chemosynthetic bacteria that directly overlie the sediments oxidize hydrogen sulfide for energy and provide elemental sulfur that reacts with iron monosulfide to form some of the pyrite. The sediments are mixtures of pyrite (??? 30 wt.%), BaSr sulfates (??? 4 wt.%), clays, and locally derived biogenic carbonates and are progressively being cemented by iron sulfides. Oxidation of hydrogen sulfide produces locally acidic conditions that corrode the adjacent limestones. Potential sources of S, H2S, Fe, Ba, and Sr are discussed. ?? 1987.

A non-invasive approach to monitor chronic lymphocytic leukemia engraftment in a xenograft mouse model using ultra-small superparamagnetic iron oxide-magnetic resonance imaging (USPIO-MRI).

PubMed

Valdora, Francesca; Cutrona, Giovanna; Matis, Serena; Morabito, Fortunato; Massucco, Carlotta; Emionite, Laura; Boccardo, Simona; Basso, Luca; Recchia, Anna Grazia; Salvi, Sandra; Rosa, Francesca; Gentile, Massimo; Ravina, Marco; Pace, Daniele; Castronovo, Angela; Cilli, Michele; Truini, Mauro; Calabrese, Massimo; Neri, Antonino; Neumaier, Carlo Emanuele; Fais, Franco; Baio, Gabriella; Ferrarini, Manlio

2016-11-01

Chronic lymphocytic leukemia (CLL) is the most prevalent leukemia among adults. Despite its indolent nature, CLL remains an incurable disease. Herein we aimed to monitor CLL disease engraftment and, progression/regression in a xenograft CLL mouse model using ultra-small superparamagnetic iron oxide-magnetic resonance imaging (USPIO-MRI). Spleen contrast enhancement, quantified as percentage change in signal intensity upon USPIO administration, demonstrated a difference due to a reduced USPIO uptake, in the spleens of mice injected with CLL cells (NSG-CLL, n=71) compared to controls (NSG-CTR, n=17). These differences were statistically significant both after 2 and 4weeks from CLL cells injection. In addition comparison of mice treated with rituximab with untreated controls for changes in spleen iron uptake confirmed that it is possible to monitor treatment efficacy in this mouse model of CLL using USPIO-enhanced MRI. Further applications could include the preclinical in vivo monitoring of new therapies and the clinical evaluation of CLL patients. Copyright © 2016 Elsevier Inc. All rights reserved.

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

PubMed

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

2017-04-19

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

Environmental, biogeographic, and biochemical patterns of archaea of the family Ferroplasmaceae.

PubMed

Golyshina, Olga V

2011-08-01

About 10 years ago, a new family of cell wall-deficient, iron-oxidizing archaea, Ferroplasmaceae, within the large archaeal phylum Euryarchaeota, was described. In this minireview, I summarize the research progress achieved since then and report on the current status of taxonomy, biogeography, physiological diversity, biochemistry, and other research areas involving this exciting group of acidophilic archaea.

Progress Towards Microwave Ignition of Explosives

NASA Astrophysics Data System (ADS)

Curling, Mark; Collins, Adam; Dima, Gabriel; Proud, William

2009-06-01

Microwaves could provide a method of propellant ignition that does away with a traditional primer, making ammunition safer and suitable for Insensitive Munitions (IM) applications. By embedding a suitable material inside a propellant, it is postulated that microwaves could be used to stimulate hotspots, through direct heating or electrostatic discharge (arcing) across the energetic material. This paper reports on progress in finding these suitable materials. Graphite rod, magnetite cubes and powders of graphite, aluminium, copper oxide, and iron were irradiated in a conventional microwave oven. Temperature measurements were made using a shielded thermocouple and thermal paints. Only graphite rod and magnetite showed significant heating upon microwave exposure. The light output from arcing of iron, steel, iron pyrite, magnetite and graphite was measured in the same microwave oven as above. Sample mass and shape were correlated with arcing intensity. A strategy is proposed to create a homogeneous igniter material by embedding arcing materials within an insulator, Polymethylpentene (TPX). External discharges were transmitted through TPX, however no embedded samples were successful in generating an electrical breakdown suitable for propellant ignition.

Mineral resource of the month: iron oxide pigments

USGS Publications Warehouse

,

2008-01-01

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

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

PubMed

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

2018-02-28

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

RGD-conjugated iron oxide magnetic nanoparticles for magnetic resonance imaging contrast enhancement and hyperthermia.

PubMed

Zheng, S W; Huang, M; Hong, R Y; Deng, S M; Cheng, L F; Gao, B; Badami, D

2014-03-01

The purpose of this study was to develop a specific targeting magnetic nanoparticle probe for magnetic resonance imaging and therapy in the form of local hyperthermia. Carboxymethyl dextran-coated ultrasmall superparamagnetic iron oxide nanoparticles with carboxyl groups were coupled to cyclic arginine-glycine-aspartic peptides for integrin α(v)β₃ targeting. The particle size, magnetic properties, heating effect, and stability of the arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide were measured. The arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide demonstrates excellent stability and fast magneto-temperature response. Magnetic resonance imaging signal intensity of Bcap37 cells incubated with arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide was significantly decreased compared with that incubated with plain ultrasmall superparamagnetic iron oxide. The preferential uptake of arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide by target cells was further confirmed by Prussian blue staining and confocal laser scanning microscopy.

Fabrication and characterization of iron oxide dextran composite layers

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Detection and Localization of Markers of Oxidative Stress by In Situ Methods: Application in the Study of Alzheimer Disease

PubMed Central

Moreira, Paula I.; Sayre, Lawrence M.; Zhu, Xiongwei; Nunomura, Akihiko; Smith, Mark A.; Perry, George

2018-01-01

Oxidative stress is a key factor involved in the development and progression of Alzheimer disease (AD), and it is well documented that free radical oxidative damage, particularly of neuronal lipids, proteins, nucleic acids, and sugars, is extensive in brains of AD patients. The complex chemistry of peroxynitrite has been the subject of intense study and is now evident that there are two principal pathways for protein modification: the first one involves homolytic hydroxyl radical-like chemistry that results in protein-based carbonyls and the second involves electrophilic nitration of vulnerable side chains, in particular the electron-rich aromatic rings of Tyr and Trp. In the presence of buffering bicarbonate, peroxynitrite forms a CO2 adduct, which augments its reactivity. Formation of 3-nitrotyrosine by this route has become the classical protein marker specifically for the presence of peroxynitrite. Protein-based carbonyls can be detected by two methods: (i) derivatization with 2,4-dinitrophenylhydrazine (DNPH) and detection of the protein-bound hydrazones using an enzyme-linked anti-2,4-dinitrophenyl antibody and (ii) derivatization with biotin-hydrazide and detection of the protein-bound acyl hydrazone with enzyme-linked avidin or streptavidin. Glycation of proteins by reducing sugars (Maillard reaction) results in a profile of time-dependent adduct evolution rendering susceptibility to oxidative elaboration. In addition, oxidative stress can result in oxidized sugar derivatives which can subsequently modify protein through a process known as glycoxidation. Of more general importance, oxidative stress results in lipid peroxidation and the production of a range of electrophilic and mostly bifunctional aldehydes that modify numerous proteins. The more important protein modifications are referred to as advanced glycation end products (AGEs) and advanced lipoxidation end products (ALEs). Protein modification can result in both non-cross-link and cross-link AGEs and ALEs, the latter arising from the potential bifunctional reactivity, such as that of the lipid-derived modifiers 4-hydroxy-2-nonenal (HNE) and malondialdehyde (MDA). Oxidative damage to nucleic acids results in base modification, substitutions, and deletions. Among the most common modifications, 8-hydroxyguanosine (8OHG) is considered a signature of oxidative damage to nucleic acid. Cells are not passive to increased oxygen radical production but rather upregulate protective responses. In neurodegenerative diseases, heme oxygenase-1 (HO-1) induction is coincident with the formation of neurofibrillary tangles. This enzyme thatconverts heme, a prooxidant, to biliverdin/bilirubin (antioxidants) and free iron has been considered an antioxidant enzyme. But seen in the context of arresting apoptosis, HO-1 and tau may play a role in maintaining the neurons free from the apoptotic signal (cytochrome c), since tau has strong iron-binding sites. Given the importance of iron as a catalyst for the generation of reactive oxygen species, changes in proteins associated with iron homeostasis can be used as an index of cellular responses. One such class of proteins is the iron regulatory proteins (IRPs) that respond to cellular iron concentrations by regulating the translation of proteins involved in iron uptake, storage, and utilization. Therefore, IRPs are considered to be the central control components of cellular iron concentration. PMID:20013193

Detection and localization of markers of oxidative stress by in situ methods: application in the study of Alzheimer disease.

PubMed

Moreira, Paula I; Sayre, Lawrence M; Zhu, Xiongwei; Nunomura, Akihiko; Smith, Mark A; Perry, George

2010-01-01

Oxidative stress is a key factor involved in the development and progression of Alzheimer disease (AD), and it is well documented that free radical oxidative damage, particularly of neuronal lipids, proteins, nucleic acids, and sugars, is extensive in brains of AD patients. The complex chemistry of peroxynitrite has been the subject of intense study and is now evident that there are two principal pathways for protein modification: the first one involves homolytic hydroxyl radical-like chemistry that results in protein-based carbonyls and the second involves electrophilic nitration of vulnerable side chains, in particular the electron-rich aromatic rings of Tyr and Trp. In the presence of buffering bicarbonate, peroxynitrite forms a CO(2) adduct, which augments its reactivity. Formation of 3-nitrotyrosine by this route has become the classical protein marker specifically for the presence of peroxynitrite. Protein-based carbonyls can be detected by two methods: (i) derivatization with 2,4-dinitrophenylhydrazine (DNPH) and detection of the protein-bound hydrazones using an enzyme-linked anti-2,4-dinitrophenyl antibody and (ii) derivatization with biotin-hydrazide and detection of the protein-bound acyl hydrazone with enzyme-linked avidin or streptavidin. Glycation of proteins by reducing sugars (Maillard reaction) results in a profile of time-dependent adduct evolution rendering susceptibility to oxidative elaboration. In addition, oxidative stress can result in oxidized sugar derivatives which can subsequently modify protein through a process known as glycoxidation. Of more general importance, oxidative stress results in lipid peroxidation and the production of a range of electrophilic and mostly bifunctional aldehydes that modify numerous proteins. The more important protein modifications are referred to as advanced glycation end products (AGEs) and advanced lipoxidation end products (ALEs). Protein modification can result in both non-cross-link and cross-link AGEs and ALEs, the latter arising from the potential bifunctional reactivity, such as that of the lipid-derived modifiers 4-hydroxy-2-nonenal (HNE) and malondialdehyde (MDA). Oxidative damage to nucleic acids results in base modification, substitutions, and deletions. Among the most common modifications, 8-hydroxyguanosine (8OHG) is considered a signature of oxidative damage to nucleic acid.Cells are not passive to increased oxygen radical production but rather upregulate protective responses. In neurodegenerative diseases, heme oxygenase-1 (HO-1) induction is coincident with the formation of neurofibrillary tangles. This enzyme that converts heme, a prooxidant, to biliverdin/bilirubin (antioxidants) and free iron has been considered an antioxidant enzyme. But seen in the context of arresting apoptosis, HO-1 and tau may play a role in maintaining the neurons free from the apoptotic signal (cytochrome c), since tau has strong iron-binding sites. Given the importance of iron as a catalyst for the generation of reactive oxygen species, changes in proteins associated with iron homeostasis can be used as an index of cellular responses. One such class of proteins is the iron regulatory proteins (IRPs) that respond to cellular iron concentrations by regulating the translation of proteins involved in iron uptake, storage, and utilization. Therefore, IRPs are considered to be the central control components of cellular iron concentration.

When Density Functional Approximations Meet Iron Oxides.

PubMed

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

2016-10-11

Three density functional approximations (DFAs), PBE, PBE+U, and Heyd-Scuseria-Ernzerhof screened hybrid functional (HSE), were employed to investigate the geometric, electronic, magnetic, and thermodynamic properties of four iron oxides, namely, α-FeOOH, α-Fe 2 O 3 , Fe 3 O 4 , and FeO. Comparing our calculated results with available experimental data, we found that HSE (a = 0.15) (containing 15% "screened" Hartree-Fock exchange) can provide reliable values of lattice constants, Fe magnetic moments, band gaps, and formation energies of all four iron oxides, while standard HSE (a = 0.25) seriously overestimates the band gaps and formation energies. For PBE+U, a suitable U value can give quite good results for the electronic properties of each iron oxide, but it is challenging to accurately get other properties of the four iron oxides using the same U value. Subsequently, we calculated the Gibbs free energies of transformation reactions among iron oxides using the HSE (a = 0.15) functional and plotted the equilibrium phase diagrams of the iron oxide system under various conditions, which provide reliable theoretical insight into the phase transformations of iron oxides.

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

PubMed Central

2014-01-01

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

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

NASA Astrophysics Data System (ADS)

Gharehaghaji, Nahideh; Divband, Baharak; Zareei, Loghman

2018-06-01

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

Analysis of Nucleotide Variations in Genes of Iron Management in Patients of Parkinson's Disease and Other Movement Disorders

PubMed Central

Castiglioni, Emanuela; Finazzi, Dario; Goldwurm, Stefano; Pezzoli, Gianni; Forni, Gianluca; Girelli, Domenico; Maccarinelli, Federica; Poli, Maura; Ferrari, Maurizio; Cremonesi, Laura; Arosio, Paolo

2011-01-01

The capacity to act as an electron donor and acceptor makes iron an essential cofactor of many vital processes. Its balance in the body has to be tightly regulated since its excess can be harmful by favouring oxidative damage, while its deficiency can impair fundamental activities like erythropoiesis. In the brain, an accumulation of iron or an increase in its availability has been associated with the development and/or progression of different degenerative processes, including Parkinson's disease, while iron paucity seems to be associated with cognitive deficits, motor dysfunction, and restless legs syndrome. In the search of DNA sequence variations affecting the individual predisposition to develop movement disorders, we scanned by DHPLC the exons and intronic boundary regions of ceruloplasmin, iron regulatory protein 2, hemopexin, hepcidin and hemojuvelin genes in cohorts of subjects affected by Parkinson's disease and idiopathic neurodegeneration with brain iron accumulation (NBIA). Both novel and known sequence variations were identified in most of the genes, but none of them seemed to be significantly associated to the movement diseases of interest. PMID:20981230

Iron and oxygen isotope fractionation during iron UV photo-oxidation: Implications for early Earth and Mars

NASA Astrophysics Data System (ADS)

Nie, Nicole X.; Dauphas, Nicolas; Greenwood, Richard C.

2017-01-01

Banded iron formations (BIFs) contain appreciable amounts of ferric iron (Fe3+). The mechanism by which ferrous iron (Fe2+) was oxidized into Fe3+ in an atmosphere that was globally anoxic is highly debated. Of the three scenarios that have been proposed to explain BIF formation, photo-oxidation by UV photons is the only one that does not involve life (the other two are oxidation by O2 produced by photosynthesis, and anoxygenic photosynthesis whereby Fe2+ is directly used as electron donor in place of water). We experimentally investigated iron and oxygen isotope fractionation imparted by iron photo-oxidation at a pH of 7.3. The iron isotope fractionation between precipitated Fe3+-bearing lepidocrocite and dissolved Fe2+ follows a Rayleigh distillation with an instantaneous 56Fe/54Fe fractionation factor of + 1.2 ‰. Such enrichment in the heavy isotopes of iron is consistent with the values measured in BIFs. We also investigated the nature of the mass-fractionation law that governs iron isotope fractionation in the photo-oxidation experiments (i.e., the slope of the δ56Fe-δ57Fe relationship). The experimental run products follow a mass-dependent law corresponding to the high-T equilibrium limit. The fact that a ∼3.8 Gyr old BIF sample (IF-G) from Isua (Greenland) falls on the same fractionation line confirms that iron photo-oxidation in the surface layers of the oceans was a viable pathway to BIF formation in the Archean, when the atmosphere was largely transparent to UV photons. Our experiments allow us to estimate the quantum yield of the photo-oxidation process (∼0.07 iron atom oxidized per photon absorbed). This yield is used to model iron oxidation on early Mars. As the photo-oxidation proceeds, the aqueous medium becomes more acidic, which slows down the reaction by changing the speciation of iron to species that are less efficient at absorbing UV-photons. Iron photo-oxidation in centimeter to meter-deep water ponds would take months to years to complete. Oxidation by O2 in acidic conditions would be slower. Iron photo-oxidation is thus likely responsible for the formation of jarosite-hematite deposits on Mars, provided that shallow standing water bodies could persist for extended periods of time. The oxygen isotopic composition of lepidocrocite precipitated from the photo-oxidation experiment was measured and it is related to the composition of water by mass-dependent fractionation. The precipitate-fluid 18O/16O isotope fractionation of ∼ + 6 ‰ is consistent with previous determinations of oxygen equilibrium fraction factors between iron oxyhydroxides and water.

Multimodal magnetic nano-carriers for cancer treatment: Challenges and advancements

NASA Astrophysics Data System (ADS)

Aadinath, W.; Ghosh, Triroopa; Anandharamakrishnan, C.

2016-03-01

Iron oxide nanoparticles (IONPs) have been a propitious topic for cancer treatment in recent years because of its multifunctional theranostic applications under magnetic field. Two such widely used applications in cancer biology are gradient magnetic field guided targeting and alternative magnetic field (AMF) induced local hyperthermia. Gradient magnetic field guided targeting is a mode of active targeting of therapeutics conjugated with iron oxide nanoparticles. These particles also dissipate heat in presence of AMF which causes thermal injury to the cells of interest, for example tumour cells and subsequent death. Clinical trials divulge the feasibility of such magnetic nano-carrier as a promising candidate in cancer biology. However, these techniques need further investigations to curtail certain limitations manifested. Recent progresses in response have shrunken the barricade to certain extent. In this context, principles, challenges associated with these applications and recent efforts made in response will be discussed.

Neutrophilic Iron-Oxidizing “Zetaproteobacteria” and Mild Steel Corrosion in Nearshore Marine Environments ▿ †

PubMed Central

McBeth, Joyce M.; Little, Brenda J.; Ray, Richard I.; Farrar, Katherine M.; Emerson, David

2011-01-01

Microbiologically influenced corrosion (MIC) of mild steel in seawater is an expensive and enduring problem. Little attention has been paid to the role of neutrophilic, lithotrophic, iron-oxidizing bacteria (FeOB) in MIC. The goal of this study was to determine if marine FeOB related to Mariprofundus are involved in this process. To examine this, field incubations and laboratory microcosm experiments were conducted. Mild steel samples incubated in nearshore environments were colonized by marine FeOB, as evidenced by the presence of helical iron-encrusted stalks diagnostic of the FeOB Mariprofundus ferrooxydans, a member of the candidate class “Zetaproteobacteria.” Furthermore, Mariprofundus-like cells were enriched from MIC biofilms. The presence of Zetaproteobacteria was confirmed using a Zetaproteobacteria-specific small-subunit (SSU) rRNA gene primer set to amplify sequences related to M. ferrooxydans from both enrichments and in situ samples of MIC biofilms. Temporal in situ incubation studies showed a qualitative increase in stalk distribution on mild steel, suggesting progressive colonization by stalk-forming FeOB. We also isolated a novel FeOB, designated Mariprofundus sp. strain GSB2, from an iron oxide mat in a salt marsh. Strain GSB2 enhanced uniform corrosion from mild steel in laboratory microcosm experiments conducted over 4 days. Iron concentrations (including precipitates) in the medium were used as a measure of corrosion. The corrosion in biotic samples (7.4 ± 0.1 mM) was significantly higher than that in abiotic controls (5.0 ± 0.1 mM). These results have important implications for the role of FeOB in corrosion of steel in nearshore and estuarine environments. In addition, this work shows that the global distribution of Zetaproteobacteria is far greater than previously thought. PMID:21131509

Astroglia overexpressing heme oxygenase-1 predispose co-cultured PC12 cells to oxidative injury.

PubMed

Song, Linyang; Song, Wei; Schipper, Hyman M

2007-08-01

The mechanisms responsible for the progressive degeneration of dopaminergic neurons and pathologic iron deposition in the substantia nigra pars compacta of patients with Parkinson's disease (PD) remain unclear. Heme oxygenase-1 (HO-1), the rate-limiting enzyme in the oxidative degradation of heme to ferrous iron, carbon monoxide, and biliverdin, is upregulated in affected PD astroglia and may contribute to abnormal mitochondrial iron sequestration in these cells. To determine whether glial HO-1 hyper-expression is toxic to neuronal compartments, we co-cultured dopaminergic PC12 cells atop monolayers of human (h) HO-1 transfected, sham-transfected, or non-transfected primary rat astroglia. We observed that PC12 cells grown atop hHO-1 transfected astrocytes, but not the astroglia themselves, were significantly more susceptible to dopamine (1 microM) + H(2)O(2) (1 microM)-induced death (assessed by nuclear ethidium monoazide bromide staining and anti-tyrosine hydroxylase immunofluorescence microscopy) relative to control preparations. In the experimental group, PC12 cell death was attenuated significantly by the administration of the HO inhibitor, SnMP (1.5 microM), the antioxidant, ascorbate (200 microM), or the iron chelators, deferoxamine (400 microM), and phenanthroline (100 microM). Exposure to conditioned media derived from HO-1 transfected astrocytes also augmented PC12 cell killing in response to dopamine (1 microM) + H(2)O(2) (1 microM) relative to control media. In PD brain, overexpression of HO-1 in nigral astroglia and accompanying iron liberation may facilitate the bioactivation of dopamine to neurotoxic free radical intermediates and predispose nearby neuronal constituents to oxidative damage. (c) 2007 Wiley-Liss, Inc.

Neutrophilic iron-oxidizing "zetaproteobacteria" and mild steel corrosion in nearshore marine environments.

PubMed

McBeth, Joyce M; Little, Brenda J; Ray, Richard I; Farrar, Katherine M; Emerson, David

2011-02-01

Microbiologically influenced corrosion (MIC) of mild steel in seawater is an expensive and enduring problem. Little attention has been paid to the role of neutrophilic, lithotrophic, iron-oxidizing bacteria (FeOB) in MIC. The goal of this study was to determine if marine FeOB related to Mariprofundus are involved in this process. To examine this, field incubations and laboratory microcosm experiments were conducted. Mild steel samples incubated in nearshore environments were colonized by marine FeOB, as evidenced by the presence of helical iron-encrusted stalks diagnostic of the FeOB Mariprofundus ferrooxydans, a member of the candidate class "Zetaproteobacteria." Furthermore, Mariprofundus-like cells were enriched from MIC biofilms. The presence of Zetaproteobacteria was confirmed using a Zetaproteobacteria-specific small-subunit (SSU) rRNA gene primer set to amplify sequences related to M. ferrooxydans from both enrichments and in situ samples of MIC biofilms. Temporal in situ incubation studies showed a qualitative increase in stalk distribution on mild steel, suggesting progressive colonization by stalk-forming FeOB. We also isolated a novel FeOB, designated Mariprofundus sp. strain GSB2, from an iron oxide mat in a salt marsh. Strain GSB2 enhanced uniform corrosion from mild steel in laboratory microcosm experiments conducted over 4 days. Iron concentrations (including precipitates) in the medium were used as a measure of corrosion. The corrosion in biotic samples (7.4 ± 0.1 mM) was significantly higher than that in abiotic controls (5.0 ± 0.1 mM). These results have important implications for the role of FeOB in corrosion of steel in nearshore and estuarine environments. In addition, this work shows that the global distribution of Zetaproteobacteria is far greater than previously thought.

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

EPA Science Inventory

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

Antioxidants Mediate Both Iron Homeostasis and Oxidative Stress.

PubMed

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

2017-06-28

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

Antioxidants Mediate Both Iron Homeostasis and Oxidative Stress

PubMed Central

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

2017-01-01

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

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

PubMed Central

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

2009-01-01

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

Ductular reaction in hereditary hemochromatosis: the link between hepatocyte senescence and fibrosis progression.

PubMed

Wood, Marnie J; Gadd, Victoria L; Powell, Lawrie W; Ramm, Grant A; Clouston, Andrew D

2014-03-01

The development of portal fibrosis following the iron loading of hepatocytes is the first stage of fibrogenesis in hereditary hemochromatosis. In other chronic liver diseases it has been shown that a ductular reaction (DR) appears early, correlates with fibrosis progression, and is a consequence of activation of an alternative pathway of hepatocyte replication. This study was designed to investigate the presence of the DR in hemochromatosis and describe its associations. Liver biopsies from 63 C282Y homozygous patients were assessed for hepatic iron concentration (HIC) and graded for iron loading, fibrosis stage, steatosis, and inflammation. Immunostaining allowed quantification of the DR, hepatocyte senescence and proliferation, and analysis incorporated clinical data. Hepatocyte senescence was positively correlated with HIC, serum ferritin, and oxidative stress. A DR was demonstrated and occurred prior to histological fibrosis. HIC, age, hepatocyte senescence and proliferation, portal inflammation, and excessive alcohol consumption all had significant associations with the extent of the DR. In multivariate analysis, iron loading, hepatocyte replicative arrest, and portal inflammation remained independently and significantly associated with the DR. Of factors associated with fibrosis progression, the DR (odds ratio [OR] 10.86 P<0.0001) and the presence of portal inflammation (OR 4.31, P=0.028) remained significant after adjustment for cofactors. The extent of the DR regressed following therapeutic venesection. Iron loading of hepatocytes leads to impaired replication, stimulating the development of the DR in hemochromatosis and this correlates strongly with hepatic fibrosis. Portal inflammation occurs in hemochromatosis and is independently associated with the DR and fibrosis, and thus its role in this disease should be evaluated further. © 2014 by the American Association for the Study of Liver Diseases.

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

PubMed

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

2017-11-01

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

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

PubMed

Yin, Yongyuan; Guo, Xuetao; Peng, Dan

2018-08-01

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

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

PubMed

Li, Yongchao; Hu, Xiaoxian; Ren, Bozhi

2016-01-01

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

Iron-oxide minerals affect extracellular electron-transfer paths of Geobacter spp.

PubMed

Kato, Souichiro; Hashimoto, Kazuhito; Watanabe, Kazuya

2013-01-01

Some bacteria utilize (semi)conductive iron-oxide minerals as conduits for extracellular electron transfer (EET) to distant, insoluble electron acceptors. A previous study demonstrated that microbe/mineral conductive networks are constructed in soil ecosystems, in which Geobacter spp. share dominant populations. In order to examine how (semi)conductive iron-oxide minerals affect EET paths of Geobacter spp., the present study grew five representative Geobacter strains on electrodes as the sole electron acceptors in the absence or presence of (semi)conductive iron oxides. It was found that iron-oxide minerals enhanced current generation by three Geobacter strains, while no effect was observed in another strain. Geobacter sulfurreducens was the only strain that generated substantial amounts of currents both in the presence and absence of the iron oxides. Microscopic, electrochemical and transcriptomic analyses of G. sulfurreducens disclosed that this strain constructed two distinct types of EET path; in the absence of iron-oxide minerals, bacterial biofilms rich in extracellular polymeric substances were constructed, while composite networks made of mineral particles and microbial cells (without polymeric substances) were developed in the presence of iron oxides. It was also found that uncharacterized c-type cytochromes were up-regulated in the presence of iron oxides that were different from those found in conductive biofilms. These results suggest the possibility that natural (semi)conductive minerals confer energetic and ecological advantages on Geobacter, facilitating their growth and survival in the natural environment.

Photoreductive dissolution of iron oxides trapped in ice and its environmental implications.

PubMed

Kim, Kitae; Choi, Wonyong; Hoffmann, Michael R; Yoon, Ho-Il; Park, Byong-Kwon

2010-06-01

The availability of iron has been thought to be a main limiting factor for the productivity of phytoplankton and related with the uptake of atmospheric CO(2) and algal blooms in fresh and sea waters. In this work, the formation of bioavailable iron (Fe(II)(aq)) from the dissolution of iron oxide particles was investigated in the ice phase under both UV and visible light irradiation. The photoreductive dissolution of iron oxides proceeded slowly in aqueous solution (pH 3.5) but was significantly accelerated in polycrystalline ice, subsequently releasing more bioavailable ferrous iron upon thawing. The enhanced photogeneration of Fe(II)(aq) in ice was confirmed regardless of the type of iron oxides [hematite, maghemite (gamma-Fe(2)O(3)), goethite (alpha-FeOOH)] and the kind of electron donors. The ice-enhanced dissolution of iron oxides was also observed under visible light irradiation, although the dissolution rate was much slower compared with the case of UV radiation. The iron oxide particles and organic electron donors (if any) in ice are concentrated and aggregated in the liquid-like grain boundary region (freeze concentration effect) where protons are also highly concentrated (lower pH). The enhanced photodissolution of iron oxides should occur in this confined boundary region. We hypothesized that electron hopping through the interconnected grain boundaries of iron oxide particles facilitates the separation of photoinduced charge pairs. The outdoor experiments carried out under ambient solar radiation of Ny-Alesund (Svalbard, 78 degrees 55'N) also showed that the generation of dissolved Fe(II)(aq) via photoreductive dissolution is enhanced when iron oxides are trapped in ice. Our results imply that the ice(snow)-covered surfaces and ice-cloud particles containing iron-rich mineral dusts in the polar and cold environments provide a source of bioavailable iron when they thaw.

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

PubMed Central

Emerson, David

2016-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2008-03-01

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

Petrographic and Isotopic Evidence for Siderite Precursors to Iron Oxide Cements

NASA Astrophysics Data System (ADS)

Loope, D.

2015-12-01

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

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

PubMed

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

2015-03-06

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

Synthesis and characterization of dextran-coated iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Method for producing iron-based catalysts

DOEpatents

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

1999-01-01

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

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2013 CFR

2013-04-01

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

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2012 CFR

2012-04-01

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

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2014 CFR

2014-04-01

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

Spatially resolved variations in reflectivity across iron oxide thin films

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2012 CFR

2012-04-01

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

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2014 CFR

2014-04-01

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

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2013 CFR

2013-04-01

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

Carbonaceous fuel combustion with improved desulfurization

DOEpatents

Yang, Ralph T.; Shen, Ming-shing

1980-01-01

Lime utilization for sulfurous oxides adsorption in fluidized combustion of carbonaceous fuels is improved by impregnation of porous lime particulates with iron oxide. The impregnation is achieved by spraying an aqueous solution of mixed iron sulfate and sulfite on the limestone before transfer to the fluidized bed combustor, whereby the iron compounds react with the limestone substrate to form iron oxide at the limestone surface. The iron oxide present in the spent limestone is found to catalyze the regeneration rate of the spent limestone in a reducing environment. Thus both the calcium and iron components may be recycled.

Geochemical and mineralogical studies of a South Texas roll-front uranium deposit

USGS Publications Warehouse

Goldhaber, Martin B.; Reynolds, Richard L.

1977-01-01

Core samples from a roll-front uranium deposit in south Texas have been analyzed for iron sulfide content and mineralogy, organic carbon content and the abundance of carbonate, iron, manganese and titanium. Sulfide occurs almost exclusively as the iron disulfides pyrite and marcasite, in concentrations as high as 2 percent of the coarse (>62 ?m) fraction. Marcasite is particularly abundant relative to pyrite in the vicinity of the roll front. Because marcasite precipitation requires acidic pH's and the most likely mechanism for generating a low pH is oxidation of preore sulfide, it is argued that marcasite formation is, at least in part, related to roll-front development. Organic carbon analyses from various representative parts of the deposit are uniformly low (<0.1 percent C). This is taken to imply that sulfate reducing bacteria were not involved in either initial sulfidation of the host rock or during later sulfidization that was related to the ore-forming episode. carbonate minerals, such as calcite, are quite abundant, but appear to have formed after the ore. The overall abundance of iron apparently is not systematically related to position with respect to the roll front, whereas manganese probably is concentrated near the redox interface. Titanium like iron does not show a systematic relationship to position about the roll. However, titanium is systematically more abundant in the fine fraction (462 ?m) relative to the coarse fraction with distance downdip. This reflects a progressively more intense alteration of precursor iron titanium oxide minerals to fine-grained TiO2.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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

PubMed

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

2012-12-01

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

Cancer Cells with Irons in the Fire

PubMed Central

Bystrom, Laura M.; Rivella, Stefano

2014-01-01

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

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

PubMed

Zhang, Peili; Li, Lin; Nordlund, Dennis; Chen, Hong; Fan, Lizhou; Zhang, Biaobiao; Sheng, Xia; Daniel, Quentin; Sun, Licheng

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

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

PubMed

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

2002-05-01

Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe3O4), calcite (CaCO3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH)2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO2, V2O3), sulfides (As2S3, ZnS), iron minerals (FeSe2, FeMoO4) and carbonate (MnCO3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.

Iron Isotope Systematics

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

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

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

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

PubMed

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

2010-12-01

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

Iron Overload Accelerates the Progression of Diabetic Retinopathy in Association with Increased Retinal Renin Expression.

PubMed

Chaudhary, Kapil; Promsote, Wanwisa; Ananth, Sudha; Veeranan-Karmegam, Rajalakshmi; Tawfik, Amany; Arjunan, Pachiappan; Martin, Pamela; Smith, Sylvia B; Thangaraju, Muthusamy; Kisselev, Oleg; Ganapathy, Vadivel; Gnana-Prakasam, Jaya P

2018-02-14

Diabetic retinopathy (DR) is a leading cause of blindness among working-age adults. Increased iron accumulation is associated with several degenerative diseases. However, there are no reports on the status of retinal iron or its implications in the pathogenesis of DR. In the present study, we found that retinas of type-1 and type-2 mouse models of diabetes have increased iron accumulation compared to non-diabetic retinas. We found similar iron accumulation in postmortem retinal samples from human diabetic patients. Further, we induced diabetes in HFE knockout (KO) mice model of genetic iron overload to understand the role of iron in the pathogenesis of DR. We found increased neuronal cell death, vascular alterations and loss of retinal barrier integrity in diabetic HFE KO mice compared to diabetic wildtype mice. Diabetic HFE KO mouse retinas also exhibited increased expression of inflammation and oxidative stress markers. Severity in the pathogenesis of DR in HFE KO mice was accompanied by increase in retinal renin expression mediated by G-protein-coupled succinate receptor GPR91. In light of previous reports implicating retinal renin-angiotensin system in DR pathogenesis, our results reveal a novel relationship between diabetes, iron and renin-angiotensin system, thereby unraveling new therapeutic targets for the treatment of DR.

Improved Yield of High Molecular Weight DNA Coincides with Increased Microbial Diversity Access from Iron Oxide Cemented Sub-Surface Clay Environments

PubMed Central

Hurt, Richard A.; Robeson, Michael S.; Shakya, Migun; Moberly, James G.; Vishnivetskaya, Tatiana A.; Gu, Baohua; Elias, Dwayne A.

2014-01-01

Despite over three decades of progress, extraction of high molecular weight (HMW) DNA from high clay soils or iron oxide cemented clay has remained challenging. HMW DNA is desirable for next generation sequencing as it yields the most comprehensive coverage. Several DNA extraction procedures were compared from samples that exhibit strong nucleic acid adsorption. pH manipulation or use of alternative ion solutions offered no improvement in nucleic acid recovery. Lysis by liquid N2 grinding in concentrated guanidine followed by concentrated sodium phosphate extraction supported HMW DNA recovery from clays high in iron oxides. DNA recovered using 1 M sodium phosphate buffer (PB) as a competitive desorptive wash was 15.22±2.33 µg DNA/g clay, with most DNA consisting of >20 Kb fragments, compared to 2.46±0.25 µg DNA/g clay with the Powerlyzer system (MoBio). Increasing PB concentration in the lysis reagent coincided with increasing DNA fragment length during initial extraction. Rarefaction plots of 16S rRNA (V1–V3 region) pyrosequencing from A-horizon and clay soils showed an ∼80% and ∼400% larger accessed diversity compared to the Powerlyzer soil DNA system, respectively. The observed diversity from the Firmicutes showed the strongest increase with >3-fold more operational taxonomic units (OTU) recovered. PMID:25033199

Magnetic Characterization of Iron Oxide Nanoparticles for Biomedical Applications.

PubMed

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

2017-01-01

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

CI chondrite-like clasts in the Nilpena polymict ureilite - Implications for aqueous alteration processes in CI chondrites

NASA Technical Reports Server (NTRS)

Brearley, Adrian J.; Prinz, Martin

1992-01-01

Petrographic studies of Nilpena polymict ureilite have revealed the presence of small quantities of carbonaceous chondrite matrix clasts. Detailed electron microprobe and TEM studies show that the chemistry and fine-scale mineralogy of one of these clasts is consistent with CI carbonaceous chondrite matrix. Compared to Orgeuil, the phyllosilicate, sulfide, and oxide mineralogy suggests that the Nilpena clasts may represent a less altered type of CI matrix. It is suggested that increased oxidation and aqueous alteration of Nilpena-type materials could result in the formation of the type of mineral assemblage observed in Orgueil. Increased alteration produces progressive more Mg-rich phyllosilicates and more Fe(3+)-rich iron oxides, such as ferrihydrite. As a function of increased alteration, Ca is also progressively leached from the matrix material to form carbonate veins. The depletion of Ca in CI chondrite matrices suggests the Ivuna and Alais may be intermediate in their degree of alteration to Nilpena and Orgueil.

Steel refining with an electrochemical cell

DOEpatents

Blander, M.; Cook, G.M.

1988-05-17

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

Steel refining with an electrochemical cell

DOEpatents

Blander, M.; Cook, G.M.

1985-05-21

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

Steel refining with an electrochemical cell

DOEpatents

Blander, Milton; Cook, Glenn M.

1988-01-01

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

Refractory lining for electrochemical cell

DOEpatents

Blander, Milton; Cook, Glenn M.

1987-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

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

PubMed

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

2017-09-05

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

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

PubMed

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

2003-01-10

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

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

PubMed

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

2016-04-01

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

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

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

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

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

Iron Oxide Silica Derived from Sol-Gel Synthesis

PubMed Central

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

2011-01-01

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

Oxidation-Induced Degradable Nanogels for Iron Chelation

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Oxidation-Induced Degradable Nanogels for Iron Chelation

PubMed Central

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

2016-01-01

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

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

NASA Astrophysics Data System (ADS)

Friedman, A.; Galazka-Friedman, J.

2017-11-01

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

Mice lacking liver-specific β-catenin develop steatohepatitis and fibrosis after iron overload.

PubMed

Preziosi, Morgan E; Singh, Sucha; Valore, Erika V; Jung, Grace; Popovic, Branimir; Poddar, Minakshi; Nagarajan, Shanmugam; Ganz, Tomas; Monga, Satdarshan P

2017-08-01

Iron overload disorders such as hereditary hemochromatosis and iron loading anemias are a common cause of morbidity from liver diseases and increase risk of hepatic fibrosis and hepatocellular carcinoma (HCC). Treatment options for iron-induced damage are limited, partly because there is lack of animal models of human disease. Therefore, we investigated the effect of iron overload in liver-specific β-catenin knockout mice (KO), which are susceptible to injury, fibrosis and tumorigenesis following chemical carcinogen exposure. Iron overload diet was administered to KO and littermate control (CON) mice for various times. To ameliorate an oxidant-mediated component of tissue injury, N-Acetyl-L-(+)-cysteine (NAC) was added to drinking water of mice on iron overload diet. KO on iron diet (KO +Fe) exhibited remarkable inflammation, followed by steatosis, oxidative stress, fibrosis, regenerating nodules and occurrence of occasional HCC. Increased injury in KO +Fe was associated with activated protein kinase B (AKT), ERK, and NF-κB, along with reappearance of β-catenin and target gene Cyp2e1, which promoted lipid peroxidation and hepatic damage. Addition of NAC to drinking water protected KO +Fe from hepatic steatosis, injury and fibrosis, and prevented activation of AKT, ERK, NF-κB and reappearance of β-catenin. The absence of hepatic β-catenin predisposes mice to hepatic injury and fibrosis following iron overload, which was reminiscent of hemochromatosis and associated with enhanced steatohepatitis and fibrosis. Disease progression was notably alleviated by antioxidant therapy, which supports its chemopreventive role in the management of chronic iron overload disorders. Lack of animal models for iron overload disorders makes it hard to study the disease process for improving therapies. Feeding high iron diet to mice that lack the β-catenin gene in liver cells led to increased inflammation followed by fat accumulation, cell death and wound healing that mimicked human disease. Administration of an antioxidant prevented hepatic injury in this model. Copyright © 2017 European Association for the Study of the Liver. Published by Elsevier B.V. All rights reserved.

Progression of natural attenuation processes at a crude-oil spill site . I. Geochemical evolution of the plume

USGS Publications Warehouse

Cozzarelli, I.M.; Bekins, B.A.; Baedecker, M.J.; Aiken, G.R.; Eganhouse, R.P.; Tuccillo, M.E.

2001-01-01

A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho-xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume. Copyright ?? 2001 .

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

PubMed

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

2016-05-01

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

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

PubMed Central

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

2015-01-01

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

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

PubMed

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

2013-08-19

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

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

PubMed

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Stabilization and functionalization of iron oxide nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

Amstad, Esther; Textor, Marcus; Reimhult, Erik

2011-07-01

Superparamagnetic iron oxide nanoparticles (NPs) are used in a rapidly expanding number of research and practical applications in the biomedical field, including magnetic cell labeling separation and tracking, for therapeutic purposes in hyperthermia and drug delivery, and for diagnostic purposes, e.g., as contrast agents for magnetic resonance imaging. These applications require good NP stability at physiological conditions, close control over NP size and controlled surface presentation of functionalities. This review is focused on different aspects of the stability of superparamagnetic iron oxide NPs, from its practical definition to its implementation by molecular design of the dispersant shell around the iron oxide core and further on to its influence on the magnetic properties of the superparamagnetic iron oxide NPs. Special attention is given to the selection of molecular anchors for the dispersant shell, because of their importance to ensure colloidal and functional stability of sterically stabilized superparamagnetic iron oxide NPs. We further detail how dispersants have been optimized to gain close control over iron oxide NP stability, size and functionalities by independently considering the influences of anchors and the attached sterically repulsive polymer brushes. A critical evaluation of different strategies to stabilize and functionalize core-shell superparamagnetic iron oxide NPs as well as a brief introduction to characterization methods to compare those strategies is given.Superparamagnetic iron oxide nanoparticles (NPs) are used in a rapidly expanding number of research and practical applications in the biomedical field, including magnetic cell labeling separation and tracking, for therapeutic purposes in hyperthermia and drug delivery, and for diagnostic purposes, e.g., as contrast agents for magnetic resonance imaging. These applications require good NP stability at physiological conditions, close control over NP size and controlled surface presentation of functionalities. This review is focused on different aspects of the stability of superparamagnetic iron oxide NPs, from its practical definition to its implementation by molecular design of the dispersant shell around the iron oxide core and further on to its influence on the magnetic properties of the superparamagnetic iron oxide NPs. Special attention is given to the selection of molecular anchors for the dispersant shell, because of their importance to ensure colloidal and functional stability of sterically stabilized superparamagnetic iron oxide NPs. We further detail how dispersants have been optimized to gain close control over iron oxide NP stability, size and functionalities by independently considering the influences of anchors and the attached sterically repulsive polymer brushes. A critical evaluation of different strategies to stabilize and functionalize core-shell superparamagnetic iron oxide NPs as well as a brief introduction to characterization methods to compare those strategies is given. This article was submitted as part of a collection of articles on surface nanotechnology for biological applications. Other papers on this topic can be found in issue 2 of vol. 3 (2011). This issue can be found from the Nanoscale homepage [http://www.rsc.org/nanoscale].

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

PubMed

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

2016-01-01

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

Hydrothermal oxidation in the Biwabik Iron Formation, MN, USA

NASA Astrophysics Data System (ADS)

Losh, Steven; Rague, Ryan

2018-02-01

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

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

PubMed Central

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

2017-01-01

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

The Application of a Modified d-ROMs Test for Measurement of Oxidative Stress and Oxidized High-Density Lipoprotein

PubMed Central

Ito, Fumiaki; Ito, Tomoyuki; Suzuki, Chinatsu; Yahata, Tomoyo; Ikeda, Kazuyuki; Hamaoka, Kenji

2017-01-01

Reactive oxygen species (ROS) are involved in the initiation and progression of atherosclerosis. ROS-derived hydroperoxides, as an indicator of ROS production, have been measured by using the diacron reactive oxygen metabolites (d-ROMs) test, which requires iron-containing transferrin in the reaction mixture. In this study we developed a modified d-ROMs test, termed the Fe-ROMs test, where iron ions were exogenously added to the reaction mixture. This modification is expected to exclude the assay variation that comes from different blood iron levels in individuals. In addition, this Fe-ROMs test was helpful for determining the class of plasma lipoproteins that are hydroperoxidized. Low-density lipoprotein/very low-density lipoprotein (LDL/VLDL) and high-density lipoprotein (HDL) were purified by use of an LDL/VLDL purification kit and the dextran sulfate-Mg2+ precipitation method, respectively; their hydroperoxide contents were assessed by performing the Fe-ROMs test. The majority of the hydroperoxides were detected only in the HDL fraction, not in the LDL/VLDL. Further detailed analysis of HDLs by size-exclusion high-performance liquid chromatography revealed that the hydroperoxide-containing molecules were small-sized HDLs. Because HDL was shown to be the principal vehicle for the plasma hydroperoxides, this Fe-ROMs test is a beneficial method for the assessment of oxidized-HDL levels. Indeed, Fe-ROMs levels were strongly associated with the levels of oxidized HDL, which were determined by performing the malondialdehyde-modified HDL enzyme immunoassay. In conclusion, the Fe-ROMs test using plasma itself or the HDL fraction after dextran sulfate-Mg2+ precipitation is useful to assess the functionality of HDL, because the oxidation of HDL impairs its antiatherogenic capacity. PMID:28230785

The Application of a Modified d-ROMs Test for Measurement of Oxidative Stress and Oxidized High-Density Lipoprotein.

PubMed

Ito, Fumiaki; Ito, Tomoyuki; Suzuki, Chinatsu; Yahata, Tomoyo; Ikeda, Kazuyuki; Hamaoka, Kenji

2017-02-21

Reactive oxygen species (ROS) are involved in the initiation and progression of atherosclerosis. ROS-derived hydroperoxides, as an indicator of ROS production, have been measured by using the diacron reactive oxygen metabolites (d-ROMs) test, which requires iron-containing transferrin in the reaction mixture. In this study we developed a modified d-ROMs test, termed the Fe-ROMs test, where iron ions were exogenously added to the reaction mixture. This modification is expected to exclude the assay variation that comes from different blood iron levels in individuals. In addition, this Fe-ROMs test was helpful for determining the class of plasma lipoproteins that are hydroperoxidized. Low-density lipoprotein/very low-density lipoprotein (LDL/VLDL) and high-density lipoprotein (HDL) were purified by use of an LDL/VLDL purification kit and the dextran sulfate-Mg 2+ precipitation method, respectively; their hydroperoxide contents were assessed by performing the Fe-ROMs test. The majority of the hydroperoxides were detected only in the HDL fraction, not in the LDL/VLDL. Further detailed analysis of HDLs by size-exclusion high-performance liquid chromatography revealed that the hydroperoxide-containing molecules were small-sized HDLs. Because HDL was shown to be the principal vehicle for the plasma hydroperoxides, this Fe-ROMs test is a beneficial method for the assessment of oxidized-HDL levels. Indeed, Fe-ROMs levels were strongly associated with the levels of oxidized HDL, which were determined by performing the malondialdehyde-modified HDL enzyme immunoassay. In conclusion, the Fe-ROMs test using plasma itself or the HDL fraction after dextran sulfate-Mg 2+ precipitation is useful to assess the functionality of HDL, because the oxidation of HDL impairs its antiatherogenic capacity.

[Various pathways leading to the progression of chronic liver diseases].

PubMed

Egresi, Anna; Lengyel, Gabriella; Somogyi, Anikó; Blázovics, Anna; Hagymási, Krisztina

2016-02-21

As the result of various effects (viruses, metabolic diseases, nutritional factors, toxic agents, autoimmune processes) abnormal liver function, liver steatosis and connective tissue remodeling may develop. Progression of this process is complex including various pathways and a number of factors. The authors summarize the factors involved in the progression of chronic liver disease. They describe the role of cells and the produced inflammatory mediators and cytokines, as well as the relationship between the disease and the intestinal flora. They emphasize the role of oxidative stress, mitochondrial dysfunction and cell death in disease progression. Insulin resistance and micro-elements (iron, copper) in relation to liver damage are also discussed, and genetic and epigenetic aspects underlying disease progression are summarized. Discovery of novel treatment options, assessment of the effectiveness of treatment, as well as the success and proper timing of liver transplantation may depend on a better understanding of the process of disease progression.

Microbial Community Phylogenetic and Functional Succession in Chromium-Reducing Aquifer-Derived Microcosms

NASA Astrophysics Data System (ADS)

Brodie, E. L.; Beller, H. R.; Goldfarb, K. C.; Han, R.; Santee, C. A.

2009-12-01

In situ reductive immobilization, whereby highly soluble Cr(VI) species are reduced to poorly soluble Cr(III) species, is a favored approach for remediating Cr-contaminated groundwater. How microbial populations respond phylogenetically and functionally to the injection of an organic electron donor to stimulate Cr(VI) reduction is unclear, as are the relative contributions of direct enzymatic Cr(VI) reduction versus indirect (e.g. sulfide-mediated) reduction. In this study, we inoculated anaerobic microcosms with groundwater from the Cr-contaminated Hanford 100H site (WA) and supplemented them with lactate and the electron acceptors nitrate, sulfate, and amorphous ferric oxyhydroxide. The microcosms progressed successively through nitrate-reducing, sulfate-reducing, and Fe(III)-reducing conditions, and after a second nitrate amendment, nitrate-dependent Fe(II)-oxidizing conditions. Cr(VI) reduction occurred during both the denitrification and the sulfate/iron reduction phases. DNA and RNA were harvested during each major biogeochemical phase and were subjected to PhyloChip analysis, qPCR, and transcript sequencing. Bacterial community succession followed a trajectory related to the sequential use of electron acceptors. During denitrification, bacterial communities were enriched in known denitrifiers within the Beta- and Gamma-proteobacteria and became phylogenetically clustered. Fermenters became enriched following nitrate reduction, preceding both iron and sulfate reduction. Iron reduction was stoichiometrically related to the formation of hydrogen sulfide and, although iron reducers were detected during this phase, their iron-reducing activity was not confirmed. Following the depletion of lactate and sulfate, iron reduction rates decreased and acetate and propionate concentrations stabilized, indicating a marginal contribution of acetate-coupled iron reduction. Rapid Fe(II) oxidation occurred following the nitrate amendment with a concomitant reduction of nitrate to nitrite and an increased abundance of Beta-proteobacterial species related to known anaerobic Fe(II)-oxidizing bacteria. To uncover the microbial mechanisms contributing to the biogeochemical complexity encountered, even under controlled laboratory incubations, requires alternatives to standard phylogenetic analyses. Our ongoing efforts in analyzing the community transcriptomes (mRNA) should provide valuable insight into the relative rates of direct versus indirect mechanisms of Cr(VI) immobilization in contaminated aquifers.

Experimental Oxidation of Iron Sulphides from Intertidal Surface Sediments: Stable Isotope Effects (S, O, C)

NASA Astrophysics Data System (ADS)

Ebersbach, F.; Böttcher, M. E.; Al-Raei, A. M.; Segl, M.

2009-04-01

Top intertidal sediments show a pronounced zone of activities of sulphate-reducing bacteria. Iron sulfides may be formed, but a substantial part is reoxidized to sulfate. Microbial or chemical reoxidation can be further enhanced by a resuspension of surface sediments by tidal currents or storms. The rates of the different processes depend on the site-secific sedimentological properties (e.g., grain size, iron and sulphur contents etc.). In the present study 3 different areas of the German Wadden Sea were studied: a mud flat in the Jade Bay, and sandy sediments in the intertidals of Spiekeroog and Sylt islands. The latter site is part of an in-situ lugworm-exclusion experiment. The goal was the experimental and field investigation of the fate of iron sulfides and the formation of sulphate upon resuspension of intertidal surface sediments in oxygenated seawater. All sites were geochemically analyzed for dissolved and solid phase iron, manganese, sulphur and carbon phases/species, and sulphate reduction rates were measured using radiotracers. Dissolved chloride and grain sizes analysis where additionally carried out. TOC, S and metal phase contents were higher in mud compared to sandy sediments. Field results demonstrate gross but only minor net sulphide production and a downcore increases in FeS contents, due to intense sulphide oxidation at the surface. Pyrite, on the other hand, was abundant through the sediments due to continuous sediment reworking. The fate of iron-sulphides and accumulation of sulphate as a function of time was followed in batch experiments using dark suspensions of surface sediments in site-bottom waters at room temperature. During the experiments, each sample was shaken continuously under exposition to oxygen, and sub-samples were taken at the beginning and after discrete time intervalls. A very fast oxidation rate of AVS led to a complete exhaustion within a day, whereas Cr(II)-reducible sulfur was inititially built up and then decreased. This observation can be explained by a formation of S° and FeOOH, followed by the oxidation of pyrite. The dissolved species (SO4/Cl ratios) reflected the continuous accumulation of sulphate as an oxidation product. Dissolved inorganic carbonate (DIC) concentrations decreased upon reaction progress, due to the liberation of protons upon iron sulphide oxidation and degassing of carbon dioxide. The 13C/12C ratio of the residual DIC increased due to the preferential desorption of 12CO2. 34S and 18O contents of dissolved sulphate further show process specific isotope discrimination. The experiments demonstrate the importance of oxidation on the fate of FeS , but less pyrite and the formation of sulphate from resuspended intertidal surface sediments. Acknowledgements: The authors gratefully acknowledge discussions and field advice by N. Volkenborn, and financial support from Deutsche Forschungsgemeinschaft during DFG-SPP ‚BioGeoChemistry of the Wadden Sea' (JO 307/4, BO 1584/4), Max Planck Society, and Leibniz-IO Warnemünde.

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

PubMed

Nolan, Michael

2011-10-28

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

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

NASA Astrophysics Data System (ADS)

Khan, M. N.; Shamim, T.

2017-08-01

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

ISOLATION AND PROPERTIES OF AN IRON-OXIDIZING THIOBACILLUS

PubMed Central

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

1963-01-01

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

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

DTIC Science & Technology

1986-09-01

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

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

PubMed Central

Nganai, Shadrack; Lomnicki, Slawo; Dellinger, Barry

2012-01-01

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

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

PubMed

Park, Jeong-Ann; Kim, Song-Bae

2015-10-01

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

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

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

Zhang, Peili; Li, Lin; Nordlund, Dennis

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

DOE PAGES

Zhang, Peili; Li, Lin; Nordlund, Dennis; ...

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

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

PubMed

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

2015-11-01

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

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

PubMed Central

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

2015-01-01

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

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

PubMed

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

2016-10-01

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

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

PubMed Central

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

2016-01-01

Diatoms are single-celled, photosynthetic, bloom-forming algae that are responsible for at least 20% of global primary production. Nevertheless, more than 30% of the oceans are considered “ocean deserts” due to iron limitation. We used the diatom Phaeodactylum tricornutum as a model system to explore diatom’s response to iron limitation and its interplay with susceptibility to oxidative stress. By analyzing physiological parameters and proteome profiling, we defined two distinct phases: short-term (<3 d, phase I) and chronic (>5 d, phase II) iron limitation. While at phase I no significant changes in physiological parameters were observed, molecular markers for iron starvation, such as Iron Starvation Induced Protein and flavodoxin, were highly up-regulated. At phase II, down-regulation of numerous iron-containing proteins was detected in parallel to reduction in growth rate, chlorophyll content, photosynthetic activity, respiration rate, and antioxidant capacity. Intriguingly, while application of oxidative stress to phase I and II iron-limited cells similarly oxidized the reduced glutathione (GSH) pool, phase II iron limitation exhibited transient resistance to oxidative stress, despite the down regulation of many antioxidant proteins. By comparing proteomic profiles of P. tricornutum under iron limitation and metatranscriptomic data of an iron enrichment experiment conducted in the Pacific Ocean, we propose that iron-limited cells in the natural environment resemble the phase II metabolic state. These results provide insights into the trade-off between optimal growth rate and susceptibility to oxidative stress in the response of diatoms to iron quota in the marine environment. PMID:27503604

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

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

PubMed Central

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

2016-01-01

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

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

PubMed Central

2016-01-01

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

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

PubMed

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

2016-06-08

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

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

PubMed Central

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

2016-01-01

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

Role of clay minerals in the transportation of iron

USGS Publications Warehouse

Carroll, D.

1958-01-01

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

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

PubMed

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

2016-05-15

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

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

DOE PAGES

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

2016-06-10

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

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

PubMed

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

2016-07-05

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

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

EPA Science Inventory

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

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

PubMed

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

2015-12-01

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

Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

USGS Publications Warehouse

Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

2009-01-01

Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

Importance of a martian hematite site for astrobiology

NASA Technical Reports Server (NTRS)

Allen, C. C.; Westall, F.; Schelble, R. T.

2001-01-01

Defining locations where conditions may have been favorable for life is a key objective for the exploration of Mars. Of prime importance are sites where conditions may have been favorable for the preservation of evidence of prebiotic or biotic processes. Areas displaying significant concentrations of the mineral hematite (alpha-Fe2O3), recently identified by thermal emission spectrometry, may have significance in the search for evidence of extraterrestrial life. Since iron oxides can form as aqueous mineral precipitates, the potential exists to preserve microscopic evidence of life in iron oxide-depositing ecosystems. Terrestrial hematite deposits proposed as possible analogs for hematite deposits on Mars include massive (banded) iron formations, iron oxide hydrothermal deposits, iron-rich laterites and ferricrete soils, and rock varnish. We report the potential for long-term preservation of microfossils by iron oxide mineralization in specimens of the approximately 2,100-Ma banded iron deposit of the Gunflint Formation, Canada. Scanning and analytical electron microscopy reveals micrometer-scale rods, spheres, and filaments consisting predominantly of iron and oxygen with minor carbon. We interpret these objects as microbial cells permineralized by an iron oxide, presumably hematite. The confirmation of ancient martian microbial life in hematite deposits will require the return of samples to terrestrial laboratories. A hematite-rich deposit composed of aqueous iron oxide precipitates may thus prove to be a prime site for future sample return.

Controlled synthesis of magnetic iron oxides@SnO2 quasi-hollow core-shell heterostructures: formation mechanism, and enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

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

2011-11-01

Iron oxide/SnO2 magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO2 quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO2 core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe2O3 seeds and commercial SnO2 products, mainly owing to the effective electron hole separation at the iron oxides/SnO2 interfaces.Iron oxide/SnO2 magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO2 quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO2 core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe2O3 seeds and commercial SnO2 products, mainly owing to the effective electron hole separation at the iron oxides/SnO2 interfaces. Electronic supplementary information (ESI) available: TEM and HRTEM images of hematite seeds and iron oxide/SnO2 (12 h and 36 h). See DOI: 10.1039/c1nr10728c

Multifunctional gold coated iron oxide core-shell nanoparticles stabilized using thiolated sodium alginate for biomedical applications.

PubMed

Sood, Ankur; Arora, Varun; Shah, Jyoti; Kotnala, R K; Jain, Tapan K

2017-11-01

In this paper we report synthesis of aqueous based gold coated iron oxide nanoparticles to integrate the localized surface plasma resonance (SPR) properties of gold and magnetic properties of iron oxide in a single system. Iron oxide-gold core shell nanoparticles were stabilized by attachment of thiolated sodium alginate to the surface of nanoparticles. Transmission electron microscope (TEM) micrograph presents an average elementary particle size of 8.1±2.1nm. High resolution TEM (HR-TEM) and X-ray photon spectroscopy further confirms the presence of gold shell around iron oxide core. Gold coating is responsible for reducing saturation magnetization (M s ) value from ~41emu/g to ~24emu/g - in thiolated sodium alginate stabilized gold coated iron oxide core-shell nanoparticles. The drug (curcumin) loading efficiency for the prepared nanocomposites was estimated to be around 7.2wt% (72μgdrug/mg nanoparticles) with encapsulation efficiency of 72.8%. Gold-coated iron oxide core-shell nanoparticles could be of immense importance in the field of targeted drug delivery along with capability to be used as contrast agent for MRI & CT. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis of iron oxides nanoparticles with very high saturation magnetization form TEA-Fe(III) complex via electrochemical deposition for supercapacitor applications

NASA Astrophysics Data System (ADS)

Elrouby, Mahmoud; Abdel-Mawgoud, A. M.; El-Rahman, Rehab Abd

2017-11-01

This work is devoted to the synthesis of magnetic iron oxides nanoparticles with very high saturation magnetization to be qualified for supercapacitor applications using, a simple electrodeposition technique. It is found that the electrochemical reduction process depends on concentration, temperature, deposition potential and the scan rate of potential. The nature of electrodeposition process has been characterized via voltammetric and chronoamperometric techniques. The morphology of the electrodeposits has been investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure and phase content of these investigated electrodeposits have been examined and calculated. The obtained iron oxides show a high saturation magnetization (Ms) of about 229 emu g-1. The data exhibited a relation between Ms of electrodeposited iron oxide and specific capacitance. This relation exhibits that the highest Ms value of electrodeposited iron oxides gives also highest specific capacitance of about 725 Fg-1. Moreover, the electrodeposited iron oxides exhibit a very good stability. The new characteristics of the electro synthesized iron oxides at our optimized conditions, strongly qualify them as a valuable material for high-performance supercapacitor applications.

Iron Oxide Deposition from Aqueous Solution and Iron Formations on Mars

NASA Technical Reports Server (NTRS)

Catling, David; Moore, Jeff

2000-01-01

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

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

PubMed

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

2014-03-01

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

Retinal iron homeostasis in health and disease

PubMed Central

Song, Delu; Dunaief, Joshua L.

2013-01-01

Iron is essential for life, but excess iron can be toxic. As a potent free radical creator, iron generates hydroxyl radicals leading to significant oxidative stress. Since iron is not excreted from the body, it accumulates with age in tissues, including the retina, predisposing to age-related oxidative insult. Both hereditary and acquired retinal diseases are associated with increased iron levels. For example, retinal degenerations have been found in hereditary iron overload disorders, like aceruloplasminemia, Friedreich's ataxia, and pantothenate kinase-associated neurodegeneration. Similarly, mice with targeted mutation of the iron exporter ceruloplasmin and its homolog hephaestin showed age-related retinal iron accumulation and retinal degeneration with features resembling human age-related macular degeneration (AMD). Post mortem AMD eyes have increased levels of iron in retina compared to age-matched healthy donors. Iron accumulation in AMD is likely to result, in part, from inflammation, hypoxia, and oxidative stress, all of which can cause iron dysregulation. Fortunately, it has been demonstrated by in vitro and in vivo studies that iron in the retinal pigment epithelium (RPE) and retina is chelatable. Iron chelation protects photoreceptors and retinal pigment epithelial cells (RPE) in a variety of mouse models. This has therapeutic potential for diminishing iron-induced oxidative damage to prevent or treat AMD. PMID:23825457

TRACE ELEMENT BINDING DURING STRUCTURAL TRANSFORMATION IN IRON OXIDES

EPA Science Inventory

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

New insights into ferritin synthesis and function highlight a link between iron homeostasis and oxidative stress in plants.

PubMed

Briat, Jean-Francois; Ravet, Karl; Arnaud, Nicolas; Duc, Céline; Boucherez, Jossia; Touraine, Brigitte; Cellier, Francoise; Gaymard, Frederic

2010-05-01

Iron is an essential element for both plant productivity and nutritional quality. Improving plant iron content was attempted through genetic engineering of plants overexpressing ferritins. However, both the roles of these proteins in plant physiology, and the mechanisms involved in the regulation of their expression are largely unknown. Although the structure of ferritins is highly conserved between plants and animals, their cellular localization differs. Furthermore, regulation of ferritin gene expression in response to iron excess occurs at the transcriptional level in plants, in contrast to animals which regulate ferritin expression at the translational level. In this review, an overview of our knowledge of bacterial and mammalian ferritin synthesis and functions is presented. Then the following will be reviewed: (a) the specific features of plant ferritins; (b) the regulation of their synthesis during development and in response to various environmental cues; and (c) their function in plant physiology, with special emphasis on the role that both bacterial and plant ferritins play during plant-bacteria interactions. Arabidopsis ferritins are encoded by a small nuclear gene family of four members which are differentially expressed. Recent results obtained by using this model plant enabled progress to be made in our understanding of the regulation of the synthesis and the in planta function of these various ferritins. Studies on plant ferritin functions and regulation of their synthesis revealed strong links between these proteins and protection against oxidative stress. In contrast, their putative iron-storage function to furnish iron during various development processes is unlikely to be essential. Ferritins, by buffering iron, exert a fine tuning of the quantity of metal required for metabolic purposes, and help plants to cope with adverse situations, the deleterious effects of which would be amplified if no system had evolved to take care of free reactive iron.

Exploring Microbial Iron Oxidation in Wetland Soils

NASA Astrophysics Data System (ADS)

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

2009-04-01

Iron is one of the most abundant elements on earth and is essential for life. Because of its importance, iron cycling and its interaction with other chemical and microbial processes has been the focus of many studies. Iron-oxidizing bacteria (FeOB) have been detected in a wide variety of environments. Among those is the rhizosphere of wetland plants roots which release oxygen into the soil creating suboxic conditions required by these organisms. It has been reported that in these rhizosphere microbial iron oxidation proceeds up to four orders of magnitude faster than strictly abiotic oxidation. On the roots of these wetland plants iron plaques are formed by microbial iron oxidation which are involved in the sequestering of heavy metals as well organic pollutants, which of great environmental significance.Despite their important role being catalysts of iron-cycling in wetland environments, little is known about the diversity and distribution of iron-oxidizing bacteria in various environments. This study aimed at developing a PCR-DGGE assay enabling the detection of iron oxidizers in wetland habitats. Gradient tubes were used to enrich iron-oxidizing bacteria. From these enrichments, a clone library was established based on the almost complete 16s rRNA gene using the universal bacterial primers 27f and 1492r. This clone library consisted of mainly α- and β-Proteobacteria, among which two major clusters were closely related to Gallionella spp. Specific probes and primers were developed on the basis of this 16S rRNA gene clone library. The newly designed Gallionella-specific 16S rRNA gene primer set 122f/998r was applied to community DNA obtained from three contrasting wetland environments, and the PCR products were used in denaturing gradient gel electrophoresis (DGGE) analysis. A second 16S rRNA gene clone library was constructed using the PCR products from one of our sampling sites amplified with the newly developed primer set 122f/998r. The cloned 16S rRNA gene sequences all represented novel culturable iron oxidizers most closely related to Gallionella spp. Based on their nucleotide sequences four groups could be identified, which were comparable to the DGGE banding pattern obtained before with the gradient tubes enrichments. The above mentioned nested PCR-DGGE method was used to study the distribution and community composition of Gallionella-like iron-oxidizing bacteria under the influence of plants species, soil depth, as well as season. Soil samples from Appels, Belgium, an intertidal, freshwater marsh known to hold intensive iron cycling, were taken from 5 different vegetation types in April, July and October 2007. Soil cores were sliced at 1-cm intervals and subjected to chemical and molecular analyses. The DGGE patterns showed that the community of iron-oxidizing bacteria differed with vegetation type, and sediment depth. Samples taken in autumn held lower diversity in Gallionella-related iron oxidizers than those sampled in spring and summer.

Modulation of estrogenic action in clear cell carcinoma of the ovary (Review)

PubMed Central

TANASE, YASUHITO; YAMADA, YOSHIHIKO; SHIGETOMI, HIROSHI; KAJIHARA, HIROTAKA; OONOGI, AKIRA; YOSHIZAWA, YORIKO; FURUKAWA, NAOTO; HARUTA, SHOJI; YOSHIDA, SHOZO; SADO, TOSHIYUKI; OI, HIDEKAZU; KOBAYASHI, HIROSHI

2012-01-01

Two histologic types, clear cell carcinoma (CCC) and endometrioid adenocarcinoma (EAC), are the common histology in ovarian cancer patients who have associated endometriosis. However, both tumor types have distinct clinicopathological characteristics and molecular phenotypes. EAC is predominantly positive for estrogen receptor (ER), but CCC specifically exhibits lower ER expression. This study reviews the current understanding of the role of the ER information in the pathogenesis of CCC, as well as the English language literature for biochemical studies on ER expression and estrogenic action in CCC. The iron-mediated oxidative stress occurs due to repeated hemorrhage in endometriosis, then this compound oxidatively modifies genomic DNA and, subsequently, ER depletion may be observed. There are a number of factors that interfere with ER expression and estrogen activity, which include DNA methylation of the promoter region, histone deacetylation, heme and iron binding, chromatin remodeling and ubiquitin ligase activity. Loss of estrogen function may be a turning point in CCC progression and aggressiveness. PMID:22969838

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

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

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

A general strategy toward graphitized carbon coating on iron oxides as advanced anodes for lithium-ion batteries.

PubMed

Ding, Chunyan; Zhou, Weiwei; Wang, Bin; Li, Xin; Wang, Dong; Zhang, Yong; Wen, Guangwu

2017-08-25

Integration of carbon materials with benign iron oxides is blazing a trail in constructing high-performance anodes for lithium-ion batteries (LIBs). In this paper, a unique general, simple, and controllable strategy is developed toward in situ uniform coating of iron oxide nanostructures with graphitized carbon (GrC) layers. The basic synthetic procedure only involves a simple dip-coating process for the loading of Ni-containing seeds and a subsequent Ni-catalyzed chemical vapor deposition (CVD) process for the growth of GrC layers. More importantly, the CVD treatment is conducted at a quite low temperature (450 °C) and with extremely facile liquid carbon sources consisting of ethylene glycol (EG) and ethanol (EA). The GrC content of the resulting hybrids can be controllably regulated by altering the amount of carbon sources. The electrochemical results reveal remarkable performance enhancements of iron oxide@GrC hybrids compared with pristine iron oxides in terms of high specific capacity, excellent rate and cycling performance. This can be attributed to the network-like GrC coating, which can improve not only the electronic conductivity but also the structural integrity of iron oxides. Moreover, the lithium storage performance of samples with different GrC contents is measured, manifesting that optimized electrochemical property can be achieved with appropriate carbon content. Additionally, the superiority of GrC coating is demonstrated by the advanced performance of iron oxide@GrC compared with its corresponding counterpart, i.e., iron oxides with amorphous carbon (AmC) coating. All these results indicate the as-proposed protocol of GrC coating may pave the way for iron oxides to be promising anodes for LIBs.

Enumeration and Characterization of Acidophilic Microorganisms Isolated from a Pilot Plant Stirred-Tank Bioleaching Operation

PubMed Central

Okibe, Naoko; Gericke, Mariekie; Hallberg, Kevin B.; Johnson, D. Barrie

2003-01-01

Microorganisms were enumerated and isolated on selective solid media from a pilot-scale stirred-tank bioleaching operation in which a polymetallic sulfide concentrate was subjected to biologically accelerated oxidation at 45°C. Four distinct prokaryotes were isolated: three bacteria (an Acidithiobacillus caldus-like organism, a thermophilic Leptospirillum sp., and a Sulfobacillus sp.) and one archaeon (a Ferroplasma-like isolate). The relative numbers of these prokaryotes changed in the three reactors sampled, and the Ferroplasma isolate became increasingly dominant as mineral oxidation progressed, eventually accounting for >99% of plate isolates in the third of three in-line reactors. The identities of the isolates were confirmed by analyses of their 16S rRNA genes, and some key physiological traits (e.g., oxidation of iron and/or sulfur and autotrophy or heterotrophy) were examined. More detailed studies were carried out with the Leptospirillum and Ferroplasma isolates. The data presented here represent the first quantitative study of the microorganisms in a metal leaching situation and confirm that mixed cultures of iron- and sulfur-oxidizing prokaryotic acidophiles catalyze the accelerated dissolution of sulfidic minerals in industrial tank bioleaching operations. The results show that indigenous acidophilic microbial populations change as mineral dissolution becomes more extensive. PMID:12676667

Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex

DOE PAGES

Hong, Seungwoo; Lu, Xiaoyan; Lee, Yong -Min; ...

2017-09-29

Here, a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [Fe V(NTs)(TAML)] – (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [Fe V(NTs)(TAML +•)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML +•). 2 is a competent oxidant in C–H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.

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

PubMed

Bonnefoy, Violaine; Holmes, David S

2012-07-01

This minireview presents recent advances in our understanding of iron oxidation and homeostasis in acidophilic Bacteria and Archaea. These processes influence the flux of metals and nutrients in pristine and man-made acidic environments such as acid mine drainage and industrial bioleaching operations. Acidophiles are also being studied to understand life in extreme conditions and their role in the generation of biomarkers used in the search for evidence of existing or past extra-terrestrial life. Iron oxidation in acidophiles is best understood in the model organism Acidithiobacillus ferrooxidans. However, recent functional genomic analysis of acidophiles is leading to a deeper appreciation of the diversity of acidophilic iron-oxidizing pathways. Although it is too early to paint a detailed picture of the role played by lateral gene transfer in the evolution of iron oxidation, emerging evidence tends to support the view that iron oxidation arose independently more than once in evolution. Acidic environments are generally rich in soluble iron and extreme acidophiles (e.g. the Leptospirillum genus) have considerably fewer iron uptake systems compared with neutrophiles. However, some acidophiles have been shown to grow as high as pH 6 and, in the case of the Acidithiobacillus genus, to have multiple iron uptake systems. This could be an adaption allowing them to respond to different iron concentrations via the use of a multiplicity of different siderophores. Both Leptospirillum spp. and Acidithiobacillus spp. are predicted to synthesize the acid stable citrate siderophore for Fe(III) uptake. In addition, both groups have predicted receptors for siderophores produced by other microorganisms, suggesting that competition for iron occurs influencing the ecophysiology of acidic environments. Little is known about the genetic regulation of iron oxidation and iron uptake in acidophiles, especially how the use of iron as an energy source is balanced with its need to take up iron for metabolism. It is anticipated that integrated and complex regulatory networks sensing different environmental signals, such as the energy source and/or the redox state of the cell as well as the oxygen availability, are involved. © 2011 Society for Applied Microbiology and Blackwell Publishing Ltd.

Single step, phase controlled, large scale synthesis of ferrimagnetic iron oxide polymorph nanoparticles by thermal plasma route and their rheological properties

NASA Astrophysics Data System (ADS)

Raut, Suyog A.; Mutadak, Pallavi R.; Kumar, Shiv; Kanhe, Nilesh S.; Huprikar, Sameer; Pol, Harshawardhan V.; Phase, Deodatta M.; Bhoraskar, Sudha V.; Mathe, Vikas L.

2018-03-01

In this paper we report single step large scale synthesis of highly crystalline iron oxide nanoparticles viz. magnetite (Fe3O4) and maghemite (γ-Fe2O3) via gas phase condensation process, where micron sized iron metal powder was used as a precursor. Selective phases of iron oxide were obtained by variation of gas flow rate of oxygen and hence partial pressure of oxygen inside the plasma reactor. Most of the particles were found to possesses average crystallite size of about 20-30 nm. The DC magnetization curves recorded indicate almost super-paramagnetic nature of the iron oxide magnetic nanoparticles. Further, iron oxide nanoparticles were analyzed using Raman spectroscopy, X-ray photoelectron spectroscopy and Mossbauer spectroscopy. In order to explore the feasibility of these nanoparticles for magnetic damper application, rheological studies have been carried out and compared with commercially available Carbonyl Iron (CI) particles. The nanoparticles obtained by thermal plasma route show improved dispersion which is useful for rheological applications.

Structural characterization, antibacterial and catalytic effect of iron oxide nanoparticles synthesised using the leaf extract of Cynometra ramiflora

NASA Astrophysics Data System (ADS)

Groiss, Silvia; Selvaraj, Raja; Varadavenkatesan, Thivaharan; Vinayagam, Ramesh

2017-01-01

In the present investigation, the leaf extract of Cynometra ramiflora was used to synthesize iron oxide nanoparticles. Within minutes of adding iron sulphate to the leaf extract, iron oxide nanoparticles were formed and thus, the method is very simple and fast. UV-VIS spectra showed the strong absorption band in the visible region. SEM images showed discrete spherical shaped particles and EDS spectra confirmed the iron and oxygen presence. The XRD results depicted the crystalline structure of iron oxide nanoparticles. FT-IR spectra portrayed the existence of functional groups of phytochemicals which are probably involved in the formation and stabilization of nanoparticles. The iron oxide nanoparticles exhibited effective inhibition against E. coli and S. epidermidis which may find its applications in the antibacterial drug development. Furthermore, the catalytic activity of the nanoparticles as Fenton-like catalyst was successfully investigated for the degradation of Rhodamine-B dye. This outcome could play a prominent role in the wastewater treatment.

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

PubMed Central

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

2015-01-01

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

Oceanic nickel depletion and a methanogen famine before the Great Oxidation Event.

PubMed

Konhauser, Kurt O; Pecoits, Ernesto; Lalonde, Stefan V; Papineau, Dominic; Nisbet, Euan G; Barley, Mark E; Arndt, Nicholas T; Zahnle, Kevin; Kamber, Balz S

2009-04-09

It has been suggested that a decrease in atmospheric methane levels triggered the progressive rise of atmospheric oxygen, the so-called Great Oxidation Event, about 2.4 Gyr ago. Oxidative weathering of terrestrial sulphides, increased oceanic sulphate, and the ecological success of sulphate-reducing microorganisms over methanogens has been proposed as a possible cause for the methane collapse, but this explanation is difficult to reconcile with the rock record. Banded iron formations preserve a history of Precambrian oceanic elemental abundance and can provide insights into our understanding of early microbial life and its influence on the evolution of the Earth system. Here we report a decline in the molar nickel to iron ratio recorded in banded iron formations about 2.7 Gyr ago, which we attribute to a reduced flux of nickel to the oceans, a consequence of cooling upper-mantle temperatures and decreased eruption of nickel-rich ultramafic rocks at the time. We measured nickel partition coefficients between simulated Precambrian sea water and diverse iron hydroxides, and subsequently determined that dissolved nickel concentrations may have reached approximately 400 nM throughout much of the Archaean eon, but dropped below approximately 200 nM by 2.5 Gyr ago and to modern day values ( approximately 9 nM) by approximately 550 Myr ago. Nickel is a key metal cofactor in several enzymes of methanogens and we propose that its decline would have stifled their activity in the ancient oceans and disrupted the supply of biogenic methane. A decline in biogenic methane production therefore could have occurred before increasing environmental oxygenation and not necessarily be related to it. The enzymatic reliance of methanogens on a diminishing supply of volcanic nickel links mantle evolution to the redox state of the atmosphere.

A method for recovery of iron, titanium, and vanadium from vanadium-bearing titanomagnetite

NASA Astrophysics Data System (ADS)

Zhang, Yi-min; Wang, Li-na; Chen, De-sheng; Wang, Wei-jing; Liu, Ya-hui; Zhao, Hong-xin; Qi, Tao

2018-02-01

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures: low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

Effect of oxidative stress induced by intracranial iron overload on central pain after spinal cord injury.

PubMed

Meng, Fan Xing; Hou, Jing Ming; Sun, Tian Sheng

2017-02-08

Central pain (CP) is a common clinical problem in patients with spinal cord injury (SCI). Recent studies found the pathogenesis of CP was related to the remodeling of the brain. We investigate the roles of iron overload and subsequent oxidative stress in the remodeling of the brain after SCI. We established a rat model of central pain after SCI. Rats were divided randomly into four groups: SCI, sham operation, SCI plus deferoxamine (DFX) intervention, and SCI plus nitric oxide synthase (NOS) inhibitor treatment. Pain behavior was observed and thermal pain threshold was measured regularly, and brain levels of iron, transferrin receptor 1 (TfR1), ferritin (Fn), and lactoferrin (Lf), were detected in the different groups 12 weeks after establishment of the model. Rats demonstrated self-biting behavior after SCI. Furthermore, the latent period of thermal pain was reduced and iron levels in the hind limb sensory area, hippocampus, and thalamus increased after SCI. Iron-regulatory protein (IRP) 1 levels increased in the hind limb sensory area, while Fn levels decreased. TfR1 mRNA levels were also increased and oxidative stress was activated. Oxidative stress could be inhibited by ferric iron chelators and NOS inhibitors. SCI may cause intracranial iron overload through the NOS-iron-responsive element/IRP pathway, resulting in central pain mediated by the oxidative stress response. Iron chelators and oxidative stress inhibitors can effectively relieve SCI-associated central pain.

A modular continuous flow reactor system for the selective bio-oxidation of iron and precipitation of schwertmannite from mine-impacted waters.

PubMed

Hedrich, Sabrina; Johnson, D Barrie

2012-02-01

A novel modular bioremediation system which facilitates the selective removal of soluble iron from extremely acidic (pH ∼2) metal-rich wastewaters by ferrous iron oxidation and selective precipitation of the ferric iron produced is described. In the first of the three modules, rapid ferrous iron oxidation was mediated by the recently-characterized iron-oxidizing autotrophic acidophile, "Ferrovum myxofaciens", which grew as long "streamers" within the reactor. Over 90% of the iron present in influent test liquors containing 280mg/L iron was oxidized at a dilution rate of 0.41h(-1), in a proton-consuming reaction. The ferric iron-rich solutions produced were pumped into a second reactor where controlled addition of sodium hydroxide caused the water pH to increase to 3.5 and ferric iron to precipitate as the mineral schwertmannite. Addition of a flocculating agent promoted rapid aggregation and settling of the fine-grain schwertmannite particles. A third passive module (a packed-bed bioreactor, also inoculated with "Fv. myxofaciens") acted as a polishing reactor, lowering soluble iron concentrations in the processed water to <1mg/L. The system was highly effective in selectively removing iron from a synthetic acidic (pH 2.1) mine water that contained soluble aluminum, copper, manganese and zinc in addition to iron. Schwertmannite was again produced, with little or no co-precipitation of other metals. Copyright © 2011 Elsevier Ltd. All rights reserved.

Iron behaving badly: inappropriate iron chelation as a major contributor to the aetiology of vascular and other progressive inflammatory and degenerative diseases

PubMed Central

Kell, Douglas B

2009-01-01

Background The production of peroxide and superoxide is an inevitable consequence of aerobic metabolism, and while these particular 'reactive oxygen species' (ROSs) can exhibit a number of biological effects, they are not of themselves excessively reactive and thus they are not especially damaging at physiological concentrations. However, their reactions with poorly liganded iron species can lead to the catalytic production of the very reactive and dangerous hydroxyl radical, which is exceptionally damaging, and a major cause of chronic inflammation. Review We review the considerable and wide-ranging evidence for the involvement of this combination of (su)peroxide and poorly liganded iron in a large number of physiological and indeed pathological processes and inflammatory disorders, especially those involving the progressive degradation of cellular and organismal performance. These diseases share a great many similarities and thus might be considered to have a common cause (i.e. iron-catalysed free radical and especially hydroxyl radical generation). The studies reviewed include those focused on a series of cardiovascular, metabolic and neurological diseases, where iron can be found at the sites of plaques and lesions, as well as studies showing the significance of iron to aging and longevity. The effective chelation of iron by natural or synthetic ligands is thus of major physiological (and potentially therapeutic) importance. As systems properties, we need to recognise that physiological observables have multiple molecular causes, and studying them in isolation leads to inconsistent patterns of apparent causality when it is the simultaneous combination of multiple factors that is responsible. This explains, for instance, the decidedly mixed effects of antioxidants that have been observed, since in some circumstances (especially the presence of poorly liganded iron) molecules that are nominally antioxidants can actually act as pro-oxidants. The reduction of redox stress thus requires suitable levels of both antioxidants and effective iron chelators. Some polyphenolic antioxidants may serve both roles. Understanding the exact speciation and liganding of iron in all its states is thus crucial to separating its various pro- and anti-inflammatory activities. Redox stress, innate immunity and pro- (and some anti-)inflammatory cytokines are linked in particular via signalling pathways involving NF-kappaB and p38, with the oxidative roles of iron here seemingly involved upstream of the IkappaB kinase (IKK) reaction. In a number of cases it is possible to identify mechanisms by which ROSs and poorly liganded iron act synergistically and autocatalytically, leading to 'runaway' reactions that are hard to control unless one tackles multiple sites of action simultaneously. Some molecules such as statins and erythropoietin, not traditionally associated with anti-inflammatory activity, do indeed have 'pleiotropic' anti-inflammatory effects that may be of benefit here. Conclusion Overall we argue, by synthesising a widely dispersed literature, that the role of poorly liganded iron has been rather underappreciated in the past, and that in combination with peroxide and superoxide its activity underpins the behaviour of a great many physiological processes that degrade over time. Understanding these requires an integrative, systems-level approach that may lead to novel therapeutic targets. PMID:19133145

The nanophase iron mineral(s) in Mars soil

NASA Technical Reports Server (NTRS)

Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

1993-01-01

A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.

Nanoscale oxidation and complex oxide growth on single crystal iron surfaces and external electric field effects.

PubMed

Jeon, Byoungseon; Van Overmeere, Quentin; van Duin, Adri C T; Ramanathan, Shriram

2013-02-14

Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.

NGP1-01, a multi-targeted polycyclic cage amine, attenuates brain endothelial cell death in iron overload conditions.

PubMed

Lockman, J A; Geldenhuys, W J; Jones-Higgins, M R; Patrick, J D; Allen, D D; Van der Schyf, C J

2012-12-13

Development and progression of neurodegenerative disorders have, amongst other potential causes, been attributed to a disruption of iron regulatory mechanisms and iron accumulation. Excess extracellular iron may enter cells via nontraditional routes such as voltage-gated calcium channels and N-methyl-d-aspartate (NMDA) receptors leading to intracellular oxidative damage and ultimately mitochondrial failure. Nimodipine, an L-type calcium channel blocker has been shown to reduce iron-induced toxicity in neuronal and brain endothelial cells. Our current study investigates NGP1-01, a multimodal drug acting as an antagonist at both the NMDA receptor and the L-type calcium channel. Our previous studies support NGP1-01 as a promising neuroprotective agent in diseases involving calcium-related excitotoxicity. We demonstrate here that NGP1-01 (1 and 10μM) pretreatment abrogates the effects of iron overload in brain endothelial cells protecting cellular viability. Both concentrations of NGP1-01 were found to attenuate iron-induced reduction in cellular viability to a similar extent, and were statistically significant. To further verify the mechanism, the L-type calcium channel agonist FPL 64176 was administered to promote iron uptake. Addition of NGP1-01 dose-dependently reduced FPL 64176 stimulated uptake of iron. These data support further evaluation of NGP1-01 as a neuroprotective agent, not only in diseases associated with excitotoxicity, but also in those of iron overload. Copyright © 2012 Elsevier B.V. All rights reserved.

Characterization of tetraethylene glycol passivated iron nanoparticles

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

Phenolic Wastewater Treatment Alternatives.

DTIC Science & Technology

1980-06-01

15 Potassium Permanganate ................ 19 Iron (VI) Ferrate ..................... 22 Catalytic Oxidation ..................... 22...carbon dioxide, potassium hydroxide, and manganese dioxide which were readily handled by the existing system. d. Iron (VI) Ferrate Ferrate is iron in...the following systems/processes: Granular Activated Carbon (GAC) adsorption, ozone oxidation, hydrogen peroxide oxidation, potassium permanganate

Prediction of iron oxide contents using diffuse reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Marques, José, Jr.; Arantes Camargo, Livia

2015-04-01

Determining soil iron oxides using conventional analysis is relatively unfeasible when large areas are mapped, with the aim of characterizing spatial variability. Diffuse reflectance spectroscopy (DRS) is rapid, less expensive, non-destructive and sometimes more accurate than conventional analysis. Furthermore, this technique allows the simultaneous characterization of many soil attributes with agronomic and environmental relevance. This study aims to assess the DRS capability to predict iron oxides content -hematite and goethite - , characterizing their spatial variability in soils of Brazil. Soil samples collected from an 800-hectare area were scanned in the visible and near-infrared spectral range. Moreover, chemometric calibration was obtained through partial least-squares regression (PLSR). Then, spatial distribution maps of the attributes were constructed using predicted values from calibrated models through geostatistical methods. The studied area presented soils with varied contents of iron oxides as examples for the Oxisols and Entisols. In the spectra of each soil is observed that the reflectance decreases with the content of iron oxides present in the soil. In soils with a high content of iron oxides can be observed more pronounced concavities between 380 and 1100 nm which are characteristic of the presence of these oxides. In soils with higher reflectance it were observed concavity characteristics due to the presence of kaolinite, in agreement with the low iron contents of those soils. The best accuracy of prediction models [residual prediction deviation (RPD) = 1.7] was obtained for goethite within the visible region (380-800 nm), and for hematite (RPD = 2.0) within the visible near infrared (380-2300 nm). The maps of goethite and hematite predicted showed the spatial distribution pattern similar to the maps of clay and iron extracted by dithionite-citrate-bicarbonate, being consistent with the iron oxide contents of soils present in the study area. These results confirm the value of DRS in the mapping of iron oxides in large areas at detailed scale.

Modulation of the antioxidative response of Spartina densiflora against iron exposure.

PubMed

Martínez Domínguez, David; Torronteras Santiago, Rafael; Córdoba García, Francisco

2009-06-01

Spartina densiflora, an invader cordgrass living in polluted salt marshes of the Odiel estuary (SW Spain), was collected and cultured under controlled laboratory conditions. After acclimation to non-polluted soils for 28 days, both metabolites and enzymes activities used as indicators of oxidative stress were reduced significantly. Then, plants were exposed to 500 and 1000 ppm Fe-ethylenediamine-N,N'-2-hydroxyphenyl acetic acid (EDDHA) for 28 days. Our data demonstrate that iron content in leaves was enhanced by iron exposure. This iron increase caused an enhancement in the concentration of H2O2, hydroperoxides and lipid peroxidation, and a decrease in chlorophyll levels. Thus, iron exposure led to oxidative stress conditions. However, oxidative indicators stabilised after first 2 weeks of exposure, although the highest iron levels in leaves were reached at the end of treatments. Iron exposure induced an enhancement of catalase, ascorbate peroxidase and guaiacol peroxidase activities, together with an increase in total and oxidised ascorbate. This response may be defensive against oxidative stress and thus help to explain why cell oxidative damages were stabilised. Thus, by using a sensitive long-time protocol, iron-dependent oxidative damages may be controlled and even reverted successfully by the activation of the antioxidative defences of S. densiflora. This efficient antioxidative system, rapidly modulated in response to excess iron and other environmental stressors, may account for S. densiflora's successful adaptation to stress conditions in its habitat.

Impact of iron and vitamin C-containing supplements on preterm human milk: in vitro.

PubMed

Friel, James K; Diehl-Jones, William L; Suh, Miyoung; Tsopmo, Apollinaire; Shirwadkar, Vaibhav P

2007-05-15

Stress due to reactive oxygen species (ROS) may lead to neonatal diseases, such as necrotizing enterocolitis and respiratory distress. Enteral supplements for premature infants (PREM) added to human milk (HM) to increase nutrient content may induce lipid oxidation due to free radical formation via Fenton chemistry. We hypothesized that ferrous iron and vitamin C-containing supplements added to HM in vitro cause oxidation of milk fats, affect intracellular redox balance, and induce DNA damage. Lipid peroxidation in HM was measured by FOX-2 and TBARS assays; fatty acid composition of supplemented HM was measured by gas chromatography. Two cell culture bioassays were used for assessing either intracellular oxidative stress or DNA damage: the former involved Caco-2BBe cells, a secondary differentiated cell line, and the latter utilized FHS-74 Int cells, a primary fetal small intestinal culture. Lipid oxidation products of HM increased after the addition of iron alone, iron and vitamin C, or iron and a vitamin C-containing supplement (Trivisol, TVS). A reduced content of mono and polyunsaturated fatty acids in HM was also observed. Iron, not iron+vitamin C, but iron+TVS induced significant intracellular oxidative stress in FHS-74 Int cells. In contrast, iron, either alone or in combination with TVS or vitamin C, increased DNA damage in Caco-2BBE cells. Iron supplementation may increase oxidative stress in PREM infants and should be given separately from vitamin C-containing supplements.

Isolation of iron bacteria from terrestrial and aquatic environments

NASA Astrophysics Data System (ADS)

Schmidt, Bertram; Szewzyk, Ulrich

2010-05-01

Bacteria, which are capable of iron oxidation or at least iron deposition are widely distributed in environments where zones of dissolved ferrous iron and oxygen gradients are overlapping [1]. They take part in the biological cycling of iron and influence other cycles of elements for example carbon [2]. Manganese can be used for similar metabolic purposes as iron, because it can be biologically oxidized by chemolithotrophs or can be reduced by respirating bacteria as well [3, 4]. Bacterial activity is responsible for the accumulation of ferric iron compounds in their surroundings. The formation of bog ore is a well known example for a soil horizon, with an extreme enrichment of biogenic ferric iron [5]. We focused on the isolation of neutrophilic iron bacteria and bacteria capable of manganese oxidation. We used samples from Tierra del Fuego (Argentina) the National Park "Unteres Odertal" (Germany) and Berlin ground water wells. Microscopic examination of the samples revealed a considerable diversity of iron encrusted structures of bacterial origin. Most of these morphologic types are already well known. The taxonomic classification of many of these organisms is based on morphologic features and is not reliable compared to recent methods of molecular biology. That is mainly due to the fact, that most of these bacteria are hardly culturable or do not show their characteristic morphologic features under culture conditions. We established a collection of more than 300 iron depositing strains. Phylogenetic analyses showed that we have many yet uncultured strains in pure culture. We obtained many isolates which form distinct branches within long known iron bacteria groups like the Sphaerotilus-Leptothrix cluster. But some of the strains belong to groups, which have not yet been associated with iron oxidation activity. The strains deposit high amounts of oxidized iron and manganese compounds under laboratory conditions. However it is unclear if these precipitations are due to biological oxidation or biological deposition of chemically oxidized iron. We examined the morphologic characteristics of selected isolates under near-natural conditions to assign them to morphologic structures which occur in native samples. Our aim for the future is to describe several strains. References: [1] Weber, K. A. ; Achenbach, L. A. ; Coates, J. D. : Microorganisms pumping iron: anaerobic microbial iron oxidation and reduction. In: Nature Reviews Microbiology 4 (2006) 752-764 [2] Van Capellen, P. ; Wang Y. : Cycling of iron and manganese in surface sediments: a general theory for the coupled transport and reaction of carbon, oxygen, nitrogen, sulfur, iron and manganese. In: American Journal of Science 296 (1996) 197-243 [3] Tebo, B. M. ; Bargar, J. R. ; Clement, B. G. ; Dick, G. J. ; Murray, K. J. ; Parker, D. Verity R. ; Webb, S. M. : Biogenic manganese oxides: properties and mechanisms of formation. In: Annual Reviews Earth Planet Science 32 (2004) 287-328 [4] Erlich, H. L. : Manganese oxide reduction as a form of anaerobic respiration. In: Geomicrobiology Journal 5 (1987) 423-431 [5] Ghiorse W. C. : Biology of iron- and manganese-depositing bacteria. In: Annual Reviews 38 (1984) 515-550

Arsenic mobilization and immobilization in paddy soils

NASA Astrophysics Data System (ADS)

Kappler, A.; Hohmann, C.; Zhu, Y. G.; Morin, G.

2010-05-01

Arsenic is oftentimes of geogenic origin and in many cases bound to iron(III) minerals. Iron(III)-reducing bacteria can harvest energy by coupling the oxidation of organic or inorganic electron donors to the reduction of Fe(III). This process leads either to dissolution of Fe(III)-containing minerals and thus to a release of the arsenic into the environment or to secondary Fe-mineral formation and immobilisation of arsenic. Additionally, aerobic and anaerobic iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II) oxidation at neutral pH that is usually followed by iron(III) mineral precipitation. We are currently investigating arsenic immobilization by Fe(III)-reducing bacteria and arsenic co-precipitation and immobilization by anaerobic iron(II)-oxidizing bacteria in batch, microcosm and rice pot experiments. Co-precipitation batch experiments with pure cultures of nitrate-dependent Fe(II)-oxidizing bacteria are used to quantify the amount of arsenic that can be immobilized during microbial iron mineral precipitation, to identify the minerals formed and to analyze the arsenic binding environment in the precipitates. Microcosm and rice pot experiments are set-up with arsenic-contaminated rice paddy soil. The microorganisms (either the native microbial population or the soil amended with the nitrate-dependent iron(II)-oxidizing Acidovorax sp. strain BoFeN1) are stimulated either with iron(II), nitrate, or oxygen. Dissolved and solid-phase arsenic and iron are quantified. Iron and arsenic speciation and redox state in batch and microcosm experiments are determined by LC-ICP-MS and synchrotron-based methods (EXAFS, XANES).

Bmp6 Regulates Retinal Iron Homeostasis and Has Altered Expression in Age-Related Macular Degeneration

PubMed Central

Hadziahmetovic, Majda; Song, Ying; Wolkow, Natalie; Iacovelli, Jared; Kautz, Leon; Roth, Marie-Paule; Dunaief, Joshua L.

2011-01-01

Iron-induced oxidative stress causes hereditary macular degeneration in patients with aceruloplasminemia. Similarly, retinal iron accumulation in age-related macular degeneration (AMD) may exacerbate the disease. The cause of retinal iron accumulation in AMD is poorly understood. Given that bone morphogenetic protein 6 (Bmp6) is a major regulator of systemic iron, we examined the role of Bmp6 in retinal iron regulation and in AMD pathogenesis. Bmp6 was detected in the retinal pigment epithelium (RPE), a major site of pathology in AMD. In cultured RPE cells, Bmp6 was down-regulated by oxidative stress and up-regulated by iron. Intraocular Bmp6 protein injection in mice up-regulated retinal hepcidin, an iron regulatory hormone, and altered retinal labile iron levels. Bmp6−/− mice had age-dependent retinal iron accumulation and degeneration. Postmortem RPE from patients with early AMD exhibited decreased Bmp6 levels. Because oxidative stress is associated with AMD pathogenesis and down-regulates Bmp6 in cultured RPE cells, the diminished Bmp6 levels observed in RPE cells in early AMD may contribute to iron build-up in AMD. This may in turn propagate a vicious cycle of oxidative stress and iron accumulation, exacerbating AMD and other diseases with hereditary or acquired iron excess. PMID:21703414

21 CFR 73.1200 - Synthetic iron oxide.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

21 CFR 73.1200 - Synthetic iron oxide.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

21 CFR 73.1200 - Synthetic iron oxide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

21 CFR 73.1200 - Synthetic iron oxide.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally...

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally...

Optimizing the Binding Energy of the Surfactant to Iron Oxide Yields Truly Monodisperse Nanoparticles.

PubMed

Sharifi Dehsari, Hamed; Harris, Richard Anthony; Ribeiro, Anielen Halda; Tremel, Wolfgang; Asadi, Kamal

2018-06-05

Despite the great progress in the synthesis of iron oxide nanoparticles (NPs) using a thermal decomposition method, the production of NPs with low polydispersity index is still challenging. In a thermal decomposition synthesis, oleic acid (OAC) and oleylamine (OAM) are used as surfactants. The surfactants bind to the growth species, thereby controlling the reaction kinetics and hence playing a critical role in the final size and size distribution of the NPs. Finding an optimum molar ratio between the surfactants oleic OAC/OAM is therefore crucial. A systematic experimental and theoretical study, however, on the role of the surfactant ratio is still missing. Here, we present a detailed experimental study on the role of the surfactant ratio in size distribution. We found an optimum OAC/OAM ratio of 3 at which the synthesis yielded truly monodisperse (polydispersity less than 7%) iron oxide NPs without employing any post synthesis size-selective procedures. We performed molecular dynamics simulations and showed that the binding energy of oleate to the NP is maximized at an OAC/OAM ratio of 3. The optimum OAC/OAM ratio of 3 is allowed for the control of the NP size with nanometer precision by simply changing the reaction heating rate. The optimum OAC/OAM ratio has no influence on the crystallinity and the superparamagnetic behavior of the Fe 3 O 4 NPs and therefore can be adopted for the scaled-up production of size-controlled monodisperse Fe 3 O 4 NPs.

Impact of Microcystis aeruginosa Exudate on the Formation and Reactivity of Iron Oxide Particles Following Fe(II) and Fe(III) Addition.

PubMed

Garg, Shikha; Wang, Kai; Waite, T David

2017-05-16

Impact of the organic exudate secreted by a toxic strain of Microcystis aeruginosa on the formation, aggregation, and reactivity of iron oxides that are formed on addition of Fe(II) and Fe(III) salts to a solution of the exudate is investigated in this study. The exudate has a stabilizing effect on the particles formed with decreased aggregation rate and increased critical coagulant concentration required for diffusion-limited aggregation to occur. These results suggest that the presence of algal exudates from Microcystis aeruginosa may significantly influence particle aggregation both in natural water bodies where Fe(II) oxidation results in oxide formation and in water treatment where Fe(III) salts are commonly added to aid particle growth and contaminant capture. The exudate also affects the reactivity of iron oxide particles formed with exudate coated particles undergoing faster dissolution than bare iron oxide particles. This has implications to iron availability, especially where algae procure iron via dissolution of iron oxide particles as a result of either reaction with reducing moieties, light-mediated ligand to metal charge transfer and/or reaction with siderophores. The increased reactivity of exudate coated particles is attributed, for the most part, to the smaller size of these particles, higher surface area and increased accessibility of surface sites.

Terrestrial Fe-oxide Concretions and Mars Blueberries: Comparisons of Similar Advective and Diffusive Chemical Infiltration Reaction Mechanisms

NASA Astrophysics Data System (ADS)

Park, A. J.; Chan, M. A.

2006-12-01

Abundant iron oxide concretions occurring in Navajo Sandstone of southern Utah and those discovered at Meridiani Planum, Mars share many common observable physical traits such as their spheriodal shapes, occurrence, and distribution patterns in sediments. Terrestrial concretions are products of interaction between oxygen-rich aquifer water and basin-derived reducing (iron-rich) water. Water-rock interaction simulations show that diffusion of oxygen and iron supplied by slow-moving water is a reasonable mechanism for producing observed concretion patterns. In short, southern Utah iron oxide concretions are results of Liesegang-type diffusive infiltration reactions in sediments. We propose that the formation of blueberry hematite concretions in Mars sediments followed a similar diagenetic mechanism where iron was derived from the alteration of volcanic substrate and oxygen was provided by the early Martian atmosphere. Although the terrestrial analog differs in the original host rock composition, both the terrestrial and Mars iron-oxide precipitation mechanisms utilize iron and oxygen interactions in sedimentary host rock with diffusive infiltration of solutes from two opposite sources. For the terrestrial model, slow advection of iron-rich water is an important factor that allowed pervasive and in places massive precipitation of iron-oxide concretions. In Mars, evaporative flux of water at the top of the sediment column may have produced a slow advective mass-transfer mechanism that provided a steady source and the right quantity of iron. The similarities of the terrestrial and Martian systems are demonstrated using a water-rock interaction simulator Sym.8, initially in one-dimensional systems. Boundary conditions such as oxygen content of water, partial pressure of oxygen, and supply rate of iron were varied. The results demonstrate the importance of slow advection of water and diffusive processes for producing diagenetic iron oxide concretions.

Interaction of fluorescent sensor with superparamagnetic iron oxide nanoparticles.

PubMed

Karunakaran, Chockalingam; Jayabharathi, Jayaraman; Sathishkumar, Ramalingam; Jayamoorthy, Karunamoorthy

2013-06-01

To sense superparamagnetic iron oxides (Fe2O3 and Fe3O4) nanocrystals a sensitive bioactive phenanthroimidazole based fluorescent molecule, 2-(4-fluorophenyl)-1-phenyl-1H-phenanthro [9,10-d] imidazole has been designed and synthesized. Electronic spectral studies show that phenanthroimidazole is bound to the surface of iron oxide semiconductors. Fluorescent enhancement has been explained on the basis of photo-induced electron transfer (PET) mechanism and apparent binding constants have been deduced. Binding of phenanthroimidazole with iron oxide nanoparticles lowers the HOMO and LUMO energy levels of phenanthroimidazole molecule. Chemical affinity between the nitrogen atom of the phenanthroimidazole and Fe(2+) and Fe(3+) ions on the surface of the nano-oxide may result in strong binding of the phenanthroimidazole derivative with the nanoparticles. The electron injection from the photoexcited phenanthroimidazole to the iron oxides conduction band explains the enhanced fluorescence. Copyright © 2013 Elsevier B.V. All rights reserved.

Magnetite-hematite transformation: correlation between natural and synthetic features

NASA Astrophysics Data System (ADS)

Barbosa, Paola F.; Lagoeiro, Leonardo; Scholz, Ricardo; Graça, Leonardo M.; Mohallem, Nelcy

2015-06-01

The iron-oxide system can be used as a marker of oxidized and reduced conditions in closed systems. However, natural rocks with iron oxide minerals also exhibit such reactions, although the natural system is typically open. To understand the behaviour of this natural system, some similarities were investigated, in terms of crystallographic textures, between the microstructures of two systems: natural open system and synthetic closed system of iron oxide phase transformation. Particular cases of phase transformation in iron oxide minerals, described as natural reactions of magnetite to hematite and synthetic reactions of hematite to magnetite, were chosen. It is observed, in both scenarios, that the transformation obeys the topotaxial and epitaxial relationship, which are well described for the iron oxide system. However, in natural open systems, the precipitation of a new phase during the in situ transformation modifies the microstructures and must be taken into account as an important factor to describe them.

Ferroxidase-Mediated Iron Oxide Biomineralization: Novel Pathways to Multifunctional Nanoparticles.

PubMed

Zeth, Kornelius; Hoiczyk, Egbert; Okuda, Mitsuhiro

2016-02-01

Iron oxide biomineralization occurs in all living organisms and typically involves protein compartments ranging from 5 to 100nm in size. The smallest iron-oxo particles are formed inside dodecameric Dps protein cages, while the structurally related ferritin compartments consist of twice as many identical protein subunits. The largest known compartments are encapsulins, icosahedra made of up to 180 protein subunits that harbor additional ferritin-like proteins in their interior. The formation of iron-oxo particles in all these compartments requires a series of steps including recruitment of iron, translocation, oxidation, nucleation, and storage, that are mediated by ferroxidase centers. Thus, compartmentalized iron oxide biomineralization yields uniform nanoparticles strictly determined by the sizes of the compartments, allowing customization for highly diverse nanotechnological applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Oxidative Stress and the Homeodynamics of Iron Metabolism

PubMed Central

Bresgen, Nikolaus; Eckl, Peter M.

2015-01-01

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

Gene identification and substrate regulation provide insights into sulfur accumulation during bioleaching with the psychrotolerant acidophile Acidithiobacillus ferrivorans.

PubMed

Liljeqvist, Maria; Rzhepishevska, Olena I; Dopson, Mark

2013-02-01

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

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

PubMed Central

Liljeqvist, Maria; Rzhepishevska, Olena I.

2013-01-01

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

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

PubMed Central

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

1972-01-01

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

Gold and gold-iron oxide magnetic glyconanoparticles: synthesis, characterization and magnetic properties.

PubMed

de la Fuente, Jesús M; Alcántara, David; Eaton, Peter; Crespo, Patricia; Rojas, Teresa C; Fernandez, Asunción; Hernando, Antonio; Penadés, Soledad

2006-07-06

The preparation, characterization and the magnetic properties of gold and gold-iron oxide glyconanoparticles (GNPs) are described. Glyconanoparticles were prepared in a single step procedure in the presence of aqueous solution of thiol functionalized neoglycoconjugates and either gold salts or both gold and iron salts. Neoglycoconjugates of lactose and maltose disaccharides with different linkers were used. Iron-free gold or gold-iron oxide GNPs with controlled gold-iron ratios were obtained. The average core-size diameters are in the range of 1.5-2.5 nm. The GNPs are fully characterized by (1)H NMR spectrometry, transmission electron microscopy (TEM), and UV-vis and X-ray absorption (XAS) spectroscopies. Inductive plasma-atomic emission spectrometry (ICP) and elemental analysis gave the average number of neoglycoconjugates per cluster. The magnetic properties were measured in a SQUID magnetometer. The most remarkable results was the observation of a permanent magnetism up to room temperature in the iron-free gold GNPs, that was not present in the corresponding gold-iron oxide GNPs.

Toward a Mechanistic Understanding of Anaerobic Nitrate-Dependent Iron Oxidation: Balancing Electron Uptake and Detoxification

PubMed Central

Carlson, Hans K.; Clark, Iain C.; Melnyk, Ryan A.; Coates, John D.

2011-01-01

The anaerobic oxidation of Fe(II) by subsurface microorganisms is an important part of biogeochemical cycling in the environment, but the biochemical mechanisms used to couple iron oxidation to nitrate respiration are not well understood. Based on our own work and the evidence available in the literature, we propose a mechanistic model for anaerobic nitrate-dependent iron oxidation. We suggest that anaerobic iron-oxidizing microorganisms likely exist along a continuum including: (1) bacteria that inadvertently oxidize Fe(II) by abiotic or biotic reactions with enzymes or chemical intermediates in their metabolic pathways (e.g., denitrification) and suffer from toxicity or energetic penalty, (2) Fe(II) tolerant bacteria that gain little or no growth benefit from iron oxidation but can manage the toxic reactions, and (3) bacteria that efficiently accept electrons from Fe(II) to gain a growth advantage while preventing or mitigating the toxic reactions. Predictions of the proposed model are highlighted and experimental approaches are discussed. PMID:22363331

Evaluation of the effect of sulfate, alkalinity and disinfector on iron release of iron pipe and iron corrosion scale characteristics under water quality changing condition using response surface methodology

NASA Astrophysics Data System (ADS)

Yang, Fan; Shi, Baoyou; Zhang, Weiyu; Guo, Jianbo; Wu, Nana; Liu, Xinyuan

2018-02-01

The response surface methodology (RSM), particularly Box-Behnken design model, was used in this study to evaluate the sulfate, alkalinity and free chlorine on iron release of pipe with groundwater supply history and its iron corrosion scale characteristics under water quality changing experiment. The RSM results together with response surface contour plots indicated that the iron release of pipe section reactors was positively related with Larson Ratio and free chlorine. The thin Corrosion scales with groundwater supply history upon collection site contained Fe3O4 (18%), α-FeOOH (64%), FeCO3 (9%), β-FeOOH (8%) and γ-FeOOH (5%), besides their averaged amorphous iron oxide content was 13.6%. After the RSM water quality changing experiment, Fe3O4, amorphous iron oxide and intermediate iron products (FeCO3, Green Rust (GR)) content on scale of Cl2Rs increased, while their α-FeOOH contents decreased and β-FeOOH disappeared. The high iron released Cl2Rs receiving higher LR water (1.40-2.04) contained highest FeCO3 (20%) and amorphous iron oxide (42%), while the low iron release Cl2Rs receiving lower LR water (0.52-0.73) had higher GR(6.5%) and the amorphous iron oxide (23.7%). In high LR water (>0.73), the thin and non-protective corrosion scale containing higher amorphous iron oxide, Fe(II) derived from new produced Fe3O4 or FeCO3 or GR was easy for oxidants and sulfate ions penetration, and had higher iron release. However the same unstable corrosion scale didn’t have much iron release in low LR water (≤0.73). RSM experiment indicated that iron release of these unstable corrosion scales had close relationship with water quality (Larson Ratio and disinfectant). Optimizing the water quality of new source water and using reasonable water purification measures can help to eliminate the red water case.

Arsenic Mobilization Influenced By Iron Reduction And Sulfidogenesis Under Dynamic Flow

NASA Astrophysics Data System (ADS)

Kocar, B. D.; Stewart, B. D.; Herbel, M.; Fendorf, S.

2004-12-01

Sulfidogenesis and iron reduction are ubiquitous processes that occur in a variety of anoxic subsurface and surface environments, which profoundly impact the cycling of arsenic. Of the iron (hydr)oxides, ferrihydrite possesses one of the highest capacities to retain arsenic, and is globally distributed within soils and sediments. Upon dissimilatory iron reduction, ferrihydrite may transform to lower surface area minerals, such as goethite and magnetite, which decreases arsenic retention, thus enhancing its transport. Here we examine how arsenic retained on ferrihydrite is mobilized under dynamic flow in the presence of Sulfurosprillum barnesii strain SES-3, a bacteria capable of reducing both As(V) and Fe(III). Ferrihydrite coated sands, loaded with 150 mg kg-1 As(V), were inoculated with S. barnesii, packed into a column and reacted with a synthetic groundwater solution. Within several days after initiation of flow, the concentration of arsenic in the column effluent increased dramatically coincident with the mineralogical transformation of ferrihydrite and As(V) reduction to As(III). Following the initial pulse of arsenic, effluent concentration then declined to less than 10 μ M. Thus, arsenic release into the aqueous phase is contingent upon the incongruent reduction of As(V) and Fe(III) as mediated by biological activity. Reaction of abiotically or biotically generated dissolved sulfide with iron (hydr)oxides may have a dramatic influence on the fate of arsenic within surface and subsurface environments. Accordingly, we examined the reaction of dissolved bisulfide and iron (hydr)oxide complexed with arsenic in both batch and column systems. Low ratios of sulfide to iron in batch reaction systems result in the formation of elemental sulfur and concomitant arsenic release from the iron (hydr)oxide surface. High sulfide to iron ratios, in contrast, appear to favor the formation of iron and arsenic sulfides. Our findings demonstrate that iron (hydr)oxides may quench reactions between sulfide and constituents sorbed to iron (hydr)oxide surfaces, forming elemental sulfur as opposed to sulfide-arsenic complexes. In addition, reductive transformation of iron (hydr)oxide by dissolved sulfide may release sorbed constituents. Hence, moderate to low concentrations of dissolved sulfide in association with iron (hydr)oxides may inhibit sequestration of important contaminants that are attenuated by Fe(III) and/or S(-II) bearing phases.

A B Cell-Driven Autoimmune Pathway Leading to Pathological Hallmarks of Progressive Multiple Sclerosis in the Marmoset Experimental Autoimmune Encephalomyelitis Model

PubMed Central

’t Hart, Bert A.; Dunham, Jordon; Faber, Bart W.; Laman, Jon D.; van Horssen, Jack; Bauer, Jan; Kap, Yolanda S.

2017-01-01

The absence of pathological hallmarks of progressive multiple sclerosis (MS) in commonly used rodent models of experimental autoimmune encephalomyelitis (EAE) hinders the development of adequate treatments for progressive disease. Work reviewed here shows that such hallmarks are present in the EAE model in marmoset monkeys (Callithrix jacchus). The minimal requirement for induction of progressive MS pathology is immunization with a synthetic peptide representing residues 34–56 from human myelin oligodendrocyte glycoprotein (MOG) formulated with a mineral oil [incomplete Freund’s adjuvant (IFA)]. Pathological aspects include demyelination of cortical gray matter with microglia activation, oxidative stress, and redistribution of iron. When the peptide is formulated in complete Freund’s adjuvant, which contains mycobacteria that relay strong activation signals to myeloid cells, oxidative damage pathways are strongly boosted leading to more intensive pathology. The proven absence of immune potentiating danger signals in the MOG34–56/IFA formulation implies that a narrow population of antigen-experienced T cells present in the monkey’s immune repertoire is activated. This novel pathway involves the interplay of lymphocryptovirus-infected B cells with MHC class Ib/Caja-E restricted CD8+ CD56+ cytotoxic T lymphocytes. PMID:28744286

Iron oxide nanoparticles supported on ultradispersed diamond powders: Effect of the preparation procedure

NASA Astrophysics Data System (ADS)

Dimitrov, Momtchil; Ivanova, Ljubomira; Paneva, Daniela; Tsoncheva, Tanya; Stavrev, Stavry; Mitov, Ivan; Minchev, Christo

2009-01-01

The state of the iron oxide nanoparticles, supported on ultradispersed diamond (UDD) powders is studied by X-ray diffraction, nitrogen physisorption, temperature-programmed reduction, FTIR and Mössbauer spectroscopy. Methanol decomposition to hydrogen and CO is used as a catalytic test. The peculiarities of the iron oxide species strongly depend on the detonation procedure used for the UDD powders preparation as well as on the iron modification procedure.

In-situ determination of the oxidation state of iron in Fe-bearing silicate melts

NASA Astrophysics Data System (ADS)

Courtial, P.; Wilke, M.; Potuzak, M.; Dingwell, D. B.

2005-12-01

Terrestrial lavas commonly contain up to 10 wt% of iron. Furthermore, rocks returned from the Moon indicate lunar lava containing up to 25 wt% of iron and planetary scientists estimated that the martian mantle has about 18 wt% of iron. An experimental challenge in dealing with Fe-bearing silicate melts is that the oxidation state, controlling the proportions of ferric and ferrous iron, is a function of composition, oxygen fugacity and temperature and may vary significantly. Further complications concerning iron originate from its potential to be either four-, six- or even five-fold coordinated in both valence states. Therefore, the oxidation state of iron was determined in air for various Fe-bearing silicate melts. Investigated samples were Na-disilicate (NS), one atmosphere anorthite-diopside eutectic (AD) and haplogranitic (HPG8) melts containing up to 20, 20 and 10 wt% of iron, respectively. XANES spectra at the Fe K-edge were collected for all the melts at beamline A1, HASYLAB, Hamburg, using a Si(111) 4-crystal monochromator. Spectra were collected for temperatures up to 1573 K using a Pt-Rh loop as heating device. The Fe oxidation state was determined from the centroid position of the pre-edge feature using the calibration of Wilke et al. (2004). XANES results suggest that oxidation state of iron does not change within error for NS melts with addition of Fe, while AD and HPG8 melts become more oxidised with increasing iron content. Furthermore, NS melts are well more oxidised than AD and HPG8 melts that exhibit relatively similar oxidation states for identical iron contents. The oxidation state of iron for NS melts appears to be slightly temperature-dependent within the temperature range investigated (1073-1573 K). However, this trend is stronger for AD and HPG8 melts. Assuming that glass reflects a picture of the homogeneous equilibria of the melt, the present in-situ Fe-oxidation states determined for these melts were compared to those obtained on quenched glasses from different temperatures, when possible, using wet-chemical analysis (i.e., K-dichromate potentiometry). Both datasets agree reasonably well (within 10 %). References: Wilke et al. (2004) Chemical Geology, 213, 71-87.

Recovery of iron oxides from acid mine drainage and their application as adsorbent or catalyst.

PubMed

Flores, Rubia Gomes; Andersen, Silvia Layara Floriani; Maia, Leonardo Kenji Komay; José, Humberto Jorge; Moreira, Regina de Fatima Peralta Muniz

2012-11-30

Iron oxide particles recovered from acid mine drainage represent a potential low-cost feedstock to replace reagent-grade chemicals in the production of goethite, ferrihydrite or magnetite with relatively high purity. Also, the properties of iron oxides recovered from acid mine drainage mean that they can be exploited as catalysts and/or adsorbents to remove azo dyes from aqueous solutions. The main aim of this study was to recover iron oxides with relatively high purity from acid mine drainage to act as a catalyst in the oxidation of dye through a Fenton-like mechanism or as an adsorbent to remove dyes from an aqueous solution. Iron oxides (goethite) were recovered from acid mine drainage through a sequential precipitation method. Thermal treatment at temperatures higher than 300 °C produces hematite through a decrease in the BET area and an increase in the point of zero charge. In the absence of hydrogen peroxide, the solids adsorbed the textile dye Procion Red H-E7B according to the Langmuir model, and the maximum amount adsorbed decreased as the temperature of the thermal treatment increased. The decomposition kinetics of hydrogen peroxide is dependent on the H(2)O(2) concentration and iron oxides dosage, but the second-order rate constant normalized to the BET surface area is similar to that for different iron oxides tested in this and others studies. These results indicate that acid mine drainage could be used as a source material for the production of iron oxide catalysts/adsorbents, with comparable quality to those produced using analytical-grade reagents. Copyright © 2012 Elsevier Ltd. All rights reserved.

Iron accumulation and dysregulation in the putamen in fragile X-associated tremor/ataxia syndrome.

PubMed

Ariza, Jeanelle; Rogers, Hailee; Hartvigsen, Anna; Snell, Melissa; Dill, Michael; Judd, Derek; Hagerman, Paul; Martínez-Cerdeño, Verónica

2017-04-01

Fragile X-associated tremor/ataxia syndrome is an adult-onset disorder associated with premutation alleles of the FMR1 gene. This disorder is characterized by progressive action tremor, gait ataxia, and cognitive decline. Fragile X-associated tremor/ataxia syndrome pathology includes dystrophic white matter and intranuclear inclusions in neurons and astrocytes. We previously demonstrated that the transport of iron into the brain is altered in fragile X-associated tremor/ataxia syndrome; therefore, we also expect an alteration of iron metabolism in brain areas related to motor control. Iron is essential for cell metabolism, but uncomplexed iron leads to oxidative stress and contributes to the development of neurodegenerative diseases. We investigated a potential iron modification in the putamen - a structure that participates in motor learning and performance - in fragile X-associated tremor/ataxia syndrome. We used samples of putamen obtained from 9 fragile X-associated tremor/ataxia syndrome and 9 control cases to study iron localization using Perl's method, and iron-binding proteins using immunostaining. We found increased iron deposition in neuronal and glial cells in the putamen in fragile X-associated tremor/ataxia syndrome. We also found a generalized decrease in the amount of the iron-binding proteins transferrin and ceruloplasmin, and decreased number of neurons and glial cells that contained ceruloplasmin. However, we found increased levels of iron, transferrin, and ceruloplasmin in microglial cells, indicating an attempt by the immune system to remove the excess iron. Overall, found a deficit in proteins that eliminate extra iron from the cells with a concomitant increase in the deposit of cellular iron in the putamen in Fragile X-associated tremor/ataxia syndrome. © 2017 International Parkinson and Movement Disorder Society. © 2017 International Parkinson and Movement Disorder Society.

Process for the synthesis of iron powder

DOEpatents

Not Available

1982-03-06

A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder.

Process for the synthesis of iron powder

DOEpatents

Welbon, William W.

1983-01-01

A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder.

Effects of aging and oxidation of palladized iron embedded in activated carbon on the dechlorination of 2-chlorobiphenyl

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

Hyeok Choi; Souhail R. Al-Abed; Shirish Agarwal

2009-06-15

Reactive activated carbon (RAC) impregnated with palladized iron has been developed to effectively treat polychlorinated biphenyls (PCBs) in the environment by coupling adsorption and dechlorination of PCBs. In this study, we addressed the dechlorination reactivity and capacity of RAC toward aqueous 2-chlorobiphenyl (2-ClBP), and its aging and longevity under various oxidizing environments. RAC containing 14.4% Fe and 0.68% Pd used in this study could adsorb 122.6 mg 2-ClBP/g RAC, and dechlorinate 56.5 mg 2-ClBP/g RAC which corresponds to 12% (yield) of its estimated dechlorination capacity. Due to Fe0 oxidation to form oxide passivating layers, Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} (oxide-watermore » interface) and FeOOH/FeO (oxide-metal interface), RAC reactivity decreased progressively over aging under N{sub 2} < H{sub 2}O + N{sub 2} < H{sub 2}O + O{sub 2} conditions. Considering nanoscale Fe/Pd corrosion chemistry, the decline was quite slow at only 5.6%, 19.5%, and 32.5% over one year, respectively. Dissolved oxygen played a crucial role in enhancing 2-ClBP adsorption but inhibiting its dechlorination. The reactivity change could be explained with the properties of the aged RAC including surface area, Fe0 content, and Fe species. During the aging and oxidation, the RAC showed limited dissolution of Fe and Pd. Finally, implementation issues regarding application of RAC system to contaminated sites are discussed. 25 refs., 6 figs., 1 tab.« less

Effect of bicarbonate on iron-mediated oxidation of low-density lipoprotein

NASA Astrophysics Data System (ADS)

Arai, Hirofumi; Berlett, Barbara S.; Chock, P. Boon; Stadtman, Earl R.

2005-07-01

Oxidation of low-density lipoprotein (LDL) may play an important role in atherosclerosis. We studied the effects of bicarbonate/CO2 and phosphate buffer systems on metal ion-catalyzed oxidation of LDL to malondialdehyde (MDA) and to protein carbonyl and MetO derivatives. Our results revealed that LDL oxidation in mixtures containing free iron or heme derivatives was much greater in bicarbonate/CO2 compared with phosphate buffer. However, when copper was substituted for iron in these mixtures, the rate of LDL oxidation in both buffers was similar. Iron-catalyzed oxidation of LDL was highly sensitive to inhibition by phosphate. Presence of 0.3-0.5 mM phosphate, characteristic of human serum, led to 30-40% inhibition of LDL oxidation in bicarbonate/CO2 buffer. Iron-catalyzed oxidation of LDL to MDA in phosphate buffer was inhibited by increasing concentrations of albumin (10-200 μM), whereas MDA formation in bicarbonate/CO2 buffer was stimulated by 10-50 μM albumin but inhibited by higher concentrations. However, albumin stimulated the oxidation of LDL proteins to carbonyl derivatives at all concentrations examined in both buffers. Conversion of LDL to MDA in bicarbonate/CO2 buffer was greatly stimulated by ADP, ATP, and EDTA but only when EDTA was added at a concentration equal to that of iron. At higher than stoichiometric concentrations, EDTA prevented oxidation of LDL. Results of these studies suggest that interactions between bicarbonate and iron or heme derivatives leads to complexes with redox potentials that favor the generation of reactive oxygen species and/or to the generation of highly reactive CO2 anion or bicarbonate radical that facilitates LDL oxidation. Freely available online through the PNAS open access option.Abbreviations: LDL, low-density lipoprotein; MDA, malondialdehyde; MetO, methionine sulfoxide.

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2012 CFR

2012-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2013 CFR

2013-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2014 CFR

2014-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.3125 - Iron oxides.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

21 CFR 73.3125 - Iron oxides.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

21 CFR 73.3125 - Iron oxides.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

21 CFR 73.3125 - Iron oxides.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

21 CFR 73.3125 - Iron oxides.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

Preparation and characterization of iron oxide magnetic nanoparticles functionalized by nisin.

PubMed

Gruskiene, Ruta; Krivorotova, Tatjana; Staneviciene, Ramune; Ratautas, Dalius; Serviene, Elena; Sereikaite, Jolanta

2018-05-08

Nisin is a known bacteriocin approved as a food additive for food preservation. It exhibits a wide spectrum antimicrobial activity against Gram-positive bacteria. Iron oxide magnetic nanoparticles were synthesized and characterized by X-ray diffraction method. A main part of iron oxide nanoparticles was found to be maghemite though a small quantity of magnetite could also be present. Magnetic nanoparticles were stabilized by citric, ascorbic, gallic or glucuronic acid coating. Stable iron oxide magnetic nanoparticles were functionalized by nisin using a simple and low cost adsorption method. Nisin loading was confirmed by FT-IR spectra, thermogravimetric analysis, dynamic light scattering and atomic force microscopy methods. Nisin-loaded iron oxide magnetic nanoparticles were stable at least six weeks as judged by the measurements of zeta-potential and hydrodynamic diameter. The antimicrobial activity of nisin-loaded iron oxide magnetic nanoparticles was demonstrated toward Gram-positive bacteria. Functionalized nanoparticles could therefore find the application as antimicrobials in innovative and emerging technologies based on the magnetic field. Copyright © 2018 Elsevier B.V. All rights reserved.

An image processing approach for investigation on transport of iron oxide nanoparticles (FE3O4) stabilized with poly acrylic acid in two-dimensional porous media

NASA Astrophysics Data System (ADS)

Golzar, M.; Azhdary Moghaddam, M.; Saghravani, S. F.; Dahrazma, B.

2018-04-01

Iron oxide nanoparticles were stabilized using poly acrylic acid (PAA) to yield stabilized slurry of Iron oxide nanoparticles. A two-dimensional physical model filled by glass beads was used to study the fate and transport of the iron oxide nanoparticles stabilized with PAA in porous media under saturated, steady-state flow conditions. Transport data for a nonreactive tracer, slurry of iron oxide nanoparticles stabilized with PAA were collected under similar flow conditions. The results show that low concentration slurry of iron oxide nanoparticles stabilized with PAA can be transported like a tracer without significant retardation. The image processing technique was employed to measure the tracer/nanoparticle concentration inside the 2-D model filled with glass beads. The groundwater flow model, Visual MODFLOW, was used to model the observed transport patterns through MT3DMS module. Finally, it was demonstrated that the numerical model MODFLOW can be used to predict the fate and transport characteristics of nanoparticles stabilized with PAA in groundwater aquifers.

Effect of Organic Substances on the Efficiency of Fe(Ii) to Fe(Iii) Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process

NASA Astrophysics Data System (ADS)

Krupińska, Izabela

2017-09-01

One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3). The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D). It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot]), efficiency of Fe(II) to Fe(III) oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII) when used as an oxidizing agent. The application of potassium manganate (VII) for oxidation of Fe(II) ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.

Ultrastructural study of iron oxide precipitates: implications for the search for biosignatures in the Meridiani hematite concretions, Mars.

PubMed

Souza-Egipsy, Virginia; Ormö, Jens; Beitler Bowen, Brenda; Chan, Marjorie A; Komatsu, Goro

2006-08-01

Two terrestrial environments that have been proposed as analogs for the iron oxide precipitation in the Meridiani Planum region of Mars include the Rio Tinto precipitates and southern Utah marble concretions. Samples of two typical Utah iron oxide concretions and iron oxide precipitates in contact with biofilms from Rio Tinto have been studied to determine whether evidence could be found for biomediation in the precipitation process and to identify likely locations for fossil microorganisms. Scanning electron microscopy, energy dispersive X-ray, and gas chromatography-mass spectrometry (GC-MS) were used to search for biosignatures in the Utah marbles. The precipitation of iron oxides resembles known biosignatures, though organic compounds could not be confirmed with GC-MS analysis. In contrast, textural variations induced by biological activity are abundant in the modern Rio Tinto samples. Although no compelling evidence of direct or indirect biomediation was found in the Utah marbles, the ultrastructure of the iron oxide cement in the concretion suggests an inward growth during concretion precipitation from an initially spherical redox front. No indication for growth from a physical nucleus was found.

Microbial Communities Associated with Biogenic Iron Oxide Mineralization in Circumneutral pH Environments

NASA Astrophysics Data System (ADS)

Chan, C. S.; Banfield, J. F.

2002-12-01

Lithotrophic growth on iron is a metabolism that has been found in a variety of neutral pH environments and is likely important in sustaining life in microaerophilic solutions, especially those low in organics. The composition of the microbial communities, especially the organisms that are responsible for iron oxidation, and carbon and nitrogen fixation, are not known, yet the ability to recognize these contributions is vital to our understanding of iron cycling in natural environments. Our approach has been to study the microbial community structure, mineralogy, and geochemistry of ~20 cm thick, 100's meters long, fluffy iron oxide-encrusted biological mats growing in the Piquette Mine tunnel, and to compare the results to those from geochemically similar environments. In situ measurements (Hydrolab) and geochemical characterization of bulk water samples and peepers (dialysis sampling vials) indicate that the environment is microaerobic, with micromolar levels of iron, high carbonate and sulfate, and typical groundwater nitrate and nitrite concentrations. 16S rDNA clone libraries show that the microbial mat and water contain communities with considerable diversity within the Bacterial domain, a large proportion of Nitrospira and Betaproteobacteria, and no Archaea. Because clone library data are not necessarily indicative of actual abundance, fluorescence in-situ hybridization (FISH) was performed on water, mat, and sediment samples from the Piquette mine and two circumneutral iron- and carbonate-rich springs in the Oregon Cascade Range. Domain- and phylum-level probes were chosen based on the clone library results (Nitrospira, Beta- and Gammaproteobacteria, Acidobacteria, Actinobacteria, Chloroflexi, and Planctomyces). FISH data reveal spatial associations between specific microbial groups and mineralized structures. The organisms responsible for making the mineralized sheaths that compose the bulk of the iron oxide mat are Betaproteobacteria (probably Leptothrix spp.). However, only a small proportion of the cells in the mat reside within the sheaths. Most are located on or around the sheaths, which provide a physical framework for the community. Preliminary results from FISH experiments on the iron-rich spring samples show some similarities, including an abundance of Betaproteobacteria. Enrichment and isolation experiments are being performed to identify the iron-oxidizing organisms. Iron-oxidizers have been enriched from all sites. In some cultures it has been difficult to isolate the iron-oxidizing organisms from a non-iron-oxidizing heterotroph, possibly indicating co-dependence. Knowledge of the microbial community structure and the metabolic activities of key members will enable us to better understand the processes and chemical conditions which generate iron oxide deposits found in the geologic record on Earth and possibly extraterrestrial habitats.

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

James K. Neathery; Gary Jacobs; Amitava Sarkar

In the previous reporting period, modifications were completed for integrating a continuous wax filtration system for a 4 liter slurry bubble column reactor. During the current reporting period, a shakedown of the system was completed. Several problems were encountered with the progressive cavity pump used to circulate the wax/catalyst slurry though the cross-flow filter element and reactor. During the activation of the catalyst with elevated temperature (> 270 C) the elastomer pump stator released sulfur thereby totally deactivating the iron-based catalyst. Difficulties in maintaining an acceptable leak rate from the pump seal and stator housing were also encountered. Consequently, themore » system leak rate exceeded the expected production rate of wax; therefore, no online filtration could be accomplished. Work continued regarding the characterization of ultra-fine catalyst structures. The effect of carbidation on the morphology of iron hydroxide oxide particles was the focus of the study during this reporting period. Oxidation of Fe (II) sulfate results in predominantly {gamma}-FeOOH particles which have a rod-shaped (nano-needles) crystalline structure. Carbidation of the prepared {gamma}-FeOOH with CO at atmospheric pressure produced iron carbides with spherical layered structure. HRTEM and EDS analysis revealed that carbidation of {gamma}-FeOOH particles changes the initial nano-needles morphology and generates ultrafine carbide particles with irregular spherical shape.« less

The formation of magnetite in the early Archean oceans

NASA Astrophysics Data System (ADS)

Li, Y. L.

2017-12-01

Banded iron formations are iron- and silica-rich chemical sedimentary rocks that were deposited throughout much of the Precambrian. It is generally accepted that biological oxidation of dissolved Fe(II) led to the precipitation of a ferric oxyhydroxide phase, such as ferrihydrite, in the marine photic zone. Upon burial, ferrihydrite was either transformed into hematite through dehydration or it was reduced to magnetite via biological or abiological Fe(III) reduction coupled to the oxidation of buried microbial biomass. However, it has always been intriguing as to why the oldest BIFs are characteristically magnetite-rich, while BIFs formed after the Neoarchean are dominated by hematite. Here, we propose that some magnetite in early Archean BIF could have precipitated directly from seawater through the reaction of settling ferrihydrite and hot, Fe(II)-rich hydrothermal fluids that vented directly into the photic zone. We conducted experiments that showed the reaction of Fe(II) with biogenic ferric iron mats under strict anoxic conditions led to the formation of a metastable green rust phase that within hours transformed into magnetite at relatively high temperatures. At lower temperatures magnetite does not form. Our model further posits that with the progressive cooling of the Earth's oceans through Archean, the above reaction shut off, and magnetite was subsequently restricted to reactions associated with diagenesis and metamorphism.

Breast cancer tumorigenicity is dependent on high expression levels of NAF-1 and the lability of its Fe-S clusters.

PubMed

Darash-Yahana, Merav; Pozniak, Yair; Lu, Mingyang; Sohn, Yang-Sung; Karmi, Ola; Tamir, Sagi; Bai, Fang; Song, Luhua; Jennings, Patricia A; Pikarsky, Eli; Geiger, Tamar; Onuchic, José N; Mittler, Ron; Nechushtai, Rachel

2016-09-27

Iron-sulfur (Fe-S) proteins are thought to play an important role in cancer cells mediating redox reactions, DNA replication, and telomere maintenance. Nutrient-deprivation autophagy factor-1 (NAF-1) is a 2Fe-2S protein associated with the progression of multiple cancer types. It is unique among Fe-S proteins because of its 3Cys-1His cluster coordination structure that allows it to be relatively stable, as well as to transfer its clusters to apo-acceptor proteins. Here, we report that overexpression of NAF-1 in xenograft breast cancer tumors results in a dramatic augmentation in tumor size and aggressiveness and that NAF-1 overexpression enhances the tolerance of cancer cells to oxidative stress. Remarkably, overexpression of a NAF-1 mutant with a single point mutation that stabilizes the NAF-1 cluster, NAF-1(H114C), in xenograft breast cancer tumors results in a dramatic decrease in tumor size that is accompanied by enhanced mitochondrial iron and reactive oxygen accumulation and reduced cellular tolerance to oxidative stress. Furthermore, treating breast cancer cells with pioglitazone that stabilizes the 3Cys-1His cluster of NAF-1 results in a similar effect on mitochondrial iron and reactive oxygen species accumulation. Taken together, our findings point to a key role for the unique 3Cys-1His cluster of NAF-1 in promoting rapid tumor growth through cellular resistance to oxidative stress. Cluster transfer reactions mediated by the overexpressed NAF-1 protein are therefore critical for inducing oxidative stress tolerance in cancer cells, leading to rapid tumor growth, and drugs that stabilize the NAF-1 cluster could be used as part of a treatment strategy for cancers that display high NAF-1 expression.

Controlled synthesis of magnetic iron oxides@SnO2 quasi-hollow core-shell heterostructures: formation mechanism, and enhanced photocatalytic activity.

PubMed

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

2011-11-01

Iron oxide/SnO(2) magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO(2) quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO(2) core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe(2)O(3) seeds and commercial SnO(2) products, mainly owing to the effective electron hole separation at the iron oxides/SnO(2) interfaces.

Protein Association and Dissociation Regulated by Ferric Ion

PubMed Central

Li, Chaorui; Fu, Xiaoping; Qi, Xin; Hu, Xiaosong; Chasteen, N. Dennis; Zhao, Guanghua

2009-01-01

Iron stored in phytoferritin plays an important role in the germination and early growth of seedlings. The protein is located in the amyloplast where it stores large amounts of iron as a hydrated ferric oxide mineral core within its shell-like structure. The present work was undertaken to study alternate mechanisms of core formation in pea seed ferritin (PSF). The data reveal a new mechanism for mineral core formation in PSF involving the binding and oxidation of iron at the extension peptide (EP) located on the outer surface of the protein shell. This binding induces aggregation of the protein into large assemblies of ∼400 monomers. The bound iron is gradually translocated to the mineral core during which time the protein dissociates back into its monomeric state. Either the oxidative addition of Fe2+ to the apoprotein to form Fe3+ or the direct addition of Fe3+ to apoPSF causes protein aggregation once the binding capacity of the 24 ferroxidase centers (48 Fe3+/shell) is exceeded. When the EP is enzymatically deleted from PSF, aggregation is not observed, and the rate of iron oxidation is significantly reduced, demonstrating that the EP is a critical structural component for iron binding, oxidation, and protein aggregation. These data point to a functional role for the extension peptide as an iron binding and ferroxidase center that contributes to mineralization of the iron core. As the iron core grows larger, the new pathway becomes less important, and Fe2+ oxidation and deposition occurs directly on the surface of the iron core. PMID:19398557

Research on solvent-refined coal. Quarterly technical progress report, July 1-September 30, 1981

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

Not Available

1982-07-01

This report describes progress on the Research on Solvent Refined Coal project by The Pittsburg and Midway Coal Mining Company's Merriam Laboratory during the third quarter of 1981. A four-part experiment was conducted with subbituminous Edna coal, pyrite and/or bituminous Ireland coal at 457/sup 0/C and 1800 psig or 450/sup 0/C and 2250 psig. The purpose was to determine the conditions appropriate for processing a 50/50 by weight blend of these coals. A total of four runs (11 experiments) discussed this quarter were directed toward the study of disposable catalysts. Subbituminous coals from the Edna and Belle Ayr Mines weremore » processed in the SRC II mode. Additives investigated were pyrite, ferric oxide, molybdenum doped ferric oxide and iron dispersed on silica-alumina. The level and type of sulfur added in conjunction with ferric oxide catalysts was also explored as well as addition of sulfur by itself. Two solvent hydrogenation runs and five SRC I runs were directed toward a preliminary investigation of short residence time processing of western (Belle Ayr) coals.« less

Synthesis of phase-pure and monodisperse iron oxide nanoparticles by thermal decomposition

NASA Astrophysics Data System (ADS)

Hufschmid, Ryan; Arami, Hamed; Ferguson, R. Matthew; Gonzales, Marcela; Teeman, Eric; Brush, Lucien N.; Browning, Nigel D.; Krishnan, Kannan M.

2015-06-01

Superparamagnetic iron oxide nanoparticles (SPIONs) are used for a wide range of biomedical applications requiring precise control over their physical and magnetic properties, which are dependent on their size and crystallographic phase. Here we present a comprehensive template for the design and synthesis of iron oxide nanoparticles with control over size, size distribution, phase, and resulting magnetic properties. We investigate critical parameters for synthesis of monodisperse SPIONs by organic thermal decomposition. Three different, commonly used, iron containing precursors (iron oleate, iron pentacarbonyl, and iron oxyhydroxide) are evaluated under a variety of synthetic conditions. We compare the suitability of these three kinetically controlled synthesis protocols, which have in common the use of iron oleate as a starting precursor or reaction intermediate, for producing nanoparticles with specific size and magnetic properties. Monodisperse particles were produced over a tunable range of sizes from approximately 2-30 nm. Reaction parameters such as precursor concentration, addition of surfactant, temperature, ramp rate, and time were adjusted to kinetically control size and size-distribution, phase, and magnetic properties. In particular, large quantities of excess surfactant (up to 25 : 1 molar ratio) alter reaction kinetics and result in larger particles with uniform size; however, there is often a trade-off between large particles and a narrow size distribution. Iron oxide phase, in addition to nanoparticle size and shape, is critical for establishing magnetic properties such as differential susceptibility (dm/dH) and anisotropy. As an example, we show the importance of obtaining the required size and iron oxide phase for application to Magnetic Particle Imaging (MPI), and describe how phase purity can be controlled. These results provide much of the information necessary to determine which iron oxide synthesis protocol is best suited to a particular application.

The role of the iron catalyst in the toxicity of multi-walled carbon nanotubes (MWCNTs).

PubMed

Visalli, Giuseppa; Facciolà, Alessio; Iannazzo, Daniela; Piperno, Anna; Pistone, Alessandro; Di Pietro, Angela

2017-09-01

This study aimed to investigate the role of iron, used as a catalyst, in the biological response to pristine and functionalized multi-walled carbon nanotubes (p/fMWCNTs) with an iron content of 2.5-2.8%. Preliminarily, we assessed the pro-oxidant activity of MWCNTs-associated iron by an abiotic test. To evaluate iron bioavailability, we measured intracellular redox-active iron in A549 cells exposed to both MWCNT suspensions and to the cell medium preconditioned by MWCNTs, in order to assess the iron dissolution rate under physiological conditions. Moreover, in exposed cells, we detected ROS levels, 8-oxo-dG and mitochondrial function. The results clearly highlighted that MWCNTs- associated iron was not redox-active and that iron leakage did not occur under physiological conditions, including the oxidative burst of specialized cells. Despite this, in MWCNTs exposed cells, higher level of intracellular redox-active iron was measured in comparison to control and a significant time-dependent ROS increase was observed (P<0.01). Higher levels of 8-oxo-dG, a marker of oxidative DNA damage, and decreased mitochondrial function, confirmed the oxidative stress induced by MWCNTs. Based on the results we believe that oxidative damage could be attributable to the release of endogenous redox-active iron. This was due to the damage of acidic vacuolar compartment caused by endocytosis-mediated MWCNT internalization. Copyright © 2017 Elsevier GmbH. All rights reserved.

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

PubMed

Geng, Caiyun; Ye, Shengfa; Neese, Frank

2014-04-28

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

Real-Time Studies of Iron Oxalate-Mediated Oxidation of Glycolaldehyde as a Model for Photochemical Aging of Aqueous Tropospheric Aerosols.

PubMed

Thomas, Daniel A; Coggon, Matthew M; Lignell, Hanna; Schilling, Katherine A; Zhang, Xuan; Schwantes, Rebecca H; Flagan, Richard C; Seinfeld, John H; Beauchamp, J L

2016-11-15

The complexation of iron(III) with oxalic acid in aqueous solution yields a strongly absorbing chromophore that undergoes efficient photodissociation to give iron(II) and the carbon dioxide anion radical. Importantly, iron(III) oxalate complexes absorb near-UV radiation (λ > 350 nm), providing a potentially powerful source of oxidants in aqueous tropospheric chemistry. Although this photochemical system has been studied extensively, the mechanistic details associated with its role in the oxidation of dissolved organic matter within aqueous aerosol remain largely unknown. This study utilizes glycolaldehyde as a model organic species to examine the oxidation pathways and evolution of organic aerosol initiated by the photodissociation of aqueous iron(III) oxalate complexes. Hanging droplets (radius 1 mm) containing iron(III), oxalic acid, glycolaldehyde, and ammonium sulfate (pH ∼3) are exposed to irradiation at 365 nm and sampled at discrete time points utilizing field-induced droplet ionization mass spectrometry (FIDI-MS). Glycolaldehyde is found to undergo rapid oxidation to form glyoxal, glycolic acid, and glyoxylic acid, but the formation of high molecular weight oligomers is not observed. For comparison, particle-phase experiments conducted in a laboratory chamber explore the reactive uptake of gas-phase glycolaldehyde onto aqueous seed aerosol containing iron and oxalic acid. The presence of iron oxalate in seed aerosol is found to inhibit aerosol growth. These results suggest that photodissociation of iron(III) oxalate can lead to the formation of volatile oxidation products in tropospheric aqueous aerosols.

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

PubMed

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

2017-01-01

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

Iron(II) Initiation of Lipid and Protein Oxidation in Pork: The Role of Oxymyoglobin.

PubMed

Zhou, Feibai; Jongberg, Sisse; Zhao, Mouming; Sun, Weizheng; Skibsted, Leif H

2016-06-08

Iron(II), added as FeSO4·7H2O, was found to increase the rate of oxygen depletion as detected electrochemically in a pork homogenate from Longissimus dorsi through an initial increase in metmyoglobin formation from oxymyoglobin and followed by formation of primary and secondary lipid oxidation products and protein oxidation as detected as thiol depletion in myofibrillar proteins. Without added iron(II), under the same conditions at 37 °C, oxygen consumption corresponded solely to the slow oxymyoglobin autoxidation. Long-lived myofibrillar protein radicals as detected by ESR spectroscopy in the presence of iron(II) were formed subsequently to oxymyoglobin oxidation, and their level was increased by lipid oxidation when oxygen was completely depleted. Similarly, the time profile for formation of lipid peroxide indicated that oxymyoglobin oxidation initiates both protein oxidation and lipid oxidation.

Thermogravimetric analysis of the interaction of ferromagnetic metal atom and multiwalled carbon nanotubes.

PubMed

Rawat, Naveen; Gudyaka, Russel; Kumar, Mohit; Joshi, Bharat; Santhanam, Kalathur S V

2008-04-01

This paper describes the thermal oxidative behavior of atomized iron or atomized cobalt in the presence of multiwalled carbon nanotubes (MWCNT). The thermogravimetric analysis shows the atomized iron thermal oxidation starts at about 500 degrees C that is absent when the atomized iron is sintered with multiwalled carbon naonotubes. The thermal oxidation of iron in the sintered samples requires the collapse of the multiwalled carbon nanotubes. A similar behavior is observed with atomized cobalt when its oxidation requires the collapse of the nanotubes. This thermal oxidative shift is interpreted as due to the atomized iron or atomized cobalt atom experiencing extensive overlap and confinement effect with multiwalled carbon nanotubes causing a spin transfer. This confinement effect is suggested to produce a transformation of iron from the outermost electronic distribution of 3d64s2 to an effective configuration of 3d84s0 and for cobalt 3d74s2 to 3d94s0 producing spintronics effect.

Iron-Anode Enhanced Sand Filter for Arsenic Removal from Tube Well Water.

PubMed

Xie, Shiwei; Yuan, Songhu; Liao, Peng; Tong, Man; Gan, Yiqun; Wang, Yanxin

2017-01-17

Sand filters are widely used for well water purification in endemic arsenicosis areas, but arsenic (As) removal is difficult at low intrinsic iron concentrations. This work developed an enhanced sand filter by electrochemically generated Fe(II) from an iron anode. The efficiency of As removal was tested in an arsenic burdened region in the Jianghan Plain, central China. By controlling a current of 0.6 A and a flow rate of about 12 L/h, the filter removed total As in the tube well water from 196 to 472 μg/L to below 10 μg/L, whereas the residual As was about 110 μg/L without electricity. Adsorption and subsequent oxidation on the surface of Fe(III) precipitates are the main processes controlling the removals of As and Fe. During a 30-day intermittent operation, both effluent As concentration and electrical energy consumption decreased progressively. Although filter clogging was observed, it can be alleviated by replacing the top layer of sand. Our findings suggest that dosing Fe(II) by an iron anode is an effective means to enhance As removal in a sand filter.

Multicopper oxidase-1 is a ferroxidase essential for iron homeostasis in Drosophila melanogaster

PubMed Central

Lang, Minglin; Braun, Caroline L.; Kanost, Michael R.; Gorman, Maureen J.

2012-01-01

Multicopper ferroxidases catalyze the oxidation of ferrous iron to ferric iron. In yeast and algae, they participate in cellular uptake of iron; in mammals, they facilitate cellular efflux. The mechanisms of iron metabolism in insects are still poorly understood, and insect multicopper ferroxidases have not been identified. In this paper, we present evidence that Drosophila melanogaster multicopper oxidase-1 (MCO1) is a functional ferroxidase. We identified candidate iron-binding residues in the MCO1 sequence and found that purified recombinant MCO1 oxidizes ferrous iron. An association between MCO1 function and iron homeostasis was confirmed by two observations: RNAi-mediated knockdown of MCO1 resulted in decreased iron accumulation in midguts and whole insects, and weak knockdown increased the longevity of flies fed a toxic concentration of iron. Strong knockdown of MCO1 resulted in pupal lethality, indicating that MCO1 is an essential gene. Immunohistochemistry experiments demonstrated that MCO1 is located on the basal surfaces of the digestive system and Malpighian tubules. We propose that MCO1 oxidizes ferrous iron in the hemolymph and that the resulting ferric iron is bound by transferrin or melanotransferrin, leading to iron storage, iron withholding from pathogens, regulation of oxidative stress, and/or epithelial maturation. These proposed functions are distinct from those of other known ferroxidases. Given that MCO1 orthologues are present in all insect genomes analyzed to date, this discovery is an important step toward understanding iron metabolism in insects. PMID:22847425

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

Unravelling the cross-talk between iron starvation and oxidative stress responses highlights the key role of PerR (alr0957) in peroxide signalling in the cyanobacterium Nostoc PCC 7120.

PubMed

Yingping, Fan; Lemeille, Sylvain; Talla, Emmanuel; Janicki, Annick; Denis, Yann; Zhang, Cheng-Cai; Latifi, Amel

2014-10-01

The cyanobacterial phylum includes oxygenic photosynthetic prokaryotes of a wide variety of morphologies, metabolisms and ecologies. Their adaptation to their various ecological niches is mainly achieved by sophisticated regulatory mechanisms and depends on a fine cross-talk between them. We assessed the global transcriptomic response of the filamentous cyanobacterium Nostoc PCC 7120 to iron starvation and oxidative stress. More than 20% of the differentially expressed genes in response to iron stress were also responsive to oxidative stress. These transcripts include antioxidant proteins-encoding genes that confirms that iron depletion leads to reactive oxygen accumulation. The activity of the Fe-superoxide dismutase was not significantly decreased under iron starvation, indicating that the oxidative stress generated under iron deficiency is not a consequence of (SOD) deficiency. The transcriptional data indicate that the adaptation of Nostoc to iron-depleted conditions displays important differences with what has been shown in unicellular cyanobacteria. While the FurA protein that regulates the response to iron deprivation has been well characterized in Nostoc, the regulators in charge of the oxidative stress response are unknown. Our study indicates that the alr0957 (perR) gene encodes the master regulator of the peroxide stress. PerR is a peroxide-sensor repressor that senses peroxide by metal-catalysed oxidation.

Iron cycling at corroding carbon steel surfaces.

PubMed

Lee, Jason S; McBeth, Joyce M; Ray, Richard I; Little, Brenda J; Emerson, David

2013-01-01

Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media.

Iron cycling at corroding carbon steel surfaces

PubMed Central

Lee, Jason S.; McBeth, Joyce M.; Ray, Richard I.; Little, Brenda J.; Emerson, David

2013-01-01

Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with three culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media. PMID:24093730

Fluoride-induced iron overload contributes to hepatic oxidative damage in mouse and the protective role of Grape seed proanthocyanidin extract.

PubMed

Niu, Qiang; He, Ping; Xu, Shangzhi; Ma, Ruling; Ding, Yusong; Mu, Lati; Li, Shugang

2018-01-01

Emerging evidence has demonstrated that iron overload plays an important role in oxidative stress in the liver. This study aimed to explore whether fluoride-induced hepatic oxidative stress is associated with iron overload and whether grape seed proanthocyanidin extract (GSPE) alleviates oxidative stress by reducing iron overload. Forty Kunming male mice were randomly divided into 4 groups and treated for 5 weeks with distilled water (control), sodium fluoride (NaF) (100 mg/L), GSPE (400 mg/kg bw), or NaF (100 mg/L) + GSPE (400 mg/kg bw). Mice exposed to NaF showed typical poisoning changes of morphology, increased aspartate aminotransferase and alanine aminotransferase activities in the liver. NaF treatment also increased MDA accumulation, decreased GSH-Px, SOD and T-AOC levels in liver, indicative of oxidative stress. Intriguingly, all these detrimental effects were alleviated by GSPE. Further study revealed that NaF induced disorders of iron metabolism, as manifested by elevated iron level with increased hepcidin but decreased ferroportin expression, which contributed to hepatic oxidative stress. Importantly, the iron dysregulation induced by NaF could be normalized by GSPE. Collectively, these data provide a novel insight into mechanisms underlying fluorosis and highlight the potential of GSPE as a naturally occurring prophylactic treatment for fluoride-induced hepatotoxicity associated with iron overload.

Microbial Iron Cycling in Acidic Geothermal Springs of Yellowstone National Park: Integrating Molecular Surveys, Geochemical Processes, and Isolation of Novel Fe-Active Microorganisms

PubMed Central

Kozubal, Mark A.; Macur, Richard E.; Jay, Zackary J.; Beam, Jacob P.; Malfatti, Stephanie A.; Tringe, Susannah G.; Kocar, Benjamin D.; Borch, Thomas; Inskeep, William P.

2012-01-01

Geochemical, molecular, and physiological analyses of microbial isolates were combined to study the geomicrobiology of acidic iron oxide mats in Yellowstone National Park. Nineteen sampling locations from 11 geothermal springs were studied ranging in temperature from 53 to 88°C and pH 2.4 to 3.6. All iron oxide mats exhibited high diversity of crenarchaeal sequences from the Sulfolobales, Thermoproteales, and Desulfurococcales. The predominant Sulfolobales sequences were highly similar to Metallosphaera yellowstonensis str. MK1, previously isolated from one of these sites. Other groups of archaea were consistently associated with different types of iron oxide mats, including undescribed members of the phyla Thaumarchaeota and Euryarchaeota. Bacterial sequences were dominated by relatives of Hydrogenobaculum spp. above 65–70°C, but increased in diversity below 60°C. Cultivation of relevant iron-oxidizing and iron-reducing microbial isolates included Sulfolobus str. MK3, Sulfobacillus str. MK2, Acidicaldus str. MK6, and a new candidate genus in the Sulfolobales referred to as Sulfolobales str. MK5. Strains MK3 and MK5 are capable of oxidizing ferrous iron autotrophically, while strain MK2 oxidizes iron mixotrophically. Similar rates of iron oxidation were measured for M. yellowstonensis str. MK1 and Sulfolobales str. MK5. Biomineralized phases of ferric iron varied among cultures and field sites, and included ferric oxyhydroxides, K-jarosite, goethite, hematite, and scorodite depending on geochemical conditions. Strains MK5 and MK6 are capable of reducing ferric iron under anaerobic conditions with complex carbon sources. The combination of geochemical and molecular data as well as physiological observations of isolates suggests that the community structure of acidic Fe mats is linked with Fe cycling across temperatures ranging from 53 to 88°C. PMID:22470372

The kinetics of the reaction of nitrogen dioxide with iron(II)- and iron(III) cytochrome c.

PubMed

Domazou, Anastasia S; Gebicka, Lidia; Didik, Joanna; Gebicki, Jerzy L; van der Meijden, Benjamin; Koppenol, Willem H

2014-04-01

The reactions of NO2 with both oxidized and reduced cytochrome c at pH 7.2 and 7.4, respectively, and with N-acetyltyrosine amide and N-acetyltryptophan amide at pH 7.3 were studied by pulse radiolysis at 23 °C. NO2 oxidizes N-acetyltyrosine amide and N-acetyltryptophan amide with rate constants of (3.1±0.3)×10(5) and (1.1±0.1)×10(6) M(-1) s(-1), respectively. With iron(III)cytochrome c, the reaction involves only its amino acids, because no changes in the visible spectrum of cytochrome c are observed. The second-order rate constant is (5.8±0.7)×10(6) M(-1) s(-1) at pH 7.2. NO2 oxidizes iron(II)cytochrome c with a second-order rate constant of (6.6±0.5)×10(7) M(-1) s(-1) at pH 7.4; formation of iron(III)cytochrome c is quantitative. Based on these rate constants, we propose that the reaction with iron(II)cytochrome c proceeds via a mechanism in which 90% of NO2 oxidizes the iron center directly-most probably via reaction at the solvent-accessible heme edge-whereas 10% oxidizes the amino acid residues to the corresponding radicals, which, in turn, oxidize iron(II). Iron(II)cytochrome c is also oxidized by peroxynitrite in the presence of CO2 to iron(III)cytochrome c, with a yield of ~60% relative to peroxynitrite. Our results indicate that, in vivo, NO2 will attack preferentially the reduced form of cytochrome c; protein damage is expected to be marginal, the consequence of formation of amino acid radicals on iron(III)cytochrome c. Copyright © 2014 Elsevier Inc. All rights reserved.

The Effect of Citric Acid on the Oxidation of Organic Contaminants by Fenton's Reagent

NASA Astrophysics Data System (ADS)

Seol, Y.; Javandel, I.; Lee, G.

2003-12-01

Combined with acids and iron catalysts, hydrogen peroxide (H2O2) as Fenton's reagent is proven to be effective in oxidizing halogenated volatile organic compounds (VOCs). The Fenton's reagent, traditionally used for waste water treatment technique, has been applied to the remediation of contaminated soil systems and numerous investigators have found intrinsic iron salts are effective source of iron catalyst for the reaction. Citric acid, which is naturally occurring nutrients to microorganisms and less destructive to soil chemical properties, is selected for an acidifying agent to create acidic soil condition. However, citric acid has been considered as a reaction inhibitant because it sequesters ferric iron from Fenton's catalytic cycle by forming strong chelates with iron. This paper presents the feasibility of using citric acid as an acidifying agent of soil matrix for the Fenton-like oxidation. Series of batch tests were performed to test disappearance of VOCs in various aqueous systems with two acidifying agents (citric acid or sulfuric acid) and three iron sources (iron sulfate, water soluble soil iron, or soil matrix). Batch results show that soluble iron is essential for near complete disappearance of VOCs and that citric acid performs similarly to sulfuric acid at low H2O2 dosage (< 1 wt%). The test soil provided water-soluble soil iron but also contained scavengers of the oxidizing agents, resulting in limited removals of VOCs. Column tests confirmed the results of the batch tests, suggesting citric acid is also as effective as sulfuric acid in providing acidic environment for the Fenton-like oxidation. The batch experiments also reveal that higher doses of H2O2 lower the degree of VOC removals in citric acid systems. Potential explanations for this declining include that excessive presence of H2O2 expedites the oxidation of ferrous to ferric iron, which then forms a strong complex with citrate, leading to the sequestration of the iron from the Fenton's reaction cycle. Consequently, additional supply of ferrous iron would be required for continuing oxidation of VOCs, as well as slow injection of H2O2. Detailed mechanistic study would be needed for factual understanding.

Additional oxidative stress reroutes the global response of Aspergillus fumigatus to iron depletion.

PubMed

Kurucz, Vivien; Krüger, Thomas; Antal, Károly; Dietl, Anna-Maria; Haas, Hubertus; Pócsi, István; Kniemeyer, Olaf; Emri, Tamás

2018-05-10

Aspergillus fumigatus has to cope with a combination of several stress types while colonizing the human body. A functional interplay between these different stress responses can increase the chances of survival for this opportunistic human pathogen during the invasion of its host. In this study, we shed light on how the H 2 O 2 -induced oxidative stress response depends on the iron available to this filamentous fungus, using transcriptomic analysis, proteomic profiles, and growth assays. The applied H 2 O 2 treatment, which induced only a negligible stress response in iron-replete cultures, deleteriously affected the fungus under iron deprivation. The majority of stress-induced changes in gene and protein expression was not predictable from data coming from individual stress exposure and was only characteristic for the combination of oxidative stress plus iron deprivation. Our experimental data suggest that the physiological effects of combined stresses and the survival of the fungus highly depend on fragile balances between economization of iron and production of essential iron-containing proteins. One observed strategy was the overproduction of iron-independent antioxidant proteins to combat oxidative stress during iron deprivation, e.g. the upregulation of superoxide dismutase Sod1, the thioredoxin reductase Trr1, and the thioredoxin orthologue Afu5g11320. On the other hand, oxidative stress induction overruled iron deprivation-mediated repression of several genes. In agreement with the gene expression data, growth studies underlined that in A. fumigatus iron deprivation aggravates oxidative stress susceptibility. Our data demonstrate that studying stress responses under separate single stress conditions is not sufficient to understand how A. fumigatus adapts in a complex and hostile habitat like the human body. The combinatorial stress of iron depletion and hydrogen peroxide caused clear non-additive effects upon the stress response of A. fumigatus. Our data further supported the view that the ability of A. fumigatus to cause diseases in humans strongly depends on its fitness attributes and less on specific virulence factors. In summary, A. fumigatus is able to mount and coordinate complex and efficient responses to combined stresses like iron deprivation plus H 2 O 2 -induced oxidative stress, which are exploited by immune cells to kill fungal pathogens.

Iron supplementation at high altitudes induces inflammation and oxidative injury to lung tissues in rats

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

Salama, Samir A., E-mail: salama.3@buckeyemail.osu.edu; Department of Biochemistry, Faculty of Pharmacy, Al-Azhar University, Cairo 11751; Department of Pharmacology and GTMR Unit, College of Clinical Pharmacy, Taif University, Al-Haweiah, Taif 21974

2014-01-01

Exposure to high altitudes is associated with hypoxia and increased vulnerability to oxidative stress. Polycythemia (increased number of circulating erythrocytes) develops to compensate the high altitude associated hypoxia. Iron supplementation is, thus, recommended to meet the demand for the physiological polycythemia. Iron is a major player in redox reactions and may exacerbate the high altitudes-associated oxidative stress. The aim of this study was to explore the potential iron-induced oxidative lung tissue injury in rats at high altitudes (6000 ft above the sea level). Iron supplementation (2 mg elemental iron/kg, once daily for 15 days) induced histopathological changes to lung tissuesmore » that include severe congestion, dilatation of the blood vessels, emphysema in the air alveoli, and peribronchial inflammatory cell infiltration. The levels of pro-inflammatory cytokines (IL-1β, IL-6, and TNF-α), lipid peroxidation product and protein carbonyl content in lung tissues were significantly elevated. Moreover, the levels of reduced glutathione and total antioxidant capacity were significantly reduced. Co-administration of trolox, a water soluble vitamin E analog (25 mg/kg, once daily for the last 7 days of iron supplementation), alleviated the lung histological impairments, significantly decreased the pro-inflammatory cytokines, and restored the oxidative stress markers. Together, our findings indicate that iron supplementation at high altitudes induces lung tissue injury in rats. This injury could be mediated through excessive production of reactive oxygen species and induction of inflammatory responses. The study highlights the tissue injury induced by iron supplementation at high altitudes and suggests the co-administration of antioxidants such as trolox as protective measures. - Highlights: • Iron supplementation at high altitudes induced lung histological changes in rats. • Iron induced oxidative stress in lung tissues of rats at high altitudes. • Iron increased the levels of IL-1β, IL-6 and TNF-α in lung tissues at high altitudes. • Trolox alleviated the iron-induced histological and biochemical changes to the lungs.« less

Process for the synthesis of iron powder

DOEpatents

Welbon, W.W.

1983-11-08

A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder. 2 figs.

Iron-mediated redox modulation in neural plasticity

PubMed Central

Muñoz, Pablo

2012-01-01

The role of iron in brain physiology has focused on the neuropathological, effects due to iron-induced oxidative stress. However, our recent work has established a physiological relationship between the iron-mediated oxidative modification and normal neuronal function. Our results obtained from hippocampal neurons, suggest that iron-generated reactive species oxygen (ROS) are involved in calcium signaling initiated by stimulation of NMDA receptors. This signal is amplified by ryanodine receptors (RyR), a redox- sensitive calcium channel, allowing the phosphorylation and nuclear translocation of ERK1/2. Furthermore, using electrophysiological approaches, we showed that iron is required for basal synaptic transmission and full expression of long-term potentiation, a type of synaptic plasticity. Our data combined suggest that the oxidative effect of iron is critical to activate processes that are downstream of NMDAR activation. Finally, due to the high reactivity of DNA with iron-generated ROS, we hypothesize an additional function of iron in gene regulation. PMID:22808323

Efficient Low-pH Iron Removal by a Microbial Iron Oxide Mound Ecosystem at Scalp Level Run.

PubMed

Grettenberger, Christen L; Pearce, Alexandra R; Bibby, Kyle J; Jones, Daniel S; Burgos, William D; Macalady, Jennifer L

2017-04-01

Acid mine drainage (AMD) is a major environmental problem affecting tens of thousands of kilometers of waterways worldwide. Passive bioremediation of AMD relies on microbial communities to oxidize and remove iron from the system; however, iron oxidation rates in AMD environments are highly variable among sites. At Scalp Level Run (Cambria County, PA), first-order iron oxidation rates are 10 times greater than at other coal-associated iron mounds in the Appalachians. We examined the bacterial community at Scalp Level Run to determine whether a unique community is responsible for the rapid iron oxidation rate. Despite strong geochemical gradients, including a >10-fold change in the concentration of ferrous iron from 57.3 mg/liter at the emergence to 2.5 mg/liter at the base of the coal tailings pile, the bacterial community composition was nearly constant with distance from the spring outflow. Scalp Level Run contains many of the same taxa present in other AMD sites, but the community is dominated by two strains of Ferrovum myxofaciens , a species that is associated with high rates of Fe(II) oxidation in laboratory studies. IMPORTANCE Acid mine drainage pollutes more than 19,300 km of rivers and streams and 72,000 ha of lakes worldwide. Remediation is frequently ineffective and costly, upwards of $100 billion globally and nearly $5 billion in Pennsylvania alone. Microbial Fe(II) oxidation is more efficient than abiotic Fe(II) oxidation at low pH (P. C. Singer and W. Stumm, Science 167:1121-1123, 1970, https://doi.org/10.1126/science.167.3921.1121). Therefore, AMD bioremediation could harness microbial Fe(II) oxidation to fuel more-cost-effective treatments. Advances will require a deeper understanding of the ecology of Fe(II)-oxidizing microbial communities and the factors that control their distribution and rates of Fe(II) oxidation. We investigated bacterial communities that inhabit an AMD site with rapid Fe(II) oxidation and found that they were dominated by two operational taxonomic units (OTUs) of Ferrovum myxofaciens , a taxon associated with high laboratory rates of iron oxidation. This research represents a step forward in identifying taxa that can be used to enhance cost-effective AMD bioremediation. Copyright © 2017 American Society for Microbiology.

Iron deficiency beyond erythropoiesis: should we be concerned?

PubMed

Musallam, Khaled M; Taher, Ali T

2018-01-01

To consider the key implications of iron deficiency for biochemical and physiological functions beyond erythropoiesis. PubMed was searched for relevant journal articles published up to August 2017. Anemia is the most well-recognized consequence of persisting iron deficiency, but various other unfavorable consequences can develop either before or concurrently with anemia. Mitochondrial function can be profoundly disturbed since iron is a cofactor for heme-containing enzymes and non-heme iron-containing enzymes in the mitochondrial electron transport chain. Biosynthesis of heme and iron-sulfur clusters in the mitochondria is inhibited, disrupting synthesis of compounds such as hemoglobin, myoglobin, cytochromes and nitric oxide synthase. The physiological consequences include fatigue, lethargy, and dyspnea; conversely, iron repletion in iron-deficient individuals has been shown to improve exercise capacity. The myocardium, with its high energy demands, is particularly at risk from the effects of iron deficiency. Randomized trials have found striking improvements in disease severity in anemic but also non-anemic chronic heart failure patients with iron deficiency after iron therapy. In vitro and pre-clinical studies have demonstrated that iron is required by numerous enzymes involved in DNA replication and repair, and for normal cell cycle regulation. Iron is also critical for immune cell growth, proliferation, and differentiation, and for specific cell-mediated effector pathways. Observational studies have shown that iron-deficient individuals have defective immune function, particularly T-cell immunity, but more evidence is required. Pre-clinical models have demonstrated abnormal myelogenesis, brain cell metabolism, neurotransmission, and hippocampal formation in iron-deficient neonates and young animals. In humans, iron deficiency anemia is associated with poorer cognitive and motor skills. However, the impact of iron deficiency without anemia is less clear. The widespread cellular and physiological effects of iron deficiency highlight the need for early detection and treatment of iron deficiency, both to ameliorate these non-erythropoietic effects, and to avoid progression to iron deficiency anemia.

Iron Oxide as an MRI Contrast Agent for Cell Tracking

PubMed Central

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

2015-01-01

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

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2011 CFR

2011-04-01

... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... food. (2) Synthetic iron oxide may be safely used for the coloring of dog and cat foods in an amount... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... food. (2) Synthetic iron oxide may be safely used for the coloring of dog and cat foods in an amount... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

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

EPA Science Inventory

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

Spectroscopic investigation and direct comparison of the reactivities of iron pyridyl oxidation catalysts

NASA Astrophysics Data System (ADS)

Song, Yang; Mayes, Howard G.; Queensen, Matthew J.; Bauer, Eike B.; Dupureur, Cynthia M.

2017-03-01

The growing interest in green chemistry has fueled attention to the development and characterization of effective iron complex oxidation catalysts. A number of iron complexes are known to catalyze the oxidation of organic substrates utilizing peroxides as the oxidant. Their development is complicated by a lack of direct comparison of the reactivities of the iron complexes. To begin to correlate reactivity with structural elements, we compare the reactivities of a series of iron pyridyl complexes toward a single dye substrate, malachite green (MG), for which colorless oxidation products are established. Complexes with tetradentate, nitrogen-based ligands with cis open coordination sites were found to be the most reactive. While some complexes reflect sensitivity to different peroxides, others are similarly reactive with either H2O2 or tBuOOH, which suggests some mechanistic distinctions. [Fe(S,S-PDP)(CH3CN)2](SbF6)2 and [Fe(OTf)2(tpa)] transition under the oxidative reaction conditions to a single intermediate at a rate that exceeds dye degradation (PDP = bis(pyridin-2-ylmethyl) bipyrrolidine; tpa = tris(2-pyridylmethyl)amine). For the less reactive [Fe(OTf)2(dpa)] (dpa = dipicolylamine), this reaction occurs on a timescale similar to that of MG oxidation. Thus, the spectroscopic method presented herein provides information about the efficiency and mechanism of iron catalyzed oxidation reactions as well as about potential oxidative catalyst decomposition and chemical changes of the catalyst before or during the oxidation reaction.

Resistance to High-Temperature Oxidation and Wear of Various Ferrous Alloys Used in Rolling Mills

NASA Astrophysics Data System (ADS)

Delaunois, Fabienne; Stanciu, Victor Ioan; Sinnaeve, Mario

2018-03-01

Various materials are commonly used to manufacture work rolls for hot rolling mills, such as ICDP (Indefinite Chill Double Pour) cast irons, high-chromium white cast irons, and high speed steels (HSS). Various chemical compositions and microstructures are studied in order to optimize the in-use behavior of those grades of rolls. In this paper, six grades of ferrous alloys (an ICDP cast iron; an ICDP cast iron enriched in vanadium, niobium, and molybdenum; a HSS; a graphitic HSS; a high-chromium white cast iron (Hi-Cr); and a niobium-molybdenum-doped high-chromium white cast iron) were investigated. High-temperature oxidation tests with gravimetric means at 575 °C in water vapor atmosphere and sliding wear tests were carried out. The oxidation kinetics was followed during oxidation test. The microstructure was observed by optical and scanning electron microscopies. The oxides formed on the surface of the samples were analyzed by XRD and EDS. The thickness of the oxide scales and the mass gain were measured after oxidation test. The results showed that the behavior of all the grades differed. The oxide scale of HSS and HSS-G grades was fine and their friction coefficient was low. The weight gain after oxidation test of HSS was high. Hi-Cr and M-Hi-Cr grades presented highly porous oxide layer and an important increase of the friction coefficient during wear test. ICDP and M-ICDP had intermediate behavior.

Investigation of Redox Metal Oxides for Carbonaceous Fuel Conversion and CO2 Capture

NASA Astrophysics Data System (ADS)

Galinsky, Nathan Lee

The chemical looping combustion (CLC) process uses metal oxides, also referred to as oxygen carriers, in a redox scheme for conversion of carbonaceous fuels into a concentrated stream of CO2 and steam while also producing heat and electricity. The unique redox scheme of CLC allows CO2 capture with minimal energy penalty. The CLC process performance greatly depends on the oxygen carrier that is chosen. To date, more than 1000 oxygen carriers have been developed for chemical-looping processes using metal oxides containing first-row transition metals. Oxygen carriers are typically mixed with an inert ceramic support to improve their overall mechanical stability and recyclability. This study focuses on design of (i) iron oxide oxygen carriers for conversion of gaseous carbonaceous fuels and (ii) development of perovskite CaMnO 3-d with improved stability and redox properties for conversion of solid fuels. Iron oxide is cheap and environmentally benign. However, it suffers from low activity with carbonaceous fuels due partially to the low ionic conductivity of iron oxides. In order to address the low activity of iron-oxide-based oxygen carriers, support addition has been shown to lower the energy barrier of oxygen anion transport within the oxygen carrier. This work adds a mixed-ionic-and-electronic-conductor (MIEC) support to iron oxide to help facilitate O2- transport inside the lattice of iron oxide. The MIEC-supported iron oxide is compared to commonly used supports including TiO2 and Al2O 3 and the pure ionic conductor support yttria-stabilized zirconia (YSZ) for conversion of different carbonaceous fuels and hydrogen. Results show that the MIEC-supported iron oxide exhibits up to 70 times higher activity than non-MIEC-supported iron oxides for methane conversion. The MIEC supported iron oxide also shows good recyclability with only minor agglomeration and carbon formation observed. The effect of support-iron oxide synergies is further investigated to understand other physical and chemical properties that lead to highly active and recyclable oxygen carriers. Perovskite and fluorite-structured MIEC supports are tested for conversion of methane. The perovskite supported iron oxides exhibit higher activity and stability resulting from the high mixed conductivity of the support. Fluorite-structured CeO2 oxygen carriers deactivated by 75% after 10 redox cycles. This deactivation was attributed to agglomeration of iron oxide. The agglomeration was determined to occur due to Fe x+ transport during the oxidation step leading to high content of Fe on the surface of the oxygen carrier. Besides the MIEC supports, inert MgAl2O4 supported iron oxide is observed to activate in methane. The activation is attributed to carbon formation causing physical degradation of the oxygen carrier and leading to higher surface area and porosity. To achieve high activity with solid fuels, chemical looping with oxygen uncoupling (CLOU) is commonly used. This process uses oxygen carriers with high PO2 that allows the oxygen carrier to release a portion of their lattice oxygen as gaseous oxygen. In turn, the gaseous oxygen can react with solid fuel particles at a higher rate than the lattice oxygen. CaMnO 3 perovskite oxygen carriers offer high potential for CLOU. However, pure CaMnO3 suffers from long-term recyclability and sulfur poisoning. Addition of A-site (Ba and Sr) and B-site (Fe, Ni, Co, Al, and V) dopants are used to improve the performance of the base CaMnO3 oxygen carrier. Sr (A-site) and Fe (B-site) exhibit high compatibility with the base perovskite structure. Both dopants observe oxygen uncoupling properties up to 200°C below that of pure CaMnO3. Additionally, the doped structures also exhibit higher stability at high temperatures (>1000°C) and during redox cycles. The doped oxygen carriers also demonstrate significantly improved activity for coal char conversion.

Iron oxide nanoparticles stabilized with dendritic polyglycerols as selective MRI contrast agents

NASA Astrophysics Data System (ADS)

Nordmeyer, Daniel; Stumpf, Patrick; Gröger, Dominic; Hofmann, Andreas; Enders, Sven; Riese, Sebastian B.; Dernedde, Jens; Taupitz, Matthias; Rauch, Ursula; Haag, Rainer; Rühl, Eckart; Graf, Christina

2014-07-01

Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 +/- 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI.Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 +/- 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI. Electronic supplementary information (ESI) available: A detailed description of the synthesis of the ligands as well as the preparation and functionalization of the iron oxide nanoparticles including their physico-chemical characterization are presented. Further, details of the cell experiments and the SPR experiments are given. Two representative movies are provided showing leukocyte rolling on the ligand coated surface of the flow chamber. See DOI: 10.1039/c3nr04793h

Oxidative 1,2-carboamination of alkenes with alkyl nitriles and amines toward γ-amino alkyl nitriles

NASA Astrophysics Data System (ADS)

Liu, Yan-Yun; Yang, Xu-Heng; Song, Ren-Jie; Luo, Shenglian; Li, Jin-Heng

2017-04-01

Difunctionalization of alkenes has become a powerful tool for quickly increasing molecular complexity in synthesis. Despite significant progress in the area of alkene difunctionalization involving the incorporation of a nitrogen atom across the C-C double bonds, approaches for the direct 1,2-carboamination of alkenes to produce linear N-containing molecules are scarce and remain a formidable challenge. Here we describe a radical-mediated oxidative intermolecular 1,2-alkylamination of alkenes with alkyl nitriles and amines involving C(sp3)-H oxidative functionalization catalysed by a combination of Ag2CO3 with iron Lewis acids. This three-component alkene 1,2-alkylamination method is initiated by the C(sp3)-H oxidative radical functionalization, which enables one-step formation of two new chemical bonds, a C-C bond and a C-N bond, to selectively produce γ-amino alkyl nitriles.

Exploring Iron Silicate Precursors of Ancient Iron Formations through Rock Record, Laboratory and Field Analogue Investigations

NASA Astrophysics Data System (ADS)

Johnson, J. E.; Rasmussen, B.; Muhling, J.; Benzerara, K.; Jezequel, D.; Cosmidis, J.; Templeton, A. S.

2016-12-01

In direct contrast to today's oceans, iron-rich chemical precipitates dominate the deep marine sedimentary record > 2.3 billion years ago. The deposition of these minerals resulted in massive iron formations and indicate that the ocean was previously ferruginous and largely anoxic. To precipitate and concentrate iron in the sediments, many hypotheses have centered on the oxidation of soluble Fe(II) to solid Fe(III)-oxyhydroxides; these ideas have stimulated extensive research using iron-oxidizing bacteria to produce Fe(III)-oxides and trace metal sorption experiments on Fe(III)-oxides, leading to inferences of trace metal availability and implications for enzymatic and microbial evolution as well as pO2 levels and seawater chemistry. However, recent discoveries of disseminated iron-silicate nanoparticles in early-silicifying chert indicate that iron-silicates may have instead been the primary precipitates from these Archean ferruginous oceans (Rasmussen et al, 2015). Considering the significant paradigm shift this discovery implies for interpretations of Archean elemental cycling, redox state and potential microbial metabolisms, we investigated these iron-silicate inclusions and their implications for ancient seawater chemistry in a multi-faceted approach using spectroscopic- and diffraction-based techniques. The crystal structure, Fe oxidation state and Fe coordination environment of iron-silicate nanoparticles have been interrogated using microscale X-ray absorption spectroscopy, TEM and nanoscale scanning transmission X-ray microscopy. To further explore the chemical and potential biological controls on iron-silicate formation, we have also performed laboratory experiments to mimic Archean seawater and precipitate iron-bearing silicate minerals under abiotic conditions and in the presence of iron-oxidizing bacteria. In a complementary study, sediments from a natural Archean analogue system were sampled to determine if iron-silicate minerals form in Mexican crater lakes that are variably iron- and silica-rich. As we continue to probe the mechanism of Fe(II/III)-silicate formation, we can constrain the activity of silica, pH, and pO2 on early Earth and describe any potential influence of microbial activity on the precipitation of these phases.

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

NASA Technical Reports Server (NTRS)

Napier, Mary E.; Stair, Peter C.

1992-01-01

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

The effect of Mg dopants on magnetic and structural properties of iron oxide and zinc ferrite thin films

NASA Astrophysics Data System (ADS)

Saritaş, Sevda; Ceviz Sakar, Betul; Kundakci, Mutlu; Yildirim, Muhammet

2018-06-01

Iron oxide thin films have been obtained significant interest as a material that put forwards applications in photovoltaics, gas sensors, biosensors, optoelectronic and especially in spintronics. Iron oxide is one of the considerable interest due to its chemical and thermal stability. Metallic ion dopant influenced superexchange interactions and thus changed the structural, electrical and magnetic properties of the thin film. Mg dopped zinc ferrite (Mg:ZnxFe3-xO4) crystal was used to avoid the damage of Fe3O4 (magnetite) crystal instead of Zn2+ in this study. Because the radius of the Mg2+ ion in the A-site (tetrahedral) is almost equal to that of the replaced Fe3+ ion. Inverse-spinel structure in which oxygen ions (O2-) are arranged to form a face-centered cubic (FCC) lattice where there are two kinds of sublattices, namely, A-site and B-site (octahedral) interstitial sites and in which the super exchange interactions occur. In this study, to increase the saturation of magnetization (Ms) value for iron oxide, inverse-spinal ferrite materials have been prepared, in which the iron oxide was doped by multifarious divalent metallic elements including Zn and Mg. Triple and quaternary; iron oxide and zinc ferrite thin films with Mg metal dopants were grown by using Spray Pyrolysis (SP) technique. The structural, electrical and magnetic properties of Mg dopped iron oxide (Fe2O3) and zinc ferrite (ZnxFe3-xO4) thin films have been investigated. Vibrating Sample Magnetometer (VSM) technique was used to study for the magnetic properties. As a result, we can say that Mg dopped iron oxide thin film has huge diamagnetic and of Mg dopped zinc ferrite thin film has paramagnetic property at bigger magnetic field.

Laboratory Investigation of Complex Conductivity and Magnetic Susceptibility on Natural Iron Oxide Coated Sand

NASA Astrophysics Data System (ADS)

Wang, C.; Slater, L. D.; Day-Lewis, F. D.; Briggs, M. A.

2017-12-01

Redox reactions occurring at the oxic/anoxic interface where groundwater discharges to surface water commonly result in iron oxide deposition that coats sediment grains. With relatively large total surface area, these iron oxide coated sediments serve as a sink for sorption of dissolved contaminants, although this sink may be temporary if redox conditions fluctuate with varied flow conditions. Characterization of the distribution of iron oxides in streambed sediments could provide valuable understanding of biogeochemical reactions and the ability of a natural system to sorb contaminants. Towards developing a field methodology, we conducted laboratory spectral induced polarization (SIP) and magnetic susceptibility (MS) measurements on natural iron oxide coated sand (Fe-sand) with grain sizes ranging from 0.3 to 2.0 mm in order to assess the sensitivity of these measurements to iron oxides in sediments. The Fe-sand was also sorted by sieving into various grain sizes to study the impact of grain size on the polarization mechanisms. The unsorted Fe-sand saturated with 0.01 S/m NaCl solution exhibited a distinct phase response ( > 4 mrad) in the frequency range from 0.001 to 100 Hz whereas regular silica sand was characterized by a phase response less than 1 mrad under the same conditions. The presence of iron oxide substantially increased MS (3.08×10-3 SI) over that of regular sand ( < 10-5 SI). An increase of both phase peak and relaxation time was found with increasing grain size of the sorted Fe-sand. Laboratory results demonstrated that SIP and MS may be well suited to mapping the distribution of iron oxides in streambed sediments associated with anoxic groundwater discharge.

Laser Flash Photolysis Generation of High-Valent Transition Metal-Oxo Species: Insights from Kinetic Studies in Real Time

PubMed Central

Zhang, Rui; Newcomb, Martin

2010-01-01

Conspectus High-valent transition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time-scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 × 103 M−1 s−1 for a corrole-iron(V)-oxo species and 1.6 × 106 M−1 s−1 for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions. PMID:18278877

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time.

PubMed

Zhang, Rui; Newcomb, Martin

2008-03-01

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species and 1.6 x 10(6) M(-1) s(-1) for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions.

Novel electrochemical-enzymatic model which quantifies the effect of the solution Eh on the kinetics of ferrous iron oxidation with Acidithiobacillus ferrooxidans.

PubMed

Meruane, G; Salhe, C; Wiertz, J; Vargas, T

2002-11-05

The influence of solution Eh on the rate of ferrous iron oxidation by Acidithiobacillus ferrooxidans is characterized. The experimental approach was based on the use of a two-chamber bioelectrochemical cell, which can determine the ferrous iron oxidation rate at controlled potential. Results enabled the formulation of a novel kinetic model, which incorporates the effect of solution Eh in an explicit form but still integrates the effect of ferrous iron concentration and ferric inhibition. The results showed that at Eh values below 650 mV (standard hydrogen electrode, SHE) the bacterial oxidative activity is mainly dependent on ferrous iron concentration. At Eh values between 650 and 820 mV (SHE) the oxidation rate is mainly controlled by ferric inhibition. Over 820 mV (SHE) the bacterial oxidative activity is strongly inhibited by the Eh increase, being completely inhibited at Eh = 840 mV (SHE). Copyright 2002 Wiley Periodicals, Inc. Biotechnol Bioeng 80: 280-288, 2002.

Reactive iron transport in an acidic mountain stream in Summit County, Colorado: A hydrologic perspective

USGS Publications Warehouse

McKnight, Diane M.; Bencala, K.E.

1989-01-01

A pH perturbation experiment was conducted in an acidic, metal-enriched, mountain stream to identify relative rates of chemical and hydrologic processes as they influence iron transport. During the experiment the pH was lowered from 4.2 to 3.2 for three hours by injection of sulfuric acid. Amorphous iron oxides are abundant on the streambed, and dissolution and photoreduction reactions resulted in a rapid increase in the dissolved iron concentration. The increase occurred simultaneously with the decrease in pH. Ferrous iron was the major aqueous iron species. The changes in the iron concentration during the experiment indicate that variation exists in the solubility properties of the hydrous iron oxides on the streambed with dissolution of at least two compartments of hydrous iron oxides contributing to the iron pulse. Spatial variations of the hydrologic properties along the stream were quantified by simulating the transport of a coinjected tracer, lithium. A simulation of iron transport, as a conservative solute, indicated that hydrologie transport had a significant role in determining downstream changes in the iron pulse. The rapidity of the changes in iron concentration indicates that a model based on dynamic equilibrium may be adequate for simulating iron transport in acid streams. A major challenge for predictive solute transport models of geochemical processes may be due to substantial spatial and seasonal variations in chemical properties of the reactive hydrous oxides in such streams, and in the physical and hydrologic properties of the stream. ?? 1989.

Oxygen in the Martian atmosphere: Regulation of PO2 by the deposition of iron formations on Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1992-01-01

During Earth's early history, and prior to the evolution of its present day oxygenated atmosphere, extensive iron rich siliceous sedimentary rocks were deposited, consisting of alternating layers of silica (chert) and iron oxide minerals (hematite and magnetite). The banding in iron formations recorded changes of atmosphere-hydrosphere interactions near sea level in the ancient ocean, which induced the oxidation of dissolved ferrous iron, precipitation of insoluble ferric oxides and silica, and regulation of oxygen in Earth's early atmosphere. Similarities between the Archean Earth and the composition of the present day atmosphere on Mars, together with the pervasive presence of ferric oxides in the Martian regolith suggest that iron formation might also have been deposited on Mars and influenced the oxygen content of the Martian atmosphere. Such a possibility is discussed here with a view to assessing whether the oxygen content of the Martian atmosphere has been regulated by the chemical precipitation of iron formations on Mars.

Effect of dietary α-tocopherol + ascorbic acid, selenium, and iron on oxidative stress in sub-yearling Chinook salmon (Oncorhynchus tshawytscha Walbaum)

USGS Publications Warehouse

Welker, T.L.; Congleton, J.L.

2009-01-01

A three-variable central composite design coupled with surface-response analysis was used to examine the effects of dietary ??-tocopherol + ascorbic acid (TOCAA), selenium (Se), and iron (Fe) on indices of oxidative stress in juvenile spring Chinook salmon. Each dietary factor was tested at five levels for a total of fifteen dietary combinations (diets). Oxidative damage in liver and kidney (lipid peroxidation, protein carbonyls) and erythrocytes (erythrocyte resistance to peroxidative lysis, ERPL) was determined after feeding experimental diets for 16 (early December) and 28 (early March) weeks. Only TOCAA influenced oxidative stress in this study, with most measures of oxidative damage decreasing (liver lipid peroxidation in December and March; ERPL in December; liver protein carbonyl in March) with increasing levels of TOCAA. We also observed a TOCAA-stimulated increase in susceptibility of erythrocytes to peroxidative lysis in March at the highest levels of TOCAA. The data suggest that under most circumstances a progressive decrease in oxidative stress occurs as dietary TOCAA increases, but higher TOCAA concentrations can stimulate oxidative damage in some situations. Higher levels of TOCAA in the diet were required in March than in December to achieve comparable levels of protection against oxidative damage, which may have been due to physiological changes associated with the parr-smolt transformation. Erythrocytes appeared to be more sensitive to variation in dietary levels of TOCAA than liver and kidney tissues. Using the March ERPL assay results as a baseline, a TOCAA level of approximately 350-600 mg/kg diet would provide adequate protection against lipid peroxidation under most circumstances in juvenile Chinook salmon. ?? 2008 The Authors.

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

PubMed

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

2016-01-01

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

Multifunctional superparamagnetic nanoparticles for enhanced drug transport in cystic fibrosis

NASA Astrophysics Data System (ADS)

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

2012-10-01

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

Interaction of aromatic amines with iron oxides: implications for prebiotic chemistry.

PubMed

Shanker, Uma; Singh, Gurinder; Kamaluddin

2013-06-01

The interaction of aromatic amines (aniline, p-chloroaniline, p-toludine and p-anisidine) with iron oxides (goethite, akaganeite and hematite) has been studied. Maximum uptake of amines was observed around pH 7. The adsorption data obtained at neutral pH were found to follow Langmuir adsorption. Anisidine was found to be a better adsorbate probably due to its higher basicity. In alkaline medium (pH > 8), amines reacted on goethite and akaganeite to give colored products. Analysis of the products by GC-MS showed benzoquinone and azobenzene as the reaction products of aniline while p-anisidine afforded a dimer. IR analysis of the amine-iron oxide hydroxide adduct suggests that the surface acidity of iron oxide hydroxides is responsible for the interaction. The present study suggests that iron oxide hydroxides might have played a role in the stabilization of organic molecules through their surface activity and in prebiotic condensation reactions.

Evaluation of the Effects of Iron Oxides on Soil Reducing Conditions and Methane Generation in Cambodian Wetland Rice Fields

NASA Astrophysics Data System (ADS)

Weaver, M.; Benner, S.; Fendorf, S.; Sampson, M.; Leng, M.

2007-12-01

Atmospheric concentrations of methane have been steadily increasing over the last 100 years, which has given rise to research of wetland rice fields, recently identified as a major anthropomorphic source of methane. Establishment of experimental soil pots, cultivating an aromatic early variety rice strain in the Kean Svay District of Cambodia, have recently been carried out to evaluate methods to minimize methane release by promoting redox buffering by iron oxides. In the first series of experiments, iron oxides were added to the soils and the rate of change in reducing conditions and methanogenesis onset was monitored. In the second series of experiments, plots are subject to periodic drying cycles to promote rejuvenation of buffering iron oxides. Initial results indicate a delay in the onset of methanogenesis, and overall methane generation, in plots where initial iron oxides concentrations are elevated.

Soft template strategy to synthesize iron oxide-titania yolk-shell nanoparticles as high-performance anode materials for lithium-ion battery applications.

PubMed

Lim, Joohyun; Um, Ji Hyun; Ahn, Jihoon; Yu, Seung-Ho; Sung, Yung-Eun; Lee, Jin-Kyu

2015-05-18

Yolk-shell-structured nanoparticles with iron oxide core, void, and a titania shell configuration are prepared by a simple soft template method and used as the anode material for lithium ion batteries. The iron oxide-titania yolk-shell nanoparticles (IO@void@TNPs) exhibit a higher and more stable capacity than simply mixed nanoparticles of iron oxide and hollow titania because of the unique structure obtained by the perfect separation between iron oxide nanoparticles, in combination with the adequate internal void space provided by stable titania shells. Moreover, the structural effect of IO@void@TNPs clearly demonstrates that the capacity retention value after 50 cycles is approximately 4 times that for IONPs under harsh operating conditions, that is, when the temperature is increased to 80 °C. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of coating an iron-based article

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

Magdefrau, Neal; Beals, James T.; Sun, Ellen Y.

A method of coating an iron-based article includes a first heating step of heating a substrate that includes an iron-based material in the presence of an aluminum source material and halide diffusion activator. The heating is conducted in a substantially non-oxidizing environment, to cause the formation of an aluminum-rich layer in the iron-based material. In a second heating step, the substrate that has the aluminum-rich layer is heated in an oxidizing environment to oxidize the aluminum in the aluminum-rich layer.

Microwave-assisted combustion synthesis of nano iron oxide/iron-coated activated carbon, anthracite, cellulose fiber, and silica, with arsenic adsorption studies

EPA Science Inventory

Combustion synthesis of iron oxide/iron coated carbons such as activated carbon, anthracite, cellulose fiber and silica is described. The reactions were carried out in alumina crucibles using a Panasonic kitchen microwave with inverter technology, and the reaction process was com...

Surface anisotropy of iron oxide nanoparticles and slabs from first principles: Influence of coatings and ligands as a test of the Heisenberg model

NASA Astrophysics Data System (ADS)

Brymora, Katarzyna; Calvayrac, Florent

2017-07-01

We performed ab initio computations of the magnetic properties of simple iron oxide clusters and slabs. We considered an iron oxide cluster functionalized by a molecule or glued to a gold cluster of the same size. We also considered a magnetite slab coated by cobalt oxide or a mixture of iron oxide and cobalt oxide. The changes in magnetic behavior were explored using constrained magnetic calculations. A possible value for the surface anisotropy was estimated from the fit of a classical Heisenberg model on ab initio results. The value was found to be compatible with estimations obtained by other means, or inferred from experimental results. The addition of a ligand, coating, or of a metallic nanoparticle to the systems degraded the quality of the description by the Heisenberg Hamiltonian. Proposing a change in the anisotropies allowing for the proportion of each transition atom we could get a much better description of the magnetism of series of hybrid cobalt and iron oxide systems.

Functional Gene Analysis of Freshwater Iron-Rich Flocs at Circumneutral pH and Isolation of a Stalk-Forming Microaerophilic Iron-Oxidizing Bacterium

PubMed Central

Chan, Clara; Itoh, Takashi; Ohkuma, Moriya

2013-01-01

Iron-rich flocs often occur where anoxic water containing ferrous iron encounters oxygenated environments. Culture-independent molecular analyses have revealed the presence of 16S rRNA gene sequences related to diverse bacteria, including autotrophic iron oxidizers and methanotrophs in iron-rich flocs; however, the metabolic functions of the microbial communities remain poorly characterized, particularly regarding carbon cycling. In the present study, we cultivated iron-oxidizing bacteria (FeOB) and performed clone library analyses of functional genes related to carbon fixation and methane oxidization (cbbM and pmoA, respectively), in addition to bacterial and archaeal 16S rRNA genes, in freshwater iron-rich flocs at groundwater discharge points. The analyses of 16S rRNA, cbbM, and pmoA genes strongly suggested the coexistence of autotrophic iron oxidizers and methanotrophs in the flocs. Furthermore, a novel stalk-forming microaerophilic FeOB, strain OYT1, was isolated and characterized phylogenetically and physiologically. The 16S rRNA and cbbM gene sequences of OYT1 are related to those of other microaerophilic FeOB in the family Gallionellaceae, of the Betaproteobacteria, isolated from freshwater environments at circumneutral pH. The physiological characteristics of OYT1 will help elucidate the ecophysiology of microaerophilic FeOB. Overall, this study demonstrates functional roles of microorganisms in iron flocs, suggesting several possible linkages between Fe and C cycling. PMID:23811518

Iron status and its relations with oxidative damage and bone loss during long-duration space flight on the International Space Station.

PubMed

Zwart, Sara R; Morgan, Jennifer L L; Smith, Scott M

2013-07-01

Increases in stored iron and dietary intake of iron during space flight have raised concern about the risk of excess iron and oxidative damage, particularly in bone. The objectives of this study were to perform a comprehensive assessment of iron status in men and women before, during, and after long-duration space flight and to quantify the association of iron status with oxidative damage and bone loss. Fasting blood and 24-h urine samples were collected from 23 crew members before, during, and after missions lasting 50 to 247 d to the International Space Station. Serum ferritin and body iron increased early in flight, and transferrin and transferrin receptors decreased later, which indicated that early increases in body iron stores occurred through the mobilization of iron to storage tissues. Acute phase proteins indicated no evidence of an inflammatory response during flight. Serum ferritin was positively correlated with the oxidative damage markers 8-hydroxy-2'-deoxyguanosine (r = 0.53, P < 0.001) and prostaglandin F2α (r = 0.26, P < 0.001), and the greater the area under the curve for ferritin during flight, the greater the decrease in bone mineral density in the total hip (P = 0.031), trochanter (P = 0.006), hip neck (P = 0.044), and pelvis (P = 0.049) after flight. Increased iron stores may be a risk factor for oxidative damage and bone resorption.

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

PubMed

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

2014-10-21

Iron-sulfur cluster proteins exhibit a range of physicochemical properties that underpin their functional diversity in biology, which includes roles in electron transfer, catalysis, and gene regulation. Transcriptional regulators that utilize iron-sulfur clusters are a growing group that exploit the redox and coordination properties of the clusters to act as sensors of environmental conditions including O2, oxidative and nitrosative stress, and metabolic nutritional status. To understand the mechanism by which a cluster detects such analytes and then generates modulation of DNA-binding affinity, we have undertaken a combined strategy of in vivo and in vitro studies of a range of regulators. In vitro studies of iron-sulfur cluster proteins are particularly challenging because of the inherent reactivity and fragility of the cluster, often necessitating strict anaerobic conditions for all manipulations. Nevertheless, and as discussed in this Account, significant progress has been made over the past decade in studies of O2-sensing by the fumarate and nitrate reduction (FNR) regulator and, more recently, nitric oxide (NO)-sensing by WhiB-like (Wbl) and FNR proteins. Escherichia coli FNR binds a [4Fe-4S] cluster under anaerobic conditions leading to a DNA-binding dimeric form. Exposure to O2 converts the cluster to a [2Fe-2S] form, leading to protein monomerization and hence loss of DNA binding ability. Spectroscopic and kinetic studies have shown that the conversion proceeds via at least two steps and involves a [3Fe-4S](1+) intermediate. The second step involves the release of two bridging sulfide ions from the cluster that, unusually, are not released into solution but rather undergo oxidation to sulfane (S(0)) subsequently forming cysteine persulfides that then coordinate the [2Fe-2S] cluster. Studies of other [4Fe-4S] cluster proteins that undergo oxidative cluster conversion indicate that persulfide formation and coordination may be more common than previously recognized. This remarkable feature suggested that the original [4Fe-4S] cluster can be restored using persulfide as the source of sulfide ion. We have demonstrated that only iron and a source of electrons are required to promote efficient conversion back from the [2Fe-2S] to the [4Fe-4S] form. We propose this as a novel in vivo repair mechanism that does not require the intervention of an iron-sulfur cluster biogenesis pathway. A number of iron-sulfur regulators have evolved to function as sensors of NO. Although it has long been known that the iron-sulfur clusters of many phylogenetically unrelated proteins are vulnerable to attack by NO, our recent studies of Wbl proteins and FNR have provided new insights into the mechanism of cluster nitrosylation, which overturn the commonly accepted view that the product is solely a mononuclear iron dinitrosyl complex (known as a DNIC). The major reaction is a rapid, multiphase process involving stepwise addition of up to eight NO molecules per [4Fe-4S] cluster. The major iron nitrosyl product is EPR silent and has optical characteristics similar to Roussin's red ester, [Fe2(NO)4(RS)2] (RRE), although a species similar to Roussin's black salt, [Fe4(NO)7(S)3](-) (RBS) cannot be ruled out. A major future challenge will be to clarify the nature of these species.

Structure and Charge Hopping Dynamics in Green Rust

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

Wander, Matthew C; Rosso, Kevin M; Schoonen, Martin A

Green rust is a family of mixed-valent iron phases formed by a number of abiotic and biotic processes under alkaline suboxic conditions. Due to its high Fe 2+ content, green rust is a potentially important phase for pollution remediation by serving as a powerful electron donor for reductive transformation. However, mechanisms of oxidation of this material are poorly understood. An essential component of the green rust structure is a mixed-valent brucite-like Fe(OH) 2 sheet comprised of a two dimensional network of edge-sharing iron octahedra. Room temperature Mössbauer spectra show a characteristic signature for intermediate valence on the iron atoms inmore » this sheet, indicative of a Fe 2+-Fe 3+ valence interchange reaction faster than approximately 10 7 s -1. Using Fe(OH) 2 as structural analogue for reduced green rust, we performed Hartree-Fock calculations on periodic slab models and cluster representations to determine the structure and hopping mobility of Fe 3+ hole polarons in this material, providing a first principles assessment of the Fe 2+-Fe 3+ valence interchange reaction rate. The calculations show that among three possible symmetry unique iron-to-iron hops within a sheet, a hop to next-nearest neighbors at an intermediate distance of 5.6 Å is the fastest. The predicted rate is on the order of 10 12 s -1 consistent the Mössbauer-based constraint. All other possibilities, including hopping across interlayer spaces, are predicted to be slower than 10 7 s -1. Collectively, the findings suggest the possibility of hole self-diffusion along sheets as a mechanism for regeneration of lattice Fe 2+ sites, consistent with previous experimental observations of edge-inward progressive oxidation of green rust.« less

Microbial Iron Oxidation in the Arctic Tundra and Its Implications for Biogeochemical Cycling

PubMed Central

Scott, Jarrod J.; Benes, Joshua; Bowden, William B.

2015-01-01

The role that neutrophilic iron-oxidizing bacteria play in the Arctic tundra is unknown. This study surveyed chemosynthetic iron-oxidizing communities at the North Slope of Alaska near Toolik Field Station (TFS) at Toolik Lake (lat 68.63, long −149.60). Microbial iron mats were common in submerged habitats with stationary or slowly flowing water, and their greatest areal extent is in coating plant stems and sediments in wet sedge meadows. Some Fe-oxidizing bacteria (FeOB) produce easily recognized sheath or stalk morphotypes that were present and dominant in all the mats we observed. The cool water temperatures (9 to 11°C) and reduced pH (5.0 to 6.6) at all sites kinetically favor microbial iron oxidation. A microbial survey of five sites based on 16S rRNA genes found a predominance of Proteobacteria, with Betaproteobacteria and members of the family Comamonadaceae being the most prevalent operational taxonomic units (OTUs). In relative abundance, clades of lithotrophic FeOB composed 5 to 10% of the communities. OTUs related to cyanobacteria and chloroplasts accounted for 3 to 25% of the communities. Oxygen profiles showed evidence for oxygenic photosynthesis at the surface of some mats, indicating the coexistence of photosynthetic and FeOB populations. The relative abundance of OTUs belonging to putative Fe-reducing bacteria (FeRB) averaged around 11% in the sampled iron mats. Mats incubated anaerobically with 10 mM acetate rapidly initiated Fe reduction, indicating that active iron cycling is likely. The prevalence of iron mats on the tundra might impact the carbon cycle through lithoautotrophic chemosynthesis, anaerobic respiration of organic carbon coupled to iron reduction, and the suppression of methanogenesis, and it potentially influences phosphorus dynamics through the adsorption of phosphorus to iron oxides. PMID:26386054

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

PubMed

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

2014-01-01

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

Adsorption of poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) polymers on zinc, zinc oxide, iron, and iron oxide surfaces.

PubMed

Seifert, Susan; Simon, Frank; Baumann, Giesela; Hietschold, Michael; Seifert, Andreas; Spange, Stefan

2011-12-06

The adsorption of poly(vinyl formamide) (PVFA) and the statistic copolymers poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) onto zinc and iron metal particles as well as their oxides was investigated. The adsorbates were characterized by means of XPS, DRIFT spectroscopy, wet chemical analysis, and solvatochromic probes. Dicyano-bis-(1,10-phenanthroline)-iron(II) (1), 3-(4-amino-3-methylphenyl)-7-phenyl-benzo-[1,2-b:4,5-b']difuran-2,6-dione (2), and 4-tert-butyl-2-(dicyano-methylene)-5-[4-(diethylamino)-benzylidene]-Δ(3)-thiazoline (3) as solvatochromic probes were coadsorbed onto zinc oxide to measure various effects of surface polarity. The experimental findings showed that the adsorption mechanism of PVFA and PVFA-co-PVAm strongly depends on the degree of hydrolysis of PVFA and pH values and also on the kind of metal or metal oxide surfaces that were employed as adsorbents. The adsorption mechanism of PVFA/PVFA-co-PVAm onto zinc oxide and iron oxide surfaces is mainly affected by electrostatic interactions. Particularly in the region of pH 5, the adsorption of PVFA/PVFA-co-PVAm onto zinc and iron metal particles is additionally influenced by redox processes, dissolution, and complexation reactions. © 2011 American Chemical Society

Identification of an iron permease, cFTR1, in cyanobacteria involved in the iron reduction/re-oxidation uptake pathway.

PubMed

Xu, Ning; Qiu, Guo-Wei; Lou, Wen-Jing; Li, Zheng-Ke; Jiang, Hai-Bo; Price, Neil M; Qiu, Bao-Sheng

2016-12-01

Cyanobacteria are globally important primary producers and abundant in many iron-limited aquatic environments. The ways in which they take up iron are largely unknown, but reduction of Fe 3+ is an important step in the process. Here we report a special iron permease in Synechocystis, cFTR1, that is required for Fe 3+ uptake following Fe 2+ re-oxidation. The expression of cFTR1 is induced by iron starvation, and a mutant lacking the gene is abnormally sensitive to iron starvation. The cFTR1 protein localizes to the plasma membrane and contains the iron-binding motif "REXXE". Point-directed mutagenesis of the REXXE motif results in a sensitivity to Fe-deficiency. Measurements of iron ( 55 Fe) uptake rate show that cFTR1 takes up Fe 3+ rather than Fe 2+ . The function of cFTR1 in Synechocystis could be genetically complemented by the iron permease, Ftr1p, of Saccharomyces cerevisiae, that is known to transport Fe 3+ produced by the oxidation of Fe 2+ via a multicopper oxidase. Unlike yeast Ftr1p, cyanobacterial cFTR1 probably obtains Fe 3+ primarily from the oxidation of Fe 2+ by oxygen. Growth assays show that the cFTR1 is required during oxygenic, photoautotrophic growth but not when oxygen production is inhibited during photoheterotrophic growth. In cyanobacteria, iron reduction/re-oxidation uptake pathway may represent their adaptation to oxygenated environments. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Prenatal iron deficiency causes sex-dependent mitochondrial dysfunction and oxidative stress in fetal rat kidneys and liver.

PubMed

Woodman, Andrew G; Mah, Richard; Keddie, Danae; Noble, Ronan M N; Panahi, Sareh; Gragasin, Ferrante S; Lemieux, Hélène; Bourque, Stephane L

2018-06-01

Prenatal iron deficiency alters fetal developmental trajectories, which results in persistent changes in organ function. Here, we studied the effects of prenatal iron deficiency on fetal kidney and liver mitochondrial function. Pregnant Sprague-Dawley rats were fed partially or fully iron-restricted diets to induce a state of moderate or severe iron deficiency alongside iron-replete control rats. We assessed mitochondrial function via high-resolution respirometry and reactive oxygen species generation via fluorescence microscopy on gestational d 21. Hemoglobin levels were reduced in dams in the moderate (-31%) and severe groups (-54%) compared with controls, which was accompanied by 55% reductions in fetal hemoglobin levels in both moderate and severe groups versus controls. Male iron-deficient kidneys exhibited globally reduced mitochondrial content and respiration, as well as increased cytosolic superoxide and decreased NO. Female iron-deficient kidneys exhibited complex II down-regulation and increased mitochondrial oxidative stress. Male iron-deficient livers exhibited reduced complex IV respiration and increased cytosolic superoxide, whereas female liver tissues exhibited no alteration in oxidant levels or mitochondrial function. These findings indicate that prenatal iron deficiency causes changes in mitochondrial content and function as well as oxidant status in a sex- and organ-dependent manner, which may be an important mechanism that underlies the programming of cardiovascular disease.-Woodman, A. G., Mah, R., Keddie, D., Noble, R. M. N., Panahi, S., Gragasin, F. S., Lemieux, H., Bourque, S. L. Prenatal iron deficiency causes sex-dependent mitochondrial dysfunction and oxidative stress in fetal rat kidneys and liver.

Labeling Efficacy of Superparamagnetic Iron Oxide Nanoparticles to Human Neural Stem Cells: Comparison of Ferumoxides, Monocrystalline Iron Oxide, Cross-linked Iron Oxide (CLIO)-NH2 and tat-CLIO

PubMed Central

Song, Miyeoun; Kim, Yunhee; Lim, Dongyeol; Song, In-Chan; Yoon, Byung-Woo

2007-01-01

Objective We wanted to compare the human neural stem cell (hNSC) labeling efficacy of different superparamagnetic iron oxide nanoparticles (SPIONs), namely, ferumoxides, monocrystalline iron oxide (MION), cross-linked iron oxide (CLIO)-NH2 and tat-CLIO. Materials and Methods The hNSCs (5 × 105 HB1F3 cells/ml) were incubated for 24 hr in cell culture media that contained 25 µg/ml of ferumoxides, MION or CLIO-NH2, and with or without poly-L-lysine (PLL) and tat-CLIO. The cellular iron uptake was analyzed qualitatively with using a light microscope and this was quantified via atomic absorption spectrophotometry. The visibility of the labeled cells was assessed with MR imaging. Results The incorporation of SPIONs into the hNSCs did not affect the cellular proliferations and viabilities. The hNSCs labeled with tat-CLIO showed the longest retention, up to 72 hr, and they contained 2.15 ± 0.3 pg iron/cell, which are 59 fold, 430 fold and six fold more incorporated iron than that of the hNSCs labeled with ferumoxides, MION or CLIO-NH2, respectively. However, when PLL was added, the incorporation of ferumoxides, MION or CLIO-NH2 into the hNSCs was comparable to that of tat-CLIO. Conclusion For MR imaging, hNSCs can be efficiently labeled with tat-CLIO alone or with a combination of ferumoxides, MION, CLIO-NH2 and the transfection agent PLL. PMID:17923778

A comparison of iron extraction methods for the determination of degree of pyritisation and the recognition of iron-limited pyrite formation

NASA Technical Reports Server (NTRS)

Raiswell, R.; Canfield, D. E.; Berner, R. A.

1994-01-01

Measurements of degree of pyritisation require an estimate of sediment iron which is capable of reaction with dissolved sulphide to form pyrite, either directly or indirectly via iron monosulphide precursors. Three dissolution techniques (buffered dithionite, cold 1 M HCl, boiling 12 M HCl) were examined for their capacity to extract iron from a variety of iron minerals, and iron-bearing sediments, as a function of different extraction times and different grain sizes. All the iron oxides studied are quantitatively extracted by dithionite and boiling HCl (but not by cold HCl). Both HCl techniques extract more iron from silicates than does dithionite but probably about the same amounts as are potentially capable of sulphidation. Modern sediment studies indicate that most sedimentary pyrite is formed rapidly from iron oxides, with smaller amounts formed more slowly from iron silicates (if sufficient geologic time is available). It is therefore recommended that the degree of pyritisation be defined with respect to the dithionite-extractable (mainly iron oxide) pool and/or the boiling HCl-extractable pool (which includes some silicate iron) for the recognition of iron-limited pyritisation.

Metal mobilization by iron- and sulfur-oxidizing bacteria in a multiple extreme mine tailings in the Atacama Desert, Chile.

PubMed

Korehi, H; Blöthe, M; Sitnikova, M A; Dold, B; Schippers, A

2013-03-05

The marine shore sulfidic mine tailings dump at the Chañaral Bay in the Atacama Desert, northern Chile, is characterized by extreme acidity, high salinity, and high heavy metals concentrations. Due to pyrite oxidation, metals (especially copper) are mobilized under acidic conditions and transported toward the tailings surface and precipitate as secondary minerals (Dold, Environ. Sci. Technol. 2006, 40, 752-758.). Depth profiles of total cell counts in this almost organic-carbon free multiple extreme environment showed variable numbers with up to 10(8) cells g(-1) dry weight for 50 samples at four sites. Real-time PCR quantification and bacterial 16S rRNA gene diversity analysis via clone libraries revealed a dominance of Bacteria over Archaea and the frequent occurrence of the acidophilic iron(II)- and sulfur-oxidizing and iron(III)-reducing genera Acidithiobacillus, Alicyclobacillus, and Sulfobacillus. Acidophilic chemolithoautotrophic iron(II)-oxidizing bacteria were also frequently found via most-probable-number (MPN) cultivation. Halotolerant iron(II)-oxidizers in enrichment cultures were active at NaCl concentrations up to 1 M. Maximal microcalorimetrically determined pyrite oxidation rates coincided with maxima of the pyrite content, total cell counts, and MPN of iron(II)-oxidizers. These findings indicate that microbial pyrite oxidation and metal mobilization preferentially occur in distinct tailings layers at high salinity. Microorganisms for biomining with seawater salt concentrations obviously exist in nature.

Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Iron-Natural Organic Matter Interactions.

PubMed

Jiang, Chao; Garg, Shikha; Waite, T David

2015-12-15

Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

Decaking of coal or oil shale during pyrolysis in the presence of iron oxides

DOEpatents

Khan, M. Rashid

1989-01-01

A method for producing a fuel from the pyrolysis of coal or oil shale in the presence of iron oxide in an inert gas atmosphere. The method includes the steps of pulverizing feed coal or oil shale, pulverizing iron oxide, mixing the pulverized feed and iron oxide, and heating the mixture in a gas atmosphere which is substantially inert to the mixture so as to form a product fuel, which may be gaseous, liquid and/or solid. The method of the invention reduces the swelling of coals, such as bituminous coal and the like, which are otherwise known to swell during pyrolysis.

Targeted iron oxide nanoparticles for the enhancement of radiation therapy

PubMed Central

Hauser, Anastasia K.; Mitov, Mihail I.; Daley, Emily F.; McGarry, Ronald C.; Anderson, Kimberly W.; Hilt, J. Zach

2017-01-01

To increase the efficacy of radiation, iron oxide nanoparticles can be utilized for their ability to produce reactive oxygen species (ROS). Radiation therapy promotes leakage of electrons from the electron transport chain and leads to an increase in mitochondrial production of the superoxide anion which is converted to hydrogen peroxide by superoxide dismutase. Iron oxide nanoparticles can then catalyze the reaction from hydrogen peroxide to the highly reactive hydroxyl radical. Therefore, the overall aim of this project was to utilize iron oxide nanoparticles conjugated to a cell penetrating peptide, TAT, to escape lysosomal encapsulation after internalization by cancer cells and catalyze hydroxyl radical formation. It was determined that TAT functionalized iron oxide nanoparticles and uncoated iron oxide nanoparticles resulted in permeabilization of the lysosomal membranes. Additionally, mitochondrial integrity was compromised when A549 cells were treated with both TAT-functionalized nanoparticles and radiation. Pre-treatment with TAT-functionalized nanoparticles also significantly increased the ROS generation associated with radiation. A long term viability study showed that TAT-functionalized nanoparticles combined with radiation resulted in a synergistic combination treatment. This is likely due to the TAT-functionalized nanoparticles sensitizing the cells to subsequent radiation therapy, because the nanoparticles alone did not result in significant toxicities. PMID:27521615

Preparation, characterization and dynamical mechanical properties of dextran-coated iron oxide nanoparticles (DIONPs).

PubMed

Can, Hatice Kaplan; Kavlak, Serap; ParviziKhosroshahi, Shahed; Güner, Ali

2018-03-01

Dextran-coated iron oxide nanoparticles (DIONPs) with appropriate surface chemistry exhibit many interesting properties that can be exploited in a variety of biomedical applications such as magnetic resonance imaging (MRI) contrast enhancement, tissue repair, hyperthermia, drug delivery and in cell separation. This paper reports the experimental detail for preparation, characterization and investigation of thermal and dynamical mechanical characteristics of the dextran-coated Fe 3 O 4 magnetic nanoparticles. In our work, DIONPs were prepared in a 1:2 ratio of Fe(II) and Fe(III) salt in the HCl solution with NaOH at given temperature. The obtained dextran-coated iron-oxide nanoparticles structure-property correlation was characterized by spectroscopic methods; attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and XRD. Coating dextran on the iron-oxide proof of important peaks can be seen from the ATR-FTIR. Dramatic crystallinity increment can be observed from the XRD pattern of the iron-oxide dextran nanoparticles. The thermal analysis was examined by differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and differential thermal analysis (DTA). Dynamical mechanical properties of dextran nanoparticles were analysed by dynamic mechanical analysis (DMA). Thermal stability of the iron oxide dextran nanoparticles is higher than that of the dextran.

Ultrasmall water-soluble metal-iron oxide nanoparticles as T1-weighted contrast agents for magnetic resonance imaging.

PubMed

Zeng, Leyong; Ren, Wenzhi; Zheng, Jianjun; Cui, Ping; Wu, Aiguo

2012-02-28

Using an improved hydrolysis method of inorganic salts assisted with water-bath incubation, ultrasmall water-soluble metal-iron oxide nanoparticles (including Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles) were synthesized in aqueous solutions, which were used as T(1)-weighted contrast agents for magnetic resonance imaging (MRI). The morphology, structure, MRI relaxation properties and cytotoxicity of the as-prepared metal-iron oxide nanoparticles were characterized, respectively. The results showed that the average sizes of nanoparticles were about 4 nm, 4 nm and 5 nm for Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles, respectively. Moreover, the nanoparticles have good water dispersibility and low cytotoxicity. The MRI test showed the strong T(1)-weighted, but the weak T(2)-weighted MRI performance of metal-iron oxide nanoparticles. The high T(1)-weighted MRI performance can be attributed to the ultrasmall size of metal-iron oxide nanoparticles. Therefore, the as-prepared metal-iron oxide nanoparticles with good water dispersibility and ultrasmall size can have potential applications as T(1)-weighted contrast agent materials for MRI.

Effect of soybean lecithin on iron-catalyzed or chlorophyll-photosensitized oxidation of canola oil emulsion.

PubMed

Choe, Jeesu; Oh, Boyoung; Choe, Eunok

2014-11-01

The effect of soybean lecithin addition on the iron-catalyzed or chlorophyll-photosensitized oxidation of emulsions consisting of purified canola oil and water (1:1, w/w) was studied based on headspace oxygen consumption using gas chromatography and hydroperoxide production using the ferric thiocyanate method. Addition levels of iron sulfate, chlorophyll, and soybean lecithin were 5, 4, and 350 mg/kg, respectively. Phospholipids (PLs) during oxidation of the emulsions were monitored by high performance liquid chromatography. Addition of soybean lecithin to the emulsions significantly reduced and decelerated iron-catalyzed oil oxidation by lowering headspace oxygen consumption and hydroperoxide production. However, soybean lecithin had no significant antioxidant effect on chlorophyll-photosensitized oxidation of the emulsions. PLs in soybean lecithin added to the emulsions were degraded during both oxidation processes, although there was little change in PL composition. Among PLs in soybean lecithin, phosphatidylethanolamine and phosphatidylinositol were degraded the fastest in the iron-catalyzed and the chlorophyll-photosensitized oxidation, respectively. The results suggest that addition of soybean lecithin as an emulsifier can also improve the oxidative stability of oil in an emulsion. © 2014 Institute of Food Technologists®

Morphology, stability, and X-ray absorption spectroscopic study of iron oxide (Hematite) nanoparticles prepared by micelle nanolithography

NASA Astrophysics Data System (ADS)

Bera, Anupam; Bhattacharya, Atanu; Tiwari, N.; Jha, S. N.; Bhattacharyya, D.

2018-03-01

Currently, considerable effort is being made towards synthesis and characterization of iron oxide nanoparticles. In this article, we report on the preparation and characterization of iron oxide nanoparticle (NP) arrays supported on natively oxidized Si(100) surface. The NPs are synthesized by reverse micelle nanolithography technique and are then deposited onto natively oxidized Si(100) surface via spin-coating. Plasma oxidation followed by high temperature annealing results in a unimodal size distribution of pseudohexagonally-ordered array of iron oxide NPs (with ∼14 nm mean diameter and ∼5 nm mean height). High temperature annealing does not fragment the NPs. Particles are sinter-resistant: the unimodal arrays are robust with respect to thermal treatment. X-ray absorption spectroscopy (XAS), including X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS), reveals that structure of the iron oxide particle resembles closely the hematite α-Fe2O3 structure. Furthermore, with the help of EXAFS spectra, we eliminate the possibility of γ-Fe2O3, Fe3O4, FeO and FeO(OH) structures for the NPs.

Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

DOEpatents

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.

Frequently Asked Questions about Monitored Natural Attenuation in Groundwater

DTIC Science & Technology

2014-02-01

Natural Attenuation of Fuels and Chlorinated Solvents book (600 citations) I? • MNA Since 2000 Although there was tremendous progress in technical and...faster with Scenario Scenario Scenario heterogen. 7 8 8 slower with Scenario Scenario Scenario heterogen. 10 I I 12 fractured / • Scenario 13...DC. 7 (W OHC-17 ( 1 E5 yr) ~ 1,2DCA VC Ethylene Glycol (W I RD-7 AH-17 (72 yr) • Mechanisms ORP CEC Sediment iron oxide Sulfur TDS CA

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species

NASA Astrophysics Data System (ADS)

Watts, Richard J.; Yu, Miao; Teel, Amy L.

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical + sulfate radical probe, and hexachloroethane as a reductant + nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole > > TCE > PCE > > nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion.

Intracellular degradation of functionalized carbon nanotube/iron oxide hybrids is modulated by iron via Nrf2 pathway

PubMed Central

Elgrabli, Dan; Dachraoui, Walid; Marmier, Hélène de; Ménard-Moyon, Cécilia; Bégin, Dominique; Bégin-Colin, Sylvie; Bianco, Alberto; Alloyeau, Damien; Gazeau, Florence

2017-01-01

The in vivo fate and biodegradability of carbon nanotubes is still a matter of debate despite tremendous applications. In this paper we describe a molecular pathway by which macrophages degrade functionalized multi-walled carbon nanotubes (CNTs) designed for biomedical applications and containing, or not, iron oxide nanoparticles in their inner cavity. Electron microscopy and Raman spectroscopy show that intracellularly-induced structural damages appear more rapidly for iron-free CNTs in comparison to iron-loaded ones, suggesting a role of iron in the degradation mechanism. By comparing the molecular responses of macrophages derived from THP1 monocytes to both types of CNTs, we highlight a molecular mechanism regulated by Nrf2/Bach1 signaling pathways to induce CNT degradation via NOX2 complex activation and O2•−, H2O2 and OH• production. CNT exposure activates an oxidative stress-dependent production of iron via Nrf2 nuclear translocation, Ferritin H and Heme oxygenase 1 translation. Conversely, Bach1 was translocated to the nucleus of cells exposed to iron-loaded CNTs to recycle embedded iron. Our results provide new information on the role of oxidative stress, iron metabolism and Nrf2-mediated host defence for regulating CNT fate in macrophages. PMID:28120861

Summary of the mineralogy of the Colorado Plateau uranium ores

USGS Publications Warehouse

Weeks, Alice D.; Coleman, Robert Griffin; Thompson, Mary E.

1956-01-01

In the Colorado Plateau uranium has been produced chiefly from very shallow mines in carnotite ores (oxidized vanadiferous uranium ores) until recent deeper mining penetrated black unoxidized ores in water-saturated rocks and extensive exploration has discovered many deposits of low to nonvanadiferous ores. The uranium ores include a wide range from highly vanadiferous and from as much as one percent to a trace of copper, and contain a small amount of iron and traces of lead, zinc, molybdenum, cobalt, nickel, silver, manganese, and other metals. Recent investigation indicates that the carnotite ores have been derived by progressive oxidation of primary (unoxidized) black ores that contain low-valent uranium and vanadium oxides and silicates. The uranium minerals, uraninite and coffinite, are associated with coalified wood or other carbonaceous material. The vanadium minerals, chiefly montroseite, roscoelite, and other vanadium silicates, occur in the interstices of the sandstone and in siltstone and clay pellets as well as associated with fossil wood. Calcite, dolomite, barite and minor amounts of sulfides, arsenides, and selenides occur in the unoxidized ore. Partially oxidized vanadiferous ore is blue black, purplish brown, or greenish black in contrast to the black or dark gray unoxidized ore. Vanadium combines with uranium to form rauvite. The excess vanadium is present in corvusite, fernandinite, melanovanadite and many other quadrivalent and quinquevalent vanadium minerals as well as in vanadium silicates. Pyrite and part or all of the calcite are replaced by iron oxides and gypsum. In oxidized vanadiferous uranium ores the uranium is fixed in the relatively insoluble minerals carnotite and tyuyamunite, and the excess vanadium commonly combines with one or more of the following: calcium, sodium, potassium, magnesium, aluminum, iron, copper, manganese, or barium, or rarely it forms the hydrated pentoxide. The relatively stable vanadium silicates are little affected by oxidation. The unoxidized nonvanadiferous ores contain uraninite and coffinite in close association with coalified wood and iron and copper sulfides, and traces of many other sulfides, arsenides and selenides. The oxidized nonvanadiferous ores differ from the vanadiferous ores because, in the absence of vanadium to complex the uranium, a great variety of secondary yellow and greenish-yellow uranyl minerals are formed. The uranyl sulfates and carbonates are more common than the oxides, phosphates, arsenates, and silicates. Because the sulfates and carbonates are much less stable that carnotite, the oxidized nonvanadiferous ores occure only as halos around cores of unoxidized ore and do not form large oxidized deposits close to the surface of the ground as carnotite ores. Oxidation has taken place since the lowering of the water table in the present erosion cycle. Because of local structures and the highly lenticular character of the fluviatile host rocks perched water tables and water-saturated lenses of sandstone are common high above the regional water table. Unoxidized ore has been preserved in these water-saturated rocks and the boundary between oxidized and unoxidized ore is very irregular.

Bacterial oxidation of ferrous iron at low temperatures.

PubMed

Kupka, Daniel; Rzhepishevska, Olena I; Dopson, Mark; Lindström, E Börje; Karnachuk, Olia V; Tuovinen, Olli H

2007-08-15

This study comprises the first report of ferrous iron oxidation by psychrotolerant, acidophilic iron-oxidizing bacteria capable of growing at 5 degrees C. Samples of mine drainage-impacted surface soils and sediments from the Norilsk mining region (Taimyr, Siberia) and Kristineberg (Skellefte district, Sweden) were inoculated into acidic ferrous sulfate media and incubated at 5 degrees C. Iron oxidation was preceded by an approximately 3-month lag period that was reduced in subsequent cultures. Three enrichment cultures were chosen for further work and one culture designated as isolate SS3 was purified by colony isolation from a Norilsk enrichment culture for determining the kinetics of iron oxidation. The 16S rRNA based phylogeny of SS3 and two other psychrotolerant cultures, SS5 from Norilsk and SK5 from Northern Sweden, was determined. Comparative analysis of amplified 16S rRNA gene sequences showed that the psychrotolerant cultures aligned within Acidithiobacillus ferrooxidans. The rate constant of iron oxidation by growing cultures of SS3 was in the range of 0.0162-0.0104 h(-1) depending on the initial pH. The oxidation kinetics followed an exponential pattern, consistent with a first order rate expression. Parallel iron oxidation by a mesophilic reference culture of Acidithiobacillus ferrooxidans was extremely slow and linear. Precipitates harvested from the 5 degrees C culture were identified by X-ray diffraction as mixtures of schwertmannite (ideal formula Fe(8)O(8)(OH)(6)SO(4)) and jarosite (KFe(3)(SO(4))(2)(OH)(6)). Jarosite was much more dominant in precipitates produced at 30 degrees C. (c) 2007 Wiley Periodicals, Inc.

Process to Produce Iron Nanoparticle Lunar Dust Simulant Composite

NASA Technical Reports Server (NTRS)

Hung, Ching-cheh; McNatt, Jeremiah

2010-01-01

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

Redox inactive metal ion triggered N-dealkylation by an iron catalyst with dioxygen activation: a lesson from lipoxygenases.

PubMed

Zhang, Jisheng; Wang, Yujuan; Luo, Nengchao; Chen, Zhuqi; Wu, Kangbing; Yin, Guochuan

2015-06-07

Utilization of dioxygen as the terminal oxidant at ambient temperature is always a challenge in redox chemistry, because it is hard to oxidize a stable redox metal ion like iron(III) to its high oxidation state to initialize the catalytic cycle. Inspired by the dioxygenation and co-oxidase activity of lipoxygenases, herein, we introduce an alternative protocol to activate the sluggish iron(III) species with non-redox metal ions, which can promote its oxidizing power to facilitate substrate oxidation with dioxygen, thus initializing the catalytic cycle. In oxidations of N,N-dimethylaniline and its analogues, adding Zn(OTf)2 to the [Fe(TPA)Cl2]Cl catalyst can trigger the amine oxidation with dioxygen, whereas [Fe(TPA)Cl2]Cl alone is very sluggish. In stoichiometric oxidations, it has also been confirmed that the presence of Zn(OTf)2 can apparently improve the electron transfer capability of the [Fe(TPA)Cl2]Cl complex. Experiments using different types of substrates as trapping reagents disclosed that the iron(IV) species does not occur in the catalytic cycle, suggesting that oxidation of amines is initialized by electron transfer rather than hydrogen abstraction. Combined experiments from UV-Vis, high resolution mass spectrometry, electrochemistry, EPR and oxidation kinetics support that the improved electron transfer ability of iron(III) species originates from its interaction with added Lewis acids like Zn(2+) through a plausible chloride or OTf(-) bridge, which has promoted the redox potential of iron(III) species. The amine oxidation mechanism was also discussed based on the available data, which resembles the co-oxidase activity of lipoxygenases in oxidative dealkylation of xenobiotic metabolisms where an external electron donor is not essential for dioxygen activation.

Iron oxide nanoparticles in geomicrobiology: from biogeochemistry to bioremediation.

PubMed

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

2013-09-25

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

Salt Stress-Induced Loss of Iron Oxidoreduction Activities and Reacquisition of That Phenotype Depend on rus Operon Transcription in Acidithiobacillus ferridurans.

PubMed

Bonnefoy, Violaine; Grail, Barry M; Johnson, D Barrie

2018-04-01

The type strain of the mineral-oxidizing acidophilic bacterium Acidithiobacillus ferridurans was grown in liquid medium containing elevated concentrations of sodium chloride with hydrogen as electron donor. While it became more tolerant to chloride, after about 1 year, the salt-stressed acidophile was found to have lost its ability to oxidize iron, though not sulfur or hydrogen. Detailed molecular examination revealed that this was due to an insertion sequence, IS Afd1 , which belongs to the IS Pepr1 subgroup of the IS 4 family, having been inserted downstream of the two promoters PI and PII of the rus operon (which codes for the iron oxidation pathway in this acidophile), thereby preventing its transcription. The ability to oxidize iron was regained on protracted incubation of the culture inoculated onto salt-free solid medium containing ferrous iron and incubated under hydrogen. Two revertant strains were obtained. In one, the insertion sequence IS Afd1 had been excised, leaving an 11-bp signature, while in the other an ∼2,500-bp insertion sequence (belonging to the IS 66 family) was detected in the downstream inverted repeat of IS Afd1 The transcriptional start site of the rus operon in the second revertant strain was downstream of the two ISs, due to the creation of a new "hybrid" promoter. The loss and subsequent regaining of the ability of A. ferridurans T to reduce ferric iron were concurrent with those observed for ferrous iron oxidation, suggesting that these two traits are closely linked in this acidophile. IMPORTANCE Iron-oxidizing acidophilic bacteria have primary roles in the oxidative dissolution of sulfide minerals, a process that underpins commercial mineral-processing biotechnologies ("biomining"). Most of these prokaryotes have relatively low tolerance to chloride, which limits their activities when only saline or brackish waters are available. The study showed that it was possible to adapt a typical iron-oxidizing acidophile to grow in the presence of salt concentrations similar to those in seawater, but in so doing they lost their ability to oxidize iron, though not sulfur or hydrogen. The bacterium regained its capacity for oxidizing iron when the salt stress was removed but simultaneously reverted to tolerating lower concentrations of salt. These results suggest that the bacteria that have the main roles in biomining operations could survive but become ineffective in cases where saline or brackish waters are used for irrigation. Copyright © 2018 American Society for Microbiology.

Alginate-Iron Speciation and Its Effect on In Vitro Cellular Iron Metabolism

PubMed Central

Horniblow, Richard D.; Dowle, Miriam; Iqbal, Tariq H.; Latunde-Dada, Gladys O.; Palmer, Richard E.

2015-01-01

Alginates are a class of biopolymers with known iron binding properties which are routinely used in the fabrication of iron-oxide nanoparticles. In addition, alginates have been implicated in influencing human iron absorption. However, the synthesis of iron oxide nanoparticles employs non-physiological pH conditions and whether nanoparticle formation in vivo is responsible for influencing cellular iron metabolism is unclear. Thus the aims of this study were to determine how alginate and iron interact at gastric-comparable pH conditions and how this influences iron metabolism. Employing a range of spectroscopic techniques under physiological conditions alginate-iron complexation was confirmed and, in conjunction with aberration corrected scanning transmission electron microscopy, nanoparticles were observed. The results infer a nucleation-type model of iron binding whereby alginate is templating the condensation of iron-hydroxide complexes to form iron oxide centred nanoparticles. The interaction of alginate and iron at a cellular level was found to decrease cellular iron acquisition by 37% (p < 0.05) and in combination with confocal microscopy the alginate inhibits cellular iron transport through extracellular iron chelation with the resulting complexes not internalised. These results infer alginate as being useful in the chelation of excess iron, especially in the context of inflammatory bowel disease and colorectal cancer where excess unabsorbed luminal iron is thought to be a driver of disease. PMID:26378798

Milk protein composition and stability changes affected by iron in water sources.

PubMed

Wang, Aili; Duncan, Susan E; Knowlton, Katharine F; Ray, William K; Dietrich, Andrea M

2016-06-01

Water makes up more than 80% of the total weight of milk. However, the influence of water chemistry on the milk proteome has not been extensively studied. The objective was to evaluate interaction of water-sourced iron (low, medium, and high levels) on milk proteome and implications on milk oxidative state and mineral content. Protein composition, oxidative stability, and mineral composition of milk were investigated under conditions of iron ingestion through bovine drinking water (infused) as well as direct iron addition to commercial milk in 2 studies. Four ruminally cannulated cows each received aqueous infusions (based on water consumption of 100L) of 0, 2, 5, and 12.5mg/L Fe(2+) as ferrous lactate, resulting in doses of 0, 200, 500 or 1,250mg of Fe/d, in a 4×4Latin square design for a 14-d period. For comparison, ferrous sulfate solution was directly added into commercial retail milk at the same concentrations: control (0mg of Fe/L), low (2mg of Fe/L), medium (5mg of Fe/L), and high (12.5mg of Fe/L). Two-dimensional electrophoresis coupled with matrix-assisted laser desorption/ionization-tandem time-of-flight (MALDI-TOF/TOF) high-resolution tandem mass spectrometry analysis was applied to characterize milk protein composition. Oxidative stability of milk was evaluated by the thiobarbituric acid reactive substances (TBARS) assay for malondialdehyde, and mineral content was measured by inductively coupled plasma mass spectrometry. For milk from both abomasal infusion of ferrous lactate and direct addition of ferrous sulfate, an iron concentration as low as 2mg of Fe/L was able to cause oxidative stress in dairy cattle and infused milk, respectively. Abomasal infusion affected both caseins and whey proteins in the milk, whereas direct addition mainly influenced caseins. Although abomasal iron infusion did not significantly affect oxidation state and mineral balance (except iron), it induced oxidized off-flavor and partial degradation of whey proteins. Direct iron addition to milk led to lipid oxidation during storage at 4°C. Oxidation level was positively associated with the concentration of added iron. Minerals (Mg, P, Na, K, Ca, Zn) in milk were not affected by the added iron in milk. This study indicated that a small amount of iron contamination in bovine drinking water at the farm or incidental iron addition from potable water sources causes oxidation, affects milk protein composition and stability, and affects final milk quality. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Study of Nanodispersed Iron Oxides Produced in Steel Drilling by Contracted Electric-Arc Air Plasma Torch

NASA Astrophysics Data System (ADS)

Stefanov, P.; Galanov, D.; Vissokov, G.; Paneva, D.; Kunev, B.; Mitov, I.

2008-06-01

The optimal conditions on the plasma-forming gas flowrate, discharge current and voltage, distance between the plasma-torch nozzle and the metal plate surface for the process of penetration in and vaporization of steel plates by the contracted electric-arc air plasma torch accompanied by water quenching, were determined. The X-ray structural and phase studies as well as Mössbauer and electron microscope studies on the samples treated were performed. It was demonstrated that the vaporized elemental iron was oxidized by the oxygen present in the air plasma jet to form iron oxides (wüstite, magnetite, hematite), which, depending on their mass ratios, determined the color of the iron oxide pigments, namely, beginning from light yellow, through deep yellow, light brown, deep brown, violet, red-violet, to black. A high degree of dispersity of the iron oxides is thus produced, with an averaged diameter of the particles below 500 nm, and their defective crystal structure form the basis of their potential application as components of iron-containing catalysts and pigments.

Liquid Phase Plasma Synthesis of Iron Oxide Nanoparticles on Nitrogen-Doped Activated Carbon Resulting in Nanocomposite for Supercapacitor Applications.

PubMed

Lee, Heon; Lee, Won-June; Park, Young-Kwon; Ki, Seo Jin; Kim, Byung-Joo; Jung, Sang-Chul

2018-03-25

Iron oxide nanoparticles supported on nitrogen-doped activated carbon powder were synthesized using an innovative plasma-in-liquid method, called the liquid phase plasma (LPP) method. Nitrogen-doped carbon (NC) was prepared by a primary LPP reaction using an ammonium chloride reactant solution, and an iron oxide/NC composite (IONCC) was prepared by a secondary LPP reaction using an iron chloride reactant solution. The nitrogen component at 3.77 at. % formed uniformly over the activated carbon (AC) surface after a 1 h LPP reaction. Iron oxide nanoparticles, 40~100 nm in size, were impregnated homogeneously over the NC surface after the LPP reaction, and were identified as Fe₃O₄ by X-ray photoelectron spectroscopy and X-ray diffraction. NC and IONCCs exhibited pseudo-capacitive characteristics, and their specific capacitance and cycling stability were superior to those of bare AC. The nitrogen content on the NC surface increased the compatibility and charge transfer rate, and the composites containing iron oxide exhibited a lower equivalent series resistance.

Ligand-Enhanced Abiotic Iron Oxidation and the Effects of Chemical versus Biological Iron Cycling in Anoxic Environments

PubMed Central

2013-01-01

This study introduces a newly isolated, genetically tractable bacterium (Pseudogulbenkiania sp. strain MAI-1) and explores the extent to which its nitrate-dependent iron-oxidation activity is directly biologically catalyzed. Specifically, we focused on the role of iron chelating ligands in promoting chemical oxidation of Fe(II) by nitrite under anoxic conditions. Strong organic ligands such as nitrilotriacetate and citrate can substantially enhance chemical oxidation of Fe(II) by nitrite at circumneutral pH. We show that strain MAI-1 exhibits unambiguous biological Fe(II) oxidation despite a significant contribution (∼30–35%) from ligand-enhanced chemical oxidation. Our work with the model denitrifying strain Paracoccus denitrificans further shows that ligand-enhanced chemical oxidation of Fe(II) by microbially produced nitrite can be an important general side effect of biological denitrification. Our assessment of reaction rates derived from literature reports of anaerobic Fe(II) oxidation, both chemical and biological, highlights the potential competition and likely co-occurrence of chemical Fe(II) oxidation (mediated by microbial production of nitrite) and truly biological Fe(II) oxidation. PMID:23402562

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

PubMed Central

Mammeri, Fayna; Ammar, Souad

2018-01-01

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

Activation of Hydrogen Peroxide by Iron-Containing Minerals and Catalysts in Circumneutral pH Solutions: Implications for ex situ and in situ Treatment of Contaminated Water and Soil

NASA Astrophysics Data System (ADS)

Pham, Anh Le Tuan

The decomposition of hydrogen peroxide (H2O2) on iron minerals can generate hydroxyl radical (•OH), a strong oxidant capable of transforming a wide range of contaminants. This reaction is critical to ex situ advanced oxidation processes employed in waste treatment systems, as well as in situ chemical oxidation processes used for soil and groundwater remediation. Unfortunately, the process in the ex situ treatment systems is relatively inefficient at circumneutral pH values. In this research, the development of iron-containing catalysts with improved efficiency was investigated. In addition, little is known about the factors that control the performance of in situ treatment systems. Another aim of this dissertation was to elucidate those factors to provide a basis for improving the efficiency of the remediation method. Two types of silica- and alumina-containing iron (hydr)oxide catalysts were synthesized by sol-gel processing techniques (Chapter 2). Relative to iron oxides, such as hematite and goethite, these catalysts were 10 to 80 times more effective in catalyzing the production of •OH from H2O2 under circumneutral conditions. The higher efficiency makes these catalysts promising candidates for ex situ advanced oxidation processes. Moreover, because alumina and silica alter the reactivity of the iron oxides with H2O2, understanding the activity of iron associated with natural aluminosilicates and silica-containing minerals in the subsurface is crucial to explaining the variability of •OH production observed in in situ treatment systems. In addition to the sol-gel technique used in Chapter 2, silica-containing iron (hydr)oxide catalysts were synthesized by immobilizing iron oxide onto mesoporous silica supports, such as SBA-15 (Chapter 5). The iron-containing SBA-15 was 10 times more effective than iron oxides in catalyzing the production of •OH from H2O2. Moreover, this catalyst could be employed for selective oxidation of small organic contaminants based on size exclusion. However, a major drawback of the mesoporous silica-based catalysts is their instability under circumneutral conditions (Chapter 6). The dissolution of mesoporous silica materials raises questions about their use for water treatment, because silica dissolution might compromise the behavior of the material. To gain insight into factors that control H2O2 persistence and •OH yield in in situ processes, the decomposition of H2O2 and transformation of contaminants were investigated in the presence of iron-containing minerals and aquifer materials (Chapter 3). Consistent with the observation described in Chapter 2, iron-containing aluminosilicates were more effective than iron oxides in converting H2O2 into •OH. In both iron-containing mineral and aquifer material systems, the yield of •OH was inversely correlated with the rate of H 2O2 decomposition. In the aquifer material systems, the yield also inversely correlated with the Mn content, consistent with the fact that the decomposition of H2O2 on manganese oxides does not produce •OH. The inverse correlation between Mn content and H2O2 loss rate and •OH yield suggests that the amount of Mn in aquifer materials could serve as a proxy for predicting H2O2 decomposition rates and contaminant oxidation efficiency. In addition to the surface and structure properties of iron solids, the presence of solutes, such as dissolved silica, also affected the decomposition of H2O2 (Chapter 4). The adsorption of dissolved silica onto mineral surfaces altered the catalytic sites, thereby decreasing the reactivity of iron- and manganese-containing minerals with H2O 2. Therefore, the presence of dissolved SiO2 could lead to greater persistence of H2O2 in groundwater, which should be considered in the design of in situ H2O 2-based treatment systems. In addition to in situ treatment, dissolved silica also can affect the reactivity of iron-containing catalysts used in ex situ processes. Therefore, its presence in contaminated industrial wastewater should be considered when ex situ treatment systems are designed.

The nature of iron deposits differs between symptomatic and asymptomatic carotid atherosclerotic plaques

DOE PAGES

Kopriva, David; Kisheev, Anastasye; Meena, Deiter; ...

2015-11-25

Iron within atherosclerotic plaque has been implicated as a catalyst of oxidative stress that causes progression of plaque, and plaque rupture. Iron is believed to accumulate within plaque by incorporation of erythrocytes following plaque rupture and hemorrhage. There is only indirect evidence to support this hypothesis. Plaque specimens were obtained from ten symptomatic and fifteen asymptomatic patients undergoing carotid endarterectomy at a single institution. Plaques were sectioned for study using synchrotron radiation induced X-ray fluorescence the study the distribution of zinc, calcium and iron. Histologic staining was carried out with Prussian Blue, and immunohistochemical staining was done to localize macrophagesmore » with CD68. Data were compared against patient clinical variables. Ten symptomatic (15 ± 10 days between index symptoms and surgery) and fifteen asymptomatic carotid plaques were studied. Zinc and calcium co-localized in mineralized areas of symptomatic and asymptomatic plaque. Iron was identified away from zinc and calcium in both symptomatic and asymptomatic plaques. Within the symptomatic plaques, iron was found within the thrombus associated with plaque rupture and hemorrhage. It did not stain with Prussian Blue, but was found in association with CD68 positive macrophages. In symptomatic plaques, the abundance of iron showed an association with the source patient’s LDL cholesterol (R 2 = 0.39, Significance F = 0.05). Iron in asymptomatic plaque was present as hemosiderin/ferritin that stained positive with Prussian Blue, and was observed in association with CD68 positive macrophages. Iron in acutely symptomatic plaques is found within thrombus, in the presence of macrophages. Moreover, the abundance of iron in symptomatic plaques is associated with the source patient’s LDL cholesterol. Within asymptomatic plaques, iron is found in association with macrophages, as hemosiderin/ferritin.« less

The Nature of Iron Deposits Differs between Symptomatic and Asymptomatic Carotid Atherosclerotic Plaques

PubMed Central

Kopriva, David; Kisheev, Anastasye; Meena, Deiter; Pelle, Shaneen; Karnitsky, Max; Lavoie, Andrea; Buttigieg, Josef

2015-01-01

Iron within atherosclerotic plaque has been implicated as a catalyst of oxidative stress that causes progression of plaque, and plaque rupture. Iron is believed to accumulate within plaque by incorporation of erythrocytes following plaque rupture and hemorrhage. There is only indirect evidence to support this hypothesis. Plaque specimens were obtained from ten symptomatic and fifteen asymptomatic patients undergoing carotid endarterectomy at a single institution. Plaques were sectioned for study using synchrotron radiation induced X-ray fluorescence the study the distribution of zinc, calcium and iron. Histologic staining was carried out with Prussian Blue, and immunohistochemical staining was done to localize macrophages with CD68. Data were compared against patient clinical variables. Ten symptomatic (15 ± 10 days between index symptoms and surgery) and fifteen asymptomatic carotid plaques were studied. Zinc and calcium co-localized in mineralized areas of symptomatic and asymptomatic plaque. Iron was identified away from zinc and calcium in both symptomatic and asymptomatic plaques. Within the symptomatic plaques, iron was found within the thrombus associated with plaque rupture and hemorrhage. It did not stain with Prussian Blue, but was found in association with CD68 positive macrophages. In symptomatic plaques, the abundance of iron showed an association with the source patient’s LDL cholesterol (R2 = 0.39, Significance F = 0.05). Iron in asymptomatic plaque was present as hemosiderin/ferritin that stained positive with Prussian Blue, and was observed in association with CD68 positive macrophages. Iron in acutely symptomatic plaques is found within thrombus, in the presence of macrophages. The abundance of iron in symptomatic plaques is associated with the source patient’s LDL cholesterol. Within asymptomatic plaques, iron is found in association with macrophages, as hemosiderin/ferritin. PMID:26606178

The nature of iron deposits differs between symptomatic and asymptomatic carotid atherosclerotic plaques

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

Kopriva, David; Kisheev, Anastasye; Meena, Deiter

Iron within atherosclerotic plaque has been implicated as a catalyst of oxidative stress that causes progression of plaque, and plaque rupture. Iron is believed to accumulate within plaque by incorporation of erythrocytes following plaque rupture and hemorrhage. There is only indirect evidence to support this hypothesis. Plaque specimens were obtained from ten symptomatic and fifteen asymptomatic patients undergoing carotid endarterectomy at a single institution. Plaques were sectioned for study using synchrotron radiation induced X-ray fluorescence the study the distribution of zinc, calcium and iron. Histologic staining was carried out with Prussian Blue, and immunohistochemical staining was done to localize macrophagesmore » with CD68. Data were compared against patient clinical variables. Ten symptomatic (15 ± 10 days between index symptoms and surgery) and fifteen asymptomatic carotid plaques were studied. Zinc and calcium co-localized in mineralized areas of symptomatic and asymptomatic plaque. Iron was identified away from zinc and calcium in both symptomatic and asymptomatic plaques. Within the symptomatic plaques, iron was found within the thrombus associated with plaque rupture and hemorrhage. It did not stain with Prussian Blue, but was found in association with CD68 positive macrophages. In symptomatic plaques, the abundance of iron showed an association with the source patient’s LDL cholesterol (R 2 = 0.39, Significance F = 0.05). Iron in asymptomatic plaque was present as hemosiderin/ferritin that stained positive with Prussian Blue, and was observed in association with CD68 positive macrophages. Iron in acutely symptomatic plaques is found within thrombus, in the presence of macrophages. Moreover, the abundance of iron in symptomatic plaques is associated with the source patient’s LDL cholesterol. Within asymptomatic plaques, iron is found in association with macrophages, as hemosiderin/ferritin.« less

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

PubMed Central

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

Intra-puff CO and CO 2 measurements of cigarettes with iron oxide cigarette paper using quantum cascade laser spectroscopy

NASA Astrophysics Data System (ADS)

Crawford, Danielle R.; Parrish, Milton E.; Gee, Diane L.; Harward, Charles N.

2007-05-01

The objective of this research was to apply Fourier transform infrared spectroscopy (FTIR) and tunable infrared laser differential absorption spectroscopy (TILDAS) for measuring selected gaseous constituents in mainstream (MS) and sidestream (SS) smoke for experimental cigarettes designed to reduce MS CO using iron oxide cigarette papers. These two complimentary analytical techniques are well suited for providing per puff smoke deliveries and intra-puff evolution profiles in cigarette smoke respectively. The quad quantum cascade (QC) laser high resolution infrared spectroscopy system has the necessary temporal and spectral resolution and whole smoke analysis capabilities to provide detailed information for CO and CO 2 as they are being formed in both MS and SS smoke. The QC laser system has an optimal data rate of 20 Hz and a unique puffing system, with a square wave shaped puff, that allows whole smoke to enter an 18 m, 0.3 L multi-pass gas cell in real time (0.1 s cell response time) requiring no syringe or Cambridge filter pad. Another similar multi-pass gas cell with a 36 m pathlength simultaneously monitors the sidestream cigarette smoke. The smoke from experimental cigarettes manufactured with two types of iron oxide papers were compared to the smoke from cigarettes manufactured similarly without iron oxide in the paper using both instrument systems. The delivery per puff determined by the QC laser method agreed with FTIR results. MS CO intra-puff evolution profiles for iron oxide prototype cigarettes demonstrated CO reduction when compared to cigarettes without iron oxide paper. Additionally, both CO and CO 2 intra-puff evolution profiles of the cigarettes with iron oxide paper showed a significant reduction at the initial portion of the 2 s puff not observed in the non-iron oxide prototype cigarettes. This effect also was observed for ammonia and ethylene, suggesting that physical parameters such as paper porosity and burn rate are important. The SS CO and CO 2 deliveries for the experimental cigarettes evaluated remained unaffected. The iron oxide paper technology remains under development and continues to be evaluated.

Intra-puff CO and CO2 measurements of cigarettes with iron oxide cigarette paper using quantum cascade laser spectroscopy.

PubMed

Crawford, Danielle R; Parrish, Milton E; Gee, Diane L; Harward, Charles N

2007-05-01

The objective of this research was to apply Fourier transform infrared spectroscopy (FTIR) and tunable infrared laser differential absorption spectroscopy (TILDAS) for measuring selected gaseous constituents in mainstream (MS) and sidestream (SS) smoke for experimental cigarettes designed to reduce MS CO using iron oxide cigarette papers. These two complimentary analytical techniques are well suited for providing per puff smoke deliveries and intra-puff evolution profiles in cigarette smoke respectively. The quad quantum cascade (QC) laser high resolution infrared spectroscopy system has the necessary temporal and spectral resolution and whole smoke analysis capabilities to provide detailed information for CO and CO(2) as they are being formed in both MS and SS smoke. The QC laser system has an optimal data rate of 20 Hz and a unique puffing system, with a square wave shaped puff, that allows whole smoke to enter an 18 m, 0.3 L multi-pass gas cell in real time (0.1s cell response time) requiring no syringe or Cambridge filter pad. Another similar multi-pass gas cell with a 36 m pathlength simultaneously monitors the sidestream cigarette smoke. The smoke from experimental cigarettes manufactured with two types of iron oxide papers were compared to the smoke from cigarettes manufactured similarly without iron oxide in the paper using both instrument systems. The delivery per puff determined by the QC laser method agreed with FTIR results. MS CO intra-puff evolution profiles for iron oxide prototype cigarettes demonstrated CO reduction when compared to cigarettes without iron oxide paper. Additionally, both CO and CO(2) intra-puff evolution profiles of the cigarettes with iron oxide paper showed a significant reduction at the initial portion of the 2 s puff not observed in the non-iron oxide prototype cigarettes. This effect also was observed for ammonia and ethylene, suggesting that physical parameters such as paper porosity and burn rate are important. The SS CO and CO(2) deliveries for the experimental cigarettes evaluated remained unaffected. The iron oxide paper technology remains under development and continues to be evaluated.

Visualized effect of oxidation on magnetic recording fidelity in pseudo-single-domain magnetite particles

PubMed Central

Almeida, Trevor P.; Kasama, Takeshi; Muxworthy, Adrian R.; Williams, Wyn; Nagy, Lesleis; Hansen, Thomas W.; Brown, Paul D.; Dunin-Borkowski, Rafal E.

2014-01-01

Magnetite (Fe3O4) is an important magnetic mineral to Earth scientists, as it carries the dominant magnetic signature in rocks, and the understanding of its magnetic recording fidelity provides a critical tool in the field of palaeomagnetism. However, reliable interpretation of the recording fidelity of Fe3O4 particles is greatly diminished over time by progressive oxidation to less magnetic iron oxides, such as maghemite (γ-Fe2O3), with consequent alteration of remanent magnetization potentially having important geological significance. Here we use the complementary techniques of environmental transmission electron microscopy and off-axis electron holography to induce and visualize the effects of oxidation on the magnetization of individual nanoscale Fe3O4 particles as they transform towards γ-Fe2O3. Magnetic induction maps demonstrate a change in both strength and direction of remanent magnetization within Fe3O4 particles in the size range dominant in rocks, confirming that oxidation can modify the original stored magnetic information. PMID:25300366

Visualized effect of oxidation on magnetic recording fidelity in pseudo-single-domain magnetite particles.

PubMed

Almeida, Trevor P; Kasama, Takeshi; Muxworthy, Adrian R; Williams, Wyn; Nagy, Lesleis; Hansen, Thomas W; Brown, Paul D; Dunin-Borkowski, Rafal E

2014-10-10

Magnetite (Fe3O4) is an important magnetic mineral to Earth scientists, as it carries the dominant magnetic signature in rocks, and the understanding of its magnetic recording fidelity provides a critical tool in the field of palaeomagnetism. However, reliable interpretation of the recording fidelity of Fe3O4 particles is greatly diminished over time by progressive oxidation to less magnetic iron oxides, such as maghemite (γ-Fe2O3), with consequent alteration of remanent magnetization potentially having important geological significance. Here we use the complementary techniques of environmental transmission electron microscopy and off-axis electron holography to induce and visualize the effects of oxidation on the magnetization of individual nanoscale Fe3O4 particles as they transform towards γ-Fe2O3. Magnetic induction maps demonstrate a change in both strength and direction of remanent magnetization within Fe3O4 particles in the size range dominant in rocks, confirming that oxidation can modify the original stored magnetic information.

Hawaiian submarine manganese-iron oxide crusts - A dating tool?

USGS Publications Warehouse

Moore, J.G.; Clague, D.A.

2004-01-01

Black manganese-iron oxide crusts form on most exposed rock on the ocean floor. Such crusts are well developed on the steep lava slopes of the Hawaiian Ridge and have been sampled during dredging and submersible dives. The crusts also occur on fragments detached from bedrock by mass wasting, on submerged coral reefs, and on poorly lithified sedimentary rocks. The thickness of the crusts was measured on samples collected since 1965 on the Hawaiian Ridge from 140 dive or dredge localities. Fifty-nine (42%) of the sites were collected in 2001 by remotely operated vehicles (ROVs). The thinner crusts on many samples apparently result from post-depositional breakage, landsliding, and intermittent burial of outcrops by sediment. The maximum crust thickness was selected from each dredge or dive site to best represent crusts on the original rock surface at that site. The measurements show an irregular progressive thickening of the crusts toward the northwest-i.e., progressive thickening toward the older volcanic features with increasing distance from the Hawaiian hotspot. Comparison of the maximum crust thickness with radiometric ages of related subaerial features supports previous studies that indicate a crust-growth rate of about 2.5 mm/m.y. The thickness information not only allows a comparison of the relative exposure ages of two or more features offshore from different volcanoes, but also provides specific age estimates of volcanic and landslide deposits. The data indicate that some of the landslide blocks within the south Kona landslide are the oldest exposed rock on Mauna Loa, Kilauea, or Loihi volcanoes. Crusts on the floors of submarine canyons off Kohala and East Molokai volcanoes indicate that these canyons are no longer serving as channelways for downslope, sediment-laden currents. Mahukona volcano was approximately synchronous with Hilo Ridge, both being younger than Hana Ridge. The Nuuanu landslide is considerably older than the Wailau landslide. The Waianae landslide southwest of Oahu has yielded samples with the greatest manganese-iron oxide crusts (9.5 mm thick) and therefore apparently represents the oldest submarine material yet found in the study area. The submarine volcanic field 100 km southwest of Oahu is apparently younger than the Waianae landslide. ?? 2004 Geological Society of America.

IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

PubMed Central

Schafer, Freya Q.; Yue Qian, Steven; Buettner, Garry R.

2013-01-01

Brain tissue being rich in polyunsaturated fatty acids, is very susceptible to lipid peroxidation. Iron is well known to be an important initiator of free radical oxidations. We propose that the principal route to iron-mediated lipid peroxidations is via iron-oxygen complexes rather than the reaction of iron with hydrogen peroxide, the Fenton reaction. To test this hypothesis, we enriched leukemia cells (K-562 and L1210 cells) with docosahexaenoic acid (DHA) as a model for brain tissue, increasing the amount of DHA from approximately 3 mole % to 32 mole %. These cells were then subjected to ferrous iron and dioxygen to initiate lipid peroxidation in the presence or absence of hydrogen peroxide. Lipid-derived radicals were detected using EPR spin trapping with α-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN). As expected, lipid-derived radical formation increases with increasing cellular lipid unsaturation. Experiments with Desferal demonstrate that iron is required for the formation of lipid radicals from these cells. Addition of iron to DHA-enriched L1210 cells resulted in significant amounts of radical formation; radical formation increased with increasing amount of iron. However, the exposure of cells to hydrogen peroxide before the addition of ferrous iron did not increase cellular radical formation, but actually decreased spin adduct formation. These data suggest that iron-oxygen complexes are the primary route to the initiation of biological free radical oxidations. This model proposes a mechanism to explain how catalytic iron in brain tissue can be so destructive. PMID:10872752

The nanosphere iron mineral(s) in Mars soil

NASA Technical Reports Server (NTRS)

Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

1993-01-01

A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.

Amphorous hydrated Fe(III) sulfate: metastable product and bio-geochemical marker of iron oxidizing thiobacilli

NASA Astrophysics Data System (ADS)

Lazaroff, Norman; Jollie, John; Dugan, Patrick R.

1998-07-01

Chemolithotrophic iron oxidation by Thiobacillus ferrooxidans and other iron oxidizing thiobacilli produce an Fe(III) sulfato complex that polymerizes as x-ray amorphous filaments approximately 40 nm in diameter. The precursor complex in solutionis seen by ATR-FTIR spectroscopy to have a sulfate spectrum resembling the v(subscript 3) and v(subscript 1) vibrational modes of the precipitated polymer. Chemically similar precipitates prepared by oxidation of acid ferrous sulfate with hydrogen peroxide have a different micromorphology, higher iron/sulfur ratio and acid solubility than the bacterial product. They possess coalescing globular microstructures composed of compacted micro-fibrils. Scanning electron microscopy and diffuse reflectance FTIR show the formation of iron polymer on the surface of immobilized cells of T. ferrooxidans, oxidizing iron during the corrosion of steel. Although spatially separated form the steel coupons by a membrane filter, the cell walls become covered with tufts of amorphous hydrated Fe(III) sulfate. The metastable polymer is converted to crystalline goethite, lepidocrocite, and magnetite in that order, as the pH rises due to proton reduction at cathodic sites on the steel. The instability of the iron polymer to changes in pH is also evidenced by the loss of sulfate when washed with lithium hydroxide solution at pH 8. Under those conditions there is little change in micromorphology, but restoration of sulfate with sulfuric acid at pH 2.5, fails to re-establish the original chemical structure. Adding sulfate salts of appropriate cations to solutions of the Fe(III) sulfato complex or suspensions of its precipitated polymer in dilute sulfuric acid, result in dissociation of the metastable complex followed by crystallization of ferric ions and sulfate in jarosites. Jarosites and other derivatives of iron precipitation by iron oxidizing thiobacilli, form conspicuous deposits in areas of natural pyrite leaching. The role of iron oxidizing thiobacilli in pyrite leaching, biohydrometallurgy, acid mine drainage, and the cycle of iron and sulfur in nature, has been studied for nearly 50 years. The manifestation of those activities, so widespread on Earth, can be a clue for seeking evidence of life elsewhere.

Diagram of Lake Stratification on Mars

NASA Image and Video Library

2017-06-01

This diagram presents some of the processes and clues related to a long-ago lake on Mars that became stratified, with the shallow water richer in oxidants than deeper water was. The sedimentary rocks deposited within a lake in Mars' Gale Crater more than three billion years ago differ from each other in a pattern that matches what is seen in lakes on Earth. As sediment-bearing water flows into a lake, bedding thickness and particle size progressively decrease as sediment is deposited in deeper and deeper water as seen in examples of thick beds (PIA19074) from shallowest water, thin beds (PIA19075) from deeper water and even thinner beds (PIA19828) from deepest water. At sites on lower Mount Sharp, inside the crater, measurements of chemical and mineral composition by NASA's Curiosity Mars rover reveal a clear correspondence between the physical characteristics of sedimentary rock from different parts of the lake and how strongly oxidized the sediments were. Rocks with textures indicating that the sediments were deposited near the edge of a lake have more strongly oxidized composition than rocks with textures indicating sedimentation in deep water. For example, the iron mineral hematite is more oxidized than the iron mineral magnetite. An explanation for why such chemical stratification occurs in a lake is that the water closer to the surface is more exposed to oxidizing effects of oxygen in the atmosphere and ultraviolet light. On Earth, a stratified lake with a distinct boundary between oxidant-rich shallows and oxidant-poor depths provides a diversity of environments suited to different types of microbes. If Mars has ever hosted microbial live, the stratified lake at Gale Crater may have similarly provided a range of different habitats for life. https://photojournal.jpl.nasa.gov/catalog/PIA21500

Iron accumulates in the lavage and explanted lungs of cystic fibrosis patients.

EPA Science Inventory

Abstract Oxidative stress participates in the pathophysiology of cystic fibrosis (CF). An underlying disruption in iron homeostasis can frequently be demonstrated in injuries and diseases associated with an oxidative stress. We tested the hypothesis that iron accumulation and ...

Diverse arsenic- and iron-cycling microbial communities in arsenic-contaminated aquifers used for drinking water in Bangladesh.

PubMed

Hassan, Zahid; Sultana, Munawar; van Breukelen, Boris M; Khan, Sirajul I; Röling, Wilfred F M

2015-04-01

Subsurface removal of arsenic by injection with oxygenated groundwater has been proposed as a viable technology for obtaining 'safe' drinking water in Bangladesh. While the oxidation of ferrous iron to solid ferric iron minerals, to which arsenic adsorbs, is assumed to be driven by abiotic reactions, metal-cycling microorganisms may potentially affect arsenic removal. A cultivation-independent survey covering 24 drinking water wells in several geographical regions in Bangladesh was conducted to obtain information on microbial community structure and diversity in general, and on specific functional groups capable of the oxidation or reduction of arsenic or iron. Each functional group, targeted by either group-specific 16S rRNA or functional gene amplification, occurred in at least 79% of investigated samples. Putative arsenate reducers and iron-oxidizing Gallionellaceae were present at low diversity, while more variation in potentially arsenite-oxidizing microorganisms and iron-reducing Desulfuromonadales was revealed within and between samples. Relations between community composition on the one hand and hydrochemistry on the other hand were in general not evident, apart from an impact of salinity on iron-cycling microorganisms. Our data suggest widespread potential for a positive contribution of arsenite and iron oxidizers to arsenic removal upon injection with oxygenated water, but also indicate a potential risk for arsenic re-mobilization by anaerobic arsenate and iron reducers once injection is halted. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Influence of experimental parameters on iron oxide nanoparticle properties synthesized by thermal decomposition: size and nuclear magnetic resonance studies

NASA Astrophysics Data System (ADS)

Belaïd, Sarah; Stanicki, Dimitri; Vander Elst, Luce; Muller, Robert N.; Laurent, Sophie

2018-04-01

A study of the experimental conditions to synthesize monodisperse iron oxide nanocrystals prepared from the thermal decomposition of iron(III) acetylacetonate was carried out in the presence of surfactants and a reducing agent. The influence of temperature, synthesis time and surfactant amounts on nanoparticle properties is reported. This investigation combines relaxometric characterization and size properties. The relaxometric behavior of the nanomaterials depends on the selected experimental parameters. The synthesis of iron oxide nanoparticles with a high relaxivity and a high saturation magnetization can be obtained with a short reaction time at high temperature. Moreover, the influence of surfactant concentrations determines the optimal value in order to produce iron oxide nanoparticles with a narrow size distribution. The optimized synthesis is rapid, robust and reproductive, and produces nearly monodisperse magnetic nanocrystals.

Shape control of the magnetic iron oxide nanoparticles under different chain length of reducing agents

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

Ngoi, Kuan Hoon; Chia, Chin-Hua, E-mail: chia@ukm.edu.my; Zakaria, Sarani

2015-09-25

We report on the effect of using reducing agents with different chain-length on the synthesis of iron oxide nanoparticles by thermal decomposition of iron (III) acetylacetonate in 1-octadecene. This modification allows us to control the shape of nanoparticles into spherical and cubic iron oxide nanoparticles. The highly monodisperse 14 nm spherical nanoparticles are obtained under 1,2-dodecanediol and average 14 nm edge-length cubic iron oxide nanoparticles are obtained under 1,2-tetradecanediol. The structural characterization such as transmission electron microscope (TEM) and X-ray diffraction (XRD) shows similar properties between two particles with different shapes. The vibrating sample magnetometer (VSM) shows no significant difference between sphericalmore » and cubic nanoparticles, which are 36 emu/g and 37 emu/g respectively and superparamagnetic in nature.« less

Plasma synthesis, Mössbauer spectroscopy and X-ray diffraction studies of nanosized iron oxides

NASA Astrophysics Data System (ADS)

Paneva, Daniela; Zaharieva, Katerina; Grabis, Janis; Mitov, Ivan; Vissokov, Gheorghi

2010-06-01

In this article synthesis and study of iron oxide nanopowders are described. The synthesis of sample 1 and sample 2—iron oxides—was carried out by electric arc plasma cutting of ordinary steel. The sample 3 was prepared by evaporation of Fe2O3/FeO mixture in radio-frequency nitrogen plasma. The characterization of the as prepared iron oxide nanoproducts was achieved by means of Mössbauer spectroscopy and X-ray diffraction analysis. The presence of different phases of iron oxide with a basic phase Fe3 - xO4 (magnetite), additional Fe1 - xO (wüstite) and α or γ-Fe2O3 (hematite or maghemite) with superparamagnetic particles for sample 1 and sample 2 and Fe3 - xO4 (magnetite) for sample 3 is observed.

Mössbauer study of oxide films of Fe-, Sn-, Cr- doped zirconium alloys during corrosion in autoclave

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Bateev, A. B.; Lauer, Yu. A.

2016-12-01

Mössbauer investigations were used to compare iron atom states in oxide films of binary Zr-Fe, ternary Zr-Fe-Cu and quaternary Zr-Fe-Cr-Sn alloys. Oxide films are received in an autoclave at a temperature of 350-360 °C and at pressure of 16.8 MPa. The corrosion process decomposes the intermetallic precipitates in alloys and forms metallic iron with inclusions of chromium atoms α-Fe(Cr), α-Fe(Cu), α-Fe 2O3 and Fe 3O4 compounds. Some iron ions are formed in divalent and in trivalent paramagnetic states. The additional doping influences on corrosion kinetics and concentration of iron compounds and phases formed in oxide films. It was shown the correlation between concentration of iron in different chemical states and corrosion resistance of alloys.

Tropical forest soil microbial communities couple iron and carbon biogeochemistry

Treesearch

Eric A. Dubinsky; Whendee L. Silver; Mary K. Firestone

2010-01-01

We report that iron-reducing bacteria are primary mediators of anaerobic carbon oxidation in upland tropical soils spanning a rainfall gradient (3500–5000 mm/yr) in northeast Puerto Rico. The abundant rainfall and high net primary productivity of these tropical forests provide optimal soil habitat for iron-reducing and iron-oxidizing bacteria. Spatially and temporally...

New developments and controversies in iron metabolism and iron chelation therapy

PubMed Central

Kontoghiorghe, Christina N; Kontoghiorghes, George J

2016-01-01

Iron is essential for all organisms including microbial, cancer and human cells. More than a quarter of the human population is affected by abnormalities of iron metabolism, mainly from iron deficiency and iron overload. Iron also plays an important role in free radical pathology and oxidative damage which is observed in almost all major diseases, cancer and ageing. New developments include the complete treatment of iron overload and reduction of morbidity and mortality in thalassaemia using deferiprone and selected deferiprone/deferoxamine combinations and also the use of the maltol iron complex in the treatment of iron deficiency anaemia. There is also a prospect of using deferiprone as a universal antioxidant in non iron overloaded diseases such as neurodegenerative, cardiovascular, renal, infectious diseases and cancer. New regulatory molecules of iron metabolism such as endogenous and dietary chelating molecules, hepcidin, mitochondrial ferritin and their role in health and disease is under evaluation. Similarly, new mechanisms of iron deposition, removal, distribution and toxicity have been identified using new techniques such as magnetic resonance imaging increasing our understanding of iron metabolic processes and the targeted treatment of related diseases. The uniform distribution of iron in iron overload between organs and within each organ is no longer valid. Several other controversies such as the toxicity impact of non transferrin bound iron vs injected iron, the excess levels of iron in tissues causing toxicity and the role of chelation on iron absorption need further investigation. Commercial interests of pharmaceutical companies and connections to leading journals are playing a crucial role in shaping worldwide medical opinion on drug sales and use but also patients’ therapeutic outcome and safety. Major controversies include the selection criteria and risk/benefit assessment in the use of deferasirox in thalassaemia and more so in idiopathic haemochromatosis, thalassaemia intermedia and ex-thalassaemia transplanted patients who are safely treated with venesection. Iron chelating drugs can override normal regulatory pathways, correct iron imbalance and minimise iron toxicity. The use of iron chelating drugs as main, alternative or adjuvant therapy is in progress in many conditions, especially those with non established or effective therapies. PMID:27019793

Decaking of coal or oil shale during pyrolysis in the presence of iron oxides

DOEpatents

Rashid Khan, M.

1988-05-05

A method for producing a fuel from the pyrolysis of coal or oil shale in the presence of iron oxide in an inert gas atmosphere is described. The method includes the steps of pulverizing feed coal or oil shale, pulverizing iron oxide, mixing the pulverized feed and iron oxide, and heating the mixture in a gas atmosphere which is substantially inert to the mixture so as to form a product fuel, which may be gaseous, liquid and/or solid. The method of the invention reduces the swelling of coals, such as bituminous coal and the like, which are otherwise known to swell during pyrolysis. 4 figs., 8 tabs.

Use of ultrasmall superparamagnetic iron oxide particles for imaging carotid atherosclerosis.

PubMed

Usman, Ammara; Sadat, Umar; Patterson, Andrew J; Tang, Tjun Y; Varty, Kevin; Boyle, Jonathan R; Armon, Mathew P; Hayes, Paul D; Graves, Martin J; Gillard, Jonathan H

2015-10-01

Based on the results of histopathological studies, inflammation within atherosclerotic tissue is now widely accepted as a key determinant of the disease process. Conventional imaging methods can highlight the location and degree of luminal stenosis but not the inflammatory activity of the plaque. Iron oxide-based MRI contrast media particularly ultrasmall supermagnetic particles of iron oxide have shown potential in assessing atheromatous plaque inflammation and in determining efficacy of antiatherosclerosis pharmacological treatments. In this paper, we review current data on the use of ultrasmall superparamagnetic iron oxides in atherosclerosis imaging with focus on ferumoxtran-10 and ferumoxytol. The basic chemistry, pharmacokinetics and dynamics, potential applications, limitations and future perspectives of these contrast media nanoparticles are discussed.

Environment friendly route of iron oxide nanoparticles from Zingiber officinale (ginger) root extract

NASA Astrophysics Data System (ADS)

Xin Hui, Yau; Yi Peng, Teoh; Wei Wen, Liu; Zhong Xian, Ooi; Peck Loo, Kiew

2016-11-01

Iron oxide nanoparticles were prepared from the reaction between the Zingiber officinale (ginger) root extracts and ferric chloride solution at 50°C for 2 h in mild stirring condition. The synthesized powder forms of nanoparticles were further characterized by using UV-Vis spectroscopy and X-ray Diffraction spectrometry. UV-Vis analysis shows the absorption peak of iron oxide nanoparticles is appeared at 370 nm. The calculation of crystallite size from the XRD showed that the average particle size of iron oxide nanoparticles was 68.43 nm. Therefore, this eco-friendly technique is low cost and large scale nanoparticles synthesis to fulfill the demand of various applications.

Nickel aluminides and nickel-iron aluminides for use in oxidizing environments

DOEpatents

Liu, Chain T.

1988-03-15

Nickel aluminides and nickel-iron aluminides treated with hafnium or zirconium, boron and cerium to which have been added chromium to significantly improve high temperature ductility, creep resistance and oxidation properties in oxidizing environments.

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

PubMed

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

2009-06-01

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

Biologically tunable reactivity of energetic nanomaterials using protein cages.

PubMed

Slocik, Joseph M; Crouse, Christopher A; Spowart, Jonathan E; Naik, Rajesh R

2013-06-12

The performance of aluminum nanomaterial based energetic formulations is dependent on the mass transport, diffusion distance, and stability of reactive components. Here we use a biologically inspired approach to direct the assembly of oxidizer loaded protein cages onto the surface of aluminum nanoparticles to improve reaction kinetics by reducing the diffusion distance between the reactants. Ferritin protein cages were loaded with ammonium perchlorate (AP) or iron oxide and assembled with nAl to create an oxidation-reduction based energetic reaction and the first demonstration of a nanoscale biobased thermite material. Both materials showed enhanced exothermic behavior in comparison to nanothermite mixtures of bulk free AP or synthesized iron oxide nanopowders prepared without the use of ferritin. In addition, by utilizing a layer-by-layer (LbL) process to build multiple layers of protein cages containing iron oxide and iron oxide/AP on nAl, stoichiometric conditions and energetic performance can be optimized.

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

NASA Technical Reports Server (NTRS)

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

1976-01-01

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

Heme Oxygenase 1 as a Therapeutic Target in Acute Kidney Injury

PubMed Central

Bolisetty, Subhashini; Zarjou, Abolfazl; Agarwal, Anupam

2017-01-01

A common clinical condition, acute kidney injury (AKI) significantly influences morbidity and mortality, particularly in critically ill patients. The pathophysiology of AKI is complex and involves multiple pathways including inflammation, autophagy, cell cycle progression, and oxidative stress. Recent evidence suggests that a single insult to the kidney significantly enhances the propensity to develop chronic kidney disease. Therefore, generation of effective therapies against AKI are timely. In this context, the cytoprotective effects of heme oxygenase 1 (HO-1) in animal models of AKI are well documented. HO-1 modulates oxidative stress, autophagy, and inflammation, and regulates the progression of cell cycle via direct and indirect mechanisms. These beneficial effects of HO-1 induction during AKI are, in part, mediated by the by-products of the HO reaction (iron, carbon monoxide, and bile pigments). This review highlights the recent advances in the molecular mechanisms of HO-1–mediated cytoprotection and discusses the translational potential of HO-1 induction in AKI. PMID:28139396

Influence of moderate pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing activated carbon.

PubMed

Wang, Zhengfang; Shi, Mo; Li, Jihua; Zheng, Zheng

2014-03-01

A novel adsorbent based on iron oxide dispersed over activated carbon (AC) were prepared, and used for phosphate removal from aqueous solutions. The influence of pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing AC were determined. Two series of ACs, non-oxidized and oxidized carbon modified by iron (denoted as AC-Fe and AC/O-Fe), resulted in a maximum impregnated iron of 4.03% and 7.56%, respectively. AC/O-Fe showed 34.0%-46.6% higher phosphate removal efficiency than the AC-Fe did. This was first attributed to the moderate pre-oxidation of raw AC by nitric acid, achieved by dosing Fe(II) after a pre-oxidation, to obtain higher iron loading, which is favorable for phosphate adsorption. Additionally, the in-situ formed active site on the surface of carbon, which was derived from the oxidation of Fe(II) by nitric acid dominated the remarkably high efficiency with respect to the removal of phosphate. The activation energy for adsorption was calculated to be 10.53 and 18.88 kJ/mol for AC-Fe and AC/O-Fe, respectively. The results showed that the surface mass transfer and intra-particle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2012-03-01

Iron oxide colloidal nanocrystals (ferrofluids) are investigated for application in the treatment of cystic fibrosis lung infections, the leading cause of mortality in cystic fibrosis patients. We investigate the use of iron oxide nanocrystals to increase the effectiveness of inhalation aerosol antibiotics therapy through two mechanisms: directed particle movement in the presence of a static external magnetic field and magnetic hyperthermia. Magnetic hyperthermia is an effective method for decreasing the viscosity of the mucus and biofilm thereby increasing drug, immune cell, and antibody penetration to the affected area. Iron oxide nanocrystals of various sizes and morphologies were synthesized and tested for specific losses (heating power) using frequencies of 111.1 kHz and 629.2 kHz, and corresponding magnetic field strengths of 9 and 25 mT. Nanocrystals in the superparamagnetic to ferromagnetic size range exhibited excellent heating power. Additionally, iron oxide-zinc selenide core-shell nanoparticles were prepared in parallel in order to allow imaging of the iron oxide nanoparticles.

Adsorption of Toluene and Paraxylene from Aqueous Solution Using Pure and Iron Oxide Impregnated Carbon Nanotubes: Kinetics and Isotherms Study

PubMed Central

Abbas, Aamir; Ihsanullah; Al-Baghli, Nadhir A. H.

2017-01-01

Multiwall carbon nanotubes (CNTs) and iron oxide impregnated carbon nanotubes (CNTs-iron oxide) were investigated for the adsorption of hazardous toluene and paraxylene (p-xylene) from aqueous solution. Pure CNTs were impregnated with iron oxides nanoparticles using wet impregnation technique. Various characterization techniques including thermogravimetric analysis, scanning electron microscopy, elemental dispersion spectroscopy, X-ray diffraction, and nitrogen adsorption analysis were used to study the thermal degradation, surface morphology, purity, and surface area of the materials. Batch adsorption experiments show that iron oxide impregnated CNTs have higher degree of removal of p-xylene (i.e., 90%) compared with toluene (i.e., 70%), for soaking time 2 h, with pollutant initial concentration 100 ppm, at pH 6 and shaking speed of 200 rpm at 25°C. Pseudo-second-order model provides better fitting for the toluene and p-xylene adsorption. Langmuir and Freundlich isotherm models demonstrate good fitting for the adsorption data of toluene and p-xylene. PMID:28386208

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

NASA Astrophysics Data System (ADS)

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

2012-07-01

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

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

USGS Publications Warehouse

Broshears, R.E.; Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

1996-01-01

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

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

PubMed Central

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

2016-01-01

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

Anchorage of iron hydro(oxide) nanoparticles onto activated carbon to remove As(V) from water.

PubMed

Nieto-Delgado, Cesar; Rangel-Mendez, Jose Rene

2012-06-01

The adsorption of arsenic (V) by granular iron hydro(oxides) has been proven to be a reliable technique. However, due to the low mechanical properties of this material, it is difficult to apply it in full scale water treatment. Hence, the aim of this research is to develop a methodology to anchor iron hydro(oxide) nanoparticles onto activated carbon, in which the iron hydro(oxide) nanoparticles will give the activated carbon an elevated active surface area for arsenic adsorption and also help avoid the blockage of the activated carbon pores. Three activated carbons were modified by employing the thermal hydrolysis of iron as the anchorage procedure. The effects of hydrolysis temperature (60-120 °C), hydrolysis time (4-16 h), and FeCl(3) concentration (0.4-3 mol Fe/L) were studied by the surface response methodology. The iron content of the modified samples ranged from 0.73 to 5.27%, with the higher end of the range pertaining to the carbons with high oxygen content. The materials containing smaller iron hydro(oxide) particles exhibited an enhanced arsenic adsorption capacity. The best adsorbent material reported an arsenic adsorption capacity of 4.56 mg As/g at 1.5 ppm As at equilibrium and pH 7. Copyright © 2012 Elsevier Ltd. All rights reserved.

Central roles of iron in the regulation of oxidative stress in the yeast Saccharomyces cerevisiae.

PubMed

Matsuo, Ryo; Mizobuchi, Shogo; Nakashima, Maya; Miki, Kensuke; Ayusawa, Dai; Fujii, Michihiko

2017-10-01

Oxygen is essential for aerobic organisms but causes cytotoxicity probably through the generation of reactive oxygen species (ROS). In this study, we screened for the genes that regulate oxidative stress in the yeast Saccharomyces cerevisiae, and found that expression of CTH2/TIS11 caused an increased resistance to ROS. CTH2 is up-regulated upon iron starvation and functions to remodel metabolism to adapt to iron starvation. We showed here that increased resistance to ROS by CTH2 would likely be caused by the decreased ROS production due to the decreased activity of mitochondrial respiration, which observation is consistent with the fact that CTH2 down-regulates the mitochondrial respiratory proteins. We also found that expression of CTH1, a paralog of CTH2, also caused an increased resistance to ROS. This finding supported the above view, because mitochondrial respiratory proteins are the common targets of CTH1 and CTH2. We further showed that supplementation of iron in medium augmented the growth of S. cerevisiae under oxidative stress, and expression of CTH2 and supplementation of iron collectively enhanced its growth under oxidative stress. Since CTH2 is regulated by iron, these findings suggested that iron played crucial roles in the regulation of oxidative stress in S. cerevisiae.

Mercury mobilization and speciation linked to bacterial iron oxide and sulfate reduction: A column study to mimic reactive transfer in an anoxic aquifer.

PubMed

Hellal, Jennifer; Guédron, Stéphane; Huguet, Lucie; Schäfer, Jörg; Laperche, Valérie; Joulian, Catherine; Lanceleur, Laurent; Burnol, André; Ghestem, Jean-Philippe; Garrido, Francis; Battaglia-Brunet, Fabienne

2015-09-01

Mercury (Hg) mobility and speciation in subsurface aquifers is directly linked to its surrounding geochemical and microbial environment. The role of bacteria on Hg speciation (i.e., methylation, demethylation and reduction) is well documented, however little data is available on their impact on Hg mobility. The aim of this study was to test if (i) Hg mobility is due to either direct iron oxide reduction by iron reducing bacteria (IRB) or indirect iron reduction by sulfide produced by sulfate reducing bacteria (SRB), and (ii) to investigate its subsequent fate and speciation. Experiments were carried out in an original column setup combining geochemical and microbiological approaches that mimic an aquifer including an interface of iron-rich and iron depleted zones. Two identical glass columns containing iron oxides spiked with Hg(II) were submitted to (i) direct iron reduction by IRB and (ii) to indirect iron reduction by sulfides produced by SRB. Results show that in both columns Hg was leached and methylated during the height of bacterial activity. In the column where IRB are dominant, Hg methylation and leaching from the column was directly correlated to bacterial iron reduction (i.e., Fe(II) release). In opposition, when SRB are dominant, produced sulfide induced indirect iron oxide reduction and rapid adsorption of leached Hg (or produced methylmercury) on neoformed iron sulfides (e.g., Mackinawite) or its precipitation as HgS. At the end of the SRB column experiment, when iron-oxide reduction was complete, filtered Hg and Fe concentrations increased at the outlet suggesting a leaching of Hg bound to FeS colloids that may be a dominant mechanism of Hg transport in aquifer environments. These experimental results highlight different biogeochemical mechanisms that can occur in stratified sub-surface aquifers where bacterial activities play a major role on Hg mobility and changes in speciation. Copyright © 2015 Elsevier B.V. All rights reserved.

Depth-dependent geochemical and microbiological gradients in Fe(III) deposits resulting from coal mine-derived acid mine drainage

PubMed Central

Brantner, Justin S.; Haake, Zachary J.; Burwick, John E.; Menge, Christopher M.; Hotchkiss, Shane T.; Senko, John M.

2014-01-01

We evaluated the depth-dependent geochemistry and microbiology of sediments that have developed via the microbially-mediated oxidation of Fe(II) dissolved in acid mine drainage (AMD), giving rise to a 8–10 cm deep “iron mound” that is composed primarily of Fe(III) (hydr)oxide phases. Chemical analyses of iron mound sediments indicated a zone of maximal Fe(III) reducing bacterial activity at a depth of approximately 2.5 cm despite the availability of dissolved O2 at this depth. Subsequently, Fe(II) was depleted at depths within the iron mound sediments that did not contain abundant O2. Evaluations of microbial communities at 1 cm depth intervals within the iron mound sediments using “next generation” nucleic acid sequencing approaches revealed an abundance of phylotypes attributable to acidophilic Fe(II) oxidizing Betaproteobacteria and the chloroplasts of photosynthetic microeukaryotic organisms in the upper 4 cm of the iron mound sediments. While we observed a depth-dependent transition in microbial community structure within the iron mound sediments, phylotypes attributable to Gammaproteobacterial lineages capable of both Fe(II) oxidation and Fe(III) reduction were abundant in sequence libraries (comprising ≥20% of sequences) from all depths. Similarly, abundances of total cells and culturable Fe(II) oxidizing bacteria were uniform throughout the iron mound sediments. Our results indicate that O2 and Fe(III) reduction co-occur in AMD-induced iron mound sediments, but that Fe(II)-oxidizing activity may be sustained in regions of the sediments that are depleted in O2. PMID:24860562

Freezing-Enhanced Dissolution of Iron Oxides: Effects of Inorganic Acid Anions.

PubMed

Jeong, Daun; Kim, Kitae; Min, Dae Wi; Choi, Wonyong

2015-11-03

Dissolution of iron from mineral dust particles greatly depends upon the type and amount of copresent inorganic anions. In this study, we investigated the roles of sulfate, chloride, nitrate, and perchlorate on the dissolution of maghemite and lepidocrocite in ice under both dark and UV irradiation and compared the results with those of their aqueous counterparts. After 96 h of reaction, the total dissolved iron in ice (pH 3 before freezing) was higher than that in the aqueous phase (pH 3) by 6-28 times and 10-20 times under dark and UV irradiation, respectively. Sulfuric acid was the most efficient in producing labile iron under dark condition, whereas hydrochloric acid induced the most dissolution of the total and ferrous iron in the presence of light. This ice-induced dissolution result was also confirmed with Arizona Test Dust (AZTD). In the freeze-thaw cycling test, the iron oxide samples containing chloride, nitrate, or perchlorate showed a similar extent of total dissolved iron after each cycling while the sulfate-containing sample rapidly lost its dissolution activity with repeating the cycle. This unique phenomenon observed in ice might be related to the freeze concentration of protons, iron oxides, and inorganic anions in the liquid-like ice grain boundary region. These results suggest that the ice-enhanced dissolution of iron oxides can be a potential source of bioavailable iron, and the acid anions critically influence this process.

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species.

PubMed

Watts, Richard J; Yu, Miao; Teel, Amy L

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical+sulfate radical probe, and hexachloroethane as a reductant+nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole>TCE>PCE >nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion. Published by Elsevier B.V.

Magnetic Nanoparticle-Based Imaging of RNA Transcripts in Breast Cancer Cells

DTIC Science & Technology

2008-06-30

control (Months 33 – 36). These studies have not yet commenced. KEY RESEARCH ACCOMPLISHMENTS: - Synthesized dextran-coated iron oxide NPs with...Size, charge, and concentration dependent uptake of iron oxide nanoparticles by non-phagocytic cells: a comparative study of USPIO, SSPIO, and MPIO...A. (2008) Size, charge, and concentration dependent uptake of iron oxide nanoparticles by non-phagocytic cells: a comparative study of USPIO, SSPIO

Targeted iron oxide nanoparticles for the enhancement of radiation therapy.

PubMed

Hauser, Anastasia K; Mitov, Mihail I; Daley, Emily F; McGarry, Ronald C; Anderson, Kimberly W; Hilt, J Zach

2016-10-01

To increase the efficacy of radiation, iron oxide nanoparticles can be utilized for their ability to produce reactive oxygen species (ROS). Radiation therapy promotes leakage of electrons from the electron transport chain and leads to an increase in mitochondrial production of the superoxide anion which is converted to hydrogen peroxide by superoxide dismutase. Iron oxide nanoparticles can then catalyze the reaction from hydrogen peroxide to the highly reactive hydroxyl radical. Therefore, the overall aim of this project was to utilize iron oxide nanoparticles conjugated to a cell penetrating peptide, TAT, to escape lysosomal encapsulation after internalization by cancer cells and catalyze hydroxyl radical formation. It was determined that TAT functionalized iron oxide nanoparticles and uncoated iron oxide nanoparticles resulted in permeabilization of the lysosomal membranes. Additionally, mitochondrial integrity was compromised when A549 cells were treated with both TAT-functionalized nanoparticles and radiation. Pre-treatment with TAT-functionalized nanoparticles also significantly increased the ROS generation associated with radiation. A long term viability study showed that TAT-functionalized nanoparticles combined with radiation resulted in a synergistic combination treatment. This is likely due to the TAT-functionalized nanoparticles sensitizing the cells to subsequent radiation therapy, because the nanoparticles alone did not result in significant toxicities. Copyright © 2016 Elsevier Ltd. All rights reserved.

Phosphate dynamics in an acidic mountain stream: Interactions involving algal uptake, sorption by iron oxide, and photoreduction

USGS Publications Warehouse

Tate, Cathy M.; Broshears, Robert E.; McKnight, Diane M.

1995-01-01

Acid mine drainage streams in the Rocky Mountains typically have few algal species and abundant iron oxide deposits which can sorb phosphate. An instream injection of radiolabeled phosphate (32P0,) into St. Kevin Gulch, an acid mine drainage stream, was used to test the ability of a dominant algal species, Ulothrix sp., to rapidly assimilate phosphate. Approximately 90% of the injected phosphate was removed from the water column in the 175-m stream reach. When shaded stream reaches were exposed to full sunlight after the injection ended, photoreductive dissolution of iron oxide released sorbed 32P, which was then also removed downstream. The removal from the stream was modeled as a first-order process by using a reactive solute transport transient storage model. Concentrations of 32P mass-’ of algae were typically lo-fold greater than concentrations in hydrous iron oxides. During the injection, concentrations of 32P increased in the cellular P pool containing soluble, low-molecular-weight compounds and confirmed direct algal uptake of 32P0, from water. Mass balance calculations indicated that algal uptake and sorption on iron oxides were significant in removing phosphate. We conclude that in stream ecosystems, PO, sorbed by iron oxides can act as a dynamic nutrient reservoir regulated by photoreduction.

Effects of quercetin on hemoglobin-dependent redox reactions: relationship to iron-overload rat liver injury.

PubMed

Lu, Nai-Hao; Chen, Chao; He, Ying-Jie; Tian, Rong; Xiao, Qiang; Peng, Yi-Yuan

2013-01-01

Flavonoids have been widely reported to protect liver injury in iron-overload diseases, where the mechanism of this therapeutic action is dependent on their antioxidant effects, including free radical scavenging and metal-chelating. In this study, in contrast to the significant decrease in iron content, quercetin (Qu) from lower diet (0.3%, w/w) showed pro-oxidant ability on protein carbonyl formation and exhibited unobvious effect on iron-overload rat liver injury. Furthermore, the anti- and pro-oxidant activities of Qu on hemoglobin (Hb)-dependent redox reactions (i.e. the oxidative stability of Hb and its cytotoxic ferryl intermediate, Hb-induced protein oxidation) were investigated to illustrate the elevated protein oxidation in lower Qu-treated iron-overload rat. It was found that superoxide (O₂·⁻) and hydrogen peroxide (H₂O₂) were generated during the reaction between Qu and Hb. Qu, however, effectively reduced ferryl intermediate back to ferric Hb in a biphasic kinetic reaction. Moreover, Qu could significantly aggravate Hb-H₂O₂-induced protein oxidation at low concentrations and exhibit protective effects at high concentrations. Different from the classic antioxidant mechanisms of Qu, the dual effects on Hb redox reactions in vitro, therefore, may provide new insights into the physiological and pharmacological implications of Qu with iron-overload disease.

Suppressing iron oxide nanoparticle toxicity by vascular targeted antioxidant polymer nanoparticles.

PubMed

Cochran, David B; Wattamwar, Paritosh P; Wydra, Robert; Hilt, J Zach; Anderson, Kimberly W; Eitel, Richard E; Dziubla, Thomas D

2013-12-01

The biomedical use of superparamagnetic iron oxide nanoparticles has been of continued interest in the literature and clinic. Their ability to be used as contrast agents for imaging and/or responsive agents for remote actuation makes them exciting materials for a wide range of clinical applications. Recently, however, concern has arisen regarding the potential health effects of these particles. Iron oxide toxicity has been demonstrated in in vivo and in vitro models, with oxidative stress being implicated as playing a key role in this pathology. One of the key cell types implicated in this injury is the vascular endothelial cells. Here, we report on the development of a targeted polymeric antioxidant, poly(trolox ester), nanoparticle that can suppress oxidative damage. As the polymer undergoes enzymatic hydrolysis, active trolox is locally released, providing a long term protection against pro-oxidant agents. In this work, poly(trolox) nanoparticles are targeted to platelet endothelial cell adhesion molecules (PECAM-1), which are able to bind to and internalize in endothelial cells and provide localized protection against the cytotoxicity caused by iron oxide nanoparticles. These results indicate the potential of using poly(trolox ester) as a means of mitigating iron oxide toxicity, potentially expanding the clinical use and relevance of these exciting systems. Copyright © 2013 Elsevier Ltd. All rights reserved.

Abdominal aorta aneurysm (AAA): Is there a role for prevention and therapy using antioxidants?

PubMed

Pincemail, Joël; Defraigne, Jean-Olivier; Courtois, Audrey; Albert, Adelin; Cheramy-Bien, Jean-Paul; Sakalihasan, Natzi

2017-09-18

Abdominal aortic aneurysm (AAA) is a degenerative disease that cause mortality in people aged > 65 years. Increased reactive oxygen species (ROS) and oxidative stress seems to play a pivotal role in AAA pathogenesis. Several sources of ROS have been identified in aortic tissues using experimental models: inflammation, increased activity of NAD(P)H or NOX, over-expression of inducible nitric oxide synthase (iNOS), uncoupled endothelial nitric oxide synthase (eNOS), platelets activation and iron release from hemoglobin. Reducing oxidative stress by antioxidants has been shown to be a potential strategy for limiting AAA development. Human studies confirmed that oxidative stress and endothelial dysfunction are well associated with AAA development. Unfortunately, there is currently no evidence showing that strategies using low molecular weight antioxidants (vitamins C and E, β-carotene) as target for ROS is effective to reduce human AAA progression. However, recent epidemiological data have highlighted the positive role of a diet enriched in fruits which contain high amounts of antioxidant polyphenols. By their ability to restore endothelial function but also their capacity to stimulate enzymatic antioxidants trough activation of the Keap1/Nrf2/ARE pathway, polyphenols can represent a promising treatment target for reducing human AAA progression. Clinical studies are therefore urgently necessary to confirm such a suggestion. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Distribution of bacteria and associated minerals in the gill chamber of the vent shrimp Rimicaris exoculata and related biogeochemical processes

NASA Astrophysics Data System (ADS)

Zbinden, M.; Le Bris, N.; Compere, P.; Gaill, F.

2004-12-01

The shrimp Rimicaris exoculata dominates the megafauna of some mid-Atlantic Ridge hydrothermal vent fields. This species harbors a rich bacterial epibiosis inside its gill chamber. At the Rainbow vent field, the epibionts are associated with iron oxide deposits. Investigation of both bacteria and minerals by scanning electron microscopy (SEM) and X-ray microanalysis (EDX) shows the occurrence of three distinct compartments in the gill chamber: (1) the lower pre-branchial chamber, housing bacteria, but devoid of minerals, (2) the "true" branchial chamber that contains the gills and remains free of both bacteria and minerals, and (3) the upper pre-branchial chamber housing the main ectosymbiotic bacterial community and associated iron oxides. According to our chemical and temperature data, abiotic iron oxidation appears to be kinetically inhibited in the environment of the shrimps and this would explain the lack of iron oxide deposits in the first two areas. We propose that, in the third area, iron oxidation is microbially promoted. The discrepancy between the spatial distribution of bacteria and minerals suggests that different bacterial metabolisms are involved in the two compartments. A possible explanation lies in the modification of physico-chemical conditions downstream of the gills, that would reduce the oxygen content and favor the development of bacterial iron-oxidizers in this Fe II-rich environment. A potential role of such iron-oxidizing symbionts in the shrimp diet is suggested. This would be unusual for hydrothermal ecosystems, where most previously described symbioses rely on sulphide or methane as an energy source.

Ferric Iron Production in Magma Oceans and Evolution of Mantle Oxidation State

NASA Astrophysics Data System (ADS)

Schaefer, L.; Elkins-Tanton, L. T.; Pahlevan, K.

2018-05-01

Self-oxidation of the magma ocean by ferric iron production at high pressure may explain the mantle oxidation state of the Earth. Partitioning during fractional crystallization can further increase the mantle oxygen fugacity during solidification.

Structural Iron (II) of Basaltic Glass as an Energy Source for Zetaproteobacteria in an Abyssal Plain Environment, Off the Mid Atlantic Ridge

PubMed Central

Henri, Pauline A.; Rommevaux-Jestin, Céline; Lesongeur, Françoise; Mumford, Adam; Emerson, David; Godfroy, Anne; Ménez, Bénédicte

2016-01-01

To explore the capability of basaltic glass to support the growth of chemosynthetic microorganisms, complementary in situ and in vitro colonization experiments were performed. Microbial colonizers containing synthetic tholeitic basaltic glasses, either enriched in reduced or oxidized iron, were deployed off-axis from the Mid Atlantic Ridge on surface sediments of the abyssal plain (35°N; 29°W). In situ microbial colonization was assessed by sequencing of the 16S rRNA gene and basaltic glass alteration was characterized using Scanning Electron Microscopy, micro-X-ray Absorption Near Edge Structure at the Fe-K-edge and Raman microspectroscopy. The colonized surface of the reduced basaltic glass was covered by a rind of alteration made of iron-oxides trapped in a palagonite-like structure with thicknesses up to 150 μm. The relative abundance of the associated microbial community was dominated (39% of all reads) by a single operational taxonomic unit (OTU) that shared 92% identity with the iron-oxidizer Mariprofundus ferrooxydans PV-1. Conversely, the oxidized basaltic glass showed the absence of iron-oxides enriched surface deposits and correspondingly there was a lack of known iron-oxidizing bacteria in the inventoried diversity. In vitro, a similar reduced basaltic glass was incubated in artificial seawater with a pure culture of the iron-oxidizing M. ferrooxydans DIS-1 for 2 weeks, without any additional nutrients or minerals. Confocal Laser Scanning Microscopy revealed that the glass surface was covered by twisted stalks characteristic of this iron-oxidizing Zetaproteobacteria. This result supported findings of the in situ experiments indicating that the Fe(II) present in the basalt was the energy source for the growth of representatives of Zetaproteobacteria in both the abyssal plain and the in vitro experiment. In accordance, the surface alteration rind observed on the reduced basaltic glass incubated in situ could at least partly result from their activity. PMID:26834704

Fossilization of Iron-Oxidizing Bacteria at Hydrothermal Vents: a Useful Biosignature on Mars?

NASA Astrophysics Data System (ADS)

Leveille, R. J.; Lui, S.

2009-05-01

Iron oxidizing bacteria are ubiquitous in marine and terrestrial environments on Earth, where they often display distinctive cell morphologies and are commonly encrusted by minerals, especially bacteriogenic iron oxides and silica. Putative microfossils of iron oxidizing bacteria have been found in jaspers as old as 490Ma and microbial iron oxidation may be an ancient metabolic pathway. In order to investigate the usefulness of mineralized iron oxidizing bacteria as a biosignature, we have examined mineral samples collected from relict hydrothermal systems along Explorer Ridge, NE Pacific Ocean. In addition, microaerophilic, neutrophilic iron oxidizing bacteria, isolated from Pacific hydrothermal vents, were grown in a Fe-enriched seawater medium at constant pH (6.5) and oxygen concentration (5 percent) in a controlled bioreactor system. Both natural samples and experimental products were examined with a combination of variable pressure scanning electron microscopy (SEM), field emission gun SEM, and in some cases by preparing samples with a focused ion beam (FIB) milling system. Natural seafloor samples display abundant filamentous forms often resembling, in both size and shape, the twisted stalks of Gallionella and the elongated filaments of Leptothrix. Generally, these filamentous features are 1-5 microns in diameter and up to several microns in length. Some samples consist entirely of low- density, porous masses of silica encrusted filamentous forms. Presumably, these masses were formed by a rapid precipitation by the influx of silica-rich fluids into a microbial mat dominated by bacteria with filamentous morphologies. The presence of rare, amorphous (unmineralized) filamentous matter rich in C and Fe suggests that these bacteria were iron oxidizers. There is no evidence that sulfur oxidizers were present. Filamentous features sectioned by FIB milling show internal material within semi-hollow tubular-like features. Silica encrustations also show pseudo-concentric growth bands. In the bioreactor cultures, constant conditions led to abundant microbial growth and formation of an iron oxyhydroxide precipitate, either in direct association with the cells or within the growth medium. This suggests that not all of the iron precipitation is biogenic in origin. Cells typically show a filamentous morphology reminiscent of the mineral-encrusted forms observed in the natural samples. Continuing work includes high-resolution TEM observations of cultured organisms, examination of 2-year long in situ seafloor incubation experiments, and bioreactor silicification experiments in order to better understand the roles of iron and silica in the fossilization process. Microaerophilic iron oxidation could have existed on the early Earth in environments containing small amounts of oxygen produced either by locally concentrated photosynthetic microorganisms (e.g., cyanobacteria) or abiotically, as proposed for the subsurface of the Fe-dominated Rio Tinto (Spain) basin system. By analogy, similar subsurface or near-surface microaerophilic environments could have existed on Mars in the past. The distinctive morphologies and mineralization patterns of iron oxidizing bacteria could be a useful biosignature to search for on Mars. Deposits and biogenic features similar to those described here could theoretically be identified on Mars with existing imaging and analytical technologies. Therefore, future missions to Mars should target ancient hydrothermal systems, some of which have been putatively identified already.

Magnetic resonance imaging with superparamagnetic iron oxide fails to track the long-term fate of mesenchymal stem cells transplanted into heart.

PubMed

Ma, Ning; Cheng, Huaibing; Lu, Minjie; Liu, Qiong; Chen, Xiuyu; Yin, Gang; Zhu, Hao; Zhang, Lianfeng; Meng, Xianmin; Tang, Yue; Zhao, Shihua

2015-03-12

MRI for in vivo stem cell tracking remains controversial. Here we tested the hypothesis that MRI can track the long-term fate of the superparamagnetic iron oxide (SPIO) nanoparticles labelled mesenchymal stem cells (MSCs) following intramyocardially injection in AMI rats. MSCs (1 × 10(6)) from male rats doubly labeled with SPIO and DAPI were injected 2 weeks after myocardial infarction. The control group received cell-free media injection. In vivo serial MRI was performed at 24 hours before cell delivery (baseline), 3 days, 1, 2, and 4 weeks after cell delivery, respectively. Serial follow-up MRI demonstrated large persistent intramyocardial signal-voids representing SPIO during the follow-up of 4 weeks, and MSCs did not moderate the left ventricular dysfunction. The TUNEL analysis confirmed that MSCs engrafted underwent apoptosis. The histopathological studies revealed that the site of cell injection was infiltrated by inflammatory cells progressively and the iron-positive cells were macrophages identified by CD68 staining, but very few or no DAPI-positive stem cells at 4 weeks after cells transplantation. The presence of engrafted cells was confirmed by real-time PCR, which showed that the amount of Y-chromosome-specific SRY gene was consistent with the results. MRI may not reliably track the long-term fate of SPIO-labeled MSCs engraftment in heart.

Long-term oxidation of candidate cast iron and stainless steel exhaust system alloys from 650 to 800 °C in air with water vapor

DOE PAGES

Brady, Michael P.; Muralidharan, Govindarajan; Leonard, Donovan .; ...

2014-08-29

Here, the oxidation behavior of SiMo cast iron, Ni-resist D 5S cast iron, cast chromia-forming austenitic stainless steels of varying Cr/Ni content based on CF8C plus, HK, and HP, and a developmental cast alumina-forming austenitic (AFA) stainless steel of interest for diesel exhaust system components were studied for up to 5000 h at 650-800 °C in air with 10% H 2O. At 650 °C, the Ni-resist D5S exhibited moderately better oxidation resistance than did the SiMo cast iron. However, the D5S suffered from oxide scale spallation issues at 700 °C and higher, whereas the oxide scales formed on SiMo castmore » iron remained adherent from 700-800 °C despite oxide scales hundreds of microns thick. The oxidation of the SiMo cast iron exhibited unusual temperature dependence, with periods of slower oxidation kinetics at 750-800 °C compared to 650-700 °C due to continuous silica-rich scale formation at the higher temperatures. The oxidation of the cast chromia-forming austenitics trended with the level of Cr and Ni additions, with small mass losses consistent with Cr oxy-hydroxide volatilization processes for the higher 25Cr/25-35Ni HK and HP type alloys, and transition to rapid Fe-base oxide formation and scale spallation in the lower 19Cr/12Ni CF8C plus type alloy. In contrast, small positive mass changes consistent with protective alumina scale formation were observed for the cast AFA alloy under all conditions studied. Implications of these findings for diesel exhaust system components are discussed.« less

Impact on the Fe redox cycling of organic ligands released by Synechococcus PCC 7002, under different iron fertilization scenarios. Modeling approach

NASA Astrophysics Data System (ADS)

Samperio-Ramos, Guillermo; González-Dávila, Melchor; Santana-Casiano, J. Magdalena

2018-06-01

The kinetics of Fe redox transformations are of crucial importance in determining the bioavailability of iron, due to inorganic Fe(II) and Fe weakly organic complexes being the most easily assimilated species by phytoplankton. The role played by the natural organic ligands excreted by the cyanobacteria Synecococcus PCC 7002 on the iron redox chemistry was studied at different stages of growth, considering changes in the organic exudation of the cyanobacteria, associated with growth under two different scenarios of iron availability. The oxidation/reduction processes of iron were studied at nanomolar levels and under different physicochemical conditions of pH (7.2- 8.2), temperature (5- 35 °C) and salinity (10- 37). The presence of natural organic exudates of Synechococcus affected the redox behavior of iron. A pH-dependent and photo-induced Fe(III) reduction process was detected in the presence of exudates produced under Fe-Low conditions. Photolytic reactions also modified the reactivity of those exudates with respect to Fe(II), increasing its lifetime in seawater. Without light mediated processes, organic ligands excreted under iron deficient conditions intensified the Fe(II) oxidation at pH < 7.5. The organic exudates released under High-Fe conditions retarded the Fe(II) oxidation rate, as a function of DOC produced. The changes in the apparent oxidation rate were fitted to polynomial functions for both of the Fe-scenarios considered. A kinetic modeling approach to describe the speciation and the contribution of individual Fe(II) species to the overall oxidation rate was applied, considering the experimental data and delimiting the equilibrium and redox constants between iron and the major ligands present in solution. Two organic type ligands for the exudates of Synechococcus PCC 7002, with different iron-chelation properties were included in the model. The Fe(II) speciation was radically affected when organic ligands were considered. The individual contributions to the overall Fe(II) oxidation rate demonstrated that these organic ligands played a key role in the oxidation process, although their contributions were dependent on the prescribed iron conditions. The study, therefore, suggests that the variability in the composition and nature of organic exudates released, due to iron availability conditions, might determine the redox behaviour of iron in seawater.

Secoisolariciresinol Diglucoside Abrogates Oxidative Stress-Induced Damage in Cardiac Iron Overload Condition

PubMed Central

Puukila, Stephanie; Bryan, Sean; Laakso, Anna; Abdel-Malak, Jessica; Gurney, Carli; Agostino, Adrian; Belló-Klein, Adriane; Prasad, Kailash; Khaper, Neelam

2015-01-01

Cardiac iron overload is directly associated with cardiac dysfunction and can ultimately lead to heart failure. This study examined the effect of secoisolariciresinol diglucoside (SDG), a component of flaxseed, on iron overload induced cardiac damage by evaluating oxidative stress, inflammation and apoptosis in H9c2 cardiomyocytes. Cells were incubated with 50 μ5M iron for 24 hours and/or a 24 hour pre-treatment of 500 μ M SDG. Cardiac iron overload resulted in increased oxidative stress and gene expression of the inflammatory mediators tumor necrosis factor-α, interleukin-10 and interferon γ, as well as matrix metalloproteinases-2 and -9. Increased apoptosis was evident by increased active caspase 3/7 activity and increased protein expression of Forkhead box O3a, caspase 3 and Bax. Cardiac iron overload also resulted in increased protein expression of p70S6 Kinase 1 and decreased expression of AMP-activated protein kinase. Pre-treatment with SDG abrogated the iron-induced increases in oxidative stress, inflammation and apoptosis, as well as the increased p70S6 Kinase 1 and decreased AMP-activated protein kinase expression. The decrease in superoxide dismutase activity by iron treatment was prevented by pre-treatment with SDG in the presence of iron. Based on these findings we conclude that SDG was cytoprotective in an in vitro model of iron overload induced redox-inflammatory damage, suggesting a novel potential role for SDG in cardiac iron overload. PMID:25822525

Secoisolariciresinol diglucoside abrogates oxidative stress-induced damage in cardiac iron overload condition.

PubMed

Puukila, Stephanie; Bryan, Sean; Laakso, Anna; Abdel-Malak, Jessica; Gurney, Carli; Agostino, Adrian; Belló-Klein, Adriane; Prasad, Kailash; Khaper, Neelam

2015-01-01

Cardiac iron overload is directly associated with cardiac dysfunction and can ultimately lead to heart failure. This study examined the effect of secoisolariciresinol diglucoside (SDG), a component of flaxseed, on iron overload induced cardiac damage by evaluating oxidative stress, inflammation and apoptosis in H9c2 cardiomyocytes. Cells were incubated with 50 μ5M iron for 24 hours and/or a 24 hour pre-treatment of 500 μ M SDG. Cardiac iron overload resulted in increased oxidative stress and gene expression of the inflammatory mediators tumor necrosis factor-α, interleukin-10 and interferon γ, as well as matrix metalloproteinases-2 and -9. Increased apoptosis was evident by increased active caspase 3/7 activity and increased protein expression of Forkhead box O3a, caspase 3 and Bax. Cardiac iron overload also resulted in increased protein expression of p70S6 Kinase 1 and decreased expression of AMP-activated protein kinase. Pre-treatment with SDG abrogated the iron-induced increases in oxidative stress, inflammation and apoptosis, as well as the increased p70S6 Kinase 1 and decreased AMP-activated protein kinase expression. The decrease in superoxide dismutase activity by iron treatment was prevented by pre-treatment with SDG in the presence of iron. Based on these findings we conclude that SDG was cytoprotective in an in vitro model of iron overload induced redox-inflammatory damage, suggesting a novel potential role for SDG in cardiac iron overload.

Protection against ultraviolet A-induced oxidative damage in normal human epidermal keratinocytes under post-menopausal conditions by an ultraviolet A-activated caged-iron chelator: a pilot study.

PubMed

Pelle, Edward; Jian, Jinlong; Declercq, Lieve; Dong, Kelly; Yang, Qing; Pourzand, Charareh; Maes, Daniel; Pernodet, Nadine; Yarosh, Daniel B; Huang, Xi

2011-10-01

Human skin is constantly exposed to ultraviolet A (UVA), which can generate reactive oxygen species and cause iron release from ferritin, leading to oxidative damage in biomolecules. This is particularly true in post-menopausal skin due to an increase in iron as a result of menopause. As iron is generally released through desquamation, the skin becomes a main portal for the release of excess iron in this age group. In the present study, we examined a strategy for controlling UVA- and iron-induced oxidative stress in skin using a keratinocyte post-menopausal cellular model system. Keratinocytes that had been cultured under normal or high-iron, low-estrogen conditions were treated with (2-nitrophenyl) ethyl pyridoxal isonicotinoyl hydrazone (2-PNE-PIH). 2-PNE-PIH is a caged-iron chelator that does not normally bind iron but can be activated by UVA radiation to bind iron. Following incubation with 2-PNE-PIH, the cells were exposed to 5 J/cm² UVA and then measured for changes in lipid peroxidation and ferritin levels. 2-PNE-PIH protected keratinocytes against UVA-induced lipid peroxidation and ferritin depletion. Further, 2-PNE-PIH was neither cytotoxic nor did it alter iron metabolism. 2-PNE-PIH may be a useful deterrent against UVA-induced oxidative stress in post-menopausal women. © 2011 John Wiley & Sons A/S.

Aceruloplasminaemia with progressive atrophy without brain iron overload: treatment with oral chelation.

PubMed

Skidmore, F M; Drago, V; Foster, P; Schmalfuss, I M; Heilman, K M; Streiff, R R

2008-04-01

Hereditary aceruloplasminaemia is a disorder of iron metabolism that is characterised by iron accumulation in the brain and other visceral organs. In previously reported cases, individuals with the disorder were noted to have evidence of iron accumulation in the brain. Oral chelating agents have not been used in neurological diseases of iron metabolism. A 54-year-old woman who presented with ataxia, lower extremity spasticity and chorea was evaluated for evidence of the source of neurological dysfunction. Blood studies revealed no detectable ceruloplasmin. Marked iron overload was defined by a liver biopsy, which showed a variegated pattern consistent with a primary cause of iron overload. Review of MRI scans showed progressive brain atrophy without visible iron accumulation occurring over a 5-year period. The history suggested that neurodegeneration was coincident with aggressive oral iron replacement. Oral chelation improved many symptoms. Our findings in this patient suggest that disorders of iron transport such as aceruloplasminaemia can be a cause of neurological symptoms such as chorea and cognitive decline, as well as progressive neurodegeneration in the absence of visible iron on MRI scans. We found that oral iron chelation was effective at improving symptoms.

Convergence of hepcidin deficiency, systemic iron overloading, heme accumulation, and REV-ERBα/β activation in aryl hydrocarbon receptor-elicited hepatotoxicity

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

Fader, Kelly A.; Nault, Rance

Persistent aryl hydrocarbon receptor (AhR) agonists elicit dose-dependent hepatic lipid accumulation, oxidative stress, inflammation, and fibrosis in mice. Iron (Fe) promotes AhR-mediated oxidative stress by catalyzing reactive oxygen species (ROS) production. To further characterize the role of Fe in AhR-mediated hepatotoxicity, male C57BL/6 mice were orally gavaged with sesame oil vehicle or 0.01–30 μg/kg 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) every 4 days for 28 days. Duodenal epithelial and hepatic RNA-Seq data were integrated with hepatic AhR ChIP-Seq, capillary electrophoresis protein measurements, and clinical chemistry analyses. TCDD dose-dependently repressed hepatic expression of hepcidin (Hamp and Hamp2), the master regulator of systemic Fe homeostasis, resultingmore » in a 2.6-fold increase in serum Fe with accumulating Fe spilling into urine. Total hepatic Fe levels were negligibly increased while transferrin saturation remained unchanged. Furthermore, TCDD elicited dose-dependent gene expression changes in heme biosynthesis including the induction of aminolevulinic acid synthase 1 (Alas1) and repression of uroporphyrinogen decarboxylase (Urod), leading to a 50% increase in hepatic hemin and a 13.2-fold increase in total urinary porphyrins. Consistent with this heme accumulation, differential gene expression suggests that heme activated BACH1 and REV-ERBα/β, causing induction of heme oxygenase 1 (Hmox1) and repression of fatty acid biosynthesis, respectively. Collectively, these results suggest that Hamp repression, Fe accumulation, and increased heme levels converge to promote oxidative stress and the progression of TCDD-elicited hepatotoxicity. - Highlights: • TCDD represses hepatic hepcidin expression, leading to systemic iron overloading. • Dysregulation of heme biosynthesis is consistent with heme and porphyrin accumulation. • Heme-activated REV-ERBα/β repress circadian-regulated hepatic lipid metabolism. • Disruption of iron homeostasis promotes TCDD-elicited steatohepatitis with fibrosis.« less

In vitro cytotoxicity of iron oxide nanoparticles: effects of chitosan and polyvinyl alcohol as stabilizing agents

NASA Astrophysics Data System (ADS)

Tran, Phong A.; Nguyen, Hiep T.; Fox, Kate; Tran, Nhiem

2018-03-01

Iron oxide magnetic nanoparticles have significant potential in biomedical applications such as in diagnosis, imaging and therapeutic agent delivery. The choice of stabilizers and surface functionalization is important as it is known to strongly influence the cytotoxicity of the nanoparticles. The present study aimed at investigating the effects of surface charges on the cytotoxicity of iron oxide nanoparticles. We used a co-precipitation method to synthesize iron oxide nanoparticles which were then stabilized with either chitosan (CS) or polyvinyl alcohol (PVA) which have net positive charge and zero charge at physiological pH, respectively. The nanoparticles were characterized in terms of size, charges and chemical oxidation state. Cytotoxicity of the nanoparticles was assessed using mouse fibroblast cells and was correlated with surface charges of the nanoparticles and their aggregation.

Synthesis and mechanical/magnetic properties of nano-grained iron-oxides prepared with an inert gas condensation and pulse electric current sintering process

NASA Astrophysics Data System (ADS)

Choa, Yong-Ho; Nakayama, Tatachika; Sekino, Tohru; Niihara, Koichi

1999-04-01

Nanocrystalline iron-oxide powder was fabricated with an inert gas condensation (IGC) method combined with evaporation, and in-situ oxidation techniques. The particle size of iron-oxide powder was controlled by varying the helium gas pressure between 0.1 and 10 Torr, with the smallest one =10 nm at 0.1 Torr. The nanostructure was characterized by TEM. Nanocrystalline iron-oxide powder was sintered with the pulse electric current sintering (PECS) method to obtain densified γ-Fe2O3 materials, and suitably densified nano-grained γ-Fe2O3 materials (≈ 40 nm) of great hardness were obtained. The correlation between the nanostructure and magnetic properties of nanocrystalline powder and densified γ-Fe2O3 materials was also investigated.

Preventive effects of zinc against psychological stress-induced iron dyshomeostasis, erythropoiesis inhibition, and oxidative stress status in rats.

PubMed

Li, Yingjie; Zheng, Yuanyuan; Qian, Jianxin; Chen, Xinmin; Shen, Zhilei; Tao, Liping; Li, Hongxia; Qin, Haihong; Li, Min; Shen, Hui

2012-06-01

Psychological stress (PS) could cause decreased iron absorption and iron redistribution in body resulting in low iron concentration in the bone marrow and inhibition of erythropoiesis. In the present study, we investigated the effect of zinc supplementation on the iron metabolism, erythropoiesis, and oxidative stress status in PS-induced rats. Thirty-two rats were divided into two groups randomly: control group and zinc supplementation group. Each group was subdivided into two subgroups: control group and PS group. Rats received zinc supplementation before PS exposure established by a communication box. We investigated the serum corticosterone (CORT) level; iron apparent absorption; iron contents in liver, spleen, cortex, hippocampus, striatum, and serum; hematological parameters; malondialdehyde (MDA); reduced glutathione (GSH); and superoxide dismutase (SOD). Compared to PS-treated rats with normal diet, the PS-treated rats with zinc supplementation showed increased iron apparent absorption, serum iron, hemoglobin, red blood cell, GSH, and SOD activities; while the serum CORT; iron contents in liver, spleen, and regional brain; and MDA decreased. These results indicated that dietary zinc supplementation had preventive effects against PS-induced iron dyshomeostasis, erythropoiesis inhibition, and oxidative stress status in rats.

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

Hong, Seungwoo; Lu, Xiaoyan; Lee, Yong -Min

Here, a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [Fe V(NTs)(TAML)] – (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [Fe V(NTs)(TAML +•)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML +•). 2 is a competent oxidant in C–H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.

Microbial iron oxidation in the Arctic tundra and its implications for biogeochemical cycling.

PubMed

Emerson, David; Scott, Jarrod J; Benes, Joshua; Bowden, William B

2015-12-01

The role that neutrophilic iron-oxidizing bacteria play in the Arctic tundra is unknown. This study surveyed chemosynthetic iron-oxidizing communities at the North Slope of Alaska near Toolik Field Station (TFS) at Toolik Lake (lat 68.63, long -149.60). Microbial iron mats were common in submerged habitats with stationary or slowly flowing water, and their greatest areal extent is in coating plant stems and sediments in wet sedge meadows. Some Fe-oxidizing bacteria (FeOB) produce easily recognized sheath or stalk morphotypes that were present and dominant in all the mats we observed. The cool water temperatures (9 to 11°C) and reduced pH (5.0 to 6.6) at all sites kinetically favor microbial iron oxidation. A microbial survey of five sites based on 16S rRNA genes found a predominance of Proteobacteria, with Betaproteobacteria and members of the family Comamonadaceae being the most prevalent operational taxonomic units (OTUs). In relative abundance, clades of lithotrophic FeOB composed 5 to 10% of the communities. OTUs related to cyanobacteria and chloroplasts accounted for 3 to 25% of the communities. Oxygen profiles showed evidence for oxygenic photosynthesis at the surface of some mats, indicating the coexistence of photosynthetic and FeOB populations. The relative abundance of OTUs belonging to putative Fe-reducing bacteria (FeRB) averaged around 11% in the sampled iron mats. Mats incubated anaerobically with 10 mM acetate rapidly initiated Fe reduction, indicating that active iron cycling is likely. The prevalence of iron mats on the tundra might impact the carbon cycle through lithoautotrophic chemosynthesis, anaerobic respiration of organic carbon coupled to iron reduction, and the suppression of methanogenesis, and it potentially influences phosphorus dynamics through the adsorption of phosphorus to iron oxides. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Iron Oxidation and Core Formation in Recombinant Heteropolymeric Human Ferritins.

PubMed

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

2017-08-01

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

Comparative electrochemical analysis of crystalline and amorphous anodized iron oxide nanotube layers as negative electrode for LIB.

PubMed

Pervez, Syed Atif; Kim, Doohun; Farooq, Umer; Yaqub, Adnan; Choi, Jung-Hee; Lee, You-Jin; Doh, Chil-Hoon

2014-07-23

This work is a comparative study of the electrochemical performance of crystalline and amorphous anodic iron oxide nanotube layers. These nanotube layers were grown directly on top of an iron current collector with a vertical orientation via a simple one-step synthesis. The crystalline structures were obtained by heat treating the as-prepared (amorphous) iron oxide nanotube layers in ambient air environment. A detailed morphological and compositional characterization of the resultant materials was performed via transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and Raman spectroscopy. The XRD patterns were further analyzed using Rietveld refinements to gain in-depth information on their quantitative phase and crystal structures after heat treatment. The results demonstrated that the crystalline iron oxide nanotube layers exhibit better electrochemical properties than the amorphous iron oxide nanotube layers when evaluated in terms of the areal capacity, rate capability, and cycling performance. Such an improved electrochemical response was attributed to the morphology and three-dimensional framework of the crystalline nanotube layers offering short, multidirectional transport lengths, which favor rapid Li(+) ions diffusivity and electron transport.

Iron and sulfur in the pre-biologic ocean

NASA Technical Reports Server (NTRS)

Walker, J. C.; Brimblecombe, P.

1985-01-01

Tentative geochemical cycles for the pre-biologic Earth are developed by comparing the relative fluxes of oxygen, dissolved iron, and sulfide to the atmosphere and ocean. The flux of iron is found to exceed both the oxygen and the sulfide fluxes. Because of the insolubility of iron oxides and sulfides the implication is that dissolved iron was fairly abundant and that oxygen and sulfide were rare in the atmosphere and ocean. Sulfate, produced by the oxidation of volcanogenic sulfur gases, was the most abundant sulfur species in the ocean, but its concentration was low by modern standards because of the absence of the river-borne flux of dissolved sulfate produced by oxidative weathering of the continents. These findings are consistent with the geologic record of the isotopic composition of sedimentary sulfates and sulfides. Except in restricted environments, the sulfur metabolism of the earliest organisms probably involved oxidized sulfur species not sulfide.

N-butylamine functionalized graphene oxide for detection of iron(III) by photoluminescence quenching.

PubMed

Gholami, Javad; Manteghian, Mehrdad; Badiei, Alireza; Ueda, Hiroshi; Javanbakht, Mehran

2016-02-01

An N-butylamine functionalized graphene oxide nanolayer was synthesized and characterized by ultraviolet (UV)-visible spectrometry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. Detection of iron(III) based on photoluminescence spectroscopy was investigated. The N-butylamine functionalized graphene oxide was shown to specifically interact with iron (III), compared with other cationic trace elements including potassium (I), sodium (I), calcium (II), chromium (III), zinc (II), cobalt (II), copper (II), magnesium (II), manganese (II), and molybdenum (VI). The quenching effect of iron (III) on the luminescence emission of N-butylamine functionalized graphene oxide layer was used to detect iron (III). The limit of detection (2.8 × 10(-6)  M) and limit of quantitation (2.9 × 10(-5)  M) were obtained under optimal conditions. Copyright © 2015 John Wiley & Sons, Ltd.

Proterozoic low-Ti iron-oxide deposits in New York and New Jersey: relation to Fe-oxide (Cu-U-Au-rare earth element) deposits and tectonic implications

USGS Publications Warehouse

Foose, M.P.; McLelland, J.M.

1995-01-01

Low-Ti iron-oxide deposits in exposed Grenville-age rocks of New York and New Jersey belong to a distinct class of iron-oxide (Cu-U-Au-rare earth element [REE]) deposits that includes similar iron deposits in southeastern Missouri and the Kiruna district of Sweden, the giant Olympic Dam U-Cu-Au-Ag deposit (Australia), and the Bayan Obo REE-Nb deposit (China). Most of the New York-New Jersey deposits exhibit features consistent with a hydrothermal origin and define a regionally significant metallogenic event that provides important clues to the evolution of this part of the Grenville orogen. In the Adirondacks, the tectonic setting of these deposits is consistent with postorogenic uplift and extensive crustal melting at 1070-1050 Ma that was accompanied by late tectonic to posttectonic deposition of iron. -Authors

Bubble nucleation and migration in a lead-iron hydr(oxide) core-shell nanoparticle

DOE PAGES

Niu, Kaiyang; Frolov, Timofey; Xin, Huolin L.; ...

2015-10-05

Iron hydroxide is found in a wide range of contexts ranging from biominerals to steel corrosion, and it can transform to anhydrous oxide via releasing O 2 gas and H 2O. However, it is not well understood how gases transport through a crystal lattice. Here, we present in situ observation of the nucleation and migration of gas bubbles in iron (hydr)oxide using transmission electron microscopy. We create Pb–FeOOH model core–shell nanoparticles in a liquid cell. Under electron irradiation, iron hydroxide transforms to iron oxide, during which bubbles are generated, and they migrate through the shell to the nanoparticle surface. Geometricmore » phase analysis of the shell lattice shows an inhomogeneous stain field at the bubbles. In conclusion, our modeling suggests that the elastic interaction between the core and the bubble provides a driving force for bubble migration.« less

Bubble nucleation and migration in a lead–iron hydr(oxide) core–shell nanoparticle

PubMed Central

Niu, Kaiyang; Frolov, Timofey; Xin, Huolin L.; Wang, Junling; Asta, Mark; Zheng, Haimei

2015-01-01

Iron hydroxide is found in a wide range of contexts ranging from biominerals to steel corrosion, and it can transform to anhydrous oxide via releasing O2 gas and H2O. However, it is not well understood how gases transport through a crystal lattice. Here, we present in situ observation of the nucleation and migration of gas bubbles in iron (hydr)oxide using transmission electron microscopy. We create Pb–FeOOH model core–shell nanoparticles in a liquid cell. Under electron irradiation, iron hydroxide transforms to iron oxide, during which bubbles are generated, and they migrate through the shell to the nanoparticle surface. Geometric phase analysis of the shell lattice shows an inhomogeneous stain field at the bubbles. Our modeling suggests that the elastic interaction between the core and the bubble provides a driving force for bubble migration. PMID:26438864

Novel Thermo-Acidophilic Bacteria Isolated from Geothermal Sites in Yellowstone National Park: Physiological and Phylogenetic Characteristics

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

D. B. Johnson; N. Okibe; F. F. Roberto

Moderately thermophilic acidophilic bacteria were isolated from geothermal (30–83 °C) acidic (pH 2.7– 3.7) sites in Yellowstone National Park. The temperature maxima and pH minima of the isolates ranged from 50 to 65 °C, and pH 1.0–1.9. Eight of the bacteria were able to catalyze the dissimilatory oxidation of ferrous iron, and eleven could reduce ferric iron to ferrous iron in anaerobic cultures. Several of the isolates could also oxidize tetrathionate. Six of the iron-oxidizing isolates, and one obligate heterotroph, were low G+C gram-positive bacteria (Firmicutes). The former included three Sulfobacillus-like isolates (two closely related to a previously isolated Yellowstonemore » strain, and the third to a mesophilic bacterium isolated from Montserrat), while the other three appeared to belong to a different genus. The other two iron-oxidizers were an Actinobacterium (related to Acidimicrobium ferrooxidans) and a Methylobacterium-like isolate (a genus within the a-Proteobacteria that has not previously been found to contain either iron-oxidizers or acidophiles). The other three (heterotrophic) isolates were also a-Proteobacteria and appeared be a novel thermophilic Acidisphaera sp. An ARDREA protocol was developed to discriminate between the iron-oxidizing isolates. Digestion of amplified rRNA genes with two restriction enzymes (SnaBI and BsaAI) separated these bacteria into five distinct groups; this result was confirmed by analysis of sequenced rRNA genes.« less

Redistribution of Iron and Titanium in High-Pressure Ultramafic Rocks

NASA Astrophysics Data System (ADS)

Crossley, Rosalind J.; Evans, Katy A.; Reddy, Steven M.; Lester, Gregory W.

2017-11-01

The redox state of iron in high-pressure serpentinites, which host a significant proportion of Fe3+ in subduction zones, can be used to provide an insight into iron cycling and constrain the composition of subduction zone fluids. In this study, we use oxide and silicate mineral textures, interpretation of mineral parageneses, mineral composition data, and whole rock geochemistry of high-pressure retrogressed ultramafic rocks from the Zermatt-Saas Zone to constrain the distribution of iron and titanium, and iron oxidation state. These data provide an insight on the oxidation state and composition of fluids at depth in subduction zones. Oxide minerals host the bulk of iron, particularly Fe3+. The increase in mode of magnetite and observation of magnetite within antigorite veins in the investigated ultramafic samples during initial retrogression is most consistent with oxidation of existing iron within the samples during the infiltration of an oxidizing fluid since it is difficult to reconcile addition of Fe3+ with the known limited solubility of this species. However, high Ti contents are not typical of serpentinites and also cannot be accounted for by simple mixing of a depleted mantle protolith with the nearby Allalin gabbro. Titanium-rich phases coincide with prograde metamorphism and initial exhumation, implying the early seafloor and/or prograde addition and late mobilization of Ti. If Ti addition has occurred, then the introduction of Fe3+, also generally considered to be immobile, cannot be disregarded. We explore possible transport vectors for Ti and Fe through mineral texture analysis.

The effect of oxidant addition on ferrous iron removal from multi-element acidic sulphate solutions

NASA Astrophysics Data System (ADS)

Mbedzi, Ndishavhelafhi; Ibana, Don; Dyer, Laurence; Browner, Richard

2017-01-01

This study was an investigation on the hydrolytic precipitation of iron from simulated pregnant leach solution (PLS) of nickel laterite atmospheric leaching. The effect of equilibrium pH, temperature and the addition of oxidant on total iron (ferrous (Fe (II)) and ferric (Fe (III)), aluminium and chromium removal was investigated together with the associated nickel and cobalt losses to the precipitate. Systematic variations of the experimental variables revealed ≥99% of the ferric iron can be removed from solution at conditions similar to those used in standard partial neutralisation in zinc and nickel production, pH of 2.5 and temperature less than 100 °C with minimal losses (<0.5%) of both nickel and cobalt. Temperature variation from 55 to 90 °C had no significant effect on the magnitude of Fe (III) precipitation but led to a significant increase in aluminium removal from 67% to 95% and improved the filterability of the precipitates. There was no ferrous iron precipitation even at a pH of 3.75 in the absence of an oxidant with its removal (98%) achieved by oxidative precipitation with oxygen gas at pH 3.5. Unlike Fe (III) precipitation, the operating temperature significantly affects oxidative precipitation of Fe (II). Hence, in practical application, the hydrolytic precipitation and oxidation to remove iron must be operated at 85 °C to ensure both ferrous and ferric iron are precipitated.

Oxidative stress in hemodialysis patients receiving intravenous iron therapy and the role of N-acetylcysteine in preventing oxidative stress.

PubMed

Swarnalatha, G; Ram, R; Neela, Prasad; Naidu, M U R; Dakshina Murty, K V

2010-09-01

To determine the contribution of injectable iron administered to hemodialysis (HD) patients in causing oxidative stress and the beneficial effect of N-acetylcysteine (NAC) in reducing it, we studied in a prospective, double blinded, randomized controlled, cross over trial 14 adult HD patients who were randomized into two groups; one group received NAC in a dose of 600 mgs twice daily for 10 days prior to intravenous iron therapy and the other group received placebo. Both the groups were subjected to intravenous iron therapy, 100 mg of iron sucrose in 100 mL of normal saline given over a period of one hour. Blood samples for the markers of oxidative stress were taken before and after iron therapy. After the allowance of a week of wash out period for the effect of N-acetylcysteine we crossed over the patients to the opposite regimen. We measured the lipid peroxidation marker, malondiaaldehyde (MDA), to evaluate the oxidative stress and total anti-oxidant capacity (TAC) for the antioxidant level in addition to the highly sensitive C-reactive protein (HsCRP). Non-invasive assessment of endothelial dysfunction was measured by digital plethysmography before and after intravenous iron therapy. There was an increase of MDA (21.97 + 3.65% vs 7.06 + 3.65%) and highly sensitive C-reactive protein (HsCRP) (11.19 + 24.63% vs 13.19 + 7.7%) after iron administration both in the placebo and the NAC groups. NAC reduced the baseline acute systemic generation of oxidative stress when compared to placebo, which was statistically significant with MDA (12.76 + 4.4% vs 9.37 + 4.40%: P = 0.032) but not with HsCRP though there was a declining trend (2.85 + 22.75 % vs 8.93 + 5.19%: P = 0.112). Pre-treatment with NAC reduced the endothelial dysfunction when compared to placebo, but it was not statistically significant, except for reflection index (RI). We conclude that in our HD patients NAC reduced the oxidative stress before and after the administration of intravenous iron therapy in addition to the endothelial dysfunction induced by this treatment.

Iron-overload injury and cardiomyopathy in acquired and genetic models is attenuated by resveratrol therapy.

PubMed

Das, Subhash K; Wang, Wang; Zhabyeyev, Pavel; Basu, Ratnadeep; McLean, Brent; Fan, Dong; Parajuli, Nirmal; DesAulniers, Jessica; Patel, Vaibhav B; Hajjar, Roger J; Dyck, Jason R B; Kassiri, Zamaneh; Oudit, Gavin Y

2015-12-07

Iron-overload cardiomyopathy is a prevalent cause of heart failure on a world-wide basis and is a major cause of mortality and morbidity in patients with secondary iron-overload and genetic hemochromatosis. We investigated the therapeutic effects of resveratrol in acquired and genetic models of iron-overload cardiomyopathy. Murine iron-overload models showed cardiac iron-overload, increased oxidative stress, altered Ca(2+) homeostasis and myocardial fibrosis resulting in heart disease. Iron-overload increased nuclear and acetylated levels of FOXO1 with corresponding inverse changes in SIRT1 levels in the heart corrected by resveratrol therapy. Resveratrol, reduced the pathological remodeling and improved cardiac function in murine models of acquired and genetic iron-overload at varying stages of iron-overload. Echocardiography and hemodynamic analysis revealed a complete normalization of iron-overload mediated diastolic and systolic dysfunction in response to resveratrol therapy. Myocardial SERCA2a levels were reduced in iron-overloaded hearts and resveratrol therapy restored SERCA2a levels and corrected altered Ca(2+) homeostasis. Iron-mediated pro-oxidant and pro-fibrotic effects in human and murine cardiomyocytes and cardiofibroblasts were suppressed by resveratrol which correlated with reduction in iron-induced myocardial oxidative stress and myocardial fibrosis. Resveratrol represents a clinically and economically feasible therapeutic intervention to reduce the global burden from iron-overload cardiomyopathy at early and chronic stages of iron-overload.

Iron-overload injury and cardiomyopathy in acquired and genetic models is attenuated by resveratrol therapy

PubMed Central

Das, Subhash K.; Wang, Wang; Zhabyeyev, Pavel; Basu, Ratnadeep; McLean, Brent; Fan, Dong; Parajuli, Nirmal; DesAulniers, Jessica; Patel, Vaibhav B.; Hajjar, Roger J.; Dyck, Jason R. B.; Kassiri, Zamaneh; Oudit, Gavin Y.

2015-01-01

Iron-overload cardiomyopathy is a prevalent cause of heart failure on a world-wide basis and is a major cause of mortality and morbidity in patients with secondary iron-overload and genetic hemochromatosis. We investigated the therapeutic effects of resveratrol in acquired and genetic models of iron-overload cardiomyopathy. Murine iron-overload models showed cardiac iron-overload, increased oxidative stress, altered Ca2+ homeostasis and myocardial fibrosis resulting in heart disease. Iron-overload increased nuclear and acetylated levels of FOXO1 with corresponding inverse changes in SIRT1 levels in the heart corrected by resveratrol therapy. Resveratrol, reduced the pathological remodeling and improved cardiac function in murine models of acquired and genetic iron-overload at varying stages of iron-overload. Echocardiography and hemodynamic analysis revealed a complete normalization of iron-overload mediated diastolic and systolic dysfunction in response to resveratrol therapy. Myocardial SERCA2a levels were reduced in iron-overloaded hearts and resveratrol therapy restored SERCA2a levels and corrected altered Ca2+ homeostasis. Iron-mediated pro-oxidant and pro-fibrotic effects in human and murine cardiomyocytes and cardiofibroblasts were suppressed by resveratrol which correlated with reduction in iron-induced myocardial oxidative stress and myocardial fibrosis. Resveratrol represents a clinically and economically feasible therapeutic intervention to reduce the global burden from iron-overload cardiomyopathy at early and chronic stages of iron-overload. PMID:26638758

The Mismetallation of Enzymes during Oxidative Stress*

PubMed Central

Imlay, James A.

2014-01-01

Mononuclear iron enzymes can tightly bind non-activating metals. How do cells avoid mismetallation? The model bacterium Escherichia coli may control its metal pools so that thermodynamics favor the correct metallation of each enzyme. This system is disrupted, however, by superoxide and hydrogen peroxide. These species oxidize ferrous iron and thereby displace it from many iron-dependent mononuclear enzymes. Ultimately, zinc binds in its place, confers little activity, and imposes metabolic bottlenecks. Data suggest that E. coli compensates by using thiols to extract the zinc and by importing manganese to replace the catalytic iron atom. Manganese resists oxidants and provides substantial activity. PMID:25160623

Combined Effects of Gamma Radiation and High Dietary Iron on Peripheral Leukocyte Distribution and Function

NASA Technical Reports Server (NTRS)

Crucian, Brian E.; Morgan, Jennifer L. L.; Quiriarte, Heather A.; Sams, Clarence F.; Smith, Scott M.; Zwart, Sara R.

2012-01-01

Both radiation and increased iron stores can independently increase oxidative damage, resulting in protein, lipid and DNA oxidation. Oxidative stress increases the risk of many health problems including cancer, cataracts, and heart disease. This study, a subset of a larger interdisciplinary investigation of the combined effect of iron overload on sensitivity to radiation injury, monitored immune parameters in the peripheral blood of rats subjected to gamma radiation, high dietary iron or both. Specific immune measures consisted of: (1) peripheral leukocyte distribution, (2) plasma cytokine levels and (3) cytokine production profiles following whole blood mitogenic stimulation

An empirical approach to predicting long term behavior of metal particle based recording media

NASA Technical Reports Server (NTRS)

Hadad, Allan S.

1991-01-01

Alpha iron particles used for magnetic recording are prepared through a series of dehydration and reduction steps of alpha-Fe2O3-H2O resulting in acicular, polycrystalline, body centered cubic (bcc) alpha-Fe particles that are single magnetic domains. Since fine iron particles are pyrophoric by nature, stabilization processes had to be developed in order for iron particles to be considered as a viable recording medium for long term archival (i.e., 25+ years) information storage. The primary means of establishing stability is through passivation or controlled oxidation of the iron particle's surface. Since iron particles used for magnetic recording are small, additional oxidation has a direct impact on performance especially where archival storage of recorded information for long periods of time is important. Further stabilization chemistry/processes had to be developed to guarantee that iron particles could be considered as a viable long term recording medium. In an effort to retard the diffusion of iron ions through the oxide layer, other elements such as silicon, aluminum, and chromium have been added to the base iron to promote more dense scale formation or to alleviate some of the non-stoichiometric behavior of the oxide or both. The presence of water vapor has been shown to disrupt the passive layer, subsequently increasing the oxidation rate of the iron. A study was undertaken to examine the degradation in magnetic properties as a function of both temperature and humidity on silicon-containing iron particles between 50-120 deg C and 3-89 percent relative humidity. The methodology to which experimental data was collected and analyzed leading to predictive capability is discussed.

In vitro biological validation and cytocompatibility evaluation of hydrogel iron-oxide nanoparticles

NASA Astrophysics Data System (ADS)

Catalano, Enrico

2017-08-01

Superparamagnetic iron oxide nanoparticles (MNPs) have recently been investigated for their excellent biocompatibility as well as multi-purpose biomedical potential with promising results, owing to their ability to be targeted and heated by magnetic fields. In this study, novel hydrogel, chitosan Fe3O4 magnetic nanoparticles were synthesized for possible use for induced magnetic hyperthermia, and targeted drug delivery. The coating of iron oxide nanoparticles plays a key-role to efficiently improve internalization of nanoparticles in many cell types. Targeting is also highly desirable for these applications. In this regard hydrophilic coating like chitosan was used to improve drug release. Uncoated (Fe3O4)and chitosan-coated iron oxide nanoparticles (CS-Fe3O4) were synthesized and characterized from the biological point of view. The aim of this study was to provide an in vitro evaluation of the cytocompatibility of Fe3O4 and CS-Fe3O4 MNPs by using different in vitro evaluation tests. In this context, the cytocompatibility and cytotoxic effects of uncoated and hydrogel chemically-engineered chitosan-coated iron oxide NPs were investigated according to the ISO standard 10993-5:2009. Fe3O4 and CS-Fe3O4 NPs were tested on human mammary epithelial cells (MCF-10A) by using direct and not direct contact cytotoxicity evaluation tests, by evaluating influence of the iron particles on the cytoskeleton with phalloidin/DAPI staining and in vitro cellular iron uptake with Perl's Prussian blue staining. The results indicate that uncoated and chitosan-coated iron oxide nanoparticles are cytocompatible, without negative influence on the cytoskeleton or higher accumulation of iron in the cytoplasm. Therefore, it is encouraging that our data suggest uncoated and chitosan-coated iron oxide nanoparticles have satisfactory proliferative and viability effects on MCF-10A cells. In conclusion data suggest that both MNP types may be differently aimed in biomedical application in relation to the dose, acting as biocompatible materials, as component of scaffolds, or as a device for theranostics.

Structural insight into the substrate- and dioxygen-binding manner in the catalytic cycle of rieske nonheme iron oxygenase system, carbazole 1,9a-dioxygenase.

PubMed

Ashikawa, Yuji; Fujimoto, Zui; Usami, Yusuke; Inoue, Kengo; Noguchi, Haruko; Yamane, Hisakazu; Nojiri, Hideaki

2012-06-24

Dihydroxylation of tandemly linked aromatic carbons in a cis-configuration, catalyzed by multicomponent oxygenase systems known as Rieske nonheme iron oxygenase systems (ROs), often constitute the initial step of aerobic degradation pathways for various aromatic compounds. Because such RO reactions inherently govern whether downstream degradation processes occur, novel oxygenation mechanisms involving oxygenase components of ROs (RO-Os) is of great interest. Despite substantial progress in structural and physicochemical analyses, no consensus exists on the chemical steps in the catalytic cycles of ROs. Thus, determining whether conformational changes at the active site of RO-O occur by substrate and/or oxygen binding is important. Carbazole 1,9a-dioxygenase (CARDO), a RO member consists of catalytic terminal oxygenase (CARDO-O), ferredoxin (CARDO-F), and ferredoxin reductase. We have succeeded in determining the crystal structures of oxidized CARDO-O, oxidized CARDO-F, and both oxidized and reduced forms of the CARDO-O: CARDO-F binary complex. In the present study, we determined the crystal structures of the reduced carbazole (CAR)-bound, dioxygen-bound, and both CAR- and dioxygen-bound CARDO-O: CARDO-F binary complex structures at 1.95, 1.85, and 2.00 Å resolution. These structures revealed the conformational changes that occur in the catalytic cycle. Structural comparison between complex structures in each step of the catalytic mechanism provides several implications, such as the order of substrate and dioxygen bindings, the iron-dioxygen species likely being Fe(III)-(hydro)peroxo, and the creation of room for dioxygen binding and the promotion of dioxygen binding in desirable fashion by preceding substrate binding. The RO catalytic mechanism is proposed as follows: When the Rieske cluster is reduced, substrate binding induces several conformational changes (e.g., movements of the nonheme iron and the ligand residue) that create room for oxygen binding. Dioxygen bound in a side-on fashion onto nonheme iron is activated by reduction to the peroxo state [Fe(III)-(hydro)peroxo]. This state may react directly with the bound substrate, or O-O bond cleavage may occur to generate Fe(V)-oxo-hydroxo species prior to the reaction. After producing a cis-dihydrodiol, the product is released by reducing the nonheme iron. This proposed scheme describes the catalytic cycle of ROs and provides important information for a better understanding of the mechanism.

Ferrous Iron Oxidation by Thiobacillus ferrooxidans: Inhibition with Benzoic Acid, Sorbic Acid, and Sodium Lauryl Sulfate

PubMed Central

Onysko, Steven J.; Kleinmann, Robert L. P.; Erickson, Patricia M.

1984-01-01

Benzoic acid, sorbic acid, and sodium lauryl sulfate at low concentrations (5 to 10 mg/liter) each effectively inhibited bacterial oxidation of ferrous iron in batch cultures of Thiobacillus ferrooxidans. The rate of chemical oxidation of ferrous iron in low-pH, sterile batch reactors was not substantially affected at the tested concentrations (5 to 50 mg/liter) of any of the compounds. PMID:16346592

Transfusion Independency and Histological Remission in a Patient with Advanced Primary Myelofibrosis Receiving Iron-Chelation Therapy with Deferasirox.

PubMed

Groepper, Stefanie; Schlue, Jerome; Haferlach, Claudia; Giagounidis, Aristoteles

2016-01-01

Iron overload is a common problem in patients with primary myelofibrosis and anemia due to transfusion dependency. This results in organ damage and toxic effects on hematopoietic cells in the bone marrow. At present, iron chelation therapy is not recommended in patients with myeloproliferative syndromes. We describe a very interesting development in a patient with primary myelofibrosis receiving iron chelation. Transfusion independency and a nearly complete histological remission of the underlying disease occurred within a few weeks of therapy. In addition, a change in molecular genetic findings was observed. Initially a JAK2 and a U2AF1 mutation were detected in the core biopsy. During and after therapy the U2AF1 mutation progressed, whereas the JAK2 mutation could no longer be verified. The improvement in hematopoiesis might results from reduction of oxidative stress on hematopoietic progenitor cells or other unclear deferasirox-mediated effects, whereas the reason for the change in molecular genetic findings is unclear. It appears that deferasirox might have a modulating effect on JAK2-kinase mutations. However, further investigation of selective molecular suppression properties of deferasirox are warranted. © 2016 S. Karger GmbH, Freiburg.

Gold nanotriangles decorated with superparamagnetic iron oxide nanoparticles: a compositional and microstructural study

DOE PAGES

Hachtel, J. A.; Yu, S.; Lupini, A. R.; ...

2016-03-11

The combination of iron oxide and gold in a single nanoparticle results in both magnetic and plasmonic properties that can stimulate novel applications in bio-sensing, medical imaging, or therapeutics. Microwave assisted heating allows the fabrication of multi-component, multi-functional nanostructures by promoting selective heating at desired sites. Recently, we reported a microwave-assisted polyol route yielding gold nanotriangles decorated with iron oxide nanoparticles. Here, we present an in-depth microstructural and compositional characterization of the system by using scanning transmission electron microscopy (STEM) and electron energy loss (EELS) spectroscopy. A method to remove the iron oxide nanoparticles from the gold nanocrystals and somemore » insights on crystal nucleation and growth mechanisms are also provided.« less

Safety Implications of High-Field MRI: Actuation of Endogenous Magnetic Iron Oxides in the Human Body

PubMed Central

Dobson, Jon; Bowtell, Richard; Garcia-Prieto, Ana; Pankhurst, Quentin

2009-01-01

Background Magnetic Resonance Imaging scanners have become ubiquitous in hospitals and high-field systems (greater than 3 Tesla) are becoming increasingly common. In light of recent European Union moves to limit high-field exposure for those working with MRI scanners, we have evaluated the potential for detrimental cellular effects via nanomagnetic actuation of endogenous iron oxides in the body. Methodology Theoretical models and experimental data on the composition and magnetic properties of endogenous iron oxides in human tissue were used to analyze the forces on iron oxide particles. Principal Finding and Conclusions Results show that, even at 9.4 Tesla, forces on these particles are unlikely to disrupt normal cellular function via nanomagnetic actuation. PMID:19412550

Experimental and theoretical identification of the Fe(vii) oxidation state in FeO4.

PubMed

Lu, Jun-Bo; Jian, Jiwen; Huang, Wei; Lin, Hailu; Li, Jun; Zhou, Mingfei

2016-11-16

The experimentally known highest oxidation state of iron has been determined to be Fe(vi) so far. Here we report a combined matrix-isolation infrared spectroscopic and theoretical study of two interconvertible iron oxide anions: a dioxoiron peroxide complex [(η 2 -O 2 )FeO 2 ] - with a C 2v -structure and a tetroxide FeO 4 - with a D 2d tetrahedral structure, which are formed by co-condensation of laser-ablated iron atoms and electrons with O 2 /Ar mixtures at 4 K. Quantum chemistry theoretical studies indicate that the Jahn-Teller distorted tetroxide FeO 4 - anion is a d 1 species with hereto the highest iron formal oxidation state Fe(vii).

21 CFR 73.1350 - Mica-based pearlescent pigments.

Code of Federal Regulations, 2011 CFR

2011-04-01

...) Identity. (1) The color additive is formed by depositing titanium and/or iron salts onto mica, followed by heating to produce one of the following combinations: Titanium dioxide on mica; iron oxide on mica; titanium dioxide and iron oxide on mica. Mica used to manufacture the color additive shall conform in...

Soluble Iron in Alveolar Macrophages Modulates Iron Oxide Particle-Induced Inflammatory Response via Prostaglandin E2 Synthesis

EPA Science Inventory

Ambient particulate matter (PM)-associated metals have been shown to play an important role in cardiopulmonary health outcomes. To study the modulation of inflammation by PM-associated soluble metal, we investigated intracellular solubility of radiolabelled iron oxide (⁵⁹

DEPLETION OF IRON AND ASCORBATE IN RODENTS DIMINISHES LUNG INJURY AFTER SILICA

EPA Science Inventory

Exposures of the lung to iron chelates can be associated with an injury. The catalysis of oxygen-based free radicals is postulated to participate in this injury. Such oxidant generation by mineral oxide particles can be dependent on availability of both iron and a reductant. We t...

OXIDANT GENERATION PROMOTES IRON SEQUESTRATION IN BEAS-2B CELLS EXPOSED TO ASBESTOS

EPA Science Inventory

Lung injury following asbestos exposure is associated with an oxidative stress that is catalyzed by iron in the fiber matrix, complexed to the surface, or both. We tested the hypothesis that the cellular response to asbestos includes the transport and sequestration of this iron ...

*OXIDANT GENERATION PROMOTES IRON SEQUESTRATION IN BEAS-2B CELLS EXPOSED TO ASBESTOS

EPA Science Inventory

Lung injury after asbestos exposure is associated with an oxidative stress that is catalyzed by iron in the fiber matrix, complexed to the surface, or both. We tested the hypothesis that the cellular response to asbestos includes the transport and sequestration of this iron throu...

Persulfate activation by subsurface minerals.

PubMed

Ahmad, Mushtaque; Teel, Amy L; Watts, Richard J

2010-06-25

Persulfate dynamics in the presence of subsurface minerals was investigated as a basis for understanding persulfate activation for in situ chemical oxidation (ISCO). The mineral-mediated decomposition of persulfate and generation of oxidants and reductants was investigated with four iron and manganese oxides and two clay minerals at both low pH (<7) and high pH (>12). The manganese oxide birnessite was the most effective initiator of persulfate for degrading the oxidant probe nitrobenzene, indicating that oxidants are generated at both low and high pH regimes. The iron oxide goethite was the most effective mineral for degrading the reductant probe hexachloroethane. A natural soil and two soil fractions were used to confirm persulfate activation by synthetic minerals. The soil and soil fractions did not effectively promote the generation of oxidants or reductants. However, soil organic matter was found to promote reductant generation at high pH. The results of this research demonstrate that synthetic iron and manganese oxides can activate persulfate to generate reductants and oxidants; however, iron and manganese oxides in the natural soil studied do not show the same reactivity, most likely due to the lower masses of the metal oxides in the soil relative to the masses studied in isolated mineral systems. 2010. Published by Elsevier B.V.

Studies of implanted iron in silicon by channeling and Rutherford backscattering

NASA Technical Reports Server (NTRS)

Wang, P. W.; Cheng, H. S.; Gibson, W. M.; Corbett, J. W.

1986-01-01

Different amounts of 100-keV iron ions have been implanted into high-resistivity p-type FZ-silicon samples. The implantation damage, recovery of damage during various annealing periods and temperatures, movement of iron atoms under annealing and oxidation, and the kinds of defects created after implantation, annealing, or oxidation are all investigated by channeling and backscattering measurements. It is found that the critical fluence of 100-keV iron implanted into silicon at room temperature is about 2.5 x 10 to the 14th Fe/sq cm, and that iron atoms are gettered by silicon oxidation. In this supersaturated region, iron atoms diffuse slightly towards bulk silicon during high-temperature annealing (greater than or equal to 1100 C) but not at all during low-temperature annealing (less than or equal to 1000 C) in dry nitrogen ambient.

Iron deficiency and iron excess damage mitochondria and mitochondrial DNA in rats

PubMed Central

Walter, Patrick B.; Knutson, Mitchell D.; Paler-Martinez, Andres; Lee, Sonia; Xu, Yu; Viteri, Fernando E.; Ames, Bruce N.

2002-01-01

Approximately two billion people, mainly women and children, are iron deficient. Two studies examined the effects of iron deficiency and supplementation on rats. In study 1, mitochondrial functional parameters and mitochondrial DNA (mtDNA) damage were assayed in iron-deficient (≤5 μg/day) and iron-normal (800 μg/day) rats and in both groups after daily high-iron supplementation (8,000 μg/day) for 34 days. This dose is equivalent to the daily dose commonly given to iron-deficient humans. Iron-deficient rats had lower liver mitochondrial respiratory control ratios and increased levels of oxidants in polymorphonuclear-leukocytes, as assayed by dichlorofluorescein (P < 0.05). Rhodamine 123 fluorescence of polymorphonuclear-leukocytes also increased (P < 0.05). Lowered respiratory control ratios were found in daily high-iron-supplemented rats regardless of the previous iron status (P < 0.05). mtDNA damage was observed in both iron-deficient rats and rats receiving daily high-iron supplementation, compared with iron-normal rats (P < 0.05). Study 2 compared iron-deficient rats given high doses of iron (8,000 μg) either daily or every third day and found that rats given iron supplements every third day had less mtDNA damage on the second and third day after the last dose compared to daily high iron doses. Both inadequate and excessive iron (10 × nutritional need) cause significant mitochondrial malfunction. Although excess iron has been known to cause oxidative damage, the observation of oxidant-induced damage to mitochondria from iron deficiency has been unrecognized previously. Untreated iron deficiency, as well as excessive-iron supplementation, are deleterious and emphasize the importance of maintaining optimal iron intake. PMID:11854522

Mineralized iron oxidizing bacteria from hydrothermal vents: targeting biosignatures on Mars

NASA Astrophysics Data System (ADS)

Leveille, R. J.

2010-12-01

Putative hydrothermal systems have been identified on Mars based on orbital imagery and rover-based analyses. Based on Earth analogs, hydrothermal systems on Mars would be highly attractive for their potential for preserving organic and inorganic biosignatures. For example, iron oxidizing bacteria are ubiquitous in marine and terrestrial hydrothermal systems, where they often display distinctive cell morphologies and are commonly encrusted by minerals, especially bacteriogenic iron oxides and silica. Microfossils of iron oxidizing bacteria have been found in ancient Si-Fe deposits and iron oxidation may be an ancient and widespread metabolic pathway. In order to investigate mineralized iron oxidizing bacteria as a biosignature, we have examined samples collected from extinct hydrothermal vents along Explorer Ridge, NE Pacific Ocean. In addition, microaerophilic iron oxidizing bacteria, isolated from active Pacific hydrothermal vents, were grown in a Fe-enriched seawater medium at constant pH (6.5) and O2 concentration (5%) in a controlled bioreactor system. Samples and experimental products were examined with a combination of variable-pressure and field-emission scanning electron microscopy (SEM), in some cases by preparing samples with a focused ion beam (FIB) milling system. Light-toned seafloor samples display abundant filamentous forms resembling, in both size and shape (1-5 microns in diameter and up to several microns in length), the twisted stalks of Gallionella and the elongated filaments of Leptothrix. Some samples consist entirely of low-density masses of silica (>90% Si) encrusted filamentous forms. The presence of unmineralized filamentous matter rich in C and Fe suggests that these are the remains of iron oxidizing bacteria. Mineralized filaments sectioned by FIB show variable internal material within semi-hollow, tubular-like features. Silica encrustations also show pseudo-concentric growth bands. In the bioreactor runs, abundant microbial growth and formation of an iron oxyhydroxide precipitate, either in direct association with the cells or within the growth medium, were observed. Preliminary analyses suggest that these precipitates are different from abiotic precipitates. Continuing work includes high-resolution TEM observations of cultured organisms and biogenic iron minerals, Raman and reflectance spectroscopy of precipitates, examination of seafloor incubation experiments, and bioreactor silicification experiments in order to better understand the Fe-Si fossilization process. Microaerophilic iron oxidation could have existed on the early Earth in environments containing small amounts of oxygen produced either by locally-concentrated photosynthetic microorganisms (e.g., cyanobacteria) or by chemical reactions. By analogy, similar subsurface or near-surface microaerophilic environments could have existed on Mars in the past, including in low-temperature hydrothermal systems. The distinctive morphologies and Fe-Si mineralization patterns of iron oxidizing bacteria could be a useful biosignature to search for on Mars. Deposits and features similar to those described here could be identified on Mars with existing technologies, and thus hydrothermal systems represent an attractive target for future surface and sample return missions.

The aerobic respiratory chain of the acidophilic archaeon Ferroplasma acidiphilum: A membrane-bound complex oxidizing ferrous iron.

PubMed

Castelle, Cindy J; Roger, Magali; Bauzan, Marielle; Brugna, Myriam; Lignon, Sabrina; Nimtz, Manfred; Golyshina, Olga V; Giudici-Orticoni, Marie-Thérèse; Guiral, Marianne

2015-08-01

The extremely acidophilic archaeon Ferroplasma acidiphilum is found in iron-rich biomining environments and is an important micro-organism in naturally occurring microbial communities in acid mine drainage. F. acidiphilum is an iron oxidizer that belongs to the order Thermoplasmatales (Euryarchaeota), which harbors the most extremely acidophilic micro-organisms known so far. At present, little is known about the nature or the structural and functional organization of the proteins in F. acidiphilum that impact the iron biogeochemical cycle. We combine here biochemical and biophysical techniques such as enzyme purification, activity measurements, proteomics and spectroscopy to characterize the iron oxidation pathway(s) in F. acidiphilum. We isolated two respiratory membrane protein complexes: a 850 kDa complex containing an aa3-type cytochrome oxidase and a blue copper protein, which directly oxidizes ferrous iron and reduces molecular oxygen, and a 150 kDa cytochrome ba complex likely composed of a di-heme cytochrome and a Rieske protein. We tentatively propose that both of these complexes are involved in iron oxidation respiratory chains, functioning in the so-called uphill and downhill electron flow pathways, consistent with autotrophic life. The cytochrome ba complex could possibly play a role in regenerating reducing equivalents by a reverse ('uphill') electron flow. This study constitutes the first detailed biochemical investigation of the metalloproteins that are potentially directly involved in iron-mediated energy conservation in a member of the acidophilic archaea of the genus Ferroplasma. Copyright © 2015 Elsevier B.V. All rights reserved.

Increased levels of advanced glycation end products positively correlate with iron overload and oxidative stress markers in patients with β-thalassemia major.

PubMed

Mirlohi, Maryam Sadat; Yaghooti, Hamid; Shirali, Saeed; Aminasnafi, Ali; Olapour, Samaneh

2018-04-01

The impaired biosynthesis of the β-globin chain in β-thalassemia leads to the accumulation of unpaired alpha globin chains, failure in hemoglobin formation, and iron overload due to frequent blood transfusion. Iron excess causes oxidative stress and massive tissue injuries. Advanced glycation end products (AGEs) are harmful agents, and their production accelerates in oxidative conditions. This study was conducted on 45 patients with major β-thalassemia who received frequent blood transfusions and chelation therapy and were compared to 40 healthy subjects. Metabolic parameters including glycemic and iron indices, hepatic and renal functions tests, oxidative stress markers, and AGEs (carboxymethyl-lysine and pentosidine) levels were measured. All parameters were significantly increased in β-thalassemia compared to the control except for glutathione levels. Blood glucose, iron, serum ferritin, non-transferrin-bound iron (NTBI), MDA, soluble form of low-density lipoprotein receptor, glutathione peroxidase, total reactive oxygen species (ROS), and AGE levels were significantly higher in the β-thalassemia patients. Iron and ferritin showed a significant positive correlation with pentosidine (P < 0.01) but not with carboxymethyl-lysine. The NTBI was markedly increased in the β-thalassemia patients, and its levels correlated significantly with both carboxymethyl-lysine and pentosidine (P < 0.05). Our findings confirm the oxidative status generated by the iron overload in β-thalassemia major patients and highlight the enhanced formation of AGEs, which may play an important role in the pathogenesis of β-thalassemia major.

Long-term aerobic exercise increases redox-active iron through nitric oxide in rat hippocampus.

PubMed

Chen, Qian; Xiao, De-Sheng

2014-01-30

Adult hippocampus is highly vulnerable to iron-induced oxidative stress. Aerobic exercise has been proposed to reduce oxidative stress but the findings in the hippocampus are conflicting. This study aimed to observe the changes of redox-active iron and concomitant regulation of cellular iron homeostasis in the hippocampus by aerobic exercise, and possible regulatory effect of nitric oxide (NO). A randomized controlled study was designed in the rats with swimming exercise treatment (for 3 months) and/or an unselective inhibitor of NO synthase (NOS) (L-NAME) treatment. The results from the bleomycin-detectable iron assay showed additional redox-active iron in the hippocampus by exercise treatment. The results from nonheme iron content assay, combined with the redox-active iron content, showed increased storage iron content by exercise treatment. NOx (nitrate plus nitrite) assay showed increased NOx content by exercise treatment. The results from the Western blot assay showed decreased ferroportin expression, no changes of TfR1 and DMT1 expressions, increased IRP1 and IRP2 expression, increased expressions of eNOS and nNOS rather than iNOS. In these effects of exercise treatment, the increased redox-active iron content, storage iron content, IRP1 and IRP2 expressions were completely reversed by L-NAME treatment, and decreased ferroportin expression was in part reversed by L-NAME. L-NAME treatment completely inhibited increased NOx and both eNOS and nNOS expression in the hippocampus. Our findings suggest that aerobic exercise could increase the redox-active iron in the hippocampus, indicating an increase in the capacity to generate hydroxyl radicals through the Fenton reactions, and aerobic exercise-induced iron accumulation in the hippocampus might mainly result from the role of the endogenous NO. Copyright © 2013 Elsevier Inc. All rights reserved.

Insights into the Structure and Metabolic Function of Microbes That Shape Pelagic Iron-Rich Aggregates (“Iron Snow”)

PubMed Central

Lu, Shipeng; Chourey, Karuna; Reiche, Marco; Nietzsche, Sandor; Shah, Manesh B.; Neu, Thomas R.; Hettich, Robert L.

2013-01-01

Microbial ferrous iron [Fe(II)] oxidation leads to the formation of iron-rich macroscopic aggregates (“iron snow”) at the redoxcline in a stratified lignite mine lake in east-central Germany. We aimed to identify the abundant Fe-oxidizing and Fe-reducing microorganisms likely to be involved in the formation and transformation of iron snow present in the redoxcline in two basins of the lake that differ in their pH values. Nucleic acid- and lipid-stained microbial cells of various morphologies detected by confocal laser scanning microscopy were homogeneously distributed in all iron snow samples. The dominant iron mineral appeared to be schwertmannite, with shorter needles in the northern than in the central basin samples. Total bacterial 16S rRNA gene copies ranged from 5.0 × 108 copies g (dry weight)−1 in the acidic central lake basin (pH 3.3) to 4.0 × 1010 copies g (dry weight)−1 in the less acidic (pH 5.9) northern basin. Total RNA-based quantitative PCR assigned up to 61% of metabolically active microbial communities to Fe-oxidizing- and Fe-reducing-related bacteria, indicating that iron metabolism was an important metabolic strategy. Molecular identification of abundant groups suggested that iron snow surfaces were formed by chemoautotrophic iron oxidizers, such as Acidimicrobium, Ferrovum, Acidithiobacillus, Thiobacillus, and Chlorobium, in the redoxcline and were rapidly colonized by heterotrophic iron reducers, such as Acidiphilium, Albidiferax-like, and Geobacter-like groups. Metaproteomics yielded 283 different proteins from northern basin iron snow samples, and protein identification provided a glimpse into some of their in situ metabolic processes, such as primary production (CO2 fixation), respiration, motility, and survival strategies. PMID:23645202

Insights into the structure and metabolic function of microbes that shape pelagic iron-rich aggregates ("iron snow").

PubMed

Lu, Shipeng; Chourey, Karuna; Reiche, Marco; Nietzsche, Sandor; Shah, Manesh B; Neu, Thomas R; Hettich, Robert L; Küsel, Kirsten

2013-07-01

Microbial ferrous iron [Fe(II)] oxidation leads to the formation of iron-rich macroscopic aggregates ("iron snow") at the redoxcline in a stratified lignite mine lake in east-central Germany. We aimed to identify the abundant Fe-oxidizing and Fe-reducing microorganisms likely to be involved in the formation and transformation of iron snow present in the redoxcline in two basins of the lake that differ in their pH values. Nucleic acid- and lipid-stained microbial cells of various morphologies detected by confocal laser scanning microscopy were homogeneously distributed in all iron snow samples. The dominant iron mineral appeared to be schwertmannite, with shorter needles in the northern than in the central basin samples. Total bacterial 16S rRNA gene copies ranged from 5.0 × 10(8) copies g (dry weight)(-1) in the acidic central lake basin (pH 3.3) to 4.0 × 10(10) copies g (dry weight)(-1) in the less acidic (pH 5.9) northern basin. Total RNA-based quantitative PCR assigned up to 61% of metabolically active microbial communities to Fe-oxidizing- and Fe-reducing-related bacteria, indicating that iron metabolism was an important metabolic strategy. Molecular identification of abundant groups suggested that iron snow surfaces were formed by chemoautotrophic iron oxidizers, such as Acidimicrobium, Ferrovum, Acidithiobacillus, Thiobacillus, and Chlorobium, in the redoxcline and were rapidly colonized by heterotrophic iron reducers, such as Acidiphilium, Albidiferax-like, and Geobacter-like groups. Metaproteomics yielded 283 different proteins from northern basin iron snow samples, and protein identification provided a glimpse into some of their in situ metabolic processes, such as primary production (CO2 fixation), respiration, motility, and survival strategies.

Biomineralogy and Morphology of the Marine Iron-oxidizing Bacterium Mariprofundus ferrooxydans

NASA Astrophysics Data System (ADS)

Chan, C. S.; Emerson, D.; Edwards, K. J.

2006-12-01

Mariprofundus ferrooxydans strain PV-1 is a lithoautotrophic iron-oxidizing proteobacterium isolated from the Loihi Seamount in Hawaii. As cells grow, they form filaments upon which iron minerals are deposited. Based on similarities in morphology, these structures appear to accumulate and form the bulk of iron mats at Loihi. Furthermore, Mariprofundus has been observed in a number of other seafloor mat samples (e.g. by microscopy and 16S rRNA gene sequencing of East Pacific Rise samples, C. M. Santelli unpublished data), suggesting that the occurrence of Mariprofundus is widespread. To learn about the effect of Mariprofundus on iron cycling, we are studying the processes by which it oxidizes iron and influences iron mineral formation. We are conducting studies on the spatial relationships between the cells, stalks, and minerals using scanning and transmission electron microscopy (SEM and TEM). Identification and imaging of stalk-bound, nanometer-sized iron oxyhydroxide minerals is being performed by high-resolution transmission electron microscopy (HRTEM). We have developed sample preparation methods to preserve in vivo spatial relationships, involving direct colonization of sample holders in cultures and in the environment. Method development has been performed on stalk-forming, iron-oxidizing Gallionella ferruginea cultures and terrestrial iron mats. Gallionella is morphologically and physiologically very similar to Mariprofundus, although 16S rRNA gene phylogeny shows that they are not closely related. Comparison of the terrestrial and marine iron-oxidizing bacteria (FeOB) gives us insight into adaptations that are particular to marine iron-oxidizers and those that are common to all FeOB. Light and fluorescence microscopy of Mariprofundus cultures has shown that a single bean-shaped cell lies at the end of each filament. SEM and TEM results have revealed that the filament is ribbon-like, sometimes twisted as with the classic Gallionella stalk, but sometimes not. Filaments formed in culture have been measured at 0.5 and 1.7 microns in width and as long as 70 microns. They are composed of a varying number of parallel subfilaments, each approximately 70 nm in width. HRTEM observations show that lightly-mineralized filaments are covered in nanometer-size, poorly crystalline, and possibly amorphous iron oxyhydroxides, which likely represent an early stage in filament mineralization. Highly-mineralized filaments are coated in lepidocrocite and akaganeite (both iron oxyhydroxides), in random crystallographic orientations. The more crystalline minerals probably result from recrystallization of the initially-deposited FeOOH and continued precipitation on the filament. We will revisit Loihi in October to collect fresh, undisturbed samples for electron microscopy, in order to compare cultured and natural samples. This work is being performed in conjunction with genomic and protein analyses aimed at identifying the genes involved in iron oxidation.

The life cycle of iron Fe(III) oxide: impact of fungi and bacteria

NASA Astrophysics Data System (ADS)

Bonneville, Steeve

2014-05-01

Iron oxides are ubiquitous reactive constituents of soils, sediments and aquifers. They exhibit vast surface areas which bind a large array of trace metals, nutrients and organic molecules hence controlling their mobility/reactivity in the subsurface. In this context, understanding the "life cycle" of iron oxide in soils is paramount to many biogeochemical processes. Soils environments are notorious for their extreme heterogeneity and variability of chemical, physical conditions and biological agents at play. Here, we present studies investigating the role of two biological agents driving iron oxide dynamics in soils, root-associated fungi (mycorrhiza) and bacteria. Mycorrhiza filaments (hypha) grow preferentially around, and on the surface of nutrient-rich minerals, making mineral-fungi contact zones, hot-spots of chemical alteration in soils. However, because of the microscopic nature of hyphae (only ~ 5 µm wide for up to 1 mm long) and their tendency to strongly adhere to mineral surface, in situ observations of this interfacial micro-environment are scarce. In a microcosm, ectomycorrhiza (Paxillus involutus) was grown symbiotically with a pine tree (Pinus sylvestris) in the presence of freshly-cleaved biotite under humid, yet undersaturated, conditions typical of soils. Using spatially-resolved ion milling technique (FIB), transmission electron microscopy and spectroscopy (TEM/STEM-EDS), synchrotron based X-ray microscopy (STXM), we were able to quantify the speciation of Fe at the biotite-hypha interface. The results shows that substantial oxidation of biotite structural-Fe(II) into Fe(III) subdomains occurs at the contact zone between mycorrhiza and biotite. Once formed, iron(III) oxides can reductively dissolve under suboxic conditions via several abiotic and microbial pathways. In particular, they serve as terminal electron acceptors for the oxidation of organic matter by iron reducing bacteria. We aimed here to understand the role of Fe(III) mineral properties, in particular the influence of solubility, in the kinetics of microbial iron reduction. We used the facultative anaerobic gram-positive bacterium Shewanella putrefaciens as model iron reducing bacterium, with several ferrihydrite, hematite, goethite or lepidocrocite as electron acceptor, and lactate as electron donor. Maximum microbial Fe(III) reduction rates and solubility of Fe(III) phases were found to positively correlated in a Linear Free Energy Relationship suggesting a rate limitation by the electron transfer between iron reductases and a Fe(III) center, or by the subsequent desorption of Fe2+ from the iron oxide mineral surface.

Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity.

PubMed

Schneider, J J; Czap, N; Hagen, J; Engstler, J; Ensling, J; Gütlich, P; Reinoehl, U; Bertagnolli, H; Luis, F; de Jongh, L J; Wark, M; Grubert, G; Hornyak, G L; Zanoni, R

2000-12-01

Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. Mössbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the Mössbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From Mössbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.

Defluoridation by Bacteriogenic Iron Oxides: Sorption Studies

NASA Astrophysics Data System (ADS)

Evans, K.; Ferris, F.

2009-05-01

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

Iron oxides stimulate sulfate-driven anaerobic methane oxidation in seeps

DOE PAGES

Sivan, Orit; Antler, Gilad; Turchyn, Alexandra V.; ...

2014-09-22

Seep sediments are dominated by intensive microbial sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Through geochemical measurements of incubation experiments with methane seep sediments collected from Hydrate Ridge, we provide insight into the role of iron oxides in sulfate-driven AOM. Seep sediments incubated with 13C-labeled methane showed co-occurring sulfate reduction, AOM, and methanogenesis. The isotope fractionation factors for sulfur and oxygen isotopes in sulfate were about 40‰ and 22‰, respectively, reinforcing the difference between microbial sulfate reduction in methane seeps versus other sedimentary environments (for example, sulfur isotope fractionation above 60‰ in sulfate reduction coupled to organicmore » carbon oxidation or in diffusive sedimentary sulfate–methane transition zone). The addition of hematite to these microcosm experiments resulted in significant microbial iron reduction as well as enhancing sulfate-driven AOM. The magnitude of the isotope fractionation of sulfur and oxygen isotopes in sulfate from these incubations was lowered by about 50%, indicating the involvement of iron oxides during sulfate reduction in methane seeps. The similar relative change between the oxygen versus sulfur isotopes of sulfate in all experiments (with and without hematite addition) suggests that oxidized forms of iron, naturally present in the sediment incubations, were involved in sulfate reduction, with hematite addition increasing the sulfate recycling or the activity of sulfur-cycling microorganisms by about 40%. Furthermore, these results highlight a role for natural iron oxides during bacterial sulfate reduction in methane seeps not only as nutrient but also as stimulator of sulfur recycling.« less

Angiotensin II promotes iron accumulation and depresses PGI₂ and NO synthesis in endothelial cells: effects of losartan and propranolol analogs.

PubMed

Mak, I Tong; Landgraf, Kenneth M; Chmielinska, Joanna J; Weglicki, William B

2012-10-01

Angiotensin may promote endothelial dysfunction through iron accumulation. To research this, bovine endothelial cells (ECs) were incubated with iron (30 µmol·L⁻¹) with or without angiotensin II (100 nmol·L⁻¹). After incubation for 6 h, it was observed that the addition of angiotensin enhanced EC iron accumulation by 5.1-fold compared with a 1.8-fold increase for cells incubated with iron only. This enhanced iron uptake was attenuated by losartan (100 nmol·L⁻¹), d-propranolol (10 µmol·L⁻¹), 4-HO-propranolol (5 µmol·L⁻¹), and methylamine, but not by vitamin E or atenolol. After 6 h of incubation, angiotensin plus iron provoked intracellular oxidant formation (2'7'-dichlorofluorescein diacetate (DCF-DA) fluorescence) and elevated oxidized glutathione; significant loss of cell viability occurred at 48 h. Stimulated prostacyclin release decreased by 38% (6 h) and NO synthesis was reduced by 41% (24 h). Both oxidative events and functional impairment were substantially attenuated by losartan or d-propranolol. It is concluded that angiotensin promoted non-transferrin-bound iron uptake via AT-1 receptor activation, leading to EC oxidative functional impairment. The protective effects of d-propranolol and 4-HO-propranolol may be related to their lysosomotropic properties.

Antioxidant-Mediated Effects in a Gerbil Model of Iron Overload

PubMed Central

Otto-Duessel, Maya; Aguilar, Michelle; Moats, Rex; Wood, John C.

2010-01-01

Introduction Iron cardiomyopathy is a lethal complication of transfusion therapy in thalassemia major. Nutritional supplements decreasing cardiac iron uptake or toxicity would have clinical significance. Murine studies suggest taurine may prevent oxidative damage and inhibit Ca2+-channel-mediated iron transport. We hypothesized that taurine supplementation would decrease cardiac iron-overloaded toxicity by decreasing cardiac iron. Vitamin E and selenium served as antioxidant control. Methods Animals were divided into control, iron, taurine, and vitamin E/selenium groups. Following sacrifice, iron and selenium measurements, histology, and biochemical analyses were performed. Results No significant differences were found in heart and liver iron content between treatment groups, except for higher hepatic dry-weight iron concentrations in taurine-treated animals (p < 0.03). Serum iron increased with iron loading (751 ± 66 vs. 251 ± 54 μg/dl, p < 0.001) and with taurine (903 ± 136 μg/dl, p = 0.03). Conclusion Consistent with oxidative stress, iron overload increased cardiac malondialdehyde levels, decreased heart glutathione peroxidase (GPx) activity, and increased serum aspartate aminotransferase. Taurine ameliorated these changes, but only significantly for liver GPx activity. Selenium and vitamin E supplementation did not improve oxidative markers and worsened cardiac GPx activity. These results suggest that taurine acts primarily as an antioxidant rather than inhibiting iron uptake. Future studies should illuminate the complexity of these results. PMID:17940334

Iron overload causes endolysosomal deficits modulated by NAADP-regulated 2-pore channels and RAB7A

PubMed Central

Fernández, Belén; Fdez, Elena; Gómez-Suaga, Patricia; Gil, Fernando; Molina-Villalba, Isabel; Ferrer, Isidro; Patel, Sandip; Churchill, Grant C.; Hilfiker, Sabine

2016-01-01

ABSTRACT Various neurodegenerative disorders are associated with increased brain iron content. Iron is known to cause oxidative stress, which concomitantly promotes cell death. Whereas endolysosomes are known to serve as intracellular iron storage organelles, the consequences of increased iron on endolysosomal functioning, and effects on cell viability upon modulation of endolysosomal iron release remain largely unknown. Here, we show that increasing intracellular iron causes endolysosomal alterations associated with impaired autophagic clearance of intracellular protein aggregates, increased cytosolic oxidative stress and increased cell death. These effects are subject to regulation by NAADP, a potent second messenger reported to target endolysosomal TPCNs (2-pore channels). Consistent with endolysosomal iron storage, cytosolic iron levels are modulated by NAADP, and increased cytosolic iron is detected when overexpressing active, but not inactive TPCNs, indicating that these channels can modulate endolysosomal iron release. Cell death triggered by altered intralysosomal iron handling is abrogated in the presence of an NAADP antagonist or when inhibiting RAB7A activity. Taken together, our results suggest that increased endolysosomal iron causes cell death associated with increased cytosolic oxidative stress as well as autophagic impairments, and these effects are subject to modulation by endolysosomal ion channel activity in a RAB7A-dependent manner. These data highlight alternative therapeutic strategies for neurodegenerative disorders associated with increased intracellular iron load. PMID:27383256

Two-zone countercurrent smelter system and process

DOEpatents

Cox, J.H.; Fruehan, R.J.; Elliott, J.F.

1995-01-03

A process for continuously smelting iron ore by use of coal to yield molten iron or semi-steel is disclosed. The process comprises the steps of establishing a melt covered by slag; inducing the slag and the molten iron to flow countercurrently to one another, toward opposite ends of the smelter; maintaining iron oxide-reducing conditions in that zone of the smelter towards which the slag flows; maintaining carbon-oxidizing conditions in that zone of the smelter towards which the molten iron flows; continuously or semicontinuously tapping the slag from the reducing zone end of the smelter; continuously or semicontinuously tapping the molten iron from the oxidizing zone end of the smelter; and adding to both zones iron ore, coal, oxygen, and flux at addition rates sufficient to keep the molten iron in the reducing zone substantially saturated with carbon, maintain in the slag being tapped an FeO content of about 5 weight percent or less, and maintain in the molten iron being tapped a carbon content of about 0.5 to 5 weight percent. A slag dam preferably is included in the smelter, to impede the backflow of the slag from the reducing zone to the oxidizing zone. A metal bath dam with one or more flow-through portals also is preferably used, submerged below the slag dam, to impede the backflow of the hot metal. 8 figures.

Two-zone countercurrent smelter system and process

DOEpatents

Cox, James H.; Fruehan, Richard J.; Elliott, deceased, John F.

1995-01-01

A process for continuously smelting iron ore by use of coal to yield molten iron or semi-steel is disclosed. The process comprises the steps of establishing a melt covered by slag; inducing the slag and the molten iron to flow countercurrently to one another, toward opposite ends of the smelter; maintaining iron oxide-reducing conditions in that zone of the smelter towards which the slag flows; maintaining carbon-oxidizing conditions in that zone of the smelter towards which the molten iron flows; continuously or semicontinuously tapping the slag from the reducing zone end of the smelter; continuously or semicontinuously tapping the molten iron from the oxidizing zone end of the smelter; and adding to both zones iron ore, coal, oxygen, and flux at addition rates sufficient to keep the molten iron in the reducing zone substantially saturated with carbon, maintain in the slag being tapped an FeO content of about 5 weight percent or less, and maintain in the molten iron being tapped a carbon content of about 0.5 to 5 weight percent. A slag dam preferably is included in the smelter, to impede the backflow of the slag from the reducing zone to the oxidizing zone. A metal bath dam with one or more flow-through portals also is preferably used, submerged below the slag dam, to impede the backflow of the hot metal.

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

The reaction of zero-valent iron (ZVI) with oxygen can lead to the formation of oxidants, which may be used to transform recalcitrant contaminants including non-polar organics and certain metals. Nanoparticulate iron might provide a practical mechanism of remediating oxygen-containing groundwater and contaminated soil. To gain insight into the reaction mechanism and to quantify the yield of oxidants, experiments were performed with model organic compounds in the presence of nanoparticulate zero-valent iron and oxygen. At pH values below 5, ZVI nanoparticles were oxidized within 30 minutes with a stoichiometry of approximately two Fe0 oxidized per O2 consumed. Using the oxidation of methanol and ethanol to formaldehyde and acetaldehyde, respectively, we found that less than 2% of the consumed oxygen was converted to reactive oxidants under acidic conditions. The yield of aldehydes increased with pH up to pH 7, with maximum oxidant yields of around 5% relative to the mass of ZVI added. The increase of aldehyde yield with pH was attributable to changes in the processes responsible for oxidant production. At pH values below 5, the corrosion of ZVI by oxygen produces hydrogen peroxide, which subsequently reacts with ferrous iron [Fe(II)] via the Fenton reaction. At higher pH values, the aldehydes are produced when Fe(II), the initial product of ZVI oxidation, reacts with oxygen. The decrease in oxidant yield at pH values above 7 may be attributable to precipitation of Fe(II). The oxidation of benzoic acid and 2-propanol to para-hydroxybenzoic acid and acetone, respectively, followed a very different trend compared to the primary alcohols. In both cases, the highest product yields (approximately 2% with respect to ZVI added) were observed at pH 3. Yields decreased with increasing pH, with no oxidized product detected at neutral pH. These results suggest that two different oxidants may be produced by the system: hydroxyl radical (OH-·) at acidic pH and a more selective oxidant such as the ferryl ion [Fe(IV)] at neutral pH. This provides insight into the type of compounds that may be oxidized using the zero-valent iron and oxygen system. The addition of certain compounds such as oxalate and polyoxometalate (POM) may improve contaminant remediation efficiencies by enhancing oxidant yields. The introduction of 1 mM oxalate improved the formaldehyde yield by approximately 20% at neutral pH. Oxalate accelerates the Fenton reaction and limits the passivation of the ZVI surface by increasing iron solubility. The presence of excess POM greatly enhanced the yield of formaldehyde, with maximum yields of 60 and 35% with respect to ZVI added at pH 2 and 7, respectively. The mechanism of POM enhancement is a function of solution pH. At acidic pH, POM acts an electron shuttle by directly transferring electrons from ZVI to oxygen to increase the hydrogen peroxide production. At neutral pH, POM may act by forming soluble iron-complexes and preventing the build-up of an iron oxide layer on the ZVI surface.

The kinetics of influenza-virus adsorption on iron oxide in the process of viral purification and concentration

PubMed Central

Larin, N. M.; Gallimore, P. H.

1971-01-01

This paper reports a study carried out to clarify the mechanisms involved in adsorption of influenza A and B viruses on iron oxide. Accordingly, the amounts of virus that are adsorbed from virus suspensions of varying concentrations per unit surface area of magnetic or non-magnetic oxide at fixed temperature and time have been determined. The principles involved are clearly the same as those involved in multiple equilibria during the interaction of particles with a large number of combining sites with different intrinsic affinity. Consequently, the amount of virus that is adsorbed per unit mass of iron oxide depends on the size of the adsorbent area, not on its magnetic property. Owing to a significant difference between the affinities of influenza A and B particles for the binding sites on iron oxide, unit surface area of the adsorbent is invariably capable of adsorbing significantly greater amounts of influenza A than B particles. The practical implications of these findings are that a better understanding of the mechanisms involved in virus adsorption on iron oxide will permit a more efficient separation of virus particles from impurities. The simplicity and the rapidity of the technique and the cheapness of the equipment required suggest that the iron oxide method is of great value for both small- or large-scale viral purification, whether it is used as a single step procedure or as a primary step followed by zonal separation. PMID:5291749

Metal ion binding to iron oxides

NASA Astrophysics Data System (ADS)

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

2006-06-01

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

Indirect Redox Transformations of Iron, Copper, and Chromium Catalyzed by Extremely Acidophilic Bacteria

PubMed Central

Johnson, D. Barrie; Hedrich, Sabrina; Pakostova, Eva

2017-01-01

Experiments were carried out to examine redox transformations of copper and chromium by acidophilic bacteria (Acidithiobacillus, Leptospirillum, and Acidiphilium), and also of iron (III) reduction by Acidithiobacillus spp. under aerobic conditions. Reduction of iron (III) was found with all five species of Acidithiobacillus tested, grown aerobically on elemental sulfur. Cultures maintained at pH 1.0 for protracted periods displayed increasing propensity for aerobic iron (III) reduction, which was observed with cell-free culture liquors as well as those containing bacteria. At. caldus grown on hydrogen also reduced iron (III) under aerobic conditions, confirming that the unknown metabolite(s) responsible for iron (III) reduction were not (exclusively) sulfur intermediates. Reduction of copper (II) by aerobic cultures of sulfur-grown Acidithiobacillus spp. showed similar trends to iron (III) reduction in being more pronounced as culture pH declined, and occurring in both the presence and absence of cells. Cultures of Acidithiobacillus grown anaerobically on hydrogen only reduced copper (II) when iron (III) (which was also reduced) was also included; identical results were found with Acidiphilium cryptum grown micro-aerobically on glucose. Harvested biomass of hydrogen-grown At. ferridurans oxidized iron (II) but not copper (I), and copper (I) was only oxidized by growing cultures of Acidithiobacillus spp. when iron (II) was also included. The data confirmed that oxidation and reduction of copper were both mediated by acidophilic bacteria indirectly, via iron (II) and iron (III). No oxidation of chromium (III) by acidophilic bacteria was observed even when, in the case of Leptospirillum spp., the redox potential of oxidized cultures exceeded +900 mV. Cultures of At. ferridurans and A. cryptum reduced chromium (VI), though only when iron (III) was also present, confirming an indirect mechanism and contradicting an earlier report of direct chromium reduction by A. cryptum. Measurements of redox potentials of iron, copper and chromium couples in acidic, sulfate-containing liquors showed that these differed from situations where metals are not complexed by inorganic ligands, and supported the current observations of indirect copper oxido-reduction and chromium reduction mediated by acidophilic bacteria. The implications of these results for both industrial applications of acidophiles and for exobiology are discussed. PMID:28239375

Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites.

PubMed

Xiao, Dianne J; Bloch, Eric D; Mason, Jarad A; Queen, Wendy L; Hudson, Matthew R; Planas, Nora; Borycz, Joshua; Dzubak, Allison L; Verma, Pragya; Lee, Kyuho; Bonino, Francesca; Crocellà, Valentina; Yano, Junko; Bordiga, Silvia; Truhlar, Donald G; Gagliardi, Laura; Brown, Craig M; Long, Jeffrey R

2014-07-01

Enzymatic haem and non-haem high-valent iron-oxo species are known to activate strong C-H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron-oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)-oxo compounds. In particular, although nature's non-haem iron(IV)-oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal-organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal-organic framework Fe2(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc), are able to activate the C-H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)-oxo species.

Exploration of pro-oxidant and antioxidant activities of the flavonoid myricetin.

PubMed

Chobot, Vladimir; Hadacek, Franz

2011-01-01

Flavonoids are ubiquitous phenolic plant metabolites. Many of them are well known for their pro- and antioxidant properties. Myricetin has been reported to be either a potent antioxidant or a pro-oxidant depending on the conditions. The reaction conditions for the pro- and antioxidant activities were therefore investigated using variations of the deoxyribose degradation assay systems. The deoxyribose degradation assay systems were conducted as follows; H(2)O(2)/Fe(III)/ascorbic acid, H(2)O(2)/Fe(III), Fe(III)/ascorbic acid, and Fe(III). Each system was carried out in two variants, FeCl(3) (iron ions added as FeCl(3)) and FeEDTA (iron added in complex with ethylenediaminetetraacetic acid). When ascorbic acid was present, myricetin showed antioxidant properties, especially when it occurred in complex with iron. In ascorbic acid-free systems, pro-oxidant activities prevailed, which where enhanced if iron was in complex with EDTA. Myricetin's antioxidant activity depends on both the reactive oxygen species (ROS) scavenging and iron ions chelation properties. The pro-oxidative properties are caused by reduction of molecular oxygen to ROS and iron(III) to iron(II). Myricetin is able to substitute for ascorbic acid albeit less efficiently.

Magnetic Nanoparticles for Cancer Diagnosis and Therapy

PubMed Central

Yigit, Mehmet V.; Moore, Anna

2013-01-01

Nanotechnology is evolving as a new field that has a potentially high research and clinical impact. Medicine, in particular, could benefit from nanotechnology, due to emerging applications for noninvasive imaging and therapy. One important nanotechnological platform that has shown promise includes the so-called iron oxide nanoparticles. With specific relevance to cancer therapy, iron oxide nanoparticle-based therapy represents an important alternative to conventional chemotherapy, radiation, or surgery. Iron oxide nanoparticles are usually composed of three main components: an iron core, a polymer coating, and functional moieties. The biodegradable iron core can be designed to be superparamagnetic. This is particularly important, if the nanoparticles are to be used as a contrast agent for noninvasive magnetic resonance imaging (MRI). Surrounding the iron core is generally a polymer coating, which not only serves as a protective layer but also is a very important component for transforming nanoparticles into biomedical nanotools for in vivo applications. Finally, different moieties attached to the coating serve as targeting macromolecules, therapeutics payloads, or additional imaging tags. Despite the development of several nanoparticles for biomedical applications, we believe that iron oxide nanoparticles are still the most promising platform that can transform nanotechnology into a conventional medical discipline. PMID:22274558

Part II. Hydrothermal steel slag valorization: hydrogen and nano-magnetite production

NASA Astrophysics Data System (ADS)

Crouzet, Camille; Brunet, Fabrice; Recham, Nadir; Auzende, Anne-Line; Findling, Nathaniel; Magnin, Valérie; Ferrasse, Jean-Henry; Goffé, Bruno

2017-10-01

The effect of acidic conditions (in a pH range of 3 to 6) and temperature on the kinetics of the hydrothermal oxidation of ferrous iron contained in BOF steel slag has been tested in the 150 – 350°C range for acid acetic concentrations from 0 to 4M. Reaction progress was monitored with the amount of produced H2. Higher temperature and lower pH are found to enhance the hydrothermal oxidation kinetics of the slag. These two parameters are believed to increase iron dissolution rate which has already been identified as the rate limiting step of the hydrothermal oxidation of pure FeO. An activation energy of 28 × 4 kJ/mole is found for the hydrothermal oxidation of the steel slag which compares very well with that of pure FeO under similar conditions. In the case of the slag run in water at 300°C for 70.5 hours, magnetite product has been separated magnetically and characterized. Particles were found to fall in three size ranges: 10 – 30 nm, 100 – 300 nm and 1 – 10 µm. The smallest fraction (10 – 30 nm) is comparable to the 10 – 20 nm size range that is achieved when nanomagnetite are synthesized by co-precipitation methods. Obviously, the production of nanomagnetite enhances the economic interest of the hydrothermal processing of steel slags, which has already proven its capacity to produce high-purity H2.

Vegetation successfully prevents oxidization of sulfide minerals in mine tailings.

PubMed

Li, Yang; Sun, Qingye; Zhan, Jing; Yang, Yang; Wang, Dan

2016-07-15

The oxidization of metal sulfide in tailings causes acid mine drainage. However, it remains unclear whether vegetation prevents the oxidization of metal sulfides. The oxidization characteristics and microbial indices of the tailings in the presence of various plant species were investigated to explore the effects of vegetation on the oxidization of sulfide minerals in tailings. The pH, reducing sulfur, free iron oxides (Fed), chemical oxygen consumption (COC) and biological oxygen consumption (BOC) were measured. Key iron- and sulfur-oxidizing bacteria (Acidithiobacillus spp., Leptospirillum spp. and Thiobacillus spp.) were quantified using real-time PCR. The results indicate that vegetation growing on tailings can effectively prevent the oxidization of sulfide minerals in tailings. A higher pH and reducing-sulfur content and lower Fed were observed in the 0-30 cm depth interval in the presence of vegetation compared to bare tailings (BT). The COC gradually decreased with depth in all of the soil profiles; specifically, the COC rapidly decreased in the 10-20 cm interval in the presence of vegetation but gradually decreased in the BT profiles. Imperata cylindrica (IC) and Chrysopogon zizanoides (CZ) profiles contained the highest BOC in the 10-20 cm interval. The abundance of key iron- and sulfur-oxidizing bacteria in the vegetated tailings were significantly lower than in the BT; in particular, IC was associated with the lowest iron- and sulfur-oxidizing bacterial abundance. In conclusion, vegetation successfully prevented the oxidization of sulfide minerals in the tailings, and Imperata cylindrica is the most effective in reducing the number of iron- and sulfur-oxidizing bacteria and helped to prevent the oxidization of sulfide minerals in the long term. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evaluation of ferrolysis in arsenate adsorption on the paddy soil derived from an Oxisol.

PubMed

Jiang, Jun; Dai, Zhaoxia; Sun, Rui; Zhao, Zhenjie; Dong, Ying; Hong, Zhineng; Xu, Renkou

2017-07-01

Iron oxides are dominant effective adsorbents for arsenate in iron oxide-rich variable charge soils. Oxisol-derived paddy soils undergo intensive ferrolysis, which results in high leaching and transformation of iron oxides. However, little information is available concerning the effect of ferrolysis on arsenate adsorption by paddy soil and parent Oxisol. In the present study, we examined the arsenate affinity of soils using arsenate adsorption/desorption isotherms, zeta potential, adsorption kinetics, pH effect and phosphate competition experiments. Results showed that ferrolysis in an alternating flooding-drying Oxisol-derived paddy soil resulted in a significant decrease of free iron oxides and increase of amorphous iron oxides in the surface and subsurface layers. There were more reactive sites exposed on amorphous than on crystalline iron oxides. Therefore, disproportionate ratios of arsenate adsorption capacities and contents of free iron oxides were observed in the studied Oxisols compared with paddy soils. The Gibbs free energy values corroborated that both electrostatic and non-electrostatic adsorption mechanisms contributed to the arsenate adsorption by bulk soils, and the kinetic adsorption data further suggested that the rate-limiting step was chemisorption. The zeta potential of soil colloids decreased after arsenate was adsorbed on the surfaces, forming inner-sphere complexes and thus transferring their negative charges to the soil particle surfaces. The adsorption/desorption isotherms showed that non-electrostatic adsorption was the main mechanism responsible for arsenate binding to the Oxisol and derived paddy soils, representing 91.42-94.65% of the adsorption capacities. Further studies revealed that arsenate adsorption was greatly inhibited by increasing suspension pH and incorporation of phosphate. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis of high intrinsic loss power aqueous ferrofluids of iron oxide nanoparticles by citric acid-assisted hydrothermal-reduction route

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

Behdadfar, Behshid, E-mail: bbehdadfar@ma.iut.ac.ir; Kermanpur, Ahmad; Sadeghi-Aliabadi, Hojjat

Monodispersed aqueous ferrofluids of iron oxide nanoparticle were synthesized by hydrothermal-reduction route. They were characterized by X-ray diffraction analysis, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy and dynamic light scattering. The results showed that certain concentrations of citric acid (CA) are required to obtain only magnetic iron oxides with mean particle sizes around 8 nm. CA acts as a modulator and reducing agent in iron oxide formation which controls nanoparticle size. The XRD, magnetic and heating measurements showed that the temperature and time of hydrothermal reaction can affect the magnetic properties of obtained ferrofluids. The synthesized ferrofluids weremore » stable at pH 7. Their mean hydrodynamic size was around 80 nm with polydispersity index (PDI) of 0.158. The calculated intrinsic loss power (ILP) was 9.4 nHm{sup 2}/kg. So this clean and cheap route is an efficient way to synthesize high ILP aqueous ferrofluids applicable in magnetic hyperthermia. - Graphical abstract: Monodispersed aqueous ferrofluids of iron oxide nanoparticles were synthesized by hydrothermal-reduction method with citric acid as reductant which is an efficient way to synthesize aqueous ferrofluids applicable in magnetic hyperthermia. Highlights: Black-Right-Pointing-Pointer Aqueous iron oxide ferrofluids were synthesized by hydrothermal-reduction route. Black-Right-Pointing-Pointer Citric acid acted as reducing agent and surfactant in the route. Black-Right-Pointing-Pointer This is a facile, low energy and environmental friendly route. Black-Right-Pointing-Pointer The aqueous iron oxide ferrofluids were monodispersed and stable at pH of 7. Black-Right-Pointing-Pointer The calculated intrinsic loss power of the synthesized ferrofluids was very high.« less

Simplifying Logistics and Avoiding the Unnecessary in Patients With Breast Cancer Undergoing Sentinel Node Biopsy. A Prospective Feasibility Trial of the Preoperative Injection of Super Paramagnetic Iron Oxide Nanoparticles.

PubMed

Karakatsanis, A; Olofsson, H; Stålberg, P; Bergkvist, L; Abdsaleh, S; Wärnberg, F

2018-06-01

Sentinel node is routinely localized with the intraoperative use of a radioactive tracer, involving challenging logistics. Super paramagnetic iron oxide nanoparticle is a non-radioactive tracer with comparable performance that could allow for preoperative localization, would simplify the procedure, and possibly be of value in axillary mapping before neoadjuvant treatment. The current trial aimed to determine the a priori hypothesis that the injection of super paramagnetic iron oxide nanoparticles in the preoperative period for the localization of the sentinel node is feasible. This is a prospective feasibility trial, conducted from 9 September 2014 to 22 October 2014 at Uppsala University Hospital. In all, 12 consecutive patients with primary breast cancer planned for resection of the primary and sentinel node biopsy were recruited. Super paramagnetic iron oxide nanoparticles were injected in the preoperative visit in the outpatient clinic. The radioactive tracer ( 99 mTc) and the blue dye were injected perioperatively in standard fashion. A volunteer was injected with super paramagnetic iron oxide nanoparticles to follow the decline in the magnetic signal in the sentinel node over time. The primary outcome was successful sentinel node detection. Super paramagnetic iron oxide nanoparticles' detection after preoperative injection (3-15 days) was successful in all cases (100%). In the volunteer, axillary signal was presented for 4 weeks. No adverse effects were noted. Conclusion and relevance: Preoperative super paramagnetic iron oxide nanoparticles' injection is feasible and leads to successful detection of the sentinel node. That may lead to simplified logistics as well as the identification, sampling, and marking of the sentinel node in patients planned for neoadjuvant treatment.

Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles.

PubMed

Gilbert, Benjamin; Katz, Jordan E; Huse, Nils; Zhang, Xiaoyi; Frandsen, Cathrine; Falcone, Roger W; Waychunas, Glenn A

2013-10-28

An emerging area in chemical science is the study of solid-phase redox reactions using ultrafast time-resolved spectroscopy. We have used molecules of the photoactive dye 2',7'-dichlorofluorescein (DCF) anchored to the surface of iron(III) oxide nanoparticles to create iron(II) surface atoms via photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(III) oxide nanoparticles has not been reported. We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(III)-dye complex. Following light absorption, excited state relaxation times of the dye of 115-310 fs were found for all samples. Comparison between TA dynamics on uncoated and dye-sensitized hematite nanoparticles revealed the dye de-excitation pathway to consist of a competition between electron and energy transfer to the nanoparticles. We analyzed the TA data for hematite nanoparticles using a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye-oxide energy transfer is energetically forbidden) even though the acceptor states are different. Comparison of the alignment of the excited states of the dye and the unoccupied states of these oxides showed that the dye injects into acceptor states of different symmetry (Ti t2gvs. Fe eg).

Iron Tolerant Cyanobacteria as an Effective Tool to Study Early Evolution of Life and the Development of Biosignatures

NASA Technical Reports Server (NTRS)

Brown, Igor; Mummey, Daniel; Sarkisova, Svetlana; Allen, Carlton; McKay, David S.

2006-01-01

We are currently conducting preliminary studies on the diversity of iron-tolerant cyanobacteria (CB) isolated from iron-depositing hot springs in and around Yellowstone National Park (WY, USA). In conclusion, there is no consensus on the divergence of cyanobacteria from a common ancestor for either anoxygenic or oxygenic phototrophs. Anoxygenic photosynthesis may have provided energy for the common ancestor, but it is unclear what environmental pressure induced the evolving of oxygenic phototrophs. It is supposed, however, that predecessors of contemporary CB were capable of oxidizing various substrates other than water , and it is likely that Fe2+ could be one of those substrates . If that were the case, the work of entire photosystems in Precambrian cyanobacteria and/or in their predecessors could follow three scenarios (at least): 1) ferrous iron may have been oxidized in PS II but without significant effects on oxygen evolution, and environmental iron could have been oxidized either enzymatically or chemically; 2) ferrous iron may have been oxidized only enzymatically by PS II, accompanied by the repression of O2 evolution; or 3) ferrous iron may have been oxidized by PS I upon the prevalence of anoxygenic photosynthesis or without any effect on PS II. All of these scenarios will be the subject of our future studies with the aim to understand which line-ages of CB could be typical for Precambrian time.

A study of the dispersity of iron oxide and iron oxide-noble metal (Me = Pd, Pt) supported systems

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z. P.; Shopska, M. G.; Krstić, J. B.; Jovanović, D. M.; Mitov, I. G.; Kadinov, G. B.

2007-09-01

Samples of one-(Fe) and two-component (Fe-Pd and Fe-Pt) catalysts were prepared by incipient wetness impregnation of four different supports: TiO2 (anatase), γ-Al2O3, activated carbon, and diatomite. The chosen synthesis conditions resulted in the formation of nanosized supported phases—iron oxide (in the one-component samples), or iron oxide-noble metal (in the two-component ones). Different agglomeration degrees of these phases were obtained as a result of thermal treatment. Ultradisperse size of the supported phase was maintained in some samples, while a process of partial agglomeration occurred in others, giving rise to nearly bidisperse (ultra-and highdisperse) supported particles. The different texture of the used supports and their chemical composition are the reasons for the different stability of the nanosized supported phases. The samples were tested as heterogeneous catalysts in total benzene oxidation reaction.

Temporal patterning of the potential induced by localized corrosion of iron passivity in acid media. Growth and breakdown of the oxide film described in terms of a point defect model.

PubMed

Sazou, Dimitra; Pavlidou, Maria; Pagitsas, Michael

2009-10-21

This work analyses the nature of temporal patterning of the anodic potential induced by chlorides during polarization of iron under current-controlled conditions in acid solutions. It is shown that potential oscillations emerged as a result of the local chloride attack of a thin oxide layer, which covers the iron surface in its passive state. The mechanism by which both the local oxide breakdown and the subsequent localized active dissolution (pitting) occur is explained by considering a point defect model (PDM) developed to describe the oxide growth and breakdown. According to the PDM, chlorides occupy oxygen vacancies resulting in the inhibition of oxide growth and autocatalytic generation of cation vacancies that destabilize the oxide layer. Simultaneous transformation of the outer surface of the inner oxide layer to non-adherent ferrous chloride or oxo-chloride species leads to a further thinning of the oxide layer and its lifting-on from the iron surface. The process repeats again yielding sustained oscillations of the anodic potential. Analysis of the oscillatory response obtained under current-controlled conditions as a function of either the current or the time allows the suggestion of a set of alternate diagnostic criteria, which might be used to characterize localized corrosion of iron in acid solutions.

The impact of degassing on the oxidation state of basaltic magmas: A case study of Kīlauea volcano

NASA Astrophysics Data System (ADS)

Moussallam, Yves; Edmonds, Marie; Scaillet, Bruno; Peters, Nial; Gennaro, Emanuela; Sides, Issy; Oppenheimer, Clive

2016-09-01

Volcanic emissions link the oxidation state of the Earth's mantle to the composition of the atmosphere. Whether the oxidation state of an ascending magma follows a redox buffer - hence preserving mantle conditions - or deviates as a consequence of degassing remains under debate. Thus, further progress is required before erupted basalts can be used to infer the redox state of the upper mantle or the composition of their co-emitted gases to the atmosphere. Here we present the results of X-ray absorption near-edge structure (XANES) spectroscopy at the iron K-edge carried out for a series of melt inclusions and matrix glasses from ejecta associated with three eruptions of Kīlauea volcano (Hawai'i). We show that the oxidation state of these melts is strongly correlated with their volatile content, particularly in respect of water and sulfur contents. We argue that sulfur degassing has played a major role in the observed reduction of iron in the melt, while the degassing of H2O and CO2 appears to have had a negligible effect on the melt oxidation state under the conditions investigated. Using gas-melt equilibrium degassing models, we relate the oxidation state of the melt to the composition of the gases emitted at Kīlauea. Our measurements and modelling yield a lower constraint on the oxygen fugacity of the mantle source beneath Kīlauea volcano, which we infer to be near the nickel nickel-oxide (NNO) buffer. Our findings should be widely applicable to other basaltic systems and we predict that the oxidation state of the mantle underneath most hotspot volcanoes is more oxidised than that of the associated lavas. We also suggest that whether the oxidation states of a basalt (in particular MORB) reflects that of its source, is primarily determined by the extent of sulfur degassing.

Randomized clinical trial on acute effects of i.v. iron sucrose during haemodialysis.

PubMed

Garcia-Fernandez, Nuria; Echeverria, Aitziber; Sanchez-Ibarrola, Alfonso; Páramo, José Antonio; Coma-Canella, Isabel

2010-03-01

Haemodialysis induces endothelial dysfunction by oxidation and inflammation. Intravenous iron administration during haemodialysis could worsen endothelial dysfunction. The aim of this study was to ascertain if iron produces endothelial dysfunction and the possible neutralizing effect of N-acetylcysteine when infused before iron. The oxidative and inflammatory effects of iron during haemodialysis were also assessed. Forty patients undergoing haemodialysis were studied in a randomized and cross-over design with and without N-acetylcysteine infused before iron sucrose (50 or 100 mg). Plasma Von Willebrand factor (vWF), soluble intercellular adhesion molecule-1 (sICAM-1) levels, malondialdehyde, total antioxidant capacity, CD11b/CD18 expression in monocytes, interleukin (IL)-8 in monocytes and plasma IL-8 were studied at baseline and during haemodialysis. Haemodialysis produced significant (P < 0.001) increase in plasma vWF, sICAM-1, malondialdehyde, IL-8 and CD11b/CD18 expression in monocytes, as well as decrease in total antioxidant capacity. Iron induced significant increase in plasma malondialdehyde and IL-8 in monocytes, but had no effect on total antioxidant capacity, CD11b/CD18 expression, plasma IL-8, vWF and sICAM-1. The addition of N-acetylcysteine to 50 mg of iron produced a significant (P = 0.040) decrease in malondialdehyde. Standard (100 mg) and low (50 mg) doses of iron during haemodialysis had no effects on endothelium. Iron only had minor effects on inflammation and produced an increase in oxidative stress, which was neutralized by N-acetylcysteine at low iron dose. Haemodialysis caused a significant increase in oxidative stress, inflammation and endothelial dysfunction markers.

Surface effects of corrosive media on hardness, friction, and wear of materials

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.; Rengstorff, G. W. P.; Ishigaki, H.

1985-01-01

Hardness, friction, and wear experiments were conducted with magnesium oxide exposed to various corrosive media and also with elemental iron and nickel exposed to water and NaOH. Chlorides such as MgCl2 and sodium containing films were formed on cleaved magnesium oxide surfaces. The MgCl2 films softened the magnesium oxide surfaces and caused high friction and great deformation. Hardness was strongly influenced by the pH value of the HCl-containing solution. The lower the pH, the lower the microhardness. Neither the pH value of nor the immersion time in NaOH containing, NaCl containing, and HNO3 containing solutions influenced the microhardness of magnesium oxide. NaOH formed a protective and low friction film on iron surfaces. The coefficient of friction and the wear for iron were low at concentrations of NaOH higher than 0.01 N. An increase in NaOH concentration resulted in a decrease in the concentration of ferric oxide on the iron surface. It took less NaOH to form a protective, low friction film on nickel than on iron.

Iron-phosphate ceramics for solidification of mixed low-level waste

DOEpatents

Aloy, Albert S.; Kovarskaya, Elena N.; Koltsova, Tatiana I.; Macheret, Yevgeny; Medvedev, Pavel G.; Todd, Terry

2000-01-01

A method of immobilizing mixed low-level waste is provided which uses low cost materials and has a relatively long hardening period. The method includes: forming a mixture of iron oxide powders having ratios, in mass %, of FeO:Fe.sub.2 O.sub.3 :Fe.sub.3 O.sub.4 equal to 25-40:40-10:35-50, or weighing a definite amount of magnetite powder. Metallurgical cinder can also be used as the source of iron oxides. A solution of the orthophosphoric acid, or a solution of the orthophosphoric acid and ferric oxide, is formed and a powder phase of low-level waste and the mixture of iron oxide powders or cinder (or magnetite powder) is also formed. The acid solution is mixed with the powder phase to form a slurry with the ratio of components (mass %) of waste:iron oxide powders or magnetite:acid solution=30-60:15-10:55-30. The slurry is blended to form a homogeneous mixture which is cured at room temperature to form the final product.

Mars Hematite Site: Potential for Preservation of Microfossils

NASA Technical Reports Server (NTRS)

Allen, Carlton C.; Westall, Frances; Longazo, Teresa; Schelble, Rachel; Probst, Luke; Flood, Beverly

2003-01-01

Defining locations where conditions may have been favorable for life is a key objective for the exploration of Mars. Of prime importance are sites where conditions may have been favorable for the preservation of evidence of pre-biotic or biotic processes. Areas displaying significant concentrations of the mineral hematite (alpha-Fe2O3) have been identified from orbit by thermal emission spectrometry. The largest such deposit, in Sinus Meridiani, is a strong candidate landing site for one of the twin Mars Exploration Rovers, scheduled to launch in 2003. The Martian hematite site may have significance in the search for evidence of extraterrestrial life. Since iron oxides can form as aqueous mineral precipitates, the potential exists for preserving microscopic evidence of life in ecosystems that deposit iron oxides. Terrestrial hematite deposits proposed as possible analogs for the hematite sites on Mars include massive (banded) iron formations, iron oxide hydrothermal deposits, iron-rich laterites and ferricrete soils, and rock varnish. We are engaged in a systematic effort to document the evidence of life preserved in iron oxide deposits from each of these environments.

Immobilization of iron- and manganese-oxidizing bacteria with a biofilm-forming bacterium for the effective removal of iron and manganese from groundwater.

PubMed

Li, Chunyan; Wang, Shuting; Du, Xiaopeng; Cheng, Xiaosong; Fu, Meng; Hou, Ning; Li, Dapeng

2016-11-01

In this study, three bacteria with high Fe- and Mn-oxidizing capabilities were isolated from groundwater well sludge and identified as Acinetobacter sp., Bacillus megaterium and Sphingobacterium sp. The maximum removal ratios of Fe and Mn (99.75% and 96.69%) were obtained by an optimal combination of the bacteria at a temperature of 20.15°C, pH 7.09 and an inoculum size of 2.08%. Four lab-scale biofilters were tested in parallel for the removal of iron and manganese ions from groundwater. The results indicated that the Fe/Mn removal ratios of biofilter R4, which was inoculated with iron- and manganese-oxidizing bacteria and a biofilm-forming bacterium, were approximately 95% for each metal during continuous operation and were better than the other biofilters. This study demonstrated that the biofilm-forming bacterium could promote the immobilization of the iron- and manganese-oxidizing bacteria on the biofilters and enhance the removal efficiency of iron and manganese ions from groundwater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Textural and Mineralogical Characteristics of Microbial Fossils Associated with Modern and Ancient Iron (Oxyhydr)Oxides: Terrestrial Analogue for Sediments in Gale Crater

PubMed Central

Chan, Marjorie A.; McPherson, Brian J.

2014-01-01

Abstract Iron (oxyhydr)oxide microbial mats in modern to ∼100 ka tufa terraces are present in a cold spring system along Ten Mile Graben, southeastern Utah, USA. Mats exhibit morphological, chemical, and textural biosignatures and show diagenetic changes that occur over millennial scales. The Jurassic Brushy Basin Member of the Morrison Formation in the Four Corners region of the USA also exhibits comparable microbial fossils and iron (oxyhydr)oxide biosignatures in the lacustrine unit. Both the modern spring system and Brushy Basin Member represent alkaline, saline, groundwater-fed systems and preserve diatoms and other similar algal forms with cellular elaboration. Two distinct suites of elements (1. C, Fe, As and 2. C, S, Se, P) are associated with microbial fossils in modern and ancient iron (oxyhydr)oxides and may be potential markers for biosignatures. The presence of ferrihydrite in ∼100 ka fossil microbial mats and Jurassic rocks suggests that this thermodynamically unstable mineral may also be a potential biomarker. One of the most extensive sedimentary records on Mars is exposed in Gale Crater and consists of non-acidic clays and sulfates possibly of lacustrine origin. These terrestrial iron (oxyhydr)oxide examples are a valuable analogue because of similar iron- and clay-rich host rock compositions and will help (1) understand diagenetic processes in a non-acidic, saline lacustrine environment such as the sedimentary rocks in Gale Crater, (2) document specific biomediated textures, (3) demonstrate how biomediated textures might persist or respond to diagenesis over time, and (4) provide a ground truth library of textures to explore and compare in extraterrestrial iron (oxyhydr)oxides, where future explorations hope to detect past evidence of life. Key Words: Biogeochemistry—Mars—Biosignatures—Diagenesis—Iron oxides. Astrobiology 14, 1–14. PMID:24380534

Females Are Protected From Iron-Overload Cardiomyopathy Independent of Iron Metabolism: Key Role of Oxidative Stress.

PubMed

Das, Subhash K; Patel, Vaibhav B; Basu, Ratnadeep; Wang, Wang; DesAulniers, Jessica; Kassiri, Zamaneh; Oudit, Gavin Y

2017-01-23

Sex-related differences in cardiac function and iron metabolism exist in humans and experimental animals. Male patients and preclinical animal models are more susceptible to cardiomyopathies and heart failure. However, whether similar differences are seen in iron-overload cardiomyopathy is poorly understood. Male and female wild-type and hemojuvelin-null mice were injected and fed with a high-iron diet, respectively, to develop secondary iron overload and genetic hemochromatosis. Female mice were completely protected from iron-overload cardiomyopathy, whereas iron overload resulted in marked diastolic dysfunction in male iron-overloaded mice based on echocardiographic and invasive pressure-volume analyses. Female mice demonstrated a marked suppression of iron-mediated oxidative stress and a lack of myocardial fibrosis despite an equivalent degree of myocardial iron deposition. Ovariectomized female mice with iron overload exhibited essential pathophysiological features of iron-overload cardiomyopathy showing distinct diastolic and systolic dysfunction, severe myocardial fibrosis, increased myocardial oxidative stress, and increased expression of cardiac disease markers. Ovariectomy prevented iron-induced upregulation of ferritin, decreased myocardial SERCA2a levels, and increased NCX1 levels. 17β-Estradiol therapy rescued the iron-overload cardiomyopathy in male wild-type mice. The responses in wild-type and hemojuvelin-null female mice were remarkably similar, highlighting a conserved mechanism of sex-dependent protection from iron-overload-mediated cardiac injury. Male and female mice respond differently to iron-overload-mediated effects on heart structure and function, and females are markedly protected from iron-overload cardiomyopathy. Ovariectomy in female mice exacerbated iron-induced myocardial injury and precipitated severe cardiac dysfunction during iron-overload conditions, whereas 17β-estradiol therapy was protective in male iron-overloaded mice. © 2017 The Authors. Published on behalf of the American Heart Association, Inc., by Wiley Blackwell.

Molecular targeting in childhood malignancies using nanoparticles

NASA Astrophysics Data System (ADS)

Satake, Noriko; Barisone, Gustavo; Diaz, Elva; Nitin, Nitin; Nolta, Jan; Lam, Kit

2012-06-01

The goal of our project is to develop a new therapy for childhood malignancies using nanoformulated siRNA targeting Mxd3, a molecule in the Sonic Hedgehog signaling pathway, which we believe is important for cell survival. We plan to use cancer-specific ligands and superparamagnetic iron oxide nanoparticles (SPIO NPs) to carry siRNA. This delivery system will be tested in mouse xenograft models that we developed with primary cancer tissues. Our current focus is acute lymphoblastic leukemia (ALL), the most common cancer in children. We report our progress to date.

Iron oxide-mediated semiconductor photocatalysis vs. heterogeneous photo-Fenton treatment of viruses in wastewater. Impact of the oxide particle size.

PubMed

Giannakis, Stefanos; Liu, Siting; Carratalà, Anna; Rtimi, Sami; Talebi Amiri, Masoud; Bensimon, Michaël; Pulgarin, César

2017-10-05

The photo-Fenton process is recognized as a promising technique towards microorganism disinfection in wastewater, but its efficiency is hampered at near-neutral pH operating values. In this work, we overcome these obstacles by using the heterogeneous photo-Fenton process as the default disinfecting technique, targeting MS2 coliphage in wastewater. The use of low concentrations of iron oxides in wastewater without H 2 O 2 (wüstite, maghemite, magnetite) has demonstrated limited semiconductor-mediated MS2 inactivation. Changing the operational pH and the size of the oxide particles indicated that the isoelectric point of the iron oxides and the active surface area are crucial in the success of the process, and the possible underlying mechanisms are investigated. Furthermore, the addition of low amounts of Fe-oxides (1mgL -1 ) and H 2 O 2 in the system (1, 5 and 10mgL -1 ) greatly enhanced the inactivation process, leading to heterogeneous photo-Fenton processes on the surface of the magnetically separable oxides used. Additionally, photo-dissolution of iron in the bulk, lead to homogeneous photo-Fenton, further aided by the complexation by the dissolved organic matter in the solution. Finally, we assess the impact of the presence of the bacterial host and the difference caused by the different iron sources (salts, oxides) and the Fe-oxide size (normal, nano-sized). Copyright © 2017 Elsevier B.V. All rights reserved.

Magnetoviscoelastic characteristics of superparamagnetic oxides (Fe, Ni) based ferrofluids

NASA Astrophysics Data System (ADS)

Katiyar, Ajay; Dhar, Purbarun; Nandi, Tandra; Das, Sarit K.

2017-08-01

Ferrofluids have been popular among the academic and scientific communities owing to their intelligent physical characteristics under external stimuli and are in fact among the first nanotechnology products to be employed in real world applications. However, studies on the magnetoviscoelastic behavior of concentrated ferrofluids, especially of superparamagnetic oxides of iron and nickel are rare. The present article comprises the formulation of magneto-colloids utilizing the three various metal oxides nanoparticles viz. Iron (II, III) oxide (Fe3O4), Iron (III) oxide (Fe2O3) and Nickel oxide (NiO) in oil. Iron (II, III) oxide based colloids demonstrate high magnetoviscous characteristics over the other oxides based colloids under external magnetic fields. The maximum magnitude of yield stress and viscosity is found to be 3.0 kPa and 2.9 kPa.s, respectively for iron (II, III) oxide based colloids at 2.6 vol% particle concentration and 1.2 T magnetic field. Experimental investigations reveal that the formulated magneto-nanocolloids are stable, even in high magnetic fields and almost reversible when exposed to rising and drop of magnetic fields of the same magnitude. Observations also reveal that the elastic behavior dominates over the viscous behavior with enhanced relaxation and creep characteristics under the magnetic field. The effect of temperature on viscosity and yield stress of magneto-nanocolloids under magnetic fields has also been discussed. Thus, the present findings have potential applications in various fields such as electromagnetic clutch and brakes of automotive, damping, sealing, optics, nanofinishing etc.

Preparation and characterization of an iron oxide-hydroxyapatite nanocomposite for potential bone cancer therapy.

PubMed

Sneha, Murugesan; Sundaram, Nachiappan Meenakshi

2015-01-01

Recently, multifunctional magnetic nanostructures have been found to have potential applications in biomedical and tissue engineering. Iron oxide nanoparticles are biocompatible and have distinctive magnetic properties that allow their use in vivo for drug delivery and hyperthermia, and as T2 contrast agents for magnetic resonance imaging. Hydroxyapatite is used frequently due to its well-known biocompatibility, bioactivity, and lack of toxicity, so a combination of iron oxide and hydroxyapatite materials could be useful because hydroxyapatite has better bone-bonding ability. In this study, we prepared nanocomposites of iron oxide and hydroxyapatite and analyzed their physicochemical properties. The results suggest that these composites have superparamagnetic as well as biocompatible properties. This type of material architecture would be well suited for bone cancer therapy and other biomedical applications.

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

PubMed

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

2016-11-03

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

Functional Iron Oxide-Silver Hetero-Nanocomposites: Controlled Synthesis and Antibacterial Activity

NASA Astrophysics Data System (ADS)

Trang, Vu Thi; Tam, Le Thi; Van Quy, Nguyen; Huy, Tran Quang; Thuy, Nguyen Thanh; Tri, Doan Quang; Cuong, Nguyen Duy; Tuan, Pham Anh; Van Tuan, Hoang; Le, Anh-Tuan; Phan, Vu Ngoc

2017-06-01

Iron oxide-silver nanocomposites are of great interest for their antibacterial and antifungal activities. We report a two-step synthesis of functional magnetic hetero-nanocomposites of iron oxide nanoparticles and silver nanoparticles (Fe3O4-Ag). Iron oxide nanoparticles were prepared first by a co-precipitation method followed by the deposition of silver nanoparticles via a hydrothermal route. The prepared Fe3O4-Ag hetero-nanocomposites were characterized by x-ray diffraction, transmission electron microscopy, high resolution transmission electron microscopy and vibrating sample magnetometry. Their antibacterial activities were investigated by using paper-disc diffusion and direct-drop diffusion methods. The results indicate that the Fe3O4-Ag hetero-nanocomposites exhibit excellent antibacterial activities against two Gram-negative bacterial strains ( Salmonella enteritidis and Klebsiella pneumoniae).

In situ functionalization and PEO coating of iron oxide nanocrystals using seeded emulsion polymerization.

PubMed

Kloust, Hauke; Schmidtke, Christian; Feld, Artur; Schotten, Theo; Eggers, Robin; Fittschen, Ursula E A; Schulz, Florian; Pöselt, Elmar; Ostermann, Johannes; Bastús, Neus G; Weller, Horst

2013-04-16

Herein we demonstrate that seeded emulsion polymerization is a powerful tool to produce multiply functionalized PEO coated iron oxide nanocrystals. Advantageously, by simple addition of functional surfactants, functional monomers, or functional polymerizable linkers-solely or in combinations thereof-during the seeded emulsion polymerization process, a broad range of in situ functionalized polymer-coated iron oxide nanocrystals were obtained. This was demonstrated by purposeful modulation of the zeta potential of encapsulated iron oxide nanocrystals and conjugation of a dyestuff. Successful functionalization was unequivocally proven by TXRF. Furthermore, the spatial position of the functional groups can be controlled by choosing the appropriate spacers. In conclusion, this methodology is highly amenable for combinatorial strategies and will spur rapid expedited synthesis and purposeful optimization of a broad scope of nanocrystals.

Activation of Nrf2/Keap1 signaling and autophagy induction against oxidative stress in heart in iron deficiency.

PubMed

Inoue, Hirofumi; Kobayashi, Ken-Ichi; Ndong, Moussa; Yamamoto, Yuji; Katsumata, Shin-Ichi; Suzuki, Kazuharu; Uehara, Mariko

2015-01-01

We investigated the effects of dietary iron deficiency on the redox system in the heart. Dietary iron deficiency increased heart weight and accumulation of carbonylated proteins. However, expression levels of heme oxygenase-1 and LC3-II, an antioxidant enzyme and an autophagic marker, respectively, in iron-deficient mice were upregulated compared to the control group, resulting in a surrogate phenomenon against oxidative stress.