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1

Tellurium content of marine manganese oxides and other manganese oxides  

USGS Publications Warehouse

Tellurium in amounts ranging from 5 to 125 parts per million was present in all of 12 samples of manganese oxide nodules from the floor of the Pacific and Indian oceans. These samples represent the first recognized points of high tellurium concentration in a sedimentary cycle. The analyses may lend support to the theory that the minor-element content of seafloor manganese nodules is derived from volcanic emanations.

Lakin, H. W.; Thompson, C. E.; Davidson, D. F.

1963-01-01

2

New layered manganese oxide halides.  

PubMed

The first layered manganese(III) oxide chlorides, Sr2MnO3Cl and Sr4Mn3O8-yCl2, have been synthesised; Sr2MnO3Cl adopts a K2NiF4 type structure with sheets of MnO5 square based pyramids linked through oxygen and separated by SrCl layers; it is the end member of a new family of Ruddlesden-Popper type manganese oxide halides which includes the three-layer member Sr4Mn3O8-yCl2 also reported herein. PMID:12120392

Knee, Christopher S; Weller, Mark T

2002-02-01

3

Microbial Formation of Manganese Oxides  

PubMed Central

Microbial manganese oxidation was demonstrated at high Mn2+ concentrations (5 g/liter) in bacterial cultures in the presence of a microalga. The structure of the oxide produced varied depending on the bacterial strain and mode of culture. A nonaxenic, acid-tolerant microalga, a Chlamydomonas sp., was found to mediate formation of manganite (?-MnOOH). Bacteria isolated from associations with crude cultures of this alga grown in aerated bioreactors formed disordered ?-MnO2 from Mn2+ at concentrations of 5 g/liter over 1 month, yielding 3.3 g of a semipure oxide per liter. All algal-bacterial cultures removed Mn2+ from solution, but only those with the highest removal rates formed an insoluble oxide. While the alga was an essential component of the reaction, a Pseudomonas sp. was found to be primarily responsible for the formation of a manganese precipitate. Medium components—algal biomass and urea—showed optima at 5.7 and 10 g/liters, respectively. The scaled-up culture (50 times) gave a yield of 22.3 g (53 mg/liter/day from a 15-liter culture) of semipure disordered ?-MnO2, identified by X-ray diffraction and Fourier transform infrared (FTIR) spectroscopy, and had a manganese oxide O/Mn ratio of 1.92. The Mn(IV) content in the oxide was low (30.5%) compared with that of mined or chemically formed ?-MnO2 (ca. 50%). The shortfall in the bacterial oxide manganese content was due to biological and inorganic contaminants. FTIR spectroscopy, transmission electron microscopy, and electron diffraction studies have identified manganite as a likely intermediate product in the formation of disordered ?-MnO2.

Greene, Anthony C.; Madgwick, John C.

1991-01-01

4

Neurotoxicity of manganese oxide nanomaterials  

Microsoft Academic Search

Manganese (Mn) toxicity in humans has been observed as manganism, a disease that resembles Parkinson’s disease. The mechanism\\u000a of Mn toxicity and the chemical forms that may be responsible for its neurotoxicity are not well understood. We examined the\\u000a toxicity of Mn oxide nanomaterials in a neuronal precursor cell model, using the MTS assay to evaluate mitochondrial function\\u000a in living

Diana M. Stefanescu; Ali Khoshnan; Paul H. Patterson; Janet G. Hering

2009-01-01

5

40 CFR 721.10011 - Barium calcium manganese strontium oxide.  

Code of Federal Regulations, 2013 CFR

...2013-07-01 2013-07-01 false Barium calcium manganese strontium oxide. 721.10011...Chemical Substances § 721.10011 Barium calcium manganese strontium oxide. (a...chemical substance identified as barium calcium manganese strontium oxide (PMN...

2013-07-01

6

Synthesis, characterization, optical and sensing property of manganese oxide nanoparticles  

NASA Astrophysics Data System (ADS)

Manganese oxide nanoparticles were prepared by thermal decomposition of manganese oxalate. Manganese oxalate was synthesized by reacting 1:1 mole ratio of manganese acetate and ammonium oxalate along with sodium dodecyl sulfate (SDS). The structural characterization of manganese oxalate and manganese oxide nanoparticles was analyzed by XRD. The XRD spectrum confirms the crystal structure of the manganese oxide and manganese oxalate. In addition, the average grain size, lattice parameter values were also calculated using XRD spectrum. Moreover, the diffraction peaks were broadened due to the smaller size of the particle. The band gap of manganese oxide was calculated from optical absorption, which was carried out by DRS UV-Visible spectroscopy. The morphology of manganese oxide nanoparticles was analyzed by SEM images. The FT-IR analysis confirms the formation of the manganese oxide from manganese oxalate nanoparticles. The electrochemical sensing behavior of manganese oxide nanoparticles were investigated using hydrogen peroxide by cyclic voltammetry.

Manigandan, R.; Suresh, R.; Giribabu, K.; Vijayalakshmi, L.; Stephen, A.; Narayanan, V.

2014-01-01

7

Environmental Controls of Biological Manganese Oxidation  

NASA Astrophysics Data System (ADS)

Biological catalysis of manganese oxidation represents an important contribution to global manganese cycling; biological oxidation rates are several orders of magnitude higher than those of abiotic processes. Despite recent genetics advances, ongoing behavioral studies, and a large pool of knowledge regarding manganese chemistry, the links between biology and environmental chemistry remain unresolved. We have performed experiments on batch cultures of Leptothrix discophora SS-1 to explore the physiology of biological manganese oxidation. We have further conducted spectroscopic and microscopic studies of the mechanism as manganese proceeds from the soluble Mn2+ species to the insoluble Mn(III) and Mn(IV) phases. These investigations suggest roles for aqueous chemistry, mineralogy, and microbial physiology in controlling manganese fluxes in metal-rich environments.

Belz, A. P.; Ahn, C. C.; Nealson, K. H.

2001-12-01

8

40 CFR 721.10011 - Barium calcium manganese strontium oxide.  

Code of Federal Regulations, 2010 CFR

...2009-07-01 2009-07-01 false Barium calcium manganese strontium oxide. ...Chemical Substances § 721.10011 Barium calcium manganese strontium oxide. ...The chemical substance identified as barium calcium manganese strontium...

2009-07-01

9

Oxidative transformation of carbamazepine by manganese oxides.  

PubMed

This study presents oxidative transformation of carbamazepine by synthetic manganese oxide (?-MnO(2)) as well as impact of variables including initial MnO(2) loading, pH, coexisting metal ions, and humic acid (HA) on transformation. Manganese oxide (?-MnO(2)) was synthesized and stored in the form of suspension. The oxidative reactions were conducted in 50 mL polyethylene (PE) centrifuge tubes with constant pH maintained by buffers. The kinetic experiment was carried out in the solution of pH 2.72 containing 5.0 mg/L of carbamazepine and 130.5 mg/L of MnO(2). Effects of initial MnO(2) loading (0-130.5 mg/L), pH (2.72-8.58) and 0.01 M of coexisting solutes (metal ions and HA) on carbamazepine oxidation were also determined. Reaction kinetics indicated that carbamazepine was rapidly degraded in the first 5 min, and approximately 95 % of carbamazepine was eliminated within 60 min. The reaction exhibited pronounced pH dependence and increased with decreasing pH values. The transformation of carbamazepine was also accelerated with increasing MnO(2) loadings. Coexisting metal ions competed with carbamazepine for reactive sites leading to reduced carbamazepine removal, and the inhibitive capacity followed the order of Mn(2+)?>?Fe(3+)?>?Ca(2+)???Mg(2+). Presence of HA in aqueous solution caused a significant reduction on the magnitude of carbamazepine transformation. This study indicated that carbamazepine can be effectively degraded by ?-MnO(2), and transformation efficiency was strongly dependent on reaction conditions. It suggests that amendment of soil with MnO(2) be a potential alternative to solve carbamazepine pollution. PMID:22565984

He, Yan; Xu, Jian; Zhang, Yuan; Guo, Changsheng; Li, Lei; Wang, Yuqiu

2012-11-01

10

Battles with iron: manganese in oxidative stress protection.  

PubMed

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

Aguirre, J Dafhne; Culotta, Valeria C

2012-04-20

11

Manganese oxidation model for rivers  

USGS Publications Warehouse

The presence of manganese in natural waters (>0.05 mg/L) degrades water-supply quality. A model was devised to predict the variation of manganese concentrations in river water released from an impoundment with the distance downstream. The model is one-dimensional and was calibrated using dissolved oxygen, biochemical oxygen demand, pH, manganese, and hydraulic data collected in the Duck River, Tennessee. The results indicated that the model can predict manganese levels under various conditions. The model was then applied to the Chattahoochee River, Georgia. Discrepancies between observed and predicted may be due to inadequate pH data, precipitation of sediment particles, unsteady flow conditions in the Chattahoochee River, inaccurate rate expressions for the low pH conditions, or their combinations.

Hess, Glen, W.; Kim, Byung, R.; Roberts, Philip, J. W.

1989-01-01

12

Manganese oxide thin films prepared by nonaqueous sol–gel processing: preferential formation of birnessite  

Microsoft Academic Search

High quality manganese oxide thin films with smooth surfaces and even thicknesses have been prepared with a nonaqueous sol–gel process involving reduction of tetraethylammonium permanganate in methanol. Spin-coated films have been cast onto soft glass, quartz, and Ni foil substrates, with two coats being applied for optimum crystallization. The addition of alkali metal cations as dopants results in exclusive formation

Stanton Ching; Steven M. Hughes; Timothy P. Gray; Eric J. Welch

2004-01-01

13

Manganese  

SciTech Connect

Manganese (Mn) is a hard, brittle, gray-white transition metal, with the most numerous oxidation states of the elements in the first series of the Periodic Table. Since the manganese atom can donate up to seven electrons from its outer two shells, manganese compounds exist with valences from -3 to +7, the most common being +2, +4, and +7. Due to its sulfur-fixing, deoxidizing, and alloying properties, as well as its low cost, the principal commercial application for manganese is in iron and steel production. Manganese is also employed in non-ferrous metallurgy, batteries and chemical processes. Although potentially harmful to the respiratory and nervous systems, manganese is an essential element for animals and humans, and a micronutrient for plants.

Major-Sosias, M.A.

1996-10-01

14

A microbial fuel cell using manganese oxide oxygen reduction catalysts  

Microsoft Academic Search

Microbial fuel cells (MFCs) are a potential method for enhanced water and waste treatment, which offer the additional benefit\\u000a of energy generation. Manganese oxide was prepared by a simple chemical oxidation using potassium permanganate. Carbon-supported\\u000a manganese oxide nanoparticles were successfully characterised as cathode materials for MFCs. The manganese oxide particles\\u000a when used in a two-chamber MFC, using inoculum from an

I. Roche; K. Katuri; K. Scott

2010-01-01

15

Electrochromic reactions in manganese oxides I. Raman analysis  

Microsoft Academic Search

Like nickel oxide, manganese oxide is a widely studied material in the primary batteries field. The reactions taking place during voltametric cycling of manganese oxides can be determined using in situ Raman spectroscopy. The main difficulty for the oxide identification is to obtain relevant Raman reference spectra because of the many possible compounds and, for some of these compounds, of

M. C. Bernard; A. Hugot-Le Goff; B. V. Thi; S. Cordoba de Torresi

1993-01-01

16

Lithium Manganese Oxide Prepared by Flux Methods  

Microsoft Academic Search

Plate-like crystals of spinel-type lithium manganese oxide with sizes in the micrometer range were obtained in a flux system\\u000a of LiCl-Mn(NO3)2. The crystals were grown by a dissolution-recrystallization mechanism. Polyhedral crystals with sizes in the millimeter range\\u000a were grown in a flux system of LiCl-Mn(NO3)2 by an evaporation-recrystallization mechanism.

W. Tang; Q. Feng; X. Yang; R. Chitrakar; K. Ooi

17

Biotransformation of manganese oxides by fungi: solubilization and production of manganese oxalate biominerals.  

PubMed

The ability of the soil fungi Aspergillus niger and Serpula himantioides to tolerate and solubilize manganese oxides, including a fungal-produced manganese oxide and birnessite, was investigated. Aspergillus niger and S.?himantioides were capable of solubilizing all the insoluble oxides when incorporated into solid medium: MnO(2) and Mn(2) O(3) , mycogenic manganese oxide (MnO(x) ) and birnessite [(Na(0.3) Ca(0.1) K(0.1) )(Mn(4+) ,Mn(3+) )(2) O(4) ·1.5H(2) O]. Manganese oxides were of low toxicity and A.?niger and S.?himantioides were able to grow on 0.5% (w/v) of all the test compounds, with accompanying acidification of the media. Precipitation of insoluble manganese and calcium oxalate occurred under colonies growing on agar amended with all the test manganese oxides after growth of A.?niger and S.?himantioides at 25°C. The formation of manganese oxalate trihydrate was detected after growth of S.?himantioides with birnessite which subsequently was transformed to manganese oxalate dihydrate. Our results represent a novel addition to our knowledge of the biogeochemical cycle of manganese, and the roles of fungi in effecting transformations of insoluble metal-containing compounds in the environment. PMID:22591055

Wei, Zhan; Hillier, Stephen; Gadd, Geoffrey M

2012-07-01

18

Oxidation state of marine manganese nodules  

USGS Publications Warehouse

Analyses of the bulk oxidation state of marine manganese nodules indicates that more than 98% of the Mn in deep ocean nodules is present as Mn(IV). The samples were collected from three quite different areas: the hemipelagic environment of the Guatemala Basin, the pelagic area of the North Pacific, and seamounts in the central Pacific. Results of the study suggest that todorokite in marine nodules is fully oxidized and has the following stoichiometry: (K, Na, Ca, Ba).33(Mg, Cu, Ni).76Mn5O22(H2O)3.2. ?? 1984.

Piper, D. Z.; Basler, J. R.; Bischoff, J. L.

1984-01-01

19

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

Code of Federal Regulations, 2013 CFR

...2013-07-01 2013-07-01 false Cobalt iron manganese oxide, carboxylic acid-modified...Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid-modified...substance identified generically as cobalt iron manganese oxide, carboxylic...

2013-07-01

20

Formation of manganese oxides by bacterially generated superoxide  

NASA Astrophysics Data System (ADS)

Manganese oxide minerals are among the strongest sorbents and oxidants in the environment. The formation of these minerals controls the fate of contaminants, the degradation of recalcitrant carbon, the cycling of nutrients and the activity of anaerobic-based metabolisms. Oxidation of soluble manganese(II) ions to manganese(III/IV) oxides has been primarily attributed to direct enzymatic oxidation by microorganisms. However, the physiological reason for this process remains unknown. Here we assess the ability of a common species of marine bacteria-Roseobacter sp. AzwK-3b-to oxidize manganese(II) in the presence of chemical and biological inhibitors. We show that Roseobacter AzwK-3b oxidizes manganese(II) by producing the strong and versatile redox reactant superoxide. The oxidation of manganese(II), and concomitant production of manganese oxides, was inhibited in both the light and dark in the presence of enzymes and metals that scavenge superoxide. Oxidation was also inhibited by various proteases, enzymes that break down bacterial proteins, confirming that the superoxide was bacterially generated. We conclude that bacteria can oxidize manganese(II) indirectly, through the enzymatic generation of extracellular superoxide radicals. We suggest that dark bacterial production of superoxide may be a driving force in metal cycling and mineralization in the environment.

Learman, D. R.; Voelker, B. M.; Vazquez-Rodriguez, A. I.; Hansel, C. M.

2011-02-01

21

Manganese oxide nanowires, films, and membranes and methods of making  

DOEpatents

Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves and methods of making the same are disclosed. A method for forming nanowires includes hydrothermally treating a chemical precursor composition in a hydrothermal treating solvent to form the nanowires, wherein the chemical precursor composition comprises a source of manganese cations and a source of counter cations, and wherein the nanowires comprise ordered porous manganese oxide-based octahedral molecular sieves.

Suib, Steven Lawrence (Storrs, CT); Yuan, Jikang (Storrs, CT)

2011-02-15

22

Incoherent Charge Dynamics in Perovskite Manganese Oxides  

NASA Astrophysics Data System (ADS)

A minimal model is proposed for the perovskite manganese oxides showing strongly incoherent charge dynamics with a suppressed Drude weight in the ferromagnetic and metallic phase near the insulator. We investigate a generalized double-exchange model whichincludes three elements; the orbital degeneracy of eg conduction bands, the Coulomb interaction and fluctuating Jahn-Teller distortions. We demonstrate that Lanczös diagonalization calculations combined with Monte Carlo sampling of the largely fluctuating lattice distortions result in the optical conductivity which quantitatively accounts for the experimental indications. It is found that all three elements are indispensable for understanding the charge dynamics in these compounds.

Nakano, Hiroki; Motome, Yukitoshi; Imada, Masatoshi

2000-05-01

23

Lithium-manganese oxide rechargeable battery  

SciTech Connect

A new type of rechargeable battery in which lithium ions shuttle between a lithium-manganese oxide electrode and a carbon electrode was unveiled recently by chemists from Bell Communications Research (Bellcore), Red Bank, N.J. The new battery--still experimental--is safer, longer lasting, and potentially cheaper to manufacture than other lithium-ion batteries. In addition, it provides three times the energy of nickel-cadmium cells, the most popular type of rechargeable battery. Bellcore scientists believe the new battery could replace nickel-cadmium and small lead-acid batteries in many applications.

Dagani, R.

1993-01-04

24

Rates of manganese oxidation in aqueous systems  

USGS Publications Warehouse

The rate of crystal growth of Mn3O4 (hausmannite) and ??MnOOH (feitknechtite) in aerated aqueous manganous perchlorate systems, near 0.01 M in total manganese, was determined at pH levels ranging from 7.00 to 9.00 and at temperatures from 0.5 to 37.4??C. The process is autocatalytic, but becomes psuedo first-order in dissolved Mn2+ activity when the amount of precipitate surface is large compared to the amount of unreacted manganese. Reaction rates determined by titrations using an automated pH-stat were fitted to an equation for precipitate growth. The rates are proportional to surface area of oxide and degree of supersaturation with respect to Mn2+. The oxide obtained at the higher temperature was Mn3O4, but at 0.5?? C only ??MnOOH was formed. At intermediate temperatures, mixtures of these solids were formed. The rate of precipitation of hausmannite is strongly influenced by temperature, and that of feitknechtite much less so. The difference in activation energy may be related to differences in crystal structure of the oxides and the geometry of polymeric hydroxy ion precursors. ?? 1981.

Hem, J. D.

1981-01-01

25

Np and Pu Sorption to Manganese Oxide Minerals  

Microsoft Academic Search

Manganese oxide minerals are a significant component of the fracture lining mineralogy at Yucca Mountain (Carlos et al., 1993) and within the tuff-confining unit at Yucca Flat (Prothro, 1998), Pahute Mesa (Drellack et al., 1997), and other locations at the Nevada Test Site (NTS). Radionuclide sorption to manganese oxide minerals was not included in recent Lawrence Livermore National Laboratory (LLNL)

P Zhao; M R Johnson; S K Roberts; M Zavarin

2005-01-01

26

Electrochromic reactions in manganese oxides I. Raman analysis  

SciTech Connect

Like nickel oxide, manganese oxide is a widely studied material in the primary batteries field. The reactions taking place during voltametric cycling of manganese oxides can be determined using in situ Raman spectroscopy. The main difficulty for the oxide identification is to obtain relevant Raman reference spectra because of the many possible compounds and, for some of these compounds, of their instability in the laser beam. As a consequence, several modifications of different tetra-, tri- and divalent manganese oxides and oxyhydroxides were carefully studied. The electrochromic behavior of three types of manganese oxides, two prepared by thermal oxidations and the other by electrochemical deposition, were then compared. The presence of nonstoichiometry in the pristine material was necessary to obtain a reversible electrochromic effect. The reaction during electrochromic cycling is more complicated than a simple passage from MnO[sub 2] to MnOOH.

Bernard, M.C.; Hugot-Le Goff, A.; Thi, B.V. (Univ. Pierre et Marie Curie, Paris (France). UPR 15 du CNRS Physique des Liquides et Electrochimie); Cordoba de Torresi, S. (Univ. Estadual de Campinas (Brazil). Dept. de Fisica Aplicada)

1993-11-01

27

Bacterial manganese reduction and growth with manganese oxide as the sole electron acceptor  

NASA Technical Reports Server (NTRS)

Microbes that couple growth to the reduction of manganese could play an important role in the biogeochemistry of certain anaerobic environments. Such a bacterium, Alteromonas putrefaciens MR-1, couples its growth to the reduction of manganese oxides only under anaerobic conditions. The characteristics of this reduction are consistent with a biological, and not an indirect chemical, reduction of manganese, which suggest that this bacterium uses manganic oxide as a terminal electron acceptor. It can also utilize a large number of other compounds as terminal electron acceptors; this versatility could provide a distinct advantage in environments where electron-acceptor concentrations may vary.

Myers, Charles R.; Nealson, Kenneth H.

1988-01-01

28

Three manganese oxide-rich marine sediments harbor similar communities of acetate-oxidizing manganese-reducing bacteria  

PubMed Central

Dissimilatory manganese reduction dominates anaerobic carbon oxidation in marine sediments with high manganese oxide concentrations, but the microorganisms responsible for this process are largely unknown. In this study, the acetate-utilizing manganese-reducing microbiota in geographically well-separated, manganese oxide-rich sediments from Gullmar Fjord (Sweden), Skagerrak (Norway) and Ulleung Basin (Korea) were analyzed by 16S rRNA-stable isotope probing (SIP). Manganese reduction was the prevailing terminal electron-accepting process in anoxic incubations of surface sediments, and even the addition of acetate stimulated neither iron nor sulfate reduction. The three geographically distinct sediments harbored surprisingly similar communities of acetate-utilizing manganese-reducing bacteria: 16S rRNA of members of the genera Colwellia and Arcobacter and of novel genera within the Oceanospirillaceae and Alteromonadales were detected in heavy RNA-SIP fractions from these three sediments. Most probable number (MPN) analysis yielded up to 106 acetate-utilizing manganese-reducing cells cm?3 in Gullmar Fjord sediment. A 16S rRNA gene clone library that was established from the highest MPN dilutions was dominated by sequences of Colwellia and Arcobacter species and members of the Oceanospirillaceae, supporting the obtained RNA-SIP results. In conclusion, these findings strongly suggest that (i) acetate-dependent manganese reduction in manganese oxide-rich sediments is catalyzed by members of taxa (Arcobacter, Colwellia and Oceanospirillaceae) previously not known to possess this physiological function, (ii) similar acetate-utilizing manganese reducers thrive in geographically distinct regions and (iii) the identified manganese reducers differ greatly from the extensively explored iron reducers in marine sediments.

Vandieken, Verona; Pester, Michael; Finke, Niko; Hyun, Jung-Ho; Friedrich, Michael W; Loy, Alexander; Thamdrup, Bo

2012-01-01

29

Carbothermal Reduction of Manganese Oxide in Different Gas Atmospheres  

Microsoft Academic Search

Carbothermal reduction of manganese oxides was studied in hydrogen, helium, and argon at different temperatures and carbon-to-manganese\\u000a oxide ratios. Isothermal and temperature programmed carbothermal reduction experiments were conducted in a fixed bed reactor\\u000a in a vertical tube furnace, with on-line monitoring of gas composition by the CO-CO2 infrared sensor. The extent of reduction was calculated using the off-gas composition and

Ring Kononov; Oleg Ostrovski; Samir Ganguly

2008-01-01

30

Manganese and Oxidative Damage in Cucumber  

Microsoft Academic Search

Micronutrients in low or high concentration can affect growth, respiration, photosynthesis, and reproduction in plants. Cucumber (Cucumis sativus, L.) is grown in India in areas low or high in manganese concentration in soils. A study was conducted to investigate the effects of manganese concentration on some metabolic activities affecting developmental responses in cucumber. Seed of cucumber, cv. Sonali, were grown

Rajeev Gopal

2008-01-01

31

Oxidative degradation of glyphosate and aminomethylphosphonate by manganese oxide.  

PubMed

Glyphosate (N-(phosphonomethyl)glycine), the most commonly used herbicide worldwide, degrades relatively rapidly in soils under most conditions, presumably by microbial processes. The most frequently detected degradation product in soil and water is AMPA (aminomethylphosphonic acid). We report the first evidence for an abiotic pathway of glyphosate and AMPA degradation under environmentally realistic conditions. Both glyphosate and AMPA degraded at 20 degrees C in dilute aqueous suspensions of birnessite, a manganese oxide common in soils, as evidenced by the accumulation of orthophosphate in solution over a period of several days. It is concluded that the abiotic degradation involved C-P bond cleavage at the Mn oxide surface, although evidence for C-N bond cleavage in the case of glyphosate and sarcosine, a likely degradation product of glyphosate, was found. The degradation of glyphosate was faster than that of AMPA, and higher temperature (50 degrees C) resulted in faster degradation of both glyphosate and AMPA. The addition of sulfate to the solution had no marked effect on the reaction rate, although Cu2+ addition inhibited degradation. As this metal ion complexes strongly with glyphosate, the inhibition can be attributed to the ability of Cu2+ to limit glyphosate coordination to reactive oxidation sites at the Mn oxide surface. Using a similar experimental design, we were unable to detect glyphosate degradation in an equimolar solution of MnCl2 (0.5 mM). However, we demonstrated that the oxidation of Mn2+ is enhanced both in solution and on an inert surface, in the presence of glyphosate (4:1 Mn-glyphosate molar ratio). This result suggests that the oxidative breakdown of glyphosate in the presence of Mn2+ may ultimately occur following the spontaneous oxygen-mediated oxidation of manganese. PMID:16382946

Barrett, K A; McBride, M B

2005-12-01

32

Arsenite oxidation by a poorly-crystalline manganese oxide. 3. Arsenic and manganese desorption.  

PubMed

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese oxides (Mn oxides) have the ability to decrease overall As mobility both by oxidizing toxic arsenite (As(III)) to less toxic arsenate (As(V)), and by sorbing As. However, the effect of competing ions on the mobility of As sorbed on Mn-oxide surfaces is not well understood. In this study, desorption of As(V) and As(III) from a poorly crystalline phyllomanganate (?-MnO(2)) by two environmentally significant ions is investigated using a stirred-flow technique and X-ray absorption spectroscopy (XAS). As(III) is not observed in solution after desorption under any conditions used in this study, agreeing with previous studies showing As sorbed on Mn-oxides exists only as As(V). However, some As(V) is desorbed from the ?-MnO(2) surface under all conditions studied, while neither desorptive used in this study completely removes As(V) from the ?-MnO(2) surface. PMID:21950706

Lafferty, Brandon J; Ginder-Vogel, Matthew; Sparks, Donald L

2011-11-01

33

Nano-sized layered aluminium or zinc-manganese oxides as efficient water oxidizing catalysts.  

PubMed

Nano-sized layered aluminium or zinc-manganese oxides were synthesized and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction spectrometry, dynamic light scattering and atomic absorption spectroscopy. These oxides showed efficient water oxidizing activity in the presence of cerium(IV) ammonium nitrate as a non-oxo transfer oxidant. Amounts of dissolved manganese, zinc or aluminium, and water oxidation activities of these oxides were reported and compared with other manganese oxides. A mechanism for oxygen evolution and possible roles for zinc or aluminium ions are also proposed. PMID:22565665

Najafpour, Mohammad Mahdi; Pashaei, Babak; Nayeri, Sara

2012-06-21

34

Oxidation kinetics of manganese (II) in seawater at nanomolar concentrations  

Microsoft Academic Search

Manganese oxidation rates were determined at low (? 20 nM) concentrations in seawater by measuring dissolved manganese (Mn(II)) using flow injection analysis with chemiluminescence detection. Mn(II) was measured in samples that had been filtered (0.2 ?m) and kept in the dark under controlled temperature and pH conditions for time periods up to 6 months. Eight 9 L carboys with mean

Peter J. von Langen; Kenneth S. Johnson; Kenneth H. Coale; Virginia A. Elrod

1997-01-01

35

Manganese-oxidizing bacteria mediate the degradation of 17?-ethinylestradiol  

PubMed Central

Summary Manganese (II) and manganese?oxidizing bacteria were used as an efficient biological system for the degradation of the xenoestrogen 17??ethinylestradiol (EE2) at trace concentrations. Mn2+?derived higher oxidation states of Mn (Mn3+, Mn4+) by Mn2+?oxidizing bacteria mediate the oxidative cleavage of the polycyclic target compound EE2. The presence of manganese (II) was found to be essential for the degradation of EE2 by Leptothrix discophora, Pseudomonas putida MB1, P.?putida MB6 and P.?putida MB29. Mn2+?dependent degradation of EE2 was found to be a slow process, which requires multi?fold excess of Mn2+ and occurs in the late stationary phase of growth, implying a chemical process taking place. EE2?derived degradation products were shown to no longer exhibit undesirable estrogenic activity.

Sabirova, Julia S.; Cloetens, L. F. F.; Vanhaecke, L.; Forrez, I.; Verstraete, Willy; Boon, N.

2008-01-01

36

Joint Electrolytic Deposition of Vanadium and Manganese Oxides  

Microsoft Academic Search

The electrolysis conditions and the character of the anodic processes were studied at the joint anodic deposition of vanadium and manganese oxides from mixed sulfate solutions in the form of double oxide systems, which are promising cathode materials of lithium batteries.

V. M. Nagirnyi; R. D. Apostolova; A. S. Baskevich; P. M. Litvin

2002-01-01

37

Manganese and iron oxidation by fungi isolated from building stone  

Microsoft Academic Search

Acid and nonacid generating fungal strains isolated from weathered sandstone, limestone, and granite of Spanish cathedrals were assayed for their ability to oxidize iron and manganese. In general, the concentration of the different cations present in the mineral salt media directly affected Mn(IV) oxide formation, although in some cases, the addition of glucose and nitrate to the culture media was

M. A. Torre; G. Gomez-Alarcon

1994-01-01

38

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation  

PubMed Central

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

2013-01-01

39

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.  

PubMed

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H; Navrotsky, Alexandra

2013-05-28

40

Comparative evaluation of oxidative stress status and manganese availability in plants growing on manganese mine  

Microsoft Academic Search

This study pioneered an approach that determined the effects of excess manganese (Mn) on three species; Datura stramonium, Alhagi camelthorn and Chenopodium ambrosioides. We investigated their levels of Mn, antioxidative enzymes and oxidative damage biomarkers in plants (zone 1) in and outside (zone 2) the Mn mine. The results showed that total and available Mn were at toxic levels for

Massod Mashhadi Akbar Boojar; Faranak Goodarzi

2008-01-01

41

Water defluoridation by aluminium oxide-manganese oxide composite material.  

PubMed

In this study, aluminium oxide-manganese oxide (AOMO) composite material was synthesized, characterized, and tested for fluoride removal in batch experiments. AOMO was prepared from manganese(II) chloride and aluminium hydroxide. The surface area of AOMO was found to be 30.7m2/g and its specific density was determined as 2.78 g/cm3. Detailed investigation of the adsorbent by inductively coupled plasma-optical emission spectrometry, inductively coupled plasma-mass spectrometry, and ion chromatography (for sulphate only) showed that it is composed of Al, Mn, SO4, and Na as major components and Fe, Si, Ca, and Mg as minor components. Thermogravimetric analysis was used to study the thermal behaviour of AOMO. X-ray diffraction analysis showed that the adsorbent is poorly crystalline. The point of zero charge was determined as 9.54. Batch experiments (by varying the proportion of MnO, adsorbent dose, contact time, initial F concentration, and raw water pH) showed that fluoride removal efficiency ofAOMO varied significantly with percentage of MnO with an optimum value of about I11% of manganese oxide in the adsorbent. The optimum dose of the adsorbent was 4 g/L which corresponds to the equilibrium adsorption capacity of 4.8 mg F-/g. Both the removal efficiency and adsorption capacity showed an increasing trend with an increase in initial fluoride concentration of the water. The pH for optimum fluoride removal was found to be in the range between 5 and 7. The adsorption data were analysed using the Freundlich, Langmuir, and Dubinirn-Radushkevich models. The minimum adsorption capacity obtained from the non-linear Freundlich isotherm model was 4.94 mg F-/g and the maximum capacity from the Langmuir isotherm method was 19.2mg F-/g. The experimental data of fluoride adsorption on AOMO fitted well to the Freundlich isotherm model. Kinetic studies showed that the adsorption is well described by a non-linear pseudo-second-order reaction model with an average rate constant of 3.1 x 10(-2) g/min mg. It is concluded that AOMO is a highly promising adsorbent for the removal of excess fluoride from drinking water. PMID:24956783

Alemu, Sheta; Mulugeta, Eyobel; Zewge, Feleke; Chandravanshi, Bhagwan Singh

2014-08-01

42

The sorption of silver by poorly crystallized manganese oxides  

USGS Publications Warehouse

The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized ??-MnO2. All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnOx at pH 7) while the ??-MnO2 showed the least (0.3 moles silver/ mole MnOx at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values. Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium. ?? 1973.

Anderson, B. J.; Jenne, E. A.; Chao, T. T.

1973-01-01

43

Facile synthesis of nitriles via manganese oxide promoted oxidative dehydrosulfurization of primary thioamides.  

PubMed

In the presence of manganese oxides, dehydrosulfurization of various kinds of primary thioamides including aromatic, heterocyclic, and aliphatic ones efficiently proceeded to give the corresponding nitriles in high yields. The observed catalysis was truly heterogeneous, and manganese oxides could be reused. PMID:23069811

Yamaguchi, Kazuya; Yajima, Kazuhisa; Mizuno, Noritaka

2012-11-25

44

Carbothermal Reduction of Manganese Oxide in Different Gas Atmospheres  

NASA Astrophysics Data System (ADS)

Carbothermal reduction of manganese oxides was studied in hydrogen, helium, and argon at different temperatures and carbon-to-manganese oxide ratios. Isothermal and temperature programmed carbothermal reduction experiments were conducted in a fixed bed reactor in a vertical tube furnace, with on-line monitoring of gas composition by the CO-CO2 infrared sensor. The extent of reduction was calculated using the off-gas composition and LECO oxygen contents in the reduced samples. In all gas atmospheres, the reaction rate increased with temperature. The reduction rate of manganese oxide in hydrogen was higher than in helium, and in helium higher than in argon. This was attributed to the involvement of hydrogen in the reduction process and the difference in CO and CO2 diffusion coefficients in helium and argon.

Kononov, Ring; Ostrovski, Oleg; Ganguly, Samir

2008-10-01

45

Characterization of Newly-Formed Manganese (Hydr)oxides in Biofilms in Pinal Creek, Arizona  

NASA Astrophysics Data System (ADS)

Active, biologically mediated precipitation of manganese (hydr)oxides (Mn-oxides) in Pinal Creek, Arizona, a stream with a history of high manganese levels due to historic mining practices, was studied to determine the identity of newly formed phases and their ability to sequester other metals. Packages of crushed grains of eight clean mineral substrates, quartz, ilmenite, microcline, rutile, magnetite, hematite and labradorite, were placed in Pinal Creek for one to three months. Glass slides were set out as well in order to characterize biofilm formation. After retrieval and drying, the coating distributions were characterized using scanning electron microscopy (SEM), energy dispersive analysis, and X-ray absorption spectroscopy. Morphologically, coating material developed on the different substrates after one month appeared similar to those developed after two and three months. Overall, the SEM images indicate poorly crystalline, aggregated particles that are small (less than a few microns in general) and lack geometric regularity, although size estimates are somewhat hindered by particle aggregation. The coatings that formed on the microscope slides are characterized as biofilms, as numerous microorganisms were observed using microscopy, both confocal and SEM. Samples were further characterized using extended x-ray absorption fine structure spectroscopy (EXAFS) on coatings that had been separated from mineral substrates. EXAFS spectra of material from rutile and quartz substrates and the biofilm were analyzed and fit, using a natural and synthetic birnessite compounds as reference spectra. This analysis suggests that the rutile, quartz, and biofilm samples are composed of a disordered Mn-oxide that is similar in local structure to a natural birnessite of low symmetry. The formation of disordered, poorly crystalline birnessite is important, as it is an extremely efficient metal scavenger and the interlayer vacancies in the birnessite structure aids in metal sequestration.

Gilbert, H.; Conklin, M.; O'Day, P.

2003-12-01

46

Electrolytic Synthesis of Binary Oxide Systems Based on Manganese(II) Oxide  

Microsoft Academic Search

Joint anodic deposition of manganese, cobalt, nickel, and chromium oxides, which form binary oxide systems, from two-component sulfate solutions of the constituent metals was studied under different electrolysis conditions.

V. M. Nagirnyi; R. D. Apostolova; A. S. Baskevich; P. M. Litvin

2002-01-01

47

Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance  

Microsoft Academic Search

We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport

Judson W. Harvey; Christopher C. Fuller

1998-01-01

48

Biogenic manganese oxides: Formation mechanisms, mineralogy and environmental relevance Term paper: Biogeochemistry and pollutant dynamics  

Microsoft Academic Search

Biogenic manganese oxides can be a tool for soil remediation. Recent papers are reviewed to gather information on their formation mechanisms, mineralogy and environmental relevance. Characterisations of the manganese oxidation products of the bacteria groups Bacillus sp., Pseudomonas putida and Leptothrix discophora are described and compared. The biochemical path- ways of bacterial manganese oxidation are discussed. It seems, that bacteria

Ruben Kretzschmar

49

40 CFR 721.10010 - Barium manganese oxide (BaMnO3).  

Code of Federal Regulations, 2010 CFR

...2009-07-01 2009-07-01 false Barium manganese oxide (BaMnO3). 721.10010...Chemical Substances § 721.10010 Barium manganese oxide (BaMnO3 ). (a...The chemical substance identified as barium manganese oxide (BaMnO3 )...

2009-07-01

50

40 CFR 721.10010 - Barium manganese oxide (BaMnO3).  

Code of Federal Regulations, 2010 CFR

...2010-07-01 2010-07-01 false Barium manganese oxide (BaMnO3). 721.10010...Chemical Substances § 721.10010 Barium manganese oxide (BaMnO3). (a...The chemical substance identified as barium manganese oxide (BaMnO3 )...

2010-07-01

51

Manganese oxide mesoporous structures: Mixed-valent semiconducting catalysts  

Microsoft Academic Search

Hexagonal and cubic phases of manganese oxide mesoporous structures (MOMS) have been prepared by means of the oxidation of Mn(OH)â. The hexagonal MOMS materials form a hexagonal array of pores with an open porous structure, thick walls (1.7 nanometers), and exceptional thermal stability (1000°C). The walls of the mesopores are composed of microcrystallites of dense phases of MnâOâ and MnâOâ,

Zheng-Rong Tian; Wei Tong; Jin-Yun Wang

1997-01-01

52

Manganese uptake and Mn(II) oxidation by the alga Scenedesmus subspicatus  

Microsoft Academic Search

To examine the relationships among manganese concentration in the culture medium, algae growth, manganese uptake and Mn(II) oxidation on the algal surface, we exposed the unicellular alga Scenedesmus subspicatus to a broad range of free Mn2+ ion concentrations. Extra- and intracellular manganese concentrations were distinguished by reducing the Mn oxides with ascorbate. A large fraction of the Mn bound by

Katja Knauer; Thomas Jabusch; Laura Sigg

1999-01-01

53

Nano-sized manganese oxides as biomimetic catalysts for water oxidation in artificial photosynthesis: a review.  

PubMed

There has been a tremendous surge in research on the synthesis of various metal compounds aimed at simulating the water-oxidizing complex (WOC) of photosystem II (PSII). This is crucial because the water oxidation half reaction is overwhelmingly rate-limiting and needs high over-voltage (approx. 1 V), which results in low conversion efficiencies when working at current densities required for hydrogen production via water splitting. Particular attention has been given to the manganese compounds not only because manganese has been used by nature to oxidize water but also because manganese is cheap and environmentally friendly. The manganese-calcium cluster in PSII has a dimension of about approximately 0.5 nm. Thus, nano-sized manganese compounds might be good structural and functional models for the cluster. As in the nanometre-size of the synthetic models, most of the active sites are at the surface, these compounds could be more efficient catalysts than micrometre (or bigger) particles. In this paper, we focus on nano-sized manganese oxides as functional and structural models of the WOC of PSII for hydrogen production via water splitting and review nano-sized manganese oxides used in water oxidation by some research groups. PMID:22809849

Najafpour, Mohammad Mahdi; Rahimi, Fahimeh; Aro, Eva-Mari; Lee, Choon-Hwan; Allakhverdiev, Suleyman I

2012-10-01

54

Thin film passivation of laser generated 3D micro patterns in lithium manganese oxide cathodes  

NASA Astrophysics Data System (ADS)

The increasing need for long-life lithium-ion batteries requires the further development of electrode materials. Especially on the cathode side new materials or material composites are needed to increase the cycle lifetime. On the one hand, spinel-type lithium manganese oxide is a promising candidate to be used as cathode material due to its non-toxicity, low cost and good thermal stability. On the other hand, the spinel structure suffers from change in the oxidation state of manganese during cycling which is also accompanied by loss of active material into the liquid electrolyte. The general trend is to enhance the active surface area of the cathode in order to increase lithium-ion mobility through the electrode/electrolyte interface, while an enhanced surface area will also promote chemical degradation. In this work, laser microstructuring of lithium manganese oxide thin films was applied in a first step to increase the active surface area. This was done by using 248 nm excimer laser radiation and chromium/quartz mask imaging techniques. In a second step, high power diode laser-annealing operating at a wavelength of 940 nm was used for forming a cubic spinel-like battery phase. This was verified by means of Raman spectroscopy and cyclic voltammetric measurements. In a last step, the laser patterned thin films were coated with indium tin oxide (ITO) layers with a thickness of 10 nm to 50 nm. The influence of the 3D surface topography as well as the ITO thickness on the electrochemical performance was studied by cyclic voltammetry. Post-mortem studies were carried out by using scanning electron microscopy and focused ion beam analysis.

Pröll, J.; Kohler, R.; Bruns, M.; Oberst, V.; Weidler, P. G.; Heißler, S.; Kübel, C.; Scherer, T.; Prang, R.; Seifert, H. J.; Pfleging, W.

2013-03-01

55

Nanoscale manganese oxide within Faujasite zeolite as an efficient and biomimetic water oxidizing catalyst.  

PubMed

Nanoscale manganese oxides within Faujasite zeolite have been synthesized with a simple method and characterized by scanning electron microscopy, X-ray diffraction spectrometry, N(2) adsorption-desorption isotherms, transmission electron microscopy, and atomic absorption spectroscopy. These oxides showed efficient water oxidizing activity in the presence of cerium(IV) ammonium nitrate as a non-oxo transfer oxidant. PMID:22833185

Najafpour, Mohammad Mahdi; Pashaei, Babak

2012-09-14

56

Transformation of bisphenol A by manganese oxide-coated sand.  

PubMed

Oxidative transformation of organic contaminants by manganese oxides was commonly investigated with pure MnO(2) suspension, which deviates from the fact that natural manganese oxides are seldom present as a pure form in the natural environment. In this study, we prepared manganese oxide-coated sand (MOCS) and evaluated its oxidative capacity using bisphenol A (BPA) as the model compound. BPA was transformed by MOCS and the reaction followed an exponential decay model. The reaction was pH dependent and followed the order of pH 4.5>pH 5.5>pH 6.5>pH 7.5>pH 8.6>pH 9.6, indicating that acidic conditions facilitated BPA transformation while basic conditions disfavored the reaction. Coexisting metal ions exhibited inhibitory effects and followed the order of Fe(3+) > Zn(2+) > Cu(2+) > Ca(2+) > Mg(2+) > Na(+). Transformation of BPA by MOCS was much slower than that by pure MnO(2) suspension. However, similar transformation products were identified in both studies, suggesting the same reaction pathways. This work suggests that the reactivity of MnO(2) in the environment might be overestimated if extrapolating the result from the pure MnO(2) suspension because natural MnO(2) is mainly present as coating on the surface of soils and sediments. PMID:22752814

Lin, Kunde; Peng, Yiwen; Huang, Xinwen; Ding, Jiafeng

2013-03-01

57

Determination of the oxidation states of manganese in brain, liver, and heart mitochondria.  

PubMed

Excess brain manganese can produce toxicity with symptoms that resemble those of Parkinsonism and causes that remain elusive. Manganese accumulates in mitochondria, a major source of superoxide, which can oxidize Mn2+ to the powerful oxidizing agent Mn3+. Oxidation of important cell components by Mn3+ has been suggested as a cause of the toxic effects of manganese. Determining the oxidation states of intramitochondrial manganese could help to identify the dominant mechanism of manganese toxicity. Using X-ray absorbance near edge structure (XANES) spectroscopy, we have characterized the oxidation state of manganese in mitochondria isolated from brain, liver, and heart over concentrations ranging from physiological to pathological. Results showed that (i) spectra from different model manganese complexes of the same oxidation state were similar to each other and different from those of other oxidation states and that the position of the absorption edge increases with oxidation state; (ii) spectra from intramitochondrial manganese in isolated brain, heart and liver mitochondria were virtually identical; and (iii) under these conditions intramitochondrial manganese exists primarily as a combination of Mn2+ complexes. No evidence for Mn3+ was detected in samples containing more than endogenous manganese levels, even after incubation under conditions promoting reactive oxygen species (ROS) production. While the presence of Mn3+ complexes cannot be proven in the spectrum of endogenous mitochondrial manganese, the shape of this spectrum could suggest the presence of Mn3+ near the limit of detection, probably as MnSOD. PMID:14690515

Gunter, Thomas E; Miller, Lisa M; Gavin, Claire E; Eliseev, Roman; Salter, Jason; Buntinas, Linas; Alexandrov, Andrei; Hammond, Sean; Gunter, Karlene K

2004-01-01

58

Nano-sized manganese oxide: a proposed catalyst for water oxidation in the reaction of some manganese complexes and cerium(IV) ammonium nitrate.  

PubMed

According to UV-visible spectroscopy, X-ray diffraction spectrometry, dynamic light scattering, Fourier transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, transmission electron microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy, nano-sized manganese oxides are proposed as active catalysts for water oxidation in the reaction of some manganese complexes and cerium(IV) ammonium nitrate. PMID:22806229

Najafpour, Mohammad Mahdi; Moghaddam, Atefeh Nemati

2012-09-14

59

BIOGENIC MANGANESE OXIDES: Properties and Mechanisms of Formation  

NASA Astrophysics Data System (ADS)

Manganese(IV) oxides produced through microbial activity, i.e., biogenic Mn oxides or Mn biooxides, are believed to be the most abundant and highly reactive Mn oxide phases in the environment. They mediate redox reactions with organic and inorganic compounds and sequester a variety of metals. The major pathway for bacterial Mn(II) oxidation is enzymatic, and although bacteria that oxidize Mn(II) are phylogenetically diverse, they require a multicopper oxidase-like enzyme to oxidize Mn(II). The oxidation of Mn(II) to Mn(IV) occurs via a soluble or enzyme-complexed Mn(III) intermediate. The primary Mn(IV) biooxide formed is a phyllomanganate most similar to -MnO2 or acid birnessite. Metal sequestration by the Mn biooxides occurs predominantly at vacant layer octahedral sites.

Tebo, Bradley M.

2004-05-01

60

Distributions of Manganese, Iron, and Manganese-Oxidizing Bacteria In Lake Superior Sediments of Different Organic Carbon Content  

NASA Technical Reports Server (NTRS)

Profiles of oxygen, soluble and particulate manganese and iron, organic carbon and nitrogen were examined in Lake Superior sediment cores, along with the distribution and abundance of heterotrophic and manganese oxidizing bacteria. Analyses were performed using cores collected with the submersible Johnson Sea Link II. Three cores, exhibiting a range of organic carbon content, were collected from the deepest basin in Lake Superior and the north and south ends of the Caribou trough, and brought to the surface for immediate analysis. Minielectrode profiles of oxygen concentration of the three cores were carried out using a commercially available minielectrode apparatus. Oxygen depletion to less than 1% occurred within 4 cm of the surface for two of the cores, but not until approximately 15 cm for the core from the south basin of the Caribou trough. The three cores exhibited very different profiles of soluble, as well as leachable, manganese and iron, suggesting different degrees of remobilization of these metals in the sediments. Vertical profiles of viable bacteria and Mn oxidizing bacteria, determined by plating and counting, showed that aerobic (and facultatively aerobic) heterotrophic bacteria were present at the highest concentrations near the surface and decreased steadily with depth, while Mn oxidizing bacteria were concentrations primarily at and above the oxic/anoxic interface. Soluble manganese in the pore waters, along with abundant organic carbon, appeared to enhance the presence of manganese oxidizing bacteria, even below the oxic/anoxic interface. Profiles of solid-phase leachable manganese suggested a microbial role in manganese reprecipitation in these sediments.

Richardson, Laurie L.; Nealson, Kenneth H.

1989-01-01

61

Temperature-dependent local atomic structure in the colossal magnetoresistive manganese oxide lanthanum strontium manganese oxide  

NASA Astrophysics Data System (ADS)

Extended X-ray Absorption Fine Structure (XAFS) measurements at the Mn, Sr, and La K-edges of the colossal magnetoresistive (CMR) manganese oxide La1.2Sr1.8 Mn2O7 show that the local atomic structure is coupled to the metal-insulator and paramagnetic-ferromagnetic transitions. These polarized and temperature dependent XAFS measurements are the first performed on a layered CMR manganite in an effort to further elucidate the strong interplay between charge, spin, and lattice degrees of freedom in these hole doped oxides. The polarization dependence of the XAFS indicates that the local distortions accompanying this electronic and magnetic phase transition are associated with Jahn-Teller type distortions to the apical (lying perpendicular to the perovskite MnO planes) oxygen distribution around the MN cations. The metal-insulator transition is accompanied by a sudden increase in the number of Jahn-Teller distorted Mn sites as well as anomalous increases in the thermal Debye-Waller factor indicating increased fluctuations of the local atomic arrangements. A possibility for the La and Sr cations to influence the electronic and magnetic transitions is suggested by their tendency to stabilize differing local arrangements of the nearest neighbor oxygen atoms. The contrasting temperature dependence of the La-oxygen and Sr-oxygen distributions shows that the temperature dependent local atomic distortions observed in the apical oxygen distribution around the Mn ions are primarily associated with Sr atoms. The observed differences in the local atomic structures surrounding Sr and La are supported by similar results in the non-CMR oxide LaSrMnO4. This element specific interaction suggests the possibility that the local dopant concentration could enhance or induce electronic, magnetic, and structural phase separation. Thus, the XAFS experiments documented here have supported the general view that local lattice distortions can play a role in the MI transition and the CMR effect in the bilayer manganite La1.2 Sr1.8Mn2O 7 while also indicating that the effects of the local chemical environment of the Mn ions may play a role in determining the nature of the phase transitions.

Villella, Phillip Michael

2002-09-01

62

A study of layered lithium manganese oxide cathode materials  

NASA Astrophysics Data System (ADS)

Substituted layered sodium manganese oxide bronzes with the P2 structure were prepared by glycine-nitrate combustion synthesis. The Na in the as-prepared materials could be completely ion-exchanged for Li under mild conditions. All lithium manganese oxide compounds obtained after ion-exchange have O2 stacking of the layers. Cyclic voltammetry and stepped potential experiments on lithium cells containing these materials show that the main redox reaction around 3.1 V is a diffusion-controlled process and is completely reversible. O2-Li 0.6[Al 0.1Mn 0.85? 0.05]O 2 and O2-Li 0.6[Ni 0.1Mn 0.85? 0.05]O 2 are particularly promising as cathode materials in lithium cells because of the high reversible discharge capacities (180 mAh/g).

Eriksson, Tom A.; Doeff, Marca M.

63

Preliminary LIBS analysis of Yucca Mountain manganese oxide minerals  

SciTech Connect

The licensing and performance of a potential repository at Yucca Mountain will require the characterization of radionuclide sorptive capacity of the host rock, which in turn calls for hundreds of analyses based on extensive sampling or in situ measurements. A rapid method specifically for characterizing the manganese oxide minerals occurring heterogeneously throughout the Yucca Mountain block as fracture surface coatings is needed. Our unique solution is a laser-induced breakdown spectroscopy (LIBS) surface-analysis technique that is usable in the field to produce high-resolution atomic emission spectra. In tests with manganese oxide minerals and fracture surface coatings from a few Yucca Mountain core samples, we used four spectral bands to show that qualitative measurement of all constituent elements except K and Na (in the presence of Mn) is possible with LIBS. Detailed calibration of final hardware will make the system quantitative.

Blacic, J.; Pettit, D.; Cremers, D.

1996-01-01

64

Manganese oxide nanocomposites with improved surface area prepared by one-pot surfactant route for electro catalytic and biosensor applications  

Microsoft Academic Search

Braunite phase manganese oxide is naturally available in manganese–silicate rocks with minor amount of silicate content. New\\u000a synthetic route is attempted to prepare the manganese oxide nanoparticle and silica incorporated manganese oxide nanocomposite\\u000a in the present study. XRD patterns reveal the braunite phase formation for as synthesized manganese oxide nanocomposite and\\u000a silica incorporated MnO2 nanocomposite materials. Improved BET surface area

R. Jothiramalingam; M. K. Wang

2010-01-01

65

Giant magnetoresistance of manganese oxides with a layered perovskite structure  

Microsoft Academic Search

MANGANESE oxides with the cubic perovskite structure (typified by LaMnO3) have stimulated considerable interest because of their magnetoresistive properties1-9 they exhibit extremely large changes in electrical resistance in response to applied magnetic fields, a property that is of technological relevance for the development of magnetic memory and switching devices. But for such applications to be viable, great improvements will be

Y. Moritomo; A. Asamitsu; H. Kuwahara; Y. Tokura

1996-01-01

66

Lithium insertion in manganese oxides: A model lithium ion system  

Microsoft Academic Search

A model lithium ion system, based on the manganese oxide, LixMn2O4, has been used to study the reversibility of the lithium insertion processes in both the approximate 3 V and 4 V versus LiLi+ voltages ranges. We have used the half-cell voltage responses for the Li1 ? xMn2O4 and Li1 + xMn2O4 electrodes to predict the voltage profile for the

Jerry Barker; René Koksbang; M. Yazid Saïdi

1995-01-01

67

Environmental oxidation rate of manganese(II): bacterial catalysis  

Microsoft Academic Search

A simple mass balance for dissolved manganese(II) in waters containing low levels of oxygen in Saanich Inlet indicates that the residence time for Mn(II) removal to the solid phase is on the order of a few days. The average oxidation state of Mn in particulate material sampled from the region of Mn removal was 2.3-2.7, and electron micrographs revealed structures

Steven Emerson; Susan Kalhorn; Lucinda Jacobs; Bradley M. Tebo; Kenneth H. Nealson; Reinhardt A. Rosson

1982-01-01

68

Electrodeposited the gold\\/manganese oxides as nano supercapacitor  

Microsoft Academic Search

In this study, the nano-supercapacitors were electrodeposited the gold\\/manganese oxides thin film with potassium permanganate and gold chloride solution on ITO substrate. It was deposited for 200 s by potentiostatic method (0.7 V v.s. open circuit). The morphology and the microstructure of the films were examined by SEM (scan electron microscopy). The thickness of the thin films was about 30~100

Yi Hu; Jiun-Shing Liu

2010-01-01

69

Diode laser heat treatment of lithium manganese oxide films  

NASA Astrophysics Data System (ADS)

The crystallization of lithium manganese oxide thin films prepared by radio frequency magnetron sputtering on stainless steel substrates under 10 Pa argon pressure is demonstrated by a laser annealing technique. Laser annealing processes were developed as a function of annealing time and temperature with the objective to form an electrochemically active lithium manganese oxide cathode. It is demonstrated, that laser annealing with 940 nm diode laser radiation and an annealing time of 2000 s at 600 °C delivers appropriate parameters for formation of a crystalline spinel-like phase. Characteristic features of this phase could be detected via Raman spectroscopy, showing the characteristic main Raman band at 627 cm-1. Within cyclic voltammetric measurements, the two characteristic redox pairs for spinel lithium manganese oxide in the 4 V region could be detected, indicating that the film was well-crystallized and de-/intercalation processes were reversible. Raman post-analysis of a cycled cathode showed that the spinel-like structure was preserved within the cycling process but mechanical degradation effects such as film cracking were observed via scanning electron microscopy. Typical features for the formation of an additional surface reaction layer could be detected using X-ray photoelectron spectroscopy.

Pröll, J.; Kohler, R.; Mangang, A.; Ulrich, S.; Bruns, M.; Seifert, H. J.; Pfleging, W.

2012-04-01

70

Laser microstructuring and annealing processes for lithium manganese oxide cathodes  

NASA Astrophysics Data System (ADS)

It is expected that cathodes for lithium-ion batteries (LIB) composed out of nano-composite materials lead to an increase in power density of the LIB due to large electrochemically active surface areas but cathodes made of lithium manganese oxides (Li-Mn-O) suffer from structural instabilities due to their sensitivity to the average manganese oxidation state. Therefore, thin films in the Li-Mn-O system were synthesized by non-reactive radiofrequency magnetron sputtering of a spinel lithium manganese oxide target. For the enhancement of the power density and cycle stability, large area direct laser patterning using UV-laser radiation with a wavelength of 248 nm was performed. Subsequent laser annealing processes were investigated in a second step in order to set up a spinel-like phase using 940 nm laser radiation at a temperature of 680 °C. The interaction processes between UV-laser radiation and the material was investigated using laser ablation inductively coupled plasma mass spectroscopy. The changes in phase, structure and grain shape of the thin films due to the annealing process were recorded using Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The structured cathodes were cycled using standard electrolyte and a metallic lithium anode. Different surface structures were investigated and a significant increase in cycling stability was found. Surface chemistry of an as-deposited as well as an electrochemically cycled thin film was investigated via X-ray photoelectron spectroscopy.

Pröll, J.; Kohler, R.; Torge, M.; Ulrich, S.; Ziebert, C.; Bruns, M.; Seifert, H. J.; Pfleging, W.

2011-09-01

71

The Overlapping Roles of Manganese and Cu/Zn SOD in Oxidative Stress Protection  

PubMed Central

In various organisms, high intracellular manganese provides protection against oxidative damage through unknown pathways. Herein we use a genetic approach in S. cerevisiae to analyze factors that promote manganese as an anti-oxidant in cells lacking Cu/Zn superoxide dismutase (sod1?). Unlike certain bacterial systems [1], oxygen resistance in yeast correlates with high intracellular manganese without a lowering of iron. This manganese for anti-oxidant protection is provided by the Nramp transporters Smf1p and Smf2p, with Smf1p playing a major role. In fact, loss of manganese transport by Smf1p together with loss of the Pmr1p manganese pump is lethal to sod1? cells in spite of normal manganese SOD2 activity. Manganese-phosphate complexes are excellent superoxide dimustase mimics in vitro [2], yet through genetic disruption of phosphate transport and storage, we observed no requirement for phosphate in manganese suppression of oxidative damage. If anything, elevated phosphate correlated with profound oxidative stress in sod1? mutants. The efficacy of manganese as an anti-oxidant was drastically reduced in cells that hyper-accumulate phosphate without effects on MnSOD activity. Non-SOD manganese can provide a critical backup for Cu/Zn SOD1, but only under appropriate physiologic conditions.

Reddi, Amit R.; Jensen, Laran T.; Naranuntarat, Amornrat; Rosenfeld, Leah; Leung, Edison; Shah, Rishita; Culotta, Valeria C.

2009-01-01

72

Manganese oxidation induced by water table fluctuations in a sand column.  

PubMed

On-off cycles of production wells, especially in bank filtration settings, cause oscillations in the local water table, which can deliver significant amounts of dissolved oxygen (DO) to the shallow groundwater. The potential for DO introduced in this manner to oxidize manganese(II) (Mn(II)), mediated by the obligate aerobe Pseudomonas putida GB-1, was tested in a column of quartz sand fed with anoxic influent solution and subject to 1.3 m water table changes every 30-50 h. After a period of filter ripening, 100 ?M Mn was rapidly removed during periods of low water table and high dissolved oxygen concentrations. The accumulation of Mn in the column was confirmed by XRF analysis of the sand at the conclusion of the study, and both measured net oxidation rates and XAS analysis suggest microbial oxidation as the dominant process. The addition of Zn, which inhibited GB-1 Mn oxidation but not its growth, interrupted the Mn removal process, but Mn oxidation recovered within one water table fluctuation. Thus transient DO conditions could support microbially mediated Mn oxidation, and this process could be more relevant in shallow groundwater than previously thought. PMID:22126514

Farnsworth, Claire E; Voegelin, Andreas; Hering, Janet G

2012-01-01

73

Manganese ion-assisted assembly of superparamagnetic graphene oxide microbowls  

NASA Astrophysics Data System (ADS)

A facile manganese ion Mn(II)-assisted assembly has been designed to fabricate microbowls by using graphene oxide nanosheets as basic building blocks, which were exfoliated ultrasonically from the oxidized soot powders in deionized water. From the morphology evolution observations of transmission electron microscope and scanning electron microscope, a coordinating-tiling-collapsing manner is proposed to interpret the assembly mechanism based on attractive Van der Waals forces, ?-? stacking, and capillary action. It is interesting to note that the as-prepared microbowls present a room temperature superparamagnetic behavior.

Tian, Zhengshan; Xu, Chunxiang; Li, Jitao; Zhu, Gangyi; Xu, Xiaoyong; Dai, Jun; Shi, Zengliang; Lin, Yi

2014-03-01

74

Isotopic evidence for organic matter oxidation by manganese reduction in the formation of stratiform manganese carbonate ore  

USGS Publications Warehouse

Unlike other marine-sedimentary manganese ore deposits, which are largely composed of manganese oxides, the primary ore at Molango (Hidalgo State, Mexico) is exclusively manganese carbonate (rhodochrosite, Mn-calcite, kutnahorite). Stable isotope studies of the carbonates from Molango provide critical new information relevant to the controversy over syngenetic and diagenetic models of stratiform manganese deposit formation. Negative ??13C values for carbonates from mineralized zones at Molango are strongly correlated with manganese content both on a whole rock scale and by mineral species. Whole rock ??13C data fall into three groups: high-grade ore = -16.4 to -11.5%.; manganese-rich, sub-ore-grade = -5.2 to 0%.; and unmineralized carbonates = 0 to +2.5%. (PDB). ??18O data show considerable overlap in values among the three groups: +4.8 to -2.8, -5.4 to -0.3%., and -7.4 to +6.2 (PDB), respectively. Isotopic data for individual co-existing minerals suggest a similar separation of ??13C values: ??13C values from calcite range from -1.1 to +0.7%. (PDB), whereas values from rhodochrosite are very negative, -12.9 to -5.5%., and values from kutnahorite or Mn-calcite are intermediate between calcite and rhodochrosite. 13C data are interpreted to indicate that calcite (i.e. unmineralized carbonate) formed from a normal marine carbon reservoir. However, 13C data for the manganese-bearing carbonates suggest a mixed seawater and organic source of carbon. The presence of only trace amounts of pyrite suggests sulfate reduction may have played a minor part in oxidizing organic matter. It is possible that manganese reduction was the predominant reaction that oxidized organic matter and that it released organic-derived CO2 to produce negative ??13C values and manganese carbonate mineralization. ?? 1988.

Okita, P. M.; Maynard, J. B.; Spiker, E. C.; Force, E. R.

1988-01-01

75

Manganese Oxidation by Spores and Spore Coats of a Marine Bacillus Species  

PubMed Central

Bacillus sp. strain SG-1 is a marine bacterial species isolated from a near-shore manganese sediment sample. Its mature dormant spores promote the oxidation of Mn2+ to MnO2. By quantifying the amounts of immobilized and oxidized manganese, it was established that bound manganese was almost instantaneously oxidized. When the final oxidation of manganese by the spores was partly inhibited by NaN3 or anaerobiosis, an equivalent decrease in manganese immobilization was observed. After formation of a certain amount of MnO2 by the spores, the oxidation rate decreased. A maximal encrustment was observed after which no further oxidation occurred. The oxidizing activity could be recovered by reduction of the MnO2 with hydroxylamine. Once the spores were encrusted, they could bind significant amounts of manganese, even when no oxidation occurred. Purified spore coat preparations oxidized manganese at the same rate as intact spores. During the oxidation of manganese in spore coat preparations, molecular oxygen was consumed and protons were liberated. The data indicate that a spore coat component promoted the oxidation of Mn2+ in a biologically catalyzed process, after adsorption of the ion to incipiently formed MnO2. Eventually, when large amounts of MnO2 were allowed to accumulate, the active sites were masked and further oxidation was prevented.

de Vrind, Johannes P. M.; de Vrind-de Jong, Elisabeth W.; de Voogt, Jan-Willem H.; Westbroek, Peter; Boogerd, Fred C.; Rosson, Reinhardt A.

1986-01-01

76

Constraints on superoxide mediated formation of manganese oxides.  

PubMed

Manganese (Mn) oxides are among the most reactive sorbents and oxidants within the environment, where they play a central role in the cycling of nutrients, metals, and carbon. Recent discoveries have identified superoxide ([Formula: see text]) both of biogenic and abiogenic origin as an effective oxidant of Mn(II) leading to the formation of Mn oxides. Here we examined the conditions under which abiotically produced superoxide led to oxidative precipitation of Mn and the solid-phases produced. Oxidized Mn, as both aqueous Mn(III) and Mn(III/IV) oxides, was only observed in the presence of active catalase, indicating that hydrogen peroxide (H2O2), a product of the reaction of [Formula: see text] with Mn(II), inhibits the oxidation process presumably through the reduction of Mn(III). Citrate and pyrophosphate increased the yield of oxidized Mn but decreased the amount of Mn oxide produced via formation of Mn(III)-ligand complexes. While complexing ligands played a role in stabilizing Mn(III), they did not eliminate the inhibition of net Mn(III) formation by H2O2. The Mn oxides precipitated were highly disordered colloidal hexagonal birnessite, similar to those produced by biotically generated superoxide. Yet, in contrast to the large particulate Mn oxides formed by biogenic superoxide, abiotic Mn oxides did not ripen to larger, more crystalline phases. This suggests that the deposition of crystalline Mn oxides within the environment requires a biological, or at least organic, influence. This work provides the first direct evidence that, under conditions relevant to natural waters, oxidation of Mn(II) by superoxide can occur and lead to formation of Mn oxides. For organisms that oxidize Mn(II) by producing superoxide, these findings may also point to other microbially mediated processes, in particular enzymatic hydrogen peroxide degradation and/or production of organic ligand metabolites, that allow for Mn oxide formation. PMID:24027565

Learman, Deric R; Voelker, Bettina M; Madden, Andrew S; Hansel, Colleen M

2013-01-01

77

Manganese  

MedlinePLUS

... the body, including processing of cholesterol, carbohydrates, and protein. It might also be involved in bone formation. ... Antibiotics (Quinolone antibiotics)Manganese might decrease how much ... antibiotics might decrease the effectiveness of some antibiotics. To avoid ...

78

Cordierite as catalyst support for cobalt and manganese oxides in oxidation–reduction reactions  

Microsoft Academic Search

Cobalt and manganese oxide samples supported on cordierite (commercial grade) were prepared by wet impregnation method using finely powdered support material and cobalt or manganese nitrate. The extent of loading was varied between 5 and 20wt.% Co3O4 or Mn2O3. The physicochemical, surface and catalytic properties of the thermally treated solids (350 and 700°C) were investigated using XRD, EDX, nitrogen adsorption

Nagi R. E. Radwan; G. A. El-Shobaky; Y. M. Fahmy

2004-01-01

79

Analysis of the Manganese Oxidation Capacity of P. putida GB1 and MnB1 Mutant Strains  

Microsoft Academic Search

Manganese (Mn) oxides of biological origin have been shown to possess the ability to reduce the toxicity of contaminated sites, including those containing heavy metal pollutants. However, relatively little is known about the actual process by which biological Manganese oxidation occurs. Liquid cultures from eleven mutant strains deficient in Mn oxide formation from the manganese oxidizer Psuedomonas putida were examined

D. B. Baron

80

First principles calculations for lithiated manganese oxides.  

SciTech Connect

First principles calculations within the local-spin-density-functional theory (LSDFF) framework are presented of densities of electronic states for MnO, LiMnO{sub 2} in the monoclinic and orthorhombic structures, cubic LiMn{sub 2}O{sub 4} spinel and {lambda}-MnO{sub 2} (delithiated spinel), all in antiferromagnetic spin configurations. The changes in energy spectra as the Mn oxidation state varies between 2+ and 4+ are illustrated. Preliminary calculations for Co-doped LiMnO{sub 2} are presented, and the destabilization of a monoclinic relative to a rhombohedral structure is discussed.

Prasad, R.

1998-12-23

81

Self-assembly of manganese oxide nanoparticles and hollow spheres. Catalytic activity in carbon monoxide oxidation.  

PubMed

Reactions between MnSO(4) and KMnO(4) in the presence of carboxylic acids provide a facile, one-pot route to nanostructured manganese oxides with high surface areas. Acetic and propionic acid induce formation of hierarchical nanosphere morphologies whereas butyric acid promotes assembly of hollow spheres. The materials are active catalysts for CO oxidation. PMID:21655565

Ching, Stanton; Kriz, David A; Luthy, Kurt M; Njagi, Eric C; Suib, Steven L

2011-08-01

82

The overlapping roles of manganese and Cu/Zn SOD in oxidative stress protection.  

PubMed

In various organisms, high intracellular manganese provides protection against oxidative damage through unknown pathways. Herein we use a genetic approach in Saccharomyces cerevisiae to analyze factors that promote manganese as an antioxidant in cells lacking Cu/Zn superoxide dismutase (sod1 Delta). Unlike certain bacterial systems, oxygen resistance in yeast correlates with high intracellular manganese without a lowering of iron. This manganese for antioxidant protection is provided by the Nramp transporters Smf1p and Smf2p, with Smf1p playing a major role. In fact, loss of manganese transport by Smf1p together with loss of the Pmr1p manganese pump is lethal to sod1 Delta cells despite normal manganese SOD2 activity. Manganese-phosphate complexes are excellent superoxide dismutase mimics in vitro, yet through genetic disruption of phosphate transport and storage, we observed no requirement for phosphate in manganese suppression of oxidative damage. If anything, elevated phosphate correlated with profound oxidative stress in sod1 Delta mutants. The efficacy of manganese as an antioxidant was drastically reduced in cells that hyperaccumulate phosphate without effects on Mn SOD activity. Non-SOD manganese can provide a critical backup for Cu/Zn SOD1, but only under appropriate physiologic conditions. PMID:18973803

Reddi, Amit R; Jensen, Laran T; Naranuntarat, Amornrat; Rosenfeld, Leah; Leung, Edison; Shah, Rishita; Culotta, Valeria C

2009-01-15

83

Photoinduced oxidation of a water-soluble manganese(III) porphyrin.  

PubMed

The photoinduced oxidation of tetra(N-methyl-4-pyridyl)porphyrinmanganese(III) has been achieved in homogeneous solution. The manganese porphyrin was used as an electron donor in a three-component system with tris-(2,2'-bipyridine)ruthenium(II) as the photosensitizer and chloropentaamminecobalt(III) as the electron acceptor. The photooxidized manganese porphyrin is unstable in aqueous solution, reverting to the starting manganese(III) porphyrin. The oxidation of manganese(III) porphyrin and the subsequent reduction of the oxidized porphyrin can be cycled repeatedly. PMID:16593699

Maliyackel, A C; Otvos, J W; Spreer, L O; Calvin, M

1986-06-01

84

Photoinduced oxidation of a water-soluble manganese(III) porphyrin  

PubMed Central

The photoinduced oxidation of tetra(N-methyl-4-pyridyl)porphyrinmanganese(III) has been achieved in homogeneous solution. The manganese porphyrin was used as an electron donor in a three-component system with tris-(2,2?-bipyridine)ruthenium(II) as the photosensitizer and chloropentaamminecobalt(III) as the electron acceptor. The photooxidized manganese porphyrin is unstable in aqueous solution, reverting to the starting manganese(III) porphyrin. The oxidation of manganese(III) porphyrin and the subsequent reduction of the oxidized porphyrin can be cycled repeatedly.

Maliyackel, Anthony C.; Otvos, John W.; Spreer, Larry O.; Calvin, Melvin

1986-01-01

85

Manganese oxide composite electrodes for lithium batteries  

DOEpatents

An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor thereof a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0.5

Johnson, Christopher S. (Naperville, IL); Kang, Sun-Ho (Naperville, IL); Thackeray, Michael M. (Naperville, IL)

2009-12-22

86

Manganese oxide composite electrodes for lithium batteries  

DOEpatents

An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor of a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0

Thackeray, Michael M. (Naperville, IL); Johnson, Christopher S. (Naperville, IL); Li, Naichao (Croton on Hudson, NY)

2007-12-04

87

Calcium manganese(IV) oxides: biomimetic and efficient catalysts for water oxidation.  

PubMed

CaMnO(3) and Ca(2)Mn(3)O(8) were synthesized and characterized by SEM, XRD, FTIR and BET. Both oxides showed oxygen evolution activity in the presence of oxone, cerium(IV) ammonium nitrate and H(2)O(2). Oxygen evolution from water during irradiation with visible light (? > 400 nm) was also observed upon adding these manganese oxides to an aqueous solution containing tris(2,2'-bipyridyl) ruthenium(II), as photosensitizer, and chloro pentaammine cobalt(III) chloride, as electron acceptor, in an acetate buffer. The amounts of dissolved manganese and calcium from CaMnO(3) and Ca(2)Mn(3)O(8) in the oxygen evolving reactions were reported and compared with other (calcium) manganese oxides. Proposed mechanisms of oxygen evolution and proposed roles for the calcium ions are also considered. PMID:22382465

Najafpour, Mohammad Mahdi; Pashaei, Babak; Nayeri, Sara

2012-04-28

88

Chemical lithium extraction from manganese oxides for lithium rechargeable batteries  

Microsoft Academic Search

Chemical lithium extraction has been carried out on the following manganese oxides: the spinel-type compounds LiMn2O4 and Li(4\\/3)Mn(5\\/3)O4, and the rocksalt-related compound Li2MnO3. Lithium can be partially removed chemically from these compounds without destroying the host framework. Some compounds obtained by this method have been tested as cathodic materials in rechargeable lithium cells. Electrochemical results and X-ray diffraction patterns of

F. Lubin; A. Lecerf; M. Broussely; J. Labat

1991-01-01

89

Manganese sulfide formation via concomitant microbial manganese oxide and thiosulfate reduction.  

PubMed

The dissimilatory metal-reducing bacterium, Shewanella oneidensis MR-1 produced ?-MnS (rambergite) nanoparticles during the concurrent reduction of MnO? and thiosulfate coupled to H? oxidation. To investigate effect of direct microbial reduction of MnO? on MnS formation, two MR-1 mutants defective in outer membrane c-type cytochromes (?mtrC/?omcA and ?mtrC/?omcA/?mtrF) were also used and it was determined that direct reduction of MnO? was dominant relative to chemical reduction by biogenic sulfide generated from thiosulfate reduction. Although bicarbonate was excluded from the medium, incubations of strain MR-1 with lactate as the electron donor produced MnCO? (rhodochrosite) as well as MnS in nearly equivalent amounts as estimated by micro X-ray diffraction (micro-XRD) analysis. It was concluded that carbonate released from lactate metabolism promoted MnCO? formation and that Mn(II) mineralogy was strongly affected by carbonate ions even in the presence of abundant sulfide and weakly alkaline conditions expected to favour the precipitation of MnS. Formation of MnS, as determined by a combination of micro-XRD, transmission electron microscopy, energy dispersive X-ray spectroscopy, and selected area electron diffraction analyses was consistent with equilibrium speciation modelling predictions. Biogenic manganese sulfide may be a manganese sink in the Mn biogeochemical cycle in select environments such as deep anoxic marine basins within the Baltic Sea. PMID:21951417

Lee, Ji-Hoon; Kennedy, David W; Dohnalkova, Alice; Moore, Dean A; Nachimuthu, Ponnusamy; Reed, Samantha B; Fredrickson, James K

2011-12-01

90

Chemical synthesis and characterization of manganese oxide coated Ni particles  

NASA Astrophysics Data System (ADS)

Nanosized Ni particles with an average diameter of about 8 nm were prepared by reducing of NiCl2 with sodium borohydride (NaBH4) in aqueous solution. By moderate annealing in protective atmosphere, the composite grew up to be 15-20 nm particles. Both of the as-prepared and annealed Ni particles were coated by a layer of manganese oxide via decomposition reaction in aqueous KMnO4 solution. Hysteresis loops of as-prepared samples show a large increase in the magnetization with decreasing temperature and an unsaturated component at high magnetic field. In contrast, the ferromagnetic characteristics of annealed one are much stronger with large magnetization and coercivity. The thermomagnetic curves verified the coexistence of ferromagnetic Ni and antiferromangetic Mn oxide phases. But there exists no exchange bias behavior in the samples, even though the interface structure between the ferromagnetic Ni core and the antiferromagnetic manganese oxides has been distinctly formed. The absence of exchange bias probably originates from the weak ferromagnetic characteristic of Ni cores.

An, Jing; Xu, LiHong; He, Jun; Zhao, DongLiang; Liu, ZhongYuan

2013-08-01

91

Water oxidation by manganese oxides formed from tetranuclear precursor complexes: the influence of phosphate on structure and activity.  

PubMed

Two types of manganese oxides have been prepared by hydrolysis of tetranuclear Mn(iii) complexes in the presence or absence of phosphate ions. The oxides have been characterized structurally using X-ray absorption spectroscopy and functionally by O2 evolution measurements. The structures of the oxides prepared in the absence of phosphate are dominated by di-?-oxo bridged manganese ions that form layers with limited long-range order, consisting of edge-sharing MnO6 octahedra. The average manganese oxidation state is +3.5. The structure of these oxides is closely related to other manganese oxides reported as water oxidation catalysts. They show high oxygen evolution activity in a light-driven system containing [Ru(bpy)3](2+) and S2O8(2-) at pH 7. In contrast, the oxides formed by hydrolysis in the presence of phosphate ions contain almost no di-?-oxo bridged manganese ions. Instead the phosphate groups are acting as bridges between the manganese ions. The average oxidation state of manganese ions is +3. This type of oxide has much lower water oxidation activity in the light-driven system. Correlations between different structural motifs and the function as a water oxidation catalyst are discussed and the lower activity in the phosphate containing oxide is linked to the absence of protonable di-?-oxo bridges. PMID:24647521

Shevchenko, Denys; Anderlund, Magnus F; Styring, Stenbjörn; Dau, Holger; Zaharieva, Ivelina; Thapper, Anders

2014-05-28

92

Population Structure of Manganese-Oxidizing Bacteria in Stratified Soils and Properties of Manganese Oxide Aggregates under Manganese-Complex Medium Enrichment  

PubMed Central

Manganese-oxidizing bacteria in the aquatic environment have been comprehensively investigated. However, little information is available about the distribution and biogeochemical significance of these bacteria in terrestrial soil environments. In this study, stratified soils were initially examined to investigate the community structure and diversity of manganese-oxidizing bacteria. Total 344 culturable bacterial isolates from all substrata exhibited Mn(II)-oxidizing activities at the range of 1 µM to 240 µM of the equivalent MnO2. The high Mn(II)-oxidizing isolates (>50 mM MnO2) were identified as the species of phyla Actinobacteria, Firmicutes and Proteobacteria. Seven novel Mn(II)-oxidizing bacterial genera (species), namely, Escherichia, Agromyces, Cellulomonas, Cupriavidus, Microbacterium, Ralstonia, and Variovorax, were revealed via comparative phylogenetic analysis. Moreover, an increase in the diversity of soil bacterial community was observed after the combined enrichment of Mn(II) and carbon-rich complex. The phylogenetic classification of the enriched bacteria represented by predominant denaturing gradient gel electrophoresis bands, was apparently similar to culturable Mn(II)-oxidizing bacteria. The experiments were further undertaken to investigate the properties of the Mn oxide aggregates formed by the bacterial isolates with high Mn(II)-oxidizing activity. Results showed that these bacteria were closely encrusted with their Mn oxides and formed regular microspherical aggregates under prolonged Mn(II) and carbon-rich medium enrichment for three weeks. The biotic oxidation of Mn(II) to Mn(III/IV) by these isolates was confirmed by kinetic examinations. X-ray diffraction assays showed the characteristic peaks of several Mn oxides and rhodochrosite from these aggregates. Leucoberbelin blue tests also verified the Mn(II)-oxidizing activity of these aggregates. These results demonstrated that Mn oxides were formed at certain amounts under the enrichment conditions, along with the formation of rhodochrosite in such aggregates. Therefore, this study provides insights into the structure and diversity of soil-borne bacterial communities in Mn(II)-oxidizing habitats and supports the contribution of soil-borne Mn(II)-oxidizing bacteria to Mn oxide mineralization in soils.

Zhang, Zhongming; Chen, Hong; Liu, Jin; Ali, Muhammad; Liu, Fan; Li, Lin

2013-01-01

93

Dimensionality dependent water splitting mechanisms on free manganese oxide clusters.  

PubMed

The interaction of ligand-free manganese oxide nanoclusters with water is investigated, aiming at uncovering phenomena which could aid the design of artificial water-splitting molecular catalysts. Gas phase measurements in an ion trap in conjunction with first-principles calculations provide new mechanistic insight into the water splitting process mediated by bi- and tetra-nuclear singly charged manganese oxide clusters, Mn2O2(+) and Mn4O4(+). In particular, a water-induced dimensionality change of Mn4O4(+) is predicted, entailing transformation from a two-dimensional ring-like ground state structure of the bare cluster to a cuboidal octa-hydroxy-complex for the hydrated one. It is further predicted that the water splitting process is facilitated by the cluster dimensionality crossover. The vibrational spectra calculated for species occurring along the predicted pathways of the reaction of Mn4O4(+) with water provide the impetus for future explorations, including vibrational spectroscopic experiments. PMID:24164444

Lang, Sandra M; Fleischer, Irene; Bernhardt, Thorsten M; Barnett, Robert N; Landman, Uzi

2013-11-13

94

Chemical Characterization of Transition Metal Spinel-Type Oxides. Part 2. Manganese-Chromium-Iron Spinels.  

National Technical Information Service (NTIS)

Spinel oxides of the type formed on Advanced Gas Cooled Reactor cladding contain manganese, chromium, and iron. A range of standard spinels containing these metals have been prepared by solid state reaction of the appropriate single oxides at temperatures...

G. C. Allen J. A. Jutson P. A. Tempest

1987-01-01

95

Catalytic asymmetric oxidations using optically active (salen)manganese(III) complexes as catalysts  

Microsoft Academic Search

This review deals with enantioselective one oxygen atom transfer reactions (epoxidation, oxidation of enolates, and oxidation of sulphide to sulphoxides) catlaysed by optically active (salen)manganese(III)complexes. Asymmetric aziridination is also discussed briefly.

Tsutomu Katsuki

1995-01-01

96

Porous manganese oxide octahedral molecular sieves and octahedral layered materials.  

PubMed

This Account first gives a historical overview of the development of octahedral molecular sieve (OMS) and octahedral layer (OL) materials based on porous mixed-valent manganese oxides. Unique properties of such systems include excellent semiconductivity and porosity. Materials that are conducting and porous are rare and can offer novel properties not normally available with most molecular sieve materials. The good semiconductivity of OMS and OL systems not only permits potential applications of the conductivity of these materials but also allows characterization of these systems where charging effects are often a problem. Porous manganese oxide natural materials are found as manganese nodules, and these materials when dredged from the ocean floors have been used as excellent adsorbents of metals such as from electroplating wastes and have been shown to be excellent catalysts. Rational for synthesis of novel OMS and OL materials is related to the superb conductivity, microporosity, and catalytic activity of these natural materials. The natural systems are often found as mixtures, are poorly crystalline, and have incredibly diverse compositions due to exposure to various aqueous environments in nature. Such exposure allows ion exchange to occur. Preparation of pure crystalline OL and OMS systems is one of the very significant goals of this work. The status of this research area is one of moderate development. Opportunities exist for preparation of a multitude of novel materials. Some applications of these materials have recently been achieved primarily in the area of catalysis and membranes, and others such as sensors and adsorptive systems are likely. Characterization studies are becoming more sophisticated as new materials and proper preparation of materials for such characterization studies are being done. The research area involved in this work is solid state chemistry. The fields of materials synthesis, characterization, and applications of materials are all important in developments of this field. Researchers in chemistry, chemical engineering, materials science, physics, and biological sciences are actively pursuing research in this area. The most significant results found in this work are related to the novel structural and physical properties of porous manganese oxide materials. Variable pore size materials have been synthesized using structure directors and with a variety of synthetic methodologies. Transformations of tunnel materials with temperature and in specific atmosphere have recently been studied with in situ synchrotron methods. Conductivities of these materials appear to be related to the structural properties of these systems with more open structures being less conductive. Catalytic properties of these OMS and OL materials have been shown to be related to the redox cycling of various oxidations states of manganese such as Mn2+, Mn3+, and Mn4+. Chemists interested in synthesis of new materials, the chemistry of solids, enhancing the rates of catalytic reactions, and finding new applications of materials would be interested in these novel materials. Fundamental properties of electron transfer are critical to this research. Concepts of nonstoichiometry, defects, oxygen vacancies, and intermediates are fundamental to many of the syntheses, characterization, and applications such as fuel cells, catalysis, adsorption, sensors, batteries, and related applications. PMID:18232663

Suib, Steven L

2008-04-01

97

Oxidation of As(III) by Hydrous Manganese Oxide: Effect of Carbonate  

Microsoft Academic Search

The mobility of arsenic in aquatic environment is largely governed by its speciation and adsorption on the surfaces of minerals. Hydrous manganese oxide (HMO) plays an important role in redox transformation of arsenic in aquatic environment and is available for remedy of groundwater with high arsenic concentration. Carbonate is often present as major anion in groundwater and its influence on

Zhixi Zhao; Shanlin Zhao; Yongfeng Jia

2011-01-01

98

Manganese sulfide formation via concomitant microbial manganese oxide and thiosulfate reduction  

SciTech Connect

The dissimilatory metal-reducing bacterium, Shewanella oneidensis MR-1 produced {gamma}-MnS (rambergite) nanoparticles during the concurrent reduction of MnO{sub 2} and thiosulfate coupled to H{sub 2} oxidation. To investigate effect of direct microbial reduction of MnO{sub 2} on MnS formation, two MR-1 mutants defective in outer membrane c-type cytochromes ({Delta}mtrC/{Delta}omcA and {Delta}mtrC/{Delta}omcA/{Delta}mtrF) were also used and it was determined that direct reduction of MnO{sub 2} was dominant relative to chemical reduction by biogenic sulfide generated from thiosulfate reduction. Although bicarbonate was excluded from the medium, incubations of strain MR-1 with lactate as the electron donor produced MnCO{sub 3} (rhodochrosite) as well as MnS in nearly equivalent amounts as estimated by micro X-ray diffraction (micro-XRD) analysis. It was concluded that carbonate released from lactate metabolism promoted MnCO{sub 3} formation and that Mn(II) mineralogy was strongly affected by carbonate ions even in the presence of abundant sulfide and weakly alkaline conditions expected to favor the precipitation of MnS. Formation of MnS, as determined by a combination of micro-XRD, transmission electron microscopy, energy dispersive X-ray spectroscopy, and selected area electron diffraction analyses was consistent with equilibrium speciation modeling predictions. Biogenic manganese sulfide may be a manganese sink in the Mn biogeochemical cycle in select environments such as deep anoxic marine basins within the Baltic Sea.

Lee, Ji-Hoon; Kennedy, David W.; Dohnalkova, Alice; Moore, Dean A.; Nachimuthu, Ponnusamy; Reed, Samantha B.; Fredrickson, Jim K.

2011-12-13

99

Manganese cluster in photosynthesis: Where plants oxidize water to dioxygen  

SciTech Connect

The essential involvement of manganese in photosynthetic water oxidation was implicit in the observation by Pirson in 1937 that plants and algae deprived of Mn in their growth medium lost the ability to evolve O{sub 2}. Addition of this essential element to the growth medium resulted in the restoration of water oxidation within 30 min. There is increased interest in the study of Mn in biological chemistry and dioxygen metabolism in the last two decades with the discovery of several Mn redox enzymes. The list of enzymes where Mn is required for redox activity includes a Mn superoxide dismutase, a binuclear Mn-containing catalase, a binuclear Mn-containing ribonucleotide reductase, a proposed binuclear Mn site in thiosulfate oxidase, a Mn peroxidase that is capable of oxidative degradation of lignin, and perhaps the most complex and important, the tetranuclear Mn-containing oxygen-evolving complex in photosystem II (Mn-OEC). Mn is well suited for the redox role with accessible oxidation states of II, III, and IV, and possibly V: oxidation states that have all been proposed to explain the mechanisms of the Mn redox enzymes.

Yachandra, V.K.; Klein, M.P. [Lawrence Berkeley National Lab., CA (United States). Structural Biology Div.] [Lawrence Berkeley National Lab., CA (United States). Structural Biology Div.; Sauer, K. [Lawrence Berkeley National Lab., CA (United States). Structural Biology Div.] [Lawrence Berkeley National Lab., CA (United States). Structural Biology Div.; [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

1996-11-01

100

Nickel and lead sequestration in manganese oxide-coated montmorillonite.  

PubMed

Amorphous hydrous manganese oxide (HMO) is an important mineral in soils and sediments influencing the mobility and bioavailability of metal contaminants. In this study, nickel and lead sorption to discrete HMO and HMO-coated montmorillonite was investigated mechanistically. The effect of pH and concentration revealed that when normalized to the mass of oxide present, the HMO-coated montmorillonite behaved similarly to the discrete Mn oxide, where both ions sorbed onto HMO-coated montmorillonite as inner-sphere complexes. Ni coordinated to the vacancy sites in the Mn oxide structure, while Pb formed bidentate corner-sharing complexes. These coordination environments were observed not only as a function of loading, pH, and ionic strength, but also in long-term studies where sorption increased by as much as 100% (from 6x10(-4) to 1.2x10(-3) mol Ni/g HMO-coated montmorillonite). In this slower sorption process, intraparticle diffusion, the internal surface sites along microporous walls appear to be no different than external ones. Best fit diffusivities ranged from 10(-12) to 10(-13) cm2/s for Ni and 10(-17) to 10(-20) cm2/s for Pb. The significant difference in the diffusivities for the two ions is consistent with site activation theory, where theoretical surface diffusivities were predicted and given their error were in agreement with experimental results. Mn oxides sequester heavy metals in the environment. PMID:16920131

Boonfueng, Thipnakarin; Axe, Lisa; Xu, Ying; Tyson, Trevor A

2006-11-01

101

The controlling effect of pH on oxidation of Cr(III) by manganese oxide minerals  

Microsoft Academic Search

Oxidation of Cr(III) by three types of manganese oxide minerals (birnessite I, birnessite II, and todorokite) and effects of pH were investigated by chemical analysis, equilibrium redox, X-ray diffraction (XRD), and transmission electron microscopy. The effects of pH in the reaction systems on the oxidation of Cr(III) were similar among the three manganese oxide minerals. As pH increased from pH

Xiong Han Feng; Li Mei Zhai; Wen Feng Tan; Wei Zhao; Fan Liu; Ji Zheng He

2006-01-01

102

Biomineral nanostructures of manganese oxides in oceanic ferromanganese nodules  

NASA Astrophysics Data System (ADS)

Manganese oxides, which are widespread and of great practical importance, are formed and transformed by the active role of microorganisms. Manganese aggregates occur as both crystallized varieties and disordered fine-grained phases with significant ore grade and up to 50-60 vol % of X-ray amorphous components. X-ray amorphous nanosized Mn oxides in Fe-Mn nodules from the Pacific Ocean floor were examined from the standpoint of their biogenic origin. SEM examination showed abundant mineralized biofilms on the studied samples. The chemical composition of bacterial mass is as follows (wt %): 28.34 MnO, 17.14 Fe2O3, 7.11 SiO2, 2.41 CaO, 17.90 TiO2, 1.74 Na2O, 1.73 Al2O3, 1.30 MgO, 1.25 P2O5, 1.25 SO3, 0.68 CoO, 0.54 CuO, 0.53 NiO, and 0.50 K2O. The chemical composition of fossilized cyanobacterial mats within the interlayer space of nodulesis as follows (wt %): 48.35 MnO, 6.23 Fe2O3, 8.76 MgO, 5.05 Al2O3, 4.45 SiO2, 3.63 NiO, 2.30 Na2O, 2.19 CuO, 1.31 CaO, and 0.68 K2O is direct evidence for participation of bacteria in Mn oxide formation. This phase consists of mineralized glycocalix consisting of nanosized flakes of todorokite. Native metals (Cu, Fe, and Zn) as inclusions 10-20 ?m in size were identified in ferromanganese nodules as well. The formation of nativemetals can be explained by their crystallization at highly reducing conditions maintained by organic matter.

Lysyuk, G. N.

2008-12-01

103

Comparative evaluation of oxidative stress status and manganese availability in plants growing on manganese mine.  

PubMed

This study pioneered an approach that determined the effects of excess manganese (Mn) on three species; Datura stramonium, Alhagi camelthorn and Chenopodium ambrosioides. We investigated their levels of Mn, antioxidative enzymes and oxidative damage biomarkers in plants (zone 1) in and outside (zone 2) the Mn mine. The results showed that total and available Mn were at toxic levels for plants growing on zone 1. The Mn levels in each plant species were higher in leaves, stems and roots. Mn was only accumulated significantly in leaf vacuoles of A. camelthorn. Antioxidative enzyme activities of C. ambrosioides and/or D. stramonium in zone 1 were higher in leaves, stems and then in their roots. Malondialdehyde (MDA) and dityrosine levels were insignificantly higher in tissues of the studied plants in zone 1 with respect to zone 2. The roots of studied plants showed significantly higher levels of these biomarkers in comparison with their leaves in zone 1. Accordingly, antioxidative enzymatic response to Mn-stress in D. stramonium and C. ambrosioides and possibly accumulation of Mn in leaf vacuoles of A. camelthorn, protected them from oxidative damages and involved in their tolerance in Mn mine. PMID:18068229

Boojar, Massod Mashhadi Akbar; Goodarzi, Faranak

2008-11-01

104

Fibrogenic Potential of Intratracheally Instilled Quartz, Ferric Oxide, Fibrous Glass, and Hydrated Alumina in Hamsters  

Microsoft Academic Search

ABSTRAC~ As a first step in the development of an animal model for determining the role of pulmonary fibrosis in the etiology and pathogenesis of lung cancer, the fibrogenic potential of quartz, quartz and ferric oxide adm'inistered together, fibrous glass, and hydrated alumina were studied by multiple intratracheal instillation in groups of male 1ak:LVG Syrian golden hamsters. Dose-related decreases in

ROGER A. RENNE; SANDRA R. ELDRIDGE; TRENT R. LEWIS; DONALD L. STEVENS

1985-01-01

105

Speciation, oxidation state, and reactivity of particulate manganese in marine sediments  

Microsoft Academic Search

Particulate manganese oxides take a significant part in benthic biogeochemical processes of modern marine sediments. Thermodynamics calculations tell us that the reactivity of the different Mn oxides is variable. We describe here a method adapted for marine sediments, which allowed us to extract Mn oxides and determine the mean oxidation state of particulate Mn. Mn oxides are known to be

Pierre Anschutz; Karine Dedieu; Franck Desmazes; Gwénaëlle Chaillou

2005-01-01

106

Cyanamide route to calcium-manganese oxide foams for water oxidation.  

PubMed

In nature, photosynthetic water oxidation is efficiently catalysed at a protein-bound ?-oxido Mn4Ca cluster. This cluster consists of earth abundant, non-toxic elements and serves as a paragon for development of synthetic catalysts. In this study we developed porous calcium-manganese oxides with a unique foam-like nanostructure prepared via a facile and robust synthetic route using cyanamide as a porogen. A series of such oxide foams annealed at different temperatures was characterized by TEM, SEM, XRD, N2 physisorption, and X-ray absorption spectroscopy (XAS) in order to correlate crystallinity, atomic structure, surface area and oxidation state of the materials with catalytic activity. Some of the resulting Ca-Mn oxides show high activity as catalysts for water oxidation in the presence of cerium(iv) ammonium nitrate as a non-oxo transfer oxidant. An amorphous calcium-manganese-oxide foam with 130 m(2) g(-1) surface area and Mn oxidation state of +3.6 was identified to be most active; its activity is superior to previously reported Ca-Mn oxides. At the atomic level, this material shares structural motifs with the biological paragon as revealed by dual-edge XAS at the Mn and Ca K-edge. Rather than nanostructure and surface area, the atomic structure of the Ca-Mn oxide and the extent of structural order appear to be crucial determinants of catalytic activity. Fully disordered low-valent Mn materials as well as high-valent but crystalline Mn-Ca oxides are unreactive. Highly disordered variants of layered manganese oxide with Ca and water molecules interfacing layer fragments are most reactive. PMID:24091767

Baktash, Elham; Zaharieva, Ivelina; Schröder, Marc; Goebel, Caren; Dau, Holger; Thomas, Arne

2013-12-28

107

Manganese(III) binding to a pyoverdine siderophore produced by a manganese(II)-oxidizing bacterium  

NASA Astrophysics Data System (ADS)

The possible roles of siderophores (high affinity chelators of iron(III)) in the biogeochemistry of manganese remain unknown. Here we investigate the interaction of Mn(III) with a pyoverdine-type siderophore (PVD MnB1) produced by the model Mn(II)-oxidizing bacterium Pseudomonas putida strain MnB1. PVD MnB1 confirmed typical pyoverdine behavior with respect to: (a) its absorption spectrum at 350-600 nm, both in the absence and presence of Fe(III), (b) the quenching of its fluorescence by Fe(III), (c) the formation of a 1:1 complex with Fe(III), and (d) the thermodynamic stability constant of its Fe(III) complex. The Mn(III) complex of PVD MnB1 had a 1:1 Mn:pvd molar ratio, showed fluorescence quenching, and exhibited a light absorption spectrum (A max = 408-410 nm) different from that of either PVD MnB1-Fe(III) or uncomplexed PVD MnB1. Mn(III) competed strongly with Fe(III) for binding by PVD MnB1 in culture filtrates (pH 8, 4°C). Equilibration with citrate, a metal-binding ligand, did not detectably release Mn from its PVD MnB1 complex at a citrate/PVD MnB1 molar ratio of 830 (pH 8, 4°C), whereas pyrophosphate under the same conditions removed 55% of the Mn from its PVD MnB1 complex. Most of the PVD MnB1-complexed Mn was released by reaction with ascorbate, a reducing agent, or with EDTA, a ligand that is also oxidized by Mn(III). Data on the competition for binding to PVD MnB1 by Fe(III) vs. Mn(III) were used to determine a thermodynamic stability constant (nominally at 4°C) for the neutral species MnHPVD MnB1 (log K = 47.5 ± 0.5, infinite dilution reference state). This value was larger than that determined for FeHPVD MnB1 (log K = 44.6 ± 0.5). This result has important implications for the metabolism, solubility, speciation, and redox cycling of manganese, as well as for the biologic uptake of iron.

Parker, Dorothy L.; Sposito, Garrison; Tebo, Bradley M.

2004-12-01

108

Manganese oxide microswitch for electronic memory based on neural networks  

NASA Technical Reports Server (NTRS)

A solid-state, resistance tailorable, programmable-once, binary, nonvolatile memory switch based on manganese oxide thin films is reported. MnO(x) exhibits irreversible memory switching from conducting (on) to insulating (off) state, with the off and on resistance ratio of greater than 10,000. The switching mechanism is current-triggered chemical transformation of a conductive MnO(2-Delta) to an insulating Mn2O3 state. The energy required for switching is of the order of 4-20 nJ/sq micron. The low switching energy, stability of the on and off states, and tailorability of the on state resistance make these microswitches well suited as programmable binary synapses in electronic associative memories based on neural network models.

Ramesham, R.; Daud, T.; Moopenn, A.; Thakoor, A. P.; Khanna, S. K.

1989-01-01

109

Unilamellar nanosheet of layered manganese cobalt nickel oxide and its heterolayered film with polycations.  

PubMed

The exfoliation of layered Li[Mn(1/3)Co(1/3)Ni(1/3)]O(2) into individual monolayers could be achieved through the intercalation of quaternary tetramethylammonium (TMA(+)) ions into protonated metal oxide. An effective exfoliation occurred when the TMA(+)/H(+) ratio was 0.5-50. Reactions outside this range produced no colloidal suspension, but all the manganese cobalt nickel oxides precipitated. Atomic force microscopy and transmission electron microscopy clearly demonstrated that exfoliated manganese cobalt nickel oxide nanosheets have a nanometer-level thickness, underscoring the formation of unilamellar nanosheets. The maintenance of the hexagonal atomic arrangement of the manganese cobalt nickel oxide layer upon the exfoliation was confirmed by selected area electron diffraction analysis. According to diffuse reflectance ultraviolet--visible spectroscopy, the exfoliated manganese cobalt nickel oxides displayed distinct absorption peaks at approximately 354 and approximately 480 nm corresponding to the d-d transitions of octahedral metal ions, which contrasted with the featureless spectrum of the pristine metal oxide. In the light of zeta potential data showing the negative surface charge of manganese cobalt nickel oxide nanosheets, a heterolayered film of manganese cobalt nickel oxide and conductive polymers could be prepared through the successive coating process with colloidal suspension and polycations. The UV--vis and X-ray diffraction studies verified the layer-by-layer ordered structure of the obtained heterolayered film, respectively. PMID:20731429

Oh, Eun-Jin; Kim, Tae Woo; Lee, Kyung Min; Song, Min-Sun; Jee, Ah-Young; Lim, Seung Tae; Ha, Hyung-Wook; Lee, Minyung; Choy, Jin-Ho; Hwang, Seong-Ju

2010-08-24

110

Photochemical water oxidation by crystalline polymorphs of manganese oxides: structural requirements for catalysis.  

PubMed

Manganese oxides occur naturally as minerals in at least 30 different crystal structures, providing a rigorous test system to explore the significance of atomic positions on the catalytic efficiency of water oxidation. In this study, we chose to systematically compare eight synthetic oxide structures containing Mn(III) and Mn(IV) only, with particular emphasis on the five known structural polymorphs of MnO2. We have adapted literature synthesis methods to obtain pure polymorphs and validated their homogeneity and crystallinity by powder X-ray diffraction and both transmission and scanning electron microscopies. Measurement of water oxidation rate by oxygen evolution in aqueous solution was conducted with dispersed nanoparticulate manganese oxides and a standard ruthenium dye photo-oxidant system. No Ru was absorbed on the catalyst surface as observed by XPS and EDX. The post reaction atomic structure was completely preserved with no amorphization, as observed by HRTEM. Catalytic activities, normalized to surface area (BET), decrease in the series Mn2O3 > Mn3O4 ? ?-MnO2, where the latter is derived from spinel LiMn2O4 following partial Li(+) removal. No catalytic activity is observed from LiMn2O4 and four of the MnO2 polymorphs, in contrast to some literature reports with polydispersed manganese oxides and electro-deposited films. Catalytic activity within the eight examined Mn oxides was found exclusively for (distorted) cubic phases, Mn2O3 (bixbyite), Mn3O4 (hausmannite), and ?-MnO2 (spinel), all containing Mn(III) possessing longer Mn-O bonds between edge-sharing MnO6 octahedra. Electronically degenerate Mn(III) has antibonding electronic configuration e(g)(1) which imparts lattice distortions due to the Jahn-Teller effect that are hypothesized to contribute to structural flexibility important for catalytic turnover in water oxidation at the surface. PMID:23391134

Robinson, David M; Go, Yong Bok; Mui, Michelle; Gardner, Graeme; Zhang, Zhijuan; Mastrogiovanni, Daniel; Garfunkel, Eric; Li, Jing; Greenblatt, Martha; Dismukes, G Charles

2013-03-01

111

Sodium perxenate permits rapid oxidation of manganese for easy spectrophotometric determination  

NASA Technical Reports Server (NTRS)

Sodium perxenate oxidizes manganese to permanganate almost instantaneously in dilute acid solution and without a catalyst. A solution is prepared by dissolving 200 mg of sodium perxenate in distilled water and diluting to 100 ml.

Bane, R. W.

1967-01-01

112

Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.  

PubMed

Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings. PMID:24733903

Birkner, Nancy; Navrotsky, Alexandra

2014-04-29

113

Serum Chemistries of 'Coturnix coturnix japonica' Given Dietary Manganese Oxide (Mn3O4).  

National Technical Information Service (NTIS)

Plasma creatinine and inorganic phosphorus were increased in manganese oxide (Mn3O4)-treated adult male Coturnix quail, but BUN, BUN/creatinine ratio, uric acid, and total calcium were decreased. Serum enzymes (alkaline phosphatase, glutamic oxaloacetic t...

F. W. Edens J. W. Laskey

1990-01-01

114

The influence of oxidation reduction potential and water treatment processes on quartz lamp sleeve fouling in ultraviolet disinfection reactors.  

PubMed

Ultraviolet (UV) disinfection systems are incorporated into drinking water production facilities because of their broad-spectrum antimicrobial capabilities, and the minimal disinfection by-product formation that generally accompanies their use. Selection of an optimal location for a UV system within a drinking water treatment facility depends on many factors; a potentially important consideration is the effect of system location on operation and maintenance issues, including the potential for fouling of quartz surfaces. To examine the effect of system location on fouling, experiments were conducted at a groundwater treatment facility, wherein aeration, chlorination, and sand filtration were applied sequentially for treatment. In this facility, access to the water stream was available prior to and following each of the treatment steps. Therefore, it was possible to examine the effects of each of these unit operations on fouling dynamics within a UV system. Results indicated zero-order formation kinetics for the fouling reactions at all locations. Increases in oxidation reduction potential, caused by water treatment steps such as aeration and chlorination, increased the rate of sleeve fouling and the rate of irradiance loss within the reactor. Analysis of metals in the sleeve foulant showed that calcium and iron predominate, and relative comparisons of foulant composition to water chemistry highlighted a high affinity for incorporation into the foulant matrix for both iron and manganese, particularly after oxidizing treatment steps. Fouling behavior was observed to be in qualitative agreement with representations of the degree of saturation, relative to the metal:ligand combinations that are believed to comprise a large fraction of the foulants that accumulate on the surfaces of quartz jackets in UV systems used to treat water. PMID:17448518

Wait, Isaac W; Johnston, Cliff T; Blatchley, Ernest R

2007-06-01

115

Preparation and electrochemical performance of novel ruthenium–manganese oxide electrode materials for electrochemical capacitors  

Microsoft Academic Search

A series of novel ruthenium–manganese oxide (denoted as RunMn1?nOx) has been formed by oxidative co-precipitating. The precursor was obtained by mixing Mn(VII) (potassium permanganate), Mn(II) (manganese acetate) and Ru(III) (ruthenium chloride) in neutral aqueous solution at room temperature. The powder of RunMn1?nOx was obtained by calcinating the precursor at appropriate temperature. The crystalline structure and electrochemical performance of the powder

Jianguo Wen; Xiangyuan Ruan; Zhentao Zhou

2009-01-01

116

Ion beam studies on reactive DC sputtered manganese doped indium tin oxide thin films  

Microsoft Academic Search

Indium based transparent conducting oxides doped with magnetic elements have been studied intensively in recent years with a view to develop novel ferromagnetic semiconductors for spin-based electronics. In the present work, we have grown manganese doped indium tin oxide (Mn:ITO) thin films, onto Si and Si\\/SiO2 substrates by DC reactive sputtering of a composite target containing indium–tin alloy and manganese,

S. R. Sarath Kumar; P. Malar; Thomas Osipowicz; S. S. Banerjee; S. Kasiviswanathan

2008-01-01

117

Electrochromic properties of manganese oxide thin films prepared by chemical vapor deposition  

SciTech Connect

Electrochromic manganese oxide thin films were prepared by chemical vapor deposition. The source material was manganese (III) acetylacetonate. Transparent Mn{sub 3}O{sub 4} thin films were obtained at a substrate temperature above 250 C. Oxidation and reduction of the films in a 0.3 M LiClO{sub 4} propylene carbonate solution resulted in desirable changes in optical absorption. Coulometry indicated that the coloration efficiency was 6.03 cm{sup 2}/C.

Maruyama, Toshiro; Osaki, Yoshinori [Kyoto Univ. (Japan). Dept. of Chemical Engineering

1995-09-01

118

Enhanced water electrolysis: Electrocatalytic generation of oxygen gas at manganese oxide nanorods modified electrodes  

Microsoft Academic Search

This study is concerned with the electrocatalytic evolution of oxygen gas at manganese oxide nanorods modified Pt, Au and GC electrodes in 0.5M KOH solution. The electrochemical measurements revealed a significant enhancement of the electrocatalytic activity of the Pt, Au and GC electrodes towards the oxygen evolution reaction (OER) upon the electrodeposition of manganese oxide nanoparticles (nano-MnOx), that is, the

Mohamed S. El-Deab; Mohamed I. Awad; Ahmad M. Mohammad; Takeo Ohsaka

2007-01-01

119

Carbon-supported manganese oxide nanocatalysts for rechargeable lithium–air batteries  

Microsoft Academic Search

Manganese oxide based catalysts were synthesised in the form of nano-particles using a redox reaction of MnSO4 and KMnO4, housed into the pores of a carbon matrix and followed by a thermal treatment. Particle sizes of the manganese oxide nanocatalysts were around 50nm, based on the tunnelling electron microscope measurement. They were uniformly distributed in the carbon matrix, which contributed

H. Cheng; K. Scott

2010-01-01

120

Adhesion enhancement of indium tin oxide (ITO) coated quartz optical fibers  

NASA Astrophysics Data System (ADS)

Transparent conductive indium tin oxide (ITO) film was prepared on optical fiber through a multi-step sol-gel process. The influence of annealing temperature on the adhesion of ITO coated optical fibers was studied. Different surface treatments were applied to improve the adhesion between ITO film and quartz optical fiber. Field emission scanning electron microscopy (FE-SEM), X-ray diffraction analysis (XRD), UV-vis spectrophotometer and Avometer were used to characterize the morphology, crystal structure and photo-electric properties. A thermal shock test was used to evaluate the adhesion. The result shows that the adhesion between ITO film and quartz optical fiber can be strongly influenced by the annealing process, and optimal adhesion can be acquired when annealing temperature is 500 °C. Surface treatments of ultrasonic cleaning and the application of surface-active agent have effectively enhanced the adhesion and photo-electric properties of indium tin oxide film coated quartz optical fiber.

Wang, Yihua; Liu, Jing; Wu, Xu; Yang, Bin

2014-07-01

121

Manganese induces oxidative impairment in cultured rat astrocytes.  

PubMed

Excessive free radical formation has been implicated as a causative factor in neurotoxic damage associated with exposures to a variety of metals, including manganese (Mn). It is well established that Mn accumulates in astrocytes, affecting their ability to indirectly induce and/or exacerbate neuronal dysfunction. The present study examined the effects of Mn treatment on the following endpoints in primary astrocyte cultures: (1) oxidative injury, (2) alterations in high-energy phosphate (adenosine 5'-triphosphate, ATP) levels, (3) mitochondrial inner membrane potential, and (4) glutamine uptake and the expression of glutamine transporters. We quantified astrocyte cerebral oxidative damage by measuring F(2)-isoprostanes (F(2)-IsoPs) using stable isotope dilution methods followed by gas chromatography-mass spectrometry with selective ion monitoring. Our data showed a significant (p < 0.01) elevation in F(2)-IsoPs levels at 2 h following exposure to Mn (100 microM, 500 microM, or 1 mM). Consistent with this observation, Mn induced a concentration-dependent reduction in ATP and the inner mitochondrial membrane potential (DeltaPsi(m)), measured by the high pressure liquid chromatography method and the potentiometric dye, tetramethyl rhodamine ethyl ester, respectively. Moreover, 30 min of pretreatment with Mn (100 microM, 500 microM, or 1 mM) inhibited the net uptake of glutamine (GLN) ((3)H-glutamine) measured at 1 and 5 min. Expression of the messenger RNA coding the GLN transporters, SNAT3/SN1 and SNAT1, was inhibited after 100 and 500 microM Mn treatment for 24 h. Our results demonstrate that induction of oxidative stress, associated mitochondrial dysfunction, and alterations in GLN/glutamate cycling in astrocytes represent key mechanisms by which Mn exerts its neurotoxicity. PMID:17468184

Milatovic, Dejan; Yin, Zhaobao; Gupta, Ramesh C; Sidoryk, Marta; Albrecht, Jan; Aschner, Judy L; Aschner, Michael

2007-07-01

122

Oxidative damage and neurodegeneration in manganese-induced neurotoxicity  

SciTech Connect

Exposure to excessive manganese (Mn) levels results in neurotoxicity to the extrapyramidal system and the development of Parkinson's disease (PD)-like movement disorder, referred to as manganism. Although the mechanisms by which Mn induces neuronal damage are not well defined, its neurotoxicity appears to be regulated by a number of factors, including oxidative injury, mitochondrial dysfunction and neuroinflammation. To investigate the mechanisms underlying Mn neurotoxicity, we studied the effects of Mn on reactive oxygen species (ROS) formation, changes in high-energy phosphates (HEP), neuroinflammation mediators and associated neuronal dysfunctions both in vitro and in vivo. Primary cortical neuronal cultures showed concentration-dependent alterations in biomarkers of oxidative damage, F{sub 2}-isoprostanes (F{sub 2}-IsoPs) and mitochondrial dysfunction (ATP), as early as 2 h following Mn exposure. Treatment of neurons with 500 {mu}M Mn also resulted in time-dependent increases in the levels of the inflammatory biomarker, prostaglandin E{sub 2} (PGE{sub 2}). In vivo analyses corroborated these findings, establishing that either a single or three (100 mg/kg, s.c.) Mn injections (days 1, 4 and 7) induced significant increases in F{sub 2}-IsoPs and PGE{sub 2} in adult mouse brain 24 h following the last injection. Quantitative morphometric analyses of Golgi-impregnated striatal sections from mice exposed to single or three Mn injections revealed progressive spine degeneration and dendritic damage of medium spiny neurons (MSNs). These findings suggest that oxidative stress, mitochondrial dysfunction and neuroinflammation are underlying mechanisms in Mn-induced neurodegeneration.

Milatovic, Dejan [Vanderbilt University Medical Center, Department of Pediatrics/Pediatric Toxicology, 2215-B Garland Avenue, 11415 MRB IV, Nashville, TN 37232-0414 (United States)], E-mail: dejan.milatovic@vanderbilt.edu; Zaja-Milatovic, Snjezana [Vanderbilt University Medical Center, Department of Pediatrics/Pediatric Toxicology, 2215-B Garland Avenue, 11415 MRB IV, Nashville, TN 37232-0414 (United States); Gupta, Ramesh C. [Murray State University, Breathitt Veterinary Center, Hopkinsville, KY (United States); Yu, Yingchun [Vanderbilt University Medical Center, Department of Pediatrics/Pediatric Toxicology, 2215-B Garland Avenue, 11415 MRB IV, Nashville, TN 37232-0414 (United States); Aschner, Michael [Vanderbilt University Medical Center, Department of Pediatrics/Pediatric Toxicology, 2215-B Garland Avenue, 11415 MRB IV, Nashville, TN 37232-0414 (United States); Pharmacology and the Kennedy Center for Research on Human Development, Nashville, TN (United States)

2009-10-15

123

A Comparison of Strontium Sorption to Hydrous Aluminum, Iron, and Manganese Oxides  

Microsoft Academic Search

Strontium sorption to hydrous aluminum (HAO) and manganese (HMO) oxides was studied using macroscopic studies on short- and long-term bases. These studies were compared with previous results for strontium sorption to hydrous ferric oxide (HFO). Sorption to these microporous oxides can be described as a two-step process: a rapid and reversible adsorption reaction to the external surface including the macropores

Paras Trivedi; Lisa Axe

1999-01-01

124

Effects of FeS on Chromium Oxidation Mediated by Manganese Oxidizers  

SciTech Connect

Reductive immobilization of Cr(VI) has been widely explored as a cost-effective approach for Cr-contaminated site remediation. The long-term stability of the immobilized Cr(III), however, is a concern. Cr(III) is known to be oxidized by Mn oxides chemically and Mn-oxides could be produced through microbially mediated Mn(II) oxidation. This study examined the effect of FeS on Cr(III) oxidation mediated by Pseudomonas putida. The results showed that commercial granular FeS did not affect Cr(III) oxidation in the culture of P. putida with Mn(II), but freshly precipitated FeS slurry inhibited Cr(III) oxidation. A 10 mg/l of FeS did not inhibit the microbial growth, but delayed the production of Mn oxides, thus postponing potential Cr(III) oxidation. In the presence of excessive FeS slurry, both Cr(VI) and Mn oxides were reduced rapidly. The reduced Cr(III) could not be re-oxidized as long as freshly formed FeS was present, even in the presence of the manganese oxidizers.

Wu, Youxian; Deng, Baolin

2004-03-31

125

Electron energy-loss safe-dose limits for manganese valence measurements in environmentally relevant manganese oxides.  

PubMed

Manganese (Mn) oxides are among the strongest mineral oxidants in the environment and impose significant influence on mobility and bioavailability of redox-active substances, such as arsenic, chromium, and pharmaceutical products, through oxidation processes. Oxidizing potentials of Mn oxides are determined by Mn valence states (2+, 3+, 4+). In this study, the effects of beam damage during electron energy-loss spectroscopy (EELS) in the transmission electron microscope have been investigated to determine the "safe dose" of electrons. Time series analyses determined the safe dose fluence (electrons/nm(2)) for todorokite (10(6) e/nm(2)), acid birnessite (10(5)), triclinic birnessite (10(4)), randomly stacked birnessite (10(3)), and ?-MnO(2) (<10(3)) at 200 kV. The results show that meaningful estimates of the mean Mn valence can be acquired by EELS if proper care is taken. PMID:22148625

Livi, Kenneth J T; Lafferty, Brandon; Zhu, Mengqiang; Zhang, Shouliang; Gaillot, Anne-Claire; Sparks, Donald L

2012-01-17

126

Water-oxidation catalysis by synthetic manganese oxides--systematic variations of the calcium birnessite theme.  

PubMed

Layered manganese oxides from the birnessite mineral family have been identified as promising heterogeneous compounds for water-oxidation catalysis (WOC), a key reaction for the conversion of renewable energy into storable fuels. High catalytic rates were especially observed for birnessites which contain calcium as part of their structures. With the aim to systematically improve the catalytic performance of such oxide materials, we used a flexible synthetic route to prepare three series of calcium birnessites, where we varied the calcium concentrations, the ripening times of the original precipitates and the temperature of the heat treatment following the initial synthetic steps (tempering) during the preparation process. The products were carefully analysed by a number of analytical techniques and then probed for WOC activity using the Ce(4+)-system. We find that our set of twenty closely related manganese oxides shows large, but somewhat systematic alterations in catalytic rates, indicating the importance of synthesis parameters for maximum catalytic performance. The catalyst of the series for which the highest water-oxidation rate was found is a birnessite of medium calcium content (Ca?:?Mn ratio 0.2?:?1) that had been subjected to a tempering temperature of 400 °C. On the basis of the detailed analysis of the results, a WOC reaction scheme for birnessites is proposed to explain the observed trends in reactivity. PMID:24225769

Frey, Carolin E; Wiechen, Mathias; Kurz, Philipp

2014-03-21

127

Electrochemistry of passive metals modified by manganese oxides deposited by Leptothrix discophora : two-step model verified by ToF-SIMS  

Microsoft Academic Search

We have applied time-of-flight secondary ion mass spectroscopy (ToF-SIMS) to study microbially induced ennoblement of 316L stainless steel and Ti–6Al–4V surfaces exposed to manganese-oxidizing bacteria Leptothrix discophora SP-6. Our observations indicate that manganese biomineralization occurs in two steps: first, the divalent manganese (Mn2+) is oxidized to manganese oxyhydroxide, MnOOH; then the MnOOH is further oxidized to manganese dioxide, MnO2. Both

Xianming Shi; Recep Avci; Zbigniew Lewandowski

2002-01-01

128

Quartz and Hydrous Iron Oxides from the Bee Bluff Structure of South Texas  

NASA Astrophysics Data System (ADS)

There is substantial information showing that the Bee Bluff structure is an impact site and that a residual crater can be identified. The thin hard cap of Carrizo Sandstone, Indio fm calcareous silt and a thin layer of iron-rich siltstone leads to impact processes in which the high pressure release wave proceeds promptly upward leading to a trapping of metamorphic products at the impact interface, a `bottom-up' pressure release. Release of water from goethite binder in the sandstone and from the iron-rich siltstone results in supersaturated steam in mixtures with iron and quartz compounds. Samples with quartz and hydrous iron oxide features are examined with optical microscopy, SEM, EDX and XRD. A quartz grain is found with a well defined PDF set. There is widespread amorphous quartz including lechatleriete. Nanocrystals of ?-goethite in the acicular form are common. A condensation sphere from the `Uvalde Crater Rosetta Stone' shows a complex mixture of hematite, goethite, and alpha quartz with a trace of trydimite. Numerous samples are yet to be analyzed. The crater appears to have features that can serve as an Earth analog to Mars craters. A companion paper in the present proceedings summarizes prior work, adds new site detail, reports impact-loading analysis, and describes overall features of impactite samples from the site.

Graham, R. A.; Martin, M.; Thadhani, N. N.; Morosin, B.

2006-07-01

129

Gold or silver deposited on layered manganese oxide: a functional model for the water-oxidizing complex in photosystem II.  

PubMed

In this report, gold or silver deposited on layered manganese oxide has been synthesized by a simple method and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction spectrometry, atomic absorption spectroscopy, and energy-dispersive X-ray mapping. The gold deposited on layered manganese oxide showed efficient catalytic activity toward water oxidation in the presence of cerium(IV) ammonium nitrate. The properties associated with this compound suggest it is a functional model for the water-oxidizing complex in photosystem II. PMID:23896796

Najafpour, Mohammad Mahdi; Rahimi, Fahimeh; Sedigh, Davood Jafarian; Carpentier, Robert; Eaton-Rye, Julian J; Shen, Jian-Ren; Allakhverdiev, Suleyman I

2013-11-01

130

Reductive leaching of manganese oxide ore in aqueous methanol–sulphuric acid medium  

Microsoft Academic Search

The reductive leaching of manganese oxide ore in aqueous methanol–sulphuric acid was investigated. Studies were conducted at low (30 and 70°C) and high (120–170°C) temperatures, using different acid (0.005–0.30 M H2SO4) and methanol (0–50 vol%) concentrations. Results showed that satisfactory levels of manganese extraction could be achieved during autoclave digestion at temperatures between 150 and 170°C with a reaction mixture

F. W. Y Momade; Zs. G Momade

1999-01-01

131

Oxidative dehydrogenation of 1-butene over manganese oxide octahedral molecular sieves  

SciTech Connect

Steady state kinetic studies of the oxidative dehydrogenation of 1-butene to 1,3-butadiene have been carried out on manganese oxide octahedral molecular sieve (OMS) and octahedral layered (OL) materials. Process parameters such as temperature, feed composition of 1-butene and oxygen, and feed flow rates were varied to study their effect on the activity and selectivity toward the oxidative dehydrogenation process. In addition to process parameters, modifications in the catalyst such as the ion-exchange of tunnel cations and framework substitution of manganese cations were also implemented in order to observe their effects on catalytic activity and the selectivity of 1,3-butadiene production. The ion-exchanged OMS and OL materials showed rapid deactivation with time when subjected to reaction mixtures of 1% 1-butene/0.7% oxygen/Ar and 1% 1-butene/1.1% oxygen/Ar at reaction temperatures greater than 400 C. Their selectivity toward 1,3-butadiene were typically from 15--20% (yield of 4--6%). The other products were cis and trans 2-butene and carbon dioxide and water (40--60% selectivity). Much of the oxidation was therefore nonselective. XRD data have shown that there is a phase change of the original precursor to a mixture of Mn{sub 3}O{sub 4}/MnO or plain MnO, in some cases after exposing the catalyst to reaction conditions for about 1--2 h. Framework substitution of some of the manganese with copper (OMS and OL), however, has led to higher yields and selectivities toward 1,3-butadiene. [Cu] OL-1 showed a yield of 11.8% and a maximum selectivity of 26% toward 1,3-butadiene. [Cu] OMS-1 shows a dramatically high selectivity of 36% and a yield of 11% toward 1,3-butadiene. The effect of framework substitution seems to also impede the phase change to Mn{sub 3}O{sub 4} (Hausmannite). The TPR spectra also show an increase in the lattice oxygen peak by about 40 C, in comparison with ion-exchanged OMS. This is sufficient indication that framework substitution of manganese by copper, partially, has enhanced the stability of the catalyst and improved its capacity for selective oxidation.

Krishnan, V.V.; Suib, S.L. [Univ. of Connecticut, Storrs, CT (United States)] [Univ. of Connecticut, Storrs, CT (United States)

1999-06-10

132

Directed vapor deposition of lithium manganese oxide films  

NASA Astrophysics Data System (ADS)

Electron beam evaporation and sputtering techniques are used to fabricate multilayered thin film structures. However, these techniques suffer several drawbacks resulting from (i) the complex chemistries of the lithiated oxide layers used for the cathode and electrolyte, (ii) the need for precise microstructure control in systems with many metastable phases, and (iii) the low deposition rate and poor material utilization efficiency, which slows the application of this energy storage approach. This dissertation has investigated the use of a novel electron-beam directed vapor deposition (EB-DVD) method for the synthesis of thin film batteries. The dissertation focuses upon the cathode layer of a representative Li-ion thin film battery system and investigates in detail the deposition of lithium manganese oxide films. Many phases with offering various electrochemical performance exist in the Li-Mn-O system and the thesis also investigates the use of processing conditions to control the structure and composition of these cathode layers. In the EB-DVD approach, a high voltage electron beam is used to evaporate a source material in the throat of a nozzle that forms a coaxial transonic gas jet around the vapor. The gas jet entrains and transports the vapor to a substrate where the deposition occurs. Directed simulation of Monte Carlo (DSMC) methods indicated that the vapor plume could be matched to a substrate diameter, and the deposition rate (and vapor utilization efficiency) therefore controlled by adjusting the pressure ratio up and downstream of the nozzle opening in the deposition chamber, and by varying the gas jet density and speed. The highest deposition rates were obtained with a high pressure ratio and the gas jet density. These observations are found to be consistent with the experimental results. Deposition rates up to 16 nm/s could be achieved using the most effective gas entrainment conditions identified by DSMC calculation. This was about a factor of ten times higher than the deposition rate reported for the growth of this material by sputtering (1.5 nm/s) and other vapor deposition techniques. As-deposited lithium manganese oxide films grown on substrates at ambient temperature using high pressure ratios were found to have a disordered structure intermediate between that of the spinel (Fd3m) and rock-salt (Fm3m) phases. Post-annealing of the films in air led to a gradual structural ordering to the Fd3m, spinel structure (the thermodynamically stable phase in air) as the temperature increased to 700°C. The fully transformed films had a pure cubic spinel structure with a slightly manganese deficient composition, Li1+xMn2-yO4 where 0.08 texture. The change in film porosity and texture could be explained by the degree of homogeneous vapor phase clustering that was controllable by the gas jet pressure ratio. When deposition was conducted at elevated temperatures up to 700°C, films with various atomic structures could be fabricated. Films grown below 500°C contained mixtures of the orthorhombic LiMnO2 and the metastable rock-salt structures. Annealing these films in air resulted in a transformation to a single phase spinel structure. Films grown above 600°C had a single phase orthorhombic LiMnO2 structure. Post-annealing of these films in air led to mixtures of t

Jin, Sang-Wan

133

Particle size control and self-assembly processes in novel colloids of nanocrystalline manganese oxide  

SciTech Connect

The synthesis of semiconducting nanocrystals of manganese oxide of controlled sizes and their manipulation to form ordered arrays is described. Nanocrystalline mixed-valent manganese oxides have been prepared as colloidal solutions via reduction of tetraalkylammonium (methyl, ethyl, propyl, and butyl) permanganate salts in aqueous solutions with 2-butanol and ethanol. Reduction with the poorly water miscible 2-butanol produces aqueous colloids for the methyl, ethyl, and propyl systems, whereas 2-butanol colloids are produced for the butyl system. The colloids are reddish-brown, have an average manganese oxidation state of 3.70--3.79, and have been prepared in manganese concentrations up to 0.57 M. The sols will gel upon aging, and the gel time depends on the cation, the amount of alcohol, the temperature, and the concentration of manganese. Small angle neutron scattering (SANS) data indicate that the particles are disklike in shape with radii in the range 20--80 {angstrom} and are largely unassociated in solution. Thin films produced from evaporation of the colloid or spreading of the gel onto glass slides demonstrate long-range order, yielding an X-ray diffraction (XRD) pattern consistent with a structure of CdI{sub 2}-type layers of manganese oxide with tetraalkylammonium cations and water molecules interspersed between the layers. The SANS and XRD evidence are consistent with a mechanism of self-assembly of unassociated layers upon concentration and evaporation. Consistent with a mechanism of quantum confinement, UV/visible spectroscopy of the colloids reveals two absorbances, one near 220 nm and the other in the range 290--310 nm, blue-shifted from the maxima observed for bulk manganese oxide (400 nm). When the samples are aged, these bands shift to the red. The growth of particles in solution with aging, indicated by the shifts in absorbance, has been confirmed by SANS experiments.

Brock, S.L.; Sanabria, M.; Suib, S.L.; Potter, D.I. [Univ. of Connecticut, Storrs, CT (United States)] [Univ. of Connecticut, Storrs, CT (United States); Urban, V.; Thiyagarajan, P. [Argonne National Lab., IL (United States). Intense Pulsed Neutron Source Div.] [Argonne National Lab., IL (United States). Intense Pulsed Neutron Source Div.

1999-09-02

134

Electrochemical Determination of Thermodynamic Properties of Manganomanganic Oxide and Manganese Sesquioxide.  

National Technical Information Service (NTIS)

The Bureau of Mines investigated thermodynamic properties of Mn3O4 (manganomanganic oxide) and Mn2O3 (manganese sesquioxide). The standard Gibbs energies of formation (delta G(f)) of Mn3O4 and Mn2O3 from their lower oxides were determined with high-temper...

S. C. Schaefer

1982-01-01

135

EFFECTS OF SOLAR RADIATION ON MANGANESE OXIDE REACTIONS WITH SELECTED ORGANIC COMPOUNDS  

EPA Science Inventory

The effects of sunlight on aqueous redox reactions between manganese oxides (MnOx) and selected organic substances are reported. o sunlight-induced rate enhancement was observed for the MnOx oxidation of substituted phenols, anisole, o-dichlorobenzene, or p-chloroaniline. n the o...

136

Characterization of the manganese oxide produced by pseudomonas putida strain MnB1  

Microsoft Academic Search

Manganese oxides form typically in natural aqueous environments via Mn(II) oxidation catalyzed by microorganisms, primarily bacteria, but little is known about the structure of the incipient solid-phase products. The Mn oxide produced by a Pseudomonas species representative of soils and freshwaters was characterized as to composition, average Mn oxidation number, and N2 specific surface area. Electron microscopy, X-ray diffraction, and

Mario Villalobos; Brandy Toner; John Bargar; Garrison Sposito

2003-01-01

137

Studies of layered and pillared manganese oxide materials  

NASA Astrophysics Data System (ADS)

Synthetic Birnessite, an octahedral layered manganese oxide material called OL-1 was synthesized with Na+, K+, Na +/Mg2+, K+/Mg2+, Na +/K+ ions as interlayer cations by redox reactions between permanganate and alcohols in a strong basic media. Chromia pillared OL-1s were prepared under reflux conditions using trinuclear chromium hydroxyl acetate as a pillaring agent followed by calcination in a N2 atmosphere at 200°C. Vanadium oxide pillared OL-1s were obtained by intercalating neutral vanadyl acetylacetonate (VOacac) or vanadium acetylacetonate (Vacac) into the interlayer of OL-1 and subsequently calcining in air at 300°C. The synthesis procedures were monitored using X-ray diffraction studies. The resultant materials were characterized by XRD, X-ray absorption, X-ray photoelectron spectra, FTIR, UV-VIS, inductively coupled plasma, transmission electron spectroscopy, scanning electron microscopy with energy dispersive X-ray analysis, potentiometric titration, thermal analyses, TPD measurements, BET surface area and pore size distribution measurements. OL-1 materials prepared using this alcohol route showed enhanced thermal stabilities and increased Mg accommodation compared to OL-1s prepared with other methods. Based on the analysis methods developed here, Na-OL-1 exhibited recoverable and reversible structural and surface O2 oxygen species while K-OL-1 showed higher stability. Na-OL-1 had predominantly Bronsted acid sites resulting from OH groups bonded to Mn on Na-OL-1 surfaces, while the Na/Mg-OL-1 had mainly Lewis acid sites. Large porosity was obtained in chromia pillared OL-1 materials with a narrow pore size distribution centered around 18 A. Although these materials remained "amorphous" as determined by XRD after calcination, TEM morphology studies suggest that the materials were still layered. EXAFS studies indicated the formation of Cr-O-Mn bonds in the resultant materials via comer-shared linkages of CrO6 and MnO6 octahedra. Good crystallinity in VOacac intercalated OL-1 was achieved, which after calcination, led to the formation of mesoporous VOx pillared OL-1 materials with the pore diameters being in the range of 36 to 41 A. The intercalation of bulky neutral inorganic species into the interlayer of OL-1 through an exfoliation route simplified the pillaring process and preparative factors and made the process and pore sizes in the pillared materials controllable.

Ma, Ying

138

Electrode properties of manganese oxide synthesized by sonochemical method in non-aqueous system  

NASA Astrophysics Data System (ADS)

Manganese oxide was prepared by an irradiation of ultrasound to an acetone solution of potassium permanganate. The chemical analyses of gas, solution and products have shown that the synthetic reaction was not peculiar to sonochemistry but similar to the reaction in the basic aqueous solution. The product contained manganese oxide and by-products such as acetate and oxalate. Those by-products were difficult to be removed thoroughly and a part of them resided even after wash. From XRD, the obtained manganese oxide was likely to be ?-MnO 2. The product was examined as electrode material of lithium ion battery, and showed 180 mAh g -1 of specific capacity under 0.5 A g -1 of current density. Moreover, it could be discharged and charged under a high level of current density (ca. 100 mAh g -1 at 17 C). The capacity deterioration caused by cycle repetition was also found to be much small.

Hibino, Mitsuhiro; Zhou, Haoshen; Honma, Itaru

139

Immobilization of methylviologen between well-ordered multilayers of manganese oxide during their electrochemical assembly.  

PubMed

Methylviologen dications (MV2+) were immobilized between layers of manganese oxide during their electrochemical assembly by an anodic route in a homogeneous aqueous Mn2+ solution. This approach yielded a well-ordered multilayer film on a platinum substrate as a result of dense packing of planar MV2+ molecules to stabilize the layered framework. A grazing angle in-plane X-ray diffraction study revealed that the manganese oxide sheets and the molecular planes of inserted MV2+ ions are oriented parallel to the electrode surface. Cyclic voltammetry of the product film indicated an electron transfer from the underlying Pt substrate to inserted methylviologen ions through the manganese oxide sheets. PMID:17279786

Nakayama, Masaharu; Hoyashita, Ryo; Komatsu, Hiroyuki; Muneyama, Etsuhiro; Shoda, Kaoru; Kunishige, Atsuhiro

2007-03-13

140

A very simple method to synthesize nano-sized manganese oxide: an efficient catalyst for water oxidation and epoxidation of olefins.  

PubMed

Nano-sized particles of manganese oxides have been prepared by a very simple and cheap process using a decomposing aqueous solution of manganese nitrate at 100 °C. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction spectrometry have been used to characterize the phase and the morphology of the manganese oxide. The nano-sized manganese oxide shows efficient catalytic activity toward water oxidation and the epoxidation of olefins in the presence of cerium(IV) ammonium nitrate and hydrogen peroxide, respectively. PMID:22858683

Najafpour, Mohammad Mahdi; Rahimi, Fahimeh; Amini, Mojtaba; Nayeri, Sara; Bagherzadeh, Mojtaba

2012-08-28

141

Manganese and Iron Oxidation During Benthic Oxygenic Photosynthesis  

NASA Astrophysics Data System (ADS)

The effect of benthic oxygenic photosynthesis on sediment-water fluxes of manganese and iron was studied for an intertidal sediment. Undisturbed sediments were incubated at an incident surface irradiance of 250 ?E m -2 s -1at 26 °C. Oxygenic photosynthesis was selectively inhibited by adding [3-(3,4-dichloro)-1,1-dimethyl-urea] (DCMU). Benthic fluxes were determined experimentally from the change in manganese and iron concentrations in the overlying water, and were predicted from the pore water concentration gradients at the sediment-water interface assuming molecular diffusion as the transport mechanism. The experimental fluxes of manganese and iron in DCMU-treated cores amounted to -0·84 and -0·59 mmol m -2day -1, respectively, and were directed from the sediment towards the overlying water. In the control cores, showing high rates of benthic oxygenic photosynthesis, the fluxes of manganese and iron were directed towards the sediment, 0·06 and 0·01 mmol m -2day -1, respectively. Mass balances for the 0·1-0·14 cm thick oxic zone, calculated from the experimental fluxes and the predicted fluxes, suggest a minimum areal reoxidation of 0·6 mmol m -2day -1for manganese and of 0·48 mmol m -2day -1for iron in cores showing benthic photosynthesis. The estimated turnover times for dissolved Mn 2+and dissolved Fe 2+in the oxic surface layer during benthic photosynthesis were 0·8 and 0·25 h, respectively. Sediment oxygen microprofiles and the sediment pH profiles suggest that chemical precipitation and reoxidation dominates the retention of manganese and iron during benthic oxygenic photosynthesis in shallow intertidal sediments.

Epping, E. H. G.; Schoemann, V.; de Heij, H.

1998-12-01

142

Efficient benzylic and aliphatic C-H oxidation with selectivity for methylenic sites catalyzed by a bioinspired manganese complex.  

PubMed

A benzimidazole-based nonheme manganese complex efficiently catalyzes benzylic, aliphatic C-H as well as tertiary C-H oxidation with hydrogen peroxide as the oxidant in the presence of acetic acid as additive. (18)O labeling experiments suggest the reaction may proceed via a high-valent manganese-oxo intermediate. PMID:24499500

Shen, Duyi; Miao, Chengxia; Wang, Shoufeng; Xia, Chungu; Sun, Wei

2014-02-21

143

Preparation and characterization of A-site doped Perovskite-type manganese oxides  

NASA Astrophysics Data System (ADS)

Perovskite type manganese oxide is a kind of in solid state chemistry and the field of condensed matter physics are used extensively in the study of materials. Application of sol-gel method on perovskite type manganese oxide doping, preparation out series of samples La0.6BaxSr(0.4-x)MnO3, including powder and flake. After annealing treatment, the X ray diffraction tests of different annealing temperature on the influence of the structure of the samples was studied.

Huang, Yingqun; Li, Xiong; Che, Xinglai; Ju, Hailang

2013-08-01

144

A critical review of the reactivity of manganese oxides with organic contaminants.  

PubMed

Naturally occurring manganese (Mn(iii/iv)) oxides are ubiquitous in a wide range of environmental settings and play a key role in numerous biogeochemical cycles. In addition, Mn(iii/iv) oxides are powerful oxidants that are capable of oxidizing a wide range of compounds. This review critically assesses the reactivity of Mn oxides with organic contaminants. Initial work with organic reductants employed high concentrations of model compounds (e.g., substituted phenols and anilines) and emphasized the reductive dissolution of the Mn oxides. Studies with lower concentrations of organic contaminants demonstrate that Mn oxides are capable of oxidizing a wide range of compounds (e.g., antibacterial agents, endocrine disruptors, and pesticides). Both model compounds and organic contaminants undergo similar reaction mechanisms on the oxide surface. The oxidation rates of organic compounds by manganese oxides are dependent upon solution conditions, such as pH and the presence of cations, anions, or dissolved organic matter. Similarly, physicochemical properties of the minerals used affect the rates of organic compound oxidation, which increase with the average oxidation state, redox potential, and specific surface area of the Mn oxides. Due to their reactivity with contaminants under environmentally relevant conditions, Mn oxides may oxidize contaminants in soils and/or be applied in water treatment applications. PMID:24791271

Remucal, Christina K; Ginder-Vogel, Matthew

2014-05-28

145

Surfactant manganese complexes as models for the oxidation of water  

SciTech Connect

Surfactant manganese complexes have been studied spectroscopically and electrochemically as models for the catalysts involved in the photooxidation of water to produce oxygen. Evidence has been obtained for the participation of the suggested redox cycle Mn/sup II/ to Mn/sup III/ to Mn/sup IV/ and back to Mn/sup II/ with the evolution of oxygen.

Wohlgemuth, R.; Otvos, J.W.; Calvin, M.

1984-02-01

146

Metal Inhibition of Growth and Manganese Oxidation in Pseudomonas putida GB1  

Microsoft Academic Search

Biogenic manganese oxides (MnO2) are ubiquitous nanoparticulate minerals that contribute to the adsorption of nutrient and toxicant metals, the oxidative degradation of various organic compounds, and the respiration of metal-reducing bacteria in aquatic and terrestrial environments. The formation of these minerals is catalyzed by a diverse and widely-distributed group of bacteria and fungi, often through the enzymatic oxidation of aqueous

J. Pena; G. Sposito

2009-01-01

147

The scavenging of silver by manganese and iron oxides in stream sediments collected from two drainage areas of Colorado  

USGS Publications Warehouse

Stream sediments of two well-weathered and aerated drainage areas of Colorado containing anomalous amounts of silver were allowed to react by shaking with nitric acid of different concentrations (1-10M). Silver, manganese, and iron simultaneously dissolved were determined by atomic absorption. The relationship between silver dissolution and the dissolution of manganese and/or iron was evaluated by linear and multiple regression analyses. The highly significant correlation coefficient (r = 0.913) between silver and manganese dissolution suggests that manganese oxides are the major control on the scavenging of silver in these stream sediments, whereas iron oxides only play a secondary role in this regard. ?? 1974.

Chao, T. T.; Anderson, B. J.

1974-01-01

148

Manganese: a transition metal protects nigrostriatal neurons from oxidative stress in the iron-induced animal model of parkinsonism.  

PubMed

It has been suggested that transition metals such as iron and manganese produce oxidative injury to the dopaminergic nigrostriatal system. which may play a critical role in the pathogenesis of Parkinson's disease. Intranigral infusion of ferrous citrate (0 to 8.4 nmol, i.n.) acutely increased lipid peroxidation in the substantia nigra and dopamine turnover in the caudate nucleus. Subsequently, it caused a severe depletion of dopamine levels in the rat caudate nucleus. In contrast to iron's pro-oxidant effect, manganese (up to 30 nmol, i.n.) causes neither lipid peroxidation nor nigral injury/dopamine depletion. Manganese (1.05 to 4.2 nmol, i.n.) dose-dependently protected nigral neurons from iron-induced oxidative injury and dopamine depletion. Manganese also suppressed acute increase in dopamine turnover and contralateral turning behaviour induced by iron. In brain homogenates manganese (0 to 10 microM) concentration-dependently inhibited propagation of lipid peroxidation caused by iron (0 to 5 microM). Without the contribution of manganese-superoxide dismutase manganese was still effective in sodium azide and/or heat-pretreated brain homogenates. Surprisingly, iron but not manganese, catalysed the Fenton reaction or the conversion of hydrogen peroxide to hydroxyl radicals. The results indicate that iron and manganese are two transition metals mediating opposite effects in the nigrostriatal system, as pro-oxidant and antioxidant, respectively. In conclusion, intranigral infusion of iron, but not manganese, provides an animal model for studying the pathophysiological role of oxidant and oxidative stress in nigrostriatal degeneration and Parkinsonism. The present results further suggest that the atypical antioxidative properties of manganese may protect substantia nigra compacta neurons from iron-induced oxidative stress. PMID:9681949

Sziráki, I; Mohanakumar, K P; Rauhala, P; Kim, H G; Yeh, K J; Chiueh, C C

1998-08-01

149

Manganese-lignin peroxidase hybrid from Bjerkandera adusta oxidizes polycyclic aromatic hydrocarbons more actively in the absence of manganese.  

PubMed

We studied polycyclic aromatic hydrocarbon (PAH) oxidation using whole cells and purified manganese-lignin peroxidase (MnLiP) from Bjerkandera adusta UAMH 8258. Although the metabolism of PAHs by B. adusta has been previously demonstrated, less than 5% mineralization of 14C-labelled PAHs occurred in this study over a 40-day period. Oxidation of PAHs was examined by a purified MnLiP hybrid isoenzyme in the presence and absence of manganous ions. The rate of PAH oxidation was decreased by the presence of Mn. The substrates were anthracene and its methyl derivatives, pyrene and benzo[a]pyrene, PAHs with ionization potentials of 7.43 eV or lower. The PAH metabolites of the Mn-independent reaction were identified as the corresponding quinones. The pH optimum of the Mn-independent oxidation was generally about 4, while for the Mn-dependent reaction it was 3. The kinetic constants for the Mn-independent oxidation of 2-methylanthracene at pH 4 were determined, and the values we obtained were a kcat of 145/min, KM,app of 23.8 mmol/L for the aromatic substrate, and KM,app of 0.2 mmol/L for hydrogen peroxide. This is the first report of PAH oxidation by a MnLiP hybrid isoenzyme from white rot fungi. PMID:14735217

Wang, Yuxin; Vazquez-Duhalt, Rafael; Pickard, Michael A

2003-11-01

150

Reduction and dissolution of manganese(III) and manganese(IV) oxides by organics. Part 2. Survey of the reactivity of organics  

SciTech Connect

Reduction and dissolution of manganese(III,IV) oxide suspensions by 27 aromatic and nonaromatic compounds resembling natural organics were examined in order to understand the solubilization reaction in nature. At pH 7.2 10/sup -3/ M formate, fumarate, glycerol, lactate, malonate, phthalate, propanol, propionaldehyde, propionate, and sorbitol did not dissolve appreciable amounts of oxide after 3 h of reaction. The following organics did dissolve manganese oxides under these conditions and are listed in order of decreasing reactivity: 3-methoxycatechol approx. catechol approx. 3,4-dihydroxybenzoic acidapprox. ascorbate > 4-nitro-catechol > thiosalicylate > hydroquinone > 2,5-dihydroxybenzoic acid > syringic acid > o-methoxyphenol > vanillic acidapprox. orcinol approx. 3,5-dihydroxybenzoic acid > resorcinol > oxalite approx. pyruvate approx. salicylate. Relative reactivities of organic substrates are discussed in terms of surface complex formation prior to electron transfer. Dissolution of manganese oxides by marine fulvic acid was enhanced by illumination, verifying that the reaction is photocatalyzed.

Stone, A.T.; Morgan, J.J.

1984-01-01

151

Growth and Dissolution of Iron and Manganese Oxide Films  

SciTech Connect

Growth and dissolution of Fe and Mn oxide films are key regulators of the fate and transport of heavy metals in the environment, especially during changing seasonal conditions of pH and dissolved oxygen. The Fe and Mn are present at much higher concentrations than the heavy metals, and, when Fe and Mn precipitate as oxide films, heavy metals surface adsorb or co-precipitate and are thus essentially immobilized. Conversely, when the Fe and Mn oxide films dissolve, the heavy metals are released to aqueous solution and are thus mobilized for transport. Therefore, understanding the dynamics and properties of Fe and Mn oxide films and thus on the uptake and release of heavy metals is critically important to any attempt to develop mechanistic, quantitative models of the fate, transport, and bioavailablity of heavy metals. A primary capability developed in our earlier work was the ability to grow manganese oxide (MnO{sub x}) films on rhodochrosite (MnCO{sub 3}) substrate in presence of dissolved oxygen under mild alkaline conditions. The morphology of the films was characterized using contact-mode atomic force microscopy. The initial growth began by heteroepitaxial nucleation. The resulting films had maximum heights of 1.5 to 2 nm as a result of thermodynamic constraints. Over the three past years, we have investigated the effects of MnO{sub x} growth on the interactions of MnCO{sub 3} with charged ions and microorganisms, as regulated by the surface electrical properties of the mineral. In 2006, we demonstrated that MnO{sub x} growth could induce interfacial repulsion and surface adhesion on the otherwise neutral MnCO{sub 3} substrate under environmental conditions. Using force-volume microscopy (FVM), we measured the interfacial and adhesive forces on a MnO{sub x}/MnCO{sub 3} surface with a negatively charged silicon nitride tip in a 10-mM NaNO3 solution at pH 7.4. The interfacial force and surface adhesion of MnOx were approximately 40 pN and 600 pN, respectively, whereas those of MnCO{sub 3} were essentially zero. The force differences between MnO{sub x} and MnCO{sub 3} suggest that oxide film growth can focus adsorbates to certain parts of the surface and thereby templating a heterogeneous layout of them. We suspected that the force differences were in part due to the differences in surface electrical properties. In 2007, we investigated two important electrical properties of MnO{sub x} and MnCO{sub 3} surfaces, namely surface potential and ion mobility. Surface potential is a composite quantity that can be linked to the local lattice structure of the reconstructed surface and the adsorption of water layers. The mobile surface ions formed by dissolution can also contribute to surface potential. Using Kelvin probe force microscopy (KPFM) and scanning polarization force microscopy (SPFM), we found that MnOx possessed excess surface potentials of over +200 mV in humid nitrogen and the excess surface potential decreased with increasing relative humidity (i.e., increasing adsorbed water layers on the mineral surface). The dependence of the excess surface potential was attributed to the change of the contributions from mobile ions. These results supported our earlier hypothesis that MnO{sub x} and MnCO{sub 3} had different surface electrical properties. In the third year, we systematically characterized that the change of the electrical double layer (EDL) structure of MnCO{sub 3} surface due to MnO{sub x} growth in aqueous solution and its dependence on pH. The structure of the electrical double layer determines the electrostatic interactions between the mineral surface and charged adsorbates. As described by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, the electrostatic force, together with van der Waals interaction, regulates surface adsorption and bacterial attachment. Once adsorbates establish contact with the surface, they must resist hydraulic shear forces through surface adhesion. The adhesion of mineral surfaces is also affected by their electrostatic interactions with adsorbates. To probe the EDL structure, we ap

Scot T. Martin

2008-12-22

152

Influence of synthesis conditions on the electrochemical properties of nanostructured amorphous manganese oxide cryogels  

NASA Astrophysics Data System (ADS)

Amorphous manganese oxides have received increasing attention in recent years as intercalation cathodes for rechargeable lithium batteries. The sol-gel method is a versatile method for achieving nanostructured amorphous oxides. In this paper, two different sol-gel routes are investigated, where nanostructured amorphous manganese oxide cryogels are obtained via freeze drying Mn(IV) oxide hydrogels formed in situ. In one route the hydrogels are formed by reaction between a solution of sodium permanganate and a solution of disodium fumarate, and in the other route by reaction between a solution of sodium permanganate and solid fumaric acid. Highly homogeneous monolithic manganese oxide hydrogels are obtained from both synthesis routes with precursor concentrations between 0.1 and 0.2 M. The freeze drying method proves to be an efficient method for obtaining nanostructured amorphous manganese oxide cryogels out of the hydrogels. Depending on the synthesis conditions of the hydrogels, the resultant cryogels can yield very high specific capacities for lithium intercalation and excellent rate performance. The cryogel with the best performance exhibits 289 mAh/g at a C/100 rate and 174 mAh/g at a 2 C rate. Strong dependence of electrochemical properties of the cryogels on the synthesis conditions of the parent hydrogels has been observed. The different electrochemical properties are believed to be due to different surface areas and local structures of the cryogels derived from hydrogels synthesized under different conditions. This strong dependence gives rise to the possibility of achieving promising intercalation materials through tailoring the surface area and the local structure of amorphous manganese oxides by adjusting sol-gel synthesis conditions.

Yang, Jingsi; Xu, Jun John

153

Enhanced dissolution of manganese oxide in ice compared to aqueous phase under illuminated and dark conditions.  

PubMed

Manganese is one of the common elements in the Earth's crust and an essential micronutrient for all living things. The reductive dissolution of particulate manganese oxide is a dominant process to enhance mobility and bioavailability of manganese for the use of living organisms. In this work, we investigated the reductive dissolution of manganese oxides trapped in ice (at -20 °C) under dark and light irradiation (visible: ? > 400 nm and UV: ? > 300 nm) in comparison with their counterparts in aqueous solution (at 25 °C). The reductive dissolution of synthetic MnO?, which took place slowly in aqueous solution, was significantly accelerated in ice phase both in the presence and absence of light: about 5 times more dissolution in ice phase than in liquid water after 6 h UV irradiation in the presence of formic acid. The enhanced dissolution in ice was observed under both UV and visible irradiation although the rate was much slower in the latter condition. The reductive dissolution rate of Mn(II)(aq) (under both irradiation and dark conditions) gradually increased with decreasing pH below 6 in both aqueous and ice phases, and the dissolution rates were consistently faster in ice under all tested conditions. The enhanced generation of Mn(II)(aq) in ice can be mainly explained in terms of freeze concentration of electron donors, protons, and MnO? in liquid-like ice grain boundaries. The outdoor solar experiment conducted in Arctic region (Ny-Ålesund, Svalbard, 78°55'N) also showed that the photoreductive dissolution of manganese oxide is enhanced in ice. The present results imply that the dissolution of natural minerals like manganese oxides can be enhanced in icy environments such as polar region, upper atmosphere, and frozen soil. PMID:23153016

Kim, Kitae; Yoon, Ho-Il; Choi, Wonyong

2012-12-18

154

Oxidation and competitive retention of arsenic between iron- and manganese oxides  

NASA Astrophysics Data System (ADS)

Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems that have high sorptive capacities for many trace metals, including arsenic (As). Although numerous studies have characterized the effects of As adsorption onto Fe and Mn oxides individually, the fate of arsenic within mixed systems representative of natural environments has not been completely resolved. Here, we examine oxidation and competitive retention of As on goethite and birnessite using a Donnan reactor, where each oxide is isolated by a semi-permeable membrane through which arsenic can migrate. To initiate the Donnan reactor experiments, As(III) was simultaneously added to both chambers. Arsenic(III) injected into the birnessite chamber is rapidly oxidized to As(V) and then slowly redistributes across both chambers, while that added to the goethite chamber undergoes rapid adsorption; the adsorbed As(III) on goethite subsequently undergoes desorption and diffusion into the birnessite chamber followed by oxidation to As(V). With increased reaction time, As(V) is generated and preferentially partitioned onto goethite due to higher adsorption affinity compared to birnessite. Furthermore, the dissolved concentration of As(V) is controlled by the adsorption capacity of the goethite surface, which when saturated, leads to increased aqueous As concentrations; despite an increase in As(V) loading on birnessite with increasing initial As(III) concentration, the resulting aqueous As(V) concentration increase appreciably once the goethite surface is saturated. Our findings show that Mn oxides in soils act as a temporary sorbent of As, but operate primarily as strong oxidants responsible for transformation of As(III) to As(V), which can then strongly adsorb on the surrounding Fe oxide matrix.

Ying, Samantha C.; Kocar, Benjamin D.; Fendorf, Scott

2012-11-01

155

Impact of interactions between metal oxides to oxidative reactivity of manganese dioxide.  

PubMed

Manganese oxides typically exist as mixtures with other metal oxides in soil-water environments; however, information is only available on their redox activity as single oxides. To bridge this gap, we examined three binary oxide mixtures containing MnO(2) and a secondary metal oxide (Al(2)O(3), SiO(2) or TiO(2)). The goal was to understand how these secondary oxides affect the oxidative reactivity of MnO(2). SEM images suggest significant heteroaggregation between Al(2)O(3) and MnO(2) and to a lesser extent between SiO(2)/TiO(2) and MnO(2). Using triclosan and chlorophene as probe compounds, pseudofirst-order kinetic results showed that Al(2)O(3) had the strongest inhibitory effect on MnO(2) reactivity, followed by SiO(2) and then TiO(2). Al(3+) ion or soluble SiO(2) had comparable inhibitory effects as Al(2)O(3) or SiO(2), indicating the dominant inhibitory mechanism was surface complexation/precipitation of Al/Si species on MnO(2) surfaces. TiO(2) inhibited MnO(2) reactivity only when a limited amount of triclosan was present. Due to strong adsorption and slow desorption of triclosan by TiO(2), precursor-complex formation between triclosan and MnO(2) was much slower and likely became the new rate-limiting step (as opposed to electron transfer in all other cases). These mechanisms can also explain the observed adsorption behavior of triclosan by the binary oxide mixtures and single oxides. PMID:22309023

Taujale, Saru; Zhang, Huichun

2012-03-01

156

The kinetics of iodide oxidation by the manganese oxide mineral birnessite  

USGS Publications Warehouse

The kinetics of iodide (I-) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (??-MnO2) was investigated over the pH range 4.5-6.25. I- oxidation to iodate (IO3-) proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I- from solution was first order with respect to I- concentration, pH, and birnessite concentration, such that -d[I-]/dt = k[I-][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ?? 0.06 ?? 107 M-2 h-1. The data are consistent with the formation of an inner sphere I- surface complex as the first step of the reaction, and the adsorption of I- exhibited significant pH dependence. Both I2, and to a lesser extent, IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and IO3-, as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

Fox, P. M.; Davis, J. A.; Luther, III, G. W.

2009-01-01

157

Retention of tannic acid and condensed tannin by Fe-oxide-coated quartz sand.  

PubMed

This paper intends to shed light on the interactions between tannin and mineral soil particles. For that purpose, aqueous solution of condensed tannin (CT) (derived from Black pine (Pinus nigra var. maritima)) and commercially available tannic acid (TA) were added to purified quartz (Qtz) sand and quartz sand coated with either goethite (Gt) or ferrihydrite (Fh). After solvent removal by evaporation the samples were extracted by water. The extracts were analysed for organic carbon, total phenolics and CT. The extractability of the two tannins was small and increased in the order Qtz-Fh < Qtz-Gt < Qtz. For all mineral samples, TA was more extractable than CT. Bonding of tannins to the mineral samples and the partial peptisation of the Fe oxide coatings upon the binding resulted in complex tannin release curves. Our results suggest that the inextractability of tannins from natural soils and the absence of tannins in soil leachates might be caused by strong adsorption on soil minerals such as Qtz and Fe (oxy)(hydr)oxides. The results of competition experiments with mixtures of both tannins demonstrate that the CTs, and TA in particular, can release large amounts of Fe (oxides), suggesting that the tannins are excellent metal-mobilising agents. We therefore suggest that the fate of tannins in the mineral soil environment is highly dependent on the abundance of weakly bonded secondary oxides. PMID:15914150

Kaal, J; Nierop, K G J; Verstraten, J M

2005-07-01

158

On some relationships between the oxide layers and the cores of deep sea manganese nodules  

Microsoft Academic Search

Some manganese nodules from the Atlantic, Pacific and Indian Ocean have been studied. The structural study with Scanning Electron Microscope (SEM) as well as the mineralogical studies or leaching experiments show that the oxide layer is supported by a frame of material derived from the core, being amorphous silica when the core is made of silicates, and calcium phosphate when

C. Lalou; E. Brichet

1976-01-01

159

Hybrid ternary rice paper-manganese oxide-carbon nanotube nanocomposites for flexible supercapacitors.  

PubMed

Modern portable electronic devices create a strong demand for flexible energy storage devices. Paper based nanocomposites are attractive as sustainable materials for such applications. Here, we directly explored the hydroxyl chemistry of cellulose fibers to synthesize hybrid ternary nanocomposites, comprised of rice paper, single-walled carbon nanotubes (SWCNTs) and manganese oxide nanoparticles. The functional groups on cellulose fibers can react with adsorbed permanganate ions, resulting in uniform deposition of manganese oxide nanoparticles. SWCNTs coated on top of manganese oxide nanoparticles form a highly conductive network connecting individual manganese oxide particles. By using the hybrid ternary composites as electrodes, the assembled two-electrode supercapacitors demonstrated high capacitance (260.2 F g(-1)), energy (9.0 W h kg(-1)), power (59.7 kW kg(-1)), and cycle stability (12% drop after 3000 cycles). In addition, the nanocomposites show good strength and excellent mechanical flexibility, and their capacitance shows negligible changes after bending more than 100 times. These findings suggest that opportunities exist to further explore the rich chemistry of cellulose fibers for innovative energy applications. PMID:24077360

Jiang, Wenchao; Zhang, Kaixi; Wei, Li; Yu, Dingshan; Wei, Jun; Chen, Yuan

2013-11-21

160

Dissociation of manganese(III) oxide as part of a thermochemical water splitting cycle  

Microsoft Academic Search

A three-step thermochemical cycle to produce renewable hydrogen was proposed, which utilizes manganese(III) oxide and thermal energy to produce hydrogen. Most work on the cycle has focused on the hydrogen generating and product recovery steps with little work on the dissociation. It is essential to understand the dissociation because the feasibility of the cycle is based on this reaction having

Todd Michael Francis

2008-01-01

161

Oxidation of cobalt and manganese in seawater via a common microbially catalyzed pathway  

Microsoft Academic Search

Cobalt and manganese uptake onto suspended particles was studied in waters collected from Waquoit Bay, Massachusetts and the upper water column of the Sargasso Sea using radiotracers, coupled with protocols used previously for Mn and Ce to distinguish biological and redox processes.Cobalt uptake onto suspended particles in Waquiot Bay was dominated by microbial oxidation. Moreover, there was a close relationship

James W. Moffett; Jackson Ho

1996-01-01

162

Synthesis and characterisation of manganese oxides from potassium permanganate and citric acid mixtures  

NASA Astrophysics Data System (ADS)

Reaction of KMnO4 and citric acid at different stoichiometric ratio found to give black precipitate after calcined at 500 %C. The black precipitate are classified as two type of manganese oxides mineral namely as bixbyite and hollandite. IR and XRD data were in agreement with the literature report.

Burhanuddin, Syazwani; Yarmo, Ambar; Yamin, Bohari M.

2013-11-01

163

IMPACT OF WATER CHEMISTRY ON MANGANESE REMOVAL DURING OXIDATION/FILTRATION TREATMENT  

EPA Science Inventory

This is a poster showing the purpose and setup of our pilot plant experiments with manganese filtration. The focus is on the differences, effectiveness, and problems with using chlorine and potassium permanganate in oxidation/filtration. The poster will show the results and findi...

164

Electropolymerized manganese porphyrin films as catalytic electrode materials for biomimetic oxidations with molecular oxygen  

Microsoft Academic Search

Some recently published results on the electrocatalytic oxidation of hydrocarbons, olefins and a thioacetamide derivative by molecular oxygen are described. The catalytic process involves electropolymerized manganese porphyrin films as electrode materials in acetonitrile or dichloromethane solution containing 1-methylimidazole and benzoic (or acetic) anhydride, with acceptable catalytic efficiency (up to 500 turnovers of the catalyst per hour) and faradaic yield (up

Fethi Bedioui; Jacques Devynck; Claude Bied-Charreton

1996-01-01

165

Investigation of nanostructured iron and manganese oxides as novel intercalation hosts for lithium  

Microsoft Academic Search

Rechargeable lithium battery systems are being pushed to the limits of their performance in modern portable devices, with increasing demands for higher energy and higher power. The intercalation cathode or positive electrode in these batteries is one of the primary bottlenecks in terms of performance. In this thesis, investigation of nanostructured iron and manganese oxide compounds that show immense promise

Gaurav Jain

2005-01-01

166

SERUM CHEMISTRIES OF COTURNIX JAPONICA GIVEN DIETARY MANGANESE OXIDE (MN3O4)  

EPA Science Inventory

Plasma creatinine and inorganic phosphorus were increased in manganese oxide (Mn3O4)-treated adult male Coturnix quail, but BUN, BUN/creatinine ratio, uric acid, and total calcium were decreased. 2. Serum enzymes (alkaline phosphatase glutamic oxaloacetic transaminase, glutamic p...

167

Diclofenac and 2-anilinophenylacetate degradation by combined activity of biogenic manganese oxides and silver.  

PubMed

The occurrence of a range of recalcitrant organic micropollutants in our aquatic environment has led to the development of various tertiary wastewater treatment methods. In this study, biogenic manganese oxides (Bio-MnOx), biogenic silver nanoparticles (Bio-Ag(0)) and ionic silver were used for the oxidative removal of the frequently encountered drug diclofenac and its dechlorinated form, 2-anilinophenylacetate (APA). Diclofenac was rapidly degraded during ongoing manganese oxidation by Pseudomonas putida MnB6. Furthermore, whereas preoxidized Bio-MnOx, Bio-Ag(0) and Ag(+) separately did not show any removal capacity for diclofenac, an enhanced removal occurred when Bio-MnOx and silver species were combined. Similar results were obtained for APA. Finally, a slow removal of diclofenac but more rapid APA degradation was observed when silver was added to manganese-free P. putida biomass. Combining these results, three mechanisms of diclofenac and APA removal could be distinguished: (i) a co-metabolic removal during active Mn(2+) oxidation by P. putida; (ii) a synergistic interaction between preoxidized Bio-MnOx and silver species; and (iii) a (bio)chemical process by biomass enriched with silver catalysts. This paper demonstrates the use of P. putida for water treatment purposes and is the first report of the application of silver combined with biogenic manganese for the removal of organic water contaminants. PMID:22221449

Meerburg, Francis; Hennebel, Tom; Vanhaecke, Lynn; Verstraete, Willy; Boon, Nico

2012-05-01

168

Manganese oxide micro-supercapacitors with ultra-high areal capacitance  

NASA Astrophysics Data System (ADS)

A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 ?A cm-2.A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 ?A cm-2. Electronic supplementary information (ESI) available: Experimental procedures; optical images of micro-supercapacitors; areal capacitances of samples M-0.3C, M-0.6C and M-0.9C; illustration of interdigital finger electrodes; Nyquist plot of Co(OH)2 deposited on micro-electrodes. See DOI: 10.1039/c3nr00210a

Wang, Xu; Myers, Benjamin D.; Yan, Jian; Shekhawat, Gajendra; Dravid, Vinayak; Lee, Pooi See

2013-05-01

169

Cobalt(II) Oxidation by the Marine Manganese(II)-Oxidizing Bacillus sp. Strain SG-1  

PubMed Central

The geochemical cycling of cobalt (Co) has often been considered to be controlled by the scavenging and oxidation of Co(II) on the surface of manganese [Mn(III,IV)] oxides or manganates. Because Mn(II) oxidation in the environment is often catalyzed by bacteria, we have investigated the ability of Mn(II)-oxidizing bacteria to bind and oxidize Co(II) in the absence of Mn(II) to determine whether some Mn(II)-oxidizing bacteria also oxidize Co(II) independently of Mn oxidation. We used the marine Bacillus sp. strain SG-1, which produces mature spores that oxidize Mn(II), apparently due to a protein in their spore coats (R.A. Rosson and K. H. Nealson, J. Bacteriol. 151:1027-1034, 1982; J. P. M. de Vrind et al., Appl. Environ. Microbiol. 52:1096-1100, 1986). A method to measure Co(II) oxidation using radioactive 57Co as a tracer and treatments with nonradioactive (cold) Co(II) and ascorbate to discriminate bound Co from oxidized Co was developed. SG-1 spores were found to oxidize Co(II) over a wide range of pH, temperature, and Co(II) concentration. Leucoberbelin blue, a reagent that reacts with Mn(III,IV) oxides forming a blue color, was found to also react with Co(III) oxides and was used to verify the presence of oxidized Co in the absence of added Mn(II). Co(II) oxidation occurred optimally around pH 8 and between 55 and 65°C. SG-1 spores oxidized Co(II) at all Co(II) concentrations tested from the trace levels found in seawater to 100 mM. Co(II) oxidation was found to follow Michaelis-Menten kinetics. An Eadie-Hofstee plot of the data suggests that SG-1 spores have two oxidation systems, a high-affinity-low-rate system (Km, 3.3 × 10-8 M; Vmax, 1.7 × 10-15 M · spore-1 · h-1) and a low-affinity-high-rate system (Km, 5.2 × 10-6 M; Vmax, 8.9 × 10-15 M · spore-1 · h-1). SG-1 spores did not oxidize Co(II) in the absence of oxygen, also indicating that oxidation was not due to abiological Co(II) oxidation on the surface of preformed Mn(III,IV) oxides. These results suggest that some microorganisms may directly oxidize Co(II) and such biological activities may exert some control on the behavior of Co in nature. SG-1 spores may also have useful applications in metal removal, recovery, and immobilization processes. Images

Lee, Yoon; Tebo, Bradley M.

1994-01-01

170

Small and low-loss IF SAW filters using zinc oxide film on quartz substrate.  

PubMed

It was previously reported that a Rayleigh wave propagating on a zinc oxide film (ZnO)/ST-cut 35 degrees X propagation quartz substrate structure has the characteristics of an excellent temperature coefficient of frequency (TCF) and a large electromechanical coupling factor k(s). This substrate was applied to various intermediate-frequency (IF) stage filters. During the filter development, it was clarified that a spurious response due to the Love wave was generated. In this study, a new quartz substrate has been developed with a specific cut and propagation angle, that has the same values of the TCF and the coupling factor as the above-mentioned ones. In addition, it does not have the spurious response due to the Love wave. The combination of this specific-cut-angle quartz and ZnO film has been applied to IF filters for wideband code division multiple access (W-CDMA) and narrow-band CDMA (N-CDMA) systems. The insertion losses of their IF filters were 3-5 dB better and their TCF was superior (deltaf/f = 0.37 ppm/degrees C: one-third) compared with the conventional surface acoustic wave (SAW) filters. PMID:15139548

Kadota, Michio; Kando, Hajime

2004-04-01

171

Preparation and characterization of polyaniline\\/manganese dioxide composites via oxidative polymerization: Effect of acids  

Microsoft Academic Search

Polyaniline\\/manganese dioxide (PANI\\/MnO2) composites have been chemically prepared by oxidative polymerization of aniline in acidic medium containing MnO2 as an oxidant. The acids used were; H2SO4, HNO3, HCl, and H3PO4 The prepared composites were characterized by SEM, elemental analysis, FT-IR, XRD, TGA, and magnetic susceptibility. XRD measurements of the composites revealed that the crystal structure of incorporated MnO2 undergone a

Ali H. Gemeay; Ikhlas A. Mansour; Rehab G. El-Sharkawy; Ahmed B. Zaki

2005-01-01

172

Reductive acid leaching of manganese dioxide with glucose: Identification of oxidation derivatives of glucose  

Microsoft Academic Search

The oxidation of glucose during the reductive leaching of pure MnO2 and manganese ore in sulphuric acid at 90 °C MnO2 was investigated. The aim was to identify the derivatives and the chemical pathway of glucose oxidation. Organic derivatives were monitored by HPLC using an Aminex HPX-78H column and UV detection. Chromatographic patterns of leaching solutions showed that major compound

G. Furlani; F. Pagnanelli; L. Toro

2006-01-01

173

In situ quartz crystal microbalance studies of nickel hydrous oxide films in alkaline electrolytes  

SciTech Connect

The microgravimetric characteristics of electrodeposited nickel and composite Ni/Co hydrous oxide films on Au electrodes in KOH electrolytes were examined in situ with a combination of quartz crystal microbalance (QCM) and voltammetric techniques. In the case of freshly prepared {alpha}-Ni(OH){sub 2} hydrous oxide films, denoted as {alpha}-Ni(OH){sub 2}(hyd), the mass increased during oxidation and then decreased upon subsequent reduction. As the redox cycling was continued, however, this behavior gradually reversed, i.e., the mass decreased upon oxidation and then increased following further reduction. This unique effect could be correlated with a shift in the position of the oxidation peak maximum (E{sub p}{sup ox}) in the voltammogram toward more positive potentials, which has been ascribed to the transformation of {alpha}-Ni(OH){sub 2}(hyd) into {beta}-Ni(OH){sub 2}(hyd). Based on these findings, it can be concluded that the mechanism of ionic charge transport in these two types of lattices is markedly different. In contrast, composite Ni/Co (9:1) hydrous oxide films displayed qualitatively the same behavior as pure freshly prepared Ni(OH){sub 2}(hyd) in the same alkaline media regardless of the extent of cycling. This observation provides evidence that the incorporation of cobalt into Ni(OH){sub 2}(hyd) modifies the structural properties of the lattice during the oxidation/reduction process.

Mo, Y.; Hwang, E.; Scherson, D.A. [Case Western Reserve Univ., Cleveland, OH (United States). Dept. of Chemistry

1996-01-01

174

Effect of Precipitation Method and Ce Doping on the Catalytic Activity of Copper Manganese Oxide Catalysts for CO Oxidation  

NASA Astrophysics Data System (ADS)

The influence of Ce doping and the precipitation method on structural properties and the catalytic activity of copper manganese oxides for CO oxidation at ambient temperature have been investigated. The catalysts were characterized by means of the powder X-ray diffraction and N2 adsorption-desorption, the inductively coupled plasma atomic emission spectrometry, the temperature programmed reduction, diffuse reflectance UV-Vis spectra, and the X-ray photoelectron spectroscopy. It was found that after doping little amount of Ce in copper manganese oxide, CeO2 phase was highly dispersed and could prevent sintering and aggregating of the catalyst, the size of the catalytic material was decreased, the reducibility was enhanced, the specific surface area was increased and the formation of the active sites for the oxidation of CO was improved significantly. Therefore, the activity of the rare earth promoted catalyst was enhanced remarkably.

Zhang, Xue-bin; Ma, Kuo-yan; Zhang, Ling-hui; Yong, Guo-ping; Dai, Ya; Liu, Shao-min

2011-02-01

175

Oxidant-induced DNA damage by quartz in alveolar epithelial cells  

Microsoft Academic Search

Respirable quartz has recently been classified as a human carcinogen. Although, studies with quartz using naked DNA as a target suggest that formation of oxyradicals by particles may play a role in the DNA-damaging properties of quartz, it is not known whether this pathway is important for DNA damage in the target cells for quartz carcinogenesis, i.e. alveolar epithelial cells.

Roel P. F. Schins; Ad M. Knaapen; Gonca D. Cakmak; Tingming Shi; Christel Weishaupt; Paul J. A. Borm

2002-01-01

176

Improved manganese-oxidizing activity of DypB, a peroxidase from a lignolytic bacterium  

PubMed Central

DypB, a dye-decolorizing peroxidase from the lignolytic soil bacterium Rhodococcus jostii RHA1, catalyzes the peroxide-dependent oxidation of divalent manganese (Mn2+), albeit less efficiently than fungal manganese peroxidases. Substitution of Asn246, a distal heme residue, with alanine, increased the enzyme’s apparent kcat and kcat/Km values for Mn2+ by 80- and 15-fold, respectively. A 2.2 Å resolution X-ray crystal structure of the N246A variant revealed the Mn2+ to be bound within a pocket of acidic residues at the heme edge, reminiscent of the binding site in fungal manganese peroxidase and very different to that of another bacterial Mn2+-oxidizing peroxidase. The first coordination sphere was entirely comprised of solvent, consistent with the variant’s high Km for Mn2+ (17 ± 2 mM). N246A catalyzed the manganese-dependent transformation of hard wood kraft lignin and its solvent-extracted fractions. Two of the major degradation products were identified as 2,6-dimethoxybenzoquinone and 4-hydroxy-3,5-dimethoxybenzaldehyde, respectively. These results highlight the potential of bacterial enzymes as biocatalysts to transform lignin.

Singh, Rahul; Grigg, Jason C.; Qin, Wei; Kadla, John F.; Murphy, Michael E.P.; Eltis, Lindsay D.

2013-01-01

177

Improved manganese-oxidizing activity of DypB, a peroxidase from a lignolytic bacterium.  

PubMed

DypB, a dye-decolorizing peroxidase from the lignolytic soil bacterium Rhodococcus jostii RHA1, catalyzes the peroxide-dependent oxidation of divalent manganese (Mn(2+)), albeit less efficiently than fungal manganese peroxidases. Substitution of Asn246, a distal heme residue, with alanine increased the enzyme's apparent k(cat) and k(cat)/K(m) values for Mn(2+) by 80- and 15-fold, respectively. A 2.2 Å resolution X-ray crystal structure of the N246A variant revealed the Mn(2+) to be bound within a pocket of acidic residues at the heme edge, reminiscent of the binding site in fungal manganese peroxidase and very different from that of another bacterial Mn(2+)-oxidizing peroxidase. The first coordination sphere was entirely composed of solvent, consistent with the variant's high K(m) for Mn(2+) (17 ± 2 mM). N246A catalyzed the manganese-dependent transformation of hard wood kraft lignin and its solvent-extracted fractions. Two of the major degradation products were identified as 2,6-dimethoxybenzoquinone and 4-hydroxy-3,5-dimethoxybenzaldehyde, respectively. These results highlight the potential of bacterial enzymes as biocatalysts to transform lignin. PMID:23305326

Singh, Rahul; Grigg, Jason C; Qin, Wei; Kadla, John F; Murphy, Michael E P; Eltis, Lindsay D

2013-04-19

178

Decreased methane formation from the hydrogenation of carbon monoxide using zeolite/cobalt-manganese oxide composite catalysts.  

PubMed

A composite catalyst comprising a physical mixture of a zeolite and a cobalt/manganese oxide Fischer-Tropsch catalyst decreases the formation of methane in the hydrogenation of carbon monoxide without significantly affecting conversion. PMID:12240011

Johns, M; Landon, P; Alderson, T; Hutchings, G J

2001-12-01

179

Uraninite oxidation and dissolution induced by manganese oxide: A redox reaction between two insoluble minerals  

NASA Astrophysics Data System (ADS)

The longevity of subsurface U(IV) produced by reduction of U(VI) during in situ bioremediation can be limited by reoxidation to more mobile U(VI) species. Coupling of the biogeochemical cycles of U and Mn may affect the fate and transport of uranium. Manganese oxides can act as a powerful oxidant that accelerates the oxidative dissolution of UO2. This study investigated the physical and chemical factors controlling the interaction between UO2 and MnO2, which are both poorly soluble minerals. A multi-chamber reactor with a permeable membrane was used to eliminate direct contact of the two minerals while still allowing transport of aqueous species. The oxidation of UO2 was not significantly enhanced by MnO2 if the two solids were physically separated. Complete mixing of MnO2 with UO2 led to a much greater extent and rate of U oxidation. When direct contact is not possible, the reaction slowly progresses through release of soluble U(IV) with its adsorption and oxidation on MnO2. Continuously-stirred tank reactors (CSTRs) were used to quantify the steady-state rates of UO2 dissolution induced by MnO2. MnO2 dramatically promoted UO2 dissolution, but the degree of promotion leveled off once the MnO2:UO2 ratio exceeded a critical value. Substantial amounts of U(VI) and Mn(II) were retained on MnO2 surfaces. The total production of Mn(II) was less than that of U(VI), indicating that the fate of Mn products and their impact on UO2-MnO2 reaction kinetics were complicated and may involve formation of Mn(III) phases. At higher dissolved inorganic carbon concentrations, UO2 oxidation by MnO2 was faster and less U(VI) was adsorbed to MnO2. Such an inverse relationship suggested that U(VI) may passivate MnO2 surfaces. A conceptual model was developed to describe the oxidation rate of UO2 by MnO2. This model is potentially applicable to a broad range of water chemistry conditions and is relevant to other environmental redox processes involving two poorly soluble minerals.

Wang, Zimeng; Lee, Sung-Woo; Kapoor, Pratyul; Tebo, Bradley M.; Giammar, Daniel E.

2013-01-01

180

Reductive dissolution of manganese(III/IV) oxides by substituted phenols  

SciTech Connect

Kinetics of the reaction of manganese(III/IV) oxides with 11 substituted phenols were examined in order to assess the importance of manganese oxides in the abiotic degradation of phenolic pollutants. At pH 4.4, 10/sup -4/ M solutions of substituted phenols reduced and dissolved synthetic manganese oxide particles in the following order: p-methylphenol > p-ethylphenol > m-methylphenol > p-chlorophenol > phenol > m-chlorophenol > p-hydroxybenzoate > o-hydroxybenzoate > 4'-hydroxyacetophenone > p-nitrophenol. Rates of reductive dissolution generally decrease as the Hammett constants of ring substituents become more positive, reflecting trends in the basicity, nucleophilicity, and half-wave potential of substituted phenols. Evidence indicates that the fraction of oxide surface sites occupied by substituted phenols is quite low. The apparent reaction order with respect to (H/sup +/) is not a constant but varies between 0.45 and 1.30 as the pH range, phenol concentration, and phenol structure are varied. A mechanism for the surface chemical reaction has been postulated to account for these effects.

Stone, A.T.

1987-10-01

181

Searching for biosignatures using electron paramagnetic resonance (EPR) analysis of manganese oxides.  

PubMed

Manganese oxide (Mn oxide) minerals from bacterial sources produce electron paramagnetic resonance (EPR) spectral signatures that are mostly distinct from those of synthetic simulants and abiogenic mineral Mn oxides. Biogenic Mn oxides exhibit only narrow EPR spectral linewidths (?500 G), whereas abiogenic Mn oxides produce spectral linewidths that are 2-6 times broader and range from 1200 to 3000 G. This distinction is consistent with X-ray structural observations that biogenic Mn oxides have abundant layer site vacancies and edge terminations and are mostly of single ionic species [i.e., Mn(IV)], all of which favor narrow EPR linewidths. In contrast, abiogenic Mn oxides have fewer lattice vacancies, larger particle sizes, and mixed ionic species [Mn(III) and Mn(IV)], which lead to the broader linewidths. These properties could be utilized in the search for extraterrestrial physicochemical biosignatures, for example, on Mars missions that include a miniature version of an EPR spectrometer. PMID:21970705

Kim, Soon Sam; Bargar, John R; Nealson, Kenneth H; Flood, Beverly E; Kirschvink, Joseph L; Raub, Timothy D; Tebo, Bradley M; Villalobos, Mario

2011-10-01

182

Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH  

PubMed Central

Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved in water oxidation by manganese oxides. Pyridine and its derivatives, which have pKa values intermediate to the water ligand bound to manganese(II) and manganese(III), are used as proton-coupled electron transfer induction reagents. The induction of concerted proton-coupled electron transfer is demonstrated by the detection of deuterium kinetic isotope effects and compliance of the reactions with the libido rule. Although proton-coupled electron transfer regulation is essential for the facial redox change of manganese in photosystem II, most manganese oxides impair these regulatory mechanisms. Thus, the present findings may provide a new design rationale for functional analogues of the oxygen-evolving complex for efficient water splitting at neutral pH.

Yamaguchi, Akira; Inuzuka, Riko; Takashima, Toshihiro; Hayashi, Toru; Hashimoto, Kazuhito; Nakamura, Ryuhei

2014-01-01

183

Studies on microbiologically influenced corrosion of SS304 by a novel manganese oxidizer, Bacillus flexus.  

PubMed

A manganese oxidizing bacterium was isolated from the surface of steel scraps and biochemical tests and 16S rRNA sequencing analysis confirmed the isolate as Bacillus flexus. Potentiodynamic polarization curves showed ennoblement of open circuit potential, increased passive current, a lowering of breakdown potential, active re-passivation potential and enhanced cathodic current in the presence of B. flexus. Adhesion studies with B. flexus on SS304 specimens with different surface treatments demonstrated decreased adhesion on passivated and FeCl(3) treated specimens due to the removal of MnS inclusions. The present study provides evidence that surface treatment of stainless steels can reduce adhesion of this manganese oxidizing bacterium and decrease the probability of microbiologically influenced corrosion. PMID:21749279

Anandkumar, B; George, R P; Tamilvani, S; Padhy, N; Mudali, U Kamachi

2011-01-01

184

Hybrid ternary rice paper-manganese oxide-carbon nanotube nanocomposites for flexible supercapacitors  

NASA Astrophysics Data System (ADS)

Modern portable electronic devices create a strong demand for flexible energy storage devices. Paper based nanocomposites are attractive as sustainable materials for such applications. Here, we directly explored the hydroxyl chemistry of cellulose fibers to synthesize hybrid ternary nanocomposites, comprised of rice paper, single-walled carbon nanotubes (SWCNTs) and manganese oxide nanoparticles. The functional groups on cellulose fibers can react with adsorbed permanganate ions, resulting in uniform deposition of manganese oxide nanoparticles. SWCNTs coated on top of manganese oxide nanoparticles form a highly conductive network connecting individual manganese oxide particles. By using the hybrid ternary composites as electrodes, the assembled two-electrode supercapacitors demonstrated high capacitance (260.2 F g-1), energy (9.0 W h kg-1), power (59.7 kW kg-1), and cycle stability (12% drop after 3000 cycles). In addition, the nanocomposites show good strength and excellent mechanical flexibility, and their capacitance shows negligible changes after bending more than 100 times. These findings suggest that opportunities exist to further explore the rich chemistry of cellulose fibers for innovative energy applications.Modern portable electronic devices create a strong demand for flexible energy storage devices. Paper based nanocomposites are attractive as sustainable materials for such applications. Here, we directly explored the hydroxyl chemistry of cellulose fibers to synthesize hybrid ternary nanocomposites, comprised of rice paper, single-walled carbon nanotubes (SWCNTs) and manganese oxide nanoparticles. The functional groups on cellulose fibers can react with adsorbed permanganate ions, resulting in uniform deposition of manganese oxide nanoparticles. SWCNTs coated on top of manganese oxide nanoparticles form a highly conductive network connecting individual manganese oxide particles. By using the hybrid ternary composites as electrodes, the assembled two-electrode supercapacitors demonstrated high capacitance (260.2 F g-1), energy (9.0 W h kg-1), power (59.7 kW kg-1), and cycle stability (12% drop after 3000 cycles). In addition, the nanocomposites show good strength and excellent mechanical flexibility, and their capacitance shows negligible changes after bending more than 100 times. These findings suggest that opportunities exist to further explore the rich chemistry of cellulose fibers for innovative energy applications. Electronic supplementary information (ESI) available: Chemical structures of functional groups on cellulose fibers, the surface water wettability of rice paper, CV curves of supercapacitors at different scan rates, galvanostatic charge-discharge curves of supercapacitors at different current densities, TGA profiles of the SWCNT-MnO2-paper composites synthesized at different temperatures, TEM images of MnO2 particles deposited on rice paper at different temperatures, photographs of supercapacitors under different bending test conditions, and a video of bending and folding the SWCNT-MnO2-paper composites. See DOI: 10.1039/c3nr03010e

Jiang, Wenchao; Zhang, Kaixi; Wei, Li; Yu, Dingshan; Wei, Jun; Chen, Yuan

2013-10-01

185

Low-temperature, manganese oxide-based, thermochemical water splitting cycle  

PubMed Central

Thermochemical cycles that split water into stoichiometric amounts of hydrogen and oxygen below 1,000?°C, and do not involve toxic or corrosive intermediates, are highly desirable because they can convert heat into chemical energy in the form of hydrogen. We report a manganese-based thermochemical cycle with a highest operating temperature of 850?°C that is completely recyclable and does not involve toxic or corrosive components. The thermochemical cycle utilizes redox reactions of Mn(II)/Mn(III) oxides. The shuttling of Na+ into and out of the manganese oxides in the hydrogen and oxygen evolution steps, respectively, provides the key thermodynamic driving forces and allows for the cycle to be closed at temperatures below 1,000?°C. The production of hydrogen and oxygen is fully reproducible for at least five cycles.

Xu, Bingjun; Bhawe, Yashodhan; Davis, Mark E.

2012-01-01

186

Low-temperature, manganese oxide-based, thermochemical water splitting cycle.  

PubMed

Thermochemical cycles that split water into stoichiometric amounts of hydrogen and oxygen below 1,000 °C, and do not involve toxic or corrosive intermediates, are highly desirable because they can convert heat into chemical energy in the form of hydrogen. We report a manganese-based thermochemical cycle with a highest operating temperature of 850 °C that is completely recyclable and does not involve toxic or corrosive components. The thermochemical cycle utilizes redox reactions of Mn(II)/Mn(III) oxides. The shuttling of Na(+) into and out of the manganese oxides in the hydrogen and oxygen evolution steps, respectively, provides the key thermodynamic driving forces and allows for the cycle to be closed at temperatures below 1,000 °C. The production of hydrogen and oxygen is fully reproducible for at least five cycles. PMID:22647608

Xu, Bingjun; Bhawe, Yashodhan; Davis, Mark E

2012-06-12

187

[Adsorption of heavy metal ions on two types of manganese oxides analyzed by AAS and AFS].  

PubMed

Two types of manganese oxides, the octahedral layer structure (OL) and the octahedral molecular tunnel structure (OMS), were controllably synthesized via a facilely hydrothermal route and used to remove heavy metal ions (Pb2+, Cu2+, Ni2+ , Hg2+) in solutions. The heavy metal ion concentrations before and after adsorption were determined by atomic absorption spectroscopy (AAS) and atomic fluorescence spectroscopy (AFS) to evaluate the material adsorption performance. The competitive adsorption of the four ions (Pb2+, Cu2+, Ni2+, Hg2+) on manganese oxides was also investigated. The results showed that OMS exhibited better adsorption ability than OL and had excellent adsorption selectivity to Pb2+, with 98% adsorption efficiency in two minutes. Therefore, this can be proposed as a simple, green and efficient method for treatment of polluted water. PMID:23285900

Xu, Liu; Zhang, Li-Chun; Hou, Xian-Deng; Xu, Kai-Lai

2012-10-01

188

Manganese Oxidizing Bacteria in Guaymas Basin Hydrothermal Fluids, Sediments, and Plumes  

NASA Astrophysics Data System (ADS)

The active seafloor hydrothermal system at Guaymas Basin in the Gulf of California is unique in that spreading centers are covered with thick sediments, and hydrothermal fluids are injected into a semi-enclosed basin. This hydrothermal activity is the source of a large input of dissolved manganese [Mn(II)] into Guaymas Basin, and the presence of a large standing stock of particulate manganese in this basin has been taken as evidence for a short residence time of dissolved Mn(II) with respect to oxidation, suggestive of bacterial catalysis. During a recent Atlantis/Alvin expedition (R/V Atlantis Cruise #7, Leg 11, Jim Cowen Chief Scientist), large amounts of particulate manganese oxides were again observed in Guaymas Basin hydrothermal plumes. The goal of the work presented here was to identify bacteria involved in the oxidation of Mn(II) in Guaymas Basin, and to determine what molecular mechanisms drive this process. Culture-based methods were employed to isolate Mn(II)-oxidizing bacteria from Guaymas Basin hydrothermal fluids, sediments, and plumes, and numerous Mn(II)-oxidizing bacteria were identified based on the formation of orange, brown, or black manganese oxides on bacterial colonies on agar plates. The Mn(II)-oxidizing bacteria were able to grow at temperatures from 12 to 50°C, and a selection of the isolates were chosen for phylogenetic (16S rRNA genes) and microscopic characterization. Endospore-forming Bacillus species accounted for many of the Mn(II)-oxidizing isolates obtained from both hydrothermal sediments and plumes, while members of the alpha- and gamma-proteobacteria were also found. Mn(II)-oxidizing enzymes from previously characterized Bacillus spores are known to be active at temperatures greater than 50°C. The presence of Mn(II)-oxidizing spores - some of which are capable of growing at elevated temperatures - in hydrothermal fluids and sediments at Guaymas Basin suggests that Mn(II) oxidation may be occurring immediately or very soon after hydrothermal fluids emerge from the seafloor.

Dick, G. J.; Tebo, B. M.

2002-12-01

189

Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance  

USGS Publications Warehouse

We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport of trace metals. The basin-scale role of the hyporheic zone is difficult to quantify because stream-tracer studies do not always reliably characterize the cumulative effects of the hyporheic zone. This study determined cumulative effects of hyporheic reactions in Pinal Creek basin by characterizing manganese uptake at several spatial scales (stream-reach scale, hyporheicflow-path scale, and sediment-grain scale). At the stream-reach scale a one-dimensional stream-transport model (including storage zones to represent hyporheic flow paths) was used to determine a reach-averaged time constant for manganese uptake in hyporheic zones, 1/??(s), of 1.3 hours, which was somewhat faster but still similar to manganese uptake time constants that were measured directly in centimeter-scale hyporheic flow paths (1/??(h) = 2.6 hours), and in laboratory batch experiments using streambed sediment (1/?? = 2.7 hours). The modeled depths of subsurface storage zones (d(s) = 4-17 cm) and modeled residence times of water in storage zones (t(s) = 3-12 min) were both consistent with direct measurements in hyporheic flow paths (d(h) = 0-15 cm, and t(h) = 1-25 min). There was also good agreement between reach-scale modeling and direct measurements of the percentage removal of dissolved manganese in hyporheic flow paths (f(s) = 8.9%, and f(h) = 9.3%). Manganese uptake experiments in the laboratory using sediment from Pinal Creek demonstrated (through comparison of poisoned and unpoisoned treatments) that the manganese removal process was enhanced by microbially mediated oxidation. The cumulative effect of hyporheic exchange in Pinal Creek basin was to remove approximately 20% of the dissolved manganese flowing out of the drainage basin. Our results illustrate that the cumulative significance of reactive uptake in the hyporheic zone depends on the balance between chemical reaction rates, hyporheic porewater residence time, and turnover of streamflow through hyporheic flow paths. The similarity between the hyporheic reaction timescale (1??(s) ??? 1.3 hours), and the hyporheic porewater residence timescale (t(s) ??? 8 min) ensured that there was adequate time for the reaction to progress. Furthermore, it was the similarity between the turnover length for stream water flow through hyporheic flow paths (L(s) = stream velocity/storage-zone exchange coefficient ??? 1.3 km) and the length of Pinal Creek (L ??? 7 km), which ensured that all stream water passed through hyporheic flow paths several times. As a means to generalize our findings to other sites where similar types of hydrologic and chemical information are available, we suggest a cumulative significance index for hyporheic reactions, R(s) = ??(s)t(s)L/L(s) (dimensionless); higher values indicate a greater potential for hyporheic reactions to influence geochemical mass balance. Our experience in Pinal Creek basin suggests that values of R(s) > 0.2 characterize systems where hyporheic reactions are likely to influence geochemical mass balance at the drainage-basin scale.

Harvey, J. W.; Fuller, C. C.

1998-01-01

190

Manganese sulfide formation via concomitant microbial manganese oxide and thiosulfate reduction  

Microsoft Academic Search

The dissimilatory metal-reducing bacterium, Shewanella oneidensis MR-1 produced γ-MnS (rambergite) nanoparticles during the concurrent reduction of MnOâ and thiosulfate coupled to Hâ oxidation. To investigate effect of direct microbial reduction of MnOâ on MnS formation, two MR-1 mutants defective in outer membrane c-type cytochromes (ÎmtrC\\/ÎomcA and ÎmtrC\\/ÎomcA\\/ÎmtrF) were also used and it was determined that direct reduction of MnOâ was

Ji-Hoon Lee; David W. Kennedy; Alice Dohnalkova; Dean A. Moore; Ponnusamy Nachimuthu; Samantha B. Reed; Jim K. Fredrickson

2011-01-01

191

Improved lithium manganese oxide spinel\\/graphite Li-ion cells for high-power applications  

Microsoft Academic Search

The degradation mechanism of lithium manganese oxide spinel\\/graphite Li-ion cells using LiPF6-based electrolyte was investigated by a Mn-dissolution approach during high-temperature storage, and by ac impedance measurement using a reference electrode-equipped cell. Through these studies, we confirmed that Mn ions were dissolved from the spinel cathode in the electrolyte and were subsequently reduced on the lithiated graphite electrode surface, due

K Amine; J Liu; S Kang; I Belharouak; Y Hyung; D Vissers; G Henriksen

2004-01-01

192

Structural and Chemical Effects of Lithium Extraction in Spinel Manganese Oxides  

Microsoft Academic Search

XAFS of the manganese K-edge in Linz04 has allowed the chemical and structural effects of lithium exh-action and reinsertion to be characterised and attributed to oxidation-reduction processes. Structural information in the experimental data at low k, as well as that relating to scatterers beyond the first two coordination shells, can be accurately analysed using ab inirio curved-wave multiple scattering simulations.

B. Arnmundsen; D. J. Jones; J. Rozikre

193

Oxidative stress and overexpression of manganese superoxide dismutase in patients with Alzheimer's disease  

Microsoft Academic Search

Substantial evidence supports the hypothesis that oxygen free radicals are involved in various neurodegenerative disorders. To assess the presence of oxidative stress in Alzheimer's disease (AD) we examined the activity of the enzyme copper-zinc superoxide dismutase (CuZnSOD) in red blood cells, the levels of the mitochondrial inducible enzyme manganese superoxide dismutase (MnSOD) mRNA in lymphocytes, and the total radical-trapping antioxidant

M. E De Leo; S Borrello; M Passantino; B Palazzotti; A Mordente; A Daniele; V Filippini; T Galeotti; C Masullo

1998-01-01

194

Studies on microbiologically influenced corrosion of SS304 by a novel manganese oxidizer, Bacillus flexus  

Microsoft Academic Search

A manganese oxidizing bacterium was isolated from the surface of steel scraps and biochemical tests and 16S rRNA sequencing analysis confirmed the isolate as Bacillus flexus. Potentiodynamic polarization curves showed ennoblement of open circuit potential, increased passive current, a lowering of breakdown potential, active re-passivation potential and enhanced cathodic current in the presence of B. flexus. Adhesion studies with B.

B. Anandkumar; R. P. George; S. Tamilvani; N. Padhy; U. Kamachi Mudali

2011-01-01

195

Densification behaviour and properties of manganese oxide doped Y-TZP ceramics  

Microsoft Academic Search

The effect of employing a short sintering holding time of 12min as compared to that of the commonly employed holding time of 120min (2h) on the properties of undoped and 1wt% manganese oxide (MnO2)-doped Y-TZP ceramics were studied. Sintering studies was conducted over the temperature range of 1150–1600°C. Bulk density, Young's modulus, Vickers hardness and fracture toughness tests were carried

S. Ramesh; M. Amiriyan; S. Meenaloshini; R. Tolouei; M. Hamdi; J. Pruboloksono; W. D. Teng

2011-01-01

196

An in situ XRD investigation of singly and doubly promoted manganese oxide methane coupling catalysts  

Microsoft Academic Search

In situ X-ray diffraction (XRD) and concurrent measurements of catalytic performance have been used to characterize the solid phases present during various stages in the history of working methane coupling catalytic systems. Three such systems were studied: unpromoted, K-promoted, and KCl-promoted manganese oxide. In each case the effect of pulses of CHClâ on the activity, selectivity, and catalyst structure was

G. D. Moggridge; T. Rayment; R. M. Lambert

1992-01-01

197

Alkali metal ion-selective electrodes based on relevant alkali metal ion doped manganese oxides  

Microsoft Academic Search

Potentiometric properties of manganese oxides doped with alkali metal ions (Na+, K+, Rb+ and Cs+), which were prepared by heating mixed solutions (starting solution) of each alkali metal and Mn2+ ions, were examined. Electrodes based on mixed phases of Nao44MnO2\\/Mn2O3 and hollandite KMn8O16\\/M2O3 found by X-ray powder diffraction (XRD) exhibited Na+- and K+-selective responses with a near-Nernstian slope, respectively, when

Yukinori Tani; Yoshio Umezawa

1998-01-01

198

Radium, thorium, and actinium extraction from seawater using an improved manganese-oxide-coated fiber  

Microsoft Academic Search

Laboratory experiments were conducted to determine the efficiency with which improved manganese-oxide-coated acrylic fibers extract radium, thorium, and actinium from seawater. Tests were made using surface seawater spiked with 227Ac, 227Th, and 223Ra. For sample volumes of approximately 30 liters and flow rates up to 0.5 liters per minute, radium and actinium are removed quantitatively. Approximately 80-95% of the thorium

David F. Reid; Robert M. Key; David R. Schink

1979-01-01

199

Overexpression of Manganese Superoxide Dismutase Protects Lung Epithelial Cells against Oxidant Injury  

Microsoft Academic Search

To determine whether overexpression of antioxidant enzymes in lung epithelial cells prevents damage from oxidant injury, stable cell lines were generated with complementary DNAs en- coding manganese superoxide dismutase (MnSOD) and\\/or catalase (CAT). Cell lines overexpressing MnSOD, CAT, or Mn- SOD 1 CAT were assessed for tolerance to hyperoxia or para- quat. After exposure to 95% O 2 for 10

Anatoliy M. Ilizarov; Hshi-Chi Koo; Jeffrey A. Kazzaz; Lin L. Mantell; Yuchi Li; Ritu Bhapat; Simcha Pollack; Stuart Horowitz; Jonathan M. Davis

200

Weathering of the Rio Blanco Quartz Diorite, Luquillo Mountains, Puerto Rico: Coupling Oxidation, Dissolution, And Fracturing  

SciTech Connect

In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers ({approx}2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive {Delta}V of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction. Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 {angstrom}, forming 'altered biotite'. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 x 10{sup -14} mol biotite m{sup -2} s{sup -1}. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 {micro}m resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone. Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 x 10{sup -13} mol hornblende m{sup -2} s{sup -1}: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O{sub 2} at the bedrock-saprolite interface.

Buss, H.L.; Sak, P.B.; Webb, S.M.; Brantley, S.L.

2009-05-12

201

Upgrading of Low-Grade Manganese Ore by Selective Reduction of Iron Oxide and Magnetic Separation  

NASA Astrophysics Data System (ADS)

The utilization of low-grade manganese ores has become necessary due to the intensive mining of high-grade ores for a long time. In this study, calcined ferruginous low-grade manganese ore was selectively reduced by CO, which converted hematite to magnetite, while manganese oxide was reduced to MnO. The iron-rich component was then separated by magnetic separation. The effects of the various reduction parameters such as particle size, reduction time, temperature, and CO content on the efficiency of magnetic separation were studied by single-factor experiments and by a comprehensive full factorial experiment. Under the best experimental conditions tested, the manganese content in the ore increased from around 36 wt pct to more than 44 wt pct, and almost 50 wt pct of iron was removed at a Mn loss of around 5 pct. The results of the full factorial experiments allowed the identification of the significant effects and yielded regression equations for pct Fe removed, Mn/Fe, and pct Mn loss that characterize the efficiency of the upgrading process.

Gao, Yubo; Olivas-Martinez, M.; Sohn, H. Y.; Kim, Hang Goo; Kim, Chan Wook

2012-12-01

202

Biological water-oxidizing complex: a nano-sized manganese-calcium oxide in a protein environment.  

PubMed

The resolution of Photosystem II (PS II) crystals has been improved using isolated PS II from the thermophilic cyanobacterium Thermosynechococcus vulcanus. The new 1.9 Å resolution data have provided detailed information on the structure of the water-oxidizing complex (Umena et al. Nature 473: 55-61, 2011). The atomic level structure of the manganese-calcium cluster is important for understanding the mechanism of water oxidation and to design an efficient catalyst for water oxidation in artificial photosynthetic systems. Here, we have briefly reviewed our knowledge of the structure and function of the cluster. PMID:22941557

Najafpour, Mohammad Mahdi; Moghaddam, Atefeh Nemati; Yang, Young Nam; Aro, Eva-Mari; Carpentier, Robert; Eaton-Rye, Julian J; Lee, Choon-Hwan; Allakhverdiev, Suleyman I

2012-10-01

203

Adsorption of Ribose Nucleotides on Manganese Oxides with Varied Mn/O Ratio: Implications for Chemical Evolution  

NASA Astrophysics Data System (ADS)

Manganese exists in different oxidation states under different environmental conditions with respect to redox potential. Various forms of manganese oxides, namely, Manganosite (MnO), Bixbyite (Mn2O3), Hausmannite (Mn3O4) and Pyrolusite (MnO2) were synthesized and their possible role in chemical evolution studied. Adsorption studies of ribose nucleotides (5'-AMP, 5'-GMP, 5'-CMP and 5'-UMP) on these manganese oxides at neutral pH, revealed a higher binding affinity to manganosite (MnO) compared to the other manganese oxides. That manganese oxides having a lower Mn-O ratio show higher binding affinity for the ribonucleotides indirectly implies that such oxides may have provided a surface onto which biomonomers could have been concentrated through selective adsorption. Purine nucleotides were adsorbed to a greater extent compared to the pyrimidine nucleotides. Adsorption data followed Langmuir adsorption isotherms, and X m and K L values were calculated. The nature of the interaction and mechanism was elucidated by infrared spectral studies conducted on the metal-oxide and ribonucleotide-metal-oxide adducts.

Bhushan, Brij; Shanker, Uma; Kamaluddin

2011-10-01

204

Graphene oxide thin film coated quartz crystal microbalance for humidity detection  

NASA Astrophysics Data System (ADS)

In this paper, we demonstrated that chemically derived graphene oxide (GO) thin film as a humidity sensitive coating deposited on quartz crystal microbalances (QCMs) for humidity detection. By exposing GO thin film coated QCMs to various relative humidity (RH) environments at room temperature, the humidity sensing characteristics of the QCMs such as sensitivity and linearity, response and recovery, humidity hysteresis were investigated. The experiment results show that GO thin film coated QCMs exhibit an excellent humidity sensing performance. Moreover, the possible humidity sensing mechanism of GO thin film coated QCMs was also investigated by monitoring the crystal's motional resistance change. It is suggested that the frequency response of the QCMs is dependent on water molecules adsorbed/desorbed masses on GO thin film in the low RH range, and on both water molecules adsorbed/desorbed masses on GO thin film and variations in interlayer expansion stress of GO thin film derived from swelling effect in the high RH range.

Yao, Yao; Chen, Xiangdong; Guo, Huihui; Wu, Zuquan

2011-06-01

205

Manganese (Mn) Oxidation Increases Intracellular Mn in Pseudomonas putida GB-1  

PubMed Central

Bacterial manganese (Mn) oxidation plays an important role in the global biogeochemical cycling of Mn and other compounds, and the diversity and prevalence of Mn oxidizers have been well established. Despite many hypotheses of why these bacteria may oxidize Mn, the physiological reasons remain elusive. Intracellular Mn levels were determined for Pseudomonas putida GB-1 grown in the presence or absence of Mn by inductively coupled plasma mass spectrometry (ICP-MS). Mn oxidizing wild type P. putida GB-1 had higher intracellular Mn than non Mn oxidizing mutants grown under the same conditions. P. putida GB-1 had a 5 fold increase in intracellular Mn compared to the non Mn oxidizing mutant P. putida GB-1-007 and a 59 fold increase in intracellular Mn compared to P. putida GB-1 ?2665 ?2447. The intracellular Mn is primarily associated with the less than 3 kDa fraction, suggesting it is not bound to protein. Protein oxidation levels in Mn oxidizing and non oxidizing cultures were relatively similar, yet Mn oxidation did increase survival of P. putida GB-1 when oxidatively stressed. This study is the first to link Mn oxidation to Mn homeostasis and oxidative stress protection.

Banh, Andy; Chavez, Valarie; Doi, Julia; Nguyen, Allison; Hernandez, Sophia; Ha, Vu; Jimenez, Peter; Espinoza, Fernanda; Johnson, Hope A.

2013-01-01

206

Manganese-oxidizing photosynthesis before the rise of cyanobacteria  

PubMed Central

The emergence of oxygen-producing (oxygenic) photosynthesis fundamentally transformed our planet; however, the processes that led to the evolution of biological water splitting have remained largely unknown. To illuminate this history, we examined the behavior of the ancient Mn cycle using newly obtained scientific drill cores through an early Paleoproterozoic succession (2.415 Ga) preserved in South Africa. These strata contain substantial Mn enrichments (up to ?17 wt %) well before those associated with the rise of oxygen such as the ?2.2 Ga Kalahari Mn deposit. Using microscale X-ray spectroscopic techniques coupled to optical and electron microscopy and carbon isotope ratios, we demonstrate that the Mn is hosted exclusively in carbonate mineral phases derived from reduction of Mn oxides during diagenesis of primary sediments. Additional observations of independent proxies for O2—multiple S isotopes (measured by isotope-ratio mass spectrometry and secondary ion mass spectrometry) and redox-sensitive detrital grains—reveal that the original Mn-oxide phases were not produced by reactions with O2, which points to a different high-potential oxidant. These results show that the oxidative branch of the Mn cycle predates the rise of oxygen, and provide strong support for the hypothesis that the water-oxidizing complex of photosystem II evolved from a former transitional photosystem capable of single-electron oxidation reactions of Mn.

Johnson, Jena E.; Webb, Samuel M.; Thomas, Katherine; Ono, Shuhei; Kirschvink, Joseph L.; Fischer, Woodward W.

2013-01-01

207

Oxidative degradation of non-phenolic lignin during lipid peroxidation by fungal manganese peroxidase.  

PubMed

A non-phenolic lignin model dimer, 1-(4-ethoxy-3-methoxyphenyl)-2-phenoxypropane-1,3-diol, was oxidized by a lipid peroxidation system that consisted of a fungal manganese peroxidase, Mn(II), and unsaturated fatty acid esters. The reaction products included 1-(4-ethoxy-3-methoxyphenyl)-1-oxo-2-phenoxy-3-hydroxypropane and 1-(4-ethoxy-3-methoxyphenyl)-1-oxo-3-hydroxypropane, indicating that substrate oxidation occurred via benzylic hydrogen abstraction. The peroxidation system depolymerized both exhaustively methylated (non-phenolic) and unmethylated (phenolic) synthetic lignins efficiently. It may therefore enable white-rot fungi to accomplish the initial delignification of wood. PMID:7957943

Bao, W; Fukushima, Y; Jensen, K A; Moen, M A; Hammel, K E

1994-11-14

208

Manganese-oxidizing photosynthesis before the rise of cyanobacteria  

NASA Astrophysics Data System (ADS)

The evolution of oxygenic photosynthesis was a singularity that fundamentally transformed our planet's core biogeochemical cycles and changed the redox structure of Earth's surface, crust, and mantle. To date, understanding the evolution of this molecular machinery has largely been derived from comparative biology. Several biochemical innovations enabled water-splitting, including a central photosynthetic pigment with a higher redox potential and coupled photosystems. However the critical photochemical invention was the water oxidizing complex (WOC) of photosystem II, a cubane cluster of four redox-active Mn atoms and a Ca atom bound by oxo bridges, that couple the single electron photochemistry of the photosystem to the four-electron oxidation of water to O2. Transitional forms of the WOC have been postulated, including an Mn-containing catalase-like peptide using an H2O2 donor, or uptake and integration of environmental Mn-oxides. One attractive hypothesis from the perspective of modern photo-assembly of the WOC posits an initial Mn(II)-oxidizing photosystem as a precursor to the WOC (Zubay, 1996; Allen and Martin, 2007). To test these hypotheses, we studied the behavior of the ancient Mn cycle captured by 2415 ± 6 Ma scientific drill cores retrieved by the Agouron Drilling Project through the Koegas Subgroup in Griqualand West, South Africa. This succession contains substantial Mn-enrichments (up to 17 wt.% in bulk). To better understand the petrogenesis and textural context of these deposits, we employed a novel X-ray absorption spectroscopy microprobe to make redox maps of ultra-thin sample sections at a 2?m scale. Coupled to light and electron microscopy and C isotopic measurements, we observe that all of the Mn is present as Mn(II), contained within carbonate minerals produced from early diagenetic reduction of Mn-oxide phases with organic matter. To assay the environmental oxidant responsible for the production of the Mn-oxides we examined two independent techniques sensitive to low levels of environmental O2—multiple sulfur isotopes analyzed using whole-rock IRMS and texture-specific SIMS techniques, and the presence of redox-sensitive detrital grains. Despite the conspicuous oxidation of Mn, both proxies reveal a lack of significant molecular oxygen present in the environment at this time (O2 << 1 ppm). These results provide strong geological support for the idea that an early Mn-oxidizing photosystem once existed as a transitional form prior to the evolution of the WOC of photosystem II and oxygenic photosynthesis. [Refs: Zubay J (1996) Origins of Life on the Earth and in the Cosmos, Academic Press: San Diego. Allen JF, Martin W (2007) Evolutionary biology: Out of thin air, Nature, 445, 610-612.

Johnson, J. E.; Webb, S.; Thomas, K. S.; Ono, S.; Kirschvink, J. L.; Fischer, W. W.

2012-12-01

209

c-Type Cytochromes and Manganese Oxidation in Pseudomonas putida MnB1  

PubMed Central

Pseudomonas putida MnB1 is an isolate from an Mn oxide-encrusted pipeline that can oxidize Mn(II) to Mn oxides. We used transposon mutagenesis to construct mutants of strain MnB1 that are unable to oxidize manganese, and we characterized some of these mutants. The mutants were divided into three groups: mutants defective in the biogenesis of c-type cytochromes, mutants defective in genes that encode key enzymes of the tricarboxylic acid cycle, and mutants defective in the biosynthesis of tryptophan. The mutants in the first two groups were cytochrome c oxidase negative and did not contain c-type cytochromes. Mn(II) oxidation capability could be recovered in a c-type cytochrome biogenesis-defective mutant by complementation of the mutation.

Caspi, Ron; Tebo, Bradley M.; Haygood, M. G.

1998-01-01

210

Active manganese oxide: a novel adsorbent for treatment of wastewater containing azo dye.  

PubMed

A new variety of active manganese oxide was prepared, characterized, and tested for its potential of adsorbing Congo Red, a dis-azo dye, from aqueous solutions. Both equilibrium and kinetics were investigated over different values of process parameters such as temperature (25-45 degrees C), adsorbent loading (0.4-0.6%), initial dye concentration (50-500 mg/L), presence of salts (sodium sulphate, 500 mg/L) and the oxygen content (MnO(x), x=1.2, 1.33 and 2) of the adsorbent. The equilibrium adsorption data were fitted to Langmuir and Freundlich isotherms. Langmuir adsorption capacity of the sorbent (x=1.33) for Congo Red was 38.6 mg/g at room temperature which is substantially higher than those for commercial manganese dioxide, red mud, coir pith, activated carbon, and fly ash. The kinetic data were best interpreted using a pseudo-second order model. The results show that the active manganese oxide used in this work removes the dye by reversible adsorption and has the potential for practical use for remediation of textile industry effluents. PMID:19955624

Chakrabarti, S; Dutta, B K; Apak, R

2009-01-01

211

Ion beam studies on reactive DC sputtered manganese doped indium tin oxide thin films  

NASA Astrophysics Data System (ADS)

Indium based transparent conducting oxides doped with magnetic elements have been studied intensively in recent years with a view to develop novel ferromagnetic semiconductors for spin-based electronics. In the present work, we have grown manganese doped indium tin oxide (Mn:ITO) thin films, onto Si and Si/SiO 2 substrates by DC reactive sputtering of a composite target containing indium-tin alloy and manganese, in a gas mixture of oxygen and argon. Glancing angle X-ray diffraction (GXRD) studies reveal the polycrystalline nature of the films. Magnetic measurements carried out using vibrating sample magnetometer (VSM) suggest that the films are ferromagnetic at room temperature, with a saturation magnetization of ˜22.8 emu/cm 3. The atomic percentages of In, Sn, Mn and O, as estimated using Rutherford backscattering spectrometry (RBS) are 37.0, 4.0, 1.6 and 57.4, respectively. RBS measurements reveal that the interface of the films with Si substrate has a ˜30 nm thick intermediate layer. This layer consists of oxygen, silicon, indium, tin and manganese, in the ratio 1:0.56:0.21:0.07:0.03, indicative of diffusion of elements across the interface. The films on Si/SiO 2, on the other hand, have a sharp interface.

Sarath Kumar, S. R.; Malar, P.; Osipowicz, Thomas; Banerjee, S. S.; Kasiviswanathan, S.

2008-04-01

212

Characterization of layered lithium nickel manganese oxides synthesized by a novel oxidative coprecipitation method and their electrochemical performance as lithium insertion electrode materials  

Microsoft Academic Search

Lithium nickel manganese oxides, LiNi{sub 1-y}Mn{sub y}O{sub 2+δ}, (0 ⤠y ⤠0.5) were prepared via a new solution technique. The corresponding mixed nickel manganese hydroxide precursors were synthesized in an oxidative coprecipitation method. Subsequent calcination in the presence of LiOH leads to crystalline products with a partially disordered layered-type α-NaFeOâ structure. X-ray photoelectron spectroscopic analysis has indicated a strong

Michael E. Spahr; P. Novak; B. Schnyder; O. Haas; R. Nesper

1998-01-01

213

Directed vapor deposition of lithium manganese oxide films  

Microsoft Academic Search

Electron beam evaporation and sputtering techniques are used to fabricate multilayered thin film structures. However, these techniques suffer several drawbacks resulting from (i) the complex chemistries of the lithiated oxide layers used for the cathode and electrolyte, (ii) the need for precise microstructure control in systems with many metastable phases, and (iii) the low deposition rate and poor material utilization

Sang-Wan Jin

2008-01-01

214

Microbial reduction of manganese oxides - Interactions with iron and sulfur  

NASA Technical Reports Server (NTRS)

Alteromonas putrefaciens (strain MR-1) is capable of rapid Mn(IV) reduction under conditions of neutral pH and temperatures characteristic of the Oneida Lake, New York, sediments from which it was isolated. MR-1 also reduces Fe(3+) to Fe(2+), and disproportionates thiosulfate to sulfide and sulfite; independently, the Fe(2+) and sulfide act as rapid reductants of Mn. The addition of Fe(3+) or thiosulfate to cultures of MR-1 in the presence of oxidized Mn increases the rate and the extent of Mn reduction relative to that observed in the absence of Fe(3+) or thiosulfate. Furthermore, when Fe(3+) and Mn oxides are present conjointly, Fe(2+) does not appear until the reduction of the oxidized Mn is complete. These results demonstrate that the observed rates of Fe(2+) and sulfide production may underestimate the total rates of Fe and sulfate reduction in those environments containing oxidized Mn. These results also demonstrate the potential impact that a single microbe can exert on sediment geochemistry, and provide the basis for preliminary models of the complexity of microbial and geochemical interactions that occur.

Myers, Charles R.; Nealson, Kenneth H.

1988-01-01

215

Synthesis, characterisation and catalytic evaluation of iron–manganese mixed oxide pillared clay for VOC decomposition reaction  

Microsoft Academic Search

A series of iron and manganese mixed oxide pillared clay with varying manganese to iron ratio has been successfully synthesized. Prepared materials were characterized by low angle XRD, TG\\/DTA, hydrogen TPR and nitrogen adsorption desorption experiment. All the materials were found to be thermally stable up to 500°C having basal spacing ?16.5?. Surface area and pore volume increases with the

T. Mishra; P. Mohapatra; K. M. Parida

2008-01-01

216

Microbial reduction of manganese oxides: Interactions with iron and sulfur  

SciTech Connect

Alteromonas putrefaciens (strain MR-1) is capable of rapid Mn(IV) reduction under conditions of neutral pH and temperatures characteristic of the Oneida Lake, New York, sediments from which it was isolated. MR-1 also reduces Fe{sup 3+} to Fe{sup 2+}, and disproportionates thiosulfate to sulfide and sulfite; independently, the Fe{sup 2+} and sulfide act as rapid reductants of Mn. The addition of Fe{sup 3+} or thiosulfate to cultures of MR-1 in the presence of oxidized Mn increases the rate and extent of Mn reduction relative to that observed in the absence of Fe{sup 3+} or thiosulfate. Furthermore, when Fe{sup 3+} and Mn oxides are present conjointly, Fe{sup 2+} and sulfide production may underestimate the total rates of Fe and sulfate reduction in those environments containing oxidized Mn. These results also demonstrate the potential impact that a single microbe can exert on sediment geochemistry, and provide the basis for preliminary models of the complexity of microbial and geochemical interactions that occur.

Myers, C.R.; Nealson, K.H. (Univ. of Wisconsin, Milwaukee (USA))

1988-11-01

217

Fragments of layered manganese oxide are the real water oxidation catalyst after transformation of molecular precursor on clay.  

PubMed

A binuclear manganese molecular complex [(OH2)(terpy)Mn(?-O)2Mn(terpy)(OH2)](3+) (1) is the most prominent structural and functional model of the water-oxidizing Mn complex operating in plants and cyanobacteria. Supported on montmorillonite clay and using Ce(IV) as a chemical oxidant, 1 has been reported to be one of the best Mn-based molecular catalysts toward water oxidation. By X-ray absorption spectroscopy and kinetic analysis of the oxygen evolution reaction, we show that [(OH2)(terpy)Mn(?-O)2Mn(terpy)(OH2)](3+) is transformed into layered type Mn-oxide particles which are the actual water oxidation catalyst. PMID:24798550

Najafpour, M M; Moghaddam, Atefeh N; Dau, Holger; Zaharieva, Ivelina

2014-05-21

218

Effects of solar radiation on manganese oxide reactions with selected organic compounds  

SciTech Connect

The effects of sunlight on aqueous redox reactions between manganese oxides (MnO{sub x}) and selected organic substances are reported. No sunlight-induced rate enhancement was observed for the MnO{sub x} oxidation of substituted phenols, anisole, o-dichlorobenzene, or p-chloroaniline. On the other hand, solar radiation did accelerate the reduction of manganese oxides by dissolved organic matter (DOM) from aquatic environments. The photoreduction of MnO{sub x} by DOM was little affected by molecular oxygen in air-saturated water (250 {mu}M), but was inhibited by 2,6-dichloroindophenol (0.5-6 {mu}M), and excellent electron acceptor. MnO{sub x} reduction also was photosensitized by anthraquinone-2-sulfonate. These results indicate that the photoreduction probably involves electron transfer from excited states of sorbed DOM to the oxide surface. Wavelength studies indicated that ultraviolet-B radiation (280-320 nm) plays an important role in this photoreduction.

Bertino, D.J.; Zepp, R.G. (Environmental Protection Agency, Athens, GA (United States))

1991-07-01

219

Characterization of manganese?gallium mixed oxide powders  

NASA Astrophysics Data System (ADS)

Mn?Ga mixed oxides have been prepared by coprecipitation of the corresponding oxo-hydroxides as powders and have been characterized in relation to their structural and optical properties. The materials have been characterized by XRD, TG-DTA, skeletal IR and UV-visible-NIR spectroscopies. Large solubility of Mn in the diaspore type ?-GaOOH oxo-hydroxide has been found. The spinel related structures of hausmannite Mn 3O 4 and of ?-gallia present large reciprocal solubilities at least in a metastable form. At high temperature also bixbyite-type ?-Mn 2O 3 solid solutions containing up to 20% at. Ga have been observed.

Sánchez Escribano, Vicente; Fernández López, Enrique; Sánchez Huidobro, Paula; Panizza, Marta; Resini, Carlo; Gallardo-Amores, José M.; Busca, Guido

2003-11-01

220

Metal Inhibition of Growth and Manganese Oxidation in Pseudomonas putida GB-1  

NASA Astrophysics Data System (ADS)

Biogenic manganese oxides (MnO2) are ubiquitous nanoparticulate minerals that contribute to the adsorption of nutrient and toxicant metals, the oxidative degradation of various organic compounds, and the respiration of metal-reducing bacteria in aquatic and terrestrial environments. The formation of these minerals is catalyzed by a diverse and widely-distributed group of bacteria and fungi, often through the enzymatic oxidation of aqueous Mn(II) to Mn(IV). In metal-impacted ecosystems, toxicant metals may alter the viability and metabolic activity of Mn-oxidizing organisms, thereby limiting the conditions under which biogenic MnO2 can form and diminishing their potential as adsorbent materials. Pseudomonas putida GB-1 (P. putida GB-1) is a model Mn-oxidizing laboratory culture representative of freshwater and soil biofilm-forming bacteria. Manganese oxidation in P. putida GB-1 occurs via two single-electron-transfer reactions, involving a multicopper oxidase enzyme found on the bacterial outer membrane surface. Near the onset of the stationary phase of growth, dark brown MnO2 particles are deposited in a matrix of bacterial cells and extracellular polymeric substances, thus forming heterogeneous biomineral assemblages. In this study, we assessed the influence of various transition metals on microbial growth and manganese oxidation capacity in a P. putida GB-1 culture propagated in a nutrient-rich growth medium. The concentration-response behavior of actively growing P. putida GB-1 cells was investigated for Fe, Co, Ni, Cu and Zn at pH ? 6 in the presence and absence of 1 mM Mn. Toxicity parameters such as EC0, EC50 and Hillslope, and EC100 were obtained from the sigmoidal concentration-response curves. The extent of MnO2 formation in the presence of the various metal cations was documented 24, 50, 74 and 104 h after the metal-amended medium was inoculated. Toxicity values were compared to twelve physicochemical properties of the metals tested. Significant correlations were found between EC50 values and reduction potential, electronegativity and the covalent index. Thus, metal toxicity in P. putida GB-1 appears to be modulated by the metals’ propensity to participate in covalent interactions and generate oxidative stress. This study provides a quantitative measure of metal tolerance in P. putida GB-1, as well as operational limits for Mn oxidation in this model system, both of which have important implications for the reactivity of P. putida-MnO2 assemblages formed in metal-impacted ecosystems.

Pena, J.; Sposito, G.

2009-12-01

221

Kinetic model for simultaneous leaching of zinc sulfide and manganese dioxide in the presence of iron-oxidizing bacteria  

Microsoft Academic Search

The effect of iron-oxidizing bacteria on the simultaneous leaching of zinc sulfide and manganese dioxide was studied. Some researchers have reported the enhancement of the leaching rate during the simultaneous leaching of metal oxides and metal sulfides. In the present study, we examined the effect of the presence of Thiobacillus ferrooxidans in the simultaneous leaching. We also examined the reaction

Takami Kai; Yo-ich Suenaga; Atsuko Migita; Takeshige Takahashi

2000-01-01

222

Kinetics of oxidation of carbon in liquid iron-carbon-silicon-manganese-sulfur alloys by carbon dioxide in nitrogen  

Microsoft Academic Search

The oxidation of carbon with the simultaneous oxidation of silicon, manganese, and iron of liquid alloys by carbon dioxide\\u000a in nitrogen and the absorption of oxygen by the alloys from the gas were studied using 1-g liquid iron droplets levitated\\u000a in a stream of the gas at 1575 C to 1715 C. Oxidation of carbon was favored over oxidation of

Haiping Sun; Robert D. Pehlke

1995-01-01

223

Manganese(II)-Oxidizing Bacillus Spores in Guaymas Basin Hydrothermal Sediments and Plumes  

PubMed Central

Microbial oxidation and precipitation of manganese at deep-sea hydrothermal vents are important oceanic biogeochemical processes, yet nothing is known about the types of microorganisms or mechanisms involved. Here we report isolation of a number of diverse spore-forming Mn(II)-oxidizing Bacillus species from Guaymas Basin, a deep-sea hydrothermal vent environment in the Gulf of California, where rapid microbially mediated Mn(II) oxidation was previously observed. mnxG multicopper oxidase genes involved in Mn(II) oxidation were amplified from all Mn(II)-oxidizing Bacillus spores isolated, suggesting that a copper-mediated mechanism of Mn(II) oxidation could be important at deep-sea hydrothermal vents. Phylogenetic analysis of 16S rRNA and mnxG genes revealed that while many of the deep-sea Mn(II)-oxidizing Bacillus species are very closely related to previously recognized isolates from coastal sediments, other organisms represent novel strains and clusters. The growth and Mn(II) oxidation properties of these Bacillus species suggest that in hydrothermal sediments they are likely present as spores that are active in oxidizing Mn(II) as it emerges from the seafloor.

Dick, Gregory J.; Lee, Yifan E.; Tebo, Bradley M.

2006-01-01

224

Efficient production of ultrapure manganese oxides via electrodeposition.  

PubMed

A new process for the production of electrolytic amorphous nanomanganese oxides (EAMD) with uniform size and morphology is described. EAMD are produced for the first time by cathodic deposition from a basic aqueous solution of potassium permanganate at a constant temperature of 16°C. The synthesized materials are characterized by XRD, SEM, TEM, and HRTEM. The materials produced at 5.0 V at constant temperature are amorphous with homogeneous size and morphology with an average particle size around 20 nm, which appears to be much lesser than the previously reported anodic EAMD. A potentiostatic electrodeposition with much lesser deposition rate (with respect to previously reported anodic depositions) is considered to be the reason behind the very low and homogenous particle size distribution due to the lesser agglomeration of our as-synthesized nanoparticles. PMID:22595552

Cheney, Marcos A; Joo, Sang Woo; Banerjee, Arghya; Min, Bong-Ki

2012-08-01

225

Metalloradical Complexes of Manganese and Chromium Featuring an Oxidatively Rearranged Ligand  

PubMed Central

Redox events involving both metal and ligand sites are receiving increased attention since a number of biological processes direct redox equivalents toward functional residues. Metalloradical synthetic analogs remain scarce and require better definition of their mode of formation and subsequent operation. The trisamido-amine ligand [(RNC6H4)3N]3?, where R is the electron-rich 4-t-BuPh, is employed in this study to generate redox active residues in manganese and chromium complexes. Solutions of [(L1)Mn(II)–THF]? in THF are oxidized by dioxygen to afford [(L1re–1)Mn(III)–(O)2–Mn(III)(L1re–1)]2? as the major product. The rare dinuclear manganese (III,III) core is stabilized by a rearranged ligand that has undergone an one-electron oxidative transformation, followed by retention of the oxidation equivalent as a ? radical in an o-diiminobenzosemiquinonate moiety. Magnetic studies indicate that the ligand-centered radical is stabilized by means of extended antiferromagnetic coupling between the S = ½ radical and the adjacent S = 2 Mn(III) site, as well as between the two Mn(III) centers via the dioxo bridge. Electrochemical and EPR data suggest that this system can store higher levels of oxidation potency. Entry to the corresponding Cr(III) chemistry is achieved by employing CrCl3 to access both [(L1)Cr(III)–THF] and [(L1re–1)Cr(III)–THF(Cl)], featuring the intact and the oxidatively rearranged ligands, respectively. The latter is generated by ligand-centered oxidation of the former compound. The rearranged ligand is perceived to be the product of an one-electron oxidation of the intact ligand to afford a metal-bound aminyl radical that subsequently mediates a radical 1,4-(N-to-N) aryl migration.

Celenligil-Cetin, Remle; Paraskevopoulou, Patrina; Lalioti, Nikolia; Sanakis, Yiannis; Staples, Richard J.; Rath, Nigam P.; Stavropoulos, Pericles

2009-01-01

226

Formation and conversion mechanisms between single-crystal gamma-MnOOH and manganese oxides  

SciTech Connect

Highlights: ? Single-crystal ?-MnOOH was obtained via hydrothermal method. ? ?-MnO{sub 2} was transformed to ?-MnOOH by a dissolution-growth-recrystallization process. ? ?-MnO{sub 2} preferred growth on (111{sup ¯}) crystal plane of ?-MnOOH. ? ?-MnOOH was a useful precursor to prepare manganese oxide via calcination. -- Abstract: Formation and conversion mechanisms between single-crystal gamma-MnOOH and manganese oxides had investigated systematically. Without extra surfactant or template, ?-MnO{sub 2} nanorods and prismatic single crystalline ?-MnOOH rods had been synthesized under hydrothermal treatment in this study. The formation and conversion mechanisms of prismatic ?-MnOOH rod were investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). It was found that the formation process includes three evolution stages: (1) formation of ?-MnO{sub 2} nanorods whiskers; (2) transformation from ?-MnO{sub 2} nanorods to prismatic ?-MnOOH rods by a dissolution-growth-recrystallization process; and (3) preferred growth on (111{sup ¯}) crystal plane. In addition, ?-MnO{sub 2}, Mn{sub 2}O{sub 3} or Mn{sub 3}O{sub 4} rods could be obtained by calcination of the ?-MnOOH rods at different temperatures, which indicated that ?-MnOOH is an important precursor for preparing manganese oxides. The morphology and dimension of ?-MnOOH rods remained unchanged after converted to ?-MnO{sub 2}, Mn{sub 2}O{sub 3} and Mn{sub 3}O{sub 4}.

Wei, Chunguang [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen, Guangdong 518055 (China) [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen, Guangdong 518055 (China); Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Xu, Chengjun; Li, Baohua [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen, Guangdong 518055 (China)] [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen, Guangdong 518055 (China); Nan, Ding [Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China)] [Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Ma, Jun [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen, Guangdong 518055 (China)] [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen, Guangdong 518055 (China); Kang, Feiyu, E-mail: fykang@tsinghua.edu.cn [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen, Guangdong 518055 (China) [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen, Guangdong 518055 (China); Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China)

2012-07-15

227

Effect of Co on the magnetism and phase stability of lithiated manganese oxides.  

SciTech Connect

We present first-principles calculations of the relative energies of various phases of lithiated manganese oxides with and without Co. We use the ultrasoft pseudopotential method as implemented in the Vienna ab initio simulation package (VASP). The calculations employ the local spin density approximation (LSDA) as well as the generalized gradient approximation (GGA). We consider monoclinic and rhombohedral structures in paramagnetic, ferromagnetic and antiferromagnetic (AF3) spin configurations. Spin-polarization significantly lowers the total energy in all cases. The effect of Co on the stability of these phases is discussed.

Prasad, R.; Benedek, R.; Thackeray, M. M.; Chemical Engineering; Indian Inst. of Tech. at Kanpur

2003-01-01

228

Anodically deposited manganese–molybdenum–tungsten oxide anodes for oxygen evolution in seawater electrolysis  

Microsoft Academic Search

Ternary manganese–molybdenum–tungsten oxides were anodically deposited on to IrO2-coated titanium substrates at current densities of 60–600 A m-2 in 0.4 M MnSO4 solutions containing 0.003 M Na2MoO4 and 0.003 M Na2WO4 at pH 0–1.5 and at 30–90 °C. The effect of anodic deposition conditions on the activity, selectivity and durability of the anodes for oxygen evolution in 0.5 M NaCl

T. Matsui; H. Habazaki; A. Kawashima; K. Asami; N. Kumagai; K. Hashimoto

2002-01-01

229

Nanostructured and layered lithium manganese oxide and method of manufacturing the same  

NASA Technical Reports Server (NTRS)

Nanostructured and layered lithium manganese oxide powders and methods of producing same. The powders are represented by the chemical formula, LixMn1-yMyO2, where 0.5

Singhal, Amit (Inventor); Skandan, Ganesh (Inventor)

2005-01-01

230

Processing-structure-property-performance investigations of lithium manganese-based oxides for lithium rechargeable batteries  

Microsoft Academic Search

A study of the processing - structure - property - performance interrelationship was performed on several lithium manganese oxides that are candidates for use in lithium rechargeable batteries. The materials studied were LiMn 2O4, Mn-substituted LiMn2O4 (LiMn 2-yMeyO4), and Li1.5Na0.5 MnO2.85I0.12. Processing evaluations pertained to the substitution of Mn by other cations (Me = Li, Co, or Ni). Atomic and

Craig Richard Horne

2000-01-01

231

Pathogenic prion protein is degraded by a manganese oxide mineral found in soils  

USGS Publications Warehouse

Prions, the aetiological agents of transmissible spongiform encephalopathies, exhibit extreme resistance to degradation. Soil can retain prion infectivity in the environment for years. Reactive soil components may, however, contribute to the inactivation of prions in soil. Members of the birnessite family of manganese oxides (MnO2) rank among the strongest natural oxidants in soils. Here, we report the abiotic degradation of pathogenic prion protein (PrPTSE) by a synthetic analogue of naturally occurring birnessite minerals. Aqueous MnO2 suspensions degraded the PrPTSE as evidenced by decreased immunoreactivity and diminished ability to seed protein misfolding cyclic amplification reactions. Birnessite-mediated PrPTSE degradation increased as a solution's pH decreased, consistent with the pH-dependence of the redox potential of MnO2. Exposure to 5.6 mg MnO2 ml-1 (PrPTSE:MnO2=1 : 110) decreased PrPTSE levels by ???4 orders of magnitude. Manganese oxides may contribute to prion degradation in soil environments rich in these minerals. ?? 2009 SGM.

Russo, F.; Johnson, C. J.; Johnson, C. J.; McKenzie, D.; Aiken, J. M.; Pedersen, J. A.

2009-01-01

232

Heterogeneous catalytic ozonation of ciprofloxacin in water with carbon nanotube supported manganese oxides as catalyst.  

PubMed

Carbon nanotube-supported manganese oxides (MnOx/MWCNT) were used as catalysts to assist ozone in degrading ciprofloxacin in water. Manganese oxides were successfully loaded on multi-walled carbon nanotube surfaces by simply impregnating the carbon nanotube with permanganate solution. The catalytic activities of MnOx/MWCNT in ciprofloxacin ozonation, including degradation, mineralization effectiveness, and antibacterial activity change, were investigated. The presence of MnOx/MWCNT significantly elevated the degradation and mineralization efficiency of ozone on ciprofloxacin. The microbiological assay with a reference Escherichia coli strain indicated that ozonation with MnOx/MWCNT results in more effective antibacterial activity inhibition of ciprofloxacin than that in ozonation alone. The effects of catalyst dose, initial ciprofloxacin concentration, and initial pH conditions on ciprofloxacin ozonation with MnOx/MWCNT were surveyed. Electron spin resonance trapping was applied to assess the role of MnOx/MWCNT in generating hydroxyl radicals (HO) during ozonation. Stronger 5,5-dimethyl-1-pyrroline-N-oxide-OH signals were observed in the ozonation with MnOx/MWCNT compared with those in ozonation alone, indicating that MnOx/MWCNT promoted the generation of hydroxyl radicals. The degradation of ciprofloxacin was studied in drinking water and wastewater process samples to gauge the potential effects of water background matrix on MnOx/MWCNT catalytic ozonation. PMID:22658829

Sui, Minghao; Xing, Sichu; Sheng, Li; Huang, Shuhang; Guo, Hongguang

2012-08-15

233

Simulation of the surface structure of lithium manganese oxide spinel  

NASA Astrophysics Data System (ADS)

Simulations of the surface structure of low-index surfaces of LiMn2O4 (LMO), a candidate Li-ion battery electrode material, have been performed within the GGA+U approximation, using the VASP code. Surfaces of (001), (110), and (111) orientation were considered, with at least two terminations treated in each case. A slab geometry was employed, with termination-layer vacancies introduced to remove the bulk dipole moment while maintaining ideal stoichiometry. To complement static-structure relaxation calculations, molecular-dynamics simulations were performed to explore the phase space of possible surface reconstructions. A reconstruction is predicted for the Mn-terminated (111) surface, in which the top layers mix in stoichiometric proportions to form an LMO termination layer with square-planar-coordinated Mn. Average surface Mn oxidation states are reduced, relative to the bulk, for all surfaces considered, as a consequence of the lower-energy cost of Jahn-Teller distortion at the surface. Threefold-coordinated surface Mn, found for two terminations, is divalent, which may enhance its vulnerability to dissolution. The Li-terminated (001) surface is lowest in energy, consistent with previous classical-potential simulations for MgAl2O4 that showed the Mg-terminated (001) surface to be lowest in energy.

Benedek, R.; Thackeray, M. M.

2011-05-01

234

Simulation of the surface structure of lithium manganese oxide spinel.  

SciTech Connect

Simulations of the surface structure of low-index surfaces of LiMn{sub 2}O{sub 4} (LMO), a candidate Li-ion battery electrode material, have been performed within the GGA+U approximation, using the VASP code. Surfaces of (001), (110), and (111) orientation were considered, with at least two terminations treated in each case. A slab geometry was employed, with termination-layer vacancies introduced to remove the bulk dipole moment while maintaining ideal stoichiometry. To complement static-structure relaxation calculations, molecular-dynamics simulations were performed to explore the phase space of possible surface reconstructions. A reconstruction is predicted for the Mn-terminated (111) surface, in which the top layers mix in stoichiometric proportions to form an LMO termination layer with square-planar-coordinated Mn. Average surface Mn oxidation states are reduced, relative to the bulk, for all surfaces considered, as a consequence of the lower-energy cost of Jahn-Teller distortion at the surface. Threefold-coordinated surface Mn, found for two terminations, is divalent, which may enhance its vulnerability to dissolution. The Li-terminated (001) surface is lowest in energy, consistent with previous classical-potential simulations for MgAl{sub 2}O{sub 4} that showed the Mg-terminated (001) surface to be lowest in energy.

Benedek, R.; Thackeray, M. M. (Chemical Sciences and Engineering Division)

2011-05-31

235

MtsABC Is Important for Manganese and Iron Transport, Oxidative Stress Resistance, and Virulence of Streptococcus pyogenes  

PubMed Central

MtsABC is a Streptococcus pyogenes ABC transporter which was previously shown to be involved in iron and zinc accumulation. In this study, we showed that an mtsABC mutant has impaired growth, particularly in a metal-depleted medium and an aerobic environment. In metal-depleted medium, growth was restored by the addition of 10 ?M MnCl2, whereas other metals had modest or no effect. A characterization of metal radioisotope accumulation showed that manganese competes with iron accumulation in a dose-dependent manner. Conversely, iron competes with manganese accumulation but to a lesser extent. The mutant showed a pronounced reduction (>90%) of 54Mn accumulation, showing that MtsABC is also involved in Mn transport. Using paraquat and hydrogen peroxide to induce oxidative stress, we show that the mutant has an increased susceptibility to reactive oxygen species. Moreover, activity of the manganese-cofactored superoxide dismutase in the mutant is reduced, probably as a consequence of reduced intracellular availability of manganese. The enzyme functionality was restored by manganese supplementation during growth. The mutant was also attenuated in virulence, as shown in animal experiments. These results emphasize the role of MtsABC and trace metals, especially manganese, for S. pyogenes growth, susceptibility to oxidative stress, and virulence.

Janulczyk, Robert; Ricci, Susanna; Bjorck, Lars

2003-01-01

236

Photocatalytic Water Oxidation Using Manganese Compounds Immobilized in Nafion Polymer Membranes  

PubMed Central

Robust water oxidation catalysts using earth abundant metals are required as part of an overall scheme to convert sunlight into fuels. Here, we report the immobilization of [Mn4IVO5(terpy)4(H2O)2](ClO4)6 (terpy = 2,2?;6?,2?-terpyridine), [Mn4O6(tacn)4](ClO4)4 (tacn = 1,4,7-triazacyclononane), and manganese dioxide nanoparticles in Nafion on fluorine-doped tin oxide conducting glass electrodes. The electrodes are illuminated with white light in the presence of an applied potential and the resulting photocurrent is assigned to the oxidation of solvent water. Photodecomposition of the tetrameric complexes results in a material that is more active for light-driven electrooxidation of water. The reactivity, wavelength dependence, and stability of the compounds in Nafion under illumination are discussed.

Young, Karin J.; Gao, Yunlong; Brudvig, Gary W.

2011-01-01

237

Electrochemical Sensor Based on Carbon Paste Electrode Modified with Nanostructured Crypotomelane-Type Manganese Oxides for Detection of Heavy Metals  

SciTech Connect

A carbon paste electrode modified with nanostructured crypotomelane type manganese oxides was evaluated as new electrochemical sensor for the detection of heavy metal ions in aqueous media. The crypotomelane type manganese oxides are nanofibrous crystals with sub-nanometer tunnels which provide excellent sites for ion-exchanges. The adsorptive stripping voltammetry (ASV) technique involves preconcentration of the metal ions into nanostructured crypotomelane type manganese oxides under an open circuit, then electrolysis of the preconcentrated species, followed by a square-wave potential sweep towards positive values. Factors affecting the preconcentration process were investigated using lead ion as the model analyte. The voltammetric responses increased with the preconcentration time from 2 to 30 min, and also linearly with lead ion concentrations ranging from 50 to 1200 ppb. The detection limits of target metal ion were 10 ppb after 4 min preconcentration and improved to 1 ppb after 20 min preconcentration. The potential for simultaneous detection of copper, silver and lead is also discussed.

Cui, Xiaoli; Liu, Guodong; Li, Liyu; Yantasee, Wassana; Lin, Yuehe

2005-02-03

238

Trace metal-rich Quaternary hydrothermal manganese oxide and barite deposit, Milos Island, Greece  

USGS Publications Warehouse

The Cape Vani Mn oxide and barite deposit on Milos Island offers an excellent opportunity to study the three-dimensional characteristics of a shallow-water hydrothermal system. Milos Island is part of the active Aegean volcanic arc. A 1 km long basin located between two dacitic domes in northwest Milos is filled with a 35-50 m thick section of Quaternary volcaniclastic and pyroclastic rocks capped by reef limestone that were hydrothermally mineralized by Mn oxides and barite. Manganese occurs as thin layers, as cement of sandstone and as metasomatic replacement of the limestone, including abundant fossil shells. Manganese minerals include chiefly ?-MnO2, pyrolusite and ramsdellite. The MnO contents for single beds range up to 60%. The Mn oxide deposits are rich in Pb (to 3.4%), BaO (to 3.1%), Zn (to 0.8%), As (to 0.3%), Sb (to 0.2%) and Ag (to 10 ppm). Strontium isotopic compositions of the Mn oxide deposits and sulphur isotopic compositions of the associated barite show that the mineralizing fluids were predominantly sea water. The Mn oxide deposit formed in close geographical proximity to sulphide-sulphate-Au-Ag deposits and the two deposit types probably formed from the same hydrothermal system. Precipitation of Mn oxide took place at shallow burial depths and was promoted by the mixing of modified sea water (hydrothermal fluid) from which the sulphides precipitated at depth and sea water that penetrated along faults and fractures in the Cape Vani volcaniclastic and tuff deposits. The hydrothermal fluid was formed from predominantly sea water that was enriched in metals leached from the basement and overlying volcanogenic rocks. The hydrothermal fluids were driven by convection sustained by heat from cooling magma chambers. Barite was deposited throughout the time of Mn oxide mineralization, which occurred in at least two episodes. Manganese mineralization occurred by both focused and diffuse flow, the fluids mineralizing the beds of greatest porosity and filling dilatational fractures along with barite.

Hein, J.R.; Stamatakis, G.; Dowling, J.S.

2000-01-01

239

The simple preparation of birnessite-type manganese oxide with flower-like microsphere morphology and its remarkable capacity retention  

SciTech Connect

Graphical abstract: Flower-like birnessite-type manganese oxide microspheres with large specific surface area and excellent electrochemical properties have been prepared by a facile hydrothermal method. Highlights: ? Birnessite-type manganese oxide with flower-like microsphere morphology and large specific surface area. ? A facile low-temperature hydrothermal method. ? Novel flower-like microsphere consists of the thin nano-platelets. ? Birnessite-type manganese oxide exhibits an ideal capacitive behavior and excellent cycling stability. -- Abstract: Birnessite-type manganese oxide with flower-like microsphere morphology and large specific surface area has been prepared by hydrothermal treating a mixture solution of KMnO{sub 4} and (NH{sub 4}){sub 2}SO{sub 4} at 90 °C for 24 h. The obtained material is characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N{sub 2} adsorption–desorption. Results indicate that the birnessite-type manganese oxide shows novel flower-like microsphere morphology and a specific surface area of 280 m{sup 2} g{sup ?1}, and the flower-like microsphere consists of the thin nano-platelets. Electrochemical characterization indicates that the prepared material exhibits an ideal capacitive behavior with a capacitance value of 278 F g{sup ?1} in 1 mol L{sup ?1} Na{sub 2}SO{sub 4} aqueous solution at a scan rate of 5 mV s{sup ?1}. Moreover, the prepared manganese oxide electrode shows excellent cycle stability, and the specific capacitance can maintain 98.6% of the initial one after 5000 cycles.

Zhu, Gang; Deng, Lingjuan; Wang, Jianfang; Kang, Liping [Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, Xi’an 710062 (China) [Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, Xi’an 710062 (China); School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710062 (China); Liu, Zong-Huai, E-mail: zhliu@snnu.edu.cn [Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, Xi’an 710062 (China) [Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, Xi’an 710062 (China); School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710062 (China)

2012-11-15

240

Competing magnetic phases in mixed-valent manganese oxide perovskites  

NASA Astrophysics Data System (ADS)

Measurement of specific heat Cp(T) below 300K of melt-grown samples of La1-xCaxMnO3 (0?x?0.3) and R0.7A0.3MnO3 (R=rare-earth,A=alkaline-earth) with room-temperature tolerance factor 0.950?t?0.996 have been supplemented by transport and magnetic measurements. Comparison of the phase diagram of La1-xCaxMnO3 with that of La1-xSrxMnO3 and the evolution with t of the R0.7A0.3MnO3 family illustrate the sensitivity to t of the crossover from localized to itinerant behavior of the ? -bonding electrons and support the model of two magnetic phases in the crossover compositional range that has been used to account for the colossal magnetoresistance (CMR) phenomenon found in these oxides. A vanishing of the specific-heat anomaly at the Curie temperature Tc and the magnetic data at crossover are typical of a spin glass, and a broad hump in Cp(T) below a Th>Tc , where there is no anomaly at the Tc signal ferromagnetic ordering within isolated pockets of a hole-rich, conductive O* minority phase at Th . On cooling through TN of the antiferromagnetic matrix, the spins freeze at a spin-glass temperature Tg in zero magnetic field H if the ferromagnetic phase does not percolate; the ferromagnetic phase grows in an applied H , and a modest H converts the spin glass to a bulk ferromagnet with a Curie temperature Tc?Tg , where the ferromagnetic phase grows to beyond percolation. As x increases in La1-xCaxMnO3 , a ferromagnetic-insulator O? phase having a charge ordering and a different orbital ordering than the parent O' phase percolates below a Tg?Tc , and the minority O' phase remains paramagnetic until it becomes antiferromagnetic below a TM

Liu, G.-L.; Zhou, J.-S.; Goodenough, J. B.

2004-12-01

241

Synthesis of a novel polyaniline-intercalated layered manganese oxide nanocomposite as electrode material for electrochemical capacitor  

Microsoft Academic Search

Polyaniline-intercalated layered manganese oxide (PANI-MnO2) nanocomposite was synthesized via exchange reaction of polyaniline (PANI) with n-octadecyltrimethylammonium-intercalated manganese oxide in N-methyl-2-pyrrolidone solvent. The PANI-MnO2 nanocomposite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, and so on. XRD analysis showed that the basal spacing was 1.47nm, corresponding to the benzene rings

Xiong Zhang; Liyan Ji; Shichao Zhang; Wensheng Yang

2007-01-01

242

Mo;ecular Modeling of Biogenic Manganese Oxides Using ab Initio Density Functional Theory  

NASA Astrophysics Data System (ADS)

Layer type manganese oxides with short-range crystalline order (birnessites) are produced by many species of bacteria.Deposits of these oxides form a highly reactive catalytic surface that plays a major role in the destruction and sequestration of organic compounds and metals.Biogenic oxides also contain vacant Mn(IV)sites;these sites,with their associated negative charge, are the probable main cause of the high sorptive reactivity of the oxide surfaces. In order to acquire a deeper understanding of the molecular mechanisms involved in these processes, a model of a biogenic oxide was built and its structure was optimized using the CASTEP three-dimensional periodic system computational package. The resulting crystal structure shows good agreement with EXAFS data from crystals formed by a strain of the common soil and freshwater bacterium, Pseudomonas putida. The greatest challenge in modeling Mn oxides (like other transition metal oxides)comes in dealing with the electronic factors that lead to their magnetic and catalytic properties: they are highly correlated systems where the spin must be taken into account in order to obtain accurate predictions of their properties.

Oconnor, M.; Sposito, G.; Refson, K.

2003-12-01

243

Structural and optical properties of polycrystalline thin films of rare earth oxides grown on fused quartz by low pressure MOCVD  

Microsoft Academic Search

We report the structural and optical properties of oriented polycrystalline thin films of rare earth oxides (REO), namely Er2O3, Gd2O3, Eu2O3, and Yb2O3 grown on fused quartz by low-pressure metalorganic chemical vapour deposition (MOCVD) in the temperature range of 450–800°C, using adducted ?-diketonate complexes of rare earth metals as precursors. The films were characterized by X-ray diffraction (XRD) and UV–visible

M. P. Singh; S. A. Shivashankar

2005-01-01

244

High-contrast visualization of graphene oxide on dye-sensitized glass, quartz, and silicon by fluorescence quenching.  

PubMed

We present a novel approach for detecting and visualizing graphene oxide (GO) with high contrast on different substrates, including glass, quartz, and silicon. Visualization of GO sheets is accomplished through quenching the fluorescence of a thiophene dye, giving high optical contrast without the need to use interference methods. A comparison of fluorescence, AFM, and XRD measurements confirmed that even a single GO sheet can completely quench the fluorescence and thus be quickly visualized. PMID:19824679

Treossi, Emanuele; Melucci, Manuela; Liscio, Andrea; Gazzano, Massimo; Samorì, Paolo; Palermo, Vincenzo

2009-11-01

245

Two-, three-, and four-component magnetic multilayer onion nanoparticles based on iron oxides and manganese oxides.  

PubMed

Magnetic multilayered, onion-like, heterostructured nanoparticles are interesting model systems for studying magnetic exchange coupling phenomena. In this work, we synthesized heterostructured magnetic nanoparticles composed of two, three, or four components using iron oxide seeds for the subsequent deposition of manganese oxide. The MnO layer was allowed either to passivate fully in air to form an outer layer of Mn(3)O(4) or to oxidize partially to form MnO|Mn(3)O(4) double layers. Through control of the degree of passivation of the seeds, particles with up to four different magnetic layers can be obtained (i.e., FeO|Fe(3)O(4)|MnO|Mn(3)O(4)). Magnetic characterization of the samples confirmed the presence of the different magnetic layers. PMID:21973012

Salazar-Alvarez, German; Lidbaum, Hans; López-Ortega, Alberto; Estrader, Marta; Leifer, Klaus; Sort, Jordi; Suriñach, Santiago; Baró, Maria Dolors; Nogués, Josep

2011-10-26

246

Electrochemical impedance spectroscopy studies of lithium diffusion in doped manganese oxide  

SciTech Connect

Cathode performance is critical to lithium ion rechargeable battery performance; effects of doping lithium manganese oxide cathode materials on cathode performance are being investigated. In this paper, Li diffusion in Al-doped LiMn{sub 2}O{sub 4} was studied and found to be controlled by the quantity of Al dopant. Electrochemical cycling was conducted at 0.5mA/cm{sub 2}; electrochemical impedance spectra were taken at open circuit potential, with impedance being measured at 65 kHz-0.01 Hz. As the Al dopant level was increased, the Li diffusion rate decreased; this was attributed to the decreased lattice parameter of the doped oxide.

Johnson, B.J.; Doughty, D.H.; Voigt, J.A.; Boyle, T.J.

1996-06-01

247

Thiol-mediated oxidation of nonphenolic lignin model compounds by manganese peroxidase of Phanerochaete chrysosporium.  

PubMed

In the presence of MnII, H2O2, and glutathione (GSH), manganese peroxidase oxidized veratryl alcohol (I) to veratraldehyde (IV). Anisyl alcohol (II) and benzyl alcohol (III) were also oxidized by this system to their corresponding aldehydes (V and VI). In the presence of GSH, chemically prepared MnIII or gamma-irradiation also catalyzed the oxidation of I, II, and III to IV, V, and VI, respectively. GSH and dithiothreitol rapidly reduced MnIII to MnII in the absence of aromatic substrates and the dithiothreitol was oxidized to its disulfide (4,5-dihydroxyl-1,2-dithiane). These results indicate that the thiol is oxidized by enzyme-generated MnIII to a thiyl radical. The latter abstracts a hydrogen from the substrate, forming a benzylic radical which reacts with another thiyl radical to yield an intermediate which decomposes to the benzaldehyde product. In the presence of MnII, GSH, and H2O2, manganese peroxidase also oxidized 1-(4-ethoxy-3-methoxy-phenyl)-2-(4'-hydroxymethyl-2'-methoxyphenoxy)- 1,3-dihydroxypropane (XII) to yield vanillyl alcohol (VII), vanillin (VIII), 1-(4-ethoxy-3-methoxyphenyl)-1,3-dihydroxypropane (XVI), 1-(4-ethoxy-3-methoxyphenyl)-1-oxo-3-hydroxypropane (XIX), and several C alpha oxidized dimeric products. Abstraction of the C alpha (A ring) hydrogen of the dimer (XII) yields a benzylic radical, leading to C beta oxygen ether cleavage. The resultant intermediates yield the ketone (XIX) and vanillyl alcohol (VII) or vanillin (VIII). Alternatively, benzylic radical formation at the C' alpha position (B ring) leads to radical cleavage, yielding a quinone methide and a C beta radical, which yield vanillin and the 1,3-diol (XVI), respectively. In these reactions, MnIII oxidizes a thiol to a thiyl radical which subsequently abstracts a hydrogen from the substrate to form a benzylic radical. The latter undergoes nonenzymatic reactions to yield the final products. PMID:2760063

Wariishi, H; Valli, K; Renganathan, V; Gold, M H

1989-08-25

248

Manganese oxide-coated redox bars as an indicator for reducing soil conditions  

NASA Astrophysics Data System (ADS)

Field identification of reducing soil conditions is of concern not only for soil pedogenesis but also for nutrient and pollutant dynamics in soils. We manufactured manganese (Mn) oxide-coated polyvinyl chloride (PVC) bars and proved their suitability for identification of reducing soil conditions in both the laboratory and field. Birnessite (?-MnO2) was synthesized according to a recently published method and was coated onto white PVC bars. We used microcosm devices with adjusted redox potentials (EH) to distinguish the onset and intensity of depletion patterns along the Mn oxide-coating and soil column experiments combined with field application to validate the enhanced removal of Mn against Fe oxide-coated bars under anaerobe soil conditions. Field application was performed at a site with shallow and strongly fluctuating water tables where water table depth and soil temperature were monitored. Three microcosm experiments adjusted to oxidizing (EH ~500 mV, pH 7), weakly reducing (EH ~175 mV, pH 7) and moderately reducing conditions (EH ~25 mV, pH 7) showed depending on the EH no, slight, or intense removal of the Mn oxide-coating, respectively. Moreover, the removal of Mn oxide (225 mm2 d-1) in soil column experiments exceeded the removal of Fe oxide (118 mm2 d-1). The enhanced removal of the Mn oxide-coating was also found under anaerobe conditions in field application. Consequently, identifying of reducing conditions in soils by Mn oxide-coated bars is possible. We recommend using this methodology for short-term monitoring, e.g. on weekly basis, since tri- and tetravalent Mn is the preferred electron acceptor compared with trivalent Fe.

Dorau, Kristof; Mansfeldt, Tim

2014-05-01

249

Photoassisted dissolution of a colloidal manganese oxide in the presence of fulvic acid  

SciTech Connect

The dissolution of a synthesized manganese dioxide by a well-characterized fulvic acid has been investigated over a range of reactant concentrations, pH, and illumination conditions, as have components of the overall dissolution process including fulvic acid and manganous ion adsorption to the oxide surface. The dissolution process is satisfactorily described by an initial rapid formation of a surface-located precursor complex followed by a slower intramolecular electron-transfer step resulting in Mn(II) formation at the oxide surface. Illumination by 365-nm light enhances the rate of electron transfer significantly, with an increase in first-order reduction rate constant from 0.31 min/sup -1/ (dark) to 0.55 min/sup -1/ (light at pH 4.00 and from 0.53 min/sup -1/ (dark) to 1.23 min/sup -1/ (light) at pH 7.10. Depending on the affinity of the oxide surface for manganous ion, a portion of the Mn(II) produced at the oxide surface will be rapidly released to solution, resulting in dissolution of the oxide.

Walte, T.D.; Wrigley, I.C.; Szymczak, R.

1988-07-01

250

Magnetoresistance of Strained Rare Earth Manganese Oxide Thin Films: Effect of Post-Deposition Thermal Treatment  

NASA Astrophysics Data System (ADS)

We have studied the effects of thermal treatment (annealing) on the properties of thin films of manganese oxide materials La0.67Ca 0.33 MnO3 and La0.67 Ba.0.33MnO3, which are known to exhibit colossal magnetoresistance (CMR) and an insulator to metal transition . These materialsshow properties which are desirable for applications such as magnetic sensors, bolometric infrared sensors, or field effect devices. Two properties of interest, magnetoresistance (MR) and insulator metal transition are especially sensitive to strain because of the relationship between the properties and the symmetry of the crystal. The properties are also sensitive to the oxygen stoichiometry of the film due to changes in the valence state of the manganese which determines the charge carrier density. Recent results from our laboratory have shown a large magnetoresistance in strained films grown on lattice mismatched substrates. The MR continues to increase with decreasing temperature in these films. In order to understand the contribution of strain to the observed MR behavior, in we employ `thermal annealing' to allow for relaxation of strain. Annealing also serves to achieve the optimum oxygen stoichiometry. We will present the results of our annealing studies and their implications for understanding the MR in strained films.

Goehringer, Tyler; Srivastava, Parul; Tanyi, E. Kevin; Schaefer, David; Kolagani, Rajeswari

2012-02-01

251

Evaluation of the nitric oxide radical scavenging activity of manganese complexes of curcumin and its derivative.  

PubMed

Curcumin manganese complex (CpCpx) and diacetylcurcumin manganese complex (AcylCpCpx) were determined as to their effect on the nitric oxide (NO) radical scavenging in vitro method using a sodium nitroprusside generating NO system compared with their parent compound and astaxanthin, an extreme antioxidant. All compounds effectively reduced the generation of NO radicals in a dose dependent manner. They exhibited strong NO radical scavenging activity with low IC(50) values. The IC(50) values of curcumin, diacetylcurcumin, CpCpx and AcylCpCpx obtained are 20.39+/-4.10 microM, 28.76+/-1.48 microM, 9.79+/-1.50 microM and 8.09+/-0.99 microM, respectively. CpCpx and AcylCpCpx show greater NO radical scavenging than their parent compounds, curcumin and acetylcurcumin, respectively. However, the IC(50) values of curcumin and related compounds were found to be less than astaxanthin, an extreme antioxidant, with the lower IC(50) value of 3.42+/-0.50 microM. PMID:14758027

Sumanont, Yaowared; Murakami, Yukihisa; Tohda, Michihisa; Vajragupta, Opa; Matsumoto, Kinzo; Watanabe, Hiroshi

2004-02-01

252

Purification and Characterization of the Manganese(II) Oxidizing Protein from Erythrobacter sp. SD-21  

NASA Astrophysics Data System (ADS)

The manganese(II) oxidizing protein (Mop) found in the alpha-proteobacterium Erythrobacter sp. SD-21 catalyzes the formation of insoluble Mn(III/IV) oxides from soluble Mn(II). These Mn(III/IV) oxides formed are one of the strongest naturally occurring oxides, next to oxygen, and can be used to adsorb and oxidize toxic chemicals from the surrounding environment. Because of the beneficial use in the treatment of contaminated sources, the mechanism and biochemical properties of this novel enzyme are being studied. Due to low expression levels in the native host strain, purification of Mop has been problematic. To overcome this problem the gene encoding Mop, mopA, was cloned from the native host into a C-terminal histidine tag vector and expressed in Escherichia coli cells. Affinity chromatography under denaturing conditions have been applied in attempts to purify an active Mop. Western blots have confirmed that the protein is being expressed and is at the expected size of 250 kDa. Preliminary characterization on crude extract containing Mop has shown a Km and vmax value of 2453 uM and 0.025 uM min-1, respectively. Heme and pyrroloquinoline quinone can stimulate Mn(II) oxidizing activity, but hydrogen peroxide does not affect activity, despite the sequence similarity to animal heme peroxidase proteins. Research has been shown that calcium is essential for Mop activity. Purifying an active Mn(II) oxidizing protein will allow for a better understanding behind the enigmatic process of Mn(II) oxidation.

Nakama, K. R.; Lien, A.; Johnson, H. A.

2013-12-01

253

Direct oxidation of polymeric substrates by multifunctional manganese peroxidase isoenzyme from Pleurotus ostreatus without redox mediators.  

PubMed

VPs (versatile peroxidases) sharing the functions of LiP (lignin peroxidase) and MnP (manganese peroxidase) have been described in basidiomycetous fungi Pleurotus and Bjerkandera. Despite the importance of this enzyme in polymer degradation, its reactivity with polymeric substrates remains poorly understood. In the present study, we first report that, unlike LiP, VP from Pleurotus ostreatus directly oxidized two polymeric substrates, bovine pancreatic RNase and Poly R-478, through a long-range electron pathway without redox mediators. P. ostreatus produces several MnP isoenzymes, including the multifunctional enzyme MnP2 (VP) and a typical MnP isoenzyme MnP3. MnP2 (VP) depolymerized a polymeric azo dye, Poly R-478, to complete its catalytic cycle. Reduction of the oxidized intermediates of MnP2 (VP) to its resting state was also observed for RNase. RNase inhibited the oxidation of VA (veratryl alcohol) in a competitive manner. Blocking of the exposed tryptophan by N-bromosuccinimide inhibited the oxidation of RNase and VA by MnP2 (VP), but its Mn2+-oxidizing activity was retained, suggesting that Trp-170 exposed on an enzyme surface is a substrate-binding site both for VA and the polymeric substrates. The direct oxidation of RNase and Poly R by MnP2 (VP) is in sharp contrast with redox mediator-dependent oxidation of these polymers by LiP from Phanerochaete chrysosporium. Molecular modelling of MnP2 (VP) revealed that the differences in the dependence on redox mediators in polymer oxidation by MnP2 (VP) and LiP were explained by the anionic microenvironment surrounding the exposed tryptophan. PMID:15461584

Kamitsuji, Hisatoshi; Watanabe, Takashi; Honda, Yoichi; Kuwahara, Masaaki

2005-03-01

254

Sorption of Ferric Iron from Ferrioxamine B to Synthetic and Biogenic Layer Type Manganese Oxides  

NASA Astrophysics Data System (ADS)

Siderophores are biogenic chelating agents produced in terrestrial and marine environments to increase the bioavailablity of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but no information appears to be available about the effect of solid-phase Mn(IV). To probe the effects of predominantly Mn(IV) oxides, we studied the sorption reaction of ferrioxamine B [Fe(III)HDFOB+, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] with two synthetic birnessites [layer type Mn(III, IV) oxides] and a biogenic birnessite produced by Pseudomonas putida MnB1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB+ over at pH 8. After 72 hours equilibration time, the sorption behavior for the synthetic birnessites could be accurately described by a Langmuir isotherm; for the biogenic oxide, a Freundlich isotherm was best utilized to model the sorption data. To study the molecular nature of the interaction between the Fe(III)HDFOB+ complex and the oxide surface, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy was employed. Analysis of the EXAFS spectra indicated that Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to into the mineral structure at multiple sites with no evidence of DFOB complexation, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that manganese oxides, including biominerals, may strongly sequester iron from soluble ferric complexes and thus may play a significant role in the biogeochemical cycling of iron in marine and terrestrial environments.

Duckworth, O.; John, B.; Sposito, G.

2006-12-01

255

Coprecipitation mechanisms and products in manganese oxidation in the presence of cadmium  

USGS Publications Warehouse

Manganese oxidation products were precipitated in an aerated open-aqueous system where a continuous influx of mixed Mn2+ and Cd2+ solution was supplied and pH was maintained with an automated pH-stat adding dilute NaOH. X-ray diffraction and electron diffraction identified the solids produced as mixtures of Cd2Mn34+O8, Mn2+2Mn4+3O8, MnO2 (ramsdellite), and CdCO3. Mean oxidation numbers of the total precipitated Mn as great as 3.6 were reached during titrations. During subsequent aging in solution, oxidation numbers between 3.8 and 3.9 were reached in some precipitates in less than 40 days. Conditional oxidation rate constants calculated from a crystal-growth equation applied to titration data showed the overall precipitation rate, without considering manganese oxidation state in the precipitate, was increased by a factor of ~4 to ~7 when the mole ratio (Cd/Mn + Cd) of cadmium in the feed solution was 0.40 compared with rate constants for hausmannite (Mn2+Mn23+O4 precipitation under similar conditions but without accessory metals. Kinetic experiments were made to test effects of various Cd/Mn + Cd mole ratios and rates of addition of the feed solution, different temperatures from 5.0 to 35??C, and pH from 8.0 to 9.0. Oxidation rates were slower when the Cd mole ratio was less than 0.40. The rate increased by a factor of ~10 when pH was raised one-half unit. The effect of temperature on the rate constants was also substantial, but the meaning of this is uncertain because the rate of formation of Mn4+ oxide in the absence of Cd or other accessory metals was too slow to be measurable in titration experiments. The increased rate of Mn4+ oxide formation in the presence of Cd2+ can be ascribed to the formation of a labile adsorbed intermediate, CdMn2O4 Int, an analog of hausmannite, formed on precipitate surfaces at the beginning of the oxidation process. The increased lability of this structure, resulting from coordination-chemical behavior of Cd2+ during the titration, causes a rapid second-stage rearrangement and facilitates disproportionation of the Mn3+ ions. The Mn2+ ions thus released provide a positive feedback mechanism that couples the two steps of the conversion of Mn2+ to Mn4+ more closely than is possible when other metal ions besides manganese are not present. During aging of precipitates in contact with solutions, proportions of Cd2Mn3O8 and MnO2 increased at the expense of other precipitate components. ?? 1991.

Hem, J. D.; Lind, C. J.

1991-01-01

256

Imidazolium or guanidinium/layered manganese (III, IV) oxide hybrid as a promising structural model for the water-oxidizing complex of Photosystem II for artificial photosynthetic systems.  

PubMed

Photosystem II is responsible for the light-driven biological water-splitting system in oxygenic photosynthesis and contains a cluster of one calcium and four manganese ions at its water-oxidizing complex. This cluster may serve as a model for the design of artificial or biomimetic systems capable of splitting water into oxygen and hydrogen. In this study, we consider the ability of manganese oxide monosheets to self-assemble with organic compounds. Layered structures of manganese oxide, including guanidinium and imidazolium groups, were synthesized and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction spectrometry, and atomic absorption spectroscopy. The compounds can be considered as new structural models for the water-oxidizing complex of Photosystem II. The overvoltage of water oxidation for the compounds in these conditions at pH = 6.3 is ~0.6 V. These compounds may represent the first step to synthesize a hybrid of guanidinium or imidazole together with manganese as a biomimetic system for the water-oxidizing complex of Photosystem II. PMID:23543329

Najafpour, Mohammad Mahdi; Tabrizi, Mahmoud Amouzadeh; Haghighi, Behzad; Eaton-Rye, Julian J; Carpentier, Robert; Allakhverdiev, Suleyman I

2013-11-01

257

THEORETICAL TECHNIQUE FOR DETERMINING THE CUMULATIVE IMPACT OF IRON AND MANGANESE OXIDATION IN STREAMS RECEIVING COAL-MINE DISCHARGE.  

USGS Publications Warehouse

Two U. S. Geological Survey computer programs are modified and linked to predict the cumulative impact of iron and manganese oxidation in coal-mine discharge on the dissolved-chemical quality of a receiving stream. The coupled programs calculate the changes in dissolved-iron, dissolved-manganese, and dissolved-oxygen concentrations, and the pH of surface water downstream from the discharge. The cumulative impact of representative discharges from several coal mines on stream quality in a small watershed in southwestern Indiana was simulated to determine the effectiveness and sensitivity of the coupled programs.

Bobay, Keith, E.; Banaszak, Konrad, J.

1985-01-01

258

Structure of Highly Divided Nonstoichiometric Iron Manganese Oxide Powders Fe 3? x Mn x ? 3 ?\\/4 O 4+ ?  

Microsoft Academic Search

Highly divided iron manganese oxide powders, Fe3?xMnx?3?\\/4O4+?, were prepared at low temperature (T?560°C) by the thermal decomposition of mixed oxalate precursors Fe1??Mn?C2O4, 2H2O (?=x\\/3). The manganese-rich compounds (x?1.5) have a complex structure that can be cubic, tetragonal, or a mixture of both tetragonal and cubic spinel phases that indicates a lack of miscibility existing in the Fe3O4–Mn3O4 phase diagram at

Sophie Guillemet-Fritsch; Sophie Viguié; Abel Rousset

1999-01-01

259

Bio-templated synthesis of lithium manganese oxide microtubes and their application in Li+ recovery.  

PubMed

Microbial transformations, a primary pathway for the Mn oxides formation in nature, provide potential for material-oriented researchers to fabricate new materials. Using Mn oxidizing fungus Paraconiothyrium sp. WL-2 as a bio-oxidizer as well as a bio-template, a special lithium ion sieve with microtube morphology was prepared through a solid-state transformation. Varying the calcination temperature from 300 to 700 °C was found to influence sample properties and consequently, the adsorption of Li(+). Lithium manganese oxide microtube (LMO-MTs) calcined at different temperatures as well as their delithiated products (HMO-MTs) were characterized by X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Calcination temperatures affect not only the content but also the crystal structure of LMO spinel, which is important in Li(+) adsorption. The optimized sample was obtained after calcination at 500 °C for 4h, which shows higher Li(+) adsorption capacity than particulate materials. PMID:24007997

Yu, Qianqian; Sasaki, Keiko; Hirajima, Tsuyoshi

2013-11-15

260

Surface characteristics and in vitro biocompatibility of a manganese-containing titanium oxide surface  

NASA Astrophysics Data System (ADS)

This study investigated the surface characteristics and in vitro biocompatibility of a titanium (Ti) oxide layer incorporating the manganese ions (Mn) obtained by hydrothermal treatment with the expectation of utilizing potent integrin-ligand binding enhancement effect of Mn for future applications as an endosseous implant surface. The surface characteristics were evaluated by scanning electron microscopy, thin-film X-ray diffractometry, X-ray photoelectron spectroscopy, optical profilometry and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The in vitro biocompatibility of the Mn-containing Ti oxide surface was evaluated in comparison with untreated bare Ti using a mouse calvaria-derived osteoblastic cell line (MC3T3-E1). The hydrothermal treatment produced a nanostructured Mn-incorporated Ti oxide layer approximately 0.6 ?m thick. ICP-AES analysis demonstrated that the Mn ions were released from the hydrothermally treated surface into the solution. Mn incorporation notably decreased cellular attachment, spreading, proliferation, alkaline phosphatase activity, and osteoblast phenotype gene expression compared with the bare Ti surface ( p < 0.05). The results indicate that the Mn-incorporation into the surface Ti oxide layer has no evident beneficial effects on osteoblastic cell function, but instead, actually impaired cell behavior.

Park, Jin-Woo; Kim, Youn-Jeong; Jang, Je-Hee

2011-11-01

261

Intermediates of a polynuclear manganese center involved in photosynthetic oxidation of water  

PubMed Central

Electron paramagnetic resonance of spinach chloroplasts given a series of laser flashes, n = 0, 1,..., 6, at room temperature and rapidly cooled to -140°C reveals a signal possessing at least 16 and possibly 21 or more hyperfine lines when observed below 35 K. The spectrum is consistent with a pair of antiferromagnetically coupled Mn ions, or possibly a tetramer of Mn ions, in which Mn(III) and Mn(IV) oxidation states are present. The intensity of this signal peaks on the first and fifth flashes, suggesting a cyclic change in oxidation state of period 4. The multiline signal produced on the first flash is not affected by the electron transport inhibitor 3-(3,4-dichlorophenyl)-1,1-dimethylurea but is abolished by agents that influence the state of bound manganese, such as incubation with alkaline Tris, or dithionite, and by extraction with cholate detergent in the presence of ammonium sulfate. These results indicate that the paramagnetic signal is monitoring oxidation state changes in the enzyme involved in oxidation of water.

Dismukes, G. Charles; Siderer, Yona

1981-01-01

262

Rare earth element sorption onto hydrous manganese oxide: a modeling study.  

PubMed

Manganese oxides are important scavengers of rare earth elements (REE) in hydrosystems. However, it has been difficult to include Mn oxides in speciation models due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), as well as discrepancies between published sorption data and predictions using the available models. Surface complexation reactions for hydrous Mn oxide were described using a two surface site model and the diffuse double layer SCM. The specific surface area, surface side density, and pH(zpc) were fixed to 746 m2/g, 2.1 mmol/g, and 2.2, respectively. Two site types (?XOH and ?YOH) were also used with pK(a2) values of 2.35 (?XOH) and 6.06 (?YOH). The fraction of the high affinity sites was fixed at 0.36. Published REE sorption data were subsequently used to determine the equilibrium surface complexation constants, while considering the influence of pH, ionic strength, and metal loading. LogK increases from light REE to heavy REE and, more specifically, displays a convex tetrad effect. At low metal loading, the ?YOH site type strongly expresses its affinity toward REE, whereas at higher metal loading, the same is true for the ?XOH site type. This study thus provides evidence for heterogeneity in the distribution of the Mn oxide binding sites among REE. PMID:23266025

Pourret, Olivier; Davranche, Mélanie

2013-04-01

263

Mesoporous iron–manganese oxides for sulphur mustard and soman degradation  

SciTech Connect

Graphical abstract: Display Omitted Highlights: ? New nanodispersive materials based on Fe and Mn oxides for degradations of warfare agents. ? The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min). ? One pot synthesis with friendly transformed to industrial conditions. -- Abstract: Substituted iron(III)–manganese(III, IV) oxides, ammonio-jarosite and birnessite, were prepared by a homogeneous hydrolysis of potassium permanganate and iron(III) sulphate with 2-chloroacetamide and urea, respectively. Synthesised oxides were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy and scanning electron microscopy (SEM). The oxides were taken for an experimental evaluation of their reactivity against sulphur mustard (HD) and soman (GD). When ammonio-jarosite formation is suppressed by adding urea to the reaction mixture, the reaction products are mixtures of goethite, schwertmannite and ferrihydrite, and their degradation activity against soman considerably increases. The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min) were observed for FeMn{sub 7}5 with 32.6 wt.% Fe (36.8 wt.% Mn) and FeMn{sub 3}7U with 60.8 wt.% Fe (10.1 wt.% Mn) samples, respectively.

Štengl, Václav, E-mail: stengl@iic.cas.cz [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic) [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic); J.E. Purkyn? University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem (Czech Republic); Grygar, Tomáš Matys [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic) [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic); J.E. Purkyn? University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem (Czech Republic); Bludská, Jana [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic)] [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 ?ež (Czech Republic); Opluštil, František; N?mec, Tomáš [Military Technical Institute of Protection Brno, Vesla?ská 230, 628 00 Brno (Czech Republic)] [Military Technical Institute of Protection Brno, Vesla?ská 230, 628 00 Brno (Czech Republic)

2012-12-15

264

A quantitative discrimination between reversible Li +-insertion and irreversible solvent oxidation at a lithium\\/manganese-spinel electrode  

Microsoft Academic Search

Oxidic Li+-insertion compounds of the donor type in aprotic Li+-electrolytes are of high practical importance as positives in rechargeable Li+-ion batteries. The manganese oxides MnOx are of special interest as host lattices due to their high reversibility and to the relatively positive potentials. However, these materials may induce irreversible anodic decomposition of the organic solvent molecules, especially towards the end

R. Chromik; F. Beck

2000-01-01

265

Determination of the point-of-zero, charge of manganese oxides with different methods including an improved salt titration method  

Microsoft Academic Search

Manganese (Mn) oxides are important components in soils and sediments. Points-of-zero charge (PZC) of three synthetic Mn oxides (birnessite, cryptomelane, and todorokite) were determined by using three classical techniques (potentiometric titration or PT, rapid PT or R-PT, and salt titration or ST) and a modified salt titration method with a prolonged equilibration time (ST method with a prolonged equilibration time

Wen-feng Tan; Si-jun Lu; Fan Liu; Xiong-han Feng; Ji-zheng He; Luuk K. Koopal

2008-01-01

266

Doubling the capacity of lithium manganese oxide spinel by a flexible skinny graphitic layer.  

PubMed

By coating nanoparticular lithium manganese oxide (LMO) spinel with a few layers of graphitic basal planes, the capacity of the material reached up to 220?mA?h?g(-1) at a cutoff voltage of 2.5?V. The graphitic layers 1)?provided a facile electron-transfer highway without hindering ion access and, more interestingly, 2)?stabilized the structural distortion at the 3?V region reaction. The gain was won by a simple method in which microsized LMO was ball-milled in the presence of graphite with high energy. Vibratory ball milling pulverized the LMO into the nanoscale, exfoliated graphite of less than 10?layers and combined them together with an extremely intimate contact. Ab?initio calculations show that the intrinsically very low electrical conductivity of the tetragonal phase of the LMO is responsible for the poor electrochemical performance in the 3?V region and could be overcome by the graphitic skin strategy proposed. PMID:24706561

Noh, Hyun Kuk; Park, Han-Saem; Jeong, Hu Young; Lee, Sang Uck; Song, Hyun-Kon

2014-05-12

267

Light-induced multistep oxidation of dinuclear manganese complexes for artificial photosynthesis  

Microsoft Academic Search

Two dinuclear manganese complexes, [Mn2BPMP(?-OAc)2]·ClO4 (1, where BPMP is the anion of 2,6-bis{[N,N-di(2-pyridinemethyl)amino]methyl}-4-methylphenol) and [Mn2L(?-OAc)2]·ClO4 (2, where L is the trianion of 2,6-bis{[N-(2-hydroxy-3,5-di-tert-butylbenzyl)-N-(2-pyridinemethyl)amino]methyl}-4-methylphenol), undergo several oxidations by laser flash photolysis, using rutheniumII-tris-bipyridine (tris(2,2-bipyridyl)dichloro-ruthenium(II) hexahydrate) as photo-sensitizer and penta-amminechlorocobalt(III) chloride as external electron acceptor. In both complexes stepwise electron transfer was observed. In 1, four Mn-valence states from the initial Mn2II,II

Ping Huang; Joakim Högblom; Magnus F. Anderlund; Licheng Sun; Ann Magnuson; Stenbjörn Styring

2004-01-01

268

Electrodeposited amorphous manganese oxide nanowire arrays for high energy and power density electrodes  

NASA Astrophysics Data System (ADS)

Arrays of manganese oxide nanowires were electrodeposited into anodized alumina membranes. These nanowire arrays were investigated in terms of their structural and electrochemical properties as cathodes for high energy and high power density Li ion batteries. The nanowire arrays were assembled with a Li counter electrode and non-aqueous electrolyte to form secondary batteries. These cells were capable of multiple charge/discharge cycles, with a cathode specific capacity of approximately 300 mA h/g. Though the cathodes were fabricated without any binder or conductive additives, the electrodes could be discharged at current densities up to 0.1 mA/cm 2 before the onset of any significant polarization.

West, W. C.; Myung, N. V.; Whitacre, J. F.; Ratnakumar, B. V.

269

Reaction of Formic Acid over Amorphous Manganese Oxide Catalytic Systems: An In Situ Study  

SciTech Connect

The interaction of formic acid with amorphous manganese oxide (AMO) is investigated using in situ photoelectron and infrared spectroscopy techniques. Soft X-ray photoelectron spectroscopy (sXPS) and in situ FTIR illustrate two possible modes of formate bound species at the AMO surface. Two peaks in the IR region from 1340-1390 cm{sup -1} are indicative of formate species bound to the surface in a bidentate configuration. However, a 224 cm{sup -1} band gap between v{sub s}OCO and v{sub as}OCO suggests formate is bound in a bridging configuration. Temperature-programmed desorption studies confirm the formate bound species desorbs as carbon dioxide from the surface at multiple binding sites. At temperatures above 700 K, the presence of K{sup +} {hor_ellipsis} OC complex suggests the bound species interacts at vacant sites related to framework oxygen and cation mobility.

J Durand; S Senanayake; S Suib; D Mullins

2011-12-31

270

Reaction of Formic Acid over Amorphous Manganese Oxide Catalytic Systems: An In Situ Study  

SciTech Connect

The interaction of formic acid with amorphous manganese oxide (AMO) is investigated using in situ photoelectron and infrared spectroscopy techniques. Soft X-ray photoelectron spectroscopy (sXPS) and in situ FTIR illustrate two possible modes of formate bound species at the AMO surface. Two peaks in the IR region from 1340-1390 cm{sup -1} are indicative of formate species bound to the surface in a bidentate configuration. However, a 224 cm{sup -1} band gap between v{sub s}OCO and v{sub as}OCO suggests formate is bound in a bridging configuration. Temperature-programmed desorption studies confirm the formate bound species desorbs as carbon dioxide from the surface at multiple binding sites. At temperatures above 700 K, the presence of K{sup +} {hor_ellipsis} OC complex suggests the bound species interacts at vacant sites related to framework oxygen and cation mobility.

Durand, Jason [University of Connecticut; Senanayake, Sanjaya D [ORNL; Mullins, David R [ORNL; Suib, Steven [ORNL

2010-01-01

271

A 4 V lithium manganese oxide cathode for rocking-chair lithium-ion cells  

SciTech Connect

Composite cathodes for lithium-ion rocking-chair cells have been fabricated based on LiMn[sub 2]O[sub 4] which was synthesized by a new solution route that may be carried out in air. These cathodes have been cycled in three-electrode cells at discharge and charging current densities of 1 and 0.5 mA cm[sup [minus]2], respectively (corresponding to a discharge rate of C/2), between limits of 4.4 and 3.3 V. The specific discharge capacity obtained initially is 110 mAhg[sup [minus]1] of active material decreasing by only 25 mAhg[sup [minus]1] to yield a capacity of 85 mAhg[sup [minus]1] at 300 cycles. This performed is very promising in the context of developing rechargeable lithium-ion batteries using lithium manganese oxide-based positive electrodes.

Huang, Haitao; Bruce, P.G. (Univ. of St. Andrews, Fife (United Kingdom). School of Chemistry)

1994-09-01

272

Deposition and release of graphene oxide nanomaterials using a quartz crystal microbalance.  

PubMed

Interactions of graphene oxide (GO) with silica surfaces were investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). Both GO deposition and release were monitored on silica- and poly-l-lysine (PLL) coated surfaces as a function of GO concentration and in NaCl, CaCl2, and MgCl2 as a function of ionic strength (IS). Under favorable conditions (PLL-coated positive surface), GO deposition rates increased with GO concentration, as expected from colloidal theory. Increased NaCl concentration resulted in a greater deposition attachment efficiency of GO on the silica surface, indicating that deposition of GO follows Derjaguin-Landau-Verwey-Overbeek (DLVO) theory; GO deposition rates decreased at high IS, however, due to large aggregate formation. GO critical deposition concentration (CDC) on the silica surface is determined to be 40 mM NaCl which is higher than the reported CDC values of fullerenes and lower than carbon nanotubes. A similar trend is observed for MgCl2 which has a CDC value of 1.2 mM MgCl2. Only a minimal amount of GO (frequency shift <2 Hz) was deposited on the silica surface in CaCl2 due to the bridging ability of Ca(2+) ions with GO functional groups. Significant GO release from silica surface was observed after adding deionized water, indicating that GO deposition is reversible. The release rates of GO were at least 10-fold higher than the deposition rates under similar conditions indicating potential high release and mobility of GO in the environment. Under favorable conditions, a significant amount of GO was released which indicates potential multilayer GO deposition. However, a negligible amount of deposited GO was released in CaCl2 under favorable conditions due to the binding of GO layers with Ca(2+) ions. Release of GO was significantly dependent on salt type with an overall trend of NaCl > MgCl2 > CaCl2. PMID:24345218

Chowdhury, Indranil; Duch, Matthew C; Mansukhani, Nikhita D; Hersam, Mark C; Bouchard, Dermont

2014-01-21

273

Recovery of manganese oxides from spent alkaline and zinc-carbon batteries. An application as catalysts for VOCs elimination.  

PubMed

Manganese, in the form of oxide, was recovered from spent alkaline and zinc-carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO4 solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnOx synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn2O3 in the EMO and the CMO samples, together with some Mn(4+) cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn3O4. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200°C, while heptane requires more than 400°C. The CMO has the highest oxide selectivity to CO2. The results show that manganese oxides obtained using spent alkaline and zinc-carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs. PMID:23562448

Gallegos, María V; Falco, Lorena R; Peluso, Miguel A; Sambeth, Jorge E; Thomas, Horacio J

2013-06-01

274

Theory of chemical bonds in metalloenzymes - Manganese oxides clusters in the oxygen evolution center -  

NASA Astrophysics Data System (ADS)

In early 1980 we have initiated broken-symmetry (BS) MO theoretical calculations of transition-metal oxo species M = O (M = Ti,V,Cr,Mn,Fe,Ni,Cu) to elucidate the nature of d?-p? and d?-p? bonds. It has been concluded that high-valent M = O species such as [Mn(IV) = O]2+ and [Fe(IV) = O]2+ exhibit electrophilic property in a sharp contrast with nucleophilic character of low-valent M = O bonds: [M(II)O2-]0, and closed-shell d?-p? bonds of high-valent M = O species often suffer the triplet-instability, giving rise to open-shell (BS) configurations with significant metal-diradical (MDR) character: •M-O•: note that these bonds are therefore regarded as typical examples of strongly correlated electron systems. Because of the MDR character, 1,4-metal diradical mechanism was indeed preferable to four-centered mechanism in the case of addition reaction of naked Mn(IV) = O to ethylene. Recently the manganese-oxo species have been receiving renewed interest in relation to catalytic cycle of oxygen evolution from water molecules in the photosynthesis II (PSII) system. Accumulated experimental results indicate that this process is catalyzed with four manganese oxide clusters coordinated with calcium ion (CaMn4O4). Past decade we have performed BS MO theoretical investigations of manganese oxide clusters related to CaMn4O4. These calculations have elucidated that high-valent Mn(X) = O (X = IV,V) bonds exhibit intermediate MDR character (y=40-60%) in the case of total low-spin (LS) configuration but the MDR character decreases with coordination of Ca2+ and water molecules. While the MDR character of the Mn-oxo bonds becomes very high at the high-spin (HS) configuration. Our computational results enabled us to propose two possible mechanisms on the theoretical ground: (A) electrophilic (EP) mechanism and (B) radical coupling (RC) mechanism. The theoretical results indicate that the EP mechanism is preferable for the low-spin (LS) state in polar media like in the protein environments (native OEC), whereas the RC mechanism is feasible at the state without such environmental stabilization: local singlet and local triplet diradical mechanisms are proposed for the OO coupling process. Possibilities of EP and RC mechanisms are examined in comparison with a lot of experimental results accumulated and theoretical results with several groups.

Yamaguchi, K.; Shoji, M.; Saito, T.; Isobe, H.; Yamada, S.; Nishihara, S.; Kawakami, T.; Kitagawa, Y.; Yamanaka, S.; Okumura, M.

2012-12-01

275

Hydrogen peroxide decomposition on manganese oxide (pyrolusite): kinetics, intermediates, and mechanism.  

PubMed

The objective of this study is the kinetic interpretation of hydrogen peroxide decomposition on manganese oxide (pyrolusite) and the explanation of the reaction mechanism including the hydroperoxide/superoxide anion. The decomposition of hydrogen peroxide on manganese oxide at pH 7 was represented by a pseudo first-order model. The maximum value of the observed first-order rates constants (k(obs)) was 0.741 min(-1) at 11.8 of [H(2)O(2)]/[triple bond MnO(2)] when [H(2)O(2)]/[triple bond MnO(2)] were ranged from 58.8 to 3.92. The pseudo first-order rate constants (kMnO(2)) approximated as the average value of 0.025 (min mM)(-1) with a standard deviation of 0.003 at [H(2)O(2)]/[triple bond MnO(2)] ranged from 39.2 to 11.8. When [H(2)O(2)]/[triple bond MnO(2)] was 3.92, the rate constants (kMnO(2)) was 0.061 (min mM)(-1) as maximum. Oxygen production showed that the initial rates increased with decreasing [H(2)O(2)]/[triple bond MnO(2)] and the total amounts of oxygen was slightly less than the stoichiometric value (0.5) in most experiments. However, oxygen was produced at more than 0.5 in low [H(2)O(2)]/[triple bond MnO(2)] (i.e. 3.92 and 9.79). The relative production of hydroperoxide/superoxide anion implied that the production increased with low [H(2)O(2)]/[triple bond MnO(2)], and the existence of anions suggested that the mechanism includes propagation reactions with intermediates such as hydroperoxide/superoxide anion in solution. In addition, both [H(2)O(2)] decomposition and the production of anion were accelerated in alkaline solution. Manganese ion dissolved into solution was negligible in neutral and alkaline conditions, but it greatly increased in acidic conditions. PMID:19136141

Do, Si-Hyun; Batchelor, Bill; Lee, Hong-Kyun; Kong, Sung-Ho

2009-03-01

276

Kinetics of oxidation of carbon in liquid iron-carbon-silicon-manganese-sulfur alloys by carbon dioxide in nitrogen  

NASA Astrophysics Data System (ADS)

The oxidation of carbon with the simultaneous oxidation of silicon, manganese, and iron of liquid alloys by carbon dioxide in nitrogen and the absorption of oxygen by the alloys from the gas were studied using 1-g liquid iron droplets levitated in a stream of the gas at 1575 °C to 1715 °C. Oxidation of carbon was favored over oxidation of silicon and manganese when cast iron (3.35 pct C, 2.0 pct Si, 0.36 pct Mn, and 0.05 pct S) reacted with CO2/N2 gas at 1635 °C. An increase in the flow rate of CO2/N2 gas increased the decarburization rate of cast iron. The rate of carbon oxidation by this gas mixture was found to be independent of temperature and alloying element concentrations (in the range of silicon = 0 to 2.0 pct manganese = 0 to 0.36 pct and sulfur = 0 to 0.5 pct) within the temperature range of the present study. Based on the results of a kinetic analysis, diffusion of CO2 in the boundary layer of the gas phase was found to be the rate-limiting step for the reactions during the earlier period of the reaction when the contents of carbon, silicon, and manganese are higher. However, the limiting step changed to diffusion of the elements in the metal phase during the middle period of the reaction and then to the diffusion of CO in the gas phase during the later period of the reaction when the content of the elements in the metal were relatively low. For the simultaneous oxidation reactions of several elements in the metal, however, the diffusion of CO2 in the gas phase is the primary limiting step of the reaction rate for the oxidation of carbon during the later period of reaction.

Sun, Haiping; Pehlke, Robert D.

1995-04-01

277

Nanostructured dimagnesium manganese oxide (Spinel): Control of size, shape and their magnetic and electro catalytic properties  

SciTech Connect

Tetravalent Mn based ternary oxides are of interest as they are important electrode materials. Dimagnesium manganate (Mg{sub 2}MnO{sub 4}) is one Mn(IV) containing oxide which has been of interest. Nanostructures of the above oxide (spinel) have been obtained by the thermal decomposition of nanostructured metal oxalate precursor at 500 Degree-Sign C. The size and anisotropy of the oxide nanostructures was controlled by choosing appropriate decomposition temperature of the oxalate precursor. Mg{sub 2}MnO{sub 4} nanorods were obtained at low temperature (500 Degree-Sign C), formed by aligned nanoparticles of size{approx}8-10 nm. These nanoparticles show Curie-Weiss behavior with Weiss constant (14 K). Below {approx}50 K there is a small deviation resulting in a negative Weiss constant (-7.36 K) indicating exchange cross over (from ferromagnetic like interactions to antiferromagnetic interactions). The high temperature magnetic moment corresponds to Mn (IV). Electrochemical experiments show that nanostructured Mg{sub 2}MnO{sub 4} is an efficient anode material for oxygen evolution reaction with a current density of 14 mA/cm{sup 2}. The stability of the anode over several cycles of oxidation and reduction is highly encouraging. - Graphical abstract: Nanostructured dimagnesium manganese with efficient electrocatalytic property synthesized by reverse micellar route. Highlights: Black-Right-Pointing-Pointer Mg{sub 2}MnO{sub 4} nanorods were synthesized by reverse micellar route. Black-Right-Pointing-Pointer Anisotropy of oxalate rods retained in oxides nanorods. Black-Right-Pointing-Pointer Nanorods show good catalytic behavior towards oxygen evolution reaction.

Garg, Neha; Menaka [Department of Chemistry, Indian Institute of Technology, Hauz Khas, New Delhi 110016 (India); Ramanujachary, Kandalam V. [Department of Chemistry and Biochemistry, Rowan University, Glassboro, NJ 08028 (United States); Lofland, Samuel E. [Department of Physics and Astronomy, Rowan University, Glassboro, NJ 08028 (United States); Ganguli, Ashok K., E-mail: ashok@chemistry.iitd.ernet.in [Department of Chemistry, Indian Institute of Technology, Hauz Khas, New Delhi 110016 (India)

2013-01-15

278

Metals, Oxidative Stress and Neurodegeneration: A focus on Iron, Manganese and Mercury  

PubMed Central

Essential metals are crucial for the maintenance of cell homeostasis. Among the 23 elements that have known physiological functions in humans, 12 are metals, including iron (Fe) and manganese (Mn). Nevertheless, excessive exposure to these metals may lead to pathological conditions, including neurodegeneration. Similarly, exposure to metals that do not have known biological functions, such as mercury (Hg), also present great health concerns. This reviews focuses on the neurodegenerative mechanisms and effects of Fe, Mn and Hg. Oxidative stress (OS), particularly in mitochondria, is a common feature of Fe, Mn and Hg toxicity. However, the primary molecular targets triggering OS are distinct. Free cationic iron is a potent pro-oxidant and can initiate a set of reactions that form extremely reactive products, such as OH•. Mn can oxidize dopamine (DA), generating reactive species and also affect mitochondrial function, leading to accumulation of metabolites and culminating with OS. Cationic Hg forms have strong affinity for nucleophiles, such as –SH and –SeH. Therefore, they target critical thiol- and selenol-molecules with antioxidant properties. Finally, we address the main sources of exposure to these metals, their transport mechanisms into the brain, and therapeutic modalities to mitigate their neurotoxic effects.

Farina, Marcelo; Avila, Daiana Silva; da Rocha, Joao Batista Teixeira

2013-01-01

279

Early diagenetic processes generate iron and manganese oxide layers in the sediments of Lake Baikal, Siberia.  

PubMed

Distinct layers of iron(III) and manganese(IV) (Fe/Mn) oxides are found buried within the reducing part of the sediments in Lake Baikal and cause considerable complexity and steep vertical gradients with respect to the redox sequence. For the on-site investigation of the responsible biogeochemical processes, we applied filter tube samplers for the extraction of sediment porewater combined with a portable capillary electrophoresis instrument for the analyses of inorganic cations and anions. On the basis of the new results, the sequence of diagenetic processes leading to the formation, transformation, and dissolution of the Fe/Mn layers was investigated. With two exemplary cores we demonstrate that the dissolution of particulate Fe and Mn is coupled to the anaerobic oxidation of CH? (AOM) either via the reduction of sulphate (SO?(2-)) and the subsequent generation of Fe(II) by S(-II) oxidation, or directly coupled to Fe reduction. Dissolved Fe(II) diffuses upwards to reduce particulate Mn(IV) thus forming a sharp mineral boundary. An alternative dissolution pathway is indicated by the occurrence of anaerobic nitrification of NH?(+) observed at locations with Mn(IV). Furthermore, the reasons and consequences of the non-steady-state sediment pattern and the resulting redox discontinuities are discussed and a suggestion for the burial of active Fe/Mn layers is presented. PMID:24619231

Torres, Natascha T; Och, Lawrence M; Hauser, Peter C; Furrer, Gerhard; Brandl, Helmut; Vologina, Elena; Sturm, Michael; Bürgmann, Helmut; Müller, Beat

2014-04-01

280

Effects of oxidative stress on apoptosis in manganese-induced testicular toxicity in cocks.  

PubMed

Manganese (Mn) is a trace element known to be essential for maintaining the proper function and regulation of many biochemical and cellular reactions. However, little is known about the reproductive toxicity of Mn in birds. To investigate the toxicity of Mn on male reproduction in birds, 50-day-old cocks were fed either a commercial diet or a Mn-supplemented diet containing 600, 900, and 1800 mg/kg MnCl?. After being treated with Mn for 30, 60, and 90 d, the following were determined: Mn content; histological and ultrastructural changes in the testes, apoptosis; the malondialdehyde (MDA) level; the activities of superoxide dismutase (SOD); the inhibition ability of hydroxyl radicals (OH); the levels of nitric oxide (NO), nitric oxide synthase (NOS), and protein carbonyl in the testes; the DNA-protein crosslinks (DPC); and the activity of the ATP enzyme. Exposure to Mn significantly lowered the activity of SOD and glutathione peroxidase (GPx) and the inhibition ability of OH. Mn exposure also increased the levels of MDA, NO, NOS, DPC, and protein carbonyl; the number of apoptotic cells; and the Mn content and caused obvious histopathological changes in the testes. These findings suggested that Mn exposure resulted in the oxidative damage of cock testicular tissue by altering radical formation, ATP enzyme systems, apoptosis, and DNA damage, which are possible underlying reproductive toxicity mechanisms induced by Mn exposure. PMID:23907021

Liu, Xiao-fei; Zhang, Li-ming; Guan, Hua-nan; Zhang, Zi-wei; Xu, Shi-wen

2013-10-01

281

Metals, oxidative stress and neurodegeneration: a focus on iron, manganese and mercury.  

PubMed

Essential metals are crucial for the maintenance of cell homeostasis. Among the 23 elements that have known physiological functions in humans, 12 are metals, including iron (Fe) and manganese (Mn). Nevertheless, excessive exposure to these metals may lead to pathological conditions, including neurodegeneration. Similarly, exposure to metals that do not have known biological functions, such as mercury (Hg), also present great health concerns. This review focuses on the neurodegenerative mechanisms and effects of Fe, Mn and Hg. Oxidative stress (OS), particularly in mitochondria, is a common feature of Fe, Mn and Hg toxicity. However, the primary molecular targets triggering OS are distinct. Free cationic iron is a potent pro-oxidant and can initiate a set of reactions that form extremely reactive products, such as OH. Mn can oxidize dopamine (DA), generating reactive species and also affect mitochondrial function, leading to accumulation of metabolites and culminating with OS. Cationic Hg forms have strong affinity for nucleophiles, such as -SH and -SeH. Therefore, they target critical thiol- and selenol-molecules with antioxidant properties. Finally, we address the main sources of exposure to these metals, their transport mechanisms into the brain, and therapeutic modalities to mitigate their neurotoxic effects. PMID:23266600

Farina, Marcelo; Avila, Daiana Silva; da Rocha, João Batista Teixeira; Aschner, Michael

2013-04-01

282

Manganese Doping of Magnetic Iron Oxide Nanoparticles: Tailoring Surface Reactivity for a Regenerable Heavy Metal Sorbent  

SciTech Connect

A method for tuning the analyte affinity of magnetic, inorganic nanostructured sorbents for heavy metal contaminants is described. The manganese-doped iron oxide nanoparticle sorbents have a remarkably high affinity compared to the precursor material. Sorbent affinity can be tuned toward an analyte of interest simply by adjustment of the dopant quantity. The results show that following the Mn doping process there is a large increase in affinity and capacity for heavy metals (i.e., Co, Ni, Zn, As, Ag, Cd, Hg, and Tl). Capacity measurements were carried out for the removal of cadmium from river water and showed significantly higher loading than the relevant commercial sorbents tested for comparison. The reduction in Cd concentration from 100 ppb spiked river water to 1 ppb (less than the EPA drinking water limit of 5 ppb for Cd) was achieved following treatment with the Mn-doped iron oxide nanoparticles. The Mn-doped iron oxide nanoparticles were able to load 1 ppm of Cd followed by complete stripping and recovery of the Cd with a mild acid wash. The Cd loading and stripping is shown to be consistent through multiple cycles with no loss of sorbent performance.

Warner, Cynthia L.; Chouyyok, Wilaiwan; Mackie, Katherine E.; Neiner, Doinita; Saraf, Laxmikant; Droubay, Timothy C.; Warner, Marvin G.; Addleman, Raymond S.

2012-02-28

283

A simple mathematical model for manganese oxide-coated montmorillonite as a catalyst for water oxidation: from nano to macro sized manganese oxide.  

PubMed

Here, we propose a mathematical model that gives a good fit to the experimental data for water oxidation by Mn oxide-coated montmorillonite with different Mn content. Our data show that the water oxidation may progress by cooperation among only neighbor Mn ions on montmorillonite. It is a promising model for finding more about the mechanism of multi-electron reactions. PMID:23797618

Najafpour, Mohammad Mahdi; Nemati Moghaddam, Atefeh; Sakha, Yousef

2013-08-14

284

Photochemical oxidation of a manganese(III) complex with oxygen and toluene derivatives to form a manganese(V)-oxo complex.  

PubMed

Visible light photoirradiation of an oxygen-saturated benzonitrile solution of a manganese(III) corrolazine complex [(TBP8Cz)Mn(III)] (1): [TBP8Cz = octakis(p-tert-butylphenyl)corrolazinato(3-)] in the presence of toluene derivatives resulted in formation of the manganese(V)-oxo complex [(TBP8Cz)Mn(V)(O)]. The photochemical oxidation of (TBP8Cz)Mn(III) with O2 and hexamethylbenzene (HMB) led to the isosbestic conversion of 1 to (TBP8Cz)Mn(V)(O), accompanied by the selective oxidation of HMB to pentamethylbenzyl alcohol (87%). The formation rate of (TBP8Cz)Mn(V)(O) increased with methyl group substitution, from toluene, p-xylene, mesitylene, durene, pentamethylbenzene, up to hexamethylbenzene. Deuterium kinetic isotope effects (KIEs) were observed for toluene (KIE = 5.4) and mesitylene (KIE = 5.3). Femtosecond laser flash photolysis of (TBP8Cz)Mn(III) revealed the formation of a tripquintet excited state, which was rapidly converted to a tripseptet excited state. The tripseptet excited state was shown to be the key, activated state that reacts with O2 via a diffusion-limited rate constant. The data allow for a mechanism to be proposed in which the tripseptet excited state reacts with O2 to give the putative (TBP8Cz)Mn(IV)(O2(•-)), which then abstracts a hydrogen atom from the toluene derivatives in the rate-determining step. The mechanism of hydrogen abstraction is discussed by comparison of the reactivity with the hydrogen abstraction from the same toluene derivatives by cumylperoxyl radical. Taken together, the data suggest a new catalytic method is accessible for the selective oxidation of C-H bonds with O2 and light, and the first evidence for catalytic oxidation of C-H bonds was obtained with 10-methyl-9,10-dihydroacridine as a substrate. PMID:24219426

Jung, Jieun; Ohkubo, Kei; Prokop-Prigge, Katharine A; Neu, Heather M; Goldberg, David P; Fukuzumi, Shunichi

2013-12-01

285

Quartz crystal microbalance coated with sol–gel-derived indium–tin oxide thin films as gas sensor for NO detection  

Microsoft Academic Search

This paper presents the possibilities and properties of indium–tin oxide (ITO)-covered quartz crystal microbalances (QCM) as a NOx toxic gas sensors. The starting sol–gel solution was prepared by mixing indium chloride dissolved in acetylacetone and tin chloride dissolved in ethanol (0–20% by weight). The ITO thin films were deposited on the gold electrodes of quartz crystals by spin-coating and annealing

J Zhang; J Hu; Z. Q Zhu; H Gong; S. J O’Shea

2004-01-01

286

Zinc oxide nanorod growth on gold islands prepared by microsphere lithography on silicon and quartz.  

PubMed

Gold islands, vapor deposited on silicon and quartz by microsphere lithography patterning, are used to nucleate arrays of ZnO nanorods. ZnO is grown on approximately 0.32 microm2 Au islands by carbothermal reduction in a tube furnace. Scanning electron microscopy (SEM) and energy dispersive atomic X-ray spectroscopy (EDS) confirm that the gold effectively controls the sites of nucleation of ZnO. Atomic force microscopy (AFM) shows that approximately 30 nm diameter nanorods grow horizontally, along the surface. Alloy droplets that are characteristic of the vapor-liquid-solid (VLS) mechanism are observed at the tips of the nanorods. The spatial growth direction of VLS catalyzed ZnO nanorods is along the substrate when they nucleate from gold islands on silicon and quartz. The energy of adhesion of the VLS droplet to the surface can account for the horizontal growth. PMID:18019171

Blackledge, Charles W; Szarko, Jodi M; Dupont, Aurélie; Chan, George H; Read, Elizabeth L; Leone, Stephen R

2007-09-01

287

Superoxide production by a manganese-oxidizing bacterium facilitates iodide oxidation.  

PubMed

The release of radioactive iodine (i.e., iodine-129 and iodine-131) from nuclear reprocessing facilities is a potential threat to human health. The fate and transport of iodine are determined primarily by its redox status, but processes that affect iodine oxidation states in the environment are poorly characterized. Given the difficulty in removing electrons from iodide (I(-)), naturally occurring iodide oxidation processes require strong oxidants, such as Mn oxides or microbial enzymes. In this study, we examine iodide oxidation by a marine bacterium, Roseobacter sp. AzwK-3b, which promotes Mn(II) oxidation by catalyzing the production of extracellular superoxide (O2(-)). In the absence of Mn(2+), Roseobacter sp. AzwK-3b cultures oxidized ?90% of the provided iodide (10 ?M) within 6 days, whereas in the presence of Mn(II), iodide oxidation occurred only after Mn(IV) formation ceased. Iodide oxidation was not observed during incubations in spent medium or with whole cells under anaerobic conditions or following heat treatment (boiling). Furthermore, iodide oxidation was significantly inhibited in the presence of superoxide dismutase and diphenylene iodonium (a general inhibitor of NADH oxidoreductases). In contrast, the addition of exogenous NADH enhanced iodide oxidation. Taken together, the results indicate that iodide oxidation was mediated primarily by extracellular superoxide generated by Roseobacter sp. AzwK-3b and not by the Mn oxides formed by this organism. Considering that extracellular superoxide formation is a widespread phenomenon among marine and terrestrial bacteria, this could represent an important pathway for iodide oxidation in some environments. PMID:24561582

Li, Hsiu-Ping; Daniel, Benjamin; Creeley, Danielle; Grandbois, Russell; Zhang, Saijin; Xu, Chen; Ho, Yi-Fang; Schwehr, Kathy A; Kaplan, Daniel I; Santschi, Peter H; Hansel, Colleen M; Yeager, Chris M

2014-05-01

288

A Quartz tuning fork-based humidity sensor using Nanocrystalline Zinc oxide thin film coatings  

Microsoft Academic Search

This paper describes an application of quartz tuning forks (QTF) coated with nanocrystalline ZnO films used as relative humidity sensors. The nanocrystalline ZnO thin films were deposited on the QTF by sol-gel method. The film was characterized by X-Ray Diffraction (XRD) and Atomic Force Microscope (AFM) to obtain the information on the structural and morphological properties. And the humidity sensitivity

Xiaofeng Zhou; Tao Jiang; Jian Zhang; Jianzhong Zhu; Xiaohua Wang; Ziqiang Zhu

2006-01-01

289

Manganese triazacyclononane oxidation catalysts grafted under reaction conditions on solid cocatalytic supports.  

PubMed

Manganese complexes of 1,4,7-trimethyl-1,4,7-triazacyclononane (tmtacn) are highly active and selective alkene oxidation catalysts with aqueous H(2)O(2). Here, carboxylic acid-functionalized SiO(2) simultaneously immobilizes and activates these complexes under oxidation reaction conditions. H(2)O(2) and the functionalized support are both necessary to transform the inactive [(tmtacn)Mn(IV)(?-O)(3)Mn(IV)(tmtacn)](2+) into the active, dicarboxylate-bridged [(tmtacn)Mn(III)(?-O)(?-RCOO)(2)Mn(III)(tmtacn)](2+). This transformation is assigned on the basis of comparison of diffuse reflectance UV-visible spectra to known soluble models, assignment of oxidation state by Mn K-edge X-ray absorption near-edge spectroscopy, the dependence of rates on the acid/Mn ratios, and comparison of the surface structures derived from density functional theory with extended X-ray absorption fine structure. Productivity in cis-cyclooctene oxidation to epoxide and cis-diol with 2-10 equiv of solid cocatalytic supports is superior to that obtained with analogous soluble valeric acid cocatalysts, which require 1000-fold excess to reach similar levels at comparable times. Cyclooctene oxidation rates are near first order in H(2)O(2) and near zero order in all other species, including H(2)O. These observations are consistent with a mechanism of substrate oxidation following rate-limiting H(2)O(2) activation on the hydrated, supported complex. This general mechanism and the observed alkene oxidation activation energy of 38 ± 6 kJ/mol are comparable to H(2)O(2) activation by related soluble catalysts. Undesired decomposition of H(2)O(2) is not a limiting factor for these solid catalysts, and as such, productivity remains high up to 25 °C and initial H(2)O(2) concentration of 0.5 M, increasing reactor throughput. These results show that immobilized carboxylic acids can be utilized and understood like traditional carboxylic acids to activate non-heme oxidation catalysts while enabling higher throughput and providing the separation and handling benefits of a solid catalyst. PMID:21970696

Schoenfeldt, Nicholas J; Ni, Zhenjuan; Korinda, Andrew W; Meyer, Randall J; Notestein, Justin M

2011-11-23

290

Energetics of the manganese oxide cluster cations MnNO+ (N=2-5): Role of oxygen in the binding of manganese atoms  

NASA Astrophysics Data System (ADS)

The photodissociation of manganese oxide cluster cations MnNO+ (N=2-5), into MnN-1O+ (one-atom loss) and MnN-2O+ (two-atom), was investigated in the photon-energy range of 1.08-2.76 eV. The bond-dissociation energies D0(MnN-1O+...Mn) for N=3, 4, and 5 were determined to be 1.84+/-0.03, 0.99+/-0.05, and 1.25+/-0.14 eV, respectively, from the threshold energies for the one- and two-atom losses. As Mn2O+ did not dissociate even at the highest photon energy used, the bond dissociation energy of Mn2O+, D0(Mn+...MnO), was obtained from a density-functional-theory calculation to be 3.04 eV. The present findings imply that the core ion Mn2O+ is bound weakly with the rest of the manganese atoms in MnNO+.

Tono, Kensuke; Terasaki, Akira; Ohta, Toshiaki; Kondow, Tamotsu

2006-05-01

291

Oxidative removal of bisphenol A by manganese dioxide: efficacy, products, and pathways.  

PubMed

Bisphenol A (BPA) is a ubiquitous environmental contaminant with endocrine disruption potential. In this study, exploiting the outstanding oxidative capacity of manganese dioxide (delta-MnO2), we explored forthe firsttime the efficacy and mechanisms of BPA removal by MnO2. In aqueous solutions, MnO2 demonstrated an extremely efficient capacity to remove BPA. Nearly all BPA (>99%) was eliminated in 6 min in a pH 4.5 solution initially containing 800 microM MnO2 and 4.4 microM BPA. While humic acid showed negligible inhibition on BPA removal, coexisting metal ions such as Mn2+, Ca2+, Mg2+, and Fe3+ displayed suppressive effects and the inhibitive capacityfollowed the order Mn2+ > Ca2+ > Mg2+ approximately Fe3+. A total of 11 products or intermediates were indentified and a detailed reaction scheme was suggested. The products could be ascribed to a suite of reactions of radical coupling, fragmentation, substitution, and elimination, triggered by the BPA radical formed through electron transfers to MnO2. The exceptional efficiency of MnO2 in removing BPA represents a potential use of MnO2 to treat waters containing phenolic compounds and also suggests a potentially important role of oxide-facilitated abiotic transformations in BPA attenuation in natural soil and sediment environments. PMID:19544899

Lin, Kunde; Liu, Weiping; Gant, Jay

2009-05-15

292

Composite manganese oxide percolating networks as a suspension electrode for an asymmetric flow capacitor.  

PubMed

In this study, we examine the use of a percolating network of metal oxide (MnO2) as the active material in a suspension electrode as a way to increase the capacitance and energy density of an electrochemical flow capacitor. Amorphous manganese oxide was synthesized via a low-temperature hydrothermal approach and combined with carbon black to form composite flowable electrodes of different compositions. All suspension electrodes were tested in static configurations and consisted of an active solid material (MnO2 or activated carbon) immersed in aqueous neutral electrolyte (1 M Na2SO4). Increasing concentrations of carbon black led to better rate performance but at the cost of capacitance and viscosity. Furthermore, it was shown that an expanded voltage window of 1.6 V could be achieved when combining a composite MnO2-carbon black (cathode) and an activated carbon suspension (anode) in a charge balanced asymmetric device. The expansion of the voltage window led to a significant increase in the energy density to ?11 Wh kg(-1) at a power density of ?50 W kg(-1). These values are ?3.5 times and ?2 times better than a symmetric suspension electrode based on activated carbon. PMID:24758221

Hatzell, Kelsey B; Fan, Lei; Beidaghi, Majid; Boota, Muhammad; Pomerantseva, Ekaterina; Kumbur, Emin C; Gogotsi, Yury

2014-06-11

293

Manganese peroxidase degrades pristine but not surface-oxidized (carboxylated) single-walled carbon nanotubes.  

PubMed

The transformation of engineered nanomaterials in the environment can significantly affect their transport, fate, bioavailability, and toxicity. Little is known about the biotransformation potential of single-walled carbon nanotubes (SWNTs). In this study, we compared the enzymatic transformation of SWNTs and oxidized (carboxylated) SWNTs (O-SWNTs) using three ligninolytic enzymes: lignin peroxidase, manganese peroxidase (MnP), and laccase. Only MnP was capable of transforming SWNTs, as determined by Raman spectroscopy, near-infrared spectroscopy, and transmission electron microscopy. Interestingly, MnP degraded SWNTs but not O-SWNTs. The recalcitrance of O-SWNTs to enzymatic transformation is likely attributable to the binding of Mn(2+) by their surface carboxyl groups at the enzyme binding site, which inhibits critical steps in the MnP catalytic cycle (i.e., Mn(2+) oxidation and Mn(3+) dissociation from the enzyme). Our results suggest that oxygen-containing surface functionalities do not necessarily facilitate the biodegradation of carbonaceous nanomaterials, as is commonly assumed. PMID:24988479

Zhang, Chengdong; Chen, Wei; Alvarez, Pedro J J

2014-07-15

294

Growth of manganese oxide nanostructures alters the layout of adhesion on a carbonate substrate.  

PubMed

Nanostructures grown under natural conditions can modify the layout of adhesion on mineral surfaces. Using force-volume microscopy and a silicon-nitride probe, we measure changes in adhesion when a patchy overgrowth of manganese oxide nanostructures forms on the surface of rhodochrosite. For the most part, the observations show that the adhesive force to the nanostructures is dominated by van-der-Waals attraction. Measurements made across an area of the surface provide a frequency distribution of adhesive forces, and the mode of this distribution is 166 pN at pH 5.0, increasing to a maximum of 692 pN at pH 7.1, followed by a decrease to 275 pN at pH 9.7. At a few sampling locations over some nanostructures, electrostatic repulsion overtakes van-der-Waals attraction and thus results in negative adhesive forces (i.e., repulsion). Local roughness causes this effect. In comparison to the oxide nanostructures, the exposed rhodochrosite substrate has negligible adhesive force with the probe over the same pH range, suggesting both weak van-der-Waals attraction and weak electrostatic repulsion over this pH range. The quantitative mapping of adhesive force applied more generally to the study of other nanostructures can lead to an improved mechanistic understanding of how nanostructure growth influences contaminant immobilization and bacterial attachment. PMID:19673293

Na, Chongzheng; Martin, Scot T

2009-07-01

295

Oxidative precipitation of arsenic(III) with manganese(II) and iron(II) in dilute acidic solution by ozone  

Microsoft Academic Search

Oxidative precipitation using ozone has been examined for removal of arsenic with manganese from dilute acidic sulfate solution under the following conditions: the initial concentrations of arsenic(III) and arsenic(V)=1–100 mg\\/L, the initial mole ratio of Mn\\/As=10–100, pH=0.4–5.0 and temperature=15–80 °C. The oxidation–reduction potential (ORP) of the system was continuously measured to monitor the process of oxidation reactions. The O3–O2 gas

T Nishimura; Y Umetsu

2001-01-01

296

Lithium extraction from orthorhombic lithium manganese oxide and the phase transformation to spinel  

SciTech Connect

Development of rechargeable lithium batteries is limited by a concern regarding their safety. Current efforts are focused on rocking-chair'' cells which avoid the use of metallic lithium electrodes and are therefore potentially far safer than conventional lithium cells. Carbon is the anode material of choice for rocking-chair'' cells as it gives good reversibility, high capacity and low average voltage versus lithium, resulting in high energy density cells. Carbon anodes must be coupled with lithium-rich or discharged cathodes. When the cell is first charged, lithium is transferred from the lithium-rich cathode to the carbon anode. However, not all the lithium can be recovered from the anode on the subsequent discharge; surplus cathode capacity is therefore required in the initial cathode to counteract this loss. Lithium transition-metal oxides are being developed as cathode materials for rocking-chair'' batteries. Lithium manganese oxides, which are cheap and non-toxic, are favored over the lithium-cobalt-oxide, LiCoO[sub 2], and lithium-nickel-oxide, LiNiO[sub 2].Here, orthorhombic LiMnO[sub 2] products, synthesized by the reaction of [gamma]-MnO[sub 2] and LiOH in argon at 600--620 C using carbon as a reducing agent, have been evaluated as electrode materials in lithium cells. Products that contained a minor proportion of a lithiated spinel phase showed greater electrochemical activity than pure LiMnO[sub 2]. On delithiation, LiMnO[sub 2] transforms irreversibly to a spinel-type structure. A mechanism for the orthorhombic Li[sub x]MnO[sub 2]-spinel phase transformation is proposed.

Gummow, R.J.; Liles, D.C.; Thackeray, M.M. (CSIR, Pretoria (South Africa). Div. of Materials Science and Technology)

1993-12-01

297

Spatially Resolved Characterization of Biogenic Manganese Oxide Production within a Bacterial Biofilm  

PubMed Central

Pseudomonas putida strain MnB1, a biofilm-forming bacterial culture, was used as a model for the study of bacterial Mn oxidation in freshwater and soil environments. The oxidation of aqueous Mn+2 [Mn+2(aq)] by P. putida was characterized by spatially and temporally resolving the oxidation state of Mn in the presence of a bacterial biofilm, using scanning transmission X-ray microscopy (STXM) combined with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy at the Mn L2,3 absorption edges. Subsamples were collected from growth flasks containing 0.1 and 1 mM total Mn at 16, 24, 36, and 48 h after inoculation. Immediately after collection, the unprocessed hydrated subsamples were imaged at a 40-nm resolution. Manganese NEXAFS spectra were extracted from X-ray energy sequences of STXM images (stacks) and fit with linear combinations of well-characterized reference spectra to obtain quantitative relative abundances of Mn(II), Mn(III), and Mn(IV). Careful consideration was given to uncertainty in the normalization of the reference spectra, choice of reference compounds, and chemical changes due to radiation damage. The STXM results confirm that Mn+2(aq) was removed from solution by P. putida and was concentrated as Mn(III) and Mn(IV) immediately adjacent to the bacterial cells. The Mn precipitates were completely enveloped by bacterial biofilm material. The distribution of Mn oxidation states was spatially heterogeneous within and between the clusters of bacterial cells. Scanning transmission X-ray microscopy is a promising tool for advancing the study of hydrated interfaces between minerals and bacteria, particularly in cases where the structure of bacterial biofilms needs to be maintained.

Toner, Brandy; Fakra, Sirine; Villalobos, Mario; Warwick, Tony; Sposito, Garrison

2005-01-01

298

Nafion\\/lead oxide–manganese oxide combined catalyst for use as a highly efficient alkaline air electrode in zinc–air battery  

Microsoft Academic Search

In this study, we report the application of an inexpensive and easily prepared lead oxide–manganese oxide catalyst combined with Nafion (designated as Nf\\/PbMnOx) as a highly efficient air-cathode for a zinc–air battery. We verify the mechanistic study of the reduction of O2 for Nf\\/PbMnOx in alkaline aqueous solution using rotating ring\\/disk electrode voltammetry, and also an electrochemical approach using a

Ting-Hao Yang; Shanmuganathan Venkatesan; Chien-Hung Lien; Jen-Lin Chang; Jyh-Myng Zen

2011-01-01

299

Curcumin protects against cytotoxic and inflammatory effects of quartz particles but causes oxidative DNA damage in a rat lung epithelial cell line  

SciTech Connect

Chronic inhalation of high concentrations of respirable quartz particles has been implicated in various lung diseases including lung fibrosis and cancer. Generation of reactive oxygen species (ROS) and oxidative stress is considered a major mechanism of quartz toxicity. Curcumin, a yellow pigment from Curcuma longa, has been considered as nutraceutical because of its strong anti-inflammatory, antitumour and antioxidant properties. The aim of our present study was to investigate whether curcumin can protect lung epithelial cells from the cytotoxic, genotoxic and inflammatory effects associated with quartz (DQ12) exposure. Electron paramagnetic resonance (EPR) measurements using the spin-trap DMPO demonstrated that curcumin reduces hydrogen peroxide-dependent hydroxyl-radical formation by quartz. Curcumin was also found to reduce quartz-induced cytotoxicity and cyclooxygenase 2 (COX-2) mRNA expression in RLE-6TN rat lung epithelial cells (RLE). Curcumin also inhibited the release of macrophage inflammatory protein-2 (MIP-2) from RLE cells as observed upon treatment with interleukin-1 beta (IL-1{beta}) and tumour necrosis factor-alpha (TNF{alpha}). However, curcumin failed to protect the RLE cells from oxidative DNA damage induced by quartz, as shown by formamidopyrimidine glycosylase (FPG)-modified comet assay and by immunocytochemistry for 8-hydroxydeoxyguanosine. In contrast, curcumin was found to be a strong inducer of oxidative DNA damage itself at non-cytotoxic and anti-inflammatory concentrations. In line with this, curcumin also enhanced the mRNA expression of the oxidative stress response gene heme oxygenase-1 (ho-1). Curcumin also caused oxidative DNA damage in NR8383 rat alveolar macrophages and A549 human lung epithelial cells. Taken together, these observations indicate that one should be cautious in considering the potential use of curcumin in the prevention or treatment of lung diseases associated with quartz exposure.

Li Hui; Berlo, Damien van; Shi Tingming [Institut fuer umweltmedizinische Forschung (IUF) at the Heinrich-Heine-University Duesseldorf gGmbH, Auf'm Hennekamp 50, 40225 Duesseldorf (Germany); Speit, Guenter [Institute of Human Genetics, University of Ulm (Germany); Knaapen, Ad M. [Department of Health Risk Analysis and Toxicology, Nutrition and Toxicology Research Institute Maastricht (NUTRIM), University of Maastricht (Netherlands); Borm, Paul J.A. [Institut fuer umweltmedizinische Forschung (IUF) at the Heinrich-Heine-University Duesseldorf gGmbH, Auf'm Hennekamp 50, 40225 Duesseldorf (Germany); Centre for Expertise in Life Sciences, Zuyd University, Heerlen (Netherlands); Albrecht, Catrin [Institut fuer umweltmedizinische Forschung (IUF) at the Heinrich-Heine-University Duesseldorf gGmbH, Auf'm Hennekamp 50, 40225 Duesseldorf (Germany); Schins, Roel P.F. [Institut fuer umweltmedizinische Forschung (IUF) at the Heinrich-Heine-University Duesseldorf gGmbH, Auf'm Hennekamp 50, 40225 Duesseldorf (Germany)], E-mail: roel.schins@uni-duesseldorf.de

2008-02-15

300

Biogenic precipitation of manganese oxides and enrichment of heavy metals at acidic soil pH  

NASA Astrophysics Data System (ADS)

The precipitation of biogenic Mn oxides at acidic pH is rarely reported and poorly understood, compared to biogenic Mn oxide precipitation at near neutral conditions. Here we identified and investigated the precipitation of biogenic Mn oxides in acidic soil, and studied their role in the retention of heavy metals, at the former uranium mining site of Ronneburg, Germany. The site is characterized by acidic pH, low carbon content and high heavy metal loads including rare earth elements. Specifically, the Mn oxides were present in layers identified by detailed soil profiling and within these layers pH varied from 4.7 to 5.1, Eh varied from 640 to 660 mV and there were enriched total metal contents for Ba, Ni, Co, Cd and Zn in addition to high Mn levels. Using electron microprobe analysis, synchrotron X-ray diffraction and X-ray absorption spectroscopy, we identified poorly crystalline birnessite (?-MnO2) as the dominant Mn oxide in the Mn layers, present as coatings covering and cementing quartz grains. With geochemical modelling we found that the environmental conditions at the site were not favourable for chemical oxidation of Mn(II), and thus we performed 16S rDNA sequencing to isolate the bacterial strains present in the Mn layers. Bacterial phyla present in the Mn layers belonged to Firmicutes, Actinobacteria and Proteobacteria, and from these phyla we isolated six strains of Mn(II) oxidizing bacteria and confirmed their ability to oxidise Mn(II) in the laboratory. The biogenic Mn oxide layers act as a sink for metals and the bioavailability of these metals was much lower in the Mn layers than in adjacent layers, reflecting their preferential sorption to the biogenic Mn oxide. In this presentation we will report our findings, concluding that the formation of natural biogenic poorly crystalline birnessite can occur at acidic pH, resulting in the formation of a biogeochemical barrier which, in turn, can control the mobility and bioavailability of heavy metals in acidic soil environments.

Mayanna, Sathish; Peacock, Caroline L.; Schäffner, Franziska; Grawunder, Anja; Merten, Dirk; Kothe, Erika; Büchel, Georg

2014-05-01

301

Optimisation of an asymmetric manganese oxide/activated carbon capacitor working at 2 V in aqueous medium  

NASA Astrophysics Data System (ADS)

The charge storage mechanism of manganese oxide and activated carbon has been studied in aqueous medium in order to optimise an asymmetric (or hybrid) supercapacitor based on these two materials as positive and negative electrode, respectively. Amorphous manganese oxide can be polarised up to potentials of 1.2 V in neutral medium. Under negative polarisation, a pseudocapacitive behaviour of activated carbon has been demonstrated, that is related with reversible hydrogen adsorption in the pores. It allows carbon to be polarised at potential values far from the thermodynamic decomposition of the electrolyte. Balancing the mass of these two materials with pseudocapacitive properties results in a practical cell voltage of 2 V in aqueous medium, with energy densities close to the values obtained with electric double layer capacitors working in organic electrolytes, while avoiding their disadvantages.

Khomenko, V.; Raymundo-Piñero, E.; Béguin, F.

302

Revisiting the coordination chemistry for preparing manganese oxide nanocrystals in the presence of oleylamine and oleic acid.  

PubMed

By pyrolyzing manganese(II) acetate in 1-octadecene in the presence of oleylamine and oleic acid, manganese oxide nanocrystals were prepared. It was observed that both MnO and Mn3O4 nanocrystals were simultaneously formed by quickly heating the reaction mixture up to 250 °C, while a preheating procedure carried out at 100 °C led to uniform MnO nanocubes that developed into eight-arm MnO nanocrystals upon prolonged reaction. To understand the mechanisms for forming these two different kinds of manganese oxide nanocrystals, i.e., Mn3O4 and MnO, the coordination between oleic acid/oleylamine and Mn(2+) was investigated. The detailed investigations suggest that Mn(2+)-oleylamine coordination is kinetically driven and favorable for the formation of Mn3O4 nanocrystals due to the relatively low electronegativity of N from oleylamine, while Mn(2+)-oleate coordination is thermodynamically driven and can prevent the central metal ion (Mn(2+)) from being oxidized owing to the relatively high electronegativity of O from the oleate ligand. Following these new insights, by properly balancing the coordination of oleic acid and oleylamine to Mn(2+), the selective synthesis of MnO and Mn3O4 nanocrystals with uniform shapes was successfully achieved. PMID:24760344

Zhang, Hongwei; Jing, Lihong; Zeng, Jianfeng; Hou, Yi; Li, Zhen; Gao, Mingyuan

2014-06-01

303

Protective effects of manganese(II) chloride on hyaluronan degradation by oxidative system ascorbate plus cupric chloride  

PubMed Central

The degradation of several high-molar-mass hyaluronan samples was investigated in the presence of ascorbic acid itself and further by an oxidative system composed of ascorbic acid plus transition metal ions, i.e. Fe(II) or Cu(II) ions. The latter oxidative system imitates conditions in a joint synovial fluid during early phase of acute joint inflammation and can be used as a model for monitoring oxidative degradation of hyaluronan under pathophysiological conditions. The system Cu(II) plus ascorbate (the Weissberger oxidative system) resulted in a more significant decrease of hyaluronan molar mass compared to the oxidative system Fe(II) plus ascorbate. Addition of manganese(II) chloride was found to decrease the rate of the oxidative damage of hyaluronan initiated by ascorbate itself and by the Weissberger system.

Valachova, Katarina; Kogan, Grigorij; Gemeiner, Peter; Soltes, Ladislav

2010-01-01

304

New divalent manganese complex with pyridine carboxylate N-oxide ligand: Synthesis, structure and magnetic properties  

NASA Astrophysics Data System (ADS)

Two new manganese complexes, [Mn 3( L1) 4(NO 3) 2] n ( 1, H L1=nicotinate N-oxide acid) and [Mn L2Cl] n ( 2, H L2=isonicotinate N-oxide acid)], have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. In 1, the L1 ligands take two different coordinated modes bridging four and three Mn II ions. The nitrate anions take chelating coordination modes, leading one type of the Mn II ions as a 4-connected node. The whole net can be viewed as a 3, 4, 6-connected 4-nodal net with Schläfli notation {4 3}2{4 4; 6 2}4{4 6; 6 6; 8 3}. Complex 2 has a honeycomb layer mixed bridged by chlorine, N-oxide and carboxylate. The adjacent layers are linked by the phenyl ring of L2 ligand, giving a 3D framework with a {3 4; 5 4} {3 2;4;5 6;6 6} 4, 6-connect net. Magnetic studies indicate that 1 is an antiferromagnet with low-dimensional characteristic, in which a - J1J1J2- coupled alternating chain is predigested. Fitting the data of 1 gives the best parameters J1=-2.77, J2=-0.67 cm -1. The magnetic properties of complex 2 represent the character of the 2D honeycomb layer with the J1=-2.05 and J2=0.55 cm -1, which results in a whole antiferromagnetic state.

Liu, Fu-Chen; Xue, Min; Wang, Hai-Chao; Ou-Yang, Jie

2010-09-01

305

Removal and recovery of toxic silver ion using deep-sea bacterial generated biogenic manganese oxides.  

PubMed

Products containing silver ion (Ag(+)) are widely used, leading to a large amount of Ag(+)-containing waste. The deep-sea manganese-oxidizing bacterium Marinobacter sp. MnI7-9 efficiently oxidizes Mn(2+) to generate biogenic Mn oxide (BMO). The potential of BMO for recovering metal ions by adsorption has been investigated for some ions but not for Ag(+). The main aim of this study was to develop effective methods for adsorbing and recovering Ag using BMO produced by Marinobacter sp. MnI7-9. In addition, the adsorption mechanism was determined using X-ray photoelectron spectroscopy analysis, specific surface area analysis, adsorption kinetics and thermodynamics. The results showed that BMO had a higher adsorption capacity for Ag(+) compared to the chemical synthesized MnO2 (CMO). The isothermal absorption curves of BMO and CMO both fit the Langmuir model well and the maximum adsorption capacities at 28°C were 8.097 mmol/g and 0.787 mmol/g, for BMO and CMO, respectively. The change in enthalpy (?H(?)) for BMO was 59.69 kJ/mol indicating that it acts primarily by chemical adsorption. The change in free energy (?G(?)) for BMO was negative, which suggests that the adsorption occurs spontaneously. Ag(+) adsorption by BMO was driven by entropy based on the positive ?S(?) values. The Ag(+) adsorption kinetics by BMO fit the pseudo-second order model and the apparent activation energy of Ea is 21.72 kJ/mol. X-ray photoelectron spectroscopy analysis showed that 15.29% Ag(+) adsorbed by BMO was transferred to Ag(0) and meant that redox reaction had happened during the adsorption. Desorption using nitric acid and Na2S completely recovered the Ag. The results show that BMO produced by strain MnI7-9 has potential for bioremediation and reutilization of Ag(+)-containing waste. PMID:24312566

Pei, Yuanjun; Chen, Xiao; Xiong, Dandan; Liao, Shuijiao; Wang, Gejiao

2013-01-01

306

Heavy metals and manganese oxides in the genesee watershed, New York state: effects of geology and land use  

USGS Publications Warehouse

Manganese oxide coatings on gravels from 255 sites on tributary streams in the Genesee River Watershed were analyzed for Mn, Fe, Zn, Cd, Co, Ni, Pb, and Cu. The results were compared with data on bedrock geology, surficial geology and land use, using factor analysis and stepwise multiple regression. All metals except Pb show strong positive correlation with Mn. This association results from the well-known tendency of Mn oxide precipitates to adsorb and incorporate dissolved trace metals. Pb may be present in a separate phase on the gravel surfaces; alternatively Pb abundance may be so strongly influenced by environmental factors that the effect of varying abundance of the carrier phase becomes relatively unimportant. When the effects of varying Mn abundance are allowed for, Pb and to a lesser extent Zn and Cu abundances are seen to be related to commercial, industrial and residential land use. In addition to this pollution effect, all the trace metals, Cd and Ni most strongly, tend to be more abundant in oxide coatings from streams in the forested uplands in the southern part of the area. This probably reflects increased geochemical mobility of the metals in the more acid soils and groundwater of the southern region. A strong Zn anomaly is present in streams draining areas underlain by the Lockport Formation. Oxide coatings in these streams contain up to 5% Zn, originating from disseminated sphalerite in the Lockport and secondary Zn concentrations in the overlying muck soils. The same group of metals, plus calcium and loss on ignition, were determined in the silt and clay (minus 230 mesh) fraction of stream sediments from 129 of the same sites, using a hot nitric acid leach. The amounts of manganese in the sediments are low (average 1020 ppm) and manganese oxides are, at most, of relatively minor significance in the trace-metal geochemistry of these sediments. The bulk of the trace metals in sediment appears to be associated with iron oxides, clays and organic matter. ?? 1981.

Whitney, P. R.

1981-01-01

307

Complexation and redox interactions between aqueous plutonium and manganese oxide interfaces  

SciTech Connect

The sorption of Pu(VI) and Pu(V) onto manganite (MnOOH) and Hausmannite (Mn3O4) was studied at pH 5. Manganite sorbed 21-24% from a 1x10-4 M plutonium solution and the hausmannite removed between 43-66% of the plutonium. The increased sorption by hausmannite results from its larger surface area (about twice that of manganite) plus a larger number of active surface sites. X-ray absorption near-edge structure (XANES) spectra taken at the Pu LIII edge were compared to standard spectra of plutonium in single oxidation states. Based on these spectra, it appears that both manganite and hausmannite reduce the higher valent plutonium species to Pu(IV). Between 53-59% of the plutonium was present as Pu(IV) in the manganite samples while 55-61% of the plutonium complexed to the hausmannite had also been reduced to Pu(IV). The exact mechanism behind this redox interaction between the plutonium and the manganese needs to be identified.

Shaughnessy, Dawn A.; Nitsche, Heino; Booth, Corwin H.; Shuh, David K.; Waychunas, Glenn A.; Wilson, Richard E.; Cantrell, Kirk J.; Serne, R. Jeffrey

2001-11-01

308

Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion.  

PubMed

The aim of this work was to study combustion of toluene (1000ppm) over MnO(2) modified with different supports. ?-Al(2)O(3) and ?-Al(2)O(3) obtained from Boehmite, ?-Al(2)O(3) (commercial), SiO(2), TiO(2) and ZrO(2) were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO(2) was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO(2)/?-Al(2)O(3)(B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289°C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity. PMID:22579460

Pozan, Gulin Selda

2012-06-30

309

The Influence of Manganese Oxide on the Sintering Behavior of Yttria Tetragonal Zirconia  

NASA Astrophysics Data System (ADS)

The sintering behavior of yttria-stabilized zirconia, with the influence of small additions of MnO2 (up to 1 wt %) sintered over the temperature range from 1250° C to 1500° C was investigated. It was found that the mechanical properties of Y-TZP were dependent on the dopant amount and sintering temperature. The results revealed that relative densities above 97.5% of theoretical (i.e. >5.95 Mgm-3) could be obtained in Y-TZPs sintered at low temperatures, 1250° C and 1300° C, with the additions of <=0.3 wt% MnO2. In comparison to the undoped samples, the additions of up to 1 wt% MnO2 and for sintering up to 1350° C was found to be beneficial in enhancing the Vickers hardness of the ceramic. The fracture toughness of Y-TZP however, was found to increase only in the 1 wt% MnO2-doped samples when sintered above 1400° C. The relation between the measured mechanical properties is discussed with the emphasis on the role of the manganese oxide.

Meenaloshini, S.; Amiriyan, M.; Sankar, U.; Tolouei, R.; Ramesh, S.

2011-01-01

310

A sodium manganese oxide cathode by facile reduction for sodium batteries.  

PubMed

A nonstoichiometric sodium manganese oxide (Na(x)MnO(2+?)) cathode useful for sodium batteries was synthesized by an ambient-temperature strategy that involved facile reduction of aqueous sodium permanganate in sodium iodide and subsequent heat treatment at 600?°C. Combined powder X-ray diffraction and synchrotron X-ray diffraction analyses confirmed the annealed sample to belong to a Na(x)MnO2 phase with a P2-hexagonal structure. The ICP-AES results confirmed the stoichiometry of the sample to be Na0.53MnO(2+?) . Electron microscopy studies revealed the particle size of the electrode to be in the range of a few hundred nanometers. The Na0.53MnO(2+?) cathode delivered an average discharge capacity of 170?mA?h?g(-1) with a stable plateau at 2.1?V for the initial 25?cycles versus sodium. Ex?situ XANES studies confirmed the reversible intercalation of sodium into Na0.53MnO(2+?) and suggested the accommodation of over-stoichiometric Mn(4+) ions to contribute towards the performance of the electrode. PMID:24692202

Song, Jinju; Gim, Jihyeon; Kim, Sungjin; Kang, Jungwon; Mathew, Vinod; Ahn, Docheon; Kim, Jaekook

2014-06-01

311

Manganese-oxide-coated alumina: a promising sorbent for defluoridation of water.  

PubMed

In this study, adsorption potential of a new sorbent manganese-oxide-coated alumina (MOCA) was investigated for defluoridation of drinking water using batch and continuous mode experiments. The effects of different parameters such as pH, initial fluoride concentration and co-existing ions (usually present in groundwater sample) were studied to understand the adsorption behavior of the sorbent under various conditions. Optimum removal of fluoride ions occurred in a pH range of 4-7. Results of the present study indicate that fluoride adsorption rate and adsorption capacity of MOCA are far superior to that of activated alumina (AA), which was used as the base material for MOCA preparation. The MOCA can be effectively regenerated using 2.5% NaOH as eluent. The Langmuir equilibrium model was found to be suitable for describing the fluoride sorption on AA and MOCA. The maximum fluoride uptake capacity for MOCA and AA was found to be 2.85 and 1.08 mg g(-1), respectively. The kinetic results showed that the fluoride sorption to MOCA followed pseudo--second-order kinetics with a correlation coefficient greater than 0.98. The fluoride sorption capacity at breakthrough point for both the adsorbents was greatly influenced by bed depth. A bed depth service time (BDST) approach was adopted to describe the continuous flow system. The batch and column studies demonstrated the superiority of MOCA over AA in removing fluoride from the drinking water system. PMID:17011020

Maliyekkal, Shihabudheen M; Sharma, Atul Kumar; Philip, Ligy

2006-11-01

312

Characterization of gamma-alumina-supported manganese oxide as an incineration catalyst for trichloroethylene.  

PubMed

Trichloroethylene (TCE) decomposition over a MnOx/ gamma-Al2O3 catalyst in a fixed-bed reactor was conducted in this study. The MnOx/gamma-Al2O3 powders were prepared by the incipient wetness impregnation method with aqueous solution of manganese nitrate. The catalysts were characterized by DTA-TGA, XRD, porosity analysis, SEM, EDX, and XPS. The results show that the main distinct weight loss is found at the temperature around 373 and 873 K,the MnO peaks (2theta = 34.9 degrees and 40.5 degrees) are only observed crystal phase on the fresh catalyst, the SEM image of the MnOx-impregnated gamma-Al2O3 support is much different from the calcined catalyst, and the Mn element quantity on the catalyst surface is higher than that of the impregnated support. The products and reactants distributions from the oxidation of TCE over MnOx/gamma-Al2O3 were analyzed by GC. The results show that the TCE conversion starts from 5% at 443 K and rises to very high values in the 673-873 K ranges and that the CO2 yield also pushes to 99% at the same temperature ranges. HCl and Cl2 are the other main products with little halogenated VOC intermediates. PMID:12542307

Tseng, Ting-Ke; Chu, Hsin; Hsu, Han-Hsuan

2003-01-01

313

Layered manganese oxide intergrowth electrodes for rechargeable lithium batteries: Part 1-substitution with Co or Ni  

SciTech Connect

Lithium manganese oxides substituted with nickel or cobalt were characterized electrochemically in lithium cell configurations. The compounds studied were either single-phase layered structures with either primarily O2 or O3 stacking arrangements, or O2/O3 intergrowths, prepared from P2, P3 and P2/P3 sodium-containing precursors, respectively. The stacking arrangements are extremely sensitive to the Na/T. M. (T. M. = transition metal) ratios and the level of substitution. Phase diagrams showing the stability regions of the various arrangements for the Na-Ni-Mn-O system are presented. A possible correlation between vacancies and electrochemical performance is suggested. For high levels of substitution with Ni, fewer defects are possible for materials containing more O3 component and higher discharge capacities can be achieved, but spinel conversion upon cycling also occurs more rapidly as the O3 content increases. Intergrowths show intermediate behavior and represent a potential route towards designing stable, high capacity electrodes.

Dolle, Mickael; Patoux, Sebastien; Doeff, Marca M.

2004-09-08

314

Sorption behavior of heavy metals on poorly crystalline manganese oxides: roles of water conditions and light.  

PubMed

The objective of this study was to determine the effects of solution properties and light on the metal uptake and release in a nanosized, poorly crystalline manganese oxide (?-MnO2) system. The results from synthetic water matrices revealed that the aggregation state was strongly affected by ionic strength, Ca(2+), and humic acid, and the particle aggregation subsequently changed the ability of ?-MnO2 to adsorb and sequester heavy metal ions (Cu(ii)). The extent of Cu(ii) uptake onto ?-MnO2 exhibited a negative correlation with the attachment efficiency value, which suggested that a lower sorption capacity could be achieved under aggregation-inducing conditions. Upon exposure to light, the adsorbed Cu(ii) was released from the ?-MnO2 surface via photoinduced dissolution of MnO2. The concentration of Cu(ii) desorbed was substantially higher when the humic acid was present together with Ca(2+). The present investigation enables us to better understand the adsorption-desorption processes of heavy metals occurring at the MnO2-solution interface in response to common environmental stimuli. PMID:24777353

Kim, Eun-Ju; Kim, Jungwon; Choi, Sung-Chan; Chang, Yoon-Seok

2014-05-28

315

Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model  

USGS Publications Warehouse

Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional sorption data for which complementary titration data were not available. The two-site model accounts for variability in the titration data and most metal sorption data are fit well using the pKa2 and ?? values reported above. A linear free energy relationship (LFER) appears to exist for some of the metals; however, redox and cation exchange reactions may limit the prediction of surface complexation constants for additional metals using the LFER. ?? 2003 Elsevier Ltd. All rights reserved.

Tonkin, J. W.; Balistrieri, L. S.; Murray, J. W.

2004-01-01

316

Synthesis of manganese oxide nanocrystal by ultrasonic bath: effect of external magnetic field.  

PubMed

A novel technique was used for the synthesis of manganese oxide nanocrystal by applying an external magnetic field (EMF) on the precursor solution before sonication with ultrasonic bath. The results were compared in the presence and absence of EMF. Manganese acetate solution as precursor was circulated by a pump at constant speed (7 rpm, equal to flow rate of 51.5 mL/min) in an EMF with intensity of 0.38 T in two exposure times (t(MF), 2h and 24h). Then, the magnetized solution was irradiated indirectly by ultrasonic bath in basic and neutral media. One experiment was designed for the effect of oxygen atmosphere in the case of magnetic treated solution in neutral medium. The as prepared samples were characterized with X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (HRTEM, TEM), energy-dispersive spectrum (EDS), and superconducting quantum interference device (SQUID) analysis. In neutral medium, the sonication of magnetized solution (t(MF), 24h) led mainly to a mixture of Mn(3)O(4) (hausmannite) and ?-MnOOH (manganite) and sonication of unmagnetized solution led to a pure Mn(3)O(4). In point of particle size, the larger and smaller size of nanoparticles was obtained with and without magnetic treatment, respectively. In addition, the EMF was retarded the nucleation process, accelerated the growth of the crystal, and increased the amount of rod-like structure especially in oxygen atmosphere. In basic medium, a difference was observed on the composition of the products between magnetic treated and untreated solution. For these samples, the magnetic measurements as a function of temperature were exhibited a reduction in ferrimagnetic temperature to T(c)=39K, and 40K with and without magnetic treatment, respectively. The ferrimagnetic temperature was reported for the bulk at T(c)=43K. A superparamagnetic behavior was observed at room temperature without any saturation magnetization and hysteresis in the measured field strength. The effect of EMF on the sample prepared in the basic medium was negligible but, in the case of neutral medium, the EMF affected the slope of the magnetization curves. The magnetization at room temperature was higher for the samples obtained in neutral medium without magnetic treatment. In addition, a horizontal shift loop was observed in neutral medium at low temperature. PMID:22221536

Bastami, Tahereh Rohani; Entezari, Mohammad H

2012-07-01

317

Catalytic oxidation of manganese(II) by multicopper oxidase CueO and characterization of the biogenic Mn oxide.  

PubMed

Manganese(II) contamination is naturally occurring in many groundwater and surface water sources. Moreover, industrial wastewater is also responsible for much of the Mn(II) contamination. Nowadays, Mn(II) contamination has become a serious environmental problem in some regions of the world. To explore a biological approach for removing excessive amounts of aqueous Mn(II) from water, we found a new biocatalyst multicopper oxidase CueO, which was firstly proved to catalyze the oxidation of Mn(II) both in vitro and in vivo. Subsequently, we established a CueO-mediated catalysis system to prepare biogenic Mn oxide (BioMnOx), which was confirmed to be ?-Mn3O4 by X-ray diffraction. This newly prepared BioMnOx consisted of 53.6% Mn(II), 18.4% Mn(III) and 28.0% Mn(IV) characterized by X-ray photoelectron spectroscopy. It exhibited distinct polyhedral structure with nanoparticles of 150-350 nm diameters observed by transmission electron microscopy. Importantly, CueO could remove 35.7% of Mn(II) after a seven-day reaction, and on the other hand, the cueO-overexpressing Escherichia coli strain (ECueO) could also oxidize 58.1% dissolved Mn(II), and simultaneously remove 97.7% Mn(II). Based on these results, we suggest that ECueO strain and CueO enzyme have potential applications on Mn(II) decontamination in water treatment. PMID:24699422

Su, Jianmei; Deng, Lin; Huang, Liangbo; Guo, Shujin; Liu, Fan; He, Jin

2014-06-01

318

Revisiting the coordination chemistry for preparing manganese oxide nanocrystals in the presence of oleylamine and oleic acid  

NASA Astrophysics Data System (ADS)

By pyrolyzing manganese(ii) acetate in 1-octadecene in the presence of oleylamine and oleic acid, manganese oxide nanocrystals were prepared. It was observed that both MnO and Mn3O4 nanocrystals were simultaneously formed by quickly heating the reaction mixture up to 250 °C, while a preheating procedure carried out at 100 °C led to uniform MnO nanocubes that developed into eight-arm MnO nanocrystals upon prolonged reaction. To understand the mechanisms for forming these two different kinds of manganese oxide nanocrystals, i.e., Mn3O4 and MnO, the coordination between oleic acid/oleylamine and Mn2+ was investigated. The detailed investigations suggest that Mn2+-oleylamine coordination is kinetically driven and favorable for the formation of Mn3O4 nanocrystals due to the relatively low electronegativity of N from oleylamine, while Mn2+-oleate coordination is thermodynamically driven and can prevent the central metal ion (Mn2+) from being oxidized owing to the relatively high electronegativity of O from the oleate ligand. Following these new insights, by properly balancing the coordination of oleic acid and oleylamine to Mn2+, the selective synthesis of MnO and Mn3O4 nanocrystals with uniform shapes was successfully achieved.By pyrolyzing manganese(ii) acetate in 1-octadecene in the presence of oleylamine and oleic acid, manganese oxide nanocrystals were prepared. It was observed that both MnO and Mn3O4 nanocrystals were simultaneously formed by quickly heating the reaction mixture up to 250 °C, while a preheating procedure carried out at 100 °C led to uniform MnO nanocubes that developed into eight-arm MnO nanocrystals upon prolonged reaction. To understand the mechanisms for forming these two different kinds of manganese oxide nanocrystals, i.e., Mn3O4 and MnO, the coordination between oleic acid/oleylamine and Mn2+ was investigated. The detailed investigations suggest that Mn2+-oleylamine coordination is kinetically driven and favorable for the formation of Mn3O4 nanocrystals due to the relatively low electronegativity of N from oleylamine, while Mn2+-oleate coordination is thermodynamically driven and can prevent the central metal ion (Mn2+) from being oxidized owing to the relatively high electronegativity of O from the oleate ligand. Following these new insights, by properly balancing the coordination of oleic acid and oleylamine to Mn2+, the selective synthesis of MnO and Mn3O4 nanocrystals with uniform shapes was successfully achieved. Electronic supplementary information (ESI) available: (1) TEM image and corresponding SAED pattern of the tiny particles shown in Fig. 1b; (2) TEM images of the branched nanoparticles (Fig. 1e) showing a self-organized superstructure; (3) TEM image and the electron diffraction pattern of the particles obtained by heating the Mn(Ac)2 in oleylamine at 100 °C for 540 min; (4) TEM image and the electron diffraction pattern of the particles obtained from the second reference experiment; (5) Temporal evolution of size and size distribution of manganese oxide nanocrystals shown in Fig. 5 and Fig. 6. See DOI: 10.1039/c4nr00761a

Zhang, Hongwei; Jing, Lihong; Zeng, Jianfeng; Hou, Yi; Li, Zhen; Gao, Mingyuan

2014-05-01

319

Unusual oxidation state distributions observed for two mixed-valence heptanuclear manganese disc-like clusters.  

PubMed

The synthesis, structures and magnetic properties of two new mixed-valence heptanuclear manganese clusters are described. Both complexes utilize triethanolamine (teaH(3)) as a bridging ligand, displaying near planar, disc-like metal topologies and are of formulae [Mn(II)(4)Mn(IV)(3)(tea)(teaH(2))(3)(peolH)(4)](BF(4))(2)·solv (1) and [Mn(II)(4)Mn(III)(3)F(3)(tea)(teaH)(teaH(2))(2)(piv)(4)(Hpiv)(chp)(3)]·0.5MeCN (2). Compound 1 is a rare mixed-valence compound containing Mn(II) and Mn(IV) ions only and is the first example of a heptanuclear disc with a {Mn(II)(4)Mn(IV)(3)} oxidation state distribution. Compound 2 is a {Mn(II)(4)Mn(III)(3)} complex and displays a unique arrangement of oxidation states within the disc, when compared to other known {Mn(II)(4)Mn(III)(3)} examples. Variable temperature DC and AC magnetic susceptibility studies were carried out for 1 and 2 in the 2-300 K temperature range. Compound 1 displayed an increase in the ?(M)T susceptibility values as the temperature is decreased indicating dominant ferromagnetic interactions are present within the cluster. Fits of the ?(M)T vs. T data reveals an S = 23/2 ground state, with several close lying excited states within 1 cm(-1). Compound 2 displays an overall decrease in the ?(M)T value as the temperature is decreased down to 2 K indicating dominant antiferromagnetic interactions present with a probable S = 4 ground state as determined from the DC and AC susceptibility data. PMID:22776898

Langley, Stuart K; Chilton, Nicholas F; Moubaraki, Boujemaa; Murray, Keith S

2012-08-28

320

New strategy to enhance phosphate removal from water by hydrous manganese oxide.  

PubMed

Hydrous manganese oxide (HMO) is generally negatively charged at circumneutral pH and cannot effectively remove anionic pollutants such as phosphate. Here we proposed a new strategy to enhance HMO-mediated phosphate removal by immobilizing nano-HMO within a polystyrene anion exchanger (NS). The resultant nanocomposite HMO@NS exhibited substantially enhanced phosphate removal in the presence of sulfate, chloride, and nitrate at greater levels. This is mainly attributed to the pHpzc shift from 6.2 for the bulky HMO to 10.5 for the capsulated HMO nanoparticles, where HMO nanoparticles are positively charged at neutral pH. The ammonium groups of NS also favor phosphate adsorption through the Donnan effect. Cyclic column adsorption experiment indicated that the fresh HMO@NS could treat 460 bed volumes (BV) of a synthetic influent (from the initial concentration of 2 mg P[PO4(3-)]/L to 0.5 mg P[PO4(3-)]/L), while only 80 BV for NS. After the first time of regeneration by NaOH-NaCl solution, the capacity of HMO@NS was lowered to ? 300 BV and then kept constant for the subsequent 5 runs, implying the presence of both the reversible and irreversible adsorption sites of nano-HMO. Additional column adsorption feeding with a real bioeffluent further validated great potential of HMO@NS in advanced wastewater treatment. This study may provide an alternative approach to expand the usability of other metal oxides in water treatment. PMID:24730751

Pan, Bingcai; Han, Feichao; Nie, Guangze; Wu, Bing; He, Kai; Lu, Lv

2014-05-01

321

Synthesis and characterization of a novel extracellular biogenic manganese oxide (bixbyite-like Mn?O?) nanoparticle by isolated Acinetobacter sp.  

PubMed

Recently, manganese oxides have been considered in the environmental remediation, MRI diagnosis and drug and pharmaceutical industries. Different numbers of physicochemical and biological methods have been reported for the preparation of nanoscale manganese oxides. Although manganese oxide biogenesis by bacterial species has been recognized as the major Mn-oxidizing agent in nature, in this research, for first time, we demonstrated the process which used to produce bixbyite-like Mn(2)O(3) nanoparticles by isolated aerobic bacterium from Persian Gulf water. The 16SRNA sequencing showed that this isolate belong to a gram-negative Acinetobacter which produced nano Mn-oxide crystal particle. Characterization of complement morphology, size and chemical structure of these particles were determined by TEM, SEM, EDAX, XRD and FTIR. The data showed that this bacterium could produce nanosized extracellular bixbyite-like Mn(2)O(3) which depend on enzymatic pathway. PMID:21761221

Hosseinkhani, Baharak; Emtiazi, Giti

2011-09-01

322

OXIDIZING BEHAVIOR OF SOIL MANGANESE: INTERACTIONS AMONG ABUNDANCE, OXIDATION STATE, AND PH  

Microsoft Academic Search

important to evaluating the potential for Mn-mediated transformations in soil systems. Due to their high degree of reactivity, Mn oxides in soil systems There are substantial gaps in knowledge of Mn in the may exert a greater influence on trace metal chemistry than that bulk soil due to difficulties in studying the typically small, suggested by their relatively low abundance.

Christine Negra; Donald S. Ross; Antonio Lanzirotti

2005-01-01

323

Iron and manganese in oxide minerals and in glasses: preliminary consideration of Eh buffering potential at Yucca Mountain, Nevada  

SciTech Connect

The tuffs of Yucca Mountain at the Nevada Test Site are currently under investigation as a possible deep burial site for high-level radioactive waste disposal. One of the main concerns is the effect of oxidizing groundwater on the transport of radionuclides. Rock components that may affect the oxygen content of groundwater include Fe-Ti oxides, Mn oxides, and glasses that contain ferrous iron. Some phenocryst Fe-Ti oxides at Yucca Mountain are in reduced states, whereas groundmass Fe-Ti oxides have been oxidized to hematite, rutile, and pseudobrookite (Fe{sup 3+}-bearing phases) exclusively. Estimates of Fe{sup 2+}-bearing oxides indicate that less than 0.33 vol% phenocrysts is available to act as solid buffering agents of Eh. Of this percentage, significant amounts of Fe-Ti oxides are isolated from effective interaction with groundwater because they occur in densely welded, devitrified tuffs that have low interstitial permeability. Manganese oxides occur primarily along fractures in the ash-flow tuffs. Because the Mn oxides are concentrated along the same pathways (fractures) where transport has occurred in the past, these small volume percentages could act as buffers. However, the oxidation states of actual Mn-oxide phases are high (Mn{sup 4+}), and these minerals have virtually no potential for reducing groundwater Eh. Manganese oxides may even act as oxidizing agents. However, regardless of their poor capabilities as reducing agents, the Mn oxides could be important as sorbents of heavy metals at Yucca Mountain. The lack of accessible, pristine Fe-Ti oxides and the generally high oxidation states of Mn oxides seem to rule out these oxides as Eh buffers of the Yucca Mountain groundwater system. Reduction of ferrous iron within glassy tuffs may have some effect on Eh, but further study is needed. At present it is prudent to assume that minerals and glasses have little or no capacity for reducing oxygen-rich groundwater at Yucca Mountain. 25 refs., 3 figs., 12 tabs

Caporuscio, F.A.; Vaniman, D.T.

1985-04-01

324

Early diagenetic quartz formation at a deep iron oxidation front in the Eastern Equatorial Pacific - A modern analogue for banded iron/chert formations?  

NASA Astrophysics Data System (ADS)

The mechanisms of early diagenetic quartz formation under low-temperature conditions are still poorly understood. In this study we investigated lithified cherts consisting of microcrystalline quartz recovered near the base of a 420 m thick Miocene-Holocene sequence of nannofossil and diatom ooze at a drill site in the Eastern Equatorial Pacific (Ocean Drilling Program Site 1226). Precipitation seems still ongoing based on a sharp depletion in dissolved silica at the depth of the cherts. Also, palaeo-temperatures reconstructed from ?18O values in the cherts are in the range of adjacent porewater temperatures. Opal-A dissolution appears to control silica concentration throughout the sequence, while the solution remains oversaturated with respect to quartz. However, at the depth of the sharp depletion in dissolved silica, quartz is still saturated while the more soluble silica phases are strongly undersaturated. Hence, precipitation of quartz was initiated by an auxiliary process. A process, previously observed to assist in the nucleation of quartz is the adsorption of silica on freshly precipitated iron oxides. Indeed, a deep iron oxidation front is present at 400 m below seafloor, which is caused by upward diffusing nitrate from an oxic seawater aquifer in the underlying oceanic crust. Sequential iron extraction showed a higher content of the adsorbed iron hydroxide fraction in the chert than in the adjacent nannofossil and diatom ooze. X-ray absorption near-edge structure (XANES) spectroscopy revealed that iron in the cherts predominantly occurs in illite and amorphous iron oxide, whereas iron in the nannofossil and diatom ooze occurs mainly in smectite. Mössbauer spectroscopy also indicated the presence of illite that is to 97% oxidized. Two possible mechanisms may be operative during early diagenetic chert formation at iron oxidation fronts: (1) silica precipitation is catalysed by adsorption to freshly precipitated iron oxide surfaces, and (2) porewater silica concentration is locally decreased below opal-A and opal-CT saturation allowing for precipitation of the thermodynamically more stable phase: quartz. This mechanism of chert formation at the iron oxidation front in suboxic zones may explain why early-diagenetic microcrystalline chert only occurs sporadically in modern marine sediments. It may also serve as a modern analogue for the deposition of much more abundant banded iron/chert formations at the time of the great oxidation event around 2.4 Ga BP, which was probably the largest iron oxidation front in Earth's history.

Meister, Patrick; Chapligin, Bernhard; Picard, Aude; Meyer, Hanno; Fischer, Cornelius; Rettenwander, Daniel; Amthauer, Georg; Vogt, Christoph; Aiello, Ivano W.

2014-07-01

325

Effect of Anions on the Binding and Oxidation of Divalent Manganese and Iron in Modified Bacterial Reaction Centers  

PubMed Central

Abstract The influence of different anions on the binding and oxidation of manganous and ferrous cations was studied in four mutants of bacterial reaction centers that can bind and oxidize these metal ions. Light-minus-dark difference optical and electron paramagnetic resonance spectroscopies were applied to monitor electron transfer from bound divalent metal ions to the photo-oxidized bacteriochlorophyll dimer in the presence of five different anions. At pH 7, bicarbonate was found to be the most effective for both manganese and iron binding, with dissociation constants around 1 ?M in three of the mutants. The pH dependence of the dissociation constants for manganese revealed that only bicarbonate and acetate were able to facilitate the binding and oxidation of the metal ion between pH 6 and 8 where the tight binding in their absence could not otherwise be established. The data are consistent with two molecules of bicarbonate or one molecule of acetate binding to the metal binding site. For ferrous ion, the binding and oxidation was facilitated not only by bicarbonate and acetate, but also by citrate. Electron paramagnetic resonance spectra suggest differences in the arrangement of the iron ligands in the presence of the various anions.

Tang, Kai; Williams, JoAnn C.; Allen, James P.; Kalman, Laszlo

2009-01-01

326

Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface  

NASA Astrophysics Data System (ADS)

Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.

den Boer, Duncan; Li, Min; Habets, Thomas; Iavicoli, Patrizia; Rowan, Alan E.; Nolte, Roeland J. M.; Speller, Sylvia; Amabilino, David B.; de Feyter, Steven; Elemans, Johannes A. A. W.

2013-07-01

327

Flow-injection photometric determination of manganese(II) based on its catalysis of the periodate oxidation of N,N'-bis(2-hydroxy-3-sulfopropyl)tolidine.  

PubMed

A novel flow-injection spectrophotometric method has been developed for the determination of manganese(II) at sub-nanogram/ml levels. The method is based on its catalytic effect on the oxidation of N,N'-bis(2-hydroxy-3-sulfopropyl)tolidine (HSPT) by periodate. The catalytic effect of manganese(II) was enhanced by the presence of 2,2'-bipyridine as an activator. By monitoring the change in absorbance of the oxidation product of HSPT at 670nm, manganese(II) ranging 0.02-3.0ngml(-1) could be determined with the relative standard deviations of less than 2%. The interfering ions were effectively suppressed by the addition of 2,2'-iminodiethanol and citric acid. The proposed method is directly applicable to the determination of manganese in lake and river water samples. PMID:18970323

Nakano, Shigenori; Matumoto, Yuko; Yoshii, Masahiro

2005-12-15

328

Kinetics of the catalytic oxidation of phenol over manganese oxide in supercritical water  

SciTech Connect

A kinetic analysis was made for the phenol disappearance rate in catalytic oxidation of phenol over MnO{sub 2} in supercritical water at a fixed temperature of 425 C and pressures between 22.7 and 27.2 MPa. The nonsupported MnO{sub 2} catalyst possessed a strong activity for promoting phenol oxidation, though the overall reaction rate was appreciably influenced by internal mass-transfer resistance. From the kinetic analysis on the reaction rate of the phenol disappearance, the global rate expression of the surface reaction was obtained, where the reaction orders with respect to phenol, oxygen, and water were almost unity, 0.7, and {minus}2.0, respectively. A Langmuir-type mechanism, in which phenol and oxygen adsorbed on the catalytic sites and water adsorbed on the same site to inhibit the phenol and oxygen adsorption, was proposed to explain the reaction orders for phenol, oxygen, and water.

Oshima, Yoshito; Tomita, Kengo; Koda, Seiichiro

1999-11-01

329

Low-potential Amperometric Determination of Hydrogen Peroxide with a Carbon Paste Electrode Modified with Nanostructured Cryptomelane-type Manganese Oxides  

SciTech Connect

Nanostructured cryptomelane-type manganese oxides were synthesized, characterized, and evaluated for chemical sensing. Cryptomelane-type manganese oxides are nanofibrous crystals with sub-nanometer open tunnels that provide a unique property for sensing applications. Carbon paste electrodes (CPEs), modified with the nanostructured cryptomelane-type manganese oxides, were investigated for amperometric detection of hydrogen peroxide. With an operating potential of +0.3 V versus Ag/AgCl, H{sub 2}O{sub 2} produces catalytic oxidation currents at the modified CPE, which can be exploited for quantitative determinations. The amperometric signals are linearly proportional to H{sub 2}O{sub 2} concentration in the range 1.0 x 10{sup -4}-6.9 x 10{sup -4} M with a correlation coefficient of 0.995 (n = 7). At a signal-to-noise ratio of 3, a detection limit of 2 {micro}M can be observed for the carbon paste electrode modified with 5.5 wt% cryptomelane-type manganese oxides. In addition, the sensor has a good stability and reproducibility. The construction and renewal are simple and inexpensive. A possible response mechanism was proposed and discussed. The significant electrocatalytic activity of the modified CPE may result from the nanostructure of cryptomelane-type manganese oxides.

Lin, Yuehe; Cui, Xiaoli; Li, Liyu

2005-02-01

330

Understanding interactions between manganese oxide and gold that lead to enhanced activity for electrocatalytic water oxidation.  

PubMed

To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnO(x), a promising OER catalyst. We conclusively demonstrate that adding Au to MnO(x) significantly enhances OER activity relative to MnO(x) in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnO(x) catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnO(x) that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnO(x). PMID:24661269

Gorlin, Yelena; Chung, Chia-Jung; Benck, Jesse D; Nordlund, Dennis; Seitz, Linsey; Weng, Tsu-Chien; Sokaras, Dimosthenis; Clemens, Bruce M; Jaramillo, Thomas F

2014-04-01

331

The thermal stability and catalytic application of manganese oxide-zirconium oxide powders  

NASA Astrophysics Data System (ADS)

MnOx-ZrO2 mixed oxide is an active catalyst for combustion, oxidation, and oxygen storage applications. MnOx-ZrO 2 mixture also has large reversible adsorption capability for NO x, which makes it a promising candidate for NOx abatement in automobile emission control. However, MnOx-ZrO 2 mixed oxide has not been used extensively because the processing and the thermal stability of resulting powders have not been studied systematically. It is critical to have thermally stable catalytic material because the application temperature can reach as high as 1000°C during service. In this study, we focused on improving the thermal stability of oxide powders, such as MnO x, ZrO2, and MnOx-ZrO2, by controlling the processing methods and parameters. For pure MnOx made from the precipitation method using Mn(NO3)2 aqueous solution and ammonium hydroxide, we found that lower concentration of Mn(NO3) 2 solution and larger amount of ammonium hydroxide resulted in higher surface area powders. For pure ZrO2, we found curing hydrous zirconia in the mother liquid produced ZrO2 powders with larger pore volume and pore size. The specific surface area was also significantly enhanced by curing for the synthesized powders before calcination or after low temperature calcinations, and this improvement could be preserved to high temperatures if SiO2 was doped in ZrO2. A Monte Carlo simulation model examining the effect of primary particle packing on the specific surface area was used to explain the curing result. MnOx-ZrO2 mixtures had higher surface area than the single component oxide at 500 and 700°C because composite powders sintered less. The sintering behavior of composite powders at 900°C was opposite to that at 500°C and the specific surface area of MnOx-ZrO2 decreased drastically at 900°C. Curing ZrO2 first or using La dopant could significantly enhance the specific surface area of MnOx-ZrO2 at 900°C. Through the tests of the redox property and NO storage capability we found a close relationship between the enhanced thermal stability and better catalytic performance.

Zhao, Qiang

332

PROGRESS REPORT. TRANSURANIC INTERFACIAL REACTION STUDIES ON MANGANESE OXIDE HYDROXIDE MINERAL SURFACES  

EPA Science Inventory

Several DOE sites have been contaminated by transuranic radionuclide (TRU) discharges including neptunium and plutonium. Their interaction with the surrounding geological media can affect the transport and remediation of these radionuclides in the environment. Manganese based min...

333

Synthesis and characterization of novel manganese and vanadium oxides as cathodes for lithium rechargeable batteries  

NASA Astrophysics Data System (ADS)

The development of advanced rechargeable lithium batteries depends on cathodes that can reversibly intercalate lithium ions. Intercalation chemistry plays a key role in the electrochemical reduction and oxidation by lithium of many solid electrodes including transition metal compounds. Intercalation compounds such as LixTiS2 and LiCoO2 exhibit some of the ideal characteristics expected of a cathode for advanced batteries. The former shows high rate capability, excellent electronic conductivity and almost perfect reversibility; the latter shows a high voltage suitable for carbon based anodes and good reversibility but an energy density no higher than that of LixTiS2, a prohibitively high cost and an environmental hazard. The spinel LiMn2O4 removes the cost issue but not the others. Thus, much effort has been directed at synthesizing new structures that exhibit enhanced electrochemical activity. Soft chemistry approaches have been applied for this purpose. One such approach is mild hydrothermal reactions which lead to the formation of new metastable transition metal oxides, not accessible by conventional high temperature methods. The nature of the reactants, the pH of the reaction medium, heating temperature and heating duration have dramatic effects on the crystal structure of the phase formed. The mild hydrothermal decomposition of aqueous permanganate solutions has been found to lead to new layered manganese oxides. In the case of alkali permanganates AMnO4, layered birnessite-type compounds are formed with the general formula AxMnO2.nH 2O (A = Li, Na, K). These compounds have R 3¯ m rhombohedral structures analogous to the layered disulfides. The water is reversibly lost on heating, and the compounds readily react with lithium through an intercalation mechanism. The capacity for lithium is a function of the alkali ion present, and the larger potassium ion maintains the capacity best. For the lithium compound, there is a tendency to convert to the spinel structure which leads to loss of capacity. In the case of hydrothermal decomposition of tetramethylammonium permanganate in the presence of nickel, a new structure compound Ni1-xMn1-yO 3 is formed that has a different structure from that of the known ilmenite form. The structure contains empty tunnels into which lithium ions can be intercalated. Reaction of this nickel manganese oxide with n-butyl lithium showed the uptake of 0.91 Li per formula unit. It converts into the known ilmenite form of NiMnO3 at around 400°C. This compound also has interesting magnetic properties. A wide variety of vanadium oxides can be prepared using hydrothermal methods. Organic templates play an important role in directing the structures formed. Although tetramethyl ammonium hydroxide is a widely used organic template, other amines and long chain amine surfactants also yield interesting new structures many of which are layered phases. The hydrothermal reaction of vanadium pentoxide with methylamine leads to a series of new layered vanadium oxides, which differ in structure from the corresponding ones prepared in the presence of the tetramethylammonium ion because of the existence of hydrogen bonding. Methylamine is the first organic to form a double sheet vanadium oxide, (CH3NH3) 0.75V4O10.0.67H2O, with delta-AgxV2O5 structure. (CH 3NH3)V3O7 shows significant buckling of the vanadium oxide layers compared with N(CH3)4V 3O7. Both of these two compounds are monoclinic. (CH 3NH2)2V8O17 has a tetrahedral unit cell and IR shows that the lone pair electrons of nitrogen bond to vanadium. Also, vanadium coordination decreases with an increase in the pH of the reaction medium and hydrogen bonding controls the orientation of the polyhedra in the vanadium sheets, in contrast to the tetramethylammonium ion where the bonding is predominantly ionic.

Chen, Rongji

334

Characterization of the Fe-Doped Mixed-Valent Tunnel Structure 2 Manganese Oxide KOMS-2  

SciTech Connect

A sol-gel-assisted combustion method was used to prepare Fe-doped manganese oxide octahedral molecular sieve (Fe-KOMS-2) materials with the cryptomelane structure. Characterization of the nanopowder samples over a wide range of Fe-doping levels (0 {le} Fe/Mn {le} 1/2) was carried out using a variety of experimental techniques. For each sample, Cu K{alpha} XRD and ICP-AES were used to index the cryptomelane structure and determine the elemental composition, respectively. A combination of SEM and TEM images revealed that the morphology changes from nanoneedle to nanorod after Fe doping. Furthermore, TGA scans indicated that the thermal stability is also enhanced with the doping. Anomalous XRD demonstrated that the Fe ions replace the Mn ions in the cryptomelane structure, particularly in the (211) planes, and results in a lattice expansion along the c axis, parallel to the tunnels. Reasonable fits to EXAFS data were obtained using a model based on the cryptomelane structure. Moessbauer spectra for selected Fe-KOMS-2 samples indicated that the Fe is present as Fe{sup 3+} in an octahedral environment similar to Mn in the MnO{sub 6} building blocks of KOMS-2. Magnetization measurements detected a small amount of {gamma}-Fe{sub 2}O{sub 3} second phase (e.g., 0.6 wt % for the Fe/Mn = 1/10 sample), the vast majority of the Fe being in the structure as Fe{sup 3+} in the high-spin state.

Hanson J. C.; Shen X.; Morey A.M.; Liu J.; Ding Y.; Cai J.; Durand J.; Wang Q.; Wen W.; Hines W.A.; Bai J.; Frenkel A.I.; Reiff W.; Aindow M.; Suib S.L.

2011-11-10

335

Nanostructured manganese oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing composites in artificial photosynthesis.  

PubMed

Herein, we report on nano-sized Mn oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing compounds in artificial photosynthesis. The composites are synthesized by different and simple procedures and characterized by a number of methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(iv) ammonium nitrate. Some composites are efficient Mn-based catalysts with TOF (mmol O2 per mol Mn per second) ? 2.6. PMID:24898625

Najafpour, Mohammad Mahdi; Rahimi, Fahime; Fathollahzadeh, Maryam; Haghighi, Behzad; Ho?y?ska, Ma?gorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

2014-06-24

336

Biological and Chemical Interactions with U(VI) During Anaerobic Enrichment in the Presence of Iron Oxide Coated Quartz  

SciTech Connect

Microcosm experiments were performed to understand chemical and biological interactions with hexavalent uranium (U(VI)) in the presence of iron oxide bearing minerals and trichloroethylene (TCE) as a co-contaminant. Interactions of U(VI) and hydrous iron oxide moieties on the mineral oxide surfaces were studied during enrichments for dissimilatory iron reducing (DIRB) and sulfate reducing bacteria (SRB). Microbes enriched from groundwater taken from the Test Area North (TAN) site at the Idaho National Engineering and Environmental Laboratory (INEEL) were able to reduce the U(VI) in the adsorption medium as well as the iron on quartz surfaces. Early in the experiment disappearance of U(VI) from solution was a function of chemical interactions since no microbial activity was evident. Abiotic removal of U(VI) was enhanced in the presence of carbonate. As the experiment proceeded, further removal of U(VI) from solution was associated with the fermentation of lactate to propionate and acetate. During later phases of the experiment when lactate was depleted from the growth medium in the microcosm containing the DIRB enrichments, U(VI) concentrations in the solution phase increased until additional lactate was added. When lactate fermentation proceeded, U(VI) concentrations in the liquid phase again returned to near zero. Similar results were shown for the SRB enrichment but less uranium was released back into solution, while in the enrichment with carbonate uranium was not released back into solution. Chemical and biological interactions appear to be important on the mobilization/immobilization of U(VI) in an iron oxide system when TCE is present as a co-contaminant. Interestingly, TCE present in the microcosm experiments was not dechlorinated which was probably an effect of redox conditions that were unsuitable for reductive dechlorination by the microbial culture tested.

Brady D. Lee; Michelle R. Walton; Jodette L. Megio

2005-11-01

337

Towards an understanding of thallium isotope fractionation during adsorption to manganese oxides  

NASA Astrophysics Data System (ADS)

We have conducted the first study of Tl isotope fractionation during sorption of aqueous Tl(I) onto the manganese oxide hexagonal birnessite. The experiments had different initial Tl concentrations, amounts of birnessite, experimental durations, and temperatures, but all of them exhibit heavy Tl isotope compositions for the sorbed Tl compared with the solution, which is consistent with the direction of isotope fractionation observed between seawater and natural ferromanganese sediments. However, the magnitude of fractionation in all experiments (? ? 1.0002-1.0015, where ?=205Tl/203Tl/205Tl/203Tl is smaller than observed between seawater and natural sediments (? ? 1.0019-1.0021; Rehkämper et al., 2002, Earth. Planet. Sci. Lett. 197, 65-81). The experimental results display a strong correlation between the concentration of Tl in the resulting Tl-sorbed birnessite and the magnitude of fractionation. This correlation is best explained by sorption of Tl to two sites on birnessite, one with large isotope fractionation and one with little or no isotope fractionation. Previous work (Peacock and Moon, 2012, Geochim. Cosmochim. Acta 84, 297-313) indicates that Tl in natural ferromanganese sediments is oxidized to Tl(III) and adsorbed over Mn vacancy sites in the phyllomanganate sheets of birnessite, and we hypothesize that this site is strongly fractionated from Tl in solution due to the change in oxidation state from aqueous Tl(I). In most experiments, which have orders of magnitude more Tl associated with the solid than in nature, these vacancy sites are probably fully saturated, so various amounts of additional Tl are likely sorbed to either edge sites on the birnessite or triclinic birnessite formed through oxidative ripening of the hexagonal starting material, with unknown oxidation state and little or no isotopic fractionation. Thus each experiment displays isotopic fractionation governed by the proportions of Tl in the fractionated and slightly fractionated sites, and those proportions are controlled by how much total Tl is sorbed per unit of birnessite. In the experiments with the lowest initial Tl concentrations in solution (˜0.15-0.4 ?g/g) and the lowest concentrations of Tl in the resulting Tl-sorbed birnessite (?17 ?g Tl/mg birnessite), we observed the largest isotopic fractionations, and fractionation is inversely proportional to the initial aqueous Tl concentration. Again, this correlation can be explained by the simultaneous occupation of two different sorption sites; vacancy sites that carry isotopically fractionated Tl and a second site carrying slightly fractionated Tl. The fractionation factors observed in nature exceed those in the experiments likely because the Tl concentrations in seawater and in ferromanganese sediments are three to four orders of magnitude lower than in our experiments, and therefore the second slightly fractionated sorption site is not significantly utilized. Temperature (6-40 °C) and experimental duration (3 min-72 h) appear to have little or no effects on isotope behaviour in this system.

Nielsen, Sune G.; Wasylenki, Laura E.; Rehkämper, Mark; Peacock, Caroline L.; Xue, Zichen; Moon, Ellen M.

2013-09-01

338

Possibilities of liquid-phase low-temperature deposition of manganese oxides on NaY synthetic zeolite  

SciTech Connect

This paper studies the possibilities of low-temperature liquid-phase deposition of manganese oxides on NaY synthetic zeolite and compares the results with literature data. The experiments were conducted in accordance with a design matrix that is presented in a table. The coefficients of regression equations are presented which describe the experimental responses against the background of the errors. A summary is given of rounded-off estimates of relative errors of determination of manganese oxides on the three zeolite types studied and the average values of responses of the same type for all the zeolites. It follows that the optimal estimates of the Mn/sub 2/O/sub 3/ and MnO/sub 2/ contents are the same for all the zeolites within the averaged error limits, while the estimates of MnO contents and conversion of Mn (II) from solution on the zeolite surface are not the same for clinoptilolite as for synthetic NaY, confirming that oxidation proceeds more actively on the NaY surface, while conversion is very pronounced in the case of clinoptilolite.

Eremeev, A.P.; Petrusevich, E.F.

1985-05-20

339

Quartz Crystal.  

National Technical Information Service (NTIS)

Electronic-grade quartz crystal is single-crystal silica that is free of all macroscopic defects and has piezoelectric properties that permit it to be used in electronic circuits for accurate frequency control, timing, and filtration. These uses generate ...

J. E. Ferrell

1985-01-01

340

Genotoxicity of nano- and micron-sized manganese oxide in rats after acute oral treatment.  

PubMed

The use of nanotechnology has led to rapid growth in various areas. Manganese oxide (MnO2) nanomaterials (NMs) are typically used for biomedical applications. However, characterizing the potential human health effects of MnO2 NMs is required before fully exploiting these materials. The aim of this study was to investigate the acute oral toxicity of MnO2 NMs and MnO2-bulk particles in female albino Wistar rats. The genotoxic effects were examined using comet, micronucleus and chromosomal aberration assays. Nanosized MnO2 (45nm) significantly (p<0.01) increased DNA damage in peripheral blood leukocytes and micronuclei and enhanced chromosomal aberrations in the bone marrow cells at 1000mg/kg bw. These findings showed that the neurotoxicity of MnO2-45nm in the brain and red blood cells, as determined through acetylcholinesterase activity, was significantly (p<0.01) inhibited at 1000 and 500mg/kg bw doses. MnO2-45nm disrupted the physicochemical state and neurological system of the animals through alterations in ATPases via the total Na(+)-K(+), Mg(2+) and Ca(2+) levels in the brain P2 fraction. In addition, 500 and 1000mg/kg bw doses of MnO2-45nm caused significant changes in AST, ALT and LDH levels in the liver, kidney and serum of treated rats. Significant tissue distribution was found in all tissues in a dose- and time-dependent manner. MnO2-45nm exhibited much higher absorptivity and tissue distribution compared with MnO2-bulk. A large fraction of MnO2-45nm was cleared in the urine and feces. The histopathological analysis revealed that MnO2-45nm caused alterations in the liver, spleen and brain. These findings will provide fundamental information regarding the potential toxicities and biodistribution of nano and bulk MnO2 generated through acute oral treatment. PMID:23618923

Singh, Shailendra Pratap; Kumari, Monika; Kumari, Srinivas I; Rahman, Mohammed F; Kamal, S S Kalyan; Mahboob, M; Grover, Paramjit

2013-06-14

341

Electrical transport properties of manganese containing pyrochlore type semiconducting oxides using impedance analyses  

SciTech Connect

Graphical abstract: DC conductivity variation of CaCe{sub 1?x}Mn{sub x}SnNbO{sub 7??} (x = 0, 0.2, 0.4 and 0.6) with inverse of temperature. Variation of conductivity with Mn concentration at 600 °C is shown in the inset. Display Omitted Highlights: ? We have observed that the structural ordering as well as grain size increase with Mn substitution. ? Impedance analysis proved that a correlated barrier hopping type conduction mechanism is involved in the materials. ? Activation energy as well as electrical conductivity increases with increase in Mn substitution. ? Localization of electrons associated with Mn{sup 2+} and structural ordering are the key factors for the increased activation energy with Mn substitution. ? All the materials showed good NTC thermistor properties. -- Abstract: A new series of manganese containing pyrochlore type semiconducting oxides CaCe{sub 1?x}Mn{sub x}SnNbO{sub 7??} (x = 0, 0.2, 0.4 and 0.6) have been synthesized to study the effect of Mn substitution on the structure, microstructure and electrical properties of these samples. X-ray diffraction and scanning electron microscopy studies revealed an increase of structural ordering and grain size respectively with increase of Mn substitution. Rietveld analysis and Raman spectroscopy were also employed to corroborate the XRD results. The bulk resistance measurements with temperature exhibit negative temperature coefficient behavior. The impedance analysis of the samples revealed a non-Debye type relaxation existed in the materials. The ac conductivity variation with temperature and frequency indicates a correlated barrier hopping type conduction mechanism in these materials. The barrier height and the intersite separation for hopping influence the electrical conductivity of these samples and are found to be a function of localization of electrons associated with the Mn{sup 2+} ions and the unit cell volume respectively. The Mn substitution increases both electrical conductivity and activation energy contrastingly. This unusual behavior has been explained by correlating the structure, microstructure, defect states, electron localization and intersite separation with the conductivity data of the samples.

Sumi, S. [Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695 019 (India)] [Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695 019 (India); Prabhakar Rao, P., E-mail: padala_rao@yahoo.com [Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695 019 (India); Mahesh, S.K. [Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695 019 (India)] [Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695 019 (India); Koshy, Peter [Mount Zion College of Engineering for Women, Chengannur 689 521 (India)] [Mount Zion College of Engineering for Women, Chengannur 689 521 (India)

2012-12-15

342

Oxidant Selection for the Treatment of Manganese (II), Iron (II), and Arsenic (III) in Groundwaters  

EPA Science Inventory

In order to comply with the United States Environmental Protection Agency?s (U.S. EPA?s) arsenic standard and the manganese and iron secondary maximum contaminant levels (MCLs) in water (10µg/L, 50µg/L, and 300µg/L, respectively), many Midwestern water utilities must add a strong...

343

Microbial Manganese Oxidation in the Lower Mississippi River: Methods and Evidence  

Microsoft Academic Search

Recent work has led to the suggestion that biologically-mediated redox processes might be important in the regulation of dissolved trace element concentrations in rivers, especially with regard to manganese. Here, we focus on the removal of dissolved Mn from lower Mississippi River water. Experiments indicate that dissolved Mn can be rapidly removed from lower Mississippi River water on a timescale

Alan M. Shiller; Tracey H. Stephens

2005-01-01

344

Process for Acid Leaching of Manganese Oxide Ores Aided by Hydrogen Peroxide.  

National Technical Information Service (NTIS)

A method of processing manganese ore by adding the ore to an aqueous solution of acid and H2O2 to form a leach pulp. The leach pulp is agitated for a predetermined time period at predetermined temperatures. The leach pulp is then separated into a solid fr...

J. P. Allen R. R. Corwin

1988-01-01

345

Manganese-catalyzed oxidative benzylic C-H fluorination by fluoride ions.  

PubMed

An efficient protocol for the selective fluorination of benzylic C-H bonds is described. The process is catalyzed by manganese salen complexes and uses nucleophilic fluorine sources, such as triethylamine trihydrofluoride and KF. Reaction rates are sufficiently high (30 min) to allow adoption for the incorporation of (18)F fluoride sources for PET imaging applications. PMID:23616443

Liu, Wei; Groves, John T

2013-06-01

346

Copper doped hollow structured manganese oxide mesocrystals with controlled phase structure and morphology as anode materials for lithium ion battery with improved electrochemical performance.  

PubMed

We develop a facile synthesis route to prepare Cu doped hollow structured manganese oxide mesocrystals with controlled phase structure and morphology using manganese carbonate as the reactant template. It is shown that Cu dopant is homogeneously distributed among the hollow manganese oxide microspherical samples, and it is embedded in the lattice of manganese oxide by substituting Mn(3+) in the presence of Cu(2+). The crystal structure of manganese oxide products can be modulated to bixbyite Mn2O3 and tetragonal Mn3O4 in the presence of annealing gas of air and nitrogen, respectively. The incorporation of Cu into Mn2O3 and Mn3O4 induces a great microstructure evolution from core-shell structure for pure Mn2O3 and Mn3O4 samples to hollow porous spherical Cu-doped Mn2O3 and Mn3O4 samples with a larger surface area, respectively. The Cu-doped hollow spherical Mn2O3 sample displays a higher specific capacity of 642 mAhg(-1) at a current density of 100 mA g(-1) after 100 cycles, which is about 1.78 times improvement compared to that of 361 mA h g(-1) for the pure Mn2O3 sample, displaying a Coulombic efficiency of up to 99.5%. The great enhancement of the electrochemical lithium storage performance can be attributed to the improvement of the electronic conductivity and lithium diffusivity of electrodes. The present results have verified the ability of Cu doping to improve electrochemical lithium storage performances of manganese oxides. PMID:24080017

Li, Qun; Yin, Longwei; Li, Zhaoqiang; Wang, Xuekun; Qi, Yongxin; Ma, Jingyun

2013-11-13

347

Temperature dependence of the absorption of nitrous oxide in the quartz ultraviolet  

NASA Astrophysics Data System (ADS)

The ultraviolet absorption of N2O has been studied by many investigators. References to earlier works are given by Zelikoff, Watanabe and Inn. There is general agreement that from 168 nm upwards nitrous oxide shows weak continuous absorption which reaches a maximum variously placed at 182 and 184 nm. Above 184 nm the absorption rapidly decreases. The weak character of the absorption suggests that the transitions in this region are forbidden. Any spectral structure in this region is absent therefore it is difficult to say what electronic transitions involved here. For the detection of N2O it is useful the knowledge of absorption coefficient N2O at 180 - 300 nm for different temperature. The dependence of the intensity of absorption on temperature was noted by Nicolle and Vodar and studied later by Holliday and Reuben. It is found that absorption increased rapidly with temperature. A graph of the logarithm of the extinction coefficient at 230 nm against the reciprocal temperature gave almost straight line with a slope corresponding to 240 nm. The absence of any fine structure of continuum is the reason to obtain the empirical formula for the calculation of absorption coefficient N2O at 180 - 300 nm and temperature 290 - 2000 degrees Kelvin. Our absorption coefficient K, in cm-1, is defined by I/I0 equals exp(minus Kx) where x is the layer thickness of nitrous oxide in cm reduced to S.T.P. To obtain the formula we used the expression for absorption coefficient at continuous profile of vibronic transition.

Saveljev, V. N.

1997-03-01

348

Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis.  

PubMed

Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). First, we electrochemically characterize the nanostructured ?-Mn(2)O(3) and find that it undergoes oxidation in two potential regions: initially, between 0.5 V and 0.8 V, a potential region relevant to the ORR and, subsequently, between 0.8 V and 1.0 V, a potential region between the ORR and the OER relevant conditions. Next, we perform density function theory (DFT) calculations to understand the changes in the MnO(x) surface as a function of potential and to elucidate reaction mechanisms that lead to high activities observed in the experiments. Using DFT, we construct surface Pourbaix and free energy diagrams of three different MnO(x) surfaces and identify 1/2 ML HO* covered Mn(2)O(3) and O* covered MnO(2), as the active surfaces for the ORR and the OER, respectively. Additionally, we find that the ORR occurs through an associative mechanism and that its overpotential is highly dependent on the stabilization of intermediates through hydrogen bonds with water molecules. We also determine that OER occurs through direct recombination mechanism and that its major source of overpotential is the scaling relationship between HOO* and HO* surface intermediates. Using a previously developed Sabatier model we show that the theoretical predictions of catalytic activities match the experimentally determined onset potentials for the ORR and the OER, both qualitatively and quantitatively. Consequently, the combination of first-principles theoretical analysis and experimental methods offers an understanding of manganese oxide oxygen electrocatalysis at the atomic level, achieving fundamental insight that can potentially be used to design and develop improved electrocatalysts for the ORR and the OER and other important reactions of technological interest. PMID:22990481

Su, Hai-Yan; Gorlin, Yelena; Man, Isabela C; Calle-Vallejo, Federico; Nørskov, Jens K; Jaramillo, Thomas F; Rossmeisl, Jan

2012-10-28

349

A comparative study of protein adsorption on titanium oxide surfaces using in situ ellipsometry, optical waveguide lightmode spectroscopy, and quartz crystal microbalance\\/dissipation  

Microsoft Academic Search

The adsorption kinetics of three model proteins—human serum albumin, fibrinogen and hemoglobin—has been measured and compared using three different experimental techniques: optical waveguide lightmode spectroscopy (OWLS), ellipsometry (ELM) and quartz crystal microbalance (QCM-D). The studies were complemented by also monitoring the corresponding antibody interactions with the pre-adsorbed protein layer. All measurements were performed with identically prepared titanium oxide coated substrates.

F Höök; J Vörös; M Rodahl; R Kurrat; P Böni; J. J Ramsden; M Textor; N. D Spencer; P Tengvall; J Gold; B Kasemo

2002-01-01

350

Catalytic oxidation of NO with O2 over FeMnOx/TiO2: Effect of iron and manganese oxides loading sequences and the catalytic mechanism study  

NASA Astrophysics Data System (ADS)

FeMnOx/TiO2 with different iron and manganese oxides adding orders were prepared through isovolumetric impregnation and tested for catalytic oxidation of NO with O2. It was found that the sample obtained from one-step impregnation method had better catalytic activity. The excellent activity was attributed to higher surface area, lower crystalline of manganese oxides, abundant Mn3+, Fe3+ and chemisorbed oxygen species on the surface. Furthermore, effects of loading sequences on FeMnOx/TiO2 catalysts were investigated. The study showed that Fe and Mn would affect each other and change the surface physicochemical properties of FeMnOx/TiO2 when they were loaded step-by-step. In addition, the inhibiting effect of H2O on catalytic activity was reversible while the conversion of NO recovered to 40% when SO2 was cut off. XPS analysis between used and fresh catalysts revealed the electron transfer between Fen+ and Mnn+ ions in FeMnOx/TiO2. Possible reaction mechanism was put forward by comprehensive analysis of XPS and FT-IR results.

Zhang, Mengying; Li, Caiting; Qu, Long; Fu, Mengfan; Zeng, Guangming; Fan, Chunzhen; Ma, Jinfeng; Zhan, Fuman

2014-05-01

351

Power generation using spinel manganese-cobalt oxide as a cathode catalyst for microbial fuel cell applications.  

PubMed

This study focused on the use of spinel manganese-cobalt (Mn-Co) oxide, prepared by a solid state reaction, as a cathode catalyst to replace platinum in microbial fuel cells (MFCs) applications. Spinel Mn-Co oxides, with an Mn/Co atomic ratios of 0.5, 1, and 2, were prepared and examined in an air cathode MFCs which was fed with a molasses-laden synthetic wastewater and operated in batch mode. Among the three Mn-Co oxide cathodes and after 300 h of operation, the Mn-Co oxide catalyst with Mn/Co atomic ratio of 2 (MnCo-2) exhibited the highest power generation 113 mW/m2 at cell potential of 279 mV, which were lower than those for the Pt catalyst (148 mW/m2 and 325 mV, respectively). This study indicated that using spinel Mn-Co oxide to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs. PMID:21944282

Mahmoud, Mohamed; Gad-Allah, Tarek A; El-Khatib, K M; El-Gohary, Fatma

2011-11-01

352

High resolution electron energy loss spectroscopy of manganese oxides: Application to Mn{sub 3}O{sub 4} nanoparticles  

SciTech Connect

Manganese oxides particularly Mn{sub 3}O{sub 4} Hausmannite are currently used in many industrial applications such as catalysis, magnetism, electrochemistry or air contamination. The downsizing of the particle size of such material permits an improvement of its intrinsic properties and a consequent increase in its performances compared to a classical micron-sized material. Here, we report a novel synthesis of hydrophilic nano-sized Mn{sub 3}O{sub 4}, a bivalent oxide, for which a precise characterization is necessary and for which the determination of the valency proves to be essential. X-ray diffraction (XRD), Transmission Electron Microscopy (TEM) and particularly High Resolution Electron Energy Loss Spectroscopy (HREELS) allow us to perform these measurements on the nanometer scale. Well crystallized 10-20 nm sized Mn{sub 3}O{sub 4} particles with sphere-shaped morphology were thus successfully synthesized. Meticulous EELS investigations allowed the determination of a Mn{sup 3+}/Mn{sup 2+} ratio of 1.5, i.e. slightly lower than the theoretical value of 2 for the bulk Hausmannite manganese oxide. This result emphasizes the presence of vacancies on the tetrahedral sites in the structure of the as-synthesized nanomaterial. - Research Highlights: {yields}Mn{sub 3}O{sub 4} bulk and nano were studied by XRD, TEM and EELS. {yields}XRD and TEM determine the degree of crystallinity and the narrow grain size. {yields}HREELS gave access to the Mn{sup 3+}/Mn{sup 2+} ratio. {yields}Mn{sub 3}O{sub 4} nano have vacancies on the tetrahedral sites.

Laffont, L., E-mail: Lydia.laffont@ensiacet.fr [Institut Carnot, Laboratoire CIRIMAT (equipe MEMO), CNRS UMR 5085, ENSIACET, 4 allee Emile Monso, BP 74233, 31432 Toulouse cedex 4 (France); Gibot, P. [Laboratoire de Reactivite et Chimie des Solides CNRS UMR 6007, Universite de Picardie Jules Verne, 33 rue Saint Leu, 80039 Amiens cedex 9 (France)

2010-11-15

353

Effect of allied and alien ions on the EPR spectrum of Mn 4+-containing lithium-manganese spinel oxides  

NASA Astrophysics Data System (ADS)

Electron paramagnetic resonance spectroscopy was used for studying the effect of allied and alien ions on the EPR spectrum of Mn 4+-containing lithium-manganese spinel oxides. Manganese spinel oxides with paramagnetic Mn 4+ and diamagnetic substituents in the 16d spinel sites were studied: Li[Mg 0.5Mn 1.5]O 4, Li[Mg 0.5- xCo 2 xMn 1.5- x]O 4, 0< x?0.5, and Li[Li 1/3Mn 5/3]O 4. Ni 2+-ions with integer-spin-ground state ( S=1) were selected as alien ions: Li[Mg 0.5- xNi xMn 1.5]O 4 (0? x?0.5), Li[Li (1-2 x)/3 Ni xMn (5- x)/3 ]O 4 (0? x?0.5), and Li[Ni 0.5Mn 1.5- yTi y]O 4 (0? y?1.0). It was shown that in Ni-substituted oxides the low temperature EPR response comes from magnetically correlated Ni-Mn spins, while at high registration temperature Mn 4+ ions give rise to the EPR profile. Analysis of the EPR line width allows differentiating between the contributions of the density of paramagnetic species and the strength of the exchange interactions in magnetically concentrated systems. The density of allied and alien paramagnetic species has no effect on the EPR line width in cases when the strengths of antiferro- and ferromagnetic interactions on an atomic site are close. On the contrary, when antiferro- or ferromagnetic interactions on an atomic site are dominant, the EPR line width increases with the density of paramagnetic species.

Zhecheva, E.; Stoyanova, R.

2005-08-01

354

Electrochemical properties of spinel-type manganese oxide/porous carbon nanocomposite powders in 1 M KOH aqueous solution  

NASA Astrophysics Data System (ADS)

Spinel-type manganese oxide/porous carbon (Mn3O4/C) nanocomposite powders have been simply prepared by a thermal decomposition of manganese gluconate dihydrate under an Ar gas flow at above 600 °C. The structure and texture of the Mn3O4/C nanocomposite powders are investigated by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS) equipped scanning transmission electron microscopy (STEM), transmission electron microscopy (TEM), selected area-electron diffraction (SA-ED), thermogravimetric and differential thermal analysis (TG-DTA) and adsorption/desorption of N2 gas at -196 °C. The electrochemical properties of the nanocomposite powders in 1 M KOH aqueous solution are studied, focusing on the relationship between their structures and electrochemical capacitance.In the nanocomposite powders, Mn3O4 nano particles approximately 5 nm in size are dispersed in a porous carbon matrix. The nanocomposite powders prepared at 800 °C exhibit a high specific capacitance calculated from cyclic voltammogram of 350 and 600 F g-1 at a sweep rate of 1 and 0.1 mV s-1, respectively. The influence of the heating temperature on the structure and the electrochemical properties of nanocomposite powders is also discussed.

Tsumura, Tomoki; Tsumori, Koichiro; Shimizu, Goichi; Toyoda, Masahiro

2012-02-01

355

Characterization of High-Velocity Solution Precursor Flame-Sprayed Manganese Cobalt Oxide Spinel Coatings for Metallic SOFC Interconnectors  

NASA Astrophysics Data System (ADS)

A modified high-velocity oxy-fuel spray (HVOF) thermal spray torch equipped with liquid feeding hardware was used to spray manganese-cobalt solutions on ferritic stainless steel grade Crofer 22 APU substrates. The HVOF torch was modified in such a way that the solution could be fed axially into the combustion chamber through 250- and 300-?m-diameter liquid injector nozzles. The solution used in this study was prepared by diluting nitrates of manganese and cobalt, i.e., Mn(NO3)2·4H2O and Co(NO3)2·6H2O, respectively, in deionized water. The as-sprayed coatings were characterized by X-ray diffraction and field-emission scanning electron microscopy operating in secondary electron mode. Chemical analyses were performed on an energy dispersive spectrometer. Coatings with remarkable density could be prepared by the novel high-velocity solution precursor flame spray (HVSPFS) process. Due to finely sized droplet formation in the HVSPFS process and the use of as delivered Crofer 22 APU substrate material having very low substrate roughness ( R a < 0.5 ?m), thin and homogeneous coatings, with thicknesses lower than 10 ?m could be prepared. The coatings were found to have a crystalline structure equivalent to MnCo2O4 spinel with addition of Co-oxide phases. Crystallographic structure was restored back to single-phase spinel structure by heat treatment.

Puranen, Jouni; Laakso, Jarmo; Kylmälahti, Mikko; Vuoristo, Petri

2013-06-01

356

Structural, optical, and magnetic studies of manganese-doped zinc oxide hierarchical microspheres by self-assembly of nanoparticles  

PubMed Central

In this study, a series of manganese [Mn]-doped zinc oxide [ZnO] hierarchical microspheres [HMSs] are prepared by hydrothermal method only using zinc acetate and manganese acetate as precursors and ethylene glycol as solvent. X-ray diffraction indicates that all of the as-obtained samples including the highest Mn (7 mol%) in the crystal lattice of ZnO have a pure phase (hexagonal wurtzite structure). A broad Raman spectrum from as-synthesized doping samples ranges from 500 to 600 cm-1, revealing the successful doping of paramagnetic Mn2+ ions in the host ZnO. Optical absorption analysis of the samples exhibits a blueshift in the absorption band edge with increasing dopant concentration, and corresponding photoluminescence spectra show that Mn doping suppresses both near-band edge UV emission and defect-related blue emission. In particular, magnetic measurements confirm robust room-temperature ferromagnetic behavior with a high Curie temperature exceeding 400 K, signifying that the as-formed Mn-doped ZnO HMSs will have immense potential in spintronic devices and spin-based electronic technologies.

2012-01-01

357

Surface structure of the proton-exchanged lithium manganese oxide spinels and their lithium-ion sieve properties  

SciTech Connect

The spinel structure and the valence states of the Mn ions both at the surface and the bulk were characterized for the Li{sup +} extracted and inserted manganese oxide spinels. The Li{sup +} extraction from the orthorhombic LiMn{sub 2}O{sub 4} spinel results in the formation of the cubic spinel, the crystal structure of which is the same as {lambda}-MnO{sub 2}. The LiMn{sub 2}O{sub 4} spinel prepared from an electrolytically prepared manganese dioxide is converted to HMn{sub 2}O{sub 4} on dilute acid treatment. X-ray photoelectron spectroscopic analysis revealed that the valence state of the surface Mn ions remains unchanged during the Li{sup +} extraction and insertion, which indicates an occurrence of the Li{sup +}-H{sup +} ion exchange reaction at the surface irrespective of the solution pH. The Fourier transform infrared photoacoustic spectra of the Li{sup +} extracted spinel demonstrated the existence of the surface hydroxyl groups, which is considered to be associated with the vacant 8a tetrahedral sites in the spinel structure. Based on the thermal stability of the surface hydroxyl groups and the bulk hydroxyl groups, the Li{sup +} extracted spinel structure is discussed in relation to its lithium-ion sieve property.

Sato, K.; Poojary, D.M.; Clearfield, A. [Texas A & M Univ., College Station, TX (United States)] [Texas A & M Univ., College Station, TX (United States); Kohno, M.; Inoue, Y. [Nagaoka Univ. of Technology, Niigata (Japan)] [Nagaoka Univ. of Technology, Niigata (Japan)

1997-06-01

358

Modeling the adsorption of mercury(II) on (hydr)oxides. 1: Amorphous iron oxide and {alpha}-quartz  

SciTech Connect

In this study, the authors provide a single model capable of describing the behavior of mercury(II) at two different solid/water interfaces. Mercury(II) sorption on amorphous ferric oxide (HFO) and {alpha}-SiO{sub 2} can be simulated using the surface complexation approach. In both cases, experiments are best reproduced when ternary surface complexes between the surface ({triple_bond}S-OH{sup 0}), Hg{sup 2+}, OH{sup {minus}} or Cl{sup {minus}} are included in the model. Sorption of ternary surface complexes predominates in the case of {alpha}-SiO{sub 2}. In addition, in the case of HFO, additional precipitation reactions of a nonideal Hg(OH){sub 2}-Fe(OH){sub 3} solid solution are needed at high sorbate to sorbent ratios. The modeling leads to a new set of surface complexation constants for the interaction between Hg{sup 2+} and these oxide surfaces which are described herein.

Tiffreau, C.; Luetzenkirchen, J.; Behra, P. [Univ. Louis Pasteur, Strasbourg (France). Inst. de Mecanique des Fluides] [Univ. Louis Pasteur, Strasbourg (France). Inst. de Mecanique des Fluides

1995-06-01

359

Structure of Highly Divided Nonstoichiometric Iron Manganese Oxide Powders Fe3- xMnx□3delta\\/4O4+delta  

Microsoft Academic Search

Highly divided iron manganese oxide powders, Fe3- xMnx□3delta\\/4O4+delta, were prepared at low temperature (T<=560 degC) by the thermal decomposition of mixed oxalate precursors Fe1-alphaMnalphaC2O4, 2H2O (alpha=x\\/3). The manganese-rich compounds (x>=1.5) have a complex structure that can be cubic, tetragonal, or a mixture of both tetragonal and cubic spinel phases that indicates a lack of miscibility existing in the Fe3O4-Mn3O4 phase

Sophie Guillemet-Fritsch; Sophie Viguié; Abel Rousset

1999-01-01

360

Synthesis of layered birnessite-type manganese oxide thin films on plastic substrates by chemical bath deposition for flexible transparent supercapacitors  

Microsoft Academic Search

Layered birnessite-type manganese oxide thin films are successfully fabricated on indium tin oxide coated polyethylene terephthalate substrates for flexible transparent supercapacitors by a facile, effective and inexpensive chemical bath deposition technology from an alkaline KMnO4 aqueous solution at room temperature. The effects of deposition conditions, including KMnO4 concentration, initial molar ratio of NH3·H2O and KMnO4, bath temperature, and reaction time,

Yu Hu; Hongwei Zhu; Jun Wang; Zhenxing Chen

2011-01-01

361

Porous nickel hydroxide-manganese dioxide-reduced graphene oxide ternary hybrid spheres as excellent supercapacitor electrode materials.  

PubMed

This paper reports the first nickel hydroxide-manganese dioxide-reduced graphene oxide (Ni(OH)2-MnO2-RGO) ternary hybrid sphere powders as supercapacitor electrode materials. Due to the abundant porous nanostructure, relatively high specific surface area, well-defined spherical morphology, and the synergetic effect of Ni(OH)2, MnO2, and RGO, the electrodes with the as-obtained Ni(OH)2-MnO2-RGO ternary hybrid spheres as active materials exhibited significantly enhanced specific capacitance (1985 F·g(-1)) and energy density (54.0 Wh·kg(-1)), based on the total mass of active materials. In addition, the Ni(OH)2-MnO2-RGO hybrid spheres-based asymmetric supercapacitor also showed satisfying energy density and electrochemical cycling stability. PMID:24797315

Chen, Hao; Zhou, Shuxue; Wu, Limin

2014-06-11

362

Lithium ion phase-transfer reaction at the interface between the lithium manganese oxide electrode and the nonaqueous electrolyte.  

PubMed

The lithium ion phase-transfer reaction between the spinel lithium manganese oxide electrode and a nonaqueous electrolyte was investigated by the ac impedance spectroscopic method. The dependence of the impedance spectra on the electrochemical potential of the lithium ion in the electrode, the lithium salt concentration in the electrolyte, the kind of solvent, and the measured temperature were examined. Nyquist plots, obtained from the impedance measurements, consist of two semicircles for high and medium frequency and warburg impedance for low frequency, indicating that the reaction process of two main steps for high and medium frequency obey the Butler-Volmer type equation and could be related to the charge-transfer reaction process accompanied with lithium ion phase-transfer at the interface. The dependency on the solvent suggests that both steps in the lithium ion phase-transfer at the electrode/electrolyte interface include the desolvation process and have high activation barriers. PMID:16852662

Kobayashi, Shota; Uchimoto, Yoshiharu

2005-07-14

363

Ketjenblack carbon supported amorphous manganese oxides nanowires as highly efficient electrocatalyst for oxygen reduction reaction in alkaline solutions.  

PubMed

A composite air electrode consisting of Ketjenblack carbon (KB) supported amorphous manganese oxide (MnOx) nanowires, synthesized via a polyol method, is highly efficient for the oxygen reduction reaction (ORR) in a Zn-air battery. The low-cost and highly conductive KB in this composite electrode overcomes the limitations due to low electrical conductivity of MnOx while acting as a supporting matrix for the catalyst. The large surface area of the amorphous MnOx nanowires, together with other microscopic features (e.g., high density of surface defects), potentially offers more active sites for oxygen adsorption, thus significantly enhancing ORR activity. In particular, a Zn-air battery based on this composite air electrode exhibits a peak power density of ?190 mW/cm2, which is far superior to those based on a commercial air cathode with Mn3O4 catalysts. PMID:22050041

Lee, Jang-Soo; Park, Gi Su; Lee, Ho Il; Kim, Sun Tai; Cao, Ruiguo; Liu, Meilin; Cho, Jaephil

2011-12-14

364

Design, synthesis, and characterization of materials for controlled line deposition, environmental remediation, and doping of porous manganese oxide material  

NASA Astrophysics Data System (ADS)

This thesis covers three topics: (1) coatings formed from sol-gel phases, (2) environmental remediation, and (3) doping of a porous manganese oxide. Synthesis, characterization, and application were investigated for each topic. Line-formations were formed spontaneously by self-assembly from vanadium sol-gels and other metal containing solutions on glass substrates. The solutions were prepared by the dissolution of metal oxide or salt in water. A more straightforward method is proposed than used in previous work. Analyses using optical microscopy, atomic force microscopy, scanning electron microscopy, energy-dispersive X-ray analysis, and infrared spectroscopy showed discreet lines whose deposition could be controlled by varying the concentration. A mechanism was developed from the observed results. Microwave heating, the addition of graphite rods, and oxidants, can enhance HCB remediation from soil. To achieve remediation, a TeflonRTM vessel open to the atmosphere along with an oxidant, potassium persulfate (PerS) or potassium hydroxide, along with uncoated or aluminum oxide coated, graphite rods were heated in a research grade microwave oven. Microwave heating was used to decrease the heating time, and graphite rods were used to increase the absorption of the microwave energy by providing thermal centers. The results showed that the percent HCB removed was increased by adding graphite rods and oxidants. Tungsten, silver, and sulfur were investigated as doping agents for K--OMS-2. The synthesis of these materials was carried out with a reflux method. The doping of K--OMS-2 led to changes in the properties of a tungsten doped K--OMS-2 had an increased resistivity, the silver doped material showed improved epoxidation of trans-stilbene, and the addition of sulfur produced a paper-like material. Rietveld refinement of the tungsten doped K--OMS-2 showed that the tungsten was doped into the framework.

Calvert, Craig A.

365

Multivariate data analysis approach to understand magnetic properties of perovskite manganese oxides  

SciTech Connect

Here we apply statistical multivariate data analysis techniques to obtain some insights into the complex structure-property relations in antiferromagnetic (AFM) and ferromagnetic (FM) manganese perovskite systems, AMnO{sub 3}. The 131 samples included in the present analyses are described by 21 crystal-structure or crystal-chemical (CS/CC) parameters. Principal component analysis (PCA), carried out separately for the AFM and FM compounds, is used to model and evaluate the various relationships among the magnetic properties and the various CS/CC parameters. Moreover, for the AFM compounds, PLS (partial least squares projections to latent structures) analysis is performed so as to predict the magnitude of the Neel temperature on the bases of the CS/CC parameters. Finally, so-called PLS-DA (PLS discriminant analysis) method is employed to find out the most influential/characteristic CS/CC parameters that differentiate the two classes of compounds from each other. - Graphical abstract: Statistical multivariate data analysis techniques are applied to detect structure-property relations in antiferromagnetic (AFM) and ferromagnetic (FM) manganese perovskites. For AFM compounds, partial least squares projections to latent structures analysis predict the magnitude of the Neel temperature on the bases of structural parameters only. Moreover, AFM and FM compounds are well separated by means of so-called partial least squares discriminant analysis method.

Imamura, N. [Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Laboratory of Inorganic Chemistry, Department of Chemistry, Helsinki University of Technology, FI-02015 TKK (Finland); Mizoguchi, T. [Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Yamauchi, H. [Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Laboratory of Inorganic Chemistry, Department of Chemistry, Helsinki University of Technology, FI-02015 TKK (Finland); Karppinen, M. [Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Laboratory of Inorganic Chemistry, Department of Chemistry, Helsinki University of Technology, FI-02015 TKK (Finland)], E-mail: maarit.karppinen@tkk.fi

2008-05-15

366

Natural manganese oxide: Combined analytical approach for solid characterization and arsenic retention  

NASA Astrophysics Data System (ADS)

To understand the retention of As on a natural manganese sand, the structural, textural and chemical properties of the solid were first investigated by combining scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron-energy-loss spectroscopy (EELS), X-ray diffraction (XRD), BET N 2 gas adsorption, diffuse reflectance Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis. Manganese sand could be mainly described as a mixture of a phyllomanganate, lithiophorite [(Al,Li)MnO 2(OH) 2], and pyrolusite (MnO 2). Iron particle, kaolinite and gibbsite type-phases were also observed. Particles organization led to the presence of a mesoporosity with pore diameters ranging from 100 to 200 Å and a specific surface area of 23 m 2 g -1. Contact with an As(V) solution (0.67 mmol L -1) led to an average fractional surface coverage of 0.4. Both As (V) and (III) were present on the surface of the sand in a 1:1 ratio. As(V) was sorbed on lithiophorite-type particles through surface complexation type reaction. As(III) was thought to result from As(V) reduction mechanism on iron particles.

Ouvrard, S.; de Donato, Ph.; Simonnot, M. O.; Begin, S.; Ghanbaja, J.; Alnot, M.; Duval, Y. B.; Lhote, F.; Barres, O.; Sardin, M.

2005-06-01

367

Oxidative aliphatic C-H fluorination with manganese catalysts and fluoride ion.  

PubMed

Fluorination is a reaction that is useful in improving the chemical stability and changing the binding affinity of biologically active compounds. The protocol described here can be used to replace aliphatic, C(sp(3))-H hydrogen in small molecules with fluorine. Notably, isolated methylene groups and unactivated benzylic sites are accessible. The method uses readily available manganese porphyrin and manganese salen catalysts and various fluoride ion reagents, including silver fluoride (AgF), tetrabutylammonium fluoride and triethylamine trihydrofluoride (TREAT·HF), as the source of fluorine. Typically, the reactions afford 50-70% yield of mono-fluorinated products in one step. Two representative examples, the fragrance component celestolide and the nonsteroidal anti-inflammatory drug ibuprofen, are described; they produced useful isolated quantities (250-300 mg, ~50% yield) of fluorinated material over periods of 1-8 h. The procedures are performed in a typical fume hood using ordinary laboratory glassware. No special precautions to rigorously exclude water are required. PMID:24177292

Liu, Wei; Huang, Xiongyi; Groves, John T

2013-12-01

368

Anti-oxidant and pro-oxidant reactivities of copper(II), manganese(II) and iron(III) 3,5-di- i -propylsalicylate chelates during peroxidation of alkylbenzenes  

Microsoft Academic Search

Bioactive copper(II), iron(III), and manganese(II) 3,5-di-i-propylsalicylate (3,5-DIPS) chelates were investigated in order to determine their ability to inhibit the free radical initiated chain reactions leading to the peroxidation of isopropylbenzene (i-PrPh) and ethylbenzene (EtPh). Quantitative kinetic studies of these chelates established the following order of anti-oxidant reactivities: manganese(II)-(3,5-DIPS)2>iron(III)(3,5-DIPS)3>copper(II)2(3,5-DIPS)4> > 3,5-DIPS acid. The mechanism of anti-oxidant reactivity of these three chelates

Levon A. Tavadyan; Gegham Z. Sedrakyan; Seyran H. Minasyan; Frederick T. Greenaway; John R. J. Sorenson

2004-01-01

369

Operation of a two-phase partitioning bioreactor for the oxidation of anthracene by the enzyme manganese peroxidase.  

PubMed

A study was conducted to determine the potential of a two-phase partitioning bioreactor (TPPB) for the treatment of a poorly soluble compound, anthracene, by the enzyme manganese peroxidase (MnP) from the fungus Bjerkandera sp. BOS55. Silicone oil was used as the immiscible solvent, which contained anthracene at high concentrations. The optimization of the oxidation process was conducted taking into account the factors which may directly affect the MnP catalytic cycle (the concentration of H(2)O(2) and malonic acid) and those that affect the mass transfer of anthracene between the organic and the aqueous phase (solvent and agitation speed). The main objective was carried out in terms of improved efficiency, i.e., maximizing the anthracene oxidized per unit of enzyme used. The TPPB reached nearly complete oxidation of anthracene at a conversion rate of 1.8mgl(-1)h(-1) in 56h, which suggests the application of enzymatic TPPBs for the removal of poorly soluble compounds. PMID:16904729

Eibes, G; Moreira, M T; Feijoo, G; Daugulis, A J; Lema, J M

2007-01-01

370

4-(Trifluoromethyl)-benzonitrile: A novel electrolyte additive for lithium nickel manganese oxide cathode of high voltage lithium ion battery  

NASA Astrophysics Data System (ADS)

In this work, 4-(Trifluoromethyl)-benzonitrile (4-TB) is used as a novel electrolyte additive for LiNi0.5Mn1.5O4 cathode of high voltage lithium ion battery. Charge-discharge tests show that the cyclic stability of LiNi0.5Mn1.5O4 is significantly improved by using 0.5 wt.% 4-TB. With using 4-TB, LiNi0.5Mn1.5O4 delivers an initial capacity of 133 mAh g-1 and maintains 121 mAh g-1 after 300 cycles with a capacity retention of 91%, compared to the 75% of that using base electrolyte (1 M LiPF6 in ethylene carbonate(EC)/dimethyl carbonate(DMC). The results from linear sweep voltammetry, density functional theory calculations, electrochemical impedance spectroscopy, scanning electron microscope, energy dispersive spectroscopy, Fourier transform infrared, and inductively coupled plasma, indicate that 4-TB has lower oxidative stability than EC and DMC, and is preferentially oxidized on LiNi0.5Mn1.5O4 forming a low-impedance protective film, which prevents the subsequent oxidation decomposition of the electrolyte and suppresses the manganese dissolution from LiNi0.5Mn1.5O4.

Huang, Wenna; Xing, Lidan; Wang, Yating; Xu, Mengqing; Li, Weishan; Xie, Fengchao; Xia, Shengan

2014-12-01

371

Cationic Distribution and Oxidation Mechanism of Trivalent Manganese Ions in Submicrometer Mn xCoFe 2- xO 4Spinel Ferrites  

NASA Astrophysics Data System (ADS)

Submicrometer Mn xCoFe 2- xO 4(0 ? x< 1) spinel particles with a spherical shape were prepared at low temperature from oxalic precursors. Because of their small crystallite size (about 50 nm), these ferrite particles can be oxidized below 400°C giving cubic deficient spinels having both Mn 3+and Mn 4+ions because of oxido-reduction phenomena. Information about the valence state of the manganese and cobalt ions and cation distribution between tetrahedral ( A) and octahedral ( B) sites are derived from lattice parameter variation, IR spectroscopy, thermogravimetric analysis, and electrical conductivity. A kinetics study of the oxidation of Mn 3+ions shows that oxidation proceeds by cation diffusion through a topotactic reaction with a constant chemical diffusion coefficient for x< 0.60 and variable above x= 0.80 and an activation energy close to 115 kJ mol -1but, however, depending on manganese substitution content.

Laarj, M.; Kacim, S.; Gillot, B.

1996-08-01

372

One-step through-mask electrodeposition of a porous structure composed of manganese oxide nanosheets with electrocatalytic activity for oxygen reduction  

SciTech Connect

Potentiostatic electrolysis of a mixed aqueous solution of Bu{sub 4}NBr and MnSO{sub 4} at +1.0 V (vs. Ag/AgCl) on Pt electrode led to the oxidation of Br{sup -} and Mn{sup 2+} ions. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and X-ray diffraction (XRD) revealed that this anodic process was followed by the deposition of insulating crystals of bromide salt of Bu{sub 4}N{sup +} and the subsequent formation of layered manganese oxide in the interstitial spaces of the bromide grains already grown. Dissolution of the bromide crystals in water left a well-dispersed porous texture composed of manganese oxide nanosheets. The resulting MnO{sub x}-modified electrode exhibited a larger catalytic current for the reduction of oxygen in alkaline solution, compared to the bare Pt electrode.

Fukuda, Masaki; Iida, Chihiro [Department of Applied Chemistry, Yamaguchi University, 2-16-1 Tokiwadai, Ube 755-8611 (Japan); Nakayama, Masaharu, E-mail: nkymm@yamaguchi-u.ac.jp [Department of Applied Chemistry, Yamaguchi University, 2-16-1 Tokiwadai, Ube 755-8611 (Japan)

2009-06-03

373

Manganese Peroxidase-Dependent Oxidation of Glyoxylic and Oxalic Acids Synthesized by Ceriporiopsis subvermispora Produces Extracellular Hydrogen Peroxide  

PubMed Central

The ligninolytic system of the basidiomycete Ceriporiopsis subvermispora is composed of manganese peroxidase (MnP) and laccase. In this work, the source of extracellular hydrogen peroxide required for MnP activity was investigated. Our attention was focused on the possibility that hydrogen peroxide might be generated by MnP itself through the oxidation of organic acids secreted by the fungus. Both oxalate and glyoxylate were found in the extracellular fluid of C. subvermispora cultures grown in chemically defined media, where MnP is also secreted. The in vivo oxidation of oxalate was measured; 14CO2 evolution was monitored after addition of exogenous [14C]oxalate to cultures at constant specific activity. In standard cultures, evolution of CO2 from oxalate was maximal at day 6, although the MnP titers were highest at day 12, the oxalate concentration was maximal (2.5 mM) at day 10, and the glyoxylate concentration was maximal (0.24 mM) at day 5. However, in cultures containing low nitrogen levels, in which the pH is more stable, a better correlation between MnP titers and mineralization of oxalate was observed. Both MnP activity and oxidation of [14C]oxalate were negligible in cultures lacking Mn(II). In vitro assays confirmed that Mn(II)-dependent oxidation of [14C]oxalate by MnP occurs and that this reaction is stimulated by glyoxylate at the concentrations found in cultures. In addition, both organic acids supported phenol red oxidation by MnP without added hydrogen peroxide, and glyoxylate was more reactive than oxalate in this reaction. Based on these results, a model is proposed for the extracellular production of hydrogen peroxide by C. subvermispora.

Urzua, Ulises; Kersten, Philip J.; Vicuna, Rafael

1998-01-01

374

Effects of Cobalt on Manganese Oxidation by Pseudomonas putida MnB1  

Microsoft Academic Search

The oxidation of Mn(II) in the environment is thought to occur predominantly through biologically mediated pathways. During the stationary phase of growth, the well-characterized freshwater and soil bacterium Pseudomonas putida MnB1 oxidizes soluble Mn(II) to a poorly crystalline layer type Mn(IV) oxide. These Mn oxide particles (2 - 5 nm thickness) are deposited in a matrix of extracellular polymeric substances

J. Pena; J. Bargar; G. Sposito

2005-01-01

375

The fate of ammonium in anoxic manganese oxide-rich marine sediment  

Microsoft Academic Search

The possibility for anaerobic NH4+ oxidation and N2 formation was explored in a Mn oxide-rich continental basin sediment from Skagerrak. The surface sediment contained 2.9 weight-% Mn(IV), and reactive Mn oxide persisted to ?10 cm depth. Microbial Mn reduction completely dominated anaerobic carbon oxidation, whereas neither Fe reduction nor sulfate reduction were significant. Accumulation rates of soluble NH4+ during anoxic

B. Thamdrup; Tage Dalsgaard

2000-01-01

376

Oxidation of isoprene by molecular oxygen in the presence of the tetraphenylpoephin complex of divalent manganese  

SciTech Connect

This paper studies the regiosele-tivity of the oxidation of isoprene and 2-methylpentene in the presence of the TPPM /SUB n/ /SUP III/ Cl system. It was found that the oxidation of isoprene proceeds regioselectively with the formation of 2-methyl-2-buten-1-01. This oxidation is more rapid for isoprene than for 2-methyl-2-pentene.

Karakozova, E.I.; Karmilova, L.V.; Solov'eva, A.B.

1986-07-01

377

Cr(III) Oxidation and Cr Toxicity in Cultures of the Manganese(II)Oxidizing Pseudomonas putida Strain GB1  

Microsoft Academic Search

Mn oxides have long been considered the primary environmental oxidant of Cr(III), however, since most of the reactive Mn oxides in the environment are believed to be of biological origin, microorganisms may indirectly mediate Cr(III) oxidation and accelerate the rate over that seen in purely abiotic systems. In this study, we examined the ability of the Mn(II)-oxidizing bacterium, Pseudomonas putida

Karen J. Murray; Mylene L. Mozafarzadeh; Bradley M. Tebo

2005-01-01

378

Nanolayered manganese oxide/C60 composite: a good water-oxidizing catalyst for artificial photosynthetic systems.  

PubMed

For the first time, we considered Mn oxide/C60 composites as water-oxidizing catalysts. The composites were synthesized by easy and simple procedures, and characterized by some methods. The water-oxidizing activities of these composites were also measured in the presence of cerium(iv) ammonium nitrate. We found that the nanolayered Mn oxide/C60 composites show promising activity toward water oxidation. PMID:24984108

Najafpour, Mohammad Mahdi; Abasi, Mahnaz; Tomo, Tatsuya; Allakhverdiev, Suleyman I

2014-07-15

379

Water oxidation by manganese oxides, a new step towards a complete picture: simplicity is the ultimate sophistication.  

PubMed

We, for the first time, report that many Mn oxides (Mn3O4, ?-Mn2O3, ?-MnO2, CaMnO3, Ca2Mn3O8, CaMn3O6 and CaMn4O8) in the presence of cerium(IV) ammonium nitrate, in the water oxidation, convert to layered Mn oxide. This layered Mn oxide is an efficient water oxidizing catalyst. PMID:23838901

Najafpour, Mohammad Mahdi; Sedigh, Davood Jafarian

2013-09-14

380

Complete oxidation of solid phase sulfides by manganese and bacteria in anoxic marine sediments  

SciTech Connect

During the physical or biological reworking of surficial marine sediments, metal oxides are often brought into contact with both solid and dissolved sulfides. Experiments simulating these mixing processes demonstrate that in natural sediments Mn-oxides can completely oxidize solid phase sulfides to SO{sup =}{sub 4} under anoxic conditions. The major source of sulfur is probably acid volatile sulfide. Minerals containing Mn{sup +4} are apparently more effective than Mn{sup +3} in driving the oxidation. There is slight or no evidence for complete sulfide oxidation by Fe-oxides under similar conditions. The reaction is inhibited by DNP (dinitrophenol) and Azide, implying biological mediation by a group of chemolithotrophic bacteria such as the thiobacilli, having a well-organized cytochrome system, oxidative phosphorylation coupled with sulfide oxidation, and possibly autotrophic CO{sub 2} fixation. Lack of sensitivity to chlorate suggests that a NO{sup {minus}}{sub 3} reductase complex is not involved. Because of metal reduction and the overall stoichiometry of reaction, this sulfide oxidation causes a rise in pH in contrast to oxidation by O{sub 2}. Alkalinity is also simultaneously depleted by Mn, Ca carbonate precipitation. Both manganoan kutnahorite and manganoan calcite are observed to form rapidly (days) during Mn reduction. The oxidation of sulfides by Mn-oxides is likely to be important, but highly variable, in organic-rich shelf sediments and environments such as hydrothermal vents where sulfidic plumes contact oxidized metals. A substantial proportion of sedimentary sulfide may be oxidized and Mn reduced by this pathway, particularly in bioturbated sediments. The relative roles of lithotrophic (S) and heterotrophic (C) Mn-reduction in marine sediments are presently unknown.

Aller, R.C.; Rude, P.D. (State Univ. of New York, Stony Brook (USA))

1988-03-01

381

Complete oxidation of solid phase sulfides by manganese and bacteria in anoxic marine sediments  

NASA Astrophysics Data System (ADS)

During the physical or biological reworking of surficial marine sediments, metal oxides are often brought into contact with both solid and dissolved sulfides. Experiments simulating these mixing processes demonstrate that in natural sediments Mn-oxides can completely oxidize solid phase sulfides to SO 4- under anoxic conditions. The major source of sulfur is probably acid volatile sulfide. Minerals containing Mn +4 are apparently more effective than Mn +3 in driving the oxidation. There is slight or no evidence for complete sulfide oxidation by Fe-oxides under similar conditions. The reaction is inhibited by DNP (dinitrophenol) and azide, implying biological mediation by a group of chemolithotrophic bacteria such as the thiobacilli, having a well-organized cytochrome system, oxidative phosphorylation coupled with sulfide oxidation, and possibly aulolrophic CO 2 fixation. Lack of sensitivity to chlorate suggests that a No 3- reductase complex is not involved. Because of metal reduction and the overall stoichiometry of reaction, this sulfide oxidation causes a rise in pH in contrast to oxidation by O 2. Alkalinity is also simultaneously depeleted by Mn, Ca carbonate precipitation. Both manganoan kutnahorite and manganoan calcite are observed to form rapidly (days) during Mn reduction. The oxidation of sulfides by Mn-oxides is likely to be important, but highly variable, in organic-rich shelf sediments and environments such as hydrothermal vents where sulfidic plumes contact oxidized metals. A substantial Proportion of sedimentary sulfide may be oxidized and Mn reduced by this pathway, particularly in bioturbated sediments. The relative roles of lithotrophic (S) and heterotrophic (C) Mn-reduction in marine sediments are presently unknown.

Aller, Robert C.; Rude, Peter D.

1988-03-01

382

The influence of manganese-cobalt oxide/graphene on reducing fire hazards of poly(butylene terephthalate).  

PubMed

By means of direct nucleation and growth on the surface of graphene and element doping of cobalt oxide (Co3O4) nano-particles, manganese-cobalt oxide/graphene hybrids (MnCo2O4-GNS) were synthesized to reduce fire hazards of poly(butylene terephthalate) (PBT). The structure, elemental composition and morphology of the obtained hybrids were surveyed by X-ray diffraction, X-ray photoelectron spectrometer and transmission electron microscopy, respectively. Thermogravimetric analysis was applied to simulate and study the influence of MnCo2O4-GNS hybrids on thermal degradation of PBT during combustion. The fire hazards of PBT and its composites were assessed by the cone calorimeter. The cone test results had showed that peak HRR and SPR values of MnCo2O4-GNS/PBT composites were lower than that of pure PBT and Co3O4-GNS/PBT composites. Furthermore, the incorporation of MnCo2O4-GNS hybrids gave rise to apparent decrease of pyrolysis products containing aromatic compounds, carbonyl compounds, carbon monoxide and carbon dioxide, attributed to combined impact of physical barrier for graphene and cat O4 for organic volatiles and carbon monoxide. PMID:24997255

Wang, Dong; Zhang, Qiangjun; Zhou, Keqing; Yang, Wei; Hu, Yuan; Gong, Xinglong

2014-08-15

383

Characterization of a mitochondrial manganese superoxide dismutase gene from Apis cerana cerana and its role in oxidative stress.  

PubMed

Mitochondrial manganese superoxide dismutase (mMnSOD) plays a vital role in the defense against reactive oxygen species (ROS) in eukaryotic mitochondria. In this study, we isolated and identified a mMnSOD gene from Apis cerana cerana, which we named AccSOD2. Several putative transcription factor-binding sites were identified within the 5'-flanking region of AccSOD2, which suggests that AccSOD2 may be involved in organismal development and/or environmental stress responses. Quantitative real-time PCR analysis showed that AccSOD2 is highly expressed in larva and pupae during different developmental stages. In addition, the expression of AccSOD2 could be induced by cold (4 °C), heat (42 °C), H2O2, ultraviolet light (UV), HgCl2, and pesticide treatment. Using a disc diffusion assay, we provide evidence that recombinant AccSOD2 protein can play a functional role in protecting cells from oxidative stress. Finally, the in vivo activities of AccSOD2 were measured under a variety of stressful conditions. Taken together, our results indicate that AccSOD2 plays an important role in cellular stress responses and anti-oxidative processes and that it may be of critical importance to honeybee survival. PMID:24269344

Jia, Haihong; Sun, Rujiang; Shi, Weina; Yan, Yan; Li, Han; Guo, Xingqi; Xu, Baohua

2014-01-01

384

Preparation of highly active manganese oxides supported on functionalized MWNTs for low temperature NOx reduction with NH3  

NASA Astrophysics Data System (ADS)

Manganese oxide catalysts (MnOx) supported on functionalized multi-walled carbon nanotubes (FMWNTs) for low temperature selective catalytic reduction (LTSCR) of nitrogen oxides (NOx) with NH3 in the presence of excess O2 were prepared by the incipient wetness impregnation method. These catalysts were characterized by N2 adsorption, Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), X-ray diffraction (XRD), thermal gravimetric analysis (TGA) and H2-temperature programmed reduction (H2-TPR) methods. The effects of reaction temperature, MnOx loading, calcination temperature and calcination time were investigated. The presence of surface nitrate species under moderate calcination conditions may play a favorable role in the LTSCR of NOx with NH3. Under the reaction conditions of 200 °C, 1 bar, NO = NH3 = 900 ppm, O2 = 5 vol%, GHSV = 30,000 h-1 and 12 wt% MnOx, NOx conversion and N2 selectivity were 97% and 99.5%, respectively. The SCR activity was reduced in the presence of 100 ppm SO2 and 2.5 vol% H2O from 97% to 92% within 6 h at 200 °C, however such an effect was shown to be reversible by exposing the catalyst to a helium flow for 2 h at 350 °C due to thermal decomposition of ammonium sulphate salts.

Pourkhalil, Mahnaz; Moghaddam, Abdolsamad Zarringhalam; Rashidi, Alimorad; Towfighi, Jafar; Mortazavi, Yadollah

2013-08-01

385

Manganese oxides with rod-, wire-, tube-, and flower-like morphologies: highly effective catalysts for the removal of toluene.  

PubMed

Nanosized rod-like, wire-like, and tubular ?-MnO(2) and flower-like spherical Mn(2)O(3) have been prepared via the hydrothermal method and the CCl(4) solution method, respectively. The physicochemical properties of the materials were characterized using numerous analytical techniques. The catalytic activities of the catalysts were evaluated for toluene oxidation. It is shown that ?-MnO(2) nanorods, nanowires, and nanotubes with a surface area of 45-83 m(2)/g were tetragonal in crystal structure, whereas flower-like spherical Mn(2)O(3) with a surface area of 162 m(2)/g was of cubic crystal structure. There were the presence of surface Mn ions in multiple oxidation states (e.g., Mn(3+), Mn(4+), or even Mn(2+)) and the formation of surface oxygen vacancies. The oxygen adspecies concentration and low-temperature reducibility decreased in the order of rod-like ?-MnO(2) > tube-like ?-MnO(2) > flower-like Mn(2)O(3) > wire-like ?-MnO(2), in good agreement with the sequence of the catalytic performance of these samples. The best-performing rod-like ?-MnO(2) catalyst could effectively catalyze the total oxidation of toluene at lower temperatures (T(50%) = 210 °C and T(90%) = 225 °C at space velocity = 20,000 mL/(g h)). It is concluded that the excellent catalytic performance of ?-MnO(2) nanorods might be associated with the high oxygen adspecies concentration and good low-temperature reducibility. We are sure that such one-dimensional well-defined morphological manganese oxides are promising materials for the catalytic elimination of air pollutants. PMID:22413904

Wang, Fang; Dai, Hongxing; Deng, Jiguang; Bai, Guangmei; Ji, Kemeng; Liu, Yuxi

2012-04-01

386

In situ X-ray absorption spectroscopy investigation of a bifunctional manganese oxide catalyst with high activity for electrochemical water oxidation and oxygen reduction.  

PubMed

In situ X-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs RHE produces a disordered Mn3(II,III,III)O4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed Mn(III,IV) oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3(II,III,III)O4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the Mn(III,IV) oxide, rather than Mn3(II,III,III)O4, is the phase pertinent to the observed OER activity. PMID:23758050

Gorlin, Yelena; Lassalle-Kaiser, Benedikt; Benck, Jesse D; Gul, Sheraz; Webb, Samuel M; Yachandra, Vittal K; Yano, Junko; Jaramillo, Thomas F

2013-06-12

387

In-situ X-Ray Absorption Spectroscopy (XAS) Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction  

PubMed Central

In-situ x-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in-situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs. RHE produces a disordered Mn3II,III,IIIO4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs. RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed MnIII,IV oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3II,III,IIIO4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the MnIII,IV oxide, rather than Mn3II,III,IIIO4, is the phase pertinent to the observed OER activity.

Benck, Jesse D.; Gul, Sheraz; Webb, Samuel M.; Yachandra, Vittal K.; Yano, Junko; Jaramillo, Thomas F.

2013-01-01

388

Manganese pavements on the blake plateau.  

PubMed

Dredge samples and photographs from the Blake Plateau, off the southeast coast of the United States, indicate that a layer of manganese oxide forms pavement that may be continuous over an area af about 5000 square kilometers. The manganese pavement grades into round manganese nodules to the south and east and into phosphate nodules to the west. The Gulf Stream probably maintains a very unusual environment that prohibits deposition of clastic sediment and permits accretion of manganese pavements. PMID:17739590

Pratt, R M; McFarlin, P F

1966-03-01

389

Effect of the addition of chromium- and manganese oxides on structural and catalytic properties of copper\\/zirconia catalysts for the synthesis of methanol from carbon dioxide  

Microsoft Academic Search

The effect of chromium- and manganese oxide on the structural and catalytic properties of copper\\/zirconia used for methanol synthesis from carbon dioxide and hydrogen has been investigated by several techniques (TGDTA, XRD, TPR, XPS, N2O-titration, nitrogen physisorption). The methanol selectivity of all catalysts is governed by the competition of the simultaneously catalyzed methanol synthesis and reverse water gas shift reaction.

M. Kilo; J. Weigel; A. Wokaun; R. A. Koeppel; A. Stoeckli; A. Baiker

1997-01-01

390

Manganese Induces Oxidative Stress, Redox State Unbalance and Disrupts Membrane Bound ATPases on Murine Neuroblastoma Cells In Vitro: Protective Role of Silymarin  

Microsoft Academic Search

Manganese (Mn) is an essential trace element required for ubiquitous enzymatic reactions. Chronic overexposure to this metal\\u000a may promote potent neurotoxic effects. The mechanism of Mn toxicity is not well established, but several studies indicate\\u000a that oxidative stress play major roles in the Mn-induced neurodegenerative processes. Silymarin (SIL) has antioxidant properties\\u000a and stabilizes intracellular antioxidant defense systems. The aim of

Yassine Chtourou; Khaled Trabelsi; Hamadi Fetoui; Ghada Mkannez; Héla Kallel; Najiba Zeghal

391

Effects of calorie restriction on the expression of manganese superoxide dismutase and catalase under oxidative stress conditions in the rotifer Brachionus plicatilis  

Microsoft Academic Search

Calorie restriction (CR) in the rotifer Brachionus plicatilis extends its lifespan, as it enhances the expression of antioxidant enzymes such as manganese superoxide dismutase (Mn SOD)\\u000a and catalase. Here we show that CR also increased the mRNA levels of these antioxidant enzymes upon exposure to oxidative\\u000a stress. Rotifers cultured under CR showed a higher survival rate than those fed ad

Muniyandi KailasamGen KanekoAung; Gen Kaneko; Aung Kyaw Swar Oo; Yori Ozaki; Arunachalam Rengasamy Thirunavukkarasu; Shugo Watabe

2011-01-01

392

Ozone Decomposition over Manganese Oxide Supported on ZrO 2 and TiO 2: A Kinetic Study Using in Situ Laser Raman Spectroscopy  

Microsoft Academic Search

Ozone decomposition on ZrO2- and TiO2-supported manganese oxide was studied using in situ laser Raman spectroscopy along with simultaneous steady-state kinetic measurements. The Raman spectra showed the presence of an adsorbed peroxide species for both catalysts under reaction conditions. The experimental data were well represented by a nonuniform surface kinetic treatment that assumed that the activation energies of adsorption and

Rakesh Radhakrishnan; S. Ted Oyama

2001-01-01

393

Formation of Metallogenium -like structures by a manganese-oxiding fungus  

Microsoft Academic Search

Structures resembling Metallogenium spp. were observed in agar and in liquid cultures of a Mn-oxidizing basidiomycetous fungus only when Mn2+ was oxidized. Fungal viability was necessary for formation of the structures; Mn2+ concentration and the presence or absence of agar in the medium were important factors determining their morphology. Slide cultures revealed no identifiable cells in any stage of development.

David Emerson; Rhea E. Garen; William C. Ghiorse

1989-01-01

394

Manganese doped Zinc oxide thin film hydrogen gas sensor at reduced operating temperature  

Microsoft Academic Search

During the pas t few decades, semiconductor metal oxide (SMO) gas sensors have become a prime technology in several domestic, commercial, and industrial gas sensing. The semiconductor properties of zinc oxide along with its dopant remain to be trapped fully in its application as gas sensor. With the advent of nanotechnology, miniaturization and high sensitivity happens to be a key

Anjali Chatterjee; Partha Bhattacharjee; P. kumbakar; Nirmal Kumar Roy

2011-01-01

395

Determining the Role of Multicopper Oxidases in Manganese(II) Oxidation by Marine Bacillus Spores  

NASA Astrophysics Data System (ADS)

Bacteria play an important role in the environmental cycling of Mn by oxidizing soluble Mn(II) and forming insoluble Mn(III/IV) oxides. These biogenic Mn oxides are renowned for their strong sorptive and oxidative properties, which control the speciation and availability of many metals and organic compounds. A wide variety of bacteria are known to catalyze the oxidation of Mn(II); one of the most frequently isolated types are Bacillus species that oxidize Mn(II) only as metabolically dormant spores. We are using genetic and biochemical methods to study the molecular mechanisms of this process in these organisms. mnxG, a gene related to the multicopper oxidase (MCO) family of enzymes, is required for Mn(II) oxidation in the model organism, Bacillus sp. strain SG-1. Mn(II)-oxidizing activity can be detected in crude protein extracts of the exosporium and as a discrete band in SDS-PAGE gels, however previous attempts to purify or identify this Mn(II)-oxidizing enzyme have failed. A direct link between the Mn(II)-oxidizing enzyme and the MCO gene suspected to encode it has never been made. We used genetic and biochemical methods to investigate the role of the MCO in the mechanism of Mn(II) oxidation. Comparative analysis of the mnx operon from several diverse Mn(II)-oxidizing Bacillus spores revealed that mnxG is the most highly conserved gene in the operon, and that copper binding sites are highly conserved. As with Mn(II) oxidases from other organ